JOURNAL OF CHEMICAL TECHNOLOGY AND BIOTECHNOLOGY
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2018
·Vol. 94
·期 1
·167-177
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IF 2.587
Xuejuan Cao,Junnan Wei,Huai Liu,Xinyue Lv,Xing Tang,Xianhai Zeng,Yong Sun,Tingzhou Lei,Shijie Liu,Lu Lin
BACKGROUND γ-Valerolactone (GVL) is a versatile biomass-derived platform molecule that could serve as a building block to produce chemicals, materials and fuels, but the production of GVL from biomass via a cost-competitive method is challenging. In this contribution, a robust Cu─Mg oxide was prepared as an efficient bifunctional catalyst for both H 2 production by MeOH reforming and hydrogenation of methyl levulinate (ML) to GVL in MeOH medium. RESULTS Cu 0.87 Mg 0.13 O x prepared by a urea hydrolysis method offered a GVL yield up to 90.6% at 220°C in 4 h without external hydrogen. This catalyst could be reused for at least seven consecutive cycles without loss of its activity. Notably, Cu 0.87 Mg 0.13 O x also provided nearly 70% GVL yield in methanolysis products of cellulose in the presence of humins. Characterization of the catalyst indicates that the incorporation of MgO greatly facilitates the stabilization of Cu + species that possess a better catalytic performance in ML hydrogenation compared with metallic Cu. CONCLUSION This robust Cu 0.87 Mg 0.13 O x could greatly contribute to develop a highly facile and desirable two-step strategy for GVL production from cellulose, through the integration of ML production by methanolysis of cellulose, H 2 formation by MeOH reforming and ML hydrogenation in MeOH medium. © 2018 Society of Chemical Industry
研究领域:
化学工程
·
可再生资源化学
✓ 已验证
产品关联
DOI
高影响因子
RENEWABLE ENERGY
·
2019
·
IF 5.439
Jian He,Hu Li,Yufei Xu,Song Yang
γ-Valerolactone (GVL) is an interesting bio-based platform molecule that is utilized as green solvent and a versatile building block for the synthesis of bio-fuels and chemicals. Herein, an investigation on the efficient production of GVL from biomass-based carbonyl compounds such as furfural, levulinic acid, and its esters using 2-propanol as H-donor and solvent over stable Zr-incorporated mesoporous silica (KIT-5) catalysts was presented. Both Lewis and Brønsted acid sites were generated by the introduction of Zr into KIT-5, and the acid density of the resulting Zr-KIT-5(Si/Zr) could be controlled by simply adjusting Si/Zr molar ratio . Among these bifunctional catalysts , Zr-KIT-5(10) showed superior catalytic performance in the production of GVL (>91% selectivity) from biomass-derived carboxides (ca. 94% conversion), which was demonstrated to positively correlate with its large amount of acidic sites and facile access of active sites to interconnected pores. Moreover, the spent catalyst held about 90% of its original activity in the sixth run. Due to the presence of Brønsted and Lewis dual acidic sites in Zr-KIT-5, the direct conversion of furfural to GVL was also permitted in a single pot via tandem reactions involving hydrogenation, ring-opening, secondary hydrogenation, and subsequent cyclization.
研究领域:
催化化学
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生物质能
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绿色化学
✓ 已验证
产品关联
DOI
高影响因子
APPLIED CATALYSIS B-ENVIRONMENTAL
·
2019
·
IF 14.229
Xiaoqing Gao,Shanhui Zhu,Mei Dong,Jianguo Wang,Weibin Fan
Highly efficient synthesis of valuable γ-valerolactone (GVL) by levulinic acid (LA) hydrogenation is still a challenge for Ru-based catalysts under mild condition. In this work, we have reported that ultrathin TiO 2 nanosheets supported Ru nanoparticles showed extraordinarily high catalytic activity, GVL yield (99.1%) and reusability owing to the formation of Ru O Ti interfacial structure. The turnover frequency (TOF) reached as high as 19,045 h −1 at 100 °C, much higher than those of Ru/SiO 2 , Ru/GO, Ru/MoS 2 , and commercial Ru/C. DFT calculation elucidates that the dominant reaction pathway of LA hydrogenation to GVL is preferentially hydrogenated to CH 3 CHOCH 2 CH 2 COOH*, followed by cyclization to CH 3 (OH)C 4 OH 4 OH* (GVL − OH) and final dehydroxylation, irrespective of surface structure. Compared to Ru (0 0 2) facet, Ru/TiO 2 interfacial structure changes the rate-determining step from initial hydrogenation to cyclization, which greatly declines the activation barrier from 0.81 eV to 0.48 eV.
研究领域:
化学工程
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材料科学
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催化反应
✓ 已验证
产品关联
DOI
高影响因子
Biomass Conversion and Biorefinery
·
2020
·Vol. 11
·期 5
·1931-1941
·
IF 2.602
Tian Xiatian,Qi Benkun,Zhang Shaofeng,Luo Jianquan,Wan Yinhua
5-Hydroxymethylfurfural (HMF) is a promising platform chemical for production of value-added chemicals and fuels. Conversion of abundantly available and cheap sucrose for HMF synthesis was systematically investigated in the present study. Results showed that Lewis acid AlCl 3 is effective in catalytic transformation of sucrose. Combining AlCl 3 with different Brønsted acids, no matter whether they were inorganic acids (HCl, H 2 SO 4 , and H 3 PO 4 ) or organic acids (malic acid, succinic acid, and oxalic acid), or variation of ratio of Lewis acid/Brønsted acid represented by AlCl 3 /HCl, did not change the obtained maximum HMF yields compared with AlCl 3 alone, but shortened the time required to reach the maximum HMF yield. Sucrose conversion in a green reaction media of aqueous γ-valerolactone (GVL) solvent resulted into comparable HMF yields with dimethyl sulfoxide (DSMO)-water system. Addition of monovalent salt NaCl and divalent salt Na 2 SO 4 produced opposite effect with Cl − promoting while SO 4 2− inhibiting HMF production. Furthermore, HMF synthesis from constituent monosaccharides of sucrose and molasses, a by-product from sugar manufacturing process, was also carried out and it was found that an equivmole mixture of glucose and fructose gave rise to almost identical HMF yield to the same mole of sucrose. Molasses, even after chemical pretreatment for removal of certain amount of inorganic salts and color substances, was significantly inferior to synthetic molasses in terms of HMF formation, indicating the complexity and difficulty in chemical valorization of molasses for production of platform molecules.
研究领域:
化学工程
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绿色化学
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生物化学工程
✓ 已验证
产品关联
DOI
高影响因子
Molecular Catalysis
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2021
·
IF 5.062
Haijun Guo,Shuai Ding,Hairong Zhang,Can Wang,Fen Peng,Lian Xiong,Xinde Chen,Xinping Ouyang
The acid-activated Palygorskite (H + -PAL) was applied to support Cu(M)NiCoB amorphous alloy catalysts with high-activity and self-regeneration ability for selective hydrogenation of butyl levulinate (BL) to γ-valerolactone (GVL). The catalysts were characterized by ICP-OES, nitrogen physisorption, XRD, FE-SEM, TEM, XPS, H 2 -TPD, NH 3 -TPD and FTIR-pyridine adsorption techniques. Compared to the unsupported Cu 0.5 Ni 1 Co 1 B catalyst, the Cu 0.5 Ni 1 Co 1 B/H + -PAL catalyst showed the highest GVL yield of 96.3 % with BL conversion of 99.7 % at 200 °C. When Mo was doped into the Cu 0.5 Ni 1 Co 1 B/H + -PAL catalyst, the GVL yield showed gradually increase to 95.7 % with BL conversion of 100 % after five times run. The high activity and self-regeneration ability was attributed to the Mo doping effect and the synthetic effect between Cu hydrogenation active species and H + -PAL support. Various characterization results indicated that Mo acted as both structural promoter to improve the dispersion of metallic Cu and CuMoNiCoB amorphous alloy and electronic promoter to enhance the formation and increase the fraction of Cu + species. In addition, the incorporation of Mo provided more Lewis acid sites to promote BL conversion to GVL and GVL conversion to 1,4-PDO and n-PeOH. On the basis of characterization and catalytic performance testing results, the synergistic effect between CuMoNiCoB amorphous alloy and Cu 2 O/Cu hydrogenation sites and Lewis/Brønsted acid site of H + -PAL support is considered to be the key to produce GVL.
研究领域:
化学工程
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催化
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材料科学
✓ 已验证
产品关联
DOI
高影响因子
FUEL
·
2017
·
IF 4.601
Chuang Li,Guangyue Xu,Yongxiang Zhai,Xiaohao Liu,Yanfu Ma,Ying Zhang
Gamma-valerolactone (GVL) has been identified as a sustainable high-value platform molecular for the production of fuels and carbon-based chemicals. In this work, a series of activated carbon supported low-cost bimetallic Ni-Fe catalysts (Ni-Fe/AC) with different molar content of Fe species were prepared by using co-precipitation method for the liquid phase hydrogenation of ethyl levulinate (EL) to produce γ-valerolactone. The Ni-Fe 0.5 /AC exhibited the highest activity among the bimetallic or monometallic catalysts under mild reaction conditions (100 °C, 4 MPa H 2 , 6 h) and achieved 99.3% conversion of EL and 99.0% yield of GVL. Under more mild conditions (60 °C, 2 MPa H 2 ) and prolonging the reaction time to 24 h, EL could be converted completely and the obtained GVL yield was more than 98%. The catalysts were characterized by various techniques including XRD, TEM, HRTEM, EDX, XPS, H 2 -TPR and NH 3 -TPD. Based on the structure and activity relationship study, the formation of highly dispersed Ni-Fe alloy structure and the co-presented FeO x nanoparticles could be responsible for the high catalytic hydrogenation activity.
研究领域:
催化化学
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可再生资源化学
✓ 已验证
产品关联
DOI
高影响因子
Reaction Chemistry & Engineering
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2021
·Vol. 6
·期 10
·1811-1818
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IF 4.239
Hongxing Wang,Guoqiang Ding,Yubo Liu,Junbo Zhang,Yongwang Li,Yulei Zhu
A sustainable and cost-competitive catalytic process for high yield production of levulinic acid (LA) and γ-valerolactone (GVL) from biomass-derived furfuryl alcohol (FOL) fluid was proposed with GVL as a self-circulation solvent. The innovative process eliminated the separation of the final product GVL and intermediate product LA from the solvent, and the actual concentration of FOL was improved enormously. A higher yield (90.5%) of LA was realized in the fixed-bed reactors than that in the conventional autoclave since the short residence time of the FOL solution could alleviate the polymerization of FOL in the continuous process. UV-Raman spectroscopy demonstrated that fewer polymers deposited on the catalysts, so superior stability of the zeolite was observed in the fixed-bed reactors. Moreover, an 89.4% high yield of GVL can be achieved since the integration of the tandem reaction of hydration and hydrogenation could substantially avoid side reactions in the fixed-bed reactors.
研究领域:
化学工程
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可再生能源
✓ 已验证
产品关联
DOI
高影响因子
FUEL
·
2023
·
IF 7.4
Zhongdi Liu,Rui Zhang,Huai Liu,Junhua Zhang,Yong Sun,Naya Li,Lincai Peng
Developing efficient and stable solid functional materials for the catalytic upgrading of biomass-based platform furanic molecules is of great significance to produce value-added chemicals and biofuels. We herein report β-zeolite (β)/biobased carbon hybrids supported Zr species towards the cascade conversion of furfural into γ-valerolactone (GVL) with high activity and favorable stability. The role and importance of carbon modifier were highlighted. The cellulose (CEL) modified Zr/β-CEL catalyst was found to be uniquely effective, leading to an increase of GVL yield from 49.3% to 81.1%. Catalyst characterizations revealed that the structural integrity of β was largely preserved using CEL as the carbon modifier, accompanied by the increased mesopore volume and pore size for better accessibility of active sites and diffusion of reactants. Simultaneously, the presence of CEL offered an appropriate ratio of Lewis and Brønsted acid sites due to the well incorporation and dispersion of Zr species, which ensured the successive transfer hydrogenation and ring-opening reactions. Kinetic studies demonstrated the positive effect of CEL modification on reducing the apparent activation energy and thereby facilitating the GVL formation. More importantly, Zr/β-CEL with enhanced structural stability also exhibited markedly higher recyclability compared with the pristine Zr/β. The understanding on the roles of carbon modifier can be employed to optimize the physicochemical properties of zeolite-based catalysts for roundly improving the catalytic reactivity of biomass-related compounds.
研究领域:
催化化学
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材料科学
✓ 已验证
DOI
高影响因子
Sustainable Chemistry and Pharmacy
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2026
·
IF 6.7
Deyang Zhao,Xinyu Zhao,Qikai Si,Kongde Li,Huawei Yang,Christophe Len
γ-valerolactone (GVL) is a renewable and sustainable platform chemical derived from biomass, with broad applications in chemical synthesis and energy-related fields. Consequently, the development of efficient strategies for GVL production has attracted significant attentions. In this study, the hydrogenation of ethyl levulinate (EL) to GVL was investigated using copper-cobalt basic carbonate, (CoCu) 2 (OH) 2 CO 3 , as a catalyst. The influence of different substrates—including esters and acids such as EL, GVL, ethyl acetate (EA), and levulinate acid (LA)-on catalyst recyclability and performance was systematically evaluated. Among the substrates tested, EL exhibited the most favorable behavior, delivering a GVL yield of up to 96% in the second recycling cycle under optimized conditions. This superior performance is attributed to the synergistic interaction between the basic sites of the catalyst and the ability of metallic Cu to activate hydrogen, as well as the formation of larger metal particle clusters when EL is used as the substrate. Notably, the catalytic activity remained largely preserved even after the third recycling cycle. In contrast, when GVL was sued as the substrate, moderate yields were obtained, accompanied by the formation of surface coatings on the catalyst particles. Furthermore, both EA and LA induced varying degrees of catalyst etching, resulting in a drastic loss of activity, with negligible catalytic performance observed in the second cycle. These findings indicate that catalyst deactivation due to etching has a more pronounced impact on catalytic performance than structural changes associated with bimetallic cluster formation. This observation indirectly highlights the critical role of basic sites in maintaining catalytic activity during the hydrogenation process.
✓ 已验证
产品关联
DOI
高影响因子
INTERNATIONAL JOURNAL OF BIOLOGICAL MACROMOLECULES
·
2025
·
IF 8.5
Tianyuan Xiao,Jiahui Song,Wenchao Jia,Yanning Sun,Yanzhu Guo,Pedram Fatehi,Haiqiang Shi
The chemical bond cleavage of lignin is a research focus for achieving depolymerized lignin for such applications as adhesives, fuels, fertilizers, etc. The depolymerization of an industrially available sustainable material, i.e., industrial alkali lignin, in LiBr·3H 2 O/HBr-γ-valerolactone (GVL) was systematically investigated in this study. It was observed that using 3/1 mL/g of HBr/lignin and 8/1 mL/g of GVL/lignin at 110 °C for 90 min, i.e., optimized conditions, resulted in lignin derivatives with an M w of 1889 g/mol and M n of 895 g/mol. The characteristics of the products were studied using FTIR, NMR, SEM, and DLS techniques. The results confirmed that the Hibbert-ketone end group was formed, while the structure of the aromatic ring was not changed on the depolymerized lignin. After the depolymerization process, the hydroxyl content in lignin increased from 1.91 mmol/g to 2.96 mmol/g. The product derived from the LiBr·3H 2 O/HBr-GVL depolymerization system displayed a spherical particle morphology. The addition of GVL to lignin depolymerization processes improved the bonding between lignin and inorganic molten salts, thereby promoting the acid-catalyzed cleavage of aryl ether bonds in lignin. Current research supports the conclusion that LiBr·3H 2 O/HBr-GVL lignin depolymerization is a sustainable and effective chemical pathway for generating depolymerized lignin.
研究领域:
化学工程
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材料科学
✓ 已验证
产品关联
DOI
PubMed
高影响因子
RSC Advances
·
2013
·Vol. 3
·期 26
·10277-10284
·
IF 2.562
Xing Tang,Lei Hu,Yong Sun,Geng Zhao,Weiwei Hao,Lu Lin
A green and efficient process was developed for the conversion of biomass-derived ethyl levulinate (EL) into γ-valerolactone (GVL) using supercritical ethanol as the hydrogen donor and the reaction medium over low-cost and eco-friendly ZrO2 catalysts, which were prepared by the precipitation method and characterized by BET, SEM, XRD, FT-IR, TGA-DTA, TPD-NH3 and TPD-CO2. The results indicated that amorphous ZrO2 with a high specific surface area and a large number of acid–base sites exhibited the highest catalytic activity, an excellent GVL yield of 81.5% with 95.5% EL conversion was achieved at 523 K over 3 h. In addition, combined with the results of poisoning experiments, a plausible mechanism of catalytic transfer hydrogenation (CTH) via a six-membered ring transition state was also presented.
研究领域:
生物质化学
·
催化反应工程
✓ 已验证
DOI
高影响因子
MOLECULES
·
2024
·Vol. 29
·期 16
·3779
·
IF 4.2
Pan Hou,Haopeng Su,Keyan Jin,Qiang Li,Wenfu Yan
γ-valerolactone (GVL), derived from biomass, is a crucial platform compound for biofuel synthesis and various industrial applications. Current methods for synthesizing GVL involve expensive catalysts and high-pressure hydrogen, prompting the search for greener alternatives. This study focuses on a novel zirconium phosphate (ZrP)-pillared zeolite MCM-36 derivative catalyst for converting levulinic acid (LA) to GVL using alcohol as a hydrogen source. The incorporation of ZrP significantly contributes to mesoporosity and greatly enhances the acidity of the catalysts. Additionally, we employed31P MAS NMR to comprehensively investigate the influence of phosphorus species on both the acidity and the catalytic conversion of LA to GVL. By adjusting the Zr-to-P ratios, we synthesized catalysts with enhanced acidity, achieving high conversion of LA and selectivity for GVL. The catalyst exhibited high recyclability, showing only minor deactivation over the course of five cycles. Furthermore, the catalyst was successfully applied to the one-pot conversion of furfural to GVL, showcasing its versatility in biomass conversion. This study highlights the potential of the MCM-ZrP1 catalyst for sustainable biomass conversion and offers insights for future research in renewable energy technologies.
研究领域:
化学工程
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可再生能源
·
催化科学
✓ 已验证
产品关联
DOI
PubMed
高影响因子
危险品化学品经营许可证（带存储）