GREEN CHEMISTRY
·
2020
·Vol. 22
·期 13
·4222-4230
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IF 9.48
Jiayuan Yu,Anker Degn Jensen,Lei Wang,Chunshan Li,Suojiang Zhang
Methacrolein (MAL) is an important chemical for the manufacture of methyl methacrylate and a key monomer in many polymerization reactions. In this study, L-proline was investigated as the catalyst for the aldol condensation of formaldehyde and propionaldehyde to produce MAL. The catalytic activity of the reaction system was closely related to the competition between the main reaction synthesizing MAL and the side reaction producing 2-methyl-2-pentenal, which could be modified by adjusting the operating parameters. The influences of several operating conditions, including temperature, reaction time and water content, on the catalytic performance of the system were systematically studied via a series of single-factor experiments, and the optimized reaction conditions were obtained. The mechanistic investigation via ESI-MS indicated that the reaction pathway followed the Mannich route. Experimental and theoretical kinetic analyses of the L-proline-catalyzed aldol condensation reaction were performed, and the reaction orders of the reactants were obtained by regression. The results showed that L-proline was an efficient catalyst for the production of MAL via aldol condensation under mild conditions.
研究领域:
化学工程
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有机化学
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产品关联
DOI
高影响因子
SEPARATION AND PURIFICATION TECHNOLOGY
·
2021
·
IF 7.312
Rui Wang,Jian Na,Xingang Li,Hong Li,Sai Gu,Xin Gao
Ethylene glycol (EG) is a widely used industrial chemical material, and integrated chemical-looping separation technology (CLS) was verified effective to remove 1,2-butanediol (1,2-BDO) and recover EG produced via the syngas to EG route. Thermodynamic experiments were carried out and employed to analyze the vapor–liquid and liquid–liquid behaviors of the system. Propyl aldehyde, apart from as the reactant, also shows excellent performance in water removal and acetals extraction. Based on the results of the thermodynamic analysis, a reactive extraction process was proposed to intensify the acetalization of EG and 1,2-BDO mixture with propyl aldehyde. The reactive extraction model was established on Aspen Plus v11, and the effects of flow mode (co-current and counter-current), number of stages, the feed-in mole ratio of aldehyde to DIOL on the conversions of EG and 1,2-BDO, the recovery of 2-ethyl-1,3-dioxolane (2ED), and the purity of acetals were investigated. Results show that co-current flow mode performs better than counter-current flow mode and an aldehyde to DIOL feed-in mole ratio of 1.35 to 1 is sufficient. The whole flowsheet, which consists of a seven-stage reactive extraction column and two distillation columns, was designed and optimized. Remarkably, the conversions of EG and 1,2-BDO are over 0.95 and the recovery of 2ED is 0.999 with the aldehyde to DIOL stoichiometric coefficient, which indicates the effectiveness of this process and provides fundamental data and guidance for industrial application.
研究领域:
化学工程
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工业化学
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产品关联
DOI
高影响因子
APPLIED CATALYSIS A-GENERAL
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2023
·
IF 5.5
Hongxian Luo,Gang Li,Longxin Ju,Qiang Lv
Herein, an environmentally friendly and compositionally tunable proline-functional polymer was prepared by copolymerization of divinylbenzene (DVB) with L-proline functional monomer . The synthesized poly[DVB-(4-APCA) x ]s were characterized by Powder X-ray diffraction (PXRD), Fourier transform infrared spectroscopy (FT-IR), solid state 13 C cross-polarization/magic angle spinning NMR (solid state 13 C CP/MAS NMR), thermogravimetry-Mass (TG-MS). The combined characterization results elucidated the skeletal structure of the polymer. The proline-functional polymer was used as catalyst in the preparation of methacrolein (MAL) by liquid phase condensation of formaldehyde (FA) and propionaldehyde (PA), in which the conversion of PA is 73.3%, the selectivity of MAL is 85.6% and the yield of MAL is 62.8% under 0.1 g poly[DVB-(APCA)]s at 75 °C for 4 h when dimethyl sulfoxide (DMSO) is used as the solvent. Its catalytic performance did not degrade markedly after five cycles. Moreover, the kinetics of the condensation reaction was also studied using the isolation method.
研究领域:
化学工程
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催化化学
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产品关联
DOI
高影响因子
INDUSTRIAL & ENGINEERING CHEMISTRY RESEARCH
·
2023
·
IF 4.2
Xiaoyan Zheng,Tianhao Zhang,Jie Li,Guoliang Zhang,Hongnan Chen,Shasha Cao,Chunshan Li,Guangzhou Jin
2-Ethyl-3-oxazolidineethanol (OE) is an important pharmaceutical intermediate for the treatment of dental plaque. A systematic investigation of the one-pot synthesis of OE from propanal (PA) and diethanolamine (DEA) was conducted herein. The process was carried out under mild reaction conditions without any addition of catalyst, and the product was characterized by Fourier transform infrared spectroscopy (FT-IR), 1H nuclear magnetic resonance (NMR), and electrospray ionization-tandem mass spectrometry (ESI-MS/MS). Additionally, the effects of the PA/DEA ratio, methanol/DEA ratio, reaction time, and temperature on the reaction results were explored. Based on the single-factor experiments, response surface methodology (RSM) was used to optimize the reaction conditions and it achieved a high OE yield of 98.48%, which is close to the prediction value of 98.38%. Furthermore, the reaction kinetics were calculated utilizing the second-order kinetic model, and activation energies of the forward and reverse reactions were 31.35 and 41.85 kJ·mol–1, respectively. Under the optimization reaction conditions, OE was efficiently synthesized, indicating a significant potential for industrial applications.
研究领域:
有机化学
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制药工程
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化工过程优化
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产品关联
DOI
高影响因子
Catalysts
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2021
·Vol. 11
·期 3
·394
·
IF 4.146
Baohe Wang,Honggang Dong,Liang Lu,Hongxia Liu,Zhaobang Zhang,Jing Zhu
A series of KxH1.1-xCu0.2Cs1(NH4)1.5PVMo11O40(KxCuCsNH4PVA) catalysts with differentxvalues were synthesized to catalyze the selective oxidation of methacrolein (MAL) to methacrylic acid (MAA). The effects of potassium (K) ions on both the structure and catalytic activity were studied in detail. The optimum K0.6CuCsNH4PVA exhibited a large surface area, more acid sites, and abundant active species (V4+/VO2+) in the secondary structure of the Keggin structure, consequently offering good catalytic performance. Furthermore, K ions increased the MAA selectivity at the expense of carbon monoxide and carbon dioxide (together defined as COX). Additionally, several process parameters for MAL oxidation were evaluated in the processing experiments. The effects of aldehyde impurities (formaldehyde and propanal) on the catalytic performance were investigated. Possible detrimental effects (catalyst poisoning and structural damage) of aldehyde impurities were excluded. A light decrease in MAL conversion could be attributed to the competitive adsorption of aldehyde impurities and MAL on the catalyst. Hopefully, this work contributes to the design of stable and feasible catalysts for the industrial production of MAA.Keywords:potassium;methacrolein;formaldehyde;propanal;selective oxidation;methacrylic acid;catalytic performance
研究领域:
化学工程
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催化材料科学
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产品关联
DOI
高影响因子
SENSORS AND ACTUATORS B-CHEMICAL
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2021
·
IF 7.46
Qianchun Zhang,Qin Zhou,Shan Tang,Yuxian Zhao,Yuguo Zheng,Li Jiang
Novel sugar-coated haws-sticklike Au/ZrO 2 nanofibers were fabricated by a solvothermal method using a simple precipitation approach. The nanostructure , surface morphology , and elementary composition of the Au/ZrO 2 nanofibers were explored by X-ray diffractometry, Fourier transform infrared spectroscopy, scanning electron microscopy, transmission electron microscopy , N 2 adsorption-desorption isotherms, and energy dispersive spectroscopy . The unique sugar-coated haws sticklike structure with multiple crystal faces (111) as active sites enhanced greatly cataluminescence property for propanal , and the developed propanal sensor based on Au/ZrO 2 nanofibers demonstrated good analytical characteristics with super-fast detection, high sensitivity, and selectivity. The response and recovery time were 1 and 5 s, respectively, the useable linear range was 0.181–38.8 mg/m 3 with a low limit of detection of 0.060 mg/m 3 , and the stability was proved to be fairly excellent for at least 120 days. Besides, the sensor was successfully applied to the analysis of propanal in real samples, and satisfactory recoveries (90.1–109%) with RSDs of 2.6–8.4% were achieved. Moreover, the cataluminescence sensing mechanism was further investigated by density functional theory and GC/MS analysis. The developed methodology has broad application prospects for the detection of propanal at low concentrations.
研究领域:
纳米材料科学
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分析化学
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环境监测
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DOI
高影响因子
JOURNAL OF INDUSTRIAL AND ENGINEERING CHEMISTRY
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2025
·
IF 6
Yuqiang Zhou,Xixi Zhou,Shuang Ou,Hongwei Zhao,Tongbo Pan,Zhongzhong Qian,Qinglong Xie,Yong Nie
1,3-Propanediol (1,3-PDO) as an important chemical intermediate can be used in the synthesis of polyesters, plasticizers, and surfactants. Catalytic hydration of acrolein to 3-hydroxypropionaldehyde (3-HPA) is a key step for the industrial production of 1,3-PDO from renewable glycerol. However, conventional acid catalytic hydration reactions have the issue of low 3-HPA yield resulting from the trade-off effect between acrolein conversion and 3-HPA selectivity, which is mainly due to the formation of unstable intermediates in the reaction pathway and the high reaction energy barriers. Here, we developed a synergistically catalytic system consisting of proton-donating carboxyl groups as the Brønsted acid sites and amino groups as the Lewis base sites, which was employed in acrolein hydration reaction. Compared with the acid catalytic process, the acrolein conversion significantly increased from 11.9 % to 89.3 % under the acid-base synergistic catalysis, with the 3-HPA selectivity increased from 95.5 % to 97.1 %. Density functional theory (DFT) calculations indicate that the reaction intermediates can be stabilized via the robust C N covalent bonds. Moreover, the energy barrier of the acrolein hydration reaction is reduced from 58.2 to 46.2 kcal/mol, which contributes to the increase in the 3-HPA yield.
研究领域:
催化化学
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有机化学
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理论化学
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工业化学
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绿色化学
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产品关联
DOI
高影响因子
JOURNAL OF WUHAN UNIVERSITY OF TECHNOLOGY-MATERIALS SCIENCE EDITION
·
2025
·Vol. 40
·期 4
·946-952
·
IF 1.1
Guo Jiahua,Wei Tao,Huagn Zhixiong,Deng Zongyi,Shi Minxian
We aimed to enhance the flame retardancy of epoxy resin (EP) by synthesizing a novel, halogen-free flame retardant through a one-pot method. The synthesis utilized 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (DOPO), furfurylamine (FA), and benzene propionaldehyde (BPA) as raw materials. We conducted differential scanning calorimetry (DSC) analysis to investigate the effects of FPD on the curing process and thermal properties of EP. Our findings reveal that incorporating FPD into EP can facilitate a faster curing process and increase the carbon residue post-combustion. Specifically, the FPD/EP-7 composite demonstrates a limiting oxygen index (LOI) of 34.9% and achieves a UL-94V-0 rating with a phosphorus content of 0.91wt%. These results indicate that FPD significantly enhances the thermal stability and charring rate of EP, thereby improving its flame retardancy. Although the addition of FPD slightly reduces the mechanical properties of EP, the composite material maintains excellent performance.
研究领域:
材料科学
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高分子科学
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消防安全工程
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化学合成
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产品关联
DOI
高影响因子
PROCEEDINGS OF THE NATIONAL ACADEMY OF SCIENCES OF THE UNITED STATES OF AMERICA
·
2020
·Vol. 117
·期 27
·15599-15608
·
IF 9.412
Jiayi Liu,Yifeng Wei,Lianyun Lin,Lin Teng,Jinyu Yin,Qiang Lu,Jiawei Chen,Yuchun Zheng,Yaxin Li,Runyao Xu,Weixiang Zhai,Yangping Liu,Yanhong Liu,Peng Cao,Ee Lui Ang,Huimin Zhao,Zhiguang Yuchi,Yan Zhang
2(S)-dihydroxypropanesulfonate (DHPS) is a microbial degradation product of 6-deoxy-6-sulfo-d-glucopyranose (sulfoquinovose), a component of plant sulfolipid with an estimated annual production of 1010 tons. DHPS is also at millimolar levels in highly abundant marine phytoplankton. Its degradation and sulfur recycling by microbes, thus, play important roles in the biogeochemical sulfur cycle. However, DHPS degradative pathways in the anaerobic biosphere are not well understood. Here, we report the discovery and characterization of two O2-sensitive glycyl radical enzymes that use distinct mechanisms for DHPS degradation. DHPS-sulfolyase (HpsG) in sulfate- and sulfite-reducing bacteria catalyzes C–S cleavage to release sulfite for use as a terminal electron acceptor in respiration, producing H2S. DHPS-dehydratase (HpfG), in fermenting bacteria, catalyzes C–O cleavage to generate 3-sulfopropionaldehyde, subsequently reduced by the NADH-dependent sulfopropionaldehyde reductase (HpfD). Both enzymes are present in bacteria from diverse environments including human gut, suggesting the contribution of enzymatic radical chemistry to sulfur flux in various anaerobic niches.
研究领域:
微生物学
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环境科学
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生物地球化学
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生物化学
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DOI
PubMed
高影响因子
CHEMICAL ENGINEERING SCIENCE
·
2023
·
IF 4.7
Qinglong Xie,Yuqiang Zhou,Yilei Wang,Tongbo Pan,Ying Duan,Shangzhi Yu,Weirong Ji,Yong Nie
Catalytic hydration of acrolein to 3-hydroxypropionaldehyde (3-HPA) is a key step for the chemical production of 1,3-propanediol (1,3-PDO) from renewable glycerol. However, a main issue of low reaction rate and long reaction time exists in the conventional hydration process. Here, we developed a microwave-assisted system for the efficient conversion of acrolein to 3-HPA. Simultaneous cooling method was adopted to maintain continuous microwave irradiation and meanwhile stable temperature during the reaction. The effects of catalyst type, temperature, catalyst loading and microwave power on acrolein conversion and 3-HPA selectivity were examined. Kinetic study showed that microwave irradiation could help for the reduction in activation energy, which led to acceleration in reaction rate during the acrolein hydration process. In addition, the density functional theory (DFT) calculations on the adsorption and reaction behavior of reactants molecules on the catalyst are consistent with the experimental results, which confirm the intensification effect of the microwave field.
研究领域:
化学工程
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催化
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可再生能源
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理论化学
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产品关联
DOI
高影响因子
JOURNAL OF AGRICULTURAL AND FOOD CHEMISTRY
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2022
·
IF 5.895
Ya’nan Shi,Rongshan Li,Jie Zheng,Yubin Xue,Yong Tao,Bo Yu
Bio-based propionate attracts increasing attention owing to its green nature and specific food additive market. To date, the time-consuming and costly fermentation process by strict anaerobes makes propionate production not ideal. In this study, we designed a new route for propionate production, in which 1,2-propanediol was first dehydrated to propionaldehyde and then to propionate by taking advantage of the robust oxidization capacity of the Pseudomonas putida KT2440 strain. The high atom economy (0.97 g/g) in this proposed pathway is more advantageous than the previous l-threonine-derived route (0.62 g/g). The molecular mechanism of the extraordinary oxidation capacity of P. putida KT2440 was first deciphered. The propionate production was realized in P. putida KT2440 by screening suitable glycerol dehydratases and optimizing the expression to eliminate the formation of 1-propanol and the accumulation of the intermediate propionaldehyde. The engineered strain produced propionate with a molar conversion rate of >99% from 1,2-propanediol. A high titer of 46.5 g/L pure propionic acid with a productivity of 1.55 g/L/h and a mass yield of 0.96 g/g was achieved in fed-batch biotransformation. Thus, this study provides another idea for the production of high-purity bio-based propionate from renewable materials with high atom economy.
研究领域:
生物技术
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微生物学
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化学工程
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代谢工程
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DOI
PubMed
高影响因子
PROCEEDINGS OF THE COMBUSTION INSTITUTE
·
2018
·Vol. 37
·期 1
·565-573
·
IF 5.336
Xiaoyuan Zhang,Yuyang Li,Chuangchuang Cao,Jiabiao Zou,Yan Zhang,Wei Li,Tianyu Li,Jiuzhong Yang,Philippe Dagaut
The kinetics of propanal oxidation was studied in a jet-stirred reactor (JSR) at atmospheric pressure. The investigated temperature range is from 450 to 800 K at two different equivalence ratios (0.35 and 4.0). Thanks to the synchrotron vacuum ultraviolet photoionization mass spectrometry (SVUV-PIMS), critical intermediates were identified, including methylperoxy, methyl hydroperoxide , ethylperoxy, ethyl hydroperoxide, α-lactone, β-propiolactone and ketohydroperoxides. A kinetic model for propanal oxidation was also developed and validated against the present experimental results, as well as those available from the literature. Main chain-branching pathways under the investigated conditions were analyzed based on present experimental data and kinetic model . The O 2 addition reaction to the propanoyl radical and subsequent oxidation reactions play an important role in determining the oxidation rate of propanal under fuel-lean conditions, especially in the low-temperature oxidation region. Under fuel-rich conditions, the decomposition of the propanoyl radical is predominant and C 2 H 5 relevant reactions consequently determine the kinetics of oxidation of propanal.
研究领域:
物理化学
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燃烧化学
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反应动力学
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分析化学
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能源化学
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DOI
高影响因子
危险品化学品经营许可证（带存储）