反应器网络综合优化方法的研究进展

反应器网络综合优化方法在选择反应器类型和反应工艺条件时,比传统的方法表现出了很大的优势。综述了各类反应器网络综合优化方法的基本原理和研究进展,并分析了它们的优缺点。这些方法有基于过程特征的方法,包括可得区法和导数分析法;超结构优化法;目标类方法,包括目标法、构造目标法和构造MINLP法;以及经验推断法和分布参数法等。最后分析了这方面研究的发展趋势。     

Modeling the continuous melt transesterification of bisphenol-A and diphenyl carbonate in a continuous stirred tank reactor

A model of continuous melt transesterification of bisphenol-A and diphenyl carbonate in a continuous stirred tank reactor is developed using phase equilibria assumption and the method of molecular weight moments. The model equations can be simplified into a polynomial system that has 17 equations and 17 unknowns. Solution of the polynomial system gives out almost every aspects of the continuous transesterification process. Molecular weight and polydispersity index, end group ratio of hydroxyl to phenyl carbonate, contents of molecular species, and lost diphenyl carbonate fractions are studied in different operation parameters.     

Polymerization Kinetics of Fischer‐Tropsch Reaction on Iron Based Catalysts and Product Grade Optimization

The polymerization kinetics of Fischer‐Tropsch reactions on a K‐promoted Fe catalyst was studied. To represent the product distribution, a kinetic model was developed based on alkyl and alkenyl mechanisms for hydrocarbon chain propagation, which were assumed to occur simultaneously in the Fischer‐Tropsch synthesis. The conclusion was drawn that superimposed Anderson‐Schulz‐Flory (ASF) distributions with different chain growth probabilities, on iron catalysts, can be the result of different chain growth mechanisms. The polymerization mechanism was used to obtain the product distribution for several conditions, and the optimum conditions for the production of transportation fuels were found.     

Optimization of anodic oxidation and Cu–Cr oxide catalyst preparation on structured aluminum plates processed by electro discharge machining

This paper describes the optimization of three processes applied in fabrication of a microstructured reactor for complete oxidation of volatile organic compounds. The first process involves the optimization of the electro discharge machining (EDM) method to produce a set of microchannels with a high length to diameter ratio of 100, with a standard deviation from the average diameter below 0.2%, and with a surface roughness not higher than 2.0 μm. To satisfy these criteria, fabrication of microchannels must be carried out with two machining passes in the Al51st alloy. Then, the effect of several parameters on the anodization current efficiency with respect to oxide formation was studied. The best process conditions to get a 30 μm porous alumina layer in a 0.4 M oxalic acid electrolyte, were found to be a temperature of 1 °C, an anodic current density of 5 mA/cm², and 23 h oxidation time. At last, the resulting coatings were impregnated with an aqueous solution of copper dichromate followed by drying and calcination at 450 °C to produce active catalysts. The effect of a copper dichromate concentration, number of impregnation cycles (1 or 2), and different after-treatments on catalytic activity and stability in complete oxidation of n-butane were studied. The catalytic activity of the obtained coatings is superior to that of alumina supported pelletized catalysts even at much lower loadings of active metals.     

Syngas production via combined oxy-CO2 reforming of methane over Gd2O3-modified Ni/SiO2 catalysts in a fluidized-bed reactor

In this research, Ni/SiO₂ catalyst was modified with different amount of Gd₂O₃ and characterized with temperature-programmed desorption of CO₂ (CO₂-TPD) and NH₃ (NH₃-TPD), temperature-programmed reduction with H₂ (H₂-TPR) and X-ray diffraction (XRD). It was found that Gd₂O₃-modified Ni/SiO₂ catalysts possessed higher CO₂ adsorption and activation ability due to the formation of surface carbonate species. H₂-TPR and XRD characterizations found that the strong interaction among nickel, Gd₂O₃ and SiO₂ took place, which improved the dispersion of Ni. Gd₂O₃-modified Ni/SiO₂ catalysts exhibited higher activity and stability for the combined oxy-CO₂ reforming of methane in fluidized-bed reactor. The H₂/CO ratio in produced syngas could be controlled via controlling reaction temperature and CO₂/O₂ ratio in feed.     

Ring-opening polymerization of decamethylcyclopentasiloxane initiated by a superbase: Kinetics and rheology

The use of phosphazene bases in combination with water was proved to be efficient in order to obtain polysiloxane polymers from cyclic monomers. Only a few minutes are necessary to obtain polymer chains with a monomer concentration of 5% at the equilibrium. For that purpose the space which is between a rheometer's plates is the most convenient device to monitor this reaction concerning a chemical and viscoelastic point of view. Therefore, here is proposed a chemo-rheology study that leads in the same time to the chemical kinetics equations and to the variation of the viscoelastic functions during the polymerization. In this way different catalysts are used and their efficiencies are compared as a function of their “basicity tank”. Whatever the experimental conditions involved are, viscosity versus polymer concentration or conversion shows a master curve for catalysts suitable to be used under extrusive conditions. Thus, only a few experiments are needed in order to develop a model which can be used to foresee the variation of the viscosity during the reaction.     

Quantitative measurement of gas hold-up distribution in a stirred chemical reactor using X-ray cone-beam computed tomography

Cone-beam type X-ray computed tomography (CBCT) is a potential method to measure three-dimensional phase distributions in vessels. An example for that is the measurement of gas profiles in stirred chemical reactors. Such data are highly valuable for the assessment and evaluation of chemical processes, for optimisation of the reactor and stirrer design, and for evaluation of computational fluid dynamics codes used to model the fluid flow and heat transfer in reactive systems. However, there are considerable difficulties for accurate quantitative measurements due to beam hardening and radiation scattering effects. In a theoretical and experimental work we have investigated the non-linear effects of both physical phenomena and developed a suitable measurement setup as well as calibration and software correction methods to achieve a highly accurate measurement of void fraction profiles with CBCT.     

乙烯裂解炉内传递和反应过程综合数值模拟Ⅱ.反应管内传递和反应过程的数值模拟

采用乙烯裂解炉传递反应过程综合数学模型中的反应管数学模型，对工业裂解炉反应管进行了系统的数值模拟，得到了反应管内流场、温度场和浓度场的详细信息，揭示了反应管内流动、传热、传质和裂解反应的基本特点。模拟结果表明，沿反应管轴向油气吸热升温，裂解反应加剧，产物产率逐渐发生变化；沿反应管径向存在明显的流体流速和温度的变化，而产物产率的变化不如流体流速和温度的变化明显。通过比较湍流粘度和分子粘度的大小，认为29．975～30mm的径向区域为层流层，层流层的存在使得临近管壁的区域内流体流速和温度变化显著。     

Adaptation of the microscopic properties of redox catalysts to the type of gas-solid reactor

Catalysts of selective oxidation usually work in a simultaneous redox mode in reactant/air cofed reactors. The solid must provide selective lattice oxygen according to a kinetic mechanism depending on operating conditions that differ from one reactor to another. Better catalytic performance can be obtained in a recirculating solids reactor because it allows separate optimization of the reduction and oxidation steps. Among the microscopic properties of the catalyst, the crystal morphology is to be taken into account because it influences its reactivity on stream. These considerations lead to a new approach of the catalyst-reaction-reactor trio.