Catalysts
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2024
·Vol. 14
·期 2
·113
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IF 3.8
Hongzhi Ding,Chenyu Yang,Congyan Jiang,Wei Luo,Qiuyue Wang,Xuefeng Guo
The use of eco-friendly biomass as a resource is an efficient way to address the problems of fossil fuel depletion and climate change. In biomass conversion, versatile γ-valerolactone (GVL) is generally obtained from levulinic acid (LA) hydrogenation via a multimetallic catalyst system. Despite conversion efficiency being enhanced in mild conditions due to metal interactions, maintaining high catalyst stability is still a challenge. In this study, we synthesized a surrounded Co0.52Ni0.48@Al2O3-IE catalyst that exhibited excellent alloying and synergistic interaction between the metal constituents. Under relatively mild reaction conditions, the GVL yield over the catalyst exceeded 99% in LA hydrogenation. The catalyst showed no deactivation in a test of five cycles, displaying superiority in stability, possibly due to reasons of the physical isolation of the shell and the alumina retention on the Co-Ni alloys surface caused by the reversibility of exchange equilibrium. The present work demonstrated that a surrounded structured catalyst fabricated by ion exchange (IE) with active metals physically enclosed can lead to high catalytic activity and superior stability.
研究领域:
催化化学
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可再生能源
✓ 已验证
产品关联
DOI
高影响因子
CHEMICAL ENGINEERING JOURNAL
·
2021
·
IF 13.273
Jinghua Wang,Hongyou Cui,Jiangang Wang,Zhihe Li,Ming Wang,Weiming Yi
Conversion of glucose to 5-hydromethyl furfural (HMF) and levulinic acid (LA) was systematically investigated in LiCl·3H 2 O without additional catalyst. Based on the experimental investigations by using glucose, fructose and HMF as the reaction substrate separately, corresponding reaction kinetics in LiCl·3H 2 O were modelled by first-order assumption. Kinetic analysis demonstrates that high temperature favors the formation of LA, while low temperature facilitates to selectively form humins. To achieve high LA yield, at least a temperature of 140 °C is required. Without additional catalyst converting glucose to LA in LiCl·3H 2 O, humins was predominantly derived from glucose and HMF, and glucose isomerization is the reaction rate-determining step. The activation energies of the main reactions are 160.96 kJ/mol (glucose to HMF), 139.20 kJ/mol (fructose to HMF), and 71.81–76.48 kJ/mol (HMF to LA) respectively. The activation energies for humins formation were 23.45 kJ/mol from glucose, 49.54 kJ/mol from fructose, and 42.15–65.85 kJ/mol from HMF, respectively. It is verified that LiCl·3H 2 O, as compared to aqueous medium, is an excellent reaction medium for converting glucose to LA as it can provide the active centers for fructose to HMF reaction and HMF to LA reaction, but lack of highly efficient Lewis acid for glucose isomerization. With the addition of Lewis acid (such as AlCl 3 and FeCl 3 ), as high as 83.4% of LA yield can be obtained respectively when directly converting glucose, with the total selectivities of LA and HMF of 95%.
研究领域:
生物化学
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催化化学
✓ 已验证
DOI
高影响因子
INDUSTRIAL & ENGINEERING CHEMISTRY RESEARCH
·
2020
·
IF 3.573
Wenlin Li,Feng Li,Junwen Chen,Luis E. Betancourt,Chunyan Tu,Mingjie Liao,Xing Ning,Jiajun Zheng,Ruifeng Li
The hydrogenation of levulinic acid (LA) to γ-valerolactone (GVL) is an essential reaction step to produce value-added renewable chemicals and fuels. In this study, it is demonstrated that the dispersed state of metal and the acid properties of the support can be tuned directly in the synthesized stage for the Ru/MCM-49 catalysts. The average metal particle size of Ru was found at ∼2.0 nm, and strong metal–support interaction was observed for the Ru/MCM-49(DP) catalyst. Mesopores presented can enhance the conversion rate for LA to GVL. The presence of a higher amount of Lewis acid sites can promote the ring closure esterification of the intermediate 4-HPA. High catalytic activity with a TOF value of >3000 h–1, as well as excellent reusability, were achieved by Ru/MCM-49(DP). The agglomeration of Ru particles and the coke formation were thought to be responsible for the deactivation of the catalyst.
研究领域:
化学工程
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催化科学
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可再生化学品
✓ 已验证
产品关联
DOI
高影响因子
ENERGY & FUELS
·
2020
·
IF 3.421
Yang Qu,Yuan Zhao,Shanshan Xiong,Chenguang Wang,Shurong Wang,Lingjun Zhu,Longlong Ma
5-Hydroxymethylfurfural (HMF) and levulinic acid (LA) are two important platform compounds that can be produced by the dehydration of hexoses from hydrolysis of cellulose. In this study, glucose dehydration was catalyzed by the SO42–/ZrO2 catalyst in the NaCl–THF/H2O biphasic solvent system. Complete conversion of glucose was achieved at 160 °C. The highest HMF yield and LA yield were 61.84% and 29.68%, respectively. The results showed that the conversion and product distribution were influenced by catalyst acidity, solvent composition, temperature, and time. The SO42– load greatly changed the acidity of the catalyst, thus affecting the product distribution. By changing the composition of the catalyst and the biphasic solvent system, different yields of HMF and LA could be obtained, so as to realize directional synthesis of the target products.
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
CATALYSIS LETTERS
·
2020
·Vol. 150
·期 9
·2709-2715
·
IF 2.482
Mao Fei-Feng,Zhao Wenguang,Tao Duan-Jian,Liu Xianxiang
Abstract A new solid acid catalyst Fe 3 O 4 @TNTs-SO 3 H was successfully prepared, characterized, and applied for efficient conversion of renewable levulinic acid to n -butyl levulinate, serving as a promising liquid fuel additive. This catalyst was demonstrated to show high catalytic activity and afford n -butyl levulinate with a yield of 94.6% under optimum conditions. Graphic Abstract
研究领域:
化学工程
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催化材料
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能源化学
✓ 已验证
产品关联
DOI
高影响因子
APPLIED CATALYSIS B-ENVIRONMENTAL
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2019
·
IF 14.229
Xiaoqing Gao,Shanhui Zhu,Mei Dong,Jianguo Wang,Weibin Fan
Highly efficient synthesis of valuable γ-valerolactone (GVL) by levulinic acid (LA) hydrogenation is still a challenge for Ru-based catalysts under mild condition. In this work, we have reported that ultrathin TiO 2 nanosheets supported Ru nanoparticles showed extraordinarily high catalytic activity, GVL yield (99.1%) and reusability owing to the formation of Ru O Ti interfacial structure. The turnover frequency (TOF) reached as high as 19,045 h −1 at 100 °C, much higher than those of Ru/SiO 2 , Ru/GO, Ru/MoS 2 , and commercial Ru/C. DFT calculation elucidates that the dominant reaction pathway of LA hydrogenation to GVL is preferentially hydrogenated to CH 3 CHOCH 2 CH 2 COOH*, followed by cyclization to CH 3 (OH)C 4 OH 4 OH* (GVL − OH) and final dehydroxylation, irrespective of surface structure. Compared to Ru (0 0 2) facet, Ru/TiO 2 interfacial structure changes the rate-determining step from initial hydrogenation to cyclization, which greatly declines the activation barrier from 0.81 eV to 0.48 eV.
研究领域:
化学工程
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材料科学
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催化反应
✓ 已验证
产品关联
DOI
高影响因子
EUROPEAN JOURNAL OF INORGANIC CHEMISTRY
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2020
·Vol. 2020
·期 10
·833-840
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IF 2.529
Ruiping Wei,Jingdeng Fan,Xumin Qu,Lijing Gao,Yuanfeng Wu,Zongqi Zhang,Feng Hu,Guomin Xiao
Graphical Esterification of levulinic acid with ethanol was catalyzed by the cooperative effects between the Lewis acid sites offered by unsaturated Zr 6 nodes and Brønsted acid sites supplied by OH in defective UiO-66 MOFs with high defect density, which was tuned by precursor ratios and modulators. Due to their high stabilities and tunable defects, zirconium terephthalate UiO-66 type metal organic frameworks (MOFs) have been promising catalysts in many catalytic reactions. The catalytic activity of UiO-66 MOFs is significantly affected by the density of defects and hydroxyl groups bonded to Zr 6 nodes, which can be tuned by modulators. In this work, a series of defective UiO-66 were synthesized via tuning the ratio of H 2 BDC/Zr and adding monocarboxylic acids with different chain length as modulators. The synthesized UiO-66 MOFs were characterized by powder X-ray diffraction, N 2 physisorption, IR and 1 H NMR spectroscopy, scanning and transmission electron microscopy. Esterification of levulinic acid with ethanol was selected to reveal the influence of modulators, defects and hydroxyl groups. The results showed that UiO-66 with 0.5 of H 2 BDC/Zr ratio and lauric acid as the modulator owned excellent catalytic activity. The cooperative effects, between the Lewis acid sites offered by unsaturated Zr 6 nodes and Brønsted acid sites supplied by OH, has been revealed to have a significant influence on the catalytic activity.
研究领域:
材料化学
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催化化学
✓ 已验证
产品关联
DOI
高影响因子
ACS Omega
·
2021
·
IF 3.512
Lei Hu,Jiayi Zheng,Qing Li,Shunhui Tao,Xiaojie Zheng,Xiaodong Zhang,Yao Liu,Xiaoqing Lin
5-hydroxymethylfurfural (5-HMF) is a promising high value-added platform chemical, which can be produced from glucose, fructose, or lignocellulosic biomass via catalysis technology. However, the effective separation of 5-HMF from aqueous solution and actual biomass hydrolysate is still challenging because 5-HMF can be further rehydrated into levulinic acid (LA) and formic acid (FA) under acidic conditions. Herein, the adsorption behavior of glucose and 5-HMF and its follow-up products (LA and FA) from aqueous solutions onto polymeric adsorbents modified with various functional groups (XAD-4, XAD7HP, and XAD761 resins) was systematically investigated. The results showed that XAD761 resin exhibited the highest adsorption selectivity (α5-HMF/glucose = 42.42 ± 5.84, α5-HMF/FA = 18.41 ± 0.50, and α5-HMF/LA = 3.01 ± 0.10) and capacity for 5-HMF (106 mg g–1 wet resin). The adsorption equilibrium was better fitted by the Freundlich isotherm model at the studied range of 5-HMF concentrations. The thermodynamic study and activation energy also revealed that the adsorption process of XAD761 resin for 5-HMF was spontaneous, exothermic, and physical. The kinetic regression results revealed that the kinetic data of 5-HMF was accurately followed by the pseudo-second-order kinetic model. In conclusion, the present study revealed that the potential of phenol formaldehyde resin with hydroxyl groups could be used as an adsorbent for aldehyde organic compounds.
研究领域:
化学工程
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生物质利用
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环境科学
✓ 已验证
产品关联
DOI
PubMed
高影响因子
RSC Advances
·
2014
·Vol. 4
·期 29
·14985-14992
·
IF 3.708
Jiang Li,Dao-jun Ding,Lu-jiang Xu,Qing-xiang Guo,Yao Fu
A biphasic system consisting of THF and water was studied to achieve the integrated conversion of cellulose and hemicellulose in lignocellulosic biomass to levulinic acid. As compared to previous studies using GVL as solvent, the utilization of a lower boiling point solvent, THF, also achieves the simultaneous hydrolysis of C6 and C5 carbohydrates in lignocellulosic biomass, and the results of simultaneous hydrolysis are comparable. Furthermore, it offers an alternative operation procedure after the hydrolysis. A distillation process is not only used to achieve the effective separation of the solid residue from the desired products, but it also helps in the complete isolation of furfural and formic acid from levulinic acid. Consequently, the utilization of by-product formic acid in the hydrogenation of furfural to furfuryl alcohol is explored, and the process is achieved with both model substrates and the feed from the lignocellulosic biomass feedstock. The hydrolysis of furfuryl alcohol gave C5 carbohydrate-derived levulinic acid. We finally explored the integrated conversion with five biomass raw materials, and the total yield of levulinic acid was quite obviously promoted by the additional conversion of pentose.
研究领域:
化学工程
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生物化工
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可再生能源
✓ 已验证
产品关联
DOI
高影响因子
Reaction Chemistry & Engineering
·
2021
·Vol. 6
·期 10
·1811-1818
·
IF 4.239
Hongxing Wang,Guoqiang Ding,Yubo Liu,Junbo Zhang,Yongwang Li,Yulei Zhu
A sustainable and cost-competitive catalytic process for high yield production of levulinic acid (LA) and γ-valerolactone (GVL) from biomass-derived furfuryl alcohol (FOL) fluid was proposed with GVL as a self-circulation solvent. The innovative process eliminated the separation of the final product GVL and intermediate product LA from the solvent, and the actual concentration of FOL was improved enormously. A higher yield (90.5%) of LA was realized in the fixed-bed reactors than that in the conventional autoclave since the short residence time of the FOL solution could alleviate the polymerization of FOL in the continuous process. UV-Raman spectroscopy demonstrated that fewer polymers deposited on the catalysts, so superior stability of the zeolite was observed in the fixed-bed reactors. Moreover, an 89.4% high yield of GVL can be achieved since the integration of the tandem reaction of hydration and hydrogenation could substantially avoid side reactions in the fixed-bed reactors.
研究领域:
化学工程
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可再生能源
✓ 已验证
产品关联
DOI
高影响因子
GREEN CHEMISTRY
·
2021
·Vol. 24
·期 1
·163-175
·
IF 10.182
Shanta Dutta,Iris K. M. Yu,Jiajun Fan,James H. Clark,Daniel C. W. Tsang
A considerable amount of food waste generated globally could be upcycled to synthesise platform chemicals to enhance environmental sustainability and realise a circular economy. This study investigates the catalytic production of the vital platform molecule levulinic acid (LA) from bread waste, a typical stream of starch-rich food waste generated worldwide. Gamma-valerolactone (GVL), isopropanol (IPA), and propylene carbonate (PC) were evaluated as bio-derived and CO2-derived green co-solvents for LA synthesis. In-vessel pressure generated in PC/H2O (1 : 1) solvent was conducive to rapid LA production from bread waste compared to GVL/H2O and IPA/H2O. In PC/H2O, 72 mol% total soluble product yield was observed quickly within 1 min in moderate reaction conditions (130 °C, 0.5 M H2SO4), whereas ∼15–20 mol% of LA could be obtained when the reaction was prolonged for 10–20 min at 130 °C. The yield of LA could be significantly enhanced in GVL/H2O through phase separation using NaCl (30 wt%(aq)). LA yield increased up to a maximum of ∼2.5 times in the biphasic system (28 mol%, 150 °C, 15 min) (representing a theoretical yield of 66%) in GVL/H2O (1 : 1) compared to the monophasic system (∼11 mol%) under the same reaction conditions. The partition coefficient for LA achieved was 4.2 in the GVL/H2O (1 : 1) biphasic medium, indicating that the system was efficient for simultaneous production and extraction of LA. Biphasic GVL/H2O facilitated selective LA production, which could be optimised by tuning the reaction conditions. These new insights can foster the development of high-performance LA production and sustainable biorefinery.
研究领域:
环境科学
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化学工程
·
生物技术
✓ 已验证
产品关联
DOI
高影响因子
FUEL
·
2022
·
IF 8.035
Lungang Chen,Yong Liu,Xinghua Zhang,Jianguo Liu,Qi Zhang,Longlong Ma
Catalytic conversion of biomass to liquid fuel is one of critical part to ease dependence on fossil fuel. Herein, a route of transformation of biomass-derived furfural and levulinic acid into long-chain hydrocarbon fuels was developed. A C20 oxygenate with 95 % mol yield was firstly synthesized through condensation-polymerization reactions catalyzed by NaOH. Various techniques were employed to verify the chemical structure of the C20 oxygenate. The condensation mixture was then directly subjected to hydrodeoxygenation reaction to prepare long-chain hydrocarbons with a catalytic system of Pd/C and H 3 PO 4 in aqueous phase. A 57.1 % weight yield of liquid fuel was obtained with main products of C12, C14, and C18 hydrocarbons. The mass percent of carbon and hydrogen in fuel was significant improved to 95.91 %, as well as the high heat value was increased to 47.04 MJ/kg.
研究领域:
能源化学
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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）