Estimation of Kinetic Parameters for Hydrogenation Reactions Using a Genetic Algorithm

The kinetics of acetylene hydrogenation in a fixed‐bed reactor of a commercial Pd/Al₂O₃ catalyst has been studied. The hydrogenation reactor considered in this work is an essential part of a vinyl chloride monomer (VCM) plant. Three well‐known kinetic models were used to simulate the hydrogenation reactor under industrial operating conditions. Since none of the models provide appropriate prediction, the industrial data and calculated values were compared and optimum kinetic parameters were evaluated utilizing a genetic algorithm (GA) technique. The best kinetic parameters for the three models were determined under specified industrial operating conditions. The hydrogenation reactor was simulated using the estimated optimum kinetic parameters of the three models. Simulation results from the three models were compared to industrial data and the best kinetic model was found. This kinetic model with the evaluated optimum kinetic parameters can well predict the behavior of the industrial hydrogenation reactor to improve the performance of the process.     

不对称合成(R)-2-羟基-4-苯基丁酸乙酯的动力学

采用10,11-二氢辛可尼定修饰的Pt/Al2O3催化体系,不对称加氢合成(R)-2-羟基-4-苯基丁酸乙酯,研究了各因素影响反应速率和光学收率的一般规律.根据推测的机理,建立了未修饰体系中加氢反应的本征动力学模型,结合实验数据选定了较佳的模型.假设不对称加氢反应总速率包括反应物在催化剂表面修饰位上和未修饰位上两部分的加氢速率,建立了不对称加氢的动力学模型,经拟合得到参数并进行了验证和讨论.     

Measurement of Micro Kinetics of Hydrogenation in Liquid Phase Using Raman Spectroscopy

Hydrogenation of liquid organic hydrogen carriers is usually carried out in liquid phase. To measure the kinetics of this hydrogenation, an experimental setup using in situ Raman spectroscopy for analysis of the reaction mixture is proposed. With this setup it is possible to perform hydrogenation reactions at temperatures of up to 573 K and pressures up to 25 MPa. For validation of the experimental setup the hydrogenation of 1‐octene was measured in liquid phase. The reaction progress can be monitored in detail by Raman spectroscopy. To determine kinetic parameters from the experimental data, two modeling approaches were applied: a classic kinetic model and a thermodynamic kinetic model. The results were compared to literature data.     

碳二加氢等温反应过程模拟与操作参数优化

以碳二加氢等温管式固定床反应器为研究对象, 利用计算流体力学(CFD)方法建立了与外界有热量交换的二维均相流反应器模型, 通过添加气固能量方程, 建立了多孔介质区内部热交换与气固耦合传热的两温度模型。采用遗传算法对反应的动力学参数进行了拟合, 并以加氢选择性最优为目标函数, 对碳二加氢反应的入口氢炔比与反应器的冷却温度进行优化, 得到最优氢炔比为1.18, 最优的冷却温度为334.66 K。最后根据模拟与优化结果, 分析了氢炔比和冷却温度对加氢反应选择性的影响, 对提高加氢反应器的操作性能具有重要的意义。     

蜡油加氢脱硫集总动力学模型研究

以减压蜡油（VGO）加氢脱硫（HDS）小试实验数据为基础,针对VGO HDS反应速率快慢,将原料中硫化物划分为快反应速率、中反应速率、慢反应速率3个集总,建立VGO HDS反应三集总动力学模型,并采用Levenberg-Marguardt算法对模型参数进行了求解。结果表明,该模型平均相对误差仅为5.18%,预测值可靠,外推性良好,模型参数计算结果符合加氢反应规律。通过模型计算,分析了液时空速、反应温度、反应压力对VGO HDS过程的影响,得到了HDS详细的反应规律,可为VGO HDS反应集总动力学研究和实验分析提供参考。     

Kinetic modeling and optimization of the operating condition of MTO process on SAPO-34 catalyst

In this paper, a new kinetic model for methanol to olefin process (MTO) over SAPO-34 catalyst was developed based on data obtained from a micro catalytic reactor using appropriate reaction network. The reaction rate equation has been introduced with consideration of reaction mechanism and the parameters were optimized on the experimental data by genetic algorithm. Comparing the experimental and predicted data showed that the predicted values from the presented model are well fitted to the experimental data. Using this kinetic model, the effect of most important operating conditions such as temperature, pressure, inlet water to methanol molar ratio and methanol space–time on the product distribution, has been examined. Finally, the optimal operating conditions for maximum production of the ethylene and the propylene were introduced.     

Modelling of citral hydrogenation kinetics on an Ni/Al2O3 catalyst

The kinetics of citral hydrogenation in ethanol over an Ni/Al₂O₃ catalyst was studied in a slurry reactor operating at atmospheric pressure and at a temperature range of 60–77°C. Citronellal was the primary reaction product, whereas the amounts of unsaturated alcohols were very minor. Citronellol was the dominating product, generated mainly through the hydrogenation of the carbonyl group of citronellal. Based on the experimental data, a kinetic model was developed for hydrogenation. The model comprises competitive and rapid adsorption steps as well as rate-determining hydrogenation steps. The mass transfer limitation of hydrogen was included in the mathematical model. The kinetic parameters and the mass transfer parameter of hydrogen were estimated from the experimental data. A comparison of the model predictions with the experimental data revealed that the proposed kinetic approach gave a satisfactory reproduction of the data.     

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.     

Detailed understanding on thermodynamic and kinetic features of phenanthrene hydroprocessing on Ni-Mo/HY catalyst

Phenanthrene hydrogenation is a key reaction for improving the quality of gasoline and diesel. Herein, we conduct detailed thermodynamic and kinetic analyses for phenanthrene hydrogenation on a Ni-Mo/HY catalyst. We establish a comprehensive reaction network for phenanthrene hydrogenation, and calculate equilibrium constant, rate constant, adsorption constant, activation energy barrier, and reaction energy for each step in the reaction network. All of the steps in the reaction network are revealed to be exothermic. A kinetic model with 28 parameters is constructed for phenanthrene hydrogenation. The deviation of the product yields calculated by the kinetic model from those obtained in experiments is less than 4.5%, indicating the reasonability and accuracy of the kinetic model. The most favorable pathway for phenanthrene hydrogenation is demonstrated to be phenanthrene → tetrahydrophenanthrene → sym-octahydrophenanthrene → 5,6-butyl-tetrahydronaphthalene → tetralin. These results are helpful for efficiently tuning catalyst properties and optimizing reaction conditions for enhancing phenanthrene hydrogenation.     

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     

Pd/C上松香催化歧化反应集总动力学

以松香为原料、改性Pd/C为催化剂、200#油为溶剂及N2为保护气,进行松香催化歧化反应集总动力学的研究。在消除内外扩散影响的条件下,在线跟踪48315～53315 K的反应产物并用毛细管柱气相色谱法测定反应体系组成随时间的变化关系。根据松香歧化反应机理和特点,借鉴集总思想和方法,按结构族组成和动力学相近原则划分该复杂反应体系的集总组分,构建了Pd/C上松香歧化集总反应网络,建立了枞酸型树脂酸、海松酸型树脂酸、氢化枞酸型树脂酸、氢化海松酸型树脂酸和脱氢枞酸五集总动力学模型;采用Levenberg-Marquart法,以Matlab编程和SPSS数理统计软件估算了模型参数,得到枞酸型树脂酸脱氢、加氢,海松酸型树脂酸加氢反应过程的活化能分别为11139 kJ·mol-1、10876 kJ·mol-1、9735 kJ·mol-1,结果表明,所建动力学模型与实验数据吻合良好,并能预测反应在54315 K的集总组分浓度分布。     

糠醛气相催化加氢制糠醇工艺开发——固定床反应器数学模拟与分析

在糠醛气相催化加氢制糠醇单管实验基础上,提出了新的反应动力学模型,建立了该反应体系的拟均相二维平推流数学模型,用Powell优化方法对模型中参数进行估值。所建立模型能正确反映操作条件对反应器内温度分布和糠醇收率的影响,将它用于反应器模拟,计算结果与实测结果吻合较好。本文还应用该模型对糠醛加氢反应器进行模拟分析,得出了优化操作条件。     

Thermodynamic and Kinetic Analyses of the Hydrogenation of Coal from the Mamytskoe Deposit

The kinetic and thermodynamic parameters (the equilibrium degree of reaction, the rates of forward and reverse reactions, the equilibrium constant, the activation energies of forward and reverse reactions, the Gibbs free energy, and the heat effect and entropy of the process) of the hydrogenation of coal from the Mamytskoe deposit of (Republic Kazakhstan) at 380–440°C were calculated with the use of equilibrium kinetic analysis (EKA). It was established that the rate of forward reaction increased whereas the rate of reverse reaction decreased with temperature. The application of the kinetic–thermodynamic model obtained to the hydrogenation of coal from the Mamytskoe deposit facilitated the understanding of the chemical conversion of the organic matter of coal.     

Modeling and simulation for an industrial reactor on hydroisomerization of C8-aromatics

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越性。     

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...     

催化剂失活条件下的碳二加氢反应器模拟与优化

乙炔加氢反应催化剂的活性与选择性随着使用时间变化而变化,操作参数需要相应的改变从而使得收益最大化。因此本文采集工业数据,通过遗传算法拟合了反应动力学模型和失活反应模型的参数;比较了国内最普遍使用的两种催化剂的选择性和活性保持方面的性能;针对串联使用的两台装填不同催化剂的反应器组合,以运行周期、乙烯产率最优为评价标准,提出了反应器3种组合优化、负荷分配优化等优化策略。将优化策略应用于实际工业装置的分析与运行,乙烯产率和总选择性提高,效果得到验证。     

二氧化硫强制动态氧化过程的模型化(Ⅳ)模型参数的修正与单级反应器的性能预测

模拟计算证明,反应器操作特性对传热参数的变化是不敏感的,但对化学反应宏观动力学参数的变化是敏感的.通过使模型预测结果与大量模试数据相拟合的办法修正了宏观动力学参数.利用所发展的数学模型和修正后的参数,对单级反应器的操作性能进行了预测与分析,所得到的结论对工业反应器的设计、运行和优化具有指导作用.     

工业Fe-Cu-K催化剂上费托合成反应动力学(Ⅱ)——模型筛选与参数估值

依据本文(Ⅰ)报获得的费托合成动力学模型及水煤气变换反应动力学模型,结合在固定床中测得的动力学数据,对几个候选动力学模型进行了参数回归。结果表明,表面碳化物烯烃再吸附机理模型和CO_2脱附为控制步骤的水煤气变换反应动力学模型能较好地拟合实验数据,所得最终费托合成机理动力学模型满足模型检验要求,且回归得到的活化能值与文献结果一致。     

MODELING OF UNSTEADY - STATE OXIDATION PROCESS OF SO_2(Ⅳ) MODEL PARAMETER MODIFICATION AND PERFORMANCE PREDICTION OF ONE - STAGE FLOW REVERSAL REACTOR

模拟计算证明,反应器操作特性对传热参数的变化是不敏感的,但对化学反应宏观动力学参数的变化是敏感的.通过使模型预测结果与大量模试数据相拟合的办法修正了宏观动力学参数.利用所发展的数学模型和修正后的参数,对单级反应器的操作性能进行了预测与分析,所得到的结论对工业反应器的设计、运行和优化具有指导作用.     

汽油加氢反应动力学的适时校正和反应器的模拟

分析了汽油加氢过程的主要反应，对复杂系统的反应动力学进行集总简化，建立了加氢反应器的数学模型，并采用适时校正的方法对汽油加氢反应器操作特性进行模拟计算，讨论了一些操作参数对加氢效率的影响，并对加氢操作进行了分析。