Distillation. JAMES R. FAIR Department of Chemical Engineering The University of Texas Austin, Texas. 5.1 INTRODUCTION 5.

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1 PART Il I N D I V I D U A L S E P A R A T I O N P R O C E S S E S

2 C H A P T E R 5 Distillation JAMES R. FAIR Department of Chemical Engineering The University of Texas Austin, Texas 5.1 INTRODUCTION 5.M Definitions Distillation is a method of separation based on the difference in composition between a liquid mixture and the vapor formed from it. The composition difference is due to differing effective vapor pressures, or volatilities, of the components of the liquid. When such a difference does not exist, as at an azeotropic point, separation by distillation is not possible. The most elementary form of the method is simple distillation in which the liquid mixture is brought to boiling and the vapor formed is separated and condensed to form a product; if the process is continuous, it is called flash distillation or an equilibrium flash, and if the feed mixture is available as an isolated batch of material, the process is a form of batch distillation and the compositions of the collected vapor and residual liquid are thus time dependent. The term fractional distillation (which may be contracted to "fractionation") originally was applied to the collection of separate fractions of condensed vapor, each fraction being segregated. Currently, the term is applied to distillation separations in general, where an effort is made to separate an original mixture into several components by means of distillation. When the vapors are enriched by contact with counterflowing liquid reflux, the process often is called rectification. When operated with a continuous feed of liquid mixture and continuous removal of product fractions, the process is continuous distillation. When steam is added to the vapors to reduce the partial pressures of the components to be separated, the term steam distillation is used; if such a process is altered to eliminate the steam, dry distillation ("conventional distillation") results. Most distillations conducted commercially operate continuously, with a more volatile fraction recovered as distillate and a less volatile fraction remaining as residue or bottoms. If a portion of the distillate is condensed and returned to the process to enrich the vapors, the liquid is called reflux. The apparatus in which the enrichment occurs is usually a vertical, cylindrical vessel called a still or distillation column. This apparatus normally contains internal devices for effecting vapor-liquid contact; the devices may be trays or packings. As stated above, a separation by distillation involves differing volatilities of the components to be separated. If the volatility difference is so small that an adequate separation cannot be made, it may be possible to increase the volatility difference by the addition of an extraneous material that can be separated later; this process is known as extractive distillation if the added material is relatively nonvolatile and leaves the column with the residue. If the added material forms an azeotrope with one or more of the components 6T the mixture and in so doing enhances the separability of the original mixture, azeotropic distillation results. In this last-named mode, the extraneous material, or azeotropic agent, may leave the column in the distillate (low-boiling azeotrope) or in the residue (high-boiling azeotrope).

3 It is clear that the difference in volatility of the various components of a liquid mixture is a key to the successful application of distillation. This difference can be related to the thermodynamic equilibrium that can exist between the liquid and vapor mixtures under conditions that can be associated with the distillation at hand. The phase equilibrium relationships are embodied in the general area of solution thermodynamics and can be measured or, in some cases, predicted from the properties of the pure materials involved. The resulting equilibrium compositions often are referred to as vapor-liquid equilibrium data, shortened to vapor-liquid equilibria and abbreviated simply as VLE. There are occasional instances when a second immiscible liquid phase is involved, with compositions of the three phases at thermodynamic equilibrium known simply as vapor-liquid-liquid equilibria, or VLLE Areas of Application Distillation is the most widely used separation method to be found in the chemical and petroleum processing industries. It is normally the least expensive of possible methods for separating a given mixture and in many cases is the only feasible method. It has the disadvantage of requiring energy in the form of heat to produce the necessary vaporization, and this can represent a significant cost. It also subjects the mxiture components to the temperatures of vaporization, and this can be detrimental to heat-sensitive materials (although operation under vacuum, to reduce temperature levels, is quite common). By definition, distillation involves the liquid phase and if it is to be applied to normally gaseous mixtures, temperatures must be lowered by the use of refrigeration. The common example of distilling a normally gaseous mixture is the cryogenic fractional distillation of air to produce high-purity streams of oxygen, nitrogen, and argon. Distillation is applied at small scales on a batch or continuous basis to separate and purify specialty chemicals. At the other extreme it is the basic method for separating commodity chemicals on a tonnage basis, a familiar example being the distillation of crude petroleum to obtain a number of hydrocarbon fractions. The reader should recognize that many of the principles involved in distillation separations apply also to absorption and stripping separations. Indeed, these unit operations all involve the contacting of liquids and gases (vapors) and utilize similar equipment when operated at the commercial scale. The reader may wish to consult Chapter 6 for detailed information on absorption and stripping General Approach to Solving Distillation Problems Problems associated with separations of any type may be approached from design or rating points of view. In the design approach, a separation is specified and the necessary equipment is designed such that the specification can be met. In the rating approach, the equipment is specified (it may be existing equipment) and the degree of separation is rated. For any distillation problem, whether rating or design, there is a sequence of steps that must be taken, and these are described below. 1. Define the Mixture. While this first step might seem obvious, it often is not considered properly. For precise separations, all components of the mixture must be identified. Furthermore, possible future additions to the mixture must be considered when new equipment is being designed. The simple textbook two-component mixtures are not often encountered commercially, and unanticipated components can play havoc with many distillations. In some instances it may not be possible to identify individual components of the mixture, as in the handling of "boiling-range" materials; in such cases it is necessary to identify pseudocomponents that can serve the computational purposes of the design or rating procedures. 2. Establish Separation Criteria. These criteria include product purities as well as component recoveries. For example, a light hydrocarbon distillation column might be designed to produce an overhead product containing a minimum ethylene mole fraction of 99.5 mol %, and at the same time to have the requirement of recovering at least 95% of the ethylene that enters with the feed. To use this example further, the separation criteria to be established should recognize whether future markets might require, say, 99.7 mol % purity and whether some safety factor should be added to these purity requirements in carrying out the design of the distillation system. 3. Obtain Property Data. These can include transport, physical, and thermochemical data as needed for computations. Importantly, they include the necessary vapor-liquid equilibrium (VLE) data, measured or predicted for the ranges of composition, temperature, and pressure to be encountered in the computations. As will be noted later, the reliability of the VLE can seriously influence many distillation designs. 4. Select a Model for Computing Stages or Transfer Units. The difficulty of making a given separation is computed in terms of equilibrium stages, if the process is to be carried out on a stagewise basis, or transfer units, if the process is to be conducted as a differential vapor-liquid contacting operation. Distillation columns with plates or trays handle the stagewise operations, and columns with packings or other special devices handle the differential operations. The models in question can range from empirical and nonfundamental approaches to the rigorous stagewise methods that require computers to handle situations involving many mixture components and many theoretical contacts. In some cases, an approximate

4 COLUMN Vent Steam CONDENSER FEEO ACCUMULATOR NETOVERHEAO REBOILER BOTTOMS FIGURE Flow diagram of typical continuous distillation system. model may suffice in the earlier stages of design or rating, to be followed by a more exact model for the final analysis. 5. Calculate Required Stages or Transfer Units. After the model is selected, the number of theoretical stages or transfer units is computed. This is an index of the difficulty of the separation and is dependent on the amount of reflux that is used. It is in this step that the familiar stages/reflux relationship is developed, with the final combination of these two parameters dependent on economics. 6. Size the Distillation Column. This includes the hydraulic analysis to establish operating ranges, pressure drop, and mass transfer efficiency. The result is a set of dimensions, including column diameter and height, number of actual trays (or height of packed bed), details of internal devices, and profiles of temperature and pressure. 7. Complete the System Design. A typical distillation system is shown in Fig It is clear that the column is only a part of the system, which also includes heat exchangers, vessels, instruments, and piping that must be dealt with by the chemical process engineer. However, in the present chapter, the column and its characteristics are the principal thrust; the other components of the system represent individual technologies (such as process control or process heat transfer) that are best covered separately. This sequence of steps has been discussed from the design approach, that is, with a needed separation leading to a final equipment specification. Close scrutiny will show that the sequence applies also to rating situations. For example, if an existing column is to be used for a new service, steps 1-5 will not change. In step 6, the accommodation of the existing column for the needed stages and vapor/liquid flows will be tested by trial-and-error until either a fit is made or modifications of the existing equipment will be defined Contents of this Chapter This chapter covers all important aspects of distillation column rating or design. It follows generally the sequence of the steps noted immediately above. The common case for discussion is conventional distillation operated in the continuous mode. Exceptions to this mode, such as extractive distillation or batch distillation, will be handled separately. Much of the material in Sections , dealing with hydraulics and mass transfer in columns, can also be used in the design and analysis of absorption columns. Perusal of Chapter 6 will show the reader how the connection may be made. 5.2 PHASEEQUiLIBRIUM Thermodynamic Relationships At thermodynamic equilibrium, the vapor and liquid phases (Fig ) show a distribution of mixture components between the phases that is determined by the relative volatility between pairs of components. This separation factor has its equivalent term in other methods of separation that are based on the equilibrium

5 Vapor Liquid FIGURE Equilibrium between vapor and liquid. The conditions for equilibrium are T v = T L and P v = P L. For a given T and />, f v = f L and /7 = /f. concept. For components i andj their relative volatility (often called the "alpha value") is defined as (5.2-1) Each component of the mixture has a distinct vapor-liquid equilibrium ratio or "AT value": (5.2-2) where y* is a vapor mole fraction in equilibrium with liquid mole fraction Jt,. Thermodynamic relationships described in Section of Chapter 1 may be used to develop the following general form for the K value, which uses Raoult's law as the basis of the liquid reference state: (5.2-3) where 7, is the activity coefficient describing the deviation of the liquid phase from ideal solution behavior, 4>i is the fugacity coefficient describing the deviation of the vapor mixture from ideal behavior, and <f>f x is the fugacity coefficient of pure vapor i at the system temperature and a pressure equal to the vapor pressure of 1 at that temperature. As described in Chapter 1, both 7, and 0, can be determined from equations of state in some instances, but it is more common to evaluate 0, from an equation of state and 7, from a model of the liquid solution. The exponential term in Eq. (5.2-3) is known as the Poynting correction. Perhaps the most important term in Eq. (5.2-3) is the liquid-phase activity coefficient, and methods for its prediction have been developed in many forms and by many workers. For binary systems the Van Laar [Eq. (1.4-18)], Wilson [Eq. (1.4-23)], NRTL [Eq. (1.4-27)], and UNIQUAC [Eq. (1.4-36)] relationships are useful for predicting liquid-phase nonidealities, but they require some experimental data. When no data are available, and an approximate nonideality correction will suffice, the UNIFAC approach [Eq. (1.4-31)], which utilizes functional group contributions, may be used. For special cases involving regular solutions (no excess entropy of mixing), the Scatchard-Hildebrand method 1 provides liquid-phase activity coefficients based on easily obtained pure-component properties. The vapor phase at low pressure normally is considered to be an ideal gas and under such circumstances the fugacity coefficient 0, is unity. For more careful determinations of the K value, however, values of 0, may be estimated from the following relationship: (5.2-4)

6 For an ideal vapor solution, Eq. (5.2-4) can be simplified to the expression (5.2-5) Equation (5,2-3) provides a rigorous thermodynamic basis for the prediction of the vapor-liquid equilibrium ratio. Sometimes it can be simplified, as the following special cases demonstrate: Liquid Incompressible. If this is the case, the Poynting correction (PC) becomes (5.2-6) Poynting Correction Negligble. This is usually the case at pressures less than 20 atm and temperatures greater than 273 K. The resulting equation is (5.2-7) Vapor Solution Ideal. For this case 0,- = <t> h which is usually the case at pressures less than 20 atm and temperatures greater than 273 K. Equation (5.2-3) is modified further then to give (5.2-8) Vapor Obeys the Ideal Gas Law. This is a familiar and frequent situation and one that can be checked easily through estimation of the compressibility factor. At pressures below about 2 atm and temperatures above 273 K, it is very probable that the ideal gas law is obeyed and Eq. (5.2-3) further reduces to (5.2-9) Since Raoult's law is p, = Jt,/?]* 1, the liquid-phase activity coefficient in Eq. (5.2-9) is a "Raoult's law correction factor" that takes into account liquid-phase nonideality. Since most distillations are carried out at relatively low pressure and moderate-to-high temperature, Eq. (5.2-9) is the most generally used relationship in distillation system analysis and design. Liquid Solution Ideal. This is the ultimate reduction in the K value equation and is represented by Raoult's law. it is likely to apply when very similar molecules form the binary or multicomponent solution. Accordingly, Eq. (5.2-3) then reduces to the simplest possible K value relationship: (5.2-10) or the simple ratio of vapor pressure to total pressure. Vapor pressures for many substances have been tabulated and usually are correlated well by the Antoine equation: (5.2-11) Values of the Antoine constants for various materials may be found in many reference works; a particularly useful listing of constants may be found in the book by Reid, Prausnitz, and Sherwood. 2 As pointed out in Chapter 1, several of the correction factors for Eq. (5.2-3) may be obtained from equations of state, when there is a significant pressure effect on the equilibrium mixture Binary Systems For a system containing only two components (a binary system), relative volatility is (5.2-12)

7 y'f, mole fraction i in vapor FIGURE Xi, mole fraction i in liquid Typical y*-x equilibrium diagram for a binary system. By convention, component 1 is the more volatile. Equation (5.2-12) can be rearranged to (5.2-13) which may be plotted as the familiar y*-x curve shown in Fig The value of a i2 might not be constant across the entire range, and thus Eq. (5.2-12) strictly applies to a given value of the liquid mole fraction JC,, at which composition the slope is (5.2-14) This slope is used primarily in mass transfer calculations, to be discussed in Sections 5.9 and Alternative equilibrium diagrams are temperature-composition (T-x) and pressure-composition (P~x) as shown in Figs and While not as useful in distillation as the y*-x diagram, they present clearly the concepts of the bubble point, dew point, and composition changes during simple vaporization and condensation. For example, a liquid of composition A may be heated at constant pressure to point B, the bubble point, at which the initial vapor is formed (Fig ). This vapor has the composition C, significantly richer in the light component than is the initial liquid. As vaporization proceeds, the vapor composition moves from C to D and the liquid composition from B to E. When the last remaining liquid disappears, the dew point has been reached and with continued heating the mixture moves to point F, in the superheated vapor region. The process could be reversed, starting with vapor at point F and finally ending with subcooled liquid at point A. For an isothermal process in which pressure is changed, the subcooled liquid at point A (Fig ) may be moved to its bubble point B by lowering the pressure. With continued pressure lowering, the vapor composition moves from C to D and the liquid composition from B to E; point D is the dew point. Further lowering of pressure produces the superheated vapor at point F. Figure shows a variety of T-x and y*-x diagrams that represent different types of binary systems. It should be clear that the simplified diagrams in Figs and do not always prevail, and yet they represent a fairly large body of binary equilibrium compositions. The important point is that the system at hand must be characterized carefully with respect to vapor-liquid equilibria. The application of nonideal correlating relationships such as the Van Laar equation is, however, much simpler for binary systems than for multicomponent systems.

8 Vapor Temperature Liquid P = const. Mole fraction i, vapor or liquid FIGURE Temperature-composition equilibrium diagram for a binary system Multicomponent Systems Equilibrium data for multicomponent systems may be measured, but because of the ranges of temperature and pressure likely to be encountered in the distillation, some sort of model must still be available for extending such experimental data. The best approach is to start with the binary data for all possible binary pairs a chore not too difficult for, say, ternary or quarternary systems, but one that is quite challenging for mixtures with more than four components. A six-component mixture, for example, would require evaluation of 15 binary pairs. The various correlating equations (Wilson, Van Laar, etc.) have multicomponent forms, but the most versatile method for combining binary pair data is that of Chien and Null. 3 This method permits use of the best-fit correlating method for each binary pair followed by combination of the binary data to give multicomponent equilibrium distributions Sources of Equilibrium Data A very large amount of effort has gone into the measurement and correlation of vapor-liquid equilibria, and the published effort has been referenced by HaIa and coworkers in several bibliographic treatises. 46 Liquid Pressure Vapor T = const. Mole fraction i\ vapor or liquid FIGURE Pressure-composition equilibrium diagram for a binary system.

9 Type Non- A2eotropic Example Methanol- Water Minimum-Boiling Azeotrope Ethanol- Water Azeo Azeo Maximum-Boiling Azeotrope Azeo Acetone- Chloroform Azeo Heterogeneous Azeotrope Normal Butanol- Water Azeo Azeo Heterogeneous NonAzeotrope Propylene Oxide- Water FIGURE Common types of equilibrium diagrams for binary systems. These works direct the reader to the source publications but do not in general report scientific data. An older work that does report data is by Chu et al.; 7 newer and more reliable data compilations have been published by Hirata et al. K and by Gmehling et al. 9 The latter is a continuing series and includes liquidliquid equilibria; an example page of data is shown in Fig Both Refs. 8 and 9 include parameters for the more popular models for correlating and predicting liquid-phase activity coefficients. It is important to note that the data of Ref. 9 are available for computer retrieval. l0 For hydrocarbon systems, many approximate K value data have been presented in the forms of graphs and nomograms. An oft-cited nomogram is that of Hadden and Grayson," which includes also hydrogen.

10 (1) ETHANOL C2H6O (2) WATER H20 PRESSURE* MM HG ( BAR ) LIT: MARGULES VAN LAAR WILSON NRTL UNIQUAC ANTOINE CONSTANTS REGION +++ CONSISTENCY C METHOD C METHOD 2 + OTHMER D.F.,MOELLER W.P.,ENGLUND S.W.,CHRISTOPHER R.G. IND.ENG.CHEM.43,707(1951), CONSTANTS: A12 A21 ALPHA12 EXPERIMENTAL DATA MARGULES VAN LAAR WILSON NRTL UNIQUAC T DEG C Xl Yl DIFF T DIFF Yl DIFF T DIFF Yl DIFF T DIFF Yl DIFF T DIFF Yl DIFF T DIFF Yl MEAN DEVIATION: MAX. DEVIATION: HILSON Water H2O C2H6O Binary Systems with FIGURE Vapor-liquid equilibrium data for elhanol-water at 1 atm. Example page from Ref. 9.

11 hydrogen sulfide, carbon dioxide, and water under special conditions. Perhaps the most reliable graphical presentation of hydrocarbon K values is that of the Natural Gas Processors Association. 12 A listing of azeotropic data has been published by Horsley. 13 General source data are included in the volume by Reid et al. 2 More information on sources of equilibrium data will be found in Chapter 1. In general, a thorough search of the literature should be made before investing in laboratory measurements, but the searcher should beware of faulty experimental data that are not thermodynamically consistent. 5.3 EQUILIBRIUMSTAGES Basic Relationships Separation calculations for distillation are based on the concept of a process that involves contacting of vapor and liquid in one or more equilibrium stages. In this process one or more feed streams enter a stage, and one or more streams leave the stage. Energy may be added to or withdrawn from the stage. Importantly, thermodynamic equilibrium is required to exist on the stage, and this concept has been discussed in the previous section (e.g., Fig ). Mass flows to and from a generalized vapor-liquid contacting stage are shown in Fig The indication of * interstage flows'* is in the context of a cascade of stages as in a distillation column, but the figure applies to other contexts as well. Figure shows the equivalent energy flows to and from the stage. A material balance across the stage is There must be equilibrium on the stage: (5.3-1) (5.3-2) where K 1 is the vapor-liquid equilibrium ratio for component i. In general, (5.3-3) Also, the summation of mole fractions must equal unity: (5.3-4) Finally, an enthalpy balance must prevail on the stage: where, in general, (5.3-5) Interstage flows Stage n Interstage flows FIGURE Component mass flows on a contacting stage.

12 Interstage flows Stage n FIGURE lnnterstage flows Stream energy flows on a contacting stage. vapor enthalpy (5.3-6) liquid enthalpy (5.3-7) These four relationships, the 44 M-E-S-H equations," are the critical ones for equilibrium stage calculations in distillation, and they are sufficient if the pressure effect in Eqs. (5.3-3), (5.3-6), and (5.3-7) can be determined deductively. Otherwise, momentum balance equations must be added Equilibrium Flash The stage shown in Figs and may be simplified for the case of a single feed and two products, one vapor and one liquid, as shown in Fig When operated on a steady-state continuous basis, this arrangement is a simple takeover distillation, or equilibrium flash separation. If there is a net increase in the total number of moles in the liquid, the arrangement can be called equilibrium condensation. The MESH equations can be used in a straightforward way to obtain material and energy balances. The separation may be isothermal, with heat added or removed, or it may be adiabatic. It often operates with a liquid feed and a reduction of pressure in the contacting zone, hence the common use of the term equilibrium flash. For the general case of a multicomponent system, the total number of moles of vapor produced by the flash is (5.3-8) Alternatively, the total number of moles of liquid produced is (5.3-9) These equations involve iterative solutions, usually based on the initial assumption of the LI V or VIL ratios. It should be noted that the terms L n IVJC n and V n K n IL n are used elsewhere in this book as the absorption factor A 1 and the stripping factor S h respectively. While Eqs. (5.3-8) and (5.3-9) are basic to the equilibrium flash process, one should not overlook the implied use of an energy balance to obtain the temperature and pressure conditions of the flash. As noted, both vapor and liquid products are withdrawn from the flash chamber of Fig This means that the flash conditions must lie between the dew point and the bubble point of the feed mixture and that the conditions of the Gibbs phase rule must be met Multistage Distillation For a multiple-stage cascade, and for a feed that enters in the midregion of the cascade, the representation of a multistage distillation column emerges, as shown in Fig In this column, vapor stream V x is

13 Flash chamber (stage n) FIGURE Single-stage equilibrium flash. generated at the base by a boiling process and this vapor passes up through the column, its composition and mass changing as the distillation process occurs. The vapor is completely or partially condensed at the top of the column at stage N. All or part of the condensed vapor is returned to the column as reflux stream L N, and this sets up a counterflow of vapor and liquid, to meet the context of the "interstage flows" in Figs and The requirement of equilibrium on each stage establishes a composition profile for the column with the result of material transport between the phases, and the model assumes that the transport is so rapid that there is no departure from equilibrium at any point in the column Binary Distillation ANALYTICAL METHOD The simplest case of multistage distillation involves only two components. Figure is an adaptation of Figure for the binary case, and it shows two envelopes that are amenable to energy and material balancing. For the top envelope a mass balance on the lighter (more volatile) component is (5.3-10) This equation provides a relationship between the composition of the vapor leaving a stage and the composition of the liquid entering the stage from above. The compositions of the vapor and liquid leaving the tray are related by the equilibrium requirement or (5.3-11) (5.3-12) For the upper envelope, an energy balance is

14 N (Condenser) 1 (Reboiler) FIGURE Cascaded stages in a distillation column. (5.3-13) Thus, with Eqs. (5.3-10)-(5.3-13), plus the requirement that on each stage the liquid and vapor mole fractions must each equal unity, the number of theoretical stages for a given separation may be determined analytically. One may start from the top condition and work down the column, taking into account the addition or removal of material or energy at any of the stages, or one may start from the bottom and work up toward the top condition. As an example of the procedure, consider the case of starting at the top of the column. Streams D and L N +, and their compositions are determined by the separation specification and the assigned reflux ratio. This then provides the flow and composition of the vapor leaving the top stage N. Equation (5.3-12) gives the composition of the liquid on the top tray, x N. The temperature of the top tray may be obtained from a dew point calculation on the vapor composition y N. For tray W - 1, Eq. (5.3-10) gives (5.3-14) Recognizing that V N _, = D + L N, the value of y N., is obtained. In turn, a dew point calculation provides the value of x N _,. An energy balance confirms the dew point temperature. And thus, calculations proceed down the column. Calculations from the bottom toward the top are analogous, with a mass balance across the bottom envelope (Fig ) providing the material balance equation.

15 Upper envelope Lower envelope FIGURE Mass and energy flows in a binary distillation column. (5.3-15) and Eq. (5.3-11) providing the equilibrium vapor composition. The terms B and x B are obtained from the separation specification, and the rate V 0 also is specified in connection with the reflux ratio. The composition y 0 is obtained from a bubble point calculation on x By which also gives the temperature of V 0. The material balance L x = V 0 + B thus gives the flow and composition of the liquid from stage 1. A bubble point on this composition yields the temperature of stage 1 and its vapor composition. Material balance L 2 = V x + B must be checked by heat balance to arrive at specific values of L 1 and V 1. In like fashion, calculations are continued up the column.

16 These stagewise calculations are easily programmed for computer solution. If the calculations are made by hand, it may not be necessary to run an energy balance at every stage, unless there are large differences between the molal latent heats of vaporization of the mixture components. At any rate, if the equilibrium and enthalpy data are at hand, the computations proceed quite rapidly, even if done by hand. MCCABE-THIELE GRAPHICAL METHOD This method is based on an interpretation of Fig and Eq. (5.3-10) (upper envelope) and (5.3-15) (lower envelope). It was first published in 1925' and is described in some detail in most unit operations textbooks (e.g., see Ref. 4). It is by far the best known and most used graphical method for determining theoretical stage requirements for binary systems. In Eq. (5.3-10), if the vapor molar flow rate V n and the liquid molar flow rate L n + 1 are constant throughout the upper envelope, then the equation represents a straight line with slope L n + JV n when y n is plotted against X n +,. The line is known as the upper operating line and is the locus of points coupling the vapor and liquid compositions of streams passing each other (see Fig ). In a like fashion, a mass balance for the lower envelope of Fig produces Eq. (5.3-15), and if the vapor and liquid molar flow rates are constant, the equation is a straight line on a plot of y m versus x m +, and is the lower operating line. At the feed stage, reference to Fig shows a mass balance as follows: (5.3-16) If the upper and lower envelopes are extended to the feed stage, then there is an intersection of the operating lines: (5.3-17) (5.3-18) The thermal condition of the feed stream introduces the need for an energy balance at the feed stage. The feed may be a subcooled liquid, a saturated liquid, a mixture of liquid and vapor, a saturated vapor, or a superheated vapor. A special term may be defined that can account for the thermal condition of the feed: heat required to convert 1 mole of feed to saturated vapor Q " ' - ' (5 3-19) molar latent heat of the feed (for feed at its boiling point, q - 1; for a saturated vapor feed, q = 0). With this q term, an energy balance across the feed stage yields (5.3-20) (5.3-21) Combining these equations with the upper and lower operating line equations and the material balance across the feed stage gives (5.3-22) This "q line equation*' also represents a straight line on a y-x plot, with slope = qf(q -1). The operating lines, the q line, and the equilibrium curve [see Eq. (5.2-13)) are all y-x functions where, by convention, the mole fractions refer to the lighter, or more volatile, component of the binary pair. It was on this basis that McCabe and Thiele 1 developed their graphical approach to binary distillation stage determination and their approach is summarized in Fig In the figure, the upper and lower operating lines are shown intersecting at the feed point with each other and with the q line. The location of the lines depends on their slopes and on the compositions of the distillate (overhead) and residue (bottoms) products, x D and x B. These compositions usually are specified on the basis of process needs for purity and recovery. The slope of the upper operating line is determined by the reflux ratio to be used. This ratio is. _ moles of liquid returned to the column L N+, Reflux ratio = R = -^- = (5.3-23) moles of product distillate D Thus, the slope of the upper operating line is

17 Equilibrium curve Rectifying operating line y = mole fraction in vapor Slope Line Stripping operating line Slope =L'/V FIGURE x = mole fraction in liquid Summary of McCabe-Thiele graphical method for binary distillation. -K = FTT = If and is always less than 1. The slope of the lower operating line is L' m + xiv' m and is always greater than 1. In Fig , which represents an arbitrary example, the theoretical stages are stepped off according to the equations of the equilibrium line and operating lines, and a total of nine theoretical stages are shown. It should be clear that a different number of stages would result if the slopes of the operating lines were changed, that is, if the reflux ratio was varied. This leads to the concept of the stages versus reflux curves, shown in Fig Each curve is the locus of points for a given separation. At their extremes, the curves become asymptotic to minimum stages and minimum reflux values. Minimum stages are stepped off when the operating lines coincide with the diagonal line and have a slope of unity; from Eq. (5.3-24) it can be seen that at this condition of minimum stages there can be no net product distillate takeoff. This is the condition of total reflux and is an important condition for starting up columns and for conducting efficiency tests on columns. Again, with reference to Fig , as the point of intersection of the operating lines is moved closer to the equilibrium curve (reflux ratio being decreased), more and more stages would be stepped off, and when the lines and curve intersect, a "pinch" results with an infinite number of stages being stepped off, in theory. This is the condition of minimum reflux and is associated with an infinite number of stages, as indicated in Fig It is clear that the design reflux ratio for a column must lie between an infinite value (minimum stages) and a minimum value (infinite stages), and thus these limiting parameters assume great importance in the analysis and design of distillation equipment. They will be taken up in greater detail later.

18 Each curve is the locus of points for a given separation Theoretical stages Minimum stages Minimum reflux ratio FIGURE Reflux ratio Stages-reflux relationship. The McCabe-Thiele graphical method is useful for preliminary designs and for general orientation of the effects of process variables. It includes one basic assumption; that there is no change in the molar flow of liquid and vapor in each section (the rectifying section above the feed and the stripping section below the feed). This assumption implies that the molar latent heat of vaporization of each component is the same, and for many practical cases this is essentially true. It is possible to remove this restriction by using heat balances and changing the slopes of the operating lines (giving, in effect, curved operating lines), but this added embellishment is rarely justified. The McCabe-Thiele method also may be used for cases of multiple feeds and of product withdrawals from intermediate stages. As mentioned earlier, standard texts on unit operations should be consulted for additional details. Steps in the use of the McCabe-Thiele method for design are: 1. Draw the equilibrium curve, based on information from sources such as those given in Chapter 1 or in Section 5.2 of the present chapter. 2. Locate the feed, distillate product, and bottoms product compositions on the diagonal line. 3. Draw the q line, based on the condition of feed, starting with the feed composition on the diagonal. The line is vertical for a saturated liquid (liquid at its boiling point) and is horizontal for a saturated vapor feed. 4. Draw the upper operating line, starting with the distillate composition on the diagonal and using a slope determined from the selected reflux ratio. 5. Draw the lower operating line, starting with the bottoms composition on the diagonal and connecting with the point of intersection of the q line and the upper operating line. 6. Step off the theoretical stages as indicated in Fig , changing operating lines at the feed stage. PONCHON-SAVARIT GRAPHICAL METHOD An alternative graphical method for handling binary mixtures is that of Ponchon 2 and Savant, 3 and while more cumbersome to use than McCabe-Thiele, it allows for variations in the molar latent heat of vaporization and thus removes the principal assumption of the McCabe-Thiele method. As basic information it requires not only a y*-x equilibrium relationship but also data on enthalpy of vaporization as a function of composition, and, except for a few mixtures, such data are not readily available. The Ponchon-Savarit method is summarized in Fig The method involves an enthalpy-concentration diagram, and the enthalpies of the saturated liquid and vapor are first plotted on the diagram. Next, the equilibrium tie lines are added, based on phase equilibria. Compositions of feed, distillate, and bottoms are then located on the diagram (in the example shown the feed is mixed vapor-liquid and the distillate and bottoms are saturated liquids). A reflux ratio is chosen, and the enthalpy of the reflux is located as the top difference point, A D. (The reflux ratio is equal numerically to the vertical distance from the difference point to the value of y N, divided by the vertical distance from y N to x D.)

19 Constant pressure Difference point Equilibrium tie-line Enthalpy, energy/unit total mass Bottoms. Saturated vapor Feed Saturated liquid Distillate - Operating line x or y, concentration in liquid or vapor FIGURE Summary of Ponchon-Sayarit graphical method for binary distillation. A series of operating lines are drawn from the top difference point A D to connect the compositions of streams passing each other (e.g., x N and y N -,), the equilibrium values (e.g., x N and y N ) being connected by tie lines. In this fashion, stages are stepped off from the top of the column down to the feed stage, at which point a shift is made to the bottom operating line. This latter line is based on a bottom difference point that is colinear with the feed point and the top difference point, and also with a composition equal to the bottoms composition. The lower part of the column is covered by stepping off stages in a fashion similar to that in the upper part of the column, and the final count of theoretical stages is then determined. The Ponchon-Savarit method may be used for many situations more complex than the simple one just described: mixed vaporliquid distillate product, side draw streams, multiple feeds, and so on. Standard unit operations textbooks should be consulted for more details on this method. As mentioned, it suffers from a need for enthalpyconcentration data, but even a crude approximation based on linear variation of enthalpy with concentration can be better than the McCabe-Thiele approach if there is a very large difference in the latent heats of vaporization of the two components being distilled Minimum Stages When a distillation column is operated under conditions of total reflux, all the vapor passing up from the top stage is condensed and returned to the column as reflux. Similarly, all the liquid flowing down from the bottom stage is vaporized and returned to the column. This is a closed system, with no feed and no products, but a concentration gradient prevails in the column and mass transfer between the phases takes

20 place. Since there is no distillate product, the reflux ratio is said to be infinite ("total reflux"). Thus, in Fig the stages-reflux curve shows the asymptotic approach to a minimum stage value at very high values of reflux ratio. Operation of a column at total reflux is important in two ways: it is a convenient startup condition that enables a column to be lined out at steady state before feed is processed, and in experimental work it is a simple and yet effective means for obtaining mass transfer information. The number of stages at total reflux is also important in design calculations in that it represents a lower limit to the required stages and it also represents a parameter used in short cut estimates of stage requirements (to be discussed in Section 5.3-7). If graphical methods are used for binary systems, the minimum number of stages may be estimated directly. For McCabe-Thiele, the upper and lower operating lines coincide with the diagonal line at total reflux, and stages are stepped off as shown in Fig For Ponchon-Savarit, the difference points are at positive and negative infinity values on the enthalpy-concentration diagram, and thus the operating lines are vertical. Stages are stepped off as shown in Fig Minimum stages may be determined analytically by means of the Fenske relationship. 5 For a binary mixture of/ (lighter component) and,/, and with the recognition that at total reflux and at any stage «, x Kn yiji -1 and x jn = y jn _,, it can be shown that (5.3-25) since Equation (5.3-25) becomes (5.3-26) (5.3-27) A convenient final form of the Fenske equation is (5.3-28) Equilibrium curve. Mole fraction in vapor Mole fraction in liquid FIGURE Minimum stages, McCabe-Thiele method.

21 Saturated vapor, Equilibrium tie-line Operating line Enthalpy Mole fraction, liquid or vapor FIGURE Minimum stages, Ponchon-Savarit method. Some comments on the use of the Fenske equation are: 1. It can be applied over any part of the column. 2. The average value of the relative volatility, a, is subject to interpretation. Strictly, it is (5.3-29) Normally, it can be simplified to a geometric average of the volatility values at the top and bottom of the column: '5.3-3O) If there is wide variation of relative volatility between top and bottom, an additional value can be used in the average: 3. The value of N includes the reboiler as an equilibrium stage. 4. It can be applied to multicomponent mixtures, as will be discussed below Minimum Reflux Ratio (5.3-31) Minimum stages at total reflux represents one limit of operation of a column. The opposite limit is represented by an infinite number of stages at a theoretically minimum reflux ratio. This is shown in Fig as the asymptotic value of reflux ratio at a very high number of theoretical stages. This lower limit of reflux ratio represents a design parameter for shortcut estimates of stage requirements (to be discussed in Section 5.3-7) and it also guides the designer in assigning an operating reflux ratio as some multiple of the minimum reflux ratio. It does not represent a feasible operating condition, as does the minimum stages case. If graphical methods are used for binary systems, the minimum reflux ratio may be estimated directly. For McCabe-Thiele, it can be determined from the minimum slope of the upper operating line, which can be found graphically and often represents coincidence with the intersection of the q line with the equilibrium curve, as shown in Fig Unusual curvature of the equilibrium relationship can limit the minimum reflux ratio to a higher value as also shown in Fig In stepping off stages, starting at the top, a

22 /\JO G IL9C{IOU IU A9DOL Pinch zone«equilibrium curve Operating line Equilibrium curve Operating line Mole fraction in liquid FIGURE Minimum reflux by McCabe-Thiele method: (a) normal equilibrium curve and (b) equilibrium curve with concavity.

23 Upper difference point Enthalpy Upper operating line and tie-line are colinear Saturated liquid Equilibrium tie-line Mole fraction, vapor or liquid FIGURE Minimum reflux by Ponchon-Savarit method. point would be reached where no further progress could be made; this represents a "pinch zone** where there is no change of composition from tray to tray. Stepping off trays from the bottom would result also in a "pinch zone,** very near the one obtained from the top-down direction. With reference to Fig , the minimum reflux ratio for the case of a saturated liquid feed is (5.3-32) For the Ponchon-Savarit method, a pinch occurs when an operating line coincides with a tie line, thus preventing further stepping of theoretical stages. This is shown in Fig , and normally the pinch occurs in the vicinity of the feed stage. An analytical approach for the estimation of minimum reflux ratio has been published by Underwood 6 and is useful for multicomponent as well as binary systems. There are three basic assumptions made by Underwood: 1. Constant value of relative volatility 2. Constant molal flow of vapor and liquid in the column 3. Pinch occurs at the feed stage The resulting equations of Underwood are (5.3-33) where q is defined as in Eq. (5.3-19) (e.g., q - 0 for saturated vapor feed and q = 1 for saturated liquid feed) and 0 is a root to be obtained from the equation and which has a value between a : and a,, the latter being assigned a value of unity. Equation (5.3-34) is then used to obtain the minimum reflux ratio: (5.3-34) A more rigorous method for estimating the minimum reflux ratio has been published by Chien. 7

24 5.3-7 Mufticomponent Distillation When the feed mixture contains more than two components, the separation is generally termed multicomponent, even though a three-component mixture is also known as a ternary, a four-component mixture as a quarternary, and so on. The key point is that when there are more than two components, the simple procedures such as McCabe-Thiele cannot be used with reliability and it is necessary to use analytical rather than graphical approaches. However, the same principles are used, and the MESH equations are applied at each theoretical stage. KEY COMPONENTS For a multicomponent mixture to be split into two streams (distillate and bottoms) by distillation, it is common to specify the separation in terms of two "key components" of the mixture. The light key will have a specified maximum limit in the bottoms product and the heavy key will have a specified maximum limit in the distillate product. Normally, the keys are adjacent to each other in the ranking of the mixture components according to relative volatility but this is not always the case, and distributed components may have volatilities intermediate to those of the keys. MINIMUM STAGES For multicomponent systems, an approximate value of the minimum number of stages (at total reflux) may be obtained from the Fenske relationship [Eq. (5.3-28)]. In the use of this relationship for multicomponent mixtures, the mole fractions and the relative volatility refer to the light and heavy keys only. However, values for the nonkey components may be inserted in the equation to determine their distribution after the number of minimum stages has been determined through the use of the key components. For a more rigorous approach to the determination of minimum stages, see the paper by Chien. 7 MINIMUM REFLUX RATIO For multicomponent systems, the Underwood method 6 may be used for estimating minimum reflux ratio. Its limitations should be recognized (see Section 5.3-6). The general equations are (5.3-35) (5.3-36) In Eq. (5.3-35), the value of the root < which lies between the values a LK and <x HK must be used. For a more rigorous approach to the determination of minimum reflux ratio for multicomponent systems, see the paper by Chien. 8 DESIGN APPROACH This approach, simply stated, starts with a given separation and reflux ratio and determines the number of theoretical stages required to make the separation. It follows the general approach given in Section for the analytical handling of binary system stage determinations. The pioneer paper on this approach was published in 1932 by Lewis and Matheson 9 and involves stage-by-stage calculations starting at the bottom and working up the column, or starting at the top and working down the column, or working from both ends and matching the feed composition at the feed stage. The difficulty with the method is that until the work is complete, the distribution of components between the distillate and the bottoms will not be known; thus the procedure is iterative and when many components are coupled with a number of stages, it is only feasible to handle the method by computer. Techniques for speeding up a converged computer solution are given by Holland. 10 The input-output information for the Lewis-Matheson method is listed in Table RATING APPROACH This approach starts with an assumed number of stages and reflux ratio and provides as output the separation that can be made. In other words, it rates a given column instead of designing it. Since this approach has convergence advantages, it is the one normally used for computer solutions to multicomponent, multitray distillation systems. The rating approach usually is referenced as the Thiele-Geddes method, based on the original reference in The technique is to assume a temperature profile throughout the column (number of stages being given) and, by starting at either end and working along the profile, arrive at a composition at the other end. If the outcome of such an iteration is a split that does not check the material balance requirements, the profile is varied through successive iterations. The experienced designer can bracket the desired answer with relatively few passes through the computer. Table shows typical input-output characteristics of the Thiele-Geddes method.

25 TABLE Input-Output for Rigorous Stagewise Calculations Input Output Number of stages Feed stage number Feed rate Feed composition Feed enthalpy Reflux ratio Distillate to feed ratio Pressure Rating Method Thiele-Geddes Design Method Lewis-Matheson Distillate composition Bottoms composition Distillate composition Number of stages Bottoms composition Feed stage Feed rate Reflux ratio Feed composition Distillate rate Feed enthalpy Design/minimum reflux ratio Optimum feed stage Pressure The Thiele-Geddes approach is summarized as follows. Consider a stage n in a cascade, the stage being intermediate between the feed and either end of the cascade and not complicated by a side draw or by extraneous heat addition or removal. A mass balance for component / on the tray is For phase equilibria on the stage, (5.3-37) or (5.3-38) (5.3-39) where A n j is the absorption factor on the stage. Combining the mass balance and phase equilibrium relationships, we obtain and (5.3-40) At the top stage N y (5.3-41) At the bottom stage 1, (5.3-42) At the feed stage, by material balance, (5.3-43)

26 Thus, there is an equation for each component for each stage. This set of equations may be solved simultaneously by matrix methods, there being a tridiagonal matrix, N by N (N + 1 by N + 1 including the neboiler or./v -f 2 by N 4-2 if there is also a partial condenser), shown in Fig This approach to the simultaneous (not stagewise) solution of the MESH equations was introduced by Amundson and Pontinen. l2 There is a large literature dealing with design and rating methods for handling multicomponent, multistage calculations rigorously. The methods of solution were discussed in some depth by Friday and Smith 13 and by Wang and Henke, 14 among others. A more recent review was provided by Wang and Wang. 15 It is clear that the computational procedures for the design approach tend to be numerically unstable and are difficult to apply to complex columns with multiple feeds and multiple side draws. Procedures used for the rating approach are not susceptible to important round-off errors and can be used more easily for complex columns. Computer software for rigorous stagewise calculations may be accessed through commercial organizations such as Chemshare Corporation, Simulation Sciences, Inc., and Aspen Technology. APPROXIMATE (SHORTCUT) METHODS It is often sufficient, and certainly expedient, to use approximate methods for estimating the stage requirements for a multicomponent separation. These methods proceed according to the following sequence: 1. Specify the separation, based on the two key components. 2. Calculate the minimum number of stages, using the Fenske relationship (Section 5.3-7). 3. Determine the distribution of nonkey components and the ratio of rectifying to stripping stages, both by the Fenske relationship. 4. Calculate the minimum reflux ratio, using the Underwood method (Section 5.3-7). 5. For a selected operating reflux ratio, employ the results from steps 2 and 4 in an empirical correlation to obtain the required number of theoretical stages. For step 3, some clarification is necessary. The Fenske equation may be used for any two pairs of components. Forcing their distributions to give a minimum number of stages equal to that obtained for the keys is a reasonable basis for estimating distribution: (5.3-44) where LLK = component lighter than the light key HHK = component heavier than the heavy key Also, (5.3-45) and (5.3-46) It will be found that the sum of the stages from Eqs. (5.3-45) and (5.3-46) equals the number of stages computed by Eq. (5.3-44). For step 5, the Gilliland correlation 16 is most often used. It was developed originally as a graphical fit to a number of stagewise calculations that were carried out by hand and is shown in Fig A fit of the curve has been provided by Eduljee: l7 (5.3-47) An alternative to the Gilliland method has been provided by Erbar and Maddox 18 and is shown in Fig This correlation is based on more extensive stagewise calculations, using rigorous computer solutions, and should give slightly better results than the method of Gilliland.

27 Top stage (AO Stage N - 1 Stage N -2 Stage / + 1 Feed stage (/) Stage/- 1 Stage 2 Stage 1 Reboiler (stage 0) FIGURE Tridiagonal matrix formulation of multistage distillation material balances. A similar matrix is required for each component.

28 FIGURE Gilliland correlation for theoretical stages as a function of reflux ratio (Ref. 16). Bosed on Underwood Extropoloted R MIN FIGURE Erbar-Maddox correlation for theoretical stages as a function of reflux ratio (Ref. 18).

29 FEED STAGE LOCATION The optimum feed stage location is the one that gives the fewest numbers of stages for the required separation. On this basis, Gilliland 19 developed criteria for evaluating the optimum feed location. He dealt with liquid, liquid-vapor, and vapor feed cases. For a liquid feed, the criterion is (5.3-48) where / is the feed stage and / + 1 the stage above the feed. This equation states that the ratio of key components in the feed should be matched closely with the ratio of keys in the downflow to the feed tray and in the downflow from the feed stage. In practice, an effort is made to match as closely as possible the composition of the feed and that of the appropriate stream (vapor or liquid) leaving the feed stage. Alternative feed locations usually are provided to allow for variations in column operation as well as inaccuracies in composition profile calculations Example Design A deethanizing column is to be designed to recover an ethane concentrate from a feed stream containing six light hydrocarbons. Operating conditions and product specifications are given in Table Determine the required number of theoretical and actual stages when the operating reflux ratio is 1.25 times the minimum. Use both shortcut and rigorous computational approaches. (Note: This problem is taken from the paper by Fair and Bolles. 20 ) The Shortcut Method. The shortcut calculation is carried out as follows: First, a preliminary material balance is set up on the assumption that no methane appears in the bottoms and no propane or heavier components appear in the distillate. The balance, in lb-mole/h is as follows: Feed Distillate Bottoms Methane Ethane (LK) Propylene (HK) Propane /-Butane /i-butane TABLE Operating Conditions and Product Specifications for a Six-Component Deethanizing Column Feed Stream Components Mole % a Methane Ethane Propylene Propane z'-butane n-butane Design Separation Concentration of propylene in distillate, 2.5 mol % Concentration of ethane in bottoms, 5.0 mol % Operating Conditions Condenser pressure, 400 psia (27.2 atm) Top-plate pressure, 401 psia (27.3 atm) Pressure drop per plate, 0.1 psi Feed condition, liquid at bubble point Distillate condition, liquid at bubble point Reflux subcooling, none Murphree plate efficiency, 75%

30 Minimum stages are then calculated by the Fenske equation (5.3-28) using mole ratios of the keys in place of mole-fraction ratios: Stages for the rectifying section (including the feed stage) are calculated by means of the same equation: Calculating in a similar fashion the stages below the feed (including the reboiler), N MS = Minimum reflux ratio is calculated by the Underwood equations. First, Eq. (5.3-35) is used to obtain a value of the root <, noting that for a liquid feed at its boiling point q = 1.0: From which, <f> = Then, substituting in Eq. (5.3-36), From which, R M» For an operating reflux ratio of (1.25 times the minimum), the Erbar-Maddox correlation is used to find the stage requirement. With reference to Fig , from which, N M /N = Accordingly, N = N M /0A7 = 6.79/0.47 = The results of the calculations are summarized in Table At the operating reflux of 1.722, the column requires 13.5 theoretical plates or 18 actual plates, assuming an overall column efficiency of 75% and a reboiler efficiency of 100%. A final step in the calculation would be to adjust the material balance TABLE Results of Shortcut Hand Calculations for the Six-Component Deethanizer Minimum Parameters Minimum reflux ratio, R M Minimum theoretical stages Feed and above 3.6 Below feed, including reboiler 3.2 6X~ Results at Reflux Ratio (mm. x 1.25) Operating reflux ratio, R Theoretical Actual Overall column efficiency, % Plates Feed and above Below feed, including reboiler 6.8 _

31 for propane and heavier materials that would be found in the distillate. The Fenske equation is used, along with the appropriate relative volatility. Rigorous Calculation. The problem was then solved using a rigorous plate-to-plate rating-type computer program. The results are shown in Table The same vapor-liquid equilibrium ratio (K) charts were used for the rigorous solution as for the shortcut. For the rigorous, however, values of K t were combined with total pressure P, and the K ( P product was treated as 4 Effective vapor pressure*' in the Antoine equation. The rigorous program was run in a trial-and-error fashion, with constant reflux ratio of (from the shortcut) and with iterations of D/F ratio, total plates, and feed plate location. The number of actual plates in the column turned out to be 20. Table shows stage-by-stage flows, temperatures, pressure, and compositions. It also shows condenser and reboiler duties. The final material balance, in lb-mole/h, is: Feed Distillate Bottoms Methane Ethane Propylene Propane /-Butane w-butane TOOO 3O0 600 After the theoretical or actual stage requirements have been calculated, the final step is that of specifying the optimum distillation column (fractionator); that is, the proper combination of column height, column diameter, and contacting internals must be chosen. 5.4 SPECIFICATION OF VARIABLES Separation There are four common ways of expressing the required separation to be made by the distillation column: purity of one or more products, allowable impurities in one or more products, recovery of one or more feed components, and measurable properties of one or more of the products. Examples of these are as follows: Purities 99.6 mol % minimum purity of light key in distillate product Impurities 0.3 mol % maximum content of heavy key in distillate product Recovery 95 % minimum of light key in feed, to be contained in distillate product Properties Distillate product to have a Reid vapor pressure of 45 Ib// in. 2 minimum These may be in combination and not limited to one of the keys. However, one must be careful not to overspecify or underspecify the separation, as discussed below Problem Specification To execute the design of a distillation column, C -H 6 variables must be specified, where C is the number of components in the feed mixture. (This assumes that reflux is saturated.) Of these, C + 2 are always specified: Feed composition C 1 Feed rate 1 Feed enthalpy 1 Pressure 1 There are many possible combinations of the other four variables. Some typical groupings are as follows:

32 TABLE Computer Results of a Rigorous Plate-to-Plate Design Calculation for a Six-Component Deethanizer Plate Liquid Compositions (mol %) n-butane /-Butane Propane Propylene Ethane Methane Vapor Flow Liquid Flow Pressure Temperature Plate Condenser Feed tray Reboiler

33 TABLE {Continued) Reflux ratio Reflux rate Plate Number Top Liquid 21 Bottom Liquid 0 Condenser duty Reboiler duty Feed D D 05 Flow rate Temperature Pressure Enthalpy Composition Methane Ethane Propylene Propane /-Butane rt-butane Percent Recovery Methane Ethane Propylene Propane /-Butane N-Butane

34 1. For "rating" approach (Thiele-Geddes, Table 5.3-1) (a) Number of stages (b) Feed stage number (c) Reflux ratio (d) Distillate to feed ratio 2. Alternative for "rating" approach (a) Rectifying stages^ f Number of stages (b) Stripping stages j (^Feed stage (c) Fractional recovery of light key in distillate (d) Concentration of light key in distillate 3. For "design" approach (Lewis-Matheson, Table 5.3-1) (a) Distillate composition (b) Bottoms composition (c) Design/minimum reflux ratio (d) Feed location (usually at optimum) 4. Alternative for "design" approach (a) Composition of light key in distillate (b) Composition of light key in bottoms (c) Reflux ratio (d) Feed location (usually at optimum) It should be clear that the above groupings are examples, and other possibilities exist. Alternative 4 commonly is used for approximate calculations. Care must be taken not to overspecify the distillation separation problem. 5.5 SPECIAL DISTILLATIONS Azeotropic Distillation AZEOTROPES Many liquid mixtures exhibit azeotropes at intermediate concentrations such that the liquid and its equilibrium vapor have the same composition. No separation of this concentration is possible by partial vaporization. A binary mixture may have a minimum boiling azeotrope, where the boiling temperature of the azeotrope is less than that of the pure components, or a maximum boiling azeotrope, where the boiling temperature is higher than that of the pure components. About 90% of the known azeotropes are of the minimum variety. The presence of an azeotrope is one indication that a mixture is not ideal, that it has deviations from Raoult's law (see Chapter 1 and Section 5.2 of the present chapter). Close-boiling mixtures are more likely to exhibit azeotropism than wide-boiling mixtures; when there is more than 30 0 C boiling point difference, it is quite unlikely that an azeotrope will be present. Thus, the combination of close-boiling and nonideality is one that can lead to the presence of an azeotrope. Figure shows equilibrium diagrams for binary systems containing maximum boiling (acetonechloroform) and minimum boiling (ethanoi-water) azeotropes. It also shows an example of an azeotrope which, when condensed, forms two liquid phases (/i-butanol-water); this is called a heterogeneous azeotrope. Most investigations of azeotropes have dealt with binary or ternary mixtures. The binary pairs of a multicomponent mixture may separately form azeotropes, but these are submerged by the possible azeotropes involving the full mixture. It is sometimes possible to utilize binary pair azeotrope information in estimating the role that a multicomponent azeotrope will play in the distillation separation. As an example, the ethanol-water system exhibits a minimum boiling azeotrope. At atmospheric pressure, the boiling points are Ethanol-water azeotrope Ethanoi Water C 78.4 C C The azeotrope distills overhead and its water content (4.0 vol %) is supplied fully by the usual content of water in the feed. If benzene is added to the azeotrope and the mixture is fed to another column, an expanded range of possible boiling points (at 1 atm) is found:

35 Ethanol-benzene-water azeotrope Ethanol-benzene azeotrope Benzene-water azeotrope Ethanol-water azeotrope Ethanol Benzene Water C C C 78.2 C C C C Now for limited amounts of water and benzene, the low-boiling ternary azeotrope dominates and becomes the distillate product. With careful control of the amount of benzene added, all the water and the benzene are taken overhead. This particular system will be used as an example later in the present section. An extensive tabulation of azeotropes has been compiled by Horsley. 1 An older compilation is that of Lecat. 2 Certain nonideal vapor-liquid equilibrium models are useful for predicting azeotropic behavior of binary systems; in particular, the model of Renon and Prausnitz 3 is useful in this regard because it can handle the two liquid phases associated with heterogeneous azeotropes. The Horsley book also contains guidelines for the prediction of azeotropes. AZEOTROPIC DISTILLATION This term usually is applied to cases where an extraneous material, called an entrainer, is added to a mixture to make a distillation separation feasible. In this way, a problem involving a close-boiling mixture is made tractable by the addition of an entrainer that will azeotrope with one of the components to give, in effect, a respectable relative volatility between the nonazeotroping component and the azeotrope (treated as a pseudocomponent). Typically, the azeotrope has the higher volatility and becomes the distillate product. A difficulty is that the extraneous material must itself be separated from the product and, if valuable, recycled back to the process. This leads to the desirability of employing a heterogeneous azeotrope that through phase separation can provide the entrainer recovery that is needed. Other entrainer separation methods include solvent extraction and distillation under a pressure such that the azeotropic composition is different or that the azeotrope is absent. Figure shows a flow diagram for the example of separating water from ethanol, using benzene as the entrainer. A low-boiling ternary azeotrope is formed, as indicated above, and is taken overhead. Note that when the azeotrope vapor is condensed, two liquid layers result (heterogeneous azeotrope). The water layer contains residual ethanol and benzene and is taken to a stripping column for recovery of the entrainer. Figure shows the distillation path on the ternary phase diagram. 4 In some cases, a mixture is separated on the basis of its contained azeotropes (i.e., no extraneous material is added) and this may also be called azeotropic distillation. An example, shown in Fig , is the azeotropic drying of toluene. 5 The water-toluene azeotrope is taken overhead, leaving the desired dry toluene as bottoms. Near-azeotrope vapor CW Condenser Alcohol-water feed if it Benzene makeun Organic layer reflux Steam Decanter Aqueous layer it IO $5 Steam Anhydrous alcohol Alcohol-water to recycle FIGURE Dehydration of alcohol by azeotropic distillation, using benzene as entrainer to form a low-boiling ethanol-water-benzene azeotrope.

36 Ethanol Bottoms, dehydration column Ethanol-water azeotrope Distillation path, below feed, dehydration column Singlephase region Feed stage Distillation path, above feed, dehydration column Benzene-ethanol azeotrope Distillation path, stripping column Bottoms, stripping column Tie line Ternary azeotrope Feed, stripping column Ref ux dehydration column Two-phase region Water Benzene FIGURE Ternary phase diagram for ethanol-benzene-water, showing distillation paths for the columns shown in Fig Composition in mole percent or mole fraction. (Based on Ref. 4.) AZEOTROPIC DISTILLATION CALCULATIONS Methods for determining equilibrium stages for azeotropic distillation are the same as those discussed in Section 5.3. As indicated in Fig , the distillation path may cross over into the two liquid phase region, and one must be cautious about the design of contacting equipment when this condition is present. Research has shown that with good aeration, conventional trays may be used when two liquid phases are present. 6 Hoffman 7 has discussed in detail methods for designing azeotropic distillation systems. Black et al. 8 provide insight on the use of computers for making azeotropic distillation calculations. Gerster 9 and Black and Ditsler 1 " show comparisons between azeotropic and extractive distillation approaches for handling the same problem. SELECTION OF ENTRAINER Guidelines for entrainer selection have been provided by Gerster 9 and Berg.! ' The latter author has listed the following desirable properties of an entrainer, for hydrocarbon separations: 1. Should boil within a limited range ( C) of the hydrocarbon to be separated. 2. Should form, on mixing with the hydrocarbon, a large positive deviation from Raoult's law to give a minimum azeotrope with one or more of the hydrocarbon types in the mixture. 3. Should be soluble in the hydrocarbon. 4. Should be easily separable from the azeotrope. 5. Should be inexpensive and readily obtainable. 6. Should be stable at the temperatures of the distillation. 7. Should be nonreactive with the hydrocarbons being separated and with the materials of construction of the equipment Extractive Distillation As in the case of azeotropic distillation, an extraneous material is added to the mixture in the case of extractive distillation. However, the function of this material, called an extractive agent or simply a solvent, is different. It is designed to enhance the relative volatility of the key components by influencing the nonideality of the mixture. The solvent is normally a high-boiling material and in some cases may form

37 Dry toluene Wet toluene below saturation 4.5 ft diam. 25 valve trays Reflux accumulator Water FIGURE Azeotropic drying of toluene, with residual water content of less than 5 ppmw (Ref. 5). loose chemical bonds with one of the keys, with the result of a suppressed effective vapor pressure; this is discussed in connection with solvent selection by Berg 11 and by Ewell et al. 12 As in the case of azeotropic distillation, there is the problem of separating the solvent from the product, but for extractive distillation the problem is much simpler, since the solvent is normally quite high boiling, beyond the range of azeotrope formation, and simple distillation usually is sufficient to separate the solvent for reuse. EXTRACTIVE DISTILLATION CALCULATIONS Determination of stage requirements for extractive distillation follows the approaches discussed in Section 5.3. It is necessary to have vapor-liquid equilibrium data, and these are measured conventionally. A representativerelationbetween solvent/nonsolvent ratio and relative volatility is shown in Fig , taken from the papers of Gerster 9 and Drickamer et al. 13 From the figure it is clear that various combinations of solvent content and stage requirements are possible, and the optimum solvent ratio must be determined. Figure deals with the separation of toluene from methylcyclohexane using phenol as the solvent. The **natural'* volatility of the binary mixture is shown as the bottom line (no phenol present) and the enhancement of this volatility by phenol addition is significant. A flow diagram of this separation process is shown in Fig The solvent, being a low boiler, must be added high in the column to ensure volatility enhancement throughout the column. Additional stages are used above the solvent feed point to remove any entrained or volatilized solvent from the vapors leading to the distillate product. In many cases it is possible to carry out stage determinations on a solvent-free basis, using a graphical approach such as McCabe-Thiele. An example of this approach is shown in Fig l4 Reflux ratio and boilup specifications are made as if there were no solvent present. If the feed stream causes a large change in the solvent/nonsolvent ratio at the feed stage, then separate equilibrium curves are needed for the rectifying and stripping sections. Computations for extractive distillation are covered in detail by Hoffman 7 and Smith. 15 Algorithms for rigorous stage-to-stage energy and material balances (such as Thiele-Geddes) may be used if the multicomponent equilibria are established. Process design considerations are discussed by Kumar et al. 16 Case studies of extractive distillation separations are provided by Black and Ditsler, 10 Gerster, 17 Hafslund,' 8 and Bannister and Buck. 19 Stage efficiencies are characteristically low, because of the heavy solvents involved, but are amenable to mass transfer modeling 16 and simulation in small-scale Oldershaw equipment (see Section 5.9). SOLVENT SELECTION Approaches to the selection of an extractive distillation solvent are discussed by Berg," Ewell et al.' 2 and Tassios. 20 In general, selection criteria follow those for azeotropic entrainers: