Pentanediol Production

Scout intake sheet

2
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. One of these products is 1,5-Pentanediol. It has a wide range of applications and can be used as intermediate applications or as an initial product for chemical syntheses, Inks and coatings, Plasticizers and Solvent, or Industrial chemicals. It can be used as an ingredient for the production of polymeric thickeners, plasticizers for polyvinyl chloride, sizing agents, surfactants, for starches and chemically modified starch for application in the paper, textile and food industry, for personal hygiene products like shampoo, creams, and for paints. Therefore, finding new ways to synthesize 1,5-Pentanediol from biorefinery products is very important to the industry. To identify new way of connecting the synthesis of 1,5-penatendiol with biorefinery products, this project will focus on identifying production paths of 1,5-Pentanediol. From this list, processes that fit the biorefinery cycle can be identified and matched.

Scope
Discover Demonstrate Develop Deploy
Current known technique(s)
  • hydrogenolysis of furfuryl alcohol
Ideal outcome

New ways of creating 1,5-Pentanediol that match current biorefinery process **Ideal outcome** An overview of the existing techniques to produce 1,5-Pentanediol

Constraint(s)
  • Any feedstock
  • Purity of the initial component (ex: furfural)
  • Complexity (# of steps)
  • Reaction medium
Functions
Action = [produce] OR [hydrogenate] OR [ hydrogenolysis]

Object = [1,5-pentanediol] OR [glutaric acid] OR [tetrahydrofurfuryl ]

Environment = [refinery] OR [process] OR [pentanediol] OR [production] OR [pentane diol] OR [pentamethylene glycol] OR [one-pot] OR [1,5-pentanediol] OR [noble] OR [one step] OR [Pd] OR [catalyst] OR [Pt] OR [ring] OR [hydrogenolysis] OR [direct] OR [1,5pentanediol] OR [1,5] OR [15ped] OR [copper] OR [dihydropyran] OR [autocatalytic] OR [pentanediol] OR [Hydroxytetrahydropyran] OR [5-aminovalerate] OR [dilute] OR [acid] OR [deltahydroxyvaleraldehyde] OR [selling] OR [direct] OR [prokaryot]
Terminology
  • HO(CH2)5OH (1,5-Pentanediol)
  • Furfural

Preliminary Results

Published 7/23/19

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 produce 1,5Pentanediol. Three concepts are distinguished based on the results: 1. From Tetrahydrofurfuryl alcohol (THFA) 2. Direct from Furfural 3. Other routes / base component Every concept comprises multiple techniques (20 in total). Below the table, short descriptions, research findings and sources per techniques 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. From Tetrahydrofurfuryl alcohol (THFA)
Using THFA as a starting block
1.1 Silica or carbon-supported rhodium catalysts modified with Re, Mo or W

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1.2 Binary catalyst of MoO3 and supported Rh nanoparticles

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1.3 Cu nanoparticles supported on variety of oxide supports

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1.4 NiY2O3 catalyst containing ruthenium (Ru/NiY2O3)

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1.5 Rh based catalysts

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2. Direct from Furfural
Direct conversion from furfural without intermediate steps
2.1 Direct one pot from Furfural/Furfuryl Alcholol ring-opening with noble metal catalyst

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2.2 From Furfural and THFA with NiY/NiLa composity catalyst

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2.3 One Pot reaction on a Pdadded Ir– ReOx/SiO2 catalysts through twostep reaction temperature

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2.4 Direct conversion based on Pt/Co2AlO4 catalyst under mild conditions

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2.5 New catalytic strategies for α,ω-diols production from lignocellulosic biomass

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3. Other routes / base component
Starting from other components than THFA or Furfural
3.1 From oxidation of cyclohexane glutaric acid byproducts with Copper containing catalyst

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3.2 Autocatalytic Hydration of Dihydropyran to 2hydroxytetrahydropyran, to 1,5-PeD

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3.3 Enzymatic production of 5-aminovalerate from L-lysine using L-lysine monooxygenase and 5-aminovaleramide amidohydrolase as a platform for 1,5PeD

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3.4 Hdrogenation of a 5,6dihydro-2H-pyran derivative with a Ni catalyst in the presence of water.

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3.5 Hydrogenation of dicarboxylic acid mixture with Ruthenium and Tin catalyst

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3.6 Hydrolysis of dihydropyran in dilute acid

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3.7 Optically active 1,5PeD

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3.8 Reaction of a specific butenal derivative with formaldehyde

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3.9 Recombinant organism (prokaryotic or eukaryotic)

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3.10 Solution polymerization in dimethyl formamide

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1. From Tetrahydrofurfuryl alcohol (THFA)

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Using THFA as a starting block


1.1 Silica or carbon-supported rhodium catalysts modified with Re, Mo or W

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The production of 1,5pentanediol from tetrahydrofurfuryl alcohol, which can be produced from biomass via furfural, is reviewed. Silica or carbonsupported rhodium catalysts modified with Re, Mo or W show high activity and selectivity, while commercial hydrogenation catalysts such as Ru/C, copper chromite and Raney Ni show much lower activity and selectivity. The formation of metal bond between rhodium metal particles and additive metal is a key to the high performance. The reaction mechanism is discussed based on the characterization data, reactivity of related substrates and kinetics. ([Art. #ARTNUM](#article-26768-2060007857))

1.1.1 1.1 Silica or carbon-supported rhodium catalysts modified with Re, Mo or W
Production of 1,5-pentanediol from biomass via furfural and tetrahydrofurfuryl alcohol
Abstract Production of 1,5-pentanediol from tetrahydrofurfuryl alcohol, which can be produced from biomass via furfural, is reviewed. Silica- or carbon-supported rhodium catalysts modified with Re, Mo or W show high activity and selectivity, while commercial hydrogenation catalysts such as Ru/C, copper chromite and Raney Ni show much lower activity and selectivity. The formation of metal bond between rhodium metal particles and additive metal is a key to the high performance. The reaction mechanism is discussed based on the characterization data, reactivity of related substrates and kinetics.
11/1/12 12:00:00 AM
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1.2 Binary catalyst of MoO3 and supported Rh nanoparticles

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The selective hydrogenolysis of biomassderived tetrahydrofurfuryl alcohol (THFA) to produce 1,5pentanediol (1,5PeD) is accomplished by a binary catalyst consisting of MoO3 and supported Rh nanoparticles; a 1,5PeD selectivity up to 80% is achieved in the present work. Moreover, a very interesting phasetransfer behavior for MoO3 during the reaction is observed with the assistance of different characterization techniques. In this process, MoO3 dissolves partially in the liquid phase under the reaction conditions and is transformed into the soluble hydrogen molybdenum oxide bronzes (HxMoO3) in the presence of H2, which are recognized as the genuinely active sites for the C–O bond breaking of THFA. Density functional theory (DFT) calculations were then carried out to simulate the plausible mechanisms and highlight the role of Mo in the ringopening process of THFA in more detail. We propose that the formation of 1,5PeD takes place in a two consecutive reactions. ([Art. #ARTNUM](#article-22910-2329301016))

1.2.1 1.2 Binary catalyst of MoO3 and supported Rh nanoparticles
Role of MoO3 on a Rhodium Catalyst in the Selective Hydrogenolysis of Biomass-Derived Tetrahydrofurfuryl Alcohol into 1,5-Pentanediol
Selective hydrogenolysis of biomass-derived tetrahydrofurfuryl alcohol (THFA) to produce 1,5-pentanediol (1,5-PeD) is accomplished by a binary catalyst consisting of MoO3 and supported Rh nanoparticles; a 1,5-PeD selectivity up to 80% is achieved in the present work. Moreover, a very interesting phase-transfer behavior for MoO3 during the reaction is observed with the assistance of different characterization techniques. In this process, MoO3 dissolves partially in the liquid phase under the reaction conditions and is transformed into the soluble hydrogen molybdenum oxide bronzes (HxMoO3) in the presence of H2, which are recognized as the genuinely active sites for the C–O bond breaking of THFA. Density functional theory (DFT) calculations were then carried out to simulate the plausible mechanisms and highlight the role of Mo in the ring-opening process of THFA in more detail. We propose that the formation of 1,5-PeD takes place in a two consecutive reactions. THFA first undergoes acid-catalyzed ring-openi...
11/6/14 12:00:00 AM
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1.3 Cu nanoparticles supported on variety of oxide supports

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Cu nanoparticles supported on a variety of oxide supports, including SiO 2 , TiO 2 , ZrO 2 , Al 2 O 3 , MgO and ZnO, were investigated for the hydrogenolysis of biomassderived furfuryl alcohol to 1,2pentanediol and 1,5pentanediol. A CuAl 2 O 3 catalyst with 10 wt% Cu loading prepared by a coprecipitation method exhibited the best performance in terms of producing pentanediols compared with the other materials. This catalyst generated an 85.8% conversion and a 70.3% combined selectivity for the target pentanediols at 413 K and 8 MPa H 2 over an 8h reaction. The catalyst could also be recycled over repeated reaction trials without any significant decrease in productivity. Characterizations with Xray diffraction, NH 3 /CO 2 temperature programmed desorption, N 2 adsorption, transmission electron microscopy and N 2 O chemisorption demonstrated that intimate and effective interactions between Cu particles and the acidic Al 2 O 3 support in this material greatly enhanced its activity and selectivity. The promotion of the hydrogenolysis reaction was found to be especially sensitive to the Cu particle size, and the catalyst with Cu particles 1.9 to 2.4 nm in size showed the highest turnover frequency during the synthesis of pentanediols. ([Art. #ARTNUM](#article-22909-2342134153))

1.3.1 1.3 Cu nanoparticles supported on variety of oxide supports
Selective hydrogenolysis of biomass-derived furfuryl alcohol into 1,2- and 1,5-pentanediol over highly dispersed Cu-Al2O3 catalysts
Abstract Cu nanoparticles supported on a variety of oxide supports, including SiO 2 , TiO 2 , ZrO 2 , Al 2 O 3 , MgO and ZnO, were investigated for the hydrogenolysis of biomass-derived furfuryl alcohol to 1,2-pentanediol and 1,5-pentanediol. A Cu-Al 2 O 3 catalyst with 10 wt% Cu loading prepared by a co-precipitation method exhibited the best performance in terms of producing pentanediols compared with the other materials. This catalyst generated an 85.8% conversion and a 70.3% combined selectivity for the target pentanediols at 413 K and 8 MPa H 2 over an 8-h reaction. The catalyst could also be recycled over repeated reaction trials without any significant decrease in productivity. Characterizations with X-ray diffraction, NH 3 /CO 2 -temperature programmed desorption, N 2 adsorption, transmission electron microscopy and N 2 O chemisorption demonstrated that intimate and effective interactions between Cu particles and the acidic Al 2 O 3 support in this material greatly enhanced its activity and selectivity. The promotion of the hydrogenolysis reaction was found to be especially sensitive to the Cu particle size, and the catalyst with Cu particles 1.9 to 2.4 nm in size showed the highest turnover frequency during the synthesis of pentanediols.
5/1/16 12:00:00 AM
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1.4 NiY2O3 catalyst containing ruthenium (Ru/NiY2O3)

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A NiY2O3 catalyst containing ruthenium (Ru/NiY2O3) was synthesized and applied to the hydrogenolysis of tetrahydrofurfuryl alcohol (THFA) to produce 1,5pentanediol (1,5PeD), which showed superior catalytic performance over that of the NiY2O3 catalyst itself. The optimized rutheniumcontaining catalyst, which was prepared by impregnation of 1.0 wt % ruthenium in NiY2O3, showed high catalytic activity for producing 1,5PeD, giving an 86.5% yield at 93.4% conversion of THFA under 2.0 MPa of H2 at 423 K after 40 h. The formation of RuNi0Y2O3 boundaries was proposed to accelerate the C–O bond scission of the tetrahydrofuran ring to give 1,5PeD. ([Art. #ARTNUM](#article-22906-2775464206))

1.4.1 1.4 NiY2O3 catalyst containing ruthenium (Ru/NiY2O3)
Hydrogenolysis of Tetrahydrofurfuryl Alcohol to 1,5-Pentanediol over a Nickel-Yttrium Oxide Catalyst Containing Ruthenium
A Ni-Y2O3 catalyst containing ruthenium (Ru/Ni-Y2O3) was synthesized and applied to the hydrogenolysis of tetrahydrofurfuryl alcohol (THFA) to produce 1,5-pentanediol (1,5-PeD), which showed superior catalytic performance over that of the Ni-Y2O3 catalyst itself. The optimized ruthenium-containing catalyst, which was prepared by impregnation of 1.0 wt % ruthenium in Ni-Y2O3, showed high catalytic activity for producing 1,5-PeD, giving an 86.5% yield at 93.4% conversion of THFA under 2.0 MPa of H2 at 423 K after 40 h. The formation of Ru-Ni0-Y2O3 boundaries was proposed to accelerate the C–O bond scission of the tetrahydrofuran ring to give 1,5-PeD.
1/5/18 12:00:00 AM
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1.4.2 1.4 NiY2O3 catalyst containing ruthenium (Ru/NiY2O3)
Synthesis of 1,5-Pentanediol by Hydrogenolysis of Furfuryl Alcohol over Ni–Y2O3 Composite Catalyst
The addition of Y2O3 into Ni formed a composite catalyst that selectively produced 1,5-pentanediol rather than 1,2-pentanediol in the hydrogenolysis of furfuryl alcohol at 2.0 MPa H2 and 423 K. Clearly, 1,5-pentanediol was produced over the Ni0–Y2O3 boundary. This report highlights the properties of Ni–Y2O3, catalytic performance, and reaction route in the synthesis of 1,5-pentanediol from furfuryl alcohol.
7/24/17 12:00:00 AM
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1.5 Rh based catalysts

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Tetrahydrofurfuryl alcohol (THFA) has been converted into valuable alcohols and ethers by selective hydrogenation/hydrogenolysis reaction over Rhbased metal catalysts. To better understand the chemistry of THFA, the reaction energies and the corresponding energy barriers of selective C–O bond hydrogenolysis and ringopening of THFA on Rh(111) for the formation of 2methyltetrahydrofuran (2MeTHF), 1,5pentanediol (1,5PeD), and 1,2pentanediol (1,2PeD) were studied using density functional theory (DFT) calculations. The results indicate that starting from THFA to produce 2MeTHF, the direct C–O bond cleavage of the CH2OH group is not favored. Alternatively and more preferentially, the reaction occurs through the initial activation of C–H bond on the side chain, followed by dehydroxylation and hydrogenation. On the other hand, in the metal catalyzed ring-opening process of THFA to 1,5-PeD and 1,2-PeD, the first dehydrogenation of secondary CH–O or primary CH2–O moiety in the ring decreases the barriers of the subsequent C–O bond dissociation. Moreover, the energy span theory shows that the ring-opening at the sterically less-hindered primary C–O bond exhibits a lower effective barrier than that for ring-opening at the more sterically hindered secondary C–O bond, as well as hydrogenolysis at the side CH2OH chain, suggesting that the formation of 1,2-PeD is much kinetically favored than the formation of 1,5-PeD and 2-MeTHF. Our theoretical results give a good explanation for the experimental fact that 1,2-PeD was the dominant product observed on unprompted Rh/SiO2. ([Art. #ARTNUM](#article-26755-2475861400))

1.5.1 1.5 Rh based catalysts
DFT Studies of the Selective C–O Hydrogenolysis and Ring-Opening of Biomass-Derived Tetrahydrofurfuryl Alcohol over Rh(111) surfaces
Tetrahydrofurfuryl alcohol (THFA) has been identified as a platform chemical of interest because of its production from biomass. It can be converted into valuable alcohols and ethers by selective hydrogenation/hydrogenolysis reaction over Rh-based metal catalysts. To better understand the chemistry of THFA, the reaction energies and the corresponding energy barriers of selective C–O bond hydrogenolysis and ring-opening of THFA on Rh(111) for the formation of 2-methyltetrahydrofuran (2-MeTHF), 1,5-pentanediol (1,5-PeD), and 1,2-pentanediol (1,2-PeD) were studied using density functional theory (DFT) calculations. The results indicate that starting from THFA to produce 2-MeTHF, the direct C–O bond cleavage of the CH2OH group is not favored. Alternatively and more preferentially, the reaction occurs through the initial activation of C–H bond on the side chain, followed by dehydroxylation and hydrogenation. On the other hand, in the metal catalyzed ring-opening process of THFA to 1,5-PeD and 1,2-PeD, the firs...
9/1/16 12:00:00 AM
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2. Direct from Furfural

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Direct conversion from furfural without intermediate steps


2.1 Direct one pot from Furfural/Furfuryl Alcholol ring-opening with noble metal catalyst

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The invention relates to a catalyst used in a ring-opening hydrogenation reaction of a furan derivative. The catalyst is applied to direct preparation of one-step ring-opening hydrogenation of 1,5-pentanediol and 1,2-pentanediol by taking furfural or furfuryl alcohol serving as a raw material under a mild condition. The catalyst can provide two active ingredients, namely the ring-opening active center of a transition metal oxide and the hydrogenation active center of Pt, Pd, Rh, Ru, Co or Ni, wherein the active center of the transition metal oxide is mainly used for adsorbing furfural or furfuryl alcohol and directly hydrogenating a furan ring for opening the furan ring; and the hydrogenation active center of a noble metal or Co, Ni and the like is mainly used for quickly hydrogenating anintermediate material and hydrogenating subsequent enol so as to obtain 1,5-pentanediol and 1,2-pentanediol. An environmentally-friendly, reproducible, low-cost, mild and effective method is providedfor producing 1,5-pentanediol and 1,2-pentanediol. The high-performance ring-opening hydrogenation catalyst is also suitable for the ring-opening hydrogenation reaction of other furan derivatives. ([Art. #ARTNUM](#article-26548-2830237051))

2.1.1 2.1 Direct one pot from Furfural/Furfuryl Alcholol ring-opening with noble metal catalyst
Catalyst used in ring-opening hydrogenation reaction of furan derivative
The invention relates to a catalyst used in a ring-opening hydrogenation reaction of a furan derivative. The catalyst is applied to direct preparation of one-step ring-opening hydrogenation of 1,5-pentanediol and 1,2-pentanediol by taking furfural or furfuryl alcohol serving as a raw material under a mild condition. The catalyst can provide two active ingredients, namely the ring-opening active center of a transition metal oxide and the hydrogenation active center of Pt, Pd, Rh, Ru, Co or Ni, wherein the active center of the transition metal oxide is mainly used for adsorbing furfural or furfuryl alcohol and directly hydrogenating a furan ring for opening the furan ring; and the hydrogenation active center of a noble metal or Co, Ni and the like is mainly used for quickly hydrogenating anintermediate material and hydrogenating subsequent enol so as to obtain 1,5-pentanediol and 1,2-pentanediol. An environmentally-friendly, reproducible, low-cost, mild and effective method is providedfor producing 1,5-pentanediol and 1,2-pentanediol. The high-performance ring-opening hydrogenation catalyst is also suitable for the ring-opening hydrogenation reaction of other furan derivatives.
11/21/12 12:00:00 AM
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2.1.2 2.1 Direct one pot from Furfural/Furfuryl Alcholol ring-opening with noble metal catalyst
One-pot controllable synthesis of the missing uniform icosidodecahedral gold nanocrystals with high-index facets and their plasmonic properties
Noble metal (e.g., Au, Pt, Pd) nanocrystals (NCs) enclosed by high-index facets have been the subject of intensive research in recent years, owing to their unconventional constructions with aesthetic beauty, peculiar synthetic approaches, significantly enhanced physicochemical properties, and potential wide variety of practical applications. However, because of their general exposed high surface energy, the challenge of chemically preparing noble metal NCs having high-index facets remains elusive. In the present paper, we develop a new, facile and effective method for the controllable synthesis of the missing high-quality icosidodecahedral Au NCs in a one-pot polyol reaction. The as-prepared icosidodecahedral Au NCs with unique hyperpolyhedral shapes and smooth surfaces were enclosed by 8 low-index {111} facets and 24 high-index {310} facets. Our proposed synthetic strategy is highlighted by its simplicity (requires no foreign metal ions, no seeds or no conductive substrates), high-yield production and particular controllability of the synthesis. Formation of the specific icosidodecahedral Au NCs was attributed to the synergistic reduction of gold ethylene glycol (EG) precursors in a refluxing 1,5-pentanediol (PD) solution assisted by the cationic surfactant poly(diallyldimethylammonium) chloride (PDDA) as well as the probable positive oxidative etching process. The morphology evolution caused by different experimental parameters and the corresponding plasmonic optical properties of icosidodecahedral Au NCs were investigated in some detail. It is expected that these uniform icosidodecahedral Au NCs with excellent stability and interesting plasmonic absorption properties would have potential applications in surface plasmonics, fuel cells, catalysis, optoelectronics, metamaterials, surface-enhanced Raman scattering (SERS) and biomedicine.
1/1/17 12:00:00 AM
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2.2 From Furfural and THFA with NiY/NiLa composity catalyst

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NiM (M = Y or La)catalyzed hydrogenolysis of furfural (FFR) to produce 1,5pentanediol (1,5PeD) has been developed through the formation of tetrahydrofurfuryl alcohol (THFA) as an intermediate product. Ni(0)Y2O3 or Ni(0)La(OH)3 composite catalysts executed cleavage of the C–O bond of THFA, giving 1,5PeD with remarkably high selectivity. Consecutive reactions including hydrogenation of the C=O and C=C bonds and subsequent hydrogenolysis of the C–O bond were performed. ([Art. #ARTNUM](#article-22908-2607236215))

2.2.1 2.2 From Furfural and THFA with NiY/NiLa composity catalyst
Hydrogenolysis of Furfural into 1,5-Pentanediol by Employing Ni-M (M = Y or La) Composite Catalysts
Ni-M (M = Y or La)-catalyzed hydrogenolysis of furfural (FFR) to produce 1,5-pentanediol (1,5-PeD) has been developed through the formation of tetrahydrofurfuryl alcohol (THFA) as an intermediate product. Ni(0)-Y2O3 or Ni(0)-La(OH)3 composite catalysts executed cleavage of the C–O bond of THFA, giving 1,5-PeD with remarkably high selectivity. Consecutive reactions including hydrogenation of the C=O and C=C bonds and subsequent hydrogenolysis of the C–O bond were performed.
5/5/17 12:00:00 AM
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2.3 One Pot reaction on a Pdadded Ir– ReOx/SiO2 catalysts through twostep reaction temperature

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Reduced to one production step: This most probably opens another avenue for competitive production of 1,5-pentanediol (PDO, or pentane-1,5-diol). The conventional pathway to PDO from furfural was via multi-step hydrogenation (via THFA/Methyl-THF). Onepot selective conversion of furfural into 1,5pentanediol (1,5PeD) was carried out over Pdadded Ir– ReOx/SiO2catalysts through twostep reaction temperatures. The Pd(0.66 wt%)–Ir–ReOx/SiO2catalyst showed the best performance in the production of 1,5PeD from furfural. The maximum yield of 1,5PeD was 71.4%. The furfural conversion and yield of 1,5PeD was almost maintained during four repeated tests when the catalyst was calcined again. The characterization results from TPR, XRD, XANES, EXAFS and FTIR of adsorbed CO indicated that Pd– Ir–ReOx/SiO2catalysts consisted of ReOxmodified Pd metal particles and ReOxmodified Ir metal particles. The lowertemperature reaction step was very crucial for the total hydrogenation of furfural into a tetrahydrofurfuryl alcohol intermediate, which was converted into 1,5PeD by hydrogenolysis during the high temperature step over the ReOxmodified Ir metal particles. ([Art. #ARTNUM](#article-26766-2017742383))

2.3.1 2.3 One Pot reaction on a Pdadded Ir– ReOx/SiO2 catalysts through twostep reaction temperature
One-pot selective conversion of furfural into 1,5-pentanediol over a Pd-added Ir–ReOx/SiO2 bifunctional catalyst
One-pot selective conversion of furfural into 1,5-pentanediol (1,5-PeD) was carried out over Pd-added Ir–ReOx/SiO2catalysts through two-step reaction temperatures. The Pd(0.66 wt%)–Ir–ReOx/SiO2catalyst showed the best performance in the production of 1,5-PeD from furfural. The maximum yield of 1,5-PeD was 71.4%. The furfural conversion and yield of 1,5-PeD was almost maintained during four repeated tests when the catalyst was calcined again. The characterization results from TPR, XRD, XANES, EXAFS and FT-IR of adsorbed CO indicated that Pd–Ir–ReOx/SiO2catalysts consisted of ReOx-modified Pd metal particles and ReOx-modified Ir metal particles. The lower-temperature reaction step was very crucial for the total hydrogenation of furfural into a tetrahydrofurfuryl alcohol intermediate, which was converted into 1,5-PeD by hydrogenolysis during the high temperature step over the ReOx-modified Ir metal particles.
1/1/14 12:00:00 AM
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2.4 Direct conversion based on Pt/Co2AlO4 catalyst under mild conditions

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A new strategy was developed for the direct conversion of furfural to 1,5-pentanediol by the hydrogenolysis of the furan ring under mild conditions based on Pt/Co2AlO4 catalyst. This is the first report of the direct catalytic conversion of furfural to 1,5-pentanediol with high yield. More information available [here](https://pubs.rsc.org/en/content/articlelanding/2011/cc/c0cc05775d#!divAbstract)


2.5 New catalytic strategies for α,ω-diols production from lignocellulosic biomass

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Catalytic strategies for the synthesis of 1,5pentanediol (PDO) with 69% yield from hemicellulose and the synthesis of 1,6hexanediol (HDO) with 28% yield from cellulose are presented. Fractionation of lignocellulosic biomass (white birch wood chips) in gammavalerolactone (GVL)/H2O generates a pure cellulose solid and a liquid stream containing hemicellulose and lignin, which is further dehydrated to furfural with 85% yield. Furfural is converted to PDO with sequential dehydration, hydration, ringopening tautomerization, and hydrogenation reactions. Acidcatalyzed cellulose dehydration in tetrahydrofuran (THF)/H2O produces a mixture of levoglucosenone (LGO) and 5hydroxymethylfurfural (HMF), which are converted with hydrogen to tetrahydrofurandimethanol (THFDM). HDO is then obtained from hydrogenolysis of THFDM. Technoeconomic analysis demonstrates that this approach can produce HDO and PDO at a minimum selling price of $4090 per ton. ([Art. #ARTNUM](#article-26761-2594054213))

2.5.1 2.5 New catalytic strategies for α,ω-diols production from lignocellulosic biomass
New catalytic strategies for α,ω-diols production from lignocellulosic biomass
Catalytic strategies for the synthesis of 1,5-pentanediol (PDO) with 69% yield from hemicellulose and the synthesis of 1,6-hexanediol (HDO) with 28% yield from cellulose are presented. Fractionation of lignocellulosic biomass (white birch wood chips) in gamma-valerolactone (GVL)/H2O generates a pure cellulose solid and a liquid stream containing hemicellulose and lignin, which is further dehydrated to furfural with 85% yield. Furfural is converted to PDO with sequential dehydration, hydration, ring-opening tautomerization, and hydrogenation reactions. Acid-catalyzed cellulose dehydration in tetrahydrofuran (THF)/H2O produces a mixture of levoglucosenone (LGO) and 5-hydroxymethylfurfural (HMF), which are converted with hydrogen to tetrahydrofuran-dimethanol (THFDM). HDO is then obtained from hydrogenolysis of THFDM. Techno-economic analysis demonstrates that this approach can produce HDO and PDO at a minimum selling price of $4090 per ton.
1/1/17 12:00:00 AM
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3. Other routes / base component

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Starting from other components than THFA or Furfural


3.1 From oxidation of cyclohexane glutaric acid byproducts with Copper containing catalyst

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Cyclohexane glutaric acid byproduct during the production of cyclohexanone is oxidized with oxygen or an oxygencontaining gas, adipic acid, carboxylic acid mixture such as 6hydroxycaproic acid, methanol, ethanol, butanol, 1,6hexanediol esterified with alcohols such as, the resulting esterified product, a process for the preparation of hydrogenated in the presence of a coppercontaining catalyst 1,6hexanediol and / or 1,5pentanediol, the deterioration of the catalyst controlled, and to provide an industrially suitable method of producing a 1,5pentanediol and / or 1,6hexanediol in a high yield. Coppercontaining catalyst and an acid value (AV value) 0.5 mgKOH / g or less of alcohol or acid value to (AV value) hydrogenating the esterified product by the prereduced catalyst in an ester of below 0.5 mgKOH / g the above problems in is solved. ([Art. #ARTNUM](#article-26544-2775997820))

3.1.1 3.1 From oxidation of cyclohexane glutaric acid byproducts with Copper containing catalyst
Aqueous Phase Hydrogenolysis of Bio-Derivable Furfuryl Alcohol to Pentanediols Using Copper Catalysts
In the context of sustainable production processes based on bio-derivable feedstocks, the hydrogenolysis of furfuryl alcohol gives access to two important diols. This work evaluates the performance of commercial copper catalysts in the aqueous phase hydrogenolysis reaching a selectivity towards 1,2-pentanediol of up to 34%. In contrast to noble metal catalysts such as supported ruthenium, the selectivity of the hydrogenation product, tetrahydrofurfuryl alcohol, is significantly lower, so the desired diols are now the main products of this reaction. Catalysis experiments show that the performance is correlated to the catalyst composition rather than the free copper surface, indicating a strong influence of the supporting material. Although the formation of oligomeric and polymeric side products is still perturbing, copper catalysts represent promising candidates for this reaction due to their low cost and wide availability.
2/7/17 12:00:00 AM
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3.1.2 3.1 From oxidation of cyclohexane glutaric acid byproducts with Copper containing catalyst
Method for producing 1,5-pentanediol and / or 1,6-hexanediol
Cyclohexane glutaric acid by-product during the production of cyclohexanone is oxidized with oxygen or an oxygen-containing gas, adipic acid, carboxylic acid mixture such as 6-hydroxycaproic acid, methanol, ethanol, butanol, 1,6-hexanediol esterified with alcohols such as, the resulting esterified product, a process for the preparation of hydrogenated in the presence of a copper-containing catalyst 1,6-hexanediol and / or 1,5-pentanediol, the deterioration of the catalyst controlled, and to provide an industrially suitable method of producing a 1,5-pentanediol and / or 1,6-hexanediol in a high yield. Copper-containing catalyst and an acid value (AV value) 0.5 mgKOH / g or less of alcohol or acid value to (AV value) hydrogenating the esterified product by the pre-reduced catalyst in an ester of below 0.5 mgKOH / g the above problems in is solved.
5/15/08 12:00:00 AM
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3.1.3 3.1 From oxidation of cyclohexane glutaric acid byproducts with Copper containing catalyst
Method for producing pentanediol through selective hydrogenolysis of furan derivative
The present invention discloses a method for producing pentanediol through selective hydrogenolysis of a furan derivative. According to the method, a highly dispersed copper-based composite metal oxide is adopted as a catalyst, methanol, ethanol, isopropanol or dioxane is adopted as a solvent, and a furan derivative is subjected to selective hydrogenolysis in an intermittent stirring reaction kettle or continuous fixed bed reactor at a reaction temperature of 120-180 DEG C under a hydrogen pressure of 1-10 MPa to prepare the pentanediol, wherein a catalyst precursor having a hydrotalcite layered structure is subjected to calcination reduction to obtain the catalyst, mainly a metal ion solution having CuM and an alkaline solution are subjected to a co-precipitation reaction so as to obtain the catalyst precursor, and in the catalyst, Cu is the main active component and has the content is 2-40%, and the content of the M-containing oxide and the spinel carrier is 60-98%. According to the present invention, the catalyst preparation method has characteristics of simpleness, easily available raw materials and low cost, and the prepared catalyst has characteristics of uniform component distribution, small particle size, large specific surface area and stable performance, and provides high reaction reactivity and high selectivity for the pentanediol production through the selective hydrogenolysis of the furan derivative.
12/9/15 12:00:00 AM
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3.1.4 3.1 From oxidation of cyclohexane glutaric acid byproducts with Copper containing catalyst
PRODUCTION METHOD OF 1,2-PENTANE DIOL AND 1,5-PENTANE DIOL
PROBLEM TO BE SOLVED: To provide a production method of industrially suitable 1,2-pentane diol and 1,5-pentane diol with furfuryl alcohol used as a production raw material.SOLUTION: A production method of 1,2-pentane diol and 1,5-pentane diol is characterized by reacting furfuryl alcohol with hydrogen, using at least one alkaline compound selected from the group consisting of compounds containing an alkali metal and an alkali earth metal in the presence of a copper-containing metal catalyst.
6/11/15 12:00:00 AM
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3.1.5 3.1 From oxidation of cyclohexane glutaric acid byproducts with Copper containing catalyst
Method for producing high-purity 1,5-pentanediol

1. A method for producing high-purity 1,5-pentanediol, the method comprising:hydrogenolyzing tetrahydrofurfuryl alcohol with hydrogen in the presence of a copper-comprising catalyst at a reaction temperature of from 200 to 350° C. and a reaction pressure of from 1 to 40 MPa until conversion rate of tetrahydrofurfuryl alcohol reaches 80% or less, thereby obtaining a crude reaction product;separating tetrahydrofurfuryl alcohol and crude 1,5-pentanediol (A) from the crude reaction product, thereby obtaining recovered tetrahydrofurfuryl alcohol and the crude 1,5-pentanediol (A), and then, supplying the recovered tetrahydrofurfuryl alcohol as a raw material for said hydrogenolyzing; anddistilling the crude 1,5-pentanediol (A), thereby obtaining the high-purity 1,5-pentanediol. 2. The method according to claim 1, wherein water content in the tetrahydrofurfuryl alcohol in said hydrogenolyzing is 1% or less by mass. 3. The method according to claim 1, wherein the copper-comprising catalyst after use is recovered by separation after ending of said hydrogenolyzing, thereby obtaining a recovered copper-comprising catalyst, which is reused in said hydrogenolyzing. 4. The method according to claim 1, wherein the crude 1,5-pentanediol (A) obtained in said separating is distilled to remove high-boiling point compounds, thereby obtaining a second crude 1,5-pentanediol, which is used in said distilling. 5. The method according to claim 1, wherein a saponification agent is added to the crude reaction product obtained in said hydrogenolyzing before said separating and said distilling. 6. The method according to claim 1, wherein a saponification agent is added to the crude 1,5-pentanediol (A) obtained in said separating before said distilling. 7. The method according to claim 1, wherein a total amount of diol compounds having a secondary hydroxy group contained in the high-purity 1,5-pentanediol obtained in said distilling is 1% or less by mole. 8. The method according to claim 1, wherein the copper-comprising catalyst used in said hydrogenolyzing comprises at least one atom "B" selected from the group consisting of zinc, iron, aluminum, chromium, and silicon. 9. The method according to claim 8, wherein the copper-comprising catalyst used in said hydrogenolyzing further comprises at least one atom "C" selected from the group consisting of barium, calcium, manganese, lanthanum, cerium, and magnesium. 10. The method according to claim 1, wherein the tetrahydrofurfuryl alcohol used in said hydrogenolyzing is tetrahydrofurfuryl alcohol synthesized by using furfural as a raw material. 11. The method according to claim 1, wherein acid value of the tetrahydrofurfuryl alcohol used in said hydrogenolyzing is 2 mg-KOH/g or less.
11/19/12 12:00:00 AM
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3.2 Autocatalytic Hydration of Dihydropyran to 2hydroxytetrahydropyran, to 1,5-PeD

0

Dihydropyran (DHP) undergoes autocatalyzed hydration to 2hydroxytetrahydropyran (2HYTHP) by carboxylic acids formed in situ in both batch and continuous flow reactors. NMR, GC–MS, and pH analysis corroborate the presence of carboxylic acids in the hydration products. Carboxylic acids, likely in the form of 5hydroxyvaleric acid, are made as low as 25 °C, increasing solution acidity and autocatalyzing DHP hydration. 1,5Pentanediol precursors 2HYTHP and C10 dimers are produced from DHP at ∼98% yields at temperatures ≤100 °C. At ≥140 °C, byproducts are formed, including acidic solid coke and a C10 dimer likely made via aldol condensationcyclodehydration of the ringopened tautomer of 2HYTHP, 5hydroxyvaleraldehyde. DHP hydration rates continuously increased up to 50 h timeonstream in continuous reactors demonstrating that the acidic byproducts catalyze this reaction. Activation rates rose with temperature due to increased acidic solid coke formation. ([Art. #ARTNUM](#article-22907-2757459757))

3.2.1 3.2 Autocatalytic Hydration of Dihydropyran to 2hydroxytetrahydropyran, to 1,5-PeD
Autocatalytic Hydration of Dihydropyran to 1,5-Pentanediol Precursors via in situ Formation of Liquid- and Solid-Phase Acids
Dihydropyran (DHP) undergoes autocatalyzed hydration to 2-hydroxytetrahydropyran (2-HY-THP) by carboxylic acids formed in situ in both batch and continuous flow reactors. NMR, GC–MS, and pH analysis corroborate the presence of carboxylic acids in the hydration products. Carboxylic acids, likely in the form of 5-hydroxy-valeric acid, are made as low as 25 °C, increasing solution acidity and autocatalyzing DHP hydration. 1,5-Pentanediol precursors 2-HY-THP and C10 dimers are produced from DHP at ∼98% yields at temperatures ≤100 °C. At ≥140 °C, byproducts are formed, including acidic solid coke and a C10 dimer likely made via aldol condensation-cyclodehydration of the ring-opened tautomer of 2-HY-THP, 5-hydroxyvaleraldehyde. DHP hydration rates continuously increased up to 50 h time-on-stream in continuous reactors demonstrating that the acidic byproducts catalyze this reaction. Activation rates rose with temperature due to increased acidic solid coke formation. The coke formed is soluble in water and its fo...
11/6/17 12:00:00 AM
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3.3 Enzymatic production of 5-aminovalerate from L-lysine using L-lysine monooxygenase and 5-aminovaleramide amidohydrolase as a platform for 1,5PeD

0

5Aminovalerate is a potential C5 platform chemical for synthesis of valerolactam, 5hydroxyvalerate, glutarate, and 1,5pentanediol. It is a metabolite of llysine catabolism through the aminovalerate pathway in Pseudomonas putida. lLysine monooxygenase (DavB) and 5aminovaleramide amidohydrolase (DavA) play key roles in the biotransformation of llysine into 5aminovalerate. Here, DavB and DavA of P. putida KT2440 were expressed, purified, and coupled for the production of 5aminovalerate from llysine. Under optimal conditions, 20.8 g/L 5aminovalerate was produced from 30 g/L llysine in 12 h. Because llysine is an industrial fermentation product, the twoenzyme coupled system presents a promising alternative for the production of 5aminovalerate. ([Art. #ARTNUM](#article-26765-1994889276))

3.3.1 3.3 Enzymatic production of 5-aminovalerate from L-lysine using L-lysine monooxygenase and 5-aminovaleramide amidohydrolase as a platform for 1,5PeD
Enzymatic production of 5-aminovalerate from L-lysine using L-lysine monooxygenase and 5-aminovaleramide amidohydrolase.
5-Aminovalerate is a potential C5 platform chemical for synthesis of valerolactam, 5-hydroxyvalerate, glutarate, and 1,5-pentanediol. It is a metabolite of l-lysine catabolism through the aminovalerate pathway in Pseudomonas putida. l-Lysine monooxygenase (DavB) and 5-aminovaleramide amidohydrolase (DavA) play key roles in the biotransformation of l-lysine into 5-aminovalerate. Here, DavB and DavA of P. putida KT2440 were expressed, purified, and coupled for the production of 5-aminovalerate from l-lysine. Under optimal conditions, 20.8 g/L 5-aminovalerate was produced from 30 g/L l-lysine in 12 h. Because l-lysine is an industrial fermentation product, the two-enzyme coupled system presents a promising alternative for the production of 5-aminovalerate.
5/1/15 12:00:00 AM
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3.4 Hdrogenation of a 5,6dihydro-2H-pyran derivative with a Ni catalyst in the presence of water.

0

To obtain pentane1,5diol easily and in high yield by hydrogenation of a 5,6dihydro-2H-pyran derivative with a Ni catalyst in the presence of water.([Art. #ARTNUM](#article-26551-2828395694))

3.4.1 3.4 Hdrogenation of a 5,6dihydro-2H-pyran derivative with a Ni catalyst in the presence of water.
PREPARATION OF 33SUBSTITUTED OR NONNSUBSTITUTEDDPENTANEE1*55DIOL
PURPOSE:To obtain pentane-1,5-diol easily and in high yield by hydrogenation of a 5,6dihydro-2H-pyran derivative with a Ni catalyst in the presence of water.
3/1/79 12:00:00 AM
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3.5 Hydrogenation of dicarboxylic acid mixture with Ruthenium and Tin catalyst

0

Disclosed is a method for producing a diol mixture comprising 1,4butanediol, 1,5pentanediol and 1,6hexanediol, which comprises: (A) providing a dicarboxylic acid mixture comprising succinic acid, glutaric acid and adipic acid and having a nitric acid content of 3% by weight or less, based on the total weight of the succinic, glutaric and adipic acids, wherein the dicarboxylic acid mixture is prepared by denitrating an aqueous byproduct solution obtained in an adipic acid production process, and (B) subjecting the dicarboxylic acid mixture to hydrogenation in the presence of water, hydrogen gas and a hydrogenation catalyst containing an active metal species comprising ruthenium and tin, to thereby obtain a hydrogenation reaction mixture comprising a diol mixture comprising 1,4butanediol, 1,5pentanediol and 1,6hexanediol. ([Art. #ARTNUM](#article-26545-US6706932B1))

3.5.1 3.5 Hydrogenation of dicarboxylic acid mixture with Ruthenium and Tin catalyst
Process for the preparation of diol mixtures
Disclosed is a method for producing a diol mixture comprising 1,4-butanediol, 1,5-pentanediol and 1,6-hexanediol, which comprises: (A) providing a dicarboxylic acid mixture comprising succinic acid, glutaric acid and adipic acid and having a nitric acid content of 3% by weight or less, based on the total weight of the succinic, glutaric and adipic acids, wherein the dicarboxylic acid mixture is prepared by denitrating an aqueous by-product solution obtained in an adipic acid production process, and (B) subjecting the dicarboxylic acid mixture to hydrogenation in the presence of water, hydrogen gas and a hydrogenation catalyst containing an active metal species comprising ruthenium and tin, to thereby obtain a hydrogenation reaction mixture comprising a diol mixture comprising 1,4-butanediol, 1,5-pentanediol and 1,6-hexanediol.
1. A method for producing a diol mixture comprising 1,4-butanediol, 1,5-pentanediol and 1,6-hexanediol, which comprises: (A) providing a dicarboxylic acid mixture comprising succinic acid, glutaric acid and adipic acid and having a nitric acid content of 0.2% by weight or less, based on the total weight of said succinic, glutaric and adipic acids, said dicarboxylic acid mixture being prepared by denitrating an aqueous by- product solution obtained in an adipic acid production process comprising subjecting at least one C6 cyclic aliphatic compound to oxidation with nitric acid in an aqueous medium in the presence of an oxidation catalyst to thereby obtain an aqueous reaction mixture comprising succinic acid, glutaric acid and adipic acid, depositing crystals of the adipic acid, and isolating the deposited crystals from said reaction mixture to obtain the aqueous by-product solution; and (B) subjecting said dicarboxylic acid mixture to hydrogenation in the presence of water, hydrogen gas and a hydrogenation catalyst containing an active metal species comprising ruthenium and tin, to thereby obtain a hydrogenation reaction mixture comprising a diol mixture comprising 1,4-butanediol, 1,5-pentanediol and 1,6-hexanediol. 2. The method according to claim 1, wherein, before step (B), said dicarboxylic acid mixture is adjusted to satisfy at least one condition selected from the group consisting of the following conditions (1) and (2): (1) the mixture has a copper content of 10 ppm by weight or less and a vanadium content of 10 ppm by weight or less, each based on the total weight of said succinic, glutaric and adipic acids; and (2) the mixture has a sulfur content of 200 ppm by weight or less, based on the total weight of said succinic, glutaric and adipic acids. 3. The method according to claim 2, wherein, in said condition (2), the mixture has a sulfur content of 40 ppm by weight or less, based on the total weight of said succinic, glutaric and adipic acids. 4. The method according to claim 1, wherein said dicarboxylic acid mixture in the form of a solution thereof in distilled water exhibits an absorption coefficient of 0.3 or less as measured at 355 nm, wherein said absorption coefficient is determined by the following formula: E=A/(c×b) wherein E represents the absorption coefficient as measured at 355 nm, A represents the absorbance of the solution of the dicarboxylic acid mixture in distilled water at room temperature, c represents the amount (g) of the dicarboxylic acid mixture dissolved in 100 g of distilled water, and b represents the length (cm) of a cell used for measuring the absorbance. 5. The method according to claim 4, wherein said dicarboxylic acid mixture in the form of a solution thereof in distilled water exhibits an absorption coefficient of 0.1 or less. 6. The method according to claim 1 or 2, wherein said dicarboxylic acid mixture contains an impurity component having an oxygen-nitrogen bond in an amount of 2,000 ppm by weight or less in terms of the amount of nitric acid, based on the total weight of said succinic, glutaric and adipic acids. 7. The method according to claim 1, wherein said active metal species contained in said hydrogenation catalyst further comprises at least one metal selected from the group consisting of metals of Group 7 of the Periodic Table. 8. The method according to claim 7, wherein said at least one metal selected from the group consisting of metals of Group 7 of the Periodic Table is rhenium. 9. The method according to claim 1 or 7, wherein said active metal species contained in said hydrogenation catalyst further comprises at least one metal selected from the group consisting of metals of Group 8 of the Periodic Table other than ruthenium and metals of Groups 9 and 10 of the Periodic Table. 10. The method according to claim 9, wherein said at least one metal selected from the group consisting of metals of Group 8 of the Periodic Table other than ruthenium and metals of Groups 9 and 10 of the Periodic Table, is platinum. 11. The method according to claim 1, wherein said hydrogenation catalyst further comprises an activated carbon having carried thereon said active metal species. 12. The method according to claim 1, wherein said hydrogenation is conducted under conditions wherein the temperature is from 100 to 300° C. and the hydrogen pressure is from 1 to 25 MPa. 13. The method according to claim 1, wherein said dicarboxylic acid mixture is prepared in the form of an aqueous solution thereof by a first purification process comprising the steps of: (a) heating said aqueous by-product solution at a temperature of from 80 to 200° C. under atmospheric or lower pressure to effect dehydration and denitration of said aqueous by-product solution to obtain a dehydrated and denitrated dicarboxylic acid mixture; (b) adding water to the obtained dehydrated and denitrated dicarboxylic acid mixture to thereby obtain an aqueous denitrated dicarboxylic acid mixture solution; and (c) contacting said aqueous denitrated dicarboxylic acid mixture solution with a cation exchange resin to thereby remove copper values and vanadium values. 14. The method according to claim 13, wherein said first purification process further comprises step (d) of contacting said aqueous denitrated dicarboxylic acid mixture solution with an anion adsorptive substance. 15. The method according to claim 13 or 14, wherein said first purification process further comprises the step of contacting said aqueous denitrated dicarboxylic acid mixture solution with an activated carbon. 16. The method according to claim 1, wherein said dicarboxylic acid mixture is prepared by a second purification process comprising the steps of: (a) heating said aqueous by-product solution at a temperature of from 80 to 130° C. under atmospheric or lower pressure, followed by heating at a temperature of from higher than 130° C. to 180° C. under atmospheric pressure, to thereby obtain a dehydrated and denitrated dicarboxylic acid mixture; (b) adding water to the obtained dehydrated and denitrated dicarboxylic acid mixture to thereby obtain an aqueous denitrated dicarboxylic acid mixture solution; (c) contacting said aqueous denitrated dicarboxylic acid mixture solution with a cation exchange resin to thereby remove copper values and vanadium values; (d) heating the resultant aqueous denitrated dicarboxylic acid mixture solution under atmospheric or lower pressure at a temperature sufficient to distill off water from said resultant aqueous denitrated dicarboxylic acid mixture solution and obtain a denitrated dicarboxylic acid mixture; (e) adding a C6-C14 aromatic hydrocarbon having a boiling point of 200° C. or less under atmospheric pressure to the denitrated dicarboxylic acid mixture obtained in step (d), and heating the resultant mixture at a temperature which is not higher than the boiling point of said aromatic hydrocarbon, followed by cooling; and (f) recovering the denitrated dicarboxylic acid mixture from said mixture by filtration, thereby preparing said dicarboxylic acid mixture. 17. The method according to claim 16, wherein said second purification process further comprises, after step (a), the step of contacting the aqueous denitrated dicarboxylic acid mixture solution or an aqueous solution of the denitrated dicarboxylic acid mixture in water, with an anion adsorptive substance. 18. The method according to claim 1, wherein said dicarboxylic acid mixture is prepared in the form of an aqueous solution thereof by a third purification process comprising: contacting said aqueous by-product solution with hydrogen gas in the presence of a reduction catalyst containing an active metal species comprising at least one metal selected from the group consisting of metals of Groups 7 to 10 of the Periodic Table, to thereby reduce nitric acid and an impurity component having an oxygen-nitrogen bond contained in said aqueous by-product solution, thereby obtaining said dicarboxylic acid mixture in the form of an aqueous solution thereof. 19. The method according to claim 18, wherein said reduction of the nitric acid and an impurity component having an oxygen-nitrogen bond in said third purification process is conducted under conditions wherein the temperature is from 50 to 200° C. and the hydrogen pressure is from 0.2 to 5 MPa. 20. The method according to claim 18 or 19, wherein said active metal species contained in said reduction catalyst used in said third purification process is at least one metal selected from the group consisting of platinum, rhenium, palladium, rhodium, nickel, iridium and ruthenium. 21. The method according to claim 18, wherein, prior to the contacting of said aqueous by-product solution with hydrogen gas in said third purification process, said aqueous by-product solution is heated at a temperature of from 80 to 130° C. under atmospheric or lower pressure and then heated at a temperature of from higher than 130° C. to 180° C. under atmospheric pressure, followed by addition of water thereto. 22. A method for recovering 1,4-butanediol and a mixture of 1,5-pentanediol and 1,6-hexanediol from the diol mixture obtained by the method of claim 1, which comprises: (i) adjusting the temperature of said hydrogenation reaction mixture comprising the diol mixture to a temperature of from room temperature to less than 100° C., followed by a gas-liquid separation under atmospheric or lower pressure under which water is not boiled at the adjusted temperature of the mixture to remove the hydrogen gas from the hydrogenation reaction mixture to remove the hydrogen gas from said hydrogenation reaction mixture; (ii) heating the hydrogen gas-removed hydrogenation reaction mixture under atmospheric pressure to thereby distill off the water and a mixture of cyclic ethers and monohydric alcohols which is by-produced in said hydrogenation reaction; (iii) subjecting the resultant mixture to multi-stage distillation to distill off the water and &ggr;-butyrolactone by-produced in the hydrogenation reaction, thereby obtaining a purified diol mixture; (iv) subjecting the purified diol mixture to multi-stage distillation to obtain 1,4-butanediol as a low boiling point component while withdrawing a high boiling point mixture; and (v) subjecting the high boiling point mixture obtained in step (iv) to multi- stage distillation to obtain a mixture of 1,5-pentanediol and 1,6-hexanediol as a distillate.
5/2/02 12:00:00 AM
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3.6 Hydrolysis of dihydropyran in dilute acid

0

This invention relates to a novel process for the production of 1,5pentanediol. It is known that 1,5pentanediol can be produced by the hydrolysis of dihydropyran in dilute acid and subsequent hydrogenation of the deltahydroxyvaleraldehyde produced. ([Art. #ARTNUM](#article-26546-2412032466))

3.6.1 3.6 Hydrolysis of dihydropyran in dilute acid
Highly pure 1,5-pentanediol
PROBLEM TO BE SOLVED: To produce 1,5-pentanediol free from impurities to lower the polymerization reaction rate in the case of using the diol as a soft segment of polycarbonate diol and polyester polyol or as a chain extender as it is for a raw material of polyurethane, polyester resin, etc. SOLUTION: The 1,5-pentanediol contains ≤0.1 wt.% each of 1,5-hexanediol and 1,4-dihydroxycyclohexane. The 1,5-pentanediol can be produced by the direct hydrogen reduction of a dicarboxylic acid mixture in the filtrate obtained by the crystallization and separation of adipic acid. COPYRIGHT: (C)2001,JPO
3/14/00 12:00:00 AM
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3.6.2 3.6 Hydrolysis of dihydropyran in dilute acid
Preparation of pentanediol
This invention relates to a novel process for the production of 1,5-pentanediol. It is known that 1,5-pentanediol can be produced by the hydrolysis of dihydropyran in dilute acid and subsequent hydrogenation of the deltahydroxyvaleraldehyde produced. However, yields of the desired product...
2/14/50 12:00:00 AM
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3.7 Optically active 1,5PeD

0

The invention discloses optically active 1,5pentanediol derivatives, and a synthesis method thereof. The structures of the optically active 1,5pentanediol derivatives are as shown in Formula (Ia) and Formula (Ib). The preparation method of the derivatives comprises the following step: by taking a diazo compound, a benzalcohol derivative and alpha,betaunsaturated aldehyde as raw materials, taking a 4A molecular sieve as a water absorbent, taking a metal catalyst, chiral diarylprolinol silyl ether and substituted benzoic acid as a catalysis system and taking a metal hydride reagent as a reducer, performing a reaction to obtain the optically active 1,5pentanediol derivatives. The synthesis method disclosed by the invention has the advantages of high atom economy, high selectivity and high yield, and is mild in reaction conditions and simple and safe to operate. The pair of optically active 1,5pentanediol derivatives obtained by the invention has high enantioselectivity and bioactivity, and is applicable to preparation of antineoplastic drugs. The Formula (Ia) and the Formula (Ib) are shown in the specification. ([Art. #ARTNUM](#article-26547-2815538969))

3.7.1 3.7 Optically active 1,5PeD
Optically active 1,5-pentanediol derivatives, and synthesis method and application thereof
The invention discloses optically active 1,5-pentanediol derivatives, and a synthesis method thereof. The structures of the optically active 1,5-pentanediol derivatives are as shown in Formula (Ia) and Formula (Ib). The preparation method of the derivatives comprises the following step: by taking a diazo compound, a benzalcohol derivative and alpha,beta-unsaturated aldehyde as raw materials, taking a 4A molecular sieve as a water absorbent, taking a metal catalyst, chiral diarylprolinol silyl ether and substituted benzoic acid as a catalysis system and taking a metal hydride reagent as a reducer, performing a reaction to obtain the optically active 1,5-pentanediol derivatives. The synthesis method disclosed by the invention has the advantages of high atom economy, high selectivity and high yield, and is mild in reaction conditions and simple and safe to operate. The pair of optically active 1,5-pentanediol derivatives obtained by the invention has high enantioselectivity and bioactivity, and is applicable to preparation of antineoplastic drugs. The Formula (Ia) and the Formula (Ib) are shown in the specification.
9/29/17 12:00:00 AM
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3.8 Reaction of a specific butenal derivative with formaldehyde

0

A butenal derivative of formula I (R , R are H, lower alkyl) is reacted with (B) formaldehyde, and the obtained reaction product mixture, preferably 5,6dihydro2H2pyranose derivative of formula II, is hydrogenated to obtain the objective derivative of formula III, e.g. 2,4diethyl1,5 pentanediol. ([Art. #ARTNUM](#article-26549-2864047813))

3.8.1 3.8 Reaction of a specific butenal derivative with formaldehyde
METHOD FOR PRODUCING 1,5-PENTANEDIOL DERIVATIVE
PURPOSE:To efficiently and industrially obtain the subject derivative useful as an intermediate for synthesizing polyesters through the reaction of a specific butenal derivative with formaldehyde. CONSTITUTION:(A) A butenal derivative of formula I (R , R are H, lower alkyl) is reacted with (B) formaldehyde, and the obtained reaction product mixture, preferably 5,6-dihydro-2H-2-pyranose derivative of formula II, is hydrogenated to obtain the objective derivative of formula III, e.g. 2,4-diethyl-1,5- pentanediol. For example, the mixture of the compound of formula II with a compound such as a 5-hydroxy-2-pentenal derivative is preferably hydrogenated, and croton aldehyde is preferably used as the component A. The components A and B are preferably reacted with each other in a molar ratio of 1:(0.5-1.5) in the presence of a basic catalyst such as NaOH.
2/20/96 12:00:00 AM
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3.9 Recombinant organism (prokaryotic or eukaryotic)

0

Recombinant hosts for producing polyhydroxyalkanoates and methods of producing polyhydroxyalkanoates from renewable carbon substrates are provided. Certain recombinant hosts that produce 5 carbon chemicals such as 5aminopentanoate (5AP), 5hydroxyvalerate (5HV), glutarate, and 1,5 pentanediol (PDO) are also provided. One embodiment provides a recombinant host expressing a gene encoding a heterologous enzyme selected from the group consisting of a polyhydroxyalkanoate synthase and a 5hydroxyvalerateCoA (5HVCoA) transferase, wherein the host produces a polymer containing 5hydroxyvalerate. Preferably, the host expresses both a polyhydroxyalkanoate synthase and a 5HVCoA transferase. The host can be prokaryotic or eukaryotic. A preferred prokaryotic host is E. coli. The polymers produced by the recombinant hosts can be homopolymers or copolymers of 5hydroxyvalerate. A preferred copolymer is poly(3hydroxybutyrateco5hydroxyvalerate). ([Art. #ARTNUM](#article-26543-2882792339))

3.9.1 3.9 Recombinant organism (prokaryotic or eukaryotic)
5 5 GREEN PROCESS AND COMPOSITIONS FOR PRODUCING POLY5HVAND 5 CARBON CHEMICALS
Recombinant hosts for producing polyhydroxyalkanoates and methods of producing polyhydroxyalkanoates from renewable carbon substrates are provided. Certain recombinant hosts that produce 5 carbon chemicals such as 5-aminopentanoate (5AP), 5-hydroxyvalerate (5HV), glutarate, and 1,5 pentanediol (PDO) are also provided. One embodiment provides a recombinant host expressing a gene encoding a heterologous enzyme selected from the group consisting of a polyhydroxyalkanoate synthase and a 5-hydroxyvalerate-CoA (5HV-CoA) transferase, wherein the host produces a polymer containing 5-hydroxyvalerate. Preferably, the host expresses both a polyhydroxyalkanoate synthase and a 5HV-CoA transferase. The host can be prokaryotic or eukaryotic. A preferred prokaryotic host is E. coli. The polymers produced by the recombinant hosts can be homopolymers or copolymers of 5-hydroxyvalerate. A preferred copolymer is poly(3-hydroxybutyrate-co-5-hydroxyvalerate).
12/4/17 12:00:00 AM
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3.9.2 3.9 Recombinant organism (prokaryotic or eukaryotic)
Green process and compositions for producing poly(5HV) and 5 carbon chemicals

1. A recombinant organism genetically engineered to convert glutarate semialdehyde into a 5-hydroxyvalerate monomer, polymer or copolymer thereof,wherein the recombinant organism expresses at least two or more heterologous genes encoding two or more enzymes selected from the group consisting of: lysine 2-monooxygenase, EC 1.13.12.2; 5-aminopentanamidase (δ-aminovaleramidase), EC 3.5.1.30; 5-aminovalerate transaminase, EC 2.6.1.48; lysine decarboxylase, EC 4.1.1.18; glutarate semialdehyde reductase, EC 1.1.1.61; 4-hydroxybutyrate dehydrogenase, EC 1.1.1.61; CoA-transferase, EC 2.8.3.14 and EC 2.8.3.n; Acyl-CoA synthetase, EC 6.2.1.3; PHA synthase, EC 2.3.1.n; β-ketoacyl-CoA thiolase, EC 2.3.1.9; acetoacetyl-CoA reductase, EC 1.1.1.36; propionaldehyde dehydrogenase, EC 1.2.1.3; alcohol dehydrogenase, EC 1.1.1.1; and 1,3-propanediol dehydrogenase EC 1.1.1.202;wherein the recombinant organism produces more 5-aminopentanoate than an unmodified organism; andwherein the 5-aminopentanoate is converted into the 5-hydroxyvalerate monomer, polymer or copolymer thereof by the recombinant organism wherein the 5-hydroxyvalerate monomer, polymer or copolymer thereof is isolatable. 2. The recombinant organism of claim 1 wherein the organism produces 1,5 pentanediol. 3. The recombinant organism of claim 1 wherein the polymer or copolymer comprises polyhydroxyalkanoate. 4. The recombinant organism of claim 1 wherein the recombinant organism converts 5-aminopentanoate into glutarate semialdehyde. 5. The recombinant organism of claim 1 wherein the recombinant organism converts lysine into 5-aminopentanoate. 6. The recombinant organism of claim 5 wherein the lysine is fed to the organism. 7. The recombinant organism of claim 1 wherein the organism used to construct the recombinant organism has been modified to overproduce lysine relative to an unmodified organism. 8. The recombinant organism of claim 1 wherein the recombinant organism is resistant to the toxic lysine analog S-(2-aminoethyl) cysteine. 9. The recombinant organism of claim 1 wherein the recombinant organism expresses a lysine feedback-resistant dihydrodipicolinate synthase. 10. The recombinant organism of claim 1 wherein the recombinant organism expresses a lysine feedback-resistant aspartate kinase III. 11. The recombinant organism of claim 1 wherein the organism is fed a renewable carbon substrate. 12. The recombinant organism of claim 1 wherein the recombinant organism is further engineered to inhibit or block lysine export. 13. The recombinant organism of claim 1 wherein the organism has been modified to reduce or eliminate glutarate semialdehyde dehydrogenase activity. 14. The recombinant organism of claim 13 wherein the glutarate semialdehyde dehydrogenase is reduced or eliminated by deleting or disrupting one or more genes selected from the group consisting of davD, yneI, and gabD or their homologs. 15. The recombinant organism of claim 1 wherein the recombinant organism releases 5-hydroxyvalerate into the extracellular environment. 16. The recombinant organism of claim 13 wherein the recombinant organism releases 5-hydroxyvalerate in the extracellular environment and the 5-hydroxyvalerate is in equilibrium with delta-valerolactone. 17. The recombinant organism of any of claim 1 wherein the recombinant organism converts 5-hydroxyvalerate into 5-hydroxyvalerate CoA. 18. The recombinant organism of claim 1 wherein the recombinant organism converts 5-hydroxyvalerate-CoA into a polyhydroxyalkanoate. 19. The recombinant organism of claim 1 wherein the recombinant organism converts 5-hydroxvalerate into 1,5 pentanediol. 20. The recombinant organism of claim 1 wherein the recombinant organism converts 5-hydroxyvalerate into poly(5-hydroxyvalerate) or a copolymer thereof. 21. The recombinant organism of claim 20 wherein the copolymer is selected from the group consisting of poly(3-hydroxypropionate-co-5HV), poly(3-hydroxybutyrate-co-5HV) and poly(4-hydroxybutyrate-co-5HV). 22. The recombinant organism of claim 1 wherein the recombinant organism is prokaryotic. 23. The recombinant organism of claim 1 wherein the recombinant organism is _E. coli._ 24. The recombinant organism of claim 1 wherein the recombinant organism is a eukaryotic microorganism. 25. A recombinant organism for producing polymers from lysinewherein the recombinant organism is genetically engineered to express at least two heterologous enzymes selected from the group consisting of: lysine 2-monooxygenase, EC 1.13.12.2; 5-aminopentanamidase (δ-aminovaleramidase), EC 3.5.1.30; 5-aminovalerate transaminase, EC 2.6.1.48; lysine decarboxylase, EC 4.1.1.18; glutarate semialdehyde reductase, EC 1.1.1.61; 4-hydroxybutyrate dehydrogenase, EC 1.1.1.61; CoA-transferase, EC 2.8.3.14 and EC 2.8.3.n; Acyl- CoA synthetase, EC 6.2.1.3; PHA synthase, EC 2.3.1.n, to produce a polyhydroxyalkanoate comprising 5-hydroxyvalerate monomers,wherein the recombinant organism produces more 5-aminopentanoate than an unmodified organism, andwherein the recombinant organism can convert 5-aminopentanoate into the 5-hydroxyvalerate wherein the 5-hydroxyvalerate monomer, polymer or copolymer thereof is isolatable. 26. The recombinant organism of claim 25 wherein the recombinant organism does not produce lysine. 27. The recombinant organism of claim 25 wherein the recombinant organism does not express a functional glutarate semialdehyde dehydrogenase enzyme activity. 28. A method for producing polymers from lysine comprising feeding the recombinant organism of claim 1 with lysine and other renewable carbon feedstock such that the polymer is produced. 29. A method for producing 5-carbon based monomers, polymers or co-polymers thereof comprisingproviding lysine or other renewable carbon feedstock to genetically engineered cells according to claim 1,wherein the genetically engineered cells are engineered to produce more 5-aminopentanoate than unmodified cells, and wherein the 5-aminopentanoate is converted by the genetically engineered cells into a 5 carbon monomer, polymer or copolymer thereof. 30. The method of claim 29 wherein the renewable carbon feedstock is selected from starch, sucrose, glucose, lactose, fructose, xylose, maltose and arabinose, or combinations thereof. 31. The method of claim 29 wherein the monomer is selected from the group consisting of glutarate, 1,5-pentanediol, and 5-hydroxyvalerate. 32. The method of claim 29 wherein the polymer comprises a polyhydroxyalkanoate. 33. The method of claim 32 wherein the polyhydroxyalkanoate comprises 5-hydroxyvalerate. 34. The method of claim 33 wherein the polyhydroxyalkanoate is selected from the group consisting of poly(5-hydroxyvalerate), poly(3-hydroxypropionate- co-5HV), poly(3-hydroxybutyrate-co-5HV) and poly(4-hydroxybutyrate-co-5HV). 35. The method of claim 32 further comprising recovering the polyhydroxyalkanoate polymer. 36. The method of claim 35 wherein polyhydroxyalkanote polymer or copolymers are recovered by solvent extraction or aqueous processing.
12/14/09 12:00:00 AM
Link to Patent

3.10 Solution polymerization in dimethyl formamide

0

New energetic chain extender (AzPD). A series of poly(glycidyl azide)/poly(tetramethylene oxide)based energetic segmented polyurethane (GAP/PTMG ESPU) with different chain extender, which is 3azidopropane1,2diol (AzPD), 1,4butane diol ( 1,4BD), or 1,5 pentane diol (1,5PD), was synthesized by solution polymerization in dimethyl formamide (DMF) and their phase behaviors were investigated. ([Art. #ARTNUM](#article-26550-2406283351))

3.10.1 3.10 Solution polymerization in dimethyl formamide
Phase Behaviors of the GAP/PTMG Polyurethanes Chain Extended with 3-Azidopropane-1,2-Diol
We perform a comparative study to investigate the properties of the new energetic chain extender (AzPD). A series of poly(glycidyl azide)/poly(tetramethylene oxide)-based energetic segmented polyurethane (GAP/PTMG ESPU) with different chain extender, which is 3-azidopropane-1,2-diol (AzPD), 1,4-butane diol (1,4-BD), or 1,5 pentane diol (1,5-PD), was synthesized by solution polymerization in dimethyl formamide (DMF) and their phase behaviors were investigated. The ESPUs were characterized with Fourier transform infrared-attenuated total reflection spectroscopy (ATR FT-IR), differential scanning calorimetry (DSC), and dynamic mechanical analysis (DMA). The results of the ATR FT-IR analysis of the urethane carbonyl group region showed that the 'free' C=O fraction was higher in GAP/PTMG AzESPU (0.5) than GAP/PTMG BDESPU (0.44) and GAP/PTMG PDESPU (0.41) for 7 days samples after preparation and that it was similar in the range of 0.26~0.29 for three 60 days ESPU samples. DMA curves of the GAP/PTMG AzESPU for 7 days samples showed amorphous polymers, but GAP/PTMG BDESPU and GAP/PTMG PDESPU showed viscoelastic behaviors with rubbery plateau and the flow region. However, DMA curves of the GAP/PTMG AzESPU for 60 days samples showed viscoelastic behaviors with rubbery plateau and the flow region like GAP/PTMG PDESPU, but GAP/PTMG BDESPU did not show the flow region. From phase behaviors with ATR FT-IR, DSC and DMA analysis, GAP/PTMG AzESPU showed good phase-mixing between components. However, it represented viscoelastic behavior of TPE similar to GAP/PTMG PDESPM according to phase equilibrium progress with aging time.
1/1/10 12:00:00 AM
Link to Article Link to deepdyve

Final Results

Published 10/2/19

After the midway results meeting, 9 production process for 1,5-PeD have been reviewed and deepened. The results are organised based on the concept and presented per production process 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 descriptions.

Table of concepts:

  1. 1. Direct from Furfural
  2. 2. Other routes / base component

Technology Radar
Requirements Table

1. Direct from Furfural

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Direct conversion from furfural without intermediate steps


1.1 Direct one pot from Furfural/Furfuryl Alcholol ring-opening with noble (Mainly Rh-Ir) metal catalyst

0

A one-pot synthesis is a strategy to improve the efficiency of a chemical reaction whereby a reactant is subjected to successive chemical reactions in just one reactor. The one pot conversions studied here are based on noble metals. A summary of the yield over different noble metals are given in this [Figure](#image-1856). **Summary of research results:** * In this work, we investigated the additive effect of other noble metals such as Ru, Rh, Pt and Pd to the Ir–ReOx/SiO2 catalyst for the one-pot aqueous phase conversion of furfural into 1,5-PeD. As a result, it was found that Pd-added Ir–ReOx/SiO2 (Pd–Ir–ReOx/SiO2) is the most effective (Art. [#ARTNUM](#article-26548-2017742383)). * it was found that Rh–Ir–ReOx/SiO2 is more effective than Pd–Ir–ReOx/SiO. The highest yield of 1,5-PeD was 71.1% from highly concentrated furfural (50 wt%) and 78.2% from diluted furfural (10 wt%) when using Rh (0.66 wt%)–Ir–ReOx/SiO2 as catalyst. The high performance of Rh(0.66)–Ir–ReOx/SiO2 could be attributed to its unique structure. The ReOx-species-modified Ir–Rh alloy enhanced the hydrogenation rate of furfural to the tetrahydrofurfuryl alcohol (THFA) intermediate in the low temperature step as compared to Ir–ReOx/SiO2. THFA was converted to 1,5-pentanediol by hydrogenolysis during the high temperature step over the same ReOx-modified Ir–Rh alloy. (Art. [#ARTNUM](#article-26548-1981986998)) * The invention relates to a catalyst used in a ring-opening hydrogenation reaction of a furan derivative. The catalyst is applied to direct preparation of one-step ring-opening hydrogenation of 1,5-pentanediol and 1,2-pentanediol by taking furfural or furfuryl alcohol serving as a raw material under a mild condition. The catalyst can provide two active ingredients, namely the ring-opening active center of a transition metal oxide and the hydrogenation active center of Pt, Pd, Rh, Ru, Co or Ni, wherein the active center of the transition metal oxide is mainly used for adsorbing furfural or furfuryl alcohol and directly hydrogenating a furan ring for opening the furan ring; and the hydrogenation active center of a noble metal or Co, Ni and the like is mainly used for quickly hydrogenating anintermediate material and hydrogenating subsequent enol so as to obtain 1,5-pentanediol and 1,2-pentanediol. An environmentally-friendly, reproducible, low-cost, mild and effective method is provided for producing 1,5-pentanediol and 1,2-pentanediol. The high-performance ring-opening hydrogenation catalyst is also suitable for the ring-opening hydrogenation reaction of other furan derivatives. (Art. [#ARTNUM](#article-26548-2830237051)) **Requirements:** * Purity of the initial component (ex: furfural): Highly concentrated furfural (50 wt%,71m1% yield ) and diluted furfural (10 wt%, yield 78,2%) * Complexity (# of steps): One pot / Two step * Reaction medium: Rh–Ir alloy catalyst

1.1.1 Direct one pot from Furfural/Furfuryl Alcholol ring-opening with noble (Mainly Rh-Ir) metal catalyst
Catalyst used in ring-opening hydrogenation reaction of furan derivative
The invention relates to a catalyst used in a ring-opening hydrogenation reaction of a furan derivative. The catalyst is applied to direct preparation of one-step ring-opening hydrogenation of 1,5-pentanediol and 1,2-pentanediol by taking furfural or furfuryl alcohol serving as a raw material under a mild condition. The catalyst can provide two active ingredients, namely the ring-opening active center of a transition metal oxide and the hydrogenation active center of Pt, Pd, Rh, Ru, Co or Ni, wherein the active center of the transition metal oxide is mainly used for adsorbing furfural or furfuryl alcohol and directly hydrogenating a furan ring for opening the furan ring; and the hydrogenation active center of a noble metal or Co, Ni and the like is mainly used for quickly hydrogenating anintermediate material and hydrogenating subsequent enol so as to obtain 1,5-pentanediol and 1,2-pentanediol. An environmentally-friendly, reproducible, low-cost, mild and effective method is providedfor producing 1,5-pentanediol and 1,2-pentanediol. The high-performance ring-opening hydrogenation catalyst is also suitable for the ring-opening hydrogenation reaction of other furan derivatives.
11/21/12 12:00:00 AM
Link to Article
1.1.2 Direct one pot from Furfural/Furfuryl Alcholol ring-opening with noble (Mainly Rh-Ir) metal catalyst
One-pot selective conversion of furfural into 1,5-pentanediol over a Pd-added Ir–ReOx/SiO2 bifunctional catalyst
One-pot selective conversion of furfural into 1,5-pentanediol (1,5-PeD) was carried out over Pd-added Ir–ReOx/SiO2catalysts through two-step reaction temperatures. The Pd(0.66 wt%)–Ir–ReOx/SiO2catalyst showed the best performance in the production of 1,5-PeD from furfural. The maximum yield of 1,5-PeD was 71.4%. The furfural conversion and yield of 1,5-PeD was almost maintained during four repeated tests when the catalyst was calcined again. The characterization results from TPR, XRD, XANES, EXAFS and FT-IR of adsorbed CO indicated that Pd–Ir–ReOx/SiO2catalysts consisted of ReOx-modified Pd metal particles and ReOx-modified Ir metal particles. The lower-temperature reaction step was very crucial for the total hydrogenation of furfural into a tetrahydrofurfuryl alcohol intermediate, which was converted into 1,5-PeD by hydrogenolysis during the high temperature step over the ReOx-modified Ir metal particles.
1/1/14 12:00:00 AM
Link to Article
1.1.3 Direct one pot from Furfural/Furfuryl Alcholol ring-opening with noble (Mainly Rh-Ir) metal catalyst
Performance and characterization of rhenium-modified Rh–Ir alloy catalyst for one-pot conversion of furfural into 1,5-pentanediol
One-pot selective conversion of highly concentrated furfural to 1,5-pentanediol (1,5-PeD) was carried out over Rh-added Ir–ReOx/SiO2 catalysts through two-step reaction temperatures. Over the optimized catalyst, Rh(0.66 wt%)–Ir–ReOx/SiO2, the maximum yield of 1,5-PeD was 71.1% from highly concentrated furfural (50 wt%) and 78.2% from diluted furfural (10 wt%). These values were higher than those obtained with Ir–ReOx/SiO2 or Pd–Ir–ReOx/SiO2 catalysts. Rh–Ir–ReOx/SiO2 showed much higher activity in the hydrogenation of furfural to tetrahydrofurfuryl alcohol intermediate in the low temperature step than Ir–ReOx/SiO2, although the hydrogenation activity was lower than that of Pd–Ir–ReOx/SiO2. A long reaction time in the low temperature step is necessary to obtain a good 1,5-PeD yield over Rh–Ir–ReOx/SiO2 in two-step reaction of furfural. The hydrogenolysis activity of Rh–Ir–ReOx/SiO2 for tetrahydrofurfuryl alcohol to 1,5-PeD in the high temperature step was higher than that of Pd–Ir–ReOx/SiO2 and was comparable to that of Ir–ReOx/SiO2. The characterization results of TPR, XRD, XANES, EXAFS, STEM-EDX and FT-IR of adsorbed CO indicated that Rh–Ir–ReOx/SiO2 catalysts showed the structure of Ir–Rh alloy particles partially covered with ReOx species. The hydrogenation activity of Rh–Ir–ReOx/SiO2 for the furan ring was higher than those of the mixture of Rh–Ir/SiO2 and Ir–ReOx/SiO2 or the mixture of Rh–ReOx/SiO2 and Ir–ReOx/SiO2. Both Ir–Rh alloy formation and ReOx modification of alloy particles are essential for the high hydrogenation activity.
1/1/14 12:00:00 AM
Link to Article

1.2 One Pot reaction on a Pdadded Ir– ReOx/SiO2 catalysts through twostep reaction temperature

0

Reducing the production of 1,5-diol to one step most probably opens another avenue for competitive production of 1,5-pentanediol (PDO, or pentane-1,5-diol) as the conventional pathway to PDO from furfural was via multi-step hydrogenation (via THFA/Methyl-THF). Onepot selective conversion of furfural into 1,5pentanediol (1,5PeD) was carried out over Pdadded Ir– ReOx/SiO2catalysts through twostep reaction temperatures. The Pd(0.66 wt%)–Ir–ReOx/SiO2catalyst showed the best performance in the production of 1,5PeD from furfural. The maximum yield of 1,5PeD was 71.4%. The furfural conversion and yield of 1,5PeD was almost maintained during four repeated tests when the catalyst was calcined again. The characterization results from TPR, XRD, XANES, EXAFS and FTIR of adsorbed CO indicated that Pd– Ir–ReOx/SiO2catalysts consisted of ReOxmodified Pd metal particles and ReOxmodified Ir metal particles. The lowertemperature reaction step was very crucial for the total hydrogenation of furfural into a tetrahydrofurfuryl alcohol intermediate, which was converted into 1,5PeD by hydrogenolysis during the high temperature step over the ReOxmodified Ir metal particles. The effect of Pd amount of Pd–Ir–ReOx/SiO2 on the conversion of furfural was investigated (entries 6–12). Under these conditions, all the catalysts achieved >99.9% furfural conversion. Both the yields of the intermediate THFA and overhydrogenolysis products (pentanols) were less than 15%. The dependence of 1,5-PeD yield on the Pd loading amount is volcano-type. Among them, Pd(0.66)–Ir–ReOx/SiO2 showed the best performance and 1,5-PeD yield reached 62.4%. ([Art. #ARTNUM](#article-26766-2017742383)) **Requirements:**([Art. #ARTNUM](#article-26766-2017742383)) * Purity of the initial component (ex: furfural): In the case of low concentration (below 20%), the yield of 1,5-PeD was almost constant. However, as furfural concentration increased to 50%, the yield of 1,5-PeD decreased significantly and furfural was polymerized to some extent. 20 to 50%. * Complexity (# of steps): One pot / Two step * Reaction medium: Pd-Ir/SiO2 catalyst

1.2.1 One Pot reaction on a Pdadded Ir– ReOx/SiO2 catalysts through twostep reaction temperature
One-pot selective conversion of furfural into 1,5-pentanediol over a Pd-added Ir–ReOx/SiO2 bifunctional catalyst
One-pot selective conversion of furfural into 1,5-pentanediol (1,5-PeD) was carried out over Pd-added Ir–ReOx/SiO2catalysts through two-step reaction temperatures. The Pd(0.66 wt%)–Ir–ReOx/SiO2catalyst showed the best performance in the production of 1,5-PeD from furfural. The maximum yield of 1,5-PeD was 71.4%. The furfural conversion and yield of 1,5-PeD was almost maintained during four repeated tests when the catalyst was calcined again. The characterization results from TPR, XRD, XANES, EXAFS and FT-IR of adsorbed CO indicated that Pd–Ir–ReOx/SiO2catalysts consisted of ReOx-modified Pd metal particles and ReOx-modified Ir metal particles. The lower-temperature reaction step was very crucial for the total hydrogenation of furfural into a tetrahydrofurfuryl alcohol intermediate, which was converted into 1,5-PeD by hydrogenolysis during the high temperature step over the ReOx-modified Ir metal particles.
1/1/14 12:00:00 AM
Link to Article

1.3 Direct conversion based on Pt/Co2AlO4 catalyst under mild conditions

1

Achieving low cost and mild reaction conditions are the prime interests for the chemical industry. Furfural is an organic compound derived from a variety of biomass, such as corncobs, oat, wheat bran and sawdust, which is the raw material of tetrahydrofurfuryl alcohol and much cheaper. Therefore, how to directly convert furfural to diols with a new kind of catalyst under mild conditions is an interesting and challenging work. Thiw work studies the development of a Pt/Co2AlO4 catalyst and its excellent catalytic performance in the direct conversion of furfural to 1,5-pentanediol at low pressure (1.0–1.5 MPa). A novel nanosized mesoporous Co–Al spinel with high surface area and suitable basicity was developed and used as a solid base catalyst or a bifunctional catalyst after loading with Pd in our group recently. The Cop-Pt/Co2AlO4 catalyst is prepared by co-precipitation for the direct conversion of furfural to 1,5-pentanediol. This new route to produce 1,5-pentanediol from furfural over Cop-Pt/Co2AlO4 catalyst. It is low cost and could be operated under mild conditions. In particular, at 1.5 MPa, 140 1C, 1,5-pentanediol yield reaches B35% after reaction for 24 h; this is the highest value reported under mild conditions so far. In this kind of catalysts, CoOx (Co3+ ions, especially) is mainly responsible for the absorption of CQC and the opening of the furan ring, while Pt works for the following hydrogenation. This rule can guide the design of more-efficient and stable catalysts for the catalytic direct conversion of furfural to 1,5-pentanediol with high stability. ([Art. #ARTNUM](#article-27210-1994790185)) **Requirements:**([Art. #ARTNUM](#article-27210-1994790185)) * Purity of the initial component (ex: furfural): N.C. * Complexity (# of steps): Direct / 5 steps (See [Figure](#image-1858) ). * Reaction medium: Pt/Co2AlO4 catalyst with nanosized mesoporous Co–Al spinel

1.3.1 Direct conversion based on Pt/Co2AlO4 catalyst under mild conditions
Direct catalytic conversion of furfural to 1,5-pentanediol by hydrogenolysis of the furan ring under mild conditions over Pt/Co2AlO4 catalyst
A new strategy was developed for the direct conversion of furfural to 1,5-pentanediol by the hydrogenolysis of the furan ring under mild conditions based on Pt/Co2AlO4 catalyst. This is the first report of the direct catalytic conversion of furfural to 1,5-pentanediol with high yield.
1/1/11 12:00:00 AM
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1.4 New catalytic strategies for α,ω-diols production from lignocellulosic biomass

1

Catalytic strategies for the synthesis of 1,5pentanediol (PDO) with 69% yield from hemicellulose and the synthesis of 1,6hexanediol (HDO) with 28% yield from cellulose are presented. In the TriVersa Process™, a white birch biomass feedstock was solubilized by dilute sulfuric acid to produce a high purity solid cellulose (90–94.5% purity and 35–42% yield), a soluble hemicellulose (>90% of hemicellulose in biomass feedstock), and a lignin stream in GVL/H2O (80/20) solvent. The soluble hemicellulose was converted into furfural at 85% yield in less than 30 seconds. Furfural has been shown to form THFA in 96% yield by vapor phase hydrogenation.20 THFA was converted into PDO in 84% overall yield via the threestep DHH process. THFA was converted into DHP in 87% yield by vapor phase dehydration with g-Al2O3. Uncatalyzed DHP hydration in water produced 2-HYTHP and 2-HY-THP dimers in 99% yield. Ru catalysts hydrogenated 2-HY-THP to PDO in 97% yield. This conversion represents an 80% yield of PDO from furfural. HDO was produced from the cellulose by first dehydrating cellulose into LGO and HMF (48% yield) in a THF/H2O mixture with acid catalysts. This mixture was then hydrogenated using Ni/SiO2, followed by hydrogenolysis over Pd/SiO2–Al2O3 with 83% overall selectivity to THFDM. A 70% yield to HDO from THFDM was obtained with Pt-based catalysts A process model was developed to estimate the economics of this process for a 1000 dry metric tons white birch per day plant. The minimum selling price for the production of HDO and PDO is $4090 per ton, which is similar to the market price of HDO derived from petroleum. Our analysis suggests that two parameters that appear to be the most important are the concentration of cellulose and THFDM and the HDO yield. In addition, further process integration and continuous flow studies are also required to evaluate the impact of contaminants and the catalyst stability. ([Art. #ARTNUM](#article-26761-2594054213)) **Requirements:**([Art. #ARTNUM](#article-26761-2594054213)) * Purity of the initial component (ex: furfural): From high puritiy ellulose * Complexity (# of steps): 5 catalytic steps * Reaction medium: Ni / Pd / Pb -based catalysts

1.4.1 New catalytic strategies for α,ω-diols production from lignocellulosic biomass
Conversion of Furfural to 1,5-Pentanediol: Process Synthesis and Analysis
A new process for the production of 1,5-pentanediol (1,5-PDO) from biomass-derived furfural is studied. In this process, furfural is converted to 1,5-PDO in a high overall yield (80%) over inexpensive catalysts via multiple steps involving hydrogenation, dehydration, hydration, and hydrogenation subsequently. To effectively recycle H2 as well as recover 1,5-PDO, detailed separation subsystems have been designed and integrated with reaction subsystems. Furthermore, a pioneer plant analysis is performed to estimate the risk on the cost growth and plant performance shortfalls. The integrated process leads to a minimum selling price of $1973 ton–1 for 1,5-PDO, which suggests that it could be a promising approach for converting biomass into oxygenated commodity chemicals, which are difficult to produce from petroleum-derived feedstocks. The sensitivity analysis also identifies that the most important economic parameters for the process include the furfural feedstock price and plant size.
6/5/17 12:00:00 AM
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1.4.2 New catalytic strategies for α,ω-diols production from lignocellulosic biomass
New catalytic strategies for α,ω-diols production from lignocellulosic biomass
Catalytic strategies for the synthesis of 1,5-pentanediol (PDO) with 69% yield from hemicellulose and the synthesis of 1,6-hexanediol (HDO) with 28% yield from cellulose are presented. Fractionation of lignocellulosic biomass (white birch wood chips) in gamma-valerolactone (GVL)/H2O generates a pure cellulose solid and a liquid stream containing hemicellulose and lignin, which is further dehydrated to furfural with 85% yield. Furfural is converted to PDO with sequential dehydration, hydration, ring-opening tautomerization, and hydrogenation reactions. Acid-catalyzed cellulose dehydration in tetrahydrofuran (THF)/H2O produces a mixture of levoglucosenone (LGO) and 5-hydroxymethylfurfural (HMF), which are converted with hydrogen to tetrahydrofuran-dimethanol (THFDM). HDO is then obtained from hydrogenolysis of THFDM. Techno-economic analysis demonstrates that this approach can produce HDO and PDO at a minimum selling price of $4090 per ton.
1/1/17 12:00:00 AM
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1.4.3 New catalytic strategies for α,ω-diols production from lignocellulosic biomass
PRODUCTION OF 1,5-PENTANEDIOL VIA UPGRADING OF TETRAHYDROFUFURYL ALCOHOL
A method of making 1,5-pentanediol from tetrahydrofurfural alcohol. The method includes the steps of dehydrating tetrahydrofurfural alcohol (THFA) to dihydropyran (DHP); hydrating at least a portion of the DHP to 2-hydroxy-tetrahydropyran (2-HY-THP) in the absence of homogeneous acid; and hydrogenating at least a portion of the 2-HY-THP to 1,5-pentanediol. The method can be conducted entirely in the absence of noble metal catalysts.
7/27/17 12:00:00 AM
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2. Other routes / base component

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Starting from other components than THFA or Furfural


2.1 Copper containing catalyst (As from oxidation of cyclohexane glutaric acid byproducts)

0

Although there has been interest in the conversion of furfuryl alcohol for more than a few decades, most of the catalysts have disadvantages regarding their environmental impact (e.g., chromium containing catalysts); necessity for special solvents or additives (e.g., Adam’s catalyst; or at least the price of the catalyst, as in the case of platinum‐based catalysts. copper-containing catalysts seems to be a promising alternative due to copper’s low price and the wide industrial availability. **Summary of research results:** * The hydrogenolysis of furfuryl alcohol gives access to two important diols. Interestingly, the amount of 1,5-pentanediol, accessible via breaking the opposite C–O bond in the furan ring, is comparatively low with regard to 1,2-pentanediol. A more pronounced but similar relation in the selectivity distribution between the two diols is observed when using ruthenium catalysts (Art. [#ARTNUM](#article-26544-2587520367)). * An industrially suitable method of producing a 1,5pentanediol and / or 1,6hexanediol in a high yield with Coppercontaining catalyst and an acid value (AV value) 0.5 mgKOH / g or less of alcohol or acid value to (AV value) hydrogenating the esterified product by the prereduced catalyst in an ester of below 0.5 mgKOH / g the above problems in is solved. Based on cyclohexane glutaric acid byproduct during the production of cyclohexanone is oxidized with oxygen or an oxygencontaining gas, adipic acid, carboxylic acid mixture such as 6hydroxycaproic acid, methanol, ethanol, butanol, 1,6hexanediol esterified with alcohols (Art.[#ARTNUM](#article-26544-2775997820) ). * According to the method, a highly dispersed copperbased composite metal oxide is adopted as a catalyst, methanol, ethanol, isopropanol or dioxane is adopted as a solvent, and a furan derivative is subjected to selective hydrogenolysis in an intermittent stirring reaction kettle or continuous fixed bed reactor at a reaction temperature of 120180 DEG C under a hydrogen pressure of 110 MPa to prepare the pentanediol, Art. [#ARTNUM](#article-26544-2814474070). * A method for efficiently producing high-purity 1,5-pentanediol by reacting tetrahydrofurfuryl alcohol with hydrogen. Through a hydrogenolysis reaction of tetrahydrofurfuryl alcohol with hydrogen carried out in the presence of a copper-containing catalyst with reaction temperature of 200 to 350° C. and reaction pressure of 1 to 40 MPa (Art. [#ARTNUM](#article-26544-US8940946B2)). **Requirements:** * Purity of the initial component (ex: furfural): N.C. * Complexity (# of steps): 3 - 4 steps * Reaction medium: Copper catalyst

2.1.1 Copper containing catalyst (As from oxidation of cyclohexane glutaric acid byproducts)
A PROCESS FOR PREPARING 1,5-PENTANEDIOL AND Δ-VALEROLACTONE FROM TETRAHYDROFURFURYL ALCOHOL
The present invention provides a method to manufacture 1,5-pentanediol under mild reaction conditions using a copper nanocomposite oxide catalyst without chromium or to manufacture δ-valerolactone by directly making tetrahydrofurfuryl alcohol react not via 1,5-pentanediol under the same catalyst, and a catalyst being used therefor.
6/20/14 12:00:00 AM
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2.1.2 Copper containing catalyst (As from oxidation of cyclohexane glutaric acid byproducts)
Aqueous Phase Hydrogenolysis of Bio-Derivable Furfuryl Alcohol to Pentanediols Using Copper Catalysts
In the context of sustainable production processes based on bio-derivable feedstocks, the hydrogenolysis of furfuryl alcohol gives access to two important diols. This work evaluates the performance of commercial copper catalysts in the aqueous phase hydrogenolysis reaching a selectivity towards 1,2-pentanediol of up to 34%. In contrast to noble metal catalysts such as supported ruthenium, the selectivity of the hydrogenation product, tetrahydrofurfuryl alcohol, is significantly lower, so the desired diols are now the main products of this reaction. Catalysis experiments show that the performance is correlated to the catalyst composition rather than the free copper surface, indicating a strong influence of the supporting material. Although the formation of oligomeric and polymeric side products is still perturbing, copper catalysts represent promising candidates for this reaction due to their low cost and wide availability.
2/7/17 12:00:00 AM
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2.1.3 Copper containing catalyst (As from oxidation of cyclohexane glutaric acid byproducts)
Catalyst and method for preparing 1, 5 pentanediol by hydrogenation of 1, 5 dimethyl glutarate
The invention relates to a catalyst for hydrogenation preparation of 1,5-pentanediol by 1,5-dimethyl glutarate and its preparation method. The catalyst consists of active component copper oxide, aid zinc oxide and alumina, in which, copper oxide is 40 to 60% by weight, zinc oxide is 20 to 50% by weight and alumina is 10 to 20% by weight. The preparation process comprises the following steps: soluble salts of copper, zinc and aluminum are mixed by weight and dissolved by water, and pH value is adjusted to 7 by aqueous alkali in the process of heating and stirring, precipitate is filtered, washed, dried and baked, and then the catalyst is obtained.
1/19/05 12:00:00 AM
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2.1.4 Copper containing catalyst (As from oxidation of cyclohexane glutaric acid byproducts)
Method for producing 1,5-pentanediol and / or 1,6-hexanediol
Cyclohexane glutaric acid by-product during the production of cyclohexanone is oxidized with oxygen or an oxygen-containing gas, adipic acid, carboxylic acid mixture such as 6-hydroxycaproic acid, methanol, ethanol, butanol, 1,6-hexanediol esterified with alcohols such as, the resulting esterified product, a process for the preparation of hydrogenated in the presence of a copper-containing catalyst 1,6-hexanediol and / or 1,5-pentanediol, the deterioration of the catalyst controlled, and to provide an industrially suitable method of producing a 1,5-pentanediol and / or 1,6-hexanediol in a high yield. Copper-containing catalyst and an acid value (AV value) 0.5 mgKOH / g or less of alcohol or acid value to (AV value) hydrogenating the esterified product by the pre-reduced catalyst in an ester of below 0.5 mgKOH / g the above problems in is solved.
5/15/08 12:00:00 AM
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2.1.5 Copper containing catalyst (As from oxidation of cyclohexane glutaric acid byproducts)
Method for producing pentanediol through selective hydrogenolysis of furan derivative
The present invention discloses a method for producing pentanediol through selective hydrogenolysis of a furan derivative. According to the method, a highly dispersed copper-based composite metal oxide is adopted as a catalyst, methanol, ethanol, isopropanol or dioxane is adopted as a solvent, and a furan derivative is subjected to selective hydrogenolysis in an intermittent stirring reaction kettle or continuous fixed bed reactor at a reaction temperature of 120-180 DEG C under a hydrogen pressure of 1-10 MPa to prepare the pentanediol, wherein a catalyst precursor having a hydrotalcite layered structure is subjected to calcination reduction to obtain the catalyst, mainly a metal ion solution having CuM and an alkaline solution are subjected to a co-precipitation reaction so as to obtain the catalyst precursor, and in the catalyst, Cu is the main active component and has the content is 2-40%, and the content of the M-containing oxide and the spinel carrier is 60-98%. According to the present invention, the catalyst preparation method has characteristics of simpleness, easily available raw materials and low cost, and the prepared catalyst has characteristics of uniform component distribution, small particle size, large specific surface area and stable performance, and provides high reaction reactivity and high selectivity for the pentanediol production through the selective hydrogenolysis of the furan derivative.
12/9/15 12:00:00 AM
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2.1.6 Copper containing catalyst (As from oxidation of cyclohexane glutaric acid byproducts)
PROCESS FOR PREPARING 1,5-PENTANEDIOL AND/OR 1,6-HEXANEDIOL
An objective is to provide a process for preparing 1,5-pentanediol and/or 1,6-hexanediol comprising esterifying, with an alcohol such as methanol, ethanol, butanol or 1,6-hexanediol, a mixture of carboxylic acids such as glutaric acid, adipic acid and 6-hydroxycaproic acid which are a by-product in preparation of cyclohexanone by oxidation of cyclohexane with oxygen or an oxygen-containing gas; and hydrogenating the resulting esterified product in the presence of a copper-containing catalyst, which process is an industrially suitable process for preparing 1,5-pentanediol and/or 1,6-hexanediol in a high yield while controlling deterioration of the catalyst. The above objective is achieved by hydrogenating the esterified product with a catalyst obtained by prereducing a copper-containing catalyst in an alcohol having an acid value (AV) of 0.5 mg KOH/g or less or an ester having an acid value (AV) of 0.5 mg KOH/g or less.
6/3/10 12:00:00 AM
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2.1.7 Copper containing catalyst (As from oxidation of cyclohexane glutaric acid byproducts)
PRODUCTION METHOD OF 1,2-PENTANE DIOL AND 1,5-PENTANE DIOL
PROBLEM TO BE SOLVED: To provide a production method of industrially suitable 1,2-pentane diol and 1,5-pentane diol with furfuryl alcohol used as a production raw material.SOLUTION: A production method of 1,2-pentane diol and 1,5-pentane diol is characterized by reacting furfuryl alcohol with hydrogen, using at least one alkaline compound selected from the group consisting of compounds containing an alkali metal and an alkali earth metal in the presence of a copper-containing metal catalyst.
6/11/15 12:00:00 AM
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2.1.8 Copper containing catalyst (As from oxidation of cyclohexane glutaric acid byproducts)
Method for producing high-purity 1,5-pentanediol

1. A method for producing high-purity 1,5-pentanediol, the method comprising:hydrogenolyzing tetrahydrofurfuryl alcohol with hydrogen in the presence of a copper-comprising catalyst at a reaction temperature of from 200 to 350° C. and a reaction pressure of from 1 to 40 MPa until conversion rate of tetrahydrofurfuryl alcohol reaches 80% or less, thereby obtaining a crude reaction product;separating tetrahydrofurfuryl alcohol and crude 1,5-pentanediol (A) from the crude reaction product, thereby obtaining recovered tetrahydrofurfuryl alcohol and the crude 1,5-pentanediol (A), and then, supplying the recovered tetrahydrofurfuryl alcohol as a raw material for said hydrogenolyzing; anddistilling the crude 1,5-pentanediol (A), thereby obtaining the high-purity 1,5-pentanediol. 2. The method according to claim 1, wherein water content in the tetrahydrofurfuryl alcohol in said hydrogenolyzing is 1% or less by mass. 3. The method according to claim 1, wherein the copper-comprising catalyst after use is recovered by separation after ending of said hydrogenolyzing, thereby obtaining a recovered copper-comprising catalyst, which is reused in said hydrogenolyzing. 4. The method according to claim 1, wherein the crude 1,5-pentanediol (A) obtained in said separating is distilled to remove high-boiling point compounds, thereby obtaining a second crude 1,5-pentanediol, which is used in said distilling. 5. The method according to claim 1, wherein a saponification agent is added to the crude reaction product obtained in said hydrogenolyzing before said separating and said distilling. 6. The method according to claim 1, wherein a saponification agent is added to the crude 1,5-pentanediol (A) obtained in said separating before said distilling. 7. The method according to claim 1, wherein a total amount of diol compounds having a secondary hydroxy group contained in the high-purity 1,5-pentanediol obtained in said distilling is 1% or less by mole. 8. The method according to claim 1, wherein the copper-comprising catalyst used in said hydrogenolyzing comprises at least one atom "B" selected from the group consisting of zinc, iron, aluminum, chromium, and silicon. 9. The method according to claim 8, wherein the copper-comprising catalyst used in said hydrogenolyzing further comprises at least one atom "C" selected from the group consisting of barium, calcium, manganese, lanthanum, cerium, and magnesium. 10. The method according to claim 1, wherein the tetrahydrofurfuryl alcohol used in said hydrogenolyzing is tetrahydrofurfuryl alcohol synthesized by using furfural as a raw material. 11. The method according to claim 1, wherein acid value of the tetrahydrofurfuryl alcohol used in said hydrogenolyzing is 2 mg-KOH/g or less.
11/19/12 12:00:00 AM
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2.2 Autocatalytic Hydration of Dihydropyran to 2hydroxytetrahydropyran, to 1,5-PeD

0

Dihydropyran (DHP) undergoes autocatalyzed hydration to 2hydroxytetrahydropyran (2HYTHP) by carboxylic acids formed in situ in both batch and continuous flow reactors. A 3-step process for the production of 1,5-PD from furfural-derived tetrahydrofurfuryl alcohol (THFA) as shown in this [Figure](#image-1862). In the first reaction step, THFA is dehydrated in the vapor phase over γ-Al2O3 to dihydropyran (DHP).14,15 The DHP is then hydrated with H2O in the liquid phase to form 2-hydroxytetrahydropyran (2-HY-THP) without the addition of any external catalyst.12 The 2-HY-THP undergoes ring-opening tautomerization in H2O to form 5-hydroxyvaleraldehyde (5HVal) which can be hydrogenated into 1,5 PD over Ru catalysts. The overall yield of all reaction steps is 90%. Although this process has more reaction steps than the traditional direct hydrogenolysis of tetrahydrofurfuryl alcohol (THFA), techno-economic analyses demonstrate that this process is the economically preferred route for the synthesis of biorenewable 1,5-PD. (Art. [#ARTNUM](#article-22907-2594109166)) More information also available [here](https://onlinelibrary.wiley.com/doi/epdf/10.1002/cssc.201700178). **Requirements:** * Purity of the initial component (ex: furfural): 20% DHP in water * Complexity (# of steps): More than traditional * Reaction medium: γ-Al2O3, Ru catalysts

2.2.1 Autocatalytic Hydration of Dihydropyran to 2hydroxytetrahydropyran, to 1,5-PeD
Autocatalytic Hydration of Dihydropyran to 1,5-Pentanediol Precursors via in situ Formation of Liquid- and Solid-Phase Acids
Dihydropyran (DHP) undergoes autocatalyzed hydration to 2-hydroxytetrahydropyran (2-HY-THP) by carboxylic acids formed in situ in both batch and continuous flow reactors. NMR, GC–MS, and pH analysis corroborate the presence of carboxylic acids in the hydration products. Carboxylic acids, likely in the form of 5-hydroxy-valeric acid, are made as low as 25 °C, increasing solution acidity and autocatalyzing DHP hydration. 1,5-Pentanediol precursors 2-HY-THP and C10 dimers are produced from DHP at ∼98% yields at temperatures ≤100 °C. At ≥140 °C, byproducts are formed, including acidic solid coke and a C10 dimer likely made via aldol condensation-cyclodehydration of the ring-opened tautomer of 2-HY-THP, 5-hydroxyvaleraldehyde. DHP hydration rates continuously increased up to 50 h time-on-stream in continuous reactors demonstrating that the acidic byproducts catalyze this reaction. Activation rates rose with temperature due to increased acidic solid coke formation. The coke formed is soluble in water and its fo...
11/6/17 12:00:00 AM
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2.2.2 Autocatalytic Hydration of Dihydropyran to 2hydroxytetrahydropyran, to 1,5-PeD
Chemicals from Biomass: Combining Ring-Opening Tautomerization and Hydrogenation Reactions to Produce 1,5-Pentanediol from Furfural
A process for the synthesis of 1,5-pentanediol (1,5-PD) with 84 % yield from furfural is developed, utilizing dehydration/hydration, ring-opening tautomerization, and hydrogenation reactions. Although this process has more reaction steps than the traditional direct hydrogenolysis of tetrahydrofurfuryl alcohol (THFA), techno-economic analyses demonstrate that this process is the economically preferred route for the synthesis of biorenewable 1,5-PD. 2-Hydroxytetrahydropyran (2-HY-THP) is the key reaction pathway intermediate that allows for a decrease in the minimum selling price of 1,5-PD. The reactivity of 2-HY-THP is 80 times greater than that of THFA over a bimetallic hydrogenolysis catalyst. This enhanced reactivity is a result of the ring-opening tautomerization to 5-hydoxyvaleraldehyde and subsequent hydrogenation to 1,5-PD.
4/10/17 12:00:00 AM
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2.3 Enzymatic production of 5-aminovalerate from L-lysine using L-lysine monooxygenase and 5-aminovaleramide amidohydrolase as a platform for 1,5PeD

0

5-Aminovalerate (5AVA) is the precursor of valerolactam, a potential building block for producing nylon 5, and can potentially be used as a C5 platform chemical for synthesizing 5-hydroxyvalerate, glutarate, and 1,5-pentanediol. **Summary of research results:** * Metabolic engineering ofE. coliby establishing a heterologouspathway composed of the P. putida davBanddavAgenes, encodinglysine 2-monooxygenase and delta-aminovaleramidase, respec-tively, allowed production of 5AVA from L-lysine. The metabolicengineering strategies developed in this study will be useful forthe production of C5 platform chemicals, including 5AVA andglutarate, both of which can be used as important precursors forproducing other C5 chemicals. (art, [#ARTNUM](#article-26765-2044151225)). * Under optimal conditions, 20.8 g/L 5-aminovalerate was produced from 30 g/L L-lysine in 12 h. Because L-lysine is an industrial fermentation product, the two-enzyme coupled system presents a promising alternative for the production of 5-aminovalerate (Art. [#ARTNUM](#article-26765-1994889276)). **Requirements:** * Purity of the initial component (ex: furfural): N.C. * Complexity (# of steps): Preliminary steps * Reaction medium: E-Coli / L-Lysine

2.3.1 Enzymatic production of 5-aminovalerate from L-lysine using L-lysine monooxygenase and 5-aminovaleramide amidohydrolase as a platform for 1,5PeD
Efficient production of 5-aminovalerate from l-lysine by engineered Escherichia coli whole-cell biocatalysts
Abstract In this study, we developed a whole-cell biocatalysis process for high-level conversion of l -lysine into 5-aminovalerate. To obtain the highly efficient whole-cell biocatalyst, five expression plasmids were constructed to optimize the expression of 5-aminovaleramide amidohydrolase and l -lysine 2-monooxygenase in Escherichia coli . The engineered strain BL-22A-RB-YB harboring plasmid pET22b-davA, pRSFDuet-davB and pACYCDuet-davB was correspondingly obtained. Subsequently, the effects of induction conditions, reaction temperature, metal ion additives, and cell permeability on the whole-cell biocatalyst system were evaluated to improve biocatalytic efficiency. Under optimized reaction conditions, 95.3 g/L 5-aminovalerate was synthesized from 120 g/L l -lysine with a yield of 99.1%, and 103.1 g/L 5-aminovalerate was produced from 150 g/L l -lysine with a molar yield of 85.7%. The 5-aminovalerate production was then further improved using a l -lysine fed-batch strategy, and a hyper 5-aminovalerate production of 240.7 g/L was achieved within 28 h with a yield of 86.8%. The whole-cell biocatalytic system described here demonstrated an environmentally friendly strategy for industrial production of 5-aminovalerate.
12/1/16 12:00:00 AM
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2.3.2 Enzymatic production of 5-aminovalerate from L-lysine using L-lysine monooxygenase and 5-aminovaleramide amidohydrolase as a platform for 1,5PeD
Enzymatic production of 5-aminovalerate from L-lysine using L-lysine monooxygenase and 5-aminovaleramide amidohydrolase.
5-Aminovalerate is a potential C5 platform chemical for synthesis of valerolactam, 5-hydroxyvalerate, glutarate, and 1,5-pentanediol. It is a metabolite of l-lysine catabolism through the aminovalerate pathway in Pseudomonas putida. l-Lysine monooxygenase (DavB) and 5-aminovaleramide amidohydrolase (DavA) play key roles in the biotransformation of l-lysine into 5-aminovalerate. Here, DavB and DavA of P. putida KT2440 were expressed, purified, and coupled for the production of 5-aminovalerate from l-lysine. Under optimal conditions, 20.8 g/L 5-aminovalerate was produced from 30 g/L l-lysine in 12 h. Because l-lysine is an industrial fermentation product, the two-enzyme coupled system presents a promising alternative for the production of 5-aminovalerate.
5/1/15 12:00:00 AM
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2.3.3 Enzymatic production of 5-aminovalerate from L-lysine using L-lysine monooxygenase and 5-aminovaleramide amidohydrolase as a platform for 1,5PeD
Metabolic engineering of Escherichia coli for the production of 5-aminovalerate and glutarate as C5 platform chemicals.
Abstract 5-Aminovalerate (5AVA) is the precursor of valerolactam, a potential building block for producing nylon 5, and is a C5 platform chemical for synthesizing 5-hydroxyvalerate, glutarate, and 1,5-pentanediol. Escherichia coli was metabolically engineered for the production of 5-aminovalerate (5AVA) and glutarate. When the recombinant E. coli WL3110 strain expressing the Pseudomonas putida davAB genes encoding delta-aminovaleramidase and lysine 2-monooxygenase, respectively, were cultured in a medium containing 20 g/L of glucose and 10 g/L of l -lysine, 3.6 g/L of 5AVA was produced by converting 7 g/L of l -lysine. When the davAB genes were introduced into recombinant E. coli strainXQ56allowing enhanced l -lysine synthesis, 0.27 and 0.5 g/L of 5AVA were produced directly from glucose by batch and fed-batch cultures, respectively. Further conversion of 5AVA into glutarate could be demonstrated by expression of the P. putida gabTD genes encoding 5AVA aminotransferase and glutarate semialdehyde dehydrogenase. When recombinant E. coli WL3110 strain expressing the davAB and gabTD genes was cultured in a medium containing 20 g/L glucose, 10 g/L l -lysine and 10 g/L α-ketoglutarate, 1.7 g/L of glutarate was produced.
3/1/13 12:00:00 AM
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2.4 Hydrolysis of dihydropyran in dilute acid

0

**Summary of research results:** * This invention relates to a novel process for the production of 1,5pentanediol. It is known that 1,5pentanediol can be produced by the hydrolysis of dihydropyran in dilute acid and subsequent hydrogenation of the deltahydroxyvaleraldehyde produced. The hydrogenation is carried out in a neutral reaction medium, as an aqueous medium which is substantially neutral. Strong acid are avoided, altough the process may be operated succefsully with certain catalysts under strongly acid or alkaline conditions, no advantage is obtained thereby and for practical operation it is desirable to utilize a substantially neutral medium. (Art. [#ARTNUM](#article-26546-2412032466)). * The 1,5pentanediol contains ≤0.1 wt.% each of 1,5hexanediol and 1,4dihydroxycyclohexane. The 1,5pentanediol can be produced by the direct hydrogen reduction of a dicarboxylic acid mixture in the filtrate obtained by the crystallization and separation of adipic acid Art. [#ARTNUM](#article-26546-2753136836) **Requirements:** * Purity of the initial component (ex: furfural): N.C. * Complexity (# of steps): * Reaction medium: Hydrochloric acid

2.4.1 Hydrolysis of dihydropyran in dilute acid
Highly pure 1,5-pentanediol
PROBLEM TO BE SOLVED: To produce 1,5-pentanediol free from impurities to lower the polymerization reaction rate in the case of using the diol as a soft segment of polycarbonate diol and polyester polyol or as a chain extender as it is for a raw material of polyurethane, polyester resin, etc. SOLUTION: The 1,5-pentanediol contains ≤0.1 wt.% each of 1,5-hexanediol and 1,4-dihydroxycyclohexane. The 1,5-pentanediol can be produced by the direct hydrogen reduction of a dicarboxylic acid mixture in the filtrate obtained by the crystallization and separation of adipic acid. COPYRIGHT: (C)2001,JPO
3/14/00 12:00:00 AM
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2.4.2 Hydrolysis of dihydropyran in dilute acid
Preparation of pentanediol
This invention relates to a novel process for the production of 1,5-pentanediol. It is known that 1,5-pentanediol can be produced by the hydrolysis of dihydropyran in dilute acid and subsequent hydrogenation of the deltahydroxyvaleraldehyde produced. However, yields of the desired product...
2/14/50 12:00:00 AM
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2.5 Recombinant organism (prokaryotic or eukaryotic)

0

Recombinant proteins are formed by transfecting foreign genes into a host cell. Recombinant proteins are commonly used to produce pharmaceutical products, protein-based polymers for drug delivery, antibodies and enzymes for disease treatment, protein scaffolds for tissue engineering, as well as for a myriad of other uses. Recombinant hosts for producing polyhydroxyalkanoates and methods of producing polyhydroxyalkanoates from renewable carbon substrates are provided. Certain recombinant hosts that produce 5 carbon chemicals such as 5aminopentanoate (5AP), 5hydroxyvalerate (5HV), glutarate, and 1,5 pentanediol (PDO). Another recombinant host is genetically engineered to overexpress 5-hydroxyvalerate CoA transferase, CoA dependent propionaldehyde dehydrogenase, and 1,3-propanediol dehydrogenase to produce 1.5 pentanediol. 1.5 pentanediol is produced using 5-hydroxyvalerate, lysine starch, Sucrose, glucose, lactose, frucrose, Xylose, maltose and arabinose alone or in combinations as feedstock. Preferably the recombinant host has deletions in adhE, ldha, and ackA-pta and expresses lysine 2-monooxygenase, 5-aminopentanami dase, 5-aminopetanoate transaminase and one or more glutarate or Succinate semialdehyde reductase encoding genes. Particularly suitable hosts have the ability to overproduce lysine and are resistant to toxic lysine analogs, like S-(2-aminoethyl) cysteine. Preferably, the organism has a reducedor no glutarate semialdehyde dehydrogenase activity. ([Art. #ARTNUM](#article-26543-2882792339)) This [Figure](#image-1867) is a schematic diagram showing biochemical pathways to 5-hydroxyvalerate containing polyhydroxy alkanoate polymers, and 5-carbon chemicals such as 5-aminopentanoate (5-APO), glutarate, 8-valerolactone (DVL) and 1.5 pentanediol. Also shown are competing metabolic pathways that may have to be removed or the activities reduced (as indicated by a cross (X)) to achieve optimal carbon flux to the desired products listed above). ([Art. #ARTNUM](#article-26543-US9090898B2)) **Requirements:** * Purity of the initial component (ex: furfural): N.C. * Complexity (# of steps): 6 steps * Reaction medium: Recombinant host

2.5.1 Recombinant organism (prokaryotic or eukaryotic)
5 5 GREEN PROCESS AND COMPOSITIONS FOR PRODUCING POLY5HVAND 5 CARBON CHEMICALS
Recombinant hosts for producing polyhydroxyalkanoates and methods of producing polyhydroxyalkanoates from renewable carbon substrates are provided. Certain recombinant hosts that produce 5 carbon chemicals such as 5-aminopentanoate (5AP), 5-hydroxyvalerate (5HV), glutarate, and 1,5 pentanediol (PDO) are also provided. One embodiment provides a recombinant host expressing a gene encoding a heterologous enzyme selected from the group consisting of a polyhydroxyalkanoate synthase and a 5-hydroxyvalerate-CoA (5HV-CoA) transferase, wherein the host produces a polymer containing 5-hydroxyvalerate. Preferably, the host expresses both a polyhydroxyalkanoate synthase and a 5HV-CoA transferase. The host can be prokaryotic or eukaryotic. A preferred prokaryotic host is E. coli. The polymers produced by the recombinant hosts can be homopolymers or copolymers of 5-hydroxyvalerate. A preferred copolymer is poly(3-hydroxybutyrate-co-5-hydroxyvalerate).
12/4/17 12:00:00 AM
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2.5.2 Recombinant organism (prokaryotic or eukaryotic)
Green process and compositions for producing poly(5hv) and 5 carbon chemicals
Recombinant hosts for producing polyhydroxyalkanoates and methods of producing polyhydroxyalkanoates from renewable carbon substrates are provided. Certain recombinant hosts that produce 5 carbon chemicals such as 5-aminopentanoate (5AP), 5-hydroxyvalerate (5HV), glutarate, and 1,5 pentanediol (PDO) are also provided. One embodiment provides a recombinant host expressing a gene encoding a heterologous enzyme selected from the group consisting of a polyhydroxyalkanoate synthase and a 5-hydroxyvalerate-CoA (5HV-CoA) transferase, wherein the host produces a polymer containing 5-hydroxyvalerate. Preferably, the host expresses both a polyhydroxyalkanoate synthase and a 5HV-CoA transferase. The host can be prokaryotic or eukaryotic. A preferred prokaryotic host is E. coli. The polymers produced by the recombinant hosts can be homopolymers or copolymers of 5-hydroxyvalerate. A preferred copolymer is poly(3-hydroxybutyrate-co-5-hydroxyvalerate).
12/14/09 12:00:00 AM
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2.5.3 Recombinant organism (prokaryotic or eukaryotic)
Metabolic engineering of Escherichia coli for the production of 5-aminovalerate and glutarate as C5 platform chemicals.
Abstract 5-Aminovalerate (5AVA) is the precursor of valerolactam, a potential building block for producing nylon 5, and is a C5 platform chemical for synthesizing 5-hydroxyvalerate, glutarate, and 1,5-pentanediol. Escherichia coli was metabolically engineered for the production of 5-aminovalerate (5AVA) and glutarate. When the recombinant E. coli WL3110 strain expressing the Pseudomonas putida davAB genes encoding delta-aminovaleramidase and lysine 2-monooxygenase, respectively, were cultured in a medium containing 20 g/L of glucose and 10 g/L of l -lysine, 3.6 g/L of 5AVA was produced by converting 7 g/L of l -lysine. When the davAB genes were introduced into recombinant E. coli strainXQ56allowing enhanced l -lysine synthesis, 0.27 and 0.5 g/L of 5AVA were produced directly from glucose by batch and fed-batch cultures, respectively. Further conversion of 5AVA into glutarate could be demonstrated by expression of the P. putida gabTD genes encoding 5AVA aminotransferase and glutarate semialdehyde dehydrogenase. When recombinant E. coli WL3110 strain expressing the davAB and gabTD genes was cultured in a medium containing 20 g/L glucose, 10 g/L l -lysine and 10 g/L α-ketoglutarate, 1.7 g/L of glutarate was produced.
3/1/13 12:00:00 AM
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2.5.4 Recombinant organism (prokaryotic or eukaryotic)
Green process and compositions for producing poly(5HV) and 5 carbon chemicals

1. A recombinant organism genetically engineered to convert glutarate semialdehyde into a 5-hydroxyvalerate monomer, polymer or copolymer thereof,wherein the recombinant organism expresses at least two or more heterologous genes encoding two or more enzymes selected from the group consisting of: lysine 2-monooxygenase, EC 1.13.12.2; 5-aminopentanamidase (δ-aminovaleramidase), EC 3.5.1.30; 5-aminovalerate transaminase, EC 2.6.1.48; lysine decarboxylase, EC 4.1.1.18; glutarate semialdehyde reductase, EC 1.1.1.61; 4-hydroxybutyrate dehydrogenase, EC 1.1.1.61; CoA-transferase, EC 2.8.3.14 and EC 2.8.3.n; Acyl-CoA synthetase, EC 6.2.1.3; PHA synthase, EC 2.3.1.n; β-ketoacyl-CoA thiolase, EC 2.3.1.9; acetoacetyl-CoA reductase, EC 1.1.1.36; propionaldehyde dehydrogenase, EC 1.2.1.3; alcohol dehydrogenase, EC 1.1.1.1; and 1,3-propanediol dehydrogenase EC 1.1.1.202;wherein the recombinant organism produces more 5-aminopentanoate than an unmodified organism; andwherein the 5-aminopentanoate is converted into the 5-hydroxyvalerate monomer, polymer or copolymer thereof by the recombinant organism wherein the 5-hydroxyvalerate monomer, polymer or copolymer thereof is isolatable. 2. The recombinant organism of claim 1 wherein the organism produces 1,5 pentanediol. 3. The recombinant organism of claim 1 wherein the polymer or copolymer comprises polyhydroxyalkanoate. 4. The recombinant organism of claim 1 wherein the recombinant organism converts 5-aminopentanoate into glutarate semialdehyde. 5. The recombinant organism of claim 1 wherein the recombinant organism converts lysine into 5-aminopentanoate. 6. The recombinant organism of claim 5 wherein the lysine is fed to the organism. 7. The recombinant organism of claim 1 wherein the organism used to construct the recombinant organism has been modified to overproduce lysine relative to an unmodified organism. 8. The recombinant organism of claim 1 wherein the recombinant organism is resistant to the toxic lysine analog S-(2-aminoethyl) cysteine. 9. The recombinant organism of claim 1 wherein the recombinant organism expresses a lysine feedback-resistant dihydrodipicolinate synthase. 10. The recombinant organism of claim 1 wherein the recombinant organism expresses a lysine feedback-resistant aspartate kinase III. 11. The recombinant organism of claim 1 wherein the organism is fed a renewable carbon substrate. 12. The recombinant organism of claim 1 wherein the recombinant organism is further engineered to inhibit or block lysine export. 13. The recombinant organism of claim 1 wherein the organism has been modified to reduce or eliminate glutarate semialdehyde dehydrogenase activity. 14. The recombinant organism of claim 13 wherein the glutarate semialdehyde dehydrogenase is reduced or eliminated by deleting or disrupting one or more genes selected from the group consisting of davD, yneI, and gabD or their homologs. 15. The recombinant organism of claim 1 wherein the recombinant organism releases 5-hydroxyvalerate into the extracellular environment. 16. The recombinant organism of claim 13 wherein the recombinant organism releases 5-hydroxyvalerate in the extracellular environment and the 5-hydroxyvalerate is in equilibrium with delta-valerolactone. 17. The recombinant organism of any of claim 1 wherein the recombinant organism converts 5-hydroxyvalerate into 5-hydroxyvalerate CoA. 18. The recombinant organism of claim 1 wherein the recombinant organism converts 5-hydroxyvalerate-CoA into a polyhydroxyalkanoate. 19. The recombinant organism of claim 1 wherein the recombinant organism converts 5-hydroxvalerate into 1,5 pentanediol. 20. The recombinant organism of claim 1 wherein the recombinant organism converts 5-hydroxyvalerate into poly(5-hydroxyvalerate) or a copolymer thereof. 21. The recombinant organism of claim 20 wherein the copolymer is selected from the group consisting of poly(3-hydroxypropionate-co-5HV), poly(3-hydroxybutyrate-co-5HV) and poly(4-hydroxybutyrate-co-5HV). 22. The recombinant organism of claim 1 wherein the recombinant organism is prokaryotic. 23. The recombinant organism of claim 1 wherein the recombinant organism is _E. coli._ 24. The recombinant organism of claim 1 wherein the recombinant organism is a eukaryotic microorganism. 25. A recombinant organism for producing polymers from lysinewherein the recombinant organism is genetically engineered to express at least two heterologous enzymes selected from the group consisting of: lysine 2-monooxygenase, EC 1.13.12.2; 5-aminopentanamidase (δ-aminovaleramidase), EC 3.5.1.30; 5-aminovalerate transaminase, EC 2.6.1.48; lysine decarboxylase, EC 4.1.1.18; glutarate semialdehyde reductase, EC 1.1.1.61; 4-hydroxybutyrate dehydrogenase, EC 1.1.1.61; CoA-transferase, EC 2.8.3.14 and EC 2.8.3.n; Acyl- CoA synthetase, EC 6.2.1.3; PHA synthase, EC 2.3.1.n, to produce a polyhydroxyalkanoate comprising 5-hydroxyvalerate monomers,wherein the recombinant organism produces more 5-aminopentanoate than an unmodified organism, andwherein the recombinant organism can convert 5-aminopentanoate into the 5-hydroxyvalerate wherein the 5-hydroxyvalerate monomer, polymer or copolymer thereof is isolatable. 26. The recombinant organism of claim 25 wherein the recombinant organism does not produce lysine. 27. The recombinant organism of claim 25 wherein the recombinant organism does not express a functional glutarate semialdehyde dehydrogenase enzyme activity. 28. A method for producing polymers from lysine comprising feeding the recombinant organism of claim 1 with lysine and other renewable carbon feedstock such that the polymer is produced. 29. A method for producing 5-carbon based monomers, polymers or co-polymers thereof comprisingproviding lysine or other renewable carbon feedstock to genetically engineered cells according to claim 1,wherein the genetically engineered cells are engineered to produce more 5-aminopentanoate than unmodified cells, and wherein the 5-aminopentanoate is converted by the genetically engineered cells into a 5 carbon monomer, polymer or copolymer thereof. 30. The method of claim 29 wherein the renewable carbon feedstock is selected from starch, sucrose, glucose, lactose, fructose, xylose, maltose and arabinose, or combinations thereof. 31. The method of claim 29 wherein the monomer is selected from the group consisting of glutarate, 1,5-pentanediol, and 5-hydroxyvalerate. 32. The method of claim 29 wherein the polymer comprises a polyhydroxyalkanoate. 33. The method of claim 32 wherein the polyhydroxyalkanoate comprises 5-hydroxyvalerate. 34. The method of claim 33 wherein the polyhydroxyalkanoate is selected from the group consisting of poly(5-hydroxyvalerate), poly(3-hydroxypropionate- co-5HV), poly(3-hydroxybutyrate-co-5HV) and poly(4-hydroxybutyrate-co-5HV). 35. The method of claim 32 further comprising recovering the polyhydroxyalkanoate polymer. 36. The method of claim 35 wherein polyhydroxyalkanote polymer or copolymers are recovered by solvent extraction or aqueous processing.
12/14/09 12:00:00 AM
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