Kinetics of hydantoin formation

The reaction of lignite in a slagging gasifier produces reactants which in turn form 5,5-dimethylhydantoin (DMH) as a major constituent in the condensate water. Variations in plant operating conditions made it impossible to accurately study the kinetics of formation of DMH in the actual gasifier water, and thus a model system was chosen. The reaction of acetone cyanohydrin in the presence of excess ammonium carbonate at concentrations approaching those obtained in the condensate water were studied at 50,70, and 90 °C. Secondorder kinetics were obeyed, and the pseudo second-order rate constants at the respective temperatures were 1.86, 3.6, and 4.62 dm³ mol^{? 1} h^{? 1}. Independent variation of the concentration of either acetone, cyanide, ammonia or carbonate gave results consistent with the interpretation that the formation of DMH is first order in all reactants: rate of formation of DMH = k[acetone][HCN][NH₃][CO₂]. The pseudo second-order rate constant is a complex rate constant including several rapid equilibria. A mechanism consistent with the kinetic data is presented.     

Rare earth oxides as carbon oxidation catalysts

The behavior of a number of rare earth oxides as catalysts for the oxidation of graphite in air has been investigated by the methods of thermal analysis. Of the oxides studied, only CeO₂ showed significant activity in accelerating the gasification of graphite by oxygen between 500 and 1000°C. Cerium salts, which decompose to a finely dispersed oxide phase at low temperatures, e.g. Ce (III) nitrate and ammonium Ce (IV) nitrate, were found to be very active catalysts. The catalytic effect may be due to a redox process involving the cyclic conversion of the oxide from the Ce (IV) to the Ce (III) oxidation state, or the oxide particles may provide sites for the dissociative chemisorption of oxygen.     

择形催化合成2,6-DMN的研究进展

介绍了2,6-二甲基萘(2,6-DMN)的制备方法,详细论述了萘、甲基萘在分子筛催化剂上择形催化合成2,6-DMN的研究进展,提出了择形催化合成2,6-DMN的研究方向。     

介孔氧化铁对正辛醇乙氧基化反应的催化性能

以十二烷基磺酸钠为模板剂、乙二胺为碱性介质,将水热法合成的氧化铁/十二烷基磺酸钠复合中孔材料在550℃、空气气氛中煅烧10h,除去模板剂,得到介孔氧化铁。通过X射线衍射、氮气吸附-脱附方法对介孔氧化铁的晶体结构和表面物性进行表征。表征结果显示,煅烧后的介孔氧化铁具有典型的六方介孔的结构特征,平均孔径为5.4nm。将介孔氧化铁用于催化正辛醇乙氧基化反应,研究结果表明,升高反应温度和初始压力、增加催化剂用量,可加快环氧乙烷的反应速率,同时产物的相对分子质量分布较窄。当平均聚合度为6.5时,正辛醇聚氧乙烯醚相对分子质量分布的选择性系数达到21.1。     

PTT直接酯化反应动力学研究

研究了不同温度下PTT(聚对苯二甲酸丙二醇酯)直接酯化反应动力学。建立了零级和一级反应动力学模型。用实验数据进行的检验表明,一级动力学模型更为接近该反应过程。     

Ring‐opening polymerization of D,L‐lactide by rare earth 2,6‐dimethylaryloxide

Ring‐opening polymerization of D,L ‐lactide (LA) has been successfully carried out by using rare earth 2,6‐dimethylaryloxide (Ln(ODMP)₃) as single component catalyst or initiator for the first time. The effects of different rare earth elements, solvents, monomers and catalyst concentration as well as polymerization temperature and time on the polymerization were investigated. The results show that La(ODMP)₃ exhibits higher activity to prepare poly(D,L ‐lactide) (PLA) with a viscosity molecular weight of 4.5 × 10⁴ g mol^?1 and the conversion of 97 % at 100 °C in 45 min. The catalytic activity of Ln(ODMP)₃ has following sequence: La > Nd > Sm > Gd > Er > Y. A kinetic study has indicated that the polymerization is first order with respect to both monomer and catalyst concentration. The apparent activation energy of the polymerization of LA with La(ODMP)₃ is 69.6 kJ mol^?1. The analyses of polymer ends indicate that the LA polymerization proceeds according to ‘coordination–insertion’ mechanism with selective cleavage of the acyl–oxygen bond of the monomer. Copyright © 2004 Society of Chemical Industry     

高温和低张应力引起的非平衡晶界偏聚动力学(Ⅱ)--实验结果的动力学模拟

以文献[1]建立的张应力引起的非平衡晶界偏聚动力学方程模拟了Shinoda T等的磷在钢中的应力时效实验结果和Misra R D K的硫在钢中的应力时效实验结果，模拟结果与实验结果互相吻合。通过模拟发现，张应力使磷-空位复合体以及硫-空位复合体在钢中的扩散系数均增加3个数量级，且磷原子和硫原子的扩散系数分别降低3个和5个数量级。     

甘油三乙酸酯超临界酯交换反应及其动力学研究

研究了在超临界条件下甘油三乙酸酯与甲醇或乙醇的酯交换反应,分别考察了超临界状态下醇油摩尔比和温度对反应的影响。实验结果表明,甲醇或乙醇与甘油三乙酸酯的摩尔比为14、反应温度为350℃、反应时间为20m in时,乙酸甲酯或乙酸乙酯的收率分别达100%和60%。对超临界状态下动力学的研究结果表明,甘油三乙酸酯与甲醇或乙醇的酯交换反应为拟一级反应,在相同的反应条件下,采用甲醇时酯交换反应速率比用乙醇时快,相应的甘油三乙酸酯的转化率也高;甘油三乙酸酯在超临界甲醇或乙醇中酯交换反应的表观活化能分别为58.7 kJ/mol和75.1 kJ/mol,甘油三乙酸酯与甲醇酯交换反应的活化能低于与乙醇酯交换反应的活化能,表明碳链短的醇更易进行酯交换反应。