FUNDAMENTALS OF MULTICOMPONENT DISTILLATION Charles D. Holland Texas A&M University McGraw-Hill Book CompanyChapter 1 CONTENTS Preface Introduction to the Fundamentals of Distillation Fundamental Principles Involved in Distillation Separation of Multicomponent Mixtures by Use of One Equilibrium Stage “Multiple Stage Separation of Binary Mixtures Separation of Multicomponent Mixtures at Total Reflux Notation Problems References Development and Application of the Theta Method of Convergence to Conventional Distillation Columns Equations Required to Deseribe Conventional Distillation Columas Formulation and Application ofthe @ Method of Convergence, the K, Method, andthe Constant- ‘Composition Method Convergence Characteristics ofthe 0 Method of Convergence, the K, Method, nd the Constant-Composition Method Other ropis: Pressure Efects, Nonidea! Solutions, and (Other Specifications Notation Problems ReferencesChapter 3 Chapter 4 4 42 43 44 Chapter 5 st Chapter 6 61 62 6a Application of the Theta Method of Convergence to Complex Columns and to Systems of Columns Complex Disillation Columns Systems of lteeonnected Distillation Columns A Generalzed Formulation fora Sytem of Columas in Which ve Tot [Ae Specified Notation Problems References The 2N Newton-Raphson Method Formulation of the 2’ Newton-Raphson Method for Single Columns [Numerical Methods for Solving the 2 Newton-Raphson Equations Systems of Columns Comparison of Procedures 1,2, 3, and the Cohumn Modular and System Modiulae Methods Problems References Almost Band Algorithms of the Newton- Raphson Method Almost Band Algorithms for Absorbers and Strippers, Independent Variables {yy} and (7) ‘Almost Band Algorithms for Conventional and Complex Disillaton Columns Modifications of Broyden's Method The Boston Sullivan Algorithm Problems References Appendix $1 Development ofthe Broyden-Householder ‘Algorithm for Sparce Matrices ‘Systems of Azeotropic and Extractive Distillation Columns ive Characteristics of Azcotropic and Extractive Processes Solution of Problems Involving Single Columns Used to et Atcouoic and Extractive Disiltions sms of Columns in the Service of Sept Nonidea Sutona Notation Problems References 87 87 101 m2 us 116 0 ni m ur 156 m 175 176, 18 180 185 195 210 2 a 216 216 2 24 246Chapter 7 nM 72 B 14 Chapter 8 ot 92 93 Chapter 10 to 102 Solution of Systems of Columns with Energy Exchange Between Recycle Streams Columns Having a Common Condenser and Reboiler EEnoray Exchange Between Recycle Streams of Systems of Distillation Columns Energy Transer by Use of rim Heat Exchangers ‘Other Applications ofthe Theta Methods Notation Problems References Distillation Accompanied by Chemical Reaction ‘Application ofthe Theta Method of Convergence 10 Distillation Columns in which Chemical Reactions Occur Formulation of the N{r + 2) Newlon-Raphson Method Formulatien of an Almost Band Algorithm Notation Problems References Optimum Design and Operation of Conventional and Complex Distillation Columns Procedure 1. Determination ofthe Minimum Number of Stages Required to Eflet Specified Separation ata Given Reflux Ratio for Conventional and Complex Distillation Columns Procedure 2. Optimum Economic Design of Conventional and Comp:x Distillation Columns Procedure 3. Minimization of the Reflux Ratio for Existing Conventional and Complex Distillation Columns Notation Problems References Appendix 1 Approximate Solutions at Total Reflux ‘Appendix $-2 Approximate Solutions at Operating Reflxes ‘Appendix 83 A’Modiied Form ofthe Complex Method of Box for Otjective Functions Having No Constraints Appendix 4 Formulation ofthe Eeonomic Objective Function Characteristics of Continuous Distillation Columns at Various Modes of Operation ‘Continuous Distition Columns at Total Reflux, Type 1 (Lj¥joy =1, F =D + B,D 40, B40) ‘Continuous and Batch Distillation Columns at Total Reflux in Both Sections, Type 2: (D = 0, 8=0, F ~0) 28 249 263 268 m m m4 as 29 302 as x20 325 26 327 328 33 335 no 340 30103 Chapter 11 ne 2 Chapter 12 4 2 Chapter 13 nt 2 83 Chapter 14 Mt 142 Operating Characteristics of Continuous Distillation Columas over Wide Ranges of Distillate and Reflux Rates, Notation Problems References Conventional and Complex Distillation Columns at Minimum Reflux Determination of Produet Distributions for Columns with Infinitely Many Stages by Use of the @ Method Determination of the Minimum Reflux Ratio by the 0 Method [A Newion-Raphson Formulation: Two Independent Variables Per Stage ‘An Almost Band Algorithm Formulation of the Newton Raphson Method Proof ofthe Existence ofthe Reetilying and Stripping Section Pinches Notation Problems References Design of Sieve and Valve Trays Single-Pass Sieve Trays with Crossflow Valve Trays Notation Problems References Application of the Fundamentals of Mass Transfer to Plate Efficiencies and Packed ‘Columns Fundamental Relationships for Mass Transfer between Vapor and Liquid Phases Plate Eficienies Packed Distillation Columns Notation Problems References Thermodynamic Relationships for Multicomponent Mixtures Fundamental Priniples of Thermodynamics Needed in the Calculation of Vapor-Liquid Equilibria and Enthalpes of Multicomponent Mixtures Equations of State and Their Use in the Prediction of K Values and Enthalpies ass 36 302 364 365 365 a2 393 or 410 43 ais a7 432 49 4a aa 45, 403 454 470 486 49 9 a2 493 suChapter 15 Ist 132 133 Use of Multiple Equations of State forthe Caleulation of K Values Estimation ofthe Fugacity Coefcients for the Vapor Phase of Polar Gas Mixtures Calculation of Liquid-Phase Activity Coefcints Notation Problems References Selected Topics in Matrix Operations and Numerical Methods for Solving Multivariable Problems Storage of Large Sparse Matrices Sealing of Mateices Numerical Methods fr Solving Multivariable Problems Problems References Appendixes Matrix Norms and Theorems Equilibrium and Enthalpy Data Indexes ‘Author Index ‘Subject Index 528 sat 50 558 539PREFACE This book constitutes ar in-depth treatment of the subject of multicomponent distillation. It begins with first principles and goes to the frontiers of the subject. Each topic is introduced in an elementary and fundamental manner which makes the book suitable for the undergraduate student, the graduate student, and the practicing engineer. The subject matter is presented in the order of increasing “ifficulty and complexity. ‘The gap between the treatment of binary and multicomponent mixtures is closed in Chap. 1. This chapter is initiated by presenting the fundamental relationships and techniques needed for making bubble-point and dew-point calculations, and it is concluded by the presentation of techniques for solving 2 variety of special types of problems such as the separation of a multicomponent mixture by a single-stage flash process and the separation of a multicomponent mixture by use of multiple stages at the operating condition of total reflux. In Chaps. 2 through 5, the theta methods and variations of the Newton- Raphson method are applied to all types of single columns and systems of ‘columns in the service of separating both ideal and nonideal solutions. Applica- tions of the techniques presented in Chaps. 2 through 5 to systems of azeotropic and extractive distillation columns are presented in Chap. 6. An extension of these same techniques as required for the solution of problems involving energy exchange between recycle streams is presented in Chap. 7. Special types of separations wherein the distillation process is accompanied by chemical reactions are treated in Chap. 8 In Chap. 9, all ofthe techniques developed in Chaps. 1 through 8 are brought to bear in the design and operation of conventional and complex distillation ‘columns. To complete the in-depth treatment of multicomponent distillation, the special topics of total reflux, minimum reflux, design of valve and sieve trays, plate efficiencies, design of packed columns, thermodynamic relationships, and selected numerical methods ate presented in Chaps. 10 through 15. A Sulu tions Manual may be obtained (without cost) by Faculty members by writing directly to me or to McGraw-Hill,Since the writings of any author are influenced by all that he has met, 1 am deeply indebted to all of my teachers, fellow faculty members, students, and the many past and present workers in the field of distillation, In particular, I wish to thank Professors P. T. Eubank and D. T. Hanson of the Department of Chemical Engineering as well as Professors Emeriti K, C. Klipple and H. A. Luther of the Department of Mathematics for their many helpful suggestions. The direction and advice generously offered by N. J. Tetlow and Ron McDaniel of Dow Chemical Company is appreciated immersely. I also want to thank Dr. Tetlow for his contributions to Chap. 14 (Thermodynamic Relationships for Multicomponent Mixtures) as coauthor. The helpful suggestions provided by W. L. Bolles of Monsantoare very much appreciated. For the support ofthe research (upon which ‘much of this book is based) by David L. Rooke, Donald A. Rikard, and Holmes H.MeClure (allof Dow ChemicalCompany), lam most thankful. Also, support of research provided by the Texas Ergineering Experiment Station and the Center for Energy and Mineral Resources is appreciated. To both former and present graduate students (Najeh S. Al-Haj-Ali, G, W. Bentzen, Andy Feng, S, E. Gallun, Alejandro Gomez M. J. R. Haas, F. E. Hess, Alicia Izarraraz, P. E. Mommessin, and G. P. Pendon) who participated inthis research, [salute you for your many contributions and I shall always be indebted to you. Finally, I want to pay special tribute to my ‘Staff Assistant, Mrs. Wanda Greer, who helped make this book possible through her loyal service and effective asistance over the past eight years in the discharge of my administrative responsibilities Charles D. HollandCHAPTER ONE INTRODUCTION TO. THE FUNDAMENTALS OF DISTILLATION {In this chapter, the fundamental principles and relationships involved in making ‘multicomponent distillation calculations are developed from first principles. To enhance the visualization of the application of the fundamental principles to this, separation process, a variety of special cases are considered which include the ‘determination of bubble-point and dew-point temperatures, single-stage flash sep- rations, multiple-stage separation of binary mixtures, and multiple-stage sepa- ration of multicomponent mixtures at the operating conditions of total reflux. ‘The general objective of distillation is the separation of compounds that have different vapor pressures at any given temperature. The word distillation as used herein refers to the physical separation of a mixture into two or more fractions that have different boiling points. + Ifa liquid mixture of two volatile materials is heated, the vapor that comes ~ off will have a higher concentration of the lower boiling material than the liquid from which it was evolved. Conversely, if a warm vapor is cooled, the higher boiling material has a tendency to condense in a greater proportion than the lower boiling material. The early distillers of alcohol for beverages applied these fundamental principles. Although distillation was known and practiced in an- tiquity and a commercial still had been developed by Coffey in 1832, the theory of distillation was not studied until the work of Sorel"* in 1893. Other early wor- kers were Lord Rayleigh" and Lewis.* Present-day technology has permitted the large-scale separation by distillation of ethylbenzene and p-xylene, which have only a 39°F difference in boiling points (Re. 1).2 FUNDAMENTALS OF MULTICOMPONENT DISTILLATION Clear oF voper-feee fiquid Figure 1-1 Interior fa column equipped with seve trays, AA distillation column consists of a space for contacting vapor and liquid streams for the purpose of effecting mass transfer between the two. phases ‘Although the contacting of two phases is generally eflected by a series of plates (or trays), packed columns are becoming more widely used as discussed in Chap. 13. However, in the development ofthe fundamentals of the various caleu Jational procedures in this and subsequent chapters, itis supposed that the column is equipped with plates, Tn normal operation, there is a certain amount of liquid on each plate, and some arrangement is made for ascending vapors to pass through the iquid and ‘make contact with it. The descending liquid flows down from the plate above through a downcomer, across the next plate, and then over a weir and into another downcomer to the next lower plate as shown in Fig. 1-1. For many Years, bubble caps were used for contacting the vapor with the liquid. A variety _of designs of bubble caps are shown in Fig, 1-2. These contacting devices pro- * mote the production of small bubbles of vapor with relatively large surface areas. Over the past 20 years, most of the bubble-cap trays have been replaced by other types of contacting devices. New columns are usually equipped with either __taloe trays (ee Fig, 1-3) or sieod Ways (see Fig. -1) sometimes called perforated > “trays. In valve trays, the valve opens wider as the vapor velocity ineveases and closes as the vapor velocity decreases. This feature of opening and closing allows the valve to remain immersed in liquid and thereby preserve a liquid seal over Wide ranges of liquid and vapor flow rates. : Distillation columns have been built as high as 338 et, Diameters as large as 50 feet have been used. Operating pressures for distillation columns have been reported which range from 15 mmHg to 500 Ibjin? abs. A typical commercial in- stallation is shown in Fig. -4INTRODUCTION TO THE FUNDAMENTALS OF DISTILLATION 3 Figure 1-2 Various types of bubble caps used i dsiltion columns (By courtesy of Glisch Ine) Figure 1-3 Portion of a Giisch Vt ballast tr: (By courtesy of Glseh ne.)INTRODUCTION TO THE FUNDAMENTALS OF DISTILLATION 5. {As indicated in Fig. 1-5, the overhead vapor V3, upon leaving the top plate, centers the condenser where itis either partially or totally condensed. The liquid formed is collected in an accumulator from which the liquid stream L, (called reflux) and the top product stream D (called the distillate) are withdrawn. When the overhead vapor ¥; is totally condensed to the liquid state and the distillate D is withdrawn as a liquid, the condenser is called a total condenser. If V2 is partially condensed to the liquid state to provide the reflux L, and the distillate D iis withdrawn as a vapor, the condenser is called a partial condenser. The i ie ty Ea Wf Trees fe fy sf (Feed plate) Figere 1-5 Sketch ofa conventional cola ia which the totabiow rates are constant within the resting and stripping sections.{6 FUNDAMENTALS OF MULTICOMPONENT DISTILLATION amount of liquid reflux i commonly expressed in terms ofthe reflux ratio, L/D. Although the internal liquidto-vapor ratio L/V is sometimes referred t0 a8 the internal refx ratio, the term reflux ratio will be reserved herein to mean L,/D. The liquid that leaves the bottom plate of the column enters the reboler, where itis partially vaporized. The vapor produced is allowed to flow back up through the column, and the liquid is withdrawn from the reboiler and called the bottoms oF bottom produet B. In practice, the reboiler is generally located ex- ternal fom the column 1-1 FUNDAMENTAL PRINCIPLES INVOLVED IN DISTILLATION To compute the composition of the top product D and the bottom product B which may be expected by use of a given distillation column operated at a given set of conditions itis necessary to obtain a solution to equations of the follow- ing types: 1. Equilibrium relationships 2. Component-material balances 3. Total-material balances 4, Energy balances Consider first the subject of equilibrium relationships. Physical Equilibrium A two-phase mixture is said to be in physical equilibrium ifthe following condi- tions are satisfied (Re. 3) 1. The temperature T" of the vapor phase is equal to the temperature T* of the liquid phase, 2. The total pressure P" throughout the vapor phase is equal to the total pressure P' throughout the liquid phase. (a) 3. The terdency of each component to escape from the liquid phase to the vapor phase is exactly equal to its tendency to escape from the vapor phase to the liquid phase. In the following analysis it is supposed that a state of equilibrium exists, Th=Te=T, PP and the escaping tendencies are equal. Now consider the special case where the third condition may be represented by Raoult’ law Py. = Pix, (1-2)INTRODUCTION TO THE FUNDAMENTALS OF DISTILLATION 7 where x; and y, are the mole factions of component 7 in the liquid and vapor phases, respectively, and P; is the vapor pressure of pure component iat the temperature T of the system ‘The separation of a binary mixture by distillation may be represented in two-dimensional space while n-dimensional space is required to represent the separation of a multicomponent mixture (i> 2).The graphical method proposed bby MoCabe and Thiele for the solution of problems involving binary mixtures is presented in a subsequent section. The MeCabe-Thiele method makes use of ‘an equilibrium curve which may be obtained from the “boiling-point diagram.” Construction and Interpret for Binary Mixtures jon of the Boiling-Point Diagram ‘When a state of equilibrium exists between a vapor and a liquid phase composed ‘of two components A and B, the system is described by the following set of independent equations Pg = Pads Eulbrium Prem Pade relationships (13) Yat yond eet eet where itis understood that Raoult’ law is obeyed. Since the vapor pressures P and Pp depend upon T alone, Eq. (I-3) consists of four equations in six un- knowns, Thus, to obtain a solution to this et of equations, two variables must be fixed. [Observe that this result is in agreement with the Gibbs phase rule: P+ =e+ 2. For the above case, the number of phases # = 2, the number of ‘components ¢ = 2, and thus the number of degrees of freedom ¥° = 2, that is, the number of variables which must be fixed is equal to 2,] In the construction of the boiling-point diagram for a binary mixture, the total pressure P is fixed and a solution is obtained for each of several temperatures iying between the boiling point temperature T, of pure A and the boiling-point temperature 7, of pure B at the total pressure P. That is, when T = Ty, P, = Pand when T = Ty, Pa = P. ‘The solution of the set of equations (Eq. (1-3)] for x, in terms of Pa, P and P is effected as follows. Addition of the first two equations followed by the elimination of the sum of the y’s by use of the third expression yields P= Paxat PoXxe (1-4) Elimination of x» by use of the fourth equation of the set given by Eq, (1-3) followed by rearrangement of the result so obtained yields xa pote (5)Figure 1-6 The boting point diagram, From the definition of a mole fraction (0 <.x4 <1), Bq. (1-8) has & meaning Solution at a given P for every T lying betwecn the botling-point temperatures , and Ty of pure 4 and pure B, respectively. Alice x, has bec computed by tse of Eq (1-5) atthe specifed P and T, the corresponding valve oly which sin esilibrium with the value of sy 50 obtained i computed by ike ofthe frst expression of Eq (13). namely, Pa vam (Bu (16) By plotting 7 versus x, and T versus y,, the lower and upper curve, respec tively, of Fig. 1-6 are typical of those obtained when component is more volatile than B. Component A is said to be more volatile than component B, if for all T in the closed interval T, << Tg, the vapor pressure of A is greater than the vapor pressure of B, that is, P, > Py. The horizontal lines such as CE that join equilibrium pairs (x, y), computed at a given T and P by use of Eqs. (1-3) and (1-6), are commonl; called te lines Example 1-1 (Taken from Ref. 6 by courtesy Instrument Society of America). By use of the following vapor pressures for benzene and toluene {taken from The Chemical Engineer's Handbook, 2d ed, J. H. Perry (ed.) MeGraw-INTRODUCTION 10 THE FUNDAMENTALS OF DISTILLATION 9 Hill, New York, 1941}. compute the three equilibrium pairs (x,y) om a boiling-point diagram which correspond to the temperatures T = 80.02°C, 100°C, and T= 1104°C. The total pressure is fixed at P= 1 atm Given: “Temperature P (benzene) P (oluene) coy (rots) (mg) 1 3000 482 ano as ano ans 590 ess roast 7000 1m the more recent editions, the vapor pressure ‘01704 Simm for toluene at 108°C inaceuraey ited 57405 06 141 mm, SoLUTION ALT = 8002°C, P, gives 100, and P = 760, Then Eq, (1-5) ‘Thus yan Ax gel Therefore at the temperature versus y, coincide at (1, 80.02). 80002°C, the curves T versus x, and T At T= 1104°C, P,= 1748, Py 7160, and P= 760, Then by Eq, (1-5) Xa Tas — 760 v and thus 748 vam [Fe] =0 Hence, the curves T versus x, and T versus y, again coincide at the point (0, 104) ‘At any temperature between T, and Ty, say T = 100°C, the calculations are carried out as follows 760-559 _ 201 *4= 344 — 559 ~ 785, meadand 1344 v= Ge, ‘These results give the point (0.256, 100) on the T versus x. curve and the point (0.453, 100) on the T versus y, curve. Other points on these curves for temperatures lying between T, and T, are located in the same manner. 02s) = 0453 A boiling-point diagram is @ most convenient aid in the visualization of phase behavior. For dfiniteness, suppose P is fixed at 1 atm. Consider fist the case ofthe liquid mixture of A and Bata temperature Tj, ata pressure of | atm, and with the compesition x, = xy. X4=1—X,. As indicated by Fig 1-6, such a mixture is inthe single-phase region, Suppose the pressure i held fixed att atm throughout the course of the following changes. Firs, suppose the mixture is heated to the temperature 7, At this temperature, the frst evidence of a vapor phase, a “bubble of vapor.” may be observed, The temperature 7, is called the bubble-point temperature of aliquid withthe composition x, The mole fraction of A in the vapor in equilibrium with this liquid is seen to be y. As the mixture is heated from 7, to 7;. vaporization continues. Since A has a greater escaping tendency than B, the liquid becomes leaner in A (xy < x,) The relative amounts of A and B vaporized also depend on thee relative amounts in the liquid phase As the liquid phase becomes richer in B, the vapor phase also becomes richer in B (y2 <1). Point D (the intersection of the horizontal fine passing through T; And the vertical line passing though x, is sen to li in the two-phase region. As outlined in Prob. 1-22. i can be shown that the ratio of the moles of vapor to the mole of liguid formed from a feed of composition x, at T, is equal to the fatio of CD/DE. Also, note that all intial liquid mixtures (atthe temperature T,) with the mole fraction of lying between x, and ys will have the same equilib- sium composition (x3. 13) atthe temperature Ty and pressure P= 1 atm. Ifthe Particular mixture x, = vy at Ty is heated until point Fis reached, the equil brium mixture (ry, 13) at; is obtgined. The temperature i called the dew- Point temperature, AtF the last point in the two-phase region, al of the liquid is ‘aporized with the exception of say, one drop, Thus, the dew-point temperature is seen tobe that temperature at which the fist drop of liquid is formed when & vapor with the composition 3 = xy is cooled from a temperature greater than its dew-point temperature to its dew-point temperature. Ty Generalized Equilibrium Relationships Unfortunately, the phase behavior of many mixtures is not adequately described by Raoult’s law. A more precise statement of the third condition ef Eq, (I-1) is that the partial molar-free energy of each component in the vapor phase is equal to its partial molar-free energy in the liquid phase (see Chap. 14), From this condition the following alternative but equivalent statement may be deduced (1)INTRODUCTION TO THE FUNDAMENTALS OF DISTILLATION L1. where and j-are the fugacites of component inthe vapor and quid phases, respectively, evaluated atthe compositions ofthe respective phases and atthe B fand T ofthe system, Equation (1-1) may be restated in the following equivalent form i fly = ab Sts, (18) where J {T= fugacities of pure component i in the liquid and vapor states, respectively, evaluated at the total pressure P and temperature T of the system ‘= mole fractions of component j in the liquid and vapor phases, respectively = activity coefficients of component i in the liquid and vapor phases, respectively. yf = yf(P, T, x1. --1 xs 8 =H(P, Ts din Vd) IF it may be assumed that the vapor forms an ideal solution, then y} = 1 for each {and Eq, (1-8) reduces to w= WK, (19) where K,= if the ideal solution K value. The expression given by Eq. (1-9) is recognized as one form of Henry's law. If the liquid phase also forms an ideal solution (7!"= I forall) then Eq, (19) reduces to ye Kx, (1-10) In some ofthe literature, the activity coefcients 3f and fare absorbed in Ky thats, the produet y£K;/7 is called K,and an equation of the form of Eq. (I-10) is obtained which is applicable o systems described by Eq. (I-8). If the elect of total pressure on the liquid fugacity #s negligible in the neighborhood of the vapor pressute of pure component i, then (eu) where P; is the vapor pressure of pure component i at the temperature T. If in addition to the assumptions required to obtain Eqs. (I-10) and (I-11), one also assumes that the vapor phase obeys the perfect gas law (Po= RT), then Eq, (I-10) reduces to Raoult’s law, Eq. (1-2). Determination of the Bubble-Point and Dew-Point Temperatures ‘of Multicomponent Mixtures In the interest of simplicity, the equilibrium relationship given by Bq. (1-10) is used in the following developments. The state of equilibrium for a two-phase (vapor and liquid) system is described by the following equations where any