ACS Sustainable Chemistry & Engineering
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2020
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IF 7.632
Junhua Zhang,Yao Liu,Shibo Yang,Junnan Wei,Liang He,Lincai Peng,Xing Tang,Yonghao Ni
Biorefinery for the purpose of producing biofuels, chemicals, and materials has received much attention. Furfural alcohol (FOL) and levulinate ester (LE) are important biomass-derived platform chemicals, and they are produced from sugar-based furfural (FAL). Unfortunately, the two products are often obtained separately in different reaction systems, which is undesirable; furthermore, it is of significant practical interest to control their selectivity so that the desired product can be accumulated in high yields. Herein, we present an efficient method for the highly selective conversion of FAL to FOL or isopropyl levulinate (IPL) in a one pot system using isopropanol as the hydrogen source and ZrO2@SBA-15 as a bifunctional catalyst with both Lewis acid and Brønsted acid sites. Under optimized reaction conditions, high yields of FOL and IPL in up to 90.4% and 87.2%, respectively, were obtained. Based on the experimental results, a kinetic model describing the catalytic conversion of FAL into FOL and IPL process has been established, which has a good correlation (R2 > 0.92) between the measured and predicted data. The developed kinetics can provide an effective tool to monitor the process and tailor the process conditions to obtain the desired product.
研究领域:
生物炼制
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催化化学
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绿色化学
✓ 已验证
产品关联
DOI
高影响因子
FUEL PROCESSING TECHNOLOGY
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2022
·
IF 8.129
Xiaoyun Li,Xuebin Lu,Wenxuan Hu,Haocheng Xu,Jingguang Chen,Jian Xiong,Lefu Lu,Zhihao Yu,Chuanling Si
Upgradation of lignocellulosic biomass to valuable chemicals has regarded as an effective way for the utilization of renewable carbon sources. Furfural is one of the important chemicals derived from biomass. However, the two-step preparation of sulfonated solid acid for furfural production is complicated. It is necessary to discover a simple one-step solid acid preparation for industrial applications. In this study, the phosphotungstic acid functionalized biochar (PA-FCB) were synthesized by the hydrothermal treatment of microcrystalline cellulose and phosphotungstic acid in one step for valorization of corncob to furfural. The catalytic performance of PA-FCB in γ-valerolactone/water solvent was evaluated, and a furfural yield of 96.06% was observed at 468 K for 120 min. The results indicate that PA-FCB exhibit excellent catalytic performance for the transformation of corncob to furfural. As the Py-FTIR and XPS of PA-FCB demonstrated, PA-FCB contained both Brønsted acid sites (carboxyl groups) and Lewis acid sites (caused by C C bonds and hydroxyl groups), which result in the high catalytic activity . Additionally, the kinetics for the PA-FCB catalyzed furfural production were systematically studied, which could provide a prediction of the overall catalytic system . The present paper gave an effective and comprehensive production strategy for furfural from lignocellulosic biomass.
研究领域:
化学工程
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催化
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可再生能源
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生化工程
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材料科学
✓ 已验证
DOI
高影响因子
JOURNAL OF PHYSICAL CHEMISTRY A
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2018
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IF 2.836
Yamin Li,Qinghui Meng,Jinglan Wang,Yan Zhang,Chuangchuang Cao,Zhanjun Cheng,Jiuzhong Yang,Fuyi Liu,Lidong Zhang,Yang Pan
The thermal decomposition of furfural is investigated in a flow tube reactor at 30 Torr by synchrotron vacuum ultraviolet photoionization mass spectrometry (SVUV-PIMS) at temperatures from 1023 to 1273 K. Over 20 kinds of pyrolysis products, including short-lived radicals, stable oxygen-containing compounds, and hydrocarbons, are identified from the scanning photoionization efficiency (PIE) spectra. Vinylketene (CH2═CH–CH═C═O), which has been shown to be an important primary product, is also directly observed. The possible steps of hydrogen atom addition and hydrogen atom abstraction in the thermal decomposition of furfural are studied by theoretical calculations at the CBS-QB3 level. In addition to unimolecular decomposition, hydrogen atom addition followed by ring opening can lead to the production of vinylketene.
研究领域:
物理化学
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燃烧化学
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反应机理
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质谱分析
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理论化学
✓ 已验证
DOI
高影响因子
ACS Catalysis
·
2024
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IF 11.3
Minghua Dong,Sen Luan,Yuxuan Wu,Bin Zhang,Ye Liu,Huizhen Liu,Buxing Han
Unveiling the mechanism behind catalyst-dependent solvent effects for hydrogenation reactions is critically important yet presents significant challenges. In this work, focusing on furfural hydrogenation over Pd-based catalysts, we observe that distinct active hydrogen species present on Pd/MgO and Pd/TiO2 exhibit different responses to solvation environments, consequently influencing the selectivity in diverse solvents. Product distribution over Pd/MgO remains unaffected by the solvents used that tetrahydrofurfural (THFAL) emerged as the primary product in both organic solvents and water. Conversely, product distribution over Pd/TiO2 highly depends on the solvents; THFAL dominates in organic solvents, whereas furfural alcohol (FOL) becomes the primary product in water. The disparate selectivity upon alteration of supports and solvents is demonstrated by neural network-enhanced molecular dynamics simulations and microkinetic modeling. The active hydrogen species on the support are stabilized in water by water-mediated charge reconstructions, facilitating the hydrogenation of C═O to produce FOL. A spillover pathway where hydrogen species transfer to supports directly without involving hydrogen bond networks is dynamically preferred in both water and organic solvents.
研究领域:
催化化学
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理论计算化学
✓ 已验证
DOI
高影响因子
Frontiers in Bioengineering and Biotechnology
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2022
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IF 6.064
Lv Xianqing,Luo Xiaolin,Cheng Xin,Liu Jing,Li Changzhi,Shuai Li
Hydroxymethylfurfural (HMF) derivatives such as 2,5-bis(hydroxymethyl)furan (BHMF) and furandicarboxylic acid (FDCA) are promising alternative of fossil-based diols and dicarboxylic acids for synthesis of polyesters such as polyethylene terephthalate (PET). However, high cost for preparing HMF from biomass discourages the commercialization of HMF-derived polyesters. Since producing furfural (FUR) from five-carbon sugars (e.g., xylose) via dehydration is an inexpensive and commercialized process, we herein reported a method to synthesize BHMF derivatives (5-(ethoxymethyl)furan-2-methanol (EMFM), 2,5-bis(hydroxymethyl)furan monoacetate (BHMFM) and 2,5-bis(hydroxymethyl)furan diacetate (BHMFD) from furfural derivatives, i.e., (2-(ethoxymethyl)furan (EMF) and furfuryl acetate (FA)). To avoid strong acid-induced side reactions (e.g., furan ring opening, condensation and carbonization), two reaction systems, i.e., a low-concentration HCl aqueous solution combined with formaldehyde and anhydrous acetic acid combined with paraformaldehyde, were found to be suitable for such a hydroxymethylation reaction and could lead to decent product yields. In order to improve the carbon utilization, condensed furanic byproducts were further converted into hydrocarbon fuels via a reported two-step hydrodeoxygenation (HDO) process. This study not only validates the possibility of synthesizing functional HMF derivatives (EMFM, BHMFM, and BHMFD) from commercially-available FUR derivatives (EMF and FA), but also provide a new way to transform condensed furanics to value-added hydrocarbon fuels.
研究领域:
化学工程
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生物质转化
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可再生材料
✓ 已验证
产品关联
DOI
PubMed
高影响因子
BIOMASS & BIOENERGY
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2025
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IF 5.8
Zhaojie Qin,Dongmei Bi,Bozheng Li,Xiang Zhu,Yu Ni,Lihong Wang
Furfural (FF) is a platform chemical with high value and wide application. The catalysts (Zinc oxide modified magnesium-aluminum spinel catalyst (Zn/MgAl 2 O 4 )) prepared in this paper allowed for the fast and efficient preparation of FF. Catalytic pyrolysis experiments were carried out on three typical biomass, and it was found that Zn/MgAl 2 O 4 had a significant enrichment effect on the production of FF in bio-oil. And the effect was more pronounced in the camphor wood experiments. Under pyrolysis conditions (400 °C, catalyst to biomass mass ratio is 1:1), FF relative content reached 64.31 wt%. Zn 2+ increased the acidic sites in Zn/MgAl 2 O 4 and accelerates proton transfer. Glycosidic bond cleavage and monomer degradation were significantly enhanced, resulting in improved FF conversion efficiency. The relative content of FF in the bio-oils obtained from pyrolysis of the three biomass feedstock in the temperature range of 400–600 °C was more than 50 wt%, and the results were better at low temperatures. The results of this paper can provide a theoretical basis for the preparation of FF from clean energy biomass.
研究领域:
能源生物学
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催化化学
✓ 已验证
产品关联
DOI
高影响因子
Molecular Catalysis
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2024
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IF 3.9
Yongxin Zhang,He Li,Zhongliang Shi,Miao Guo,Yanming Hu,Guangyuan Zhou
Total hydrogenation of furfural (FAL) is an efficient way to produce the industrially important tetrahydrofurfuryl alcohol (THFOL). However, it is a challenge to obtain highly selective catalysts for this transformation especially under mild reaction conditions. Herein, we report that the β-ketoenamine-linked covalent organic framework (TpBD COF) supported ultrafine Pd nanoparticles exhibit significantly enhanced selectivity for THFOL compared to Pd/C (95% vs. 82 %) at almost full FAL conversion. This heightened selectivity is attributed to the increased electronic density on the Pd surface, resulting from the electron-donating effect of pendant groups in the TpBD COF. Moreover, kinetic investigations reveal that the activity of total FAL hydrogenation on Pd surface is linked to the rate-determining step in its first C = O hydrogenation process. Additionally, Pd/TpBD COF could catalyse various other bio-based furanic compounds to the corresponding furan ring saturated products in high yields. This work provides guidance for the rational design catalysts to improve its tandem hydrogenation efficiency.
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
ENERGY & FUELS
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2020
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IF 3.421
Qiang Liu,Xinghua Zhang,Qi Zhang,Qiying Liu,Chenguang Wang,Longlong Ma
In this work, high-density jet fuel range cycloalkanes were synthesized in high yields (∼80%) by solvent-free aldol condensation of cyclopentanone and furfural followed by hydrodeoxygenation (HDO). Sodium-promoted magnesium–aluminum mixed oxides (Na–MgAlO) exhibited a high catalytic activity in the aldol condensation of cyclopentanone and furfural under a solvent-free condition. Furfural conversion of 99.4% with almost 100% selectivity for 2-(2-furylmethylidene) cyclopentanone and 2,5-bis(2-furylmethylidene) cyclopentanone were obtained over the 5.7%Na–MgAlO catalyst under mild conditions (80 °C, 2 h). The Na–MgAlO catalysts were characterized by multiple technologies, such as N2 physisorption, powder X-ray diffraction, Fourier transform infrared spectra, and CO2 temperature-programmed desorption, and so on. It was found that the high catalytic activity for aldol condensation of cyclopentanone and furfural was clearly related to the amount and strength of basicity of Na–MgAlO catalysts. Finally, the condensation products were converted to jet fuel range cycloalkanes by HDO over Pd/C and HZSM-5 catalysts. The density, heating value, and freezing point of the HDO liquid products were 0.83 g/cm3, 43.1 MJ/Kg, and −27.7 °C, respectively. The results suggest that these cycloalkanes are promising as blending components for jet fuel.
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
Frontiers in Bioengineering and Biotechnology
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2023
·
IF 5.7
Huang Lizhen,Bian Zelun,Li Dalin,Cheng Xin,Luo Xiaolin,Shuai Li,Liu Jing
Biobased furfural is a sustainable alternative to petrochemical intermediates for bulk chemicals and fuel production. However, existing methods for the conversion of xylose or lignocelluloses in mono-/bi-phasic systems to furfural involve non-selective sugar isolation or lignin condensation, limiting the valorisation of lignocelluloses. Herein, we used diformylxylose (DFX), a xylose derivative that is formed during the lignocellulosic fractionation process with formaldehyde protection, as a substitute for xylose to produce furfural in biphasic systems. Under kinetically optimized conditions, over 76 mol% of DFX could be converted to furfural in water-methyl isobutyl ketone system at a high reaction temperature with a short reaction time. Finally, isolation of xylan in eucalyptus wood as DFX with formaldehyde protection followed by converting DFX in a biphasic system gave a final furfural yield of 52 mol% (on the basis of xylan in wood), which was more than two times of that without formaldehyde. Combined with the value-added utilization of formaldehyde-protected lignin, this study would enable the full and efficient utilization of lignocellulosic biomass components and further improve the economics of the formaldehyde protection fractionation process.
研究领域:
化学工程
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可持续化学
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生物化学工程
✓ 已验证
产品关联
DOI
PubMed
高影响因子
Journal of Cleaner Production
·
2022
·
IF 11.072
Dong Feng,Ao Xia,Shuai Wu,Yun Huang,Xianqing Zhu,Xun Zhu,Balakrishnan Deepanraj,Pau-Loke Show,Qiang Liao
Conductive materials may boost the anaerobic digestion of thermal pretreated biomass by overcoming the inhibition effect from by-products generated during the thermochemical pretreatments . The purpose of this study was to explore the influence of magnetite on the anaerobic digestion of furfural, which is found in most biomass hydrolysates . When adding 10 g/l magnetite , the methane yield was enhanced by 125% in comparison to the control. Cyclic voltammetry analysis suggested that the electroactive aggregates were formed after magnetite was added. The microbial community results showed that the Sedimentibacter was significantly enriched (0.2%–18.8%) in the magnetite addition trails; meanwhile, the relative abundance of Methanosaeta was increased by 22.9% compared with the control. Magnetite-amended group of 10 g/l had the lowest hydrogenotrophic methanogens abundance (5.6%) but the highest electrotrophic methanogens abundance (85.3%) than other groups. The energy production efficiency in 10 g/l magnetite addition was 2.3 times higher than that of the control. These evidences indicated that the direct interspecies electron transfer pathway in furfural digestion may be established between Sedimentibacter and Methanosaeta in the presence of magnetite.
研究领域:
环境科学
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微生物学
✓ 已验证
产品关联
DOI
高影响因子
FUEL PROCESSING TECHNOLOGY
·
2022
·
IF 8.129
Kun Yuan,Huangxian Zhang,Qiao Sun,Xiaohua Zhang,Dan Hou,Jing Chen,Changxiang Liu,Jinzhu Chen,Wanming Xiong
Biomass-based platform compound furfural can be upgraded to C 10 furoin, which is significant to the development and utilization of biomass energy . In this work, a series of diimidazole ILs were applied to explore a feasible way for upgrading of furfural to furoin. The results showed that the catalytic performance of diimidazole ILs were affected by the solvent and the structure of the anion and cation . Furoin yield could increase from 14.8% to 45.0% with the extension of the side chain, and it could be greatly enhanced by the transformation of ethyl group into unsaturated vinyl group. Theoretical calculations revealed it was due to the higher absorption energy and shorter distance between the di (vinylimidazole) ILs and furfural. Furthermore, the anion of diimidazole ILs also displayed influence by affecting the acidity and the electron distribution on the imidazole ring. Finally, the optimized yields of 84.4%, 82.0% and 84.8% were obtained by optimizing the BV 4 , FV 4 and SV 4 catalytic systems , respectively. Mechanistic studies suggested that C-2 deprotonation was the key to the reaction, and both the σ hyperconjugation and π-π conjugation with the imidazole ring could facilitated the reaction. This work may provide some reference in upgrading biomass energy
研究领域:
化学工程
·
生物质能
✓ 已验证
DOI
高影响因子
Energy Sources Part A-Recovery Utilization and Environmental Effects
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2018
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IF 0.555
Xiong Peng,Li Chen,Zongcheng Yan
Furfural (FF) is an important precursor material used for producing high-value chemicals. Here, we have developed sulfonated porous polymers catalysts with tunable surface area and acidity for converting FF to C4 chemicals. The performance of the obtained catalysts was studied using Fourier transform infrared spectroscopy, nitrogen adsorption–desorption, CHNS elemental analysis, and acid–base titration. The influence of various reaction conditions including reaction temperature, reaction time, and catalyst dosage on the oxidation of FF was systematically investigated. It was found that the physicochemical properties of catalysts had remarkable effects on the selectivity of C4 products. Given the higher surface area and acidity, P-2.0-SO3H provided a relative high activity that about 79% C4 chemicals yield accompany with 53% C4 dicarboxylic acid and 26% 2(5H)-furanone selectivity were achieved at 80°C for 12 h. Finally, the corresponding reaction mechanism was discussed.
✓ 已验证
DOI
高影响因子
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