Selective Hydrogenation of 1‐Butene Rich Cuts: the Impact of the Intraparticle Diffusion Limitations on the Selectivity

The impact of intraparticle diffusion limitations on the selectivity of an industrial reactor for selective hydrogenation of 1‐butyne and 1,3‐butadiene contained in 1‐butene rich cuts was evaluated. To this end, a simple model of a trickle‐bed reactor was employed and actual process operating conditions were chosen. A kinetic model was chosen whose parameters correspond to a commercial catalyst. These parameters were calculated from experiments conducted under industrial operating conditions. The complex diffusion and reaction phenomena occurring inside catalyst pellets placed at different depths of the reactor are comprehensively described. 1‐Butene losses in the range 20–30 %, which are usual in commercial plants, were predicted. It was concluded that the operating pressure is crucial for enhancing process selectivity.     

Simulation of an Industrial Pyrolysis Gasoline Hydrogenation Unit

A model is developed based on a two‐stage hydrogenation of pyrolysis gasoline to obtain a C₆–C₈ cut suitable for extraction of aromatics. In order to model the hydrogenation reactors, suitable hydrodynamic and reaction submodels should be solved simultaneously. The first stage hydrogenation takes place in a trickle bed reactor. The reaction rates of different di‐olefines as well as hydrodynamic parameters of the trickle bed (i.e., catalyst wetting efficiency, pressure drop, mass transfer coefficient and liquid hold‐up) have been combined to derive the equations to model this reactor. The second stage hydrogenation takes place in a two compartment fixed bed reactor. Hydrogenation of olefines takes place in the first compartment while sulfur is eliminated from the flow in the second compartment. These reactions occur at relatively higher temperature and pressure compared to the first stage. The key component in this stage is considered to be cyclohexene, of which the hydrogenation was found to be the most difficult of the olefines present in the feed. The Langmuir‐Hinshelwood kinetic expression was adopted for the hydrogenation of cyclohexene and its kinetic parameters were determined experimentally in a micro‐reactor in the presence of the industrial catalyst. The model was solved for the whole process of hydrogenation, including hydro‐desulfurization. The predictions of the model were compared with actual plant data from an industrial scale pyrolysis gasoline hydrogenation unit and satisfactory agreement was found between the model and plant data.     

STUDY ON THE ACETYLENE HYDROGENATION PROCESS FOR ETHYLENE PRODUCTION: SIMULATION,MODIFICATION, AND OPTIMIZATION

In this study, an industrial acetylene hydrogenation unit is simulated utilizing three available kinetic models. The results are compared against six-day experimental data and the best model is selected. Effects of feed temperature and the amount of injected hydrogen on ethylene selectivity are also studied. According to the simulation results, the unit is not working under its optimum conditions. Furthermore, by reduction of the hydrogen flow rate to 52 kg/h, process selectivity is increased. In addition, a new approach is proposed to modify the hydrogenation process and reduce undesired by-products. In the simulation of the modified process, hydrogenation reactors temperature, hydrogen flow rate, and H-1/H-2 ratio were regulated as adjustable parameters for the process optimization. The simulation shows that ethylene selectivity increases by 12%, while acetylene concentration and hydrogenation reactor temperature remains within acceptable ranges. Such selectivity could be achieved at the hydrogen flow rate of 50 kg/h with H-1/H-2 ratio of 0.1/0.9.     

Modeling of an industrial fixed bed reactor based on lumped kinetic models for hydrogenation of pyrolysis gasoline

In this work, a mathematical model of an industrial fixed bed reactor for the catalytic hydrogenation of pyrolysis gasoline produced from olefin production plant is developed based on a lumped kinetic model. A pseudo-homogeneous system for liquid and solid phases and three pseudo-components: diolefins, olefins, and parraffins, are taken into account in the development of the reactor model. Temperature profile and product distribution from real plant data on a gasoline hydrogenation reactor are used to estimate reaction kinetic parameters. The developed model is validated by comparing the results of simulation with those collected from the plant data. From simulation results, it is found that the prediction of significant state variables agrees well with the actual plant data for a wide range of operating conditions; the developed model adequately represents the fixed-bed reactor.     

Sugar hydrogenation over a Ru/C catalyst

BACKGROUND: In recent years, exploitation of renewable resources has gained considerable attention. In this respect, polyols derived from the hydrogenation of sugar molecules are versatile molecules with a variety of uses, such as low‐caloric sweeteners. The hydrogenation of D‐maltose, D‐galactose, L‐rhamnose and L‐arabinose was carried out on a finely dispersed Ru/activated carbon catalyst with the objective of studying the kinetics of the production of the corresponding polyols. The reactions were carried out in a stirred tank reactor at temperatures ranging from 90 to 130 °C and hydrogen pressures from 40 to 60 bar. RESULTS: Sugar conversions up to 100% were achieved. Some by‐product formation affecting the quality of the selectivity was also observed at elevated operating conditions. The catalyst was characterized by scanning electron microcopy (SEM), transmission electron microscopy (TEM), inductively coupled plasma optical emission spectrometry (ICP‐OES) and nitrogen physisorption. Kinetic models based on the Langmuir Hinshelwood assumptions were proposed for the reactions and a nonlinear regression was performed to obtain the numerical values of the kinetic parameters. CONCLUSIONS: The kinetic models predicted well the sugar hydrogenation process and the kinetic parameters were established. The model can be used to predict the behaviour of batchwise operating slurry reactors. Copyright © 2011 Society of Chemical Industry     

Preparation of sorbitol from D‐glucose hydrogenation in gas–liquid–solid three‐phase flow airlift loop reactor

A new process for D ‐glucose hydrogenation in 50 wt% aqueous solution, into sorbitol in a 1.5 m³ gas–liquid–solid three‐phase flow airlift loop reactor (ALR) over Raney Nickel catalysts has been developed. Five main factors affecting the reaction time and molar yield to sorbitol, including reaction temperature (T_R), reaction pressure (P_R), pH, hydrogen gas flowrate (Q_g) and content of active hydrogen, were investigated and optimized. The average reaction time and molar yield were 70 min and 98.6% under the optimum operating conditions, respectively. The efficiencies of preparation of sorbitol between the gas–liquid–solid three‐phase flow ALR and stirred tank reactor (STR) under the same operating conditions were compared. Copyright © 2004 Society of Chemical Industry     

Analysis of attainable reactor performance for the oxidative methane coupling process

In this work, a comparative analysis of attainable performance is presented for three different reactor structures including a fixed-bed reactor, and two different feeding structures of packed bed membrane reactors. For this purpose, three types of kinetic models, namely La₂O₃/CaO, Mn/Na₂WO₄/SiO₂, and PbO/Al₂O₃ have been used under a wide range of operating conditions. Thus, the effect of several variables such as operating temperature, membrane thickness, methane-to-oxygen ratio, feed flow rate, gas streams composition, and reactor length are investigated.Moreover, kinetic-analysis based on a proposed graphical approach enables determination of the suitable operational condition range and allows analysis of the feasible and optimal performance that corresponds to the effect of several dependent operating variables. The results show that tracking the optimum area of operation has a monotonic direction under some range of operating conditions, while it reflects qualitative trade-offs under some other ranges of operating conditions. For all investigated reactor concepts and catalysts, optimal operating conditions and the best corresponding performance are presented.     

Modelling of kinetics and mass transfer in the hydrogenation of xylose over Raney nickel catalyst

This paper discusses the modelling of xylose hydrogenation kinetics over Raney nickel in aqueous solutions, the determination of the hydrogen solubility in the reaction mixture as well as evaluation of mass transfer effects in the reaction system. The hydrogenation experiments were carried out batchwise in an automatic laboratory‐scale reactor. The reactor system operated at a pressure range of 40–70 bar and at temperatures between 80 and 140 °C. The catalyst‐to‐xylose ratio was approximately 5 wt‐% of the xylose weight normally. The reactor contents were analysed off‐line with a high performance liquid chromatograph. Hydrogen solubility in the reaction medium was determined with a gas‐chromatographic system. The solubility was found to remain fairly constant during the hydrogenation. Only a slight increase in the hydrogen solubility was detected as xylose was hydrogenated to xylitol. The overall hydrogen solubility in the reaction mixture was significantly lower than in pure water, as expected. The main hydrogenation product was xylitol, but small amounts of xylulose and arabinitol were detected as by‐products. A semi‐competitive kinetic model, based on hydrogen and xylose adsorption, was developed. The model accounts for the very different areas covered by a hydrogen atom and an organic species on the catalyst surface. The parameters of the kinetic model were determined with non‐linear regression analysis. It turned out that the kinetic model is able to describe the formation of both xylitol and the by‐products. The mass transfer effects in the batch hydrogenation were evaluated by using measured viscosities and estimated diffusion and mass transfer coefficients. A process simulator, utilizing the kinetic and mass transfer effects, was developed to predict the behaviour of industrial reactors. © 1999 Society of Chemical Industry     

复合膜生物反应器有机物去除动力学的研究

本研究对向膜生物反应器中投加陶粒填料的复合式膜生物反应器（HMBR）处理生活污水的工艺条件进行了系统试验。在优化的工艺条件下进行了HMBR去除有机物的反应动力学研究，确定了该反应器生物处理反应动力学参数，并建立了反应器中有机底质降解动力学模型。     

Fischer‐Tropsch Synthesis: Modeling and Performance Study for Fe‐HZSM5 Bifunctional Catalyst

A water‐cooled fixed bed Fischer‐Tropsch reactor packed with Fe‐HZSM5 catalyst has been modeled in two dimensions (radial and axial) using the intrinsic reaction rates previously developed at RIPI. The reactor is used for production of high‐octane gasoline from synthesis gas. The Fischer‐Tropsch synthesis reactor was a shell and tube type with high pressure boiling water circulating on the shell side. By the use of a two‐dimensional model, the effects of some important operating parameters such as cooling temperature, H₂/CO ratio in syngas and reactor tube diameter on the performance capability of the reactor were investigated. Based on these results, the optimum operating conditions and the tube specification were determined. The model has been used to estimate the optimum operating conditions for the pilot plant to be operated in RIPI.     

Optimal hybrid modeling approach for polymerization reactors using parameter estimation techniques

The dynamics of polymerization catalytic reactors have been investigated by many researchers during the past five decades; however, the emphasis of these studies was directed towards correlating process model parameters using empirical investigation based on small scale experimental setup and not on real process conditions. The resulting correlations are of limited practical use for industrial scale operations. A statistical study for the relative correlation of each of the effective process parameters revealed the best combination of parameters that could be used for optimizing the process model performance. Parameter estimation techniques are then utilized to find the values of these parameters that minimize a predefined objective function. Published real industrial scale data for the process was used as a basis for validating the process model. To generalize the model, an artificial neural network approach is used to capture the functional relationship of the selected parameters with the process operating conditions. The developed ANN-based correlation was used in a conventional fluidized catalytic bed reactor (FCR) model and simulated under industrial operating conditions. The new hybrid model predictions of the melt-flow index and the emulsion temperature were compared to industrial measurements as well as published models. The predictive quality of the hybrid model was superior to other models. The suggested parameter estimation and modeling approach can be used for process analysis and possible control system design and optimization investigations.     

Chemical kinetic modeling of i‐butane and n‐butane catalytic cracking reactions over HZSM‐5 zeolite

A chemical kinetic model for i‐butane and n‐butane catalytic cracking over synthesized HZSM‐5 zeolite, with SiO₂/Al₂O₃ = 484, and in a plug flow reactor under various operating conditions, has been developed. To estimate the kinetic parameters of catalytic cracking reactions of i‐butane and n‐butane, a lump kinetic model consisting of six reaction steps and five lumped components is proposed. This kinetic model is based on mechanistic aspects of catalytic cracking of paraffins into olefins. Furthermore, our model takes into account the effects of both protolytic and bimolecular mechanisms. The Levenberg–Marquardt algorithm was used to estimate kinetic parameters. Results from statistical F‐tests indicate that the kinetic models and the proposed model predictions are in satisfactory agreement with the experimental data obtained for both paraffin reactants. © 2011 American Institute of Chemical Engineers AIChE J, 58: 2456–2465, 2012     

Hydrogenation of Nitrobenzene over a Pd/Al2O3 Catalyst – Mechanism and Effect of the Main Operating Conditions

The catalytic hydrogenation of nitrobenzene (NB) was studied in a three‐phase basket reactor with a commercial Pd/Al₂O₃ sample as catalyst. The kinetic experiments allowed a better understanding of the mechanism behind the formation of aniline (ANL) and by‐products, a topic not yet well comprehended. The effect of some operating conditions was studied and the existence of more by‐products than mentioned in the literature was stated; specifically, benzene formation was verified. Both the reaction kinetics and selectivity were found to be strongly dependent on the temperature, while the effect of total pressure is not that pronounced. Moreover, the high selectivity of the catalyst used in the present work was proved, and as such the deep hydrogenation of ANL to form by‐products only occurs in considerable extension when the NB concentration in the reaction mixture becomes negligible.     

A DNA based genetic algorithm for parameter estimation in the hydrogenation reaction

Inspired by the mechanism of the biological DNA, a DNA based genetic algorithm (DNA-GA) is proposed to determine the kinetic parameters for the hydrogenation reaction. The considered chemical process contains five reactions and 25 unknown parameters. The DNA-GA uses the DNA encoding method to represent the potential parameters and genetic operators inspired from the biological DNA are designed to find the global optimum. The study on the performance for typical benchmark functions shows that the DNA-GA outperforms the other two methods in both convergence speed and accuracy. Based on the operating data gathered from an industrial hydrogenation unit, 25 parameters are obtained by the DNA-GA and the kinetic model for the hydrogenation reaction is established. To verify the validity of the established model, another four groups of data are used to test the established model and two previously reported models. The comparison results show that the sum of square relative errors of the model obtained by the DNA-GA is the least of the test models, and its prediction is in good agreement with the practical operating data.     

Kinetics and Modeling of Fatty Alcohol Ethoxylation in an Industrial Spray Loop Reactor

The kinetics of the ethoxylation of fatty alcohols catalyzed by potassium hydroxide was studied to obtain the rate constants for modeling of the industrial process. Experimental data obtained in a lab‐scale semibatch autoclave reactor were used to evaluate kinetic and equilibrium parameters. The kinetic model was employed to model the performance of an industrial‐scale spray tower reactor for fatty alcohol ethoxylation. The reactor model considers that mass transfer and reaction occur independently in two distinct zones of the reactor. Good agreement between the model predictions and real data was found. These findings confirm the reliability of the kinetic and reactor model for simulating fatty alcohol ethoxylation processes under industrial conditions.     

Numerical investigation and experimental validation of the performance of a tubular packed bed reactor for hydrogenation of diene‐based polymers

A process which comprised a tubular reactor (that can be packed with different internal structures) has been modeled and theoretically analyzed for conducting the hydrogenation of nitrile butadiene rubber (NBR). The dynamics of the tubular reactor and the intrinsic hydrogenation kinetics are coupled, and detailed numerical simulations are performed under isothermal and isobaric conditions. The proposed model thus obtained involves coupled, nonlinear, partial differential equations (distributed parameter system). The effect of different reactor design parameters such as Peclet number, carbon–carbon double bond loading, mass transfer to reaction resistance, and solubility of hydrogen with respect to hydrogenation of the NBR has been investigated numerically. The conversions predicted using the proposed model for tubular packed bed reactor are compared with those possible in conventional plug flow reactor and continuous stirred tank reactor models. The optimal parameters and operating conditions for efficient production of hydrogenated NBR are suggested. Finally, the validity of the proposed model is confirmed by comparing the predicted and the experimental degree of hydrogenation obtained in a tubular reactor packed with Intalox saddles. POLYM. ENG. SCI., 2009. © 2009 Society of Plastics Engineers     

Numerical simulation and optimisation of unconventional three‐section simulated countercurrent moving bed chromatographic reactor for oxidative coupling of methane reaction

The simulated countercurrent moving‐bed chromatographic reactor (SCMCR) has been reported to significantly enhance methane conversion and C₂ product yield for oxidative coupling of methane (OCM) reaction, which is otherwise a low per pass conversion reaction. A mathematical model of an unconventional three‐section SCMCR for OCM was first developed and solved using numerically tuned kinetic and adsorption parameters. The model predictions showed good agreement with available experimental results of SCMCR for OCM. Effects of several process parameters on the performance of SCMCR were investigated. A multi‐objective optimisation problem was solved at the operating stage using state‐of‐the‐art AI‐based non‐dominated sorting genetic algorithm with jumping genes adaptations (NSGA‐II‐JG), which resulted in Pareto Optimal solutions. It was found that the performance of the SCMCR could be significantly improved under optimal operating conditions. © 2011 Canadian Society for Chemical Engineering     

环氧乙烷合成银催化剂宏观动力学及失活分析

在工业生产的条件下用无梯度反应器研究了工业颗粒银催化剂上乙烯氧化合成环氧乙烷宏观动力学 ,得到了能反映该系统主副反应特性的双速率方程 .建立了二维非均相反应器模型 ,模拟并比较了工业生产操作数据 ,获得了该种催化剂的活性校正因子随使用时间变化的经验关联式和主副反应失活速率方程     

Modeling of Kinetic Expressions for the Reduction of NOx by Hydrogen in Oxygen‐Rich Exhausts Using a Gradient‐Free Loop Reactor

The reduction of NO_x by hydrogen under lean conditions is investigated in a gradient‐free loop reactor. Using this computer‐controlled reactor, the reaction rates can be measured under exact isothermal conditions. Systematic variation of the input concentrations of hydrogen, nitric oxide, oxygen as well as reaction temperature provides a complete data set of reaction rates for the given reaction system. A number of kinetic rate expressions were evaluated for their ability to fit the experimental data by using toolboxes of MATLAB. The temperature influence on reaction rate constants and adsorption equilibrium constants were correlated simultaneously using Arrhenius and van’t Hoff equations, respectively. The kinetic rate expression based on a Langmuir‐Hinshelwood‐type model describes the data and the model can be improved by introducing a correction term in square root of hydrogen partial pressure over the range of conditions investigated.     

工业异构化反应器建模及仿真

将3个二甲苯异构体集总为一个组分,提出一个新的异构化三角反应网络,建立工业异构化反应器模型.基于多组平衡的工业数据,采用传统的优化方法估计动力学参数,然后对不同操作条件下的大量工业数据进行仿真,结果表明模型估计值与观测值相当吻合.与其他模型相比,文中开发的模型在相对误差、相对均方误差和参数估计时间等性能指标上均体现出优...