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RENEWABLE ENERGY · 2024 · IF 9

A high-performance liquid biofuel produced from biomass-derived 2-cyclopentenone as an intermediate

Cuicui Wu,Meng Wang,Yunming Fang

The productive motivation of high-energy-density fuels from sustainable feedstocks has been prompted by environmental concerns and resource scarcities. To address this demand, here, the energy-rich C10 cycloalkanes were first afforded with biomass-derived 2-cyclopentenone (2CPE). Initially, bio-based 2CPE can be converted to tricyclo-diketones by (2 + 2) cycloaddition under UV irradiation or zeolite catalysis. The UV-light photocatalysis for dimerization of 2CPE to diketol-cycloadducts disclosed outstanding advantages of cost-effectiveness and feasibility than traditional zeolite-catalyzed manner, with a yield of 53.61 % at ambient temperature for 2 h. Despite the potential for high dimer yield (77.28 %) under thermo-catalysis of H-ZSM-5 zeolite, the reaction conditions (120 °C, 18 h) were found to be suboptimal. Subsequently, diketol-cycloadducts were selectively and efficiently hydrodeoxygenated to provide cyclopentane-based hydrocarbons using a Huang-Minlon methodology with a yield of 97.04 %, where the target components were directly distilled during the reaction. Specifically, the as-synthesized C10 cycloalkane mixture originated from 2CPE possess high density of 0.96 g mL −1 , large volumetric heat net of combustion (NHOC) of 40.02 MJ L −1 , along with low freezing point of −49 °C. These properties suggest that the bio-liquid cycloalkanes can be used as a standalone high-energy fuel or as a blending agent to enhance the performance of conventional jet fuels.

研究领域: 生物化学 · 能源科学
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GREEN CHEMISTRY · 2020 ·Vol. 22 ·期 8 ·2549-2557 · IF 9.48

Double-metal cyanide as an acid and hydrogenation catalyst for the highly selective ring-rearrangement of biomass-derived furfuryl alcohol to cyclopentenone compounds

Xiang Li,Qiang Deng,Lian Yu,Rui Gao,Zhikun Tong,Chenxi Lu,Jun Wang,Zheling Zeng,Ji-Jun Zou,Shuguang Deng

Herein, novel green synthetic routes to 4-hydroxy-2-cyclopentenone (HCP) and 2-cyclopentenone (CPE) from biomass-derived furfuryl alcohol via double-metal cyanide catalysis are proposed. For the synthesis of HCP, in comparison to conventional solid acids (i.e., Amberlyst-15), MOFs with coordinatively unsaturated metal ions as pure Lewis acid sites exhibit advantageous catalytic selectivity in the reaction under an N2 atmosphere in a bi-phasic water/n-hexane solvent system. FeZn and FeZn-P result in an HCP yield of 77.4% and 88.2%, respectively. For the CPE synthesis, the reaction conditions are the same as those for HCP, except a mono-phasic water solvent system and H2 atmosphere were employed. In addition to the acid-catalyzed rearrangement reaction, FeZn-DMC exhibits catalytic hydrogenation capability via heterolytic cleavage of the H–H bond over Zn–N frustrated Lewis pairs, and a CPE yield of 61.5% is obtained. The DFT simulation indicates that the acid sites and catalytic acid sites are ascribed to the tri-coordinatively unsaturated Zn2+ site (Zn(N)3) on the catalyst surface. Moreover, the DMC catalyst shows excellent stability and recycling performance. This work not only provides an efficient and green catalytic system for CPE and HCP preparation but also demonstrates the interesting bifunctional catalysis of both acid and hydrogenation catalysis over DMC.

研究领域: 化学工程 · 生物质能 · 催化化学
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Processes · 2025 ·Vol. 13 ·期 5 ·1435 · IF 2.8

Development of a Computer-Aided Process for Recovering and Purifying 2-Methyl-2-Cyclopentenone Based on Measured Phase Equilibrium Data

Zhongfeng Geng,Yunfei Bai,Ke Zhang,Feng Shi

2-Methyl-2-cyclopentenone (MCP) is the main by-product of the newly developed heterogeneous catalysis process for producing crotonaldehyde, which serves as an important intermediate for drug synthesis. However, how to recover and purify MCP from the product mixture is not known. To decipher this, a computer-aided process based on the measured phase-equilibrium data was developed. The improved Rose–Williams equilibrium kettle was used to measure the vapor–liquid equilibrium data for MCP–crotonaldehyde and MCP–water. Surprisingly, MCP and water formed a minimum azeotrope, which aided its own recovery from its dilute solution. The mole fraction of MCP in the azeotrope was 9.1%, the mole fraction of water was 90.9%, and the azeotropic temperature was 96.8 °C. Equilibrium data from the two binary systems were correlated using the Wilson and NRTL activity coefficient models. The NRTL-RK model was selected to simulate the process for recovering and purifying MCP. A two-column process was developed and optimized in this study, and the aim of effectively utilizing the by-product MCP was achieved with this process.

研究领域: 化学工程 · 药物合成
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APPLIED BIOCHEMISTRY AND BIOTECHNOLOGY · 2022 ·Vol. 194 ·期 11 ·4999-5016 · IF 3.094

Asymmetric Hydrogenation of C = C Bonds in a SpinChem Reactor by Immobilized Old Yellow Enzyme and Glucose Dehydrogenase

Ma Teng,Kong Weixi,Liu Yunting,Zhao Hao,Ouyang Yaping,Gao Jing,Zhou Liya,Jiang Yanjun

The application of immobilized enzymes in pharmaceutical and bulk chemical production has been shown to be economically viable. We demonstrate the exceptional performance of a method that immobilizes the old yellow enzyme YqjM and glucose dehydrogenase (GDH) on resin for the asymmetric hydrogenation (AH) of C = C bonds in a SpinChem reactor. When immobilized YqjM and GDH are reused 10 times, the conversion of 2-methylcyclopentenone could reach 78%. Which is because the rotor of the SpinChem reactor effectively reduces catalyst damage caused by shear force in the reaction system. When the substrate concentration is 175 mM, an 87% conversion of 2-methylcyclopentenone is obtained. The method is also observed to perform well for the AH of C = C bonds in other unsaturated carbonyl compounds with the SpinChem reactor. Thus, this method has great potential for application in the enzymatic production of chiral compounds.

研究领域: 生物催化 · 酶工程 · 药物化学 · 有机合成
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