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02638762/04/$30.00+0.00 # 2004 Institution of Chemical Engineers Trans IChemE, Part A, February 2004 Chemical Engineering Research and Design, 82(A2): 140147

PROCESS ALTERNATIVES FOR COUPLING REACTION AND DISTILLATION

S.B. GADEWAR1, L. TAO2, M.F. MALONE2 and M.F. DOHERTY3*
1 PDC Process Design Center Inc., Santa Barbara, CA 93111, USA Department of Chemical Engineering, University of Massachusetts, Amherst, MA 01003, USA 3 Department of Chemical Engineering, University of California, Santa Barbara, CA 93106, USA 2

reactive distillation column combines reaction with distillation, and is known to be advantageous for some reaction systems, but not for others. Sometimes it is a breakthrough technology, yet in others a reactive distillation column does not give pure products, and is therefore infeasible. For cases where a reactive distillation column is not feasible, it is useful to determine alternatives with combined reaction and distillation that rely on conventional distillation systems to give pure products. The advantage of such alternatives is the use of simultaneous reaction and distillation to improve the yields and=or selectivities to products, and also that they require smaller recycle ows. Many alternatives can be generated with a potential advantage over the conventional process of reaction followed by distillation. During the conceptual design stage of a process it is vital to decide quickly whether reactive distillation is likely to be a good process concept. We describe an approach that rst determines feasible product splits for single-feed continuous reactive distillation. For chemistries where one or more products cannot be obtained as a pure product stream from the column, the geometric method of attainable regions is used to determine the feasible products and alternatives using simultaneous reaction and distillation. These alternatives are then combined with conventional separation systems to get pure products. Using systematic methods, a large number of owsheets are generated, which are then evaluated for feasibility using rules, heuristics and mass balances. Keywords: process alternatives; partially coupled; reactive distillation; attainable region.

INTRODUCTION Global competition among chemical companies has contributed to the industrial interest in cutting capital and operating costs. At the same time, as environmental regulations become increasingly stringent, the costs associated with waste management are expected to rise. Separation technologies could be improved in terms of energy efciency, productivity or raw materials use by coupling it with chemical synthesis (reactions). At the same time, reaction system efciency can be improved by coupling it with separation. The potential is greatest when both aspects are important. The combination has a potential for capital productivity improvements (from enhanced overall rates, by overcoming very low reaction equilibrium constants, and by avoiding or eliminating difcult separations), selectivity improvements (which reduce excess raw materials use, and waste generation), reduced energy use and the reduction or elimination of solvents. Representative examples for the various separation technologies coupled with reaction are: reactive distillation (Xu et al., 1985; Malone
*Correspondence to: Professor M.F. Doherty, Department of Chemical Engineering, University of California, Santa Barbara, CA 93106, USA. E-mail: mfd@engineering.ucsb.edu

and Doherty, 2000), reactive extraction (Trambouze and Piret, 1960; Pai et al., 2002), reactive adsorption (Petroulas et al., 1985; Mazzotti et al., 1996), reactive crystallization (Mullin, 1972; Kelkar and Ng, 1999), and reactive absorption (Jhaveri and Sharma, 1969; Gaikar and Sharma, 1989). Many existing, and potential, applications of reactive distillation are discussed by Sharma and Mahajani (2003). Some of the successes of reactive distillation are so dramatic that we might ask if all liquid-phase chemical processes should be based on simultaneous reaction and separation instead of more traditional separate steps. The answer is no, because using a reactive distillation column is not always advantageous; in some cases it may not even produce a pure product stream! A key question is How can we decide quickly whether reactive distillation is a good process concept? This question is addressed mainly by studies in conceptual design, which is the major focus of this article. The appropriate starting point is the treatment of feasibility and identication of the minimal data requirements for a reliable answer. Progress in the understanding of distillation systems using geometric methods, particularly for nonideal and azeotropic mixtures without reactions, and conventional reactor network theory, provides a basis for developing conceptual designs rapidly. An effective way of 140

PROCESS ALTERNATIVES decomposing the design and development of reactive distillation involves four stages: (1) feasibility and alternatives; (2) conceptual design and evaluation; (3) equipment selection and hardware design; and (4) operability and control. Methods for determining feasible products in the kinetic regime are much more recent. In this paper, we use a method published by Chadda et al. (2001) to determine feasible sharp splits for staged reactive columns in cases of nite rates of reaction and multicomponent mixtures. For systems where a reactive distillation column does not give pure products, reaction combined with distillation is used to exploit the yield (or selectivity) advantages, and is then coupled with a conventional distillation system to get pure products. The aim is to make the best out of an infeasible reactive distillation (that does not produce pure products), and also to nd alternatives to feasible but costly reactive distillation columns. Figure 1 shows a conventional owsheet where there is no integration between reaction and distillation. A reactive distillation column on the other hand is a result of full integration between reaction and distillation. The goal of this paper is to outline a methodology to generate feasible owsheets with partial integration between reaction and distillation that have potential advantages over a conventional owsheet and also over fully integrated reaction with distillation. There are relatively few general methods available for generating reactor alternatives that involve simultaneous reaction and separation. Attainable regions (AR) is a geometric methodology normally used to systematically generate reactor alternatives consisting of combinations of single phase reactors with a potential of improved yields and selectivities over conventional reactor congurations (Glasser et al., 1987). The advantage of this method lies in determining non-intuitive reactor alternatives without prior specication of a reactor network. The AR methodology can be applied to simultaneous reaction and distillation and can identify multifunctional reactor alternatives that can offer potential improvements in conversion, yield and selectivity over conventional technology (Gadewar et al., 2002). The overall scheme of determining feasible reactive distillation alternatives rst involves estimating the

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feasible product splits for a reactive distillation column. If a reactive distillation column cannot give pure products, simultaneous reaction and distillation alternatives are generated using the attainable regions methodology. The next step is to generate ow-sheets by combining conventional distillation systems with these reactor alternatives, and determining their feasibility. We demonstrate our methodology for the production of iso-propyl acetate from isopropanol and acetic acid. FEASIBLE PRODUCTS FROM REACTIVE DISTILLATION Flash Cascade Model In a distillation column, each section (rectifying or stripping) can be effectively represented by a countercurrent cascade of ashes. Chadda et al. (2001) simplied the cascade for the purpose of estimating feasible product compositions, by removing the countercurrent recycles of liquid and vapour ows among successive ash units, leaving a cocurrent arrangement shown in Figure 2. The compositions of the liquid and vapour streams in the ash cascade arrangement are close to those of the countercurrent cascade and by extension, to those in a column section. The two arrangements (countercurrent vs cocurrent) differ mainly in that the recovery of the key components in the countercurrent cascade is much higher than in the ash cascade arrangement. In a feasibility analysis, it is the product compositions that we are trying to estimate, so we use the simpler cocurrent ash cascades to study the feasibility of reactive mixtures in continuous columns. A schematic of the cocurrent ash cascade arrangement is shown in Figure 2. There are two sections. In the rectifying cascade, vapours from each ash reactor are partially condensed and fed to the next unit. This vapour cascade is similar to the rectifying section of a continuous distillation column but without any liquid recycle. The opposite is done for the stripping cascade shown in the bottom half of the gure, where the liquid stream from each

Figure 1. A schematic of processes with integration of reaction and distillation.

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GADEWAR et al. We represent the kinetics by a homogeneous model ! aIPOAc aH2 O (4) r kf aHOAc aIPA Keq where kf is approximately independent of temperature, (kf=kf,ref) 1, and the reaction equilibrium constant has a value of 8.7 in the temperature range of interest (Lee and Kuo, 1996). The VLE was modelled using the Antoine vapour pressure equation, the NRTL equation for activity coefcients, and including vapour phase dimerization of acetic acid. The physical property models were taken from Table 3 in Venimadhavan et al. (1999). Solutions of equations (1) and (2), the rectifying and stripping cascade ash trajectories, can be represented in mole fraction space (three-dimensional for the IPOAc system). However, we represent the solutions in transformed composition space, which is two-dimensional for the IPOAc system (for a derivation and properties of these transformed variables, see Ung and Doherty, 1995a). This transformed composition space is a projection of a three-dimension mole fraction space onto a two-dimensional transformed composition subspace for the IPOAc system. Even though the correspondence between real compositions and transformed compositions is not one-to-one in the kinetic regime, we will make use of these transforms for the following reasons: (i) ease of visualization of the trajectories; and (ii) overall mass balance for reactive systems (kinetically or equilibrium limited) can be represented with a lever rule in transformed compositions. We use this property to assess feasible splits for continuous reactive distillation. If we select IPOAc as the reference component, then the denition given in Ung and Doherty (1995a) gives the transformed variables: X1 xHOAc xIPOAc X2 xIPA xIPOAc (5)

Figure 2. A cocurrent ash cascades arrangement: the top half is the rectifying cascade and the bottom half is the stripping cascade.

ash device is partially vapourized and sent as feed to the next unit in the series. Each ash device in Figure 2 is a two phase CSTR reactorseparator with chemical reaction occurring only in the liquid phase. The ash devices operate under isobaric conditions, so that the temperature changes from stage to stage according to the boiling point of the stage composition. We use mole fractions and activity based kinetic models for reasons explained in Nisoli et al. (1997). The model for the stripping cascade is given as (Chadda et al., 2001):    kf D r(xj ) xi, j1 fyi, j (1 f)xi, j ni kf ,ref 1 D (i 1, . . . , c 1) ( j 1, 2, . . . , N ) (1)

where x0 xF , and f is the ratio of the vapour ow rate to the liquid ow rate. The parameter D represents the amount of reaction, with D 0 corresponding to no reaction and D 1 corresponding to reaction equilibrium. Detailed derivation of the model can be found in Chadda et al. (2001). Equation (1) can be solved recursively for given values of the parameters, f and D starting with the initial condition, x0 xF . The solution is a trajectory of liquid compositions for the stripping cascade. The corresponding model for the rectifying cascade is:    kf D r(xj ) yi, j1 fyi, j (1 f)xi, j ni kf ,ref 1 D (i 1, . . . , c 1) ( j 2, 3, . . . , M ) (2) where y1 ys , and ys is the vapour stream composition 1 1 from the rst ash device of the stripping cascade shown in Figure 2. The solution to equation (2) is a trajectory of vapour phase compositions along the rectifying cascade. Consider the esterication of acetic acid with isopropanol at a pressure of 1 atm IPA HOAc , IPOAc H2 O (3)

Similar expressions are obtained for the transformed variables in the vapour phase, Yi. The stripping cascade is solved recursively for an equimolar feed (xF,HOAc 0.5, xF,IPA 0.5) via equation (1) for a large number of stages until a point is reached where the composition is essentially constant from stage to stage. This pinch point (stable node) is acetic acid. The mole fraction iterates are then converted to the transformed compositions using equation (5). In similar fashion, the rectifying cascade model [equation (2)] is solved recursively for a large number of stages until a pinch point (stable node) is reached; in this case it is a quaternary mixture. These vapour mole fractions so obtained are then converted to transformed compositions and are shown in Figure 3. Bifurcation theoretic methods are an abstraction of residue curve map feasibility analysis, and these rely on numerical continuation methods for solutions. Using the continuation approach described by Chadda et al. (2001), feasible products from a single feed reactive distillation column are determined. Figure 4 shows the feasibility diagram for the isopropyl acetate system. The feasibility diagram provides a global view of the feasible products to expect from a continuous distillation at any rate of reaction (D). For any feed composition and for D in the range, 0 D 0.395, it is possible to obtain acetic acid as bottoms

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PROCESS ALTERNATIVES Attainable Region

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Figure 3. Rectifying and stripping cascade trajectories for a saturated liquid equimolar reactant feed for the IPOAc system at D 0.25 and D 0.75. The trajectories are plotted in transformed mole fraction space. For the stripping cascade, X1 xHOAc xIPOAc, X2 xIPA xIPOAc and for the rectifying cascade, Y1 yHOAc yIPOAc, Y2 yIPA yIPOAc.

from a continuous reactive distillation. However, for 0.395 D 1 we can obtain either isopropanol or acetic acid as the bottoms product depending on the feed composition. The potential distillates are all quaternary mixtures, with compositions that depend on D. Thus, different splits are feasible for different ranges of the Damkohler number. Conversely, any given split may or may not be feasible as the reaction rate or residence time is changed, so that the feasibility of a given separation may depend on production rates, catalyst levels and liquid holdup. The results mean that IPOAc cannot be obtained as a pure product from a single-feed fully reactive column, no matter what rate of reaction the column is operated at.

A method for assessing the performance of reactor systems that has gained prominence in the past decade seeks attainable regions. This approach does not assume a reactor network a priori, but only the set of fundamental processes (such as reaction, mixing etc.) that can occur. The concept was rst proposed by Horn (1964) and later developed by Glasser and co-workers. Glasser et al. (1987) dene the attainable region (AR) as a domain in the concentration space that can be achieved by using any system of steady-ow chemical reactors, i.e. by using the processes of mixing and reaction. Gadewar et al. (2002) used the fundamental processes of reaction, mixing and separation for the attainable region methodology to determine feasible products from counter-current cascades of vapourliquid CSTRs. The framework for generating the feasible product region also accomplishes the task of generating alternatives that allow access to the points in the region. The attainable region methodology is one of the very few general methods for determining alternatives with combined reaction and distillation. The alternatives often have to be combined with conventional separation systems to get pure products. As discussed in the previous section, IPOAc cannot be obtained as a pure product from a single-feed reactive distillation column. We therefore use the AR methodology to get promising alternatives for isopropyl acetate production using simultaneous reaction and distillation. The application of the AR methodology and the model development of a counter-current cascade of vapourliquid CSTRs is given in Gadewar et al. (2002). The products from a single-phase reactor for a very large residence time will lie on the equilibrium curve. The equilibrium composition depends on Keq(T ) and on the activity coefcients, and, hence, on the temperature of the reaction mixture. When the reaction mixture is at its boiling point, the equilibrium is given by curve 1 in Figure 5. Based on the reaction chemistry, the overall input composition to any singlephase reactor or a cascade of two-phase CSTRs and its overall product composition lies on a line with a slope 1. Also, the stoichiometrically feasible space is the entire triangle in Figure 5. The mole fraction of isopropyl acetate in the reaction mixture can be at most 0.5. The model by Gadewar et al. (2002) is solved for specied values of the parameters Damko hler number (Da), vapour to liquid ratio (f), and number of stages (N). The aim is to map out the boundary of the feasible product region. For a pure liquid feed of acetic acid and a vapour feed of pure isopropanol, curve 2 is the locus of the mole fraction of isopropyl acetate in the overall output from a countercurrent cascade of vapourliquid CSTRs with a large number of stages (>40) and a large Da. Each point on curve 2 is at a different value of f; a very low value of f corresponds to the overall feed very close to the acetic acid vertex and a very large value of f corresponds to an overall feed close to the isopropanol vertex. A mixture of acetic acid and isopropanol is used as the liquid feed and the vapour feed to the cascade. The composition of both feeds is the same. The overall mole fraction of isopropyl acetate in the product increases with each of the parameters. The effect of increasing the number of stages diminishes after N 40. Also, a very large value of Da corresponds to liquid in each stage reaching reaction equili-

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brium. The effect of f diminishes after its value is above 100. Therefore, we calculate the overall output mole fraction of isopropyl acetate for a cascade with a large number of stages N > 40, large Da, and f 100. The locus of the overall product mole fraction of isopropyl acetate is given by curve 3. The region enclosed by curve 3 is convex and also encloses the locus for pure feeds, i.e. curve 2. The countercurrent cascade structures that give curves 2 and 3 are shown in Figure 5. The feasible region for the isopropyl acetate system is given in Figure 6. A substantial increase in conversion can be achieved by using simultaneous reaction and distillation over conventional reactors. A single vapourliquid CSTR at large values of f also gives overall product compositions that lie on the boundary of the feasible region. A counter-current cascade with multiple stages can achieve the same product compositions with lower values of f. The resulting multi-functional reactor alternatives offer potential improvements, but must be combined with conventional distillation systems to get pure products.

GENERATION OF FEASIBLE ALTERNATIVES To generate a feasible process alternative, the reaction distillation alternative generated using the AR concept is combined with a separation system. Tao et al. (2003) published a systematic procedure to generate feasible distillation alternatives for separating mixtures into highpurity products using decanters, distillation, mixing and recycle. Their approach is to rst generate feasible highpurity column sequences without considering recycle. These are obtained by studying the phase equilibria for each intermediate stream and its relation to the distillation boundaries in order to make decisions about the separation tasks. After the high-purity column sequences are generated, the recycle streams and their destinations are dened to achieve high recovery alternatives. All possible recycle loops are considered using combinatorial theory. Tracking the large number of alternatives is simplied using graph theoretic data structures. Closing some of these recycle loops may cause a feasible high purity sequence to become infeasible. Infeasibility tests for high recovery closed-loop process owsheets are used to screen out the infeasible sequences in a simple way. The method is based on the composition of the exit streams and the reachability of certain components in the recycle loop. Application of the method signicantly reduces the effort in evaluating alternatives for feasibility. The boundary of the feasible products region in Figure 6 for the isopropyl acetate system can be reached either by using a two-phase CSTR or a counter-current cascade with multiple stages. A logical extension of the procedure by Tao et al. (2003) is to incorporate the alternatives generated by the AR methodology and combine them with the framework for generating distillation sequences. To reach a product composition in the feasible region, the residence time and the ratio of the vapour rate to the liquid rate for a two-phase CSTR will be different from a cascade with multiple stages. The advantage of using one alternative over the other depends on the total cost of the reaction system (reactive distillation) together with the separation system.

Figure 4. Feasibility diagram showing the feasible distillates and feasible bottom products for the IPOAc system.

Applying the systematic procedure for distillation synthesis (Tao et al., 2003), nine high-purity owsheets are generated. Each high-purity owsheet consists of a reaction system connected to a distillation system that gives pure product streams, and also streams consisting of a mixture of components. The streams consisting of a mixture of components are potential recycle streams, and alternatives can be developed when the recycle destinations are any of the units other than the source of the recycle stream. Table 1 lists all the high-purity owsheets, recycle streams, and potential alternatives for the isopropyl acetate system. As shown in Table 1, a very large number of recycle alternatives are generated, and it would be a tremendous amount of work to determine the feasibility of all the recycle alternatives by carrying out the closed loop mass balance calculations. Application of rules and heuristics that constitute the infeasibility tests eliminate a substantial number of infeasible alternatives. Additional rules as a result of the presence of a reaction system are given in Tao (2003). The calculations required in these feasibility tests are much simpler than the full mass balances. High-purity owsheet 1 is shown in Figure 7, and has three potential recycle streams. Among the 16 possible recycle alternatives, 10 alternatives were found infeasible using the rules and heuristics. The remaining six alternatives were evaluated for feasibility using closed loop mass balances. Only three alternatives satisfy closed loop mass balances, and are therefore feasible. Figure 8 shows one feasible recycle owsheet for IPOAc production. The reaction takes place in a counter-current cascade of vapour liquid CSTRs with four stages, and an isopropanol conversion of 73% is reached. The reactant recycles R1 and R3 go back as feed to the counter-current cascade. A recycle stream R2 consisting the product IPOAc is recycled to the

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obtained by intuition or heuristics. Also, a very large number of alternatives can be quickly screened using the methods described here. AVENUES FOR FURTHER RESEARCH Many important aspects of reactive distillation= multifunctional reactors remain to be resolved, as discussed by Malone and Doherty (2000), Taylor and Krishna (2000) and throughout the monograph edited by Sundmacher and Kienle (2002). We would like to emphasize two that are especially relevant to feasibility, design, and process alternatives. Multiple Liquid Phases In many applications where combining reaction and separation is considered as a process alternative, the liquid mixture is only partially miscible all the way up to the boiling temperature for some compositions. Examples include esterication of acetic acid with butanol or higher alcohols, fatty acid esterication. This creates opportunities as well as challenges. The main opportunity involves exploiting a liquidliquid phase split to perform a separation. However, the challenges are signicant, and include: (1) Reliable measurement and correlation of the reaction rate in each liquid phase. Reaction rate models for these strongly nonideal mixtures are often expressed in terms of activities rather than concentrations, but the activity coefcients are not known reliably for liquidliquid mixtures, which makes the rate models sensitive to the activity coefcient model used to correlate the rate data. It is worth mentioning that the same activity coefcient model should be used for the reaction rate and phase equilibrium calculations (Hasse, 2003). Very little has been published on this topic, which is more important than the attention it has received. (2) For feasibility studies it is often useful to study the limiting case of fast reactions or large reaction holdups that correspond to the limit of reaction equilibrium. This limit eliminates the need for a kinetic model but requires that the model equations for phase and chemical equilibrium can be reliably solved and interpreted. It is widely known how to do this for mixtures involving one vapour, one liquid and either a single or multiple reactions. The case of two equilibrium liquids with one equilibrium chemical reaction has also been studied (Ung and Doherty, 1995b), including the interesting interactions between the liquidliquid equilibrium envelope and the reaction equilibrium curve. However, very little has been published on simultaneous VLLE and chemical reaction, which is critical to understanding feasibility and process alternatives in this limit. It is known that, without a reliable global phase stability test, these complex calculations will sometimes predict the existence of phase envelopes that do not exist in nature or in the model. This is a fertile area of research for application to process synthesis (Jiang et al., 1995; McDonald and Floudas, 1997).

Figure 5. (a) Locus of overall product compositions for feed consisting of acetic acid and isopropanol: curve 1 is the locus for single phase reactors; curve 2 is the locus for cascades with pure feeds; curve 3 is the locus for cascades with mixed feeds. (b) Countercurrent cascade of two-phase CSTRs for pure feeds and mixed feeds.

distillation column II. The recycle ow for the owsheet in Figure 8 is 86% lower than a conventional process using a plug ow reactor. An important advantage of a systematic approach for alternatives generation is that it gives many feasible alternatives some of which cannot be easily

Figure 6. Feasible region for the synthesis of isopropyl acetate from acetic acid and isopropanol shown as a hatched region.

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Table 1. Nine high purity alternatives for producing isopropyl acetate. Number of devices 4 4 4 5 5 6 6 7 8 Number of recycles 3 3 3 3 5 5 5 6 6 Number of recycle alternatives 16 16 64 125 625 216 1296 2401 4096

Alternative 1 2 3 4 5 6 7 8 9

(3) Feasibility methods have not yet been fully developed for reacting mixtures involving VLLE. Important progress has been made by Qi et al. (2002) who have developed a detailed treatment of the simple distillation of such mixtures. Extension to rectifying cascades and bifurcation feasibility diagrams, along with interpretation of the results, would be most useful.

Figure 8. A feasible recycle alternative from the high purity sequence shown in Figure 7, with reactant recycles R1 and R3 going to unit I, recycle R2 going to unit II.

External Reactors The idea of using side reactors for distillation columns is gathering attention. The concept involves diverting liquid ow from the stages of a distillation column into an external reactor and returning the reactor outlet back into the column. An important advantage is to decouple the conditions for reaction and distillation, since the operating conditions for improving reaction are not always benecial for the separation. External reactors are also expected to ameliorate operational problems of reactive distillation columns such as compensation for catalyst deactivation, insufcient residence time for reaction. Schoenmakers and Buehlet (1982) published one of the earliest descriptions of a distillation

column with external reactors. Okasinski and Doherty (2003) use a single external reactor coupled with a distillation column for converting raceimic propylene oxide into enantiomerically pure propylene oxide and propylene glycol. They used an external reactor since a distillation column cannot accommodate the required reactive holdup without excessive liquid height (and adverse pressure drop). Baur and Krishna (2003) describe four congurations in which external reactors can be attached to a distillation column. They also present an algorithmic procedure to determine the number and locations of side reactors to achieve maximum conversion in the production of methyl acetate. Citro and Lee (2003) suggest using external reactors to simplify the control of reactive distillation processes.

CONCLUSIONS Feasibility for reactive distillation is now more advanced with methods that are maturing, and can be implemented relatively easily. The geometric method of attainable region (AR) gives an estimate of the feasible products using simultaneous reaction and separation. AR methods are still relatively underexplored and a lot of potential exists for developing a framework to generate alternatives with combined reaction and separation. A single feed reactive distillation column can be one of these alternatives and the feasibility methods complement the tools for AR estimation. We have linked the attainable region methods to a synthesis methodology for generating and screening alternatives consisting of combined reaction and separation. Our approach provides for systematic tools to determine feasible products and alternatives for reactive distillation. The overall scheme of determining feasible reactive distillation alternatives involves estimating rst the feasible product splits for a reactive distillation column. If a reactive distillation column cannot give pure products, simultaneous reaction and distillation alternatives are generated using the AR methodology.

Figure 7. A feasible high purity structure for an equimolar feed of acetic acid and isopropanol. Unit I is a countercurrent cascade of vapourliquid CSTRs.

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PROCESS ALTERNATIVES The next step is to generate owsheets by combining conventional distillation systems with these reactor alternatives, and determining their feasibility using graph theoretic data structures, rules for infeasibility, heuristics and closed loop material balances. Application of geometric methods signicantly reduces engineering effort in the generation and screening of process alternatives.

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NOMENCLATURE
ai c D Da kf kf,ref M N r(x) r xi Xi yi Yi activity of i total number of components scaled Damkohler number, dimensionless Damkohler number, dimensionless forward reaction rate constant, time1 forward reaction rate constant at the reference temperature index for rectifying cascade ash unit index for stripping cascade ash unit driving force for the reaction reux ratio mole fraction of i in the liquid phase transformed mole fraction of i in the liquid phase mole fraction of i in the vapour phase transformed mole fraction of i in the vapour phase

Greek symbols ni stoichiometric coefcient for i summation of all stoichiometric coefcients nT fraction of feed vapourized in jth ash unit fj Subscripts 0 F i j k ref and superscripts initial condition feed component index stage index for ash cascade reference component reference

REFERENCES
Baur, R. and Krishna, R., 2003, Distillation column with reactive pump arounds: an alternative to reactive distillation, Catal Today, 7980: 113. Chadda, N., Malone, M.F. and Doherty, M.F., 2001, Effect of chemical kinetics on feasible splits for kinetically controlled reactive distillation, AIChE J, 47: 590. Citro, F. and Lee, J.W., 2003, Widening the applicability of reactive distillation technology by using concurrent design, Ind Eng Chem Res (submitted). Gadewar, S.B., Malone, M.F. and Doherty, M.F., 2002, Feasible region for a counter-current cascade of vapourliquid CSTRs, AIChE J, 48: 800. Gaikar, V.G. and Sharma, M.M., 1989, Separations through reactions and other novel strategies, Sep Purif Meth, 18: 111. Glasser, D., Hildebrandt, D. and Crowe, C., 1987, A geometric approach to steady ow reactors: the attainable region and optimization in concentration space, Ind Eng Chem Res, 26: 1803. Hasse, H., 2003, Thermodynamics of reactive separations, in Reactive Distillation, Sundmacher, K. and Kienle, A. (eds) (Wiley-VCH, Weinheim, Germany), pp 6596. Horn, F., 1964, Attainable and non-attainable regions in chemical reaction technique, in European Symposium on Chemical Reaction Engineering (Pergamon Press, New York), p 293.

Jhaveri, A.S. and Sharma, M.M., 1969, Absorption with fast chemical reaction, Chem Eng Sci, 24: 189. Jiang, Y., Smith, W.R. and Chapman, G.R., 1995, Global optimality conditions and their geometric interpretation for the chemical and phase equilibrium problem, SIAM J Opt, 5: 813. Kelkar, V.V. and Ng, K.M., 1999, Design of reactive crystallization systems incorporating kinetics and mass-transfer effects, AIChE J, 45: 69. Lee, L.-S. and Kuo, M.-Z., 1996, Phase and reaction equilibria of the acetic acidisopropanolisopropyl acetatewater system at 760 mmHg, Fluid Phase Equilib, 123: 147. Malone, M.F. and Doherty, M.F., 2000, Reactive distillation, Ind Eng Chem Res, 39: 3953. Mazzotti, M., Kruglov, A., Neri, B., Gelosa, D. and Morbidelli, M. 1996, Continuous Chromatographic Reactor: SMBR, Chem Eng Sci, 51: 1827 McDonald, C.M. and Floudas, C.A., 1997, GLOPEQ: a new computational tool for the phase and chemical equilibrium problem, Comput Chem Eng, 21: 1. Mullin, J.W., 1972, Crystallization, 2nd edition (Butterworths, London, UK), Chap 4. Nisoli, A., Malone, M.F. and Doherty, M.F., 1997, Attainable region for reaction with separation, AIChE J, 43: 374. Okasinski, M.J. and Doherty, M.F., 2003, A simultaneous kinetic resolution of chiral propylene oxide and propylene glycol in a continuous reactive distillation column, Chem Eng Sci, 58: 1289. Pai, R.A., Doherty, M.F. and Malone, M.F., 2002, Design of reactive extraction systems for bioproduct recovery, AIChE J, 48: 514. Petroulas, T., Aris, R. and Carr, R.W., 1985, Analysis and performance of a counter-current moving-bed chromatographic reactor, Chem Eng Sci, 40: 2233. Qi, Z., Kolah, A. and Sundmacher, K., 2002, Residue curve maps for reactive distillation systems with liquid-phase splitting, Chem Eng Sci, 57: 163. Sharma, M.M. and Mahajani, S.M., 2003, Industrial applications of reactive distillation, in Reactive Distillation, Sundmacher, K. and Kienle, A. (eds) (Wiley-VCH, Weinheim, Germany), pp 326. Schoenmakers, H.G. and Buehler, W.K., 1982, Distillation column with external reactors an alternative to the reaction column, Ger Chem Eng, 5: 292296. Sundmacher, K. and Kienle, A., 2002, Preface, in Reactive Distillation, Sundmacher, K. and Kienle, A. (eds) (Wiley-VCH, Weinheim, Germany), pp XIXVII. Tao, L., 2003, Feasibility and synthesis of reactionseparation systems with recycles, PhD Dissertation, University of Massachusetts, Amherst, MA, USA. Tao, L., Malone, M.F. and Doherty, M.F., 2003, Synthesis of azeotropic distillation systems with recycles, Ind Eng Chem Res, 42: 17831794. Taylor, R. and Krishna, R., 2000, Modelling reactive distillation, Chem Eng Sci, 55: 5183. Trambouze, P.J. and Piret, E.L., 1960, Extractive reaction: batch- and continuous-ow chemical-reaction systems, concentrated case, AIChE J, 6: 574. Ung, S. and Doherty, M.F., 1995a, Synthesis of reactive systems with multiple equilibrium chemical reactions, Ind Eng Chem Res, 34: 2555. Ung, S. and Doherty, M.F., 1995b, Theory of phase equilibria in multireaction systems, Chem Eng Sci, 50: 3201. Venimadhavan, G., Malone, M.F. and Doherty, M.F., 1999, Bifurication study of kinetic effects in reactive distillation, AIChE J, 45: 546. Wahnschafft, O.M., Koehler, J.W., Blass, E. and Westerberg, A.W., 1992, Product composition regions of single-feed azeotropic distillation columns, Ind Eng Chem Res, 31: 2345. Xu, X., Zhu, B. and Chen, H., 1985, Reactive distillation, Shiyou Huagong, 14: 480. This paper was presented at ISMR-3CCRE18, the joint research symposium of the 3rd International Symposium on Multifunctional Reactors and the 18th Colloquia on Chemical Reaction Engineering held in Bath, UK, 2730 August 2003. The manuscript was received 18 July 2003 and accepted for publication after revision 5 November 2003.

Trans IChemE, Part A, Chemical Engineering Research and Design, 2004, 82(A2): 140147