Deactivation of metal catalysts in liquid phase organic reactions

The paper gives a general survey of the factors contributing to the deactivation of metal catalysts employed in liquid phase reactions for the synthesis of fine or intermediate chemicals. The main causes of catalyst deactivation are particle sintering, metal and support leaching, deposition of inactive metal layers or polymeric species, and poisoning by strongly adsorbed species. Weakly adsorbed species, poisons at low surface coverage and solvents, may act as selectivity promoters or modifiers. Three examples of long term stability studies carried out in trickle-bed reactor (glucose to sorbitol hydrogenation on Ru/C catalysts, hydroxypropanal to 1,3-propanediol hydrogenation on Ru/TiO₂ catalysts, and wet air oxidation of paper pulp effluents on Ru/TiO₂) are discussed.     

Chemical Reaction Engineering and Research and development of gas solid systems

A general procedure is proposed for innovative research and development of gas-solid reactor systems, with a brief explanation of the significance of each step in the procedureBased upon the contacting mode between gas and solid phases, as well as the ways of supplying thermal energy to the reacting regions, various types of gas-solid reactor systems are classified by using tables of so called “matrix” form, for thermal cracking and gasification of heavy oils, gasification of coal, gasification of solid waste, calcination of limestone, clinkering of cement and reduction of iron ore.The importance of fundamental concepts is emphasized for successful research and development by presenting several examples; namely, calcination of limestone, thermal cracking of heavy oils and gasification of solid waste materials.In connection with the direction in which fundamental research should be oriented, four primary ways of thinking are proposed, which can be applied to obtain innovative ideas for further research and development in this field.One example of the author's practical experience was selected to show the role of the fundamental research in the course of large scale development. Finally the author outlines the role of chemical reaction engineering to innovate the novel gas-solid reactor systems which may be inevitable for simultaneous solution of the three big E's; namely, Energy, Environment and Economy.     

一种数字光盘数据保密方法

提出了一种支持数据保密的光盘文件系统以及适用于数字光盘的数据保密方法。改进了ISO 9660 Level 2标准的光盘文件系统, 划分为明文区、保密区和参数区三部分, 分别存储明文、密文和参数数据。光盘制作模块将明文数据、密文数据及参数数据制作成光盘文件系统的镜像文件, 同时将光盘阅读模块注入到明文区。光盘阅读模块专门存取保密区数据。该方法能实现明文、密文数据及其解密工具并存于同一光盘, 无需安装额外的软件, 该文件系统兼容目前所有的光盘设备。     

现场总线技术在非能动压水堆核岛中的应用

本文结合非能动压水堆核电控制系统结构,详细介绍Profibus现场总线和Modbus现场总线在非能动压水堆核电控制系统中的应用,包括两种现场总线技术的结构配置及和现场智能仪控设备的连接,并简要分析现场总线技术在核电行业应用的优点和需克服的技术问题。     

工业变换炉最佳催化剂粒度

本文在建立数学模型的基础上，用计算机模拟变换炉的操作工况，考察改变催化剂粒度对经济效益的影响，从而得到工业变换炉催化剂颗粒最佳尺寸，开发了以经济效益为考察依据，工业反应器中催化剂颗粒最佳尺寸的计算方法。     

OXIDATION OF SULFUR DIOXIDE IN DIFFERENT TYPES OF THREE PHASE REACTORS

Five different types of three-phase reactors are compared with each other by using oxidation of sulfur dioxide on activated carbon. The kinetic measurements were carried out by changing concentrations of sulfur dioxide from 0.04 to 0.17% (volume) and those of oxygen from 2 to 21%. The reaction rate was 0.2 order with respect to sulfur dioxide and 0.5 order with respect to oxygen. The catalytic effectiveness factor and intraparticle diffusivity were evaluated by changing particle sizes of activated carbon from 0.03 to 1.6 mm. Resistances of gas-liquid, liquid-solid mass transfer and intraparticle diffusion were estimated for individual reactors. The optimum reactor was dependent on operating conditions such as gas flow rates, rotating speeds and particle sizes.     

水合肼生产中氧化反应的研究和应用

分析了尿素法生产水合肼的氧化反应历程及影响因素，改进了反应器，并找到了最佳的工艺控制条件：①控制n(尿素)：n(次氯酸钠)=(1．05～1．10)：1，各原料的消耗较低，总经济效益佳；②采用-5℃冷冻盐水移走尿素、次氯酸钠混合段内氯化反应放出的热量，控制物料混合终点温度在15～30℃；③采用列管式加热器，将氯化反应与水解反应在不同的设备中进行，水合肼的收率提高到83％～85％；④采用列管式加热器代替双夹套反应器，提高了加热强度，生产能力大，1套合成反应器可生产1万t／a80％的水合肼。     

Control policies for an industrial acetylene hydrogenation reactor

This paper addresses the problem of finding optimal operational policies for an acetylene reactor for day to day operation. A lumped parameter model based on four main reactions is developed and used to examine the effects of the reactor manipulated variables on key reaction parameters. An optimal and a sub-optimal operational policy which minimize the ethylene loss over time are formulated and the solution techniques are presented. The results indicate that the reactor model is in good agreement with industrial plant data. The performance of the optimal control policy is very similar to the performance of the sub-optimal control policy. However, the sub-optimal formulation, while retaining the dominant features of the optimal response, reduces the computational requirements. Finally, some issues concerning the real-time implementation of an advanced acetylene reactor control scheme are presented. These include the estimation of the optimum regeneration cycle, a recursive model update algorithm, the process optimizer and their overall coordination. A preliminary analysis of the benefits associated with the advanced control scheme suggests a considerable reduction in the yearly ethylene loss.     

Methyl tert-butyl ether decomposition over heteropoly acid catalyst in a cellulose acetate membrane reactor

In this study the methyl tert-butyl ether (MTBE) decomposition over H₃PW₁₂O₄₀ was carried out in a cellulose acetate membrane reactor. The permeability of methanol through the cellulose acetate membrane was about 30 and 300 times higher than that of either isobutene or MTBE, respectively. The isobutene selectivity in the fixed bed reactor was only slightly higher than the methanol selectivity due to the side reaction. In the cellulose acetate membrane reactor, however, the isobutene selectivity in the rejected stream was 68% and the methanol selectivity in the permeated stream was up to 97%. The MTBE conversion in the membrane reactor was about 7% higher than that in the membrane-free fixed bed reactor under the same reaction conditions. The enhanced performance of the membrane reactor in this reversible reaction was mainly due to the selective permeation of methanol which resulted in a methanol-deficient condition suppressing MTBE synthesis reaction.