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Journal of Materials Chemistry A · 2024 · IF 10.7

Atomic scale niobium implantation in dealuminated industrial H-β zeolite catalyst for enhanced furfural production

Yuhui Huang,Yehan Tao,Qingqing Wang,Jian Du,Jinwen Hu,Jie Lu,Yanna Lv,Haisong Wang

To develop an industrial zeolite-based catalyst for efficient furfural production, the acidity, pore structure, and electronic properties of H-β zeolite were modulated by synergistic deatomization and atomic implantation treatments. The dealumination effectively decreased the intrinsic aluminum-related Lewis and Brosted acid sites, thus decreasing the occurrence of unwanted side reactions. Meanwhile, the removed skeleton aluminum can create voids for the following atomic implantation of introducing higher valent-state niobium species, which would provide new kinds of catalytic active sites, increase the average pore size by distorting the zeolite skeleton, and enhance the interaction with reactant molecules by acting as more electron deficient centers. In a single-phase water/γ-valerolactone reaction system, the optimum catalyst can efficiently convert both xylan and xylose with a conversion of 100 % at a medium temperature of 130 ℃ within 3 hours. Compared with the furfural yield over untreated H-β (12.7%), the yield over deAlβ/Nb(20%) catalyst was greatly enhanced by 54% with xylose as raw material. The catalyst can be recovered by simple cleaning and thermal regeneration and then reused. The proposed post-treatment strategy could maintain the integrity of the zeolite structure, ensure uniform and stable metal dispersion under harsh conditions, manage the complexity and cost of the preparation process, and most importantly, optimize the catalytic performance. Addressing these issues is essential for improving the efficiency and practical application of industrial zeolite catalysts by this general approach and benefiting industrial furfural production.

研究领域: 化学工程 · 催化材料
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BIORESOURCE TECHNOLOGY · 2014 · IF 5.039

Role of Brønsted acid in selective production of furfural in biomass pyrolysis

Haiyan Zhang,Xuejun Liu,Meizhen Lu,Xinyue Hu,Leigang Lu,Xiaoning Tian,Jianbing Ji

In this work, the role of Brønsted acid for furfural production in biomass pyrolysis on supported sulfates catalysts was investigated. The introduction of Brønsted acid was shown to improve the degradation of polysaccharides to intermediates for furfural, which did not work well when only Lewis acids were used in the process. Experimental results showed that CuSO 4 /HZSM-5 catalyst exhibited the best performance for furfural (28% yield), which was much higher than individual HZSM-5 (5%) and CuSO 4 (6%). The optimum reaction conditions called for the mass ratio of CuSO 4 /HZSM-5 to be 0.4 and the catalyst/biomass mass ratio to be 0.5. The recycled catalyst exhibited low productivity (9%). Analysis of the catalysts by Py-IR revealed that the CuSO 4 /HZSM-5 owned a stronger Brønsted acid intensity than HZSM-5 or the recycled CuSO 4 /HZSM-5. Therefore, the existence of Brønsted acid is necessary to achieve a more productive degradation of biomass for furfural.

研究领域: 化学工程 · 催化 · 可再生能源
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CARBOHYDRATE POLYMERS · 2015 · IF 4.074

Effect of structural characteristics of corncob hemicelluloses fractionated by graded ethanol precipitation on furfural production

Huiling Li,Qingqing Dai,Junli Ren,Longfei Jian,Feng Peng,Runcang Sun,Guoliang Liu

In the present study, a graded ethanol precipitation technique was employed to obtain hemicelluloses from the alkali-extracted corncob liquid. The relationship between the structural characteristics of alkali-soluble corncob hemicelluloses and the production of furfural was investigated by a heterogeneous process in a biphasic system. Results showed that alkali-soluble corncob hemicelluloses mainly consisted of glucuronoarabinoxylans and l -arabino-(4- O -methylglucurono)- d -xylans, and the drying way had less influence on the sugar composition, molecular weights and the functional groups of hemicelluloses obtained by the different ethanol concentration precipitation except for the thermal property, the amorphous structure and the ability for the furfural production. Furthermore, alkali-soluble corncob hemicelluloses with higher xylose content, lower branch degree, higher polydispersity and crystallinity contributed to the furfural production. A highest furfural yield of 45.41% with the xylose conversion efficiency of 99.06% and the furfural selectivity of 45.84% was obtained from the oven-dried hemicelluloses precipitated at the 30% (v/v) ethanol concentration.

研究领域: 生物化学 · 可再生资源与环境科学
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GREEN CHEMISTRY · 2019 ·Vol. 22 ·期 2 ·532-539 · IF 9.405

Solvent effect on xylose conversion under catalyst-free conditions: insights from molecular dynamics simulation and experiments

Qixuan Lin,Shouwei Liao,Libo Li,Weiying Li,Fengxia Yue,Feng Peng,Junli Ren

In this study, experiments and molecular dynamics simulations were combined to get insights into the role of solvent during the process of xylose conversion under catalyst-free conditions. Solvents used for furfural production were comparatively discussed, including traditional and emerging biomass-derived solvents – water, dimethyl sulfoxide (DMSO), dimethyl formamide (DMF), isopropanol (ISO), γ-butyrolactone (GBL) and γ-valerolactone (GVL). The degradation behavior of solvents, the solubility and α/β ratio of xylose, the distribution of the solvent around xylose/furfural and the hydrogen bonding between them were also studied. The results showed that in pure solvents, the different hydrogen bonding between xylose and the solvent resulted in different products. Water was a favourable solvent for xylose to form furfural among these pure solvents because less formic acid was produced from xylose in water under catalyst-free conditions. Furfural could be produced in mixed solvents if there was more water around xylose, which was similar to the case in pure water. Otherwise, the situation in mixed solvents was similar to that in the corresponding pure organic solvents. GBL and GVL, as green solvents, had weaker affinities with xylose than DMSO, DMF and ISO, but were intensively attracted by furfural, thus they could provide protective shells for furfural, which played a positive role during the production of furfural. The highest furfural yield of 46.4% was achieved in GBL–H2O at 180 °C – 150 min in the absence of catalysts.

研究领域: 化学工程 · 生物质转化 · 分子动力学模拟 · 绿色化学
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