APPLIED SURFACE SCIENCE
·
2024
·
IF 6.3
Rui Kang,Dayi Guo,Xinyi Luo,Hui Pan
Catalytic hydrogenation of ethyl levulinate (EL) to 1,4-pentanediol (1, 4-PDO) could provide a potential approach to obtain valuable chemicals from renewable biomass. In this study, a CuZr/CoOx catalyst was developed based on a structural topotactic transformation process of layered double hydroxides. The prepared CuZr/CoOx catalysts possess a double functionality of metal-acid sites and showed superior catalytic activity in the production of 1, 4-PDO from cascade conversion of EL. A complete EL conversion (100 %) and 93.1 % 1, 4-PDO yield were obtained under optimized conditions over catalyst CuZr/CoOx-400. The co-existence of Cu 0 and Cu + on the surface of catalyst CuZr/CoOx was confirmed by XRD and XAES characterizations. In addition, the XPS results suggested a strong interaction between Co and Cu, which would effectively stabilize the Cu + species in the catalyst. The Cu 0 was believed to activate hydrogen, while the Cu + could promote the adsorption of carbonyl group of the substrate thus facilitating the hydrogenolysis. The introducing of Zr in the catalyst greatly improved the dispersion of Cu species and increased the abundance of the acid sites as revealed by the TEM and NH 3 -TPD analysis. Catalyst CuZr/CoOx-400 also exhibited highly catalytic activity after five reaction cycles. Together with the low cost of the non-precious metals, the CuZr/CoOx catalysts demonstrate a potential for the scaled-up application in the biomass refinery process.
研究领域:
催化化学
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生物质能
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可再生资源
✓ 已验证
产品关联
DOI
高影响因子
CHINESE JOURNAL OF CATALYSIS
·
2019
·
IF 4.914
Xuejuan Cao,Huai Liu,Junnan Wei,Xing Tang,Xianhai Zeng,Yong Sun,Tingzhou Lei,Geng Zhao,Lu Lin
The production of γ-valerolactone (GVL) from lignocellulosic biomass has become a focus of research owing to its potential applications in fuels and chemicals. In this study, ( n )CuO x -CaCO 3 (where n is the molar ratio of Cu to Ca) compounds were prepared for the first time and shown to function as efficient bifunctional catalysts for the conversion of biomass-derived methyl levulinate (ML) into GVL, using methanol as the in-situ hydrogen source. Among the catalysts with varied Cu/Ca molar ratios, (3/2)CuO x -CaCO 3 provided the highest GVL yield of 95.6% from ML. The incorporation of CaCO 3 with CuO resulted in the formation of Cu + species in a CuO x -CaCO 3 catalyst, which greatly facilitated the hydrogenation of ML. Notably, CuO x -CaCO 3 also displayed excellent catalytic performance in the methanolysis products of cellulose, even in the presence of humins. Therefore, a facile two-step strategy for the production of GVL from cellulose could be developed over this robust and inexpensive catalyst, through the integration of cellulose methanolysis catalyzed by sulfuric acid, methanol reforming, and ML hydrogenation in methanol medium.
研究领域:
化学工程
·
可再生能源
✓ 已验证
DOI
高影响因子
INDUSTRIAL & ENGINEERING CHEMISTRY RESEARCH
·
2018
·
IF 3.141
Fukun Li,Zhangmin Li,Liam John France,Jiali Mu,Changhua Song,Yuan Chen,Lilong Jiang,Jinxing Long,Xuehui Li
Novel and selective strategies for platform chemical production from renewable biomass are highly attractive in respect to value-added utilization of sustainable resources. In this study, a series of low-cost, commercially available, transition metal carbonates (Zr, Ni, Mg, Zn, and Pb) were investigated for catalytic transfer hydrogenation of levulinate esters to γ-valerolactone (GVL) via the cascade process of Meerwein–Ponndorf–-Verley (MPV) reduction and lactonization reaction. Among the selected catalysts, basic zirconium carbonate is the most active, with the highest turnover frequency (TOF) of 3.1 h–1 and a surface reaction rate of 0.21 mol m–2 h–1. At 453 K, 3.0 h, and 1.0 MPa N2, 100% ethyl levulinate conversion, 96.3% GVL yield, and 91.9% hydrogen donor utilization are observed due to the cooperative effect between acid (Mn+) and base (−OH) sites. Furthermore, this catalyst shows high recyclability under the optimized conditions, where a satisfactory catalytic activity is shown even after six consecutive runs.
研究领域:
化学工程
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催化科学
✓ 已验证
产品关联
DOI
高影响因子
Catalysts
·
2015
·Vol. 5
·期 4
·1897-1910
·
IF 2
Shiqiang Zhao,Guizhuan Xu,Chun Chang,Shuqi Fang,Ze Liu,Fengguang Du
A series of metal-modified phosphotungstates were prepared and performed for direct synthesis of ethyl levulinate from fructose in ethanol. Considering the cost of catalysts, catalytic activity of catalysts, and easy separation of catalysts together, K-HPW-1 was chosen as the most suitable catalyst for synthesis of ethyl levulinate from fructose. A high ethyl levulinate yield of 64.6 mol% was obtained at 150 °C within 2 h in ethanol. The introduction of low polar toluene as a co-solvent improved the yield of ethyl levulinate to 68.7 mol%. The recovered catalyst remained high activity with the yield of ethyl levulinate converted from fructose above 50 mol% after being used five times. Moreover, the generality of the catalyst was further demonstrated by glucose, sucrose, inulin, and cellulose with ethyl levulinate yielding 14.5, 35.4, 52.3, and 14.8 mol%, respectively.Keywords:ethyl levulinate;carbohydrates;potassium phosphotungstate
研究领域:
催化化学
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可再生化学
✓ 已验证
产品关联
DOI
高影响因子
Open Chemistry
·
2021
·Vol. 19
·期 1
·1294-1300
·
IF 1.554
Yuli Bai,Yi Liu,Fudong Bai,Qimei Sun,Lanpeng Li,Tong Zhang
The one-pot acid-catalyzed the conversion of furfuryl alcohol (FA) to ethyl levulinate (EL) was investigated in the presence of mesoporous aluminosilicate (TUD-1) with a high surface area (up to 579 m 2 g −1 ) and well-interconnected mesospheres synthesized via a solvothermal process and characterized using scanning electron microscope, transmission electron microscope, X-ray diffraction, 27 Al-NMR, and N 2 sorption isotherm. The resulting solid acid catalyst was tested for the alcoholysis of FA with ethanol, affording 87.8% EL yield under the optimal reaction conditions of 120°C and 4 h. Moreover, the catalyst showed a good reusability with less loss of activity after a simple solvent washing and calcination procedure.
研究领域:
催化
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化学工程
·
材料科学
✓ 已验证
产品关联
DOI
高影响因子
Journal of Biobased Materials and Bioenergy
·
2020
·Vol. 14
·期 2
·273-279
·
IF 1.126
Chen Zhiyong,Guan Qian,Xu Haiyan,Lei Tingzhou,Lin Lu,Wang Zhiwei,He Xiaofeng,Zhu Jinling
Glucose and microcrystalline cellulose were selected as model compounds to investigate the formation of ethyl levulinate (EL). Optimal glucose and microcrystalline cellulose transformation conditions resulted in yields of 41.05 wt.% and 38.56 wt.% for EL, 0.73 wt.% and 2.63 wt.% for
ethyl-glucoside (EG), 0.42 wt.% and 0.36 wt.% for 5-hydroxymethylfurfural (HMF), and 2.18 wt.% and 2.16 wt.% for 5-ethoxy methyl furfural (EMF), respectively. Increasing the reaction time and temperature resulted in an optimized yield of EL. These increases also resulted in decreased EG and
EMF yield, and the change trend of HMF was not significant. EMF, HMF, and EG are intermediates in the formation of EL. Finally, we concluded that biomass conversion occurs first through cellulose degradation to glucose followed by the production of EG through alcoholysis and hydrolysis and
dehydration of the reaction products to produce EL.
研究领域:
化学工程
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生物化学工程
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可再生能源
✓ 已验证
DOI
高影响因子
ACS Omega
·
2017
·
IF 0
Tingting Yang,Hu Li,Jian He,Yanxiu Liu,Wenfeng Zhao,Zhongwei Wang,Xiaoxiao Ji,Song Yang
γ-Valerolactone (GVL) is one of the versatile platform molecules and biofuel additives derived from the lignocellulosic biomass. Herein, the efficient synthesis of GVL from biobased ethyl levulinate (EL) using alcohol as both H-donor and solvent without an external hydrogen source has been achieved over porous Ti/Zr microspheres. The catalysts (TixZry) with different Ti/Zr molar ratios were synthesized using hexadecylamine (HDA) as a structure-directing agent via a sol–gel process combined with solvothermal treatment and characterized by scanning electron microscopy, transmission electron microscopy, X-ray diffraction, thermal gravimetric analysis, NH3/CO2-TPD, N2 adsorption–desorption, and pyridine-IR. A high GVL yield of 90.1% at 100% EL conversion was obtained at 180 °C for 6 h over Ti2Zr8 in 2-propanol. The microspheric and porous structure, enhanced surface areas, and acid/base contents by the proper introduction of Ti species into Zr oxide were demonstrated to be responsible for the pronounced performance. The microspheric Ti2Zr8 porous catalyst could be reused at least six times with no decrease in catalytic activity.
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
✓ 已验证
DOI
COLLOIDS AND SURFACES A-PHYSICOCHEMICAL AND ENGINEERING ASPECTS
·
2025
·
IF 5.4
Xiangbiao Li,Hu Li,Qingmei Ge,Wenfeng Zhao,Hang Cong
The efficient transformation of cellulose from renewable biomass into the fuel additive methyl levulinate remains a significant challenge. Herein, the hydrothermal post-synthesis method was employed to synthesize a series of tin-based bimetallic Beta zeolites with multifunctional properties, Sn-M-Beta-SO 3 H (M = Al 3 + , In 3+ , Ti 4+ , and Zr 4+ ), for the direct conversion of cellulose to ML. The as-prepared Sn-M-Beta-SO 3 H catalysts were systematically analyzed via XRD, SEM, TEM, UV-Vis, XPS, FT-IR, NH 3 -TPD, and Py-IR techniques. The results revealed that the synergistic interaction between Sn and M influences the composition of acidic sites and the physical properties of these multifunctional zeolites. Notably, Sn-Al-Beta-SO 3 H, with an optimal balance of Lewis and Brønsted acidic sites, achieved an impressive ML yield of 69.7 % at 180 °C within 6 h—one of the highest reported values among heterogeneous catalysts to date. Furthermore, based on experimental findings, a potential reaction pathway for cellulose conversion over Sn-Al-Beta-SO 3 H was proposed, with fructose identified as a key intermediate.
研究领域:
催化
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可再生能源
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绿色化学
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生物质转化
·
材料科学
✓ 已验证
产品关联
DOI
高影响因子
ACS Sustainable Chemistry & Engineering
·
2025
·
IF 7.3
Qikai Si,Yang Yu,Wenjie Xu,Zhenglong Yang,Hongwu Zhang,Ting Su,Christophe Len,Deyang Zhao
Five biomass-based materials: sesame straw (SS), corn cobs (CC), bamboo powder (BP), wheat straw (WS), and furfural residue (FR), were sulfonated using sulfuric acid, as well as some commercial sulfonated catalysts, like Amberlyst, Nafion were compared for the production of ethyl levulinate (EL) from furfuryl alcohol (FAL). Remarkably, under optimum conditions (50 mg of 8% SO3H-FR at 170 °C for 5 h), 100% FAL conversion and 90% EL yield were achieved, along with stable recyclability in continuous flow. Dynamic evolution of GC in the function of reaction time under different temperatures was performed, indicating that FAL conversion to ethoxymethylfuran (EMF) occurs under a lower temperature (150 °C) and short time (45 min). On the contrary, the intermediates 5, 6, and 7 required a higher temperature for EL formation with the concomitant release of diethyl ether (DEE). Comprehensive characterizations demonstrated significant changes in the chemical composition of sulfur- or nitrogen-containing functional groups after sulfonation. In particular, the −S–O types (especially −SO3H) play a more critical role in EL production than the sulfur content alone. The adsorption energies and charge density differences of FAL (Eads) on pristine FR and the sites of −SO3H, −SO4, pyrrolic N, pyridinic N, and their complexes were compared. The FAL adsorption energy followed the order: Eads (complex) > Eads (−SO4) > Eads (−SO3H) > Eads (pyrrolic N) > Eads (pyridinic N)>Eads (pristine), indicating a synergistic adsorption effect among these functional groups in FR. Additionally, the electron transfer capacity was significantly enhanced after −SO3H doping.
研究领域:
化学工程
·
生物质能源
·
催化化学
✓ 已验证
产品关联
DOI
高影响因子
JOURNAL OF INDUSTRIAL AND ENGINEERING CHEMISTRY
·
2016
·
IF 4.179
Jian He,Hu Li,Yanxiu Liu,Wenfeng Zhao,Tingting Yang,Wei Xue,Song Yang
A series of mesoporous acid–base bifunctional Zr/B mixed oxides with different molar ratios were prepared by a sol–gel method, and developed for conversion of ethyl levulinate (EL) to γ -valerolactone (GVL) by using alcohol as hydrogen source. The morphological structures and physico-chemical characteristics of the synthesized materials were identified by various techniques. A high GVL yield of 88.5% was achieved from EL in 2-propanol when Zr 1 B 1 was used. And acid–base sites played a synergic role in synthesizing GVL from EL as evident by poisoning experiments. Furthermore, the catalyst could be reused several times without significant loss of its catalytic activity.
研究领域:
化学工程
·
催化材料科学
✓ 已验证
产品关联
DOI
高影响因子
RSC Advances
·
2016
·Vol. 6
·期 93
·90232-90238
·
IF 3.289
Xiao-Fang Liu,Hu Li,Heng Zhang,Hu Pan,Shan Huang,Kai-Li Yang,Song Yang
Catalytic ethanolysis of furfuryl alcohol (FA) to ethyl levulinate (EL) with MIL-101(Cr)–SO3H, prepared by simple one-pot hydrothermal treatment, is presented for the first time. The as-prepared catalyst with high surface area, hydrothermal and chemical stability, good dispersion, and feasible accessibility of –SO3H Brønsted acid sites was found to show superior performance to other sulfonic acid-functionalized solid catalysts. Besides the special textural properties, the obtained good catalytic activity of 79.2% EL yield and 100% FA conversion were also dependent on the density and strength of the Brønsted acid and the reaction parameters. A slight loss of catalytic activity after five consecutive recycles and the hot filtration experiment confirmed the good stability of MIL-101(Cr)–SO3H. Two coexisting reaction paths for the ethanolysis of FA to EL catalyzed by MIL-101(Cr)–SO3H were proposed, wherein 2-ethoxymethylfuran (2-EMF) was observed to be the dominant intermediate.
研究领域:
化学工程
·
催化科学
✓ 已验证
产品关联
DOI
高影响因子
Catalysts
·
2016
·Vol. 6
·期 9
·143
·
IF 2.964
Lincai Peng,Ruili Tao,Yu Wu
Levulinate ester has been identified as a promising renewable fuel additive and platform chemical. Here, the use of a wide range of common metal salts as acid catalysts for catalytic upgrading of biomass-derived furfuryl alcohol to butyl levulinate was explored by conventional heating. Both alkali and alkaline earth metal chlorides did not lead effectively to the conversion of furfuryl alcohol, while several transition metal chlorides (CrCl3, FeCl3, and CuCl2) and AlCl3exhibited catalytic activity for the synthesis of butyl levulinate. For their sulfates (Cr(III), Fe(III), Cu(II), and Al(III)), the catalytic activity was low. The reaction performance was correlated with the Brønsted acidity of the reaction system derived from the hydrolysis/alcoholysis of cations, but was more dependent on the Lewis acidity from the metal salts. Among these investigated metal salts, CuCl2was found to be uniquely effective, leading to the conversion of furfuryl alcohol to butyl levulinate with an optimized yield of 95%. Moreover, CuCl2could be recovered efficiently from the resulting reaction mixture and remained with almost unchanged catalytic activity in multiple recycling runs.Keywords:biofuel;furfuryl alcohol;catalytic upgrading;metal salt;levulinate ester
研究领域:
化学工程
·
可再生能源
✓ 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）