A comparison of the equilibrium and nonequilibrium models for a multicomponent reactive distillation column

Apropriate models and computational algorithms were developed and a series of simulations for a reactive distillation tray column were performed in order to compare the equilibrium and nonequilibrium model. The homogeneous liquid phase reversible reaction between acetic acid and ethanol in production of ethyl acetate was employed as a test chemical reaction. Both the Newton–Raphson and homotopy-continuation methods were applied to solve the set of model equations. The homotopy-continuation method was found superior to the Newton–Raphson method in guaranteeing the desired solution for the nonequilibrium model. The comparison between the equilibrium and the nonequilibrium model reveals that the nonequilibrium model is to be preferred for the simulation of a tray column for reactive distillation because of the difficulty in the accurate prediction of tray efficiency for the equilibrium model. Close agreement in the prediction of the two models arises only when the tray efficiency can be correctly guessed for the equilibrium model. The effects of reaction rate and reflux ratio on the column performance were illustrated using the nonequilibrium model. The use of the heat generated by the exothermic reaction as an internal heat source in the column is discussed.     

一种改进的多元精馏塔动态模型

综合了精馏塔的物料及能量平衡、塔板水力学方程、塔板效率及再沸器动态特性,给出一种改进的非理想多元物系精馏塔通用动态数学模型.增加了汽液平衡计算,从而弥补了文献[1]所提出的动态模型的缺陷,提高了其精度和通用性.模型仿真算法采用Gear积分方法,稳定性好,对解刚性比很高的精馏塔微分方程组十分有效.通过对某丙烯腈萃取精馏塔的仿真表明,该动态模型能够较好地反映对象的动态形为.     

A modified model of computational mass transfer for distillation column

The computational mass transfer (CMT) model is composed of the basic differential mass transfer equation, closing with auxiliary equations, and the appropriate accompanying CFD formulation. In the present modified CMT model, the closing auxiliary equations [Liu, B.T., 2003. Study of a new mass transfer model of CFD and its application on distillation tray. Ph.D. Dissertation, Tianjin University, Tianjin, China; Sun, Z.M., Liu, B.T., Yuan, X.G., Liu, C.J., Yu, K.T., 2005. New turbulent model for computational mass transfer and its application to a commercial-scale distillation column. Industrial and Engineering Chemistry Research 44, 4427-4434] are further simplified for reducing the complication of computation. At the same time, the CFD formulation is also improved for better velocity field prediction. By this complex model, the turbulent mass transfer diffusivity, the three-dimensional velocity/concentration profiles and the efficiency of mass transfer equipment can be predicted simultaneously. To demonstrate the feasibility of the proposed simplified CMT model, simulation was made for distillation column, and the simulated results are compared with the experimental data taken from literatures. The predicted distribution of liquid velocity on a tray and the average mass transfer diffusivity are in reasonable agreement with the reported experimental measurement [Solari, R.B., Bell, R.L., 1986. Fluid flow patterns and velocity distribution on commercial-scale sieve trays. AI.Ch.E. Journal 32, 640-649; Cai, T.J., Chen, G.X., 2004. Liquid back-mixing on distillation trays. Industrial and Engineering Chemistry Research 43, 2590-2597]. In applying the modified model to a commercial scale distillation tray column, the predictions of the concentration at the outlet of each tray and the tray efficiency are satisfactorily confirmed by the published experimental data [Sakata, M., Yanagi, T., 1979. Performance of a commercial scale sieve tray. Institution of Chemical Engineers Symposium Series, vol. 56, pp. 3.2/21-3.2/34]. Furthermore, the validity of the present model is also shown by checking the computed results with a reported pilot-scale tray column [Garcia, J.A., Fair, J.R., 2000. A fundamental model for the prediction of distillation sieve tray efficiency. 1. Database development. Industrial and Engineering Chemistry Research 39, 1809-1817] in the bottom concentration and the overall tray efficiency under different operating conditions. The modified CMT model is expected to be useful in the design and analysis of distillation column.     

Comparison between the design of experiments and simulation in the three-phase distillation in a sieve tray column for glycerine dehydration

Design of experiments (DOE) is a value scientific approach used to understand the processes in a better way and to determine how the inputs affect the response(s). In this work, this method has been applied to study the behavior of the three-phase distillation in a sieve tray column, through the effects of the process and geometrical variables. The experimental values were compared with predicted values obtained by simulation using the equilibrium and nonequilibrium models. Three-phase distillation has been used for glycerine dehydration using toluene as entrainer, in order to avoid the glycerol degradation by distillation at atmospheric pressure. The best conditions found were: vapor flow rate of toluene = 23.5 kg/h, feed flow rate = 2.2 kg/h and feed concentration = 50 wt% glycerol, using the layout L₄ with fractional hole area = 0.04 and weir height = 70 mm. The nonequilibrium model based on Eckert and Vanek's approach (2001) and Chen–Chuang's correlation (1993) have been used to estimate the binary coefficients of mass transport. The predicted values obtained by the experimental model and by the nonequilibrium model have represented the behavior of the dehydration in the sieve tray column studied. Both models underpinned the experimental results obtained for this column.     

蒸馏塔板上汽液传质系数的确定——非平衡池法(Ⅰ)模型的建立及求解

本文提出一种确定蒸馏塔板上汽液传质系数的新方法——非平衡池法.该法将塔板沿液流方向分为适当数目的串联非平衡池,通过联立求解每一池各相的物料衡算、能量衡算、相平衡和传质传热速率方程,可从塔板入口组成得到出口组成.调整汽液传质系数使计算的出口组成与实测值相等,从而可确定出两相传质系数.方程组用混合牛顿法求解.     

计算传质法预测精馏塔效率(英文)

A computational mass transfer model is proposed for predicting the concentration profile and Murphree efficiency of sieve tray distillation column. The proposed model is based on using modified two equations formulation for closing the differential turbulent mass transfer equation with improvement by considering the vapor injected from the sieve hole to be three dimensional. The predicted concentration distributions by using proposed model were checked by experimental work conducted on a sieve tray simulator of 1.2 meters in diameter for de-sorbing the dissolved oxygen in the feed water by blowing air. The model predictions were confirmed by the ex-perimental measurement. The validation of the proposed model was further tested by comparing the simulated re-sult with the performance of an industrial scale sieve tray distillation column reported by Kunesh et al. for the strip-ping of toluene from its water solution. The predicted outlet concentration of each tray and the Murphree tray effi-ciencies under different operating conditions were in agreement with the published data. The simulated turbulent mass transfer diffusivity on each tray was within the range of the experimental result in the same sieve column re-ported by Cai et al. In addition, the prediction of the influence of sieve tray structure on the tray efficiency by using the proposed model was demonstrated.     

一个用于精馏塔模拟的新模型

A new computational mass transfer model is proposed for simulating the distillation process by solving the fluctuating mass flux for the closure of turbulent mass transfer equation in order to obtain the concentration profile and the separation efficiency of distillation column. The feather of the proposed model is to abandon the conventional way of introducing the turbulent mass transfer diffusivity (dispersion coefficient) to the turbulent mass transfer equation. To verify the validity of the proposed model, a commercial scale packed column and a sieve tray column were simulated and compared with published experimental data. The simulated results were satisfactorily confirmed in both concentration distribution and separation efficiency.     

The second law optimal state of a diabatic binary tray distillation column

A new numerical procedure to minimize the entropy production in diabatic tray distillation columns has been developed. The method was based on a least square regression of the entropy production at each tray. A diabatic column is a column with heat exchangers on all trays. The method was demonstrated on a distillation column separating propylene from propane. The entropy production included contributions from the heat transfer in the heat exchangers and the mass and heat transfer between liquid and vapor inside the distillation column. It was minimized for a number of binary tray distillation columns with fixed heat transfer area, number of trays, and feed stream temperature and composition. For the first time, the areas of heat exchange were used as variables in the optimization. An analytical result is that the entropy production due to heat transfer is proportional to the area of each heat exchanger in the optimal state. For many distillation columns, this is equivalent to a constant driving force for heat transfer. The entropy production was reduced with up to 30% in the cases with large heat transfer area and many trays. In large process facilities, this reduction would ideally lead to 1-2 GWh of saved exergy per year. The most important variable in obtaining these reductions is the total heat transfer area. The investigation was done with a perspective to later include the column as a part in an optimization of a larger process. We found that the entropy production of the column behaved almost as a quadratic function when the composition of the feed stream changed. This means that the feed composition is a natural, easy variable for a second law optimization when the distillation column is a part of a process. The entropy production was insensitive to variations in the feed temperature.     

传质系数与浓度的关系

在含 6块塔板的板式塔中选择 2个非理想性较大的二元物系进行全回流蒸馏传质实验 ,同时从描述多组分扩散过程的普遍化方程———Maxwell-Stefan(MS)方程出发建立一个求算传质系数的数学模型 .数据处理和计算的结果表明 ,传质系数不仅与该塔板的浓度有关 ,还与相邻塔板的浓度有关 .对于非理想程度大的醇水物系 ,在不同浓度下的传质系数最大值与最小值相差可达约 1个数量级 .因此 ,对于非理想物系 ,在设计计算中将传质系数当作常数的处理将会产生较大误差 .     

Overall efficiency evaluation of commercial distillation columns with valve and dualflow trays

The main objective of this work is to establish appropriated ways for estimating the overall efficiencies of industrial distillation columns with valve trays with downcomer and dualflow trays. The knowledge of efficiencies has fundamental importance in the design and performance evaluation of distillation columns. Searching in the literature, a tree of alternatives was identified to compose the tray efficiency model, depending on the mass transfer models, the liquid distribution and vapor flow models on the tray, the liquid entrainment model, the multicomponent mixture equilibrium model, the physical properties models, the height of froth on the tray model and the efficiency definition. In this work, different methods to predict the overall efficiency of distillation columns with valve and dualflow trays were composed and compared with data from three commercial distillation columns under different operating conditions. The models were inserted in the Aspen Plus 12.1 simulator, in Fortran language, together with tray geometrical data, fluid properties and operating data of the distillation columns. For each column, the best thermodynamic package was chosen by checking the temperature profile and overhead and bottom compositions obtained via simulation against the corresponding actual data of industrial columns. A modification in the fraction of holes evaluation that is jetting parameter of the Garcia's hydraulic model of dispersion above the tray was proposed. This modification produced better results than the original model to predict the fraction of holes that are jetting and in the efficiency of dualflow trays and similar results to Garcia model in the efficiency evaluation of valve trays. © 2010 American Institute of Chemical Engineers AIChE J, 2010     

A REACTIVE DISTILLATION PROCESS FOR AN AZEOTROPIC REACTION SYSTEM: TRANSESTERIFICATION OF ETHYLENE CARBONATE WITH METHANOL

A reactive distillation process is proposed for manufacturing dimethyl carbonate (DMC) through the transesterification reaction of ethylene carbonate (EC) with methanol. Modeling and simulation of the reactive distillation column have been carried out to study the effects of operating conditions, such as the reflux ratio, the number of theoretical plates, the feed ratio, the top effluent, the liquid holdup, and the feed location, on EC conversion and product composition at the top of the reactive distillation column. The calculated results show that a complete EC conversion can be achieved. The model reliability is analyzed under different Murphree tray efficiencies, showing no considerable difference between the equilibrium and nonequilibrium models for this system. And the calculated results are verified by experimental data and commercial operation of a dimethyl carbonate plant of 10,000 tons per year.     

A REACTIVE DISTILLATION PROCESS FOR AN AZEOTROPIC REACTION SYSTEM: TRANSESTERIFICATION OF ETHYLENE CARBONATE WITH METHANOL

A reactive distillation process is proposed for manufacturing dimethyl carbonate (DMC) through the transesterification reaction of ethylene carbonate (EC) with methanol. Modeling and simulation of the reactive distillation column have been carried out to study the effects of operating conditions, such as the reflux ratio, the number of theoretical plates, the feed ratio, the top effluent, the liquid holdup, and the feed location, on EC conversion and product composition at the top of the reactive distillation column. The calculated results show that a complete EC conversion can be achieved. The model reliability is analyzed under different Murphree tray efficiencies, showing no considerable difference between the equilibrium and nonequilibrium models for this system. And the calculated results are verified by experimental data and commercial operation of a dimethyl carbonate plant of 10,000 tons per year.     

An Extensive Analysis on the Start‐up of a Simple Distillation Column with Multiple Steady States

The impact of start‐up procedures on the behaviour of simple distillation columns with multiple steady states is analyzed. A well‐known system with hysteresis is studied in this paper and transient responses for a binary distillation column yielding different steady states during the start‐up operation are shown. Several dynamic simulation results showing an interesting behaviour are presented. Through the examination of the profile evolutions corresponding to given start‐up policies, it can be seen how the column arrives to different steady states. It is shown that it is possible to identify a set of critical values for the start‐up supervision. Also, guidelines of general validity are achieved with the aim of finding the appropriate start‐up policy to obtain the desired solution.     

Vapour- and liquid-side volumetric mass transfer coefficients measured in distillation column. Comparison with data calculated from absorption correlations

Volumetric mass transfer coefficients in liquid and vapour phases in distillation column were measured by the method consisting of a fitting of the concentration profile of liquid phase along the column obtained by the integration of a differential model to the experimental one. The mathematical model of distillation process includes mass and energy balances and the heat and mass transfer equations. The film model flux expressions with the convective transport contributions have been considered in the transfer equations. Vapour and liquid phases are supposed to be at their saturated temperatures along the column. Effect of changes of phase flows and physical properties of phases on the mass transfer coefficients along the column and non-ideal thermodynamic behaviour of the liquid phase have been taken into account. The concentration profiles of liquid phase are measured in the binary distillation of the ethanol-water and methanol-ethanol systems at total reflux on metal Pall Rings and Intalox saddles 25 mm in the column with diameter of 150 mm. The distillation mass transfer coefficients obtained by the fitting procedure are compared with those calculated from absorption data using Onda's, Billet's and Linek's correlations. The distillation heat transfer coefficients calculated from the model assuming saturated temperatures in both phases are compared with those calculated from the Chilton-Colburn and penetration model analogy between mass and heat transfer. The results have confirmed an agreement neither between distillation and from absorption correlations calculated mass transfer coefficients nor between analogy and from enthalpy balance calculated heat transfer coefficients. Also the concentration profiles obtained by the integration of the differential model of the distillation column using the coefficients from absorption correlation have differed from the experimental profiles considerably.     

Efficiencies of Sieve Tray Distillation Columns by CFD Simulation

A 3‐D two‐fluid CFD model in the Eulerian‐Eulerian framework was developed to predict the hydrodynamics and heat and mass transfer of sieve trays. Interaction between the two phases occurs via interphase momentum and heat and mass transfer. The tray geometries are based on the large rectangular tray of Dribika and Biddulph and FRI commercial‐scale sieve tray of Yanagi and Sakata. In this work a CFD simulation is developed to give predictions of the fluid flow patterns, hydraulics, and mass transfer efficiency of distillation sieve trays including a downcomer. The main objective has been to find the extent to which CFD can be used as a design and prediction tool for real behavior, concentration and temperature distributions, and efficiencies of industrial trays. Despite the use of simple correlations for closure models, the efficiencies obtained are very close to experimental data. The results show that values of point efficiency vary with position on the tray because of variation of affecting parameters, such as velocities, temperature and concentration gradients, and interfacial area. The simulation results show that CFD can be used as a powerful tool in tray design and analysis, and can be considered as a new approach for efficiency calculations and as a new tool for testing mixing models in both phases. CFD can be used as a “virtual experiment” to simulate tray behavior under operating conditions.     

Determination of catalytic packing characteristics for reactive distillation

Catalytic distillation still expands its field of applications. New structured catalytic column internals have been developed in recent years and new studies have been reported. A modern structured catalytic packing MULTIPAK^® is a subject of the investigations presented in this paper.

Important parameters of MULTIPAK^® have been examined experimentally in a 250 mm ID laboratory column: pressure drop for dry, prewetted and irrigated packings, flooding line and mass transfer coefficients for the gas and liquid phases.

The correlations obtained have been incorporated into a software tool for the simulation of catalytic distillation processes and simulations have been performed assuming methyl acetate synthesis as a model process. The calculations have been verified using the experiments performed for the same synthesis in a 50 mm ID catalytic distillation column operating continuously and thus reflecting industrial applications. It is concluded that the model represents the real process with satisfactory accuracy, although some deviations can be observed, especially within the reactive zone.     

Transesterification of methyl myristate in a continuous reactive distillation column: simulation and experiment

The transesterification of methyl myristate with isopropanol to methanol and isopropyl myristate is presented. This reactive system is suitable for reactive distillation and is used for the investigation carried out in this paper. A simulation model for the steady state and dynamic simulation of the reactive distillation processes was developed. For the validation of this model experiments were carried out. Based on dimensioning calculations, a 6 meter high reactive distillation column (0.1 m i.d.) with 22 bubble cap trays and a total liquid holdup of about 10 litres was constructed and built up. The stationary results obtained from the column show a good comparison between the simulated and the experimental concentration and temperature profiles. The experimentally determined dynamic time constants and sensitivities of the temperature profile of the column could be reproduced very well by the simulation tool developed.     

A study of mass transfer behaviour in a catalytic distillation column

Catalytic distillation (CD) is a process where reaction and separation take place simultaneously in a distillation column. Recently, a new CD process for the aldol condensation of acetone to diacetone alcohol and mesityl oxide was developed in our laboratory. Owing to the unique structure used to support catalysts in the CD column, mass transfer data are needed to model the CD process. The mass transfer behaviour in the CD column has been studied both for the reactive and non-reactive sections of the column in our laboratory. Based on the experimental results, general correlations for the mass transfer coefficients have been established and the 95% confidence intervals for the associated parameters were obtained. The experimental results indicated that the catalyst bags did not play a significant role for the separation between the vapour and liquid phases. The mass transfer correlations developed in this study have been used successfully to model the CD process for the aldol condensation of acetone carried out in our laboratory.     

Efficiency of dualflow trays in distillation

The mass transfer efficiencies of dualflow trays with open hole areas of 20, 28 and 37% were experimentally investigated under total reflux conditions in a 300-mm diameter distillation column using methanol-water and methanol-isopropanol systems. The results indicate that the efficiency of a dualflow tray is a strong function of the open hole area, the vapor/liquid load, and liquid properties such as surface tension and density. A fundamental model was developed to predict tray efficiency. The prediction was found to agree with the measured data to within 15.3%.     

非平衡级速率模型用于催化精馏过程的模拟计算

采用非平衡级速率模型对醋酸甲酯水解的催化精馏中试过程进行了模拟计算,反应精馏段催化剂填料层的气相和液相传质系数用自行测定的经验关联式计算,提馏段的填料层传质系数用Onta的关联式,反应速率根据所测定的宏观反应动力学方程结合催化剂包的效率因子进行计算,得到令人满意的结果．