“拟原位”法测定积炭催化剂有效扩散系数

用新设计的单片反应器制备积炭催化剂试样,与动态法测定催化剂微孔有效扩散系数的装置相配合,并采用以水为吸附介质的动态毛细凝聚法和毛细上升法测定积炭催化剂压片的孔隙率,实现了积炭催化剂粒内有效扩散系数的“拟原位”测定要求,避免了催化剂颗粒反应积炭后再研磨、压片对有效扩散系数测定带来的假象。本文利用提出的“拟原位”方法得到了ZSM-5沸石催化剂上乙苯/乙烯烷基化过程中反应-失活全过程的有效扩散系数变化曲线。     

Ameliorating effect of silica addition in the anode-catalyst layer of the membrane electrode assemblies for polymer electrolyte fuel cells

Incorporation of silica particles through a sol-gel process into the anode-catalyst layer with a sol-gel modified Nafion-silica composite membrane renders easy retention of back-diffused water from the cathode to anode through the composite membrane electrolyte, increases the catalyst-layer wettability and improves the performance of the Polymer Electrolyte Fuel Cell (PEFC) while operating under relative humidity (RH) values ranging between 18% and 100% with gaseous hydrogen and oxygen reactants at atmospheric pressure. A peak power density of 300 mW cm⁻² is achieved at a load current-density value of 1200 mA cm⁻² for the PEFC employing a sol-gel modified Nafion-silica composite membrane and operating at 18% RH. Under similar operating conditions, the PEFC with a Membrane Electrode Assembly (MEA) comprising Nafion-silica composite membrane with silica in the anode-catalyst layer delivers a peak power density of 375 mW cm⁻². By comparison, the PEFC employing commercial Nafion membrane fails to deliver satisfactory performance at 18% RH due to the limited availability of water at its anode, acerbated electro-osmotic drag of water from anode to cathode and insufficient water back diffusion from cathode to anode causing the MEA to dehydrate.     

合成气制烃的催化过程和催化剂发展动态

4 合成气直接制烃催化剂提高合成过程竞争力的总趋势是控制选择性,开发定向合成催化过程和催化剂。目的产品是液体燃料汽油、柴油,化工原料乙烯、丙烯、异丁烯等低碳烯烃以及裂解原料低碳烷烃。4.1 合成低碳烯烃     

杂多酸催化合成柠檬酸三丁酯的研究

本文报道了杂多酸－１２－钨磷酸催化合成柠檬酸三丁酯的实验方法和实验结果。对实验条件如酯化时间、原料比、催化剂用量等进行了探索；提出了合适的酯化条件。并利用气相色谱对反应速率进行了初步考察。结果表明：磷钨酸对催化合成柠檬酸三丁酯具有良好的催化效果，酯化率接近１００％，收率达９７％。     

Soybean oil transesterification over zinc oxide modified with alkali earth metals

Fatty acid methyl esters, derived from vegetable oils or animal fats and better known as biodiesel, have received considerable attention because of their environmental benefits and the limited resources of fossil fuels. Most biodiesel is usually produced by the transesterification of vegetable oils with methanol in the presence of a catalyst. This study reports on the preliminary results of using alkaline earth metal-doped zinc oxide as a heterogeneous catalyst for transesterification of soybean oil. The highest catalytic activity was obtained with ZnO loaded with 2.5 mmol Sr(NO₃)₂/g, followed by calcination at 873 K for 5 h. When the transesterification reaction was carried out at reflux of methanol (338 K), with a 12:1 molar ratio of methanol to soybean oil and a catalyst amount of 5 wt.%, the conversion of soybean oil was 94.7%. Besides, tetrahydrofuran (THF), when used as a co-solvent, could increase the conversion up to 96.8%. However, the recovered catalyst exhibited the lower catalytic activity with a conversion of soybean oil of 15.4%. Furthermore, DTA-TG, IR and the Hammett indicator method were employed for the catalyst characterizations.     

煤间接液化技术及其发展状况

介绍了煤间接液化技术的特点,从其原理、工艺路线、关键技术及发展现状等方面对间接液化技术进行了详细的阐述,指出发展煤间接液化是解决我国油品短缺的根本途径。     

以888-JH为催化剂Na_2CO_3为碱源的脱硫技术

本文着重介绍以888-JH为催化剂,Na2CO3为碱源焦炉煤气(COG)湿式氧化法脱硫工艺的脱硫原理、影响因素,并介绍了现场试验结果。认定单独使用888-JH可以替代PDS+RTS获得脱硫效率99%以上和出口H2S含量小于5mg/m3的较佳脱硫效果。     

Kinetics modelling of Fischer-Tropsch synthesis over an industrial Fe-Cu-K catalyst

The kinetic experiments of Fischer-Tropsch synthesis (FTS) over an industrial Fe-Cu-K catalyst are carried out in a micro-fixed-bed reactor under the conditions as follows: temperature of 493-542 K, pressure of 10.9-30.9 bar, H₂/CO feed ratio of 0.98-2.99, and space velocity of 4000-10?000 h⁻¹. The effects of secondary reactions of olefins are investigated by co-feeding C₂H₄ and C₃H₆. A detailed kinetics model taking into account the increasingly proven evidence of the olefin re-adsorption mechanism is then proposed. In this model, different sites are assumed for FTS reactions and water gas shift (WGS) reaction, respectively. Rate expressions for FTS reactions are based on the carbide polymerisation mechanism, in which olefin re-adsorption is considered to be a reverse step of olefin desorption reaction. Rate expression for WGS reaction is based on the formate mechanism. An integral reactor model considering both FTS and WGS kinetics is used to describe the reaction system, and the simultaneous estimation of kinetic parameters is conducted with non-linear regression procedure. The optimal model shows that the rate determining steps in FTS reactions proceed via the desorption of hydrocarbon products and the adsorption of CO and the slowest step in WGS reaction is the desorption of gaseous carbon dioxide via formate intermediate species. The activation energies of FTS reactions and WGS reaction are in good agreement with literature values.     

Catalyst Design of Pt-Modified Ni/Al2O3 Catalyst with Flat Temperature Profile in Methane Reforming with CO2 and O2

Pt(0.3)/Ni(10)/Al₂O₃, prepared by a sequential impregnation method, exhibited a more excellent performance in methane reforming with CO₂ and O₂ in terms of the catalytic activity and the temperature profile of the catalyst bed than Pt(0.3) + Ni(10)/Al₂O₃ prepared by a coimpregnation method, Ni(10)/Al₂O₃, Pt(0.3)/Al₂O₃, and Pt(10)/Al₂O₃. It is thought that this is because the surface Pt atoms on Ni catalyst can contribute to the enhancement of the catalyst reducibility.     

Synthesis of nanodispersed oxides of vanadium, titanium, molybdenum, and tungsten on mesoporous silica using atomic layer deposition

The advantages of the atomic layer deposition (ALD) method for preparation of tungsten, vanadium, titanium, and molybdenum oxide catalyst supported on mesoporous silica are discussed, with emphasis on the importance of synthesis conditions on dispersion, structure and activity of the resulting materials. A suite of complementary techniques such as DRS-UV/Vis, BET, ¹H-NMR, XRD, and TEM were used to study the structural properties of the supported metal oxides, and probe reactions such as 2-butanol dehydration and ethanol partial oxidation were used to demonstrate the potential advantages of the ALD-prepared catalysts. Specifically, highly dispersed oxides of titanium, molybdenum, and tungsten oxide on mesoporous silica were synthesized using the ALD method. It is also demonstrated that attainment of high dispersions of vanadium oxide on mesoporous silica requires the presence of at least a single layer of titanium oxide due to the well-known poor interaction between vanadia and silica. The highly dispersed catalysts prepared here by ALD methods exhibited superior catalytic performance relative to those prepared using conventional incipient wetness impregnation.