Microcalorimetric Adsorption of Alumina Oxide Catalysts for Combination of Ethylbenzene dehydrogenation and carbon Dioxide Shift-reaction

Styrene (STY) is now produced industrially in fairly large quantities by the dehydrogenation of ethylbenzene (EB) using promoted iron oxide catalyst with superheated steam.In this case, small amount of carbon dioxide formed as a by-product was known to inhibit the catalytic activity of commercial catalyst. Recently, there have been some reports which carbon dioxide showed positive effects to promote catalytic activities on the reaction over several catalysts.In this study, we attempted to combine the dehydrogenation of EB to STY with the carbon dioxide shift-reaction. The combine reaction (EB + CO2 → STY + H2O + CO) can be considered as one of the ways of using CO2 resources and can yield simultaneously STY and Carbon oxide.Alumina oxide catalysts such as Al2O3, Na2O/Al2O3 and K2O/Al2O3 were prepared by the usual impregnation method with an aqueous solution of NaNO3 and KNO3, and then calcined at 650℃ for 5 h in a stream of air. The reaction condition is 600℃, flow of CO2 38ml/mon and space velocity (EB) 1.28h-1.     

Modulated DSC for gas hydrates analysis

Modulated DSC has been applied to the study of methane, ethane and propane hydrates at different hydrate and ice concentrations. The reversing component of the TMDSC curves, makes it possible to characterize such hydrates. Methane and ethane hydrates show the melting-decomposition peak at a temperatures higher than the ice contained in the sample, while propane hydrate melts and decomposes at lower temperature than the ice present in the sample. The hydrate peaks tend to disappear if the hydrate is stored at atmospheric pressure. Guest size and cavity occupation fix the heat of dissociation and stability of the hydrates, as confirmed by parallel tests on tetrahydrofurane hydrates.     

Self‐curable polyester by a reaction of glycidol with maleic anhydride

The controlled reaction of equimolar quantities of maleic anhydride and glycidol in dimethoxyethane gives soluble polyesters with one hydroxyl group in each repeating unit. The reaction proceeds with stepwise ring opening of the components and gives highly viscous clear solutions in relatively short periods. In the first step, monomaleate ester formation takes place around 80 °C. The ring opening of the oxirane group is the second step, and it occurs at 120 °C. The overall reaction is the formation of soluble polyesters with moderate molecular weights (6000–18,000), without the elimination of water. The soluble polyesters can be crosslinked tightly by direct heating at 190 °C without additional vinyl monomer. © 2003 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 41: 2549–2555, 2003     

A Mössbauer spectroscopic study of an industrial catalyst for dehydrogenation of etylbenzene to styrene

Iron oxide catalyst with spinel structure used for dehydrogenation of ethylbenzene is one kind of important catalyst in petrochemical industry. In this work several series of industrial catalyst were prepared with different components and different manufacturing processes. Mössbauer Spectroscopy has been used to determine the optimal components and the better manufacturing process for spinel structure formation. The results may prove useful for producing the industrial dehydrogenation catalyst with better catalytic property.     

Triruthenium dodecacarbonyl/triphenylphosphine catalyzed dehydrogenation of primary and secondary alcohols

Dehydrogenation of alcohols into aldehydes and ketones by Ru₃(CO)₁₂/PPh₃ based homogeneous catalysis has been investigated as an alternative for the classical Oppenauer oxidation. Several catalytic systems have been screened in the Oppenauer-like oxidation of alcohols. A systematic study of various combinations of Ru₃(CO)₁₂, mono- and bidentate ligands and hydride acceptors was performed to enable dehydrogenation of primary alcohols to stop at the aldehyde stage. Among many H-acceptors screened, diphenylacetylene (tolane) proved the most suitable judged from its smooth reduction. Electron rich and deficient analogues of tolane have been synthesized and, based on competition experiments between these H-acceptors, a tentative catalytic cycle for the Ru₃(CO)₁₂/PPh₃-catalyzed dehydrogenations has been proposed.     

Morphologies of microporous polyethylene and polypropylene crystallized from solution in supercritical propane

The morphologies of solvent-free, microporous, mechanically self-supporting cylinders of linear polyethylene and isotactic polypropylene, crystallized from solution in supercritical propane, were examined by an SEM technique. The morphology of gels (or foams), obtained with little or no shrinkage from 2% to 35% solutions by weight of polyethylene (99% to 85% porosities), is shown in some detail. Lamellae with very little or considerable mutual organization occur, often in the form of stacks with straight or coiled axes (axialites). Further growth of these can lead to particles with a roughly spherical overall shape and a predominantly radial orientation of the lamellae at the particle surface. Subcooled isotactic polypropylene, on the other hand, crystallizes in the form of perfectly shaped birefringent microspheres of very uniform size. ©1995 John Wiley & Sons, Inc.     

双甲基丙烯酰氧苯基丙烷与苯乙烯共聚物的光学性能

标题共聚物的耐冲击性与丙烯酸酯均聚物相比有明显改善,但随着双烯单体含量的降低,共聚物的耐热性和表面硬度有所下降。丙烯酸酯含量为70%的共聚物的吸收紫外光能力最强(<370nm全吸收),含量为5%～10%的共聚物耐吸水性、耐酸耐碱性及耐冲击性最好。     

Preparation of AgBiVMoO/-Al2O3 Catalysts for the Partial Oxidation of Propane

A novel mixed sol method was developed for the preparation of supported catalysts. Analyses by means of XRD and BET show that a 40%AgBiVMoO/γ-Al2O3 catalyst prepared by this method possessed high specific surface area and high dispersion of the active phase. As a result, high acrylic acid selectivity of 8.5% was obtained when the catalyst was used in the reaction of propane partial oxidation to acrylic acid in a fixed-bed reactor.     

四（五氟化苯基）卟啉氯化铁选择催化氧化超临界丙烷的反应机理

 以BHT为自由基捕捉剂，研究了四（五氟化苯基）卟啉氯化铁（Ⅲ）将超临界丙烷高选择性催化氧化为丙醇的反应机理．通过GC－MS分析发现，反应产物中有PBHT，故可认为在超临界丙烷氧化反应过程中有丙基自由基存在，初步推断反应涉及自由基机理．同时发现高浓度BHT抑制反应，低浓度BHT促进反应的现象，而以戊烷为底物时没有促进作用．这是由于BHT的位阻效应所致．并对BHT存在时超临界丙烷氧化反应机理进行了初步的推断．     

Kinetics of the Oxidative Dehydrogenation of Propane over a VMgO Catalyst

The reaction kinetics of the oxidative dehydrogenation of propane was studied at 475-550℃ over a VMgO catalyst. Vanadium-magnesium-oxides are among the most selective and active catalysts for the dehydrogenation of propane to propylene. Selectivity to propylene up to about 60% was obtained at 10% conversion, but the selectivity decreased with increasing conversion. No oxygenates were detected, the only by-products were CO and CO2. The reaction rate of propane was found to be first order in propane and close to zero order in oxygen, which is in agreement with a Mars van Krevelen mechanism with the activation of the hydrocarbon as the rate determining step. The activation energy of the conversion of propane was found to be 122±6 kJ/mol.