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
·
催化化学
✓ 已验证
DOI
高影响因子
Energy Sources Part A-Recovery Utilization and Environmental Effects
·
2021
·
IF 3.447
Xialing Lin,Mingrui Li,Yumei Jian,Jinshu Huang,Song Yang,Hu Li
γ-Valerolactone (GVL) is widely used as a green solvent and in the generation of liquid fuels. GVL can be obtained from biomass-derived furanic compounds through a cascade reaction process, which is extremely challenging due to the need for different active sites in a single pot. Here, we reported a domino conversion process of directly upgrading furfural (FF) to GVL in isopropanol over a commercially available and budget catalyst ZrCl4 that can in-situ release Brønsted acid (HCl) and Lewis acid/base species (ZrO(OH)n·xH2O). The in-situ formed bifunctional catalyst can significantly enable twice transfer hydrogenation, etherification, the ring-opening, and cyclization reactions, giving a high GVL yield of 56.5% from FF at 180°C for 6 h. In addition, the solid residues collected after reaction could be calcined to obtain t-ZrO2-(C) nanoparticles with a rough surface, in which the insoluble humin attached to the hydrolyzed solid was demonstrated to improve the layered aggregate structure of the resulting t-ZrO2-(C). Interestingly, t-ZrO2-(C) showed good performance in catalytic conversion of FF to furfuryl alcohol (FAOL) with ca. 80% yield. The developed bifunctional and recyclable catalytic system exhibits potential for one-pot multi-step biomass valorization.
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DOI
高影响因子
APPLIED CATALYSIS A-GENERAL
·
2020
·
IF 5.006
Mo Qiu,Tianmeng Guo,Ran Xi,Danni Li,Xinhua Qi
In this paper, the as-prepared metal-organic frameworks material UiO-66 and other Zr-MOFs were directly used as catalytic transfer hydrogenation (CTH) catalysts to catalyze furfural (FF) to furfuryl alcohol (FAL) with 2-propanol (IPA) acted as both solvent and hydrogen donor. The results showed that the as-prepared UiO-66 had satisfactory catalytic activity and selectivity in yielding FAL (97 %) from the CTH of FF at 140 °C within 5 h. Moreover, the as-prepared UiO-66 exhibited relatively stable catalytic activity over five cycles and easy regeneration. Interestingly, UiO-66 was also applicable for the CTH of the other aldehydes such as 5-hydroxymethyfurfural, 5-methylfurfural, 4-methoxybenzaldehyde, and n-hexanal to the corresponding alcohols, affording high product yields up to 98 %. This work provides a green, simple and sustainable process for the catalytic production of FAL from biomass-based furfural, which has certain significance for the sustainable utilization of biomass.
研究领域:
催化化学
·
生物质能源
·
绿色化学
·
材料化学
·
有机合成
✓ 已验证
DOI
高影响因子
BIOMASS & BIOENERGY
·
2026
·
IF 7
Yahui Zhang,Haowen Cui,Haian Xia
The selective oxidation of furfural (FF) to 2-furoic acid (FA) represents a significant route toward sustainable chemical production. However, existing catalytic systems often suffer from limitations such as low substrate concentrations, harsh reaction conditions, and inadequate selectivity. In this study, a series of Ag/ZrO 2 catalysts with varying Ag loadings were prepared via a deposition–precipitation method and were used for the aerobic oxidation of FF to FA under mild conditions. The effects of metal loading, catalyst mass, reaction temperature, reaction time, and oxygen pressure on FF conversion and FA selectivity were systematically investigated. Under optimized conditions, nearly 100% FA was achieved under 10 wt% FF concentration at low-temperature (ca. 5 °C), while a high selectivity of 90.3% toward FA was maintained even at 20 wt% FF. The catalysts also exhibited excellent recyclability, retaining over 85% FA selectivity after five consecutive cycles. Comprehensive characterization techniques, including XRD, XPS, and HRTEM, were employed to elucidate the structure-activity relationship of the catalysts. The experimental and characterization findings propose a possible reaction mechanism involving synergistic effects of Ag 0 sites for dehydrogenation and ZrO 2 oxygen vacancies for O 2 activation. This work represents a notable advance in the field, as it develops the high efficient catalytic system under high FF concentrations and low-temperature conditions for the first time.
✓ 已验证
产品关联
DOI
高影响因子
JOURNAL OF RARE EARTHS
·
2026
·
IF 9.6
Yangjian Zhu,Jiaqin Han,Weiming Xiao,Shunmin Ding,Dan Zhao,Chao Chen
The rational modulation of the electronic state via interaction of components is pivotal for optimizing the performance of solid materials in particular for heterogeneous catalysts. Unlike the electron-withdrawing effect of popular supports, herein, it is discovered that a unique electron modulation effect of SmPO 4 (a rare earth phosphate) on nickel (Ni) nanoparticles (10 wt%) supported on AlPO 4 -SmPO 4 composite carrier, enables efficient hydrogenation of furfural (FAL) to tetrahydrofurfuryl alcohol (THFA) under mild conditions (423 K, 1.0 MPa H 2 ). In comparison to the influence of AlPO 4 , comprehensive characterizations (X-ray photoelectron spectroscopy (XPS), high-resolution transmission electron microscopy (HRTEM), and H 2 temperature-programmed reduction (H 2 -TPR)) confirm that SmPO 4 can act as an efficient electron donor, transferring electron to Ni along the AlPO 4 -SmPO 4 interface and forming electron-enriched Ni active sites. This electron-enriched state, coupled with the interface structure of the composite support, constructs a double-site activation system: electron-enriched Ni sites on AlPO 4 -SmPO 4 interface synergistically activate the conjugated C=O and C=C bonds, facilitating efficient and selective complete hydrogenation of FAL. The Ni/AlPO 4 -SmPO 4 catalyst with the optimized Al:Sm ratio exhibits exceptional catalytic performance with a FAL conversion of 99.2% and a THFA selectivity of 94.0%, outperforming most reported Ni-based catalysts under milder conditions. Additionally, the catalyst demonstrates attractive stability and broad applicability for a scope of cyclic unsaturated substrates like FAL. This work highlights the unique electron modulation function of rare earth phosphates in tailoring metal electronic states, and provides a promising strategy for designing high-performance non-noble metal materials for corresponding technically important chemical engineering processes.
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产品关联
DOI
高影响因子
Green Chemical Engineering
·
2026
·
IF 11.9
Yi Duan,Shangzhong Zhang,Lifeng Yan
Lignocellulosic biomass is an abundant, renewable, and environmentally benign resource that can be catalytically converted into valuable bio-based feedstocks and high-value chemicals through appropriate processes. However, achieving such transformation through environmentally benign and efficient routes remains a significant challenge. In this study, we demonstrate a fully green solvent system composed of a zinc chloride–choline chloride deep eutectic solvent (DES) combined with ethyl acetate to form a biphasic system, which enables the direct one-pot conversion of corncob biomass after a brief microwave-assisted pretreatment under remarkably mild conditions (atmospheric pressure and 90 °C). A high furfural yield of up to 86.5% was achieved via the selective degradation of hemicellulose, while cellulose remained largely unconverted and ultimately enabled the isolation of cellulose and lignin with high contents in the biphasic system. Simultaneously, effective fractionation of lignocellulosic components was achieved, with a lignin removal rate of 78.1%. To the best of our knowledge, there are very limited reports achieving such a high furfural yield directly from lignocellulosic biomass under such mild conditions. Most conventional and recently reported systems typically require elevated temperatures (160–240 °C) to obtain moderate to high furfural yields. The separated cellulose retained high crystallinity, and 2D-HSQC NMR analysis revealed well-preserved characteristic structural units in the extracted lignin, indicating that its fundamental framework was largely maintained. Furfural was predominantly extracted into the ethyl acetate phase, and the low boiling point of ethyl acetate significantly facilitated downstream separation. In addition, the DES exhibited excellent recyclability, maintaining over 80% of the furfural yield after more than five reuse cycles, highlighting its considerable economic potential.
✓ 已验证
DOI
高影响因子
Journal of Bioresources and Bioproducts
·
2021
·
IF 0
Jingwen Shao,Yong Ni,Lifeng Yan
Furfural is an alternative feedstock and has been used for the production of maleic acid (MA) and fumaric acid (FA) by an oxidation process. Deep eutectic solvents (DESs) were used as the green solvents while sodium chlorate was used as an oxidant and vanadium pentoxide was used as the catalyst at 70–90 °C under atmospheric pressure. It was found that several acidic DESs are valid, such as acetic acid/choline chloride (AA/ChCl) and propionic acid/choline chloride (PA/ChCl), and AA/ChCl DES was selected as the solvent for the conversion. The optimal DES is AA/ChCl, and the effect of the amount of oxidant, time, and temperature on the yield of the MA and FA has been systematically studied, and the conversion of furfural can reach 100% while the yield of the MA and FA reached 66.5% under reaction temperature of 80 °C for 12 h, which provides a new green route to synthesis valuable monomers from furfural.
研究领域:
化学工程
·
绿色化学
·
有机合成
·
催化
✓ 已验证
DOI
Molecular Catalysis
·
2017
·
IF 0
Hao Chen,Houhang Ruan,Xilei Lu,Jie Fu,Timothy Langrish,Xiuyang Lu
Catalytic transfer hydrogenation of furfural to furfuryl alcohol is considered to be a very important industrial process. In this work, non-noble Cu supported on MgO-Al 2 O 3 catalysts have been prepared by co-precipitation and have shown excellent catalytic performance for conversion of furfural to furfuryl alcohol in near-critical iso-propanol. The effects of the Cu state (reduction degree and dispersion) and loading in Cu/MgO-Al 2 O 3 , acidity of catalysts have been investigated by X-ray diffraction (XRD), coupled plasma optical emission spectrometry (ICP-OES), N 2 adsorption and desorption (N 2 -BET) and temperature-programmed desorption of ammonia (NH 3 -TPD), which have led to high activity for producing furfuryl alcohol. The results have shown that the selectivity of furfuryl alcohol has been influenced by the Cu state, Lewis acidity, reaction temperature and reaction time. The mechanisms, Lewis acid- and metal mediated hydrogenation, have shown that a desirable balance of Cu loading and Lewis acidity of catalyst has influenced the activity significantly. Almost 100% furfural conversion, with 89.3% furfuryl alcohol yield has been obtained. Cycling tests have shown that the prepared catalysts have been stable, where recycling the catalysts at least four times has not shown any reduction in activity.
研究领域:
化学工程
·
催化材料
✓ 已验证
DOI
BIOMASS & BIOENERGY
·
2023
·
IF 6
Lihe Zhu,Xueting Shao,Xuejun Pan,Zhong Sun,Xiangyu Li,Xixin Duan,Junyou Shi
Catalytic conversion of waste biomass to furfural (FF) is an important valorization of lignocellulose . Heteropolyacid catalysts were designed for efficient aqueous-phase dehydration of saccharides by supporting phosphotungstic acid (H 3 PW 12 O 40 , abbreviated as PW 12 ) on H-ZSM-5 zeolite at different loadings (xPW 12 /ZSM-5, x = 10%, 20%, 30%, 40%, 50%). The PW 12 /ZSM-5 was used in the one-pot conversion of biomass (xylose, xylan , and corn stover) to FF in LiBr aqueous solution. The low PW 12 loading catalyst (10%PW 12 /ZSM-5) could efficiently convert biomass to FF with the yields of 73.3% (xylose) and 75.1% (xylan) at moderate temperature (130 °C), respectively. The PW 12 loading and acid sites distribution were crucial to the catalytic performance. Moreover, LiBr enhanced the yield of FF because of its Lewis acidity. The PW 12 /ZSM-5 based solid polyacid was a promising catalyst for the efficient FF production from biomass with high yield and easy separation.
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产品关联
DOI
高影响因子
RENEWABLE ENERGY
·
2023
·
IF 8.7
Mengxue Song,Chonghao Qiu,Pengfei Ma,Jiawei Zhong,Zhuohan Zhang,Weiping Fang,Wenjing Song,Jianqiang Fan,Weikun Lai
Reductive etherification is an attractive and practical strategy to convert bio-platform compounds into valuable chemicals. In directed synthesis of furfuryl ethers, reductive etherification of bioderived furfurals is still challenging due to the complexity of catalytic reaction . Herein, reductive etherification of furfural with alcohol was investigated over Ni/ZSM-5 catalyst, which found that Si/Al ratios in ZSM-5 played an important role on the catalytic performance. For Ni/ZSM-5 with Si/Al ratio of 50, 80.9% yield of furfuryl ether at 90.8% conversion of furfural was achieved under the condition of 2 MPa H 2 and 180 °C for 3 h in isopropanol. The catalyst exhibited superior stability and recyclability during the consecutive cycle run. Catalysts characterization demonstrated that both acidic properties and furfural adsorption were influenced by the Si/Al ratios in Ni/ZSM-5, which correlated to the reaction route and catalytic performance. Lewis acid sites enhanced furfural hydrogenation into furfuryl alcohol, while Brønsted acid sites on ZSM-5 effectively catalyzed sequential etherification of furfuryl alcohol to furfuryl ether. Under optimization conditions, various furfuryl ethers could be obtained with yields above 80% over Ni/ZSM-5 catalyst in different primary alcohols, demonstrating the general versatility of the approach. Our findings offered opportunities to develop an efficient furfuryl ethers synthesis method .
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产品关联
DOI
高影响因子
ChemistrySelect
·
2023
·Vol. 8
·期 16
·e202300902
·
IF 2.1
Panli Liu,Shengbin Shi,Ruiping Wei,Lijing Gao,Jin Zhang,Guomin Xiao
Graphical P-Zr-SBA-15 catalyst with bifunctional acidity was synthesized by introducing Zr 4+ into the mesoporous material SBA-15 structure for intra skeleton modification, and then impregnated with phosphoric acid solution to modify the outer skeleton. The catalyst exhibits excellent catalytic activity, good thermal stability, and recoverability in the preparation of furfural. A series of bifunctional P-Zr-SBA-15 catalysts with Lewis acid and Brønsted acid sites were prepared by modifying mesoporous material SBA-15 with Zr 4+ and phosphate group, which were used in the conversion of xylose and xylan into furfural. The structure and acidic characteristics of the catalyst were analyzed by X-ray diffraction, Fourier transform infrared spectroscopy, N 2 adsorption desorption, scanning/transmission electron microscopy, X-ray photoelectron spectroscopy, thermogravimetric analysis, NH 3 temperature programmed desorption, and pyridine adsorption infrared spectroscopy. The effects of different process parameters on the catalytic performance of the catalyst were studied. when using the xylose and xylan as substrates, the furfural yield were 80.3 % and 68.8 % under the optimal conditions in the H 2 O (NaCl) /toluene (3/3 mL) biphasic solvent system, respectively, and 52.5 % furfural yield was obtained using xylose as substrate in aqueous system. In addition, the catalyst has good thermal stability and easy recovery in the recycling experiment.
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产品关联
DOI
高影响因子
CHEMICAL ENGINEERING JOURNAL
·
2023
·
IF 15.1
Jingyun Zhang,Zhen Jia,Shitao Yu,Shiwei Liu,Lu Li,Congxia Xie,Qiong Wu,Youzheng Zhang,Hailong Yu,Yuxiang Liu,Jinhui Pang,Yue Liu
Controllable carbonyl group (C O) hydrogenation is the key to the transformation of furfural molecules into high-value furfuryl alcohol chemicals. Herein, a non-noble copper metal catalyst (Cu/MgO) was prepared for the efficient hydrogenation of furfural to furfuryl alcohol under mild conditions. At 383 K and 2 MPa H 2 , 99.9% conversion of furfural with 99.9% selectivity to furfuryl alcohol was achieved within 80 min while the turnover frequency (TOF) was 56.87 h −1 . The temperature of a reductive pretreatment can be used to tune the nature of the interfaces between reduced copper and the metal oxides present in copper-magnesium oxide catalysts. The valence copper species exhibited unique catalytic properties in the hydrogenation of furfural to furfuryl alcohol. Besides, the Cu/MgO-350 exhibited excellent stability and reusability without significant activity loss. These results were accounted for by the MgO alkaline interface contributing to the effective formation and high dispersion of different valence Cu species. The active site had strong adaptability to the adsorption of reactants and desorption of products, thus avoiding excessive hydrogenation of furfural. According to the analysis of the characterization data, furfural adsorption mainly existed in η 1 (O)-aldehyde binding mode which was consistent with the density functional theory (DFT) calculation. DFT calculations of the reaction process showed that the theoretical results favored the hydrogenation of furfural through a hydroxyalkyl intermediate rather than of an alkoxide intermediate.
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产品关联
DOI
高影响因子
危险品化学品经营许可证（带存储）