Purify cellulosic sugars

Scout intake sheet

4
Challenge description

The biorefinery is a recognized approach for transforming renewable raw materials into biobased process streams, and ultimately chemicals and fuels. Developing broad based technologies capable of producing families of high value chemicals will provide a significant opportunity for the biorefinery. The starting block of the biorefinery is the breakdown of ligno-cellulosic biomass into cellulosic sugars by hydrolysis. However, different type of feedstock contain different composition of monomeric C5/C6 sugars (xylose, arabinose, mannose, galactose or glucose). This distribution is critical for production yields and process economics. Indeed, C5/C6 sugars provide the highest value when they are isolated and purified into separate components. Therefore, this project will focus on the purification and separation of hemicellulosic sugars to improve the quality of a biomass hydrolysate.

Scope
Discover Demonstrate Develop Deploy
Current known technique(s)
  • Simulated Moving Bed
  • Crystallization
  • Chromatography
  • Novasep
Ideal outcome

A technology that allows separating all hemicellulosic biomass hydrolysate compositions into pure monomeric sugar components. **Minimum Viable Outcome** An overview of the available techniques to purify hemicellulosic sugars.

Objective(s)
  • Purify biomass hydrolysate
Constraint(s)
  • Cost (Selectivity; concentration; solvents; throughput)
  • Scalability (Unit operations; concentration)
  • Lignin handling
Functions
Action = [separate] OR [purify] OR [present] OR [perform] OR [recover] OR [extract] OR [enable] OR [enhance] OR [present] OR [concentrate] OR [be] OR [recover]

Object = [hydrolysate] OR [hemicellulosic sugar] OR [purification process] OR [separation] OR [xylose] OR [sugar] OR [separation] OR [separation] OR [purification process] OR [feed] OR [membrane] OR [sugar]

Environment = [lignocellulose] OR [biomass] OR [hemicellulose] OR [hydrolysate] OR [separation] OR [C5 sugar] OR [xylose] OR [hexose] OR [refine] OR [hemicellulose hydrolysate] OR [recovery] OR [Monosaccharide purification] OR [sugar separation] OR [single sugar] OR [boronic] OR [extractant] OR [purity] OR [enzyme] OR [xylose] OR [mannose] OR [arabinose] OR [simulated moving bed] OR [low fouling] OR [high performance] OR [graphene] OR [harsh operating condition] OR [smb] OR [biomass hydrolyzate]
Terminology
  • Hemicellulose hydrolysis

Preliminary Results

Published 7/31/19

Based on the case described above we have executed the first line of queries in IGOR^AI. The goal was to obtain a broad set of techniques that separate (hemicellulosic) sugar monomers. 6 concepts are distinguished based on the results: 1. Extraction 2. Chromatography 3. Filtration 4. Boronic acid-based (BAB) complexation 5. Integrated Approaches 6. Other techniques Every concept comprises multiple techniques (30 in total). Below the table, short descriptions, research findings and sources per technique are listed as well. You can use this information to get a better understanding of the techniques. During the midway meeting, we would like to discuss the techniques and concepts, determine their relevance and select the top selection that needs to be deepened in the second phase of the project.

To determine which technologies are relevant to proceed to the next scouting phase you can play the technology selection game by clicking on the button below.

Concept Technology Selection
1. Extraction
Extraction in chemistry is a separation process consisting in the separation of a substance from a matrix. It includes Liquid-liquid extraction, and Solid phase extraction. The distribution of a solute between two phases is an equilibrium condition described by partition theory.
1.1 Ionic liquid extraction

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1.2 Deep eutectic solvents

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1.3 Emulsion Liquid Membrane

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2. Chromatography
Chromatography is a laboratory technique for the separation of a mixture. The mixture is dissolved in a fluid called the mobile phase, which carries it through a structure holding another material called the stationary phase. The various constituents of the mixture travel at different speeds, causing them to separate.
2.1 Ion exchange chromatography

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2.2 Thin layer chromatography

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2.3 Simulated Moving Bed Chromatography

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2.4 Steady state recycling chromatography

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2.5 Centrifugal partition chromatograohy (CPC)

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2.6 High performance liquid chromatography

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2.7 Over-pressure Layer Chromatography (OPLC)

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2.8 Low affinity pair size exclusion chromatography

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2.9 Reversible reaction based separation resins

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3. Filtration
Filtration is any of various mechanical, physical or biological operations that separates solids from fluids (liquids or gases) by adding a medium through which only the fluid can pass. The fluid that passes through is called the filtrate.
3.1 Ultrafiltration

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3.2 Thin Film Composite Nanofiltration

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3.3 Hollow Fiber Nanofiltration

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3.4 Enzyme-assisted Nanofiltration

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3.5 Spiral wound Nanofiltration

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3.6 Surface-modified nanofiltration

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3.7 Calcium alginate membranes

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4. Boronic acid-based (BAB) complexation
Boronic acids have a selectivity for binding the 1,2- and/or 1,3-diol sites commonly found in saccharides. This specificity has led to the use of boronic acids as tunable sensors for saccharides: the structure of a given BA will determine to which sugar it will preferentially bind. This principle is exploited in BAB separation technologies
4.1 BAB solvent extraction

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4.2 BAB Supported liquid membrane (SLM) Extraction

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4.3 BAB Aldose-ketose transformation extraction

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5. Integrated Approaches
Integrated approaches make use of several technologies in series to perform the separation.
5.1 Electrodyalysis, simulated moving bed chromatography and crystallization

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5.2 Cocrystallization, ion exchange chromatiography and crystallization of xylose

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5.3 Separation by chromatography and crystallization

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5.4 Reaction separation and solvent extraction

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6. Other techniques
6.1 Biological treatment

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6.2 Capilary zone electrophoresis (CZE)

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6.3 Zeolite-based separation

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6.4 Pretreatments that enhance separation

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1. Extraction

Back

Extraction in chemistry is a separation process consisting in the separation of a substance from a matrix. It includes Liquid-liquid extraction, and Solid phase extraction. The distribution of a solute between two phases is an equilibrium condition described by partition theory.


1.1 Ionic liquid extraction

1

An ionic liquid (IL) is a salt in the liquid state. In some contexts, the term has been restricted to salts whose melting point is below some arbitrary temperature, such as 100 °C (212 °F). While ordinary liquids such as water and gasoline are predominantly made of electrically neutral molecules, ionic liquids are largely made of ions and short-lived ion pairs. [[Wiki]](https://en.wikipedia.org/wiki/Ionic_liquid). Ionic Liquid can be used in an aqueous extraction to separate sugars (e.g. glucose). **Research findings:** IL-based aqueous two-phase systems were formed by adding NaOH, K3PO4, or K2HPO4 into the ILs containing glucose or cellulose hydrolyzates, which were able to partition the glucose into the bottom salt-rich phase. Under the optimum condition, 4 vol 50% NaOH or K3PO4 solution was able to partition 90% glucose, resulting in 16 g/L glucose in the salt-rich phase that could be further used for ethanol fermentation. Art. [#ARTNUM](#article-25970-2578172333)

1.1.1 1.1 Ionic liquid extraction
Saccharification of cellulose in the ionic liquids and glucose recovery
High-efficiency hydrolysis of lignocellulose is critical for the production of second-generation bioethanol. In the present work, the acid hydrolysis of cellulose in ionic liquids (ILs) 1-butyl-3-methylimidazolium chloride ([Bmim]Cl), 1-allyl-3-methylimidazolium chloride ([Amim]Cl), and 1-ethyl-3-methylimidazolium chloride ([Emim]Cl), respectively, was investigated and aqueous two-phase systems were constructed by adding salt solutions to ILs to recover glucose from cellulose hydrolyzates in the ILs. The effects of reaction temperature, reaction time and acid consumption on the cellulose hydrolysis efficiencies in the ILs were determined. The optimal cellulose hydrolysis conditions in ILs were found to be [Bmim]Cl, a reaction time of 0.5 h, an acid consumption of 0.25 mL/g (cellulose) and a reaction temperature of 100 °C. The yield of glucose under the optimal hydrolysis conditions reached 92.88%. IL-based aqueous two-phase systems were formed by adding NaOH, K3PO4, or K2HPO4 into the ILs containing glucose or cellulose hydrolyzates, which were able to partition the glucose into the bottom salt-rich phase. Under the optimum condition, 4 vol 50% NaOH or K3PO4 solution was able to partition 90% glucose, resulting in 16 g/L glucose in the salt-rich phase that could be further used for ethanol fermentation.
6/1/17 12:00:00 AM
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1.2 Deep eutectic solvents

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Deep eutectic solvents (DES) are systems formed from a eutectic mixture of Lewis or Brønsted acids and bases which can contain a variety of anionic and/or cationic species. They are classified as types of ionic solvents with special properties. They incorporate one or more compound in a mixture form, to give a eutectic with a melting point much lower than either of the individual components. [[Wiki]](https://en.wikipedia.org/wiki/Deep_eutectic_solvent) DES have been used to recover xylose. **Research findings** -In this study, a sequential pretreatment comprising of a DES (choline chloride:urea in a ratio of 1:2) and divalent inorganic salt (CuCl 2 ) was evaluated, with the aim of recovering xylose from oil palm fronds (OPF). At a solidtoliquid ratio of 1:10 (w/v), DES alone was ineffective in promoting xylose extraction from OPF. However, a combination of DES (120 °C, 4 h) and 0.4 mol/L of CuCl 2 (120 °C, 30 min) resulted in a pretreatment hydrolysate containing 14.76 g/L of xylose, remarkably yielding 25% more xylose than the CuCl 2 only pretreatment (11.87 g/L). Art. [#ARTNUM](#article-25710-2741963893)

1.2.1 1.2 Deep eutectic solvents
Deep eutectic solvent and inorganic salt pretreatment of lignocellulosic biomass for improving xylose recovery
Abstract Deep eutectic solvents (DESs) have received considerable attention in recent years due to their low cost, low toxicity, and biodegradable properties. In this study, a sequential pretreatment comprising of a DES (choline chloride:urea in a ratio of 1:2) and divalent inorganic salt (CuCl 2 ) was evaluated, with the aim of recovering xylose from oil palm fronds (OPF). At a solid-to-liquid ratio of 1:10 (w/v), DES alone was ineffective in promoting xylose extraction from OPF. However, a combination of DES (120 °C, 4 h) and 0.4 mol/L of CuCl 2 (120 °C, 30 min) resulted in a pretreatment hydrolysate containing 14.76 g/L of xylose, remarkably yielding 25% more xylose than the CuCl 2 -only pretreatment (11.87 g/L). Characterization studies such as FE-SEM, BET, XRD, and FTIR confirmed the delignification of OPF when DES was implemented. Thus, the use of this integrated pretreatment system enabled xylose recoveries which were comparable with other traditional pretreatments.
2/1/18 12:00:00 AM
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1.3 Emulsion Liquid Membrane

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Emulsion liquid membrane (ELM) is a promising technique for the separation of contaminants such as metals, weak acids/bases, inorganic species, and hydrocarbons due to the high interfacial area for mass transfer, the ability to remove and to concentrate selectively or collectively, and the requirement of only small quantities of organic solvent. In the ELM process, both extraction and stripping are combined in one stage, which leads to simultaneous purification and concentration of the solute. Art. [#ARTNUM](#article-25468-2076496702) **Research findings:** - Purification of xylose in simulated hemicellulosic hydrolysates was attempted using a two-step emulsion liquid membrane (ELM) process. The effects of various experimental variables on extraction of each component in the hydrolysates were investigated in the ELM steps. In the first ELM step, acetic acid could be selectively removed from the hydrolysates and highly enriched in the stripping phase, and loss of xylose was insignificant. In the second ELM step, sulfuric acid could be selectively removed from simulated acetic acid-free hemicellulosic hydrolysates and somewhat enriched in the stripping phase. There was just small loss of xylose, and the final pH of the feed phase approached a pH level suitable for ethanol fermentation. Also, concentration of xylose in the feed phase was attained as an incidental outcome during each ELM run. Conclusively, the two-step ELM process was found to be a promising futuristic technology for purification of sugars in real hemicellulosic hydrolysates. Art. [#ARTNUM](#article-25468-2057595511)

1.3.1 1.3 Emulsion Liquid Membrane
Emulsion liquid membrane for heavy metal removal: An overview on emulsion stabilization and destabilization
Abstract Extraction processes using emulsion liquid membrane (ELM) have received significant attention due to their potential as an effective technique for treatment of industrial liquid wastes. However, the need to obtain desired level of stability is very important in order to overcome the obstacle of the application of ELM at industrial scale. The small droplet diameter of emulsion is a key criterion that will provide a stable emulsion and a larger mass transfer area. Two important factors related to the stability of emulsion such as method of emulsification and mechanism of emulsion breaking is discussed in detail. Various emulsification methods such as mechanical agitation and ultrasound emulsification, as well as the emulsion formulation which includes composition, selection of agent, and operation parameters on emulsion stabilization were presented. Emulsion destabilization in term of emulsion breakdown mechanisms such as coalescence, swelling and leakage was also discussed.
7/1/11 12:00:00 AM
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1.3.2 1.3 Emulsion Liquid Membrane
METHOD OF PURIFICATION OF SUGARS IN LIGNOCELLULOSE BIOMASS HYDROLYSATES
The present invention relates to a method for purifying sugar from a hemicellulose hydrolysate which is obtained by hydrolyzing lignocellulosic biomass. More specifically, the present invention relates to a method for purifying sugar from a hemicellulose hydrolysate of lignocellulosic biomass which contains a small amount of organic acid, a furan derivative, and a phenol compound by means of an adsorption and emulsion liquid membrane (ELM) method.
5/11/16 12:00:00 AM
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1.3.3 1.3 Emulsion Liquid Membrane
Purification of xylose in simulated hemicellulosic hydrolysates using a two-step emulsion liquid membrane process.
Abstract Purification of xylose in simulated hemicellulosic hydrolysates was attempted using a two-step emulsion liquid membrane (ELM) process. The effects of various experimental variables on extraction of each component in the hydrolysates were investigated in the ELM steps. In the first ELM step, acetic acid could be selectively removed from the hydrolysates and highly enriched in the stripping phase, and loss of xylose was insignificant. In the second ELM step, sulfuric acid could be selectively removed from simulated acetic acid-free hemicellulosic hydrolysates and somewhat enriched in the stripping phase. There was just small loss of xylose, and the final pH of the feed phase approached a pH level suitable for ethanol fermentation. Also, concentration of xylose in the feed phase was attained as an incidental outcome during each ELM run. Conclusively, the two-step ELM process was found to be a promising futuristic technology for purification of sugars in real hemicellulosic hydrolysates.
10/1/14 12:00:00 AM
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2. Chromatography

Back

Chromatography is a laboratory technique for the separation of a mixture. The mixture is dissolved in a fluid called the mobile phase, which carries it through a structure holding another material called the stationary phase. The various constituents of the mixture travel at different speeds, causing them to separate.


2.1 Ion exchange chromatography

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Ion chromatography (or ion-exchange chromatography) is a chromatography process that separates ions and polar molecules based on their affinity to the ion exchanger. It works on almost any kind of charged molecule—including large proteins, small nucleotides, and amino acids. [[Wiki]](https://en.wikipedia.org/wiki/Ion_chromatography) A lot of different ion exchange resisns have been used in separating and/or purifying hemicellulosic sugars (e.g. mannose, galactose, arabinose, xylose), also on analytical levels. **Research Findings** - Chromatographic separation of galactose from carbohydrate mixtures was studied with strong acid cation exchange resins in Na+, Ca2+ forms and strong base anion exchange resin in SO42– form. The feed solutions were hydrolysates from three possible galactose sources: lactose, gum arabic and hemicellulose in spent sulfite liquor. The main monosaccharide impurities in these raw materials were glucose, arabinose, and xylose. It was demonstrated that large scale liquid chromatography can be used effectively for galactose separation from complex carbohydrate mixtures such as plant hydrolysates as well as lactose hydrolysate. [#ARTNUM](#article-25376-2169675019) - An advantageous separation sequence for mannose from the presented hydrolysate is SBA(SO42–) to remove xylose→SAC (Ba2+) to remove glucose. In the process, ion removal should be applied between the chromatographic steps to avoid formation of BaSO4, which would block the column. The target mannose content 65 % on DS can be reached with an acceptable step yield (> 80 %). The created chromatographic separation sequence seems to be viable based on the experiments. After the chromatographic steps, ion removal and finally crystallization are needed to achieve a crystalline mannose product. Art. [#ARTNUM](#article-25376-2135912353) - Acid hydrolysate was successfully fractionated with ion exchange chromatography and the hydrolysis acid was recovered for reuse. The product fractions obtained include polyphenols and high molar mass hemicelluloses (from UF stage 1), arabinose (from UF stage 2), as well as acetic acid and a mixture of monosaccharides (xylose, galactose, mannose, glucose) from chromatography. Art. [#ARTNUM](#article-25376-1971852480)

2.1.1 2.1 Ion exchange chromatography
Analysis of carbohydrates in paper-making materials by ion chromatography
Seven monosaccharides and two uronic acids were determined by ion chromatography after paper-making material was hydrolyze.Seven monosaccharides and two uronic acids were optimally separated with Dionex CarboPacTM PA20anion exchange column eluted isocratically with 2mmol/L NaOH for the first 20 minutes and eluted gradiently with NaAc(50-200 mmol/L)and 2 mmol/L NaOH for the next 10 minutes at 0.5 mL/min flow rate.RSD of each monosaccharide were0.73%-1.64%.When applying for determining the kind and content of monosaccharides and uronic acids in acidic hydrolysate of cellulose and hemicellulose in eucalyptus and corn stover,the results showed the major glucose followed by xylose.Fructose and galacturonic acid were not detected in eucalyptus and fructose was not detected in corn stover.Holocellulose content and pentosan content in those two materials were calculated to be equivalent to the results obtained by national standard methods.
1/1/13 12:00:00 AM
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2.1.2 2.1 Ion exchange chromatography
Chromatographic separation of glucose, xylose and arabinose from lignocellulosic hydrolysates using cation exchange resin
Abstract Recovery of monosaccharides from hydrolysates of biomass wastes can bring environmental and economic benefits. This study aimed to explore the feasibility to separate major monosaccharides from hydrolysates of lignocellulosic biomass, i.e. glucose, xylose and arabinose by using column chromatography process. Cation exchange resin Amberlite IR120 and Amberlite IRP69 in Na + and Ca 2+ forms were chosen as adsorbents. The adsorption behaviors were firstly inspected by adsorption equilibrium and mass transfer coefficients. Then the optimal chromatography conditions were determined by using synthetic solution. Finally, hydrothermal liquefaction hydrolysate of pine branches was separated. The results showed that cation resin Amberlite IRP69 (Ca 2+ ) had high adsorption selectivity for arabinose which could be recovered from synthetic solution with purity of 92%. The highest purity of 88% was achieved for xylose when using this resin to separate pretreated hydrolysate. This work suggests that cation exchange resin could be further developed for effective separation of monosaccharides mixture.
4/1/18 12:00:00 AM
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2.1.3 2.1 Ion exchange chromatography
Evaluation of Alkaline Earth and Transition Metals for Use in the Ion Moderated Partition Chromatography of Sugars
Abstract The elution behavior of 28 sugars and related compounds from high performance chromatography columns packed with alkaline earth and transition metals was investigated. As expected from the well-known chromatography of the commercially available calcium, silver, and lead form columns, elution behavior is highly metal-ion form specific. A significant data base of sugar elution versus column cationic-form was generated to permit the selection of new columns to enhance the separation of specific eluting species. Sugars resulting from the hydrolysis of wood were closely examined. Arabinose and galactose, known to be difficult to separate on commercially available lead and silver-form columns, were well separated on custom-packed rubidium and cesium-form columns.
2/1/90 12:00:00 AM
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2.1.4 2.1 Ion exchange chromatography
FROM BIOMASS TO SUGAR ALCOHOLS: PURIFICATION OF WHEAT BRAN HYDROLYSATES USING BORONIC ACID CARRIERS FOLLOWED BY HYDROGENATION OF SUGARS OVER RU/H-ZSM-5
Wheat bran is a lignocellulosic waste of milling industry. It contains hemicelluloses which can be valorized into arabitol and xylitol via a few-step approach. It begins with extraction and hydrolysis of hemicelluloses to produce a solution of xylose and arabinose along with proteins and inorganic salts. This work focusses on the purification of sugars of this hydrolysate and the subsequent catalytic production of sugar alcohols. A purification process based on the recovery of sugars by anionic extraction with a boronic acid, followed by back-extraction and a further refining step with ion exchange resins is described. After this process, a high purity sugars solution (~90%) free of inorganic elements and proteins was obtained. The feasibility of the process was also highlighted by a successful recycling of the organic phase containing the boronic acid. The hydrogenation of purified sugars was then performed over Ru/H-ZSM-5. A high yield into pentitols of ~70% with 100% selectivity was achieved. Important...
9/4/18 12:00:00 AM
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2.1.5 2.1 Ion exchange chromatography
Ion exchange separation for recovery of monosaccharides, organic acids and phenolic compounds from hydrolysates of lignocellulosic biomass
Abstract This paper describes two effective ion exchange chromatography processes to separate and recover monosaccharides, organic acids and phenolic compounds from two kinds of hydrothermal liquefaction (HTL) hydrolysates derived under different temperatures. Anion exchange resin Amberlyst A21 (OH − ) and cation exchange resin Amberlite IR-120 (Na + ) were selected to separate synthetic solution and real hydrolystes by column chromatography. The results showed that glucose and acetic acid could be successfully separated by anion resin with purities of 87% and 98%, respectively. Acetic acid and phenol could be recovered by cation resin with purities up to 97% and 81%. In separation processes of real HTL hydrolysates, monosaccharides and organic acids in hydrolysate derived from low-temperature HTL were separated by anion exchange resin with recoveries of about 80% and 90%, respectively. Phenolic compounds in high-temperature HTL hydrolysate were recovered by cation exchange resin with recovery of about 70%.
1/1/17 12:00:00 AM
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2.1.6 2.1 Ion exchange chromatography
Process Synthesis Principles in the Chromatographic Separation of Sugars from Biomass Hydrolysates
Processing of biomass hydrolysates will increase in future as the sugar platform in biorefineries is employed to an increasing extent. Monosaccharides in the hydrolysates may be separated as a sugar group for fermentation or as individual sugars for use in the food and pharmaceutical industry. Chromatographic separation of sugars using ion exchange (IEX) resins is an interesting alternative for these purposes. The current status and use of IEX resins in the chromatographic separation of sugars is discussed. Based on industrial practice, process synthesis principles and heuristics are presented for the selection of a feasible IEX resin and separation sequence. Two case studies are presented and the viability of the synthesized sequences is verified experimentally.
2/1/11 12:00:00 AM
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2.1.7 2.1 Ion exchange chromatography
Production and recovery of monosaccharides from lignocellulose hot water extracts in a pulp mill biorefinery.
Abstract Processing of hemicelluloses obtained with pressurized hot water extraction (PHWE) from Scots pine to monosaccharides and other chemicals was investigated experimentally. A process scheme consisting of ultrafiltration, acid hydrolysis, and chromatographic separation was proposed and evaluated. A two-stage ultrafiltration was found necessary for efficient fractionation of the wood extract. It was shown that the monosaccharides can be released from a concentrated hemicellulose fraction with sulfuric acid hydrolysis without a significant loss of yield due to decomposition of monosaccharides. Acid hydrolysate was successfully fractionated with ion exchange chromatography and the hydrolysis acid was recovered for reuse. The product fractions obtained include polyphenols and high molar mass hemicelluloses (from UF stage 1), arabinose (from UF stage 2), as well as acetic acid and a mixture of monosaccharides (xylose, galactose, mannose, glucose) from chromatography.
5/1/13 12:00:00 AM
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2.1.8 2.1 Ion exchange chromatography
Study on Industrial Scale Chromatographic Separation Methods of Galactose from Biomass Hydrolysates
Galactose is an aldohexose, which has commercial uses in the pharmaceutical and food industries. Since monomeric galactose is not a freely occurring compound, it must be produced from galactose-containing hydrolysates. This paper reports the results of experimental studies of the chromatographic separation of galactose in aqueous solutions by ion exchange resins on an industrial scale. Until now, galactose has only been determined from various solutions by liquid chromatography (HPLC) on an analytical scale. Chromatographic separation of galactose from carbohydrate mixtures was studied with strong acid cation exchange resins in Na+, Ca2+ forms and strong base anion exchange resin in SO42– form. The feed solutions were hydrolysates from three possible galactose sources: lactose, gum arabic and hemicellulose in spent sulfite liquor. The main monosaccharide impurities in these raw materials were glucose, arabinose, and xylose. It was demonstrated that large scale liquid chromatography can be used effectively for galactose separation from complex carbohydrate mixtures such as plant hydrolysates as well as lactose hydrolysate.
1/1/10 12:00:00 AM
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2.1.9 2.1 Ion exchange chromatography
Xylose-based hydrolysate from eucalyptus extract as feedstock for poly(lactate-co-3-hydroxybutyrate) production in engineered Escherichia coli
Abstract Woody extract-derived hemicellulosic hydrolysate, which was obtained from dissolving pulp manufacturing, was utilized as feedstock for the production of poly(lactate- co -3-hydroxybutyrate) [P(LA- co -3HB)] in engineered Escherichia coli . The hydrolysate was composed of mainly xylose and galactose, and contained impurities mainly acetate, which was found to inhibit the polymer synthesis rather than the cell growth. Thus, acetate and other impurities were removed through active charcoal and ion-exchange columns. Using the purified hydrolysate, P(LA- co -3HB) was successfully produced (cell dry weight 8.6 g/L, polymer concentration 5.4 g/L, LA fraction 5.5 mol%, polymer content 62.4%), the amount of which was comparable to that obtained using reagent grade xylose and galactose. Therefore, the hydrolysate from woody extract is considered as an abundant, inexpensive and efficient feedstock applicable to consolidated process for P(LA- co -3HB) production, when the removal of acetic acid was satisfactorily accomplished.
3/1/17 12:00:00 AM
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2.1.10 2.1 Ion exchange chromatography
Process for separating arabinose from a mixture of aldoses
Both selectivities and resolutions indicated that some degree of separation of arabinose from mannose, glucose, xylose and galactose was possible. However, Tables 2 and 3 indicate that the Ca/NH.sub.4 -resin is a far better performer in the arabinose separation than the Ca-resin. The difference can be noted clearly from the lower resolution achieved with the Ca-resin (Table 3) than that achieved by the Ca/NH.sub.4 -resin (Table 2). This difference is also demonstrated in FIG. 2, in which resolution is plotted for Ca-resin and Ca/NH.sub.4 -resin. There is higher resolution in all cases for Ca/NH.sub.4 -resin compared to Ca-resin.
1. A process for separating arabinose rom an aqueous feed mixture containing arabinose and at least one other monosaccharide, selected from the group consisting of aldopentoses and aldohexoses, which comprises contacting at adsorption conditions said mixture with an adsorbent comprising a nuclearly sulfonated cationic exchange resin having a crosslinked vinylaromatic resin matrix exchanged with Ca.sup.++ and NH.sub.4.sup.+ ions, selectively adsorbing said arabinose to the substantial exclusion of the other monosaccharides, removing the nonadsorbed portion of the feed mixture from contact with the adsorbent, and hereafter recovering high purity arabinose by desorption at desorption conditions. 2. The process of claim 1 wherein said feed mixture contains arabinose and at least one other monosaccharide selected form the group consisting of xylose, glucose, galactose, mannose, and rhamnose. 3. The process of claim 1 wherein said desorbent comprises water. 4. The process of claim 3 wherein said exchange resin is a sulfonated polystyrene polymer having a crosslinked divinylbenzene matrix. 5. The process of claim 4 wherein said exchange resin is crosslinked from about 4% to 6%. 6. The process of claim 5 wherein said separation is effected by a countercurrent simulated moving bed scheme. 7. The process of claim 5 wherein said separation is effected by a cocurrent simulated moving bed scheme.
12/31/86 12:00:00 AM
Link to Patent
2.1.11 2.1 Ion exchange chromatography
Separation and recovery of xylose using weakly basic anion exchange resins

1. A method of separating and recovering xylose from a xylose containing plant-based solution, comprising:performing the separation in a chromatographic separation system, which comprises one or more weak base anion exchange resins or a combination thereof and optionally one or more other resins selected from strong acid cation exchange resins and weak acid cation exchange resins, by passing the solution through the separation system; andrecovering at least one fraction enriched in xylose wherein the recovered xylose fraction has a xylose purity of more than 45% on dissolved dry solids based on weight %. 2. The method according to claim 1, wherein if the chromatographic separation system comprises one or more weak base anion exchange resins in combination with one or more weak acid cation exchange resins, the method further comprises recovering a fraction enriched in rhamnose. 3. The method according to claim 2, wherein the yield of the fraction enriched in rhamnose recovered is at least 15%. 4. The method according to claim 1, wherein the separation comprises first a separation with said one or more strong acid cation exchange resins and then a separation with said one or more weak base anion exchange resins. 5. The method according to claim 1, wherein the separation comprises first a separation with said one or more weak acid cation exchange resins and then a separation with said one or more weak base anion exchange resins. 6. The method according to claim 1, wherein said one or more weak base anion exchange resins and each of said other resins are arranged in one or more separate columns with one or more compartments. 7. The method according to claim 1, wherein the strong acid cation exchange resin is in a multivalent, divalent, or monovalent cation form. 8. The method according to claim 1, wherein the weak base anion exchange resin is based on a resin selected from the group consisting of acrylic resins, polystyrene resins, epichlorohydrin based anion exchange resins, aminated products of phenol or formaldehyde resins, aliphatic amines, and ammonia polycondensation resins. 9. The method according to claim 8, wherein the weak base anion exchange resin is a resin with an acrylic matrix. 10. The method according to claim 9, wherein the weak acid cation exchange resin is in a H+, Na+, K+, Ca2+, Mg2+, or combination thereof form. 11. The method according to claim 1, wherein the resins are crosslinked with an aromatic crosslinker. 12. The method according to claim 1, wherein the eluent for the chromatographic separation is selected from water, an aqueous solution, an alcohol, an evaporation condensate, an evaporation condensate containing acetic acid, or mixtures thereof. 13. The method according to claim 12, wherein a portion of the eluent is replaced by one or more fractions collected from the chromatographic separation. 14. The method according to claim 1, wherein the separation is performed at a temperature of 20° C. to 95° C. 15. The method as claimed in claim 1, wherein the separation is performed by a method selected from a sequential simulated moving bed method, continuous simulated moving bed method, a batch method or combinations thereof. 16. The method as claimed in claim 1, wherein the separation system comprises one or more loops and different resins are arranged in the same loop or in different loops. 17. The method as claimed in claim 16, wherein the separation system comprises one or more separation profiles in a loop. 18. The method as claimed in claim 1, wherein the method provides a xylose yield of more than 80%. 19. The method as claimed in claim 1, wherein the xylose-containing plant- based solution used as the feed is selected from plant-based hydrolysates, plant-based extracts, or derivatives thereof. 20. The method as claimed in claim 19, wherein the plant-based hydrolysate is a spent liquor obtained from a pulping process, hardwood pulping, or sulphite pulping. 21. The method as claimed in claim 19, wherein the xylose-containing plant- based solution used as the feed is a mother liquor obtained from the crystallization of xylose. 22. The method according to claim 7, wherein the strong acid cation exchange resin is in a divalent cation form, wherein said form is a Mg2+ or Ca2+ form. 23. The method according to claim 10, wherein the weak acid cation exchange resin is a resin with an acrylic matrix in a H+/Mg2+ form. 24. The method according to claim 13, wherein a portion of the eluent is replaced by one or more residual fractions collected from the chromatographic separation. 25. The method according to claim 14, wherein the separation is performed at a temperature of 60° to 80° C.
9/19/13 12:00:00 AM
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2.1.12 2.1 Ion exchange chromatography
Separation method

1. A process of recovering galactose from a plant-based hemicellulose hydrolyzate solution containing a galactose content of at least 5% by weight, said process comprising(a) subjecting said solution to chromatographic fractionations, said chromatographic fractionations comprising one or more fractionations using a strongly basic anion exchange resin, wherein the anion is selected from SO42−, SO32−, HSO3−, CH3COO−, and one or more fractionations using a cation exchange resin, wherein the cation exchange resin is selected from strong or weak cation exchange resin;(b) recovering at least one fraction enriched in galactose, having a galactose content of 38 to 95% on RDS;(c) subjecting said at least one fraction enriched in galactose to crystallization; and(d) recovering a plant-based crystalline galactose product having a purity of more than 90% on DS. 2. A process as claimed in claim 1, wherein said one or more chromatographic fractionations comprise one or more chromatographic fractionation steps using a column filling material selected from strongly basic anion exchange resins in HSO3− form. 3. A process as claimed in claim 2, wherein said one or more chromatographic fractionations comprise two chromatographic fractionation steps with a resin in HSO3− form. 4. A process as claimed in claim 1, wherein the ion form of said cation exchange resin is selected from Ba2+, Pb2+, Ca2+ and Sr2+. 5. A process as claimed in claim 1, wherein said one or more chromatographic fractionations comprise one or more chromatographic fractionation steps using a column filling material selected from strongly basic anion exchange resins and one or more chromatographic fractionation steps using a column filling material selected from strongly acid cation exchange resins, in any desired sequence. 6. A process as claimed in claim 1, wherein the crystallization is carried out using a solvent selected from water and a mixture of water and alcohol as the crystallization solvent. 7. A process as claimed in claim 6, wherein the crystallization solvent is a mixture of ethanol and water. 8. A process as claimed in claim 6, wherein the crystallization solvent is water. 9. A process as claimed in claim 1, wherein the crystallization provides crystalline galactose having a purity of more than 95% on DS. 10. A process as claimed in claim 1, wherein the crystallization provides crystalline galactose having a purity of more than 98% on DS. 11. A process as claimed in claim 1, wherein the crystallization provides crystalline galactose having a purity of more than 99.5% on DS. 12. A process as claimed in claim 1, wherein the crystallization provides crystalline galactose having a maximum content of D-glucose of 0.50% on DS. 13. A process as claimed in claim 1, wherein the crystallization provides crystalline galactose having a maximum content of D-glucose of 0.30%. 14. A process as claimed in claim 1, wherein the crystallization provides crystalline galactose having an impurity profile comprising at least one sugar selected from xylose, arabinose, rhamnose and mannose. 15. A process as claimed in claim 14, wherein the crystallization provides crystalline galactose, where the impurity profile comprises at least one of said sugars in an amount of 0.03% on DS or more. 16. A process as claimed in claim 15, wherein the crystallization provides crystalline galactose, where the impurity profile comprises arabinose in an amount of 0.03% on DS or more. 17. A process as claimed in claim 15, wherein the crystallization provides crystalline galactose, where the impurity profile comprises mannose in an amount of 0.03% on DS or more. 18. A process as claimed in claim 14, wherein the crystallization provides crystalline galactose, where the impurity profile comprises at least one of said sugars in an amount of 0.10% or more. 19. A process as claimed in claim 1, wherein the process further comprises one or more purification steps selected from membrane filtration, ion exchange, evaporation and filtration carried out before, after or between said chromatographic fractionation step/steps. 20. A process as claimed in claim 1, wherein the process further comprises crystallization between said chromatographic fractionation steps. 21. A process as claimed in claim 20, wherein said crystallization comprises precipitation crystallization of xylose. 22. A process as claimed in claim 1, wherein said plant-based hemicellulose hydrolysate is hydrolysate derived from wood material. 23. A process as claimed in claim 1, wherein said plant-based hemicellulose hydrolysate is a hydrolysate derived from softwood or hardwood. 24. A process as claimed in claim 1, wherein said solution derived from the plant-based hemicellulose hydrolyzate is a spent liquor obtained from a pulping process. 25. A process as claimed in claim 24, wherein said spent liquor obtained from a pulping process is a spent sulphite pulping liquor. 26. A process as claimed in claim 25, wherein said spent sulphite pulping liquor is a spent sulphite pulping liquor recovered after the separation of the main part of xylose. 27. A process as claimed in claim 1, wherein said solution derived from the plant-based hemicellulose hydrolyzate contains galactose and one or more further sugars selected from arabinose and mannose. 28. A process as claimed in claim 1, wherein said galactose is D-galactose. 29. A process as claimed in claim 14, wherein said xylose is D-xylose, said arabinose is L-arabinose, said mannose is D-mannose and said rhamnose is L-rhamnose.
3/5/07 12:00:00 AM
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2.2 Thin layer chromatography

1

Thin-layer chromatography (TLC) is a chromatography technique used to separate non-volatile mixtures. Thin-layer chromatography is performed on a sheet of glass, plastic, or aluminium foil, which is coated with a thin layer of adsorbent material, usually silica gel, aluminium oxide (alumina), or cellulose. This layer of adsorbent is known as the stationary phase. [[Wiki]](https://en.wikipedia.org/wiki/Thin-layer_chromatography) **Research findings:** - Thinlayer chromatographic methods are described for the separation of the following monosaccharides: glucose, galactose, glucosamine, galactosamine, N acetylglucosamine, N acetylgalactosamine and neuraminic acids. Neutral solvent systems and unaltered silica gel G plates were used. The monosaccharides are separated sharply, which allows these methods to be used for the determination of these compounds. The feasibility of these procedures was demonstrated with a hydrolyzate of human erythrocyte globoside. Art. [#ARTNUM](#article-25973-1982552002)

2.2.1 2.2 Thin layer chromatography
Separation and identification of monosaccharides from biological materials by thin-layer chromatography
Abstract Thin-layer chromatographic methods are described for the separation of the following monosaccharides: glucose, galactose, glucosamine, galactosamine, N -acetylglucosamine, N -acetylgalactosamine and neuraminic acids. Neutral solvent systems and unaltered silica gel G plates were used. The monosaccharides are separated sharply, which allows these methods to be used for the determination of these compounds. The preparation and use is discussed of seven facile spray reagents that afford further specificity for detection and evaluation of the sugars at the microgram level. The feasibility of these procedures was demonstrated with a hydrolyzate of human erythrocyte globoside.
9/1/68 12:00:00 AM
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2.3 Simulated Moving Bed Chromatography

0

In manufacturing, the simulated moving bed (SMB) process is a highly engineered process for implementing chromatographic separation. It is used to separate one chemical compound or one class of chemical compounds from one or more other chemical compounds to provide significant quantities of the purified or enriched material at a lower cost than could be obtained using simple (batch) chromatography. [[Wiki]](https://en.wikipedia.org/wiki/Simulated_moving_bed). This is a very relevant chromatographic technique for the separation of hemicellulosic sugars on a larger scale. It is often used in combination with other techniques, such as crystallization in integrated approaches. An ion exchange type of resin is usually employed. **Research findings:** - L-arabinose and D-xylose were extracted from bagasse pith by phosphoric acid. Continuous fractionation of xylose crystalline mother liquid from extraction of bagasse pith was done by simulated moving bed chromatography. The Ca2+ resin was used as a separation agent and water as eluent. L-arabinose and D-xylose were separated with the best parameters and product purity was 81.94% and 91.89%, which made crystallization possible. Art. [#ARTNUM](#article-25375-2375703715) - The economicallyefficient separation of galactose, levulinic acid (LA), and 5hydroxymethylfurfural (5HMF) in acid hydrolyzate of agarose has been a key issue in the area of biofuel production from marine biomass. To address this issue, an optimal simulated moving bed (SMB) process for continuous separation of the three agarosehydrolyzate components with high purities, high yields, and high throughput was developed in this study. Finally, the optimized SMB process was tested experimentally using a selfassembled SMB unit with four zones. The SMB experimental results and the relevant computer simulations verified that the developed process in this study was quite successful in the economicallyefficient separation of galactose, LA, and 5HMF in a continuous mode with high purities and high yields. Art. [#ARTNUM](#article-25375-774350849) - In this study, simulated moving bed (SMB) chromatography equipped with ion exclusion column (containing [Emim] + cation) was investigated to separate sugars (glucose and xylose) which are the main products from biomass hydrolysate and 1Ethyl3methylimidazolium acetate (EmimAc) which is the ILs used for biomass pretreatment. A fourzone SMB system with a configuration of 2222 (2 ion exclusion columns in each zone) was used to recover glucose, xylose and EmimAc from their aqueous mixture with yield of 71.38, 99.37 and 98.92%, respectively. Art. [#ARTNUM](#article-25375-1992379546)

2.3.1 2.3 Simulated Moving Bed Chromatography
Application on separation of bagasse pith extract to produce L-arabinose and D-xylose by simulate moving bed chromatography
L-arabinose and D-xylose were extracted from bagasse pith by phosphoric acid. Continuous fractionation of xylose crystalline mother liquid from extraction of bagasse pith by simulate moving bed chromatography. The Ca2+ resin was used as a separation agent and water was eluent. L-arabinose and D-xylose were separated with the best parameters and product purity was 81.94% and 91.89% which can be crystallize. This process was high extraction rate and purity, easy operation and low running cost. The phosphate which in hydrolysate and ion exchanging eluate can be reused in clarification process of cane sugar. There is no discharge of waste liquid and phosphoric acid was realized resource recycling. This process effectively solved the environmental protection problem of L-arabinose traditional processing technology, and opened up a new field of raw material for L-arabinose and suitable for industrialized production.
1/1/15 12:00:00 AM
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2.3.2 2.3 Simulated Moving Bed Chromatography
Chapter Five - Chromatographic Fractionation of Lignocellulosic Hydrolysates
Abstract Monosaccharides (glucose, xylose, etc.) are valuable platform chemicals that can be produced from lignocellulosic (polysaccharide containing) biomasses via hydrolysis. Their cost-effective recovery from lignocellulosic biomass hydrolysates and further purification requires sophisticated separation technology. Adsorption and electrolyte exclusion chromatography can be used for the fractionation of hydrolysates containing mineral acids. The recovered hydrolysis acid can be recycled, which saves and reduces chemicals consumption. Chromatographic separation can be done either batchwise, using steady-state recycling chromatography, or using continuous simulated moving bed chromatography. The latter two process options offer significant increase in productivity when compared to the batchwise fractionation process. In this chapter, chromatographic and adsorptive fractionation techniques for the treatment of acidic lignocellulosic hydrolysates are reviewed. The relevant physical phenomena affecting the separation efficiency as well as various industrially applicable process options are discussed.
1/1/13 12:00:00 AM
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2.3.3 2.3 Simulated Moving Bed Chromatography
Method for separating and purifying xylose and arabinose from hemicellulose acid hydrolysis liquid
The invention relates to a method for separating and purifying xylose and arabinose from hemicellulose acid hydrolysis liquid. The method comprises the following separating and purifying steps of: (1) carrying out electrodialysis and membrane filtration concentrate pretreatment on hemicellulose acid hydrolysis liquid directly obtained by adopting acid hydrolysis, deoxidizing and filtering for later use by adopting high-purity water; (2) putting the hemicellulose acid hydrolysis liquid after pretreatment into a simulated moving bed chromatography separating device and carrying out separation to obtain two discharging liquids; and (3) concentrating, cooling and crystallizing the two discharging liquids by adopting a multi-effect falling film evaporator to obtain xylose and arabinose products. In the invention, monosaccharide is extracted by adopting the simulated moving bed chromatography separation device (SSMB), a plurality of adsorption columns are serially connected into a closed loop, and inlet and outlet positions of all portions of materials can be changed by continuously switching valves, therefore, the relative motion between solid phase and liquid phase is realized, and the separation and the extraction among different components are carried out. The invention not only has the advantages of simple fixed bed adsorption operation, but also has the continuous operation capacity of a moving bed and is suitable for large-scale industrial production.
3/30/10 12:00:00 AM
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2.3.4 2.3 Simulated Moving Bed Chromatography
Method for separating and purifying xylose and arabinose from hemicellulose acid hydrolysis liquid
The invention relates to a method for separating and purifying xylose and arabinose from hemicellulose acid hydrolysis liquid. The method comprises the following separating and purifying steps of: (1) carrying out electrodialysis and membrane filtration concentrate pretreatment on hemicellulose acid hydrolysis liquid directly obtained by adopting acid hydrolysis, deoxidizing and filtering for later use by adopting high-purity water; (2) putting the hemicellulose acid hydrolysis liquid after pretreatment into a simulated moving bed chromatography separating device and carrying out separation to obtain two discharging liquids; and (3) concentrating, cooling and crystallizing the two discharging liquids by adopting a multi-effect falling film evaporator to obtain xylose and arabinose products. In the invention, monosaccharide is extracted by adopting the simulated moving bed chromatography separation device (SSMB), a plurality of adsorption columns are serially connected into a closed loop, and inlet and outlet positions of all portions of materials can be changed by continuously switching valves, therefore, the relative motion between solid phase and liquid phase is realized, and the separation and the extraction among different components are carried out. The invention not only has the advantages of simple fixed bed adsorption operation, but also has the continuous operation capacity of a moving bed and is suitable for large-scale industrial production.
7/25/12 12:00:00 AM
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2.3.5 2.3 Simulated Moving Bed Chromatography
Method for separating glucose and xylose in straw fiber enzymatic hydrolysate
The invention relates to a method for separating glucose and xylose in straw fiber enzymatic hydrolysate. The method for separating glucose and xylose in straw fiber enzymatic hydrolysate comprises the following steps: a) blending feeding syrup, namely, adjusting the concentration of desalted, decolored and concentrated straw fiber enzymatic hydrolysate to be 40-60%; b) filtering, namely, filtering the syrup solution obtained in the step a) by using a micron-order filter so as to prepare a clear liquid in which impurities visible to the naked eyes do not exist; c) performing sequential simulated moving bed chromatographic separation, namely, performing sequential simulated moving bed chromatographic separation on the obtained syrup, wherein deionized water is adopted as an eluent, high-acidity cation exchange resin is adopted as an adsorbent, the separation temperature is 60-70 DEG C, and the sequential simulated moving bed chromatographic separation equipment comprises 9 chromatographic columns arranged in sequence, and is provided with two inlets and two outlets which are alternated sequentially; d) concentrating, namely, concentrating an obtained solution of a component A to be 70-75%, mixing an obtained component B, and further concentrating to be 70-75%. The method is low in operation cost, a product obtained from separation is high in purity, concentration and yield, and continuous and industrial production is achieved.
7/16/14 12:00:00 AM
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2.3.6 2.3 Simulated Moving Bed Chromatography
Process for separating arabinose.
Arabinose can be separated from an aqueous feed mixtrue of monosaccharides containing arabinose along with other aldopentoses and aldohexoses by a liquid phase adsorptive process in which the feed is contacted with a calcium-Y or calcium X type zeolite. Arabinose is selectively adsorbed to the substantial exclusion of other aldoses and thereafter is recovered in high purity by desorption with water or ethanol. The process can be carried out on a commercial scale by means of a simulated moving bed flow scheme.
11/17/88 12:00:00 AM
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2.3.7 2.3 Simulated Moving Bed Chromatography
Recovery of ionic liquid and sugars from hydrolyzed biomass using ion exclusion simulated moving bed chromatography
Abstract Efficient recovery of ionic liquid (IL) from aqueous mixture of ILs and sugars (which derived from enzymatic or chemical catalyzed hydrolysis of ILs-pretreated biomass) is a major drawback for commercialization of biofuel and platform chemicals production from biomass utilized ILs as pretreatment solvent. In this study, simulated moving bed (SMB) chromatography equipped with ion exclusion column (containing [Emim] + cation) was investigated to separate sugars (glucose and xylose) which are the main products from biomass hydrolysate and 1-Ethyl-3-methylimidazolium acetate (EmimAc) which is the ILs used for biomass pretreatment. A four-zone SMB system with a configuration of 2-2-2-2 (2 ion exclusion columns in each zone) was used to recover glucose, xylose and EmimAc from their aqueous mixture with yield of 71.38, 99.37 and 98.92%, respectively. Moreover, the optimization of SMB zone configuration by simulation results in a complete recovery of ILs. This result indicates that for the first time, ion exclusion SMB chromatography could be used for complete recovery of ILs from aqueous sugar mixture.
3/1/12 12:00:00 AM
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2.3.8 2.3 Simulated Moving Bed Chromatography
Simulated moving bed separation of agarose-hydrolyzate components for biofuel production from marine biomass
The economically-efficient separation of galactose, levulinic acid (LA), and 5-hydroxymethylfurfural (5-HMF) in acid hydrolyzate of agarose has been a key issue in the area of biofuel production from marine biomass. To address this issue, an optimal simulated moving bed (SMB) process for continuous separation of the three agarose-hydrolyzate components with high purities, high yields, and high throughput was developed in this study. As a first step for this task, the adsorption isotherm and mass-transfer parameters of each component on the qualified adsorbent were determined through a series of multiple frontal experiments. The determined parameters were then used in optimizing the SMB process for the considered separation. Finally, the optimized SMB process was tested experimentally using a self-assembled SMB unit with four zones. The SMB experimental results and the relevant computer simulations verified that the developed process in this study was quite successful in the economically-efficient separation of galactose, LA, and 5-HMF in a continuous mode with high purities and high yields. It is thus expected that the developed SMB process in this study will be able to serve as one of the trustworthy ways of improving the economic feasibility of biofuel production from marine biomass.
8/1/15 12:00:00 AM
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2.3.9 2.3 Simulated Moving Bed Chromatography
Methods and controllers for simulated moving bed chromatography for multicomponent separation

1. A system for reacting and separating solid and fluid components, the system comprising:a series of sequential simulated moving bed (SMB) chromatography columns connected to form a circulation loop, each SMB chromatography column comprising an inlet and an outlet; anda reactor configured to receive a solid reactant, the reactor having an inlet and an outlet, wherein the reactor inlet is fluidly connected to an outlet of a first SMB chromatography column of the series of sequential SMB chromatography columns, and the reactor outlet is fluidly connected to an inlet of a second SMB chromatography column of the series of sequential SMB chromatography columns. 2. The system of claim 1, wherein the reactor comprises a first reactor, and the system further comprises a second reactor having an inlet and an outlet, wherein the second reactor inlet is fluidly connected to an outlet of a third SMB column of the series of sequential SMB columns, and the second reactor outlet is fluidly connected to an inlet of a fourth SMB column of the series of sequential SMB columns. 3. The system of claim 2, wherein the first reactor comprises two or more reactors connected in a series. 4. The system of claim 3, wherein the second reactor comprises two or more reactors connected in a series. 5. The system of claim 2, wherein the first reactor and the second reactor are hydrolysis reactors. 6. The system of claim 5, wherein a temperature of the first reactor is different than a temperature of the second reactor. 7. The system of claim 2, further comprising a lignocellulosic biomass in the first reactor. 8. The system of claim 7, wherein the first reactor is configured to react cellulose from a lignocellulosic biomass. 9. The system of claim 8, wherein the second reactor is configured to react hemicelluloses from a lignocellulosic biomass. 10. The system of claim 9, wherein the series of sequential SMB chromatography columns are configured to separate hemicellulosic sugars from biomass components of lignocellulosic biomass in the first and second reactors. 11. The system of claim 1, wherein the reactor comprises two or more reactors connected in a series. 12. A method for separating materials from a reaction, the method comprising:positioning a solid material in a reactor; the reactor having an inlet and an outlet; andflowing a liquid through a series of sequential simulated moving bed (SMB) chromatography columns connected to form a circulation loop, each SMB chromatography column comprising an inlet and an outlet, wherein the reactor inlet is fluidly connected to an outlet of a first SMB chromatography column of the series of sequential SMB chromatography columns, and the reactor outlet is fluidly connected to an inlet of a second SMB chromatography column of the series of sequential SMB chromatography columns so that the liquid flowing through the series of sequential SMB chromatographic columns comprises at least one reaction product from the reactor. 13. The method of claim 12, wherein the reactor comprises a first reactor, and a second reactor having an inlet and an outlet is fluidly connected to the series of SMB chromatographic columns so that the second reactor inlet is fluidly connected to an outlet of a third SMB column of the series of sequential SMB columns, and the second reactor outlet is fluidly connected to an inlet of a fourth SMB column of the series of sequential SMB columns. 14. The method of claim 13, wherein the first reactor comprises two or more reactors connected in a series. 15. The method of claim 13, wherein the second reactor comprises two or more reactors connected in a series. 16. The method of claim 13, wherein the first reactor and the second reactor are hydrolysis reactors. 17. The method of claim 16, wherein a temperature of the first reactor is different than a temperature of the second reactor. 18. The method of claim 13, wherein the solid material comprises a lignocellulosic biomass. 19. The method of claim 18, further comprising maintaining the first reactor under conditions sufficient to react cellulose from a lignocellulosic biomass. 20. The method of claim 19, further comprising maintaining the second reactor under conditions sufficient to react hemicelluloses from a lignocellulosic biomass. 21. The method of claim 20, further comprising separating hemicellulosic sugars from biomass components of lignocellulosic biomass in the first and second reactors and further separating hemicellulosic sugars from acid in the series of sequential SMB chromatography columns. 22. The method of claim 12, wherein the reactor comprises two or more reactors connected in a series.
3/28/14 12:00:00 AM
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2.3.10 2.3 Simulated Moving Bed Chromatography
Process for obtaining stereoisomers from biomass
The present invention includes a process for extracting a stereoisomer fro biomass. The method comprises providing biomass and subjecting the biomass to substantially instantaneous pressurization and depressurization to separate cellulose, hemicellulose, and lignin from the biomass. The hemicellulose is hydrolyzed to form hemicellulose hydrolysates. The hydrolysates are separated using chromatography.
1. A process for extracting one or more hemicellulose hydrolysate stereoisomers from biomass, comprising: providing biomass; subjecting the biomass to substantially instantaneous pressurization and de- pressurization in a manner effective to separate lignin, hemicellulose and cellulose in the biomass; hydrolyzing the hemicellulose to form hemicellulose hydrolysates; and separating one or more stereoisomers from the hemicellulose hydrolysates using adsorption. 2. The process of claim 1 and further comprising reducing size of the biomass prior to pressurization. 3. The process of claim 1 and further comprising compacting the biomass prior to pressurization. 4. The process of claim 1 wherein the biomass provided is one or more of wood, beets, corn, soy, wheat, and plant biomass. 5. The process of claim 1 wherein the stereoisomer separated is L-arabinose. 6. The process of claim 1 wherein the biomass is subjected to pressurization at a temperature of about 390 to 460 degrees Fahrenheit. 7. The process of claim 1 wherein the biomass is subjected to pressurization for not more than about 10 minutes. 8. The process of claim 2 wherein the biomass is reduced to a size of sawdust. 9. The process of claim 1 and further comprising feeding the biomass for pressurization continuously. 10. The process of claim 1 and further comprising adding moisture to the biomass before pressurization. 11. The process of claim 1 wherein the hydrolysis occurs in a reactor/static mixer. 12. The process of claim 11 wherein the hydrolysis occurs at about 329 to 347 degrees Fahrenheit, under pressure. 13. The process of claim 11 wherein sodium hydroxide is added to the static mixer in a flowpath that is counter-current to the flow of hemicellulose. 14. The process of claim 12 wherein the stereoisomer separation is performed with co-polymer beads. 15. A system for obtaining monosaccharides, oligosaccharides and polysaccharides from biomass, comprising: a mechanism for substantially instantaneously pressurizing and de-pressurizing biomass to separate the biomass into hemicellulose, cellulose, and lignin; a heater for heating the hemicellulose to liquefy the hemicellulose; a reactor/mixer for mixing a sodium hydroxide with hemicellulose and for making hemicellulose hydrolysates; and a mechanism for selectively separating a hemicellulose hydrolysate based upon the component's stereoisomeric identity. 16. The system of claim 15 wherein a biomass comprises sugar beet pulp. 17. The system of claim 15 wherein the hemicellulose product does not enter a glassy state but is liquefied. 18. The system of claim 15 wherein the hemicellulose product is free of caramelized hemicellulose product. 19. The system of claim 15 wherein the sodium hydroxide is in the aqueous phase. 20. The system of claim 15 wherein the hemicellulose hydrolysates comprise d-arabinose, l-arabinose, d-xylose, l-xylose, d-glucose, l-glucose, and any other racemic carbohydrates. 21. The system of claim 15 wherein the hemicellulose hydrolysates comprise polygalacturonic acid. 22. The system of claim 15 wherein the hemicellulose hydrolysates comprise any backbone polymer. 23. The system of claim 15 and further comprising a mechanism which receives the hemicellulose hydrolysates. 24. The system of claim 15 wherein the hemicellulose hydrolysates are separated into optically pure products. 25. A process for extracting L-arabinose from sugar beet pulp, comprising: providing sugar beet pulp; subjecting the sugar beet pulp to substantially instantaneous pressurization and de-pressurization in a manner effective to separate lignin, hemicellulose and cellulose in the sugar beet pulp; hydrolyzing the hemicellulose to form hemicellulose hydrolysates; and separating L-arabinose from the hemicellulose hydrolysates using chromatography. 26. The process of claim 24 wherein the L-arabinose is produced at a rate of at least 1000 pounds per day. 27. The process of claim 1 and further comprising extracting derivatives and substituents from cellulose and lignin. 28. The process of claim 1 and further comprising crystallizing the separated product. 29. The process of claim 28 wherein the crystallizing is performed using a low intensity ultrasonic agitation.
7/10/00 12:00:00 AM
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2.4 Steady state recycling chromatography

0

In steady state recycling chromatography the purity of the product fractions can be increased substantially if the middle (unresolved) part of the chromatogram is recycled back to the column-inlet. If a constant amount of fresh feed is introduced to the process on every cycle (e.g., by mixing it with the recycled fraction), the mass that leaves the process eventually becomes equal to the mass of freshfeed. The process thus operates at a periodic steady state. **Research findings:** - The advantages of solvent removal for a difficult separation task at conditions typical for industrial scale chromatography were demonstrated by investigating the performance of SSR–SR in separation of glucose and galactose. Art. [#ARTNUM](#article-25894-2000096812)

2.4.1 2.4 Steady state recycling chromatography
Chapter Five - Chromatographic Fractionation of Lignocellulosic Hydrolysates
Abstract Monosaccharides (glucose, xylose, etc.) are valuable platform chemicals that can be produced from lignocellulosic (polysaccharide containing) biomasses via hydrolysis. Their cost-effective recovery from lignocellulosic biomass hydrolysates and further purification requires sophisticated separation technology. Adsorption and electrolyte exclusion chromatography can be used for the fractionation of hydrolysates containing mineral acids. The recovered hydrolysis acid can be recycled, which saves and reduces chemicals consumption. Chromatographic separation can be done either batchwise, using steady-state recycling chromatography, or using continuous simulated moving bed chromatography. The latter two process options offer significant increase in productivity when compared to the batchwise fractionation process. In this chapter, chromatographic and adsorptive fractionation techniques for the treatment of acidic lignocellulosic hydrolysates are reviewed. The relevant physical phenomena affecting the separation efficiency as well as various industrially applicable process options are discussed.
1/1/13 12:00:00 AM
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2.4.2 2.4 Steady state recycling chromatography
Steady state recycling chromatography with an integrated solvent removal unit – Separation of glucose and galactose
Abstract A process concept where a solvent removal unit is integrated to a steady-state recycling chromatography process (SSR–SR) offers a possibility to significantly increase the performance of single column chromatographic separation. The advantages of solvent removal for a difficult separation task at conditions typical for industrial scale chromatography were demonstrated by investigating the performance of SSR–SR in separation of glucose and galactose. Two limits for the extent of solvent removal were imposed: maximum total concentration of the solution fed into the column (viscosity limit) and the maximum total concentration achievable in the solvent removal unit (solubility or osmotic pressure limit). The process was optimized using numerical simulation. Three SSR–SR configurations with different positions of the solvent removal unit were compared with (1) the conventional batch process, (2) SSR without solvent removal, and (3) batch process with solvent removal. SSR–SR was found to always improve the productivity. In addition, solvent removal reduced eluent consumption in most cases. The concentration limits and the concentration of the fresh feed were shown to determine which SSR–SR configuration yields the best performance.
8/1/12 12:00:00 AM
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2.5 Centrifugal partition chromatograohy (CPC)

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Centrifugal partition chromatography is a special chromatographic technique where both stationary and mobile phase are liquid, and the stationary phase is immobilized by a strong centrifugal force. Centrifugal partition chromatography consists of a series-connected network of extraction cells, which operates as elemental extractors, and the efficiency is guaranteed by the cascade. [[Wiki]](https://en.wikipedia.org/wiki/Centrifugal_partition_chromatography) **Research findings** - Highly polar two-phase systems containing ethanol and aqueous ammonium sulphate are examined here for the separation of monosaccharides present in hydrolysed SBP pectin: l-rhamnose, l-arabinose, d-galactose and d-galacturonic acid. Dimethyl sulfoxide (DMSO) was selected as an effective phase system modifier improving monosaccharide separation. The best phase system identified was ethanol:DMSO:aqueous ammonium sulphate (300gL(-1)) (0.8:0.1:1.8, v:v:v) which enabled separation of the SBP monosaccharides by CPC (200mL column) in ascending mode (upper phase as mobile phase) with a mobile phase flow rate of 8mLmin(-1). A mixture containing all four monosaccharides (1.08g total sugars) in the proportions found in hydrolysed SBP was separated into three main fractions; a pure l-rhamnose fraction (>90%), a mixed l-arabinose/d-galactose fraction and a pure d-galacturonic acid fraction (>90%). The separation took less than 2h demonstrating that CPC is a promising technique for the separation of these sugars with potential for application within an integrated, whole crop biorefinery. Art. [#ARTNUM](#article-25568-1061727677)

2.5.1 2.5 Centrifugal partition chromatograohy (CPC)
Building a Synthetic Pathway For Nylon precursor Biosynthesis
Biorefineries allow for the sustainable production of higher value products from biomass. In addition to bioethanol, they can produce added value chemicals and pharmaceutical intermediates from isolated component compounds such as sugars. Sugar beet pulp (SBP) is a high volume, low value by-product from sugar beet processing with a low lignin and a high carbohydrate content, making it an attractive biomass feedstock for biorefinery processing. The pectin fraction of SBP can be isolated via steam explosion, which, after complete acid hydrolysis, gives a hydrolysate rich in monosaccharides: primarily L-arabinose (Ara) and D-galacturonic acid (GA), with some D-galactose (Gal) and L-rhamnose (Rha). Isolation of these sugars is therefore a critical step in realising an integrated, whole crop biorefinery. Currently, little work has been reported on the separation and utilisation of SBP hydrolysates. The aim of this thesis is to establish novel, scalable separation processes for the isolation of the component monosaccharides from crude hydrolysed sugar beet pulp pectin. Centrifugal partition chromatography (CPC) is a liquid-liquid separation technique with no solid stationary phase and offers an alternative to traditional resin-based chromatographic techniques. As such it can more easily cope with crude feedstreams such as hydrolysates. Hydrophilic ethanol : ammonium sulphate two-phase systems were examined based on monosaccharide partition coefficients and phase settling times. An ethanol : aqueous ammonium sulphate (300 g L-1 ) (0.8:1.8 v:v) system was chosen for CPC separations of the crude SBP hydrolysate and was shown to be capable of removing the coloured contaminants and isolating three sugar fractions in a single step: Rha, Ara and Gal, and GA. The separation was optimised and the throughput was increased by maximising the sample loading. Operation in an elution-extrusion mode allowed for reproducible separations in 100 min without additional column regeneration. The process was scaled up from a 250 to a 950 mL column providing a final throughput of 1.9 gmonosaccharides L -1 column h -1 using the crude SBP. The following purities and recoveries of the three main fractions were achieved: Rha at 92% purity and 93% recovery; Ara at 84% purity and 97% recovery; and GA at 96% purity and 95% recovery. Simulated moving bed (SMB) allows for continuous chromatographic separations using multiple columns, improving separation performance and throughputs. Isolation of Ara from the neutral sugars Gal and Rha was performed with resins and conditions screened on single columns leading to the selection of a Dowex 50W X8 resin in the Ca2+ form. SMB separation using 8 columns was performed in the 4-zone and 3-zone setups and achieved 94% purity with 99% recovery at a throughput of 4.6 gmonosaccharides L -1 column h -1 with a synthetic mixture of the neutral sugars (Ara, Gal and Rha). However, equivalent separations could not be achieved using the crude SBP hydrolysate which needed pretreatment before SMB. Decolourisation with activated carbon was able to remove 97% of the coloured contaminants with sugar losses of 15% (w/w) in a batch process demonstrated to 50 mL scale. Anion exchange chromatography using a Dowex 1x8 resin was then found to be capable of isolating GA from a synthetic crude mixture of GA and neutral sugars with a dynamic binding capacity of 1.31 mmol mL-1 resin. However, further work is needed to enable this anion exchange step to achieve satisfactory separations with the decolourised crude hydrolysate. The isolated neutral sugars, after GA removal, can be processed on the SMB with comparable separation performance and throughput to a mixture of neutral sugars prepared without GA. In summary, this thesis presents two possible process paths each with their own benefits and drawbacks. CPC is capable of processing the crude SBP hydrolysate directly, isolating the sugars and removing the coloured contaminants in a single step. However, Ara co-elutes with Gal providing a stream that is only 84% pure. In SMB, the potential throughputs and separation performance are higher, however, this could only be experimentally demonstrated with synthetic crude mixtures of sugars and not with the crude SBP hydrolysate. Further pretreatment or SMB method development would be required in order to process the crude hydrolysate, and the resulting multistep processes may reduce the overall viability. Overall this thesis demonstrates two feasible approaches to the preparative scale separation of SBP pectin hydrolysates and supports development of an integrated SBP biorefinery.
10/28/18 12:00:00 AM
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2.5.2 2.5 Centrifugal partition chromatograohy (CPC)
Centrifugal partition chromatography in a biorefinery context: separation of monosaccharides from hydrolysed sugar beet pulp.
A critical step in the bioprocessing of sustainable biomass feedstocks, such as sugar beet pulp (SBP), is the isolation of the component sugars from the hydrolysed polysaccharides. This facilitates their subsequent conversion into higher value chemicals and pharmaceutical intermediates. Separation methodologies such as centrifugal partition chromatography (CPC) offer an alternative to traditional resin-based chromatographic techniques for multicomponent sugar separations. Highly polar two-phase systems containing ethanol and aqueous ammonium sulphate are examined here for the separation of monosaccharides present in hydrolysed SBP pectin: l-rhamnose, l-arabinose, d-galactose and d-galacturonic acid. Dimethyl sulfoxide (DMSO) was selected as an effective phase system modifier improving monosaccharide separation. The best phase system identified was ethanol:DMSO:aqueous ammonium sulphate (300gL(-1)) (0.8:0.1:1.8, v:v:v) which enabled separation of the SBP monosaccharides by CPC (200mL column) in ascending mode (upper phase as mobile phase) with a mobile phase flow rate of 8mLmin(-1). A mixture containing all four monosaccharides (1.08g total sugars) in the proportions found in hydrolysed SBP was separated into three main fractions; a pure l-rhamnose fraction (>90%), a mixed l-arabinose/d-galactose fraction and a pure d-galacturonic acid fraction (>90%). The separation took less than 2h demonstrating that CPC is a promising technique for the separation of these sugars with potential for application within an integrated, whole crop biorefinery.
9/1/15 12:00:00 AM
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2.5.3 2.5 Centrifugal partition chromatograohy (CPC)
Using Centrifugal Partition Chromatography to Separate Xylose from Glucose: SOP Development
Efficient methods of extracting natural compounds from their native source are essential to the medical, biological, and food industries. Xylose and glucose are two major sugars used in a variety of food, bioenergy, and environmental industries and are found in hemicellulose, a compound present in all biomass. The aim of this project was to generate protocols for an effective separation of xylose from glucose using centrifugal partition chromatography (CPC). CPC, commonly used for the separation of natural products, operates on the combined concepts of rotary motion and biphasic liquid separation. It is preferred to other chromatographic techniques for natural product recovery because the liquid stationary phase allows for complete recovery of compounds as compared to conventional chromatography using a solid stationary phase. Our specific goal was to develop standard operating procedures (SOPs) to separate xylose from glucose. The two liquid phases present in the CPC rotor—generally termed the solvent-system—separate compounds depending on their affinity for each liquid phase. The suitability of a solvent-system is based on two different chromatography measures, partition coefficient (K) and separation factor (α), which were determined using the shake-flask method. We tested three solvent-systems mixed in various ratios: butanol-ethanolwater (BEW), butanol-ethyl acetate-water (BEAW), and hexane-ethyl acetate-methanol-water (HEMWat). The concentration of each compound in each phase of the three solvent-systems was determined using high performance liquid chromatography (HPLC). The BEW system, mixed in a 3:1:4 ratio by volume, was chosen as most appropriate as it produced K and α values within acceptable ranges. This solvent-system was then used in the CPC to purify xylose from glucose. Protocols based on these findings were documented and will be helpful to add proficiency in creating bioproducts in future.
1/1/13 12:00:00 AM
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2.6 High performance liquid chromatography

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High-performance liquid chromatography (HPLC; formerly referred to as high-pressure liquid chromatography) is a technique in analytical chemistry used to separate, identify, and quantify each component in a mixture. It relies on pumps to pass a pressurized liquid solvent containing the sample mixture through a column filled with a solid adsorbent material. Each component in the sample interacts slightly differently with the adsorbent material, causing different flow rates for the different components and leading to the separation of the components as they flow out of the column. [[Wiki]](https://en.wikipedia.org/wiki/High-performance_liquid_chromatography) HPLC is used mainly for analytical types of separation, usually with the goal of quantifying sugar content. **Research findings:** - A new approach by which free plant monosaccharides were separated directly and determined with high performance liquid chromatography by using internal standard method was established and β indolylacetic acid was selected as the internal standard substance The separation time for xylose(Xyl), fructose(Fru), glucose(Glu), sucrose(Suc), maltose(Mal), lactose(Lac) and raffinose(Raf) was within 18 min;and the detection limits were 1 8 μg,2 3 μg,2 7 μg,1 8 μg,3 5 μg,4 1 μg and 4 3 μg respectively while the linear dynamics varied within the range of 5 0 μg/L 750 μg/L In this work, the effects of the concentration of CH 3CN and pH values in the mobile phase to the separation of the 7 sugars and β indolylacetic acid were studied as well The method can be used to the determinations of jujube,apple samples Moreover,the recovery experiment was also conducted. The results showed that the the recoveries of 5 determinations to Xyl,Fru,Glu and Suc were 97.4% 102.1%,97.3% 101.8%,98.7% 102.2%,97.7% 102.5%,respectively. Art. [#ARTNUM](#article-25714-2377824992)

2.6.1 2.6 High performance liquid chromatography
Separation and determination of monosaccharides with high performance liquid chromatography by using internal standard method
A new approach by which free plant monosaccharides were separated directly and determined with high performance liquid chromatography by using internal standard method was established and β indolylacetic acid was selected as the internal standard substance The separation time for xylose(Xyl), fructose(Fru), glucose(Glu),sucrose(Suc),maltose(Mal),lactose(Lac) and raffinose(Raf) was within 18 min;and the detection limits were 1 8 μg,2 3 μg,2 7 μg,1 8 μg,3 5 μg,4 1 μg and 4 3 μg respectively while the linear dynamics varied within the range of 5 0 μg/L 750 μg/L In this work, the effects of the concentration of CH 3CN and pH values in the mobile phase to the separation of the 7 sugars and β indolylacetic acid were studied as well The method can be used to the determinations of jujube,apple samples Moreover,the recovery experiment was also conducted The results showed that the relative standard deviations of 5 determinations to Xyl,Fru,Glu and Suc were 1 66% 3 45%,1 54% 3 01%,1 29% 2 91%,1 09% 2 65% and the recoveries were 97 4% 102 1%,97 3% 101 8%,98 7% 102 2%,97 7% 102 5%,respectively
11/1/00 12:00:00 AM
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2.7 Over-pressure Layer Chromatography (OPLC)

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In overpressured layer chromatography forced flow is achieved by application of an external pressure. In OPLC the vapor phase is completely eliminated, the chromatographic plate being covered with an elastic membrane under external pressure, and the separation can thus be performed under controlled conditions. The method is a hybrid between conventional TLC and HPLC and incorporates several of the attractive features of each technique. Like HPLC, this technology is mainly used analytically, for sugar content quantification. **Research findings:** - A new OPLC method has been established for separation and quantitative determination of three alditols (d xylitol, l arabitol, and d glucitol) and four aldoses (d xylose, l arabinose, d glucose, and l rhamnose). The aldoses are present in hemicellulose hydrolyzates used as substrates in the production of d xylitol from d xylose by yeast, and all seven sugars could be found in the final fermented broth. The separation was performed in approximately sixteen minutes, on aluminum foilbacked silica gel OPLCHPTLC plates with overrunning elution. Acetonitrileacetic acidwater, 63 + 33 + 5 ( v/v ), was used as mobile phase. Art. [#ARTNUM](#article-25547-2085173814)

2.7.1 2.7 Over-pressure Layer Chromatography (OPLC)
Separation and quantitative determination of aldoses and alditols by over-pressured layer chromatography (OPLC)
A new OPLC method has been established for separation and quantitative determination of three alditols (d -xylitol, l -arabitol, and d -glucitol) and four aldoses (d -xylose, l -arabinose, d -glucose, and l -rhamnose). The aldoses are present in hemicellulose hydrolyzates used as substrates in the production of d -xylitol from d -xylose by yeast, and all seven sugars could be found in the final fermented broth. The separation was performed in approximately sixteen minutes, on aluminum foil-backed silica gel OPLC-HPTLC plates with overrunning elution. Acetonitrile-acetic acid-water, 63 + 33 + 5 ( v/v ), was used as mobile phase. The upper limits of linearity were in the range 140–600 ng and detection limits were 15–50 ng per spot. The method has been used successfully to screen fermentation samples for aldoses and alditols.
2/1/06 12:00:00 AM
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2.8 Low affinity pair size exclusion chromatography

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Low affinity pair size exclusion chromatography (LAPSEC) is herein described as a novel approach specifically for lectin based monosaccharide separation but with the potential for wider application using weak antibody‐antigen interactions. This technique exploits weak ligand receptor interactions and the difference in molecular size between free and receptor‐bound ligand, to effect separations using a size exclusion chromatographic column. While such carrier‐based separations are achievable with high affinity interactions, the advantage of the approach described here is that the use of weak interactions also allows separation of ligand from carrier in the same column, allowing recycling of the carrier. The utility of the LAPSEC approach is shown by results obtained using Concanavalin A and Lotus Tetragonolobus lectin to separate their specific monosaccharides (D‐mannose and L‐fucose, respectively) from unbound monosaccharides. Art. [#ARTNUM](#article-25982-1987858415)

2.8.1 2.8 Low affinity pair size exclusion chromatography
Low Affinity Pair Size Exclusion Chromatography
Abstract Low affinity pair size exclusion chromatography (LAPSEC) is herein described as a novel approach specifically for lectin based monosaccharide separation but with the potential for wider application using weak antibody‐antigen interactions. This technique exploits weak ligand receptor interactions and the difference in molecular size between free and receptor‐bound ligand, to effect separations using a size exclusion chromatographic column. While such carrier‐based separations are achievable with high affinity interactions, the advantage of the approach described here is that the use of weak interactions also allows separation of ligand from carrier in the same column, allowing recycling of the carrier. The utility of the LAPSEC approach is shown by results obtained using Concanavalin A and Lotus Tetragonolobus lectin to separate their specific monosaccharides (D‐mannose and L‐fucose, respectively) from unbound monosaccharides. These systems have been simulated using a simple multi‐sectional equil...
6/1/05 12:00:00 AM
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2.9 Reversible reaction based separation resins

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By using adsorbents that have functionalized group with the capability of reversible interaction with specific sugars their separation can be enhanced. **Research findings:** - The goal of this work was to enchance the selectivity of the separation of fructose or glucose from carbohydrate mixtures with adsorbents capable of reversible reaction. The experimental data presented demonstrate the feasibility of separating glucose from transgalactooligosaccharides and fructose from fructooligosaccharides using resins as adsorbents. Comparison of the sorption properties of a resin functionalised with the bisulphite (HSO3) ion with its original chloride (Cl) form showed that the sorption of glucose increased due to interaction with the bisulphite group. In addition, functionalisation with bisulphite resulted in selectivity towards glucose relative to fructose and lactose. Moreover, chromatographic separation of glucose from transgalactooligosaccharides on a bisulphiteloaded resin was improved compared to the same resin in the chloride form. However, the bisulphite unfortunately oxidised. Boronic acidfunctionalised resin was selective towards fructose at pH 6.0 compared to glucose, indicating complex formation between fructose and boronic acid. Although complex formation with boronate has been assumed to be even stronger than with boronic acid, increasing the pH to a value above the pKa of the functional group did not improve fructose sorption. Chromatographic separation of fructose from fructooligosaccharides was obtained on boronic acidfunctionalised resin as a result of complex formation with fructose. These results show that reversible chemical reactions can lead to an improvement in the performance of adsorbents for sugar separations. Art. [#ARTNUM](#article-30463-2169199868)

2.9.1 2.9 Reversible reaction based separation resins
Sorption and separation of sugars with adsorbents based on reversible chemical interaction
The goal of this work was to enchance the selectivity of the separation of fructose or glucose from carbohydrate mixtures with adsorbents capable of reversible reaction. The experimental data presented demonstrate the feasibility of separating glucose from trans-galacto-oligosaccharides and fructose from fructo-oligosaccharides using resins as adsorbents. Comparison of the sorption properties of a resin functionalised with the bisulphite (HSO-3) ion with its original chloride (Cl-) form showed that the sorption of glucose increased due to interaction with the bisulphite group. In addition, functionalisation with bisulphite resulted in selectivity towards glucose relative to fructose and lactose. Moreover, chromatographic separation of glucose from trans-galacto-oligosaccharides on a bisulphite-loaded resin was improved compared to the same resin in the chloride form. However, the bisulphite unfortunately oxidised. Boronic acid-functionalised resin was selective towards fructose at pH 6.0 compared to glucose, indicating complex formation between fructose and boronic acid. Although complex formation with boronate has been assumed to be even stronger than with boronic acid, increasing the pH to a value above the pKa of the functional group did not improve fructose sorption. Chromatographic separation of fructose from fructo-oligosaccharides was obtained on boronic acid-functionalised resin as a result of complex formation with fructose. These results show that reversible chemical reactions can lead to an improvement in the performance of adsorbents for sugar separations.
11/1/06 12:00:00 AM
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3. Filtration

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Filtration is any of various mechanical, physical or biological operations that separates solids from fluids (liquids or gases) by adding a medium through which only the fluid can pass. The fluid that passes through is called the filtrate.


3.1 Ultrafiltration

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Ultrafiltration (UF) is a variety of membrane filtration in which forces like pressure or concentration gradients lead to a separation through a semipermeable membrane. Suspended solids and solutes of high molecular weight are retained in the so-called retentate, while water and low molecular weight solutes pass through the membrane in the permeate (filtrate). This separation process is used in industry and research for purifying and concentrating macromolecular (103 - 106 Da) solutions, especially protein solutions. [[Wiki]](https://en.wikipedia.org/wiki/Ultrafiltration) **Patent findings:** - The invention discloses a method for preparing xylose functional sugar from hemicellulose polysaccharide in hydrolyzed agricultural waste, and belongs to the field of xylose. Membrane separation with an ultrafiltration membrane is performed to obtain a xylose product, and concentrating and drying the xylose product. Through the method, redundant byproducts are removed through hydrolysis in order to obtain xylose with the purity being 90-95%. Art. [#ARTNUM](#article-25546-2878215405)

3.1.1 3.1 Ultrafiltration
Method for preparing xylose functional sugar from hemicellulose polysaccharide in hydrolyzed agricultural waste
The invention discloses a method for preparing xylose functional sugar from hemicellulose polysaccharide in hydrolyzed agricultural waste, and belongs to the field of xylose. The method comprises: selecting wheat straw, performing processes such as drying, pulverizing, and alkaline extraction to obtain coarse hemicellulose polysaccharide, performing purification to obtain pure hemicellulose polysaccharide, adding a cellulase degradation agent and an ethanol solution into pure hemicellulose polysaccharide for ultrasonic degradation, concentrating the obtained degraded liquid through pressurization, performing membrane separation with an ultrafiltration membrane to obtain a xylose product, and concentrating and drying the xylose product. Through the method, redundant by-products are removed through hydrolysis in order to obtain xylose with the purity being 90-95%. The prepared xylose can be added into food and is wide in application. The enzyme and un-degraded xylan in a xylooligosaccharide liquid are removed through the ultrafiltration membrane, so that loss of xylose is reduced. The method is abundant in preparation resources and low in cost.
6/8/16 12:00:00 AM
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3.2 Thin Film Composite Nanofiltration

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Thin-film composite membranes (TFC or TFM) are semipermeable membranes manufactured principally for use in water purification or water desalination systems. They also have use in chemical applications such as batteries and fuel cells. A TFC membrane can be considered as a molecular sieve constructed in the form of a film from two or more layered materials. TFC membranes are commonly classified as nanofiltration (NF) and reverse osmosis (RO) membranes. Both types are typically made out of a thin polyamide layer (<200 nm) deposited on top of a polyethersulfone or polysulfone porous layer (about 50 microns) on top of a non-woven fabric support sheet. The three layer configuration gives the desired properties of high rejection of undesired materials (like salts), high filtration rate, and good mechanical strength. The polyamide top layer is responsible for the high rejection and is chosen primarily for its permeability to water and relative impermeability to various dissolved impurities including salt ions and other small, unfilterable molecules. [[Wiki]](https://en.wikipedia.org/wiki/Thin-film_composite_membrane) **Research findings:** - The aim of this study is to evaluate the ability of membrane developed by interfacial polymerization reaction between triethanolamine (TEOA) (6 % w/v) and trimesoyl chloride (TMC) (0.15 % w/v) as monomers on polyethersulfone (PES) microporous substrate to separate xylose from glucose. In this study, factors affecting the process, namely pressure, concentration of total sugars in solution, and composition of monosaccharides in total sugar, were investigated using twolevel factorial analysis. Overall from the present study, it can be concluded that nanofiltration has high potential to replace currently in use chromatographic method in xylose separation. Art. [#ARTNUM](#article-25562-2092236646)

3.2.1 3.2 Thin Film Composite Nanofiltration
Optimisation of interfacial polymerization factors in thin-film composite (TFC) polyester nanofiltration (NF) membrane for separation of xylose from glucose
Abstract A tailored thin-film composite (TFC) NF membrane may offer alternative separation technique to widely used chromatographic techniques in separating two monosaccharides with similar properties. The aim of this paper is to pinpoint the optimum condition in preparing TFC membranes with the highest xylose separation factor. To achieve this, curing time, curing temperature, and reaction time were optimised using central composite design (CCD). Polyethersulfone (PES) was used as a support membrane for interfacial polymerisation (IP) of two active monomers, namely triethanolamine (TEOA) and trimesoyl chloride (TMC). The xylose separation factor was chosen as the response for this study. In addition, occurrence of IP reaction was verified by visual interpretation using field emission scanning electron microscope (FESEM). The chemical elements in TFC membrane and its functional groups were determined using FESEM equipped with energy dispersive X-ray and Attenuated total reflectance–Fourier transform infrared (ATR-FTIR), respectively and compared to the initial PES membrane. A quadratic model was developed and tested with analysis of variance (ANOVA). The model was used to simulate and locate the optimum point. The optimum point was within the studied region and validation tests were conducted to confirm this point. The tests showed little error of less than 2% from the predicted optimal points. The optimum IP conditions for xylose separation were 45.25 min, 15.53 min, and 58.4 °C for reaction time, curing time, and curing temperature, respectively. Under these optimum conditions, a maximum xylose separation factor of 1.334 ± 0.007 was achieved. The optimised TFC membrane exhibited comparable xylose separation factor to commercial membranes.
1/1/19 12:00:00 AM
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3.2.2 3.2 Thin Film Composite Nanofiltration
Optimization of interfacial polymerization thin film composite membrane for separation of xylose from glucose
Most hydrolysis studies on biomass in Malaysia produce high amount of xylose and glucose compared to other monosaccharides. These monosaccharides are important ingredients often needed in pure fraction in food and pharmaceutical industries. Chromatography and commercial nanofiltration membrane were able to separate xylose from glucose. However, few treatment steps on biomass hydrolysate were needed because most biomass hydrolysate are acidic. Acidity reduces the performance of these separation technology by inhibiting chromatography resins and fouling of membrane. Thin film composite membrane developed via interfacial polymerization using triethanolamine and trimesoyl chloride as monomers allows separation at low pH to occur without damaging its performance. Currently, almost none has attempted to separate xylose from glucose using self-made thin-film composite membrane that is specially tailored for biomass hydrolysate. The aim of this present study was to produce optimized thin-film composite nanofiltration membrane for separation of xylose from glucose using triethanolamine and trimesoyl chloride as monomers on polyethersulfone membrane via interfacial polymerization using a series of experimental design. Success of thin layer formation was probed by attenuated total reflectance-Fourier transform infrared spectroscopy, and prepared membranes were characterized by field emission scanning electron microscope, contact angle and pure water permeability. Separation performance of thin-film composite membranes are affected by several factors during formation of thin upper layer. Series of experimental designs were applied to screen and optimize the different interfacial polymerization factors studied. In screening, 25-1 fractional factorial design were used to find significant factors affecting xylose separation factor, which are reaction time and curing process. Also, the responses in screening were fitted with a multiple linear regression equation and obtained a high correlation (R2 = 0.9998) between the experimental data and model data. Then central composite design was used to identify the optimum interfacial polymerization conditions for the highest xylose separation factor. The response was fitted with the second-order polynomial equation with R2 of 0.92, implying a high correlation between the observed and predicted values. The optimum interfacial polymerization conditions were determined to be reaction time of 45.25 minutes, curing time of 15.53 minutes, and curing temperature of 58.4 ℃. At optimum conditions, the xylose separation factor was found to be 1.334 ±0.007. The developed model in this study is adequate for predicting xylose separation factor under different interfacial polymerization conditions within the range used. This study will provide valuable guideline to develop membrane that specially tailored for xylose separation from glucose as alternative to the cost intensive chromatographic processes in use.
4/1/16 12:00:00 AM
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3.2.3 3.2 Thin Film Composite Nanofiltration
Separation of Xylose From Glucose Using Thin Film Composite (TFC) Nanofiltration Membrane: Effect of Pressure, Total Sugar Concentration and Xylose/Glucose Ratio
Xylose is an abundant raw material coexists with other sugars that can be turned into useful products, such as ethanol, xylitol and 2, 3-butanediol by microorganism such as yeasts, bacteria, and mycelial fungi. However, more than 80 % of the production cost of these products comes solely from the production of xylose. Presently, the separation of xylose from hemicellulose hydrolysate relies on chromatographic separation alone. The use of nanofiltration membrane may offer alternative in recovering xylose due to the differences in size compared to other sugars. The aim of this study is to evaluate the ability of membrane developed by interfacial polymerization reaction between triethanolamine (TEOA) (6 % w/v) and tri-mesoyl chloride (TMC) (0.15 % w/v) as monomers on polyethersulfone (PES) microporous substrate to separate xylose from glucose. In this study, factors affecting the process, namely pressure, concentration of total sugars in solution, and composition of monosaccharides in total sugar, were investigated using two-level factorial analysis. The experiment was performed using Amicon Milipore stirred cell (Model 8200) with constant stirring speed at 300 rpm and temperature at ambient. The glucose and xylose concentration was quantified using high performance liquid chromatography (HPLC). It is found that the developed nanofiltration membrane has the ability to separate xylose from glucose.The analysis of the experimental response revealed that the total sugar concentration and composition ratio of xylose: glucose had significant interactive effect on xylose separation factor. Overall from the present study, it can be concluded that nanofiltration has high potential to replace currently in use chromatographic method in xylose separation.
8/27/14 12:00:00 AM
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3.2.4 3.2 Thin Film Composite Nanofiltration
Separation of xylose using a thin-film composite nanofiltration membrane: screening of interfacial polymerization factors
Most hydrolysis studies on biomass produce a high amount of xylose and glucose compared to other monosaccharides. A specially tailored thin-film composite (TFC) membrane prepared via interfacial polymerization (IP) using triethanolamine (TEOA) and trimesoyl chloride (TMC) as monomers on a polyethersulfone (PES) membrane was used to separate xylose from glucose. Differences between the support (PES) and TFC membrane in surface chemistry were probed using attenuated total reflectance-Fourier transform infrared (ATR-FTIR) spectroscopy and contact angle. Both membranes were also characterized by field emission scanning electron microscopy (FESEM) and pure water permeability to observe changes to membrane morphology and properties. The performance of the TFC membrane is highly stimulated by variation of preparative factors in IP. This study screens and reports the effect of five preparative factors, namely monomer concentrations (TEOA and TMC), pH of the aqueous phase, reaction time, and curing toward the performance of xylose separation from glucose. A 25−1 fractional factorial design was used to narrow down significant preparative factors, saving lots of time and resources. It was found that curing and reaction time significantly affected the separation of xylose from glucose. High correlation (R2 = 0.9998) between the experimental data and model data was obtained. The developed model in this study is adequate for predicting the xylose separation factor under different IP conditions within the range used. This study will provide valuable guidelines to develop membranes that are specially tailored for xylose separation from glucose as an alternative to the cost intensive chromatographic processes in use.
1/1/16 12:00:00 AM
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3.2.5 3.2 Thin Film Composite Nanofiltration
Synthesis of Nanofiltration Membrane Developed from Different Concentration of Triethanolamine (TEOA) for Separation of Xylose from Glucose
Synthesis of thin film composite (TFC) nanofiltration membrane has experienced tremendous development since the concept of interfacial polymerization (IP) was first introduced. One of it new application is on the separation of xylose from glucose in biomass hydrolysate. In this present study, thin film composite (TFC) nanofiltration (NF) membrane has been produced through interfacial polymerization by manipulation the concentration of triethanolamine (TEOA) at different reaction time with 0.15 % w/v. of trimesoyl chloride (TMC). The membrane was then characterized in term of their chemical and physical properties, and separation performance between xylose and glucose. The growth of thin layer film depends on concentration of the monomer (TEOA) and reaction time. It was found that as concentration of TEOA and reaction time increased, the layer of the TFC become thicker thus decreases the permeability of the membrane. In contrast, the lowest and the highest permeability were recorded at 4% w/v of TEOA and 8% w/v of TEOA at reaction time of 35-minute in TMC, respectively. Moreover, higher sugar rejection of 0.896 % was obtained at 4% w/v TEOA after 35-minute reaction in TMC.
1/1/15 12:00:00 AM
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3.3 Hollow Fiber Nanofiltration

0

Nanofiltration membranes could offer a relatively cost-competitive separation steps, less complex and easier to maintain compared to chromatographic methods. **Research findings** - The objective of this study is to produce PES hollow fiber nanofiltration membrane for the separation of xylose and glucose. The performances test of membrane was carried out by separated a xylose and glucose. HPLC separation test was used to analyse the samples from the separation process. The result from this experiment is the composition of xylose in permeate is larger than glucose since xylose has lower molecular size than glucose. The results showed that, as the concentration of additive increase, the fluxes also increase and the sugar rejection will lower. As the concentration of PVP increase, the separation of xylose and glucose increase based on the xylose separation factor and solute rejection of xylose and glucose in the mixture solution. Art. [#ARTNUM](#article-25567-2354048319) - The results indicate that the separation of xylose from glucose by nanofiltration is possible to a limited extent. The mass ratio of xylose to glucose in the permeate was 1.5–3.0 times higher than their ratio in the feed. The observed monosaccharide retentions depend highly on permeate flux, and retentions increase to certain reproducible level as pressure and consequently flux is increased. The observed xylose retentions were from 0 to 80% and the glucose retentions were from 10 to 90%. The effect of total monosaccharide concentration on the observed retention is smaller than the effect of flux. The largest difference between xylose and glucose retentions was detected at permeate fluxes between 5 to 30 kg m −2  h −1. Art. [#ARTNUM](#article-25567-2029323095)

3.3.1 3.3 Hollow Fiber Nanofiltration
Fabrication of nanofiltration hollow-fiber membrane for the separation of xylose-glucose
Biomass is a biological material derived from living things, or recently living organism. Abundant plant biomass has the potential to become a renewable energy source of fuels and chemicals. Monosaccharide produced from the fermentation of biomass could produce various types of biofuels such as ethanol, butanol, methane, biodiesel, and hydrogen which greatly useful as sustainable energy. By the hydrolysis process of biomass, glucose and xylose were the most hemicelluloses sugar found in biomass. Nanofiltration membranes could offer a relatively cost-competitive separation steps, less complex and easier to maintain compared to chromatographic methods. The objective of this study is to produce PES hollow fiber nanofiltration membrane for the separation of xylose and glucose. Polyethersulfone (PES) polymer was used in a spinning solution with polyvinylpyrrolidone (PVP) as an additive to the solution. The performances of the membrane were investigated by varying the concentration of PVP from 1 wt. %, 3 wt. %, 7 wt. % and 9 wt. %. The surface morphological structure of the NF membrane were clarifying using SEM test. The performances test of membrane was carried out by separated a xylose and glucose. HPLC separation test was used to analyse the samples from the separation process. The result from this experiment is the composition of xylose in permeate is larger than glucose since xylose has lower molecular size than glucose. The results showed that, as the concentration of additive increase, the fluxes also increase and the sugar rejection will lower. As the concentration of PVP increase, the separation of xylose and glucose increase based on the xylose separation factor and solute rejection of xylose and glucose in the mixture solution.
6/1/14 12:00:00 AM
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3.3.2 3.3 Hollow Fiber Nanofiltration
Separation of xylose from glucose by nanofiltration from concentrated monosaccharide solutions
Abstract Complex separation of monosaccharides from each other is commercially carried out by chromatographic methods. The possibility of nanofiltration in a demanding separation of a pentose sugar, xylose, from a hexose sugar, glucose, is studied here. Xylose is an intermediate product in xylitol production and glucose interferes in the process. Feed solutions were made of xylose and glucose in different mass ratios and total monosaccharide concentrations. The mass ratios of xylose to glucose in solutions were 1:9, 1:1 and 9:1 and the monosaccharide concentrations of the solutions were 2, 10 and 30 wt.%. Desal-5 DK, -DL and NF270 membranes were used. Filtrations were done in total reflux mode (i.e. both permeate and retentate were recycled back to the feed tank) at 50 °C and the applied pressures were from 2 to 40 bar. The results indicate that the separation of xylose from glucose by nanofiltration is possible to a limited extent. The mass ratio of xylose to glucose in the permeate was 1.5–3.0 times higher than their ratio in the feed. The observed monosaccharide retentions depend highly on permeate flux, and retentions increase to certain reproducible level as pressure and consequently flux is increased. The observed xylose retentions were from 0 to 80% and the glucose retentions were from 10 to 90%. The effect of total monosaccharide concentration on the observed retention is smaller than the effect of flux. The largest difference between xylose and glucose retentions was detected at permeate fluxes between 5 to 30 kg m −2  h −1 . The ratio of xylose to glucose in the feed had an influence on permeate flux and on xylose retentions. Xylose retentions decreased as the proportion of glucose increased in the feed. The higher the proportion of xylose in the feed the higher was the total permeate flux.
4/5/07 12:00:00 AM
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3.3.3 3.3 Hollow Fiber Nanofiltration
Aldose-ketose transformation for separation and/or chemical conversion of C6 and C5 sugars from biomass materials

1. A method for converting an aldose in a biomass hydrolysate to its ketose isomer, comprising:adjusting a pH of a saccharified biomass hydrolysate containing one or more aldose sugars to a value between about 7.5 and about 9, to produce a pH-adjusted hydrolysate;contacting the pH-adjusted hydrolysate with an isomerization catalyst, wherein at least a portion of the aldose sugar in the pH-adjusted hydrolysate is converted to its ketose isomer, to produce an isomerized hydrolysate;contacting the ketose isomer in the isomerized hydrolysate with an aryl boronic acid (ABA) at a pH in the range of from 7.5 to 8.5 to form a complex of ketose-conjugate base form of the ABA; wherein the contacting comprises bringing the isomerized hydrolysate into contact with an immiscible organic phase that dissolves the ABA and a lipophilic salt (QX), and allowing the ketose in the isomerized hydrolysate to be extracted into the immiscible organic phase via ester formation with a conjugate base form of the ABA that is coupled via ion pair formation with Q+, thereby reducing the concentration of ketose in the isomerized hydrolysate and forming a ketose- rich organic phase, in turn shifting the aldose/ketose equilibrium in favor of more ketose formation in the pH-adjusted hydrolysate;preparing a low pH medium having a pH in the range of from about 2 to about 4.5, that contains an acid HX, wherein X is the same anion as X in the lipophilic salt (QX);bringing the low pH medium into contact with the ketose-rich organic phase; wherein, at the low pH, the ketose and hydroxyl ions are released into the low pH medium and the ABA is converted to its non-ionic conjugate acid; and, wherein, at the same time, the Q+ ion that formed the ion pair combines with an X− ion from the low pH medium to reform the lipophilic salt; andrecovering the ketose from the organic phase into the low pH medium as a concentrated ketose-rich solution. 2. The method of claim 1, including controlling the volume of the low pH medium such that the concentration of ketose in the ketose-rich medium is higher than the initial concentration of aldose in the hydrolysate. 3. The method of claim 1, further including reusing the organic phase containing the ABA and the lipophilic salt for a subsequent batch of hydrolysate. 4. The method of claim 1, wherein the steps of contacting the ketose isomer in the isomerized hydrolysate with ABA, and bringing the low pH medium into contact with the ketose-rich organic phase, are carried out using a micro- porous hollow fiber contactor. 5. The method of claim 4, wherein the micro-porous hollow fiber contactor comprises a shell having a first set of porous hollow fibers adapted for carrying the isomerized hydrolysate; and a second set of porous hollow fibers adapted for carrying the low-pH medium;the shell being configured for containing the organic extraction phase in a shell-side space substantially surrounding the first and second sets of fibers. 6. The method of claim 5, wherein the ketose is transported from the hydrolysate to the immiscible organic phase and from the organic phase to the low-pH medium, wherein the transport of the ketose is facilitated by ABA and QX combination dissolved in the immiscible organic phase. 7. The method of claim 5, wherein the first and second sets of micro-porous hollow fibers are commingled within the shell. 8. The method of claim 5, wherein the saccharified biomass hydrolysate contains glucose and xylose, and the method comprises:passing the hydrolysate through a packed bed reactor containing immobilized xylose isomerase (XI) or solid acid/base catalyst;allowing the isomerized hydrolysate to flow through the first set of fibers within the micro-porous hollow fiber contactor, the isomerized hydrolysate coming into contact with the immiscible organic phase containing lipophilic ABA and a lipophilic salt (QX) that fills the shell;extracting the xylulose in the isomerized hydrolysate, wherein the pH of the isomerized hydrolysate is in the range of from 7.5 to 8.5, into the organic phase via ester formation with a conjugate base form of the ABA coupled by ion pair formation with Q+, thereby reducing concentration of xylulose in the hydrolysate, and shifting the xylose/xylulose equilibrium in favor of more xylulose formation;concurrently with the extracting, allowing the low pH medium to flow through the second set of fibers and contact the organic phase contained on the shell side; whereby:the xylulose and hydroxyl ions attached to the ABA are released into the low pH medium, the ABA is re- converted to its non-ionic conjugate acid, andthe Q+ ion, which formed the ion pair with ABA, combines with an X− ion from the low pH medium to re-form the lipophilic salt. 9. The method of claim 1, including selecting an ABA having a property to enhance selectivity for a specific sugar. 10. The method of claim 1, further including controlling the volume of the low pH medium such that the ketose concentration in the recovered solution is higher than the aldose concentration in the saccharified biomass hydrolysate. 11. The method of claim 1, wherein both glucose and xylose from the hydrolysate are simultaneously isomerized by the isomerization catalyst into ketoses, the ketoses are extracted into the organic phase via binding to the ABA and QX, and the ketoses are recovered from the organic phase via back- extraction into the low pH medium while leaving behind other inhibitory compounds in the biomass hydrolysate. 12. The method of claim 1, wherein a micro-porous hollow fiber contactor physically separates the ketose-rich organic phase from the low pH medium during the ketose recovery. 13. The method of claim 1, wherein the step of contacting the pH-adjusted hydrolysate with an isomerization catalyst comprises passing the pH-adjusted hydrolysate through a packed bed reactor containing the isomerization catalyst, wherein the isomerization catalyst facilitates conversion of glucose to fructose. 14. The method of claim 1, wherein the pH of the recovered ketose is adjusted slightly to a pH suitable for converting the ketose to lactic acid, succinic acid, or fumaric acid by native microorganisms. 15. The method of claim 1, wherein the isomerization catalyst preferentially isomerizes xylose into xylulose compared to glucose into fructose, the ABA preferentially binds to ketoses compared to aldoses, and the system is used to separate C5 sugars from C6 sugars. 16. The method of claim 1, wherein the pH of the recovered ketose corresponds to a pH suitable for dehydration of the ketose to furans via an acid-catalyzed chemical reaction. 17. The method of claim 1, wherein the isomerization catalyst comprises xylose isomerase (XI) particles that facilitate the isomerization of both glucose and xylose. 18. The method of claim 1, comprising:a first micro-porous hollow fiber contactor having a lumen side and a shell side, wherein the hydrolyzate flows through the lumen-side in the first micro-porous hollow fiber contactor and the immiscible organic phase flows through the shell-side; anda second micro- porous hollow fiber contactor that physically separates the ketose-rich organic phase from the low pH medium during ketose recovery. 19. The method of claim 1, wherein the saccharified biomass hydrolysate is a lignocellulosic biomass hydrolysate. 20. The method of claim 19, wherein one or more of the ABA, the pH, and temperature of the hydrolysate, are altered to selectively isomerize and extract one or more specific sugars. 21. The method of claim 1, wherein the ABA is present in an immiscible organic phase that is physically separated by a permeable device from the isomerized hydrolysate, the permeable device allowing transport of the sugar from the isomerized hydrolysate into the immiscible organic phase, while substantially preventing dispersion of the immiscible organic phase in the isomerized hydrolysate. 22. The method of claim 7, wherein the immiscible organic phase comprises one or more of octanol, ethyl acetate, dichloromethane, o-nitrophenyl octyl ether (NPOE), or diethyl ether. 23. The method of claim 21, wherein the permeable device is a micro-porous hollow fiber contactor. 24. The method of claim 1, wherein the step of contacting the pH-adjusted- hydrolysate with an isomerization catalyst comprises passing the pH-adjusted hydrolysate through a packed bed reactor containing the isomerization catalyst, wherein the isomerization catalyst facilitates conversion of xylose into xylulose. 25. The method of claim 24, wherein the packed bed reactor is connected in a loop to a micro-porous hollow fiber contactor having a shell side and a fiber side, such that the hydrolysate flows through the packed bed and the fiber side of the micro-porous hollow fiber contactor, and the ketose is extracted from the hydrolysate to the immiscible organic phase on the shell side of the micro-porous hollow fiber contactor. 26. The method of claim 1, including: selecting the ABA such that, at selected pH and temperature conditions, the ABA mainly binds to xylulose, and does not bind to any appreciable amounts of glucose, xylose, or fructose. 27. The method of claim 1, including circulating the hydrolysate through at least a first column comprised of a packed bed of immobilized xylose isomerase (XI), and through a vessel having an ABA-enriched phase therein. 28. The method of claim 1, wherein the pH of the recovered ketose is a pH suitable for converting the ketose to ethanol by native _S. cerevisiae_ or other native microorganisms. 29. The method of claim 1, including controlling a volume of the low pH medium sufficient to recover the ketose as a concentrated solution. 30. The method of claim 1, including separating xylose from other C6 sugars as its keto-isomer and allowing for the recovery of xylulose as a concentrated solution. 31. The method of claim 1, comprising passing the isomerized hydrolysate and the ABA containing organic phase through a micro-porous hollow fiber contactor. 32. The method of claim 1, wherein the ABA is selected from the group consisting of PBA, 3aPBA, 4cPBA, naphthalene-2-boronic acid (N2B), and 4-biphenylboronic acid. 33. The method of claim 1, wherein the ABA has the formula Ar--B(OH)2, where Ar represents an unsubstituted or substituted aryl group. 34. The method of claim 33, wherein the ABA comprises one or more of the aryl groups: 4-PhC6H4--; 4-MeC6H4--, where Me is methyl; 2-iPrC6H4-, where iPr is isopropyl; 2-naphthyl; 3-BnOC6H4--, where Bn is benzyl; 4-MeO2CC6H4--, where Me is methyl; and 4-pyridinyl. 35. The method of claim 33, wherein the ABA comprises a diboronic acid that exhibits a higher selectivity toward ketose binding compared to monoboronic acids. 36. The method of claim 33, wherein the ABA comprises a multi-dentate boronic acid carrier. 37. The method of claim 36, wherein the ABA comprises one or more of: wherein A and C are B(OH)2, and B and D are H groups. 38. The method of claim 1, wherein the ABA comprises a hydrophobic substituted aryl boronic acid. 39. The method of claim 38, wherein the ABA comprises: 40. The method of claim 38, wherein the hydrophobic substituted aryl boronic acid is used in a liquid-liquid extraction followed by stripping or micro- porous hollow fiber contactor implementation.
4/19/11 12:00:00 AM
Link to Patent

3.4 Enzyme-assisted Nanofiltration

0

By selectively converting one of the sugars into another product, followed by subsequent nanofiltration, sugar monomers can be separated. In this way next to monomer recovery, added-value products could be produced. **Research findings:** - The purpose of the present study was to assess the efficiency of enzymeassisted nanofiltration for separation of xylose from glucose present in genuine biorefinery liquors obtained from hydrothermal pretreatment of wheat straw, corn stover and Miscanthus stalks. Glucose oxidase and catalase were used to convert the glucose contained in the liquors into gluconic acid, so xylose could be more easily recovered in the subsequent nanofiltration. The best separation factor of gluconic acid over xylose in the subsequent nanofiltration was 2.7, 2.5 and 2.2 for wheat straw, corn stover and Miscanthus stalks, respectively. All represented a significant improvement compared to the benchmark separation of xylose and glucose, in which case the separation factor was only 1.4. Art. [#ARTNUM](#article-30331-2769701877)

3.4.1 3.4 Enzyme-assisted Nanofiltration
Membrane separation of enzyme-converted biomass compounds: Recovery of xylose and production of gluconic acid as a value-added product
Abstract The purpose of the present study was to assess the efficiency of enzyme-assisted nanofiltration for separation of xylose from glucose present in genuine biorefinery liquors obtained from hydrothermal pretreatment of wheat straw, corn stover and Miscanthus stalks. Glucose oxidase and catalase were used to convert the glucose contained in the liquors into gluconic acid, so xylose could be more easily recovered in the subsequent nanofiltration. Subjecting the biomass liquors to dilute acid treatment and centrifugation before the enzymatic reaction and filtration led to maximum biocatalytic performance of the membrane bioreactor (neglectable fouling and no enzyme activity loss) during five consecutive reaction-filtration cycles. The best separation factor of gluconic acid over xylose in the subsequent nanofiltration was 2.7, 2.5 and 2.2 for wheat straw, corn stover and Miscanthus stalks, respectively. All represented a significant improvement compared to the benchmark separation of xylose and glucose, in which case the separation factor was only 1.4. However, the higher ionic strength of the biomass liquors compared to the pure model solution probably led to a less negative zeta potential of the nanofiltration membrane, which significantly reduced the xylose purification performance as compared to the model system, for which the separation factor was 34.
4/1/18 12:00:00 AM
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3.5 Spiral wound Nanofiltration

0

Nanofiltration membranes are available in many different configurations, including hollow fiber, tubular, flat sheet, and spiral-wound. When total suspended solids can be largely removed via prefiltration, Spiral-wound nanofiltration elements are often preferred because they offer a balanced combination of packing density (membrane area vs. module volume), physical durability, membrane life, and unit cost. [[Source]](https://synderfiltration.com/nanofiltration/spiral-wound-elements/) **Research findings:** - Separation of biomass hydrolysate that contain glucose and xylose was done in a cross-flow system, using a commercial spiral wound nanofiltration (NF) membrane with molecular weight cut off (MWCO) ranging from 150 to 1000 g/mol. The xylose separation factor was up to 1.63 when increased in feed pressure while inhibitors present in OPF bagasse hydrolysate are retained more due its lower separation factor. The inhibitors most probably cannot pass through the membrane due to xylose molecule size was bigger and block them. Overall, it can be concluded that the spiral wound nanofiltration membrane offers costeffective and easymaintenance, which has a potential in xylose-glucose separation. Art. [#ARTNUM](#article-30332-2940278890)

3.5.1 3.5 Spiral wound Nanofiltration
Separation of xylose from glucose in oil palm frond (OPF) bagasse hydrolysate using nanofiltration membrane system
Separation of biomass hydrolysate that contain glucose and xylose was done in a cross-flow system, using a commercial spiral wound nanofiltration (NF) membrane with molecular weight cut off (MWCO) ranging from 150 to 1000 g/mol. Xylose is an intermediate product in xylitol production and glucose interferes in the process of separation. The molecular weight of glucose is 1.2 times higher than the molecular weight of xylose. These two different types of monosaccharides can possibly be separated using NF membrane according to their molecular size rather than diffusivities. Thus the aim of this study are to develop and evaluate the performance of pilot scale commercial spiral wound NF membrane namely Desal-5 DK, Desal-5 DL and NF90 for separation of xylose from glucose. The feedstock used was biomass from oil palm frond (OPF) bagasse. The separation of sugar was started using xylose-glucose model solution before run with OPF hydrolysate. The filtration was operated in total recycled mode at 5 to 10 bar. The sugar concentration was analyzed using high performance liquid chromatography (HPLC). From this study, Desal-5 DK membrane gave the higher xylose separation factor at 1.17 as compare to Desal-5 DL (0.81) and NF90 membranes (0.84) when using model solution. There are several operating parameter used to evaluate the performance of membrane, which are transmembrane pressure (TMP), total feed concentration (C0) and ratio xylose to glucose. The crossflow effect from the operating parameter was tested using binary model solution. Xylose and glucose rejection are dependent on the effective filtration pressure. According to the result in this study, glucose rejection is up to 90 % and xylose rejections up to 80 % when pressure increased. Maximum separation factor 2.47 was achieved when xylose concentration ratio was 3.2 % in total feed concentration with 10 % of glucose. This is due to higher concentration of larger molecule (glucose) pushes smaller molecule (xylose) through the membrane, enhancing xylose permeation. Meanwhile, equal ratio of xylose to glucose (50:50) at high feed concentration, 10 % promoted to high separation factor which is 2.16. The separation of OPF hydrolysate in this present work gave low rejection of xylose between 10 to 30 %. This is due to low pressure at 5 to 10 bar was applied during the separation. The xylose separation factor was up to 1.63 when increased in feed pressure while inhibitors present in OPF bagasse hydrolysate are retained more due its lower separation factor. The inhibitors most probably cannot pass through the membrane due to xylose molecule size was bigger and block them. Overall, it can be concluded that the spiral wound nanofiltration membrane offers cost-effective and easy-maintenance, which has a potential in xylose-glucose separation.
7/1/18 12:00:00 AM
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3.6 Surface-modified nanofiltration

0

By modification of the surface of the membranes used in nanofiltration, their perfomance for the separation of sugars can be improved. **Research findings:** - Optimizing of the thermal treatment was investigated. A treatment at 170 °C for 2 h was found optimal, with higher solubilzation of hemicellulose than that at 150 °C and lower degradation of sugar monomers than 190 °C. Recovery of xylose was high and the purity of xylose solution (78%) allows expecting an easy purification and separation of xylose before hydrogenation. Analysis of thermal hydrolyzates shows the presence of xylan oligomers and polymers with large distribution of DPs. This fraction should be submitted to enzymatic treatment to recover more xylose monomer. Art. [#ARTNUM](#article-30461-2342180376)

3.6.1 3.6 Surface-modified nanofiltration
Sugar fractionation using surface-modified nanofiltration membranes
Abstract Nanofiltration (NF) membranes were prepared using layer-by-layer (LbL) deposition of poly(sodium 4-styrenesulfonate) (PSS) and poly(diallyldimethylammonium chloride) (PDADMAC) on polysulfone (PSf) ultrafiltration (UF) membranes. The feasibility of using these NF membranes for fractionation of sugars was investigated. Deposition of polyelectrolyte multilayer (PEM) on the PSf membrane substrates was also confirmed by various characterization methods. Characterization results along with NF tests confirmed that pore-filling took place for 50 and 100 kDa PSf membranes. Results show that modified membranes were capable of separation/rejection of compounds with molecular weights in the range of mono- and disaccharide solutes. The 50 kDa base UF membrane modified with [PSS/PDADMAC] 7 PSS showed the best NF performance with sucrose to glucose selectivity of more than 11. In order to further enhance the separation factor and ensure a stable modification of the membrane, a novel method to convert the ionic bonded coatings into covalently bonded coatings has been developed.
6/1/16 12:00:00 AM
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3.7 Calcium alginate membranes

2

Calcium alginate is a water-insoluble, gelatinous, cream-coloured substance that can be created through the addition of aqueous calcium chloride to aqueous sodium alginate. [[Wiki]](https://en.wikipedia.org/wiki/Calcium_alginate) Membranes can be made from calcium alginate and they have been explored for the purification of sugars. **Research findings:** - Glucose was selectively separated from an aqueous solution of mixed sugars (glucose 180 Da, maltose 342 Da, and raffinose 504 Da) by static diffusion, and not ultrafiltration, without the driving force of pressure. The calcium alginate membrane described in this study provides a simple technical medium for sugar separation. Excellent selectivity based on the molecular size of sugar was realized. The mass fraction of homopolymeric blocks of guluronate in alginate polymer chains ( F GG ) was defined as a gravimetric ratio of homopolymeric blocks of α l guluronate in sodium alginate to the total mass of the sodium alginate polymer. F GG was a key factor for regulating the mass transfer characteristics of the calcium alginate membrane. Two different F GG membranes were employed to assess the selective separation of glucose. The effective diffusion coefficient in the membrane ( D eff ) was determined from the mass transfer flux through the calcium alginate membrane. The effective diffusion coefficient in the F GG 0.56 membrane exhibited a 38fold decrease in the mixed system of the three sugars, even when the molecular weight showed only a 2.8fold increase from glucose to raffinose. In the F GG 0.18 membrane, the effective diffusion coefficient exhibited a 14fold decrease. The mass fraction of guluronate blocks was a dominant factor that regulated the selective diffusion of the sugars. The design of a calcium alginate membrane based on the mass fraction of guluronate blocks is promising for desirable selective sugar separation in industrial applications. Art. [#ARTNUM](#article-30462-2553706189)

3.7.1 3.7 Calcium alginate membranes
Selective diffusion of glucose, maltose, and raffinose through calcium alginate membranes characterized by a mass fraction of guluronate
Abstract Glucose was selectively separated from an aqueous solution of mixed sugars (glucose 180 Da, maltose 342 Da, and raffinose 504 Da) by static diffusion, and not ultrafiltration, without the driving force of pressure. The calcium alginate membrane described in this study provides a simple technical medium for sugar separation. Excellent selectivity based on the molecular size of sugar was realized. The mass fraction of homopolymeric blocks of guluronate in alginate polymer chains ( F GG ) was defined as a gravimetric ratio of homopolymeric blocks of α- l -guluronate in sodium alginate to the total mass of the sodium alginate polymer. F GG was a key factor for regulating the mass transfer characteristics of the calcium alginate membrane. Two different F GG membranes were employed to assess the selective separation of glucose. The effective diffusion coefficient in the membrane ( D eff ) was determined from the mass transfer flux through the calcium alginate membrane. The effective diffusion coefficient in the F GG 0.56 membrane exhibited a 38-fold decrease in the mixed system of the three sugars, even when the molecular weight showed only a 2.8-fold increase from glucose to raffinose. In the F GG 0.18 membrane, the effective diffusion coefficient exhibited a 14-fold decrease. The mass fraction of guluronate blocks was a dominant factor that regulated the selective diffusion of the sugars. The design of a calcium alginate membrane based on the mass fraction of guluronate blocks is promising for desirable selective sugar separation in industrial applications.
3/1/17 12:00:00 AM
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4. Boronic acid-based (BAB) complexation

Back

Boronic acids have a selectivity for binding the 1,2- and/or 1,3-diol sites commonly found in saccharides. This specificity has led to the use of boronic acids as tunable sensors for saccharides: the structure of a given BA will determine to which sugar it will preferentially bind. This principle is exploited in BAB separation technologies


4.1 BAB solvent extraction

1

A lipophilic boronic acid dissolved in an organic solvent is contacted with an immiscible aqueous solution containing dissolved sugars and buffered to a pH greater than the pKa of the boronic acid (ie generally a pH of 9 or greater). At the interface between the organic and aqueous phases the boronic acid ionises to form a tetrahedral anion that then forms an anion complex with the cis‐diols of a sugar molecule (Scheme 2). This anion complex is then dissolved within the organic solvent by forming an ion pair with a lipophilic quaternary ammonium cation, such as trioctylmethylammonium ion. This process is reversible and the complex decomposes in acidic solution thus releasing the bound sugar. Art. [#ARTNUM](#article-25427-1984506405) **Research Findings** - In this research, the isolation of C5 sugars from a wheat bran hydrolysate using anionic extraction of saccharides, followed by back-extraction and a further purification process by means of ion exchange resins was studied. The extraction is based on a reversible complexation of saccharides with boronic acids. A purification process based on the recovery of sugars by anionic extraction with a boronic acid, followed by backextraction and a further refining step with ion exchange resins is described. After this process, a high purity sugars solution (~90%) free of inorganic elements and proteins was obtained. Art. [#ARTNUM](#article-25427-2883754868) - Experimental trials of the extraction of xylose, glucose, and fructose from aqueous solutions were conducted using 3,5-dimethylphenylboronic acid (DMPBA) and modified Aliquat® 336 (MA) as combined extractants dissolved in Exxal®10 diluent. Extraction of xylose and glucose from solutions derived from the acid hydrolysis of bagasse was performed. By varying the volumetric ratio of strip to organic phases, strip solutions with xylose concentrations up to 4× that of the original hydrolysate were produced while reducing the concentration of the undesirable acid soluble lignin by up to 90%. Art. [#ARTNUM](#article-25427-2078806658)

4.1.1 4.1 BAB solvent extraction
FROM BIOMASS TO SUGAR ALCOHOLS: PURIFICATION OF WHEAT BRAN HYDROLYSATES USING BORONIC ACID CARRIERS FOLLOWED BY HYDROGENATION OF SUGARS OVER RU/H-ZSM-5
Wheat bran is a lignocellulosic waste of milling industry. It contains hemicelluloses which can be valorized into arabitol and xylitol via a few-step approach. It begins with extraction and hydrolysis of hemicelluloses to produce a solution of xylose and arabinose along with proteins and inorganic salts. This work focusses on the purification of sugars of this hydrolysate and the subsequent catalytic production of sugar alcohols. A purification process based on the recovery of sugars by anionic extraction with a boronic acid, followed by back-extraction and a further refining step with ion exchange resins is described. After this process, a high purity sugars solution (~90%) free of inorganic elements and proteins was obtained. The feasibility of the process was also highlighted by a successful recycling of the organic phase containing the boronic acid. The hydrogenation of purified sugars was then performed over Ru/H-ZSM-5. A high yield into pentitols of ~70% with 100% selectivity was achieved. Important...
9/4/18 12:00:00 AM
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4.1.2 4.1 BAB solvent extraction
Isolation of C5-Sugars from the Hemicellulose-Rich Hydrolyzate of Distillers Dried Grains
A three-stage process for isolation and separation of C5-sugars in dry form from the hydrolyzate of distillers dried grains (DDG) is described. The salient features include extraction of bis(boronic ester) adducts of xylose and arabinose into toluene on treatment of neutralized hydrolyzate with phenylboronic acid (PBA) and subsequent addition of propylene glycol to the organic phase to induce sugar precipitation for ready collection. The PBA used in the process is largely reclaimed on hydrolysis of the propylene glycol boronic ester formed during the process. A preparative scale example afforded 48% of the xylose content in DDG as a crystalline solid also containing an additional 11% of the arabinose content.
10/5/15 12:00:00 AM
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4.1.3 4.1 BAB solvent extraction
Purification and Concentration of Xylose and Glucose from Neutralized Bagasse Hydrolysates Using 3,5-Dimethylphenylboronic Acid and Modified Aliquat 336 as Coextractants
Experimental trials of the extraction of xylose, glucose, and fructose from aqueous solutions were conducted using 3,5-dimethylphenylboronic acid (DMPBA) and modified Aliquat® 336 (MA) as combined extractants dissolved in Exxal®10 diluent. MA was produced by contacting an Aliquat 336/Exxal 10 solution with a concentrated caustic soda solution so that the quaternary ammonium ions of Aliquat 336 would ion pair with hydroxide ions. The DMPBA/MA/Exxal 10 organic solution containing equimolar amounts of MA and DMPBA was contacted with a neutral aqueous solution containing one of glucose, xylose, or fructose and the extraction isotherms were determined. The molar ratio of DMPBA:sugar in a fully loaded organic solution was 2:1. The use of the MA instead of Aliquat 336 enabled significant proportions of the sugars to be extracted from aqueous solutions over a wide pH range (∼2-11). Loaded organic solutions were stripped using aqueous hydrochloric acid solutions. Complete recovery of the sugar was possible by ensuring sufficient acidity was available in the strip solution. Solutions of MA in Exxal 10 were also found to extract sugar, although to a lesser extent than when DMPBA was included. Extraction of xylose and glucose from solutions derived from the acid hydrolysis of bagasse was performed. By varying the volumetric ratio of strip to organic phases, strip solutions with xylose concentrations up to 4× that of the original hydrolysate were produced while reducing the concentration of the undesirable acid soluble lignin by up to 90%. Hence, this process has the potential to produce high concentration monosaccharide solutions suitable for direct fermentation.
8/1/05 12:00:00 AM
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4.1.4 4.1 BAB solvent extraction
Solvent extraction and purification of sugars from hemicellulose hydrolysates using boronic acid carriers
Research was performed to determine whether it was technically feasible to use boronic acid extractants to purify and concentrate the sugars present in hemicellulose hydrolysates. Initially, five types of boronic acids (phenylboronic acid, 3,5-dimethylphenylboronic acid, 4-tert-butylphenylboronic acid, trans-β-styreneboronic acid or naphthalene-2-boronic acid) dissolved in an organic diluent (Shellsol 2046 or Exxal 10) containing the quaternary amine Aliquat 336 were tested for their ability to extract sugars (fructose, glucose, sucrose and xylose) from a buffered, immiscible aqueous solution. Naphthalene-2-boronic acid was found to give the greatest extraction of xylose regardless of which diluent was used. Trials were then conducted to extract xylose and glucose from solutions derived from the dilute acid hydrolysis of sugar cane bagasse and to then strip the loaded organic solutions using an aqueous solution containing hydrochloric acid. This produced a strip solution in which the xylose concentration had been increased over 7× that of the original hydrolysate while reducing the concentration of the undesirable acid-soluble lignin by over 90%. Hence, this process can be exploited to produce high concentration xylose solutions suitable for direct fermentation.
5/1/04 12:00:00 AM
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4.2 BAB Supported liquid membrane (SLM) Extraction

0

Boronic acids can be used as carriers in supported liquid membranes. **Research findings:** - Research on the extraction of sugars using boronic acids has centred on the measurement of the transport rates of fructose, glucose and sucrose across supported liquid membranes (SLMs) or plasticised liquid membranes (PLMs) using a wide variety of boronic acid carriers. Art. [#ARTNUM](#article-25716-1984506405) - The work conducted aims to achieve this separation by transporting the monosaccharides (glucose and xylose) contained in an ionic liquid (1ethyl3methylimidazolium acetate)/aqueous mixture via a supported liquid membrane impregnated with phenylboronic acid and quaternary amine (Aliquat 336) extractants and the diluent, 2nitrophenyl octyl ether. The monosaccharides are transported to an aqueous neutral receiving phase. Art. [#ARTNUM](#article-25716-2607720443)

4.2.1 4.2 BAB Supported liquid membrane (SLM) Extraction
BORONIC ACIDS SELECTIVELY FACILITATE GLUCOSE TRANSPORT THROUGH A LIQUID BILAYER
Glucose is the most important carbohydrate in human metabolism. Many body tissues depend on glucose as a primary source of energy. To ensure that a sufficient supply is always available, the blood glucose concentration is maintained around 5 mM. In addition, the tissues retain an abundance of glucose transporters to facilitate glucose movement across the cell membranes.' The transporters are integral proteins that act as passive and/or active membrane transport systems. Currently, there is much interest in elucidating the mechanism of these biotic transporters. While much structural data has been accumulated, the kinetic picture is still largely unknown.2 The development of artificial transporters for carbohydrate compounds, such as glucose, is a complementary research goal. In terms of applied technology, artificial transporters have potential as reagents for modulating the membrane permeability of selective biochemicals, or as drug transport devices for improving therapeutic efficacy. From the perspectiveof basic research, artificial systems represent simplified models that allow some of the structural and kinetic aspects of membrane transport theory to be tested.' Previously, we and others have investigated the ability of boronic acids to facilitate the transport of saccharide derivatives through liquid organic membranes." Herein, we report that simple arylboronic acids, 1-7, and thealkylderivative9areable toselectivelyfacilitate the efflux of glucose from liposomes. To our knowledge this represents the first exampleof selective transport of a carbohydrate compound through a lipid bilayer mediated by an abiotic carrier. Glucose (typically 300 mM) was encapsulated inside large unilamellar vesicles (LUVs, 80 nm diameter, encapsulation volume 1.1 pL/pmol of lipid), composed of dipalmitoylphosphatidyl choline (DPCC), cholesterol (C), and phosphatidic acid (PA) in the ratio 20:15:2. The liposomes were prepared by the rapid extrusion technique and were found to be essentially impermeable to glucose leakage over a number of days.596 Figure 1 describes the glucose efflux experiment, which uses the standard hexokinase/glucose-6-phosphate dehydrogenase enzyme system for detection of escaped glucose.7 The enzymes are unable to penetrate the liposomes, thus an absorbance reading at 340 nm,
10/1/94 12:00:00 AM
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4.2.2 4.2 BAB Supported liquid membrane (SLM) Extraction
Isolation of C5-Sugars from the Hemicellulose-Rich Hydrolyzate of Distillers Dried Grains
A three-stage process for isolation and separation of C5-sugars in dry form from the hydrolyzate of distillers dried grains (DDG) is described. The salient features include extraction of bis(boronic ester) adducts of xylose and arabinose into toluene on treatment of neutralized hydrolyzate with phenylboronic acid (PBA) and subsequent addition of propylene glycol to the organic phase to induce sugar precipitation for ready collection. The PBA used in the process is largely reclaimed on hydrolysis of the propylene glycol boronic ester formed during the process. A preparative scale example afforded 48% of the xylose content in DDG as a crystalline solid also containing an additional 11% of the arabinose content.
10/5/15 12:00:00 AM
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4.2.3 4.2 BAB Supported liquid membrane (SLM) Extraction
Liquid membrane transport using boronic acid carriers
Abstract This review summarizes the recent research on a new application with boronic acids, namely their ability to act as transport carriers in bulk, liquid organic membranes. To date, boronic acids have been shown to facilitate the transport of reducing monosaccharides, ribonucleosides, aryl glycosides, catecholamines, a-amino acids, and riboflavin. The transport can either be passive (down a solute concentration gradient) or active (against a solute concentration gradient). The various chemical mechanisms for boronic acid mediated transport are described, as well as the chemical and physical factors that control transport rates.
4/1/96 12:00:00 AM
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4.2.4 4.2 BAB Supported liquid membrane (SLM) Extraction
Solvent extraction and purification of sugars from hemicellulose hydrolysates using boronic acid carriers
Research was performed to determine whether it was technically feasible to use boronic acid extractants to purify and concentrate the sugars present in hemicellulose hydrolysates. Initially, five types of boronic acids (phenylboronic acid, 3,5-dimethylphenylboronic acid, 4-tert-butylphenylboronic acid, trans-β-styreneboronic acid or naphthalene-2-boronic acid) dissolved in an organic diluent (Shellsol 2046 or Exxal 10) containing the quaternary amine Aliquat 336 were tested for their ability to extract sugars (fructose, glucose, sucrose and xylose) from a buffered, immiscible aqueous solution. Naphthalene-2-boronic acid was found to give the greatest extraction of xylose regardless of which diluent was used. Trials were then conducted to extract xylose and glucose from solutions derived from the dilute acid hydrolysis of sugar cane bagasse and to then strip the loaded organic solutions using an aqueous solution containing hydrochloric acid. This produced a strip solution in which the xylose concentration had been increased over 7× that of the original hydrolysate while reducing the concentration of the undesirable acid-soluble lignin by over 90%. Hence, this process can be exploited to produce high concentration xylose solutions suitable for direct fermentation.
5/1/04 12:00:00 AM
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4.2.5 4.2 BAB Supported liquid membrane (SLM) Extraction
Transport of monosaccharides contained in an ionic liquid/aqueous mixture via a supported liquid membrane
Lignocellulosic materials are renewable biomass that can be utilized in the development of biofuels such as ethanol. Hydrolysis of hemicellulose and cellulose, contained in pretreated biomass, produces monosaccharides that are fermented to produce ethanol. Since lignocellulosic materials possess resistance to hydrolysis, the methods currently involved are not cost-effective for large scale ethanol production. Ionic liquid pretreatment of biomass is a relatively new approach that has gained popularity due to its capability of decrystallizing cellulose effectively. The cellulose contained within an ionic liquid is more readily available for hydrolysis by acids or bases to their constituent monosaccharides. These monosaccharides need to be separated from the other constituents (lignin and other impurities), which may inhibit the downstream fermentation process. This technique can be implemented to produce high quality feed solutions for fermentation thus increasing the yield of ethanol produced. The work conducted aims to achieve this separation by transporting the monosaccharides (glucose and xylose) contained in an ionic liquid (1-ethyl-3-methylimidazolium acetate)/aqueous mixture via a supported liquid membrane impregnated with phenylboronic acid and quaternary amine (Aliquat 336) extractants and the diluent, 2-nitrophenyl octyl ether. The monosaccharides are transported to an aqueous neutral receiving phase. Comparisons are made to similar trials where the departure phase is an aqueous pH 11 buffer.
1/1/15 12:00:00 AM
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4.3 BAB Aldose-ketose transformation extraction

0

By isomerization though pH adjustment and catalysis of sugars in hydrolysates, aldoses can be converted to ketoses. These ketoses can then be complexed with aryl boronic acid; an immiscible organic phase can extract this complex. **Patent findings** - By isomerization, and contacting with aryl boronice acid (ABA) the ABA preferentially binds to ketoses compared to aldoses, and the system is used to separate C5 sugars from C6 sugars. By contacting the pH-adjusted hydrolysate with an isomerization catalyst, wherein at least a portion of the aldose sugar in the pHadjusted hydrolysate is converted to its ketose isomer, to produce an isomerized hydrolysate;contacting the ketose isomer in the isomerized hydrolysate with an aryl boronic acid (ABA) at a pH in the range of from 7.5 to 8.5 to form a complex of ketoseconjugate base form of the ABA; wherein the contacting comprises bringing the isomerized hydrolysate into contact with an immiscible organic phase that dissolves the ABA and a lipophilic salt (QX), and allowing the ketose in the isomerized hydrolysate to be extracted into the immiscible organic phase via ester formation with a conjugate base form of the ABA that is coupled via ion pair formation with Q+, thereby reducing the concentration of ketose in the isomerized hydrolysate and forming a ketose rich organic phase, in turn shifting the aldose/ketose equilibrium in favor of more ketose formation in the pHadjusted hydrolysate;preparing a low pH medium having a pH in the range of from about 2 to about 4.5, that contains an acid HX, wherein X is the same anion as X in the lipophilic salt (QX);bringing the low pH medium into contact with the ketoserich organic phase; wherein, at the low pH, the ketose and hydroxyl ions are released into the low pH medium and the ABA is converted to its nonionic conjugate acid; and, wherein, at the same time, the Q+ ion that formed the ion pair combines with an X− ion from the low pH medium to reform the lipophilic salt; andrecovering the ketose from the organic phase into the low pH medium as a concentrated ketoserich solution. Pat. [#ARTNUM](#article-25715-US9242222B2)

4.3.1 4.3 BAB Aldose-ketose transformation extraction
Production of keto-pentoses via isomerization of aldo-pentoses catalyzed by phosphates and recovery of products by anionic extraction
Xylulose and ribulose are rare keto-pentoses which are in high demand for the synthesis of commodities and fine chemicals. The production of keto-pentoses via isomerization of aldo-pentoses presents a carbon-efficient synthetic method. However, the isomerizations are equilibrium processes with thermodynamically limited yields of the products. In this work we examined isomerization of aldo-pentoses into keto-pentoses in the presence of NaH2PO4 + Na2HPO4 as a soluble catalyst at pH 7.5. A reaction network was proposed based on product distribution with D-(1-13C)-ribose as a substrate. Additionally, kinetics of the isomerization reactions was addressed. Selectivity for the keto-pentoses dramatically depends on the structure of the substrate. Arabinose and xylose give rise to a number of isomeric pentoses with low selectivities for the target products. Investigation of the reaction kinetics suggests that xylose and arabinose slowly isomerize into xylulose and ribulose, respectively. The latter react further significantly quicker to produce a number of isomers as subsequent products. This causes a complex mixture of products with low selectivity for the keto-pentoses. In contrast, ribose and lyxose as substrates yield ribulose and xylulose with rather high selectivities of 68–79% at 20% conversion. Ribose and lyxose quickly isomerize into ribulose and xylulose, respectively, whereas the subsequent processes are relatively slow. This results in a high selectivity for the keto-pentoses based on ribose and lyxose. Moreover, the isolation of xylulose from the reaction mixture was also studied. Xylulose can be selectively recovered after the isomerization of lyxose using anionic extraction with o-hydroxymethyl phenylboronic acid (HMPBA). After extraction, the aqueous phase containing phosphates and remaining lyxose can be recycled. After four cycles, the yield of xylulose reached 37% though only 19% can be achieved under batch conditions. Xylulose can be further recovered from the organic phase by back extraction using an acidified solution. Ribulose can also be extracted as an anionic complex with HMPBA, though ribose is co-extracted in this case and a separation of ribulose from ribose cannot be achieved. Extraction of the keto-pentoses occurs due to formation of β-xylulose–HMPBA and α-ribulose–HMPBA anionic complexes, whose molecular structures were established by NMR and MS.
1/1/17 12:00:00 AM
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4.3.2 4.3 BAB Aldose-ketose transformation extraction
Aldose-ketose transformation for separation and/or chemical conversion of C6 and C5 sugars from biomass materials

1. A method for converting an aldose in a biomass hydrolysate to its ketose isomer, comprising:adjusting a pH of a saccharified biomass hydrolysate containing one or more aldose sugars to a value between about 7.5 and about 9, to produce a pH-adjusted hydrolysate;contacting the pH-adjusted hydrolysate with an isomerization catalyst, wherein at least a portion of the aldose sugar in the pH-adjusted hydrolysate is converted to its ketose isomer, to produce an isomerized hydrolysate;contacting the ketose isomer in the isomerized hydrolysate with an aryl boronic acid (ABA) at a pH in the range of from 7.5 to 8.5 to form a complex of ketose-conjugate base form of the ABA; wherein the contacting comprises bringing the isomerized hydrolysate into contact with an immiscible organic phase that dissolves the ABA and a lipophilic salt (QX), and allowing the ketose in the isomerized hydrolysate to be extracted into the immiscible organic phase via ester formation with a conjugate base form of the ABA that is coupled via ion pair formation with Q+, thereby reducing the concentration of ketose in the isomerized hydrolysate and forming a ketose- rich organic phase, in turn shifting the aldose/ketose equilibrium in favor of more ketose formation in the pH-adjusted hydrolysate;preparing a low pH medium having a pH in the range of from about 2 to about 4.5, that contains an acid HX, wherein X is the same anion as X in the lipophilic salt (QX);bringing the low pH medium into contact with the ketose-rich organic phase; wherein, at the low pH, the ketose and hydroxyl ions are released into the low pH medium and the ABA is converted to its non-ionic conjugate acid; and, wherein, at the same time, the Q+ ion that formed the ion pair combines with an X− ion from the low pH medium to reform the lipophilic salt; andrecovering the ketose from the organic phase into the low pH medium as a concentrated ketose-rich solution. 2. The method of claim 1, including controlling the volume of the low pH medium such that the concentration of ketose in the ketose-rich medium is higher than the initial concentration of aldose in the hydrolysate. 3. The method of claim 1, further including reusing the organic phase containing the ABA and the lipophilic salt for a subsequent batch of hydrolysate. 4. The method of claim 1, wherein the steps of contacting the ketose isomer in the isomerized hydrolysate with ABA, and bringing the low pH medium into contact with the ketose-rich organic phase, are carried out using a micro- porous hollow fiber contactor. 5. The method of claim 4, wherein the micro-porous hollow fiber contactor comprises a shell having a first set of porous hollow fibers adapted for carrying the isomerized hydrolysate; and a second set of porous hollow fibers adapted for carrying the low-pH medium;the shell being configured for containing the organic extraction phase in a shell-side space substantially surrounding the first and second sets of fibers. 6. The method of claim 5, wherein the ketose is transported from the hydrolysate to the immiscible organic phase and from the organic phase to the low-pH medium, wherein the transport of the ketose is facilitated by ABA and QX combination dissolved in the immiscible organic phase. 7. The method of claim 5, wherein the first and second sets of micro-porous hollow fibers are commingled within the shell. 8. The method of claim 5, wherein the saccharified biomass hydrolysate contains glucose and xylose, and the method comprises:passing the hydrolysate through a packed bed reactor containing immobilized xylose isomerase (XI) or solid acid/base catalyst;allowing the isomerized hydrolysate to flow through the first set of fibers within the micro-porous hollow fiber contactor, the isomerized hydrolysate coming into contact with the immiscible organic phase containing lipophilic ABA and a lipophilic salt (QX) that fills the shell;extracting the xylulose in the isomerized hydrolysate, wherein the pH of the isomerized hydrolysate is in the range of from 7.5 to 8.5, into the organic phase via ester formation with a conjugate base form of the ABA coupled by ion pair formation with Q+, thereby reducing concentration of xylulose in the hydrolysate, and shifting the xylose/xylulose equilibrium in favor of more xylulose formation;concurrently with the extracting, allowing the low pH medium to flow through the second set of fibers and contact the organic phase contained on the shell side; whereby:the xylulose and hydroxyl ions attached to the ABA are released into the low pH medium, the ABA is re- converted to its non-ionic conjugate acid, andthe Q+ ion, which formed the ion pair with ABA, combines with an X− ion from the low pH medium to re-form the lipophilic salt. 9. The method of claim 1, including selecting an ABA having a property to enhance selectivity for a specific sugar. 10. The method of claim 1, further including controlling the volume of the low pH medium such that the ketose concentration in the recovered solution is higher than the aldose concentration in the saccharified biomass hydrolysate. 11. The method of claim 1, wherein both glucose and xylose from the hydrolysate are simultaneously isomerized by the isomerization catalyst into ketoses, the ketoses are extracted into the organic phase via binding to the ABA and QX, and the ketoses are recovered from the organic phase via back- extraction into the low pH medium while leaving behind other inhibitory compounds in the biomass hydrolysate. 12. The method of claim 1, wherein a micro-porous hollow fiber contactor physically separates the ketose-rich organic phase from the low pH medium during the ketose recovery. 13. The method of claim 1, wherein the step of contacting the pH-adjusted hydrolysate with an isomerization catalyst comprises passing the pH-adjusted hydrolysate through a packed bed reactor containing the isomerization catalyst, wherein the isomerization catalyst facilitates conversion of glucose to fructose. 14. The method of claim 1, wherein the pH of the recovered ketose is adjusted slightly to a pH suitable for converting the ketose to lactic acid, succinic acid, or fumaric acid by native microorganisms. 15. The method of claim 1, wherein the isomerization catalyst preferentially isomerizes xylose into xylulose compared to glucose into fructose, the ABA preferentially binds to ketoses compared to aldoses, and the system is used to separate C5 sugars from C6 sugars. 16. The method of claim 1, wherein the pH of the recovered ketose corresponds to a pH suitable for dehydration of the ketose to furans via an acid-catalyzed chemical reaction. 17. The method of claim 1, wherein the isomerization catalyst comprises xylose isomerase (XI) particles that facilitate the isomerization of both glucose and xylose. 18. The method of claim 1, comprising:a first micro-porous hollow fiber contactor having a lumen side and a shell side, wherein the hydrolyzate flows through the lumen-side in the first micro-porous hollow fiber contactor and the immiscible organic phase flows through the shell-side; anda second micro- porous hollow fiber contactor that physically separates the ketose-rich organic phase from the low pH medium during ketose recovery. 19. The method of claim 1, wherein the saccharified biomass hydrolysate is a lignocellulosic biomass hydrolysate. 20. The method of claim 19, wherein one or more of the ABA, the pH, and temperature of the hydrolysate, are altered to selectively isomerize and extract one or more specific sugars. 21. The method of claim 1, wherein the ABA is present in an immiscible organic phase that is physically separated by a permeable device from the isomerized hydrolysate, the permeable device allowing transport of the sugar from the isomerized hydrolysate into the immiscible organic phase, while substantially preventing dispersion of the immiscible organic phase in the isomerized hydrolysate. 22. The method of claim 7, wherein the immiscible organic phase comprises one or more of octanol, ethyl acetate, dichloromethane, o-nitrophenyl octyl ether (NPOE), or diethyl ether. 23. The method of claim 21, wherein the permeable device is a micro-porous hollow fiber contactor. 24. The method of claim 1, wherein the step of contacting the pH-adjusted- hydrolysate with an isomerization catalyst comprises passing the pH-adjusted hydrolysate through a packed bed reactor containing the isomerization catalyst, wherein the isomerization catalyst facilitates conversion of xylose into xylulose. 25. The method of claim 24, wherein the packed bed reactor is connected in a loop to a micro-porous hollow fiber contactor having a shell side and a fiber side, such that the hydrolysate flows through the packed bed and the fiber side of the micro-porous hollow fiber contactor, and the ketose is extracted from the hydrolysate to the immiscible organic phase on the shell side of the micro-porous hollow fiber contactor. 26. The method of claim 1, including: selecting the ABA such that, at selected pH and temperature conditions, the ABA mainly binds to xylulose, and does not bind to any appreciable amounts of glucose, xylose, or fructose. 27. The method of claim 1, including circulating the hydrolysate through at least a first column comprised of a packed bed of immobilized xylose isomerase (XI), and through a vessel having an ABA-enriched phase therein. 28. The method of claim 1, wherein the pH of the recovered ketose is a pH suitable for converting the ketose to ethanol by native _S. cerevisiae_ or other native microorganisms. 29. The method of claim 1, including controlling a volume of the low pH medium sufficient to recover the ketose as a concentrated solution. 30. The method of claim 1, including separating xylose from other C6 sugars as its keto-isomer and allowing for the recovery of xylulose as a concentrated solution. 31. The method of claim 1, comprising passing the isomerized hydrolysate and the ABA containing organic phase through a micro-porous hollow fiber contactor. 32. The method of claim 1, wherein the ABA is selected from the group consisting of PBA, 3aPBA, 4cPBA, naphthalene-2-boronic acid (N2B), and 4-biphenylboronic acid. 33. The method of claim 1, wherein the ABA has the formula Ar--B(OH)2, where Ar represents an unsubstituted or substituted aryl group. 34. The method of claim 33, wherein the ABA comprises one or more of the aryl groups: 4-PhC6H4--; 4-MeC6H4--, where Me is methyl; 2-iPrC6H4-, where iPr is isopropyl; 2-naphthyl; 3-BnOC6H4--, where Bn is benzyl; 4-MeO2CC6H4--, where Me is methyl; and 4-pyridinyl. 35. The method of claim 33, wherein the ABA comprises a diboronic acid that exhibits a higher selectivity toward ketose binding compared to monoboronic acids. 36. The method of claim 33, wherein the ABA comprises a multi-dentate boronic acid carrier. 37. The method of claim 36, wherein the ABA comprises one or more of: wherein A and C are B(OH)2, and B and D are H groups. 38. The method of claim 1, wherein the ABA comprises a hydrophobic substituted aryl boronic acid. 39. The method of claim 38, wherein the ABA comprises: 40. The method of claim 38, wherein the hydrophobic substituted aryl boronic acid is used in a liquid-liquid extraction followed by stripping or micro- porous hollow fiber contactor implementation.
4/19/11 12:00:00 AM
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5. Integrated Approaches

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Integrated approaches make use of several technologies in series to perform the separation.


5.1 Electrodyalysis, simulated moving bed chromatography and crystallization

0

The following patent describes an integrated approach to purify xylose and arabinose. **Patent finding:** The invention relates to a method for separating and purifying xylose and arabinose from hemicellulose acid hydrolysis liquid. The method comprises the following separating and purifying steps of: (1) carrying out electrodialysis and membrane filtration concentrate pretreatment on hemicellulose acid hydrolysis liquid directly obtained by adopting acid hydrolysis, deoxidizing and filtering for later use by adopting highpurity water; (2) putting the hemicellulose acid hydrolysis liquid after pretreatment into a simulated moving bed chromatography separating device and carrying out separation to obtain two discharging liquids; and (3) concentrating, cooling and crystallizing the two discharging liquids by adopting a multieffect falling film evaporator to obtain xylose and arabinose products. Pat.[#ARTNUM](#article-25606-2734458194)

5.1.1 5.1 Electrodyalysis, simulated moving bed chromatography and crystallization
Method for separating and purifying xylose and arabinose from hemicellulose acid hydrolysis liquid
The invention relates to a method for separating and purifying xylose and arabinose from hemicellulose acid hydrolysis liquid. The method comprises the following separating and purifying steps of: (1) carrying out electrodialysis and membrane filtration concentrate pretreatment on hemicellulose acid hydrolysis liquid directly obtained by adopting acid hydrolysis, deoxidizing and filtering for later use by adopting high-purity water; (2) putting the hemicellulose acid hydrolysis liquid after pretreatment into a simulated moving bed chromatography separating device and carrying out separation to obtain two discharging liquids; and (3) concentrating, cooling and crystallizing the two discharging liquids by adopting a multi-effect falling film evaporator to obtain xylose and arabinose products. In the invention, monosaccharide is extracted by adopting the simulated moving bed chromatography separation device (SSMB), a plurality of adsorption columns are serially connected into a closed loop, and inlet and outlet positions of all portions of materials can be changed by continuously switching valves, therefore, the relative motion between solid phase and liquid phase is realized, and the separation and the extraction among different components are carried out. The invention not only has the advantages of simple fixed bed adsorption operation, but also has the continuous operation capacity of a moving bed and is suitable for large-scale industrial production.
3/30/10 12:00:00 AM
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5.2 Cocrystallization, ion exchange chromatiography and crystallization of xylose

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The following patent describes an integrated approach to extract xylose. **Patent finding:** The invention relates to a method for extracting xylose from viscoce chemical fiber squeezed alkali liquor. According to the technical scheme, the method comprises the following steps: prefiltering to obtain preconcentrated liquor; filtering the preconcentrated liquor through a nanofiltration membrane to obtain concentrated liquor; adding hydrochloric acid to the concentrated liquor to obtain hydrolysate; adding hydrolysate to NaOH until being neutral; decolorizing; regulating the concentration of NaCl; cooling at constant speed until reaching room temperature; enabling glucose in hydrolysate to cocrystallize with NaCl to remove glucose; treating filtrate through ion exchange columns to obtain purified liquor; crystallizing and purifying the purified liquor for the second time to obtain coarse xylose; refining the coarse xylose to obtain final xylose. Art. [#ARTNUM](#article-25972-2841332760)

5.2.1 5.2 Cocrystallization, ion exchange chromatiography and crystallization of xylose
Method for extracting xylose from viscoce chemical fiber squeezed alkali liquor
The invention relates to a method for extracting xylose from viscoce chemical fiber squeezed alkali liquor. According to the technical scheme, the method comprises the following steps: pre-filtering to obtain pre-concentrated liquor; filtering the pre-concentrated liquor through a nanofiltration membrane to obtain concentrated liquor; adding hydrochloric acid to the concentrated liquor to obtain hydrolysate; adding hydrolysate to NaOH until being neutral; decolorizing; regulating the concentration of NaCl; cooling at constant speed until reaching room temperature; enabling glucose in hydrolysate to cocrystallize with NaCl to remove glucose; treating filtrate through ion exchange columns to obtain purified liquor; crystallizing and purifying the purified liquor for the second time to obtain coarse xylose; refining the coarse xylose to obtain final xylose. With the adoption of the method, the resource is saved, the economic benefit is brought to enterprises, and the environment is protected.
5/13/15 12:00:00 AM
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5.3 Separation by chromatography and crystallization

0

This integrated approach recovers galactose from hemicellulose hydrolyzates by chromatographic fractionations (anion and cationic exchanges), followed by crystallization. **Patent findings:** One or more chromatographic fractionation steps are used in any desired sequence: - One or more chromatographic fractionatation steps using a column filling material selected from strongly basic anion exchange resins in HSO3− form are used. - One or more chromatographic fractionation steps where the ion form of said cation exchange resin is selected from Ba2+, Pb2+, Ca2+ and Sr2+. - One or more chromatographic fractionations comprise one or more chromatographic fractionation steps using a column filling material selected from strongly basic anion exchange resins. - one or more chromatographic fractionation steps using a column filling material selected from strongly acid cation exchange resins. Ccrystallization is carried out using a solvent selected from water and a mixture of water and alcohol as the crystallization solvent to obtain galactose. Pat. [#ARTNUM](#article-25563-US7722721B2)

5.3.1 5.3 Separation by chromatography and crystallization
Separation method

1. A process of recovering galactose from a plant-based hemicellulose hydrolyzate solution containing a galactose content of at least 5% by weight, said process comprising(a) subjecting said solution to chromatographic fractionations, said chromatographic fractionations comprising one or more fractionations using a strongly basic anion exchange resin, wherein the anion is selected from SO42−, SO32−, HSO3−, CH3COO−, and one or more fractionations using a cation exchange resin, wherein the cation exchange resin is selected from strong or weak cation exchange resin;(b) recovering at least one fraction enriched in galactose, having a galactose content of 38 to 95% on RDS;(c) subjecting said at least one fraction enriched in galactose to crystallization; and(d) recovering a plant-based crystalline galactose product having a purity of more than 90% on DS. 2. A process as claimed in claim 1, wherein said one or more chromatographic fractionations comprise one or more chromatographic fractionation steps using a column filling material selected from strongly basic anion exchange resins in HSO3− form. 3. A process as claimed in claim 2, wherein said one or more chromatographic fractionations comprise two chromatographic fractionation steps with a resin in HSO3− form. 4. A process as claimed in claim 1, wherein the ion form of said cation exchange resin is selected from Ba2+, Pb2+, Ca2+ and Sr2+. 5. A process as claimed in claim 1, wherein said one or more chromatographic fractionations comprise one or more chromatographic fractionation steps using a column filling material selected from strongly basic anion exchange resins and one or more chromatographic fractionation steps using a column filling material selected from strongly acid cation exchange resins, in any desired sequence. 6. A process as claimed in claim 1, wherein the crystallization is carried out using a solvent selected from water and a mixture of water and alcohol as the crystallization solvent. 7. A process as claimed in claim 6, wherein the crystallization solvent is a mixture of ethanol and water. 8. A process as claimed in claim 6, wherein the crystallization solvent is water. 9. A process as claimed in claim 1, wherein the crystallization provides crystalline galactose having a purity of more than 95% on DS. 10. A process as claimed in claim 1, wherein the crystallization provides crystalline galactose having a purity of more than 98% on DS. 11. A process as claimed in claim 1, wherein the crystallization provides crystalline galactose having a purity of more than 99.5% on DS. 12. A process as claimed in claim 1, wherein the crystallization provides crystalline galactose having a maximum content of D-glucose of 0.50% on DS. 13. A process as claimed in claim 1, wherein the crystallization provides crystalline galactose having a maximum content of D-glucose of 0.30%. 14. A process as claimed in claim 1, wherein the crystallization provides crystalline galactose having an impurity profile comprising at least one sugar selected from xylose, arabinose, rhamnose and mannose. 15. A process as claimed in claim 14, wherein the crystallization provides crystalline galactose, where the impurity profile comprises at least one of said sugars in an amount of 0.03% on DS or more. 16. A process as claimed in claim 15, wherein the crystallization provides crystalline galactose, where the impurity profile comprises arabinose in an amount of 0.03% on DS or more. 17. A process as claimed in claim 15, wherein the crystallization provides crystalline galactose, where the impurity profile comprises mannose in an amount of 0.03% on DS or more. 18. A process as claimed in claim 14, wherein the crystallization provides crystalline galactose, where the impurity profile comprises at least one of said sugars in an amount of 0.10% or more. 19. A process as claimed in claim 1, wherein the process further comprises one or more purification steps selected from membrane filtration, ion exchange, evaporation and filtration carried out before, after or between said chromatographic fractionation step/steps. 20. A process as claimed in claim 1, wherein the process further comprises crystallization between said chromatographic fractionation steps. 21. A process as claimed in claim 20, wherein said crystallization comprises precipitation crystallization of xylose. 22. A process as claimed in claim 1, wherein said plant-based hemicellulose hydrolysate is hydrolysate derived from wood material. 23. A process as claimed in claim 1, wherein said plant-based hemicellulose hydrolysate is a hydrolysate derived from softwood or hardwood. 24. A process as claimed in claim 1, wherein said solution derived from the plant-based hemicellulose hydrolyzate is a spent liquor obtained from a pulping process. 25. A process as claimed in claim 24, wherein said spent liquor obtained from a pulping process is a spent sulphite pulping liquor. 26. A process as claimed in claim 25, wherein said spent sulphite pulping liquor is a spent sulphite pulping liquor recovered after the separation of the main part of xylose. 27. A process as claimed in claim 1, wherein said solution derived from the plant-based hemicellulose hydrolyzate contains galactose and one or more further sugars selected from arabinose and mannose. 28. A process as claimed in claim 1, wherein said galactose is D-galactose. 29. A process as claimed in claim 14, wherein said xylose is D-xylose, said arabinose is L-arabinose, said mannose is D-mannose and said rhamnose is L-rhamnose.
3/5/07 12:00:00 AM
Link to Patent

5.4 Reaction separation and solvent extraction

0

Xylose and arabinose can be separated by reaction to xylose monoacetal and arabinose diacetal. This mixture can then be effectively separated by solvent extraction: the xylose monoacetal by a polar solvent and the diacetal by a non-polar solvent. They can then hydrolyzed to give xylose and arabinose. **Patent findings:** - A process for the separation of arabinose diacetal and xylose monoacetal from a mixture comprised of saccharides which comprises:(a) reacting the mixture with a ketone or an aldehyde so as to form the arabinose diacetal and xylose monoacetal;(b) concentrating the mixture to a syrup;(c) extracting the syrup with a nonpolar organic solvent in which the acetals of arabinose diacetal and xylose monoacetal are soluble to provide the arabinose diacetal and xylose monoacetal in the organic solvent;(d) separating the arabinose diacetal and xylose monoacetal from the organic solvent; and(e) separating the arabinose diacetal from the xylose monoacetal by a polar solvent and a non polar solvent extraction, so that there is a phase separation with the xylose monoacetal in the polar solvent and the arabinose diacetal in the nonpolar organic solvent. The mixture of step (a) is a syrup from a hydrolysate of corn fiber or sugar beet pulp. The xylose monoacetal is extracted from the mixture with water or a polar organic solvent as the polar solvent and then separated from the water or the polar organic solvent. In addition after step (e) the xylose monoacetal and arabinose diacetal are separately hydrolyzed to form xylose and arabinose. In step (e) the arabinose diacetal and the xylose monoacetal which are separated are pure isomers. The mixture of saccharides in step (a) is produced by enzyme or acid hydrolysis of saccharides. Pat.[#ARTNUM](#article-25713-US7498430B2)

5.4.1 5.4 Reaction separation and solvent extraction
Process for the preparation and separation of arabinose and xylose from a mixture of saccharides

1. A process for the separation of arabinose and xylose acetals which comprises:(a) providing a mixture comprising xylose and arabinose;(b) reacting the mixture with a ketone or aldehyde so as to form a mixture of xylose monoacetal and arabinose diacetal; and(c) separating the arabinose diacetal and xylose monoacetal from the reaction mixture by a polar solvent and non- polar solvent extraction so that there is a phase separation with the of xylose monoacetal in the polar solvent and the diacetal arabinose in the non- polar organic solvent. 2. The process of claim 1 wherein the mixture in step (a) is from a hydrolysate of corn fiber or sugar beet pulp. 3. The process of claim 1 wherein the xylose monoacetal is extracted from the mixture in step (c) with an acid in water as the polar solvent for the xylose monoacetal and the arabinose diacetal by the non-polar solvent, so that there is a phase separation. 4. The process of any one of claims 1, 2, or 3 wherein the arabinose diacetal and xylose monoacetal which are separated in step (c) are pure isomers. 5. A process for the separation of arabinose diacetal and xylose monoacetal from a mixture comprised of saccharides which comprises:(a) reacting the mixture with a ketone or an aldehyde so as to form the arabinose diacetal and xylose monoacetal;(b) concentrating the mixture to a syrup;(c) extracting the syrup with a non-polar organic solvent in which the acetals of arabinose diacetal and xylose monoacetal are soluble to provide the arabinose diacetal and xylose monoacetal in the organic solvent;(d) separating the arabinose diacetal and xylose monoacetal from the organic solvent; and(e) separating the arabinose diacetal from the xylose monoacetal by a polar solvent and a non- polar solvent extraction, so that there is a phase separation with the xylose monoacetal in the polar solvent and the arabinose diacetal in the non-polar organic solvent. 6. The process of claim 5 wherein the mixture of step (a) is a syrup from a hydrolysate of corn fiber or sugar beet pulp. 7. The process of claim 5 or 6 wherein xylose monoacetal is extracted from the mixture with water or a polar organic solvent as the polar solvent and then separated from the water or the polar organic solvent. 8. The process of claim 5 or 6 wherein in addition after step (e) the xylose monoacetal and arabinose diacetal are separately hydrolyzed to form xylose and arabinose. 9. The process of claim 5 or 6 wherein in step (e) the arabinose diacetal and the xylose monoacetal which are separated are pure isomers. 10. The process of claims 1, 2, 4 or 3 wherein the mixture of saccharides in step (a) is produced by enzyme or acid hydrolysis of saccharides.
11/9/04 12:00:00 AM
Link to Patent

6. Other techniques

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6.1 Biological treatment

0

By treating hemicellulosic hydrolysis biologically, one or several monomers can be selectively converted, which means that further purification can be easier. **Research Findings** - It was seen that the optimal results were obtained when 5. 7 g /L( NH4)2SO4,2.0 g /L KH2PO4 and 2 . 4 g /L yeast were applied. The removal of glucose and galactose were 100% and 67%,and the purity of xylose increased from 47% to 60% after the optimal biological treatment. Art. [#ARTNUM](#article-25544-2360514753)

6.1.1 6.1 Biological treatment
Purification of Sugars Liquid of Corncob Hemicelluloses by Biological Treatment
Biological treatment was used to remove glucose and galactose in this paper to purify the hemicellulose liquid sugars.Single factor and central composite experiments were used to optimize the medium components in the biological treatment. It was seen that the optimal results were obtained when 5. 7 g /L( NH4)2SO4,2.0 g/L KH2PO4 and 2. 4 g /L yeast were applied. The removal of glucose and galactose were 100% and 67%,and the purity of xylose increased from 47% to 60% after the optimal biological treatment. Acclimatization of strain used in the biotreatment of the liquor was also conducted to handle the high sugar consistency liquor which was diluted 6 times.
1/1/14 12:00:00 AM
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6.2 Capilary zone electrophoresis (CZE)

1

In CZE methods, analytes migrate through electrolyte solutions under the influence of an electric field. Analytes can be separated according to ionic mobility and/or partitioning into an alternate phase via non-covalent interactions. Additionally, analytes may be concentrated or "focused" by means of gradients in conductivity and pH. [[Wiki]](https://en.wikipedia.org/wiki/Capillary_electrophoresis) Monosaccharides can be separated by CZE, but often need to be derivatized to achieve proper separation. It is sometimes used as an analytical method to quantify sugar monomers. There are also other types of capillary electrophoresis, as can be seen in the picture. **Research findings:** - Neutral and acidic monosaccharides, commonly present as structural units in woodderived hemicelluloses, were derivatized by reductive amination using 6aminoquinoline (6AQ) and subsequently separated as their borate complexes by capillary zone electrophoresis. Art. [#ARTNUM](#article-25983-1969173874) - The separation of derivatized carbohydrates has been performed by coelectroosmotic capillary electrophoresis. Derivatization was performed by reductive amination of the carbohydrates with ethylpaminobenzoate or withpaminobenzonitrile. Separation selectivity is optimized using buffer electrolytes containing high concentrations of borate, organic solvents, and mixtures thereof; this enabled separation of the carbohydrate derivatives then direct UV detection. Codirectional migration of the anionic analytes with the electroosmotic flow was achieved by adding a cationic polyer (hexadimethrine bromide, HDB) to the electrolyte. With this method it is possible to determine specific carbohydrates, such as arabinose, mannose, and glucose, which are difficult to separate by other CE methods. The applicability of the method is demonstrated for the analysis of plant hydrolyzates. Art. [#ARTNUM](#article-25983-2008827897)

6.2.1 6.2 Capilary zone electrophoresis (CZE)
Characterisation of natural polysaccharides (plant gums) used as binding media for artistic and historic works by capillary zone electrophoresis
Abstract The monosaccharide constituents of plant gums were separated by capillary electrophoresis at pH 12.1 and detected with indirect UV absorbance. The plant gums investigated were gum arabic, gum acacia, gum tragacanth, cherry gum and locust bean gum (carob gum). The monosaccharides obtained after hydrolysis with 2 M trifluoroacetic acid and lyophilisation of the hydrolysate were arabinose, galactose, mannose, rhamnose, xylose, fucose, and glucose, and the two sugar acids galacturonic and glucuronic acid, in accordance with the literature. They were separated in a background electrolyte consisting of NaOH to adjust the pH, 20 mM 2,6-pyridinedicarboxylic acid as chromophore for detection and 0.5 mM cetyltrimethylammonium bromide as additive to reverse the electroosmotic flow. Based on their electropherograms, the plant gums could be identified by their typical composition (depicted in a decision scheme) as follows: a peak of glucuronic acid, together with that of rhamnose, is indicative for gum arabic. Peaks of galacturonic acid and fucose point to gum tragacanth. Locust bean gum shows a major peak for mannose (with the concomitant galactose peak in ratio 4–1), whereas a glucuronic acid and a mannose peak together with a prominent arabinose peak indicates cherry gum. The method was applied to identify the plant gums in samples like watercolours and in several paint layers like gum tempera or those with egg white or drying oils as additives. Artificial aging experiments of thin layers of gum arabic on paper or glass carried out with UV-A radiation (366 nm) did not result in changes of the saccharide patterns, in contrast to the simultaneously conducted aging of a drying oil layer.
6/1/05 12:00:00 AM
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6.2.2 6.2 Capilary zone electrophoresis (CZE)
Efficient capillary zone electrophoretic separation of wood-derived neutral and acidic mono- and oligosaccharides
Abstract Neutral and acidic monosaccharides, commonly present as structural units in wood-derived hemicelluloses, were derivatized by reductive amination using 6-aminoquinoline (6-AQ) and subsequently separated as their borate complexes by capillary zone electrophoresis. By using a quite concentrated (420 mmol 1 −1 ) alkaline borate buffer, a fused-silica capillary column with a small inner diameter (30 μm nominal I.D.) and a constant power of 1200 mW (corresponding to an applied voltage of approximately 21 kV), optimal separation was achieved. Under these conditions, the monosaccharides investigated were separated with a resolution, R s , of 1.0–1.2 or greater. On-column UV detection at 245 nm was found to provide highly sensitive detection of the 6-AQ-derivatized monosaccharides. The minimum detectable concentrations were on the order of 10 −6 mol 1 −1 (corresponding to an estimated limit of detection of a few fmol). The linear calibration range of the method, including the 6-AQ derivatization step, was found to be about two orders of magnitude. Several neutral β(1–4)- d -xylooligomers and acidic oligosaccharides containing 4-O-methyl- d -glucuronic acid units, which are common structural elements in hemicelluloses such as birch and spruce xylan, were also efficiently separated as 6-AQ derivatives, using the same buffer system. Finally, the usefulness of this analytical method has been demonstrated using a spruce wood xylan sample subjected to chemical and enzymatic hydrolysis.
6/1/96 12:00:00 AM
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6.2.3 6.2 Capilary zone electrophoresis (CZE)
Separation of derivatized carbohydrates by co-electroosmotic capillary electrophoresis
The separation of derivatized carbohydrates has been performed by co-electroosmotic capillary electrophoresis. Derivatization was performed by reductive amination of the carbohydrates with ethylp-aminobenzoate or withp-aminobenzonitrile. Separation selectivity is optimized using buffer electrolytes containing high concentrations of borate, organic solvents, and mixtures thereof; this enabled separation of the carbohydrate derivatives then direct UV detection. Co-directional migration of the anionic analytes with the electroosmotic flow was achieved by adding a cationic polyer (hexadimethrine bromide, HDB) to the electrolyte. With this method it is possible to determine specific carbohydrates, such as arabinose, mannose, and glucose, which are difficult to separate by other CE methods. The applicability of the method is demonstrated for the analysis of plant hydrolyzates
8/1/97 12:00:00 AM
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6.2.4 6.2 Capilary zone electrophoresis (CZE)
Separation of reducing monosaccharides by capillary zone electrophoresis
The separation of reducing monosaccharides derived from glycosidoproteins and glycolipids by capillary zone electrophoresis (CZE) is dependent on the pH and concentration of the borate buffer. Five saccharides were completely separated in a fused silica capillary tube (50 μm i.d., 65 cm) containing 50 mM borate buffer (pH 10.5) as carrier, with high resolution, at an applied potential of 20 kV after the reducing saccharides were derivatized with 1-naphthylamine. On-column UV (254 nm) monitoring allowed quantitation of these saccharides at least in the concentration range of 10–100 mM in reaction solution. This method was applied to the determination of the monosaccharides composition of various carbohydrate materials to demonstrate its usefulness.
7/1/94 12:00:00 AM
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6.3 Zeolite-based separation

0

Zeolites are microporous, aluminosilicate minerals commonly used as commercial adsorbents and catalysts. [[Wiki]](https://en.wikipedia.org/wiki/Zeolite) Zeolites can be employed in (parts of) the separation of sugar monomers. **Patent findings:** - the solution comprises one or more salts and/or mineral acids, b) the solution is contacted with a zeolite adsorbent for adsorbing the monosaccharide on the zeolite, c) the zeolite with the adsorbed monosaccharide is separated from the solution, d) the monosaccharide is separated from the zeolite absorbent. The separation process steps b) - d) are for example conveniently carried out in a chromatography type of process wherein the zeolite adsorbent is the stationary phase and water is used as eluent. Pat. [#ARTNUM](#article-25971-2816226352) - Arabinose can be separated from an aqueous feed mixtrue of monosaccharides containing arabinose along with other aldopentoses and aldohexoses by a liquid phase adsorptive process in which the feed is contacted with a calciumY or calcium X type zeolite. Arabinose is selectively adsorbed to the substantial exclusion of other aldoses and thereafter is recovered in high purity by desorption with water or ethanol. The process can be carried out on a commercial scale by means of a simulated moving bed flow scheme. Pat. [#ARTNUM](#article-25971-2244478410)

6.3.1 6.3 Zeolite-based separation
PROCESS FOR THE ISOLATION OF MONOSACCHARIDES
A process for the separation of a monosaccharide from an aqueous solution comprising the monosaccharide, in particular a hydrolysate of a polysaccharide containing biomass, characterized in that a) the solution comprises one or more salts or mineral acids, b) the solution is contacted with a zeolite adsorbent preferably of BEA zeotype for adsorbing the monosaccharide on the zeolite, c) the zeolite with the adsorbed monosaccharide is separated from the solution, d) the monosaccharide is separated from the zeolite absorbent. The process in a chromatographic process, in particular SMB, produces relatively highly concentrated and pure monosaccharide solution in water.
6/16/16 12:00:00 AM
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6.3.2 6.3 Zeolite-based separation
Process for separating arabinose.
Arabinose can be separated from an aqueous feed mixtrue of monosaccharides containing arabinose along with other aldopentoses and aldohexoses by a liquid phase adsorptive process in which the feed is contacted with a calcium-Y or calcium X type zeolite. Arabinose is selectively adsorbed to the substantial exclusion of other aldoses and thereafter is recovered in high purity by desorption with water or ethanol. The process can be carried out on a commercial scale by means of a simulated moving bed flow scheme.
11/17/88 12:00:00 AM
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6.4 Pretreatments that enhance separation

0

Several types of pretreatments were found that enhance the recovery of monomeric sugars; since the focus was on the separation itself this is out of scope. However due to the volume of techniques found, it is worth mentioning. **Research findings:** - In this work nanofiltration technology has been employed for removal of inhibitors and recovery of monosaccharides from dilute acid lignocellulose hydrolysates. The influences of feed solution pH, permeate flux, and Na2SO4 concentration on the rejection of monosaccharides and inhibitors were investigated. This process allowed the removal of 90% inhibitors, while 93.55% glucose, 90.75% xylose, and 90.53% arabinose were recovered. Finally, a batch column equipped with a strong acid cation exchange resin was employed to recover the monosaccharides from the hydrolysate. Using water as an eluent, 95.37% of the sulfuric acid and 94.87% of the monosaccharides were recovered. In all, we demonstrated that the combination of nanofiltration with electrolyte exclusion chromatography is a promising integrated process for the recovery of monosaccharides and inorganic acids from dilute acid corncob hydrolysates. Art. [#ARTNUM](#article-29968-2796257764) - Ultrafiltration is carried out with an organic membrane in a first time to remove precipitating macromolecules. Afterwards conventional electrodialysis allows the sulfuric acid recovery from hydrolysate in order to recycle it for the hydrolysis step. ED is a key step as it allows a double chemical saving: less fresh sulfuric acid is needed for hydrolysis and no alkaline chemicals are consumed to neutralize acid and precipitate macromolecules. Thus the salts content is considerably decreased, facilitating the further demineralization by ion-exchange and also resulting in the reduction of chemicals consumption. After activated carbon treatment, the product contains only sugars (glucose, xylose and arabinose). They can be separated from each other by continuous chromatography or crystallization. Pat. [#ARTNUM](#article-29968-2535941283) - In shortterm filtrations, the nanofiltered permeate of the original hydrolyzate had 78–82% xylose of the TDS p (total dry solids in permeate) and the modified hydrolyzate 86–88% xylose of the TDS p . Thus, considerable xylose purification was obtained. The addition of crystalline xylose into the hemicellulose hydrolyzate gave a notable increase in permeate fluxes. The 20h filtration showed fouling and compaction effects as a flux decrease of approximately 10–25% was detected in the retention integrity test. According to the results, xylose purification from hemicellulose hydrolyzate could be enhanced by nanofiltration. Art.[#ARTNUM](#article-29968-1984209600) - Optimizing of the thermal treatment was investigated. A treatment at 170 °C for 2 h was found optimal, with higher solubilzation of hemicellulose than that at 150 °C and lower degradation of sugar monomers than 190 °C. Recovery of xylose was high and the purity of xylose solution (78%) allows expecting an easy purification and separation of xylose before hydrogenation. Analysis of thermal hydrolyzates shows the presence of xylan oligomers and polymers with large distribution of DPs. This fraction should be submitted to enzymatic treatment to recover more xylose monomer. Art. [#ARTNUM](#article-29968-2003335961)

6.4.1 6.4 Pretreatments that enhance separation
Optimization of sugarcane bagasse conversion by hydrothermal treatment for the recovery of xylose
Abstract This work aims at the valorization of sugarcane bagasse by extracting xylose which is destined to the production of xylitol after purification and hydrogenation. Our approach consists in applying the principle of biorefinery to sugarcane bagasse because of its hemicellulose composition (particularly rich in xylan: (92%)). Optimizing of the thermal treatment was investigated. A treatment at 170 °C for 2 h was found optimal, with higher solubilzation of hemicellulose than that at 150 °C and lower degradation of sugar monomers than 190 °C. Recovery of xylose was high and the purity of xylose solution (78%) allows expecting an easy purification and separation of xylose before hydrogenation. Analysis of thermal hydrolyzates shows the presence of xylan oligomers and polymers with large distribution of DPs. This fraction should be submitted to enzymatic treatment to recover more xylose monomer.
12/1/09 12:00:00 AM
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6.4.2 6.4 Pretreatments that enhance separation
Purification of pentoses from hemicellulosic hydrolysates without neutralization for sulfuric acid recovery
Abstract The agro-industrial sector generates large amounts of coproducts such as lignocellulosic biomass which could be valorized into many chemicals and bio-based intermediates (sugars, paper pulp, surfactants, polymers or bioethanol). However, in the case of biomass hydrolysis by diluted sulfuric acid, current downstream processes involve a partial or complete neutralization which are not satisfactory for economic and environmental reasons. This work presents a purification process of pentoses from hemicellulosic hydrolysates without neutralization for sulfuric acid recovery. Compared to conventional processes, less energy, water and chemicals are required. Very promising results were obtained at pilot scale with 100 L of wheat bran hydrolysates. The process is based on the combination of ultrafiltration, conventional electrodialysis and ion-exchange. Ultrafiltration with a 10 kDa organic membrane totally removed harmful macromolecules which precipitate during electrodialysis operation because of pH rise. Till a volumetric concentration factor 3.6, the average flux kept good for industrial application (27 L·h −1 ·m −2 ). However suspended materials have to be filtered before ultrafiltration. Besides, a 2.5 diafiltration is required to recover most of sugars (99%). Then conventional electrodialysis was performed to recover most of sulfuric acid (80%). The average faradic yield was quite good (80%) and the specific energy consumption of the electrodialysis stack was quite interesting (1.1 kW h per kg of H 2 SO 4 recovered and 8.4 kW h per m 3 of hydrolysate). Finally, the complete demineralization (conductivity  −1 ) and discoloration (420 nm absorbance
3/1/17 12:00:00 AM
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6.4.3 6.4 Pretreatments that enhance separation
Recovery of monosaccharides from dilute acid corncob hydrolysate by nanofiltration: modeling and optimization
In this work nanofiltration technology has been employed for removal of inhibitors and recovery of monosaccharides from dilute acid lignocellulose hydrolysates. The influences of feed solution pH, permeate flux, and Na2SO4 concentration on the rejection of monosaccharides and inhibitors were investigated. The results showed that the pH for the separation of carboxylic acids and furans from monosaccharides should be as low as possible. With increase of Na2SO4 concentration carboxylic acid and furan rejection decreased. Subsequently, the Donnan steric pore and dielectric exclusion model coupled with mass balance was used to predict the rejection of solutes at different permeate fluxes. In order to select a suitable permeate flux and operating time, multi-objective optimization was carried out to obtain the maximum total inhibitor removal efficiency, the maximum monosaccharide recovery rate, and the minimum water consumption. The optimal operating conditions were then verified using the real hydrolysate as feed solutions. More specifically, for the treatment of 6 L of a hydrolysate solution, 13 L of water and a treatment time of 35 min were required. This process allowed the removal of 90% inhibitors, while 93.55% glucose, 90.75% xylose, and 90.53% arabinose were recovered. Finally, a batch column equipped with a strong acid cation exchange resin was employed to recover the monosaccharides from the hydrolysate. Using water as an eluent, 95.37% of the sulfuric acid and 94.87% of the monosaccharides were recovered. In all, we demonstrated that the combination of nanofiltration with electrolyte exclusion chromatography is a promising integrated process for the recovery of monosaccharides and inorganic acids from dilute acid corncob hydrolysates.
1/1/18 12:00:00 AM
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6.4.4 6.4 Pretreatments that enhance separation
Xylose recovery by nanofiltration from different hemicellulose hydrolyzate feeds
Abstract Xylose is an intermediate product in xylitol production. Nanofiltration could simplify and enhance this separation step conventionally done by chromatographic methods. Here different hemicellulose hydrolyzate feeds were nanofiltered to recover xylose into the permeate. Two different batches of hemicellulose hydrolyzate were prepared: the hydrolyzate as such and modified with crystalline xylose addition. Both feed solutions were diluted to a total dry solids (TDS) content of approximately 21 wt.% and the xylose contents were 48.7% and 59.1% of the TDS f (total dry solids in feed). The filtration experiments were made at 40, 50 and 60 °C in total reflux mode for approximately 30 min at each pressure of 20, 25, 30, 35 and 40 bar. In addition, a 20-h filtration was made at 50 °C and 30 bar. A DDS LabStak M20-filter was used and it was equipped with Desal-5 DK, Desal-5 DL and NF270 membranes. In short-term filtrations, the nanofiltered permeate of the original hydrolyzate had 78–82% xylose of the TDS p (total dry solids in permeate) and the modified hydrolyzate 86–88% xylose of the TDS p . Thus, considerable xylose purification was obtained. The addition of crystalline xylose into the hemicellulose hydrolyzate gave a notable increase in permeate fluxes. The 20-h filtration showed fouling and compaction effects as a flux decrease of approximately 10–25% was detected in the retention integrity test. According to the results, xylose purification from hemicellulose hydrolyzate could be enhanced by nanofiltration.
3/5/08 12:00:00 AM
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Final Results

Published 9/30/19

After the midway results meeting, 11 separation technologies have been reviewed and deepened. The results are organised based on the concept and presented per separation technologies comprising a description, findings, suppliers (if applicable), images, videos, useful links and a reference list. The technology requirements are measured and shown in the [requirements table](#requirements-table). By using the concept links below, you can quickly navigate to the concepts and their separation technologies descriptions.

Table of concepts:

  1. 1. Extraction
  2. 2. Chromatography
  3. 3. Filtration
  4. 4. Integrated Approaches
  5. 5. Other techniques

Technology Radar
Requirements Table

1. Extraction

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Extraction in chemistry is a separation process consisting in the separation of a substance from a matrix. It includes Liquid-liquid extraction, and Solid phase extraction. The distribution of a solute between two phases is an equilibrium condition described by partition theory.


1.1 Ionic liquid extraction

1

An ionic liquid (IL) is a salt in the liquid state. In some contexts, the term has been restricted to salts whose melting point is below some arbitrary temperature, such as 100 °C (212 °F). While ordinary liquids such as water and gasoline are predominantly made of electrically neutral molecules, ionic liquids are largely made of ions and short-lived ion pairs. [\[Wiki\]](https://en.wikipedia.org/wiki/Ionic_liquid). Ionic Liquid can be used in an aqueous extraction or a solid phase extraction to separate sugars (e.g. glucose/xylose). IL-based treatments specifically aimed at separating sugars have only been performed at small scales, whereas IL-based pretreatments have been performed in pilot scales. [\[More information\]](https://biotechnologyforbiofuels.biomedcentral.com/articles/10.1186/s13068-016-0694-8) **IL-based aqueous two-phase extraction:** Small scale experiments (10-100 mL) were done on crystalline cellulose and switchgrass, using two steps: acidolysis using IL and aqueous extraction using salts; **centrifugation** was applied to aid phase separation. * The glucose extraction efficiencies of K3PO4 and NaOH solutions were over 90%. It is notable that the glucose concentration in the bottom salt-rich phase was over 16 g/L, which could be used for ethanol fermentation. Art. [#ARTNUM](#article-25970-2578172333) * Maximum yields of 54% glucose and 88% xylose can be recovered in the alkaline phase with pretreatment condition of 160°C for 1.5 h and 105°C for 6 h respectively followed by acidolysis. Improved sugar yields could be achieved by further optimizing the amount of acid and water used in the acidolysis step and the alkali salts used for sugar extraction. **See figure** [\[More info\]](https://biotechnologyforbiofuels.biomedcentral.com/articles/10.1186/1754-6834-6-39) **IL-based solid-phase extraction:** Solid-phase extraction (SPE) is a sample preparation process by which compounds that are dissolved or suspended in a liquid mixture are separated from other compounds in the mixture according to their physical and chemical properties. SPE uses the affinity of solutes dissolved or suspended in a liquid (known as the mobile phase) for a solid through which the sample is passed (known as the stationary phase) to separate a mixture into desired and undesired components. [Wiki](https://en.wikipedia.org/wiki/Solid_phase_extraction) SPE has been performed using ILs grafted to silica or polymers in columns, these columns have been applied in sugar separations and quatifications in small scale experiments, with hydrolysates. Art. [#ARTNUM](#article-25970-1990198170); Art. [#ARTNUM](#article-25970-2129919788)

1.1.1 Ionic liquid extraction
One-pot ionic liquid pretreatment and saccharification of switchgrass
Biomass pretreatment using certain ionic liquids (ILs), such as 1-ethyl-3-methylimidazolium acetate ([C2mim][OAc]), can be highly effective at reducing the recalcitrance of lignocellulosic biomass to enzymatic degradation. However, current commercial enzyme cocktails, derived from filamentous fungi and developed for dilute acid pretreatment, are inhibited by the most effective ILs used for pretreatment and require excessive amounts of water to remove the ILs from biomass after pretreatment in order to be effective. The associated IL recycling and waste disposal costs of this process pose significant economic and process engineering challenges for the commercial scale-up of IL pretreatment-based technologies. For the first time, we have demonstrated a one-pot, wash-free process that combines IL pretreatment and saccharification into a single vessel. After treating the switchgrass with [C2mim][OAc] and dilution with water to a final IL concentration of 10–20%, the pretreatment slurry was directly hydrolyzed using a thermostable IL tolerant enzyme cocktail previously developed at the Joint BioEnergy Institute (JBEI). This one-pot process liberated 81.2% glucose and 87.4% xylose (monomers and oligomers) at 72 h at 70 °C with an enzyme loading of 5.75 mg g−1 of biomass at 10% [C2mim][OAc]. Glucose and xylose were selectively separated by liquid–liquid extraction with over 90% efficiency, thus eliminating extensive water washing as a unit operation. This study opens avenues for developing more efficient and cost effective processes for product recovery and IL recycling.
1/1/13 12:00:00 AM
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1.1.2 Ionic liquid extraction
Saccharification of cellulose in the ionic liquids and glucose recovery
High-efficiency hydrolysis of lignocellulose is critical for the production of second-generation bioethanol. In the present work, the acid hydrolysis of cellulose in ionic liquids (ILs) 1-butyl-3-methylimidazolium chloride ([Bmim]Cl), 1-allyl-3-methylimidazolium chloride ([Amim]Cl), and 1-ethyl-3-methylimidazolium chloride ([Emim]Cl), respectively, was investigated and aqueous two-phase systems were constructed by adding salt solutions to ILs to recover glucose from cellulose hydrolyzates in the ILs. The effects of reaction temperature, reaction time and acid consumption on the cellulose hydrolysis efficiencies in the ILs were determined. The optimal cellulose hydrolysis conditions in ILs were found to be [Bmim]Cl, a reaction time of 0.5 h, an acid consumption of 0.25 mL/g (cellulose) and a reaction temperature of 100 °C. The yield of glucose under the optimal hydrolysis conditions reached 92.88%. IL-based aqueous two-phase systems were formed by adding NaOH, K3PO4, or K2HPO4 into the ILs containing glucose or cellulose hydrolyzates, which were able to partition the glucose into the bottom salt-rich phase. Under the optimum condition, 4 vol 50% NaOH or K3PO4 solution was able to partition 90% glucose, resulting in 16 g/L glucose in the salt-rich phase that could be further used for ethanol fermentation.
6/1/17 12:00:00 AM
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1.1.3 Ionic liquid extraction
Separation of monosaccharides by solid‐phase extraction with ionic liquid‐modified microporous polymers
Ionic liquid-modified porous polymers with large surface area and large amount of functional groups were developed and used in SPE to separate four monosaccharides. Adsorption isotherm showed that the sorbent with amino ionic liquid groups had the highest interaction with the target compounds. The mobile phase of acetonitrile/water 85:15 and 73:30 v/v can successfully separate the monosaccharides. The sorbent produced reproducible results and performed stably, demonstrating its potential applicability in the separation of extract from natural plant.
11/1/11 12:00:00 AM
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1.1.4 Ionic liquid extraction
Separation of xylose and glucose on different silica-confined ionic liquid stationary phases.
Xylose and glucose, as the main hydrolyzed products of plant cell wall, were separated by silica-confined ionic liquid (IL) stationary phases. Five different stationary phases were synthesized and characterized. Instead of using the traditional NH2 column, the imidazolium stationary phases exhibit excellent retention to the xylose and glucose. The retention factor and resolution of the monosaccharides decreased with decreasing acetonitrile concentration. In addition, the effects of the IL cations and anions on the retention of xylose and glucose were studied and the adsorption behavior of these two monosaccharides on the stationary phases was investigated. Then the mobile phase and temperature were optimized to improve the performance for the separation of xylose and glucose.
9/1/10 12:00:00 AM
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1.1.5 Ionic liquid extraction
Simple purification of ionic liquid solvents by nanofiltration in biorefining of lignocellulosic substrates
Abstract Ionic liquids are excellent but expensive solvents to dissolve lignocellulose for biofuel production. Since it is presumed that ionic liquids cannot be cost-effectively purified in large-scale processes, they are simply avoided as solvents. Thus, this study aims to investigate the feasibility of ionic liquid purification via nanofiltration membranes with regards to permeate flux and rejection performance. Two commercially available polyamide and one polyimide membranes were used to separate saccharide products from various feed concentrations of the ionic liquid 1,3-dimethylimidazolium dimethylphosphate. At high concentrations of ionic liquid, there was a marked decrease in permeate flux for all tested membranes due to low permeability of the ionic liquid and due to osmotic pressure differences. At low feed concentrations of this ionic liquid, the concentration of products in the permeate was significantly lower using the polyamide membranes than with the polyimide membranes. Conversely, at high feed ionic liquid concentrations, the contaminant concentrations significantly decreased using the polyimide membrane. In conclusion it is feasible to recover ionic liquid solvent up to a purity of 80% by using both polyamide and polyimide membranes. Since they are non-volatile and environmentally friendly in general, ionic liquids are very suitable candidates to replace conventional organic solvents in lignocellulose refining.
7/1/12 12:00:00 AM
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1.1.6 Ionic liquid extraction
Recovery of sugars from ionic liquid biomass liquor by solvent extraction

1. A composition comprising a solution comprising (a) an ionic liquid (IL) or ionic liquid-aqueous (ILA) phase, wherein the IL or ILA phase comprises a cellulase, and (b) an organic phase, wherein the solution comprises a sugar and a boronic acid. 2. The composition of claim 1, wherein the organic phase comprises a sugar- boronic acid complex. 3. The composition of claim 1, wherein the sugar is a 6-carbon monosaccharide, 5-carbon monosaccharide, or a cellobiose. 4. The composition of claim 1, wherein the IL or ILA phase has a pH of more than about 9. 5. The composition of claim 4, wherein the IL or ILA phase has a pH equal to or greater than 10, 11, or 12. 6. The composition of claim 1, wherein the organic phase comprises an organic molecule that is immiscible with the IL and ILA solutions, and the organic molecule does not react with the boronic acid and the sugar. 7. The composition of claim 1, wherein the IL or ILA phase comprises 1-alkyl-3-alkylimidazolium alkanate, 1-alkyl-3-alkylimidazolium alkylsulfate, 1-alkyl-3-alkylimidazolium methylsulfonate, 1-alkyl-3-alkylimidazolium hydrogensulfate, 1-alkyl-3-alkylimidazolium thiocyanate, or 1-alkyl-3-alkylimidazolium halide, or a mixture thereof, wherein an "alkyl" is an alkyl group comprising from 1 to 10 carbon atoms, and an "alkanate" is an alkanate comprising from 1 to 10 carbon atoms. 8. The composition of claim 1, wherein the IL or ILA phase comprises 1-ethyl-3-methylimidazolium acetate (EMIN Acetate), 1-ethyl-3-methylimidazolium chloride (EMIN Cl), 1-ethyl-3-methylimidazolium hydrogensulfate (EMIM HOSO3), 1-ethyl-3-methylimidazolium methylsulfate (EMIM MeOSO3), 1-ethyl-3-methylimidazolium ethylsulfate (EMIM EtOSO3), 1-ethyl-3-methylimidazolium methanesulfonate (EMIM MeSO3), 1-ethyl-3-methylimidazolium tetrachloroaluminate (EMIM AlCl4), 1-ethyl-3-methylimidazolium thiocyanate (EMIM SCN), 1-butyl-3-methylimidazolium acetate (BMIM Acetate), 1-butyl-3-methylimidazolium chloride (BMIM Cl), 1-butyl-3-methylimidazolium hydrogensulfate (BMIM HOSO3), 1-butyl-3-methylimidazolium methanesulfonate (BMIM MeSO3), 1-butyl-3-methylimidazolium methylsulfate (BMIM MeOSO3), 1-butyl-3-methylimidazolium tetrachloroaluminate (BMIM AlCl4), 1-butyl-3-methylimidazolium thiocyanate (BMIM SCN), 1-ethyl-2,3-dimethylimidazolium ethylsulfate (EDIM EtOSO3), Tris(2-hydroxyethyl)methylammonium methylsulfate (MTEOA MeOSO3), 1-methylimidazolium chloride (MIM Cl), 1-methylimidazolium hydrogensulfate (MIM HOSO3), 1,2,4-trimethylpyrazolium methylsulfate, tributylmethylammonium methylsulfate, choline acetate, or choline salicylate, or a mixture thereof. 9. The composition of claim 1, wherein the IL is of a concentration of more than 0% to less than 60% of the composition or solution. 10. The composition of claim 1, wherein the boronic acid has the formula: R-α-B(OH)2 (I); wherein α is a bond or an alkyl or alkenyl chain of 1-10 carbons, R comprises at least 1 aromatic ring. 11. The composition of claim 10, wherein R comprises 1, 2, or 3 aromatic rings. 12. The composition of claim 10, wherein R is a benzene. 13. The composition of claim 12, wherein the benzene comprises 1 or 2 methyl groups. 14. The composition of claim 11, wherein R is a naphthalene. 15. The composition of claim 10, wherein at least one aromatic ring is substituted by one or more alkyl groups comprising 1-10 carbons. 16. The composition of claim 10, wherein α is a bond or an alkyl or alkenyl chain of 1-4 carbons. 17. The composition of claim 16, wherein α is a bond or an alkyl or alkenyl chain of 1-2 carbons. 18. The composition of claim 17, wherein α is a --C═C--. 19. The composition of claim 1, wherein the boronic acid is phenylboronic acid, 3,5-dimethylphenylboronic acid, 4-tert-butylphenylboronic acid, trans-β- styreneboronic acid, or naphthalene-2-boronic acid, or a mixture thereof. 20. A method of removing a sugar from a solution, comprising: (a) providing a solution comprising (i) an ionic liquid (IL) or ionic liquid-aqueous (ILA) phase and (ii) an organic phase, wherein the solution comprises an ionic liquid, a sugar and a boronic acid, wherein the providing step (a) comprises: (i) introducing a cellulase to the IL or ILA phase comprising a cellulose, such that the cellulase hydrolyzes the cellulose to produce the sugar, and (ii) mixing the IL or ILA phase and the organic phase comprising the boronic acid to produce the solution; (b) contacting the sugar with the boronic acid to form a sugar-boronic acid complex, and (c) separating the organic phase and the aqueous phase, wherein the organic phase contains the sugar-boronic acid complex. 21. The method of claim 20 further comprising: (d) separating the sugar from the organic phase. 22. The method of claim 21, wherein the (d) separating step comprises adding a second IL, ILA, or aqueous solution comprising a stripping agent to the organic solution, such that the sugar-boronic acid complex dissociates and the sugar moves into the second IL, ILA, or aqueous solution. 23. The method of claim 22, wherein the stripping agent is an acid which decreases the pH of the organic phase. 24. The method of claim 20, wherein the (a) providing step comprises contacting (i) an IL or ILA solution and an organic solution. 25. The method of claim 20, wherein the IL or ILA solution comprises an ionic liquid (IL) and the sugar. 26. The method of claim 20, wherein the organic solution comprises the boronic acid. 27. The method of claim 26, wherein the organic solution further comprises an organic solvent which ensures the boronic acid is fully dissolved in the organic phase. 28. The method of claim 27, wherein the organic solvent is n-hexane or 1-octanol, or a mixture thereof. 29. The method of claim 20, wherein the (b) contacting step comprises having the sugar and the boronic acid in the solution to essentially come to equilibrium. 30. The method of claim 29, wherein the (b) contacting step comprises increasing the contact between the sugar in the IL or ILA phase and the boronic acid in the organic phase. 31. The method of claim 21, wherein the (d) separating step further comprises separating the second IL, ILA, or aqueous solution from the organic phase. 32. The method of claim 21 further comprising: (e) culturing a cell using the sugar obtained from the (d) separating step. 33. The method of claim 20, wherein the IL or ILA phase comprises a biomass comprising the sugar. 34. The method of claim 33, wherein the biomass is a cellulose biomass, hemicellulose biomass, ligno-cellulose biomass, or a mixture thereof. 35. The composition of claim 1, wherein the sugar is cellobiose. 36. The method of claim 20, wherein the sugar is cellobiose.
3/29/12 12:00:00 AM
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1.2 Deep eutectic solvents

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Deep eutectic solvents (DES) are systems formed from a eutectic mixture of Lewis or Brønsted acids and bases which can contain a variety of anionic and/or cationic species. They are classified as types of ionic solvents with special properties. They incorporate one or more compound in a mixture form, to give a eutectic with a melting point much lower than either of the individual components. [\[Wiki\]](https://en.wikipedia.org/wiki/Deep_eutectic_solvent) DES have been used together with inorganic salts to recover xylose or glucose. This process usually consists of two steps: DES pre-treatment and salt and enzyme hydrolysis and extraction. DES that have been used for sugar extractions: ChCl:Urea, Foraceline **Research findings:** * The synergistic effects of DES and inorganic salt were investigated for recovering xylose from OPF. The combination of ChCl:urea (120 °C, 4 h) and CuCl2 (120 °C, 30 min) produced significantly higher xylose yields (14.76 g/L) than CuCl2-alone pretreatment (11.87 g/L), this is a recovery of 74%. Glucose and arabinose were also liberated at concentrations of 0.26 (less than 1% recovery) and 0.8 g/L, respectively. Art. [#ARTNUM](#article-25710-2741963893) * Glucose was recovered at a concentration of 37.3 g/L (total sugar conc. 422.76 g/L) by a two-step process consisting of a two-stage pretreatment with Foraceline (choline chloride, formic acid and acetic acid) and Na2CO3 and subsequent hydrolysis with (solid bound) enzymes (celluloses). Art. [#ARTNUM](#article-25710-2760285358)

1.2.1 Deep eutectic solvents
Deep eutectic solvent and inorganic salt pretreatment of lignocellulosic biomass for improving xylose recovery
Abstract Deep eutectic solvents (DESs) have received considerable attention in recent years due to their low cost, low toxicity, and biodegradable properties. In this study, a sequential pretreatment comprising of a DES (choline chloride:urea in a ratio of 1:2) and divalent inorganic salt (CuCl 2 ) was evaluated, with the aim of recovering xylose from oil palm fronds (OPF). At a solid-to-liquid ratio of 1:10 (w/v), DES alone was ineffective in promoting xylose extraction from OPF. However, a combination of DES (120 °C, 4 h) and 0.4 mol/L of CuCl 2 (120 °C, 30 min) resulted in a pretreatment hydrolysate containing 14.76 g/L of xylose, remarkably yielding 25% more xylose than the CuCl 2 -only pretreatment (11.87 g/L). Characterization studies such as FE-SEM, BET, XRD, and FTIR confirmed the delignification of OPF when DES was implemented. Thus, the use of this integrated pretreatment system enabled xylose recoveries which were comparable with other traditional pretreatments.
2/1/18 12:00:00 AM
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1.2.2 Deep eutectic solvents
High-Solid Lignocellulose Processing Enabled by Natural Deep Eutectic Solvent for Lignin Extraction and Industrially Relevant Production of Renewable Chemicals
This study investigated high-solid loading deep eutectic solvent (DES) pretreatment for lignocellulose fractionation and subsequent conversion into platform chemicals (i.e., furfural, 2,3-butanediol). Switchgrass was pretreated with choline chloride:ethylene glycol (ChCl:EG) under acidic condition at high solid loadings of 20% and 27%. Cellulose was enriched to as high as 72.6% in pretreated switchgrass due to substantial removal of lignin and xylan but minor cellulose loss. Highly concentrated sugar hydrolysate containing up to 241.2 g/L fermentable sugars (206.5 g/L glucose and 34.7 g/L xylose) with 86.2% glucose yield was obtained from pretreated switchgrass via 25% solid loading enzymatic hydrolysis for only 48 h. The high sugar concentration allowed the production of 90.2 g/L 2,3-butanediol upon fermentation, a record high titer produced from lignocellulose hydrolysate without additional sugar concentration. ChCl:EG showed good recyclability, and its reuse facilitated lignin recovery from pretreatmen...
9/4/18 12:00:00 AM
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1.2.3 Deep eutectic solvents
Novel dihydrogen-bonding deep eutectic solvents: Pretreatment of rice straw for butanol fermentation featuring enzyme recycling and high solvent yield
Abstract Rice straw (RS) is one of the most abundant lignocellulosic biomasses in China, which contains mainly of cellulose, hemicellulose and lignin. In this study, a novel deep eutectic solvent (DES), foraceline, was prepared with choline chloride and double hydrogen bond donors (formic acid and acetic acid). By combining foraceline and sodium carbonate (1%), a two-stage pretreatment method was developed and applied in RS pretreatment to improve the biodegradability of lignocellulose. The highest glucose and total sugar of 37.3 g·L −1 and 42.8 g·L −1 were obtained after hydrolysis of 24 h using 50 FPU· g total solid - 1 of cellulase. The cellulase attached to RS was reutilized for five continuous cycles in which enzyme loading was reduced from 50 FPU· g total solid - 1 (Cycle I) to 30 FPU· g total solid - 1 (Cycle V), resulting in total sugar of 41.3–42.6 g·L −1 for each cycle. RS hydrolysates (Cycle I and V) was utilized in butanol fermentation by Clostridium saccharobutylicum DSM 13864, achieving butanol titer and yield of 9.5 g·L −1 and 0.25 g· g total sugar - 1 , similar to those of glucose medium. This study demonstrated the feasibility of this newly developed biomass pretreatment by dihydrogen bonding DES featuring cellulase recycling and high butanol yield.
2/1/18 12:00:00 AM
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1.2.4 Deep eutectic solvents
Recovery of metabolites from natural deep eutectic solvent matrices by countercurrent separation
NAtural Deep Eutectic Solvents (NADES) were discovered in 2011 as being mixtures of polar “primary metabolites” that exhibit unexpected solubilizing and stabilizing abilities for hydrophobic and/or bioactive ingredients. However, due to the inherent low vapor pressure of NADES, it is challenging to recover analytes such as “secondary” metabolites from a NADES-analyte(s) matrix by conventional liquid chromatography. The present study shows that countercurrent separation (CCS) can perform this task successfully. The resolution capability of CCS depends on the differential distribution coefficients (K values) of the analytes. Compared to most bioactive constituents, the NADES components have extreme K values (close to 0 or ∞, in RP or NP, resp.) because of their high polarity. Glucose-choline chloride-water (2:5:5, mole/mole) with rutin, quercetin, kaempferol, or daidzein were chosen as the test matrices. The CCS fraction analysis by UV-UHPLC and qHNMR showed that CCS can recover the target analyte completely from the NADES-analyte matrix, and at the same time yield the NADES quantitatively, allowing further study of “primary” NADES vs. bioactive “secondary” metabolites in botanical extracts. *represents equal contribution to this work
6/25/15 12:00:00 AM
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1.2.5 Deep eutectic solvents
Rice straw pretreatment using deep eutectic solvents with different constituents molar ratios: Biomass fractionation, polysaccharides enzymatic digestion and solvent reuse
Lignocellulosic biomass pretreatment with deep eutectic solvents (DESs) is a promising and challenging process for production of biofuels and valuable platform chemicals. In this work, rice straw was mainly fractionated into carbohydrate-rich materials (CRMs) and lignin-rich materials (LRMs) by 90% lactic acid/choline chloride (LC)-water solution with different molar ratio of hydrogen bond donor (HBD, lactic acid) and hydrogen bond acceptor (HBA, choline chloride). It was found that high HBD/HBA molar ratio of DESs was favorable for achieving CRMs and LRMs with high purity, and both HBD and HBA were responsible for effective biomass fractionation possibly due to their synergistic effect on highly efficient breakage of the linkage between hemicellulose and lignin and thus lignin extraction. About 30%–35% of lignin in native rice straw was fractionated as LRMs, and exceeding 70% of xylan were removed and fractionated into the liquid stream as forms of xylose, furfural and humins after pretreatment using aqueous LC (3:1, 5:1) solution. Consequently, polysaccharides enzymatic hydrolysis of the CRMs were significantly enhanced. Moreover, all the DESs could be recovered with high yields of around 90%, and 69% of the LC (3:1) was recovered after 5 cycles reuse at 90 °C. Besides, the recycled DES maintained a good pretreatment ability, and glucose yields of 60–70% were achieved in the enzymatic hydrolysis of CRMs obtained in each cycle. The facile process established in present work is promising for large scale production of fermentable sugars and other chemicals.
9/1/18 12:00:00 AM
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1.2.6 Deep eutectic solvents
Sequential ultrasonication and deep eutectic solvent pretreatment to remove lignin and recover xylose from oil palm fronds
Abstract This study demonstrated the effect of two-pot sequential pretreatment, comprising of ultrasound assisted deep eutectic solvent (DES) with the aim to investigate the effects of ultrasound amplitude and duration in enhancing delignification. Oil palm fronds (OPF) were ultrasonicated in a water medium, followed by a pretreatment using DES (choline chloride:urea). Fourier transform infra-red spectroscopy, X-ray diffraction, field emission scanning electron microscope, Brunauer-Emmet-Teller and solubilised lignin concentration were conducted to confirm the effectiveness of ultrasound assisted DES on the pretreatment of OPF. The recommended ultrasound conditions were determined to be 70% amplitude and duration of 30 min, where the sequential DES pretreatment was able to reduce lignin content of OPF to 14.01%, while improving xylose recovery by 58%.
5/1/19 12:00:00 AM
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2. Chromatography

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Chromatography is a laboratory technique for the separation of a mixture. The mixture is dissolved in a fluid called the mobile phase, which carries it through a structure holding another material called the stationary phase. The various constituents of the mixture travel at different speeds, causing them to separate.


2.1 Simulated Moving Bed Chromatography

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In manufacturing, the simulated moving bed (SMB) process is a highly engineered process for implementing chromatographic separation. It is used to separate one chemical compound or one class of chemical compounds from one or more other chemical compounds to provide significant quantities of the purified or enriched material at a lower cost than could be obtained using simple (batch) chromatography. [\[Wiki\]](https://en.wikipedia.org/wiki/Simulated_moving_bed). This is a very relevant chromatographic technique for the separation of hemicellulosic sugars on a larger scale. It is often used in combination with other techniques, such as crystallization in integrated approaches. An ion-exchange type of resin is usually employed. **How it works:** In SMB chromatography, the continuous movement of the solid phase is simulated by periodically shifting the inlet and outlet ports in the direction of the liquid flow. This results in a countercurrent movement of the solid and liquid phases. If the time between the port switching and the column lengths are infinitely short, SMB and TMB (True moving bed) processes are equal. The principle of a conventional SMB system which can be used to separate binary mixtures into two fractions is shown in Fig. 1. This system consists of four zones which all have different functions. The basic four-zone SMB system has two inlet streams (feed and eluent) and two outlet streams (extract and raffinate). The eluent and the feed solution are continuously fed to the first column of zones I and III, respectively. The less retained component is continuously taken out from the system as raffinate stream at the outlet of the last column of zone III. Similarly, the more retained component is taken out from the system as extract stream at the outlet of the last column of zone I. When the ports in an SMB system are shifted toward the liquid flow, the solid phase moves to the opposite direction. This means that the first column of zone III becomes the last column of zone II and the first column of zone II becomes the last column of zone I, etc. The separation of components of a binary mixture is achieved by adjusting the flow rates and the port switching time so that the more retained component moves with the solid phase toward the extract outlet and the less retained component with the liquid phase toward the raffinate outlet. Art. [#ARTNUM](#article-25375-48874317) The most basic configuration of SMB chromatography contains four zones and is used in binary separations. To separate more components several modifications exist with more zones, cascaded units, extra pump systems, intermittent and sequential SMB. The complexity increases with the number of components that need to be separated. Art. [#ARTNUM](#article-25375-48874317); [#ARTNUM](#article-25375-2901405806) SMB chromatography has also been used to recover ionic liquids, salts and acids from hydrolysates and aqueous mixtures and concentrate sugars. Art. [#ARTNUM](#article-25375-1992379546); [#ARTNUM](#article-25375-2337744957); [#ARTNUM](#article-25375-2005706581); [#ARTNUM](#article-25375-48874317); [#ARTNUM](#article-25375-2036909878) **Process descriptions:** * Galactose separation: Using the aforementioned laboratory-scale SMB unit (Fig. 3), two sets of process experiments for continuous separation were carried out at 40 °C. The first one was the g-SMB process experiment, which was aimed at the continuous separation of galactose from LA and 5-HMF. The second one was the lh-SMB process experiment, which was aimed at the continuous separation between LA and 5-HMF. Each of these experiments was started by turning on the pumps and triggering the timer of the valve controller (Labview 8.0) simultaneously. Feed, desorbent-1, and desorbent-2 were continuously pumped into the columns. The feed to the g-SMB process was composed of 4.5 g/L galactose, 2 g/L LA, and 3 g/L 5-HMF while the feed to the lh-SMB process was composed of 2 g/L LA and 3 g/L 5-HMF. Such feed compositions were adopted considering the real concentration ranges of galactose, LA, and 5-HMF in the actual agarose hydrolyzate. The desorbent-1 and the desorbent-2 were both DDW. Each SMB experiment was continued for 32 steps and then stopped at the middle of the final step. At this moment, the pumps were shut down and the column profile samples were taken from the bottom of each column. [Link](https://www.researchgate.net/publication/273623151_Application_of_a_Dowex-50WX8_chromatographic_process_to_the_preparative-scale_separation_of_galactose_levulinic_acid_and_5-hydroxymethylfurfural_in_acid_hydrolysate_of_agarose) * **Fructose-glucose** pilot: A strongly acid cationic resin of gel-type (Ca2+ form) Dowex Monosphere (dp = 320 μm) was used in a pilot SMB unit of twelve 26 × 300 mm (ID × length) columns. They were carried out in pilot systems from Novasep: LICOSEP 12-26. Operating temperatures ranged from 20C to 60C. Located between every two columns was a four-port valve that was actuated by the control system. When required, the valves allowed either pumping of feed/eluent into the system or withdrawal of extract/raffinate streams. Flowrate: 20-120 mL/min. The maximum allowable pressure was 60 bar. Extract and raffinate purities around 90% were found, with concentrations around 15 g/L and productivities around 7 kg sugar/m3sorbent\*h. Art. [#ARTNUM](#article-25375-1970092017) * ribose - arabinose: Three zone system with 3 columns. Dowex Ca2+ resin was used in a glass batch chromatography column. This resin has a styrene–divinylbenzene (DVB) matrix and sulfonyl group. 70 mL of Dowex Ca2+ 350 resin was packed in XK16 glass column (20 × 350 mm, Amersham Biosciences, Sweden). This column was adjusted at 50°C by circulator. Reaction mixture was injected into injection valve (1 × 10−3 L sample loop, Rhodyne, USA) and P-500 pump (Pharmacia, Sweden) used for pumping eluent to the Dowex Ca2+ column. Eluent absorbance at 197 nm measured by 757 UV detector (Applied Biosystems, USA). Separated product fraction was analyzed by NH2-HPLC column. Acetonitrile–water (85:15 v/v) was selected as the eluent (mobile phase). Result: ribose 98% purity (raffinate), arabinose 83% purity (extract). Art. [#ARTNUM](#article-25375-2007165402) * With corn-stover hydrolysate: The SMB unit built for this study consists of 12 packed columns and 14 Valco ST rotary valves (VICI, Houston, TX). Five pumps with a pulse dampener and pressure gauges controlled the washing, regeneration, elution, feed, and raffinate flow rates. The separations were performed at 65 °C to prevent bacteria growth in the corn-stover hydrolyzate and to reduce viscosity during the purification process. Laboratory-scale columns (2.69 cm × 30 cm) were packed with PVP. The hydrolyzate was filtered with 0.2-μm nylon filter paper prior to the experiment. A NaOH or NH4OH solution is used for regeneration. Art. [#ARTNUM](#article-25375-2011511327)

2.1.1 Simulated Moving Bed Chromatography
A Five-Zone Simulated Moving Bed for the Isolation of Six Sugars from Biomass Hydrolyzate
A five-zone simulated moving bed (SMB) process was developed in this study to recover sugars from corn-stover hydrolyzate. The sugars can serve as fermentation feedstock for ethanol production. The major hydrolyzate components are six sugars (arabinose, mannose, xylose, galactose, glucose, cellobiose) and four impurities (sulfuric acid, acetic acid, furfural and hydroxymethyl furfural). An eight-zone SMB based on Dowex99 and a five-zone nonisocratic SMB based on poly-4-vinyl pyridine (PVP) were designed with pseudolinear standing wave design and then optimized. Cost analysis and fermentation tests indicated that the PVP SMB is the most cost-effective. The design was tested using VErsatile Reaction and SEparation (VERSE) simulations and SMB experiments. Two different feed compositions, two different feed flow rates, and two different regenerants were tested in three PVP SMB experimental runs. All runs had 99+% yields. The sugars purities ranged from 93% to 95%, because some sulfate and acetate co-eluted wi...
12/1/05 12:00:00 AM
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2.1.2 Simulated Moving Bed Chromatography
A Nine-Zone Simulating Moving Bed for the Recovery of Glucose and Xylose from Biomass Hydrolyzate
A nine-zone simulated moving bed (SMB) process was developed to recover two sugars, glucose and xylose, from biomass hydrolyzate with 88% recovery and near 100% purity. The SMB system consists of two coupled binary SMB rings which are operated at the same switching time. The first ring consists of five zones, in which sulfuric acid (a fast-moving solute) is recovered as the raffinate product, acetic acid (a slow-moving solute) is partially recovered as the extract product, and a mixture of the two sugars (intermediate solute) and the rest of the acetic acid is recovered in a bypass stream, which is input as the feed to the second ring. The second ring consists of four zones, in which the sugars are recovered as the raffinate product and acetic acid is recovered as the extract product. Experimental SMB data obtained using either hydrolyzate or synthetic mixtures of glucose, xylose, sulfuric acid, and acetic acid are presented and analyzed with a lumped mass-transfer model. Single-component and multicompone...
9/1/98 12:00:00 AM
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2.1.3 Simulated Moving Bed Chromatography
Application on separation of bagasse pith extract to produce L-arabinose and D-xylose by simulate moving bed chromatography
L-arabinose and D-xylose were extracted from bagasse pith by phosphoric acid. Continuous fractionation of xylose crystalline mother liquid from extraction of bagasse pith by simulate moving bed chromatography. The Ca2+ resin was used as a separation agent and water was eluent. L-arabinose and D-xylose were separated with the best parameters and product purity was 81.94% and 91.89% which can be crystallize. This process was high extraction rate and purity, easy operation and low running cost. The phosphate which in hydrolysate and ion exchanging eluate can be reused in clarification process of cane sugar. There is no discharge of waste liquid and phosphoric acid was realized resource recycling. This process effectively solved the environmental protection problem of L-arabinose traditional processing technology, and opened up a new field of raw material for L-arabinose and suitable for industrialized production.
1/1/15 12:00:00 AM
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2.1.4 Simulated Moving Bed Chromatography
Chapter Five - Chromatographic Fractionation of Lignocellulosic Hydrolysates
Abstract Monosaccharides (glucose, xylose, etc.) are valuable platform chemicals that can be produced from lignocellulosic (polysaccharide containing) biomasses via hydrolysis. Their cost-effective recovery from lignocellulosic biomass hydrolysates and further purification requires sophisticated separation technology. Adsorption and electrolyte exclusion chromatography can be used for the fractionation of hydrolysates containing mineral acids. The recovered hydrolysis acid can be recycled, which saves and reduces chemicals consumption. Chromatographic separation can be done either batchwise, using steady-state recycling chromatography, or using continuous simulated moving bed chromatography. The latter two process options offer significant increase in productivity when compared to the batchwise fractionation process. In this chapter, chromatographic and adsorptive fractionation techniques for the treatment of acidic lignocellulosic hydrolysates are reviewed. The relevant physical phenomena affecting the separation efficiency as well as various industrially applicable process options are discussed.
1/1/13 12:00:00 AM
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2.1.5 Simulated Moving Bed Chromatography
Dowex 1X4 and Dowex 1X8 as substitute of Diaion MA03SS in simulated moving bed chromatographic separation of sulfuric acid and sugars in concentrated sulfuric acid hydrolysates of bamboo
Abstract To find commercially available ion exchange resins comparable to a strong-base anion exchange resin Diaion MA03SS, which is specialized for the separation of sulfuric acid and sugars in concentrated sulfuric acid hydrolysates of non-food biomass by means of a simulated moving bed (SMB) chromatography, the screening test of 6 kinds of commercially available resins containing quaternary ammonium groups was carried out by a batch column-mode chromatographic separation of glucose and sulfuric acid at 50 °C. Based on results of the screening test, Dowex 1X4 and Dowex 1X8 were selected as replacements of Diaion MA03SS. The following SMB study using Diaion MA03SS, Dowex 1X4 and Dowex 1X8 at 50 °C clarified that Dowex 1X8 showed performances almost the same as those of Diaion MA03SS in the separations of sulfuric acid and sugars (mainly glucose and xylose) in hydrolysates of bamboo with 27 wt% sulfuric acid under the averaged flow rate of feed loading from 0.136 to 0.273 L/(h L-resin). For Dowex 1X8, recoveries of sulfuric acid were 90.5–93.4% and recoveries of glucose and xylose were 94.9–99.7% and 82.8–88.3%, respectively. Dowex 1X4 showed slightly higher recoveries for three solutes; namely sulfuric acid recoveries were 95.0–95.5% and glucose and xylose recoveries were 100–101% and 86.1–91.7%, respectively. However, the highest averaged flow rate of feed loading for Dowex 1X4 was 0.205 L/(h L-resin) because of the higher column pressure loss owing to its high shrinking in 30 wt% sulfuric acid. Thus, it became clear that Dowex 1X8 exhibit excellent performances comparable to or higher than those of Diaion MA03SS in the SMB chromatographic separation of sulfuric acid and sugars in concentrated sulfuric acid hydrolysate of bamboo.
6/1/16 12:00:00 AM
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2.1.6 Simulated Moving Bed Chromatography
Fructose–glucose separation in a SMB pilot unit: Modeling, simulation, design, and operation
Glucose was separated from fructose experimentally using a simulated moving-bed (SMB) adsorber. A strongly acid cationic resin of gel type (Ca2+ form) Dowex Monosphere (dp = 320 μm) was used in a pilot SMB unit of twelve 26 × 300 mm (ID × length) columns. A recently proposed design procedure was applied to overcome the inherent strong mass-transfer resistance present in this kind of adsorbent. The fluid/solid velocity ratios in SMB sections 1, 2 and 3 leading to at least 90% product purity were followed by simulation and plotted in a 3-D parameter space. The design methodology, called “separation volume analysis,” also considered the geometric parameters, as well as allowable working flow rates, temperature and pressure of the plant. Operating conditions from this procedure were used to operate the SMB unit, and the expected performance was achieved experimentally. Simulation strategies based on a true countercurrent and a real SMB were used and the predicted performance of both agreed well with experimental data. Furthermore, experimental results confirmed predictions of the separation volume analysis, which shows the potential of the technique for optimizing existing SMB equipment.
9/1/01 12:00:00 AM
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2.1.7 Simulated Moving Bed Chromatography
Material and Heat Balances of Bioethanol Production Process by Concentrated Acid Saccharification Process from Lignocellulosic Biomass
The process for bioethanol production from lignocellulosic biomass was studied through process simulation using PRO/II. Process integration was conducted with concentrated acid pretreatment, hydrolysis process, SMB (simulated moving bed chromatography) process and pervaporation process. Energy consumption could be minimized by the heat recovery process. In addition, material and energy balance were calculated based on the results from the simulation and literature data. A net production yield of 4.07 kg-biomass and energy consumption value of 3,572 kcal per 1 kg ethanol were calculated, which is indicating that 26% yield increase and 30% energy saving compared to the bioethanol production process with dilute-acid hydrolysis (SRI report). In order to make it possible, sugar conversion yield of cellulose and hemi-cellulose is to be reached up to 90% and fermentation of xylose needs to be developed. In order to reduce the energy consumption up to 30%, the concentration of acid solution after being separated by SMB should exceed 20%. If acid/sugar separation by SMB process is to be practical, the bioethanol process designed in this study can be commercially feasible.
1/1/11 12:00:00 AM
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2.1.8 Simulated Moving Bed Chromatography
Method for separating and purifying xylose and arabinose from hemicellulose acid hydrolysis liquid
The invention relates to a method for separating and purifying xylose and arabinose from hemicellulose acid hydrolysis liquid. The method comprises the following separating and purifying steps of: (1) carrying out electrodialysis and membrane filtration concentrate pretreatment on hemicellulose acid hydrolysis liquid directly obtained by adopting acid hydrolysis, deoxidizing and filtering for later use by adopting high-purity water; (2) putting the hemicellulose acid hydrolysis liquid after pretreatment into a simulated moving bed chromatography separating device and carrying out separation to obtain two discharging liquids; and (3) concentrating, cooling and crystallizing the two discharging liquids by adopting a multi-effect falling film evaporator to obtain xylose and arabinose products. In the invention, monosaccharide is extracted by adopting the simulated moving bed chromatography separation device (SSMB), a plurality of adsorption columns are serially connected into a closed loop, and inlet and outlet positions of all portions of materials can be changed by continuously switching valves, therefore, the relative motion between solid phase and liquid phase is realized, and the separation and the extraction among different components are carried out. The invention not only has the advantages of simple fixed bed adsorption operation, but also has the continuous operation capacity of a moving bed and is suitable for large-scale industrial production.
3/30/10 12:00:00 AM
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2.1.9 Simulated Moving Bed Chromatography
Method for separating and purifying xylose and arabinose from hemicellulose acid hydrolysis liquid
The invention relates to a method for separating and purifying xylose and arabinose from hemicellulose acid hydrolysis liquid. The method comprises the following separating and purifying steps of: (1) carrying out electrodialysis and membrane filtration concentrate pretreatment on hemicellulose acid hydrolysis liquid directly obtained by adopting acid hydrolysis, deoxidizing and filtering for later use by adopting high-purity water; (2) putting the hemicellulose acid hydrolysis liquid after pretreatment into a simulated moving bed chromatography separating device and carrying out separation to obtain two discharging liquids; and (3) concentrating, cooling and crystallizing the two discharging liquids by adopting a multi-effect falling film evaporator to obtain xylose and arabinose products. In the invention, monosaccharide is extracted by adopting the simulated moving bed chromatography separation device (SSMB), a plurality of adsorption columns are serially connected into a closed loop, and inlet and outlet positions of all portions of materials can be changed by continuously switching valves, therefore, the relative motion between solid phase and liquid phase is realized, and the separation and the extraction among different components are carried out. The invention not only has the advantages of simple fixed bed adsorption operation, but also has the continuous operation capacity of a moving bed and is suitable for large-scale industrial production.
7/25/12 12:00:00 AM
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2.1.10 Simulated Moving Bed Chromatography
Method for separating glucose and xylose in straw fiber enzymatic hydrolysate
The invention relates to a method for separating glucose and xylose in straw fiber enzymatic hydrolysate. The method for separating glucose and xylose in straw fiber enzymatic hydrolysate comprises the following steps: a) blending feeding syrup, namely, adjusting the concentration of desalted, decolored and concentrated straw fiber enzymatic hydrolysate to be 40-60%; b) filtering, namely, filtering the syrup solution obtained in the step a) by using a micron-order filter so as to prepare a clear liquid in which impurities visible to the naked eyes do not exist; c) performing sequential simulated moving bed chromatographic separation, namely, performing sequential simulated moving bed chromatographic separation on the obtained syrup, wherein deionized water is adopted as an eluent, high-acidity cation exchange resin is adopted as an adsorbent, the separation temperature is 60-70 DEG C, and the sequential simulated moving bed chromatographic separation equipment comprises 9 chromatographic columns arranged in sequence, and is provided with two inlets and two outlets which are alternated sequentially; d) concentrating, namely, concentrating an obtained solution of a component A to be 70-75%, mixing an obtained component B, and further concentrating to be 70-75%. The method is low in operation cost, a product obtained from separation is high in purity, concentration and yield, and continuous and industrial production is achieved.
7/16/14 12:00:00 AM
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2.1.11 Simulated Moving Bed Chromatography
Modified simulated moving bed chromatography with two pumps for sugar separation
A modified SMB system composed of two pumps was developed for the separation of L-ribose and L-arabinose from its binary mixture. In two-pump SMB operation, the flow rates required for separation in every column zones and product ports are identical to those in conventional SMB equipped with four pumps and are controlled by appropriate operation of valves during a cycle of switching time. The purity, yield and enrichment of sugars obtained by two-pump SMB separation were comparable to that of conventional SMB. The two-pump SMB system is therefore considered to be more economically efficient than conventional SMB by reducing the cost for SMB installation and pump operation.
1/1/19 12:00:00 AM
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2.1.12 Simulated Moving Bed Chromatography
Process for separating arabinose.
Arabinose can be separated from an aqueous feed mixtrue of monosaccharides containing arabinose along with other aldopentoses and aldohexoses by a liquid phase adsorptive process in which the feed is contacted with a calcium-Y or calcium X type zeolite. Arabinose is selectively adsorbed to the substantial exclusion of other aldoses and thereafter is recovered in high purity by desorption with water or ethanol. The process can be carried out on a commercial scale by means of a simulated moving bed flow scheme.
11/17/88 12:00:00 AM
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2.1.13 Simulated Moving Bed Chromatography
Process innovation in the sugar industry : Chromatographic sugar separation using SMB technology
The chromatographic separation of sugar from raw juice was identified as a promising alternative for the current juice purification. Simulated moving bed technology (SMB) was chosen as the most suitable technology on the basis of the purification, limited degree of dilution and increased sugar yield. An adsorbent was selected which binds sucrose selectively compared to glucose, glutamine and betaine. The binding mechanism on a molecular scale (CH-π interaction) is weak enough to allow for a sensible desorption strategy. An SMB process model was used to evaluate the performance of the adsorbents. Experiments on the laboratory scale were done using micro-filtration and reverse osmosis. SMB experiments were carried out on pilot scale using the selected adsorbent. A temperature swing resulted in a concentration step during adsorption/desorption. This lowers the energy costs for water evaporation prior to the crystallization process. The process is economically feasible when all identified savings are realized. Important issues are the reduction of sugar losses in the total process, a higher sucrose yield in crystallization as a result of a higher purity, and limited operational costs due to prevention of dilution.
1/1/07 12:00:00 AM
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2.1.14 Simulated Moving Bed Chromatography
Production of fuel ethanol from bamboo by concentrated sulfuric acid hydrolysis followed by continuous ethanol fermentation
An efficient process for the production of fuel ethanol from bamboo that consisted of hydrolysis with concentrated sulfuric acid, removal of color compounds, separation of acid and sugar, hydrolysis of oligosaccharides and subsequent continuous ethanol fermentation was developed. The highest sugar recovery efficiency was 81.6% when concentrated sulfuric acid hydrolysis was carried out under the optimum conditions. Continuous separation of acid from the saccharified liquid after removal of color compounds with activated carbon was conducted using an improved simulated moving bed (ISMB) system, and 98.4% of sugar and 90.5% of acid were recovered. After oligosaccharide hydrolysis and pH adjustment, the unsterilized saccharified liquid was subjected to continuous ethanol fermentation using Saccharomyces cerevisiae strain KF-7. The ethanol concentration, the fermentation yield based on glucose and the ethanol productivity were approximately 27.2 g/l, 92.0% and 8.2 g/l/h, respectively. These results suggest that the process is effective for production of fuel ethanol from bamboo.
12/1/11 12:00:00 AM
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2.1.15 Simulated Moving Bed Chromatography
Recovery of ionic liquid and sugars from hydrolyzed biomass using ion exclusion simulated moving bed chromatography
Abstract Efficient recovery of ionic liquid (IL) from aqueous mixture of ILs and sugars (which derived from enzymatic or chemical catalyzed hydrolysis of ILs-pretreated biomass) is a major drawback for commercialization of biofuel and platform chemicals production from biomass utilized ILs as pretreatment solvent. In this study, simulated moving bed (SMB) chromatography equipped with ion exclusion column (containing [Emim] + cation) was investigated to separate sugars (glucose and xylose) which are the main products from biomass hydrolysate and 1-Ethyl-3-methylimidazolium acetate (EmimAc) which is the ILs used for biomass pretreatment. A four-zone SMB system with a configuration of 2-2-2-2 (2 ion exclusion columns in each zone) was used to recover glucose, xylose and EmimAc from their aqueous mixture with yield of 71.38, 99.37 and 98.92%, respectively. Moreover, the optimization of SMB zone configuration by simulation results in a complete recovery of ILs. This result indicates that for the first time, ion exclusion SMB chromatography could be used for complete recovery of ILs from aqueous sugar mixture.
3/1/12 12:00:00 AM
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2.1.16 Simulated Moving Bed Chromatography
Simulated moving bed separation of agarose-hydrolyzate components for biofuel production from marine biomass
The economically-efficient separation of galactose, levulinic acid (LA), and 5-hydroxymethylfurfural (5-HMF) in acid hydrolyzate of agarose has been a key issue in the area of biofuel production from marine biomass. To address this issue, an optimal simulated moving bed (SMB) process for continuous separation of the three agarose-hydrolyzate components with high purities, high yields, and high throughput was developed in this study. As a first step for this task, the adsorption isotherm and mass-transfer parameters of each component on the qualified adsorbent were determined through a series of multiple frontal experiments. The determined parameters were then used in optimizing the SMB process for the considered separation. Finally, the optimized SMB process was tested experimentally using a self-assembled SMB unit with four zones. The SMB experimental results and the relevant computer simulations verified that the developed process in this study was quite successful in the economically-efficient separation of galactose, LA, and 5-HMF in a continuous mode with high purities and high yields. It is thus expected that the developed SMB process in this study will be able to serve as one of the trustworthy ways of improving the economic feasibility of biofuel production from marine biomass.
8/1/15 12:00:00 AM
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2.1.17 Simulated Moving Bed Chromatography
Standing‐wave design of tandem SMB for linear multicomponent systems
The standing-wave design was extended to achieve any desired split of mixtures containing three or more components in a single-ring and a tandem two-ring simulated moving bed (SMB). Mass-transfer effects were considered in the design for nonideal systems. The separation of a four-component mixture of glucose, xylose, acetic acid and sulfuric acid was chosen to illustrate the design method. Rate-model simulations confirmed that the standing-wave design method could guarantee high purity and high yield. If all the components in a ternary mixture need to be recovered with high purity and high yield, the easier separation should be performed in the first ring of a tandem SMB to achieve the lowest desorbent consumption and the highest product concentration. If only the intermediate component needs to be recovered in high purity, one of the impurities should be allowed to distribute between the two product ports in the first ring to achieve a lower desorbent consumption and a higher product concentration. These strategies also apply to the separation of a mixture containing more than three components.
12/1/02 12:00:00 AM
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2.1.18 Simulated Moving Bed Chromatography
l-Ribose from l-arabinose by epimerization and its purification by 3-zone simulated moving bed chromatography
l-Ribose has recently received attention as the starting material for nucleoside drugs. As it is not found in nature, it is being produced by enzymatic or epimerization reaction. We investigated an epimerization reaction by molybdenium oxide and examined the effects of temperature, solvent, and molybdenum oxide amount on epimerization. l-Ribose has a yield of 22% under the conditions of 100 kg/m3 l-arabinose, 20% methanol, 5 kg/m3 MoO3, and 90°C. In addition, simulated moving bed (SMB) that was equipped with three NH2-HPLC columns was used to separate l-arabinose and l-ribose resulting from l-arabinose epimerization. A 3-zone SMB process was developed to eliminate the high pressure problem in the conventional 4-zone SMB. Aspen simulation was performed to determine the operating variables such as switching time, raffinate, and extract flow rates. Experimental purities of extract and raffinate were compared with the theoretical ones and they are found to be fairly well correlated.
1/1/10 12:00:00 AM
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2.1.19 Simulated Moving Bed Chromatography
A METHOD FOR RECOVERING GALACTOSE FROM A SOLUTION DERIVED FROM PLANT-BASE BIOMASS USING CHROMATOGRAPHIC FRACTIONATION STEPS AND

A process of recovering galactose from a solution derived from plant-based biomass containing galactose and arabinose, comprising subjecting said solution to chromatographic fractionation, whereby the chromatographic fractionation comprises one or more chromatographic fractionation steps using a column filling material selected from strongly basic anion exchange resins where the ion form is selected from SO42-, SO32- and HSO3- and one or more chromatographic fractionation steps using a column filling material selected from strongly acid cation exchange resins, in any desired sequence, recovering at least one fraction enriched in galactose having a galactose content of 38 to 95% on RDS, subjecting said at least one fraction enriched in galactose to crystallization, and recovering a plant-based crystalline galactose product having a purity of more than 90% on DS. A process as claimed in claim 1, wherein the ion form of said strongly basic anion exchange resins is HSO3-. A process as claimed in claim 1, wherein said fractionation with strongly basic anion exchange resins comprises two steps with a resin in HSO3- form. A process as claimed in claim 1, wherein the ion form of said strongly acid cation exchange resin is selected from Ba2+, Pb2+, Ca2+ and Sr2+. A process as claimed in claim 1, wherein the ion form of said strongly acid cation exchange resin is Ba2+. A process as claimed in claim 1, wherein the chromatographic fractionation provides a yield of galactose of 35 to 95%. A process as claimed in claim 1, wherein the crystallization is carried out using a solvent selected from water and a mixture of water and alcohol as the crystallization solvent. A process as claimed in claim 7, wherein the crystallization solvent is a mixture of ethanol and water. A process as claimed in claim 8, wherein the crystallization solvent is water. A process as claimed in claim 1, wherein the crystallization provides crystalline galactose having a purity of more than 95% on DS. A process as claimed in claim 1, wherein the crystallization provides crystalline galactose having a purity of more than 98% on DS. A process as claimed in claim 1, wherein the crystallization provides crystalline galactose having a purity of more than 99.5% on DS. A process as claimed in claim 1, wherein the crystallization provides crystalline galactose having a maximum content of D-glucose of 0.50% on DS. A process as claimed in claim 1, wherein the crystallization provides crystalline galactose having a maximum content of D-glucose of 0.30%. A process as claimed in claim 1, wherein the crystallization provides crystalline galactose having an impurity profile comprising arabinose and optionally at least one sugar selected from xylose and mannose. A process as claimed in claim 15, wherein the crystallization provides crystalline galactose, where the impurity profile comprises at least one of said sugars in an amount of 0.03% on DS or more. A process as claimed in claim 16, wherein the crystallization provides crystalline galactose, where the impurity profile comprises arabinose in an amount of 0.03% on DS or more. A process as claimed in claim 17, wherein the crystallization provides crystalline galactose, where the impurity profile comprises mannose in an amount of 0.03% on DS or more. A process as claimed in claim 15, wherein the crystallization provides crystalline galactose, where the impurity profile comprises at least one of said sugars in an amount of 0.10% or more. A process as claimed in claim 1, wherein the process further comprises one or more purification steps selected from membrane filtration, ion exchange, evaporation and filtration carried out before, after or between said chromatographic fractionation step/steps. A process as claimed in claim 1, wherein the process further comprises crystallization between said chromatographic fractionation steps. A process as claimed in claim 21, wherein said crystallization comprises precipitation crystallization of xylose. A process as claimed in claim 1, wherein said plant-based biomass is hydrolyzate derived from wood material. A process as claimed in claim 23, wherein said plant-based biomass is a hydrolyzate derived from softwood or hardwood. A process as claimed in claim 1, wherein said solution derived from plant- based biomass is a spent liquor obtained from a pulping process. A process as claimed in claim 25, wherein said spent liquor obtained from a pulping process is a spent sulphite pulping liquor. A process as claimed in claim 26, wherein said spent sulphite pulping liquor is a spent sulphite pulping liquor recovered after the separation of the main part of xylose. A process as claimed in claim 1, wherein said galactose is D-galactose. A process as claimed in claim 15, wherein said xylose is D-xylose, said arabinose is L-arabinose and said mannose is D-mannose.
6/24/04 12:00:00 AM
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2.1.20 Simulated Moving Bed Chromatography
Mannose production from palm kernel meal using simulated moving bed separation

1. A process for the production of a high purity d-mannose product from fermented palm oil kernel meal using simulated moving bed separation, said process comprising:a. passing a palm kernel meal stream comprising water, d-mannose, d-glucose, other sugars, color agents, salts and biomass at a pH of between about 5 and 7 to a filtration zone comprising a filter media effective to remove at least a portion of the biomass to provide a filtered feedstream comprising water, d-mannose, d-glucose, salts, other sugars, and color agents:b. passing the filtered feedstream to a simulated moving bed (SMB) zone to provide a highly pure mannose extract stream comprising d-mannose, color agents, salts and water and a primary raffinate stream comprising water, d-glucose, salts, and other sugars, and a secondary raffinate stream consisting essentially of water, said SMB zone comprising a plurality of adsorption beds containing a stationary phase agent comprising a strong acid cation exchange resin in which exchange sites are a metal selected from the group consisting of Ca2+, Na+ and K+, and introducing a mobile phase stream consisting of water to said SMB zone, said SMB zone being operated at effective conditions and an effective SMB cycle to provide a continuous process for producing the highly pure mannose stream and the secondary raffinate stream and returning at least a portion of the secondary raffinate stream to the SMB zone to be admixed with the mobile phase stream;c. passing the highly pure mannose stream to a decolorization zone wherein the highly pure mannose extract stream is contacted with a medium effective to at least partially remove the color agents to provide a decolorized stream comprising d-mannose, salts and water;d. passing the decolorized stream to a first evaporation zone to remove at least a portion of the water and provide a first evaporated stream;e. passing the first evaporated stream to a desalination zone to provide a desalinized stream;f. passing the desalinized stream to a second evaporation zone to provide an evaporated desalinized stream;g. passing the evaporated desalinated extract stream to a precipitation zone or a crystallization zone to provide wet mannose crystals; and,h. passing the wet mannose crystal stream to a vacuum drying zone to provide the high purity d-mannose product. 2. The process of claim 1, wherein the plurality of adsorption beds is 8 and the effective SMB cycle comprises a 2-3-2-1 SMB cycle. 3. The process of claim 1, wherein the effective conditions for the operation of the SMB zone include a temperature of from about 50 to about 65 ° C. 4. The process of claim 1, wherein the the exchange sites are calcium. 5. The process of claim 1, wherein the filter media is a membrane having at least a 10 Da molecular weight cut off to remove at least a portion of the biomass. 6. The process of claim 1, wherein the medium effective to at least partially remove the color agents is an adsorbent or absorbent comprising activated carbon. 7. The process of claim 1, wherein the decolorized stream comprises an optical density or absorbance less than or equal to 0.2. 8. The process of claim 1, wherein the first evaporization zone provides a first evaporated stream having a Brix value of from about 25 to about 30 Brix. 9. The process of claim 1, wherein the feedstream comprises from about 35 to about 70 wt-% d-mannose relative to the total sugar in the feedstream. 10. The process of claim 1, wherein the desalinized zone comprises two resin zones connected in series, wherein the first resin zone comprises an anion exchange resin, and the second resin zone comprises a cation exchange resin and the first evaporated stream is passed to the first resin zone to provide a desalting eluent and the desalting eluent is passed to the second resin zone to provide the desalinized stream. 11. The process of claim 1, wherein the high purity d-mannose product comprises from 95 to about 99.9 wt-% d-mannose. 12. The process of claim 1, wherein the high purity d-mannose product is a solid in the form of a powder or a crystal. 13. The process of claim 1, wherein the highly pure mannose extract stream comprises more than about 95 wt-% d-mannose with respect to the total sugar in the highly pure mannose extract stream. 14. The process of claim 1, wherein the crystallization zone further comprises the steps of admixing the evaporated desalinized stream with acetic acid, nucleating the admixture, maintaining the admixture at effective crystallization conditions, cooling, filtering and recovering retained d-mannose crystals and washing the retained d-mannose crystals with ethanol to provide the wet mannose crystals. 15. The process of claim 13, wherein the effective crystallization conditions include a crystallization temperature of less than about 10 ° C. 16. The process of claim 1, wherein the precipitation zone further comprises the steps of contacting the evaporated desalinated stream with ethanol at effective precipitation conditions, recovering wet mannose crystals. 17. The process of claim 1, wherein filtered feedstream comprises less than about 0.5 wt-% biomass. 18. A process for the production of a high purity d-mannose product from fermented palm oil kernel meal using simulated moving bed separation, said process comprising:a. passing a palm kernel meal stream comprising water, d-mannose, d-glucose, other sugars, color agents, salts and biomass at a pH of between about 5 and 7 to a filtration zone comprising a filter media effective to remove at least a portion of the biomass to provide a filtered feedstream comprising water, d-mannose, d-glucose, salts, other sugars, and color agents:b. passing the filtered feedstream to a simulated moving bed (SMB) zone to provide a highly pure mannose extract stream comprising d-mannose, color agents, salts and water and a primary raffinate stream comprising water, d-glucose, salts, and other sugars, and a secondary raffinate stream consisting essentially of water, said SMB zone comprising a plurality of adsorption beds containing a stationary phase agent comprising a strong acid calcium cation exchange resin, and introducing a mobile phase stream consisting of water to said SMB zone, said SMB zone being operated at effective conditions and being operated in an effective SMB cycle to provide a continuous process for producing the highly pure mannose stream and the secondary raffinate stream and returning at least a portion of the secondary raffinate stream to the SMB zone to be admixed with the mobile phase stream;c. passing the highly pure mannose stream to a decolorization zone wherein the highly pure mannose stream is contacted with a medium effective to at least partially remove the color agents to provide a decolorized extract stream comprising d-mannose, salts and water;d. passing the decolorized stream to a first evaporation zone to remove at least a portion of the water and provide a first evaporation stream;e. passing the first evaporation stream to a desalination zone to provide a desalinized stream;f. passing the desalinized stream to a second evaporation zone to provide a second evaporated stream;g. passing the second evaporated stream to a precipitation zone or a crystallization zone to provide wet mannose crystals; and,h. passing the wet mannose crystal stream to a vacuum drying zone to provide the high purity d-mannose product. 19. The process of claim 18, wherein the second evaporation stream is passed to a precipitation zone comprising the steps of contacting the second evaporation stream with ethanol at effective precipitation conditions including a precipitation temperature of from about 10° C. to about 60 ° C. and recovering wet mannose crystals to provide wet mannose crystals. 20. A simulated moving bed separation process for the production of a high purity d-mannose extract stream from fermented palm oil kernel meal using simulated moving bed separation, said process comprising passing a palm kernel meal stream comprising water, d-mannose, d-glucose, other sugars, color agents, biomass and salts at a pH of between about 5 and 7 to a simulated moving bed (SMB) zone to provide a highly pure mannose stream comprising d-mannose, color agents, salts, biomass, and water and a primary raffinate stream comprising water, d-glucose, salts, and other sugars, and a secondary raffinate stream consisting essentially of water, said SMB zone comprising a plurality of adsorption beds containing a stationary phase agent comprising a strong acid cation exchange resin in which exchange sites are Ca2+, and introducing a mobile phase stream containing water to said SMB zone, said SMB zone being operated at effective conditions to provide a continuous process for producing the highly pure mannose stream comprising greater than about 95 wt-% d-mannose based on the total sugar in the highly pure mannose stream and returning at least a portion of the secondary raffinate stream to the SMB zone to be admixed with the mobile phase stream, and subsequently removing the biomass from the highly pure mannose stream.
8/6/12 12:00:00 AM
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2.1.21 Simulated Moving Bed Chromatography
Method of obtaining a product sugar stream from cellulosic biomass

1. A process for obtaining a product sugar stream from cellulosic biomass comprising cellulose and hemicellulose, the process comprising:a) pretreating the cellulosic biomass at a pH of about 0.4 to about 2.0 by adding one or more than one acid to the cellulosic biomass to hydrolyze a portion of the cellulose and at least a portion of the hemicellulose in the cellulosic biomass to produce a pretreated cellulosic biomass comprising glucose, acetic acid and a sugar monomer selected from the group consisting of xylose, arabinose, mannose, galactose and a combination thereof;b) adding one or more than one base to the pretreated cellulosic biomass to adjust the pretreated cellulosic biomass to a pH of about 4.0 to about 6.0, thereby producing a neutralized cellulosic biomass comprising inorganic salt and acetate salt;c) hydrolyzing the neutralized cellulosic biomass with cellulase enzymes to produce a crude sugar stream;d) separating insoluble residue from the crude sugar stream to produce a clarified sugar stream;e) treating the clarified sugar stream by ion exclusion chromatography with a cation exchange resin at a pH from 5.0 to 10.0 to produce one or more than one raffinate stream comprising the inorganic salt and acetate salt and a product sugar stream comprising sugar, wherein the concentration of acetic acid plus acetate salt in the clarified sugar stream fed to the ion exclusion chromatography step is greater than 5 g/L; andf) recovering the product sugar stream. 2. The process of claim 1 wherein, the ion exclusion chromatography of step e) is performed at a pH of between 6 and 10. 3. The process of claim 2 further comprising a step of recovering the one or more than one raffinate stream. 4. The process of claim 2 wherein, the ion exclusion chromatography of step e) is carried out using a Simulated Moving Bed (SMB) system or an Improved Simulated Moving Bed (ISMB) system. 5. The process of claim 2 wherein the clarified sugar stream is characterized by having a lignosulfonate content of from about 0 to about 4% of the total solids present in the clarified sugar stream. 6. The process of claim 2 wherein the cellulosic biomass is obtained from a feedstock selected from the group consisting of an agricultural waste, corn stover, wheat straw, barley straw, canola straw, oat straw, rice straw, soybean stover, a grass, switch grass, miscanthus, cord grass, reed canary grass, a forestry residue, aspen wood or sawdust, a sugar residue, bagasse and beet pulp. 7. The process of claim 2 wherein the acid is sulfuric acid and the inorganic salt comprises a sulfate salt. 8. The process of claim 2 wherein the dosage of the cellulase enzymes is about 5 to about 50 IU per gram of cellulose. 9. The process of claim 2 wherein pretreatment is selected from the group consisting of steam explosion and dilute acid prehydrolysis. 10. The process of claim 2 wherein the cellulosic biomass is pressed or leached prior step a. 11. The process of claim 4 wherein the SMB system or ISMB system is operated with 4 to 16 shifts of feed and collection positions per cycle. 12. The process of claim 11 wherein the SMB system or ISMB system is operated with 4 to 12 shifts of feed and collection positions per cycle. 13. The process of claim 3 wherein the recovered raffinate stream is used as a fertilizer. 14. The process of claim 2 wherein, in the step of adding (step b)), the one or more than one base is a soluble base. 15. The process of claim 14 wherein the soluble base is selected from the group consisting of sodium hydroxide, potassium hydroxide, ammonia and ammonium hydroxide. 16. The process of claim 2 wherein, in step d, the insoluble residue is separated from the crude sugar stream by microfiltration, plate and frame filtration, crossflow filtration, pressure filtration, vacuum filtration or centrifugation. 17. The process of claim 2 wherein the ion exclusion chromatography is performed at a pH of between 6.5 and 10. 18. The process of claim 2 wherein the ion exclusion chromatography is performed at a pH of between 6 and 8. 19. The process of claim 2 wherein the clarified sugar stream produced in step d) is concentrated prior to or during step e. 20. The process of claim 2 wherein the product sugar stream produced in step e) is concentrated. 21. The process of claim 2 wherein, in step e, one raffinate stream comprising the inorganic salt and acetate salt is produced. 22. A process for producing ethanol comprising:a) obtaining cellulosic biomass comprising cellulose and hemicellulose from a feedstock selected from the group consisting of an agricultural waste, corn stover, wheat straw, barley straw, canola straw, oat straw, rice straw, soybean stover, a grass, switch grass, miscanthus, cord grass, reed canary grass, a forestry residue, aspen wood or sawdust, a sugar residue, bagasse and beet pulp;b) pretreating the cellulosic biomass at a pH of about 0.4 to about 2.0 by adding one or more than one acid to the cellulosic biomass to hydrolyze a portion of the cellulose and at least a portion of the hemicellulose in the cellulosic biomass to produce a pretreated cellulosic biomass comprising glucose, acetic acid and a sugar monomer selected from the group consisting of xylose, arabinose, mannose, galactose and a combination thereof;c) adding one or more than one base to the pretreated cellulosic biomass to adjust the pretreated cellulosic biomass to a pH of about 4.0 to about 6.0, thereby producing a neutralized cellulosic biomass comprising inorganic salt and acetate salt;d) hydrolyzing the neutralized cellulosic biomass with cellulase enzymes to produce a crude sugar stream;e) separating insoluble residue from the crude sugar stream to produce a clarified sugar stream;f) treating the clarified sugar stream by ion exclusion chromatography with a cation exchange resin at a pH from 5.0 to 10.0 to produce one or more than one raffinate stream comprising the inorganic salt and acetate salt and a product sugar stream comprising sugar, wherein the concentration of acetic acid plus acetate salt in the clarified sugar stream fed to the ion exclusion chromatography step is greater than 5 g/L;g) recovering the product sugar stream, and the one or more than one raffinate stream; andh) fermenting the sugar in the product sugar stream to ethanol. 23. The process of claim 22 wherein, the ion exclusion chromatography of step e) is performed at a pH of between 6 and 10. 24. The process of claim 23 wherein, in step d, the dosage of cellulase enzymes is about 5 to about 50 IU per gram of cellulose. 25. The process of claim 23 wherein, in step b, pretreatment is selected from the group consisting of steam explosion and dilute acid prehydrolysis. 26. The process of claim 23 wherein the acid is sulfuric acid and the inorganic salt comprises a sulfate salt. 27. The process of claim 23 wherein, in step e, the insoluble residue is separated from the crude sugar stream by microfiltration, plate and frame filtration, crossflow filtration, pressure filtration, vacuum filtration or centrifugation. 28. The process of claim 23 wherein, in the step of pretreating (step b)), the clarified sugar stream is characterized by having a lignosulfonate content of from about 0 to about 4% of the total dry solids present in the clarified sugar stream. 29. The process of claim 23 wherein, prior to the step of pretreating (step b)), the cellulosic biomass is pressed or leached. 30. The process of claim 23 wherein, the ion exclusion chromatography of step f) is carried out using a Simulated Moving Bed (SMB) system or an Improved Simulated Moving Bed (ISMB) system. 31. The process of claim 30 wherein the SMB system or the ISMB system is operated with 4 to 16 shifts of feed and collection positions per cycle. 32. The process of claim 31 wherein the SMB system or the ISMB system is operated with 4 to 12 shifts of feed and collection positions per cycle. 33. The process of claim 23 wherein, the recovered raffinate stream is used as a fertilizer. 34. The process of claim 23 wherein, in the step of adding (step c)), the one or more than one base is a soluble base. 35. The process of claim 34 wherein the soluble base is selected from the group consisting of sodium hydroxide, potassium hydroxide, ammonia and ammonium hydroxide. 36. The process of claim 23 wherein, the ion exclusion chromatography of step f) is performed at a pH of between 6 and 8. 37. The process of claim 23 wherein, the ion exclusion chromatography of step f) is performed at a pH of between 6.5 and 10. 38. The process of claim 23 wherein the clarified sugar stream produced in step e) is concentrated prior to or during step f). 39. The process of claim 23 wherein the product sugar stream produced in step f) is concentrated. 40. The process of claim 23 wherein, in step f), one raffinate stream comprising the inorganic salt and acetate salt is produced. 41. A process for obtaining a product sugar stream from a crude sugar stream, the crude sugar stream produced from conversion of cellulosic biomass to sugar, the process comprising:a) separating insoluble residue from the crude sugar stream to produce a clarified sugar stream;b) treating the clarified sugar stream by ion exclusion chromatography with a cation exchange resin at a pH from 5.0 to 10.0 to produce one or more than one raffinate stream comprising sulfate and acetate salts, and a product stream comprising sugar, wherein the concentration of acetic acid plus acetate salt in the clarified sugar stream fed to the ion exclusion chromatography step is greater than 5 g/L; andc) obtaining the product sugar stream. 42. The process of claim 41 wherein, during step c), the one or more than one raffinate stream is recovered. 43. The process of claim 41 wherein, the ion exclusion chromatography of step b) is carried out using a Simulated Moving Bed (SMB) system or an Improved Simulated Moving Bed (ISMB) system. 44. The process of claim 41 wherein, the ion exclusion chromatography of step b) is performed at a pH of between 6 and 10. 45. A process for obtaining one or more than one raffinate stream enriched in inorganic salt and acetate salt, the process comprising:a) obtaining a clarified stream comprising sugar, inorganic salt and at least one of an acetate salt and acetic acid originating from a previous hydrolysis of the cellulosic biomass; andb) treating the clarified stream by ion exclusion chromatography with a cation exchange resin at a pH from 5.0 to 10.0 to produce the one or more than one raffinate stream enriched in inorganic salt and acetate salt, and a stream comprising sugar, wherein the concentration of acetic acid plus acetate salt in the clarified stream fed to the ion exclusion chromatography step is greater than 5 g/L. 46. The process of claim 45, wherein the clarified stream comprising sugar is a still bottoms stream resulting from the steps of (i) fermentation of a sugar stream resulting from hydrolysis of the cellulosic biomass, said fermentation resulting in a fermentation broth comprising ethanol; and (ii) distillation of the fermentation broth to produce concentrated ethanol and the still bottoms stream, wherein insoluble residue is removed in a solid-liquid separation step conducted prior to step b. 47. The process of claim 46, wherein the insoluble residue is removed prior to the step of fermentation (step i)). 48. The process of claim 46, wherein insoluble residue is removed from the still bottoms stream.
7/15/05 12:00:00 AM
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2.1.22 Simulated Moving Bed Chromatography
Methods and controllers for simulated moving bed chromatography for multicomponent separation

1. A system for reacting and separating solid and fluid components, the system comprising:a series of sequential simulated moving bed (SMB) chromatography columns connected to form a circulation loop, each SMB chromatography column comprising an inlet and an outlet; anda reactor configured to receive a solid reactant, the reactor having an inlet and an outlet, wherein the reactor inlet is fluidly connected to an outlet of a first SMB chromatography column of the series of sequential SMB chromatography columns, and the reactor outlet is fluidly connected to an inlet of a second SMB chromatography column of the series of sequential SMB chromatography columns. 2. The system of claim 1, wherein the reactor comprises a first reactor, and the system further comprises a second reactor having an inlet and an outlet, wherein the second reactor inlet is fluidly connected to an outlet of a third SMB column of the series of sequential SMB columns, and the second reactor outlet is fluidly connected to an inlet of a fourth SMB column of the series of sequential SMB columns. 3. The system of claim 2, wherein the first reactor comprises two or more reactors connected in a series. 4. The system of claim 3, wherein the second reactor comprises two or more reactors connected in a series. 5. The system of claim 2, wherein the first reactor and the second reactor are hydrolysis reactors. 6. The system of claim 5, wherein a temperature of the first reactor is different than a temperature of the second reactor. 7. The system of claim 2, further comprising a lignocellulosic biomass in the first reactor. 8. The system of claim 7, wherein the first reactor is configured to react cellulose from a lignocellulosic biomass. 9. The system of claim 8, wherein the second reactor is configured to react hemicelluloses from a lignocellulosic biomass. 10. The system of claim 9, wherein the series of sequential SMB chromatography columns are configured to separate hemicellulosic sugars from biomass components of lignocellulosic biomass in the first and second reactors. 11. The system of claim 1, wherein the reactor comprises two or more reactors connected in a series. 12. A method for separating materials from a reaction, the method comprising:positioning a solid material in a reactor; the reactor having an inlet and an outlet; andflowing a liquid through a series of sequential simulated moving bed (SMB) chromatography columns connected to form a circulation loop, each SMB chromatography column comprising an inlet and an outlet, wherein the reactor inlet is fluidly connected to an outlet of a first SMB chromatography column of the series of sequential SMB chromatography columns, and the reactor outlet is fluidly connected to an inlet of a second SMB chromatography column of the series of sequential SMB chromatography columns so that the liquid flowing through the series of sequential SMB chromatographic columns comprises at least one reaction product from the reactor. 13. The method of claim 12, wherein the reactor comprises a first reactor, and a second reactor having an inlet and an outlet is fluidly connected to the series of SMB chromatographic columns so that the second reactor inlet is fluidly connected to an outlet of a third SMB column of the series of sequential SMB columns, and the second reactor outlet is fluidly connected to an inlet of a fourth SMB column of the series of sequential SMB columns. 14. The method of claim 13, wherein the first reactor comprises two or more reactors connected in a series. 15. The method of claim 13, wherein the second reactor comprises two or more reactors connected in a series. 16. The method of claim 13, wherein the first reactor and the second reactor are hydrolysis reactors. 17. The method of claim 16, wherein a temperature of the first reactor is different than a temperature of the second reactor. 18. The method of claim 13, wherein the solid material comprises a lignocellulosic biomass. 19. The method of claim 18, further comprising maintaining the first reactor under conditions sufficient to react cellulose from a lignocellulosic biomass. 20. The method of claim 19, further comprising maintaining the second reactor under conditions sufficient to react hemicelluloses from a lignocellulosic biomass. 21. The method of claim 20, further comprising separating hemicellulosic sugars from biomass components of lignocellulosic biomass in the first and second reactors and further separating hemicellulosic sugars from acid in the series of sequential SMB chromatography columns. 22. The method of claim 12, wherein the reactor comprises two or more reactors connected in a series.
3/28/14 12:00:00 AM
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2.1.23 Simulated Moving Bed Chromatography
Process for obtaining stereoisomers from biomass
The present invention includes a process for extracting a stereoisomer fro biomass. The method comprises providing biomass and subjecting the biomass to substantially instantaneous pressurization and depressurization to separate cellulose, hemicellulose, and lignin from the biomass. The hemicellulose is hydrolyzed to form hemicellulose hydrolysates. The hydrolysates are separated using chromatography.
1. A process for extracting one or more hemicellulose hydrolysate stereoisomers from biomass, comprising: providing biomass; subjecting the biomass to substantially instantaneous pressurization and de- pressurization in a manner effective to separate lignin, hemicellulose and cellulose in the biomass; hydrolyzing the hemicellulose to form hemicellulose hydrolysates; and separating one or more stereoisomers from the hemicellulose hydrolysates using adsorption. 2. The process of claim 1 and further comprising reducing size of the biomass prior to pressurization. 3. The process of claim 1 and further comprising compacting the biomass prior to pressurization. 4. The process of claim 1 wherein the biomass provided is one or more of wood, beets, corn, soy, wheat, and plant biomass. 5. The process of claim 1 wherein the stereoisomer separated is L-arabinose. 6. The process of claim 1 wherein the biomass is subjected to pressurization at a temperature of about 390 to 460 degrees Fahrenheit. 7. The process of claim 1 wherein the biomass is subjected to pressurization for not more than about 10 minutes. 8. The process of claim 2 wherein the biomass is reduced to a size of sawdust. 9. The process of claim 1 and further comprising feeding the biomass for pressurization continuously. 10. The process of claim 1 and further comprising adding moisture to the biomass before pressurization. 11. The process of claim 1 wherein the hydrolysis occurs in a reactor/static mixer. 12. The process of claim 11 wherein the hydrolysis occurs at about 329 to 347 degrees Fahrenheit, under pressure. 13. The process of claim 11 wherein sodium hydroxide is added to the static mixer in a flowpath that is counter-current to the flow of hemicellulose. 14. The process of claim 12 wherein the stereoisomer separation is performed with co-polymer beads. 15. A system for obtaining monosaccharides, oligosaccharides and polysaccharides from biomass, comprising: a mechanism for substantially instantaneously pressurizing and de-pressurizing biomass to separate the biomass into hemicellulose, cellulose, and lignin; a heater for heating the hemicellulose to liquefy the hemicellulose; a reactor/mixer for mixing a sodium hydroxide with hemicellulose and for making hemicellulose hydrolysates; and a mechanism for selectively separating a hemicellulose hydrolysate based upon the component's stereoisomeric identity. 16. The system of claim 15 wherein a biomass comprises sugar beet pulp. 17. The system of claim 15 wherein the hemicellulose product does not enter a glassy state but is liquefied. 18. The system of claim 15 wherein the hemicellulose product is free of caramelized hemicellulose product. 19. The system of claim 15 wherein the sodium hydroxide is in the aqueous phase. 20. The system of claim 15 wherein the hemicellulose hydrolysates comprise d-arabinose, l-arabinose, d-xylose, l-xylose, d-glucose, l-glucose, and any other racemic carbohydrates. 21. The system of claim 15 wherein the hemicellulose hydrolysates comprise polygalacturonic acid. 22. The system of claim 15 wherein the hemicellulose hydrolysates comprise any backbone polymer. 23. The system of claim 15 and further comprising a mechanism which receives the hemicellulose hydrolysates. 24. The system of claim 15 wherein the hemicellulose hydrolysates are separated into optically pure products. 25. A process for extracting L-arabinose from sugar beet pulp, comprising: providing sugar beet pulp; subjecting the sugar beet pulp to substantially instantaneous pressurization and de-pressurization in a manner effective to separate lignin, hemicellulose and cellulose in the sugar beet pulp; hydrolyzing the hemicellulose to form hemicellulose hydrolysates; and separating L-arabinose from the hemicellulose hydrolysates using chromatography. 26. The process of claim 24 wherein the L-arabinose is produced at a rate of at least 1000 pounds per day. 27. The process of claim 1 and further comprising extracting derivatives and substituents from cellulose and lignin. 28. The process of claim 1 and further comprising crystallizing the separated product. 29. The process of claim 28 wherein the crystallizing is performed using a low intensity ultrasonic agitation.
7/10/00 12:00:00 AM
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2.1.24 Simulated Moving Bed Chromatography
SEPARATION PROCESS

A process of separating and recovering at least one product from a feed solution containing at least one product compound selected from sugars, sugar alcohols, sugar acids, organic acids and betaine, whereby the process is carried out in a chromatographic sequential simulated moving bed (SMB) system, which comprises a plurality of columns containing one or more partial packed beds, wherein the columns form one or more loops, comprising creating three successive separation profiles in the system by repeating a predetermined separation sequence, whereby said three successive separation profiles are simultaneously present in the system, and each separation profile comprises at least one product subprofile, a residual subprofile and optionally other subprofiles, moving said three separation profiles forward through the system by repeating the predetermined separation sequence, and recovering at least one product fraction enriched in one product compound from a column and also recovering at least one further fraction from one or more other columns of the system, whereby said at least one further fraction is a further product fraction enriched in the same product compound and/or a recycle fraction containing the same product compound. A process as claimed in claim 1, wherein said at least one product fraction enriched in one product compound and said at least one further fraction are recovered from one and the same separation profile during more than one separation sequences or from more than one separation profiles during one and the same separation sequence. A process as claimed in claim 1, wherein said at least one product fraction enriched in one product compound is recovered from the last column of the system. A process as claimed in claim 1, wherein said one or more other columns are selected from any upstream columns of the system in regard to the column from which said at least one product fraction is recovered. A process as claimed in claim 1, wherein said three separation profiles are present in a loop formed by all columns of the system. A process as claimed in claim 1, wherein said plurality of columns form three separate loops and a separation profile is simultaneously moved forward in each loop. A process as claimed in claim 1, wherein the process further comprises recovering one or more further fractions enriched in at least one further product compound. A process as claimed in claims 1 and 7, wherein said one product compound is a sugar selected from sucrose and said further product compound is betaine. A process as claimed in claim 8, wherein the process comprises recovering at least one sucrose fraction from a column and at least one further sucrose fraction from one or more other columns of the system and also recovering at least one betaine fraction from any columns of the system. A process as claimed in claim 1, wherein the sugar is xylose. A process as claimed in claim 10, wherein the process comprises recovering at least one xylose fraction from a column and also recovering at least one further xylose fraction and/or at least one recycle fraction containing xylose from one or more other columns of the system. A process as claimed in claim 1, wherein said feed solution is selected from sugar beet based solutions, preferably low green and molasses, and wood hydrolysates, preferably spent sulphite pulping liquor. A process as claimed in claim 1 for recovering sucrose and betaine from a sugar beet based solution in a chromatographic sequential simulated moving bed (SMB) system, which comprises a plurality of columns containing one or more partial packed beds, wherein the columns form one or more loops, comprising creating three successive separation profiles in the system by repeating a predetermined separation sequence, whereby said three successive separation profiles are simultaneously present in the system, and each separation profile comprises a sucrose subprofile, a betaine subprofile, a residual subprofile and optionally other subprofiles, moving said three separation profiles forward through the system by repeating the predetermined separation sequence, and recovering at least one sucrose fraction from a column and at least one further sucrose fraction from one or more other columns of the system and also recovering one or more betaine fractions from any columns of the system. A process as claimed in claim 13, wherein the sugar beet based solution is selected from low green, molasses, thick juice and raw juice. A process as claimed in claim 13, wherein the sucrose content of the sucrose fractions is more than 90%, preferably more than 92% and more preferably more than 94% on the dry substance (DS), and wherein the dry substance amount of said further sucrose fraction recovered is more than 10%, preferably more than 30% and more preferably more than 50%, based on the dry substance amount of the combined sucrose fractions recovered, wherein the process provides to combined sucrose fractions a sucrose yield of more than 90%, preferably more than 92% and more preferably more than 94% based on the sucrose of the feed solution, wherein the betaine content of the betaine fractions is more than 35%, preferably more than 45% and more preferably more than 55% on DS and wherein the yield of betaine to the betaine fraction(s) is more than 85%, preferably more than 92% and more preferably more than 94%. A process as claimed in claim 1 for recovering xylose from a plant-based hydrolysate in a chromatographic sequential simulated moving bed system, which comprises a plurality of columns containing one or more partial packed beds, wherein the columns form one or more loops, comprising creating three successive separation profiles in the system by repeating a predetermined separation sequence, whereby said three successive separation profiles are simultaneously present in the system, and each separation profile comprises a xylose subprofile, a residual subprofile and optionally other subprofiles, moving said three separation profiles forward through the system by repeating the predetermined separation sequence, and recovering at least one xylose fraction from a column and also recovering at least one further xylose fraction and/or at least one recycle fraction containing xylose from one or more other columns of the system. A process as claimed in claim 16, wherein the plant-based hydrolysate is a hemicellulose hydrolysate, preferably spent sulphite pulping liquor. A process as claimed in claim 16, wherein the xylose content of the xylose fraction(s) is more than 45%, preferably more than 50% and more preferably more than 55% on DS, and wherein the process provides a xylose yield of more than 85%, preferably more than 90% and more preferably more than 93% on the xylose of the feed solution. A process as claimed in claim 1, wherein the process further comprises introducing one or more parts of said three separation profiles back to one or more eluent introduction positions of the system to substitute a portion of the eluent, wherein said parts comprise components selected from product compounds and residual components.
3/29/11 12:00:00 AM
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2.2 Centrifugal partition chromatograohy (CPC)

0

Centrifugal partition chromatography is a special chromatographic technique where both stationary and mobile phase are liquid, and the stationary phase is immobilized by a strong centrifugal force. Centrifugal partition chromatography consists of a series-connected network of extraction cells, which operates as elemental extractors, and the efficiency is guaranteed by the cascade. [\[Wiki\]](https://en.wikipedia.org/wiki/Centrifugal_partition_chromatography) The lack of a solid stationary phase, simplicity of complete column regeneration and no irreversible adsorption, makes CPC an interesting technology for the separation of crude process streams with little pretreatment, potentially capable of removing impurities and isolating multiple target compounds in a single step. **Process description:** CPC was used to separate Arabinose, Galacturonic acid, Rhamnose and Galactose from a pectin hydrolysate. The two-phase system used throughout this work was ethanol: aqueous ammonium sulphate (300 g L−1) (0.8:1.8 v:v). Then, the soluble sugar beet pectin was fully hydrolysed with 2.5% (v/v) sulphuric acid, heated to 121 °C for 1 h in an autoclave and then adjusted to pH 6 with NaOH. The crude material contained a total dissolved solids content of ∼100 g L−1 with a total sugars concentration of ∼20 g L−1. Crude samples were prepared for CPC by using the crude hydrolysate as the water proportion of the lower phase and adding appropriate amounts of ammonium sulphate (332 g L−1) and ethanol (13% v/v). Samples were filtered through a 0.45 μm filter prior to injection. CPC separations were performed on a Kromaton FCPC-A on a semi-preparative and a preparative column with experimentally determined total volumes of 250 mL and 950 mL respectively. Both columns feature a twin-cell design with 840 cells on the semi-preparative column and 800 cells on the preparative column. A puriFlash 450 (Interchim, Montluçon, France) system was attached to the CPC providing a flow controller, pump, injection valve and fraction collector. The throughput for the scaled up system was 9.4 g L−1 h−1 total solids. Three fractions were separated: Rhamnose, arabinose and galactose, and galacturonic acid. Purities and recoveries were around 90%. [#ARTNUM](#article-25568-1061727677)

2.2.1 Centrifugal partition chromatograohy (CPC)
Building a Synthetic Pathway For Nylon precursor Biosynthesis
Biorefineries allow for the sustainable production of higher value products from biomass. In addition to bioethanol, they can produce added value chemicals and pharmaceutical intermediates from isolated component compounds such as sugars. Sugar beet pulp (SBP) is a high volume, low value by-product from sugar beet processing with a low lignin and a high carbohydrate content, making it an attractive biomass feedstock for biorefinery processing. The pectin fraction of SBP can be isolated via steam explosion, which, after complete acid hydrolysis, gives a hydrolysate rich in monosaccharides: primarily L-arabinose (Ara) and D-galacturonic acid (GA), with some D-galactose (Gal) and L-rhamnose (Rha). Isolation of these sugars is therefore a critical step in realising an integrated, whole crop biorefinery. Currently, little work has been reported on the separation and utilisation of SBP hydrolysates. The aim of this thesis is to establish novel, scalable separation processes for the isolation of the component monosaccharides from crude hydrolysed sugar beet pulp pectin. Centrifugal partition chromatography (CPC) is a liquid-liquid separation technique with no solid stationary phase and offers an alternative to traditional resin-based chromatographic techniques. As such it can more easily cope with crude feedstreams such as hydrolysates. Hydrophilic ethanol : ammonium sulphate two-phase systems were examined based on monosaccharide partition coefficients and phase settling times. An ethanol : aqueous ammonium sulphate (300 g L-1 ) (0.8:1.8 v:v) system was chosen for CPC separations of the crude SBP hydrolysate and was shown to be capable of removing the coloured contaminants and isolating three sugar fractions in a single step: Rha, Ara and Gal, and GA. The separation was optimised and the throughput was increased by maximising the sample loading. Operation in an elution-extrusion mode allowed for reproducible separations in 100 min without additional column regeneration. The process was scaled up from a 250 to a 950 mL column providing a final throughput of 1.9 gmonosaccharides L -1 column h -1 using the crude SBP. The following purities and recoveries of the three main fractions were achieved: Rha at 92% purity and 93% recovery; Ara at 84% purity and 97% recovery; and GA at 96% purity and 95% recovery. Simulated moving bed (SMB) allows for continuous chromatographic separations using multiple columns, improving separation performance and throughputs. Isolation of Ara from the neutral sugars Gal and Rha was performed with resins and conditions screened on single columns leading to the selection of a Dowex 50W X8 resin in the Ca2+ form. SMB separation using 8 columns was performed in the 4-zone and 3-zone setups and achieved 94% purity with 99% recovery at a throughput of 4.6 gmonosaccharides L -1 column h -1 with a synthetic mixture of the neutral sugars (Ara, Gal and Rha). However, equivalent separations could not be achieved using the crude SBP hydrolysate which needed pretreatment before SMB. Decolourisation with activated carbon was able to remove 97% of the coloured contaminants with sugar losses of 15% (w/w) in a batch process demonstrated to 50 mL scale. Anion exchange chromatography using a Dowex 1x8 resin was then found to be capable of isolating GA from a synthetic crude mixture of GA and neutral sugars with a dynamic binding capacity of 1.31 mmol mL-1 resin. However, further work is needed to enable this anion exchange step to achieve satisfactory separations with the decolourised crude hydrolysate. The isolated neutral sugars, after GA removal, can be processed on the SMB with comparable separation performance and throughput to a mixture of neutral sugars prepared without GA. In summary, this thesis presents two possible process paths each with their own benefits and drawbacks. CPC is capable of processing the crude SBP hydrolysate directly, isolating the sugars and removing the coloured contaminants in a single step. However, Ara co-elutes with Gal providing a stream that is only 84% pure. In SMB, the potential throughputs and separation performance are higher, however, this could only be experimentally demonstrated with synthetic crude mixtures of sugars and not with the crude SBP hydrolysate. Further pretreatment or SMB method development would be required in order to process the crude hydrolysate, and the resulting multistep processes may reduce the overall viability. Overall this thesis demonstrates two feasible approaches to the preparative scale separation of SBP pectin hydrolysates and supports development of an integrated SBP biorefinery.
10/28/18 12:00:00 AM
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2.2.2 Centrifugal partition chromatograohy (CPC)
Centrifugal partition chromatography in a biorefinery context: Optimisation and scale-up of monosaccharide fractionation from hydrolysed sugar beet pulp
The authors would like to thank the UK Engineering and Physical Sciences Research Council (EPSRC) for financial support of this work (EP/K014897/1) as part of their Sustainable Chemical Feedstocks programme. Input and advice from the project Industrial Advisory Board is also acknowledged. DPW would also like to thank the EPSRC for the award of a Ph.D. studentship.
5/1/17 12:00:00 AM
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2.2.3 Centrifugal partition chromatograohy (CPC)
Centrifugal partition chromatography in a biorefinery context: separation of monosaccharides from hydrolysed sugar beet pulp.
A critical step in the bioprocessing of sustainable biomass feedstocks, such as sugar beet pulp (SBP), is the isolation of the component sugars from the hydrolysed polysaccharides. This facilitates their subsequent conversion into higher value chemicals and pharmaceutical intermediates. Separation methodologies such as centrifugal partition chromatography (CPC) offer an alternative to traditional resin-based chromatographic techniques for multicomponent sugar separations. Highly polar two-phase systems containing ethanol and aqueous ammonium sulphate are examined here for the separation of monosaccharides present in hydrolysed SBP pectin: l-rhamnose, l-arabinose, d-galactose and d-galacturonic acid. Dimethyl sulfoxide (DMSO) was selected as an effective phase system modifier improving monosaccharide separation. The best phase system identified was ethanol:DMSO:aqueous ammonium sulphate (300gL(-1)) (0.8:0.1:1.8, v:v:v) which enabled separation of the SBP monosaccharides by CPC (200mL column) in ascending mode (upper phase as mobile phase) with a mobile phase flow rate of 8mLmin(-1). A mixture containing all four monosaccharides (1.08g total sugars) in the proportions found in hydrolysed SBP was separated into three main fractions; a pure l-rhamnose fraction (>90%), a mixed l-arabinose/d-galactose fraction and a pure d-galacturonic acid fraction (>90%). The separation took less than 2h demonstrating that CPC is a promising technique for the separation of these sugars with potential for application within an integrated, whole crop biorefinery.
9/1/15 12:00:00 AM
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2.2.4 Centrifugal partition chromatograohy (CPC)
Using Centrifugal Partition Chromatography to Separate Xylose from Glucose: SOP Development
Efficient methods of extracting natural compounds from their native source are essential to the medical, biological, and food industries. Xylose and glucose are two major sugars used in a variety of food, bioenergy, and environmental industries and are found in hemicellulose, a compound present in all biomass. The aim of this project was to generate protocols for an effective separation of xylose from glucose using centrifugal partition chromatography (CPC). CPC, commonly used for the separation of natural products, operates on the combined concepts of rotary motion and biphasic liquid separation. It is preferred to other chromatographic techniques for natural product recovery because the liquid stationary phase allows for complete recovery of compounds as compared to conventional chromatography using a solid stationary phase. Our specific goal was to develop standard operating procedures (SOPs) to separate xylose from glucose. The two liquid phases present in the CPC rotor—generally termed the solvent-system—separate compounds depending on their affinity for each liquid phase. The suitability of a solvent-system is based on two different chromatography measures, partition coefficient (K) and separation factor (α), which were determined using the shake-flask method. We tested three solvent-systems mixed in various ratios: butanol-ethanolwater (BEW), butanol-ethyl acetate-water (BEAW), and hexane-ethyl acetate-methanol-water (HEMWat). The concentration of each compound in each phase of the three solvent-systems was determined using high performance liquid chromatography (HPLC). The BEW system, mixed in a 3:1:4 ratio by volume, was chosen as most appropriate as it produced K and α values within acceptable ranges. This solvent-system was then used in the CPC to purify xylose from glucose. Protocols based on these findings were documented and will be helpful to add proficiency in creating bioproducts in future.
1/1/13 12:00:00 AM
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3. Filtration

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Filtration is any of various mechanical, physical or biological operations that separates solids from fluids (liquids or gases) by adding a medium through which only the fluid can pass. The fluid that passes through is called the filtrate.


3.1 Ultrafiltration

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Ultrafiltration (UF) is a variety of membrane filtration in which forces like pressure or concentration gradients lead to a separation through a semipermeable membrane. Suspended solids and solutes of high molecular weight are retained in the so-called retentate, while water and low molecular weight solutes pass through the membrane in the permeate (filtrate). This separation process is used in industry and research for purifying and concentrating macromolecular (103 - 106 Da) solutions, especially protein solutions. [\[Wiki\]](https://en.wikipedia.org/wiki/Ultrafiltration) Ultrafiltration can be used in multiple steps in the process. It has been applied for final separation of sugars, Art. [#ARTNUM](#article-25546-2878215405); [#ARTNUM](#article-25546-2371418284), but more commonly it is applied as pretreatment, Art. [#ARTNUM](#article-25546-2535941283). **Process**: Micellar enhanced ultrafiltration: All experiments were performed in a temperature-controlled dead end ultrafiltration cell. The transmembrane pressure in the filtration cell was adjusted to 4.5 bar with nitrogen. The solution was stirred during the filtration process to avoid concentration polarization. Membranes (Millipore, YM-10, regenerated cellulose) with a molecular weight cut off of 10 kDa were used. The filtration of the mono- and disaccharides (arabinose, cellobiose, glucose, sucrose) was carried out using different surfactants and phenylboronic acid. The pH values in the solution were adjusted to pH = 11 with 1 mol/L KOH. The two cationic surfactants used within this work are CTAB and Aliquat 336TM. While CTAB was used in a system of purely cationic surfactant (0.2 wt%), Aliquat 336TM (0.75 wt%) was used in combination with the non-ionic surfactant Triton X-100TM (5 wt%) and the anionic surfactant SDS (5 wt%), respectively. Thus, it can be assumed that the surfactant in solution is mainly present in micellar form. The aqueous surfactant/sugar/carrier mixture was incubated prior to filtration in a temperature-controlled shaker (Grant OLS 200) at 25 °C. The membrane was regenerated with ethanol and deionized water after each filtration run. Monosaccharides were recovered efficiently and with high selectivity (up to 64%). Art. [#ARTNUM](#article-25546-2070996945) **Findings:** * The invention discloses a method for preparing xylose functional sugar from hemicellulose polysaccharide in hydrolyzed agricultural waste, and belongs to the field of xylose. Membrane separation with an ultrafiltration membrane is performed to obtain a xylose product, and concentrating and drying the xylose product. Through the method, redundant byproducts are removed through hydrolysis in order to obtain xylose with the purity being 90-95%. Art. [#ARTNUM](#article-25546-2878215405) * In the current industry,the xylose is manufactured by corncobs through hydrolysis, neutralization, two decoloring steps with activated carbon, two ion-exchange treatments and some other steps. But the process is costly and complex. In this paper,ultrafiltration was introduced into the production process of xylose. The result showed the ultrafiltration treatment can cut down impurity and purify the xylose solution. In the ultrafiltration, gas sparging was used to deal with problems such as concentration polarization and membrane fouling. Art.[#ARTNUM](#article-25546-2371418284)

3.1.1 Ultrafiltration
Application of Gas Sparging to the Production Process of Xylose by Ultrafiltration
In the current industry,the xylose is manufactured by corncobs through hydrolysis,neutralization,twice decoloring with activated carbon,twice ion-exchange treatments and some other steps.But the process is costly and complex.In this paper,ultrafiltration was introduced into the production process of xylose.The effect on ultrafiltration treatment was analyzed,such as trans-membrane pressure,fluid flux,and temperature.The result showed the ultrafiltration treatment can cut down impurity and purify the xylose solution.In the ultrafiltration, gas sparging was used to deal with the tricky problems such as concentration polarization and membrane fouling.Lots of tests proved ultrafiltration can replace one decoloring with activated carbon,simplify the process,and can be applied to the production of xylose.
1/1/07 12:00:00 AM
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3.1.2 Ultrafiltration
Method for preparing xylose functional sugar from hemicellulose polysaccharide in hydrolyzed agricultural waste
The invention discloses a method for preparing xylose functional sugar from hemicellulose polysaccharide in hydrolyzed agricultural waste, and belongs to the field of xylose. The method comprises: selecting wheat straw, performing processes such as drying, pulverizing, and alkaline extraction to obtain coarse hemicellulose polysaccharide, performing purification to obtain pure hemicellulose polysaccharide, adding a cellulase degradation agent and an ethanol solution into pure hemicellulose polysaccharide for ultrasonic degradation, concentrating the obtained degraded liquid through pressurization, performing membrane separation with an ultrafiltration membrane to obtain a xylose product, and concentrating and drying the xylose product. Through the method, redundant by-products are removed through hydrolysis in order to obtain xylose with the purity being 90-95%. The prepared xylose can be added into food and is wide in application. The enzyme and un-degraded xylan in a xylooligosaccharide liquid are removed through the ultrafiltration membrane, so that loss of xylose is reduced. The method is abundant in preparation resources and low in cost.
6/8/16 12:00:00 AM
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3.1.3 Ultrafiltration
Purification of pentoses from hemicellulosic hydrolysates without neutralization for sulfuric acid recovery
Abstract The agro-industrial sector generates large amounts of coproducts such as lignocellulosic biomass which could be valorized into many chemicals and bio-based intermediates (sugars, paper pulp, surfactants, polymers or bioethanol). However, in the case of biomass hydrolysis by diluted sulfuric acid, current downstream processes involve a partial or complete neutralization which are not satisfactory for economic and environmental reasons. This work presents a purification process of pentoses from hemicellulosic hydrolysates without neutralization for sulfuric acid recovery. Compared to conventional processes, less energy, water and chemicals are required. Very promising results were obtained at pilot scale with 100 L of wheat bran hydrolysates. The process is based on the combination of ultrafiltration, conventional electrodialysis and ion-exchange. Ultrafiltration with a 10 kDa organic membrane totally removed harmful macromolecules which precipitate during electrodialysis operation because of pH rise. Till a volumetric concentration factor 3.6, the average flux kept good for industrial application (27 L·h −1 ·m −2 ). However suspended materials have to be filtered before ultrafiltration. Besides, a 2.5 diafiltration is required to recover most of sugars (99%). Then conventional electrodialysis was performed to recover most of sulfuric acid (80%). The average faradic yield was quite good (80%) and the specific energy consumption of the electrodialysis stack was quite interesting (1.1 kW h per kg of H 2 SO 4 recovered and 8.4 kW h per m 3 of hydrolysate). Finally, the complete demineralization (conductivity  −1 ) and discoloration (420 nm absorbance
3/1/17 12:00:00 AM
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3.1.4 Ultrafiltration
Recovery of sugars from aqueous solution by micellar enhanced ultrafiltration
Abstract The separation of hydrophilic substances, like sugars, from aqueous solutions is still a huge challenge. Within this work the extraction of sugars with micellar systems was performed by means of the micellar enhanced ultrafiltration (MEUF) and compared to the state of the art extraction based on organic solvents. Phenylboronic acid was used as carrier to solubilize sugars (arabinose, cellobiose, glucose, and sucrose) in different kind of micelles (formed by the cationic surfactant CTAB and the non-ionic/cationic surfactant mixture Triton X-100™/Aliquat 336™). It was shown that the partition coefficients of the sugars in micellar systems are higher than those achieved with organic solvents, especially using the cationic surfactant. Monosaccharides were recovered efficiently and with a high selectivity (up to 64% for the monosaccharides compared to 17% for the disaccharides). It was shown, that the recovery can be enhanced with increasing cationic surfactant content. Furthermore the equilibration time can be reduced significantly compared to the extraction with organic solvents. Thus, micellar enhanced ultrafiltration is a promising method for the recovery of sugars and other hydrophilic components from aqueous streams without any use of organic solvents.
8/1/12 12:00:00 AM
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3.1.5 Ultrafiltration
Separation of sugarcane bagasse mild alkaline extract components by ultrafiltration – Membrane screening and effect of filtration parameters
Abstract Mild alkaline treatment (1.5% NaOH (w/v), solid:liquid ratio of 1:20, 60 °C, 6 h) of sugarcane bagasse (SCB) produced an extract composed of hemicelluloses, lignin, phenolic monomers and acetic acid. The purification of this extract, usually considered a by-product in lignocellulosic biorefineries, is of major importance to give value to the whole mild alkaline fractionation process. Ultrafiltration was assessed to separate the components of the SCB alkaline extract which is a prerequisite for their further valorization. The permeate flux and the retention of the extract components were studied on seven membranes (polysulfone hollow fiber and ceramic tubular) with different molecular weight cut-offs, under various operating conditions. On all the membranes tested, oligomers of lignin and hemicelluloses were separated from salts, phenolic monomers and acetic acid. The 10 kDa polysulfone hollow fiber membrane presented the highest lignin and hemicelluloses retention, exceeding 85 and 90%, respectively, regardless of shear rate and with a limited influence of transmembrane pressure. For salts, acetic acid and phenolic monomers, retention levels of about 0–10% were recorded for this membrane. At 2.8 bar and at 20 °C, the permeate flux reached 16 L/h/m 2 and the critical flux was not reached.
3/1/19 12:00:00 AM
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3.2 Thin Film Composite Nanofiltration

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Thin-film composite membranes (TFC or TFM) are semipermeable membranes manufactured principally for use in water purification or water desalination systems. They also have use in chemical applications such as batteries and fuel cells. A TFC membrane can be considered as a molecular sieve constructed in the form of a film from two or more layered materials. TFC membranes are commonly classified as nanofiltration (NF) and reverse osmosis (RO) membranes. Both types are typically made out of a thin polyamide layer (<200 nm) deposited on top of a polyethersulfone or polysulfone porous layer (about 50 microns) on top of a non-woven fabric support sheet. The three layer configuration gives the desired properties of high rejection of undesired materials (like salts), high filtration rate, and good mechanical strength. The polyamide top layer is responsible for the high rejection and is chosen primarily for its permeability to water and relative impermeability to various dissolved impurities including salt ions and other small, unfilterable molecules. [\[Wiki\]](https://en.wikipedia.org/wiki/Thin-film_composite_membrane) Thin film composite membranes have been researched mainly with regard to separation of xylose and glucose. There has been some research for use in biomass hydroysates. Research is mainly focussed on types of membranes and membrane production and improving separation factors. **No research or processes have been developed with actual biomass hydrolysates, only pure components in water.** **Research findings:** * The aim of this study is to evaluate the ability of membrane developed by interfacial polymerization reaction between triethanolamine (TEOA) (6 % w/v) and trimesoyl chloride (TMC) (0.15 % w/v) as monomers on polyethersulfone (PES) microporous substrate to separate xylose from glucose. In this study, factors affecting the process, namely pressure, concentration of total sugars in solution, and composition of monosaccharides in total sugar, were investigated using twolevel factorial analysis. Overall from the present study, it can be concluded that nanofiltration has high potential to replace currently in use chromatographic method in xylose separation. Art. [#ARTNUM](#article-25562-2092236646) * One of the newest applications of the membrane technology is for the separation of sugar component and inhibitor removal during biomass processing in biorefinery. Most of the membranes used in biorefinery were commercially purchased and not specifically customise for the biomass hydrolysate processing. In the current study, a series of thin film composite (TFC) hollow fiber membranes were fabricated to tailor the performance toward xylose/glucose refinement and acetic acid removal in biomass processing. Polysulfone (PSf) hollow fiber membrane support was prepared using 20wt% PSf, 2wt% Polyvinylpyrrolidone K30(PVP K30) and 78wt% dimethylformamide (DMF) through dry/wet spinning process. Three types of aqueous monomers were studied in interfacial polymerization process, which are piperazine (PIP), triethanolamine (TEOA) and polyethyleneimine (PEI). TFC hollow fiber membrane prepared using TEOA monomer showed the best performance for separation of biomass hydrolysate component. It exhibited rejection value 50.98% of xylose, 71.72% of glucose and 5.45% of acetic acid. Art. [#ARTNUM](#article-25562-2623952816)

3.2.1 Thin Film Composite Nanofiltration
Effects of polyethersulfone membrane substrate on the separation performance of thin film composite membrane in biorefinery
This study was aimed to develop a customised thin film composite (TFC) membrane for the separation in biorefinery. After the biomass hydrolysis stage, sugars component (i.e. glucose and xylose) need further refinement to remove any inhibitor (i.e. acetic acid) that can decrease the yield of the product during the fermentation stage. Substrate layer properties and the condition of thin film formation during interfacial polymerisation (IP) influenced the performance of the TFC membrane. Not much attention is given on the effects of substrate membrane properties asmost support membranes were purchased commercially. Polyethersulfone (PES) membrane substrate was fabricated in the current study at different PES concentration range of 15 wt% to 23 wt%. IP was performed using the piperazine and trimesoyl chloride monomers. As the PES concentration in the membrane substrate increased, the pure water permeability (PWP) decreased. The PWP of the membrane substrate prepared from 15 % PES and 23 % PES were 231.67 ± 16.59 L/m2.h.bar and 24.49 ± 6.54 L/m2.h.bar. After the IP, the PWP decreased to the range of nanofiltration. The PWP value were 28.07 ± 5.42 L/m2.h.bar and 3.94 ± 1.21 L/m2.h.bar for the TFC membrane prepared using 15 % PES and 23 % PES membrane support. TFC membrane prepared using 23 % PES showed the rejection value 24.07 ± 5.96 % of xylose, 47.56 ± 1.99 % of glucose and 2.67 ± 1.05 % of acetic acid. This is corresponding to the ideal separation factor of 1.45 ± 0.06 for xylose/glucose, 1.86 ± 0.05 for acetic acid/glucose and 1.29 ± 0.09 for acetic acid/xylose.
1/1/17 12:00:00 AM
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3.2.2 Thin Film Composite Nanofiltration
Lipid Pore-Filled Silica Thin-Film Membranes for Biomimetic Recovery of Dilute Carbohydrates
Selectively permeable biological membranes containing lipophilic barriers inspire the design of biomimetic carrier-mediated membranes for aqueous solute separation. The recovery of glucose, which can reversibly bind to boronic acid (BA) carriers, is examined in lipid pore-filled silica thin-film composite membranes with accessible mesopores. The successful incorporation of lipids (1,2-dipalmitoyl-sn-glycero-3-phosphocholine, DPPC) and BA carriers (4-((N-Boc-amino)methyl)phenylboronic acid, BAMP-BA) in the pores of mesoporous silica (∼10 nm pore diameter) through evaporation deposition is verified by confocal microscopy and differential scanning calorimetry. In the absence of BA carriers, lipids confined inside the pores of silica thin films (∼200 nm thick) provide a factor of 14 increase in diffusive transport resistance to glucose, relative to traditional supported lipid bilayers formed by vesicle fusion on the porous surface. The addition of lipid-immobilized BAMP-BA (59 mol % in DPPC) facilitates the t...
12/12/17 12:00:00 AM
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3.2.3 Thin Film Composite Nanofiltration
Optimisation of interfacial polymerization factors in thin-film composite (TFC) polyester nanofiltration (NF) membrane for separation of xylose from glucose
Abstract A tailored thin-film composite (TFC) NF membrane may offer alternative separation technique to widely used chromatographic techniques in separating two monosaccharides with similar properties. The aim of this paper is to pinpoint the optimum condition in preparing TFC membranes with the highest xylose separation factor. To achieve this, curing time, curing temperature, and reaction time were optimised using central composite design (CCD). Polyethersulfone (PES) was used as a support membrane for interfacial polymerisation (IP) of two active monomers, namely triethanolamine (TEOA) and trimesoyl chloride (TMC). The xylose separation factor was chosen as the response for this study. In addition, occurrence of IP reaction was verified by visual interpretation using field emission scanning electron microscope (FESEM). The chemical elements in TFC membrane and its functional groups were determined using FESEM equipped with energy dispersive X-ray and Attenuated total reflectance–Fourier transform infrared (ATR-FTIR), respectively and compared to the initial PES membrane. A quadratic model was developed and tested with analysis of variance (ANOVA). The model was used to simulate and locate the optimum point. The optimum point was within the studied region and validation tests were conducted to confirm this point. The tests showed little error of less than 2% from the predicted optimal points. The optimum IP conditions for xylose separation were 45.25 min, 15.53 min, and 58.4 °C for reaction time, curing time, and curing temperature, respectively. Under these optimum conditions, a maximum xylose separation factor of 1.334 ± 0.007 was achieved. The optimised TFC membrane exhibited comparable xylose separation factor to commercial membranes.
1/1/19 12:00:00 AM
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3.2.4 Thin Film Composite Nanofiltration
Optimization of interfacial polymerization thin film composite membrane for separation of xylose from glucose
Most hydrolysis studies on biomass in Malaysia produce high amount of xylose and glucose compared to other monosaccharides. These monosaccharides are important ingredients often needed in pure fraction in food and pharmaceutical industries. Chromatography and commercial nanofiltration membrane were able to separate xylose from glucose. However, few treatment steps on biomass hydrolysate were needed because most biomass hydrolysate are acidic. Acidity reduces the performance of these separation technology by inhibiting chromatography resins and fouling of membrane. Thin film composite membrane developed via interfacial polymerization using triethanolamine and trimesoyl chloride as monomers allows separation at low pH to occur without damaging its performance. Currently, almost none has attempted to separate xylose from glucose using self-made thin-film composite membrane that is specially tailored for biomass hydrolysate. The aim of this present study was to produce optimized thin-film composite nanofiltration membrane for separation of xylose from glucose using triethanolamine and trimesoyl chloride as monomers on polyethersulfone membrane via interfacial polymerization using a series of experimental design. Success of thin layer formation was probed by attenuated total reflectance-Fourier transform infrared spectroscopy, and prepared membranes were characterized by field emission scanning electron microscope, contact angle and pure water permeability. Separation performance of thin-film composite membranes are affected by several factors during formation of thin upper layer. Series of experimental designs were applied to screen and optimize the different interfacial polymerization factors studied. In screening, 25-1 fractional factorial design were used to find significant factors affecting xylose separation factor, which are reaction time and curing process. Also, the responses in screening were fitted with a multiple linear regression equation and obtained a high correlation (R2 = 0.9998) between the experimental data and model data. Then central composite design was used to identify the optimum interfacial polymerization conditions for the highest xylose separation factor. The response was fitted with the second-order polynomial equation with R2 of 0.92, implying a high correlation between the observed and predicted values. The optimum interfacial polymerization conditions were determined to be reaction time of 45.25 minutes, curing time of 15.53 minutes, and curing temperature of 58.4 ℃. At optimum conditions, the xylose separation factor was found to be 1.334 ±0.007. The developed model in this study is adequate for predicting xylose separation factor under different interfacial polymerization conditions within the range used. This study will provide valuable guideline to develop membrane that specially tailored for xylose separation from glucose as alternative to the cost intensive chromatographic processes in use.
4/1/16 12:00:00 AM
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3.2.5 Thin Film Composite Nanofiltration
Separation Of Xylose From Glucose Using Thinfilm Composite Membrane: A Study On Separation Performance And Fouling Properties
Separation of xylose from xylose-glucose solution using polyester thin-film composite (TFC) membrane was investigated using fractional factorial design with manipulation of interfacial polymerization (IP) factors between triethanoamine (TEOA) and trimesoyl chloride (TMC). In previous study, the relation between xylose separation factor and all affecting factors were developed in a model. In this present study, a new TFC membrane were produced from this model by the reaction between 4 % (w/v) TEOA concentration, 0.25 % (w/v) TMC concentration, reaction time of 44.85 minutes, pH 8, and curing at 60 ℃ for 30 minutes. Evaluation on the performance of TFC membrane shows that the xylose separation factor obtained in the study was 1.686, which has an error of 4.27 % compared to the predicted value. Membrane fouling has been studied for a course of 6 hours where the normalized relative flux (NRF) was at 16.61 (±3.53) %. From this value, irreversible fouling resulted in 11.02 (±5.60) % which might due to internal pore blockage of glucose and xylose. In contrast, reversible fouling of 5.59 % can be obtained back after cleaning with ultrapure water.
1/1/15 12:00:00 AM
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3.2.6 Thin Film Composite Nanofiltration
Separation of Xylose From Glucose Using Thin Film Composite (TFC) Nanofiltration Membrane: Effect of Pressure, Total Sugar Concentration and Xylose/Glucose Ratio
Xylose is an abundant raw material coexists with other sugars that can be turned into useful products, such as ethanol, xylitol and 2, 3-butanediol by microorganism such as yeasts, bacteria, and mycelial fungi. However, more than 80 % of the production cost of these products comes solely from the production of xylose. Presently, the separation of xylose from hemicellulose hydrolysate relies on chromatographic separation alone. The use of nanofiltration membrane may offer alternative in recovering xylose due to the differences in size compared to other sugars. The aim of this study is to evaluate the ability of membrane developed by interfacial polymerization reaction between triethanolamine (TEOA) (6 % w/v) and tri-mesoyl chloride (TMC) (0.15 % w/v) as monomers on polyethersulfone (PES) microporous substrate to separate xylose from glucose. In this study, factors affecting the process, namely pressure, concentration of total sugars in solution, and composition of monosaccharides in total sugar, were investigated using two-level factorial analysis. The experiment was performed using Amicon Milipore stirred cell (Model 8200) with constant stirring speed at 300 rpm and temperature at ambient. The glucose and xylose concentration was quantified using high performance liquid chromatography (HPLC). It is found that the developed nanofiltration membrane has the ability to separate xylose from glucose.The analysis of the experimental response revealed that the total sugar concentration and composition ratio of xylose: glucose had significant interactive effect on xylose separation factor. Overall from the present study, it can be concluded that nanofiltration has high potential to replace currently in use chromatographic method in xylose separation.
8/27/14 12:00:00 AM
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3.2.7 Thin Film Composite Nanofiltration
Separation of xylose using a thin-film composite nanofiltration membrane: screening of interfacial polymerization factors
Most hydrolysis studies on biomass produce a high amount of xylose and glucose compared to other monosaccharides. A specially tailored thin-film composite (TFC) membrane prepared via interfacial polymerization (IP) using triethanolamine (TEOA) and trimesoyl chloride (TMC) as monomers on a polyethersulfone (PES) membrane was used to separate xylose from glucose. Differences between the support (PES) and TFC membrane in surface chemistry were probed using attenuated total reflectance-Fourier transform infrared (ATR-FTIR) spectroscopy and contact angle. Both membranes were also characterized by field emission scanning electron microscopy (FESEM) and pure water permeability to observe changes to membrane morphology and properties. The performance of the TFC membrane is highly stimulated by variation of preparative factors in IP. This study screens and reports the effect of five preparative factors, namely monomer concentrations (TEOA and TMC), pH of the aqueous phase, reaction time, and curing toward the performance of xylose separation from glucose. A 25−1 fractional factorial design was used to narrow down significant preparative factors, saving lots of time and resources. It was found that curing and reaction time significantly affected the separation of xylose from glucose. High correlation (R2 = 0.9998) between the experimental data and model data was obtained. The developed model in this study is adequate for predicting the xylose separation factor under different IP conditions within the range used. This study will provide valuable guidelines to develop membranes that are specially tailored for xylose separation from glucose as an alternative to the cost intensive chromatographic processes in use.
1/1/16 12:00:00 AM
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3.2.8 Thin Film Composite Nanofiltration
Synthesis and characterization of polyester thin film composite membrane via interfacial polymerization: Fouling behaviour of uncharged solute
Most hydrolysis studies on biomass in Malaysia produce high amount of xylose and glucose compared to other monosaccharides and most of them are acidic. Thin film composite (TFC) membrane developed via interfacial polymerization using triethanolamine (TEOA) and trimesoyl chloride (TMC) as monomers allows separation at low pH to occur without damaging its performance. Comparative studies were carried out on membranes with and without the thin film layer formed via interfacial polymerization on the polyethersulfone (PES) support. The surfaces of the membranes were characterized by field emission scanning electronic microscopy (FESEM), attenuated total reflectance Fourier transform infrared (ATR-FTIR) spectroscopy, and hydrophilicity via contact angle measurement. In addition, the performance and uncharged solute fouling behaviour of TFC membrane were also investigated. The TFC membrane used for characterization purposes was prepared at TEOA concentration of 4 % w/v in 1 × 10-6 M sodium hydroxide solution, TMC concentration of 0.25 % w/v in pure hexane, reaction time of 45 minutes, and cured at temperature of 60 °C. Characterization results showed a huge different between the synthesized TFC membrane and the un-synthesized PES membrane in term of surface properties and morphology. Nanofiltration results indicate that the formation of thin layer on top of PES support membrane improved the separation performance compared to PES support membrane. The synthesised polyester TFC membrane have irreversible fouling of 11.02 (±5.60) % and reversible fouling of 5.59 % using water as cleaning agent.
11/1/16 12:00:00 AM
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3.2.9 Thin Film Composite Nanofiltration
Synthesis of Nanofiltration Membrane Developed from Different Concentration of Triethanolamine (TEOA) for Separation of Xylose from Glucose
Synthesis of thin film composite (TFC) nanofiltration membrane has experienced tremendous development since the concept of interfacial polymerization (IP) was first introduced. One of it new application is on the separation of xylose from glucose in biomass hydrolysate. In this present study, thin film composite (TFC) nanofiltration (NF) membrane has been produced through interfacial polymerization by manipulation the concentration of triethanolamine (TEOA) at different reaction time with 0.15 % w/v. of trimesoyl chloride (TMC). The membrane was then characterized in term of their chemical and physical properties, and separation performance between xylose and glucose. The growth of thin layer film depends on concentration of the monomer (TEOA) and reaction time. It was found that as concentration of TEOA and reaction time increased, the layer of the TFC become thicker thus decreases the permeability of the membrane. In contrast, the lowest and the highest permeability were recorded at 4% w/v of TEOA and 8% w/v of TEOA at reaction time of 35-minute in TMC, respectively. Moreover, higher sugar rejection of 0.896 % was obtained at 4% w/v TEOA after 35-minute reaction in TMC.
1/1/15 12:00:00 AM
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3.2.10 Thin Film Composite Nanofiltration
Thin Film Composite Hollow Fiber Membrane for Separation in Biorefinery
One of the newest applications of the membrane technology is for the separation of sugar component and inhibitor removal during biomass processing in biorefinery. Most of the membranes used in biorefinery were commercially purchased and not specifically customise for the biomass hydrolysate processing. In the current study, a series of thin film composite (TFC) hollow fiber membranes were fabricated to tailor the performance toward xylose/glucose refinement and acetic acid removal in biomass processing. Polysulfone (PSf) hollow fiber membrane support was prepared using 20wt% PSf, 2wt% Polyvinylpyrrolidone K30(PVP K30) and 78wt% dimethylformamide (DMF) through dry/wet spinning process. Three types of aqueous monomers were studied in interfacial polymerization process, which are piperazine (PIP), triethanolamine (TEOA) and polyethyleneimine (PEI). TFC hollow fiber membrane prepared using TEOA monomer showed the best performance for separation of biomass hydrolysate component. It exhibited rejection value 50.98  4.11 % of xylose, 71.72  3.92 % of glucose and 5.45  1.93 % of acetic acid. This is corresponding to the ideal separation factor of 1.75  0.10 for xylose/glucose, 3.42  0.54 for acetic acid/glucose and 1.95  0.20 for acetic acid/xylose.
1/1/17 12:00:00 AM
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3.3 Hollow Fiber Nanofiltration

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Nanofiltration membranes could offer a relatively cost-competitive separation step, less complex and easier to maintain compared to chromatographic methods. **Hollow fiber membranes have been used in biological systems, but not in this direct context. They have also been applied for xylose-glucose separation in pure systems.** **Research findings** * The objective of this study is to produce PES hollow fiber nanofiltration membrane for the separation of xylose and glucose. The performances test of membrane was carried out by separated a xylose and glucose. HPLC separation test was used to analyse the samples from the separation process. The result from this experiment is the composition of xylose in permeate is larger than glucose since xylose has lower molecular size than glucose. The results showed that, as the concentration of additive increase, the fluxes also increase and the sugar rejection will lower. As the concentration of PVP increase, the separation of xylose and glucose increase based on the xylose separation factor and solute rejection of xylose and glucose in the mixture solution. Art. [#ARTNUM](#article-25567-2354048319) * The results indicate that the separation of xylose from glucose by nanofiltration is possible to a limited extent. The mass ratio of xylose to glucose in the permeate was 1.5–3.0 times higher than their ratio in the feed. The observed monosaccharide retentions depend highly on permeate flux, and retentions increase to certain reproducible level as pressure and consequently flux is increased. The observed xylose retentions were from 0 to 80% and the glucose retentions were from 10 to 90%. The effect of total monosaccharide concentration on the observed retention is smaller than the effect of flux. The largest difference between xylose and glucose retentions was detected at permeate fluxes between 5 to 30 kg m −2  h −1. Art. [#ARTNUM](#article-25567-2029323095)

3.3.1 Hollow Fiber Nanofiltration
Fabrication of nanofiltration hollow-fiber membrane for the separation of xylose-glucose
Biomass is a biological material derived from living things, or recently living organism. Abundant plant biomass has the potential to become a renewable energy source of fuels and chemicals. Monosaccharide produced from the fermentation of biomass could produce various types of biofuels such as ethanol, butanol, methane, biodiesel, and hydrogen which greatly useful as sustainable energy. By the hydrolysis process of biomass, glucose and xylose were the most hemicelluloses sugar found in biomass. Nanofiltration membranes could offer a relatively cost-competitive separation steps, less complex and easier to maintain compared to chromatographic methods. The objective of this study is to produce PES hollow fiber nanofiltration membrane for the separation of xylose and glucose. Polyethersulfone (PES) polymer was used in a spinning solution with polyvinylpyrrolidone (PVP) as an additive to the solution. The performances of the membrane were investigated by varying the concentration of PVP from 1 wt. %, 3 wt. %, 7 wt. % and 9 wt. %. The surface morphological structure of the NF membrane were clarifying using SEM test. The performances test of membrane was carried out by separated a xylose and glucose. HPLC separation test was used to analyse the samples from the separation process. The result from this experiment is the composition of xylose in permeate is larger than glucose since xylose has lower molecular size than glucose. The results showed that, as the concentration of additive increase, the fluxes also increase and the sugar rejection will lower. As the concentration of PVP increase, the separation of xylose and glucose increase based on the xylose separation factor and solute rejection of xylose and glucose in the mixture solution.
6/1/14 12:00:00 AM
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3.3.2 Hollow Fiber Nanofiltration
Membrane extraction for detoxification of biomass hydrolysates
Membrane extraction was used for the removal of sulfuric acid, acetic acid, 5-hydroxymethyl furfural and furfural from corn stover hydrolyzed with dilute sulfuric acid. Microporous polypropylene hollow fiber membranes were used. The organic extractant consisted of 15% Alamine 336 in: octanol, a 50:50 mixture of oleyl alcohol:octanol or oleyl alcohol. Rapid removal of sulfuric acid, 5-hydroxymethyl and furfural was observed. The rate of acetic acid removal decreased as the pH of the hydrolysate increased. Regeneration of the organic extractant was achieved by back extraction into an aqueous phase containing NaOH and ethanol. A cleaning protocol consisting of flushing the hydrolysate compartment with NaOH and the organic phase compartment with pure organic phase enabled regeneration and reuse of the module. Ethanol yields from hydrolysates detoxified by membrane extraction using 15% Alamine 336 in oleyl alcohol were about 10% higher than those from hydrolysates detoxified using ammonium hydroxide treatment.
5/1/12 12:00:00 AM
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3.3.3 Hollow Fiber Nanofiltration
Separation of xylose from glucose by nanofiltration from concentrated monosaccharide solutions
Abstract Complex separation of monosaccharides from each other is commercially carried out by chromatographic methods. The possibility of nanofiltration in a demanding separation of a pentose sugar, xylose, from a hexose sugar, glucose, is studied here. Xylose is an intermediate product in xylitol production and glucose interferes in the process. Feed solutions were made of xylose and glucose in different mass ratios and total monosaccharide concentrations. The mass ratios of xylose to glucose in solutions were 1:9, 1:1 and 9:1 and the monosaccharide concentrations of the solutions were 2, 10 and 30 wt.%. Desal-5 DK, -DL and NF270 membranes were used. Filtrations were done in total reflux mode (i.e. both permeate and retentate were recycled back to the feed tank) at 50 °C and the applied pressures were from 2 to 40 bar. The results indicate that the separation of xylose from glucose by nanofiltration is possible to a limited extent. The mass ratio of xylose to glucose in the permeate was 1.5–3.0 times higher than their ratio in the feed. The observed monosaccharide retentions depend highly on permeate flux, and retentions increase to certain reproducible level as pressure and consequently flux is increased. The observed xylose retentions were from 0 to 80% and the glucose retentions were from 10 to 90%. The effect of total monosaccharide concentration on the observed retention is smaller than the effect of flux. The largest difference between xylose and glucose retentions was detected at permeate fluxes between 5 to 30 kg m −2  h −1 . The ratio of xylose to glucose in the feed had an influence on permeate flux and on xylose retentions. Xylose retentions decreased as the proportion of glucose increased in the feed. The higher the proportion of xylose in the feed the higher was the total permeate flux.
4/5/07 12:00:00 AM
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3.3.4 Hollow Fiber Nanofiltration
Thin Film Composite Hollow Fiber Membrane for Separation in Biorefinery
One of the newest applications of the membrane technology is for the separation of sugar component and inhibitor removal during biomass processing in biorefinery. Most of the membranes used in biorefinery were commercially purchased and not specifically customise for the biomass hydrolysate processing. In the current study, a series of thin film composite (TFC) hollow fiber membranes were fabricated to tailor the performance toward xylose/glucose refinement and acetic acid removal in biomass processing. Polysulfone (PSf) hollow fiber membrane support was prepared using 20wt% PSf, 2wt% Polyvinylpyrrolidone K30(PVP K30) and 78wt% dimethylformamide (DMF) through dry/wet spinning process. Three types of aqueous monomers were studied in interfacial polymerization process, which are piperazine (PIP), triethanolamine (TEOA) and polyethyleneimine (PEI). TFC hollow fiber membrane prepared using TEOA monomer showed the best performance for separation of biomass hydrolysate component. It exhibited rejection value 50.98  4.11 % of xylose, 71.72  3.92 % of glucose and 5.45  1.93 % of acetic acid. This is corresponding to the ideal separation factor of 1.75  0.10 for xylose/glucose, 3.42  0.54 for acetic acid/glucose and 1.95  0.20 for acetic acid/xylose.
1/1/17 12:00:00 AM
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3.3.5 Hollow Fiber Nanofiltration
Aldose-ketose transformation for separation and/or chemical conversion of C6 and C5 sugars from biomass materials

1. A method for converting an aldose in a biomass hydrolysate to its ketose isomer, comprising:adjusting a pH of a saccharified biomass hydrolysate containing one or more aldose sugars to a value between about 7.5 and about 9, to produce a pH-adjusted hydrolysate;contacting the pH-adjusted hydrolysate with an isomerization catalyst, wherein at least a portion of the aldose sugar in the pH-adjusted hydrolysate is converted to its ketose isomer, to produce an isomerized hydrolysate;contacting the ketose isomer in the isomerized hydrolysate with an aryl boronic acid (ABA) at a pH in the range of from 7.5 to 8.5 to form a complex of ketose-conjugate base form of the ABA; wherein the contacting comprises bringing the isomerized hydrolysate into contact with an immiscible organic phase that dissolves the ABA and a lipophilic salt (QX), and allowing the ketose in the isomerized hydrolysate to be extracted into the immiscible organic phase via ester formation with a conjugate base form of the ABA that is coupled via ion pair formation with Q+, thereby reducing the concentration of ketose in the isomerized hydrolysate and forming a ketose- rich organic phase, in turn shifting the aldose/ketose equilibrium in favor of more ketose formation in the pH-adjusted hydrolysate;preparing a low pH medium having a pH in the range of from about 2 to about 4.5, that contains an acid HX, wherein X is the same anion as X in the lipophilic salt (QX);bringing the low pH medium into contact with the ketose-rich organic phase; wherein, at the low pH, the ketose and hydroxyl ions are released into the low pH medium and the ABA is converted to its non-ionic conjugate acid; and, wherein, at the same time, the Q+ ion that formed the ion pair combines with an X− ion from the low pH medium to reform the lipophilic salt; andrecovering the ketose from the organic phase into the low pH medium as a concentrated ketose-rich solution. 2. The method of claim 1, including controlling the volume of the low pH medium such that the concentration of ketose in the ketose-rich medium is higher than the initial concentration of aldose in the hydrolysate. 3. The method of claim 1, further including reusing the organic phase containing the ABA and the lipophilic salt for a subsequent batch of hydrolysate. 4. The method of claim 1, wherein the steps of contacting the ketose isomer in the isomerized hydrolysate with ABA, and bringing the low pH medium into contact with the ketose-rich organic phase, are carried out using a micro- porous hollow fiber contactor. 5. The method of claim 4, wherein the micro-porous hollow fiber contactor comprises a shell having a first set of porous hollow fibers adapted for carrying the isomerized hydrolysate; and a second set of porous hollow fibers adapted for carrying the low-pH medium;the shell being configured for containing the organic extraction phase in a shell-side space substantially surrounding the first and second sets of fibers. 6. The method of claim 5, wherein the ketose is transported from the hydrolysate to the immiscible organic phase and from the organic phase to the low-pH medium, wherein the transport of the ketose is facilitated by ABA and QX combination dissolved in the immiscible organic phase. 7. The method of claim 5, wherein the first and second sets of micro-porous hollow fibers are commingled within the shell. 8. The method of claim 5, wherein the saccharified biomass hydrolysate contains glucose and xylose, and the method comprises:passing the hydrolysate through a packed bed reactor containing immobilized xylose isomerase (XI) or solid acid/base catalyst;allowing the isomerized hydrolysate to flow through the first set of fibers within the micro-porous hollow fiber contactor, the isomerized hydrolysate coming into contact with the immiscible organic phase containing lipophilic ABA and a lipophilic salt (QX) that fills the shell;extracting the xylulose in the isomerized hydrolysate, wherein the pH of the isomerized hydrolysate is in the range of from 7.5 to 8.5, into the organic phase via ester formation with a conjugate base form of the ABA coupled by ion pair formation with Q+, thereby reducing concentration of xylulose in the hydrolysate, and shifting the xylose/xylulose equilibrium in favor of more xylulose formation;concurrently with the extracting, allowing the low pH medium to flow through the second set of fibers and contact the organic phase contained on the shell side; whereby:the xylulose and hydroxyl ions attached to the ABA are released into the low pH medium, the ABA is re- converted to its non-ionic conjugate acid, andthe Q+ ion, which formed the ion pair with ABA, combines with an X− ion from the low pH medium to re-form the lipophilic salt. 9. The method of claim 1, including selecting an ABA having a property to enhance selectivity for a specific sugar. 10. The method of claim 1, further including controlling the volume of the low pH medium such that the ketose concentration in the recovered solution is higher than the aldose concentration in the saccharified biomass hydrolysate. 11. The method of claim 1, wherein both glucose and xylose from the hydrolysate are simultaneously isomerized by the isomerization catalyst into ketoses, the ketoses are extracted into the organic phase via binding to the ABA and QX, and the ketoses are recovered from the organic phase via back- extraction into the low pH medium while leaving behind other inhibitory compounds in the biomass hydrolysate. 12. The method of claim 1, wherein a micro-porous hollow fiber contactor physically separates the ketose-rich organic phase from the low pH medium during the ketose recovery. 13. The method of claim 1, wherein the step of contacting the pH-adjusted hydrolysate with an isomerization catalyst comprises passing the pH-adjusted hydrolysate through a packed bed reactor containing the isomerization catalyst, wherein the isomerization catalyst facilitates conversion of glucose to fructose. 14. The method of claim 1, wherein the pH of the recovered ketose is adjusted slightly to a pH suitable for converting the ketose to lactic acid, succinic acid, or fumaric acid by native microorganisms. 15. The method of claim 1, wherein the isomerization catalyst preferentially isomerizes xylose into xylulose compared to glucose into fructose, the ABA preferentially binds to ketoses compared to aldoses, and the system is used to separate C5 sugars from C6 sugars. 16. The method of claim 1, wherein the pH of the recovered ketose corresponds to a pH suitable for dehydration of the ketose to furans via an acid-catalyzed chemical reaction. 17. The method of claim 1, wherein the isomerization catalyst comprises xylose isomerase (XI) particles that facilitate the isomerization of both glucose and xylose. 18. The method of claim 1, comprising:a first micro-porous hollow fiber contactor having a lumen side and a shell side, wherein the hydrolyzate flows through the lumen-side in the first micro-porous hollow fiber contactor and the immiscible organic phase flows through the shell-side; anda second micro- porous hollow fiber contactor that physically separates the ketose-rich organic phase from the low pH medium during ketose recovery. 19. The method of claim 1, wherein the saccharified biomass hydrolysate is a lignocellulosic biomass hydrolysate. 20. The method of claim 19, wherein one or more of the ABA, the pH, and temperature of the hydrolysate, are altered to selectively isomerize and extract one or more specific sugars. 21. The method of claim 1, wherein the ABA is present in an immiscible organic phase that is physically separated by a permeable device from the isomerized hydrolysate, the permeable device allowing transport of the sugar from the isomerized hydrolysate into the immiscible organic phase, while substantially preventing dispersion of the immiscible organic phase in the isomerized hydrolysate. 22. The method of claim 7, wherein the immiscible organic phase comprises one or more of octanol, ethyl acetate, dichloromethane, o-nitrophenyl octyl ether (NPOE), or diethyl ether. 23. The method of claim 21, wherein the permeable device is a micro-porous hollow fiber contactor. 24. The method of claim 1, wherein the step of contacting the pH-adjusted- hydrolysate with an isomerization catalyst comprises passing the pH-adjusted hydrolysate through a packed bed reactor containing the isomerization catalyst, wherein the isomerization catalyst facilitates conversion of xylose into xylulose. 25. The method of claim 24, wherein the packed bed reactor is connected in a loop to a micro-porous hollow fiber contactor having a shell side and a fiber side, such that the hydrolysate flows through the packed bed and the fiber side of the micro-porous hollow fiber contactor, and the ketose is extracted from the hydrolysate to the immiscible organic phase on the shell side of the micro-porous hollow fiber contactor. 26. The method of claim 1, including: selecting the ABA such that, at selected pH and temperature conditions, the ABA mainly binds to xylulose, and does not bind to any appreciable amounts of glucose, xylose, or fructose. 27. The method of claim 1, including circulating the hydrolysate through at least a first column comprised of a packed bed of immobilized xylose isomerase (XI), and through a vessel having an ABA-enriched phase therein. 28. The method of claim 1, wherein the pH of the recovered ketose is a pH suitable for converting the ketose to ethanol by native _S. cerevisiae_ or other native microorganisms. 29. The method of claim 1, including controlling a volume of the low pH medium sufficient to recover the ketose as a concentrated solution. 30. The method of claim 1, including separating xylose from other C6 sugars as its keto-isomer and allowing for the recovery of xylulose as a concentrated solution. 31. The method of claim 1, comprising passing the isomerized hydrolysate and the ABA containing organic phase through a micro-porous hollow fiber contactor. 32. The method of claim 1, wherein the ABA is selected from the group consisting of PBA, 3aPBA, 4cPBA, naphthalene-2-boronic acid (N2B), and 4-biphenylboronic acid. 33. The method of claim 1, wherein the ABA has the formula Ar--B(OH)2, where Ar represents an unsubstituted or substituted aryl group. 34. The method of claim 33, wherein the ABA comprises one or more of the aryl groups: 4-PhC6H4--; 4-MeC6H4--, where Me is methyl; 2-iPrC6H4-, where iPr is isopropyl; 2-naphthyl; 3-BnOC6H4--, where Bn is benzyl; 4-MeO2CC6H4--, where Me is methyl; and 4-pyridinyl. 35. The method of claim 33, wherein the ABA comprises a diboronic acid that exhibits a higher selectivity toward ketose binding compared to monoboronic acids. 36. The method of claim 33, wherein the ABA comprises a multi-dentate boronic acid carrier. 37. The method of claim 36, wherein the ABA comprises one or more of: wherein A and C are B(OH)2, and B and D are H groups. 38. The method of claim 1, wherein the ABA comprises a hydrophobic substituted aryl boronic acid. 39. The method of claim 38, wherein the ABA comprises: 40. The method of claim 38, wherein the hydrophobic substituted aryl boronic acid is used in a liquid-liquid extraction followed by stripping or micro- porous hollow fiber contactor implementation.
4/19/11 12:00:00 AM
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3.4 Enzyme-assisted filtration

0

By selectively converting one of the sugars into another product, followed by subsequent nanofiltration, sugar monomers can be separated. In this way next to monomer recovery, added-value products could be produced. **Process:** Enzymatic reactions and filtrations were conducted in a magnetically stirred dead-end cell (Amicon 8050, Millipore, USA). Dead-end filtration was selected as filtration mode, as it provides the most comprehensive insight of the effects of fouling during filtration. The biomass liquors were obtained after hydrothermal pretreatment (190 °C, 10 min) and pressing (leading to solid-liquid fractionation). In order to optimize the flux and biocatalytic performance of the membrane bioreactor, the biomass pretreatment liquors were subjected to different post treatments. First, the biomass pretreatment liquor was subjected to centrifugation (Heraeus Multifuge 4 KR Centrifuge, Thermo Scientific, Waltham, MA, USA). Secondly, the biomass pretreatment liquor was subjected to acid hydrolysis in order to decompose the soluble poly- and oligosaccharides and in turn increase the yield of monosaccharides. Acid hydrolysis was accomplished by adding 9 mL H2SO4 (97 w/w%) to 400 mL biomass pretreatment liquor, which was subsequently autoclaved at 121 °C for 10 min. After acid hydrolysis, CaCO3 (16–18 g pr. 400 mL liquor) was added to the liquor (pH < 1) in order to precipitate CaSO4 and thereby increase the pH to 5.5. 19.5 mL pretreated and post-treated WS liquor, respectively, was transferred to the dead-end cell equipped with the PLGC membrane and a stir bar. 300 U GOD (∼500 μl) and 900 U CAT (∼4 μl) were then added, and hydrogen peroxide solution (∼68 μl) was added to a total concentration of 30 mM. Biocatalytic reactions were conducted for 40 min at 35 °C, pH 5.5 and 100 rpm. The liquors were then subjected to NF with the NF270 membrane at 4 bar and room temperature. Art. [#ARTNUM](#article-30331-2769701877) **Research findings:** * The purpose of the present study was to assess the efficiency of enzymeassisted nanofiltration for separation of xylose from glucose present in genuine biorefinery liquors obtained from hydrothermal pretreatment of wheat straw, corn stover and Miscanthus stalks. Glucose oxidase and catalase were used to convert the glucose contained in the liquors into gluconic acid, so xylose could be more easily recovered in the subsequent nanofiltration. The best separation factor of gluconic acid over xylose in the subsequent nanofiltration was 2.7, 2.5 and 2.2 for wheat straw, corn stover and Miscanthus stalks, respectively. All represented a significant improvement compared to the benchmark separation of xylose and glucose, in which case the separation factor was only 1.4. Art. [#ARTNUM](#article-30331-2769701877) * The resulting purity of xylose with respect to gluconic acid was 91% (vs. >99% for the model solution), whereas the purity of xylose with respect to all components was only 60%. In both cases, the yield of xylose was 30%. Generally, the WP loss obtained for the biomass liquors (∼14% irrespective of biomass) was comparable with the WP loss obtained for the model solution, which indicated that despite the increasing complexity of the real biomass feedstocks, fouling was not a big limitation in the real system either. [#ARTNUM](#article-30331-2769701877)

3.4.1 Enzyme-assisted filtration
High performance separation of xylose and glucose by enzyme assisted nanofiltration
Abstract An integrated membrane system was investigated for the separation of mixtures of xylose and glucose. Separation of these sugars is extremely challenging due to their similar structure, size and charge. In order to enhance the xylose separation factor in nanofiltration (NF), we present an enzymatic process for converting glucose to gluconic acid followed by separation of xylose from gluconic acid by nanofiltration. Process conditions which favored the negative charge repulsions between gluconic acid and the NF270 membrane were examined. At the best conditions (9:1 feed molar ratio of xylose to gluconic acid, 0.15 M total feed concentration, pH 9.5, 25 °C and 4 bar), we achieved a xylose separation factor of 34 and a throughput of 18.7 L m −2  h −1 . In comparison, the separation factor was only 1.4 for solutions of xylose and glucose at the same process conditions, thus demonstrating the huge potential of the integrated system. Full conversion of glucose to gluconic acid assisted by glucose oxidase (GOD) could be achieved by coupling a parallel reaction catalyzed by catalase (CAT), where H 2 O 2 (GOD-inhibitor formed in the first reaction) was decomposed to water and oxygen. GOD has a high oxygen-demand and it was demonstrated that sufficient oxygen could be obtained by controlling the CAT-catalyzed reaction through initial H 2 O 2 addition. The new strategy suggested in this study, integrating reaction and nanofiltration to enhance separation while obtaining another value-added stream, presents new options for separating compounds with similar molecular weights by nanofiltration.
10/1/15 12:00:00 AM
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3.4.2 Enzyme-assisted filtration
Membrane separation of enzyme-converted biomass compounds: Recovery of xylose and production of gluconic acid as a value-added product
Abstract The purpose of the present study was to assess the efficiency of enzyme-assisted nanofiltration for separation of xylose from glucose present in genuine biorefinery liquors obtained from hydrothermal pretreatment of wheat straw, corn stover and Miscanthus stalks. Glucose oxidase and catalase were used to convert the glucose contained in the liquors into gluconic acid, so xylose could be more easily recovered in the subsequent nanofiltration. Subjecting the biomass liquors to dilute acid treatment and centrifugation before the enzymatic reaction and filtration led to maximum biocatalytic performance of the membrane bioreactor (neglectable fouling and no enzyme activity loss) during five consecutive reaction-filtration cycles. The best separation factor of gluconic acid over xylose in the subsequent nanofiltration was 2.7, 2.5 and 2.2 for wheat straw, corn stover and Miscanthus stalks, respectively. All represented a significant improvement compared to the benchmark separation of xylose and glucose, in which case the separation factor was only 1.4. However, the higher ionic strength of the biomass liquors compared to the pure model solution probably led to a less negative zeta potential of the nanofiltration membrane, which significantly reduced the xylose purification performance as compared to the model system, for which the separation factor was 34.
4/1/18 12:00:00 AM
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3.5 Robust membranes

0

Robust membranes are an important field of research in the domain of filtration. Robust membranes are required in biomass applications as these have high fouling potential. Robust membranes have not been explored much for sugar separations, but have been used to concentrate steams and separate/remove salts from biomass streams, waste water or black liquor. Most 'robust' membranes are based on or composed of graphene (oxide). Thin-film graphene and graphene oxide (GO) membranes have unique attributes such as a pseudo-2D structure, high flexibility, and mechanical strength. GO is a chemical derivative of graphene with large number of oxidized functional groups on the surface and has been great of interest for development of large surface area GO thin film membranes. Promising performance of GO membranes has been demonstrated in certain gas separation and fluid filtration (NF and RO) applications, in terms of high water fluxes and significant rejections of organic and inorganic solids. **Research findings:** * We report a detailed study of graphene oxide (GO) membranes for concentration of Kraft black liquor (BL), which is a caustic (pH ∼ 12), hot (80–95 °C), and highvolume (∼500 gal/min in a typical pulp mill) byproduct of the papermaking process. Membranebased concentration of BL is attractive as an energyefficient alternative to thermally driven evaporation processes but challenging due to the harsh operating conditions and high fouling potential of BL (15–18 wt % solids). We fabricate thin (<300 nm) GO membranes supported on macroporous poly(ethersulfone) (PES) supports by vacuum filtration techniques and discuss in detail their morphology, structure, thermomechanical stability, and chemical stability as characterized by several techniques. Furthermore, detailed permeation measurements at transmembrane pressures (TMPs) up to 50 bar and temperatures up to 85 °C show that the membranes have high performance in concentrating BL feeds containing high and low TS (total solids) Art. [#ARTNUM](#article-38667-2560546809) * Acetic acid is one of the inhibitors mainly found in biomass hydrolysates after acid hydrolysis of lignocellulose biomass. The presence of this compound can affect the final yield of bioethanol. Supported liquid membrane (SLM) is an efficient method for solute extraction from aqueous solution. However, unsuitable membrane structure and insufficient membrane strength are the typical problems experienced by the membrane support in the SLM system. In the current study, graphene nanopowder was incorporated into polyethersulfone (PES) dope polymer solution to fabricate flat sheet PES membrane support. Art. [#ARTNUM](#article-38667-2586633763) * Grafted polymer membranes (GPM) composed of a polymer support and an extractive agent are original materials to improve the performance in the separation process of organic molecules. In this study, a GPM was elaborated with polysulfone (PSU) and poly(1vinylpyrrolidone) (PVP) as support containing Gluconic acid (GA) as extractive agent. The main objective is to develop a new GPM for recovering Glucose, Fructose, and Sucrose from sugar industry discharges. The membranes were prepared by the phase inversion technique after dissolution of all various constituents. The results show that the adopted GPM is more efficient for the extraction of glucose relative to sucrose and fructose compounds, and that a selective extraction remains possible. Art. [#ARTNUM](#article-38667-2792493113) This study reports the synthesis and physicochemical properties of a silicacrosslinked graphene oxide (GO) membrane, and highlights its unique capability to remove neutral organic molecules from water. The silicacrosslinked GO membrane was formed by soaking a layerstacked GO film in saturated silica solution and remained stable under various test conditions. Comparison of the chemical compositions of the GO membrane before and after silica crosslinking indicates that silica mainly reacted with the carboxyl groups in GO. The GO membrane was negatively charged and found to remove the tested neutral organic molecules (glucose and sucrose) (∼84% to 90%) much more efficiently than the tested negatively charged ionic species (trisodium citrate/TSC) (∼22%). This unique separation behavior is quite interesting, as it is generally known that a charged nanofiltration or reverse osmosis membrane would remove charged species much better than neutral molecules of comparable sizes. Art. [#ARTNUM](#article-38667-2383870047)

3.5.1 Robust membranes
Anti-fouling and high water permeable forward osmosis membrane fabricated via layer by layer assembly of chitosan/graphene oxide
Abstract To date, forward osmosis (FO) has received considerable attention due to its potential application in seawater desalination. FO does not require external hydraulic pressure and consequently is believed to have a low fouling propensity. Despite the numerous privileges of FO process, a major challenge ahead for its development is the lack of high performance membranes. In this study, we fabricated a novel highly-efficient FO membrane using layer-by-layer (LbL) assembly of positive chitosan (CS) and negative graphene oxide (GO) nanosheets via electrostatic interaction on a porous support layer. The support layer was prepared by blending hydrophilic sulfonated polyethersulfone (SPES) into polyethersulfone (PES) matrix using wet phase inversion process. Various characterization techniques were used to confirm successful fabrication of LbL membrane. The number of layers formed on the SPES-PES support layer was easily adjusted by repeating the CS and GO deposition cycles. Thin film composite (TFC) membrane was also prepared by the same SPES-PES support layer and polyamide (PA) active layer to compare membranes performances. The water permeability and salt rejection of the fabricated membranes were obtained by two kinds of draw solutions (including Na 2 SO 4 and sucrose) under two different membrane orientations. The results showed that membrane coated by a CS/GO bilayers had water flux of 2–4 orders of magnitude higher than the TFC one. By increasing the number of CS/GO bilayers, the selectivity of the LbL membrane was improved. The novel fabricated LbL membrane showed better fouling resistance than the TFC one in the feed solution containing 200 ppm of sodium alginate as a foulant model.
8/1/17 12:00:00 AM
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3.5.2 Robust membranes
Black Liquor Concentration by a Membrane Comprising Graphene Oxide on Porous Polymer
The disclosed technology includes a membrane-based device configured to concentrate black liquor, which results from papermaking. Certain embodiments may comprise a nanofiltration membrane configured to remove lignin from black liquor, and the nanofiltration membrane may include a first macroporous polymer substrate and a first graphene oxide membrane covering the first macroporous polymer substrate. Some embodiments may comprise a reverse osmosis membrane, which may include a second macroporous polymer substrate and a second graphene oxide membrane covering the second macroporous polymer substrate.
3/15/18 12:00:00 AM
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3.5.3 Robust membranes
Cross-linked graphene membrane for high-performance organics separation of emulsions
Abstract Recently, graphene oxide (GO) membranes are highly attractive for their exceptional separation performance. However, their sieving characteristics limit GO membranes for some important applications where organics are preferred or organic solvents are employed. In this work, a novel cross-linked graphene (CG) membrane is fabricated through compressing and then reducing a cross-linked GO aerogel. It achieved high-performance of organics separation with high flux (225 L m −2  h −1 ) and purity (>99.98%) even in a cross-flow separation model, where water was intercepted. Deep insight revealed that both the converted surface wettability and the remaining channels in the CG membrane were crucial for the high-performance of organics separation. Beyond that, this CG membrane offers many advantages, such as facile preparation, self-supporting, structural stability and adaptation in harsh acidic/basic/high-temperature conditions, demonstrating its great potential for practical applications.
12/1/15 12:00:00 AM
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3.5.4 Robust membranes
Dipeptide polyethyleneimine polymer as well as preparation method and application thereof
The invention relates to a dipeptide polyethyleneimine polymer as well as a preparation method and an application thereof. The dipeptide polyethyleneimine polymer is obtained by grafting a dipeptide chloridized by acetyl chloride onto a side chain of the polyethyleneimine with a polymerization degree of 5 to 200000 through a substitution reaction. The dipeptide polyethyleneimine polymer is grafted to a porous matrix to obtain a sugar separation polymer material, and the sugar separation polymer material is used as a chromatographic support to be used in monosaccharide chiral separation, monosaccharide chemical separation, disaccharide chemical separation, oligomeric polysaccharide chemical separation or hydrotropic substance separation. The material structure and a synthetic circuit are simple, the repeatability is good, and the mass production is likely to realize. In the sugar separation field, the material has a remarkable advantage, the dipeptide polyethyleneimine polymer can be used for high selectively distinguishing and separating monosaccharide enantiomer, monosaccharide or disaccharide, the weaknesses of a traditional material are overcome, and the development value is very high.
12/30/15 12:00:00 AM
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3.5.5 Robust membranes
Emerging investigators series: silica-crosslinked graphene oxide membrane and its unique capability in removing neutral organic molecules from water
This study reports the synthesis and physicochemical properties of a silica-crosslinked graphene oxide (GO) membrane, and highlights its unique capability to remove neutral organic molecules from water. The silica-crosslinked GO membrane was formed by soaking a layer-stacked GO film in saturated silica solution and remained stable under various test conditions. Comparison of the chemical compositions of the GO membrane before and after silica crosslinking indicates that silica mainly reacted with the carboxyl groups in GO. The GO membrane was negatively charged and found to remove the tested neutral organic molecules (glucose and sucrose) (∼84% to 90%) much more efficiently than the tested negatively charged ionic species (trisodium citrate/TSC) (∼22%). This unique separation behavior is quite interesting, as it is generally known that a charged nanofiltration or reverse osmosis membrane would remove charged species much better than neutral molecules of comparable sizes. Our experimental evidence suggests that neither size exclusion nor ionic strength is responsible for such unique behavior. Characterization of the interactions between the GO membrane and the tested neutral organic species indicates that the low partitioning and irreversible adsorption of neutral organic molecules into the GO membrane (much less than that of charged ionic species) is most likely responsible for their better removal by the GO membrane.
1/1/16 12:00:00 AM
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3.5.6 Robust membranes
Evaluation of ultra-and nanofiltration for refining soluble products from rice husk xylan
Liquors from water treatments of rice husks (containing soluble xylan-derived products) were processed with NF and UF membranes for concentrating and removing both monosaccharides and non-saccharide compounds. Among the commercial membranes assayed, the best results were achieved with the 4 kDa polymeric tubular ESP04 (PCI Membranes), and the 1 kDa ceramic monolithic Kerasep Nano (Novasep). Several trade-offs were identified both in membrane selection and in operating conditions. The ESP04 polymeric membrane provided the best fractionation, but lower recovery under comparable experimental conditions, while its fluxes were about half of those of the ceramic Kerasep Nano membrane. Increase in transmembrane pressure resulted in improved product recovery, at the expense of a lower purity. Additional data on product refining by coupling membrane processing with extraction and ion exchange are provided.
9/1/08 12:00:00 AM
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3.5.7 Robust membranes
Graphene Oxide Membranes in Extreme Operating Environments: Concentration of Kraft Black Liquor by Lignin Retention
We report a detailed study of graphene oxide (GO) membranes for concentration of Kraft black liquor (BL), which is a caustic (pH ∼ 12), hot (80–95 °C), and high-volume (∼500 gal/min in a typical pulp mill) byproduct of the papermaking process. Membrane-based concentration of BL is attractive as an energy-efficient alternative to thermally driven evaporation processes but challenging due to the harsh operating conditions and high fouling potential of BL (15–18 wt % solids). We fabricate thin (<300 nm) GO membranes supported on macroporous poly(ethersulfone) (PES) supports by vacuum filtration techniques and discuss in detail their morphology, structure, thermomechanical stability, and chemical stability as characterized by several techniques. Furthermore, detailed permeation measurements at transmembrane pressures (TMPs) up to 50 bar and temperatures up to 85 °C show that the membranes have high performance in concentrating BL feeds containing high and low TS (total solids): high flux (in the range of 5–50...
1/3/17 12:00:00 AM
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3.5.8 Robust membranes
Graphene oxide based membrane intercalated by nanoparticles for high performance nanofiltration application
Abstract A free-standing sandwich-structured polyamide 6 (PA 6)@GO@PA 6 nanofiltration membrane intercalated by nanoparticles with high water flux was prepared using electrospraying combined with electrospinning method. According to the XRD patterns, the interlayer spacing of the membrane increases with the TiO 2 nanoparticle (NP) intercalated. The TiO 2 NP intercalated PA 6@GO (120)@ PA 6 nanofiltration membrane shows a pure water flux up to 13.77 L m −2  h −1  bar −1 even under an extremely low external pressure (1.0 bar), which increased by 80.7% than that of PA 6@GO (120)@PA 6 nanofiltration membrane (7.62 L m −2  h −1  bar −1 ) without nanoparticles intercalated, and maintains high organic dye rejection capabilities (>85% for BF, >92% for MB, >99% for MO, and 99.85% for EB). Besides TiO 2 , other nanoparticles, such as SiO 2 and Si 3 N 4 can also improve the water flux and maintain high rejection rate for MO and MB. Furthermore, TiO 2 intercalated PA 6@GO (120)@PA 6 nanofiltration membrane is very stable even under ultrasonication, and shows a high flux for some common solvents (12.32, 4.91, and 1.26 L m −2  h −1  bar −1 for methanol, ethanol, and NMP, respectively).
9/1/18 12:00:00 AM
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3.5.9 Robust membranes
High performance graphene oxide nanofiltration membrane prepared by electrospraying for wastewater purification
Abstract A high performance graphene oxide nanofiltration membrane (GO NFM) was prepared using the electrospraying technique instead of the traditional vacuum filtration method, which is a facial and scalable method to prepare GO NFMs with diameter of 100 mm. The permeate performance of this novel nanofiltration membrane was evaluated using a dead end filtration device, which gave us a high flux value for pure water (11.13–20.23 L m −2  h −1 bar −1 ) even under an extremely low external pressure (1.0 bar). The GO(120) NFM demonstrated high organic dyes rejection rate (98.88%, 98.97%, 100%, and 99.99%, for BF, MB, MO, and EB, respectively). The rejection mechanism for charged dyes was discussed and the results revealed that physical size sieving and electrostatic interaction dominated the rejection mechanism. The rejections rate of GO NFMs for the Na 2 SO 4 , NaCl, MgSO 4 , and MgCl 2 were 63.13%, 27.86%, 41.82%, and 15.00%, respectively, based on the mechanism of Donnan exclusion theory and steric hindrance effect. Furthermore, the GO NFM shows high flux recovery ratio ( FRR ) values (89.58% and 95.54% for SA and HA), suggesting that the GO NFM is easier to be recovered by DI water washing due to the smooth and hydrophilic surface.
1/1/18 12:00:00 AM
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3.5.10 Robust membranes
New Grafted Polymer Membrane for extraction, separation and recovery processes of Sucrose, Glucose and Fructose from the sugar industry discharges.
Abstract Grafted polymer membranes (GPM) composed of a polymer support and an extractive agent are original materials to improve the performance in the separation process of organic molecules. In this study, a GPM was elaborated with polysulfone (PSU) and poly(1-vinylpyrrolidone) (PVP) as support containing Gluconic acid (GA) as extractive agent. The main objective is to develop a new GPM for recovering Glucose, Fructose, and Sucrose from sugar industry discharges. The membranes were prepared by the phase inversion technique after dissolution of all various constituents. Morphology of the membranes, with and without extractive agent was observed by scanning electron microscopy (SEM) analysis, and the compositions identified using; Fourier Transform Infrared (FTIR) spectroscopy. The obtained membranes were used to study the oriented process of facilitated extraction of the sugars, as well as the influence of temperature factor on their performance. A kinetic and thermodynamic model was developed to determine the values of macroscopic parameters, permeability P and initial flux J 0 microscopic parameters, association constant K ass and apparent diffusion coefficient D ∗ , and activation parameters ( E a , Δ H # and Δ S # ) related to the transition state of the pseudo entity [ ST ] formed by the association/dissociation of the substrate S with extractive agent T , required for migration of each substrate across the membrane organic phase. The parameters determined were used to explain the results and confirm the mechanism related to this oriented process. A notable difference between the values of K ass and D ∗ was observed that confirms the molecular recognition principle during the interaction of the extractive agent (GA) with the extracted sugars. The results show that the adopted GPM is more efficient for the extraction of glucose relative to sucrose and fructose compounds, and that a selective extraction remains possible.
1/1/18 12:00:00 AM
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3.5.11 Robust membranes
Supported Liquid Membrane Using Hybrid Polyethersulfone/ Graphene Flat Sheet Membrane for Acetic Acid Removal
Acetic acid is one of the inhibitors mainly found in biomass hydrolysates after acid hydrolysis of lignocellulose biomass. The presence of this compound can affect the final yield of bioethanol. Supported liquid membrane (SLM) is an efficient method for solute extraction from aqueous solution. However, unsuitable membrane structure and insufficient membrane strength are the typical problems experienced by the membrane support in the SLM system. In the current study, graphene nanopowder was incorporated into polyethersulfone (PES) dope polymer solution to fabricate flat sheet PES membrane support. The hydrophobicity of the PES membrane was increased from 85° to 120° when the graphene was added. The force required to break the PES/graphene membrane was 4.3N. This force was higher compared to the pristine PES membrane which was 1.9N. Both membranes however showed almost similar acetic acid removal percentages which were 86% and 83% for pristine PES and PES/graphene membrane, respectively.
2/15/17 12:00:00 AM
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3.5.12 Robust membranes
Sustainable Water Purification Using Engineered Solvothermal Carbon Based Membrane Derived from a Eutectic System
Surface water is widely adulterated by hazardous pollutants such as dyes, pharmaceutical wastes, surfactants, heavy metals, hormones, etc. Hence, there is a necessity to develop a water treatment technology that can overcome all the major water-related problems. The conventional methods for water disinfection are very specific and expensive. The challenge is to devise a purification protocol without forming harmful byproducts, which opens up the opportunity for new technologies with efficient materials toward water treatment. The present work demonstrates a sustainable strategy for robust water purification through a powder based membrane fabricated from a highly oxygenated and Al-functionalized solvothermal carbon (Al-STC) composite. AlOOH/Al(OH)3 functionalized Al-STCs with improved surface acidity were prepared by a low temperature solvothermal process from a eutectic system (ES) comprising ethylene glycol (EG), choline chloride (ChoCl), glucose (Glu), and aluminum salt. The ES acts as both carbon prec...
5/9/19 12:00:00 AM
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4. Integrated Approaches

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Integrated approaches make use of several technologies in series to perform the separation.


4.1 Reaction separation and solvent extraction

0

Xylose and arabinose can be separated by reaction to xylose monoacetal and arabinose diacetal. This mixture can then be effectively separated by solvent extraction: the xylose monoacetal by a polar solvent and the diacetal by a non-polar solvent. They can then hydrolyzed to give xylose and arabinose. **Process:** A mixture of the pentose sugars from the enzymatic treatment of the lignocellulose was dried and treated with acetone or other ketones or aldehydes in the presence of acid. The use of an acyclic acetal such as 2,2-dimethoxypropane aids acetalization by preventing hydrolysis of the acetal or ketal. Water scavengers such as orthoesters can also be added to aid the acetalization. After neutralization with an organic or inorganic base, the solvents were removed and the mixture was extracted with hexane or other hydrocarbon solvent. The extract contains the diacetals of L-arabinose (1) and D-xylose (2). Alternatively, the diacetals can be extracted with a non-polar supercritical solvent such as carbon dioxide or they can be recovered together by distillation from the mixture. The polarity of the solvent needs to be low enough that any acetals of hexose sugars, oligosaccharides or polysaccharides are not extracted. The mixture of diacetals was treated in a polar solvent such as methanol or water under conditions that react only the 3,5-acetal group of D-xylose to give a 3,5-diol of xylose. The mixture was then neutralized with base and an immiscible (non-polar) solvent was added. The layers were separated to give the individual protected pentoses. The acetals were deprotected by acid hydrolysis to give the pentoses, xylose and arabinose. Xylose is formed as a five-membered ring from the acetal protected D-xylofuranose. Art. [#ARTNUM](#article-25713-US7498430B2)

4.1.1 Reaction separation and solvent extraction
Aldose-ketose transformation for separation and/or chemical conversion of C6 and C5 sugars from biomass materials

1. A method for converting an aldose in a biomass hydrolysate to its ketose isomer, comprising:adjusting a pH of a saccharified biomass hydrolysate containing one or more aldose sugars to a value between about 7.5 and about 9, to produce a pH-adjusted hydrolysate;contacting the pH-adjusted hydrolysate with an isomerization catalyst, wherein at least a portion of the aldose sugar in the pH-adjusted hydrolysate is converted to its ketose isomer, to produce an isomerized hydrolysate;contacting the ketose isomer in the isomerized hydrolysate with an aryl boronic acid (ABA) at a pH in the range of from 7.5 to 8.5 to form a complex of ketose-conjugate base form of the ABA; wherein the contacting comprises bringing the isomerized hydrolysate into contact with an immiscible organic phase that dissolves the ABA and a lipophilic salt (QX), and allowing the ketose in the isomerized hydrolysate to be extracted into the immiscible organic phase via ester formation with a conjugate base form of the ABA that is coupled via ion pair formation with Q+, thereby reducing the concentration of ketose in the isomerized hydrolysate and forming a ketose- rich organic phase, in turn shifting the aldose/ketose equilibrium in favor of more ketose formation in the pH-adjusted hydrolysate;preparing a low pH medium having a pH in the range of from about 2 to about 4.5, that contains an acid HX, wherein X is the same anion as X in the lipophilic salt (QX);bringing the low pH medium into contact with the ketose-rich organic phase; wherein, at the low pH, the ketose and hydroxyl ions are released into the low pH medium and the ABA is converted to its non-ionic conjugate acid; and, wherein, at the same time, the Q+ ion that formed the ion pair combines with an X− ion from the low pH medium to reform the lipophilic salt; andrecovering the ketose from the organic phase into the low pH medium as a concentrated ketose-rich solution. 2. The method of claim 1, including controlling the volume of the low pH medium such that the concentration of ketose in the ketose-rich medium is higher than the initial concentration of aldose in the hydrolysate. 3. The method of claim 1, further including reusing the organic phase containing the ABA and the lipophilic salt for a subsequent batch of hydrolysate. 4. The method of claim 1, wherein the steps of contacting the ketose isomer in the isomerized hydrolysate with ABA, and bringing the low pH medium into contact with the ketose-rich organic phase, are carried out using a micro- porous hollow fiber contactor. 5. The method of claim 4, wherein the micro-porous hollow fiber contactor comprises a shell having a first set of porous hollow fibers adapted for carrying the isomerized hydrolysate; and a second set of porous hollow fibers adapted for carrying the low-pH medium;the shell being configured for containing the organic extraction phase in a shell-side space substantially surrounding the first and second sets of fibers. 6. The method of claim 5, wherein the ketose is transported from the hydrolysate to the immiscible organic phase and from the organic phase to the low-pH medium, wherein the transport of the ketose is facilitated by ABA and QX combination dissolved in the immiscible organic phase. 7. The method of claim 5, wherein the first and second sets of micro-porous hollow fibers are commingled within the shell. 8. The method of claim 5, wherein the saccharified biomass hydrolysate contains glucose and xylose, and the method comprises:passing the hydrolysate through a packed bed reactor containing immobilized xylose isomerase (XI) or solid acid/base catalyst;allowing the isomerized hydrolysate to flow through the first set of fibers within the micro-porous hollow fiber contactor, the isomerized hydrolysate coming into contact with the immiscible organic phase containing lipophilic ABA and a lipophilic salt (QX) that fills the shell;extracting the xylulose in the isomerized hydrolysate, wherein the pH of the isomerized hydrolysate is in the range of from 7.5 to 8.5, into the organic phase via ester formation with a conjugate base form of the ABA coupled by ion pair formation with Q+, thereby reducing concentration of xylulose in the hydrolysate, and shifting the xylose/xylulose equilibrium in favor of more xylulose formation;concurrently with the extracting, allowing the low pH medium to flow through the second set of fibers and contact the organic phase contained on the shell side; whereby:the xylulose and hydroxyl ions attached to the ABA are released into the low pH medium, the ABA is re- converted to its non-ionic conjugate acid, andthe Q+ ion, which formed the ion pair with ABA, combines with an X− ion from the low pH medium to re-form the lipophilic salt. 9. The method of claim 1, including selecting an ABA having a property to enhance selectivity for a specific sugar. 10. The method of claim 1, further including controlling the volume of the low pH medium such that the ketose concentration in the recovered solution is higher than the aldose concentration in the saccharified biomass hydrolysate. 11. The method of claim 1, wherein both glucose and xylose from the hydrolysate are simultaneously isomerized by the isomerization catalyst into ketoses, the ketoses are extracted into the organic phase via binding to the ABA and QX, and the ketoses are recovered from the organic phase via back- extraction into the low pH medium while leaving behind other inhibitory compounds in the biomass hydrolysate. 12. The method of claim 1, wherein a micro-porous hollow fiber contactor physically separates the ketose-rich organic phase from the low pH medium during the ketose recovery. 13. The method of claim 1, wherein the step of contacting the pH-adjusted hydrolysate with an isomerization catalyst comprises passing the pH-adjusted hydrolysate through a packed bed reactor containing the isomerization catalyst, wherein the isomerization catalyst facilitates conversion of glucose to fructose. 14. The method of claim 1, wherein the pH of the recovered ketose is adjusted slightly to a pH suitable for converting the ketose to lactic acid, succinic acid, or fumaric acid by native microorganisms. 15. The method of claim 1, wherein the isomerization catalyst preferentially isomerizes xylose into xylulose compared to glucose into fructose, the ABA preferentially binds to ketoses compared to aldoses, and the system is used to separate C5 sugars from C6 sugars. 16. The method of claim 1, wherein the pH of the recovered ketose corresponds to a pH suitable for dehydration of the ketose to furans via an acid-catalyzed chemical reaction. 17. The method of claim 1, wherein the isomerization catalyst comprises xylose isomerase (XI) particles that facilitate the isomerization of both glucose and xylose. 18. The method of claim 1, comprising:a first micro-porous hollow fiber contactor having a lumen side and a shell side, wherein the hydrolyzate flows through the lumen-side in the first micro-porous hollow fiber contactor and the immiscible organic phase flows through the shell-side; anda second micro- porous hollow fiber contactor that physically separates the ketose-rich organic phase from the low pH medium during ketose recovery. 19. The method of claim 1, wherein the saccharified biomass hydrolysate is a lignocellulosic biomass hydrolysate. 20. The method of claim 19, wherein one or more of the ABA, the pH, and temperature of the hydrolysate, are altered to selectively isomerize and extract one or more specific sugars. 21. The method of claim 1, wherein the ABA is present in an immiscible organic phase that is physically separated by a permeable device from the isomerized hydrolysate, the permeable device allowing transport of the sugar from the isomerized hydrolysate into the immiscible organic phase, while substantially preventing dispersion of the immiscible organic phase in the isomerized hydrolysate. 22. The method of claim 7, wherein the immiscible organic phase comprises one or more of octanol, ethyl acetate, dichloromethane, o-nitrophenyl octyl ether (NPOE), or diethyl ether. 23. The method of claim 21, wherein the permeable device is a micro-porous hollow fiber contactor. 24. The method of claim 1, wherein the step of contacting the pH-adjusted- hydrolysate with an isomerization catalyst comprises passing the pH-adjusted hydrolysate through a packed bed reactor containing the isomerization catalyst, wherein the isomerization catalyst facilitates conversion of xylose into xylulose. 25. The method of claim 24, wherein the packed bed reactor is connected in a loop to a micro-porous hollow fiber contactor having a shell side and a fiber side, such that the hydrolysate flows through the packed bed and the fiber side of the micro-porous hollow fiber contactor, and the ketose is extracted from the hydrolysate to the immiscible organic phase on the shell side of the micro-porous hollow fiber contactor. 26. The method of claim 1, including: selecting the ABA such that, at selected pH and temperature conditions, the ABA mainly binds to xylulose, and does not bind to any appreciable amounts of glucose, xylose, or fructose. 27. The method of claim 1, including circulating the hydrolysate through at least a first column comprised of a packed bed of immobilized xylose isomerase (XI), and through a vessel having an ABA-enriched phase therein. 28. The method of claim 1, wherein the pH of the recovered ketose is a pH suitable for converting the ketose to ethanol by native _S. cerevisiae_ or other native microorganisms. 29. The method of claim 1, including controlling a volume of the low pH medium sufficient to recover the ketose as a concentrated solution. 30. The method of claim 1, including separating xylose from other C6 sugars as its keto-isomer and allowing for the recovery of xylulose as a concentrated solution. 31. The method of claim 1, comprising passing the isomerized hydrolysate and the ABA containing organic phase through a micro-porous hollow fiber contactor. 32. The method of claim 1, wherein the ABA is selected from the group consisting of PBA, 3aPBA, 4cPBA, naphthalene-2-boronic acid (N2B), and 4-biphenylboronic acid. 33. The method of claim 1, wherein the ABA has the formula Ar--B(OH)2, where Ar represents an unsubstituted or substituted aryl group. 34. The method of claim 33, wherein the ABA comprises one or more of the aryl groups: 4-PhC6H4--; 4-MeC6H4--, where Me is methyl; 2-iPrC6H4-, where iPr is isopropyl; 2-naphthyl; 3-BnOC6H4--, where Bn is benzyl; 4-MeO2CC6H4--, where Me is methyl; and 4-pyridinyl. 35. The method of claim 33, wherein the ABA comprises a diboronic acid that exhibits a higher selectivity toward ketose binding compared to monoboronic acids. 36. The method of claim 33, wherein the ABA comprises a multi-dentate boronic acid carrier. 37. The method of claim 36, wherein the ABA comprises one or more of: wherein A and C are B(OH)2, and B and D are H groups. 38. The method of claim 1, wherein the ABA comprises a hydrophobic substituted aryl boronic acid. 39. The method of claim 38, wherein the ABA comprises: 40. The method of claim 38, wherein the hydrophobic substituted aryl boronic acid is used in a liquid-liquid extraction followed by stripping or micro- porous hollow fiber contactor implementation.
4/19/11 12:00:00 AM
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4.1.2 Reaction separation and solvent extraction
Process for the preparation and separation of arabinose and xylose from a mixture of saccharides

1. A process for the separation of arabinose and xylose acetals which comprises:(a) providing a mixture comprising xylose and arabinose;(b) reacting the mixture with a ketone or aldehyde so as to form a mixture of xylose monoacetal and arabinose diacetal; and(c) separating the arabinose diacetal and xylose monoacetal from the reaction mixture by a polar solvent and non- polar solvent extraction so that there is a phase separation with the of xylose monoacetal in the polar solvent and the diacetal arabinose in the non- polar organic solvent. 2. The process of claim 1 wherein the mixture in step (a) is from a hydrolysate of corn fiber or sugar beet pulp. 3. The process of claim 1 wherein the xylose monoacetal is extracted from the mixture in step (c) with an acid in water as the polar solvent for the xylose monoacetal and the arabinose diacetal by the non-polar solvent, so that there is a phase separation. 4. The process of any one of claims 1, 2, or 3 wherein the arabinose diacetal and xylose monoacetal which are separated in step (c) are pure isomers. 5. A process for the separation of arabinose diacetal and xylose monoacetal from a mixture comprised of saccharides which comprises:(a) reacting the mixture with a ketone or an aldehyde so as to form the arabinose diacetal and xylose monoacetal;(b) concentrating the mixture to a syrup;(c) extracting the syrup with a non-polar organic solvent in which the acetals of arabinose diacetal and xylose monoacetal are soluble to provide the arabinose diacetal and xylose monoacetal in the organic solvent;(d) separating the arabinose diacetal and xylose monoacetal from the organic solvent; and(e) separating the arabinose diacetal from the xylose monoacetal by a polar solvent and a non- polar solvent extraction, so that there is a phase separation with the xylose monoacetal in the polar solvent and the arabinose diacetal in the non-polar organic solvent. 6. The process of claim 5 wherein the mixture of step (a) is a syrup from a hydrolysate of corn fiber or sugar beet pulp. 7. The process of claim 5 or 6 wherein xylose monoacetal is extracted from the mixture with water or a polar organic solvent as the polar solvent and then separated from the water or the polar organic solvent. 8. The process of claim 5 or 6 wherein in addition after step (e) the xylose monoacetal and arabinose diacetal are separately hydrolyzed to form xylose and arabinose. 9. The process of claim 5 or 6 wherein in step (e) the arabinose diacetal and the xylose monoacetal which are separated are pure isomers. 10. The process of claims 1, 2, 4 or 3 wherein the mixture of saccharides in step (a) is produced by enzyme or acid hydrolysis of saccharides.
11/9/04 12:00:00 AM
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5. Other techniques

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5.1 Pretreatments that enhance separation

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Several types of pretreatments were found that enhance the recovery of monomeric sugars: **Ionic liquid-based pretreatments:** * After treating the switchgrass with \[C2mim\]\[OAc\] and dilution with water to a final IL concentration of 10–20%, the pretreatment slurry was directly hydrolyzed using a thermostable IL tolerant enzyme cocktail previously developed at the Joint BioEnergy Institute (JBEI). This onepot process liberated 81.2% glucose and 87.4% xylose (monomers and oligomers) at 72 h at 70 °C with an enzyme loading of 5.75 mg g−1 of biomass at 10% \[C2mim\]\[OAc\]. Glucose and xylose were selectively separated by liquid–liquid extraction with over 90% efficiency, thus eliminating extensive water washing as a unit operation. Art. [#ARTNUM](#article-29968-1982632394) * Fractionation of sugarcane bagasse into three pure streams of chemical constituents was addressed through dissolution of constituents with the ionic liquids, 1ethyl3methylimidazolium acetate (\[EMiM\]CH3COO) or 1butyl3methylimidazolium methyl sulfate (\[BMiM\]MeSO4). Constituents were isolated from the reaction mixture with the antisolvents acetone (Ā), acetone–water (AW), and sodium hydroxide (NaOH). Delignification was enhanced by NaOH, although resulting in impure product streams. Xylose preextraction (75 % w/w) by dilute acid pretreatment, prior to ionic liquid treatment, improved lignin purity after antisolvent separation. Fractionation efficiency of the combined process was maximized (84 %) by ionic liquid treatment at 125 °C for 120 min, resulting in 80.2 % (w/w) lignin removal and 76.5 % (w/w) lignin recovery. Ionic liquids achieved similar degrees of delignification, although fully digestible celluloserich solids were produced only by \[EMiM\]CH3COO treatment. Art. [#ARTNUM](#article-29968-2098558767) * Cholinium ILs were found to be effective pretreatment solvents for grass lignocelluloses as well as eucalyptus, resulting in significant improvements in the glucose yields (58–75%) in subsequent enzymatic hydrolysis, while they were inefficient to make pine susceptible to biodegradation. Approximately 46% of lignin in native rice straw was fractionated as LRM after pretreatment using cholinium argininate (\[Ch\]\[Arg\]). \[Ch\]\[Arg\] showed excellent recyclability, and the total recovery was as high as 75% after reused for 8 cycles. Art. [#ARTNUM](#article-29968-2211929158) * Herein, an ionic liquid/water (IL/w) system was developed to separate hemicelluloses from the chemical pulp with enhanced efficiency by employing xylanase. In the traditional IL/w process, when the water content was in the range 2015%, the extraction of hemicelluloses was 71–80%. However, the highly efficient hemicelluloses removal was always accompanied with an increased cellulose loss. In this regard, xylanase (X) pretreatment was introduced to facilitate the IL/w process for improving the separation selectivity/efficiency of the hemicelluloses. In the case of the IL/w20 (water content is 20%) procedure, X 30 (30 mg/g xylanase) pretreatment could increase hemicelluloses removal from 71 to 78%, while the separation selectivity increased from 11.0 to 43.8. Art. [#ARTNUM](#article-29968-2757843086) **Other solvent-based pretreatments:** * This dissertation outlines the inception, development, and application of a novel biomass conversion technology called Cosolvent Enhanced Lignocellulosic Fractionation, or CELF, that applies tetrahydrofuran (THF) as a miscible aqueous cosolvent to greatly augment the dilute acidcatalyzed deconstruction of lignocellulosic biomass to enable production of renewable fuels and chemicals at unprecedented yields. CELF directly enhances the production of primary fuel precursors such as monomeric sugars. Reducing the reaction severity of CELF with dilute sulfuric acid drastically improved total sugar recovery, achieving 95% xylose recovery from corn stover after first stage pretreatment and subsequent > 99% glucose recovery after enzymatic hydrolysis of the remaining solids at an enzyme dosage of only 2 mgprotein gglucan1. In all cases, CELF was effective at delignifying the biomass, dissolving up to 90% of the lignin into the liquid phase. Art. [#ARTNUM](#article-29968-87783891) * Herein, a biomassderived deep eutectic solvent (DES) pretreatment was developed to deconstruct the recalcitrant structure of Eucalyptus for further cellulose enzymatic hydrolysis and lignin valorization. The DES consisted of biomassderived chemicals (lactic acid and choline chloride). The results showed that DES pretreatment resulted in notable removal of hemicelluloses and lignin, and drastically reduced “biomass recalcitrance”. Under the optimum conditions (DES ratio: 10 : 1, temperature: 110 °C, time: 6 h), the glucose yield by enzymatic hydrolysis reached 94.3%, which was significantly enhanced 9.8 times compared to that of the original biomass without DES pretreatment. Art. [#ARTNUM](#article-29968-2902977272) **Filtration-based pretreatment:** * In this work nanofiltration technology has been employed for removal of inhibitors and recovery of monosaccharides from dilute acid lignocellulose hydrolysates. The influences of feed solution pH, permeate flux, and Na2SO4 concentration on the rejection of monosaccharides and inhibitors were investigated. This process allowed the removal of 90% inhibitors, while 93.55% glucose, 90.75% xylose, and 90.53% arabinose were recovered. Finally, a batch column equipped with a strong acid cation exchange resin was employed to recover the monosaccharides from the hydrolysate. Using water as an eluent, 95.37% of the sulfuric acid and 94.87% of the monosaccharides were recovered. In all, we demonstrated that the combination of nanofiltration with electrolyte exclusion chromatography is a promising integrated process for the recovery of monosaccharides and inorganic acids from dilute acid corncob hydrolysates. Art. [#ARTNUM](#article-29968-2796257764) * Ultrafiltration is carried out with an organic membrane in a first time to remove precipitating macromolecules. Afterwards conventional electrodialysis allows the sulfuric acid recovery from hydrolysate in order to recycle it for the hydrolysis step. ED is a key step as it allows a double chemical saving: less fresh sulfuric acid is needed for hydrolysis and no alkaline chemicals are consumed to neutralize acid and precipitate macromolecules. Thus the salts content is considerably decreased, facilitating the further demineralization by ion-exchange and also resulting in the reduction of chemicals consumption. After activated carbon treatment, the product contains only sugars (glucose, xylose and arabinose). They can be separated from each other by continuous chromatography or crystallization. Pat. [#ARTNUM](#article-29968-2535941283) * In shortterm filtrations, the nanofiltered permeate of the original hydrolyzate had 78–82% xylose of the TDS p (total dry solids in permeate) and the modified hydrolyzate 86–88% xylose of the TDS p . Thus, considerable xylose purification was obtained. The addition of crystalline xylose into the hemicellulose hydrolyzate gave a notable increase in permeate fluxes. The 20h filtration showed fouling and compaction effects as a flux decrease of approximately 10–25% was detected in the retention integrity test. According to the results, xylose purification from hemicellulose hydrolyzate could be enhanced by nanofiltration. Art.[#ARTNUM](#article-29968-1984209600) * Ultrafiltration was assessed to separate the components of the SCB alkaline extract which is a prerequisite for their further valorization. The permeate flux and the retention of the extract components were studied on seven membranes (polysulfone hollow fiber and ceramic tubular) with different molecular weight cutoffs, under various operating conditions. On all the membranes tested, oligomers of lignin and hemicelluloses were separated from salts, phenolic monomers and acetic acid. The 10 kDa polysulfone hollow fiber membrane presented the highest lignin and hemicelluloses retention, exceeding 85 and 90%, respectively, regardless of shear rate and with a limited influence of transmembrane pressure. For salts, acetic acid and phenolic monomers, retention levels of about 0–10% were recorded for this membrane. Art. [#ARTNUM](#article-29968-2909881858) **Other pretreatments:** * Optimizing of the thermal treatment was investigated. A treatment at 170 °C for 2 h was found optimal, with higher solubilzation of hemicellulose than that at 150 °C and lower degradation of sugar monomers than 190 °C. Recovery of xylose was high and the purity of xylose solution (78%) allows expecting an easy purification and separation of xylose before hydrogenation. Analysis of thermal hydrolyzates shows the presence of xylan oligomers and polymers with large distribution of DPs. This fraction should be submitted to enzymatic treatment to recover more xylose monomer. Art. [#ARTNUM](#article-29968-2003335961) * Ultrasound (US) can be used to disrupt microcrystalline cellulose to give nanofibers via ultrasonic cavitation. Sodium percarbonate (SP), consisting of sodium carbonate and hydrogen peroxide, generates highly reactive radicals, which cause oxidative delignification. Here, we describe a novel pretreatment technique using a combination of US and SP (US–SP) for the efficient saccharification of cellulose and hemicellulose in lignocellulosic corn stover. Although US–SP pretreatment was conducted under mild condition (i.e., at room temperature and atmospheric pressure), the pretreatment greatly increased lignin removal and cellulose digestibility. We also determined the optimum US–SP treatment conditions, such as ultrasonic power output, pretreatment time, pretreatment temperature, and SP concentration for an efficient cellulose saccharification. Moreover, xylose could be effectively recovered from US–SP pretreated biomass without the formation of microbial inhibitor furfural. Art. [#ARTNUM](#article-29968-2138906300) * In this research, dilute acid hydrolysis is applied for the treatment toward OPF and parameters of reaction time (30, 60 and 90min) and acid concentration (2%, 3% and 4%) are taken into account in order to get the optimum conditions for xylose recovery from OPF. The result shows that, highest yield of xylose concentration is at 30 minutes of reaction time and 4% of H2SO4 acid concentration at condition of 1000C, solid to liquid ratio of 1:10. Besides these parameters, xylose recovery before and after detoxification process were also observed. The detoxification process help to increases the concentration of xylose at 1:10 of solid liquid ratio and temperature of 1000C, the xylose concentration before detoxification process was 6.638g/L and 7.759 g/L after detoxification process Art. [#ARTNUM](#article-29968-2175989301) * The present work evaluates a twostep pretreatment process based on steam explosion and extrusion technologies for the optimal fractionation of lignocellulosic biomass. Twostep pretreatment of barley straw resulted in overall glucan, hemicellulose and lignin recovery yields of 84%, 91% and 87%, respectively. Precipitation of the collected ligninrich liquid fraction yielded a solid residue with high lignin content, offering possibilities for subsequent applications. Moreover, hydrolysability tests showed almost complete saccharification of the pretreated solid residue, which when combined with the low concentration of the generated inhibitory compounds, is representative of a good pretreatment approach. Art. [#ARTNUM](#article-29968-2609343073)

5.1.1 Pretreatments that enhance separation
A Sequential Steam Explosion and Reactive Extrusion Pretreatment for Lignocellulosic Biomass Conversion within a Fermentation-Based Biorefinery Perspective
The present work evaluates a two-step pretreatment process based on steam explosion and extrusion technologies for the optimal fractionation of lignocellulosic biomass. Two-step pretreatment of barley straw resulted in overall glucan, hemicellulose and lignin recovery yields of 84%, 91% and 87%, respectively. Precipitation of the collected lignin-rich liquid fraction yielded a solid residue with high lignin content, offering possibilities for subsequent applications. Moreover, hydrolysability tests showed almost complete saccharification of the pretreated solid residue, which when combined with the low concentration of the generated inhibitory compounds, is representative of a good pretreatment approach. Scheffersomyces stipitis was capable of fermenting all of the glucose and xylose from the non-diluted hemicellulose fraction, resulting in an ethanol concentration of 17.5 g/L with 0.34 g/g yields. Similarly, Saccharomyces cerevisiae produced about 4% (v/v) ethanol concentration with 0.40 g/g yields, during simultaneous saccharification and fermentation (SSF) of the two-step pretreated solid residue at 10% (w/w) consistency. These results increased the overall conversion yields from a one-step steam explosion pretreatment by 1.4-fold, showing the effectiveness of including an extrusion step to enhance overall biomass fractionation and carbohydrates conversion via microbial fermentation processes.
4/20/17 12:00:00 AM
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5.1.2 Pretreatments that enhance separation
Co-Solvent Enhanced Production of Platform Fuel Precursors From Lignocellulosic Biomass
Lignocellulosic biomass is the most abundant source of organic carbon on Earth with the highest potential to economically and sustainably replace fossil resources for large-scale production of liquid fuels. However, although lignocellulosic biomass itself is much less expensive than petroleum, its natural resistance to chemical and biological breakdown is the major obstacle that must be overcome for biomass-derived fuels to be economically competitive. This dissertation outlines the inception, development, and application of a novel biomass conversion technology called Co-solvent Enhanced Lignocellulosic Fractionation, or CELF, that applies tetrahydrofuran (THF) as a miscible aqueous co-solvent to greatly augment the dilute acid-catalyzed deconstruction of lignocellulosic biomass to enable production of renewable fuels and chemicals at unprecedented yields. CELF directly enhances the production of primary fuel precursors such as monomeric sugars and secondary fuel precursors such as furfural, 5-HMF, and levulinic acid (LA) from biomass to integrate with downstream catalytic and biological processes to convert the fuel precursors into liquid fuels and renewable chemicals. In this dissertation, three different process configurations for CELF are evaluated. First, coupling CELF with sulfuric acid at higher reaction severities achieved 87% furfural yield from maple wood and produced a glucan enriched solid that was further reacted to LA at 75% yield in a subsequent reaction. Second, coupling CELF with metal halides achieved simultaneous production of furfural at 95% yield and 5-HMF at 51% yield from maple wood and corn stover. Third, reducing the reaction severity of CELF with dilute sulfuric acid drastically improved total sugar recovery, achieving 95% xylose recovery from corn stover after first stage pretreatment and subsequent > 99% glucose recovery after enzymatic hydrolysis of the remaining solids at an enzyme dosage of only 2 mg-protein g-glucan-1. In all cases, CELF was effective at de-lignifying the biomass, dissolving up to 90% of the lignin into the liquid phase. Afterwards, recovery of THF by low temperature distillation caused the dissolved lignin to precipitate as a solid. In addition to enhancing fuel precursor yields, CELF can also serve as a valuable tool to help understand biomass recalcitrance and deconstruction.
1/1/14 12:00:00 AM
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5.1.3 Pretreatments that enhance separation
Facile fractionation of lignocelluloses by biomass-derived deep eutectic solvent (DES) pretreatment for cellulose enzymatic hydrolysis and lignin valorization
A low-cost and green biorefinery will increase the economy and revenue from lignocellulosic biomass. Herein, a biomass-derived deep eutectic solvent (DES) pretreatment was developed to deconstruct the recalcitrant structure of Eucalyptus for further cellulose enzymatic hydrolysis and lignin valorization. The DES consisted of biomass-derived chemicals (lactic acid and choline chloride). The results showed that DES pretreatment resulted in notable removal of hemicelluloses and lignin, and drastically reduced “biomass recalcitrance”. Under the optimum conditions (DES ratio: 10 : 1, temperature: 110 °C, time: 6 h), the glucose yield by enzymatic hydrolysis reached 94.3%, which was significantly enhanced 9.8 times compared to that of the original biomass without DES pretreatment. The state-of-the-art analysis indicated that the regenerated lignin exhibited well-preserved structures (i.e., β-O-4, β–β linkages) without contaminated carbohydrates, and it had a relatively low and homogeneous molecular weight. All these structural characteristics suggested that lignin has great potential application in its conversion into bio-based chemicals and materials. Besides, it is urgent to develop low-cost recycled DESs as green solvents for sustainable biomass pretreatment. The lifetime and recyclability experiment of the DES solution showed that the recovery yield of the DES was at least 90% and the fundamental structural properties of the recycled DES were almost unchanged throughout the recycling cycles. More importantly, the pretreatment efficiency (delignification and enzymatic saccharification) was still largely maintained after the recycling process. Overall, this work demonstrated that biomass pretreatment with the recycled DES was promising for a low-cost biorefinery to achieve an efficient fractionation of lignocellulosic biomass into fermentable glucose and high-quality lignin with tailored chemical structures.
1/1/19 12:00:00 AM
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5.1.4 Pretreatments that enhance separation
Facilitate hemicelluloses separation from chemical pulp in ionic liquid/water by xylanase pretreatment
Abstract Herein, an ionic liquid/water (IL/w) system was developed to separate hemicelluloses from the chemical pulp with enhanced efficiency by employing xylanase. In the traditional IL/w process, when the water content was in the range 20-15%, the extraction of hemicelluloses was 71–80%. However, the highly efficient hemicelluloses removal was always accompanied with an increased cellulose loss. In this regard, xylanase (X) pretreatment was introduced to facilitate the IL/w process for improving the separation selectivity/efficiency of the hemicelluloses. In the case of the IL/w-20 (water content is 20%) procedure, X 30 (30 mg/g xylanase) pretreatment could increase hemicelluloses removal from 71 to 78%, while the separation selectivity increased from 11.0 to 43.8. Additionally, X pretreatment also reduced IL usage/charge to achieve the same degree of hemicelluloses removal.
12/1/17 12:00:00 AM
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5.1.5 Pretreatments that enhance separation
Fractionation of Sugarcane Bagasse Using a Combined Process of Dilute Acid and Ionic Liquid Treatments
Biorefineries processing lignocellulose will produce chemicals and fuels from chemical constituents, cellulose, hemicelluloses, and lignin to replace fossil-derived products. Fractionation of sugarcane bagasse into three pure streams of chemical constituents was addressed through dissolution of constituents with the ionic liquids, 1-ethyl-3-methylimidazolium acetate ([EMiM]CH3COO) or 1-butyl-3-methylimidazolium methyl sulfate ([BMiM]MeSO4). Constituents were isolated from the reaction mixture with the anti-solvents acetone (Ā), acetone–water (AW), and sodium hydroxide (NaOH). Delignification was enhanced by NaOH, although resulting in impure product streams. Xylose pre-extraction (75 % w/w) by dilute acid pretreatment, prior to ionic liquid treatment, improved lignin purity after anti-solvent separation. Fractionation efficiency of the combined process was maximized (84 %) by ionic liquid treatment at 125 °C for 120 min, resulting in 80.2 % (w/w) lignin removal and 76.5 % (w/w) lignin recovery. Ionic liquids achieved similar degrees of delignification, although fully digestible cellulose-rich solids were produced only by [EMiM]CH3COO treatment.
8/1/12 12:00:00 AM
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5.1.6 Pretreatments that enhance separation
One-pot ionic liquid pretreatment and saccharification of switchgrass
Biomass pretreatment using certain ionic liquids (ILs), such as 1-ethyl-3-methylimidazolium acetate ([C2mim][OAc]), can be highly effective at reducing the recalcitrance of lignocellulosic biomass to enzymatic degradation. However, current commercial enzyme cocktails, derived from filamentous fungi and developed for dilute acid pretreatment, are inhibited by the most effective ILs used for pretreatment and require excessive amounts of water to remove the ILs from biomass after pretreatment in order to be effective. The associated IL recycling and waste disposal costs of this process pose significant economic and process engineering challenges for the commercial scale-up of IL pretreatment-based technologies. For the first time, we have demonstrated a one-pot, wash-free process that combines IL pretreatment and saccharification into a single vessel. After treating the switchgrass with [C2mim][OAc] and dilution with water to a final IL concentration of 10–20%, the pretreatment slurry was directly hydrolyzed using a thermostable IL tolerant enzyme cocktail previously developed at the Joint BioEnergy Institute (JBEI). This one-pot process liberated 81.2% glucose and 87.4% xylose (monomers and oligomers) at 72 h at 70 °C with an enzyme loading of 5.75 mg g−1 of biomass at 10% [C2mim][OAc]. Glucose and xylose were selectively separated by liquid–liquid extraction with over 90% efficiency, thus eliminating extensive water washing as a unit operation. This study opens avenues for developing more efficient and cost effective processes for product recovery and IL recycling.
1/1/13 12:00:00 AM
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5.1.7 Pretreatments that enhance separation
Optimization of sugarcane bagasse conversion by hydrothermal treatment for the recovery of xylose
Abstract This work aims at the valorization of sugarcane bagasse by extracting xylose which is destined to the production of xylitol after purification and hydrogenation. Our approach consists in applying the principle of biorefinery to sugarcane bagasse because of its hemicellulose composition (particularly rich in xylan: (92%)). Optimizing of the thermal treatment was investigated. A treatment at 170 °C for 2 h was found optimal, with higher solubilzation of hemicellulose than that at 150 °C and lower degradation of sugar monomers than 190 °C. Recovery of xylose was high and the purity of xylose solution (78%) allows expecting an easy purification and separation of xylose before hydrogenation. Analysis of thermal hydrolyzates shows the presence of xylan oligomers and polymers with large distribution of DPs. This fraction should be submitted to enzymatic treatment to recover more xylose monomer.
12/1/09 12:00:00 AM
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5.1.8 Pretreatments that enhance separation
Pretreatment combining ultrasound and sodium percarbonate under mild conditions for efficient degradation of corn stover.
Abstract Ultrasound (US) can be used to disrupt microcrystalline cellulose to give nanofibers via ultrasonic cavitation. Sodium percarbonate (SP), consisting of sodium carbonate and hydrogen peroxide, generates highly reactive radicals, which cause oxidative delignification. Here, we describe a novel pretreatment technique using a combination of US and SP (US–SP) for the efficient saccharification of cellulose and hemicellulose in lignocellulosic corn stover. Although US–SP pretreatment was conducted under mild condition (i.e., at room temperature and atmospheric pressure), the pretreatment greatly increased lignin removal and cellulose digestibility. We also determined the optimum US–SP treatment conditions, such as ultrasonic power output, pretreatment time, pretreatment temperature, and SP concentration for an efficient cellulose saccharification. Moreover, xylose could be effectively recovered from US–SP pretreated biomass without the formation of microbial inhibitor furfural.
3/1/16 12:00:00 AM
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5.1.9 Pretreatments that enhance separation
Pretreatment of lignocellulosic biomass with renewable cholinium ionic liquids: Biomass fractionation, enzymatic digestion and ionic liquid reuse
Abstract Pretreatment of lignocelluloses is a key step in the biorefinery for production of biofuels and valuable platform chemicals. In this work, various lignocelluloses were pretreated using cholinium ionic liquids (ILs) that are wholly composed of biomaterials, and fractionated into carbohydrate-rich materials (CRMs) and lignin-rich materials (LRMs). Cholinium ILs were found to be effective pretreatment solvents for grass lignocelluloses as well as eucalyptus, resulting in significant improvements in the glucose yields (58–75%) in subsequent enzymatic hydrolysis, while they were inefficient to make pine susceptible to biodegradation. Approximately 46% of lignin in native rice straw was fractionated as LRM after pretreatment using cholinium argininate ([Ch][Arg]). [Ch][Arg] showed excellent recyclability, and the total recovery was as high as 75% after reused for 8 cycles. Besides, rice straw pretreated by the recycled IL remained highly digestible, and good glucose yields (63–75%) were achieved after its enzymatic hydrolysis.
9/1/15 12:00:00 AM
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5.1.10 Pretreatments that enhance separation
Purification of pentoses from hemicellulosic hydrolysates without neutralization for sulfuric acid recovery
Abstract The agro-industrial sector generates large amounts of coproducts such as lignocellulosic biomass which could be valorized into many chemicals and bio-based intermediates (sugars, paper pulp, surfactants, polymers or bioethanol). However, in the case of biomass hydrolysis by diluted sulfuric acid, current downstream processes involve a partial or complete neutralization which are not satisfactory for economic and environmental reasons. This work presents a purification process of pentoses from hemicellulosic hydrolysates without neutralization for sulfuric acid recovery. Compared to conventional processes, less energy, water and chemicals are required. Very promising results were obtained at pilot scale with 100 L of wheat bran hydrolysates. The process is based on the combination of ultrafiltration, conventional electrodialysis and ion-exchange. Ultrafiltration with a 10 kDa organic membrane totally removed harmful macromolecules which precipitate during electrodialysis operation because of pH rise. Till a volumetric concentration factor 3.6, the average flux kept good for industrial application (27 L·h −1 ·m −2 ). However suspended materials have to be filtered before ultrafiltration. Besides, a 2.5 diafiltration is required to recover most of sugars (99%). Then conventional electrodialysis was performed to recover most of sulfuric acid (80%). The average faradic yield was quite good (80%) and the specific energy consumption of the electrodialysis stack was quite interesting (1.1 kW h per kg of H 2 SO 4 recovered and 8.4 kW h per m 3 of hydrolysate). Finally, the complete demineralization (conductivity  −1 ) and discoloration (420 nm absorbance
3/1/17 12:00:00 AM
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5.1.11 Pretreatments that enhance separation
Recovery of monosaccharides from dilute acid corncob hydrolysate by nanofiltration: modeling and optimization
In this work nanofiltration technology has been employed for removal of inhibitors and recovery of monosaccharides from dilute acid lignocellulose hydrolysates. The influences of feed solution pH, permeate flux, and Na2SO4 concentration on the rejection of monosaccharides and inhibitors were investigated. The results showed that the pH for the separation of carboxylic acids and furans from monosaccharides should be as low as possible. With increase of Na2SO4 concentration carboxylic acid and furan rejection decreased. Subsequently, the Donnan steric pore and dielectric exclusion model coupled with mass balance was used to predict the rejection of solutes at different permeate fluxes. In order to select a suitable permeate flux and operating time, multi-objective optimization was carried out to obtain the maximum total inhibitor removal efficiency, the maximum monosaccharide recovery rate, and the minimum water consumption. The optimal operating conditions were then verified using the real hydrolysate as feed solutions. More specifically, for the treatment of 6 L of a hydrolysate solution, 13 L of water and a treatment time of 35 min were required. This process allowed the removal of 90% inhibitors, while 93.55% glucose, 90.75% xylose, and 90.53% arabinose were recovered. Finally, a batch column equipped with a strong acid cation exchange resin was employed to recover the monosaccharides from the hydrolysate. Using water as an eluent, 95.37% of the sulfuric acid and 94.87% of the monosaccharides were recovered. In all, we demonstrated that the combination of nanofiltration with electrolyte exclusion chromatography is a promising integrated process for the recovery of monosaccharides and inorganic acids from dilute acid corncob hydrolysates.
1/1/18 12:00:00 AM
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5.1.12 Pretreatments that enhance separation
Separation of ionic liquid [Mmim][DMP] and glucose from enzymatic hydrolysis mixture of cellulose using alumina column chromatography
Pretreatment of cellulose with ionic liquids (ILs) can improve the efficiency of the hydrolysis by increasing the surface area of the substrates accessible to solvents and cellulases. However, the IL methods are facing challenges to separate the hydrolyzed sugar products as well as the renewable ILs from the complex hydrolysis mixtures. In this study, an alumina column chromatography (ACC) method was developed for the separation of hydrophilic IL N-methyl-N-methylimidazolium dimethyl phosphate ([Mmim][DMP]) and glucose, which was the main ingredient of the monosaccharide hydrolyzate. The processing parameters involved in ACC separation were investigated in detail. Our results showed that the recovery yields of [Mmim][DMP] and glucose can reach up to 93.38% and 90.14%, respectively, under the optimized parameters: the sampling ratio of 1:20 between the applied sample volume and the bed volume of the column; a gradient elution using methanol (100%, 150 ml) and then water (170 ml) as eluents with 1 ml/min flow rate. The recovered [Mmim][DMP] showed qualified property and was effective in a new hydrolysis reaction. In addition, scale-up ACC separations were successfully done with satisfied separation performance. The results indicated that the ACC is one of the available methods for the separation of ILs and monosaccharides from the hydrolysis mixtures.
7/1/11 12:00:00 AM
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5.1.13 Pretreatments that enhance separation
Separation of sugarcane bagasse mild alkaline extract components by ultrafiltration – Membrane screening and effect of filtration parameters
Abstract Mild alkaline treatment (1.5% NaOH (w/v), solid:liquid ratio of 1:20, 60 °C, 6 h) of sugarcane bagasse (SCB) produced an extract composed of hemicelluloses, lignin, phenolic monomers and acetic acid. The purification of this extract, usually considered a by-product in lignocellulosic biorefineries, is of major importance to give value to the whole mild alkaline fractionation process. Ultrafiltration was assessed to separate the components of the SCB alkaline extract which is a prerequisite for their further valorization. The permeate flux and the retention of the extract components were studied on seven membranes (polysulfone hollow fiber and ceramic tubular) with different molecular weight cut-offs, under various operating conditions. On all the membranes tested, oligomers of lignin and hemicelluloses were separated from salts, phenolic monomers and acetic acid. The 10 kDa polysulfone hollow fiber membrane presented the highest lignin and hemicelluloses retention, exceeding 85 and 90%, respectively, regardless of shear rate and with a limited influence of transmembrane pressure. For salts, acetic acid and phenolic monomers, retention levels of about 0–10% were recorded for this membrane. At 2.8 bar and at 20 °C, the permeate flux reached 16 L/h/m 2 and the critical flux was not reached.
3/1/19 12:00:00 AM
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5.1.14 Pretreatments that enhance separation
Xylose production from oil palm frond (opf)
The biotechnological routes increasing interests among the researchers in employing lignocellulosic biomass since these biomass are cheap, renewable and have potential as sugar sources. Oil palm frond (OPF) is one of the oil palm biomass which is available in a large amount annually worldwide in oil palm plantation. OPF is a cheap, widely available and potential renewable source for the production of xylose. This xylose is very useful as a substrate for the production of natural sweetener of xylitol. In order to recover xylose from biomass of OPF, the process of hydrolysis toward OPF need to be done together with suitable parameter as xylose will be used as medium in xylitol production for the next process. Dilute acid hydrolysis is commonly used for sugar recovery from biomass (lignocellulosic sources). In this research, dilute acid hydrolysis is applied for the treatment toward OPF and parameters of reaction time (30, 60 and 90min) and acid concentration (2%, 3% and 4%) are taken into account in order to get the optimum conditions for xylose recovery from OPF. The result shows that, highest yield of xylose concentration is at 30 minutes of reaction time and 4% of H2SO4 acid concentration at condition of 1000C, solid to liquid ratio of 1:10. Besides these parameters, xylose recovery before and after detoxification process were also observed. The detoxification process help to increases the concentration of xylose at 1:10 of solid liquid ratio and temperature of 1000C, the xylose concentration before detoxification process was 6.638g/L and 7.759 g/L after detoxification process
1/1/14 12:00:00 AM
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5.1.15 Pretreatments that enhance separation
Xylose recovery by nanofiltration from different hemicellulose hydrolyzate feeds
Abstract Xylose is an intermediate product in xylitol production. Nanofiltration could simplify and enhance this separation step conventionally done by chromatographic methods. Here different hemicellulose hydrolyzate feeds were nanofiltered to recover xylose into the permeate. Two different batches of hemicellulose hydrolyzate were prepared: the hydrolyzate as such and modified with crystalline xylose addition. Both feed solutions were diluted to a total dry solids (TDS) content of approximately 21 wt.% and the xylose contents were 48.7% and 59.1% of the TDS f (total dry solids in feed). The filtration experiments were made at 40, 50 and 60 °C in total reflux mode for approximately 30 min at each pressure of 20, 25, 30, 35 and 40 bar. In addition, a 20-h filtration was made at 50 °C and 30 bar. A DDS LabStak M20-filter was used and it was equipped with Desal-5 DK, Desal-5 DL and NF270 membranes. In short-term filtrations, the nanofiltered permeate of the original hydrolyzate had 78–82% xylose of the TDS p (total dry solids in permeate) and the modified hydrolyzate 86–88% xylose of the TDS p . Thus, considerable xylose purification was obtained. The addition of crystalline xylose into the hemicellulose hydrolyzate gave a notable increase in permeate fluxes. The 20-h filtration showed fouling and compaction effects as a flux decrease of approximately 10–25% was detected in the retention integrity test. According to the results, xylose purification from hemicellulose hydrolyzate could be enhanced by nanofiltration.
3/5/08 12:00:00 AM
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