Simulation of continuous packed bed reactive distillation column for the esterification process using activity based kinetic model

A mathematical model for the continuous packed bed reactive distillation process of esterification of acetic acid with methanol is developed. The kinetic rate equation, which plays a major role for the performance of reactive distillation and it is the part of model, is required for the liquid phase reversible esterification reaction. The mineral sulphuric acid is used as the catalyst. The kinetic experiments are carried out under different temperatures in the range of 305.15 to 333.15 K and catalyst concentrations in the range of 0.1267 mole H⁺/lit to 0.6537 mole H⁺/lit. From that experimental data the kinetic model is developed and the same is used for the simulation of reactive distillation process. Equilibrium stage model, in which the vapour and the liquid leaving a stage are assumed to be in equilibrium with each other, has been used for the simulation of reactive distillation process by incorporating our kinetic model. Conversion of acetic acid as function of reflux ratio and reboiler ratio has been predicted. The liquid composition and temperature profiles versus stage number have been also predicted. Finally, the optimum operating conditions obtained from the simulation results for high pure methyl acetate by reactive distillation process.     

Kinetics of the oxidative dehydrogenation (ODH) of methanol to formaldehyde by supported vanadium-based nanocatalysts

The aim of the present contribution was to develop a detailed kinetic analysis of the oxidative dehydrogenation (ODH) reaction of methanol to formaldehyde on a nano-structured supported vanadium oxide catalyst, selected in a preliminary screening. The chosen vanadium catalyst, supported on TiO₂/SiO₂, has been prepared by grafting vanadyl alkoxide, dissolved in dioxane, and characterized by BET, XRD, Raman, XPS and SEM. An exhaustive set of experimental runs has been conducted in an isothermal packed bed tubular reactor by investigating several operative conditions, such as: temperature, contact time, methanol/oxygen feed molar ratio and water feed concentration. Depending on the operative conditions adopted, the main products observed were formaldehyde and dimethoxymethane while lower amounts of methyl formate and CO₂ were also found. At low contact time, the main reaction product was dimethoxymethane which was then converted into formaldehyde through the reverse equilibrium reaction with water. As a confirmation of this observation, a peculiar behaviour was detected consisting in an increase of selectivity to formaldehyde by increasing methanol conversion. The obtained experimental data of methanol conversion and selectivity towards products were modelled by means of an integral reactor model and the related kinetic parameters were determined by non-linear regression analysis. The adopted reaction rate expressions were of the Mars van Krevelen–Langmuir Hinshelwood type and a good agreement was found between the model theoretical prediction and the experimental data. A reaction mechanism and a detailed reaction scheme (rake-type) were proposed for methanol ODH on a nano-structured catalyst that were able to interpret correctly the collected experimental observations.     

Kinetic study of the methanol to olefin process on a SAPO-34 catalyst

In this paper, a new kinetic model for methanol to olefin process over SAPO-34 catalyst was developed using elementary step level. The kinetic model fits well to the experimental data obtained in a fixed bed reactor. Using this kinetic model, the effect of the most important operating conditions such as temperature, pressure and methanol space-time on the product distribution has been examined. It is shown that the temperature ranges between 400 °C and 450 °C is appropriate for propene production while the medium temperature (450 °C) is favorable for total olefin yield which is equal to 33%. Increasing the reactor pressure decreases the ethylene yield, while medium pressure is favorable for the propylene yield. The result shows that the ethylene and propylene and consequently the yield of total olefins increase to approximately 35% with decreasing the molar ratio of inlet water to methanol.     

Simulation of activity loss of fixed bed catalytic reactor of MTO conversion using percolation theory

In this investigation, a reactor model for prediction of the deactivation behavior of MTO's porous catalyst in a fixed bed reactor is developed. Effect of coking on molecular transport in the porous structure of SAPO-34 has been simulated using the percolation theory. Thermal effects of the reaction were considered in the model and the temperature profile of the gas stream in the reactor was predicted. The predicted loss in catalyst activity with time-on-stream was in very good agreement with the experimental data. The resulting coke deposition and gas temperature profiles along the length of reactor suggested a reaction front moving toward the outlet of the fixed bed reactor at the operating experimental conditions of 1 h⁻¹ and 723 K for methanol space velocity and inlet temperature, respectively. Effects of space time, coordination of Bethe network, and effective diffusivity of component in reaction mixture on the reactor performance are presented.     

Reaction scheme and kinetic modelling for the MTO process over a SAPO-18 catalyst

A kinetic model for simulation of the MTO process over SAPO-18 catalyst in a wide range of operating conditions has been proposed. The kinetic model predicts the experimental evolution of reaction products with time on stream, which follows three consecutive periods: initiation (where olefin production increases), a period of maximum olefin production and a period in which this production decreases. The kinetic scheme takes into account these three steps that evolve with time on stream: formation of active intermediate compounds, an step where olefins are formed by reaction of oxygenates (methanol/DME) with these intermediates and deactivation of intermediates by degradation to coke. The presence of water in the reaction medium attenuates the reaction rate of these steps. Discrimination of kinetic equations and calculation of the parameters of best fit have been carried out by solving the mass conservation equations of the individual components of the kinetic scheme together with the kinetic equation for deactivation and taking into account the effect of water on the kinetics of each step.     

Esterification of acrylic acid with methanol by reactive chromatography: Experiments and simulations

The esterification of acrylic acid with methanol using Amberlyst 15 as a stationary phase has been investigated using a chromatographic reactor. Several experimental runs at various operating conditions have been conducted on a batch column. A classical reactive chromatography model including lumped kinetics, a linear driving force transport model and a heterogeneous kinetic model for the catalytic reaction has been developed. The additional dispersion of concentration fronts due to density gradient effects has been accounted for in the model. The model parameters have been determined in a fast and reliable way by directly fitting the batch column experiments. In general, a good agreement between experimental and calculated results is obtained. The evaluation of the covariance of the fitted model parameters reveals important insights about the system behavior.Based on the detailed batch column model, a complete model of a simulated-moving-bed reactor has been implemented and its optimal point of operation for the synthesis of methyl acrylate from acrylic acid has been determined. Particularly when considering the low-operating temperature, we can regard this process as a possible competition for current technologies.     

Fluid phase equilibria of the reacting mixture in the dimethyl carbonate synthesis from supercritical CO2

In order to investigate the dimethyl carbonate synthesis from methanol and supercritical CO₂, the thermodynamic behaviour of the reacting mixture, i.e. the quaternary methanol–CO₂–DMC–water mixture, has to be known. The SRK equation of state with MHV2 mixing rules has been chosen to predict fluid phase equilibria in the reactor. The first part of this work is dedicated to the determination of binary interaction parameters, needed in the use of this model. These parameters are deduced from the fitting of experimental data concerning binary or ternary sub-systems existing in the quaternary mixture. Literature data was used for most of the binary sub-systems, but for the DMC–CO₂ and DMC–water mixtures, specific experiments were carried out. The agreement between experimental and predicted fluid phase equilibria was found to be satisfactory. With a view to studying of the operating conditions for the reaction, the thermodynamic model was used to predict fluid phase equilibria in the reactor, by considering several hypothetical feed ratios and conversions. This work shows that CO₂ has to be used in large excess in order to be sure of running the reaction in a homogeneous fluid medium.     

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.     

ADDITION OF PORE DIFFUSION LIMITATION TO THE “UCKRON-I” KINETIC RATE OF METHANOL SYNTHESIS

Kinetic data with pore diffusion limitation on methanol synthesis were generated by extending the “UCKRON-I” kinetic rate expression. The best fit model and the extended “true” model were compared using their respective rates to simulate temperature profiles in a non-isothermal plug flow tubular reactor.

The objective of this work was to add pore diffusion resistance to the UCKRON-1 kinetic rate for methanol synthesis (Berty, et al. 1983). Kinetic modeling of the data with 5% experimental error added, showed the best model to be that developed from a previous kinetic model (Shalabi, et al. 1983) with apparent activation energy approximately one-half the activation energy at no pore diffusion.

Methods used in this work to determine and evaluate pore diffusion parameters can be utilized for other reaction systems where pore diffusion may play a role in reaction rate.

Temperature profiles estimated from reactor simulation studies showed good argeement between ideal and predicted models for temperature.     

An intrinsic kinetic model for liquid-phase photocatalytic hydrogen production

A kinetic study was accomplished to describe the photocatalytic production of hydrogen in liquid phase. A reaction mechanism and a kinetic model were proposed to predict the rate of hydrogen production, which is a function of light intensity, catalyst loading, substrate concentration, and time. To assess the capability of the proposed model, glycerol and ethanol were selected as representative hydrogen sources (substrates). The experimental data performed under different operating conditions, based on Box–Behnken experimental design, were used to train the developed kinetic model, optimize the parameters using genetic algorithms and check its accuracy. The analysis confirms the validity of the model under different operating conditions. In addition, the ability of the model to predict the rate of hydrogen production for other substrates, photocatalysts, and operating conditions was confirmed by comparing model predictions with experimental data from literature.     

Combined experimental and kinetic modeling studies for the conversion of gasoline range hydrocarbons from methanol over modified HZSM-5 catalyst

The reaction was carried out in fixed bed reactor. The effect of process variables on the activity of oxalic acid treated 0.5 wt% ZnO/7 wt% CuO/HZSM5 catalyst for the conversion of methanol to gasoline range hydrocarbons was studied. The catalyst was prepared by incipient wetness impregnation method. After impregnation the catalyst was treated with oxalic acid. The validity of kinetic model proposed for the methanol to gasoline range hydrocarbon process at zero time on stream was studied, from the experimental results obtained in a wide range of operating conditions. The kinetic parameters for various models were calculated by solving the equation of mass conservation in the reactor for the lumps of the kinetic models. The kinetic model fitted well for simulating the operation in the fixed bed reactor in the range of 635 to 673 K, with regression coefficient (R²) higher than 0.96.     

低温液相甲醇合成反应动力学模型与参数估计

由低温液相甲醇合成的反应机理出发 ,考虑了均相和多相催化剂的不同作用及不同的吸附方式 ,导出了两步法低温液相甲醇合成的动力学模型 .结合搅拌釜中测得的动力学数据 ,对动力学模型进行了筛选和参数回归 .结果表明氢气为分子吸附 ,反应为双位吸附反应 ,甲醇脱附为反应控制步骤的反应动力学模型能较好地拟合实验数据 .由此得到了低温液相甲醇合成反应动力学模型方程 ,模型满足F检验 ,且参数符合各自的物理意义 .该动力学模型由于是对两步反应综合起来进行动力学分析 ,因而结果可在反应器数学模型中应用     

Refinement of the kinetic model for guaiacol hydrodeoxygenation over platinum catalysts

In our prior work (Ind Eng Chem Res, 2015, 54, 10638-10644), hydrodeoxygenation (HDO) kinetics of guaiacol, a well-known model compound of bio-oil, over Pt/AC (activated carbon) catalysts were investigated under integral operating conditions. It was found that the pseudo-homogeneous plug-flow model utilizing these kinetics describes the experimental observations well (with normalized RMS error = 7.6%). In the present work, under differential operating conditions instead, we refine the kinetic model for the same reaction network over the same catalyst. We show that among the five reaction steps in the network, the reaction order of one step differs from our prior work, while the orders remain unchanged for the other four steps. The activation energies of two steps differ from our prior values by 10–15 kJ/mol, and for the other three steps remain essentially consistent with our prior work. The kinetic parameters from the present work are used to predict fixed-bed reactor performance under integral operating conditions as well. The comparison between experimental and predicted values for both the prior and new sets of data is excellent and even better than our prior model (with reduced normalized RMS error = 4.2%). The kinetic analysis additionally proposed that the direct and indirect pathways of phenol formation from guaiacol HDO depend on guaiacol conversion values. The present work demonstrates that kinetic expressions and parameters obtained from a gradientless differential reactor are more reliable and can be used to successfully predict integral reactor performance data.     

MTBE synthesis in a novel riser simulator

MTBE synthesis, from methanol and iso-butylene, is studied in a novel Riser Simulator using a ZSM-5 catalyst. Conditions selected for the operation of the Riser Simulator unit are as follows: 1-5 catalyst/reactant ratios, 80 to 160°C temperatures, 1.09 methanol/iso-butylene mol ratio, 25 to 34 kPa methanol partial pressures and 10 to 120 s reaction times. Injection of methanol, with enough time for the methanol to reach adsorption equilibrium, followed by an isobuty-lene injection is found to be the best operating mode to achieve 100% iso-butylene selectivity toward MTBE with 4 to 6.8% isobutylene conversions. With the gathered experimental data, a reaction rate model based on the Rideal-Eley kinetic model is successfully developed.     

Modeling Hydrodynamic Cavitation

A simplified and unified model has been proposed to study the cavitation phenomena in hydraulic devices, with emphasis on the venturi tube and high-speed homogenizer. A turbulence model analogous to the acoustic cavitation has been developed and the dynamics of the cavities as a cluster has been considered. The prediction of the cavitation inception number has been made for various operating conditions and has been compared with the experimental observations. The effect of operating parameters, such as inlet pressure and fully recovered downstream pressure, has been studied numerically and compared with the data in the literature for the case of the venturi. The predicted cavitation intensities were compared indirectly with the experimental results. It has been found that optimum operating conditions do exist at which the observable cavitational effect is maximum. In the case of the high-speed homogenizer, the predicted effects as a function of rotational speed have been compared with the results of the aqueous KI decomposition reaction and have been found to match well. The study concludes with the recommendations and methods for possibly optimizing hydrodynamic cavitation phenomena for maximum effect.     

The effects of geometric and operating conditions on the hydrogen production performance of a micro-methanol steam reformer

The present study is concerned with the influence of the geometric and the operating conditions on the performance of a micro-methanol steam reformer. A three-dimensional numerical model is built for predicting the effects of wall temperature, channel geometry, inlet and outlet manifold configuration, and flow rate on the performance of chemical reaction. Distributions of velocity, temperature and gases concentrations are predicted and the methanol conversion ratios are evaluated. In addition, the mole fraction of CO contained in the reformed gas, which is essential to prevent the catalyst layers of fuel cells from poisoning, is investigated. Comparison between the present predictions and some existing experimental data is made, and close agreement has been found. A correlation expression for the methanol conversion ratio is presented in terms of the geometric and operating parameters. The solution model is used to improve the design of the micro-reformer. Results showed that the configuration of central inlet/two outlets cannot only improve the methanol conversion ratio from 32.4% to 42.3% but also decrease the carbon monoxide from 0.39% to 0.27% for the particular case at 1 cm³ min^?1 flow rate if the geometric and operating parameters are properly designed.     

Kinetics of heterogeneously MgO-catalyzed transesterification

The transesterification of ethyl acetate with methanol over magnesium oxide as solid base catalyst was investigated. Intrinsic kinetic data have been obtained in a perfectly mixed slurry batch reactor. The influence of the temperature (283–323 K) and the initial methanol to ethyl acetate molar ratio (M/E: from 0.1 to 10) was investigated over a broad ethyl acetate conversion range (1–95%). A kinetic model was developed based on a three-step ‘Eley–Rideal’ type of mechanism applied in liquid phase, describing the experimental data over the investigated range of experimental conditions. Transesterification reaction occurs between methanol adsorbed on a magnesium oxide free basic site and ethyl acetate from the liquid phase. Methanol adsorption is assumed to be rate-determining. Other models derived from other mechanisms were rejected based on statistical analysis, mechanistic considerations and physicochemical interpretation of the parameters. The calculation of activity coefficients accounting for non-ideality had to be incorporated in the parameter estimation procedure.     

Simulations of grafting monomers and associated degradation of polypropylene in a modular co‐rotating twin screw extruder

Kinetic models of grafting maleic anhydride (MAH) and methyl methacrylate (MMA) on polypropylene (PP) were developed for screw extrusion. However, the kinetic models were insufficient to explain the grafting reactions along the length of modular co‐rotating twin screw extruders because the rheological properties and the residence time of PP changed owing to degradation of PP during the grafting reaction. In order to model this system for a modular co‐rotating twin screw extruder, the kinetic model of grafting reaction and models for degradation of PP were combined with fluid mechanics and heat transfer. Given the geometrical configurations of the screw, the operating conditions, and the physical properties of the polypropylene, the simulations predicted variation of molecular weight and mean residence time due to degradation of PP. The weight percent of grafted MAH or MMA on PP profiles along the screw axis was also calculated in the simulation. These predictions were compared with experimental data for various operating conditions. J. VINYL. ADDIT. TECHNOL. 11:143–149, 2005. © 2005 Society of Plastics Engineers.     

间苯二甲酸连续多级结晶的数学模拟

以粒数衡算为基础,对间苯二甲酸精制的多级连续蒸发结晶流程建模。通过对模型预测和实测最终产品的比较,确定了间苯二甲酸在水中的结晶动力学参数,并利用所建模型和得到的结晶动力学方程分析了各种操作参数对结晶产品粒度分布的影响,提出了改善结晶产品的粒度分布的条件并实际应用于工业生产。     

Numerical simulation and experimental validation of bubble behavior in 2D gas–solid fluidized beds with immersed horizontal tubes

The two-fluid model based on the kinetic theory of granular flow is considered to be a fundamental tool for modeling gas–solid fluidized beds and has been extensively used for the last couple of decades. However its verification and quantitative validation still remain insufficient for a wide range of reactor geometries and operating conditions. In this study simulations were performed using the two-fluid model for two-dimensional (2D) bubbling gas–solid fluidized beds with and without immersed horizontal tubes. The bubble characteristics – aspect ratio, shape factor, diameter and rise velocity – predicted by the simulation were compared and validated with experimental data obtained from pseudo-2D fluidized beds using digital image analysis technique. The predicted bubble shape and diameter were in good agreement with the experimental data for fluidized beds with and without immersed tubes. The simulation predicted higher bubble rise velocity compared to the experimental results obtained. This was due to the wall effect, which was not taken into consideration during the 2D simulation. In addition the influences of different drag laws, friction packing limits and solid-wall boundary conditions on the different bubble properties were investigated. The results showed that the choice of friction packing limits, drag laws and specularity coefficients have little influence on bubble properties.