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Rosin side chain type catalyst-free vitrimers with high cross-link density, mechanical strength, and thermal stability

《化学科学与工程前沿(英文)》 2023年 第17卷 第9期   页码 1267-1279 doi: 10.1007/s11705-022-2291-7

摘要: The emergence of vitrimer, a new class of polymer materials can address the problem of recyclability, reprocess ability and recyclability of thermosetting plastics. Rosin, a natural product, is an ideal raw material for the preparation of polymers in a more sustainable way. Nevertheless, due to the huge steric hindrance caused by the hydrogenated phenanthrene ring structure, the cross-link density of materials is frequently lowered. In this study, hydrogenated rosin was adopted for preparing hydrogenated rosin side-chain type diacids, which were reacted with mixed epoxy to obtain rosin side-chain type vitrimers. It was completely characterized by differential scanning calorimetry test, thermogravimetric analysis, shape memory test and self-healing test. The prepared vitrimers exhibited good self-healing properties, excellent heat resistance (Td = 352 °C) as well as high mechanical properties (tensile strength of 46.75 MPa). The tricyclic diterpene structure of rosin was introduced into the side chain in order to avoid the reduction of cross-link density resulting from the huge steric hindrance of the rigid tricyclic hydrophenylene skeleton. Vitrimers can undergo dynamic transesterification reaction without external catalysts due to the autocatalytic effect of tertiary amines from epoxy. Moreover, our work expanded the application field of rosin, increased the added value of rosin, and provided a novel method for preparing rosin-based vitrimers with ideal properties.

关键词: vitrimers     rosin     catalyst-free     high mechanical properties     dynamic transesterification reaction    

Biodiesel production by the transesterification of cottonseed oil by solid acid catalysts

CHEN He, PENG Baoxiang, WANG Dezheng, WANG Jinfu

《化学科学与工程前沿(英文)》 2007年 第1卷 第1期   页码 11-15 doi: 10.1007/s11705-007-0003-y

摘要: Methyl esters (biodiesel) were produced by the transesterification of cottonseed oil with methanol in the presence of solid acids as heterogeneous catalysts. The solid acids were prepared by mounting HSO on TiO · nHO and Zr(OH), respectively, followed by calcining at 823K. TiO-SO and ZrOSO showed high activity for the transesterification. The yield of methyl esters was over 90% under the conditions of 230°C, methanol/oil mole ratio of 12:1, reaction time 8 h and catalyst amount (catalyst/oil) of 2% (w). The solid acid catalysts showed more better adaptability than solid base catalysts when the oil has high acidity. IR spectral analysis of absorbed pyridine on the samples showed that there were Lewis and BrØnsted acid sites on the catalysts.

关键词: BrØnsted     reaction     presence     cottonseed     biodiesel    

of carbon dioxide photoreduction process in a laboratory-scale photoreactor by computational fluid dynamicand reaction kinetic modeling

《化学科学与工程前沿(英文)》 2022年 第16卷 第7期   页码 1149-1163 doi: 10.1007/s11705-021-2096-0

摘要: The production of solar fuels via the photoreduction of carbon dioxide to methane by titanium oxide is a promising process to control greenhouse gas emissions and provide alternative renewable fuels. Although several reaction mechanisms have been proposed, the detailed steps are still ambiguous, and the limiting factors are not well defined. To improve our understanding of the mechanisms of carbon dioxide photoreduction, a multiphysics model was developed using COMSOL. The novelty of this work is the computational fluid dynamic model combined with the novel carbon dioxide photoreduction intrinsic reaction kinetic model, which was built based on three-steps, namely gas adsorption, surface reactions and desorption, while the ultraviolet light intensity distribution was simulated by the Gaussian distribution model and Beer-Lambert model. The carbon dioxide photoreduction process conducted in a laboratory-scale reactor under different carbon dioxide and water moisture partial pressures was then modeled based on the intrinsic kinetic model. It was found that the simulation results for methane, carbon monoxide and hydrogen yield match the experiments in the concentration range of 10−4 mol·m–3 at the low carbon dioxide and water moisture partial pressure. Finally, the factors of adsorption site concentration, adsorption equilibrium constant, ultraviolet light intensity and temperature were evaluated.

关键词: carbon dioxide photoreduction     computational fluid dynamic simulation     kinetic model     Langmuir adsorption    

Transesterification of soybean oil to biodiesel over kalsilite catalyst

Guang WEN, Zifeng YAN

《化学科学与工程前沿(英文)》 2011年 第5卷 第3期   页码 325-329 doi: 10.1007/s11705-010-0574-x

摘要: The transesterification reaction of soybean oil with methanol over kalsilite-based heterogeneous catalysts was investigated. The kalsilite was synthesized from potassium silicate, potassium hydroxide, and aluminum nitrate aqueous solutions by controlling the pH value at 13. After calcination in air at 1200°C, a very porous kalsilite (KAlSiO ) was obtained with surface pores ranging from 0.2 to 1.0 μm. However, this kalsilite had relatively low catalytic activity for the transesterification reaction. A biodiesel yield of 54.4% and a kinematic viscosity of 7.06 cSt were obtained at a high reaction temperature of 180°C in a batch reactor. The catalytic activity of kalsilite was significantly enhanced by introducing a small amount of lithium nitrate in the impregnation method. A biodiesel yield of 100% and a kinematic viscosity of 3.84 cSt were achieved at a temperature of only 120°C over this lithium modified catalyst (2.3 wt-% Li). The test of this lithium modified catalyst in pellet form in a laboratory-scale fixed-bed reactor showed that it maintained a stable catalytic performance with a biodiesel yield of 100% over the first 90 min.

关键词: kalsilite     heterogeneous catalyst     transesterification     biodiesel    

酯交换反应在制备生物柴油上的应用

张怀渊,宋元达

《中国工程科学》 2010年 第12卷 第1期   页码 24-29

摘要:

生物柴油因其环境友好且可再生作为矿物柴油的替代燃料而备受关注,生物柴油主要通过均相酸碱催化、脂肪酶催化、超临界法和固体酸碱催化的酯交换反应制备得到,但各种制备方法各有优劣,均相酸碱催化法反应迅速,转化率高但存在后续处理复杂,污染严重等问题;脂肪酶催化法反应条件温和,对原料中的水和游离脂肪酸不敏感,不需要过量的甲醇参与反应,后续处理工序简单,但酶的成本过高,这是制约其商业化发展的最大阻碍;超临界法是制备生物柴油的新技术,反应迅速,不需要催化剂,油脂转化率非常高,但其反应需要高温高压且能耗很大;固体酸碱催化剂

关键词: 生物柴油     酯交换反应     均相酸碱     固体酸碱     脂肪酶     超临界法    

Application of heterogeneous catalysis to biodiesel synthesis using microalgae oil

《环境科学与工程前沿(英文)》 2021年 第15卷 第5期 doi: 10.1007/s11783-020-1343-9

摘要:

• Microalgae oil application for biodiesel synthesis is discussed.

关键词: Biodiesel     Heterogeneous catalysis     Transesterification     Microalgae oil    

Metakaolinite as a catalyst for biodiesel production from waste cooking oil

Jorge RAMIREZ-ORTIZ, Merced MARTINEZ, Horacio FLORES

《化学科学与工程前沿(英文)》 2012年 第6卷 第4期   页码 403-409 doi: 10.1007/s11705-012-1224-2

摘要: The use of metakaolinite as a catalyst in the transesterification reaction of waste cooking oil with methanol to obtain fatty acid methyl esters (biodiesel) was studied. Kaolinite was thermally activated by dehydroxylation to obtain the metakaolinite phase. Metakaolinite samples were characterized using X-ray diffraction, N adsorption-desorption, simultaneous thermo-gravimetric analyse/differential scanning calorimetry (TGA/DSC) experiments on the thermal decomposition of kaolinite and Fourier-transform infrared spectrometer (FTIR) analysis. Parameters related to the transesterification reaction, including temperature, time, the amount of catalyst and the molar ratio of waste cooking oil to methanol, were also investigated. The transesterification reaction produced biodiesel in a maximum yield of 95% under the following conditions: metakaolinite, 5 wt-% (relative to oil); molar ratio of oil to methanol, 1∶23; reaction temperature, 160°C; reaction time, 4 h. After eight consecutive reaction cycles, the metakaolinite can be recovered and reused after being washed and dried. The biodiesel thus obtained exhibited a viscosity of 5.4?mm ?s and a density of 900.1 kg?m . The results showed that metakaolinite is a prominent, inexpensive, reusable and thermally stable catalyst for the transesterification of waste cooking oil.

关键词: biodiesel     metakaolinite     transesterification     waste cooking oil    

Thermodynamic analysis of reaction pathways and equilibrium yields for catalytic pyrolysis of naphtha

《化学科学与工程前沿(英文)》 2022年 第16卷 第12期   页码 1700-1712 doi: 10.1007/s11705-022-2207-6

摘要: The chain length and hydrocarbon type significantly affect the production of light olefins during the catalytic pyrolysis of naphtha. Herein, for a better catalyst design and operation parameters optimization, the reaction pathways and equilibrium yields for the catalytic pyrolysis of C5–8 n/iso/cyclo-paraffins were analyzed thermodynamically. The results revealed that the thermodynamically favorable reaction pathways for n/iso-paraffins and cyclo-paraffins were the protolytic and hydrogen transfer cracking pathways, respectively. However, the formation of light paraffin severely limits the maximum selectivity toward light olefins. The dehydrogenation cracking pathway of n/iso-paraffins and the protolytic cracking pathway of cyclo-paraffins demonstrated significantly improved selectivity for light olefins. The results are thus useful as a direction for future catalyst improvements, facilitating superior reaction pathways to enhance light olefins. In addition, the equilibrium yield of light olefins increased with increasing the chain length, and the introduction of cyclo-paraffin inhibits the formation of light olefins. High temperatures and low pressures favor the formation of ethylene, and moderate temperatures and low pressures favor the formation of propylene. n-Hexane and cyclohexane mixtures gave maximum ethylene and propylene yield of approximately 49.90% and 55.77%, respectively. This work provides theoretical guidance for the development of superior catalysts and the selection of proper operation parameters for the catalytic pyrolysis of C5–8 n/iso/cyclo-paraffins from a thermodynamic point of view.

关键词: naphtha     catalytic pyrolysis     reaction pathway     equilibrium yield    

催化裂化过程反应化学的进展

许友好,汪燮卿

《中国工程科学》 2007年 第9卷 第8期   页码 6-14

摘要:

面对催化裂化工艺所遇到的挑战,提出了催化裂化过程反应化学的多维反应结构模式。多维反应结构模式的建立是基于对烃类在酸性催化剂上反应化学认识而进行的知识创新,但多维反应结构不同于烃类在酸性催化剂上反应化学。具有多维反应结构的催化裂化工艺更具有多样性和灵活性,基于此已成功地开发了多产异构烷烃的催化裂化工艺和生产清洁汽油和多产丙烯的催化裂化工艺。

关键词: 催化裂化     反应化学     催化剂     多维反应结构     两个反应区    

Ti incorporation in MCM-41 mesoporous molecular sieves using hydrothermal synthesis

Shengping WANG, Changqing MA, Yun SHI, Xinbin MA

《化学科学与工程前沿(英文)》 2014年 第8卷 第1期   页码 95-103 doi: 10.1007/s11705-014-1405-2

摘要: Titanium-containing mesoporous materials (Ti-MCM-41) were obtained by hydrothermal synthesis. Such materials are active catalysts for the transesterification of dimethyl oxalate and phenol to produce diphenyl oxalate. To understand the role of the Ti in the catalytic process, Ti-MCM-41 samples with different Si/Ti ratios (from 5 to 100) were prepared and the samples were analyzed by Fourier transform infrared spectroscopy, UV-visible spectroscopy, and ammonia temperature programmed desorption. It was concluded that the Ti is incorporated into the framework of the MCM-41 and formed weak Lewis acid sites. In addition, the number of Ti(IV) sites increased as the amount of titanium increased. X-ray powder diffraction, N adsorption-desorption and transmission electron microscopy results showed that the Ti-MCM-41 samples have a hexagonal arrangement of mono-dimensional pores. A large number of Ti(IV) sites coupled with the mesoporous structure and large pore diameters are favorable for the transesterification catalytic properties of Ti-MCM-41.

关键词: Ti-MCM-41     mesoporous molecular sieve     acid sites     transesterification     hydrothermal synthesis    

Heterogeneous reaction mechanism of gaseous HNO

Nan ZHAO,Qingzhu ZHANG,Wenxing WANG

《环境科学与工程前沿(英文)》 2016年 第10卷 第5期 doi: 10.1007/s11783-016-0836-z

摘要: We studied the heterogeneous reaction mechanism of gaseous HNO with solid NaCl. HCl is released from heterogeneous reactions between gaseous HNO and solid NaCl. Water molecules induce surface reconstruction of NaCl to facilitate the reaction. Sea salt particles containing NaCl are among the most abundant particulate masses in coastal atmosphere. Reactions involving sea salt particles potentially generate Cl radicals, which are released into coastal atmosphere. Cl radicals play an important role in the nitrogen and O cycles, sulfur chemistry and particle formation in the troposphere of the polluted coastal regions. This paper aimed at the heterogeneous reaction between gaseous HNO and solid NaCl. The mechanism was investigated by density functional theory (DFT). The results imply that water molecules induce the surface reconstruction, which is essential for the heterogeneous reaction. The surface reconstruction on the defective (710) surface has a barrier of 10.24 kcal·mol and is endothermic by 9.69 kcal·mol , whereas the reconstruction on the clean (100) surface has a barrier of 18.46 kcal·mol and is endothermic by 12.96 kcal·mol . The surface reconstruction involved in water-adsorbed (710) surface is more energetically favorable. In comparison, water molecules adsorbed on NaCl (100) surface likely undergo water diffusion or desorption. Further, it reveals that the coordination number of the Cl is reduced after the surface reconstruction, which assists Cl to accept the proton from HNO . HCl is released from heterogeneous reactions between gaseous HNO and solid NaCl and can react with OH free radicals to produce atomic Cl radicals. The results will offer further insights into the impact of gaseous HNO on the air quality of the coastal areas.

关键词: Seasalt particles     NaCl     HNO3     Heterogeneous reaction     Reaction mechanism     Density functional theory    

Dual-reaction-center catalytic process continues Fenton’s story

Chao Lu, Kanglan Deng, Chun Hu, Lai Lyu

《环境科学与工程前沿(英文)》 2020年 第14卷 第5期 doi: 10.1007/s11783-020-1261-x

摘要: Abstract • Dual-reaction-center (DRC) system breaks through bottleneck of Fenton reaction. • Utilization of intrinsic electrons of pollutants is realized in DRC system. • DRC catalytic process well continues Fenton’s story. Triggered by global water quality safety issues, the research on wastewater treatment and water purification technology has been greatly developed in recent years. The Fenton technology is particularly powerful due to the rapid attack on pollutants by the generated hydroxyl radicals (•OH). However, both heterogeneous and homogeneous Fenton/Fenton-like technologies follow the classical reaction mechanism, which depends on the oxidation and reduction of the transition metal ions at single sites. So even after a century of development, this reaction still suffers from its inherent bottlenecks in practical application. In recent years, our group has been focusing on studying a novel heterogeneous Fenton catalytic process, and we developed the dual-reaction-center (DRC) system for the first time. In the DRC system, H2O2 and O2 can be efficiently reduced to reactive oxygen species (ROS) in electron-rich centers, while pollutants are captured and oxidized by the electron-deficient centers. The obtained electrons from pollutants are diverted to the electron-rich centers through bonding bridges. This process breaks through the classic Fenton mechanism, and improves the performance and efficiency of pollutant removal in a wide pH range. Here, we provide a brief overview of Fenton’s story and focus on combing the discovery and development of the DRC technology and mechanism in recent years. The construction of the DRC and its performance in the pollutant degradation and interfacial reaction process are described in detail. We look forward to bringing a new perspective to continue Fenton’s story through research and development of DRC technology.

关键词: Dual reaction centers     Fenton     Pollutant utilization     Electron transfer    

Graphene-reinforced metal-organic frameworks derived cobalt sulfide/carbon nanocomposites as efficient multifunctional electrocatalysts

《化学科学与工程前沿(英文)》 2021年 第15卷 第6期   页码 1487-1499 doi: 10.1007/s11705-021-2085-3

摘要: Developing cost-effective electrocatalysts for oxygen reduction reaction (ORR), oxygen evolution reaction (OER) and hydrogen evolution reaction (HER) is vital in energy conversion and storage applications. Herein, we report a simple method for the synthesis of graphene-reinforced CoS/C nanocomposites and the evaluation of their electrocatalytic performance for typical electrocatalytic reactions. Nanocomposites of CoS embedded in N, S co-doped porous carbon and graphene (CoS@C/Graphene) were generated via simultaneous sulfurization and carbonization of one-pot synthesized graphite oxide-ZIF-67 precursors. The obtained CoS@C/Graphene nanocomposites were characterized by X-ray diffraction, Raman spectroscopy, thermogravimetric analysis-mass spectroscopy, scanning electronic microscopy, transmission electronic microscopy, X-ray photoelectron spectroscopy and gas sorption. It is found that CoS nanoparticles homogenously dispersed in the in situ formed N, S co-doped porous carbon/graphene matrix. The CoS@C/10Graphene composite not only shows excellent electrocatalytic activity toward ORR with high onset potential of 0.89 V, four-electron pathway and superior durability of maintaining 98% of current after continuously running for around 5 h, but also exhibits good performance for OER and HER, due to the improved electrical conductivity, increased catalytic active sites and connectivity between the electrocatalytic active CoS and the carbon matrix. This work offers a new approach for the development of novel multifunctional nanocomposites for the next generation of energy conversion and storage applications.

关键词: MOF derivative     graphene     electrocatalyst     oxygen reduction reaction     oxygen evolution reaction     hydrogen evolution reaction    

Impact and inhibitory mechanism of phenolic compounds on the formation of toxic Maillard reaction products

Jing TENG, Xiaoqian HU, Ningping TAO, Mingfu WANG

《农业科学与工程前沿(英文)》 2018年 第5卷 第3期   页码 321-329 doi: 10.15302/J-FASE-2017182

摘要:

As one of the dominant reactions occurring during thermal treatment of food, the Maillard reaction not only leads to the formation of aroma, browning color and taste compounds, but also contributes to the formation of some unpleasant toxic substances including acrylamide, heterocyclic amines and advanced glycation end products. Polyphenols, one of the most abundant antioxidants in the human diet, are contained in different kinds of foods. In this review, some recent studies on the impact of dietary polyphenols on the formation of acrylamide, heterocyclic amines and advanced glycation end products formed during the Maillard reaction are summarized, including the research work conducted with both chemical model systems and real food model systems; the possible inhibitory mechanisms of different polyphenols are also summarized and discussed in this review. Basically we found that some dietary polyphenols not only scavenge free radicals, but also react with reactive carbonyl species, thus lowering the formation of toxic Maillard reaction products. This review provides a useful theoretical foundation for the application of polyphenols in food safety, and suggests some directions for further study of natural products as inhibitors against the formation of toxic substances in thermally processed food.

关键词: advanced glycation end products     acrylamide     food safety     heterocyclic amine     Maillard reaction     polyphenols    

Challenge of biodiesel production from sewage sludge catalyzed by KOH, KOH/activated carbon, and KOH/CaO

Xuemin Wu,Fenfen Zhu,Juanjuan Qi,Luyao Zhao,Fawei Yan,Chenghui Li

《环境科学与工程前沿(英文)》 2017年 第11卷 第2期 doi: 10.1007/s11783-017-0913-y

摘要: The preparation reactions were catalyzed by base solid catalysts. The preparation reactions were catalyzed by two loaded catalysts and KOH. KOH/activated carbon was a better catalyst for biodiesel production. The considerable compounds content, abundance, and low costs involved has led to the proposal to use sewage sludge as raw material for biodiesel production. The transesterification reaction is catalyzed using an acid catalyst instead of base catalysts because of the high free fatty acid concentration. However, the use of a base catalyst, particularly a solid base catalyst, has certain advantages, including faster reaction speed and easier separation. In this study, we utilize in situ transesterification by base catalyst (KOH, KOH/activated carbon (AC) and KOH/CaO) with sewage sludge as raw material. Many conditions have been tested to increase biodiesel yield through single-factor tests, including mass fraction and catalyst dosage. Preliminary experiments have optimized reaction time and temperature. However, the three catalysts did not work better than H SO , which had a maximum yield of 4.6% (dry sewage sludge base) considering the purity by KOH, KOH/CaO, and KOH/AC. The features of the catalyst were analyzed using XRD, BET and SEM. As to BET of KOH/AC and the good spiculate formation of KOH crystal appears to be essential to its function. As for KOH/CaO, the formation of K O and absorption points is likely essential.

关键词: Biodiesel     Sewage sludge     Base catalyst     In situ transesterification    

标题 作者 时间 类型 操作

Rosin side chain type catalyst-free vitrimers with high cross-link density, mechanical strength, and thermal stability

期刊论文

Biodiesel production by the transesterification of cottonseed oil by solid acid catalysts

CHEN He, PENG Baoxiang, WANG Dezheng, WANG Jinfu

期刊论文

of carbon dioxide photoreduction process in a laboratory-scale photoreactor by computational fluid dynamicand reaction kinetic modeling

期刊论文

Transesterification of soybean oil to biodiesel over kalsilite catalyst

Guang WEN, Zifeng YAN

期刊论文

酯交换反应在制备生物柴油上的应用

张怀渊,宋元达

期刊论文

Application of heterogeneous catalysis to biodiesel synthesis using microalgae oil

期刊论文

Metakaolinite as a catalyst for biodiesel production from waste cooking oil

Jorge RAMIREZ-ORTIZ, Merced MARTINEZ, Horacio FLORES

期刊论文

Thermodynamic analysis of reaction pathways and equilibrium yields for catalytic pyrolysis of naphtha

期刊论文

催化裂化过程反应化学的进展

许友好,汪燮卿

期刊论文

Ti incorporation in MCM-41 mesoporous molecular sieves using hydrothermal synthesis

Shengping WANG, Changqing MA, Yun SHI, Xinbin MA

期刊论文

Heterogeneous reaction mechanism of gaseous HNO

Nan ZHAO,Qingzhu ZHANG,Wenxing WANG

期刊论文

Dual-reaction-center catalytic process continues Fenton’s story

Chao Lu, Kanglan Deng, Chun Hu, Lai Lyu

期刊论文

Graphene-reinforced metal-organic frameworks derived cobalt sulfide/carbon nanocomposites as efficient multifunctional electrocatalysts

期刊论文

Impact and inhibitory mechanism of phenolic compounds on the formation of toxic Maillard reaction products

Jing TENG, Xiaoqian HU, Ningping TAO, Mingfu WANG

期刊论文

Challenge of biodiesel production from sewage sludge catalyzed by KOH, KOH/activated carbon, and KOH/CaO

Xuemin Wu,Fenfen Zhu,Juanjuan Qi,Luyao Zhao,Fawei Yan,Chenghui Li

期刊论文