Reaction Kinetics Mechanisms and Catalysis
·
2018
·Vol. 124
·期 2
·683-699
·
IF 1.515
Zhu Min,Chen Changlin
A series of Pt–yLi 2 B 4 O 7 /WO x /ZrO 2 (y = 0, 0.5, 1, 2 wt%) catalysts were prepared by varying the content of Li 2 B 4 O 7 through the method of coimpregnation-calcination. The obtained catalysts were used for the selective hydrogenolysis of glycerol to 1,3-propanediol. Meanwhile, these catalysts were characterized by N 2 adsorption and desorption (BET), CO chemisorption, X-ray diffraction (XRD), NH 3 -temperature programmed desorption (NH 3 -TPD), H 2 -temperature programmed reduction (H 2 -TPR), Fourier transform infrared spectroscopy (FTIR) and transmission electron microscopy (TEM). The results showed that Pt–1Li 2 B 4 O 7 /WO x /ZrO 2 achieved the highest activity with glycerol conversion of 90.7% at 150 °C and 4 MPa and exhibited excellent stability over 200 h. Pt/WO x /ZrO 2 catalyst modified with Li 2 B 4 O 7 was able to enhance catalytic activity and stability, since Li 2 B 4 O 7 promoted the dispersion of Pt, increased the acid amount of the catalyst and strengthened the interaction between active components and support.
研究领域:
化学工程
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催化科学
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产品关联
DOI
高影响因子
Reaction Kinetics Mechanisms and Catalysis
·
2015
·Vol. 117
·期 1
·239-251
·
IF 1.17
Geng Gaoli,Wei Ruiping,Liang Ting,Zhou Minghao,Xiao Guomin
A series of Cu–Ca–Al hydrotalcite derived catalysts were prepared by the co-precipitation method. Their catalytic activities were evaluated in the hydrogenolysis of glycerol. The catalysts were characterized by XRD, SEM, TEM, ICP, NH 3 -TPD, CO 2 -TPD and H 2 -TPR. It was observed that the incorporation of calcium and aluminum in the Cu–Ca–Al catalyst improved the conversion of glycerol and promoted the generation of 1,3-PDO. This is due to the appropriate acidity and basicity of the catalyst, which is confirmed by NH 3 -TPD and CO 2 -TPD. The conversion of glycerol over the catalyst with a Cu–Ca–Al mole ratio of 1:3:5 was up to 73.2 % with 42.6 % selectivity to 1,2-PDO and 9.1 % selectivity to 1,3-PDO. Effects of the reaction time, reaction temperature and initial hydrogen pressure on the conversion and selectivity were systematically investigated.
研究领域:
化学工程
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催化材料科学
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DOI
高影响因子
CHINESE JOURNAL OF CATALYSIS
·
2018
·
IF 3.525
Man Yang,Xiaochen Zhao,Yujing Ren,Jia Wang,Nian Lei,Aiqin Wang,Tao Zhang
Selective hydrogenolysis of glycerol to 1,3-propanediol (1,3-PD) is an important yet challenging method for the transformation of biomass into value-added chemicals due to steric hindrance and unfavorable thermodynamics. In previous studies, chemoselective performances were found demanding and sensitive to H 2 pressure. In this regard, we manipulate the chemical/physical characteristics of the catalyst supports via doping Nb into WO x and prepared 1D needle-, 2D flake-, and 3D sphere-stack mesoporous structured Nb-WO x with increased surface acid sites. Moreover, Nb doping can successfully inhibit the over-reduction of active W species during glycerol hydrogenolysis and substantially broaden the optimal H 2 pressure from 1 to 5 MPa. When Nb doping is 2%, supported Pt catalysts showed promising performance for the selective hydrogenolysis of glycerol to 1,3-PD over an unprecedentedly wide H 2 pressure range, which will guarantee better catalyst stability in the long run, as well as expand their applications to other hydrogen-related reactions.
研究领域:
催化化学
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生物质转化
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材料科学
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产品关联
DOI
高影响因子
SEPARATION AND PURIFICATION TECHNOLOGY
·
2018
·
IF 3.927
Zhen Li,Ling Yan,Jinjie Zhou,Xiaoli Wang,Yaqin Sun,Zhi-Long Xiu
The separation of 1,3-propanediol (1,3-PD), butyric acid (BA) and acetic acid (HAc) from the fermentation broth was studied by two-step salting-out extraction. In the first salting-out extraction, the partition coefficient and recovery of BA reached 42.21 and 96.42%, respectively, under the optimal condition of 25 wt% NaH 2 PO 4 /30 wt% n-butyl acetate. Subsequently, 91.28% of BA in the organic phase could be recovered through back-extraction when sodium carbonate solution was mixed with organic phase with initial phase ratio of n-butyl acetate solution to alkaline solution being 2:1, in which the molar ratio of sodium carbonate to organic acids was 3:5. Finally, 50% (v/v) ethanol (95%) was added to the bottom phase for the second step salting-out extraction. And the partition coefficient and recovery of 1,3-PD were 9.40 and 95.50%, and those of HAc were 7.46 and 94.40%, respectively. All the cells and most of the proteins (97.16%) could be removed. Effective separation of 1,3-PD from BA was realized by two-step salting-out extraction, which provides a potential method for separation of 1,3-PD, BA and HAc on an industrial scale.
研究领域:
生物工程
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化学工程
✓ 已验证
DOI
高影响因子
BIOTECHNOLOGY LETTERS
·
2014
·Vol. 37
·期 1
·183-188
·
IF 1.736
He Yu-Cai,Tao Zhi-Cheng,Zhang Dan-Ping,Yang Zhen-Xing,Gao Shan,Ma Cui-Luan
Rhodococcus sp. CGMCC 4911 transformed 1,3-propanediol cyclic sulfate (1,3-PDS) and its derivatives into corresponding diols. Ethylene sulfate, glycol sulfide, 1,3-PDS, and 1,2-propanediol cyclic sulfate were effectively hydrolyzed with growing cells. ( R )-1,2-Propanediol (>99 % e.e. ) was obtained at 44 % yield with growing cells. Glycol sulfide, ethylene sulfate, and 1,3-PDS were converted into the corresponding diols at 94.6, 96.3, and 98.3 %, respectively. Optimal reaction conditions with lyophilized resting cells were 30 °C, pH 7.5, and cell dosage 17.9 mg cell dry wt/ml. 1,3-Propanediol was obtained from 50 mM 1,3-PDS at 97.2 % yield by lyophilized cells after 16 h. Lyophilized cells were entrapped in calcium alginate with a half-life of 263 h at 30 °C, and the total operational time of the immobilized biocatalysts could reach over 192 h with a high conversion rate.
研究领域:
微生物学
·
生物催化
✓ 已验证
DOI
PubMed
高影响因子
CHINESE JOURNAL OF CHEMICAL ENGINEERING
·
2024
·
IF 3.7
Lifang Ge,Meizhen Gao,Xiaosheng Zhang,Jiang Wang,Qi Shi,Jinxiang Dong
The adsorption and separation of diols from dilute aqueous solution using hydrophobic materials is very challenging due to the strong diol–water hydrogen-bonding interactions. Herein, we screened hydrophobic zeolitic imidazolate frameworks (ZIFs) with chabazite (CHA) topology for separation of 2,3-butanediol (2,3-BDO) and 1,3-propanediol (1,3-PDO), which had junctional and hydrophobic traps matching the two end methyl groups of the 2,3-BDO molecule. Based on CHA-ZIFs with the same small-sized ligand 2-methylimidazole (mIm) and different large-sized ligand benzimidazole derivatives (RbIm), CHA-ZIFs with larger surface areas were obtained by the addition of excess small-sized ligand mIm in the synthesis process. We showed that all of the hydrophobic CHA-ZIFs preferentially adsorbed 2,3-BDO over 1,3-PDO by static batch adsorption and dynamic column adsorption experiments. But ZIF-301 and ZIF-300 with halogen groups exhibited better adsorptive separation performance for 2,3-BDO/1,3-PDO than ZIF-302 with methyl groups. For a typical ZIF-301, its adsorption capacity for 2,3-BDO was 116.4 mg·g –1 and selectivity for 2,3-BDO/1,3-PDO was 3.8 in dynamic column adsorption of the binary-component system (2,3-BDO/1,3-PDO: 50/50 g·L –1 ). Computational simulations revealed that 2,3-BDO preferentially adsorbed in a trap at the junction between the cha and d6r cages of CHA-ZIFs, meaning the strong host–guest interactions. Therefore, the hydrophobic CHA-ZIFs with a junctional trap were promising candidate materials for adsorbing 2,3-BDO, which also provided a new perspective for separating diols in dilute aqueous solutions.
研究领域:
材料科学
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化学工程
✓ 已验证
产品关联
DOI
高影响因子
Catalysts
·
2020
·Vol. 10
·期 3
·312
·
IF 3.52
Zhiwen Xi,Zhe Hong,Fangtao Huang,Zhirong Zhu,Wenzhi Jia,Junhui Li
A series of Pt/WOx-ZrO2-TiO2catalysts with different Ti/Zr molar ratios was prepared by an evaporation induced self-assembly method, and used to efficient hydrogenolysis of glycerol to 1-PO and 1,3-PDO. BET, XRD, Raman, TEM, XPS and Py-IR were employed to characterize the physicochemical properties of the catalysts. The structural and acidic properties of the catalysts were affected by the Ti/Zr ratio of the support ZrO2-TiO2. Two new crystalline phases of ZrTiO4and Ti2ZrO6and the amount of acid sites were detected in the Pt/WOx-ZrO2-TiO2catalysts. 1-PO is dominant in all products of glycerol hydrogenolysis over the supported Pt-WOx catalysts, which is attributed to more Lewis acid sites on the catalyst surface. The Pt/WOx-ZrO2-TiO2catalyst with a Ti/Zr ratio of 7/3 showed the highest 1,3-PDO yield (25.3%) and 1-PO yield (42.3%), due to its more acid sites including Brønsted and Lewis, and higher concentration of surface Pt0.Keywords:hydrogenolysis of glycerol;1,3-propanediol;1-propanediol;Pt-WOx;ZrO2-TiO2
研究领域:
催化化学
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材料科学
·
能源化学
✓ 已验证
产品关联
DOI
高影响因子
JOURNAL OF CATALYSIS
·
2019
·
IF 7.723
Xiaoyue Wan,Qi Zhang,Mingming Zhu,Yi Zhao,Yongmei Liu,Chunmei Zhou,Yanhui Yang,Yong Cao
Site-selective deoxygenation of hydroxyl groups represents essential processes to access valuable functionalized bio-based compounds with industrial potential. One of the challenging tasks in this context is to convert biodiesel-derived glycerol in the presence of abundant water directly to 1,3-propanediol (1,3-PDO), a key component of the emerging polymer industry. Herein, a monometallic iridium supported on H-ZSM-5 in the absence of Re oxophilic metal oxides was prepared via grinding-assisted impregnation procedures and attempted as an effective and recyclable catalyst for the aqueous-phase selective hydrogenolysis of glycerol toward 1,3-PDO in the absence of acid additives. The results revealed the necessity to control the Ir domain dispersions, Ir 0 /Ir 3+ ratio and the amounts of overall acid/Brönsted acid sites. Activity depended linearly on the amount of overall and Brönsted acid sites, and 1,3-PDO selectivity increased in the presence of Ir-induced Brönsted acid sites, denoted as Ir-O(H)-H-ZSM-5. We speculate that Ir-O(H)-H-ZSM-5 are generated by the interfacial synergistic interaction between IrO x and H-ZSM-5 through hydrogen spillover and reverse hydrogen spillover according to the reported literatures. The reaction mechanism to elucidate the role of Ir-O(H)-H-ZSM-5 sites in glycerol hydrogenolysis was also postulated based on extensive characterization and catalytic reaction results.
研究领域:
催化化学
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材料科学
✓ 已验证
产品关联
DOI
高影响因子
JOURNAL OF CHEMICAL TECHNOLOGY AND BIOTECHNOLOGY
·
2016
·Vol. 91
·期 11
·2793-2801
·
IF 2.738
Shaoqu Xie,Xueqing Qiu,Weini Ji,Conghua Yi
BACKGROUND The cost of 1,3-propanediol (1,3-PD) microbial production depends very much on the separation of 1,3-PD from the fermentation broth. This work develops a salting-out process separating 1,3-PD from aqueous solutions. The salting-out effects of K 2 CO 3 , K 3 PO 4 , and K 4 P 2 O 7 on the liquid–liquid phase equilibria for different aqueous solutions of 1,3-PD were investigated at 298.15 K. RESULTS The distribution coefficient and selectivity coefficient of 1,3-PD increased significantly with increase of the initial salt concentration in the salting-out systems. Increasing the initial 1,3-PD concentration in the aqueous solution improved the distribution coefficient and selectivity coefficient of 1,3-PD, resulting in higher recovery of 1,3-PD. CONCLUSION The solubility of 1,3-PD in the aqueous phase was mainly determined by the salt species and its concentration. The initial 1,3-PD concentration in the aqueous solution had a negligible effect on the solubility of 1,3-PD in the aqueous phase, which showed a linear relation with the molality of salt in the aqueous phase. Moreover, the solubility of 1,3-PD in the organic phase or the aqueous phase could be predicted by the initial salt concentration. © 2016 Society of Chemical Industry
研究领域:
生物工程
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化学工程
✓ 已验证
产品关联
DOI
高影响因子
Frontiers in Chemistry
·
2022
·
IF 5.545
Wang Yaju,Zhou Zhiming,Wang Chao,Zhao Leihong,Xia Qineng
The selective hydrogenolysis of glycerol to 1,3-propanediol (1,3-PDO) with high added value is attraction but challenging. Pt-WOx-based catalysts have been extensively studied in the selective hydrogenolysis of glycerol. The catalyst support and the physicochemical state of WOx play important roles on this reaction. In this paper, Pt-WOx catalysts supported on TiO2 with different crystal forms were prepared and studied for their catalytic performance in hydrogenolysis of glycerol. It was observed that the catalytic performance of anatase-type (A-type) TiO2-supported catalyst (Pt/W/A-Ti) is much better than that of the rutile-type (R-type) TiO2 catalyst (Pt/W/R-Ti) due to its higher stability. Furthermore, the influence of W loading amount and state were thoroughly investigated for the Pt/W/A-Ti catalysts, and Pt/W/A-TiO2 with 5 wt% loading of WOx achieved the best catalytic performance (100% conversion of glycerol and 41% yield of 1,3-PDO under the optimal reaction conditions), owing to the suitable WOx domains and high dispersion of W species, as evidenced by XRD patterns and TEM images. Mechanism study by in-situ DRIFTS experiments indicated that glycerol was first converted to 3-hydroxypropanal and then converted to 1,3-PDO through subsequent reactions.
研究领域:
催化化学
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材料科学
✓ 已验证
产品关联
DOI
PubMed
高影响因子
Bioresources and Bioprocessing
·
2025
·Vol. 12
·期 1
·1-13
·
IF 5.1
Ning Zisheng,Li Yuhan,Dai Lingmei,Liu Dehua,Du Wei
Trimethylene carbonate (TMC) is an innovative modifier for polylactic acid and a promising biodegradable polymer monomer with broad application potential. However, industrial production of TMC faces challenges such as high catalyst costs, safety issues, and environmental impacts. Enzymatic catalysis offers a potential alternative, but its low product yields have hindered progress. In this study, we introduce a novel synthesis route for TMC using bio-based 1,3-propanediol (1,3-PDO) and dimethyl carbonate (DMC) as substrates. This process involves lipase-catalyzed formation of the intermediate 3-hydroxypropyl methyl carbonate (P1), which is then cyclized to produce TMC. Notably, the by-product, C,C’-1,3-propanediyl C,C’-dimethyl ester (P2), reacts with 1,3-PDO to regenerate P1, further enhancing the overall TMC yield. The mechanism exploration reveals that 1,3-PDO acts as both a reactant and an acid catalyst, initiating a nucleophilic substitution reaction on P2 to produce P1. Under optimized conditions, we achieved a total TMC yield of 88%, the highest reported to date.This study provides a novel green synthesis route for TMC that holds great promise for industrial application, given its safer conditions and competitive yields.
研究领域:
生物化学
·
环境科学
·
材料科学
✓ 已验证
产品关联
DOI
PubMed
高影响因子
CATALYSIS TODAY
·
2017
·
IF 4.636
Zhijie Wu,Min Zhang,Yirong Yao,Jingtuo Wang,Danhong Wang,Minghui Zhang,Yongfeng Li
1,3-propanediol (1,3-PDO) and γ-valerolactone (GVL) were simultaneously obtained via the hydrogenolysis of glycerol in levulinic acid (LA) using Ru/C catalysts. Ru/C catalyst exhibited a high LA conversion (∼99%) and a high GVL selectivity (∼99%) for the hydrogenation of LA; while a low conversion (∼11%) and little selectivity of 1,3-PDO for the hydrogenolysis of glycerol. LA promoted the hydrogenolysis of glycerol over Ru/C catalyst, in which LA catalyzed dehydration of glycerol into acetol (precursor of 1,2-propanediol (1,2-PDO)), and glycerol acetalization with the hydrogenated GVL into cyclic acetals, resulting in the formation of 1,3-PDO. A reaction scheme involves the formation of cyclic acetal ethers between GVL and glycerol was proposed to explain the product distributions in the one-pot synthesis of 1,3-PDO and GVL. 64.5% conversion of glycerol and 35.8% selectivity of 1,3-PDO together with 99.1% conversion of LA and 85.8% selectivity of GVL were obtained during one-pot converting glycerol and LA with 3.0 MPa H 2 at 200 °C for 6 h. We reported an effective strategy for the preparation of 1,3-PDO by selective hydrogenolysis of dioxan originated from glycerol with aldehydes or ketones.
研究领域:
生物化学
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催化化学
✓ 已验证
产品关联
DOI
高影响因子
危险品化学品经营许可证（带存储）