Computers and Chemical Engineering 24 (2000) 2043 2054 www.elsevier.

com/locate/compchemeng

Synthesis of distillation-based processes for non-ideal mixtures

Arthur W. Westerberg *, Jae Woo Lee, Steinar Hauan
Department of Chemical Engineering, Carnegie Mellon Uni6ersity, Pittsburgh, PA 15213, USA

Abstract Our understanding of how to design distillation-based processes to separate mixtures displaying azeotropic behavior has grown enormously in the past quarter century. We elegantly sketch distillation column behavior on a composition diagram where we display VLE and column behavior using residue and distillation curves. In the presence of azeotropes, these curves partition composition space into distillation regions that trap the performance of individual columns. We can view liquid liquid behavior as a tearing of composition space, a tear that always spawns from a minimum binary azeotrope. A material balance across a column section leads to a difference point, which we can use to understand column tray-by-tray and limiting behavior for ordinary, extractive and even reactive distillation. We demonstrate how to synthesize alternative separation processes, concentrating on those that produce pure products. We use boundary curvature, solvent addition, extractive agents, liquid liquid behavior and strategically placed reaction to step across distillation boundaries. We show that these processes always contain recycles to gain feasibility but also to have economically attractive processes. 2000 Elsevier Science Ltd. All rights reserved.
Keywords: Distillation based processes; Azeotropic behavior; Non-ideal mixtures; Reactive distillation; Difference points

1. Introduction We were invited to prepare a paper on the synthesis of distillation-based separation processes for the CEPAC Workshop held September 2 and 3, 1999, at INTEC in Santa Fe, Argentina. We elected to prepare a tutorial paper that looks at the series of improvements we have had in chemical engineering of our understanding of these processes in the last 15 20 years. 20 years ago we had reasonable methods to aid engineers to synthesize processes that separated relatively ideal mixtures, using a series of conventional two product columns. We were just beginning to develop visualization methods to aid us to nd the better heat integrated sequences, including the use of more complex congurations such as side strippers and enrichers and so-called Petlyuk congurations. There were already at this time some very notable publications guiding us to understand the behavior of azeotropic mixtures the book by Hoffman (1964),
Paper presented at CEPEC, Santa Fe, Argentina, September 2 3, 1999. * Corresponding author. Tel.: +1-412-2682344; fax: + 1-4122687139. E-mail address: a.westerberg@cmu.edu (A.W. Westerberg).


ex-Soviet Union literature (see the references in Petlyuk, 1998) and papers by Doherty and Perkins (1978) and then a large number of papers by Dohertys group at the University of Massachusetts. The theme for this paper will be visual insights, which we strongly believe aid designers to be innovative. Very powerful insights are often based on simple approximate sketches that expose the essence of a design problem. The grand composite curve for heat exchanger network synthesis is one example (described in Chapter 10 in Biegler, Grossmann & Westerberg, 1997). Another classic example is the McCabeThiele diagram for binary distillation. We often teach our students the mechanics for constructing a McCabe Thiele diagram and show them how to determine the number of trays for a column. However, determining the number of trays is not the primary use for such a diagram. We would almost always use a readily available computer program instead. Perhaps the most important use is when experienced engineers use it to visualize how columns behave. For example, knowing how the operating lines on a McCabeThiele diagram shift when one preheats the feed allows one to decide if preheating the feed is likely to useful for a given column.

0098-1354/00/$ - see front matter 2000 Elsevier Science Ltd. All rights reserved. PII: S0098-1354(00)00575-5

2044

A.W. Westerberg et al. / Computers and Chemical Engineering 24 (2000) 20432054

In this paper we shall focus on the development of insights that have become available for separating mixtures that display azeotropic behavior. We shall end this paper by presenting some of the recent insights that are becoming available for reactive distillation. If these are successful, we may at times be able to use sketches to decide if we should use reactive distillation and, if so, even where we should place the reaction within the column. We rst present a number of fundamental concepts to aid in the design of distillation-based separation processes. We shall generally limit ourselves to ternary mixtures so we can visualize the geometry. We shall use a fairly informal writing style to be consistent with our intent that this paper be tutorial and, hopefully, easy to read.

2.2. Residue cur6es

It is useful to sketch the vaporliquid (VL) equilibrium behavior of a set of species on a composition diagram. There are two characterizations commonly used: residue curves and distillation curves. The former relates to boiling a liquid in a pot while the latter corresponds to liquid compositions we would see in a staged distillation column. For residue curves, consider having the pot of boiling liquid shown in Fig. 1. We can determine the composition of the liquid remaining in the pot. We write the following component material balance dM dxi dxi M + M = yi V =xi dt dt dt (1)

We note that dM/dt is V. We also dene a dimension-less time ~= tV/M. Eq. (1) then becomes 2. Basics In this section we shall review the use of composition diagrams to display VL(L) behavior and to allow for the geometric construction of the tray-by-tray behavior of columns. Very recent developments allow us to consider columns in which reaction is also occurring. dx =x y 6 6 d~ (2)

2.1. Composition diagrams

Composition diagrams are particularly useful to visualize the performance of distillation columns, especially ternary diagrams as we can readily sketch them on a sheet of paper. A ternary diagram is triangular in shape, and it lies entirely within a plane. A four-component diagram forms a tetrahedron in three-space a bit difcult for visualization while a binary diagram is simply a line which does not convey too much insight. A composition diagram for nc components has nc 1 degrees of freedom as the compositions all must add to unity, which is, for example, why a three component diagram lies in a two-dimensional plane. When we examine difference points later, we shall nd individual component compositions that lie outside the range 0 1; these add some interesting geometry to these diagrams.

Assuming the vapor compositions y are in equi6 librium with the liquid compositions x, and if we plot 6 the trajectory for the liquid compositions x on a com6 position diagram, we get what is termed a residue curve, i.e. the composition trajectory for the residue that is left in a boiling pot as we boil away the liquid versus time. Looking at this last equation as a vector equation, we see that the direction for the vapor composition y in equilibrium with the liquid composition in 6 the pot x lies on the tangent line that touches the 6 residue curve at x. 6

2.3. Distillation cur6es

The other type of curve we can draw, which generates a very similar diagram, is the curve passing through the tray-by-tray liquid compositions in a staged distillation column operating at total reux. Looking at Fig. 2, material balance requires that the two streams are identical that ow counter to each other between any two stages. Assume the vapor leaving a tray is in equilibrium with the liquid leaving. To step from tray to tray, we start with any arbitrary composition xn. We compute yn in equilibrium with xn, a bubble point computation. We then set xn 1 =yn. We compute yn 1 in equilibrium with xn 1, set xn 2 = yn 1, etc. Thus a series of bubble point calculations will move us up the column. In a similar fashion, we can use a series of dew point calculations to move down the column. Just where will these curves head that we produce? With increasing time, a residue curve will move upward in temperature, terminating ultimately at a local maximum temperature. Such a point is called a stable node as the time trajectory ends there as time goes to innity.

Fig. 1. Batch still.

A.W. Westerberg et al. / Computers and Chemical Engineering 24 (2000) 20432054

2045

from this previous bubble point computation. Repeating enough times will generate a set of points leading to the unstable node from which the curve emanates. When close enough to this unstable node, return to the original liquid composition and carry out a dew point calculation for it. Repeat this step by carrying out a dew point computation for the liquid resulting from this previous dew point computation. Eventually the points will approach the stable node towards which this curve is moving. When close enough to the stable node, this curve is complete. Develop another curve by placing another rst composition point in the composition diagram and develop, as above, the curve for it. Repeat until curves are developed throughout the composition diagram.

2.4. Distillation regions

Fig. 2. Total reux column.

Fig. 3 illustrates the shape of residue curves for a ternary mixture of ethanol, water and glycol. All trajectories start at the unstable node the minimum boiling azeotrope between water and ethanol, move toward the components having intermediate boiling points (toward water or ethanol, depending on which direction we move away from the minimum boiling azeotrope) and then towards the stable node corresponding to pure glycol where they terminate. Points like those for pure water and ethanol are called saddle points as each has a trajectory that enters it, turns, and leaves in another direction. For water for example, the trajectory enters from the right along the lower edge, turns and leaves along the left edge toward glycol. Of interest are topologies where there are two or more stable and/or unstable nodes. Fig. 4 illustrates a rather complicated composition diagram. Here there are two unstable nodes (at local minimum temperatures of 120C at the top and 155C along the bottom edge)

Fig. 3. Trajectories for composition in still pot.

Stepping down a column will create a set of points that move upward in temperature, also ending at a stable node. Integrating the differential equations for the residue curve backwards in time or heading upward in a column will lead downward in temperature, ultimately to a local minimum point in temperature. Such a point is known as an unstable node for the residue curve as all curves will leave such a point as time increases. We can develop distillation curves by repeatedly using bubble and dew point ash computations, such as available in commercial simulators. Pick an arbitrary composition somewhere in the composition diagram. Do a bubble point calculation for it. Repeat this step by nding the bubble point for the vapor composition

Fig. 4. Complicated distillation or residue curve diagram.

2046

A.W. Westerberg et al. / Computers and Chemical Engineering 24 (2000) 20432054

Fig. 5. Vapor liquid liquid behavior on a ternary diagram.

and two stable nodes at local maximum temperatures of 160 and 170C at the lower right and left. This diagram has four different distillation regions. In region I, residue curves emanate from the upper unstable node and terminate at the lower left stable node. Region II has the same unstable node, but all of its residue curves head to the lower right stable node. Regions III and IV have trajectories that start from the second unstable node. The ternary azeotrope in the middle is a saddle point with the trajectories coming from the unstable nodes, turning, and leaving toward the stable nodes. Discovering distillation regions by plotting residue or distillation curves is one of the most important geometric insights we can get from them. Experience with such diagrams has told us that we cannot design conventional distillation columns to operate such that their distillate and bottoms products are in two different regions (Doherty & Perkins, 1978). These regions essentially trap where the products can lie as a result. The trick to designing separation processes for species displaying this type of complex behavior is to gure out ways to cross these boundaries.

2.5. Liquidliquid beha6ior

It is interesting to think about what will happen when a mixture of three components breaks into two or more liquid phases that are in equilibrium with a single vapor phase. We will use Fig. 5 to illustrate. Liquid liquid behavior occurs when the Gibbs free energy of a mixture decreases if the material breaks into two liquid phases. (A discussion of this behavior is in most chemical engineering thermodynamics textbooks see for example, Smith and Van Ness (1987). It also appears in Biegler et al. (1997)). When generating a distillation curve, select a physical property option that allows

liquidliquid behavior to be computed. Also attach two liquid product steams to the ash unit. Select an arbitrary overall liquid composition (point x). If it lies in the VLL (vaporliquidliquid) equilibrium region, a bubble point ash computation will produce two liquid products with differing compositions (points a and b) and a vapor composition (point c) in equilibrium with both of them. The two liquid compositions must lie at the end of a tie-line that passes through the overall liquid composition x (a bubble point produces no vapor so the original mixture partitions into the two liquid phases). If we choose any other liquid composition on that same tie-line, say x*, we will again produce the exact same compositions a, b, and c. Only the amount of the liquids having compositions a and b will differ to satisfy the lever rule. Thus to discover the structure of the VLL region, we need only place one liquid composition on each tie-line of interest. If the vapor composition happens to lie on precisely the same tie-line as the overall liquid composition that produced it, then it corresponds to a ternary azeotrope. We could have selected an overall liquid composition equal to that vapor composition and produced a calculation in which the overall liquid composition is the same as the vapor composition produced from it-which is the denition of an azeotrope. All the vapor compositions in the VLL region will lie along a single line. If we select our overall liquid compositions closer and closer to the lower edge, the vapor composition must also approach that edge as in the limit we will have only a binary mixture of species A and B. That vapor composition will be an azeotrope as it lies on the tie-line that produced it. It will, in fact, be the minimum boiling azeotrope that must occur between species A and B. If we start with a liquid composition outside the VLL region, then we may produce a vapor that lies within that region if it were condensed. Thus the distillation curve we are discovering using bubble point computations would move inside the VLL region and immediately jump to be on the vapor line we described above. We can approach the VLL region from either side of it, jumping to the vapor line once we enter it. Thus one can think of the VLL region as a tear i.e. a ssure in the composition space for the components. As an exercise, think what the geometry will be if there are three liquid phases in equilibrium with a single vapor, i.e. a VLLL problem. Also think about how many liquid compositions are needed to establish its geometry.

2.6. Reachable products for a simple distillation column

Once we know the structure of the VL(L(L)) behavior as displayed on a ternary composition diagram, we can approximate the behavior of conventional distilla-

A.W. Westerberg et al. / Computers and Chemical Engineering 24 (2000) 20432054

2047

tion columns, i.e. a column with a single feed and a top (distillate) product and a bottoms product (Westerberg & Wahnschafft, 1996; Biegler et al., 1997; Stichlmair & Fair, 1998). Because the feed is the sum of the two products by material balance, we know that the feed composition must lie on a straight line between the top and bottom product compositions. Also the lever rule tells us just where along this line the feed composition lies. In Fig. 6, the line lengths a, b, and a + b are proportional to the owrates for B, D and F, respectively. If we assume the column operates at total reux, the product compositions must also both lie on the same distillation curve. We normally would also like to get fairly pure products from a column. We would get fairly pure products if the column has a large number of stages, which is well approximated by assuming an innite number of stages. Thus the bottom end will be close to a stable node or the top to an unstable node. Fig. 7 illustrates the products regions we can expect. For

one option, we place the distillate product at the unstable node and draw a straight line from it through the feed to the opposite edge of the region containing the distillate top product to locate approximately the corresponding bottom product. For the other option, we place the bottom product at the stable node and draw a straight line from it through the feed and onward to the opposite side of the region containing the bottom product to locate approximately the corresponding top product. We get a bow-tie shaped region as shown in Fig. 7. It is possible to argue that any products lying in the shaded region and along a straight line through the feed can correspond to a feasible distillation column. The usual way to assess quickly the possible products is to assume either (1) the stable node is the bottom product (b1) or the unstable node the top product (d2). The other product for each of these two cases (d1 or b2) is then that which is most distant along the straight line through the feed and in the same distillation region. The feed does not have to lie in the same region as the two products. When it does not, the feed tray composition must be different from the feed composition. The feed tray composition will lie in the same region as the products as will all the liquid tray composition while the feed composition lies in the other region. One can always have the feed and feed tray composition more or less the same for a binary column but not in general for columns having three or more components in them.

Fig. 6. Lever rule on composition diagrams.

2.7. Difference points the geometry of component material balances

The next interesting geometric insight we can observe for a distillation column is the notion of a difference point (Westerberg & Wahnschafft, 1996; Biegler et al., 1997; Hauan, Ciric, Westerberg & Lien, 2000). In Fig. 8 we write the overall material balance for the top section of an ordinary distillation column. We see the form for the balance suggests that the entering vapor, Vn + 1, is the sum of the distillate product and the liquid ow leaving, Ln. Thus the composition for Vn + 1 lies on a straight line between the compositions for D and Ln. Assume the species are A, B and C, with A being the most volatile and that we want our distillate product to be relatively pure A. We sketch this geometry for an arbitrary composition for Ln. The level rule says we place Vn + 1 such that the line segments D Vn + 1, Vn + 1 Ln and DLn are proportional to D, Ln and Vn + 1, respectively. Ln /D is the reux ratio for the column so, if we set the reux ratio, we know exactly where to place Vn + 1 along this line. This line represents a material balance. It allows us to nd the composition for the vapor owing counter to the liquid between two stages just as the operating line does on a McCabe Thiele diagram for a binary column.

Fig. 7. Bow-tie shaped reachable region for a two-product column operating at total reux.

Fig. 8. Difference point for top part of ordinary distillation column.

2048

A.W. Westerberg et al. / Computers and Chemical Engineering 24 (2000) 20432054

Fig. 9. Difference point for an extractive distillation column.

exactly where as the line lengths DD, D S and D S, must correspond to the ratio of the ows of S, D and D, respectively. If the solvent ow is nearly zero, the composition of D is very close to D. As the ow of solvent increases, it will eventually be equal to D. At that point the composition for D will have moved out along the line to innity. When S increases past D, the ow D becomes negative, and its composition jumps to innity at the other end of the line. As S increases, the composition for D moves towards that for S, which it equals when S has an innite ow. In Fig. 9 we construct a material balance line to nd Vn + 1; only this time we use the compositions for Ln and D.

2.8. The reaction difference point for a column (Hauan, Westerberg & Lien, 1999)
We are now ready to examine the impact of reaction on a column. Reaction can be viewed as two ows. The reactants ow out from the stage while the products ow into it. If we were to do our material balances using mass ows rather than molar ows, there would be no loss or gain in material because of reaction. In other words, 1 kg of reactants will always produce 1 kg of products (disallowing nuclear reactions). However, we can easily gain or lose moles. For example, the reaction A+BUC converts two moles into one mole each time the reaction turns over as written. We characterize the rate of reaction as a turnover, which is a owrate (e.g. mol s 1) corresponding to the owrate at which the reaction occurs as written. We designate reaction turnover by the symbol x. Fig. 10 aids in understanding the following ideas. We can write the reaction A+BUC in the form A B+ C= 0. The vector of stoichiometric coefcients w for this reaction is the transpose of [ 1, 1, 1]. If the turnover of the reaction as written is x mol s 1, then the net ow due to reaction into the column is wtotx= 1x, i.e. there will be two moles leaving and one entering for a net of 1x mol s 1 entering. The composition of this ow is 1 mol s 1 of A, 1 mol s 1 of B and + 1mol s 1 of C, rescaled to add to unity, i.e. w/wtot = [1, 1, 1]T. We illustrate this composition in Fig. 10. Note it is on the line where the compositions for A and B are one and C is negative one. (To see this, note that the composition of A is 1 in the lower left corner of the composition triangle and zero all along the right edge of the triangle. Lines of constant A are parallel to each other so along the line joining D and the reaction difference point the composition of A is one.) There is an interesting signicance to this reaction composition. It is a difference point for reaction. Select any arbitrary composition within the composition triangle and draw a straight line through it and the

Fig. 10. Difference point when reaction occurs.

The point D is called a difference point. The distillate D is the xed difference (Vn + 1 Ln ) for all stages n above the feed in the column. Thus all material balance lines such as we have constructed are straight lines that pass through this single point for the top section of our column. Let us now add a solvent as an extractive agent to our column (see Fig. 9). Let us assume it is the heaviest species in the mixture, component C, which lies at the upper corner of our composition diagram. The solvent is a second feed to the column. We examine the material balance for trays just below this feed. Again we write a material balance around the top section, but this time the constant difference point is D S rather than D. As is routinely done in the textbooks, we call this difference D. We see that D is the difference between D and S rather than the sum. If the solvent ow S is very small relative to D, then D is positive, and we can move S to the other side, giving us D = S +D, with all ows being positive. Thus the composition for D should lie between the compositions for S and D. However, D lies in the lower left corner, and S lies at the upper corner. How can D lie between S and D? The composition for D must lie outside the feasible composition diagram. The lever rule tells us

A.W. Westerberg et al. / Computers and Chemical Engineering 24 (2000) 20432054

2049

reaction composition point. All points along this line within the composition triangle can be converted into each other by carrying out the reaction to different extents. The projections developed by Doherty (e.g. Barbosa & Doherty, 1987) and his students map all the points on one of these lines onto a single point using his projection equations (Stichlmair & Fair, 1998). The projection for A+ BUC +D results in a two-dimensional square (see Fig. 11). To understand why it becomes a square, construct a tetrahedron out of paper. The reaction difference point is at innity for this reaction, as there are moles that are neither created nor destroyed. The lines passing through this innite difference point are parallel to the line going from a 50 50 mixture of A and B that reacts to become a 50 50 mixture of C and D. Viewed from the difference point at innity, the tetrahedron projects into a square. We now return to the material balance equations written at the top of Fig. 10. We see that D for extractive distillation is replaced by D wtotx for extractive distillation with reaction. D has a xed composition and ow. However, the reaction extent can change from tray to tray. The ow wtotx varies as x (in mol

s 1) varies. We locate the composition for the ow D wtotx by drawing a line between the composition for D and for the reaction (both xed). We split this line using the lever rule to give line length ratios that correspond to the ratio for the two ows D and wtotx. As both of these ows are positive for this example, the resulting difference point here lies between their two compositions. The composition for Vn + 1 must then lie on a straight line connecting this composition to that for Ln. The point can move as we step from tray to tray because the reaction ow, wtotx, is the total of all the reaction occurring within the stages around which we have written our material balance. We now point out one reason this construction is interesting. Examine Fig. 12. Pick an arbitrary point for the composition of Ln in the column. The composition for Vn is on the line tangent to the residue curve passing though Ln (or along the distillation line passing through Ln ). For an ordinary column, Vn + 1 will be along a line passing through the composition for the distillate, D. If we introduce an extractive agent and/or reaction, we move the difference point. We show it moving as for a case in which we have reaction occurring. We see that Vn + 1 is to the left of Vn for an ordinary column and to the right for a reactive column. We have caused the direction the compositions change from tray-to-tray to reverse. The trays below this tray continue to use this same difference point if they do not have any reaction occurring on them. Thus we can have a non-reactive tray in which the compositions seem to change in a direction that is the reverse of what we expect. The temperature could actually decrease as we move down the column.

Fig. 11. A square projection for A + BUC+ D.

3. Using geometric insights to aid design The above insights can help us to design separation processes. We will emphasize separation tasks that involve mixtures displaying azeotropic behavior. We will present this section using examples. The purpose is not to be all-inclusive but rather to explain why the geometry is suggesting these solutions. Thus it is hoped the reader will see other alternatives based on similar reasoning for these and other problems.

3.1. Example: sol6ent selection to break a binary azeotrope

Fig. 12. Strategic use of difference point placement to steer plate-byplate composition trajectories in a column.

Fig. 13. Node behavior for a minimum binary azeotrope.

Our goal here is to nd a third component that will allow us to break a binary azeotrope. The approach we shall investigate is to nd a third component that will allow us to step around the azeotrope using conventional distillation. Fig. 13 illustrates the situation when the binary species A and B form a minimum boiling azeotrope. We note that A has the lower normal boiling

2050

A.W. Westerberg et al. / Computers and Chemical Engineering 24 (2000) 20432054

is no B in this top product; we distill it to separate A from the entrainer. We recycle the entrainer. It should not be difcult now to describe the characteristics of an entrainer to break a maximum boiling azeotrope. The entrainer can form azeotropes with A and B; we need only to have a single region in which A becomes a saddle. Doherty and Caldarola (1985) and Stichlmair and Fair (1998) present an extensive set of rules for picking a suitable entrainer to break binary azeotropes. They involve this type of thinking.
Fig. 14. Breaking a binary azeotrope with an intermediate boiler.

3.2. Example: crossing distillation boundaries to break an azeotrope

Another way to think about breaking an azeotrope is to add a third component that converts the azeotrope into a saddle. If the azeotrope is a minimum boiling azeotrope, we need to select a light entrainer (Fig. 15). This species will cause a distillation boundary to exist that connects the entrainer with the azeotrope. We want this boundary to be very curved, so we have a second requirement: namely, that in regions where the entrainer concentration is high (near the entrainer corner of the triangle), the two species have a very different volatility. Here species A is much more volatile that B. When that happens distillation curves leave the entrainer (a stable node) and head toward the species that is acting like the intermediate boiler-here A. They then turn toward the high boiler as shown. As a result, the distillation boundary is very curved as shown. We rst mix the entrainer and the azeotrope, moving the feed for the rst column well into the three component part of the diagram so as to take maximum advantage of the curvature of the boundary. We distill, getting species B as the bottom product. The distillate is close to the distillation boundary. This distillate becomes the feed to the second column. While the feed is in the right region, we can have both products in the left region at the same time that both lie on a straight line through the feed. As noted earlier, only the products have to be in the same distillation region. A third column recovers A and azeotrope. We recycle the azeotrope back to the feed. This type of reasoning is involved in inventing separation processes for the acetone, chloroform and benzene system described in Westerberg and Wahnschafft (1996) and Biegler et al. (1997).

Fig. 15. Breaking a minimum boiling azeotrope with a low boiling entrainer that forms a strongly curved distillation boundary.

point for the two components. Because the azeotrope is a minimum one, it will typically lie closer to the lower boiling component, as shown. If we can alter our problem so A, B and the azeotrope are all in the same distillation region, we will be able to break the azeotrope using distillation. To be in the same distillation region, we must have only one stable and one unstable node. We have to convert at least one of these nodes to a saddle. For example, we can convert A into a saddle in the three component composition diagram by picking a third component that forms no azeotrope with them and that has a boiling point that is between that for A and B. We would get the behavior shown in Fig. 14. In this diagram, the binary azeotrope remains the unstable node. B remains a stable node, while A and C are saddles. All distillation curves will emanate from the azeotrope and end up at pure B. To invent a separation process, we could rst mix our entrainer with the azeotropic mixture, forming a mixture that is away from the lower edge of the composition diagram. In the three component region, we can have a column whose bottom product is the stable node, species B, the highest boiling component in the distillation region. The top product is along the straight line passing through the feed and as far as the furthest edge of the distillation region, here the left edge. There

3.3. Decantation
If we have a three component mixture to separate where the species have a region in which there is liquidliquid behavior, we often can readily develop a separation process. Separating pyridine, toluene and water is an example. Fig. 16 shows the structure of the

A.W. Westerberg et al. / Computers and Chemical Engineering 24 (2000) 20432054

2051

distillation (or residue) curve map. The two phase region boundary can either correspond to having a vapor phase in equilibrium, or it can be the result of cooling the liquid well below this point and having only two liquid phases present. The more one cools, the larger the two liquid phase region typically is. We start by decanting the feed, to form water- and toluene-rich phases. We can then distill each of the phases to get pure water and pure toluene bottoms products, respectively. Mixing the distillate products, which lie along the distillation boundaries shown, produces a mixture in the distillation region where we can distill to recover pyridine, which we do. The distillate from this distillation lies somewhere in the two-phase region; we recycle it to the decanter. Here the appearance of a VLL region allows us to use decanting to cross distillation boundaries and thus to develop a process fairly easily. Using this type of reasoning, we can invent other possible processes for this feed.

3.4. Extracti6e distillation

We can also use extractive distillation to effect a separation. What are the geometric clues that would suggest this approach? Consider trying to break the waterisopropylalcohol (IPA) binary azeotrope. Fig. 17 shows a typical extractive distillation column. In such a column, we usually select a very heavy solvent one that boils at a much higher temperature than either of

Fig. 16. A process to separate species having a region with VLL behavior.

Fig. 17. Extractive distillation example.

the other two species. We also want a solvent in which the two species will have very different volatilities; i.e. we want a solvent that is increases the activity coefcient of one of the species much more than it does for the other. The species with an increased activity coefcient becomes relatively much more volatile. We can detect this behavior by examining innite dilution Kvalues for the water and IPA in the presence of a number of candidate solvents. If volatilities in a high concentration of solvent are very different, we have a candidate solvent. In a matter of a few seconds, we can readily examine thousands of components using a computer, provided we have the appropriate data on each to allow us to estimate physical properties. We should nd ethylene glycol to be a good candidate here. It is readily available, fairly safe to handle, boils at a much higher temperature than either water or IPA, and it has a large innite dilution activity coefcient with IPA. The composition diagram in Fig. 17 illustrates the shape of the distillation curves for these components. Examine the portion of the composition diagram to the right of the curve ab where EG is in high concentration. The shape of the distillation curves in this region suggests that water is the intermediate component while IPA is the light or most volatile component. Only when the curves are near the minimum azeotrope do they bend to move toward the minimum boiling azeotrope, which here is the unstable node. The shape on the right suggests that water is the intermediate and IPA is the light component. If this shape appears in high concentrations of a proposed solvent, then extractive distillation will allow us to break the azeotrope. We note that the IPA corner is a saddle yet, with extractive distillation, we can have it as the top product. To understand this, return to our earlier discussion on difference points for extractive distillation. The D point (see Fig. 9) for extractive distillation will lie on the straight lines that pass through the IPA product and EG feed compositions. It will lie outside the composition triangle. If the solvent ow is less than the distillate product ow, it will be in the direction shown. If the solvent ow is larger than the distillate, it will wrap around and be below and to the right of the EG corner along this same straight line. In either case, if we take a tray-by-tray step, as shown in Fig. 12, somewhere along the curve ab, we would nd movement up the extractive column just below the EG feed would be toward the IPA/EG edge of the composition space. We could get arbitrarily close to that edge, effectively eliminating all the water from the top part of the column. The top of the column above the EG feed is then separating IPA from EG, a binary separation that is done in one or two trays as EG is much heavier than IPA.

2052

A.W. Westerberg et al. / Computers and Chemical Engineering 24 (2000) 20432054

we have B+ A= 0 and the stoichiometric coefcients are [1, 1]. Here wtot = 1+1= 0 as there are no net moles lost or produced as this reaction proceeds. The reaction difference point is at innity. We shall construct a McCabeThiele diagram for this system (Lee, Hauan & Westerberg, 2000a). Our goal is to discover how reaction alters this diagram. If we write a material balance around the top of a column (as in Fig. 10) for the component A, we get Vn + 1yn + 1, A = Lnxn, A + DxD, A x = Lnxn + D xD, A

x D

(3)

Since there is no net production or loss of moles, Vn + 1 = Ln + D. If we let yn + 1 = xn to nd where this operating line intersects the 45 line, we nd that it occurs when
Fig. 18. McCabe Thiele diagram for column having reaction on stages 2 and 3 from the top.

xA = xD, A

x D

(4)

Fig. 19. McCabe Thiele diagram when placing reaction in bottom section.

4. Reactive distillation We will complete this paper by looking at interesting geometry for reactive distillation. In particular we shall look at the geometry for binary columns. We have already examined the use of a difference point for reaction in ternary systems. We start by supposing we have one component that can rearrange to form the other; thus our system can be reactive and binary. We shall assume the reactant is the less volatile species and write our reaction as B A. Written in standard form,

Thus the intersection point shifts down by the fraction the reaction turnover (owrate) is of the distillation top product owrate. For example, if we feed 10 mol s 1 of B along with some A and run the column to convert 50% of the B in the feed into A, the turnover will be 5 mol s 1 for the entire column. Fig. 18 is a McCabeThiele diagram (McCabe & Thiele, 1925), where we have allowed reaction to occur. We start at the top tray where we specify that the composition of A to be recovered in the distillate to be 0.95. The original top operating line intersects the 45 line at this composition. We (arbitrarily) specify that we shall have no reaction on the top stage; we step off this stage using this original operating line. We place catalyst on stage 2 so that we can get a reaction turnover of x2. The operating line shifts downward. We step to this operating line below stage 2. Let us suppose that we also place catalyst on stage 3. We again shift the operating line down as shown. Note that x3 as shown is the sum of the turnover rates on and above stage 3 (the material balance has to account for all stages above the tray of interest). If we choose to put catalyst on no other stages, we should then use this last operating line for all stages below stage 4 and above the feed tray. We analyze the bottom of the column as we would for a non-reactive column. We note that each time we allow reaction, the operating line moves down. Having reaction in the top of the column makes our separation task easier. We ask next what happens to our diagram if we allow reaction for this case to occur in the bottom of the column. We carry out a similar analysis, but this time we place reaction in on a bottom stage of a column. We construct the resulting McCabeThiele diagram in Fig. 19 for the same case for which we constructed Fig. 18.

A.W. Westerberg et al. / Computers and Chemical Engineering 24 (2000) 20432054

2053

This time we shall number from the bottom of the column. Assume reaction occurs only on the second stage from the bottom. When we allow reaction and because of the sign changes that occur in the analysis, the intersection point for the operating line and the 45 line moves downward here also. However, doing so now shifts the new operating line upward, leading to a more difcult separation; indeed, we can make the operating line move above the equilibrium curve, which would cause us to reverse the direction we separate the mixture, i.e. we would start to step back to the left. The second dashed operating line illustrates a shifted operating line that just touches the equilibrium curve leading to a pinch situation. Thus we can conclude that, for this case of the heavy species forming the light species, we make the separation task easier by having the reaction occur in the top section of the column (Lee, Hauan, Lien & Westerberg, 2000b).

operating line is also well below the equilibrium line even though the equilibrium line is below the 45 line. We can observe several interesting things about this diagram. First, if we had used total reux to decide how to design this column, the operating line would coincide with the 45 line, and we would not be able to step past the azeotrope. Thus, it is our use of a nite reux ratio that gives us this possibility. Second, we step past the azeotrope below the trays where reaction occurs. Once past the azeotrope, the more volatile species, B, is enriching as we go down the column. This behavior is similar to the behavior we discussed earlier for a ternary diagram when we add reaction and possibly an extractive agent ow to the column. As before this enrichment says the temperature is decreasing on non-reactive trays as we step down the column. This behavior is very counter-intuitive for most chemical engineers. It is occurring because reaction has altered the material balance for the column, here dramatically. 5. Conclusion We have examined some of the very interesting geometry associated with analyzing distillation processes. In particular we rst looked at residue and distillation curves to expose VL(L) equilibrium phase behavior. We next showed that difference points are how we account geometrically for the material balances of a column. We then looked at altering material balances for a column by adding a solvent feed to and/or allowing reaction within the column and showed we could make the tray-by-tray behavior of a column change directions and even reverse directions. We also showed how to use these insights to discover useful column designs that can break binary azeotropes. Finally we looked at binary reactive distillation and showed that we can construct and use a McCabeThiele diagram for this situation. Again we showed that altering the material balance by having reaction occur within the column can lead to some very interesting and we think not so intuitive behavior. We could also derive a rule of thumb from just a sketch that tells us where to place the reaction in the column. References
Barbosa, D., & Doherty, M. F. (1987). A new set of composition variables for the representation of reactive phase diagram. Proceedings of the Royal Society of London, A413, 459. Biegler, L. T., Grossmann, I. E., & Westerberg, A. W. (1997). Systematic methods of chemical process design (pp. 455 494). Upper Saddle River, NJ: Prentice-Hall Chapter 14. Doherty, M. F., & Perkins, J. D. (1978). On the dynamics of distillation processes I (the simple distillation of multicomponent non-reacting homogeneous liquid mixtures). Chemical Engineering Science, 33, 281 301.

4.1. Stepping past a binary azeotrope (Lee, Hauan & Westerberg, 2000c)
Again consider the reaction B A. Only this time we have two species that form a maximum boiling azeotrope as shown in Fig. 20. Note that the equilibrium curve crosses the 45 line. This shape is indicative of a maximum boiling azeotrope. In the upper part of the diagram A is more volatile while in the bottom, B is. We start at the top where we again ask for 95% pure A as the top product. Arbitrarily, we do not allow reaction to occur on the top stage. We place catalyst on stages 2 and 3, each time causing the indicated reaction turnover and shifting downward of the operating line. The operating line is, by this time, well below the 45 line. We nd we can now step past the azeotrope as the

Fig. 20. Stepping past a binary azeotrope in a reactive distillation column.

2054

A.W. Westerberg et al. / Computers and Chemical Engineering 24 (2000) 20432054 The McCabe Thiele diagram. Proceedings: Mathematical, Physical and Engineering Sciences (2000b) accepted. Lee, J. W., Hauan, S., & Westerberg, A. W. (2000c). Graphical methods for reaction distribution in a reactive distillation column. Proceedings: Mathematical, Physical and Engineering Sciences (2000c) accepted. McCabe, W. L., & Thiele, E. W. (1925). Graphical design of fractionating columns. Industrial Engineering Chemistry, 17, 605. Petlyuk, F. B. (1998). Simple methods for predicting feasible sharp separations of azeotropic mixtures. Theoretical Foundations of Chemical Engineering, 32 (3), 245 253. Smith, J. M., & Van Ness, H. C. (1987). Introduction to chemical engineering thermodynamics (4th ed.). New York: McGraw Hill. Stichlmair, J. G., & Fair, J. R. (1998). Distillation: principle and practice. New York: Wiley-VCH. Westerberg, A. W., & Wahnschafft, O. (1996). Synthesis of distillation-based separation processes. In J. L. Anderson, Ad6ances in chemical engineering. In: Process synthesis, vol. 23 (pp. 63 170). New York: Academic.

Doherty, M. F., & Caldarola, G. A. (1985). Design and synthesis of homogeneous azeotropic distillations. 3. The sequencing of columns for azeotropic and extractive distillations. Industrial Engineering Chemistry Fundamentals, 24, 474485. Hauan, S., Westerberg, A. W., & Lien, K. M. (1999). Phenomena based analysis of xed points in reactive separation systems. Chemical Engineering Science, 55 (6), 10531075. Hauan, S., Ciric, A. R., Westerberg, A. W., & Lien, K. M. (2000). Difference points in extractive and reactive cascades. I Basic properties and analysis. Chemical Engineering Science, 55(16), 31453159. Hoffman, E. J. (1964). Azeotropic and extracti6e distillation. New York: Interscience-Wiley. Lee, J. W., Hauan, S., & Westerberg A. W. (2000a). Circumventing an azeotrope in reactive distillation. Ind Eng. Chem. Res., 39, 10611063. Lee J. W., Hauan, S., Lien, K. M., & Westerberg A. W. (2000b). A graphical method for designing reactive distillation columns. II