BIOCHEMICAL ENGINEERING JOURNAL
·
2022
·
IF 4.446
Xi Cheng,Qingge Feng,Dachao Ma,Feifan Xing,Xu Zeng,Xiaoxiao Huang,Jiayang Teng,Lin Feng
A CH 3 -SBA-15-SO 3 H catalyst was synthesized for the conversion of glucose to levulinic acid. The performance of the catalyst was demonstrated by comparative experiments using γ-valerolactone solution system versus pure water system. Significantly, the conversion efficiency was almost five times higher for γ-valerolactone solution than that of the pure water. The side reactions of the γ-valerolactone solution system were probably less than that of water system. In order to provide a better understanding of the catalytic reaction and guide the engineering design, the kinetics of levulinic acid production from glucose over CH 3 -SBA-15-SO 3 H catalyst in γ-valerolactone solution were investigated. The kinetic model was established based on four differential equations, and the model results were fitted well to the experimental results. Notably, the activation energies of the production of 5-HMF and levulinic acid were 76.55 kJ/mol and 62.66 kJ/mol, respectively, which were obviously smaller than those previously reported, this may be attributed to the synergistic effect of the solid acid and the high concentration of γ-valerolactone solution.
研究领域:
化学工程
·
催化反应动力学
✓ 已验证
DOI
高影响因子
Journal of Energy Chemistry
·
2021
·
IF 9.676
Ziyi Li,Haigang Hao,Jingjing Lu,Chengming Wu,Rui Gao,Jifan Li,Chun-Ling Liu,Wen-Sheng Dong
Here we exquisitely fabricated Cu/ZrO 2 -dp catalysts with plentiful Cu-ZrO 2 interfaces by depositing amorphous ZrO 2 onto Cu nanoparticles for the hydrogenation of levulinic acid (LA) to γ-valerolactone (GVL). With the created plentiful Cu-ZrO 2 interfaces, the optimal catalyst 3Cu/ZrO 2 -dp exhibited exceptional catalytic performance under mild reaction conditions, and achieved the highest GVL mass productivity of 266.0 mmol GVL·h −1 ·g −1 Cu, which was 12.5 and 2.3 times of Cu/ZrO 2 catalysts with equivalent Cu loadings prepared by traditional impregnation (3Cu/ZrO 2 -im) or co-precipitation (3Cu/ZrO 2 -cp). As far as we know, this GVL mass productivity stood at the highest level compared with those obtained using non-noble metal catalysts under similar reaction conditions. By systematic investigation with multiple characterizations, density functional theory (DFT) calculations, and kinetic studies, it was found that interfacial active centers were created at Cu-ZrO 2 interfaces, which contained oxygen vacancies (O v ), negatively charged Cu δ− and partially reduced Zr 3+ . The O v favored the adsorption and activation of LA via its ketone group, while negatively charged Cu δ− was able to enhance heterolysis of H 2 , which resulted in the formation of H + -Cu δ− and Zr 3+ -H − active species via hydrogen spillover. Also, plentiful acid sites, which derived from coordinatively unsaturated and defective Zr species, generated at Cu-ZrO 2 interfaces. With the cooperation of interfacial active centers (Cu δ− -O v -Zr 3+ ) and acid sites, the fabricated 3Cu/ZrO 2 -dp with plentiful Cu-ZrO 2 interfaces achieved excellent catalytic performance for the hydrogenation of LA to GVL. Hence, the synergistic catalysis of Cu-ZrO 2 interfaces provided an effective strategy for designing catalysts with a satisfactory performance for the hydrogenation of LA, which also can be expanded to other hydrodeoxygenation reactions.
研究领域:
催化
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化学工程
·
材料科学
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物理化学
✓ 已验证
DOI
高影响因子
JOURNAL OF COLLOID AND INTERFACE SCIENCE
·
2025
·
IF 9.7
Mingya Liu,Hanli Zheng,Xiaohui Yang,Zewei Hu,Yunxi Hou,Lu Shen,Dongyu Liu,Shitao Yu,Lu Li,Shiwei Liu,Yue Liu
The high efficiency production of renewable resources has been widely used in fuel and synthetic chemistry. In this work, a series of novel, efficient Pd@mSiO 2 -xCeO 2 bifunctional yolk-shell catalysts have been developed and applied to the preparation of γ-valerolactone by the hydrogenation of levulinic acid. The results showed that CeO 2 can effectively improve the catalytic performance of the catalyst, then achieve 100 % conversion of levulinic acid and 97 % selectivity of γ-valerolactone. The characterization results showed that the addition of CeO 2 regulated the acid sites of the catalyst, promoted the reduction of PdO, thus promoting the formation of more Pd 0 . In addition, the kinetic experiment results showed that the activation energy of the reaction effectively decreased with the addition of CeO 2 . Then, the reaction mechanism was studied using Density functional theory (DFT) calculations. Finally, the encapsulation strategy of mesoporous silica shell provided a stable environment for the catalyst and maintains high activity after 5 cycles. The efficient and stable noble metal catalysts developed in this study significantly enhance the yield of biomass-derived γ-valerolactone. Their large-scale application not only supports the green production of biofuels and biodegradable materials but also establishes a material foundation for the generation of renewable energy, thereby contributing to the realization of a low-carbon circular economy.
研究领域:
催化化学
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绿色化学
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可再生能源
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材料科学
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化学工程
·
理论化学
✓ 已验证
产品关联
DOI
PubMed
高影响因子
INTERNATIONAL JOURNAL OF BIOLOGICAL MACROMOLECULES
·
2025
·
IF 8.5
Zicheng Du,Jiao Li,Yi Xie,Baojie Liu,Wenxuan Mo,Chengrong Qin,Chen Liang,Caoxing Huang,Shuangquan Yao
Directed hydrolysis of hemicellulose to produce high-purity derivative sugars offers a green and value-added utilization pathway. This study investigates the catalytic hydrolysis kinetics of hemicellulose using levulinic acid (Lev), focusing on the effects of temperature, reaction time, and acid concentration on the distribution of target products (xylose, arabinose) and inhibitory by-products (furfural, acetic acid). Under optimized conditions, xylose and arabinose concentrations reached 8.02 and 0.86 g/L. A two-phase kinetic model reveals that reaction temperature optimization enhances monosaccharides selectivity and limits by-product accumulation. Incorporating the pKa of Lev into the kinetic rate constant improves model accuracy across varying acid concentrations. In the Lev system, the activation energy for xylose degradation (87.06 kJ·mol −1 ) exceeds that of the hydrolysis (51.28 kJ·mol −1 in the fast stage and 78.31 kJ·mol −1 in the slow stage), a trend opposite to that observed with inorganic acids, indicating enhanced selectivity for monosaccharide production. Density functional theory analysis reveals that the carboxyl group in Lev facilitates glycosidic bond cleavage through hydrogen bonding at the molecular level. Thermodynamic analysis shows that hemicellulose hydrolysis is an endothermic, non-spontaneous process driven by temperature, with a more favorable energy profile for xylose formation than degradation, which helps to achieve the effective accumulation of monosaccharides. These findings reveal the catalytic role of Lev in hemicellulose hydrolysis and support its application in the efficient and sustainable production of value-added sugars.
研究领域:
生物能源
·
绿色化学
·
碳水化合物化学
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反应动力学
·
催化
✓ 已验证
产品关联
DOI
PubMed
高影响因子
CHEMICAL ENGINEERING RESEARCH & DESIGN
·
2022
·
IF 4.119
Bin Wang,Haifeng Cong,Xingang Li,Hong Li,Xin Gao
The recovery of levulinic acid (LA) and formic acid (FA) from aqueous solutions and actual biomass hydrolysates by using the stepwise adsorption method was investigated for the first time. The carbon molecular sieve was used as the adsorbent for FA and microporous activated carbon was used as the adsorbent for LA according to the steric hindrance effect of the pore channels and the difference in molecular diameter of FA and LA. The adsorption data of LA and FA onto their respective adsorbents were measured and numerically analyzed by adopting batch adsorption experiment and fixed-bed column methods. In the study of static adsorption equilibrium experiment, the Langmuir equation fitted the data of LA adsorption on activated carbon, while the Freundlich equation fitted well the adsorption data of FA adsorption on carbon molecular sieve. In the kinetic study, the LA adsorption on activated carbon and FA adsorption on carbon molecular sieve confirmed the PSO model. Moreover, the effect of various conditions on fixed-bed column adsorption progress was investigated, which indicated that the adsorption property improved with feed flow rate, column length, temperature decreasing and initial concentration increasing. The Yoon-Nelson model was adopted to predict and analyze the whole process of adsorption breakthrough and consistent well with the experimental data. The separation of LA and FA was realized by continuous fractional adsorption.
研究领域:
化学工程
·
环境科学
✓ 已验证
DOI
高影响因子
NEW JOURNAL OF CHEMISTRY
·
2021
·Vol. 45
·期 32
·14406-14413
·
IF 3.591
Yubo Liu,Guoqiang Ding,Guoping Zhao,Haohao She,Yulei Zhu,Yong Yang
Combining glucose dehydration and the subsequent hydrogenation in one pot is a preferable approach for process development as such a method allows in situ generation of the reactive intermediate to undergo further reaction without extra energy-intensive separation. Herein, phosphotungstic acid and various types of titania (anatase, rutile, P25) supported Ru-based catalysts were considered as the dehydration and hydrogenation catalysts, respectively. Modulating the different reactant media (N2, H2), various products were obtained with GBL–H2O as the solvent. A considerable yield (42%) of levulinic acid (LA) and γ-valerolactone (GVL) (40%) were obtained in nitrogen and subsequent hydrogen. Ru/TiO2 (rutile) was the favorable hydrogenation catalyst among the three types of Ru/TiO2. Meanwhile, a certain amount of sorbitol (36%) was obtained in pure hydrogen. The hydrogenation of glucose is more likely to occur than the glucose dehydration. The physicochemical properties of the catalysts were characterized by XRD, BET, TPR, STEM and in situ CO/FT-IR, and the results show that well-dispersed Ru particles are located on the rutile crystallites, which facilitated the hydrogenation of LA. A strong metal support interaction (SMSI) was responsible for the various microstructure properties and the different hydrogenation reactivity. This work allows a better understanding of the reaction paths of glucose conversion.
研究领域:
催化
·
化学工程
·
材料科学
✓ 已验证
产品关联
DOI
高影响因子
Catalysts
·
2020
·Vol. 10
·期 9
·1096
·
IF 3.52
Ligang Luo,Xiao Han,Qin Zeng
A series of Ni-Fe/SBA-15 catalysts was prepared and tested for the catalytic hydrogenation of levulinic acid to γ-valerolactone, adopting methanol as the only hydrogen donor, and investigating the synergism between Fe and Ni, both supported on SBA-15, towards this reaction. The characterization of the synthesized catalysts was carried out by XRD (X-ray powder diffraction), TEM (transmission electron microscopy), H2-TPD (hydrogen temperature-programmed desorption), XPS (X-ray photoelectron spectroscopy), and in situ FT-IR (Fourier transform–infrared spectroscopy) techniques. H2-TPD and XPS results have shown that electron transfer occurs from Fe to Ni, which is helpful both for the activation of the C=O bond and for the dissociative activation of H2molecules, also in agreement with the results of the in situ FT-IR spectroscopy. The effect of temperature and reaction time on γ-valerolactone production was also investigated, identifying the best reaction conditions at 200 °C and 180 min, allowing for the complete conversion of levulinic acid and the complete selectivity to γ-valerolactone. Moreover, methanol was identified as an efficient hydrogen donor, if used in combination with the Ni-Fe/SBA-15 catalyst. The obtained results are promising, especially if compared with those obtained with the traditional and more expensive molecular hydrogen and noble-based catalysts.Keywords:biomass ester derivatives;solvothermal processing;levulinic acid;γ-valerolactone;Ni-Fe bimetallic catalysts
研究领域:
化学工程
·
催化反应
·
可再生能源
✓ 已验证
产品关联
DOI
高影响因子
Biomass Conversion and Biorefinery
·
2021
·Vol. 13
·期 4
·2933-2946
·
IF 4.987
Zhao Sibo,Wang Zihua,Chang Chun,Li Pan,Xu Guizhuan,Pang Shusheng
A two-stage alcoholysis was developed for improved conversion of furfural residue (FR) into levulinic acid (LA) and methyl levulinate (ML). Mixed acids including 0.01 M of H 2 SO 4 and Al 2 (SO 4 ) 3 and methanol/water (50/50 v/v%) were identified as the suitable catalyst and reaction medium. The optimum alcoholysis conditions were 198 °C and 1.5 h for the 1st stage and then 163 °C and 1.3 h for the 2nd stage, and the maximum total yield of LA and ML can reach 25.64%. The reaction kinetics and possible conversion pathways for ML and LA production were proposed. On the basis, HCOOH/H 2 O 2 pretreatment was screened for the pretreatment of FR, which increased the cellulose content of FR from 40.01 to 71.91%. The maximum total yield of LA and ML from pretreated FR was 44.96% under the optimum conditions of 195 °C and 1.9 h for the 1st stage and then 166 °C and 1.1 h for the 2nd stage, which was 16.09% higher than that of isothermal alcoholysis. The reusability tests showed that the Al 2 (SO 4 ) 3 was stable and can be reused at least 5 times. This study developed a new method for high-value utilization of FR and cleaner production of LA and ML.
研究领域:
化学工程
·
可再生能源
✓ 已验证
产品关联
DOI
高影响因子
PROCESS BIOCHEMISTRY
·
2018
·
IF 2.616
Chen Liang,Yangdong Hu,Yan Wang,Lianying Wu,Weitao Zhang
Levulinic acid (LA) is an important platform chemical, the production of which by using biomass resources such as corncob is of great significance to the sustainable development. Traditional hydrolysis processes yield low concentrations of levulinic acid with large amounts of acid being consumed. In this paper, a new fed-batch process for hydrolyzing corncob residues with sulfuric acid being utilized as the catalysis to produce levulinic acid at high concentrations is proposed. The mass concentration of the levulinic acid increased with growing the times of feeding and a 107.93 g/L of the levulinic acid can be reached at the 7th hydrolysis. However, the yield of levulinic acid reduces gradually during the fed-batch process. To explore the phenomenon, the reaction mechanism of cellulose acid hydrolysis was experimentally studied. It can be deduced that the reduction of the levulinic acid yield was caused by the polymerization of the soluble humin analogues and the 5-hydroxymethyl furfural (5-HMF) as well as the glucose.
研究领域:
化学工程
·
生物技术
·
可持续化学
✓ 已验证
产品关联
DOI
高影响因子
Molecular Catalysis
·
2019
·
IF 2.938
Zhi-Xin Li,Xian-Yong Wei,Guang-Hui Liu,Xing-Long Meng,Zheng Yang,Shuo Niu,Di Zhang,Hua-Shuai Gao,Zhi-Hao Ma,Zhi-Min Zong
Highly selective hydrogenation of furfural and levulinic acid (LA) was studied over Ni 0.09 Zn/NC 600 derived from zeolitic imidazolate frameworks. The existence of active Ni 3 ZnC 0.7 particles in Ni 0.09 Zn/NC 600 was confirmed by multiple characterizations. As a result, over Ni 0.09 Zn/NC 600 , 99.7% of furfural conversion (FC) and 100% of furan-2-ylmethanol selectivity (FMS) were achieved in isopropanol (IP) at 170 °C for 2 h, while FC and (tetrahydrofuran-2-yl)methanol (THFM) selectivity are 97.5% and 86.4% in water at 150 °C for 1 h. Over the same catalyst, LA was completely converted to γ-valerolactone in water at 95 °C for 0.5 h. The catalyst is still highly active after 6 cycles of recycling with 92.8% of FC and 100% of FMS in IP at 170 °C for 1.5 h and 90.1% of LA conversion and 100% of γ-valerolactone selectivity in water at 80 °C for 0.5 h.
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
Russian Journal of Physical Chemistry A
·
2020
·Vol. 93
·期 13
·2620-2627
·
IF 0.719
Yanyan Xu,Lu Tianliang,Bu Ningning,Luo Qianqian,Qing Yashi,Lin Li
Abstract Catalytic conversion of biomass based platform chemicals to value added chemicals has attracted much attention recently. In this work, Ni-based catalysts were developed for the conversion of levulinic acid to γ-valerolactone. By investigation of reduction behavior of NiO, it was found that a relatively low reduction temperature (300°C) can provide the reduction of NiO to Ni 0 . The high reduction temperature (500°C) generally applied in literature is not necessary. The effect of supports was also studied, and hierarchical AlPO 4 -5 (AlPO 4 -5-meso) supported Ni showed the best catalytic performance due to the proper pore size of AlPO 4 -5-meso, which contains both micropores and mesopores. The effect of Ni loading was also investigated, 10 wt % of Ni is enough for this reaction, which is lower than the reported amount of Ni loading. By using Ni/AlPO 4 -5-meso with 10 wt % Ni as catalyst, 84% γ-valerolactone yield and 100% levulinic acid conversion can be obtained after reaction for 10 h at 180°C.
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
INDUSTRIAL CROPS AND PRODUCTS
·
2020
·
IF 4.244
Xiaoyun Li,Xuebin Lu,Shuangxi Nie,Min Liang,Zhihao Yu,Bingyu Duan,Jiaxin Yang,Rui Xu,Lefu Lu,Chuanling Si
A feasible approach to convert glucose and cellulose to levulinic acid applying phosphotungstic acid as catalyst in deep eutectic solvent was proposed. In our study, phosphotungstic acid was considered to be an effective catalyst for levulinic acid production. A considerable yield of levulinic acid (98.9 %) from glucose was achieved using 30 g/L phosphotungstic acid as catalyst at 468 K for 80 min. The peak levulinic acid yield from cellulose was 88.6 % for 120 min at the present temperature and phosphotungstic acid concentration. The reaction system exhibits efficient performance for the conversion of glucose and cellulose, which was due to the combation of phosphotungstic acid and deep eutectic solvent enhanced the levulinic acid production. Additionally, the kinetic study of levulinic acid formation from cellulose was investigated to supply a further insight on the whole biorefining process. The kinetic model agreed with the experiment data well. The activation energy for levulinic acid formation was 47.2 kJ/mol, which obtained from a modified Arrhenius equation.
研究领域:
生物化学
·
可再生资源转化
✓ 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）