A reactive distillation process with a sidedraw stream to enhance the production of isopropyl acetate

This paper designs an entrainer combined with a sidedraw to enhance the reactive distillation (RD) process of isopropyl acetate (IPAc). Acetic acid (HAc) reacts with isopropanol (IPOH) to generate IPAc and water (H₂O). The ratio of IPAc to H₂O in the products of esterification is smaller than that in the minimum boiling IPAc–IPOH–H₂O azeotrope, resulting in a mass of organic phase reflux to remove the surplus H₂O from the top of the RD column. This process consumes a high amount of energy. For better energy efficiency, a feasible design flowsheet includes an RD column, a stripper, a top decanter, a middle decanter, and a sidedraw stream to intensify the azeotropic separation where an entrainer is introduced to carry out the surplus water from the middle of the RD column in the form of a liquid phase. The key design variables in the proposed flowsheet are determined to obtain a minimal total annual cost (TAC). As a result, an optimal process design is drawn out while satisfying the stringent specifications for product purity. These results show that the energy requirements of the IPAc system can be decreased by 27.55%.     

Design and control of butyl acrylate reactive distillation column system

In this study, the design and control of a reactive distillation column system for the production of butyl acrylate has been investigated. The proposed design is quite simple including only one reactive distillation column and an overhead decanter. The optimal design is selected based on the minimization of total annual cost (TAC) for the overall system. At this optimized flowsheet condition, output multiplicity was found with reboiler duty or feed ratio as the bifurcation parameter. The highest purity stable steady state was selected as the base case condition for the control study. The overall control of this system can be achieved with no on-line composition measurements. Simple single-point tray temperature control loop is designed to infer final product purity. From results of dynamic simulation, the proposed control strategy performs very well in rejecting various disturbances while maintaining butyl acrylate product at high purity. One of the important finding in this paper is that it is better to operate this reactive distillation column not at the exact feed stoichiometric balance point for better operability reason. The control performances of the proposed operating point and the operating condition right at the exact stoichiometric balance point will be compared.     

Design and control of acetic acid dehydration system via heterogeneous azeotropic distillation

Acetic acid dehydration is an important operation in the production of aromatic acid, such as terephthalic acid or in the manufacture of cellulose acetate. Although acetic acid and water does not form azeotrope, but using simple distillation to separate these two components is not practical. The reason is because the system has tangent pinch on the pure water end, thus it is more customary in industry to use an entrainer via a heterogeneous azeotropic distillation column system for the separation. In this study, a suitable entrainer is selected from three candidate acetates through rigorous steady-state simulation of this system. Optimum process design and operating condition are determined to keep high-purity bottom acetic acid composition and also keep a small acetic acid loss through top aqueous draw. Furthermore, the overall control strategy of this column system is proposed to hold both bottom and top product specifications in spite of feed rate and feed composition load disturbances. The proposed overall control strategy is very simple requiring only one tray temperature control loop inside the heterogeneous azeotropic column.     

Reactive distillation for methyl acetate production

We describe a hierarchy of methods, models, and calculation techniques that support the design of reactive distillation columns. The models require increasingly sophisticated data needs as the hierarchy is implemented. The approach is illustrated for the production of methyl acetate because of its commercial importance, and because of the availability of adequate published data for comparison. In the limit of reaction and phase equilibrium, we show (1) the existence of both a minimum and a maximum reflux, (2) there is a narrow range of reflux ratios that will produce high conversions and high purity methyl acetate, and (3) the existence of multiple steady states throughout the entire range of feasible reflux ratios. For finite rates of reaction, we find (4) that the desired product compositions are feasible over a wide range of reaction rates, up to and including reaction equilibrium, and (5) that multiple steady states do not occur over the range of realistic reflux ratios, but they are found at high reflux ratios outside the range of normal operation. Our calculations are in good agreement with experimental results reported by Bessling et al., [Chemical Engineering Technology 21 (1998) 393].     

Design and control of transesterification reactive distillation with thermal coupling

In the study, the design and control strategies of a reactive distillation process with partially thermal coupling for the production of methanol and n-butyl acetate by transesterification reaction of methyl acetate and n-butanol are investigated. Since methanol and methyl acetate formed an azeotrope, the products of a reactive distillation column include n-butyl acetate and the mixture of methanol and methyl acetate, which must be separated by an additional column. Partially thermal coupling can be used to eliminate the condenser of the second column. Not only energy reduction but also better operability and controllability can be obtained for the thermally coupled reactive distillation process. Proper selection and pairing of controlled and manipulated variables chosen for three control objectives were determined by using steady-state analysis. A simple control scheme with three temperature control loops is sufficient to maintain product purities and stoichiometric balance between the reactant feeds.     

Experiments and dynamic modeling of a reactive distillation column for the production of ethyl acetate by considering the heterogeneous catalyst pilot complexities

Great effort has been applied to model and simulate the dynamic behavior of the reactive distillation as a successful process intensification example. However, very little experimental work has been carried out in transient conditions. The work presents a series of experiments for the production of ethyl acetate from esterification of acetic acid and ethanol in a reactive distillation pilot column. The steady-state approach performed experiments with both excess of alcohol and stoichiometric feed configuration. Predicted and measured results show good agreement and reveal a strong dependency of the structured packing catalyst activity on the pilot geometry and its operating conditions. The transient process behavior of the heterogeneously catalyzed system was deeply investigated and continuous and dynamic data were collected for an equilibrium model validation, after different perturbations on parameters. The experimental validation is shown to be essential to provide realistic hydrodynamic parameters, to understand the sensitive parameters such as heat losses and to adapt values for the catalyst holdup as a function of the system.     

Optimization and control of a reactive and extractive distillation process for the synthesis of isopropyl acetate

A conventional reactive distillation column will not be able to produce high purity isopropyl acetate (IPAc) due to the existence of a minimum boiling azeotrope in the system. In this work, a novel reactive and extractive distillation (RED) process was proposed and used for the synthesis of IPAc. Results showed that the purity of IPAc reached 99.5%. Then, the RED flowsheet was optimized with minimum total annual cost (TAC), and a number of key variables were determined with the assistance of program written in Visual Basic 6.0 (VB). After that, two control structures of the RED process were developed: a basic control structure with temperature/proportional cascade control and an improved control structure with composition/temperature cascade control. The integral of squared error (ISE) was introduced to evaluate the performance of control systems, it revealed that the improved control structure had better controllability.     

Comparative control study of ideal and methyl acetate reactive distillation

The control of an ideal reactive distillation column is compared with that of a similar, but somewhat different, real chemical system, the production of methyl acetate. Similarities and differences are observed. Three control structures are evaluated for both systems. A control structure with one internal composition controller and one temperature controller provides effective control of both systems for both high and moderate conversion designs. A two-temperature control structure is effective when the system is overdesigned in terms of number of reactive trays, holdup and/or catalyst load. Direct control of product purity for the high-conversion/high-purity design is difficult because of system nonlinearity and interaction. Tray temperature control avoids the nonlinearity problem.     

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.     

间歇反应精馏合成乙酸异丙酯

以乙酸和异丙醇为原料通过间歇式反应精馏合成乙酸异丙酯,正交实验给出最佳合成条件为:回流比3、反应时间1.5h、乙酸与异丙醇的物质的量比1∶1.5、催化剂用量为乙酸体积2%,乙酸异丙酯的最大收率为92.8%。     

Design and control of reactive distillation for ethyl and isopropyl acetates production with azeotropic feeds

Reactive distillations for the production of ethyl acetate (EtAc) and isopropyl acetate (IPAc) are classified as the type-II process where the first column consists of a reactive zone and a rectifying section followed by a stripper [Tang et al., 2005. Design of reactive distillations for acetic acid esterification with different alcohols. A.I.Ch.E. Journal 51, 1683-1699]. Instead of using pure alcohols and acetic acid as reactants, this paper studies the effects of reactant purity on the design and control of reactive distillation. This offers significant economical incentives (by reducing raw materials costs), because ethanol forms an azeotrope with water at 90 mol% and isopropanol/water has an azeotrope at 68%. The purities of the acid is set to 95% for acetic acid (industrial grade), 87% for ethanol, and 65% for isopropanol. The results show that the total annual costs (TAC) increase by a factor of 5% for EtAc and 8% for IPAc production using reactive distillation. Next, the operability of the reactive distillations with azeotrope feeds is explored. Three disturbances, feed flow, acid feed purity, and alcohol feed composition, are introduced to assess control performance using dual-temperature control and one-temperature-one-composition control. Simulation results indicate good control performance can be achieved for reactive distillation with azeotropic feeds.     

Methodology for design and analysis of reactive distillation involving multielement systems

A new methodology for design and analysis of reactive distillation has been developed. In this work, the element-based approach, coupled with a driving force diagram, has been extended and applied to the design of a reactive distillation column involving multielement (multicomponent) systems. The transformation of ordinary systems to element-based ones and the aggregation of non-key elements allow the important design parameters, such as the number of stages, feed stage and minimum reflux ratio, to be determined by using simple diagrams similar to those regularly employed for non-reactive systems consisting of two components. Based on this methodology, an optimal design configuration is identified using the equivalent binary-element-driving force diagram. Two case studies of methyl acetate (MeOAc) synthesis and methyl-tert-butyl ether (MTBE) synthesis have been considered to demonstrate the successful applications of the methodology. Moreover, energy requirements for various column configurations corresponding to different feed locations are determined to verify whether the optimal design can be identified by following the proposed methodology.     

反应精馏技术的研究进展

针对国内外反应精馏技术及其应用的最新研究情况,较全面地归纳和分析了反应精馏工艺的研究进展,并介绍了SYNTHESISER、ASPEN PLUS等计算机模拟软件在反应精馏工艺的应用情况。     

Feasible separations and entrainer selection rules for heteroazeotropic batch distillation

A feasibility analysis is presented for the separation of close-boiling and azeotropic (minimum- and maximum-boiling) binary mixtures into pure components by the addition of an entrainer introducing a heterogeneous azeotrope. The analysis is done for both the conventional batch rectifier and the multivessel batch column. The analysis is theoretical and based on the assumptions of total reflux/reboil ratios and infinite number of stages. Two feasibility conditions are formulated that make it possible to investigate feasibility based on information coming solely from the distillation line map along with the binodal curve of the ternary mixture. Serafimov's classification is used for classifying the azeotropic phase diagrams. The feasibility analysis provides the necessary background and information for formulating rules for entrainer selection for the process. Two simple rules are then proposed, which make it possible to “screen” entrainers for heteroazeotropic batch distillation with minimum efforts.     

Heat-integrated reactive distillation process for synthesis of fatty esters

Catalytic reactive distillation (RD) offers novel opportunities for manufacturing fatty acid alkyl esters involved in specialty chemicals and at a larger scale in biodiesel. The integration of reaction and separation into one RD unit, corroborated with the use of a heterogeneous catalyst, provides major benefits such as low capital investment and operating costs. This work presents a novel heat-integrated process based on reactive distillation that aims to reduce furthermore the energy requirements for biodiesel production, leading to competitive operating costs. Despite the high degree of integration, the process is well controllable using an efficient control structure proposed in this work. Rigorous simulations embedding experimental results were performed using computer aided process engineering tools, such as AspenTech Aspen Plus and Aspen Dynamics. The RD column was simulated using the rigorous RADFRAC unit with RateSep (rate-based) model, and explicitly considering three phase balances. Steady-state and dynamic simulation results are given for a plant producing 10 ktpy fatty acid methyl esters (FAME) from methanol and waste vegetable oil with high free fatty acids (FFA) content, using sulfated zirconia as green catalyst. The heat-integrated RD process eliminates all conventional catalyst related operations, efficiently uses the raw materials and the reactor volume offering complete conversion of the fatty acids and allowing significant energy savings. Remarkably, compared to previously reported RD processes, the energy requirements of this process are about 45% lower - only 108.8 kW h/ton biodiesel - while the capital investment cost remains the same as no additional equipment is required.     

A systematic synthesis framework for extractive distillation processes

An effective extractive distillation process depends on the choice of the extractive agent. In this contribution, heuristic rules for entrainer selection and the design of entrainers through computer-aided molecular design are reviewed. The potential of the generated alternatives is then evaluated by their selectivity at infinite dilution and by the rectification body method (RBM). It is shown that a screening based on selectivity alone is not sufficient and could possibly lead to an unfavorable entrainer choice. The minimum entrainer flowrate and the minimum energy demand, calculated from the RBM, allow a more comprehensive evaluation of different entrainer alternatives. In a third step a rigorous mixed-integer optimization of the entire extractive flowsheet for the remaining entrainer candidates is executed to fix the remaining design degrees of freedom and to determine the best entrainer. Since a number of alternative entrainers have already been eliminated, only a few optimizations are necessary. These steps form a framework which facilitates the systematic generation and evaluation of entrainer alternatives. The suggested synthesis framework is illustrated with a case study where acetone and methanol are to be separated.     

Supported catalytic packing prepared from ceramic packing for reactive distillation of ethyl acetate

In this work, a strategy of “etching-modification filling-graft copolymerization” was proposed to load the acidic ionic polyionic liquid on the smooth ceramic surface. In this way, commercial ceramic Raschig rings were successfully transformed into the supported catalytic packing for the reactive distillation, and were further evaluated with esterification reaction of ethyl acetate by means of the fully mixed reactor, the ultrasonic destruction, the cyclic catalysis reaction and the lab-scale distillation column experiment. This catalyst coating has good adhesion with the substrate. It can withstand 24 h of ultrasound damage and shows good stability in three cycle catalytic experiments. This kind of coated catalyst has better catalytic activity than the commercial Amberlyst 15 dry. In the lab-scale reaction distillation, the supported catalyst Raschig ring can achieve a higher conversion in comparison with the tea bag catalytic packing of Amberlyst 15 dry under some conditions.     

Investigating the need of a pre-concentrator column for acetic acid dehydration system via heterogeneous azeotropic distillation

In our previous study [Chien, I.L., Zeng, K.L., Chao, H.Y., Liu, J.H. (2004). Design and control of acetic acid dehydration system via heterogeneous azeotropic distillation. Chemical Engineering Science 59(21), 4547-4567.], an acetic acid dehydration system has been designed. The suitable entrainer selected for that system is iso-butyl acetate. Design and control of the system has been studied in detail to maintain high-purity bottom acetic acid concentration and also keep a small acetic acid loss through top aqueous draw. In that previous study, the feed composition is assumed to contain equal molar of acetic acid and water. However, in a typical waste acid recovery application, the above assumption may be too rich in acetic acid. In this paper, a feed stream containing 80 mol% water and 20 mol% of acetic acid is investigated. Several design alternatives can be deduced including one commonly used in industry by adding a pre-concentrator column in the upstream of a heterogeneous azeotropic distillation column. The necessity of this pre-concentrator column from design and control view points will be thoroughly investigated in this paper. The final recommended process design is a tradeoff between total annual cost (TAC) and operability of the system. The recommended design is a single heterogeneous azeotropic distillation column with aqueous reflux stream. Very wide feed composition and flow rate changes can be handled by this design with proper choice of the overall control strategy.     

Optimization and control of a reactive distillation process for the synthesis of dimethyl carbonate

Dimethyl carbonate is an environmentally benign and biodegradable chemical. Based on integration of reactive distillation and pressure-swing distillation technologies, a novel process for synthesis of dimethyl carbonate through transesterification with propylene carbonate and methanol has been developed by Huang et al. In this work, the optimization of this process was performed by minimizing the total TAC. The results show that the op-timal design flowsheet can save energy consumption by 18.6％with the propylene carbonate conversion of 99.9％. Then, an effective plant-wide control structure for the process was developed. Dynamic simulation results dem-onstrate that the temperature/flow rate cascade control plus with simple temperature control can keep not only product purity but also the conversion of the reactant at their desired values in the face of the disturbance in re-actant feed flow rate and feed composition.     

Hybrid reactive distillation systems for n-butyl acetate production from dilute acetic acid

The recovery of dilute acetic acid, regarding as a waste stream in many chemical and petrochemical processes, becomes an important issue due to economic and environmental awareness. In this work, a simulation study on the direct utilization of dilute acetic acid to produce n-butyl acetate via esterification with butanol in a reactive distillation is presented by using Aspen Plus. The performance of a hybrid reactive distillation with a pretreatment unit, i.e., a conventional distillation or a pervaporation, is investigated. For a single reactive distillation system, it is found that higher overall energy of the system is required when the concentration of acetic acid is lowered. By considering the enrichment of acetic acid in the reactive distillation column feed from 35 to 65 wt.%, a hybrid pervaporation–reactive distillation requires lower energy than both the conventional distillation–reactive distillation system and the single reactive distillation.