Waste and Biomass Valorization
·
2017
·Vol. 10
·期 5
·1141-1150
·
IF 1.337
Fang Chengjiang,Liu Yanxiu,Wu Weibo,Li Hu,Wang Zhongwei,Zhao Wenfeng,Yang Tingting,Yang Song
Liquid-phase catalytic hydrogenation of furfural, followed by hydration to levulinic acid has been considered as one of efficient approaches for upgrading pentose sugars. However, a two-step process is generally employed, which involves the separation and purification of the key intermediate furfuryl alcohol from the reaction mixture. To simplify this catalytic process with improved efficiency, Cu-doped niobium phosphate ( x Cu/NbP; x = 0.1–5.0 wt%, denoted as Cu loading) catalysts with different Cu loadings were prepared by impregnation and reduction, which could catalyze furfural conversion to levulinic acid through a one pot single-step process. The as-prepared x Cu/NbP catalysts were characterized by H 2 -TPR, XRD, NH 3 -TPD, XPS, the pore size and pore volume and pyridine-adsorption FT-IR. In this study, the effect of Cu loading, formic acid amount, support type, reaction temperature/time and catalyst reusability on the reaction were investigated. It was found that 1.5 wt% Cu/NbP loading exhibited predominant catalytic activity in the cascade conversion of furfural, producing levulinic acid with a high yield of up to 67.0 mmol% using ten equivalent of formic acid at 160 °C for 3 h. Moreover, the possible mechanism was further elucidated. Also, the catalyst could be easily separated from the mixture, and reused with no remarkable loss of reactivity.
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高影响因子
CHEMICAL ENGINEERING SCIENCE
·
2025
·
IF 4.3
Chanjuan Yang,Shoukang Xiao,Liyu Chen,Yingwei Li,Kui Shen
γ-Valerolactone (GVL) as an important high-value chemical can be readily produced through the catalytic hydrogenation of renewable levulinic acid (LA). However, high reaction temperatures (70–240 ℃) and H 2 pressures (0.5–6 MPa) are usually required to achieve full LA conversion and desired GVL yield in previous studies. Herein, we report, for the first time, the ambient-condition upgrading of LA to GVL by rationally constructing a series of metallic–acidic Ru x Pt y /MIL-101 catalysts comprising RuPt-alloyed nanoparticles (NPs) and Lewis-acid sites within a chromium-based MOF (namely MIL-101). Benefiting from the favorable synergy between Ru and Pt in their alloyed NPs and abundant Lewis-acid sites in MIL-101, the best Ru 4 Pt 1 /MIL-101 featuring an optimized Ru/Pt molar ratio of 4:1 shows a complete LA conversion with > 99.9 % yield of GVL under unprecedented ambient temperature and pressure, affording a high turnover frequency (TOF) of 1480.5h −1 , which is 15.1 and 10.1 times that of its monometallic Pt/MIL-101 (98.3 h −1 ) and Ru/MIL-101 (146.7 h −1 ) counterparts, respectively. Detailed experiments and density functional theory (DFT) calculations suggest the RuPt-alloyed effect and Lewis-acid sites in Ru 4 Pt 1 /MIL-101 can optimize the adsorption energy of 4-hydroxyvaleric acid (HPA) to remarkably boosting its catalytic performance for this reaction.
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ChemCatChem
·
2022
·Vol. 14
·期 13
·e202200311
·
IF 5.497
Yuyao Zeng,Bowei Wang,Fanyong Yan,Wensheng Xu,Guoyi Bai,Yang Li,Xilong Yan,Ligong Chen
Graphical Through a convenient impregnation method, highly-distributed and stable Cu nanoparticles were dispersed on the boron doped γ-Al 2 O 3 support, which catalyzed continuous reductive amination of levulinic acid to corresponding N-substituted pyrrolidinones. The reductive amination of biomass-derived levulinic acid (LA) to value-added N-substituted pyrrolidinones with amine and molecular hydrogen over heterogeneous catalyst represents an atom-economical and scalable route. In this paper, a series of boron doped Cu/Al 2 O 3 catalysts via kneading and impregnation method are developed for the continuous reductive amination of LA. Compared with Cu/Al 2 O 3 , Cu 10 /AlB 3 O catalyst exhibits greatly improved catalytic performance for this reaction at low operation temperature. Structure-property correlation investigations were performed with diverse characterization methods, and the results revealed that the excellent catalytic performance of boron doped Cu/Al 2 O 3 catalysts was mainly attributed to the synergistic effect of its well-dispersed Cu nanoparticles, appropriate surface Cu electronic state and surface acidic sites nearby. Besides, Cu 10 /AlB 3 O shows great stability during the reaction over 200 h. This work provides a low-cost, efficient and environmentally friendly heterogeneous catalytic system for the continuous production of N-substituted pyrrolidinones.
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高影响因子
RENEWABLE ENERGY
·
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.
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高影响因子
Molecular Catalysis
·
2021
·
IF 5.062
Shengbin Shi,Yuanfeng Wu,Mengting Zhang,Ruiping Wei,Lijing Gao,Guomin Xiao
A series of new SO 3 H-functionalized ionic liquids (ILs) were synthesized and characterized, which were successfully applied to catalyze cellulose to produce levulinic acid (LA) via one-pot reaction. The structure, thermal property, and acidity of ILs were characterized by NMR, TGA, and Hammett acidity measurement. The Hammett acidity (H 0 ) of ILs increase in the following order: [BSim]H 2 PO 4 <[BSim]TsO < [BSim]CF 3 SO 3 < [BSim]HSO 4 , which is consistent with their yield of LA order using these ILs as catalysts. Under the optimum conditions, the yield reached up to 65% when [BSim]HSO 4 was used as catalyst and solvent, which is one of the best results compared to those reported in literature. Moreover, the ILs were easily recycled without structural change even after four cycles, and the yield of LA was up to 44% at the fifth cycle. Furthermore, TGA indicated that these SO 3 H-functionalized ILs exhibited excellent thermal stability. These efficient ILs will provide new options for converting biomass resources to LA and other chemicals.
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高影响因子
GREEN CHEMISTRY
·
2013
·Vol. 15
·期 10
·2967-2974
·
IF 6.828
Tao Pan,Jin Deng,Qing Xu,Yang Xu,Qing-Xiang Guo,Yao Fu
The development of the catalytic conversion of biomass-based platform molecules into oxygenated fuel molecules is of great significance in order to reduce the dependence on fossil resources and to solve environmental problems. Alkyl valerate esters were proven to have the potential to be renewable additives of gasoline and diesel. In this work, we studied the hydrogenation of levulinic acid (LA) to valerate esters over supported Ru catalysts, and found that the acidity was an important factor for the catalyst performance. A bifunctional catalyst Ru/SBA-SO3H was developed as an active catalyst, and a highest yield of 94% to ethyl valerate (EV) was achieved. The catalyst was characterized by nitrogen adsorption/desorption methods, X-ray power diffraction (XRD), transmission electron spectroscopy (TEM) and X-ray photoelectron spectroscopy (XPS). The effects of reaction conditions were comprehensively investigated and probable reaction pathways were proposed and verified. The conversion of LA to various alkyl valerate esters can also be catalyzed by the bifunctional catalyst. In addition, supported Cu and Ni catalysts were also screened under similar reaction conditions as Ru-based catalysts, and the combination of Ni/SBA-15 and SBA-SO3H exhibited activity for the conversion of LA to EV.
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高影响因子
FUEL
·
2022
·
IF 8.035
Lungang Chen,Yong Liu,Xinghua Zhang,Jianguo Liu,Qi Zhang,Longlong Ma
Catalytic conversion of biomass to liquid fuel is one of critical part to ease dependence on fossil fuel. Herein, a route of transformation of biomass-derived furfural and levulinic acid into long-chain hydrocarbon fuels was developed. A C20 oxygenate with 95 % mol yield was firstly synthesized through condensation-polymerization reactions catalyzed by NaOH. Various techniques were employed to verify the chemical structure of the C20 oxygenate. The condensation mixture was then directly subjected to hydrodeoxygenation reaction to prepare long-chain hydrocarbons with a catalytic system of Pd/C and H 3 PO 4 in aqueous phase. A 57.1 % weight yield of liquid fuel was obtained with main products of C12, C14, and C18 hydrocarbons. The mass percent of carbon and hydrogen in fuel was significant improved to 95.91 %, as well as the high heat value was increased to 47.04 MJ/kg.
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高影响因子
GREEN CHEMISTRY
·
2021
·Vol. 24
·期 1
·163-175
·
IF 10.182
Shanta Dutta,Iris K. M. Yu,Jiajun Fan,James H. Clark,Daniel C. W. Tsang
A considerable amount of food waste generated globally could be upcycled to synthesise platform chemicals to enhance environmental sustainability and realise a circular economy. This study investigates the catalytic production of the vital platform molecule levulinic acid (LA) from bread waste, a typical stream of starch-rich food waste generated worldwide. Gamma-valerolactone (GVL), isopropanol (IPA), and propylene carbonate (PC) were evaluated as bio-derived and CO2-derived green co-solvents for LA synthesis. In-vessel pressure generated in PC/H2O (1 : 1) solvent was conducive to rapid LA production from bread waste compared to GVL/H2O and IPA/H2O. In PC/H2O, 72 mol% total soluble product yield was observed quickly within 1 min in moderate reaction conditions (130 °C, 0.5 M H2SO4), whereas ∼15–20 mol% of LA could be obtained when the reaction was prolonged for 10–20 min at 130 °C. The yield of LA could be significantly enhanced in GVL/H2O through phase separation using NaCl (30 wt%(aq)). LA yield increased up to a maximum of ∼2.5 times in the biphasic system (28 mol%, 150 °C, 15 min) (representing a theoretical yield of 66%) in GVL/H2O (1 : 1) compared to the monophasic system (∼11 mol%) under the same reaction conditions. The partition coefficient for LA achieved was 4.2 in the GVL/H2O (1 : 1) biphasic medium, indicating that the system was efficient for simultaneous production and extraction of LA. Biphasic GVL/H2O facilitated selective LA production, which could be optimised by tuning the reaction conditions. These new insights can foster the development of high-performance LA production and sustainable biorefinery.
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高影响因子
ACS Sustainable Chemistry & Engineering
·
2021
·
IF 8.198
Lungang Chen,Yong Liu,Canshuo Gu,Gang Feng,Xinghua Zhang,Jianguo Liu,Qi Zhang,Chenguang Wang,Longlong Ma
Selective production of 2-butanol from levulinic acid (LA) hydrogenolysis over a non-precious catalyst is long desirable. However, the process requires the precious metal Ru, and the yield of 2-butanol was less than 65%. Herein, we prepared Ni-based bimetallic catalysts, among which the NiMn catalyst exhibited the highest efficiency and reached an 84.5% yield of 2-butanol at 100% LA conversion under optimal conditions. The electronic states and surface properties were characterized by various techniques such as X-ray diffraction, X-ray photoelectron spectroscopy, temperature-programmed desorption, temperature-programmed reduction, and scanning electron microscopy/transmission electron microscopy. The high efficiency of the NiMn catalyst was due to the synergy between Ni0 and Mn2+ species, and the modified surface showed a high basicity and a high affinity to adsorb LA and LA-derived molecules with C═O or COOH. The high affinity of the NiMn catalyst was further confirmed by density functional theory calculations.
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Reaction Chemistry & Engineering
·
2021
·Vol. 6
·期 10
·1811-1818
·
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.
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高影响因子
ACS Omega
·
2021
·
IF 3.512
Lei Hu,Jiayi Zheng,Qing Li,Shunhui Tao,Xiaojie Zheng,Xiaodong Zhang,Yao Liu,Xiaoqing Lin
5-hydroxymethylfurfural (5-HMF) is a promising high value-added platform chemical, which can be produced from glucose, fructose, or lignocellulosic biomass via catalysis technology. However, the effective separation of 5-HMF from aqueous solution and actual biomass hydrolysate is still challenging because 5-HMF can be further rehydrated into levulinic acid (LA) and formic acid (FA) under acidic conditions. Herein, the adsorption behavior of glucose and 5-HMF and its follow-up products (LA and FA) from aqueous solutions onto polymeric adsorbents modified with various functional groups (XAD-4, XAD7HP, and XAD761 resins) was systematically investigated. The results showed that XAD761 resin exhibited the highest adsorption selectivity (α5-HMF/glucose = 42.42 ± 5.84, α5-HMF/FA = 18.41 ± 0.50, and α5-HMF/LA = 3.01 ± 0.10) and capacity for 5-HMF (106 mg g–1 wet resin). The adsorption equilibrium was better fitted by the Freundlich isotherm model at the studied range of 5-HMF concentrations. The thermodynamic study and activation energy also revealed that the adsorption process of XAD761 resin for 5-HMF was spontaneous, exothermic, and physical. The kinetic regression results revealed that the kinetic data of 5-HMF was accurately followed by the pseudo-second-order kinetic model. In conclusion, the present study revealed that the potential of phenol formaldehyde resin with hydroxyl groups could be used as an adsorbent for aldehyde organic compounds.
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PubMed
高影响因子
EUROPEAN JOURNAL OF INORGANIC CHEMISTRY
·
2020
·Vol. 2020
·期 10
·833-840
·
IF 2.529
Ruiping Wei,Jingdeng Fan,Xumin Qu,Lijing Gao,Yuanfeng Wu,Zongqi Zhang,Feng Hu,Guomin Xiao
Graphical Esterification of levulinic acid with ethanol was catalyzed by the cooperative effects between the Lewis acid sites offered by unsaturated Zr 6 nodes and Brønsted acid sites supplied by OH in defective UiO-66 MOFs with high defect density, which was tuned by precursor ratios and modulators. Due to their high stabilities and tunable defects, zirconium terephthalate UiO-66 type metal organic frameworks (MOFs) have been promising catalysts in many catalytic reactions. The catalytic activity of UiO-66 MOFs is significantly affected by the density of defects and hydroxyl groups bonded to Zr 6 nodes, which can be tuned by modulators. In this work, a series of defective UiO-66 were synthesized via tuning the ratio of H 2 BDC/Zr and adding monocarboxylic acids with different chain length as modulators. The synthesized UiO-66 MOFs were characterized by powder X-ray diffraction, N 2 physisorption, IR and 1 H NMR spectroscopy, scanning and transmission electron microscopy. Esterification of levulinic acid with ethanol was selected to reveal the influence of modulators, defects and hydroxyl groups. The results showed that UiO-66 with 0.5 of H 2 BDC/Zr ratio and lauric acid as the modulator owned excellent catalytic activity. The cooperative effects, between the Lewis acid sites offered by unsaturated Zr 6 nodes and Brønsted acid sites supplied by OH, has been revealed to have a significant influence on the catalytic activity.
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