ACS Sustainable Chemistry & Engineering
·
2020
·
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
·
催化化学
·
绿色化学
✓ 已验证
产品关联
DOI
高影响因子
ENERGY & FUELS
·
2018
·
IF 3.024
Lincai Peng,Xueying Gao,Xin Yu,Hui Li,Junhua Zhang,Liang He
An integrated multistep catalytic process in a one-pot cascade model to realize conversion is preferred in terms of process economics and energy efficiency. Here, we present the noble-metal-free but highly effective catalytic transfer hydrogenation and acid-catalyzed conversion of biomass-derived furfural for direct production of biofuel alkyl levulinate using alcohols as the hydrogen donor and reaction medium. With optimization of the process variables, a high yield of alkyl levulinate at up to 85.3% could be captured under mild conditions in isopropanol medium with the combination of Zr-MCM-41 and Amberlyst-15 catalysts. The reaction proceeds via the catalytic transfer hydrogenation of furfural to furfuryl alcohol over Zr-MCM-41, which is then converted to alkyl levulinate by an Amberlyst-15 acid catalyst. The spent hybrid catalysts could be effectively recovered from the resulting reaction mixture and reused 5 times with little deactivation after plain regeneration treatment.
研究领域:
化学工程
·
可再生资源与环境科学
✓ 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
Biomass Conversion and Biorefinery
·
2022
·
IF 4.05
Zhou Shuolin,Long Min,Wu Lu,Lei Min,Bai JunZhuo,Huang Keying,Liu XianXiang,Yin Dulin
Covalently bonded sulfamic acid on the titanate nanotubes (TNTs-N(SO 3 H)-(CH 2 ) 2 -NHSO 3 H) was designed and successfully fabricated by the post-synthesis modification method. The as-prepared catalyst was characterized by a variety of characterization techniques such as FT-IR, TEM, XRD, XPS, and TG-DTG. The catalytic activity of TNTs-N(SO 3 H)-(CH 2 ) 2 -NHSO 3 H was evaluated for the synthesis of n-butyl levulinate (BL) from levulinic acid (LA). It was found that the tube-like structure of the TNTs still maintained during the modification process, and Brønsted and Lewis acid sites can be efficiently immobilized on the TNTs. The effects of reaction factors such as reaction time, reaction temperature, and catalyst dosage on the esterification of LA were systematically studied. Under the optimal reaction conditions, a relatively high yield of BL (95.3%) was achieved for esterification of levulinic acid owing to the strong Brønsted acidic sites. Furthermore, the hybrid catalyst TNTs-N(SO 3 H)-(CH 2 ) 2 -NHSO 3 H was used at least five times without significant decrease in activity, and no leaching of the active species in hot filtration test was observed. Graphical abstract
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
ACS Sustainable Chemistry & Engineering
·
2022
·
IF 9.224
Yafei Li,Shiqing Wang,Shunxin Fan,Babar Ali,Xiaocheng Lan,Tiefeng Wang
For the ethanolysis of biomass-derived furfuryl alcohol (FA) to value-added ethyl levulinate (EL), the development of an efficient solid acid catalyst is very important for industrial application with high FA concentration. Herein, a H-ZSM-5 catalyst with nano b-axis channels (NB-H-ZSM-5) was synthesized and used for the conversion of FA. Detailed catalyst characterization proved that the NB-H-ZSM-5 catalysts (Si/Al = 25∼125) with ∼70 nm b-axis channels were successfully prepared. The NB-H-ZSM-5 catalyst with Si/Al = 75 showed the highest activity. Its structural characteristics allowed for fast diffusion of reactants and products and full utilization of active sites, which endowed it with higher activity compared to commercial H-ZSM-5 (C-H-ZSM-5). Its moderate acidity effectively inhibited the polymerization of FA even at a high FA concentration of 20 wt %. The spent catalyst was easily regenerated by coke burn-off to give a good recyclability. Furthermore, based on the proposed reaction network, a method of physically mixing the NB-H-ZSM-5 (75) catalyst with a small amount of Amberlyst-15 was proposed to further increase the EL yield from 64.7 to 82.1% at an FA concentration of 6 wt %.
研究领域:
催化化学
·
可再生资源化学
·
材料科学
✓ 已验证
DOI
高影响因子
RENEWABLE ENERGY
·
2022
·
IF 8.634
Yue Wang,Huai Liu,Junhua Zhang,Yuan Cheng,Wansi Lin,Rulu Huang,Lincai Peng
The development of efficient and reusable catalysts to improve the catalytic transfer hydrogenation (CTH) of biomass-derived platform molecules into high value-added chemicals is always desired. For this purpose, the magnetic Fe 3 O 4 @Zr-FDCA hybrid with Lewis acid and Lewis base sites was first designed by simple assembly of biomass derived 2,5-furandicarboxylic acid (FDCA) with zirconium and grown directly on the surface of carboxylated Fe 3 O 4 . The resulting Fe 3 O 4 @Zr-FDCA exhibited a unique core-shell structure with high specific surface area and proper acid/basic strength, it performed well in CTH reaction of diverse carbonyl compounds, especially for the conversion of ethyl levulinate to γ-valerolactone with the yield of 94.5% at 180 °C for 5 h. Furthermore, the good magnetic responsibility of Fe 3 O 4 @Zr-FDCA made it could be easily separated from the reaction mixture by an external magnet, and displayed a good reusability with no significant loss in the activity after reuse for five runs.
研究领域:
化学工程
·
材料科学
✓ 已验证
DOI
高影响因子
CHEMISTRY-A EUROPEAN JOURNAL
·
2021
·Vol. 27
·期 49
·12659-12666
·
IF 5.236
Mingwei Ma,Na Liang,Pan Hou,Peng Zhang,Jingjie Cao,Hui Liu,Xingliang Xu,Huijuan Yue,Ge Tian,Shouhua Feng
Graphical The by-product (called humins) is accompanied by a one-pot catalytic conversion reaction of furfural (FAL) to isopropyl levulinate (PL), which is carbonized (Humins-700) and applied to a new experiment of electromagnetic wave absorption, showing superior electromagnetic wave absorption performance. The minimum reflection loss (RLmin) value is −47.3 dB at 13.0 GHz with a thickness of 2.0 mm. This provides inspiration that humins can be applied to electromagnetic wave absorption. Both one-pot catalytic conversion of furfural (FAL) to isopropyl levulinate (PL) and carbonization of by-product (humins) for electromagnetic wave absorption are discussed, which provides inspiration that humins can be applied to electromagnetic wave absorption. In the former, phosphotungstic acid (PW) is employed as a homogeneous catalyst to convert FAL to PL via a tandem reaction in one pot, with the formation of a vast amount of humins. With FAL and various intermediates as substrates, it was found that humins was a polymerization product of FAL, furfuryl alcohol (FOL) and furfuryl ester (FE) with furan rings. In addition, the in situ attenuated total reflection infrared (ATR-IR) spectra also provided a basis for the proposed reaction route. In the latter, with the humins as raw material, P species and WO 3 doped nano-porous carbon (Humins-700) platform formed after high-temperature annealing is used for electromagnetic wave absorption and manifests desirable absorption performance. The minimum reflection loss (RL min ) value is −47.3 dB at 13.0 GHz with a thickness of 2.0 mm and the effective absorption bandwidth reaches 4.5 GHz (11.2–5.7 GHz).
研究领域:
化学工程
·
材料科学
✓ 已验证
产品关联
DOI
PubMed
高影响因子
Molecular Catalysis
·
2017
·
IF 0
Ruiying Wang,Jianjia Wang,Huimin Zi,Yongmei Xia,Haijun Wang,Xiang Liu
Zr(IV)-salphen-MCM-41 was prepared by immobilizing a zirconium(IV) Schiff base complex onto the surface of MCM-41. The structural properties of the heterogeneous catalysts were characterized by FT-IR, UV, TG, XRD, SEM, TEM, BET, EDX, CO 2 -TPD, NH 3 -TPD and ICP-OES. Studies on the catalytic properties of the immobilized Zr(IV)-Schiff base complexes were performed using the reduction and cyclization of ethyl levulinate (EL) to γ-valerolactone (GVL) with isopropanol as the hydrogen source. Various reaction parameters, such as temperature, reaction time, solvent and catalyst loading were carefully investigated. The optimal conditions (GVL yield up to 90%) involved the utilization of Zr(Salphen)-MCM-41 as the catalyst in isopropanol. The key to heightened reaction performance was the incorporation of the phenolate and aniline groups in the ligands of bound to Zr. This increased the basicity of the catalyst, which subsequently enhances the efficiency of the transfer hydrogenation reported herein. Meanwhile, the immobilized catalyst can be easily separated and efficiently recycled at least five times without significant loss of activity. Finally, we proposed a plausible reaction mechanism based on experimental and characterization data.
研究领域:
化学工程
·
催化材料科学
✓ 已验证
产品关联
DOI
FUEL
·
2016
·
IF 3.611
Zhenhuan Xiao,Huacong Zhou,Jianmin Hao,Hailong Hong,Yinmin Song,Runxia He,Keduan Zhi,Quansheng Liu
As the fast depletion of coal resources, exploring the value-added utilization approaches of low rank coals or their components and, in parallel, promoting the conversion of sustainable resources (such as biomass) into useful chemicals are critical issues facing human society. In this work, we used humic acids (HAs), an abundant material in nature (mainly derived from low rank coals), and the transition metal zirconium (Zr) to prepare a novel Zr-containing hydrogen transfer catalyst. The prepared catalyst was applied into the conversion of biomass-derived ethyl levulinate (EL) into gamma-valerolactone (GVL) via hydrogen transfer reaction. Both the preparation conditions of the catalysts and the reaction parameters during the conversion of EL into GVL were systematically investigated. The catalyst was characterized by SEM, TEM, FTIR, powder XRD, and TG analysis. The results demonstrated that the as-prepared catalyst was highly efficient for the conversion of EL into GVL. Under optimized conditions, EL could be completely converted and the GVL yield could reach up to 88.3%. The catalyst could be used at least 11 times without notable changes in both activity and structures, indicating an excellent stability. As far as we know, this is the first work using HAs to prepare Zr-containing catalyst and its application to the conversion of EL into GVL in biomass utilization.
研究领域:
化学工程
·
可再生能源
·
催化化学
✓ 已验证
产品关联
DOI
高影响因子
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
BIORESOURCE TECHNOLOGY
·
2022
·
IF 11.889
Luxin Zhang,Xu Xing,Yuting Liu,Weiwei Shi,Mingzhe Wang
To add value to ordinary kitchen waste, heterogeneous acid-base catalytic methanolysis was conducted to produce high-value liquid biofuels, methyl levulinate (ML) and fatty acid methyl esters (FAMEs). Yields of 53.3 % ML and 98.5 % FAME were achieved by methanolysis of kitchen waste under the co-catalysis of carbon–silica composite (C/Si-SO 3 H) and zirconium modified ultrastable Y zeolite (Zr/USY). These target products can be easily recovered from the methanolic phase and can be purified at the end of the reaction. The collaborative combination of C/Si-SO 3 H and Zr/USY exhibited higher activity than their commercial counterpart. This strategy can be applied to differently composed kitchen waste and kitchen waste with different water content. Product yields were predicted using an artificial neural network method, and the relative importance of the influencing factors was investigated by the random forest method. The systematic insight gained from this work supports the value-added utilization of kitchen waste.
研究领域:
生物能源
·
催化化学
·
机器学习应用
✓ 已验证
产品关联
DOI
PubMed
高影响因子
INTERNATIONAL JOURNAL OF BIOLOGICAL MACROMOLECULES
·
2024
·
IF 7.7
Mingqiang Chen,Longyang Li,Yishuang Wang,Defang Liang,Zinan Zhou,Haosheng Xin,Chang Li,Gang Yuan,Jun Wang
Converting cellulose (Cel) into ethyl levulinate (EL) is one of the promising strategies for supplying liquid fuels. In this paper, the prepared sulfonated P-W-modified N-containing carbon-based solid acid catalyst (PWNCS), in which the Polyaniline (PANI) was employed as N and C precursors, successfully converted Cel into EL under the water-ethanol medium. The characterization results demonstrated that a tiny addition of P increased the Brønsted acid sites (BAS) content and defective WO 3 provided the Lewis acid sites (LAS), meanwhile, the sulfonation process did not change the fundamental structure but introduced the sulfonic groups to dramatically increase the acidic content. Therefore, under optimized reaction conditions, PWNCS realized about 100% Cel conversion and 71.61% of EL yield, furthermore, the selectivity of EL reached 89.14%. In addition, the effect of water on the reaction pathway of Cel to EL over PWNCS was proposed. The addition of water generally resulted in the hydration of defective WO 3 to reduce the LAS and increase BAS, which significantly inhibited the side reactions of retro-aldol condensation (RAC) and subsequent etherification reactions during Cel conversion and then improved the selectivity of EL.
研究领域:
催化
·
化学工程
·
可再生能源
·
生物化学
✓ 已验证
DOI
PubMed
高影响因子
危险品化学品经营许可证（带存储）