MOLECULES
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2010
·Vol. 15
·期 8
·5258-5272
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IF 1.738
Lu Lin,Junping Zhuang
The catalytic performance of various metal chlorides in the conversion of cellulose to levulinic acid in liquid water at high temperatures was investigated. The effects of reaction parameters on the yield of levulinic acid were also explored. The results showed that alkali and alkaline earth metal chlorides were not effective in conversion of cellulose, while transition metal chlorides, especially CrCl3, FeCl3and CuCl2and a group IIIA metal chloride (AlCl3), exhibited high catalytic activity. The catalytic performance was correlated with the acidity of the reaction system due to the addition of the metal chlorides, but more dependent on the type of metal chloride. Among those metal chlorides, chromium chloride was found to be exceptionally effective for the conversion of cellulose to levulinic acid, affording an optimum yield of 67 mol % after a reaction time of 180 min, at 200 °C, with a catalyst dosage of 0.02 M and substrate concentration of 50 wt %. Chromium metal, most of which was present in its oxide form in the solid sample and only a small part in solution as Cr3+ion, can be easily separated from the resulting product mixture and recycled. Finally, a plausible reaction scheme for the chromium chloride catalyzed conversion of cellulose in water was proposed.Keywords:metal chlorides;cellulose;catalytic conversion;levulinic acid
研究领域:
化学工程
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可再生资源转化
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DOI
PubMed
高影响因子
ChemCatChem
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2015
·Vol. 7
·期 8
·1372-1379
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IF 4.556
Xing Tang,Xianhai Zeng,Zheng Li,Weifeng Li,Yetao Jiang,Lei Hu,Shijie Liu,Yong Sun,Lu Lin
Graphical In situ generated catalyst system: HCl/ZrO(OH) 2 catalysts are prepared in situ by the autonomous decomposition of ZrOCl 2 ⋅ 8 H 2 O in levulinic acid (LA)/2-butanol solution. The esterification of LA was catalyzed in tandem with hydrocyclization to γ-valerolactone (GVL) by Meerwein–Ponndorf–Verley reduction. This is the first report of HCl/ZrO(OH) 2 catalysts prepared in situ by the autonomous decomposition of ZrOCl 2 ⋅ 8 H 2 O in levulinic acid (LA)/2-butanol solution, which catalyzed the esterification of LA in tandem with hydrocyclization to γ-valerolactone (GVL) by Meerwein–Ponndorf–Verley (MPV) reduction without the use of external H 2 . A maximum GVL yield of 92.4 % from neat LA and a GVL formation rate of 1092.2 μmol g −1 min −1 were achieved in 2-butanol at 240 °C in 2 h. The in situ generated ZrO(OH) 2 was characterized comprehensively and its unexpected catalytic efficiency was attributed mainly to its extremely high surface area. A crude LA stream from the acid hydrolysis of cellulose was extracted into 2-butanol and subjected to this catalyst system to give a GVL yield of 82.0 % even in the presence of humins.
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
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DOI
高影响因子
JOURNAL OF CHEMICAL TECHNOLOGY AND BIOTECHNOLOGY
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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
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DOI
高影响因子
GREEN CHEMISTRY
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2021
·Vol. 23
·期 18
·7065-7073
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IF 10.182
Liang Jiang,Guangyue Xu,Yao Fu
The conversion of levulinic acid (LA) to γ-valerolactone (GVL) is one of the most important reactions from biomass-derived platform chemicals to value-added chemicals. In this work, nitrogen-doped carbon was introduced into a Ni/Al2O3 catalyst and was employed for the hydrogenation of LA to GVL with a full conversion and equivalent yield under mild conditions, at as low as ambient hydrogen pressure and 130 °C for 6 h. The doping of nitrogen introduced NiNx species and the imperfection of modified nitrogen-doped carbon were beneficial for the selective hydrogenation of carbonyl groups. This catalyst showed excellent activity and selectivity in various solvents and could be recycled for at least 6 runs with little deactivation. In addition to LA, various substrates with both carbonyl and carboxyl groups could also be selectively hydrogenated to the corresponding lactones. This study offers both theoretical foundation and practical instructions for the high-efficiency conversion of LA to GVL over non-noble metal catalysts under mild conditions, especially ambient H2 pressure.
研究领域:
催化化学
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生物质能转化
✓ 已验证
DOI
高影响因子
CATALYSIS TODAY
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2016
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IF 4.312
Kun Jiang,Dong Sheng,Zihao Zhang,Jie Fu,Zhaoyin Hou,Xiuyang Lu
Mixed MgO–Al 2 O 3 (with different Mg/Al ratio) supported nickel catalysts were prepared via co-precipitation method and used for hydrogenation of levulinic acid to γ-valerolactone under mild condition. Characterization results indicated that mixed MgO–Al 2 O 3 supported Ni catalysts possessed bigger surface area than that of Ni/MgO and Ni/Al 2 O 3 , and Ni dispersed highly on the surface of mixed MgO–Al 2 O 3 support. It was found that mixed MgO–Al 2 O 3 supported Ni catalysts were more active and selective for the hydrogenation of levulinic acid to γ-valerolactone than that of Ni/MgO and Ni/Al 2 O 3 , and the best yield of γ-valerolactone at 160 °C, 1 h and 3 MPa H 2 reached 99.7% over Ni/MgAlO 2.5 , and Ni/Mg 2 Al 2 O 5 could be recycled without obvious loss of its initial activity.
研究领域:
化学工程
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催化化学
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DOI
高影响因子
INDUSTRIAL & ENGINEERING CHEMISTRY RESEARCH
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2020
·
IF 3.573
Jun Jiang,Teng Li,Kexin Huang,Guangyu Sun,Jing Zheng,Jinlong Chen,Weiran Yang
As a bio-based platform chemical, it is desirable to convert levulinic acid (LA) to varieties of value-added biochemicals. n-Butane, mainly from nonrenewable fossil resources, is a basic chemical to produce some important chemicals, such as butadiene and ethylene. In this paper, 95.5% yield of n-butane was obtained from LA in one-step over base-treated Pt/C at around 300 °C in 4 h. The reaction pathway was confirmed to be the hydrodeoxygenation of LA to valeric acid (VA) and then the VA decarboxylation to n-butane by kinetic studies. Base-treated Pt/C had better reactivity due to its improved decarboxylation activity. Detailed characterization of the catalyst revealed that the Pt particle size is the key reason for the activity improvement, and further studies showed that Pt nanoparticles with a size of 2–4 nm showed the highest decarboxylation activity. This is the first report on the direct conversion of LA to n-butane.
研究领域:
化学工程
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可再生资源
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催化科学
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DOI
高影响因子
Journal of Biobased Materials and Bioenergy
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2019
·Vol. 13
·期 5
·677-682
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IF 0
Zhu Qiao-Qiao,Zhuang Jun-Ping,Wang Lan-Ying,Liu Ying,Wu Shu-Bin
Three kinds of silicotungstate, Zn2SiW12O40, Ag4SiW12O40 and Al4/3SiW12O40 were performed for the dehydration reaction to produce valuable platform chemicals levulinic acid
(LA) and 5-hydroxymethylfurfural (HMF) from glucose. The results showed that Al4/3SiW12O40 seemed beneficial for LA and HMF production from glucose. The highest LA yield of 50.4% was obtained when the glucose conversion was almost 100% at 180 °C
for 120 min with glucose was 0.5 g and the catalyst dosage was 0.45 g. The recycling of Al4/3SiW12O40 catalyst can be reused at least for four times with the activity loss less than 18.4% and the SEM images showed that the activity loss less may
due to the formation of the clustered fine particles on catalyst surface. This work provided a promising strategy for the production of LA from carbohydrates using inexpensive silicotungstate catalysts in aqueous medium.
研究领域:
化学工程
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可再生化学
✓ 已验证
DOI
JOURNAL OF CHEMICAL TECHNOLOGY AND BIOTECHNOLOGY
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2024
·Vol. 99
·期 4
·922-930
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IF 2.8
Dingshuo Zhang,Heqian Zhang,Yue Li,Daolai Sun,Jianhua Lv
BACKGROUND Levulinic acid is an important platform chemical derivable from lignocellulosic biomass. In this work, the hydrogenolysis of levulinic acid to produce 1,4-pentanediol was performed over some Co-based non-noble catalysts. The relationship between the catalyst properties and the catalytic activity was investigated, and the effects of the reaction conditions on the catalytic activity were studied. RESULTS The Co/ZrO 2 catalyst prepared by a coprecipitation method showed a high catalytic performance in the hydrogenolysis of levulinic acid to form 1,4-pentanediol. The calcination of Co/ZrO 2 significantly affected the catalytic activity, and a high calcination temperature of 750 °C could promote the formation of 1,4-pentanediol. Meanwhile, the reduction of Co/ZrO 2 at 400 °C in an H 2 flow was beneficial for producing 1,4-pentanediol, and the Co species after the reduction existed as the forms of Co 2+ and Co 0 . A high H 2 pressure and a moderate reaction temperature of 200 °C were beneficial for producing 1,4-pentanediol, and a high 1,4-pentanediol selectivity of 85.6% with a complete conversion of levulinic acid was obtained over the Co/ZrO 2 catalyst at 200 °C under an H 2 pressure of 7 MPa. CONCLUSION The Co species in the 400 °C-reduced Co/ZrO 2 catalyst existed as the forms of Co 2+ and Co 0 . It was proposed that the synergistic effect of Co 2+ and Co 0 contributed to the effective formation of 1,4-pentanediol from levulinic acid. © 2024 Society of Chemical Industry (SCI).
研究领域:
化学工程
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可再生能源
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DOI
高影响因子
Processes
·
2025
·Vol. 13
·期 4
·1110
·
IF 2.8
Shikang Zhao,Guohong Chen,Kaiqi Zheng,Shaojie Li,Jiaqi Xu,Fanan Wang,Xueping Liu,Rengui Weng
γ-Valerolactone (GVL) is a promising bio-based platform molecule with significant potential for energy applications. The production of GVL via biomass-based levulinic acid (LA) is an important reaction. To enhance the conversion and selectivity of non-precious-metal catalysts in the LA-to-GVL process and to better understand the key factors influencing this conversion, we conducted a series of experiments. In this study, supported Cu-Ni bimetallic catalysts (Cu-Ni2/Al2O3) were prepared using layered double hydroxides (LDHs) as a precursor. Compared with Cu-Ni catalysts synthesized via the conventional impregnation method, the Cu-Ni2/Al2O3catalysts exhibit higher catalytic activity and stability. The results demonstrated that efficient conversion was achieved with isopropanol as the hydrogen donor solvent, a reaction temperature of 180 °C, and a reaction time of 1 h. The yield of GVL reached nearly 90%, with a decrease of approximately only 6% after six consecutive cycles. The Cu-Ni2/Al2O3catalyst proved to be effective for converting biomass-derived LA to GVL, offering a route that not only reduces production costs and environmental impact but also enables efficient biomass-to-energy conversion.
研究领域:
催化化学
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能源科学
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生物质利用
✓ 已验证
产品关联
DOI
高影响因子
GREEN CHEMISTRY
·
2017
·Vol. 19
·期 9
·2201-2211
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IF 9.125
Wenxiu Cao,Wenhao Luo,Hongguang Ge,Yang Su,Aiqin Wang,Tao Zhang
The hydrogenation of levulinic acid (LA) to γ-valerolactone (GVL) is a crucial reaction included in many biorefinery schemes for the production of renewable chemicals and fuels. The development of highly stable supported Ru-based catalysts in the polar protic liquid phase under hydrothermal conditions is still a major challenge. Here, we prepared a 0.85 wt% Ru/ZrO2@C catalyst using a new stabilization strategy based on the UiO-66 (Zr-MOF) material. The catalytic performance of this Ru/ZrO2@C in LA-to-GVL was tested and compared with commercial 5 wt% Ru/C at 10 bar H2, 413 K in water and also in high protic aqueous solution (pH = 1). The full conversion of LA and quantitative yield of GVL were achieved with both catalysts. However, the 5 wt% Ru/C showed poor resistance to deactivation already after the first run. ICP, XPS, HRTEM, AC-STEM, TPR and physisorption data showed that quick deactivation of Ru/C was mainly caused by the leaching of ruthenium in addition to the loss of surface area via carbonaceous deposition in micro-pores. In contrast, the self-prepared Ru/ZrO2@C catalyst showed no apparent drop in catalytic performance either in water or in high protic aqueous solution upon multiple recycling, and no leaching of ruthenium was found even under harsh conditions (pH = 1). Remarkably, in the Ru/ZrO2@C catalyst, Ru (probable single-atom) was highly dispersed on nanotetragonal ZrO2 (3.3 nm), embedded in the amorphous carbon, and no apparent Ru nanoclusters were observed even after reactions. TPR results indicated that this excellent stability might be attributed to strong metal–support interaction between Ru and nanotetragonal ZrO2.
研究领域:
化学工程
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催化材料科学
✓ 已验证
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DOI
高影响因子
RENEWABLE ENERGY
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2019
·
IF 5.439
Xueyan Zhang,Xiaoyu Zhang,Ningyue Sun,Shengtian Wang,Xiaohong Wang,Zijang Jiang
Heteropolyacids (HPAs), super strong Brønsted acid solids, were recently reported to achieve cellulose conversion with high efficiency. To achieve higher levulinic acid (LA) yield, a series of Lewis metal-substituent phosphotungstic acids H n PW 11 LO 39 (HPWL, L = Cu II , Sn IV , Cr III , Zn II , Fe III ; L = Ti IV , Zr IV , oxygen is 40) were used as catalysts in polysaccharides conversion. Identification of the reaction intermediates and products provided some information for cellulose conversion pathway. H 5 PW 11 TiO 40 (Brønsted/Lewis acid = 2.84:1) was found to be most active with highest cellulose conversion giving highest glucose yield in water and highest LA yield in methyl isobutyl ketone (MIBK)/water. In addition, for overcome the drawbacks in mass transferring and separation, the temperature-responsive catalyst of HOCH 2 CH 2 N(CH 3 ) 3 H 4 PW 11 TiO 40 (ChH 4 PWTi) was prepared giving as high as 76.1% LA yield at 93.8% cellulose conversion more than those by HPWTi (65.6%, 90.5%). Also, ChH 4 PWTi was obtained 93.7% conversion and 70.9% yield at microwave. ChH 4 PWTi also presented higher feedstocks - tolerance to mono-, di- or polysaccharides and even lignocellulose (corn straw, pinewood, husk of xanthoceras, coconut shell) to LA. As highest as 33.0% LA yield at 68.0% conversion was obtained by ChH 4 PWTi from husk of xanthoceras under mild conditions. ChH 4 PWTi could be recycled 12 times without significant loss of activity, which showed longer duration.
研究领域:
生物化学
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催化化学
✓ 已验证
DOI
高影响因子
MATERIALS RESEARCH BULLETIN
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2020
·
IF 4.019
Jingru Wang,Shanhui Zhu,Yunwei Wang,Yingyong Wang,Guoqiang Jin,Xili Tong,Xiangyun Guo
The hydrogenation of levulinic acid (LA) to γ-valerolactone (GVL) under mild condition is a promising but challenging process. Herein, SiC supported Ru-Ir bimetallic catalyst exhibit enhanced catalytic activity for aqueous hydrogenation of LA into GVL under mild conditions. Comparing with monometallic Ir 3 /SiC and Ru 3 /SiC, the conversion of LA over bimetallic Ru 0.5 -Ir 2.5 /SiC catalyst increase from 51.2 % and 45.9% to 100% at 25 °C and 0.2 MPa of H 2 pressure. The enhanced catalytic activity of Ru 0.5 -Ir 2.5 /SiC catalyst originates from the electronic synergistic effect among Ru, Ir and SiC. Due to the electron transfer, electron-richened Ir nanoparticles show stronger ability for H 2 dissociation, and the SiC surface produces more active sites to accommodate hydrogen species that spill over from Ir and Ru. The adsorption and hydrogenation of LA molecules occur on the surface of SiC.
研究领域:
催化化学
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能源化学
✓ 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）