GREEN CHEMISTRY
·
2021
·Vol. 23
·期 18
·7065-7073
·
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.
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高影响因子
CARBOHYDRATE POLYMERS
·
2021
·
IF 9.381
Feng He,Jinhui Chen,Zhiwei Gong,Qinqin Xu,Wang Yue,Haibo Xie
In this study, an economically competitive and sustainable levulinic acid-based protic ionic liquids were identified to be good solvents for the dissolution pretreatment of cellulose towards enhanced enzymatic hydrolysis . The influences of protic ionic liquids species, dissolution pretreatment time, and pretreatment temperature on the physico-chemical structures of cellulose were systematically investigated by various analytical techniques. The findings indicate that the pretreatment efficiency was correlated to the basicity of the organic bases, and the presence of ketone group in the levulinate anion with particular hydrogen bonding forming ability via keto–enol tautomerism. The DBN derived protic ionic liquids exhibited best performance at 100 °C in 1 h, as evidenced by a 94% glucose yield. This solvent system was also suitable for the dissolution pretreatment of corn stover-based lignocellulosic biomass for sugars production, although a higher temperature and longer pretreatment time was required. Furthermore, the solvent system could be recycled and reused.
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JOURNAL OF CHEMICAL THERMODYNAMICS
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2015
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IF 2.679
Meizhen Lu,Guoqiang Han,Yaotai Jiang,Xudong Zhang,Dongshun Deng,Ning Ai
The solubilities of carbon dioxide (CO 2 ) in the renewable deep eutectic solvents (DESs) containing levulinic acid (or furfuryl alcohol) and choline chloride were determined at temperatures (303.15, 313.15, 323.15, and 333.15) K and pressures up to 600.0 kPa using an isochoric saturation method. The mole ratios of levulinic acid (or furfuryl alcohol) to choline chloride were fixed at 3:1, 4:1 and 5:1. Standard Gibbs free energy , dissolution enthalpy and dissolution entropy were calculated from Henry’s law constant of CO 2 in the DESs. Results indicated that levulinic acid based DESs are more effective to capture CO 2 than furfuryl alcohol based ones. The solubility of CO 2 in the DESs increased with increasing mole ratio of levulinic acid (or furfuryl alcohol) to choline chloride as well as pressure and decreased with increasing temperature.
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CHEMICAL ENGINEERING SCIENCE
·
2026
·
IF 5.1
Yufei Li,Kai Cui,Junwen Chen,Qingsong Xue,Peng Wu,Xiaohong Li
Levulinic acid (LA), as a pivotal biomass platform compound, has attracted significant interest in the field of biorefining, particularly owing to its importance in the synthesis of the high value-added 1,4-pentanediol (1,4-PeD) via a two-step conversion, the hydrogenation of LA and dehydrative lactonization to the intermediate γ-valerolactone (GVL), and the subsequent ring-opening hydrogenolysis of GVL to 1,4-PeD. However, the ring-opening hydrogenolysis of GVL is kinetically restricted by a high reaction energy barrier. Therefore, the development of outstanding non-noble metal catalysts remains a significant challenge for the efficient conversion of GVL to 1,4-PeD. Herein, ternary CuMgAl catalysts were prepared via a coprecipitation method and applied to the one-pot cascade hydrogenation of LA to 1,4-PeD in water. Notably, a Cu 1 Mg 0.5 Al 1 catalyst achieved an impressive 1,4-PeD yield of 94.2% under mild conditions. The structure-performance relationship investigation on the Cu 1 Mg 0.5 Al 1 catalyst revealed a remarkable synergistic effect among Cu 0 sites, Cu + sites, oxygen vacancies and a well-balanced acid-base microenvironment. In particular, the medium-to-strong acidity derived from Cu + species and oxygen vacancies promotes GVL adsorption and subsequent ring-opening hydrogenolysis, while the basic sites effectively buffered the acidity to suppress the dehydrative side reaction of 1,4-PeD. Concurrently, adjacent highly dispersed Cu 0 sites supplied dissociated hydrogen atoms, a synergy that was crucial for achieving high 1,4-PeD yields. This work presents a feasible and sustainable route for producing 1,4-PeD from bio-based LA and offers valuable insights into the mechanism of GVL ring-opening hydrogenolysis.
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ChemCatChem
·
2023
·Vol. 15
·期 5
·e202201274
·
IF 4.5
Shengbin Shi,Wenting Wu,Panli Liu,Guomin Xiao
Graphical Polymeric ionic liquids for conversion of cellulose into levulinic acid : A high levulinic acid yield of 79.4 % was achieved when used cellulose as substrates and sulphonic acid-functionalized polymeric ionic liquids as catalyst. Sulphonic acid-functionalized polymeric ionic liquids (PILs) were synthesized and applied into catalytic conversion of cellulose into levulinic acid (LA). The structure, thermal stability, and Hammett acidity function (H 0 ) of PILs were characterized and all were more thermostable than those of small-molecular ionic liquids (IL). At the optimum reaction conditions, the LA yield was maximized to 79.4 % by catalyst [Pim]CH 3 SO 3 . More importantly, catalyst [Pim]CH 3 SO 3 performed well in other biomass conversion, such as cellobiose, starch and rice husk. The product LA can be easily extracted by methyl isobutyl ketone from the reaction mixture. The PILs with high catalytic activity were easily recycled with an LA yield up to 68.9 % even after five cycles. These sufficient PILs will offer new approaches for transforming biomass to platform chemicals.
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Catalysts
·
2022
·Vol. 12
·期 11
·1361
·
IF 4.501
Wenli Feng,Xuebin Lu,Jian Xiong,Zhihao Yu,Yilin Wang,Jianguo Cui,Rui Zhang,Rengui Weng
Three common solid wastes (waste incineration fly ash, sewage sludge, and polluted soil) were the raw materials used in the synthesis of a geopolymer–type zeolite–like product, which was then used as a catalyst carrier to prepare a nickel hydrogenation catalyst for the catalytic hydrogenation of levulinic acid to γ–valerolactone. Under optimum synthesis conditions, the synthesized geopolymer zeolite has excellent structure and performance. The characterization results show that the composites have a three–dimensional network structure, and the pore structure is homogeneous mesoporous or microporous. In this work, the results of catalytic hydrogenation show that the yield of γ–valerolactone can achieve up to 94% using the synthesized catalyst, which is comparable to that of commercial catalysts and the concentrations of typical polluting heavy metals of Cu, Zn, Pb, and Cd in the reaction solution were all below the emission concentration limit (Class I standard) after five cycles of reaction. In summary, this geopolymer–type zeolite–like catalyst is cheap and has excellent performance; it is, therefore, expected to be widely used in catalysis instead of commercial carriers.Keywords:geopolymer–type zeolite–like catalyst;levulinic acid;hydrogenation
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FUEL
·
2022
·
IF 8.035
Yao Liu,Feiyi Chen,Junhua Zhang,Liang He,Lincai Peng
Acid treatment is the key to improve the physicochemical properties of metal-lignocellulosic hybrid, thus contributing to the catalytic performance for catalytic transfer hydrogenation (CTH) of carbonyl compounds to their corresponding alcohols. Herein, a series of organic acids were introduced to assist the design of Zr- Pennisetum sinese hybrid. Comprehensive studies demonstrated the dramatic changes of specific surface and acid/base sites of the prepared hybrid. Remarkably, formic acid-assisted Zr@ PS -FA possessed the largest surface area and enhanced interaction effects between acids (Lewis acid and Brønsted acid) and Lewis base sites, which exhibited excellent catalytic activity for CTH of levulinic acid to γ-valerolactone with a high yield of 95.6% in isopropanol under moderate reaction conditions (180 °C and 1.5 h). Zr@ PS -FA also showed remarkable cycle stability, and it could be consecutively used at least six runs without a significant loss in catalytic activity. More gratifyingly, Zr@ PS -FA displayed a superior universality for CTH of various carbonyl compounds to their corresponding alcohols, demonstrating great potential for upgrading biomass-derived aldehydes/ketones.
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CHEMICAL ENGINEERING JOURNAL
·
2022
·
IF 16.744
Yanlin Liu,Zhen Yu,Guangming Lu,Wanding Chen,Zixian Ye,Yueran He,Zhaobin Tang,Jin Zhu
Bio-based dynamic covalent thermosets have attracted extensive attention as they are expected to break conventional thermosets' reliance on fossil resources and address the recycling issue after disposal. However, there has always been a contradiction between using bio-based feedstocks and possessing high properties, as well as a conflict between high performance and rapid recycling (reprocessing and degradation). In this work, a simple approach was developed to prepare bio-based thermosets with high performance, rapid reprocessing, high flame retardancy, and antibacterial properties enabled by in-situ generated dynamic covalent imine (Schiff base) bonds and multiple hydrogen bonds. The levulinic acid epoxy (ELA) was successfully synthesized and cured with 2-(4-aminophenyl)-1H-benzimidazol-5-amine (BIA) containing benzimidazole structures. The high concentration of Schiff bases and multiple hydrogen bonds of ELA-BIA endowed it with high glass transition temperature and mechanical properties, as well as satisfactory catalyst-free malleability, rapid reprocessing and repairing. Furthermore, due to the combined effect of the in-situ Schiff base and benzimidazole structure, ELA-BIA exhibited excellent condensed phase char formation ability, resulting in intrinsic flame retardancy with a limiting oxygen index of 33.8 % and a UL-94 V-0 rating, both of which were significantly higher than 4, 4′-diaminodiphenyl methane (DDM) cured ELA or DDM cured bisphenol A epoxy. Moreover, the Schiff bases bonded in the networks provided 100 % of the intrinsic antibacterial rates. This work provides a feasible and simple strategy for the preparation of high-performance and versatile bio-based dynamic covalent thermosets.
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RENEWABLE ENERGY
·
2021
·
IF 8.001
Ruoqing Wang,Feng Shen,Yiwei Tang,Haixin Guo,Richard Lee Smith,Xinhua Qi
Levulinic acid in high yields (90%) was produced from hemicellulose-derived furfuryl alcohol catalyzed by a uniform, dandelion-like, SO 3 H-modified silica nanoflower solid acid (SiNF–SO 3 H). The SiNF–SO 3 H catalyst was prepared by soft template method in microemulsion system, followed by grafting of –SH and oxidation of –SH to –SO 3 H at room temperature to avoid use of corrosive sulfonating agents such as concentrated H 2 SO 4 . Dandelion-like porous structures of the SiNF–SO 3 H catalyst provided accessible and abundant catalytic sites ensuring high activity for furfuryl alcohol conversion (100%). Mixed-solvent γ -valerolactone-water (GVL-H 2 O) inhibited undesirable furfuryl alcohol polymerization reactions ensuring highly selective conversion of furfuryl alcohol to levulinic acid. Combination of catalyst and solvent system allowed achievement of the highest levulinic acid yields that have been reported to date. Both the catalyst synthesis protocol and reaction solvent (GVL-H 2 O) are green and sustainable. The SiNF–SO 3 H/(GVL-H 2 O) catalytic system has application to many acid catalyzed schemes for lignocellulosic biomass conversion.
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JOURNAL OF APPLIED POLYMER SCIENCE
·
2020
·Vol. 137
·期 36
·49066
·
IF 2.52
Yigane Wang,Xiaoan Nie,Guigan Fang,Laihui Xiao
Epoxy bisphenol acid isooctyl ester (EBAIE) was synthesized and characterized by FTIR and H-NMR. EBAIE was used as poly(vinyl chloride) (PVC) plasticizer for the first time, and its addition amount was 30 wt% of PVC. The mechanical properties, thermal stability, compatibility, and decomposition activation energy of PVC blends were systematically studied. Compared to the commercial plasticizer-dioctyl phthalate (DOP), the tensile strength had been significantly increased from 30.64 to 45.07 MPa, while the elongation at break had little difference. The thermal stability analysis showed that the static stability time at 180°C had been extended from 40 to 300 min. The decomposition activation energy indicated that the EBAIE plasticized PVC was with a higher thermal stability. The extraction and volatility resistance of the novel plasticizer were superior to those of DOP.
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Molecular Catalysis
·
2018
·
IF 0
Zhongzhe Wei,Xuefeng Li,Jiang Deng,Jing Wang,Haoran Li,Yong Wang
The catalytic transformation from levulinic acid (LA) into γ-valerolactone (GVL) is of great interest as it is an impressive strategy to convert lignocellulosic platform chemical into high value-added compounds. Herein, a novel heterogeneous catalyst made of Ru nanoparticles (NPs) supported on N-doped hierarchically porous carbon from biomass, Ru/NHPC, was shown to be highly active, selective and stable in this transformation. The reaction can proceed smoothly under mild conditions in aqueous media even at room temperature. The catalyst Ru/NHPC could be recycled for 13 consecutive runs exhibiting no obvious activity decay, much better than that of Ru NPs supported on activated carbon. The process offers an efficient, environmentally responsible, and safe approach to high production of GVL.
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CELLULOSE
·
2019
·Vol. 26
·期 15
·8313-8323
·
IF 3.917
Wang Chao,Yang Guihua,Zhang Xueming,Shao Lupeng,Lyu Gaojin,Mao Jianzhen,Liu Shijie,Xu Feng
Levulinic acid (LA) production from corncob acid hydrolysis residues (CAHR) using FeCl 3 as Lewis acid catalyst in green solutions of salt was investigated. The reaction kinetic relationships were determined in the temperature range of 160–180 °C, with FeCl 3 concentrations of 0.12–0.36 M, and a reaction time of 0–60 min. The maximum LA concentration of 59.0 mol% (24.5 g/L) was achieved at 170 °C in a 30% NaCl solution containing 0.24 M FeCl 3 . A pseudo first-order kinetic model was proposed to describe the cellulose deconstruction to LA. The model agreed perfectly with the evolution in the concentrations of the major compounds such as glucose, 5-hydroxymethylfurfural and LA during the CAHR hydrolysis. The kinetic model developed for CAHR was in good agreement with that previously developed for other lignocellulosic systems. Based on our kinetic model and reaction system, the LA yield is increased at the lower end of the temperature range with the higher acid concentrations. The results indicated that the concentrated seawater after desalination could be a green solvent in the biorefinery.
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危险品化学品经营许可证（带存储）