Catalysts
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2015
·Vol. 5
·期 4
·1897-1910
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IF 2
Shiqiang Zhao,Guizhuan Xu,Chun Chang,Shuqi Fang,Ze Liu,Fengguang Du
A series of metal-modified phosphotungstates were prepared and performed for direct synthesis of ethyl levulinate from fructose in ethanol. Considering the cost of catalysts, catalytic activity of catalysts, and easy separation of catalysts together, K-HPW-1 was chosen as the most suitable catalyst for synthesis of ethyl levulinate from fructose. A high ethyl levulinate yield of 64.6 mol% was obtained at 150 °C within 2 h in ethanol. The introduction of low polar toluene as a co-solvent improved the yield of ethyl levulinate to 68.7 mol%. The recovered catalyst remained high activity with the yield of ethyl levulinate converted from fructose above 50 mol% after being used five times. Moreover, the generality of the catalyst was further demonstrated by glucose, sucrose, inulin, and cellulose with ethyl levulinate yielding 14.5, 35.4, 52.3, and 14.8 mol%, respectively.Keywords:ethyl levulinate;carbohydrates;potassium phosphotungstate
研究领域:
催化化学
·
可再生化学
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产品关联
DOI
高影响因子
Journal of Cleaner Production
·
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
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DOI
高影响因子
ACS Sustainable Chemistry & Engineering
·
2025
·
IF 7.3
Zilong Rao,Yu Zhang,Shuailong Zhao,Huai Liu,Rui Zhang,Wenlong Jia,Junhua Zhang,Yong Sun,Lincai Peng
Ethyl levulinate (EL) is a crucial biomass-derived compound with diverse applications in pesticides, rubber, pharmaceuticals, and fuel. The efficient conversion of straw into EL presents significant challenges, primarily due to the interference of inorganic components (IOCs). In this study, we aim to enhance the alcoholysis of straw by identifying the specific inhibitory factors and mechanisms of IOCs. A case study on rice straw as a reactant in ethanol over Al(OTf)3 revealed that K+ is a critical inhibitory factor impeding the hydrolysis of cellulose into glucose. Specifically, K+ is adsorbed on O of S–O–Al in [Al(EtOH)m](OTf)3, thus inhibiting the release of H+ and the cleavage of the glycosidic bond. Further, simulating computation reveals that K+ exhibits stronger electrophilicity than H of O–H in [Al(EtOH)m](OTf)3, thus inhibiting the cleavage of H from O–H in ethanol. Consequently, a simple, green acetic acid pretreatment strategy has been developed to enhance the alcoholysis of straw by efficiently eliminating K+, resulting in an EL yield of more than 10 times that of the pristine straw. In conclusion, this study improves the alcoholysis activity of straw and provides novel insights and potential strategies for biorefinery.
研究领域:
生物化学
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生物质能
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DOI
高影响因子
JOURNAL OF CHEMICAL TECHNOLOGY AND BIOTECHNOLOGY
·
2019
·Vol. 94
·期 10
·3093-3101
·
IF 2.659
Jiaming Wu,Yuewen Shao,Guojian Jing,Zhanming Zhang,Zhengmao Ye,Xun Hu
Background Graphene oxide (GO) has abundant oxygen-containing functionalities such as hydroxyl groups and carboxyl groups with distinct acidities. This feature makes GO a potential solid acid catalyst for the acid-catalyzed reactions such as the production of ethyl levulinate (EL), a platform chemical, from the acid-treatment of furfuryl alcohol (FA). The structure and functionalities of GO are closely related to its catalytic performance, and thus it is necessary to establish the relationship between the chemical structure and the catalytic properties of GO. To achieve this aim, in this work, the GO catalysts were designed by a facile one-pot synthetic route with no subsequent modification. By controlling the parameters of oxidation process in preparation, multiple functional groups were immobilized onto graphitic substrate, significantly impacting the catalytic activity of GO in the conversion of FA to EL in an ethanol (EtOH) medium. Results The results showed that, the oxidation process significantly influenced the distribution of oxygen-containing functionalities on the surface of GO. The amount of the oxygen-containing functionalities can be adjusted by the oxidation parameters such as oxidizing agent equivalent, reaction time and temperature, while the organosulfate can only be remained at a moderate oxidation temperature. The existence of the synergistic effect between the oxygen-containing functionalities and the organosulfate functionalities promoted the catalytic activity of GO for the acid-catalyzed conversion of FA to EL. Conclusions This work provides a new strategy of design and development of functional graphene-based catalysts for the acid-catalyzed reactions, and lays foundation of the practicability of GO in biomass conversion. © 2019 Society of Chemical Industry
研究领域:
化学工程
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催化科学
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材料科学
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产品关联
DOI
高影响因子
ACS Omega
·
2019
·
IF 2.584
Xiaofang Liu,Hu Pan,Heng Zhang,Hu Li,Song Yang
Enlarging the dispersed micropores of metal-organic frameworks to the well-ordered mesostructure can enhance the accessibility of acidic sites for reactants resulting in the improvement of selectivity. With the regulation of cetyltrimethylammonium bromide/Cr3+ and ClSO3H sulfonation, a series of mesoporous MIL-101(Cr)-SO3H (MMSs) with multiple pore sizes and acidic properties were synthesized and explored to further facilitate the furfuryl alcohol (FA) ethanolization to ethyl levulinate (EL) for the first time. The optimal catalytic activity of 83.8% EL yield at full FA conversion demonstrated that the appropriate mesopore size, acidic density, and accessible −SO3H sites contributed to the superior performance of the MMS(0.3)-0.15. The turnover frequency value (14.8 h–1) obtained with MMS(0.3)-0.15 was comparable to the commercial Nafion NR50 (18.3 h–1) and much higher than the classical Amberlyst-15 (1.9 h–1), confirming the predominant catalytic performance. Furthermore, two coexistent reaction paths with 2-ethoxymethylfuran and 4,5,5-triethoxy-pentan-2-one as intermediates indicated the possibility of producing EL from FA.
研究领域:
化学工程
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材料科学
✓ 已验证
DOI
高影响因子
FUEL PROCESSING TECHNOLOGY
·
2020
·
IF 4.982
Chaonan Tao,Lincai Peng,Junhua Zhang,Liang He
Efficient production of fuels and chemicals from lignocellulosic biomass is the main goal of biorefinery processes. Herein, the metal-modified heteropolyacids with tunable Lewis and Brønsted acid sites were designed as the monolithic multifunctional catalyst for valorizing cellulose and lignocellulosic biomass to alkyl levulinate, a versatile platform molecule. Among them, Al-exchanged two protons of H 4 SiW 12 O 40 (Al 2/3 H 2 SiW 12 O 40 ) was found to be uniquely effective. The kinetic behavior describing the conversion of cellulose to ethyl levulinate was investigated to monitor the process, and compared between parent H 4 SiW 12 O 40 and Al 2/3 H 2 SiW 12 O 40 to understand the mechanistic role of Al 3+ . The introduction of Al 3+ substantially facilitated cellulose depolymerization and glucose-to-fructose isomerization , leading to a high rate and product selectivity. The estimated activation energies for cellulose degradation and glucopyraoside alcoholysis decreased by 50.6 kJ/mol and 40.9 kJ/mol, respectively. 50–72% yields of ethyl levulinate were accomplished from cellulosic biomasses such as pine wood, eucalyptus, bamboo, bagasse and Napier grass. Al 2/3 H 2 SiW 12 O 40 allowed cellulose conversion in various linear alcohols producing high-yield alkyl levulinate, and could be reused multiple times with a good stability. This study opens a reliable and promising avenue for one-pot transformation of cellulose and raw lignocellulosic biomass to ester compounds.
研究领域:
生物化学
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可再生资源工程
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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
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可再生资源化学
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材料科学
✓ 已验证
DOI
高影响因子
FUEL
·
2023
·
IF 7.4
Honghui Gong,Juan Zhang,Qi Li,Longxing Wei,Ya Hu,Yifan Rui,Xian-Lei Shi
A series of sulfonic acid functionalized coffee biochar (SFCB-x) with high acid density and strength were prepared by using sulfuric acid as the sulfating agent. The obtained catalysts could be directly used for esterification of levulinic acid (LA) and alcoholysis of furfural alcohol (FA) affording ethyl levulinate (EL). Further activity tests and characterization confirmed the linear correlation between the catalytic activity and -SO 3 H density of the catalyst, SFCB-4 holds the highest -SO 3 H density and thus exhibits the highest catalytic activity towards the production of EL. Under mild conditions, about 97.6% and 81.7% yield of EL could be obtained for LA esterification and alcoholysis of FA, respectively. The catalyst also shows high stability during consecutive catalytic recycles. Furthermore, hot filtration testing suggested that the leaching of the active species was not observed during catalytic recycles, which could be attributed to the covalently linked -SO 3 H groups on SFCB-4 skeleton. The rational design and construction of SFCB-4 will drive the development of solid acid catalyst derived from natural biomass for the production of bio-based chemicals.
研究领域:
化学工程
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生物质能
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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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2021
·
IF 9.297
Fengjiao Lai,Feng Yan,Pengju Wang,Fan Qu,Xuehua Shen,Zuotai Zhang
Efficient conversion of biomass-derived carbohydrates to alkyl levulinates is an important goal of biorefinery process, but is still challenging on applicable catalyst. Ce–Si pillared montmorillonite (CeSiM) clay heterostructures , incorporated with Wells-Dawson tungstophosphoric acid (H 6 P 2 W 18 O 64 , DPW), were prepared for the first time and used as the multifunctional catalyst for direct production of ethyl levulinate (EL) from various biomass-derived sugars. The DPW introduced by sol-gel method (DPW-CeSiM) has been effectively incorporated into the framework of porous CeSiM, while part of DPW was just absorbed on the surface of CeSiM by impregnation method (DPW-CeSiM-I). The DPW-CeSiM catalyst has large specific surface area owing to the insertion of Ce–Si pillars, and possesses strong Brønsted acidity and moderate Lewis acidity originated from the incorporated DPW and the Ce-doping, respectively. Due to the well synergistic effect of porous structure and dual acid, the DPW-CeSiM catalyst efficiently catalyzed the conversion of glucose into EL with 56.2% yield and nearly 100% conversion at 170 °C for 4 h. The recyclability studies certified that DPW-CeSiM catalyst showed higher stability than DPW-CeSiM-I over cycles and could be easily recovered from consecutive alcoholysis of biomass-derived sugars. The DPW-CeSiM catalyst also displayed high activity toward the conversion of other biomass-derived carbohydrates (fructose, sucrose, cellobiose and cellulose) into EL. Therefore, this work provides an instructive strategy for the design of efficient and stable DPW-based catalysts with dual acid sites uniformly distributed over the porous structure, which is obviously potential for industrial production of alkyl levulinates from carbohydrates and biomass.
研究领域:
化学工程
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生物质能
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催化化学
✓ 已验证
产品关联
DOI
高影响因子
NEW JOURNAL OF CHEMISTRY
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2021
·Vol. 45
·期 12
·5526-5539
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IF 3.591
Zhi Zhang,Zhihang Huang,Hong Yuan
KCC-1/Al–SO3H solid acids with different Si/Al molar ratios were prepared by sulphonic acid functionalisation using fibrous nanoporous silica particles (KCC-1/Al) as carriers. Field emission scanning electron and transmission electron microscopy measurements revealed that the sulphonation did not change the spherical morphology and fibrous structure of KCC-1/Al. The Brunauer–Emmett–Teller (BET) analysis indicated that the BET surface area of KCC-1/Al–SO3H could reach 293–372 m2 g−1, while the average pore size was 7.31–7.43 nm. In addition, pyridine adsorption infrared profiles showed that KCC-1/Al–SO3H contained abundant Lewis–Brønsted acid sites, while based on ammonia temperature-programmed desorption characterisation, a total ammonia desorption quantity of 91 cm3 g−1 could be achieved using a Si/Al molar ratio equal to 5. The efficiency of the prepared KCC-1/Al–SO3H was examined in the synthesis of ethyl levulinate (EL) from cellulose in a mixture of ethanol and toluene. Among them, 5KCC-1/Al–SO3H exhibited superior performance, affording EL in 28.8 mol% yield under the optimal reaction conditions (200 °C, 6 h). Furthermore, a mechanism demonstrating the synergistic effect of the Lewis–Brønsted acid sites was proposed based on the reaction activity of different biomass sugars at the acidic sites.
研究领域:
化学工程
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催化材料科学
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产品关联
DOI
高影响因子
Molecular Catalysis
·
2023
·
IF 4.6
Xiaoqing Gao,Shanhui Zhu,Hongyan Zheng,Feng Wang,Wanjun Li,Huifang Wang,Yulan Niu
In order to relieve greenhouse effect, it is highly urgent to convert carbon-neutral biomass to value-added chemicals and liquid fuels by designing new process. 96.5% yield of biofuel alkyl levulinate was achieved in the alcoholysis of furfuryl alcohol with ethanol over highly active Ag + exchanged H 3 PW 12 O 40 (AgPW) catalyst at low temperature. In situ XRD, 31 P MAS NMR, XPS and NH 3 -TPD results confirm that AgPW contains large amounts of strong acid sites and stable Keggin structure, resulting in the excellent performance. Subsequently, new process was developed to synthesize biofuel 2-methyl-1,3-dioxolanes (MDL) with ∼70% yields via a tandem furfuryl alcohol alcoholysis and acetalization reaction over AgPW. Additionally, MDL can be availably obtained from furfural, xylose and hemicellulose by an integrated multi-step process.
研究领域:
化学工程
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可再生能源
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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）