GREEN CHEMISTRY
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2022
·Vol. 25
·期 3
·1056-1066
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IF 11.034
Fengan Han,Yanting Liu,Guangyi Li,Lin Yuan,Aiqin Wang,Feng Wang,Tao Zhang,Ning Li
Selective hydrodeoxygenation (HDO) of lignocellulose-derived ketones to olefins is a promising method for upgrading lignocellulosic biomass-derived molecules. Herein, zinc molybdate (ZnMoO4–E) with a disordered layered stacking structure was first prepared using a facile and environmentally friendly evaporation method and it exhibited outstanding catalytic performance for the selective HDO of lignocellulose-derived ketones to olefins. Using it, 4-heptanone, a representative of lignocellulose-derived ketones, was totally converted, and a high carbon yield of heptene (90%) was achieved at 673 K. On the basis of the characterization results, the outstanding catalytic performance of ZnMoO4–E was attributed to its porous structure, higher oxygen vacancy (or the Mo5+ species) concentration and higher acidity. Analogously, ZnMoO4–E also exhibited good catalytic performances for the selective HDO of other lignocellulose-derived ketones (such as acetone, butanone, 2-pentanone, 3-pentanone, cyclohexanone, acetophenone and 5-nonanone) to their corresponding olefins.
研究领域:
催化
·
化学工程
·
材料科学
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可再生能源
✓ 已验证
产品关联
DOI
高影响因子
GREEN CHEMISTRY
·
2024
·
IF 9.3
Shan Jiang,Riyang Shu,Anqi Wang,Zhuoli Deng,Yuhong Xiao,Jiajin Li,Qingwei Meng,Qian Zhang
High-quality liquid biofuels can be produced from renewable lignin-derived phenolic compounds through the efficient hydrodeoxygenation (HDO) process, in which the traditional catalysts usually include metal site and acid site that catalyzes hydrogenation and deoxygenation procedures respectively. This work presented a novel acid-free NixMoyN/C catalyst from the perspective of green chemistry, providing a new pathway for HDO of lignin-derived phenolic compounds that involves hydrogenation, deoxygenation and hydrogenolysis at the same time. A series of NixMoyN/C catalysts were prepared by varying Ni and Mo molar ratio, where the Ni1Mo3N/C catalyst showed the best HDO performance. Guaiacol was completely converted at 260 °C after 4 h, with 95.8% cyclohexane selectivity. And a small amount of benzene can be obtained as a valuable fuel additive by-product by altering the conventional HDO reaction path. By shortening the reaction time, benzene can be obtained as the intermediate products with a relative high selectivity. Based on the characterizations of XRD, BET, SEM, TEM, XPS, H2-TPD and EPR, the results demonstrate that the multiple active components of Ni1Mo3N/C catalyst allow it to efficiently catalyze the hydrogen activation and C-O bond cleavage even under acid-free condition. The existence of the active phase of Ni, Ni2Mo3N and β-Mo2C, as well as the interaction between Ni and Mo metals, contributes together to achieve an efficient HDO performance. Not only for the various phenolic model compounds, the feasibility of Ni1Mo3N/C catalysts for upgrading raw lignin-oil was also demonstrated, with the hydrocarbon content increasing from 5.7% to 88.4%. Notably, arenes account for 18.2% in the hydrocarbon products, which confirms the occurrence of hydrogenolysis in the catalytic process. This work provides a novel route for the conversion of lignin-derived phenolic compounds to the production of high-quality hydrocarbon liquid biofuels, especially the direct production of arene component.
研究领域:
化学工程
·
催化
·
可再生能源
·
绿色化学
✓ 已验证
产品关联
DOI
高影响因子
Catalysis Science & Technology
·
2022
·Vol. 12
·期 16
·5178-5188
·
IF 6.177
Zegang Qiu,Xiaoxia He,Zhiqin Li,Qichen Guan,Liang Ding,Yanan Zhu,Yueling Cao
The development of non-noble metal catalysts with high efficiency for the hydrodeoxygenation (HDO) of bio-oil is of great importance for the utilization of lignin biomass resources. As a crucial lignin-based platform chemical, vanillin is a promising candidate for the production of fine chemicals and polymers. Here, a promising non-noble Co–Zn/NPC catalyst (NPC: nitrogen-doped porous carbon materials) for the HDO of vanillin was prepared by pyrolysis of Co–Zn zeolite imidazolate framework/graphitic carbon nitride (Co–Zn-ZIF/g-C3N4) composites. Full vanillin conversion with 99% MMP (2-methoxy-4-methylphenol) selectivity could be achieved at 100 °C and 1 MPa H2 over 4Co–1Zn/NPC. Characterization results indicate that the presence of g-C3N4 promotes the formation of mesopores, which is beneficial for fast mass transfer. Additionally, the introduction of Zn downsizes the size of Co nanoparticles, and lowers the electron density around the Co atoms in Co–Zn/NPC catalysts, which can accelerate the hydrogenation of vanillin. More importantly, the Zn introduced in the catalyst may function as a basic site to facilitate the conversion of the intermediate HMP (4-hydroxy-3-methoxybenzyl alcohol) into MMP, thus enhancing the MMP selectivity. Moreover, Co–Zn/NPC presents excellent stability in the HDO reaction of vanillin. This work provides some useful insights into the design of novel non-noble metal catalysts with high efficiency for HDO of bio-oil.
研究领域:
催化
·
材料科学
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化学工程
·
生物化学工程
✓ 已验证
产品关联
DOI
高影响因子
ACS Sustainable Chemistry & Engineering
·
2019
·
IF 6.97
Changhui Zhu,Haiyong Wang,Chilu Cai,Kang Bi,Bijuan Cai,Xiangbo Song,Qiying Liu,Longlong Ma
Biomass-derived 2,5-dimethylfuran (DMF) is an ideal, renewable gasoline additive, and its production with high productivity is highly desirable. A continuous production route was developed to yield DMF from fructose via a tandem strategy, where dehydration catalysts (HY zeolite and niobium phosphate) assisted by 1-butyl-3-methylimidazolium chloride ([BMim]Cl) and hydrodeoxygenation (HDO) catalyst Cu–Ru/C were integrated into one reaction system with γ-butyrolactone (GBL) as the mobile phase. Optimum conditions, such as temperature, H2 pressure, weight hourly space velocity, and [BMim]Cl concentration, were investigated systematically, with an initial HDO study by using 5-hydroxymethylfurfural (HMF) as substrate and subsequent tandem dehydration and HDO to produce DMF with fructose as substrate. Among the conditions, the highest yield of DMF at 55.2% was gained by niobium phosphate and Cu–Ru/C, with the aid of [BMim]Cl in a fixed bed. Meanwhile, [BMim]Cl facilitated fructose dehydration to HMF and also mediated HDO of the resultant HMF by stabilization, which was clarified by 1H NMR and FTIR spectroscopy. Finally, the fact that carbon deposit led to catalyst deactivation was examined thoroughly via a series of characterization techniques. This work achieved continuous DMF production from fructose and laid a foundation for future possible amplification of DMF.
研究领域:
化学工程
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催化
·
可再生能源
·
生物燃料
✓ 已验证
产品关联
DOI
高影响因子
ENERGY & FUELS
·
2020
·
IF 3.421
Xiangchen Kong,Chao Liu,Yue Han,Ming Lei,Yuyang Fan,Ming Li,Rui Xiao
The development of an economic and sustainable catalytic system was crucial for lignin-based biorefinery. Herein, we reported a low-cost Cu/CuMgAlOx catalyst with promising activity toward lignin hydrodeoxygenation (HDO) through a H2-free method. Supercritical methanol was used as the hydrogen donor, solvent, and reactant simultaneously. Guaiacol was employed as a representative lignin model compound to reveal the HDO mechanism of lignin derivatives. HDOs of guaiacol performed at 250, 275, 300, and 350 °C with durations ranging from 15 to 120 min indicated a high HDO efficiency of the catalytic system. The obtained liquid products were categorized to oxygen-containing unsaturated products (OUPs), oxygen-containing saturated products (OSPs), and cycloalkanes. A kinetic model based on a simplified reaction process containing the three following conversion steps was established: guaiacol transformed to OUPs through the initial HDO, then hydrogenated to OSPs (medium HDO), and eventually turned to cycloalkanes by the deep HDO. The deep HDO was the rate-determining step, and the apparent activation energies of the three steps were all lower than those in the literature. Phenol, 1,2-cyclohexanediol, anisole, and veratrole were the major intermediates, the HDOs of which were programed for pathway verification. Remarkably, catechol (the culprit of condensation) was not produced in this system. Overall, a detailed reaction network of guaiacol HDO was established, and the veil of Cu/CuMgAlOx-catalyzed lignin-derivatives HDO in supercritical methanol was revealed. This work paved the way for the application of Cu/CuMgAlOx catalyst in lignin-derivatives upgrading.
研究领域:
化学工程
·
催化
·
生化工程
·
可再生能源
✓ 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）