CATALYSIS TODAY
·
2018
·
IF 4.667
Xiaoyan Liu,Guojun Lan,Panpan Su,Lihua Qian,Tomas Ramirez Reina,Liang Wang,Ying Li,Jian Liu
The hydrogenation of levulinic acid to γ-valerolactone with water as solvent is a crucial reaction for producing fine chemicals. However, the development of highly stable catalysts is still a major challenge. Here, we prepared a Ru nanoparticles incorporated in mesoporous-carbon (Ru-MC) catalyst to achieve high stability in acidic aqueous medium. The Ru-MC showed excellent catalytic performance (12024 h −1 turnover frequency) in the hydrogenation of LA-to-GVL. Compared with Ru supported on mesoporous carbon catalyst (Ru/MC) prepared by conventional wet impregnation method, the Ru-MC showed excellent reusability (more than 6 times) and thermal stability (up to 600 °C). Based on H 2 -TPR-MS characterization, it was proposed that the incorporated structure significantly increased the interaction between Ru nanoparticles and carbon support, which effectively prevent the leaching and sintering of Ru nanoparticles and contributed to increased high reusability and thermal stability of the Ru-MC.
研究领域:
催化化学
·
绿色化学
·
生物质转化
·
纳米材料
·
能源化学
·
有机合成
✓ 已验证
DOI
高影响因子
ChemSusChem
·
2015
·Vol. 8
·期 9
·1601-1607
·
IF 7.657
Xing Tang,Zheng Li,Xianhai Zeng,Yetao Jiang,Shijie Liu,Tingzhou Lei,Yong Sun,Lu Lin
Graphical Two-faced copper: Methyl levulinate (ML) in the methanolysis products of cellulose is hydrogenated directly to γ-valerolactone (GVL) with methanol as the in situ hydrogen source over a nanocopper catalyst. The nanocopper catalyst plays a dual role in hydrogen production by methanol reforming and the subsequent hydrogenation of ML to GVL. In this work, the hydrocyclization of methyl levulinate (ML) to γ-valerolactone (GVL) was performed in MeOH over an in situ prepared nanocopper catalyst without external H 2 . This nanocopper catalyst served as a dual-functional catalyst for both hydrogen production by MeOH reforming and hydrogenation of ML. Nearly quantitative ML conversion with a GVL selectivity of 87.6 % was achieved at 240 °C in 1 h in MeOH under a nitrogen atmosphere. ML in the methanolysis products of cellulose also could be hydrogenated effectively to GVL over this nanocopper catalyst even in the presence of humins to give an ML conversion of 94.1 % and a GVL selectivity of 73.2 % at 240 °C in 4 h. The absorption behavior of humins on the surface of the nanocopper catalyst was observed, which resulted in a pronounced increase in the acidic sites of the nanocopper catalyst that facilitate ring-opening and the hydrocarboxylation/alkoxycarbonylation of GVL to byproducts.
研究领域:
生物化学
·
催化化学
✓ 已验证
DOI
高影响因子
CHINESE JOURNAL OF CATALYSIS
·
2019
·
IF 4.914
Xuejuan Cao,Huai Liu,Junnan Wei,Xing Tang,Xianhai Zeng,Yong Sun,Tingzhou Lei,Geng Zhao,Lu Lin
The production of γ-valerolactone (GVL) from lignocellulosic biomass has become a focus of research owing to its potential applications in fuels and chemicals. In this study, ( n )CuO x -CaCO 3 (where n is the molar ratio of Cu to Ca) compounds were prepared for the first time and shown to function as efficient bifunctional catalysts for the conversion of biomass-derived methyl levulinate (ML) into GVL, using methanol as the in-situ hydrogen source. Among the catalysts with varied Cu/Ca molar ratios, (3/2)CuO x -CaCO 3 provided the highest GVL yield of 95.6% from ML. The incorporation of CaCO 3 with CuO resulted in the formation of Cu + species in a CuO x -CaCO 3 catalyst, which greatly facilitated the hydrogenation of ML. Notably, CuO x -CaCO 3 also displayed excellent catalytic performance in the methanolysis products of cellulose, even in the presence of humins. Therefore, a facile two-step strategy for the production of GVL from cellulose could be developed over this robust and inexpensive catalyst, through the integration of cellulose methanolysis catalyzed by sulfuric acid, methanol reforming, and ML hydrogenation in methanol medium.
研究领域:
化学工程
·
可再生能源
✓ 已验证
DOI
高影响因子
BIORESOURCE TECHNOLOGY
·
2026
·
IF 8.2
Shasha Fang,Ran Hao,Wenjiong Li,Yixin Luo,Fu Li,Qingxin Guan,Jia Wang,Wei Li,Daniel C.W. Tsang
The conversion of biomass-derived levulinic acid (LA) to γ-valerolactone (GVL) offers a sustainable route for chemical production. Achieving efficient and selective electrocatalytic hydrogenation in aqueous media remains challenging due to limited supply of active hydrogen (H*) and selectivity–efficiency trade-off. Herein, we propose an electrochemical reconstruction strategy to generate Pb/PbO nanosheet electrocatalysts that can enable efficient aqueous-phase electrocatalytic hydrogenation of LA to GVL at room temperature, achieving a Faradaic efficiency of 59.2% and a yield rate of 22.2 mg h −1 cm −2 at –1.1 V vs. RHE, outperforming most previously reported aqueous LA-to-GVL systems. In-situ experiments reveal that the superior performance resulted from the synergy of Pb/PbO heterostructures and oxygen vacancies: heterostructures facilitated efficient electron transfer, oxygen vacancies optimized LA adsorption and H* activation, and a high surface area exposed additional active sites. Integration of a flow electrolyzer with an extraction–distillation unit provided continuous LA conversion and high-purity GVL recovery, demonstrating practical feasibility. This work provides a rational design of efficient electrocatalysts for hydrogenation of biomass-derived platform molecules.
✓ 已验证
产品关联
DOI
PubMed
高影响因子
RENEWABLE ENERGY
·
2021
·
IF 8.001
Junwei Yao,Xiaobao Xie,Qingshan Shi
In this work, we report that FeCl 3 , a benign Lewis acid, could be used as a catalyst in the γ-valerolactone (GVL)/H 2 O solvent system to facilitate efficient pretreatment of Chinese silvergrass. The results showed that approximately 87.8% of xylan and 75.8% of lignin were removed by 80% GVL under 170 °C using 50 mM FeCl 3 as a catalyst. The solubilized carbohydrate fractions in the pretreatment liquor were mainly composed of monosaccharides (glucose and xylose) rather than oligosaccharides (glucose oligomers and xylose oligomers) and inhibitors (furfural, hydroxymethylfurfural, formic acid and acetic acid). Moreover, FeCl 3 decreased the transesterification of GVL with hydroxyl groups on the cellulose surface and resulted in more easily degraded cellulose. Approximately 96.5% of cellulose and 92.2% of xylan in the pretreated Chinese silvergrass were converted to fermentable monosaccharides by 10 FPU/g cellulases . This study indicated that FeCl 3 -catalyzed GVL solvent could efficiently deconstruct biomass and increase the cellulose digestibility, which provided a novel, GVL-based pretreatment system for processing biomass.
研究领域:
生物化学
·
可再生资源与环境科学
✓ 已验证
产品关联
DOI
高影响因子
CATALYSIS COMMUNICATIONS
·
2020
·
IF 3.612
Jingru Wang,Yingyong Wang,Xili Tong,Yunwei Wang,Guoqiang Jin,Xiangyun Guo
A 3 wt% Ir/SiC catalyst prepared by the wet impregnation method showed excellent catalytic activity and stability for the aqueous hydrogenation of levulinic acid (LA) to γ-valerolactone (GVL) in a batch reactor system. LA was completely converted to GVL at 50 °C and 0.2 MPa of H 2 pressure with 100% selectivity and a high turnover frequency (TOF) of 333 h −1 . The high activity of Ir/SiC catalyst could be related to the Schottky-type contact between Ir and SiC solid phases, which promotes electron transfer between support and metal. Due to the excellent acid resistance of SiC support, the Ir/SiC catalyst showed high catalytic stability and nearly no loss of activity after 5 consecutive catalytic operation cycles.
研究领域:
化学工程
·
催化科学
✓ 已验证
DOI
高影响因子
INDUSTRIAL & ENGINEERING CHEMISTRY RESEARCH
·
2018
·
IF 3.141
Fukun Li,Zhangmin Li,Liam John France,Jiali Mu,Changhua Song,Yuan Chen,Lilong Jiang,Jinxing Long,Xuehui Li
Novel and selective strategies for platform chemical production from renewable biomass are highly attractive in respect to value-added utilization of sustainable resources. In this study, a series of low-cost, commercially available, transition metal carbonates (Zr, Ni, Mg, Zn, and Pb) were investigated for catalytic transfer hydrogenation of levulinate esters to γ-valerolactone (GVL) via the cascade process of Meerwein–Ponndorf–-Verley (MPV) reduction and lactonization reaction. Among the selected catalysts, basic zirconium carbonate is the most active, with the highest turnover frequency (TOF) of 3.1 h–1 and a surface reaction rate of 0.21 mol m–2 h–1. At 453 K, 3.0 h, and 1.0 MPa N2, 100% ethyl levulinate conversion, 96.3% GVL yield, and 91.9% hydrogen donor utilization are observed due to the cooperative effect between acid (Mn+) and base (−OH) sites. Furthermore, this catalyst shows high recyclability under the optimized conditions, where a satisfactory catalytic activity is shown even after six consecutive runs.
研究领域:
化学工程
·
催化科学
✓ 已验证
产品关联
DOI
高影响因子
JOURNAL OF LOSS PREVENTION IN THE PROCESS INDUSTRIES
·
2022
·
IF 3.916
Yong Pan,Chaoqin Ren,Gan Wang,Yanjun Wang,Xin Zhang,Juncheng Jiang,Chi-Min Shu
Aiming at the green and sustainable energy substitution and supply, biomass valorization has become a potential strategy to face the energy crisis and increasing demand all over the world from long-term perspectives. Among the bio-based chemicals, γ-valerolactone (GVL) production from hydrogenation of levulinic acid (LA) and its esters has attracted great interests due to its wide applications, such as fuel, solvent, and additives. However, the safety evaluation for this hydrogenation reaction has received few attentions. To fill this gap, thermal hazard evaluation for GVL production from LA hydrogenation by using formic acid (FA) as hydrogen donor was first performed. The process conditions were optimized by using orthogonal experimental method for further calorimetry study. Thermal stability of chemicals and thermal risk of reaction process under adiabatic conditions were investigated by applying differential scanning calorimetry and accelerating rate calorimeter Phi-Tec II, respectively. The results revealed that the chemicals were stable in temperature range from 30 to 250 °C except FA due to its evaporation and decomposition with endothermic behaviors. The reaction process under isothermal and adiabatic conditions demonstrates that the decomposition of FA was rapid and followed by the hydrogenation of LA to GVL. Based on kinetic model under adiabatic conditions and risk matrix , the thermal runaway risk was found to be medium, indicating that certain safety measures should be properly designed and taken for loss prevention. This work could benefit the safety design and thermal risk prevention for GVL production by using FA as hydrogen donor.
研究领域:
化学工程
·
能源科学
·
安全工程
✓ 已验证
产品关联
DOI
高影响因子
ACS Sustainable Chemistry & Engineering
·
2021
·
IF 8.198
Zuojun Wei,Qing Li,Yuran Cheng,Mei Dong,Zuyi Zhang,Xinmiao Zhu,Yingxin Liu,Yong Sun
CoRe bimetallic catalysts with low loading were designed for hydrodeoxygenation of levulinic acid to γ-valerolactone. Results show that the 1 wt % Co0.5Re0.5/TiO2 catalyst achieved the highest yield of γ-valerolactone (>99%) at 220 °C, 3 h, a 1,4-dioxane solvent and Co/levulinic acid molar ratio of 1:1760, with a turnover frequency (TOF) of 1328 h–1. The catalyst can be reused four times with only slight activity loss. The catalyst was characterized with various physicochemical measurements, and its adsorption styles with H2 and levulinic acid were calculated by density functional theory. The results reveal that four main factors are related to its excellent catalytic performance. First, the Re oxides synergize with Co by spillover of the dissociated H atoms, which increases the apparent dispersion of Co and promotes the reaction. Second, the low loading of 1 wt % allowed the metal nanoparticles to be well dispersed with a very fine size of ca. 1.24 nm, which may expose more active sites to the substrate and result in a higher catalytic efficiency. Third, CoRe formed an amorphous alloy with the formula Co-ReO1.6, which showed a synergistic effect during the reaction. Finally, the TiO2 support was nonporous and hydrophilic, which would be beneficial for the mass diffusion of the reaction components to be adsorbed/desorbed onto the vicinity of the metallic active sites and lead to a high TOF in the hydrodeoxygenation process.
研究领域:
化学工程
·
催化科学
✓ 已验证
产品关联
DOI
高影响因子
Biomass Conversion and Biorefinery
·
2022
·
IF 4.05
Yu Nanxi,Lu Houfang,Yang Wei,Zheng Yuxin,Hu Qiang,Liu Yingying,Wu Kejing,Liang Bin
In the process of converting biomass into high value-added chemicals, transfer hydrogenation as a mild hydrogenation method has attracted more and more attention. The catalysts with hydrogenation sites (nano CuNi alloy) and acid sites (Al oxide) highly dispersed on the surface of a stable support (active carbon) were prepared and the importance of acid sites for the activity of CuNi catalysts in transfer hydrogenation was demonstrated. The catalysts showed promising catalytic activity on the transfer hydrogenation of levulinic acid (LA) to γ-valerolactone (GVL). The CuNi-1Al/AC with 5 wt.% CuNi alloy and 5 wt.% Al got 97.2% GVL yield and 100% LA conversion at 220 ℃ in isopropanol for 2 h. The high activity of the catalyst is attributed to the promoted esterification by the supported acid sites. The Al-modified catalyst also showed activity for esterification reaction in different alcohol hydrogen donors. The catalyst occurs inactive during the cycle due to the shedding of the active components, and the stability of catalyst is effectively improved by a stepwise impregnation. Graphical abstract
研究领域:
催化化学
·
可再生资源化学
✓ 已验证
产品关联
DOI
高影响因子
RSC Advances
·
2018
·Vol. 8
·期 71
·40989-40995
·
IF 2.936
Ruifeng Wang,Lungang Chen,Xinghua Zhang,Qi Zhang,Yuping Li,Chenguang Wang,Longlong Ma
Novel catalytic material with high catalytic activity and hydrothermal stability plays a key role in the efficient conversion of levulinic acid (LA) to γ-valerolactone (GVL) in water. In this study, mixed oxides Al2O3–TiO2, Al2O3–MoO3 and Al2O3–Co3O4 were synthesized by co-precipitation using aqueous solution of NaOH as precipitant. Ru catalysts supported on mixed oxides were prepared by impregnation method and their catalytic performances were tested in the hydrogenation of LA to GVL on a fixed bed reactor. The physicochemical properties of the catalysts were characterized by XRD, H2-TPR, NH3-TPD, and BET techniques. The TiO2 component significantly affected the acidity of the catalyst, and thus its catalytic activity for the GVL yield was affected. The desired product GVL with a yield of about 97% was obtained over the Ru/Al2O3–TiO2 catalyst under mild conditions (WHSV = 1.8 h−1, T = 80 °C). Moreover, the catalyst Ru/Al2O3–TiO2 exhibited excellent thermal stability in the test period of time.
研究领域:
催化
·
化学工程
·
材料科学
✓ 已验证
DOI
PubMed
高影响因子
INDUSTRIAL & ENGINEERING CHEMISTRY RESEARCH
·
2019
·
IF 3.375
Xue Wang,Jing Zeng,Xingmei Lu,Jiayu Xin,Suojiang Zhang
Butene plays an essential role in the area of petrochemical industry. The production of butene from the biomass-derived platform molecule γ-valerolactone (GVL) is of great interest. GVL decarboxylation reaction occurred under high temperature because the catalytic activity of the catalysts used before was not efficient for this reaction. In this work, beta zeolite with Si:Al = 5 was synthesized and used for GVL decarboxylation. It exhibited a higher catalytic performance than other commercial zeolites due to a large number of Lewis acid sites and relatively large micropore size. At 300 °C, 99.5% GVL conversion and 98% butene yield were obtained after condition optimizing. For further research, the influence of the Brønsted/Lewis acid ratio was investigated, and it turned out that Lewis acid was more active than Brønsted acid in crystalline material on GVL decarboxylation for the first time.
研究领域:
石油化工
·
催化
·
绿色化学
·
可再生能源
✓ 已验证
DOI
高影响因子
危险品化学品经营许可证（带存储）