RSC Advances
·
2016
·Vol. 6
·期 26
·22174-22178
·
IF 3.289
Dezhang Ren,Jun Fu,Lu Li,Yunjie Liu,Fangming Jin,Zhibao Huo
An efficient process for the production of levulinate esters from biomass-derived furfuryl alcohol in liquid alcohol over commercial α-Fe2O3 was firstly investigated. Among the catalysts we tested, α-Fe2O3, a cheap, commercially available and environmentally benign catalyst, exhibited a remarkable catalytic performance for the transformation and gives levulinate esters in good yield compared to the previous studies. The corresponding esters such as methyl levulinate, ethyl levulinate and butyl levulinate were obtained in high yields under optimized reaction conditions. Several influence factors for the formation of levulinate esters were also discussed. A plausible reaction mechanism for the formation of levulinate ester from furfuryl alcohol was proposed. From the viewpoint of practice and economy, the present study provides a potential application for the efficient synthesis of fine chemicals from biomass-derived compounds over cheap, commercially available and environmentally benign catalysts.
研究领域:
化学工程
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可再生资源利用
✓ 已验证
DOI
高影响因子
ChemSusChem
·
2016
·Vol. 9
·期 23
·3307-3316
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IF 7.116
Changhua Song,Sijie Liu,Xinwen Peng,Jinxing Long,Wenyong Lou,Xuehui Li
Graphical Iconic ionic : Heteropolyanion-based ionic liquids are used as catalysts for the conversion of renewable carbohydrates to levulinate esters. The process can be operated under mild conditions, and the catalyst can be recovered readily by self-separation through temperature control. The catalyst shows excellent reusability, and a satisfactory yield can be obtained even after the 10th run. An efficient one-pot approach for the production of levulinate ester from renewable carbohydrates is demonstrated over heteropolyanion-based ionic liquid (IL-POM) catalysts with alcohols as the promoters and solvents. The relationships between the structure, acidic strength, and solubility of the IL-POM in methanol and the catalytic performance were studied intensively. A cellulose conversion of 100 % could be achieved with a 71.4 % yield of methyl levulinate over the catalyst [PyPS] 3 PW 12 O 40 [PyPS=1-(3-sulfopropyl)pyridinium] at 150 °C for 5 h. This high efficiency is ascribed to the reasonably high activity of the ionic liquid (IL) catalyst and reaction coupling with rapid in situ esterification of the generated levulinic acid with the alcohol promoter, which allows the insolubility of cellulose encountered in biomass conversion to be overcome. Furthermore, the present process exhibits high feedstock adaptability for typical carbohydrates and handy catalyst recovery by a simple self-separation procedure through temperature control.
研究领域:
化学工程
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可再生资源
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绿色化学
✓ 已验证
产品关联
DOI
PubMed
高影响因子
JOURNAL OF CHEMICAL TECHNOLOGY AND BIOTECHNOLOGY
·
2020
·Vol. 95
·期 8
·2251-2260
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IF 2.75
Yanli Xu,Pengkun Guo,Chun Chang,Pan Li,Shiqiang Zhao,Guizhuan Xu
BACKGROUND Methyl levulinate (ML) is a promising green candidate for bio-based diesel fuels and fuel additives. An effective method for synthesizing ML from levulinic acid (LA) catalyzed by cheap metal salt catalyst under mild conditions was developed. A series of metal salts were screened for the synthesis of ML from LA, and aluminum chloride was identified as a suitable catalyst for this process. RESULTS The effects of catalyst loading, the molar ratio of methanol to LA, reaction temperature and reaction time on LA conversion and ML yield were investigated. The response surface method was used to optimize the process, and the model validation experiment showed that the predicted values corresponded well with the actual ones. Under the optimum conditions of reaction temperature 343 K, reaction time 1.5 h, aluminum chloride 1.14 g and molar ratio of methanol to LA 8:1, a high ML yield of 95.0 mol% could be obtained. Moreover, a kinetic model was proposed to evaluate the reaction process at a temperature range of 30–70 °C. The first-order pseudo model was considered most suitable ( R 2 > 0.99), and the activation energy of the reaction E a was estimated to be 32.28 kJ mol −1 . Investigation of the reuse of the catalyst revealed that it retained good catalytic activity after repeated use for ten times. CONCLUSION A green and efficient process of ML production from LA catalyzed by the metal salt aluminum chloride was developed. © 2020 Society of Chemical Industry
研究领域:
化学工程
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可再生资源
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催化化学
✓ 已验证
产品关联
DOI
高影响因子
FUEL
·
2021
·
IF 6.609
Xin Yu,Lincai Peng,Jun Dai,Hui Li,Chaonan Tao,Fa Yang,Junhua Zhang
Conversion of carbohydrates at concentrated feeds represents highly desirable for the industrial deployment of biobased fuels and chemicals but challenging. One key bottleneck is that the excessive formation of polymeric humins greatly diminishes the utilization rate of feedstocks and the destination product yield. We report that the use of ethylene glycol as co-solvent for acid-catalyzed conversion of concentrated sugars enhances desirable alkyl levulinate (AL) production compared to reactions carried out in single monohydric alcohols (e.g., methanol, ethanol). Ethylene glycol served not only as a solubilizer of sugars in the reaction medium to lessen their tendency to polymerize by protecting reactive hydroxyl groups in sugars with alcohols, but also as a supporter to restrain the condensation of furan intermediates. With 10 vol% ethylene glycol as the co-solvent of ethanol, an improved yield of ethyl levulinate (EL) from 45% to 56% was accomplished from concentrated feeds of glucose (200 g/L). In particular, high space time yield and EL concentration respectively up to 30 kg/m 3 ·h and 90 g/L were obtained in a batch reactor. The solvents and catalyst could be isolated from the products, and showed good reusability. This contribution opens a reliable avenue for converting highly concentrated feeds of biomass-related sugars to oxygenated liquid fuels and versatile chemicals.
研究领域:
生物化学
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可再生资源与环境工程
✓ 已验证
产品关联
DOI
高影响因子
MICROPOROUS AND MESOPOROUS MATERIALS
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2021
·
IF 5.455
Jingyu Liu,Chaoyue Zhang,Daiyu Song,Yihang Guo,Jiyan Leng
Brønsted acidic ionic liquid (BAIL) functionalized dendritic fibrous nanosilica sphere catalysts, [C 3 PrIm][SO 3 CF 3 ]-DFNS (C 3 = PrSO 3 H), are prepared via a hexadecylpyridinium bromide reverse micelle-directed co-condensation of tetraethoxysilane and 3-chloropropyltriethoxysilane in a water-in-oil emulsion system followed by successive chemical modification with imidazole , 1,3-propanesultone and trifluoromethane sulfonic acid , and the particle diameter, fiber thickness and fiber density of the catalysts are well-adjusted by changing the composition of the starting materials. The [C 3 PrIm][SO 3 CF 3 ]-DFNS catalysts are successfully applied in transformation of 5-hydroxymethylfurfural (HMF) to ethyl levulinate (EL). Combination of superstrong Brønsted acidity and unique open three-dimensional dendritic fibrous nanostructures , the [C 3 PrIm][SO 3 CF 3 ]-DFNS can transform HMF in ethanol media rapidly and completely; nevertheless, the selectivity to EL remarkably depends on the fiber thickness and fiber density, which affect diffusion and mass transfer of the reactants and products as well as the accessibility to the acid sites. Among the tested [C 3 PrIm][SO 3 CF 3 ]-DFNS catalysts, the [C 3 PrIm][SO 3 CF 3 ]-DFNS- 1 with the thinnest fiber sheet and considerably high fiber density exhibits the highest selectivity to EL (93.0%). The [C 3 PrIm][SO 3 CF 3 ]-DFNS catalysts also show good reusability, and they can be reused at least for five times without obvious changes of the reactivity, total selectivity, morphology, textural properties and chemical structure .
研究领域:
催化
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纳米技术
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有机化学
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材料科学
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绿色化学
✓ 已验证
DOI
高影响因子
ENERGY & FUELS
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2018
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IF 3.024
Jin Tan,Chenguang Wang,Qi Zhang,Longlong Ma,Minghong He
A novel and efficient method for the use of non-edible cassava to synthesize biofuel precursors with long carbon chains in two steps was proposed. The finally produced precursors were based on the decomposition of cassava and condensation between furans and levulinates. The reaction parameters for levulinate production from cassava were optimized, and the results showed that the highest carbon mole yield of levulinates was up to 51.3% at 473 K, 4.0 MPa N2, and 6.0 h. After that, precursors with yields of 88.0 and 90.5% could be obtained when the mole ratios between furans and levulinates were 1:1 and 2:1, respectively. Characterization of precursors using elemental analysis, 13C nuclear magnetic resonance, gel permeation chromatography, and Fourier transform infrared spectroscopy demonstrated that different and intersecting routes of condensation resulted in the complex components of precursors. Moreover, the mechanism of condensation was proven to excessively depend upon the mole ratio between furans and levulinates in this investigation. This technical route indicates a simple and feasible method to produce renewable biofuel with long carbon chains from cassava directly.
研究领域:
生物化学
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可再生能源
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有机合成
✓ 已验证
产品关联
DOI
高影响因子
ChemCatChem
·
2023
·Vol. 15
·期 5
·e202201352
·
IF 4.5
Qingpo Peng,Yongjun Jiang,Bei-Bei Xu,Xiuge Zhao,Sheng Dai,Ye-Feng Yao,Zhenshan Hou
Graphical Zr oxo cluster bifunctional catalyst : The Zr oxo cluster [Zr 6 O 4 (OH) 4 (HSCH 2 CH 2 COO) 12 ] 2 has been developed, and then the molecular catalyst with Lewis acid and Brönsted acid sites were attained by the oxidation of the sulfhydryl group of the Zr oxo cluster with H 2 O 2 . The resulting bifunctional catalyst showed a superior catalytic activity for alcoholysis of furfural to alkyl levulinates. A novel dodecanuclear Zr oxo cluster [Zr 6 O 4 (OH) 4 (HSCH 2 CH 2 COO) 12 ] 2 (ZrO-SH-10) has been constructed under the room temperature, followed by oxidation of the sulfhydryl group with H 2 O 2 to achieve a bifunctional catalyst with Lewis acid and Brönsted acid sites. The characterization of catalysts indicated that {Zr 6 O 4 } cluster core can be stabilized with a shell of carboxylate ligands, and the resulting ZrO-SO 3 H was formed as a discrete molecular catalyst, exhibiting superior activity and recyclability for the cascade conversion of furfural to alkyl levulinate by the integration of transfer hydrogenation and alcoholysis in n-butanol. The yield of n-butyl levulinate can achieve as high as 91 % under the optimum conditions. Meanwhile, no leaching of the active species was found, which confirmed the structure of the Zr oxo cluster was air and moisture-stable. On the basis of the studies on the reaction kinetics and isotope tracking, the reaction mechanism was proposed accordingly.
研究领域:
化学
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催化科学
✓ 已验证
产品关联
DOI
高影响因子
Journal of Cleaner Production
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2020
·
IF 7.246
Lu Tian,Luxin Zhang,Yuting Liu,Yunfei He,Yujie Zhu,Ruijun Sun,Simin Yi,Junping Xiang
A clean and highly efficient catalytic system for the synthesis of ethyl levulinate (EL) from kitchen waste was developed. A heterogeneous catalyst (Sn/ZrP–SO 3 H) was prepared and the Brønsted and Lewis acid sites on the surface of the catalyst were evaluated by pyridine FT-IR. Other physicochemical properties were also characterized using XRD, SEM, FT-IR, XPS , BET, NH 3 -TPD. The yield of EL obtained was 49.27%, when glucose was used as the starting material and subjected to 170 °C for 10 h in the presence of the solid acid catalyst , Sn/ZrP–SO 3 H. The prepared catalyst was also combined with several metal triflates; (Al(OTf) 3 , Fe(OTf) 3 , Sm(OTf) 3 ) to form a catalytic system for the efficient preparation of EL from kitchen waste. Sn/ZrP–SO 3 H/Al(OTf) 3 had superior activity compare to other catalyst combinations. In single factor experiments, the yield of EL reached 52.52% after heating at 170 °C for 4 h. In addition, four-factor and three-level experiments were performed using response surface methodology (RSM) to analyze the interaction between each factor. The optimal reaction conditions predicted by the model (163 °C, 7.63 h, 20 mg Al(OTf) 3 , 40 mg Sn/ZrP–SO 3 H and 79.98 mg of kitchen waste) estimated a maximal yield for EL of 51.24%. The experimental yield of EL however was 52.03% which confirms the reliability of the model. This work provides a cleaner production technology for the synthesis of the high value-added chemical EL, and a sustainable route for the utilization of kitchen waste.
研究领域:
化学工程
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环境科学
✓ 已验证
DOI
高影响因子
APPLIED CATALYSIS A-GENERAL
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2011
·
IF 3.384
Lincai Peng,Lu Lin,Junhua Zhang,Jianbin Shi,Shijie Liu
A series of solid acid catalysts including SO 4 2− /ZrO 2 , SO 4 2− /TiO 2 , SO 4 2− /ZrO 2 –TiO 2 and SO 4 2− /ZrO 2 –Al 2 O 3 were prepared by precipitation and impregnation method for ethyl levulinate production from glucose in ethanol. Effects of various reaction parameters and catalyst reuse cycle towards the reaction performance were studied. Experimental results showed that different components of the sulfated metal oxides had markedly different catalytic effects on the ethanolysis of glucose. SO 4 2− /ZrO 2 –Al 2 O 3 could significantly suppress the formation of ethyl levulinate due to the incorporation of Al 2 O 3 . With SO 4 2− /ZrO 2 as the catalyst, an optimized ethyl levulinate yield of above 30 mol% was obtained at 200 °C for 3 h with catalyst dosage of 2.5 wt%, and the recovered catalyst after calcination was found to remain active with an almost unchanged product yield after being reused five times. The main liquid substances including ethyl levulinate, diethyl ether and ethanol can be easily separated from the resulting product mixture by fractionation and the excess ethanol was recycled. The physicochemical properties of the prepared and thermally regenerated catalysts were characterized using BET surface area, XRD, NH 3 -TPD and XPS techniques.
研究领域:
化学工程
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可再生资源转化
✓ 已验证
DOI
高影响因子
APPLIED ENERGY
·
2011
·
IF 3.915
Lincai Peng,Lu Lin,Hui Li,Qiulin Yang
The catalytic performances of common solid acids (ZSM-5(25), ZSM-5(36), NaY, H-mordenite, Zr 3 (PO 4 ) 4 , SO 4 2 - /ZrO 2 , SO 4 2 - /TiO 2 , and TiO 2 ) for the conversion of carbohydrates such as glucose to methyl levulinate in near-critical methanol were investigated to develop an environmentally benign catalyst with high activity. Among these catalysts employed, sulfated metal oxides (especially SO 4 2 - /TiO 2 ) were found to be a type of potential catalysts for prospective utilization, which showed remarkably high selectivity and yield of methyl levulinate and had negligible undesired dimethyl ether formation from the dehydration of methanol. With SO 4 2 - /TiO 2 as the catalyst, methyl levulinate in ca. 43, 33 and 59 mol% yields could be obtained from sucrose, glucose and fructose, respectively, at 473 K for 2 h reaction time with a catalyst loading of 2.5 wt.%. The heterogeneous catalyst ( SO 4 2 - /TiO 2 ) was easily recovered by filtration and exhibited good catalytic activities after calcination in five cycles of reusing. The surface structure and acidity variations of the fresh and recycled SO 4 2 - /TiO 2 catalysts after calcination were characterized by XRD and NH 3 -TPD techniques. The results indicate that the catalyst crystallization structure was preserved after multiple cycles, the acid amount and acid strength of the catalyst reduced gradually as the increasing of recycling times.
研究领域:
化学工程
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催化科学
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可再生资源转化
✓ 已验证
DOI
高影响因子
Asia-Pacific Journal of Chemical Engineering
·
2024
·Vol. 19
·期 4
·e3076
·
IF 1.4
Haoran Zhao,Yu Jia,Yihang Chen,Xuanyu Liang,Jinbo Hao,Binglin Chen,Chao He,Liang Liu,Chun Chang,Guizhuan Xu
Ethyl levulinate (EL) production from steam-exploded corn straw (SCS) in a cascade of reaction using a Brønsted (B) acid and a Lewis (L) acid in ethanol was studied. The entangled structure of corn straw could be obviously damaged through steam explosion when the pressure was 1.5 MPa holding 10 min. The content of cellulose can be increased from 35.9% to 46.8%, and the contents of hemicellulose and lignin were changed from 16.7% to 8.8% and 22.6% to 27.5%, respectively. EL yield was significantly increased from 10.7 to 24.6 wt% under optimal reaction conditions (L/B = 1/20 [mol/mol], 205°C, 90 min, 1.8 g of SCS, 60 mL of ethanol). According to kinetic models, the activation energies for the main and side reactions were 56.8 and 110.5 kJ mol −1 , respectively. It suggested that SCS was more easily to be converted to EL rather than other by-products. The highest occupied molecular orbital (HOMO)–lowest unoccupied molecular orbital (LUMO) energy gaps (HOMO-LUMO gaps) of cellobiose over the mixed acids in ethanol were significantly reduced with frontier molecular orbital (FMO) theory. This work provides an effective strategy for EL production from agricultural waste straws.
研究领域:
生物化学
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可再生资源与环境科学
✓ 已验证
产品关联
DOI
高影响因子
PROCESS BIOCHEMISTRY
·
2019
·
IF 2.883
Xiaohui Di,Yu Zhang,Junying Fu,Qiang Yu,Zhongming Wang,Zhenhong Yuan
High value-added utilization of biomass-based platform chemicals has attracted increasing attention in recent years. The present study addresses the upgrading of levulinic acid (LA), an important biomass-based platform chemical, to methyl levulinate via a green and efficient enzymatic approach. Various lipases were assessed, with Novozym ® 435 displaying the best results for the esterification of LA. Subsequently, the effect of reaction medium on Novozym ® 435 catalyzed esterification was also studied. Compared with other reaction media, 1-butyl-3-methylimidazolium hexafluorophosphate ([bmim][PF 6 ]) showed the greatest enhancement in yield by suppressing hydrolysis activity. The catalysts reusability was also improved by protection from [bmim][PF 6 ] with 43.2% activity remained after 5 cycles, compared to that of 19.1% in 2-Me THF. Reaction temperature exerted an unusual double-peak relationship over methyl levulinate yield because Novozym ® 435 can simultaneously catalyze the esterification of LA and hydrolysis of methyl levulinate, each of which has a different optimal reaction temperature: ca. 30 °C and ca. 40 °C, respectively. When the molar ratio of LA/methanol, and the volume ratio of methanol/[bmim][PF 6 ] were 1:5 and 1:3, respectively, methyl levulinate was obtained in 93% yield at 30 °C after 24 h with 10 mg/mL catalytic loading.
研究领域:
生物化学
·
绿色化学
✓ 已验证
DOI
高影响因子
危险品化学品经营许可证（带存储）