A comparison of a pseudo-homogeneous non-equilibrium model and a three-phase non-equilibrium model for catalytic distillation

A comparison of computer simulation results of catalytic distillation (CD) obtained from a three-phase non-equilibrium model and a pseudo-homogeneous non-equilibrium model was performed. Simulations were carried out on the CD processes for the production of ethyl cellosolve (EC) and diacetone alcohol (DAA) using both the pseudo-homogeneous non-equilibrium model and the three-phase non-equilibrium model. Similar results for the synthesis of EC were obtained using these two models. However, only the three-phase non-equilibrium model could adequately describe the CD process for the aldol condensation of acetone (Ac) at low reflux flow rates. Hence our results suggest that for a reaction system that is kinetically controlled, a pseudo-homogeneous non-equilibrium may adequately simulate the temperature profile, yield and selectivity for a CD process. However, for a CD process that is sensitive to solid–liquid mass transfer, the three-phase non-equilibrium model is required.     

On the modelling of mass transfer in extractive distillation

Mass transfer in extractive distillation in plate columns on a laboratory and pilot-plant scale was investigated experimentally by the separation of an azeotropic mixture, acetone—methanol, with water and 1,2-propylene glycol as solvents. The decrease in mass transfer efficiency with increasing solvent concentration was explained by a decrease and partial blocking of the interfacial area caused by the solvent. A mathematical model was established for mass transfer in extractive distillation on valve plates of diameter 0.4 m. This model was applied successfully to an industrial column.     

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.     

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.     

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.     

Experimental Investigations of Three‐Phase Distillation in a Packed Column

An experimental study with three different heterogeneous azeotropic mixtures (acetone/toluene/water, 1‐propanol/1‐butanol/water and ethanol/cyclohexane/water) has been carried out with the object to analyze the separation efficiency of three‐phase distillation in a packed column. The experiments were made under total reflux in a 70 mm column packed with Sulzer Optiflow C.36. The results show the influence of the second liquid phase on the mass transfer and with that on the separation efficiency in a packed column.     

萃取精馏的计算传质学模拟与实验验证

提出了萃取精馏过程模拟的计算传质学方法,并针对以N-甲基吡咯烷酮(NMP)为溶剂分离苯和噻吩的萃取精馏过程进行了模拟计算。在散堆填料实验塔内进行了相同的萃取精馏实验,得到了萃取精馏塔内浓度分布。将模拟计算结果与实验结果进行比较表明,提出的计算传质学方法能够有效预测萃取精馏塔内浓度和速度分布,为萃取精馏过程设计提供依据。     

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．     

Impact of mass transfer coefficient correlations on prediction of reactive distillation column behaviour

A significant part of the safety analysis of a reactive distillation column is the identification of multiple steady states and their stability. A reliable prediction of multiple steady states in a reactive distillation column is influenced by the selection of an adequate mathematical model.For modelling reactive distillation columns, equilibrium (EQ) and nonequilibrium (NEQ) models are available in the literature. The accuracy of the nonequilibrium stage model seems to be limited mainly by the accuracy of the correlations used to estimate the mass transfer coefficient and interfacial area.The binary mass transfer coefficients obtained from empirical correlations are functions of the tray design and layout, or of the packing type and size, as well as of the operational conditions and physical properties of the vapour and liquid mixtures.In this contribution, the nonequilibrium model was used for the simulation of a reactive distillation column. For prediction of the binary mass transfer coefficient for a sieve tray, four correlations were chosen to show their impact on the prediction of the reactive distillation column behaviour. As a model reactive distillation system, the synthesis of methyl tertiary-butyl ether (MTBE) was chosen. The steady-state analysis and the dynamic simulation of the model system were done. Qualitative differences between the steady states were predicted using the chosen correlations.     

羟醛缩合体系反应精馏研究进展

对反应精馏技术在羟醛缩合反应体系中的研究和应用现状进行了综述与展望,主要介绍了丙酮缩合反应,甲醇、甲醛缩合反应及乙醛缩合反应精馏的实验研究进展以及相应的反应精馏过程模拟。     

Efficiency of a vortex contact stage in thermal distillation

The results of studying the process of distillation in a column with 21 vortex contact stages have been reported. The partial condensation of an ascending ethanol–water mixture vapor at the contact stages has been shown to intensify the mixture distillation process by threefold compared to adiabatic distillation. The process parameters that intensify heat and mass transfer in thermal distillation have been established. Some relationships for estimating the efficiency of a vortex contact stage have been derived.     

精馏技术研究进展与工业应用

精馏是化学工业中应用最广泛的关键共性技术,广泛应用于石油、化工、化肥、制药、环境保护等行业。精馏具有应用广泛、技术成熟等优点,但存在设备投资大、分离能耗高等问题,因此研究开发新型高效传质元件、开发新型节能精馏技术,具有重要的社会意义和经济价值。本文从精馏塔类型、流体力学性能、传质性能、塔器大型化、过程节能、过程强化等方面,介绍了精馏技术的研究进展与工业应用。对于板式塔,从气液两相流动状态、压降、漏液和雾沫夹带方面研究了塔板的流体力学性能;对于填料塔,从压降、液泛和持液量方面研究了填料塔的流体力学性能,但目前的研究仍以经验关联式为主,缺乏严谨的的理论模型。对于气液两相的传质性能研究,简述了气液两相传质理论,但科学、精准的传质模型尚未提出。对于塔器大型化的应用研究,介绍了塔板、气液分布器和支撑装置等大型化关键技术的工业应用。从精馏过程典型节能技术、耦合节能技术、流程节能技术、低温余热回收和特殊精馏等方面,介绍了精馏过程节能与强化的应用进展。文章最后对精馏过程的传质、强化和集成进行了展望。     

A mass and energy balance stage model for cyclic distillation

Cyclic distillation is an emerging process intensification technology, which can improve separation efficiency compared to conventional distillation. As most current models only account for the mass transfer, there is a lack of a stage model for cyclic distillation processes, which includes considerations of both mass and energy transfer. Such a model is presented in this article, and using this model, selected case studies, describing binary and multiple component systems with both ideal and nonideal liquid phases, are investigated. The presented stage model allows for the modeling of both mass and energy transfer for a cyclic distillation process and allows for multiple feed locations, as well as side draws. With the energy balances included, the dynamic vapor flow rate can be described. This was shown to have a significant effect on the separation, especially for cases where the change in the vapor flow over the column height was high.     

炼油减压精馏塔汽提工艺传质过程模拟与分析

为了揭示减压塔汽提工艺的传质过程特性,进而改进汽提操作,采用改进的减压精馏过程模拟方法和传质计算方法,分析了炼油常减压装置的汽提工艺的传质特点。在深化对于汽提工艺的理解基础上论证了采用填料汽提塔(段)的必要性以及设计、分析的基本方法。计算分析结果表明侧线汽提塔内填料分离性能保持恒定,汽提塔的分离效率与减压塔对应分离段接近,所以在设计和操作中应给予汽提塔(段)充分重视。减压塔底汽提段的工艺和水力学特点与侧线汽提塔相同。塔底汽提蒸汽质量流率应小于减压塔进料质量流率1%,否则将导致减压塔整体分离效率降低。     

Attainable regions of reactive distillation—Part I. Single reactant non-azeotropic systems

Reactive distillation (RD), a promising multifunctional reactor, can be used to improve the selectivity of the desired product by manipulating the concentration profiles in the reactive zone of the column. In this work, a new approach has been proposed to obtain the feasible regions of RD for the reactive systems involving single reactants, e.g. dimerization, aldol condensation, etc. Two new models namely the reactive condenser and the reactive re-boiler have been proposed. These models indicate the best location of the reactive zone in a column. Multistage versions of these models namely, reactive rectification and reactive stripping further expand the feasible region and are capable of representing the performance offered by a conventional RD unit. Several hypothetical non-azeotropic ideal systems have been extensively studied using these models and it has been shown that selectivity close to 100% is attainable over the entire range of conversion for a series as well as a combination of series and parallel reactions with positive reaction orders. Two industrially important cases of aldol condensation of acetone and dimerization of isobutylene have also been addressed using this approach. For porous catalysts, the presence of intra-particle diffusion resistance may limit the feasible region and even in the case of ideal non-azeotropic systems it may not be possible to obtain 100% selectivity. A methodology to incorporate pore diffusion effects is also illustrated.     

Understanding process intensification in cyclic distillation systems

The most effective separation possible in distillation columns takes place in the hydrodynamic regime where there is perfect displacement of the liquid and vapor streams. This can be achieved in distillation equipment with separate phase movement (SPM). Such an innovative route for process intensification in distillation is called cyclic distillation. The required process conditions are the lack of liquid outflow from the tray during vapor admission and the lack of liquid mixing in adjacent trays upon outflow of liquid. Remarkably, the throughput of such a column that operates in a controlled cycle mode is two or more times higher than the throughput reachable with conventional operation, at equivalent separation performance.In this study, a theoretical stage model with perfect displacement is proposed and the theory of the process working lines is developed. An adequate mass transfer model is also described along with the mode of calculation of tray columns operating in the cyclic operation mode. Sensitivity analysis was used to determine the effect of the key model parameters. The theoretical developments were implemented at industrial scale and subsequent testing showed an increase in the separation efficiency of 2-3 times as compared to the standard process.     

Separation performance investigation of packed distillation columns using simple NEQ approach based on packing multicomponent efficiencies and effective mass transfer coefficients

A simple non-equilibrium modeling approach is proposed to simulate multicomponent distillation process in packed columns. The real behavior of the column is simply considered by the evaluation of interphase mass transfer rate based on the overall mass transfer coefficient. Two distinct methods are used to calculate this overall coefficient including the effective mass transfer coefficient method and the packing efficiency method. The modelling procedure consists of an iterative segment-wise algorithm implemented in a MATLAB home-code. For verification, the obtained composition profiles from a structured and a random packed column are compared with reported experimental data. Comparisons show that the packing efficiency-based model could acceptably predict the experimental profiles with an average relative deviation of 18% and 25% for structured and random packed columns, respectively. This confirms that our simple non-equilibrium approach is a reliable and robust model for the performance evaluation of packed columns.     

Experimental study on pressure drops in a dividing wall distillation column

Previous studies in the fields of process design and process control [1] have shown the potential benefits that can be achieved through the implementation of thermally coupled distillation sequences, in particular, the dividing wall distillation column. The dividing wall distillation column meets important goals of process intensification, including energy savings, reduction in carbon dioxide emissions and miniaturization. In this paper, an experimental study on the hydrodynamic behavior of a dividing wall distillation column is presented. Several different values for gas and liquid velocities were tested in order to measure pressure drops and identify operational regions; the air/water system was used as the basis for the experimental setup. Results regarding pressure drops (fitted to the model of Stichlmair et al.) provide operational limits for the operation of the packed dividing wall distillation column. According to the results, the experimental dividing wall column can be operated at turbulent regime that is associated to proper mass transfer.     

Batch extractive distillation under constant reflux ratio

The process of batch extractive distillation may provide the advantages of both batch and extractive distillation. So far this process has not been applied at all probably due to its complexity. An algorithm and a computer program were developed for simulating the experiments of a batch extractive distillation process (separation of acetone and methanol on a pilot-plant column containing 32 bubble cap trays applying water as solvent, the reflux ratio is kept constant) on a PC/AT/486. For the integration of the set of nonlinear differential equations (component material balances) the Runge-Kutta method was used. For saving computation time a 2-D linear interpolation method was applied for the ternary mixture when calculating VLE. The experimental and calculated results are compared. Thqe influence of the operational parameters on the process was studied by simulation. Calculations were carried out for another (nonazeotropic, low relative volatility) mixture with a new professional program “PROSIM BATCH”.     

Hydrodynamic analogy approach for modelling of reactive stripping with structured catalyst supports

Modelling of gas/vapour–liquid separation processes usually requires experimentally determined parameters, e.g., mass transfer coefficients. This results in expensive experimental work, especially for new types of column internals. A novel modelling approach based on hydrodynamic analogies (HA) has recently been developed for distillation units equipped with structured corrugated sheet packings. The HA model takes the packing geometry directly into account whereas the experimental determination of mass transfer coefficients is not required.In this work, the HA approach is extended to cover heterogeneously catalysed reactive stripping processes. Experimental investigations are performed with a test system, esterification of hexanoic acid and 1-octanol, using different types of catalytically coated supports as column internals (one corrugated sheet packing and three film-flow monoliths with different channel geometries). Simulation results obtained with the extended HA model are in a good agreement with experimental values.