Kinetic modelling of the catalytic conversion of synthesis gas

A kinetic study for the one-step conversion of synthesis gas to gasoline on a ZnO–Cr₂O₃–ZSM-5 catalyst is described. On this catalyst, three reactions are involved in the overall transformation of synthesis gas: the methanol synthesis, the conversion of methanol to hydrocarbons and the water–gas shift reaction. Under the operating conditions selected for the study, it was found that the water–gas shift was at equilibrium and the methanol was completely converted to hydrocarbons. Consequently, it was postulated that the kinetics of the limiting reaction step, the methanol synthesis on the ZnO–Cr₂O₃ component, was the one that controls the overall reaction rate. Three kinetic model equations describing the rate of synthesis gas conversion on the bifunctional catalyst, were considered to fit the data of the experimental runs performed in a Berty well-mixed reactor. Those equations were derived under very special conditions where the methanol decomposition term could be neglected. It was also observed that in the kinetic equations a term involving the fugacity of CO₂ was required to predict the rate properly. The catalyst deactivation was also taken into account in the analysis.     

Fischer–Tropsch synthesis: Deactivation of promoted and unpromoted cobalt–alumina catalysts

The loss in activity of Pt-promoted and unpromoted 25 wt% Co–Al₂O₃ catalysts has been compared under identical conditions except for adjustment of the space velocity to give the same initial CO-conversion. Both catalysts underwent a 200 h period of rapid, initial decline in CO conversion and then a slower, linear decline during the next 1000 h. Pt-promotion did not alter the cobalt dispersion (or average particle size) from that of the unpromoted catalyst but did increase the amount of cobalt that was reduced. When compared not by time-on-stream, but by the moles of Co converted per unit weight of catalyst, both the Pt-promoted and unpromoted catalysts decline in activity at the same rate.     

EFFECT OF PORE DIFFUSION ON DEACTIVATING RATES OF SECOND ORDER REACTION

The research and development of catalysts, the design and operation of catalytic reactors are complicated by the phenomenon of catalyst deactivation which is affected by various factors. In this paper, the effect of internal mass transfer resistance in the second order catalytic reaction system of uniform independent deactivation on both reaction and deactivation rates of straight cylindrical pore model has been discussed. In addition, the quantitative relations between effectiveness factor and Thiele modulus in second order reaction and first order deactivation system have been correlated     

PORE-MOUTH POISONING OF NON-UNIFORM CATALYSTS

Impurity poisoning of a catalyst particle having a non-uniform activity distribution is analyzed. Equations that relate the position of the poison-front with time for different activity profiles are derived. It is shown that the effect of the activity distribution on the poisoning rate is apparent in the case of intraparticle-diffusion control. The performance of a non-uniform bifunctional catalyst in such conditions is also studied.     

乙苯/乙烯烷基化反应中EA-8402分子筛催化剂的失活动力学研究

用内循环无梯度反应器,在593～633K范围内考察了在乙苯/乙烯进行定向烷基化反应合成对二乙苯时,EA-8402分子筛催化剂的失活行为,建立了相应的失活动力学模型: -da/dt=0.3271exp(-12.94/T)P_(EB)~(0.02)P_(E(?))~(0.383)·α这一模型可作为该反应的宏观动力学模型的补充。由失活级数d=1,按Levenspiel判据推断:其失活机理应该是不受内扩散阻力控制的平行-连串失活。     

Optimal temperature policies for catalytic transport reactors under periodic operation

The influence of inlet gas concentration cycling on the optimal temperature policy of catalytic transport reactors is studied theoretically. The model considered is based on plug flow of gas and catalyst particles with negligible interand intra-particle diffusional resistances and concentration dependent deactivation kinetics. To utilise the concentration of the reactant and the activity of the deactivating catalyst fully a proper temperature sequence along the reactor is needed. Thus, a general optimal temperature policy using the continuous minimum principle is derived for the reactor under periodic operation. The model equations are solved analytically for gas concentration, activity and temperature profiles. Resonance behaviour (maximum in conversion with pulse width) is obtained using the optimal temperature policy for certain sets of parameters. The effects of activation energy groups, reaction and deactivation constant groups and inlet temperature on the optimal temperature policy under periodic operation are evaluated. In all cases an improvement in conversion with the optimal temperature policy under periodic operation over that with an isothermal policy under periodic operation is obtained. A suboptimal policy, comprising constant temperature over different reactor sections, which is useful for implementation purposes is also discussed.     

Methanol Selective Oxidation to Formaldehyde over Iron-Molybdate Catalysts

This review deals with the important industrial reaction of formaldehyde manufacture by methanol oxidation over iron molybdate catalysts. Detailed reference is made to the used catalyst, preparation techniques (coprecipitation, sol-gel like, mechanical mixing, etc.) including unsupported and supported catalysts, promoters and characterization methods. The controversial active phase assignment (stoichiometric versus Mo rich iron molybdate) is discussed. The proposed reaction mechanisms and kinetic laws for the main and side reactions are examined. The catalyst deactivation processes are reviewed and the role of Mo excess on these processes is underlined. Finally conclusions and perspectives are presented.     

Catalyst pore plugging effects on hydrocracking reactions in an Ebullated bed reactor operation

This paper analyzes the deactivation effects of NiMo/Al₂O₃ catalyst during the operation in an Ebullated bed reactor for Heavy residue hydrocracking. The spent catalysts were characterized by chemical analysis, ¹³C NMR, ESM, DRX, and by using thermal programmed oxidation and diffusion studies in a shallow bed micro-reactor. The deactivations were performed in a 5 l continuously stirred tank reactor, while the spent catalysts were tested in a 0.05 l micro-reactor. The study focused on determining the properties of the external layer of the catalyst and on evaluating the internal coke and metal deposition. The results indicated that initial deactivation is mainly due to coke depositions, while its impact on mass transfer reaction control depends on temperature. In long-term deactivation, the metal deposition plays a more important role in blocking the internal micro- and meso-structures and in building up the external layer of the pellets.     

ZnHZSM-5催化丙烷芳构化的失活动力学研究

在等温积分反应器中实验研究了由丙烷制取轻质芳烃BTX（苯、甲苯及二甲苯）的芳构化过程中，锌改性的HZSM－5催化剂的积炭失活对反应过程的影响，通过对常压、不同反应温度下的实验数据所进行的动力学分析，建立起了失活动力学模型，并通过拟合实验数据对模型做了筛选，最终确定了基于Langumir-Hinshelwood模型的反应速率方程和由独立失活机理推出的2级独立失活速率方程，该模型对深入了解轻烃芳构化反应及指导反应器设计均具有重要的意义。