- Baeyer-villiger oxidation of acyl carrier protein-tethered thioester to acyl carrier protein-linked thiocarbonate catalyzed by a monooxygenase domain in FR901464 biosynthesis
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Baeyer-Villiger monooxygenases (BVMOs), generally catalyzing the transformation of carbonylic compounds into the corresponding esters or lactones known as Baeyer-Villiger oxidation in organic chemistry, are widely distributed among microorganisms and have stimulated great interest as biocatalysts for organic synthesis. The physiological roles of this type of MOs are usually classified as degradation of organic compounds involved in primary metabolism. Recently, increasing numbers of BVMOs have been found to be involved in the biosynthesis of secondary metabolites, especially for postmodification; however, to date, none of them has been reported functionally as a tailoring domain within polyketide synthase (PKS) acting on carrier protein-tethered substrates. FR901464, an antitumor natural product that targets spliceosome and inhibits both splicing and nuclear retention of pre-mRNA, was elucidated to be biosynthesized by a hybrid acyltransferase-less PKS/nonribosomal peptide synthetase (NRPS) system. Within the hybrid system, an unprecedented domain that was proposed to mediate the chain release process was located in the termination module. In this paper, we report the in vitro biochemical characterization of this domain to be a BVMO tailoring domain that catalyzes the BV oxidation of an acyl carrier protein (ACP)-tethered thioester to an ACP-linked thiocarbonate, which represents the first example of BVMOs operating in cis within the PKS and NRPS biosynthetic paradigm.
- Tang, Man-Cheng,He, Hai-Yan,Zhang, Feng,Tang, Gong-Li
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Read Online
- Chromium-Catalyzed Production of Diols From Olefins
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Processes for converting an olefin reactant into a diol compound are disclosed, and these processes include the steps of contacting the olefin reactant and a supported chromium catalyst comprising chromium in a hexavalent oxidation state to reduce at least a portion of the supported chromium catalyst to form a reduced chromium catalyst, and hydrolyzing the reduced chromium catalyst to form a reaction product comprising the diol compound. While being contacted, the olefin reactant and the supported chromium catalyst can be irradiated with a light beam at a wavelength in the UV-visible spectrum. Optionally, these processes can further comprise a step of calcining at least a portion of the reduced chromium catalyst to regenerate the supported chromium catalyst.
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Paragraph 0111
(2021/03/19)
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- Hydrogenolysis of Furfuryl Alcohol to 1,2-Pentanediol Over Supported Ruthenium Catalysts
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Hydrogenolysis of the furan rings of furfural and furfuryl alcohol, which can be obtained from biomass, has attracted attention as a method for obtaining valuable chemicals such as 1,2-pentanediol. In this study, we examined the hydrogenolysis of furfuryl alcohol to 1,2-pentanediol over Pd/C, Pt/C, Rh/C, and various supported Ru catalysts in several solvents. In particular, we investigated the effects of combinations of solvents and supports on the reaction outcome. Of all the tested combinations, Ru/MgO in water gave the best selectivity for 1,2-pentanediol: with this catalyst, 42 % selectivity for 1,2-pentanediol was achieved upon hydrogenolysis of furfuryl alcohol for 1 h at 463 K. In contrast, reaction in water in the presence of Ru/Al2O3 afforded cyclopentanone and cyclopentanol by means of hydrogenation and rearrangement reactions.
- Yamaguchi, Aritomo,Murakami, Yuka,Imura, Tomohiro,Wakita, Kazuaki
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p. 731 - 736
(2021/06/12)
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- Unravelling the one-pot conversion of biomass-derived furfural and levulinic acid to 1,4-pentanediol catalysed by supported RANEY Ni-Sn alloy catalysts
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Bimetallic Ni-Sn alloys have been recognised as promising catalysts for the transformation of furanic compounds and their derivatives into valuable chemicals. Herein, we report the utilisation of a supported bimetallic RANEY nickel-tin alloy supported on aluminium hydroxide (RNi-Sn(x)/AlOH; x is Ni/Sn molar ratio) catalysts for the one-pot conversion of biomass-derived furfural and levulinic acid to 1,4-pentanediol (1,4-PeD). The as prepared RNi-Sn(1.4)/AlOH catalyst exhibited the highest yield of 1,4-PeD (78%). The reduction of RNi-Sn(x)/AlOH with H2 at 673-873 K for 1.5 h resulted in the formation of Ni-Sn alloy phases (e.g., Ni3Sn and Ni3Sn2) and caused the transformation of aluminium hydroxide (AlOH) to amorphous alumina (AA). The RNi-Sn(1.4)/AA 673 K/H2 catalyst contained a Ni3Sn2 alloy as the major phase, which exhibited the best yield of 1,4-PeD from furfural (87%) at 433 K, H2 3.0 MPa for 12 h and from levulinic acid (up to 90%) at 503 K, H2 4.0 MPa, for 12 h. Supported RANEY Ni-Sn(1.5)/AC and three types of supported Ni-Sn(1.5) alloy (e.g., Ni-Sn(1.5)/AC, Ni-Sn(1.5)/c-AlOH, and Ni-Sn(1.5)/γ-Al2O3) catalysts afforded high yields of 1,4-PeD (65-87%) both from furfural and levulinic acid under the optimised reaction conditions.
- Ansyah, Fathur Razi,Astuti, Maria Dewi,Hara, Takayoshi,Husain, Sadang,Mustikasari, Kamilia,Rodiansono,Shimazu, Shogo
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p. 241 - 250
(2022/01/19)
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- Selective Activation of C-OH, C-O-C, or Ca? C in Furfuryl Alcohol by Engineered Pt Sites Supported on Layered Double Oxides
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The selective activation of targeted bonds in biomass-derived furfural or furfuryl alcohol with complex chemical linkages (C-C/C-H/C-O, Ca? C/Ca? O, or C-O-H/C-O-C) is of great challenge for biomass upgrading, expecting well-defined catalyst and definite catalytically active sites. This work demonstrates an efficient targeted activation to C-OH, C-O-C, or Ca? C by engineering the structure of catalytic Pt sites, affording 2-methylfuran (2-MF), tetrahydrofurfuryl alcohol (THFA), or 1,2-pentanediol (1,2-PeD) as product in the hydroconversion of furfuryl alcohol. The catalytic Pt sites have been engineered as atomic Pt, coordination unsaturated Pt-Pt in atom-thick dispersion, or coordination unsaturated 3D Pt-Pt by tailoring the Pt dispersion (single atom, 2D cluster, or 3D cluster) on Mg and Al-containing layered double oxide (Mg(Al)O) support. The selective activation of C-OH, C-O-C, or Ca? C has been traced with the FT-IR spectra recorded surface reaction. On atomic Pt, C-O-H is easily activated, with the assistance of Mg(Al)O support, with O-terminal adsorption without affecting furan C-O and Ca? C. However, Ca? C in the furan ring is easier to be activated on coordination-unsaturated Pt-Pt in atom-thick dispersion, resulting in a step-by-step hydrogenation to generate THFA. On coordination-unsaturated 3D Pt-Pt, the hydrogenolysis of furan ring is favored, resulting in the cleavage of furan C-O to produce 1,2-PeD. Also, the Mg(Al)O supports derived from Mg and Al layered double hydroxides (LDHs) here also play a key role in promoting the selectivity to 1,2-PeD by providing basic sites.
- An, Zhe,He, Jing,Jiang, Yitao,Ma, Xiaodan,Shu, Xin,Song, Hongyan,Xiang, Xu,Zhang, Jian,Zhang, Zhijun,Zhao, Wenfang,Zheng, Lirong,Zhu, Yanru
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p. 8032 - 8041
(2020/09/23)
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- COMPOSITIONS COMPRISING ODORLESS 1,2-PENTANEDIOL
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Suggested is a cosmetic or pharmaceutical or detergent composition comprising 1,2 pentanediol, wherein said 1,2-pentanediol is obtained from a process comprising the follow ing steps: (a) providing at least one starting material selected from furfuryl alcohol and furfural; (b) reacting at least one of said starting materials with hydrogen in the presence of a heterogeneous catalyst to form 1,2-pentanediol, wherein said heterogeneous catalyst comprises: one or more metals selected from the group consisting of platinum, rhodium, ruthenium, nickel, palladium and iridium in metallic form and/or one or more compounds of metals selected from the group consisting of platinum, rhodium, ruthenium, nickel, palladium and iridium; and one or more support materials selected from the group consisting of activated carbon, aluminum oxide, silicon dioxide, and silicon carbide; and (c) removing the 1,2-pentanediol thus obtained from the reaction mixture.
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Paragraph 00316
(2020/04/25)
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- Highly selective 1-pentene epoxidation over Ti-MWW with modified microenvironment of Ti active sites
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A titanosilicate/H2O2catalytic system was applied to process the liquid-phase selective epoxidation of 1-pentene to 1,2-epoxypentane (EP). The effects of titanosilicate topology (MWW, MFI, MSE, MEL, MOR, and *BEA), solvent, H2O/H2O2ratio, catalyst amount, reaction temperature, pressure, and time on the EP production were investigated systematically. The Ti-MWW/H2O2/acetonitrile system exhibited the highest 1-pentene conversion of 72.9% together with high EP selectivity of 99.9% and H2O2utilization efficiency of 91.5%. Moreover, it was proved that the Ti active sites located inside the intralayer 10-membered ring sinusoidal channels catalyzed the epoxidation process primarily owing to their supplying more steric fitness for 1-pentene molecules. A piperidine (PI)-assisted structural rearrangement of Ti-MWW was performed to further enhance the catalytic activity, almost doubling the turnover number value. The evolution of the microenvironment of Ti active sites in this structural rearrangement process was carefully investigated, revealing the coordination of N atoms in PI molecules to the Ti atoms. More importantly, we identified that the hexa-coordinated Ti sites with the PI molecules as ligand could significantly accelerate H2O2activation, the effect of which far exceeded the inhibition effect caused by the electronegativity increase of Ti active sites.
- Jiang, Jingang,Tian, Wenwen,Wang, Bowen,Wu, Peng,Xu, Hao,Yin, Jianyong,Yin, Jinpeng
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p. 6050 - 6064
(2020/09/23)
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- Hydrogenation of furfural by noble metal-free nickel modified tungsten carbide catalysts
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Nickel-tungsten carbide catalysts convert furfural to high value products in a liquid phase catalytic reaction. The product distribution depends on the solvent and the Ni-W-ratio of the catalyst. In isopropyl alcohol a combination of Ni and WxC enables the opening of the furan ring to yield 1,2-pentanediol. Nickel accelerates the tungsten oxide reduction in the tungsten carbide catalyst synthesis and facilitates the carbon insertion. Nickel modified tungsten carbide is a promising, noble metal-free catalyst system for the upgrading of furfural based renewable resources. Its preparation is facilitated compared to unmodified tungsten carbide catalysts.
- Bretzler, Patrick,Huber, Michael,K?hler, Klaus,Nickl, Simon
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p. 27323 - 27330
(2020/09/01)
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- PROCESS OF PREPARATION OF 1,2-PENTANEDIOL FROM FURFURAL
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The present invention relates to hydrogenolysis process for preparation of 1,2-pentanediol from furfural. In particular, the present invention provides a conversion of 1,2-pentanediol from furfural in presence of methanol and using a catalyst based on Rhodium on porous Manganese dioxide octahedral molecular sieve in a single step carried out at temperature range between 130 °C to 170 °C. The advantages of present invention is that it avoids formation of Intermediate-2 and directly give product 1,2-pentanediol with good selectivity over 1,5-pentanediol.
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Page/Page column 10-15
(2020/08/22)
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- Topotactic Conversion of Alkali-Treated Intergrown Germanosilicate CIT-13 into Single-Crystalline ECNU-21 Zeolite as Shape-Selective Catalyst for Ethylene Oxide Hydration
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The conversion of the alkali-treated intergrowth germanosilicate CIT-13 into the single-crystalline high-silica ECNU-21 (named after East China Normal University) zeolite, with a novel topology and a highly crystalline zeolite framework, has been realized through a creative top-down strategy involving a mild alkaline-induced multistep process consisting of structural degradation and reconstruction. Instead of acid treatment, hydrolysis in aqueous ammonia solution not only readily cleaved the chemically weak Ge(Si)?O?Ge bonds located within the interlayer double four ring (D4R) units of CIT-13, but also cleaved the metastable Si?O?Si bonds therein. This led to extensive removal of the D4R units, and also generated silanol groups on adjacent silica-rich layers, which then condensed to form a novel daughter structure upon calcination. Individual oxygen bridges in the reassembled ECNU-21 replaced the germanium-rich D4R units in CIT-13, thereby eliminating the original intergrowth phenomenon along the b axis. With an ordered crystalline structure of 10-ring (R) channels as well as suitable germanium-related Lewis acid sites, ECNU-21 serves as a stable solid Lewis acid catalyst for the shape-selective hydration of ethylene oxide (EO) to ethylene glycol (EG) at greatly reduced H2O/EO ratios and reaction temperature in comparison with the noncatalytic industrial process.
- Liu, Xue,Mao, Wenting,Jiang, Jingang,Lu, Xinqing,Peng, Mingming,Xu, Hao,Han, Lu,Che, Shun-ai,Wu, Peng
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p. 4520 - 4529
(2019/03/07)
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- Hydro-Oxygenation of Furfural in the Presence of Ruthenium Catalysts Based on Al-HMS Mesoporous Support
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Ru-containing catalyst based on an Al-HMS mesoporous aluminosilicate was synthesized. The mesoporous support and the catalyst on its basis were characterized by the methods of low-temperature desorption/adsorption of nitrogen, temperature-programmed desorption of ammonia, transmission electron microscopy, X-ray photoelectron microscopy, and energy-dispersive X-ray fluorescence analysis. The synthesized catalyst was investigated in the hydrodeoxygenation of the model compound of bio-oil, furfural, in the presence of H2O. The reaction was carried out at initial hydrogen pressures of 1–7 MPa at 200°C–300°C temperature range. The results revealed that the synthesized catalyst displayed a high activity in the hydrotransformation of furfural. The conversion was 100% in 1 hr at a 5 MPa hydrogen pressure and 200°C.
- Roldugina,Shayakhmetov,Maksimov,Karakhanov
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p. 1306 - 1315
(2019/11/03)
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- Method and System for Hybrid Catalytic Biorefining of Biomass to Methylated Furans and Depolymerized Technical Lignin
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A method is disclosed for converting biomass into a fuel additive, the method comprising: liquefying the biomass to form a liquor; neutralizing the liquor; precipitating lignin out of the liquor; extracting furfural (FF) and 5-hydroxymethylfurfural (HMF) from the liquor; and hydrodeoxygenating (HDO) the extracted furfurals over a Cu—Ni/TiO2 catalyst. The catalyst for hydrodeoxygenating (HDO) furfural (FF) and 5-hydroxymethylfurfural (HMF) to methylated furans comprises copper-nickel (Cu—Ni) particles supported on titanium dioxide (TiO2), and wherein the copper-nickel particles form core-shell structures in which copper (Cu) is enriched at a surface of the catalyst.
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- Insights on the One-Pot Formation of 1,5-Pentanediol from Furfural with Co?Al Spinel-based Nanoparticles as an Alternative to Noble Metal Catalysts
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CoAl-spinel nanoparticles prepared by liquid-feed flame spray pyrolysis (L?F FSP) and activated by reduction at different temperatures were used to investigate the hydrogenation process of furfural (FA) under mild conditions. Reduction of the spinel at 500 °C resulted in high FA conversion and selectivity to furfuryl alcohol (FFA, 81 % yield, in 1 hour). Reduction at higher temperatures (i. e., 700 and 850 °C) led to the direct formation of diols (i. e., 1,5-PeD and 1,2-PeD) from FA. The differences in activity are attributed to the formation of surface metallic cobalt nanoparticles upon reduction at high temperature. A maximum of 30 % 1,5-PeD was yielded after 8 hours of reaction under the optimized conditions of150 °C, 30 bar of H2 and with 40 mg of catalyst reduced at 700 °C. This is the first report on the direct catalytic conversion of furfural to1,5-pentanediol with a non-noble metal solid catalyst.
- Gavilà,L?hde,Jokiniemi,Constanti,Medina,del Río,Tichit,álvarez
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p. 4944 - 4953
(2019/09/17)
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- One-pot selective conversion of C5-furan into 1,4-pentanediol over bulk Ni-Sn alloy catalysts in an ethanol/H2O solvent mixture
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Inexpensive bulk Ni-Sn alloy-based catalysts demonstrated a unique catalytic property in the selective conversion of C5-furan compounds (e.g., furfuraldehyde (FFald), furfuryl alcohol (FFalc), and 2-methylfuran (2-MTF)) in an ethanol/H2O solvent mixture and selectively produced 1,4-pentanediol (1,4-PeD) in a one-pot reaction. The synergistic actions between the bulk Ni-Sn alloy catalyst, hydrogen gas, and the hydroxylated H2O or ethanol/H2O solvents are believed to play a prominent role in the catalytic reactions. Bulk Ni-Sn alloy catalysts that consisted of Ni3Sn or Ni3Sn2 alloy phases allowed an outstanding yield of 1,4-PeD up to 92% (from FFald), 67% (from FFalc), and 48% (from 2-MTF) in ethanol/H2O (1.5:2.0 volume ratio) at 433 K, 3.0 MPa H2 and 12 h. As the reaction temperature increased to 453 K, the yield of 1,4-PeD slightly decreased to 87% (from FFald), whereas it slightly increased to 71% (from FFalc). The bulk Ni-Sn alloy catalysts were reusable without any significant loss of selectivity.
- Rodiansono,Dewi Astuti, Maria,Hara, Takayoshi,Ichikuni, Nobuyuki,Shimazu, Shogo
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supporting information
p. 2307 - 2315
(2019/05/21)
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- Method for preparing 1,2-pentanediol by liquid-phase catalytic selective hydrogenolysis of furfuryl alcohol
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The invention provides a method for preparing 1,2-pentanediol by liquid-phase catalytic selective hydrogenolysis of furfuryl alcohol. The method is characterized by comprising the following steps: dissolving furfuryl alcohol, a Cu-based catalyst and a reaction solvent into a reaction kettle, filling the reaction kettle with hydrogen for replacing air in the kettle, carrying out hydrogen filling until the pressure is 0.5-8 Mpa, carrying out stirring and heating to 100-180 DEG C, and carrying out a reaction for 1-18 hours to obtain the 1,2-pentanediol. In the method for preparing 1,2-pentanediol, the raw material furfuryl alcohol can be completely derived from natural plant resources, the condition of the catalytic hydrogenation reaction condition is mild, the preparation method of the usedcatalyst is simple, the reaction activity of the catalyst is high, and the method has high practicability and economical efficiency.
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Paragraph 0065; 0070; 0075; 0076; 0078 0080; 0085; 0086
(2019/01/07)
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- C?O Hydrogenolysis of Tetrahydrofurfuryl Alcohol to 1,5-Pentanediol Over Bi-functional Nickel-Tungsten Catalysts
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In this study, we report a series of bimetallic Ni?WOx catalyst for the ring-opening of THFA into 15PDO. The structure-performance relationship of the catalysts was discussed based on extensive characterization using techniques such as BET, H2-TPR, NH3-TPD, Pyr-IR, IPA-TPD-MS, XRD, XPS and EXAFS/XANES. The acidity measurements show that higher W density leads to the higher amount of acid density, which could be assigned to the creation of Lewis acid sites mainly on the surface of the calcined catalysts. H2-TPR profiles of Ni?WOx catalysts show that there is a strong interaction between Ni and W species, enhancing the reducibility of WOx. XRD measurements of calcined Ni?WOx catalysts reveal that the dispersion of Ni particles is enhanced after addition of WOx species. After reduction, different peaks corresponding to metallic Ni and WO3?x are identified for 10Ni?WOx catalysts, as well as new peak assigned to Ni?W intermetallic phase on 10Ni?30WOx catalyst. The formation of Ni?W intermetallic phase was further proved using XPS and EXAFS studies. THFA hydrogenolysis was also conducted under aqueous-phase conditions over Ni?WOx catalysts, yielding up to 47 % selectivity to 15PDO, along with a highest combined C5 polyols (i. e., 15PDO and 125PTO) selectivity of approximately 64 %. However, the Ni?WOx catalytic system suffers from deactivation process due to the hydrothermal dissolution of the active phase. Further investigation reveals the better stability of metallic tungsten and Ni?W intermetallic phase (Ni4W) against leaching since their corresponding peaks in the XRD patterns of spent catalysts remains nearly unchanged. Finally, 1,4-dioxane as an organic solvent was employed in THFA hydrogenolysis reaction, resulting in different product distribution, with a THP yield of around 54 %. The catalyst crystalline structure is preserved because of very low Ni and W leaching when 1,4-dioxane is used as solvent.
- Soghrati, Elmira,Kok Poh, Chee,Du, Yonghua,Gao, Feng,Kawi, Sibudjing,Borgna, Armando
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p. 4652 - 4664
(2018/10/02)
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- A one-pot synthesis of 1, 2 - pentanediol method
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The invention relates to a method for high-yield synthesis of 1,2-pentanediol from n-pentene under low-temperature condition by a one-pot method. According to the method, the reaction temperature is low, so that the risk of leakage caused by high-temperature volatilization of a 1-pentene raw material, and meanwhile, the requirements on pressure resistance of equipment are lowered; by adopting a multistep one-pot method process, process flows are shortened; corrosive, polluting and harmful compounds are not adopted as raw materials during reaction, so that the condition in the traditional process that an organic acid oxygen carrying agent, of which the weight is multiple that of the raw materials, is adopted is avoided; the environment-friendliness of the process is good; and the method has the advantages that the source of raw materials is wide, the production cost is low, and the economical efficiency is high.
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Paragraph 0057; 0058; 0059; 0060; 0061; 0062; 0063-0082
(2018/03/26)
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- A method for synthesis of 1, 2 - pentanediol (by machine translation)
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The invention relates to the field of organic synthetic technology, in particular to a 1, 2 - pentanediol synthetic method, comprises the following steps: (1) heating the raw material-butyraldehyde, adjusting the pH after adding the hydrocyanic acid, obtained by the reaction of 2 - hydroxy pentanonitrile; (2) taking step (1) in 2 - hydroxy pentanonitrile, adding an alcohol as a solvent to stir and mix, add water to stir and mix, hydrogen chloride gas, in 5 °C the following reaction under the condition for a period of time, to continue the reaction temperature, after the reaction product after the neutralization reaction, centrifugal separation, obtained after the distillation is 2 - hydroxy valeric acid ester compound; (3) heating the step (2) in 2 - hydroxy valeric acid ester compound, under the effects of catalyst after hydrogenation reaction to obtain the 1, 2 - pentanediol. Using the synthesis method of the invention, the 1, 2 - pentanediol yield, and reduces the production cost. (by machine translation)
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Paragraph 0026; 0031; 0036; 0041; 0042; 0046; 0051
(2018/10/19)
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- Preparation method of alcohol compound
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The invention discloses a preparation method of an alcohol compound. The preparation method is characterized by carrying out ring opening under combined action of an esterifying agent, lewis acid anda hydrogenation catalyst by taking a furan derivative as a raw material, thus obtaining an ester intermediate; further saponifying, thus obtaining the alcohol compound. According to the preparation method disclosed by the invention, the product selectivity is high, byproducts are few, the yield is high, the purity is good, product separation is convenient, and the technology is simple.
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Paragraph 0050; 0054; 0056; 0062; 0064; 0065; 0066; 0068
(2018/09/20)
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- Selective hydrogenolysis of furfuryl alcohol to 1,5- and 1,2-pentanediol over Cu-LaCoO3 catalysts with balanced Cu0-CoO sites
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Selective hydrogenolysis of biomass-derived furfuryl alcohol (FFA) to 1,5- and 1,2-pentanediol (PeD) was conducted over Cu-LaCoO3 catalysts with different Cu loadings; the catalysts were derived from perovskite structures prepared by a one-step citrate complexing method. The catalytic performances of the Cu-LaCoO3 catalysts were found to depend on the Cu loading and pretreatment conditions. The catalyst with 10 wt% Cu loading exhibited the best catalytic performance after prereduction in 5%H2-95%N2, achieving a high FFA conversion of 100% and selectivity of 55.5% for 1,5-pentanediol (40.3%) and 1,2-pentanediol (15.2%) at 413 K and 6 MPa H2. This catalyst could be reused four times without a loss of FFA conversion but it resulted in a slight decrease in pentanediol selectivity. Correlation between the structural changes in the catalysts at different states and the simultaneous variation in the catalytic performance revealed that cooperative catalysis between Cu0 and CoO promoted the hydrogenolysis of FFA to PeDs, especially to 1,5-PeD, while Co0 promoted the hydrogenation of FFA to tetrahydrofurfuryl alcohol (THFA). Therefore, it is suggested that a synergetic effect between balanced Cu0 and CoO sites plays a critical role in achieving a high yield of PeDs with a high 1,5-/1,2-pentanediol selectivity ratio during FFA hydrogenolysis.
- Gao, Fangfang,Liu, Hailong,Hu, Xun,Chen, Jing,Huang, Zhiwei,Xia, Chungu
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p. 1711 - 1723
(2018/08/21)
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- Method for co-production of chemical products of dimethyl benzyl alcohol and 1,2-pentanediol
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The invention provides a method for co-production of chemical products of dimethyl benzyl alcohol and 1,2-pentanediol. The method comprises the following steps: reacting by taking 1-pentene and cumenehydroperoxide as reaction raw materials under the action of a main catalyst and an auxiliary catalyst to obtain the dimethyl benzyl alcohol and the 1,2-pentanediol, wherein the main catalyst is acetylacetonate salt or 2-ethyl caproate; the auxiliary catalyst is one or more of ferric trichloride, stannic chloride, tin trifluoromethanesulfonate, lithium chloride, lithium bromide and boron trifluoride. According to the method disclosed by the invention, the reaction is not required to be subjected to post-treatment; an open-loop reaction of the next step can be performed directly; the selectivity for simultaneously producing the products of the 1,2-pentanediol and the dimethyl benzyl alcohol can reach 96 percent and 98 percent or more respectively; a reaction process is greatly simplified and the production efficiency is improved.
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Paragraph 0013; 0014; 0015; 0017; 0018; 0019; 0022
(2018/06/16)
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- CATALYST FOR ONE CARBON-REDUCTION REACTION, AND METHOD FOR PRODUCING ONE CARBON-REDUCTION COMPOUND USING THE SAME
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PROBLEM TO BE SOLVED: To provide a method for producing selectively a one carbon-reduction compound, using a compound having a primary hydroxy group, a carboxyl group, or an alkoxycarbonyl group, or a lactone compound, as a substrate. SOLUTION: A method of obtaining a one carbon-reduction compound includes the reaction of a compound as a substrate represented by formula (1-1) or (1-2) or (1-3) with hydrogen in the presence of a catalyst in which a metal selected from Ru, Rh, Pd, Ir, and Pt is supported on a support selected from CeO2, hydroxyapatite, ZrO2, TiO2, hydrotalcite, SiO2, MgO, and Al2O3 (R1-R3 independently represent H, a substituted/unsubstituted monovalent hydrocarbon group, or a monovalent group in which two or more hydrocarbon groups are bound together through a linking group; R1-R3 may form a ring with adjacent carbon; L is a substituted/unsubstituted divalent hydrocarbon group or the like; and n is an integer of 0 or greater). SELECTED DRAWING: None COPYRIGHT: (C)2018,JPOandINPIT
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Paragraph 0060; 0070; 0071
(2018/07/28)
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- Palladium–Ruthenium Catalyst for Selective Hydrogenation of Furfural to Cyclopentanol
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Bimetallic Pd–Ru/C catalyst was shown to be much more active in the aqueous-phase hydrogenation of furfural (473 K, 8 MPa) in comparison with both Pd/C and Ru/C catalysts. The enhanced hydrogenation activity manifested itself as an increased yield of cyclopentanol (77%) at a complete conversion of furfural. The observed synergistic effect between palladium and ruthenium in the tested reaction can be related to changes in the electronic state and particle size of supported metals upon interaction with each other and the Pd–Ru alloy formation.
- Mironenko,Belskaya,Lavrenov,Likholobov
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p. 339 - 346
(2018/06/11)
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- Acid catalysis dominated suppression of xylose hydrogenation with increasing yield of 1,2-pentanediol in the acid-metal dual catalyst system
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One-pot conversion of xylose to 1,2-pentanediol was investigated in a dual catalyst system composed of Ru/C and niobium phosphate as hydrogenation and acid catalysts, respectively. A series of niobium phosphate catalysts well-characterized by XRD, N2 physisorption, FT-IR, NH3-TPD, Py-IR and XPS were tested regarding the effect of their acid properties on product selectivity for the studied process. A systematic study was reported on the effect of reaction conditions. The combined yield of 21–27% to 1,2-pentanediol and its precursor 1-hydroxyl-2-pentanone was accomplished at 423 K under 3.0 Mpa hydrogen pressure in water-γ-valerolactone/cyclohexane biphasic system. At optimized conditions, the correlation between the product yield and the surface Lewis/Br?nsted ratio were analyzed. The results revealed that the lower apparent activation energy of xylose dehydration reaction catalyzed by Lewis acid site accounted for the high product selectivity for sugar intermediate and furfural hydrogenation processes, especially for the combined selectivity to 1,2-pentanediol and 1-hydroxyl-2-pentanone. This study lays the grounds for further design of improved solid acid catalysts with high selectivity of 1, 2-pentanediol.
- Wang, Nailiang,Chen, Zhipeng,Liu, Licheng
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- Defining Pt-compressed CO2 synergy for selectivity control of furfural hydrogenation
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The development of a sustainable methodology for catalytic transformation of biomass-derived compounds to value-added chemicals is highly challenging. Most of the transitions are dominated by the use of additives, complicated reaction steps and large volumes of organic solvents. Compared to traditional organic solvents, alternative reaction media, which could be an ideal candidate for a viable extension of biomass-related reactions are rarely explored. Here, we elucidate a selective and efficient transformation of a biomass-derived aldehyde (furfural) to the corresponding alcohol, promoted in compressed CO2 using a Pt/Al2O3 catalyst. Furfural contains a furan ring with CC and an aldehyde group, and is extremely reactive in a hydrogen atmosphere, resulting in several by-products and a threat to alcohol selectivity as well as catalyst life. The process described has a very high reaction rate (6000 h-1) with an excellent selectivity/yield (99%) of alcohol, without any organic solvents or metal additives. This strategy has several key features over existing methodologies, such as reduced waste, and facile product separation and purification (reduced energy consumption). Combining the throughput of experimental observation and molecular dynamics simulation, indeed the high diffusivity of compressed CO2 controls the mobility of the compound, and eventually maintains the activity of the catalyst. Results are also compared for different solvents and solvent-less conditions. In particular, combination of an effective Pt catalyst with compressed CO2 provides an encouraging alternative solution for upgradation of biomass related platform molecules.
- Chatterjee, Maya,Chatterjee, Abhijit,Ishizaka, Takayuki,Kawanami, Hajime
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p. 20190 - 20201
(2018/06/11)
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- Direct conversion of carbohydrates to diol by the combination of niobic acid and a hydrophobic ruthenium catalyst
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Tetrahydro-2,5-furandimethanol (THFDM) was obtained directly from a wide variety of carbohydrates by the combination of niobic acid and a hydrophobic ruthenium catalyst. Fructose, glucose, and polysaccharides consisting of fructose or glucose could be converted to THFDM in one-step. The selectivity to THFDM was kept around 60% while the glucose conversion varied from 9% to 49%. The as-synthesized niobic acid was characterized by TEM, N2 adsorption/desorption, XRD, NH3-TPD and FT-IR spectra of adsorpted pyridine. The niobic acid was proved to have medium and strong acid sites with a high Br?nsted/Lewis ratio, which played a great role for keeping high THFDM selectivity using glucose as a substrate.
- Duan, Ying,Zhang, Jun,Li, Dongmi,Deng, Dongsheng,Ma, Lu-Fang,Yang, Yanliang
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p. 26487 - 26493
(2017/07/07)
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- Method for synthesizing ortho-diol compound by using macroporous anion exchange resin as catalyst
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The invention discloses a method for synthesizing an ortho-diol compound by using macroporous anion exchange resin as a catalyst. According to the method, hydrocarbon epoxide is used as a raw material, the anion exchange resin is used as the catalyst, and a fixed bed continuous hydrolysis reaction technology is adopted for preparing the ortho-diol compound; the anion exchange resin is halogen ortho-substituted macroporous polystyrene-divinyl benzene quaternary phosphonium salt type anion exchange resin. The synthesis method is simple, the catalyst can be used repeatedly, the conversion rate of the raw material is high, and the yield of the ortho-diol compound is high.
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Paragraph 0024; 0025; 0026; 0028; 0029; 0030-0035
(2017/05/27)
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- Method for preparing vicinal diol compound through ring-opening reaction
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The present invention discloses a method for preparing a vicinal diol compound through a ring-opening reaction. The method takes a hydrocarbons epoxide as a raw material and takes an anion exchange resin as a catalyst. The vicinal diol compound is prepared by using a fixed bed continuous hydrolysis reaction technology. The anion exchange resin is a halogen-substituted macroporous polystyrene-divinyl benzene quaternary ammonium salt type anion exchange resin. The synthesis method is simple, the catalyst can be used many times, the raw material conversion rate is high, and the yield of the vicinal diol compound is high.
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Paragraph 0015; 0031; 0033; 0036
(2017/03/28)
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- Method of using anion exchange resin as catalyst to synthesize vicinal diol compound
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The invention discloses a method of using anion exchange resin as a catalyst to synthesize a vicinal diol compound. The method includes: using hydrocarbon epoxide as a raw material and the anion exchange resin as the catalyst; adopting a fixed bed continuous hydrolysis reaction process to obtain the vicinal diol compound, wherein the anion exchange resin is halogen substituted macroporous polystyrene-divinyl benzene quaternary ammonium salt type anion exchange resin. The method is simple, the catalyst can be utilized repeatedly, the raw material is high in conversion rate, and the vicinal diol compound is high in yield.
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Paragraph 0027; 0029; 0030; 0036
(2017/07/06)
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- Method for synthesizing vicinal diol compound which takes hydrocarbon epoxide as raw material
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The present invention discloses a method for preparing a vicinal diol compound which takes a hydrocarbon epoxide as a raw material. The method takes the hydrocarbon epoxide as the raw material and takes an anion exchange resin as a catalyst. The vicinal diol compound is prepared by using a fixed bed continuous hydrolysis reaction technology. The anion exchange resin is a halogen-substituted macroporous polystyrene-divinyl benzene quaternary ammonium salt type anion exchange resin. The synthesis method is simple, the catalyst can be used many times, the raw material conversion rate is high, and the yield of the vicinal diol compound is high.
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Paragraph 0027-0028; 0032; 0037
(2017/08/03)
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- Preparation method for 1,2-pentanediol
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The invention provides a preparation method for 1,2-pentanediol. The preparation method comprises the following steps: step 1, preparing an intermediate 1-hydroxy-2-pentanone by successively adding n-butyraldehyde, paraformaldehyde, a reaction solvent--an alcohol solvent, an alkali reagent--triethylamine and a catalyst--3-ethylbenzothiazole bromide into an enclosed reactor equipped with a magnetic stirring device, placing the enclosed reactor in a thermostat water bath after completion of addition, introducing nitrogen for protection and carrying out a reaction for a period of time at a constant temperature; and step 2, adding the intermediate 1-hydroxy-2-pentanone, a catalyst--Pd/C and a solvent--anhydrous ethanol into a reaction vessel, carrying out stirring, cooling the reaction vessel to room temperature after completion of a reaction, discharging air, opening the reaction vessel, and discharging material liquid so as to obtain the product 1,2-pentanediol. Directed at the problems of complex process flow, high production cost, severe corrosion of equipment and the like of conventional preparation methods for1,2-pentanediol, the invention provides the preparation method with mild reaction conditions, low cost, high yield and environment friendliness.
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Paragraph 0013
(2017/08/28)
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- Vapor Phase Hydrogenolysis of Furanics Utilizing Reduced Cobalt Mixed Metal Oxide Catalysts
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Vapor phase hydrogenolysis of both furfuryl alcohol and furfural are investigated over reduced Co based mixed metal oxides derived from the calcination of a layered double hydroxide precursor. Although a reduced cobalt-aluminum oxide sample displays promising selectivity towards 2-methylfuran (2-MF) production, the addition of an Fe dopant into the oxide matrix significantly enhances the activity and selectivity per gram of catalyst. Approximately 82 % 2-MF yield is achieved at high conversion if furfuryl alcohol is fed into the reactor at 180 °C over the reduced 3Co-0.25Fe-0.75Al catalyst. Based on structural characterization studies including temperature-programmed reduction (TPR), X-ray photoelectron spectroscopy (XPS), and in situ X-ray absorption spectroscopy (XAS) it is suggested that Fe facilitates the reduction of Co, allowing for formation of more metallic species. Overall, this study demonstrates that non-precious metal catalysts offer promise for the selective conversion of a key biomass oxygenate to a proposed fuel additive.
- Sulmonetti, Taylor P.,Hu, Bo,Ifkovits, Zachary,Lee, Sungsik,Agrawal, Pradeep K.,Jones, Christopher W.
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p. 1815 - 1823
(2017/05/29)
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- Switchable synthesis of furfurylamine and tetrahydrofurfurylamine from furfuryl alcohol over RANEY nickel
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RANEY Ni proved to be an effective heterogeneous catalyst for switchable reductive amination of furfuryl alcohol to tetrahydrofurfurylamine and furfurylamine with NH3 by simply adding or not adding 1.0 MPa H2 into the reaction bulk. After further optimization of the reaction conditions, we finally obtained 94.0% yield of tetrahydrofurfurylamine and 78.8% yield of furfurylamine with high selectivity. By extensively studying the catalytic pathways and mechanism of catalyst deactivation with XRD and XPS characterization, we have confirmed that an excess amount of H2 in the reaction bulk leads to the deep hydrogenation of the furan ring while an insufficient amount of H2 leads to the formation of Ni3N and the deactivation of the catalyst.
- Liu, Yingxin,Zhou, Kuo,Shu, Huimin,Liu, Haiyan,Lou, Jiongtao,Guo, Dechao,Wei, Zuojun,Li, Xiaonian
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p. 4129 - 4135
(2017/09/25)
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- Selective aqueous-phase hydrogenation of furfural to cyclopentanol over PdRu/C catalyst
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The bimetallic PdRu catalyst supported on carbon nanotubes were found ot provide an efficient synthesis of cyclopentanol in aqueous-phase hydrogenation of furfural. Under the chosen reaction conditions (temperature of 473 K, total pressure of 8 MPa), the selectivity towards cyclopentanol reaches 77% at a complete conversion of furfural. A high activity of this catalyst can be associated with changes in the electronic state and dispersion of the supported metals caused by their mutual interaction and formation of PdRu alloy.
- Mironenko,Belskaya,Lavrenov,Likholobov
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p. 673 - 676
(2017/09/11)
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- Efficient Synthesis of Furfuryl Alcohol and 2-Methylfuran from Furfural over Mineral-Derived Cu/ZnO Catalysts
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Two kinds of typical mineral-derived Cu/ZnO catalysts consisting of aurichalcite and zincian malachite were introduced for furfural hydrogenation to furfuryl alcohol (FOL) and 2-methylfuran (2-MF) in a fixed-bed reactor. Under proper reaction conditions, high yields of FOL (above 99 %) and 2-MF (94.5 %) could be obtained over the aurichalcite Cu/ZnO catalyst (AC-CZ), whereas the best yield of 2-MF was only 76.9 % (0.5 h?1) over the zincian malachite Cu/ZnO catalyst (ZM-CZ). The normalized productivity of 2-MF was 43.5 mol kgCu ?1 h?1 and 17.4 mol kgCu ?1 h?1 for AC-CZ and ZM-CZ, respectively (LHSV=1.5 h?1). The catalysts were characterized by XRD analysis, Raman spectra, CO IR spectroscopy, H2 temperature-programmed reduction, N2O titration, NH3 temperature-programmed desorption, and X-ray photoelectron spectroscopy. The far better performance of AC-CZ in furfural hydrogenation was ascribed to its higher dispersion of copper species, superior copper surface area, better surface acidity distribution, and stronger Cu0–ZnO synergy. In addition, the surface acidity of the catalysts seemed to have a higher influence on 2-MF production than the Cu surface area, but the optimal balance of both factors still needs to be investigated systematically.
- Yang, Xiaohai,Xiang, Xiaomin,Chen, Hongmei,Zheng, Hongyan,Li, Yong-Wang,Zhu, Yulei
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p. 3023 - 3030
(2017/08/15)
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- 1, 2 - pentanediol manufacturing method
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PROBLEM TO BE SOLVED: To provide a method for selectively obtaining 1,2-pentane diol in a high yield from furfural, obtained by mainly using non-edible parts of biomass as raw material.SOLUTION: A method for producing 1,2-pentane diol is characterized by obtaining 1,2-pentane diol by subjecting furfural to hydrogenolysis in the presence of a catalyst, obtained by supporting zero-valent platinum on hydrotalcite, and hydrogen. The hydrogenolysis reaction is preferably carried out in the presence of an alcoholic solvent and/or an ether-based solvent.
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Paragraph 0044; 0045
(2017/08/02)
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- Preparation method of 1,2-pentanediol
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The invention provides a preparation method of 1,2-pentanediol. The preparation method specifically includes the following steps that 1, after 2-hydroxy valeronitrile and methyl alcohol are mixed to be uniform, an inorganic acid catalyst is added, the materials are heated to 55-75 DEG C, a heat preservation reaction is carried out for 12-24 h, and 2-hydroxy methyl valerate is generated; 2, a hydrogenation reactor is filled with a hydrogenation catalyst-alloy catalyst, the temperature in the reactor is kept at 165-225 DEG C, hydrogen pressure is kept at 10-14 MPa, the materials enter the hydrogenation reactor from the lower end, 2-hydroxy methyl valerate obtained in the step 1 is added into the hydrogenation reactor from the lower end, a product obtained after a hydrogenation reaction flows out from the top end of the hydrogenation reactor, after efflux is cooled to 60 DEG C through a condenser, the efflux is transferred into a distillation still to be distilled at the temperature of 160 DEG C, and a main distillate fraction is 1,2-pentanediol. Prepared 1,2-pentanediol is stable in component and high in purity and yield.
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Paragraph 0031; 0032; 0036; 0037; 0041; 0042
(2017/02/28)
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- Influence of the functional groups of multiwalled carbon nanotubes on performance of Ru catalysts in sorbitol hydrogenolysis to glycols
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Different functional groups (i.e. [sbnd]NH2, [sbnd]COOH, [sbnd]OH and nitrogen-doping) modified CNTs (denoted as AMCN, CMCN, HMCN and NMCN, respectively) supported ruthenium catalysts (Ru/AMCN, Ru/CMCN, Ru/HMCN and Ru/NMCN) were prepared by incipient wetness impregnation method. They were fully characterized by XRD, TG, Raman, XPS, TPD and TEM to elucidate the relationship between the physical property and their catalytic performance. TEM results shown that Ru particles were well dispersed on the surface for all the samples with the size of 1.48–1.99 nm. The effects of functional groups of carbon nanotubes (CNTs), nitrogen doping and base additive types on activity and selectivity of ethylene glycol (EG) and propylene glycol (1,2-PD) were investigated. In addition, the activity and final products distribution were much influenced by the properties of functional groups on CNTs and the type of metal cation of the base promoters, which probably participated in the reaction for accelerating a retro-aldol reaction for C[sbnd]C cleavage. Among the catalysts, Ru supported on AMCN exhibited the best catalytic activities and glycols selectivities than on MCN, CMCN, HMCN and NMCN.
- Guo, Xingcui,Dong, Huihuan,Li, Bin,Dong, Linlin,Mu, Xindong,Chen, Xiufang
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-
- A furfuryl alcohol-phase selective hydrogenolysis of preparing 1,2-pentanediol method
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The invention discloses a method for preparing 1,2-pentanediol by furfuryl alcohol liquid phase selectivity and hydrogenolysis. According to the invention, a non-precious metal catalyst with environmental protection and high efficiency is selected, which concretely relates to the supported Bu-based catalyst, and then furfural is used for preparing 1,2-pentanediol with high activity and high selectivity under mild hydrogenation condition. The catalyst of the present invention uses furfuryl alcohol with high concentration even pure furfuryl alcohol as a raw material, so that energy consumption for separating a solvent can be reduced.
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Paragraph 0063; 0064; 0065; 0066; 0067
(2016/10/08)
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- Method for preparing 1,2-pentanediol from xylose
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The present invention discloses a method for preparing 1,2-pentanediol by using xylose as a raw material through catalytic hydrogenation. According to the method, a supported Rh or Pd based hydrogenation catalyst is used, water is adopted as a solvent, and xylose is converted at a temperature of 80-180 DEG C in a 0.5-10 MPa hydrogen atmosphere to generate 1,2-pentanediol, wherein xylose is a biomass resource with the wide source. According to the present invention, the xylose is adopted as the raw material so as to well solve the problem of the difficult source of the C5 component; and the used xylose aqueous solution can be the hydrolyzate of corn cobs, bagasse, cotton seed hulls and the like, such that the production cost can be further reduced, and the maximum yield can achieve 46%.
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Paragraph 0032; 0033
(2017/03/28)
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- Preparation of 1,2-pentanediol through oxidative hydrolysis of alpha-amylene
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The invention provides a preparation method for 1,2-pentanediol. According to the method, 1,2-pentanediol is prepared from cyclopentene through epoxidation synthesis under the condition of normal pressure in the presence of an organic solvent and an auxiliary agent with a Ti-MCM-41 molecular sieve as a catalyst and hydrogen peroxide with a mass percentage of 25 to 50% as an oxidizing agent. The method is simple in process, low in production cost and high in a reaction conversion rate.
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Paragraph 0027; 0028
(2017/03/28)
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- Selective hydrogenolysis of biomass-derived furfuryl alcohol into 1,2- and 1,5-pentanediol over highly dispersed Cu-Al2O3 catalysts
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Cu nanoparticles supported on a variety of oxide supports, including SiO2, TiO2, ZrO2, Al2O3, MgO and ZnO, were investigated for the hydrogenolysis of biomass-derived furfuryl alcohol to 1,2-pentanediol and 1,5-pentanediol. A Cu-Al2O3 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 H2 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, NH3/CO2-temperature programmed desorption, N2 adsorption, transmission electron microscopy and N2O chemisorption demonstrated that intimate and effective interactions between Cu particles and the acidic Al2O3 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.
- Liu, Hailong,Huang, Zhiwei,Kang, Haixiao,Xia, Chungu,Chen, Jing
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p. 700 - 710
(2016/05/19)
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- Tailored one-pot production of furan-based fuels from fructose in an ionic liquid biphasic solvent system
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The one-pot catalytic transformation of biomass to useful products is desirable for saving cost and time. The integration of the various reaction steps need to address the presence of incompatible reaction conditions and numerous side reactions. We report a novel process for the one-pot production of furan-based fuels, 2,5-dimethylfuran (DMF) and 2,5-dihmethyltetrahydrofuran (DMTF), from fructose by optimizing the synergic effect of an ionic liquid promoted Ru/C catalyst and the solvent effect. The dehydration of fructose and subsequent in situ hydrodeoxygenation of HMF to DMF and DMTF on Ru/C were enhanced by the use of an ionic liquid and a biphasic [BMIm]Cl/THF solvent. Elemental analysis, X-ray Photoelectron Spectroscopy, Raman spectroscopy and H2-temperature programmed reduction-mass spectroscopy characterization showed that the ionic liquid modified the electronic density of the Ru species to favor HMF in situ hydrodeoxygenation. Moreover, THF served as a reaction-extraction solvent that extracted DMF and DMTF from the reaction layer to avoid further side reactions. A rational design that gave enhancement of the catalytic performance and product protection provides a promising strategy for the one-pot conversion of biomass to desired fuels.
- Li, Changzhi,Cai, Haile,Zhang, Bo,Li, Weizhen,Pei, Guangxian,Dai, Tao,Wang, Aiqin,Zhang, Tao
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p. 1638 - 1646
(2015/09/15)
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- Highly Efficient Synthesis of Optically Pure (S)-1-phenyl-1,2-ethanediol by a Self-Sufficient Whole Cell Biocatalyst
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Terminal vicinal diols are important chiral building blocks and intermediates in organic synthesis. Reduction of α-hydroxy ketones provides a straightforward approach to access these important compounds. In this study, it has been found that asymmetric reduction of a series of α-hydroxy aromatic ketones and 1-hydroxy-2-pentanone, catalyzed by Candida magnolia carbonyl reductase (CMCR) with glucose dehydrogenase (GDH) from Bacillus subtilis for cofactor regeneration, afforded 1-aryl-1,2-ethanediols and pentane-1,2-diol, respectively, in up to 99 % ee. In order to evaluate the efficiency of the bioreduction, lyophilized recombinant Escherichia coli whole cells coexpressing CMCR and GDH genes were used as the biocatalyst and α-hydroxy acetophenone as the model substrate, and the reaction conditions, such as pH, cosolvent, the amount of biocatalyst and the presences of a cofactor (i.e., NADP+), were optimized. Under the optimized conditions (pH6, 16h), the bioreduction proceeded smoothly at 1.0 m substrate concentration without the external addition of cofactor, and the product (S)-1-phenyl-1,2-ethanediol was isolated with 90 % yield and 99 % ee. This offers a practical biocatalytic method for the preparation of these important vicinal diols. Self-sufficient catalysis! Lyophilized recombinant Escherichia coli coexpressing Candida magnolia carbonyl reductase (CMCR) and glucose dehydrogenase (GDH) genes served as an effective self-sufficient biocatalyst for the reduction of α-hydroxy acetophenones at high substrate concentrations. The products were isolated with high yield and excellent optical purity, offering a practical biocatalytic method for the preparation of vicinal diols.
- Chen, Xi,Mei, Ting,Cui, Yunfeng,Chen, Qijia,Liu, Xiangtao,Feng, Jinhui,Wu, Qiaqing,Zhu, Dunming
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p. 483 - 488
(2015/10/06)
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- Due to the reduction of alcohol ether bond by hydrogenation synthesis (by machine translation)
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PROBLEM TO BE SOLVED: To provide a synthetic method for alcohols by the reduction of an ether bond by a hydrogenation reaction. SOLUTION: There is provided a method of manufacturing alcohol by the reduction reaction of an ether compound by using, as a reaction medium, carbon dioxide having a pressure of normal pressure (0.1 MPa) or more and 20 MPa or less and a temperature of 32°C or more and 200°C or less and containing 0 mol% or more and 1,000 mol% or less of water with respect to the amount of carbon dioxide, using, as a catalyst, a solid catalyst containing mesoporous silica carrying nanoparticles composed of at least one of palladium and rhodium as a carrier, and using, as a reducing agent, hydrogen whose pressure is 0.1 MPa or more and 10 MPa or less. There is provided a new technology/new product relating to alcohol synthesis by the reduction of an ether bond for directly synthesizing an alcohol by cleaving the ether bond, which is difficult in a conventional manner, by a reduction reaction by hydrogen. COPYRIGHT: (C)2013,JPO&INPIT
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Paragraph 0023-0025
(2016/12/22)
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- PRODUCTION METHOD OF 1,2-PENTANE DIOL AND 1,5-PENTANE DIOL
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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. COPYRIGHT: (C)2015,JPOandINPIT
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Paragraph 0045
(2018/12/01)
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- Method For Producing 1,2-Pentanediol
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A process for the preparation of 1,2-pentanediol by reaction of a starting material comprising one or both compounds from the group consisting of furfuryl alcohol and furfural with hydrogen in the presence of a first heterogeneous catalyst is described.
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Paragraph 0257-0259
(2014/03/25)
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- HYDROGENOLYSIS OF FURFURYL ALCOHOL TO 1,2-PENTANEDIOL
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The present invention provides a process for preparing 1,2-pentanediol by reacting furfuryl alcohol with hydrogen in the presence of a catalyst system. The catalyst system contains platinum oxide or contains ruthenium supported on aluminum oxide or activated carbon. The invention also relates to the respective catalysts and processes for producing the catalyst system.
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Paragraph 0226
(2014/09/03)
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- METHOD FOR PREPARING TRIOLS AND DIOLS FROM BIOMASS-DERIVED REACTANTS
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A method to make triols and diols is described. The method includes the steps of performing an aqueous-phase hydrodeoxygenation reaction on a feedstock containing a biomass-derived reactant in aqueous solution. The feedstock is contacted with a heterogeneous metal-containing bifunctional catalyst or a combination of two or more heterogeneous metal-containing catalysts that catalyze cleavage of C—C and C—O bonds, for a time, temperature, pressure, and weight hourly space velocity to yield a product mix comprising triols, diols, or combinations thereof.
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Paragraph 0092; 0093
(2014/09/30)
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- SINGLE STEP PROCESS FOR CONVERSION OF FURFURAL TO TETRAHYDROFURAN
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The present patent discloses a one step process for the synthesis of THF and related ring hydrogenated products form furfural using Palladium metal based carbon supported catalyst with high selectivity and 100% conversion in both batch and continuous modes.
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Page/Page column 10-15
(2014/08/19)
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- Biphasic catalytic conversion of fructose by continuous hydrogenation of HMF over a hydrophobic ruthenium catalyst
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The production of chemicals directly from sugars is an important step in biomass conversion. Herein, tetrahydro-2,5-furandimethanol (THFDM), obtained from fructose, is formed by using a combination of acid and hydrophobic Ru/SiO2 in a water/cyclohexane biphasic system. Two key factors enable the high selectivity towards THFDM: modifying the hydrogenation catalyst so that it has hydrophobic properties, and the continuous hydrogenation of generated 5-(hydroxymethyl)furfural in the cyclohexane phase. Moreover, the selectivity towards THFDM is found to depend strongly on the acid catalyst used. Divide and conquer: A method for direct catalytic conversion of fructose to tetrahydro-2,5-furandimethanol (THFDM) via 5-(hydroxymethyl)furfural (HMF) is reported. High selectivity towards THFDM is achieved by using a catalyst combination of acid and a hydrophobic ruthenium catalyst (Ru/SiO2-TM) in a water/cyclohexane biphasic system by continuous hydrogenation of generated HMF. The use of the hydrophobic Ru/SiO2-TM is the key, as it prevents hydrogenation of fructose to mannitol and sorbitol in the water phase.
- Yang, Yanliang,Du, Zhongtian,Ma, Jiping,Lu, Fang,Zhang, Junjie,Xu, Jie
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p. 1352 - 1356
(2014/06/09)
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