KOREAN JOURNAL OF CHEMICAL ENGINEERING
·
2019
·Vol. 36
·期 5
·740-752
·
IF 2.476
Gong Chen,Wei Junnan,Tang Xing,Zeng Xianhai,Sun Yong,Lin Lu
Biomass-derived levulinic acid (LA) and its esters are currently envisaged as versatile, renewable platform chemicals. In this study, cellulosic pulp derived from the cooking of lignocellulosic biomass with active oxygen and solid alkali was employed as raw material for the formation of LA or ethyl levulinate (EL). This pretreatment process is highly effective for the delignification and deconstruction of lignocellulose matrix, making a facile degradation of the resulting cellulosic pulp to LA or EL. At this point, the acid-catalyzed hydrolysis or ethanolysis of cellulosic pulp was optimized by response surface methodology (RSM), offering desirable LA yield of 65.3% or EL yield of 62.7%, which is significantly higher than those obtained from raw biomass. More importantly, coking behavior on the inwall of the reactor was eliminated during the hydrolysis or ethanolysis of cellulosic pulp, which is one of the top challenges for the acid-catalyzed conversion of biomass in an industrial scale.
研究领域:
生物化学
·
可再生化学
✓ 已验证
产品关联
DOI
高影响因子
INDUSTRIAL & ENGINEERING CHEMISTRY RESEARCH
·
2020
·
IF 3.573
Yanying Hao,Anping Tian,Jin Zhu,Jinshi Fan,Yong Yang
5-Hydroxymethyl-2-furancarboxylic acid (HFCA), a promising biomonomer from renewable resources, was used to synthesize two bio-based plasticizers, namely, hexyl 5-((hexanoyloxy)methyl)-2-furancarboxylate (HHMFC) and dihexyl 5,5′-(oxybis(methylene))bis(furan-2-carboxylate) (DHOBFC). The chemical structures of these prepared plasticizers were confirmed using Fourier transform infrared and nuclear magnetic resonance, and then, their plasticization effects on poly(vinyl chloride) (PVC) were also studied. As a result, HFCA-based plasticizers were miscible with PVC and exhibited excellent plasticization performances, compared with commercial dioctyl phthalate. It was noted that HHMFC had a much better plasticizing effect on the PVC film than DHOBFC; however, it displayed a poorer volatility resistance and exudation resistance, which could be attributed to its smaller molecular weight. Besides, because each rigid furan ring of the synthesized plasticizers contained one oxygen atom, the polarity of HFCA-based plasticizers was improved, which inhibited them from migrating from the PVC matrix into nonpolar solvents. Therefore, the HFCA-based plasticizers have good potential as primary plasticizers for PVC.
研究领域:
材料科学
·
化学工程
·
高分子科学
✓ 已验证
产品关联
DOI
高影响因子
JOURNAL OF POWER SOURCES
·
2024
·
IF 8.1
Jia Cheng,Zhiwei Zeng,Xun Huang,Zidong Wei
The electrocatalytic oxidation of furfural (FA) for the production of valuable chemicals, such as 2-furancarboxylic acid (FAC), presents an attractive alternative to the sluggish oxygen evolution reaction during water electrolysis for hydrogen production. However, the activity and stability of the current electrocatalysts still require further enhancement. In this study, NiMoP is fabricated on Ni foam through pulsed electrodeposition to facilitate the electrooxidation of FA for FAC production in an alkaline environment. A low voltage of 1.43 V vs. reversible hydrogen electrode (RHE) is adequate to achieve a current density of 500 mA cm −2 , with FAC selectivity and Faraday efficiency reaching 97.5 % and 95.2 %, respectively. The extended electrolysis of FA using a continuous-flow electrolytic cell under high current density (500 mA cm −2 ) demonstrates consistent stability at a cell voltage around 1.8 V over a 35-h duration.
研究领域:
化学工程
·
电催化
✓ 已验证
产品关联
DOI
高影响因子
Sugar Tech
·
2020
·Vol. 22
·期 5
·830-841
·
IF 1.198
Chen Shuai,Zheng Wenjing,Liu Weixi,Liu Lei,Sun Weidong
Levulinic acid (LA) is an important biomass-based chemical. The preparation of LA from bagasse is of great practical significance for the comprehensive and efficient utilization of biomass. Biomass bagasse is mainly composed of cellulose, hemicellulose, and lignin. The cellulose is mainly degraded to glucose, and hemicellulose is mainly degraded to xylose, with dilute acid treatment at high temperature. In this research, we produced the LA from bagasse with dilute acid treatment at high temperature. The influences of residence time (10–60 min), reaction temperature (170–240 °C), liquid-to-solid ratio (5:1–25:1 mL/g), and acid concentration (1–5%) on the synthesis of LA were investigated by statistical methods, achieving a maximum LA yield of 16.25%. Additionally, LA was isolated and extracted from bagasses hydrolysate by ion exchange and vacuum distillation. The adsorption capacity of different resins was determined and compared. The optimal resin to acquire better adsorption capacity was determined. The better adsorption capacity was obtained when the D301 resin was selected as the filter for ion exchange. The height-to-diameter rate, eluent flow rate, elution volume of ion exchange column were 10, 0.84 BV/h, 56.4 mL, respectively. The eluent was then distilled under vacuum, collecting the components at 130–140 °C. The total yield and purity of LA were 67.1% and 78%, respectively.
研究领域:
生物化学
·
可再生资源工程
✓ 已验证
DOI
高影响因子
JOURNAL OF MOLECULAR LIQUIDS
·
2025
·
IF 5.2
Zi-Quan Wang,Ya-Peng Du,Xiao-Ping Zheng,Yu Chai,Yu-Cang Zhang,Yan-Zhen Zheng
The direct conversion of raw lignocellulosic waste into specialty chemicals such as levulinic acid (LA) has the potential to significantly enhance biorefinery profitability. Here, we demonstrated that incorporating γ-valerolactone (GVL) as a co-solvent during the SO 3 H-functionalized ionic liquid-catalyzed conversion of bagasse in water markedly enhanced reaction rates and catalytic activity, achieving a LA yield as high as 76.1 % with a 1:1 vol ratio of GVL to water. This catalytic system also effectively converted other lignocellulosic waste to LA. Reaction constants and activation energies for the bagasse dehydration process to LA were obtained. Comprehensive characterization via Fourier transform infrared spectroscopy (FTIR), scanning electron microscopy (SEM), and X-ray diffraction (XRD) elucidated significant changes in functional groups, surface morphology, and crystallinity index of solid residues over extended reaction times. Notably, hemicellulose and cellulose were converted within 4 h, with lignin remaining in the solid residues and forming by-products after prolonged reaction times. This efficient one-pot conversion method showed promise as a sustainable approach to transform agricultural waste into LA, offering new opportunities for eco-friendly resource utilization.
研究领域:
生物化学
·
可再生能源
✓ 已验证
产品关联
DOI
高影响因子
Molecular Catalysis
·
2022
·
IF 5.089
Pengxin Yu,Guangyu Sun,Lu Xiong,Boying Zheng,Teng Li,Jun Jiang,Yantao Wang,Weiran Yang
Salicylic acid, generally produced by chemical synthesis based on petrochemical products, is a vital organic acid and widely used in the pharmaceutical synthesis. This work developed a new and green route for the production of salicylic acid from biomass-derived 2-furoic acid in two steps. Firstly, 2 mmol 2-furoic acid was creatively converted to 2,3-benzofuran using HZSM-5 (Si/Al=130) at 280 °C for 1.5 h under 100 psi N 2 ; and then the oxidation of 2,3-benzofuran to salicylate was conducted with tert‑ butyl hydroperoxide under basic condition without metal catalyst at 120 °C for 1 h. The stability of the catalyst for the first step and the possible reaction pathway for the second step based on the control experiments was properly envisioned. Regardless of limited salicylic acid yield (16%) from 2-furoic acid, this work paves a potentially feasible pathway for the preparation of drugs from biomass.
研究领域:
生物化学
·
药物化学
·
绿色化学
✓ 已验证
产品关联
DOI
高影响因子
ACS Catalysis
·
2025
·
IF 13.1
Ruiqi Fang,Jie Kang,Fengliang Wang,Xin Zhao,Yingwei Li
The production of valerate esters, a class of transportation biofuels (additives), usually undergoes alternate hydrogenation and acid-catalysis dehydration processes that suffer from inevitable coke deposition and undesirable side reactions. We report a one-pot esterification–hydrogenolysis reaction pathway for valeric biofuels synthesis from biomass-derived 2-furoic acid, which was proceeded over the elaborate CoPtX@Co3O4-NC (X = 0.01, 0.02, 0.05, and 0.1) catalysts. The catalysts were constructed through a MOF-engaged etching-pyrolysis-replacement strategy to obtain mesoporous pocket cube nanoboxes-in-nanobox morphology and uniform CoPtX@Co3O4 core–shell nanoparticles with Pt moieties in tunable content and size (from single-atom scale to 2.4 nm). The obtained acid-free CoPtX@Co3O4-NC catalyst achieved an average 92.2% yield of ethyl valerate at a complete conversion of 2-furoic acid, and the reaction ran steadily in a microchannel continuous flow reactor for at least 200 h, which also inhibited the byproduct generation and coke deposition. A mechanistic study suggested that 2-furoic acid was preferably adsorbed on the oxyphilic Co3O4 shell for esterification initially; then the generated esters underwent sequential and exclusive hydrogenolysis steps over the CoPt core to yield valerate esters. The high industrial application prospect of this reaction pathway was additionally highlighted by producing 12 kinds of valeric biofuels from 2-furoic acid and the corresponding C1 ∼ C7 primary, secondary, and tertiary alcohols.
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
Catalysts
·
2023
·Vol. 13
·期 4
·663
·
IF 3.9
Xu Wu,Heqin Guo,Litao Jia,Yong Xiao,Bo Hou,Debao Li
The base-free oxidation of furfural by non-noble metal systems has been challenging. Although MnO2emerges as a potential catalyst application in base-free conditions, its catalytic efficiency still needs to be improved. The crystalline form of MnO2is an important factor affecting the oxidation ability of furfural. For this reason, four crystalline forms of MnO2(α, β, γ, and δ-MnO2) were selected. Their oxidation performance and surface functional groups were analyzed and compared in detail. Only δ-MnO2exhibited excellent activity, achieving 99.04% furfural conversion and 100% Propo.FA(Only furoic acid was detected by HPLC in the product) under base-free conditions, while the furfural conversion of α, β, and γ-MnO2was below 10%. Characterization by XPS, IR, O2-TPD and other means revealed that δ-MnO2has the most abundant active oxygen species and surface hydroxyl groups, which are responsible for the best performance of δ-MnO2. This work achieves the green and efficient oxidation of furfural to furoic acid over non-noble metal catalysts.Keywords:base-free;MnO2;crystal type;furfural oxidation to furoic acid
研究领域:
催化化学
·
绿色化学
✓ 已验证
产品关联
DOI
高影响因子
Sustainable Energy & Fuels
·
2020
·Vol. 4
·期 4
·2018-2025
·
IF 5.503
Songyan Jia,Jiao Ma,Dongping Wang,Kangjun Wang,Qiang Zheng,Chunshan Song,Xinwen Guo
Levulinic acid (LA) is a promising renewable platform compound derived from biomass for the manufacture of various valuable chemicals, among which levulinate esters have been demonstrated to be good fuel additives. Many previous studies have focused on the production of short-chain levulinates for biofuels such as methyl and ethyl levulinates, but these esters suffer from some essential issues including a high oxygen content, low energy density (or heating value) and water solubility. Long-chain levulinate esters have similar structures to biodiesel. The long carbon chain may provide a higher carbon content and strong hydrophobicity, therefore improving the energy density and water insolubility. In this work, the synthesis of a long-chain levulinate ester, n-hexyl levulinate (HL), has been fast and efficiently achieved by the catalytic esterification of LA and 1-hexanol at low temperature. Tungsten hexachloride (WCl6) showed the most superior activity among the tested metal salt catalysts under mild conditions. A HL yield of ∼85% with almost complete LA conversion could be obtained at 50 °C after only 30 min. Other hexanols that have larger steric hindrances, such as 2-ethyl-1-butanol, 2-hexanol, 3-hexanol and cyclohexanol, could also promote efficient esterification with LA over the WCl6 catalyst, resulting in excellent product yields of ∼82–91%. The strategy applies to the efficient synthesis of longer chain levulinate esters such as n-octyl levulinate (OL) as well. The WCl6 catalyst was reusable several times in a consecutive batch reaction mode. The method reported herein offers a strategy for the efficient production of liquid fuels from LA, potentially bridging raw biomass feedstocks and terminal utilization of biobased products.
研究领域:
化学工程
·
可再生资源利用
✓ 已验证
产品关联
DOI
高影响因子
CELLULOSE
·
2019
·Vol. 27
·期 3
·1451-1463
·
IF 3.917
Zhou Lipeng,Gao Dongting,Yang Jingru,Yang Xiaomei,Su Yunlai,Lu Tianliang
Abstract Conversion of cellulose to chemicals is an economic and environmental route for biomass utilization. In this work, efficient conversion of cellulose to alkyl levulinates and levulinic acid was realized by oxidation pretreatment combined with alcoholysis over Al 2 (SO 4 ) 3 catalyst. Proper pre-oxidation conditions including oxidation temperature and time are important. By pre-oxidation, part of hydroxymethyl groups on cellulose was converted to carboxyl groups which provide the Brønsted acid sites near the glycosidic bonds to improve the depolymerization of cellulose to monosaccharide. Al 2 (SO 4 ) 3 ·18H 2 O can play both Brønsted and Lewis acid roles in methanol and catalyze the conversion of monosaccharide to alkyl levulinates and levulinic acid. After pre-oxidation at optimized conditions, cellulose can be converted into methyl levulinate and levulinic acid over Al 2 (SO 4 ) 3 in methanol efficiently, and total yield of methyl levulinate and levulinic acid can reach 66.8% at 180 °C for 3 h. Furthermore, the simple and cheap Al 2 (SO 4 ) 3 catalyst is recyclable which is important for the practical application. Graphic abstract
研究领域:
生物化学
·
可再生资源化学
✓ 已验证
产品关联
DOI
高影响因子
INDUSTRIAL CROPS AND PRODUCTS
·
2018
·
IF 3.849
Chun Chang,Lin Deng,Guizhuan Xu
Wheat straw can be converted into biofuel candidate-methyl levulinate with copper sulfate as the cheap catalyst. To take advantage of the whole components of wheat straw, a two-stage pretreatment process was developed in this study. In the first-stage process, the hemicellulose component in wheat straw can be converted into biosurfactant at the mild conditions, and the lignin component can be extracted as another value added by-product in the second stage. On the basis, the pretreated wheat straw was used as raw material for methyl levulinate production, and a yield of 20.2 wt% can be obtained under the optimum reaction conditions. Meanwhile, the catalyst recycling experiments showed that copper sulfate was stable and can be reused more than five times. The results of mass balances and preliminary economic analysis further indicated that the production of integrated biorefinery processes producing diversified products offers potential for the sustainable valorization of wheat straw.
研究领域:
生物化学
·
可再生能源
✓ 已验证
产品关联
DOI
高影响因子
CELLULOSE
·
2019
·Vol. 26
·期 17
·9135-9147
·
IF 3.917
Zhou Shengqiang,Yang Xiaomei,Zhang Yali,Jiang Lingyun,Zhou Lipeng,Lu Tianliang,Su Yunlai
Abstract One-pot conversion of cellulose to valued-added platform chemicals such as alkyl levulinate is a promising and challenging process of biomass utilization due to the insolubility of cellulose in alcohol. In this work, commercial heteropoly acid combined with postsynthesized Sn-Beta zeolite was employed to transform cellulose to methyl levulinate (MLE) in one pot. The synergistic catalysis of the homogeneous strong Brønsted (B) acid and the solid strong Lewis (L) acid can effectively realize the depolymerization of solid cellulose and the subsequent isomerization, dehydration and hydration steps to MLE. 55% and 62% of MLE yields were obtained from α-cellulose and microcrystalline cellulose, respectively, at 160 °C for 10 h. Various carbohydrates besides cellulose can also be efficiently converted to MLE in high yields over the bifunctional catalyst system. The effects of the amount of B acid and L acid, the reaction temperature and time and the amount of cellulose on the production of MLE were investigated in detail. Finally, the reaction pathway of cellulose to MLE was revealed. Recyclability tests indicated that the binary catalyst can be reused without decrease of catalytic activity. Graphic abstract
研究领域:
生物质化学
·
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）