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Distillation*

M. F. Doherty, Ph.D. Professor of Chemical Engineering, University of California—Santa Barbara (Section Editor) Z. T. Fidkowski, Ph.D. Process Engineer, Air Products and Chemicals Inc. (Distillation Systems) M. F. Malone, Ph.D. Professor of Chemical Engineering and Dean of Engineering, University of Massachusetts—Amherst (Batch Distillation) R. Taylor, Ph.D. Professor of Chemical Engineering, Clarkson University (Simulation of Distillation Processes)

INTRODUCTION TO DISTILLATION OPERATIONS General Principles . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Equilibrium and Nonequilibrium-Stage Concepts . . . . . . . . . . . . . . . . . Related Separation Operations . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . THERMODYNAMIC DATA AND MODELS Phase Equilibrium Data . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Graphical K Value Correlations . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Analytical K Value Correlations . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . SINGLE-STAGE EQUILIBRIUM FLASH CALCULATIONS Bubble Point and Dew Point . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Isothermal Flash . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Adiabatic Flash . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Other Flash Specifications . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Three-Phase Flash . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Complex Mixtures. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . GRAPHICAL METHODS FOR BINARY DISTILLATION Phase Equilibrium Diagrams . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . McCabe-Thiele Method. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Operating Lines . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Thermal Condition of the Feed . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Equilibrium-Stage Construction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Total Column Construction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Feed-Stage Location . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Minimum Stages . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Minimum Reflux. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Intermediate Reboilers and Condensers . . . . . . . . . . . . . . . . . . . . . . . Optimum Reflux Ratio . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Difficult Separations. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .

13-4 13-5 13-5

Equation-Based Design Methods . . . . . . . . . . . . . . . . . . . . . . . . . . . . Stage Efficiency . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Miscellaneous Operations . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .

13-25 13-25 13-25

13-6 13-8 13-9

APPROXIMATE MULTICOMPONENT DISTILLATION METHODS Fenske-Underwood-Gilliland (FUG) Shortcut Method . . . . . . . . . . . . 13-25 Example 1: Calculation of FUG Method . . . . . . . . . . . . . . . . . . . . . . 13-26 Kremser Equation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 13-28 Example 2: Calculation of Kremser Method. . . . . . . . . . . . . . . . . . . . 13-28 SIMULATION OF DISTILLATION PROCESSES Equilibrium-Stage Modeling . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . The MESH Equations (The 2c + 3 Formulation). . . . . . . . . . . . . . . . Degrees-of-Freedom Analysis and Problem Formulation . . . . . . . . . The 2c + 1 Formulation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . The c + 3 Formulation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Condenser and Reboiler. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Solution of the MESH Equations . . . . . . . . . . . . . . . . . . . . . . . . . . . . Tearing Methods. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Inside-Out Methods . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Simultaneous Convergence Methods . . . . . . . . . . . . . . . . . . . . . . . . . Continuation Methods (for Really Difficult Problems) . . . . . . . . . . . Other Methods . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Examples . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Example 3: Simple Distillation Column . . . . . . . . . . . . . . . . . . . . . . . Example 4: Light Hydrocarbon Distillation . . . . . . . . . . . . . . . . . . . . Example 5: Absorber . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Example 6: Reboiled Stripper . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Example 7: An Industrial i-Butane/n-Butane Fractionator . . . . . . . . Efficiencies . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Example 8: The Industrial i-Butane/n-Butane Fractionator (Again) . Example 9: HETP of a Packed Absorber . . . . . . . . . . . . . . . . . . . . . .

13-15 13-15 13-16 13-16 13-16 13-16

13-17 13-18 13-18 13-19 13-19 13-21 13-22 13-22 13-24 13-24 13-24 13-24

13-30 13-30 13-31 13-32 13-32 13-32 13-32 13-33 13-33 13-33 13-33 13-34 13-34 13-34 13-36 13-38 13-38 13-41 13-43 13-44 13-45

* Certain portions of this section draw heavily on the work of J. D. Seader, Jeffrey J. Siirola, and Scott D. Barnicki, authors of this section in the 7th edition. 13-1

13-2

DISTILLATION

13-45 13-46 13-46 13-49 13-49 13-49 13-50 13-50 13-51 13-51 13-51 13-51 13-52 13-52 13-55 PETROLEUM AND COMPLEX-MIXTURE DISTILLATION Characterization of Petroleum and Petroleum Fractions . . . . . . . . . . . . 13-99 Applications of Petroleum Distillation . . . . . . . . . . . . . . . . . . . . . . . . . . 13-102 Design Procedures . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 13-103 Example 15: Simulation Calculation of an Atmospheric Tower . . . . . 13-107 BATCH DISTILLATION Simple Batch Distillation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Batch Distillation with Rectification . . . . . . . . . . . . . . . . . . . . . . . . . . . . Operating Methods. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Approximate Calculation Procedures for Binary Mixtures . . . . . . . . . . . Batch Rectification at Constant Reflux . . . . . . . . . . . . . . . . . . . . . . . . Batch Rectification at Constant Distillate Composition . . . . . . . . . . . Other Operating Methods and Optimization . . . . . . . . . . . . . . . . . . . Effects of Column Holdup. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Shortcut Methods for Multicomponent Batch Rectification . . . . . . . . . Calculation Methods and Simulation . . . . . . . . . . . . . . . . . . . . . . . . . . . Constant-Level Distillation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Alternative Equipment Configurations . . . . . . . . . . . . . . . . . . . . . . . . . . Batch Distillation of Azeotropic Mixtures . . . . . . . . . . . . . . . . . . . . . . . . Exploiting Pressure Sensitivity. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Exploiting Boundary Curvature . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Exploiting Azeotropy and Liquid-Phase Immiscibility . . . . . . . . . . . . Design and Operation of Azeotropic Distillation Columns . . . . . . . . Extractive Distillation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Solvent Effects in Extractive Distillation. . . . . . . . . . . . . . . . . . . . . . . Extractive Distillation Design and Optimization . . . . . . . . . . . . . . . . Solvent Screening and Selection . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Extractive Distillation by Salt Effects . . . . . . . . . . . . . . . . . . . . . . . . . Reactive Distillation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Simulation, Modeling, and Design Feasibility . . . . . . . . . . . . . . . . . . Mechanical Design and Implementation Issues . . . . . . . . . . . . . . . . . Process Applications . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Synthesis of Multicomponent Separation Systems . . . . . . . . . . . . . . . . . 13-82 13-83 13-85 13-87 13-87 13-88 13-89 13-91 13-93 13-93 13-94 13-95 13-97 13-98

Using a Simulator to Solve Distillation Problems . . . . . . . . . . . . . . . . Example 10: Multiple Steady States in Distillation. . . . . . . . . . . . . . . Nonequilibrium Modeling . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Degrees of Freedom. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Physical Properties . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Flow Models . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Mass-Transfer Coefficients. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Example 11: Mass-Transfer Coefficient in a Tray Column. . . . . . . . . Example 12: Mass-Transfer Coefficients in a Packed Column. . . . . . Solving the NEQ Model Equations . . . . . . . . . . . . . . . . . . . . . . . . . . . Equipment Design . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Example 13: A Nonequilibrium Model of a C4 Splitter . . . . . . . . . . . Maxwell-Stefan Approach . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Example 14: The Need for Rigorous Maxwell-Stefan-Based NEQ Models. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Software for Distillation Column Simulations . . . . . . . . . . . . . . . . . . . . DEGREES OF FREEDOM AND DESIGN VARIABLES Definitions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Analysis of Elements . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Analysis of Units . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Other Units and Complex Processes . . . . . . . . . . . . . . . . . . . . . . . . . . . . DISTILLATION SYSTEMS Possible Configurations of Distillation Columns . . . . . . . . . . . . . . . . . . Thermally Coupled Systems and Dividing Wall Columns . . . . . . . . . . . Thermodynamic Efficiency . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Heat Integration . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Imbalanced Feeds . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ENHANCED DISTILLATION Azeotropy . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Residue Curve Maps and Distillation Region Diagrams . . . . . . . . . . . . Applications of RCM and DRD. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Azeotropic Distillation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Exploiting Homogeneous Azeotropes . . . . . . . . . . . . . . . . . . . . . . . . .

13-55 13-56 13-56 13-58

13-59 13-60 13-65 13-65 13-67

13-68 13-69 13-71 13-81 13-81

13-109 13-109 13-110 13-111 13-112 13-113 13-113 13-113 13-114 13-114 13-114 13-115 13-116

DISTILLATION

Nomenclature and Units Symbol A A C D D E E E F H H H K KD Kd L N Nc Ni Nmin Np Nr No N N P P sat Q Qc Qr R Rmin S S S Sc T U V W X Y a a b c c d d e f f Definition Absorption factor Area Number of chemical species Distillate flow rate Diffusion coefficient Efficiency Energy flux Energy transfer rate Feed flow rate Column height Enthalpy Liquid holdup Height of a transfer unit Vapor-liquid equilibrium ratio (K value) Chemical equilibrium constant for dimerization Liquid-liquid distribution ratio Liquid flow rate Number of equilibrium stages Number of relationships Number of design variables Minimum number of equilibrium stages Number of phases Number of repetition variables Number of variables Rate of mass transfer Molar flux Number of transfer units Pressure Vapor pressure Heat-transfer rate Condenser duty Reboiler duty External-reflux ratio Minimum-reflux ratio Sidestream flow rate Stripping factor Vapor-sidestream ratio Schmidt number Temperature Liquid-sidestream rate Vapor flow rate Vapor-sidestream rate Relative mole fraction in liquid phase Relative mole fraction in vapor phase Activity Area Component flow rate in bottoms Number of chemical species Molar density Component flow rate in distillate Mass-transfer driving force Rate of heat transfer Component flow rate in feed Fugacity SI units m2 kg·mol/s m2/s kW/m2 kW kg·mol/s m J/(kg·mol) kg·mol m U.S. Customary System units ft2 lb·mol/h ft2/h Btu/(ft 2·h) Btu/h lb·mol/h ft Btu/(lb·mol) lb·mol ft Symbol h h k l p q q qc qr r s t u v w x y z Definition Height Heat-transfer coefficient Mass-transfer coefficient Component flow rate in liquid Pressure Measure of thermal condition of feed Heat flux Condenser duty Reboiler duty Sidestream ratio Liquid-sidestream ratio Time Velocity Component flow rate in vapor Weight fraction Mole fraction in liquid Mole fraction in vapor Mole fraction in feed SI units m kW/m2 m/s kg·mol/s kPa kW/m2 kW kW s m/s kg·mol/s

13-3

U.S. Customary System units ft Btu/(ft2⋅h) ft/h lb·mol/h psia Btu/ (ft2⋅h) Btu/h Btu/h H ft/h lb·mol/h

kg·mol/s

lb·mol/h

Greek Symbols α γ ε ξ ρ µ σ θ Θ Φ ˆ Φ ΦA ΦS Ψ K kg·mol/s kg·mol/s kg·mol/s °R lb·mol/h lb·mol/h lb·mol/h Relative volatility Activity coefficient TBK efficiency Dimensionless time Density Viscosity Surface tension Time for batch distillation Parameter in Underwood equations Fugacity coefficient of pure component Fugacity coefficient in mixture Fraction of a component in feed vapor that is not absorbed Fraction of a component in entering liquid that is not stripped Factor in Gilliland correlation

kg·mol/s kg·mol/(m2·s) Pa Pa kW kW kW kg·mol/s

lb·mol/h lb·mol/(ft 2·h) psia psia Btu/h Btu/h Btu/h lb·mol/h

kg/m3 N/m2 N/m s

lb/ft3 h

Subscripts and Superscripts EQ f hk i j L lk MV o s t V * Equilibrium Froth Heavy key Component index Stage index Liquid Light key Murphree vapor Overall Superficial Mixture or total Vapor Equilibrium composition Acronyms

m2 kg·mol/s kg·mol/m3 kg·mol/s kW kg·mol/s Pa

ft2 lb·mol/h lb·mol/ft3 lb·mol/h Btu/h lb·mol/h psia

HETP n.b.p. NTU

Height equivalent to a theoretical plate Normal boiling point (1-atm pressure) Number of transfer units

1988. 156 (Apr. contacting liquid at each tray. Fundamentals of Multicomponent Distillation.. New York. 4th ed. 1967. C. 1981. McGraw-Hill. 1979. as typified in Fig. Reinhold. which is often referred to as the stripping section. Trays are stacked one above the other and enclosed in a cylindrical shell to form a column. Each molecular species in the mixture to be separated responds in a unique way to differing environments offered by these zones. Equilibrium-Stage Separation Operations in Chemical Engineering. Chemical Publishing. Also heat is removed from a condenser at the top of the column. New York. as the system moves toward equilibrium. Doherty and Malone. Henley and Seader. “An Analysis of the Equilibrium Stage Separation Problem—Formulation and Convergence.” Chem. Distillation Engineering. Hoffman. The result is a vapor phase that becomes richer in light components as it passes up the column and a liquid phase that becomes richer in heavy components as it cascades downward. The remainder of the bottom liquid is withdrawn as bottoms. Because of the difference in density between vapor and liquid phases. In multiple-feed columns and in columns from 13-4 which a liquid or vapor sidestream is withdrawn. Vapor-Liquid Equilibria Using UNIFAC. N. energy required to separate the species is added in the form of heat to the reboiler at the bottom of the column. Vapor and liquid phases on a given tray approach thermal. New York. New York. Distillation Design. the number of contacting trays in each column section. 1975. 1963. 1992. McGraw-Hill.. Kister. Smith.D.. Eng. Mass Transfer Operations. Conceptual Design of Distillation Systems. or overhead product. Part of this liquid is returned to the column as reflux to provide liquid overflow. McGraw-Hill. In some cases only part of the vapor is condensed so that a vapor distillate can be withdrawn. Hengstebeck. 1980. INTRODUCTION TO DISTILLATION OPERATIONS GENERAL PRINCIPLES Separation operations achieve their objective by the creation of two or more coexisting zones which differ in temperature. Wiley-Interscience. Seader and Henley. which is often called the rectifying section. Consequently. “The B. Distillation—Principles and Design Procedures. the column is divided into an upper section. If the feed is introduced at one point along the column shell. New York. New York. 1987. Friday and Smith. New York.” Chem. New York. 1980. 14(2) (Spring 1985). Seader. as described below in the subsection Distillation Systems. McGraw-Hill.” AIChE J. 13-1 Schematic diagram and nomenclature for a simple continuous distillation column with one feed. 10. B3. 1998. Elements of Fractional Distillation. and this results in a separation between the species.. Separation Processes. Van Winkle. 3d ed. Design of Equilibrium Stage Processes. Distillation. New York. Liquid reaching the bottom of the column is partially vaporized in a heated reboiler to provide boil-up. The feed material. New York. Fair and Bolles. Chem. Robinson and Gilliland. vol. pressure. McGraw-Hill. Gmehling. 698 (1964). Holland. and Rasmussen. Weinheim. 85(10). Wiley. 13-1. Kister. The notion of a column section is a useful concept for finding alternative systems (or sequences) of columns for separating multicomponent mixtures. Eng. Azeotropic and Extractive Distillation. 1981. 22. The separation operation called distillation utilizes vapor and liquid phases at essentially the same temperature and pressure for the coexisting zones.GENERAL REFERENCES: Billet. composition. New York. Wiley. or bottom product. A typical tray-type continuous distillation column plus major external accessories is shown schematically in Fig. each species establishes a different concentration in each zone. New York. where the temperature is lowest. 41 (1989). pressure. is introduced at one or more points along the column shell. Holland. Handbook of Separation Process Technology.J. while the heavier (higher-boiling temperature) components concentrate in the liquid phase. 1961. Educ. This overall flow pattern in a distillation column provides countercurrent contacting of vapor and liquid streams on all the trays through the column. Prentice-Hall. In the conventional distillation operation. Distillation Operation. Eng. New York.. which is sent back up the column. 2001. New York. Packings are also generally contained in a cylindrical shell between hold-down and support plates. there are more than two column sections between the two end-product streams. Multicomponent Mass Transfer. Ullmann’s Encyclopedia of Industrial Chemistry. The overall separation achieved between the distillate and the bottoms depends primarily on the relative volatilities of the components. This frequently results in a FIG. McGraw-Hill. McGraw-Hill. 1990. . Various kinds of devices such as random or structured packings and plates or trays are used to bring the two phases into intimate contact.. King. 2d ed. The lighter (lower-boiling temperature) components tend to concentrate in the vapor phase. Amsterdam. 1968). A Group Contribution Method. Progress. 1950. Englewood Cliffs. 1993. Wiley.. Separation Process Principles. The column may be operated continuously or in batch mode depending on a number of factors such as scale and flexibility of operations and solids content of feed. McGraw-Hill. (Before Computers) and A. All separation operations require energy input in the form of heat or work. while vapor flows up the column. New York. and/or phase state. Rousseau. a total overhead condenser. New York. “Modern Design of Distillation Columns. which is to be separated into fractions. 13-1. Fundamentals and Modeling of Separation Processes. The remainder of the overhead stream is withdrawn as distillate. Wiley. 75(9). liquid runs down the column. and a lower section. 1964. of Equilibrium-Stage Operations. Elsevier. Fredenslund. Seader. Vapor reaching the top of the column is cooled and condensed to liquid in the overhead condenser. where the temperature is highest. and composition equilibria to an extent dependent upon the efficiency of the contacting tray. cascading from tray to tray. 1977.. VCH. and a partial reboiler. and the ratio of the liquid-phase flow rate to the vapor-phase flow rate in each section. McGraw-Hill. Taylor and Krishna. Treybal. ed.

This is needed so that thermodynamic phase equilibrium relations can be used to determine the temperature and composition of the equilibrium streams at a given pressure. This section deals primarily with equilibrium and rate-based models of distillation. and multiphase flows. (a) (b) (c) (d) (e) (f) FIG. other batch configurations are possible as discussed in the subsection Batch Distillation.” In this mode the feed is charged to a still which provides vapor to a column where the separation occurs. which describe the extent to which the performance of an actual contact tray duplicates the performance of an equilibrium stage. The number of hypothetical equilibrium stages required is then converted to a number of actual trays by means of tray efficiencies. 13-2 (g) (h) (i) Separation operations related to distillation. rates of intra. (i) Azeotropic distillation. Complex distillation operations that offer higher thermodynamic efficiency and lower energy-input requirements have been developed and are also discussed below in the subsection Distillation Systems. Many of the concepts and methods discussed for continuous distillation are useful for developing models and design methods for batch distillation. (2) The number of equilibrium stages and the energy input required to accomplish a specified separation.or multiple-stage vapor-liquid separation operations. Simplifications are necessary to develop tractable models. Section 14 covers equipment design. tray inefficiencies can be accounted for by using rate-based models that are described below. (h) Extractive distillation. (e) Reboiled stripping. (c) Rectifier. Alternatively and preferably. Sometimes. this is the only stream leaving the device. and (2) the separation is effected only by the addition and removal of energy and not by the addition of any mass separating agent (MSA) such as in liquid-liquid extraction. (g) Refluxed stripping. are calculated. Much of the third step is eliminated if a rate-based model is used. of the types shown in Fig. (a) Flash vaporization or partial condensation. 13-2. alternative single.and interphase mass and energy transport. A hypothetical column composed of equilibrium stages (instead of actual contact trays) is 13-5 designed to accomplish the separation specified for the actual column. EQUILIBRIUM AND NONEQUILIBRIUMSTAGE CONCEPTS The transfer processes taking place in an actual distillation column are a complicated interplay between the thermodynamic phase equilibrium properties of the mixture. Use of the equilibrium-stage concept separates the design of a distillation column into three major steps: (1) Thermodynamic data and methods needed to predict equilibrium-phase compositions are assembled. and the column diameter is determined. (3) The number of equilibrium stages is converted to an equivalent number of actual contact trays or height of packing. in which the liquid in each stage is considered to be well mixed and such that the vapor and liquid streams leaving the stage are in thermodynamic equilibrium with each other. (d) Stripping. Section 4 covers the first step.INTRODUCTION TO DISTILLATION OPERATIONS large energy-input requirement and low overall thermodynamic efficiency. may be more suitable than distillation for the specified task. but a summary of methods and some useful data are included in this section. or the separation that will be accomplished in a given number of equilibrium stages for a given energy input. (f) Reboiled absorption. Vapor leaving the top of the column is condensed to provide liquid reflux back to the column as well as a distillate stream containing the product. The landmark concept of the equilibriumstage model was developed by Sorel in 1893. . (b) Absorption. Under normal operation. RELATED SEPARATION OPERATIONS The simple and complex distillation operations just described all have two things in common: (1) Both rectifying and stripping sections are provided so that a separation can be achieved between two components that are adjacent in volatility. Batch distillation is preferred for small feed flows or seasonal production which is carried out intermittently in “batch campaigns. In addition to the batch rectifier just described. especially if the heat removed in the condenser is wasted.

H2O. at a pressure of 101. and. in which an overhead condenser is added. and extrapolating (care is needed here) the data. then refluxed stripping. Butterworth. Failure of equipment to perform at specified levels is often attributable. Many of these simulators also provide graphical display of the data for easy visualization and interpretation. Non-azeotrope-forming mixtures such as benzene and toluene in Figs. may be used. may be appropriate if (1) the relative volatility between the two components to be separated is very large. This subsection summarizes and presents examples of phase equilibrium data currently available to the designer. and/or a pump upstream of the vessel. it may be partially condensed or partially vaporized in a socalled flash operation. as shown in Fig. This section also includes a treatment of distillation-type separations from a rate-based point of view that uses principles of mass. and as T versus y and x. The distillate and bottoms products obtained depend upon the feed composition and whether a minimum-boiling azeotrope is formed as with the ethyl acetate–ethanol mixture in Fig. or with boil-up produced by a partial reboiler. Walas (Phase Equilibria in Chemical Engineering. A small selection of such data. as shown in Fig. PHASE EQUILIBRIUM DATA For a binary mixture. Such a configuration is sometimes used to steam-strip sour water containing NH3. 4. such as that . 1976. from which it is recovered and recycled. the trend is toward single generalized digital computer program packages that compute many or all distillation-type separation operations. pressure and temperature fix the equilibrium vapor and liquid compositions. Amsterdam. shown in Fig. with a line of 45° slope included for reference. An alternative to extractive distillation is azeotropic distillation. are referred to here as distillation-type separations because they have much in common with respect to calculations of (1) thermodynamic properties. 1979). is the azeotropic composition. at least in part. an MSA that forms a heterogeneous minimum-boiling azeotrope with one or more components of the feed is used. Extensive databases of phase equilibrium measurements are readily available in most process simulators together with models for correlating. 1985). Thus. This is the case in Figs.13-6 DISTILLATION When the volatility difference between the two components to be separated is so small that a very large number of stages would be required.3 kPa (1 atm. If the recovery of only one component is required rather than a sharp separation between two components of adjacent volatility. without regard to the separation of the other components.. to the lack of such data. phenol. absorption is used either with a liquid MSA absorbent of relatively low volatility. or (3) only a partial separation is to be made. If the feed is vapor at separation conditions. interpolating. Two systems of this type. For application to distillation (a nearly isobaric process) binarymixture data are frequently plotted. and Nagahama (Computer Aided Data Book of Vapor-Liquid Equilibria. 13-2e. The azeotropic liquid may be homogeneous or heterogeneous (two immiscible liquid phases). 13-3 to 13-8. Here. or azeotrope. The desired temperature and pressure of a flash may be established by the use of heat exchangers. 1990). Pergamon. a valve. as shown in Fig. If a relatively sharp separation is required between two components of adjacent volatility. and HCN. DECHEMA Chemistry Data ser. Wichterle. Usually. Supplement II. 1 (parts 1–10). Such mixtures are known as azeotropic mixtures. The thermodynamic concepts used are presented in the subsection Thermodynamics of Sec. 13-2d. the choice of MSA follows the same consideration given for simple absorption and stripping. where benzene is more volatile than toluene. Supplement I. Amsterdam. For example. then extractive distillation. as well as the simple and complex distillation operations described earlier. or reboiled absorption. as will be evident from the remaining treatment of this section. as shown in Fig. One important variation of a stripper. In fact. as in Fig. Ohe (Vapor-Liquid Equilibrium Data. a compressor. as in Fig. In either case. is a refluxed stripper. and Hala (VaporLiquid Equilibrium Data Bibliography. 13-2b. THERMODYNAMIC DATA AND MODELS Reliable thermodynamic data are essential for the accurate design or analysis of distillation columns. 1. Elsevier. which is shown in Fig. Elsevier.6 kPa (1 and 2 atm). an MSA is selected that increases the volatility difference sufficiently to reduce the stage requirement to a reasonable number. 13-2a. Frankfurt. Above these concentrations. 13-2f. Gmehling and Onken [Vapor-Liquid Equilibrium Data Collection. one of the components is more volatile over only a part of the composition range. 13-7. Amsterdam. as shown in Fig. More extensive presentations and bibliographies of such data may be found in Hala. one of the components is more volatile than the other over the entire composition range. The azeotrope is taken overhead. The choice depends on the ease of partially reboiling the bottoms or of recovering and recycling the stripping agent. volatility is reversed.013 bar). and the composition in which the reversal occurs. 13-3 and 13-4 for the benzenetoluene system at pressures of both 101. 13-2d. and (3) column sizing. which is the composition in which vapor and liquid compositions are equal. 13-2. Figure 13-5 shows that chloroform is less volatile than acetone below a concentration of 66 mol % chloroform and that ethyl acetate is more volatile than ethanol below a concentration of 53 mol % ethyl acetate. Section 14 also presents details of that subject as applied to absorption and stripping. Polak. By contrast. 13-6 or a maximum-boiling azeotrope is formed as with the chloroform-acetone mixture in Fig. 1975). simple distillation of azeotropic mixtures will at best yield the azeotrope and one essentially pure species. 1977]. either with an externally supplied vapor stripping agent of relatively high volatility. Oxford. The choice usually depends on the ease of partially condensing the overhead vapor or of recovering and recycling the absorbent. (2) the recovery of only one component in one of the two product streams is to be achieved. It is introduced in an appreciable amount near the top stage of the column so as to affect the volatility difference over most of the stages. or with reflux produced by an overhead partial condenser. 13-3 and 13-4 can be separated by simple distillation into two essentially pure products. Ohe. as y versus x. 13-5 to 13-7. Depending on the original condition of the feed. Two of the binary mixtures of Table 13-1 form homogeneous azeotropes. For other binary systems. as in Fig. Ohe (Vapor-Liquid Equilibrium Data at High Pressure. used to separate the product vapor and liquid phases. as shown in Figs. for a fixed pressure. (2) vapor-liquid equilibrium stages. and the MSA-rich phase is decanted and returned to the top of the column as reflux. Some reflux to the top stage is used to minimize the MSA content in the distillate. Amsterdam. Wichterle. particularly. Elsevier. 13-2h. stripping is used. Numerous other multistaged configurations are possible. and Boublik (Vapour-Liquid Equilibrium Data at Normal Pressures.and heat-transfer rates. 13-2g. for four nonideal binary systems is given in Table 13-1. if a mixture of 30 mol % chloroform and 70 mol % acetone is fed to a simple distillation column. 1968). 1973.3 and 202. 13-2i in just one of its many modes. A single-stage flash. Elsevier. experimental data are frequently presented in the form of tables of vapor mole fraction y and liquid mole fraction x for one constituent over a range of temperature T for a fixed pressure P or over a range of pressure for a fixed temperature. ethyl acetate–ethanol and chloroform-acetone. the MSA is a polar compound of low volatility that leaves in the bottoms. vol. should be considered. but either an undesirably low temperature is required to produce reflux at the column operating pressure or an undesirably high temperature is required to produce boil-up. 1989). In some binary systems. their absorption or stripping in a single section of stages may be sufficient. If the feed is liquid at separation conditions. In a common mode. Hirata. 13-2c. Linek. A common example is the separation of light gases such as hydrogen and methane from aromatics. All the separation operations shown in Fig. Boston. are shown in Figs.

644 0. NOTE: 1 2 shown in Fig.3 76.9 72. Kojima.6 103.389 0. Tochigi.30 0.3 kPa.800 0.726 0.4582 0. operating at 101. Distillation Equilibrium Data. and phase compositions in the form of tables. Phase splitting into two separate liquid phases (one with 3 mol % butanol and the other with 40 mol % butanol) occurs for any overall liquid composition between 3 and 40 mol % butanol.5299 0. For mixtures containing more than two species.010 0.47 1. which are defined by y Ki = i (13-1) xi and are correlated empirically or theoretically in terms of temperature. Brennecke. are commonly represented in terms of K values (vapor-liquid equilibrium ratios).4000 0. Instead.02 63. Kato. °C = (°F − 32)/1.87 60.837 0.2000 0.49 56.300 0. temperature.400 0.8000 0.35 64.9075 0.003 0. the distillate could approach pure acetone and the bottoms could approach the maximumboiling azeotrope.3000 0.68 56. 13-8 for the water–normal butanol system at 101. and Hashimoto. for a fourcomponent system.0 77.31 0.93 0.50 62.600 0.0 0.7078 0.82 63. °C 62.8 72. graphs.8302 0.1000 0.33 62.85 0.950 1. pressure.8000 0.700 0.8269 0. Getty.95 59.9000 0.1500 0.7301 0. 32. Ind.000 0.540 0.7000 0.9500 0. and the ratio of the K values of two species. 149 (1968). the liquid phase is homogeneous.3 kPa (1 atm).100 0.9000 0.2000 0. such data. and Paul.8 71.3888 0. Kagaku Kogaku.53 65.9 83. and mole fractions of two com- ponents are set.1 118.5000 0.7 76.13 0.7916 0.0 74.3000 0.9627 0. 66 (1935). Chem.457 0.37 64.THERMODYNAMIC DATA AND MODELS TABLE 13-1 Constant-Pressure Liquid-Vapor Equilibrium Data for Selected Binary Systems Component A Acetone B Chloroform Temperature.1000 0. and equations. the equilibrium vapor and liquid compositions are fixed only if the pressure.6 75.59 61. To convert kilopascals to pounds-force per square inch.8124 0.0500 0.22 0.914 1.00 Total pressure. 32.5000 0.900 0.6000 0.0 0.3162 0.40 0.3 2 Ethyl acetate Ethanol 101.9500 0.7 145.305 0.8.4 4 To convert degrees Celsius to degrees Fahrenheit.5 73. Kagaku Kogaku.000 0.30 64.8950 0.0 0.7716 0. as well as binary-system data.26 63.050 0.30 78.020 0.7000 0. Representation of multicomponent vapor-liquid equilibrium data in tabular or graphical form of the type shown earlier for binary systems is either difficult or impossible.97 1.516 0.0 134. Kojima.9 72. multiply by 0.6106 0. 3 Chu. Eng.3500 0. 4 Trimble and Potts.00 Vapor 0.71 57.80 68.102 0.8532 0.200 0.540 0. K αij = i (13-2) Kj .5 76.73 0.7 Mole fraction A in Liquid 0.3535 0.2 73.8 71.29 57.500 0.1 89.75 59.0 0. an additional degree of freedom is available for each additional component.3 13-7 Reference 1 Acetone Water 101. 337 (1968). kPa 101. At liquid compositions between 0 and 3 mol % butanol and between 40 and 100 mol % butanol. and Watase.1 71.90 0. A minimum-boiling heterogeneous azeotrope occurs at 92°C (198°F) when the vapor composition and the overall composition of the two liquid phases are 25 mol % butanol.2338 0.145.9335 0.576 0.8712 0.1 78.6000 0.83 64.06 0. 1950.23 0. Seki.. 27.12 58. New York.0 160. The K values are widely used in multicomponent distillation calculations.1 69. 13-1. Thus.4 128.3 3 Ethylene glycol Water 30.54 0.23 60. called the relative volatility.002 0.0500 0.187 0.8387 0.72 58.6381 0.1390 0.4000 0. An example of heterogeneous-azeotrope formation is shown in Fig.48 74.0817 0. Sunaga.

mole fraction of benzene in vapor 0.4 Chloroform–acetone 0.and liquid-phase compositions. 7. Staged Cascades in Chemical Processing. Symp. 13-6 110 Bubble-point temperature T vs.6 0. 49.6 0. The easiest to use are the DePriester charts [Chem.8 Mole fraction benzene 1.8 X b .2 0 0 0.4 Azeotrope 0.. mole fraction of benzene in liquid 1.) Liquid boiling points and vapor condensation temperatures for minimum-boiling azeotrope mixtures of ethyl acetate and ethanol at 101. (Brian. several major graphical K value correlations are available for light-hydrocarbon systems.6 0.6 0. the K value of a species is a complex function of temperature. 13-5 0 0. Englewood Cliffs. 13-3 Isobaric y-x curves for benzene-toluene.x b Va po 90 Azeotrope 0.) Vapor-liquid equilibria for the ethyl acetate–ethanol and chloroform-acetone systems at 101.2 0. 130 120 Temperature (°C) 174 172 Temperature (°F) 2 atm 100 170 168 166 164 162 160 80 1 atm 0 0.4 0. 1 (1953)]. Eng. Rarely is distillation used on a large scale if the relative volatility is less than 1. GRAPHICAL K VALUE CORRELATIONS As discussed in Sec. Liq uid p Va or r uid Liq .0 FIG..0 FIG. Englewood Cliffs. Prentice-Hall.0 FIG.8 Mole fraction chloroform or ethyl acetate in liquid 1.J.8 P = 1 atm 0. pressure. Staged Cascades in Chemical Processing. 4.13-8 1.4 Mole fraction ethyl acetate 1.2 0. with i more volatile than j.0 DISTILLATION 1.05.6 2 atm Mole fraction chloroform or ethyl acetate in vapor 0. N.2 0.0 158 0 FIG.0 Yb . (Brian. 13-4 Isobaric vapor-liquid equilibrium curves for benzene-toluene.8 0. Prog. 1972. 1972. Prentice-Hall. the K value depends mainly on temperature and pressure. Ser.3-kPa (1-atm) total pressure.3 kPa (1 atm).6 Ethyl acetate– ethanol 0. For example. N. for mixtures of compounds of similar molecular structure and size.2 0. However.4 0. 140 Dew-point temperature T vs. and equilibrium vapor.2 0.4 0.J.8 Azeotrope 0.yb is a convenient index of the relative ease or difficulty of separating components i and j by distillation.

An alternative measure of composition is the convergence pressure of the system. Tulsa. 47. 13-12 for the methane-propane-pentane ternary. and a critical locus can be drawn for the pseudobinary by interpolation between various real binary curves. n-pentane. 53 (1953)] for the prediction of convergence pressure as a function of composition. 80(25). Data. Prog. 13-8 Va Va po r function of T and P only. propane. and Cajander.THERMODYNAMIC DATA AND MODELS 150 148 r po Va 13-9 146 144 Temperature (°F) 142 140 138 136 134 132 130 0 Va po r Azeotrope 0. The basis for Hadden’s method is illustrated in Fig. Hadden and Grayson (op. Associated K values for pentane at 104°C (220°F) are shown to the right as a function of mixture composition (or convergence pressure).2 0.6 0. are based primarily on the Benedict-WebbRubin equation of state [Chem. Chem. 207 (1961)]. ethane. and hence the DePriester charts.2 0. Eng. Eng. For K as a 250 240 230 Temperature (°F) 220 210 200 190 180 170 0 FIG. which is defined as that pressure at which the K values for all the components in an isothermal mixture converge to unity. 48. It is analogous to the critical point for a pure component in the sense that the two phases become indistinguishable. n-hexane.) The critical loci for the ternary mixtures vary linearly. phase splitting and heterogeneous-azeotrope formation. The GPA convergence pressure charts are primarily for alkane and alkene systems but do include charts for nitrogen. MWK Equilibrium Constants. Hipkin. the formulation used is ˆi ΦL Ki = V (13-3) ˆ Φi . Eng. The heavy component is a pseudosubstance whose critical temperature is an average of all other components in the multicomponent mixture. isopentane. Symp. Two major graphical correlations based on convergence pressure as the third parameter (besides temperature and pressure) are the charts published by the Gas Processors Association (GPA. Engineering Data Book. 1966) based on the procedures from Hadden and Grayson [Hydrocarbon Process.4 0. This method is illustrated in the left half of Fig.5 MPa (5000 psia) is illustrated in Fig. ethylene. When a single pressure-volume-temperature (P-V-T) equation of state is applicable to both vapor and liquid phases. Eng. 40(9).). at constant temperature. 1950) and include additional experimental data.. 7. 13-11. 49..0 FIG. ANALYTICAL K VALUE CORRELATIONS id qu Li Liq uid po r u Liq id 0. 13-9. 419 (1951). The behavior of a complex mixture of hydrocarbons for a convergence pressure of 34. The essential point is that critical loci for mixtures are independent of the concentration of the lightest component in a mixture. This pseudocritical point can then be located on a P-T diagram containing the critical points for all compounds covered by the charts. 2. as derived in Sec. and Lenoir [J.. 449 (1951)]. (This behavior is not always typical of more nonideal systems. isobutane. This permits representation of a multicomponent mixture as a pseudobinary. Polyco Data. Symp. 251 (1960)]. 9th ed. New York. The Kellogg and DePriester charts and their subsequent extensions and generalizations use the molar average boiling points of the liquid and vapor phases to represent the composition effect. 1981) and the charts of the American Petroleum Institute (API. 47. SI versions of these charts have been developed by Dadyburjor [Chem.8 1. isobutylene. Prog. 85 (1978)]. Useful extensions of the convergence pressure concept to more varied mixtures include the nomographs of Winn [Chem. Regression equations and coefficients for various versions of the GPA convergence pressure charts are available from the GPA. Prog. The former uses the method proposed by Hadden [Chem. Ser. McWilliams [Chem. and those cannot be known until the K values are available to calculate them.. Prog. 13-9a and b.6 Mole fraction chloroform 0. 13-10. where it is shown that the critical loci for various mixtures of methanepropane-pentane fall within the area circumscribed by the three binary loci. 13-7 Liquid boiling points and vapor condensation temperatures for maximum-boiling azeotrope mixtures of chloroform and acetone at 101. One cannot calculate K values until phase compositions are known. and n-heptane). carbon dioxide. A trial-and-error procedure is required with any K value correlation that takes into account the effect of composition. 74(4). These charts are a simplification of the Kellogg charts (Liquid-Vapor Equilibria in Mixtures of Light Hydrocarbons. n-butane. 5. Preferred analytical correlations are less empirical and most often are theoretically based on one of two exact thermodynamic formulations. propylene. The widespread availability and use of digital computers for distillation calculations have given impetus to the development of analytical expressions for K values. which can represent both the liquid and the vapor phases and can predict K values quite accurately when the equation constants are available for the components in question. The Kellogg charts. cit. 138 (1973)] presents a regression equation and accompanying regression coefficients that represent the DePriester charts of Fig. Pet. Convergence pressure for the mixture at the desired temperature is read from the assumed loci at the desired system temperature. the DePriester charts provide good starting values for the iteration.4 0. Technical Data Book—Petroleum Refining. 4. 121 (1952)]. Ser. The charts may not be valid when appreciable amounts of naphthenes or aromatics are present. Eng. the API charts use special procedures for such cases. with weight percent propane on a methane-free basis.. Refiner. These nomographs are shown in Fig.8 Mole fraction normal butanol 1. The light component in this pseudobinary is the lightest species present (to a reasonable extent) in the multicomponent mixture. Eng. and hydrogen sulfide. which cover 12 hydrocarbons (methane.0 Vapor-liquid equilibrium data for an n-butanol–water system at 101.3 kPa (1 atm).3-kPa (1-atm) total pressure.

59 (1976)]. (13-4) can be applied. Symp. (b) High-temperature range. (13-4).. the former is generally preferred because it involves only a single equation of state applicable to both phases and thus would seem to offer greater consistency.. (13-4) is hypothetical for i any components that are supercritical. a modification of Eq. Eng. Gulf. isopentane.. Fundam. the quantity Φ L in Eq. Sci. At low i to moderate pressures.13-10 DISTILLATION (a) The K values (K = y/x) in light-hydrocarbon systems. 13-9 ˆi ˆi where the mixture fugacity coefficients Φ L for the liquid and ΦV for the vapor are derived by classical thermodynamics from the P-V-T expression. Computer programs for K values derived from the SRK. Eng. The ability of the SRK correlation to predict K values even when the pressure approaches the convergence pressure is shown for a multicomponent system in Fig. 49. When either Eq. accurate prediction of the latter is crucial to the application of Eq. Until recently. as shown in a reformulated version by Orbey and Sandler [AIChE J. An alternative K value formulation that has received wide application to mixtures containing polar and/or nonpolar compounds is Ki = γ L ΦL i i ˆi ΦV (13-4) where different equations of state may be used to predict the purecomponent liquid fugacity coefficient Φ iL and the vapor-mixture fugacity coefficient. and Peng-Robinson (PR) [Ind. equations of state that have been successfully applied to Eq. namely. Chem. Consistent equations for enthalpy can be similarly derived. and any one of a number of mixture free-energy models may be used to obtain the liquid activity coefficient γ L. who extended the remarkable Redlich-Kwong equation. 7. 15. The Wong-Sandler mixing rules for cubic equations of state now permit such equations to be extended to mixtures of organic chemicals. The SRK and PR equations belong to a family of so-called cubic equations of state. In addition. 1973) predicts K values and enthalpies of the normal paraffins up through n-octane. (13-4) that uses Henry’s law is sometimes applied. 41. nitrogen. 1197 (1972)]. Chem. carbon dioxide.] FIG. (13-3) or Eq. hydrocarbons and light gases. ethylene. Eng. and other equations of state are widely available in all computer-aided process design and simulation programs. propylene. Similar results are achieved with the PR correlation. Ser. as well as isobutane. including the cryogenic region. 1 (1953). (13-3) have been restricted to mixtures of nonpolar compounds. The Starling extension of the BWR equation (Fluid Thermodynamic Properties for Light Petroleum Systems. Prog. [DePriester. 27. In that case. 13-13. (a) Low-temperature range. and hydrogen sulfide. These equations include those of Benedict-Webb-Rubin (BWR). Houston. Soave (SRK) [Chem. PR. 683 (1995)].. .

). Consistent Antoine vapor pressure constants and liquid molar volumes are listed in Table 13-4. whose activity coefficients are shown in Fig. i The predictive ability of the last-named theory is exhibited in Fig. June. cit. For mixtures containing polar substances. with the vapor pressure P sat given by a threeconstant Antonie equation. Sixth World Pet. 41. van Laar. (13-4) by using an empirical expression for Φ L based on the generalized corresponding-states P-V-T i ˆi correlation of Pitzer et al.. respectively. and UNIQUAC equations. Five purecomponent constants for each species (Tv . (13-4).3 kPa (1 atm) from best fits of the experimental T-y-x equilibrium data by setting ΦV and Φ iL to their ideal-gas..0 i and P sat/P. Wilson. Revised coefficients of Grayson and Streed (GS) (Paper 20-P07. 249 (1967)]. and Chao [AIChE J. 1963) for the Φ L expression permit application of the CS correlation to higher i temperatures and pressures and give improved predictions for hydrogen. ω. 4. 13-9 (Continued) For mixtures of hydrocarbons and light gases. The Wilson equation is particularly useful for systems that are highly nonideal but do not undergo phase splitting. and the regular solution theory of Scatchard and Hildebrand for γ L. For systems such as this.THERMODYNAMIC DATA AND MODELS 13-11 (b) FIG. UNIFAC. δ. 13-14 for the heptane-toluene system at 101. NRTL. 598 (1961)] applied Eq. 7. Conf. gives good results. Table 13-2 lists their parameters for selected binary systems based on the binary system activity coefficient equation forms given in Table 13-3. 46(11).. Frankfurt. whose values they tabulate. Chao and Seader (CS) [AIChE J. as discussed in Sec. Extensive listings of binary-interaction parameters for use in all but the UNIFAC equation are given by Gmehling and Onken (op. They obtained the parameters for binary systems at 101. the Redlich-Kwong equation of state for ΦV.3 kPa (1 atm). Pv . ideal-solution limits of 1. The preferred expressions for representing activity coefficients are the NRTL and UNIQUAC equations. more complex predictive equations for γ L that involve binary-interaction parameters for each i pair of components in the mixture are required for use in Eq. as exemplified by the ethanol-hexane system. Six popular expressions are the Margules. in which activity coefficients in dilute regions may exceed values of . Greenkorn. when applied within the restrictions discussed by Lenoir and Koppany [Hydrocarbon Process. 13-15. and v L) are required to use the CS method which. 1602 (1995)] present a revised correlation for the standard-state liquid fugacity of hydrogen. Jin. applicable from 200 to 730 K.

Prog. 129 (1972). [Katz and Hachmuth. 1072 (1937). FIG. 53 (1953)]. New York. respectively. 49.. J. Sec. Eng. 58 (1953). 17. 13-11 Critical loci for a methane-propane-pentane system according to Hadden [Chem. 13-13 Comparison of experimental K value data and SRK correlation. PD and PM are partial pressures of dimer and monomer. Chem.13-12 DISTILLATION FIG. Symp. Light hydrocarbons in admixture with crude oil. Equilibrium-Stage Separation Operations in Chemical Engineering. Eng. Eng.] approximately 7. Chem.] . 13-12 Effect of mixture composition on K value for n-pentane at 104°C (220°F). Sec. the van Laar equation erroneously predicts phase splitting. 29. 13-10 Typical variation of K values with total pressure at constant temperature for a complex mixture. Symp. 49. Chem. Parameter W is weight fraction propane on a methane-free basis. Ind. weight fraction propane on a methane-free basis for the methane-propane-pentane system. Prog. data of Yarborough. [Hadden. FIG. 7. The K values are shown for various values of W. Data. 1981. Tables 13-2 and 13-4 include data on formic acid and acetic acid. two substances that tend to dimerize in the vapor phase according to the chemical equilibrium expression KD = PD 2 PM = 10 A + B T (13-5) where KD is the chemical equilibrium constant for dimerization. Eng. 7. in torr.5. Wiley.] FIG. [Henley and Seader.

0016 0.0524 0. Gmehling.7476 2.5619 1. Dev.3319 2.7947 0.0911 1.9436 1.0459 −361. benzene (2) Chloroform (1).7926 111.5461 0. water (2) Water (1). methanol (2) Ethanol (1).8900 906.4410 982. 1-butanol (2) Water (1).9095 2. Commun.2133 59.3611 1666. 209 (1975)] to compute Φ V in Eq.8463 1.4348 1396.J.5899 0.9614 2.0241 266.3346 7.6022 0.8608 −0.9227 0.4047 344.6398 1230.9398 2.7526 2.100 B 3083 3166 3316 3040 These equations when combined with Eq.8552 1.4702 3. 1980) and in terms of the UNIFAC group contribution method by Fredenslund.2715 van Laar A12 −0. 1980). Chem.1041 0.2942 1482.5555 0. water (2) Tetrahydrofuran (1). Englewood Cliffs. when only compound 1 dimerizes in the vapor phase. Vapor-Liquid Equilibrium Data Collection.7054 1.5 (2 − y1){1 + [1 + 4KDPy1(2 − y1)]0.5 (13-8) (13-9) As shown by Marek and Standart [Collect.6184 2.8869 320..1623 1.2935 A21 −0.0948 0.1171 −114.9533 3..6458 847.0439 2189. 1074 (1954)].0017 0.THERMODYNAMIC DATA AND MODELS TABLE 13-2 Binary-Interaction Parameters* System Acetone (1). Process Des.6798 0. formic acid (2) A12 −0.5 1 1 + [1 + 4KDPy1(2 − y1)]0.6579 2050.2792 570. (13-4). and T is in kelvins.5434 1.7172 0.0996 −0.1760 −0. acetic acid (2) Water (1).8320 1.7944 1264.0126 1. 19.9605 2.7905 1.6184 2.8519 545. Amsterdam.2966 Margules A21 −0. are given in terms of the UNIQUAC equation by Prausnitz et al. water (2) 2-Propanol (1).4973 1..8860 1. (Computer Calculations for Multicomponent Vapor-Liquid and Liquid-Liquid Equilibria.8404 0.1572 1.4178 0. methanol (2) Acetone (1). vol.5788 1.1411 1.0517 0. Eng. λ ij = λ ji . Frankfurt.5876 1549.8570 1.6118 953.2583 705. Czech.0951 0.9317 520.0120 0. Values of A and B for the first four normal aliphatic acids are A Formic acid Acetic acid n-Propionic acid n-Butyric acid −10.4717 0. When the system temperature is greater than the critical TABLE 13-3 Activity-Coefficient Equations in Binary Form for Use with Parameters and Constants in Tables 13-2 and 13-4 Type of equation Margules Adjustable parameters A12 A21 A12 A21 Wilson λ12 − λ11 λ 21 − λ22 where Λ12 = L L λ12 − λ11 λ 21 − λ 22 v2 v1 exp − Λ21 = L exp − L RT RT v1 v2 Equations in binary form ln γ1 = [A 12 + 2(A21 − A12)x1]x 2 2 2 ln γ2 = [A 21 + 2(A12 − A21)x2]x 1 ln γ1 = A12 ln γ2 = A21 A21x2 A12 x1 + A21 x2 A12x1 A12 x1 + A21 x2 2 van Laar 2 ln γ1 = −ln (x1 + Λ12 x2) + x2 ln γ2 = −ln (x2 + Λ21 x1) − x1 Λ12 Λ21 − x1 + Λ12 x2 Λ21 x1 + x2 Λ21 Λ12 − x1 + Λ12 x2 Λ21 x1 + x2 vL = molar volume of pure-liquid component i i λ ij = interaction energy between components i and j. (13-5) lead to the following equations for liquid-phase activity coefficients in terms of measurable quantities: γ1 = γ2 = Py1 P satx1 1 1 + (1 + 4KDP sat)0.7925 1.8557 1.2689 82.6233 1694. 1 (parts1–10).7923 0. 1977.0216 0.8258 0.2051 −0.9356 1.2896 227. including computer programs for evaluating binary-interaction parameters from experimental data and then using these parameters to predict K values and phase equilibria. Chem.2569 1180.5473 1475.0922 1. Both use the method of Hayden and O’Connell ˆi [Ind. ethyl acetate (2) Methanol (1).9195 2.9876 −93. benzene (2) Ethanol (1). it is preferable to correlate and use liquid-phase activity coefficients for the dimerizing component by considering separately the partial pressures of the monomer and dimer.421 −10.8976 1.2126 −172.843 −10. methanol (2) 1-Propanol (1). water (2) Ethyl acetate (1) ethanol (2) n-Hexane (1).7365 1.5256 659.6600 −310. Prentice-Hall.8040 *Abstracted from Gmehling and Onken. water (2) Carbon tetrachloride (1). benzene (2) Methanol (1).5610 0. ethanol (2) Methanol (1). chloroform (2) Acetone (1).7070 2.1060 (λ21 − λ22) −506.0938 1.8643 0. 14. DECHEMA Chemistry Data ser.743 −10.2757 13-13 Wilson (cal/mol) (λ12 − λ11) 116.9450 0.2080 1844. and Rasmussen (Vapor-Liquid Equilibria Using UNIFAC.5797 1. for a binary system of components 1 and 2.8362 1..5} Detailed procedures. the following equations apply if an ideal gas is assumed: P1 = PD + PM PM + 2PD y1 = P (13-6) (13-7) Py1 P satx2 2 2(1 − y1 + [1 + 4KDPy1(2 − y1)]0. Elsevier.0623 4.0757 58. N.0400 0.8041 0.4785 0.4318 325. water (2) Methyl acetate (1). For example.

07131 B 1936.010 1210.84083 6.630 1788.] TABLE 13-4 Antoine Vapor-Pressure Constants and Liquid Molar Volume* Antoine constants† Species Acetic acid Acetone Benzene 1-Butanol Carbon tetrachloride Chloroform Ethanol Ethanol Ethyl acetate Formic acid n-Hexane Methanol Methyl acetate 1-Propanol 2-Propanol Tetrahydrofuran Water A 8. °C 18–118 (−13)–55 8–80 89–126 (−20)–77 (−10)–60 78–203 20–93 16–76 36–108 (−30)–170 15–84 2–56 (−15)–98 (−26)–83 23–100 1–100 vL. To convert cubic centimeters per gram-mole to cubic feet per pound-mole.198 1177.08097 7.91058 8.67 58. Wiley. Wiley.95465 7. 1981.36366 6. multiply by 0.951 1295.61 40. New York. AIChE J.881 218.02100 7.68 98. 5.280 239.254 233.92 81.726 219.427 220. NOTE: To convert degrees Celsius to degrees Fahrenheit.016.11220 7. [Henley and Seader.11714 6. 13-15 FIG. data of Sinor and Weber. 1981.760 1305. DECHEMA Chemistry Data ser.07 *Abstracted from Gmehling and Onken.05 89.55 18..91 131. liquid molar volume.232 193..87987 7.640 1582.426 Applicable temperature region.3 kPa (1 atm).864 1244. °F = 1.68 58.09 80.49 37. data of Yerazunis et al.13-14 DISTILLATION FIG.020 2010.590 1592. Vapor-Liquid Equilibrium Data Collection.94459 6. Chem. 1 (parts 1–10).630 C 258. †Antoine equation is log P sat = A − B/(T + C) with P sat in torr and T in °C.636 226.54 74.58670 8.73 79.451 229.595 1196.910 1170. Data.290 1730. J. 660 (1964). 1977.271 1157. Equilibrium-Stage Separation Operations in Chemical Engineering.84 75.37895 8. . cm3/ g⋅mol 57. 10.184 217. [Henley and Seader.99515 8.000 226.726 227.664 219. New York.438 252.576 226.768 226.8°C + 32.06524 8.87829 6.. vol.161 173.260 1189. Frankfurt.966 1281.97 97. 13-14 Liquid-phase activity coefficients for an n-heptane–toluene system at 101.10179 6.] Liquid-phase activity coefficients for an ethanol–n-hexane system. 243–247 (1960).320 1202. Equilibrium-Stage Separation Operations in Chemical Engineering.14 76. Eng.41 91.

ISOTHERMAL FLASH The calculation for a point on the flash curve that is intermediate between the bubble point and the dew point is referred to as an isothermal flash calculation because T2 is specified. phase distribution relation (K i = yi /xi). the dew point pressure can be calculated. composition. 19. Since yi = Kixi and since the xi’s still equal the feed compositions (denoted by zi). perhaps Constant Pressure Temperature. f V F = i K i zi 1 + (V/F)(K i − 1) zi(1 − K i) =0 1 + (V/F)(K i − 1) (13-13) (13-14) Equation (13-14) is solved iteratively for V/F. 30. Chem. 1. . Any one of a number of numerical root-finding procedures such as the Newton-Raphson. and sec.0. BUBBLE POINT AND DEW POINT For a given drum pressure and feed composition.. Or.0 Equilibrium flash separator. At the bubble point temperature. Pet.. Otherwise. one can find the bubble point pressure that satisfies this relationship. Values of Ki are constants if they are independent of liquid and vapor compositions. SINGLE-STAGE EQUILIBRIUM FLASH CALCULATIONS The simplest continuous distillation process is the adiabatic singlestage equilibrium flash process pictured in Fig.g.0 in the bubble formed.. A popular and recommended method is the following. 13-17. If. then Φ iL = P isat/P and ΦiV = 1. use a Henry’s law constant Hi. As in the case of the bubble point. The most common way to use these is to specify the feed rate. FIG. 2352 (1991)]. and it follows that yi = 1. and this fact can be used to calculate T2 (or T1 to give a desired T2). Technol. makes Kizi = 1. the bubble and dew point temperatures bracket the temperature range of the equilibrium flash. a trial-and-error search for the dew point temperature at a specified pressure is involved. Prausnitz et al. if the temperature is specified. 13-17 Equilibrium flash curve. 13-16 1. procedures for calculating an isothermal flash are iterative. (13-4). The expansion across the valve is at constant enthalpy. 4(10). followed by the calculation of values of xi and yi from Eqs. at the specified pressure. (13-14). due to Rachford and Rice [J. 2. The component mole balance (Fzi = Vyi + Lxi). the total vapor pressure exerted by the mixture becomes equal to the confining drum pressure. p.0 when the first droplet of liquid is about to form (saturated vapor) is the dew point temperature. [Ind. This operation will give one point on the equilibrium flash curve shown in Fig.M in place of the product γ L Φ L in i i Eq. see Hansen et al. (13-12) and (13-13) and L from the total mole balance. Equation (13-4) then reduces to Ki = γ LP sat i i P (13-10) 13-15 which is referred to as a modified Raoult’s law K value. If instead the temperature is specified. 13-16. Res. sec. Except for an ideal binary mixture. false-position. and total mole balance (F = V + L) can be combined to give zi xi = (13-12) 1 + (V/F)(K i − 1) yi = Since xi − yi = 0. while the drum provides disengaging space to allow the vapor to separate from the liquid. and the value at V/F = 1. 3 (October 1952)].0 must be satisfied. This curve shows the relation at constant pressure between the fraction V/F of the feed flashed and the drum temperature. Then the resulting calculations are straightforward. then γ L = 1. Otherwise Φ iL is evaluated from vapor pressure data with a Poynting saturated-vapor fugacity correction. The UNIFAC method is being periodically updated with new group contributions. furthermore. When the total pressure is less than about 202. the liquid phase is ideal. A degrees-of-freedom analysis indicates that the variables subject to the designer’s control are C + 3 in number.6 kPa (2 atm) and all components in the mixture have a critical temperature that is greater than the system temperature. the Ki values must be periodically updated for composition effects. calculation of the bubble point temperature involves a trial-and-error search for the temperature which.0 and i Ki = P sat i P (13-11) which is referred to as a Raoult’s law K value that is dependent solely on the vapor pressure P isat of the component in the mixture. e. Feed temperature and the pressure drop across the valve are adjusted to vaporize the feed to the desired extent. and pressure (C + 1 variables) plus the drum temperature T2 and pressure P2. °F 0. secant. or bisection method can be used to solve Eq. The temperature at V/F = 0.0 V/F FIG.0 when the first bubble of vapor is about to form (saturated liquid) is the bubble point temperature of the feed mixture. Eng.SINGLE-STAGE EQUILIBRIUM FLASH CALCULATIONS temperature of one or more components in the mixture. p. At the dew point temperature yi still equals zi and the relationship xi = zi Ki = 1.0.

after. as discussed by Michelsen [Comp. 2. (13-12) to (13-14) and the total mole balance. (13-14) reduces to the bubble point equation K i xi = 1 i (13-15) and the dew point equation. Research. McGraw-Hill. 41. which can then be corrected to the desired operating pressure. they can be considered separately and relatively simple procedures apply. COMPLEX MIXTURES Feed analyses in terms of component compositions are usually not available for complex hydrocarbon mixtures with a final normal boiling point above about 38°C (100°F) (n-pentane). the calculation proceeds as described above for multicomponent mixtures. 1685 (1955)] and Maxwell (Data Book on Hydrocarbons. it may be best to invert the sequence and assume a value for V. yi. 35. One method of handling such a feed is to break it down into pseudocomponents (narrow-boiling fractions) and then estimate the mole fraction and K value for each such component. 76. steady-state operating conditions is widely used in practice to separate a variety of mixtures. Eng. 1395 (1996)]. or in place of the valve with the required heat duty being calculated from an energy balance. (13-14) becomes f1{V. and water with higher alcohols (containing four or more carbon atoms). and the dew point. Computer-aided process design and simulation programs all contain a Gibbs free-energy routine that can compute a three-phase flash by minimization of the Gibbs free energy. Chem. and. solve Eq. OTHER FLASH SPECIFICATIONS Flash drum specifications in addition to (P2. the flash curve can be calculated directly without iteration. V. Chem.0 mol and eliminating L with the total mole balance. at which L = 0 and yi = zi. and.. xi and yi will each be very close to a value of 1. 47. Eng. and especially if the feed contains components of a narrow range of volatility. ADIABATIC FLASH In Fig. 21 (1982)]. The design of multistage columns can be accomplished by graphical techniques when the feed mixture contains only two components. 13-16. (13-17) becomes f2{V. which are given for the general case by Henley and Rosen (Material and Energy Balance Computations. which is also suitable for difficult isothermal flash calculations. The method is exact only for those systems in which energy effects on vapor and liquid rates leaving the stages are negligible. zi. 1963). 9. Weinberg. if P2 and the feed-stream conditions (that is. Mod.. T2 } = HF − V(HV − HL) − HL = 0 With T2 now unknown. (13-19) for T2. Wiley. i yi =1 Ki (13-16) For a binary feed. among other things. chap. Eq. equal latent heat for both components). as mentioned earlier. and then repeat the cycle. after each iteration. Condensation of such mixtures may result in one liquid phase being formed before the other. F. A discussion of this method and the necessary charts is presented in a later subsection Petroleum and Complex-Mixture Distillation. New York. 17. THREE-PHASE FLASH Single-stage equilibrium flash calculations become considerably more complex when an additional liquid phase can form. Most computer-aided process design and simulation programs permit a wide variety of flash specifications.. the following energy balance around both the valve and the flash drum combined must be included: HFF = HVV + HLL (13-17) By taking a basis of F = 1. Engng. Edmister [Ind. (13-18) and (13-19) simultaneously by a Newton or other suitable iterative technique. McDonald and Floudas [AIChE J.. (13-19) is solved iteratively by the isothermal flash procedure. [Ind. (13-18) is solved iteratively for a new approximation of T2. solve Eq. it may be necessary to solve Eqs.. Table 13-5. if T1 is fixed. using prorated values of xi and yi from Eqs. . 1958) give charts that are useful for this estimation. Many important and subtle aspects of three-phase flash calculations are discussed by Michelsen [Fluid Phase Equil. Dweck.. The x-y diagram method developed by McCabe and Thiele [Ind. and Armstrong [AIChE Symp. However. (13-12) and (13-13). respectively. Eng. T1. Chem. at which V = 0 and xi = zi. At these limits Eq. (13-18) for V.13-16 DISTILLATION until T2 and V converge. Van Nostrand. Alternatively. taken from the study of Mix. Princeton. Chem. Alternatively. The limits of applicability of Eqs. 431 (1993)]. Another approach to complex mixtures is to obtain an American Society for Testing and Materials (ASTM) or true-boiling point (TBP) curve for the mixture and then use empirical correlations to construct the atmospheric-pressure equilibrium flash vaporization (EFV) curve.. Eq. the two-tier method of Boston and Britt [Comput. L. P1) are known. Eng. T2) and (P2. specification of the flash drum temperature and pressure fixes the equilibrium-phase compositions. which is then used to initiate the next cycle GRAPHICAL METHODS FOR BINARY DISTILLATION Multistage distillation under continuous. 605 (1925)] uses only phase equilibrium and mole balance relationships. as in mixtures of water with hydrocarbons. 17. Ser. 10 (1980)] lists key components along with typical stage requirements to perform the separation for 27 industrial distillation processes. 1798 (1995)]. adiabatic) are possible but must be applied with care. Procedures for computing such situations are referred to as three-phase flash methods. However. Eq. If the K values and/or enthalpies are sensitive to the unknown phase compositions. 8). which are related to the K values by K1K2 − K1 1 − K2 and y1 = K2 − K1 K1 − K2 The mole balance can be rearranged to x1 = z1(K1 − K2) (1 − K2) − 1 V = K1 − 1 F If K1 and K2 are functions of temperature and pressure only (ideal solutions). 109 (1978)]. Eq. Chem. Generally the iterations are continued until the change in the absolute value of V/F is sufficiently small and until the absolute value of the residual f(V/F) is close to zero. 192. N. 1. a heat exchanger must be added before.T2} = i (13-18) zi(1 − K i) =0 1 + V(K i − 1) (13-19) A number of iterative procedures have been developed for solving Eqs. and xi is referred to as an adiabatic flash. if the feed contains components of a wide range of volatility. (13-12) to (13-14) are the bubble point. New York. 13. Once K values are available.. may be applied. convergence is rapid for a tearing method in which a value of T2 is assumed. then the calculation of T2. if desired. (13-18) and (13-19) simultaneously for V and T2. water with ethers. as discussed by Smith (Design of Equilibrium Stage Processes. When converged. The method assumes an adiabatic column (no heat losses through the column walls) and constant latent heat for the binary mixture at all compositions (which requires. using that value of V.J. 1968. the approach is simple and gives a useful first estimate of the column design which can be refined by using the enthalpy composition diagram method of Ponchon [Tech. When the two liquid phases are almost mutually insoluble. In addition to Eqs. and Wasylkiewicz et al. Frequently. T1 can be computed from an energy balance around the valve if no heat exchanger is used.

diagrams are useful for quick approximations. The approach is exact when the enthalpy composition surfaces are linear. 2001. ethanol-water) in which the component that is more volatile at low values of x1 becomes less volatile than the other component at high values of x1. weight. Consequently. 53 20 50 28 45 34 130 23 30 50 32 90 16 38 39. The vapor and liquid compositions are identical for the homogeneous azeotrope where curve B crosses the 45° diagonal (that is. 241. Doherty and Malone (Conceptual Design of Distillation Systems. An approximate equation-based approach based on the enthalpy composition diagram was proposed by Peters [Ind. (13-2) to components 1 and 2. 307 (1922)]. 1963) and Henley and Seader (Equilibrium-Stage Separation Operations in Chemical Engineering. for interpreting the results of equation-based methods. . Wiley. 55 (1921)] and Savarit [Arts Metiers. composition. system with heterogeneous azeotrope (two liquid phases in equilibrium with one vapor phase). approximate expression for representing the equilibrium y = x diagram. which gives insight into how a design changes under variations or uncertainty in design parameters such as thermodynamic properties. 20. Eng. 65. McGrawHill. and for demonstrating the effect of various design variables. New York. are applied here. The units used later for the phase flow rates must.00.25 is the azeotropic composition. feed flow rate. Then by applying Eq. 2001. Curve B. At a constant pressure of 1 atm these include benzene + toluene. McGrawHill. Nevertheless. Doherty and Malone (Conceptual Design of Distillation Systems. 142. 54 15 40 60 60 12 35 50 16 13-17 FIG. Mole fractions. benzene + p-xylene. It is sometimes permissible to assume constant relative volatility to approximate the equilibrium curve quickly.g. The y-x diagram is almost always plotted for the component that is the more volatile (denoted by the subscript 1) in the region where distillation is to take place. 178. of course. the preferred approach to design is equation-based since it provides answers rapidly and repeatedly without the tedium of redrawing graphs.. The y-x diagram can be plotted in mole.34. a feed with x1 = 0. 476 (1922)] with additional aspects developed later by others.9 could produce a bottom-product composition no lower than the azeotrope. and pressure. Curve C. α = 4.. The use of the enthalpy composition diagram is given by Smith (Design of Equilibrium Stage Processes. agree with those used for the equilibrium data. For the system described by curve B. and hexane + p-xylene. α = 7. The x-y diagram is the most convenient for these purposes. and data in Table 13-1 correspond to that case. Curve B is typical of many systems (e. app. 1981). Curve A shows the common case in which component 1 remains more volatile over the entire composition range. Similarly. 14. Curve A. 13-18. system with normal volatility. 13-18 can be plotted at either constant temperature or constant pressure but not both. 266. This approach uses the energy balance in addition to mole balance and phase equilibrium relationships and is rigorous when enough calorimetric data are available to construct the diagram without assumptions. in which there are two equilibrium liquid phases and one equilibrium vapor phase. temperature. Chem. McGraw-Hill. 2. the maximum overhead-product concentration that could be obtained from a feed with z1 = 0. sec. the curves in Fig. α= K1 y1x2 = K2 x1y2 which can be rewritten as (using x2 = 1 − x1 and y2 = 1 − y1) y1 = x1α 1 + (α − 1) x1 (13-20) With a constant value for α this equation provides a simple. New York. system with homogeneous azeotrope (one liquid phase). A) describe this method for binary mixtures and extend it to multicomponent systems. α = 2. and desired product compositions. Such an approach is especially useful for sensitivity analysis. or volume fractions.3) discuss this approximation in greater detail and give a selection of binary mixtures for which the approximation is reasonable.GRAPHICAL METHODS FOR BINARY DISTILLATION TABLE 13-5 Key Components and Typical Number of (Real) Stages Required to Perform the Separation for Distillation Processes of Industrial Importance Key components Hydrocarbon systems Ethylene-ethane Propylene-propane Propyne–1–3-butadiene 1–3 Butadiene-vinyl acetylene Benzene-toluene Benzene-ethyl benzene Benzene–diethyl benzene Toluene–ethyl benzene Toluene-xylenes Ethyl benzene–styrene o-Xylene-m-xylene Organic systems Methonol-formaldehyde Dichloroethane-trichloroethane Acetic acid–acetic anhydride Acetic anhydride–ethylene diacetate Vinyl acetate–ethyl acetate Ethylene glycol–diethylene glycol Cumene-phenol Phenol-acetophenone Aqueous systems HCN-water Acetic acid–water Methanol-water Ethanol-water Isopropanol-water Vinyl acetate–water Ethylene oxide–water Ethylene glycol–water Typical number of trays 73 138 40 130 34. An azeotrope limits the separation that can be obtained between components by simple distillation. The latter is more common. The phase rule permits only two variables to be specified arbitrarily in a binary two-phase mixture at equilibrium.82. and its use is developed in detail here. 13-18 Typical binary equilibrium curves. which are almost always used. x1 = y1). A heterogeneous azeotrope is formed by curve C. PHASE EQUILIBRIUM DIAGRAMS Three types of binary phase equilibrium curves are shown in Fig. With the widespread availability of computers.

Equation (13-21) has the analytical form of a straight line where L/V is the slope and DxD /V is the y intercept at x = 0. where S represents a sidestream product withdrawn above the feed plate. . the vapor rate must also be constant. FIG. 13-19 Two material balance envelopes in the top section of a distillation column. 13-20. The lines are made straight by the assumption of constant molar overflow. The liquid-phase flow rate is assumed to be constant from tray to tray in each section of the column between addition (feed) and withdrawal (product) points. These assumptions are most closely approximated for close-boiling isomers. For the envelope shown in Fig.13-18 DISTILLATION McCABE-THIELE METHOD Operating Lines The McCabe-Thiele method is based upon representation of the material balance equations as operating lines on the y-x diagram. The material balance equation for the column section below the sidestream is L′ DxD + SxS yn = xn+1 + V′ V′ (13-22) Material balance envelope which contains two external streams D and S. The result of these assumptions on the calculation method can be illustrated with Fig. The constant-molar-overflow assumption rests on several underlying thermodynamic assumptions. The other assumptions are adiabatic operation (no heat leaks) and no heat of mixing or sensible heat effects. 13-20 If the sidestream in Fig. 13-21 Material balance envelope around the bottom end of the column. The partial reboiler is equilibrium stage 1. If the liquid rate is constant. which eliminates the need for an energy balance. If the liquid flow rate Ln + 1 is assumed to be identical to Ln−1. the balance for the section below the feed becomes yn = L′ DxD − FzF xn + 1 + V′ V′ (13-23) where the primes designate the L and V below the sidestream. FIG. 13-19. The most important one is equal molar heats of vaporization for the two components. 13-20 is a feed (not necessarily a saturated liquid or vapor). V = V′ if a liquid sidestream is withdrawn and L = L′ if it is a vapor. Similar equations can be written for the bottom section of the column. 13-21. then Vn = Vn − 2 and the component material balance for both envelopes 1 and 2 can be represented by yn = L DxD xn+1 + V V (13-21) where y and x have a stage subscript n or n + 1. which shows two material balance envelopes cutting through the top section (above the top feed stream or sidestream) of the column. Since the sidestream must be a saturated phase. The effect of a sidestream withdrawal point is illustrated by Fig. FIG. but L and V need be identified only with the section of the column to which they apply.

furnish a set of operating lines. To calculate this change. Slope of q line is q/(q − 1).GRAPHICAL METHODS FOR BINARY DISTILLATION ym = L′ BxB xm + 1 − V′ V′ (13-24) 13-19 where the subscript m is used to identify the stage number in the bottom section. The known points on an operating line are usually its intersection with the y-x diagonal and/or its intersection with another operating line. It is easily shown that the q line must intersect the diagonal at zF. 13-23 All five cases of q lines: (1) superheated vapor feed. The quantity q can be used to derive the “q line equation” for a feed stream or a sidestream. The value of q is a measure of the thermal condition of the feed and represents the moles of saturated liquid formed in the feed stage per mole of feed. (2) saturated vapor feed. which meet at the feed stream or sidestream stage. Thermal Condition of the Feed The slope of the operating line changes whenever a feed stream or a sidestream is passed. (13-21) and using V − L = D to reduce the resulting equation to x = xD. when combined with Eqs. The derivation of Eq. the same y. This can be shown by substituting y = x in Eq. the same result is obtained for other column configurations. Typical q line constructions for sidestream stages are shown in Fig. This ratio in the operating line equation for the top section of the column [see Eq. it is convenient to introduce a quantity q which is defined by the following equations for a feed stream F: L′ = L + qF V = V′ + (1 − q)F (13-26) (13-27) FIG. An operating line can be located on the y-x diagram if (1) two points on the line are known or (2) one point and the slope are known. The slope of the q line is q/(q − 1). but the value of q will be either 1 or 0 depending upon whether the sidestream is taken from the liquid or the vapor stream. 13-24. However. A point on an operating line represents two passing streams. x point must satisfy both the operating line equation above the feed stream (or sidestream) stage and the one below the feed stream (or sidestream) stage. gives the q line equation zF q y= x− (13-28) q−1 q−1 A q line construction for a partially flashed feed is given in Fig. Figure 13-24 also shows the intersections of the operating lines with the diagonal construction line. Similarly (except for columns in which open steam is introduced at the bottom). (4) saturated liquid feed. Subtracting one equation from the other gives for a feed stage (V − V′)y = (L − L′)x + FzF which. 13-25. The q line is the locus of all points of intersection of the two operating lines. All five q line cases are shown in Fig. The q line shown is for a partially flashed feed. If yn and xn represent the compositions (in terms of the more volatile FIG. The plotted portions of the equilibrium curve (curved) and the operating line (straight) cover the composition range existing in the column section shown in the lower right-hand corner of the figure. The primes denote the streams below the stage to which the feed is introduced. The top operating line must always intersect the diagonal at the overhead-product composition xD. Equilibrium-Stage Construction Use of the equilibrium curve and the operating lines to “step off” equilibrium stages is illustrated in Fig. Note that when q = 1. (13-21)] is related to the external reflux ratio R = LN +1 /D by LN+1 L R RD = = = VN V (1 + R)D 1+R (13-25) when the reflux stream LN + 1 is a saturated liquid. (13-26) and (13-27). . (13-28) assumes a single-feed column and no sidestream. and (5) subcooled liquid feed. 13-22 Typical intersection of the two operating lines at the q line for a feed stage. the q line has infinite slope and is vertical. The slope L/V of the operating line is termed the internal reflux ratio. 13-22. This intersection must occur along that section of the q line between the equilibrium curve and the y = x diagonal. when plotted on the y-x diagram. (3) partially vaporized feed. Equations such as (13-21) through (13-24). At the point of intersection. the bottom operating line must always intersect the diagonal at the bottom-product composition xB. and the operating line itself is the locus of all possible pairs of passing streams within the column section to which the line applies. 13-23. The value of q for a particular feed can be estimated from q= energy to convert 1 mol of feed to saturated vapor molar heat of vaporization It takes on the following values for various thermal conditions of the feed: Subcooled liquid feed: q>1 Saturated liquid feed: q=1 Partially flashed feed: 0<q<1 Saturated vapor feed: q=0 Superheated vapor feed: q<0 Equations analogous to (13-26) and (13-27) can be written for a sidestream. Note that the q line for a sidestream must always intersect the diagonal at the composition (yS or xS) of the sidestream.

(a) Liquid sidestream near the top of the column. 13-25 Illustration of how equilibrium stages can be located on the x-y diagram through the alternating use of the equilibrium curve and the operating line. FIG.13-20 DISTILLATION FIG. . 13-24 Typical construction for a sidestream showing the intersection of the two operating lines with the q line and with the x-y diagonal. (b) Vapor sidestream near the bottom of the column.

is an existing column with a number of actual trays equivalent to eight equilibrium stages. and the resulting lower operating line is drawn.126 kg·mol/s (1000 lb·mol/h) of saturated liquid (q = 1). which is assumed to be 0.95. This is necessary because the vapor and liquid streams passing each other between the fourth and fifth stages must fall on the upper line. The feedstage location is fixed at stage 4 and the total number of stages at eight. The process. xB was used in this case. The equilibrium stages above and below stage n can be located by a vertical line through (yn. These may be used as follows as the basis for a graphical solution: Specifications Stage pressures (including reboiler) Condenser pressure Stage heat leaks (except reboiler) Pressure and heat leak in reflux divider Feed stream Feed-stage location Total number of stages N One overhead purity Reflux temperature Eternal reflux ratio Degrees of freedom N 1 N–1 2 C+2 1 1 1 1 1 C + 2N + 9 Pressures can be specified at any level below the safe working pressure of the column. The overhead purity is specified as xD = 0. Total Column Construction The graphical construction for an entire column is shown in Fig.818. (13-25) to convert the external reflux ratio of 4. In this problem. xn +1) to find (yn +1. and therefore a horizontal line (dashed) at yn must pass through the point (yn.GRAPHICAL METHODS FOR BINARY DISTILLATION 13-21 FIG. what bottom-product composition xB will the column produce under these specifications? Second. If the xB value were known. and the external reflux ratio is set at R = 4. and the upper operating line is drawn as shown in Fig. xn) on the equilibrium curve must represent the equilibrium stage n. 13-26 Construction for a column with a bubble point feed. An xB value is assumed. . Answers are desired to the following two questions. since the number of stages is fixed. and the feed rate is 0. what is the value of the top vapor rate VN in this operation. and all pressure drops within the column will be neglected. (13-111)]. 13-26 represents data at that pressure. This procedure can be repeated by alternating the use of equilibrium and operating lines upward or downward through the column to find the total number of equilibrium stages. component) of the equilibrium vapor and liquid leaving stage n. 13-26. The reflux temperature is the bubble point temperature (saturated reflux).5. at which time the construction switches to the upper operating line. xn +1) on the operating line since yn and xn+1 represent passing streams. All heat leaks will be assumed to be zero. and will it exceed the maximum vapor rate capacity for this column.95 is then located on the diagonal. The condenser pressure will be set at 275. xn) to find (yn−1. especially Fig.252 kg·mol/s (2000 lb·mol/h) at the top-tray conditions? The solution is started by using Eq. Likewise. The distillate composition xD = 0. This column configuration has C + 2N + 9 design variables (degrees of freedom) which must be specified to define one unique operation [see subsection Degrees of Freedom and Design Variables.8 kPa (40 psia). The equilibrium curve in Fig. a vertical line (dashed) at xn must intersect the operating line at point (yn −1. 13-62 and Eq. the bottom operating line could be immediately drawn from the xB value on the diagonal up to its required intersection point with the upper operating line on the feed q line. The stages can be stepped off by starting from either xB or xD. then point (yn. xn−1). a total condenser. The operating line is the locus for compositions of all possible pairs of passing streams within the section.5 to an internal reflux ratio of L/V = 0. The feed composition is 40 mol % of the more volatile component 1. 13-26. and a partial reboiler. the value of xB which gives a lower operating line that will require exactly eight stages must be found by trial and error. xn). A partial reboiler (equivalent to an equilibrium stage) and a total condenser are used. First. Note that the lower operating line is used until the fourth stage is passed. xn +1) and a horizontal line through (yn−1. pictured in the lower right-hand corner of the diagram.

will result in the widest separation between xD and xB for a given number of stages. The specified L/V ratio in the top section is 0. The xB that requires exactly eight equilibrium stages is xB = 0.051 kg·mol/s (405 lb·mol/h). If the distillate specification (xD = 0. 13-27 Graphical solution for a column with a partially flashed feed. The xB value must then move upward along the diagonal because the eight stages will not “reach” as far as before. and the rounding up to an integral number of actual trays should be done after that division. a liquid sidestream rate equal to D withdrawn from the second stage from the top. The 11. if the number of stages is not specified.5 + 1.848 1. Minimum Stages A column operating at total reflux is represented in Fig.) The lower operating line must run from the specified xB value on the diagonal to the required point of intersection on the feed q line.8 = 14. The new intersection of the upper line with the q line will lie closer to the equilibrium curve.0 + 1. that should be the designer’s choice.051(4.05. 13-27 is 80 percent. The operating line below the sidestream must intersect the diagonal at the “blend” of the sidestream and the overhead stream.95) is retained.4 will be divided by a tray efficiency.0)(0. The stages are stepped off from the top down in this case.4 stages are required to reach the specified xB = 0. with a given set of other operating specifications. xB = 0.95) = 0. For example.746) permits the location of the middle operating line. a liquid sidestream. Either of these criteria will always be satisfied if the operating line farthest from the equilibrium curve is used in each step.746. and the overhead condensate drum to their working levels. The specified compositions are zF = 0. the intersection point is x= (1. Another entire column with a partially vaporized feed. as in Fig. which is rounded up to 15. The column is then operated with no feed and with all the condensed overhead stream returned as reflux (LN+1 = VN and D = 0). the optimum feed location is the one that requires the lowest number of stages to accomplish a specified separation between xD and xB. and a total condenser is shown in Fig. If a new column were being designed. An overall component balance gives D = 0. Feed-Stage Location The optimum feed-stage location is that location which.95 on the diagonal. 13-28a.026. then the number of actual trays required is 11. the reflux rate must be reduced.746) + (1. These specifications permit the top operating line to be located and the two top stages stepped off to determine the liquid sidestream composition xs = 0. and a total condenser. Enough material has been charged to the column to fill the reboiler. However.0) = 0. 13-27. Either the purity specification must be reduced. if the average tray efficiency for the process modeled in Fig.4/0. Also all the liquid reaching the reboiler is . This will cause the upper operating line to pivot upward around its fixed point of xD = 0. and xD = 0.13-22 DISTILLATION FIG. the trays.818.95.5 percent at 95 percent purity. or we must be satisfied with a lower yield.0 This point plus the point of intersection of the two operating lines on the sidestream q line (vertical at xs = 0. It can be seen from Fig. 13-26.3. (The slope of the middle operating line could also have been used. Fractional equilibrium stages have meaning.40. and a total of about 11. Then VN = VB = LN+1 + D = D(R + 1) = 0. It can be seen that a badly mislocated feed (a feed that requires one to remain with an operating line until it closely approaches the equilibrium curve) can be very wasteful insofar as the effectiveness of the stages is concerned. Since S was specified to be equal to D in rate. The higher xB composition will reduce the recovery of component 1 in the 95 percent overhead product. 13-26 that the optimum feed location would have been the fifth tray for that operation.0)(0. This means that the column cannot provide an overhead-product yield of 40.05.280 kg⋅mol/s (2230 lb⋅mol/h) which exceeds the column capacity of 0. the feed stage on the diagram should correspond as closely as possible to the actual feed tray in the column. Or.252 kg·mol/s (2007 lb·mol/h). The sixth stage from the top is the feed stage. when an existing column is being modeled.

(a) Minimum stages for a column operating at total reflux with no feeds or products. .GRAPHICAL METHODS FOR BINARY DISTILLATION 13-23 (a) (b) FIG. (b) Minimum reflux for a binary system of normal volatility. 13-28 McCabe-Thiele diagrams for limiting cases.

FIG. 4. operating costs. the contact occurs at the feed q line. With a slope of unity (L/V = 1. and the sum of these is shown in Fig. [A distillation column of this type is shown in Perry’s Chemical Engineers’ Handbook. 13-29 McCabe-Thiele diagram for columns with and without an intermediate reboiler and an intermediate condenser. and a zone of constant composition is formed (see Doherty and Malone. As shown by Kayihan [AIChE Symp. Total reflux operation gives the minimum number of stages required to effect a specified separation between xB and xD. resulting in a tangent pinch point. 13-30. Generally. Intermediate Reboilers and Condensers When a large temperature difference exists between the ends of the column due to a wide boiling point difference between the components. Total boiling and condensing heat loads are the same for both columns. Difficult Separations Some binary separations may pose special problems because of extreme purity requirements for one or both FIG.] A column operating with an intermediate reboiler and an intermediate condenser in addition to a regular reboiler and a condenser is illustrated with the solid lines in Fig. and very steeply as the operating reflux ratio decreases. Minimum Reflux The minimum reflux ratio is defined as that ratio which if decreased by an infinitesimal amount would require an infinite number of stages to accomplish a specified separation between two components. . 13-31 Application of a 50 percent Murphree vapor-phase efficiency to each stage (excluding the reboiler) in the column. For equilibrium curves shaped like the one shown. the operating line must coincide with the diagonal throughout the column. 2001. pivoting around the specified xB and xD values. 76. 13-29.13-24 DISTILLATION vaporized and returned to the column as vapor. as is clear from the positions of the operating lines in Fig. Often an equilibrium curve will dip down closer to the diagonal at higher compositions. Figure 13-28b illustrates the minimum reflux condition. resulting in a feed pinch point. 13-30 Location of the optimum reflux for a given feed and specified sep- aration. 13-29. As the reflux ratio is reduced. it is recommended to select operating reflux ratios closer to 1. the two operating lines swing upward. Each step in the diagram corresponds to an actual stage. 2001. until one or both touch the equilibrium curve. Optimum Reflux Ratio The general effect of the operating reflux ratio on fixed costs. 7th ed.0 times the minimum value (see Doherty and Malone. the total cost curve rises slowly from its minimum value as the operating reflux ratio increases. Since F. Wherever the contact appears. Ln +1 = Vn at all points in the column.0). D. and B are all zero. Fig. the minimum on the total cost curve will generally occur at an operating reflux ratio in the inter- FIG. 1 (1980)]. 6 for additional discussion). or remove heat at a higher temperature. In ordinary situations. respectively.6 for additional information). the upper operating line may make contact before its intersection point on the q line reaches the equilibrium curve. chap. The concept has meaning only if a separation between two components is specified and the number of stages is not specified. 13-2a. (1986). 192. intermediate reboilers and/or condensers may be used to add heat at a lower temperature. the addition of intermediate reboilers and intermediate condensers increases thermodynamic efficiency but requires additional stages. In such cases.5 to 2. The dashed lines correspond to simple distillation with only a bottoms reboiler and an overhead condenser. In the absence of a detailed cost analysis for the specific separation of interest. the intersection of the operating line with the equilibrium curve produces a pinch point which contains a very large number of stages. 3 and sec. Ser. chap.1 to 2 times the minimum value. val 1.

News. However. The SB method is not presented here. the steps in Fig. 37.5 (13-30) where Ψ = (R − R min)/(R + 1). Two approximate multicomponent shortcut methods for simple distillation are the Smith-Brinkley (SB) method. 1930)] for application to absorbers and strippers is discussed at the end of this subsection. Chem. 48. cit. 22(21). Eng. The yn −1 and yn are the actual (nonequilibrium) values for vapor streams leaving the n − 1 and n stages. Eng.APPROXIMATE MULTICOMPONENT DISTILLATION METHODS products or because of a relative volatility close to 1.. The empirical correlation of Gilliland [Ind. but are not discussed here. application of a constant efficiency to each stage as in Fig. The y-x diagram is convenient for stepping off stages at extreme purities if it is plotted on log-log paper. satisfies the endpoints and fits the Gilliland curve reasonably well: N − Nmin = 1 − exp N+1 1 + 54. Chem. The Murphree efficiency is defined for the vapor phase as yn − yn−1 EMV = (13-29) y* − yn−1 n where y* is the composition of the vapor that would be in equilibrium n with the liquid leaving stage n and is the value read from the equilibrium curve. the derivation of the equation is shown. 482 (1932)] is used to calculate Nmin. Extensions of the SB method to nonideal mixtures and complex configurations are developed by Eckert and Hlavacek [Chem. which is based on an analytical solution of the finite-difference equations that can be written for staged separation processes when stages and interstage flow rates are known or assumed. Eng. Am. 1801 (1990). 34. minimum reflux from the Underwood equation... Chem. Both methods work best when mixtures are nearly ideal. but for all other stages the vapor leaving each stage is assumed to approach the equilibrium value y* only 50 percent of the way.. Underwood’s equations [J.e. 209 (1972)].4Ψ Ψ−1 × 11 + 117. Inst.. 43 (May 21. (13-31) and (13-32) is the effective value calculated from Eq. Or in extensive design and optimization studies. Miscellaneous Operations The y-x diagrams for several other column configurations have not been presented here. op. .. Chem. Stage Efficiency The use of the Murphree plate efficiency is particularly convenient on y-x diagrams. The application of a 50 percent Murphree vapor-phase efficiency on a y-x diagram is illustrated in Fig.).. APPROXIMATE MULTICOMPONENT DISTILLATION METHODS Some approximate calculation methods for the solution of multicomponent. which can then be investigated more exactly with a rigorous method. 13-31. Equation-Based Design Methods Exact design equations have been developed for mixtures with constant relative volatility. which is not covered here. cit. who also describe the more rigorous Ponchon-Savarit method. Eng. Sci. 603 (1948)] are used to estimate the minimum reflux ratio Rmin. 12(2). 425 (1982)]. 13-31 represent actual trays. Eng.. 1981). but is presented in detail in the 6th edition of Perry’s Chemical Engineers’ Handbook. 32. Also see Doherty and Malone (op. Thus. 32. [Int. 77 (1978)] and Eckert [Chem. respectively. 614 (1946). Eng. the minimum value of N. the approximate and very useful method of Kremser [Nat. and the Fenske-Underwood-Gilliland (FUG) method. and Chem. 1761 (1991)]. chap. The prediction and use of stage efficiencies are described in detail in Sec. Chem. and the total number of stages in each section of the column from either the Smoker equation (Trans.. 13-31 will not give the same answer as obtained when the number of equilibrium stages (obtained by using the true equilibrium curve) is divided by the same efficiency factor.. 598 (1946). The available phase equilibrium and enthalpy data may not be accurate enough to justify the longer rigorous methods. the SB and FUG methods are rating and design methods. 13-32 then uses these values to give N for any specified R. Sci. or Underwood’s method. respectively. The omitted items are partial condensers. which combines Fenske’s total reflux equation and Underwood’s minimum reflux equation with a graphical correlation by Gilliland that relates actual column performance to total and minimum reflux conditions for a specified separation between two key components. and Fidkowski et al.. 45. i. 24. 14. 1367 (1993)]. An analogous efficiency can be defined for the liquid phase. 31. Minimum stages can be computed with the Fenske equation. 1220 (1940)] shown in Fig. FENSKE-UNDERWOOD-GILLILAND (FUG) SHORTCUT METHOD In this approach. Inst. In general. 4). The Fenske total reflux equation can be written as xi xr or as Nmin = = (α i)N D min xi xr (13-31) B log[(DxD/BxB)i(BxB/DxD)r] log α i (13-32) where i is any component and r is an arbitrarily selected reference component in the definition of relative volatilities K yx αi = i = i r (13-33) Kr yrxi The particular value of αi used in Eqs. cit. chap. 44.). New York. as described in the subsection below. Pet.) and Henley and Seader (op. and introduction of open steam to the bottom stage to eliminate the reboiler. Eng. 37. developed by Molokanov et al. Alternative approaches based on mass-transfer rates are preferred. or R for any specified N. [AIChE J. respectively. These configurations are discussed in Smith (op. and its use is illustrated by Smith. rectifying columns (feed introduced to the bottom stage). The true equilibrium curve is used for the first stage (the partial reboiler is assumed to be an equilibrium stage).. Eng. 111 (1945). stripping columns (feed introduced to the top stage). Note that 13-25 for the yn −1 and yn values we assume that the vapor streams are completely mixed and uniform in composition.2Ψ Ψ 0. Pet.. 33. Equation-based methods have also been developed for nonconstant relative volatility mixtures (including nonideal and azeotropic mixtures) by Julka and Doherty [Chem. A pseudoequilibrium curve is drawn halfway (on a vertical line) between the operating lines and the true equilibrium curve. Conn sequently. such cases are best treated by equationbased design methods. Nonequilibrium Modeling. A detailed treatment of these approaches is given in Doherty and Malone (op. multistage separation problems continue to serve useful purposes even though computers are available to provide more rigorous solutions. 3).. However. a large number of cases can be worked quickly and cheaply by an approximate method to define roughly the optimum specifications. Sci. cit. (13-34) defined in terms of values for each stage in the column by α N = αN αN−1 · · · α 2 α1 (13-34) Equations (13-31) and (13-32) are exact relationships between the splits obtained for components i and r in a column at total reflux. Limitations of the Gilliland correlation are discussed by Henley and Seader (Equilibrium-Stage Separation Operations in Chemical Engineering. 165 (1938). Prog. Sci. The following equation. Eng. Wiley. Fenske’s equation [Ind. multiple feeds. which is the number of plates required to make a specified separation at total reflux. 32. cit. total reflux in the top section but not in the bottom section.

13-26

DISTILLATION equations developed by Underwood for a column at minimum reflux with separate zones of constant composition in each section. The common root value must fall between αhk and αlk, where hk and lk stand for heavy key and light key, respectively. The key components are the ones the designer wants to separate. In the butane-pentane splitter problem in Example 1, the light key is n-C4 and the heavy key is i-C5. The αi values in Eqs. (13-37) and (13-38) are effective values obtained from Eq. (13-35) or Eq. (13-36). Once these values are available, Θ can be calculated in a straightforward iteration from Eq. (13-38). Since the α-Θ difference can be small, Θ should be determined to four decimal places to avoid numerical difficulties. The (x iD)min values in Eq. (13-37) are minimum reflux values, i.e., the overhead composition that would be produced by the column operating at the minimum reflux with an infinite number of stages. When the light key and the heavy key are adjacent in relative volatility and the specified split between them is sharp or the relative volatilities of the other components are not close to those of the two keys, only the two keys will distribute at minimum reflux and the (xiD)min values are easily determined. This is often the case and is the only one considered here. Other cases in which some of or all the nonkey components distribute between distillate and bottom products are discussed in detail by Henley and Seader (op. cit.). The FUG method is convenient for new column design with the following specifications: 1. A value for R/Rmin 2. Desired split on the reference component (usually chosen as the heavy key) 3. Desired split on one other component (usually the light key) However, the total number of equilibrium stages N, N/Nmin, or the external reflux ratio can be substituted for one of these three specifications. Note that the feed location is automatically specified as the optimum one; this is assumed in the Underwood equations. The assumption of saturated liquid reflux is also inherent in the Fenske and Underwood equations (i.e., the reflux is not subcooled). An important limitation on the Underwood equations is the assumption of constant molar overflow. As discussed by Henley and Seader (op. cit.), this assumption can lead to a prediction of the minimum reflux that is considerably lower than the actual value. No such assumption is inherent in the Fenske equation. An exact calculation technique for minimum reflux is given by Tavana and Hansen [Ind. Eng. Chem. Process Des. Dev., 18, 154 (1979)]. Approximate explicit expressions for minimum reflux for various types of splits in three- and four-component mixtures were developed by Glinos and Malone [Ind. Eng. Chem. Process Des. Dev., 23, 764 (1984)] as well as lumping rules for applying their expressions to mixtures containing more than four components. These expressions are fairly accurate (usually within 5 percent of the exact value for Rmin) and are extremely convenient for using in the FUG method since they remove the tedious calculation of Rmin via the Underwood equations. A computer program for the FUG method is given by Chang [Hydrocarbon Process., 60(8), 79 (1980)]. The method is best applied to mixtures that form ideal or nearly ideal solutions, and should not be used for strongly nonideal or azeotropic mixtures. Example 1: Application of FUG Method A large butane-pentane splitter is to be shut down for repairs. Some of its feed will be diverted temporarily to an available smaller column, which has only 11 trays plus a partial reboiler. The feed enters on the middle tray. Past experience with similar feeds indicates that the 11 trays plus the reboiler are roughly equivalent to 10 equilibrium stages and that the column has a maximum top vapor capacity of 1.75 times the feed rate on a mole basis. The column will operate at a condenser pressure of 827.4 kPa (120 psia). The feed will be at its bubble point (q = 1.0) at the feed tray conditions and has the following composition on the basis of 0.0126 kg·mol/s (100 lb·mol/h):

Component C3 i-C4 n-C4 i-C5 n-C5 FxiF 5 15 25 20 35 100

FIG. 13-32 Comparison of rigorous calculations with Gilliland correlation. [Henley and Seader, Equilibrium-Stage Separation Operations in Chemical Engineering, Wiley, New York, 1981; data of Van Winkle and Todd, Chem. Eng., 78(21), 136 (Sept. 20, 1971); data of Gilliland, Elements of Fractional Distillation, 4th ed., McGraw-Hill, New York, 1950; data of Brown and Martin, Trans. Am. Inst. Chem. Eng., 35, 679 (1939).]

However, the value of α i must always be estimated, and this is where the approximation enters. It is usually estimated from α = (α top α bottom)1 2 or α = (α topα middleα bottom)1 3 (13-35) (13-36)

As a side note, the separation that will be accomplished in a column with a known number of equilibrium stages can often be reasonably well estimated by specifying the split of one component (designated as the reference component r), setting Nmin equal to 40 to 60 percent of the number of equilibrium stages (not actual trays), and then using Eq. (13-32) to estimate the splits of all the other components. This is an iterative calculation because the component splits must first be arbitrarily assumed to give end compositions that can be used to give initial end-temperature estimates. The αtop and αbottom values corresponding to these end temperatures are used in Eq. (13-5) to give αi values for each component. The iteration is continued until the αi values do not change from trial to trial. The Underwood minimum reflux equations of main interest are those that apply when some of the components do not appear in either the distillate or the bottom products at minimum reflux. These equations are α i(xiD)min = Rmin + 1 αi − Θ α iziF =1−q αi − Θ (13-37) (13-38)

i

and

i

The relative volatilities αi are defined by Eq. (13-33), Rmin is the minimum reflux ratio, and q describes the thermal condition of the feed (1 for a saturated liquid feed and 0 for a saturated vapor feed). The zi,F values are available from the given feed composition. The Θ is the common root for the top section equations and the bottom section

**APPROXIMATE MULTICOMPONENT DISTILLATION METHODS
**

The original column normally has less than 7 mol % i-C5 in the overhead and less than 3 mol % n-C4 in the bottom product when operating at a distillate rate of D/F = 0.489. Can these product purities be produced on the smaller column at D/F = 0.489? Pressure drops in the column will be neglected, and the K values will be read at 827 kPa (120 psia) in both column sections from the DePriester nomograph in Fig. 13-9b. When constant molar overflow is assumed in each section, the rates in pound moles per hour in the upper and lower sections are as follows: Top section D = (0.489)(100) = 48.9 V = (1.75)(100) = 175 L = 175 − 48.9 = 126.1 V = 1.388 L Bottom section B = 100 − 48.9 = 51.1 V′ = V = 175 L′ = L + F = 226.1 V′ = 0.7739 L′

13-27

composition for i-C5 is 7 percent; so it will be assumed that DxD = (0.07)(48.25) = 3.4 for i- C5 and that the split on that component will be 3.4/16.6. The results obtained with the new αi’s and the new i-C5 split are as follows: Component C3 i-C4 n-C4 i-C5 n-C5 α i6.0 322 68 1.00 0.415 0.2048α i6.0 65.9 13.9 0.205 0.085 FxiF 5 15 25 20 35 100 DxiD 5.0 14.8 23.3 3.4 2.7 49.2 BxiB 0.0 0.2 1.7 16.6 32.3 50.8 xiD 0.102 0.301 0.473 0.069 0.055 1.000 xiB 0.000 0.004 0.033 0.327 0.636 1.000

**L 126.1 = = 0.5577 L′ 226.1
**

R= 126.1 = 2.579 48.9

NOTE: To convert pound-moles per hour to kilogram-moles per second, multiply by 1.26 × 10−4.

Application of the FUG method is demonstrated on the splitter. Specifications necessary to model the existing column include these: 1. N = 10, total number of equilibrium stages 2. Optimum feed location (which may or may not reflect the actual location) 3. Maximum V/F at the top tray of 1.75 4. Split on one component given in the following paragraphs The solution starts with an assumed arbitrary split of all the components to give estimates of top and bottom compositions that can be used to get initial end temperatures. The αi’s evaluated at these temperatures are averaged with the α at the feed-stage temperature (assumed to be the bubble point of the feed) by using Eq. (13-36). The initial assumption for the split on i-C5 is DxD /BxB = 3.15/16.85. As mentioned earlier, Nmin usually ranges from 0.4N to 0.6N, and the initial Nmin value assumed here will be (0.6)(10) = 6.0. Equation (13-32) can be rewritten as DxD FxF − DxD or = α 6.0 i

i

The calculated i-C5 composition in the overhead stream is 6.9 percent, which is close enough to the target value of 7.0 for now. Table 13-6 shows subsequent calculations using the Underwood minimum reflux equations. The α and xD values in Table 13-6 are those from the Fenske total reflux calculation. As noted earlier, the xD values should be those at minimum reflux. This inconsistency may reduce the accuracy of the Underwood method; but to be useful, a shortcut method must be fast, and it has not been shown that a more rigorous estimation of xD values results in an overall improvement in accuracy. The calculated Rmin is 0.9426. The actual reflux assumed is obtained from the specified maximum top vapor rate of 0.022 kg⋅mol/s [175 lb⋅ (mol/h)] and the calculated D of 49.2 (from the Fenske equation). LN +1 = VN − D 175 R = VN − 1 = − 1 = 2.557 D 49.2 The values of Rmin = 0.9426, R = 2.557, and N = 10 are now used with the Gilliland correlation in Fig. 13-32 or Eq. (13-30) to check the initially assumed value of 6.0 for Nmin. Equation (13-30) gives Nmin = 6.95, which differs from the assumed value. Repetition of the calculations with Nmin = 7 gives R = 2.519, Rmin = 0.9782, and a calculated check value of Nmin = 6.85, which is close enough. The final product compositions and the α values used are as follows: Component C3 i-C4 n-C4 i-C5 n-C5 αi 4.98 2.61 2.02 1.00 0.851 DxiD 5.00 14.91 24.16 3.48 2.23 49.78 BxiB 0 0.09 0.84 16.52 32.87 50.32 xiD 0.1004 0.2996 0.4852 0.0700 0.0448 1.0000 xiB 0.0 0.0017 0.0168 0.3283 0.6532 1.0000

3.15 16.85

= α 6.0(0.1869) i

DxiD =

0.1869α 6.0 i FxiF 1 + 0.1869α 6.0 i

The evaluation of this equation for each component is as follows: Component C3 i-C4 n-C4 i-C5 n-C5 αi 5.00 2.63 2.01 1.00 0.843 α 6.0 i 330 66 1.00 0.36 0.1869α 6.0 i 61.7 12.3 0.187 0.0672 FxiF 5 15 25 20 35 100 DxiD 5.0 14.8 25.1 3.15 2.20 48.25 BxiB 0.0 0.2 1.9 16.85 32.80 51.75

These results indicate that the 7 percent composition of i-C5 in D and the 3 percent composition of i-C4 in B obtained in the original column can also be obtained with the smaller column. These results disagree somewhat with the answers obtained from a rigorous computer solution, as shown in the following comparison. However, given the approximations that went into the FUG method, the agreement is good. xiD Component C3 i-C4 n-C4 i-C5 n-C5 Rigorous 0.102 0.299 0.473 0.073 0.053 1.000 FUG 0.100 0.300 0.485 0.070 0.045 1.000 Rigorous 0.0 0.006 0.037 0.322 0.635 1.000 xiB FUG 0.0 0.002 0.017 0.328 0.653 1.000

The end temperatures corresponding to these product compositions are 344 K (159°F) and 386 K (236°F). These temperatures plus the feed bubble point temperature of 358 K (185°F) provide a new set of α i’s which vary only slightly from those used earlier. Consequently, the D = 48.25 value is not expected to vary greatly and will be used to estimate a new i-C5 split. The desired distillate

TABLE 13-6 Application of Underwood Equations θ = 1.36 Component C3 i-C4 n-C4 i-C5 n-C5 xF 0.05 0.15 0.25 0.20 0.35 1.00 α 4.99 2.62 2.02 1.00 0.864 αxF 0.2495 0.3930 0.5050 0.2000 0.3024 α−θ 3.63 1.26 0.66 −0.36 −0.496 αxF α−θ α−θ θ = 1.365 αxF α−θ 0.0688 0.3131 0.7710 −0.5479 −0.6036 +0.0014 αxD 0.5090 0.7886 0.9555 0.0690 0.0475 α−θ 3.6253 1.2553 0.6553 −0.3647 −0.5007 αxD α−θ 0.1404 0.6282 1.4581 −0.1892 −0.0949 1.9426 = Rm + 1

xD 0.102 0.301 0.473 0.069 0.055 1.000

0.0687 0.3119 0.7651 −0.5556 −0.6097 −0.0196

3.625 1.255 0.655 −0.365 −0.501

Interpolation gives θ = 1.3647.

13-28

DISTILLATION

KREMSER EQUATION Starting with the classical method of Kremser (op. cit.), approximate methods of increasing complexity have been developed to calculate the behavior of groups of equilibrium stages for a countercurrent cascade, such as is used in simple absorbers and strippers of the type shown in Fig. 13-2b and d. However, none of these methods can adequately account for stage temperatures that are considerably higher or lower than the two entering stream temperatures for absorption and stripping, respectively, when appreciable composition changes occur. Therefore, only the simplest form of the Kremser method is presented here. Fortunately, rigorous computer methods described later can be applied when accurate results are required. The Kremser method is most useful for making preliminary estimates of absorbent and stripping agent flow rates or equilibrium-stage requirements. The method can also be used to extrapolate quickly results of a rigorous solution to a different number of equilibrium stages. Consider the general adiabatic countercurrent cascade of Fig. 13-33 where v and are molar component flow rates. Regardless of whether the cascade is an absorber or a stripper, components in the entering vapor will tend to be absorbed and components in the entering liquid will tend to be stripped. If more moles are stripped than absorbed, the cascade is a stripper; otherwise, the cascade is an absorber. The Kremser method is general and applies to either case. Application of component material balance and phase equilibrium equations successively to stages 1 through N − 1, 1 through N − 2, etc., as shown by Henley and Seader (op. cit.), leads to the following equations originally derived by Kremser. For each component i, (vi)N = (vi)0(Φi)A = (li)N+1[1 − (Φi)s] where (Φi)A = (A i)c − 1 (Ai)N+1 − 1 c (Si)c − 1 (Si)N+1 − 1 c (13-39) (13-40)

FIG. 13-33

General adiabatic countercurrent cascade for simple absorption

or stripping.

is the fraction of component i in the entering vapor that is not absorbed, (Φi)s = (13-41)

is the fraction of component i in the entering liquid that is not stripped, L (Ai)e = (13-42) K iV e is the effective or average absorption factor for component i, and 1 (13-43) (Ai)e is the effective or average stripping factor for component i. When the entering streams are at the same temperature and pressure and negligible absorption and stripping occur, effective component absorption and stripping factors are determined simply by entering stream conditions. Thus, if K values are composition-independent, then LN +1 1 (Ai)e = = (13-44) K i(TN +1, PN +1)V0 (Si)e (Si)e =

When entering stream temperatures differ and/or moderate to appreciable absorption and/or stripping occurs, values of A i and Si should be based on effective average values of L, V, and K i in the cascade. However, even then Eq. (13-44) with TN+1 replaced by (TN+1 + T0)/2 may be able to give a first-order approximation of (Ai)e. In the case of an absorber, LN+1 < Le and V0 > Ve will be compensated to some extent by Ki{(TN+1 + T0)/2, P)} < K i{Te, P}. A similar compensation, but in opposite directions, will occur in the case of a stripper. Equations (13-40) and (13-41) are plotted in Fig. 13-34. Components having large values of Ae or Se absorb or strip, respectively, to a large extent. Corresponding values of ΦA and ΦS approach a value of 1 and are almost independent of the number of equilibrium stages. An estimate of the minimum absorbent flow rate for a specified amount of absorption from the entering gas of some key component K for a cascade with an infinite number of equilibrium stages is obtained from Eq. (13-40) as (LN +1)min = KKV0[1 − (ΦK)A] (13-45)

The corresponding estimate of minimum stripping agent flow rate for a stripper is obtained as (V0)min = LN +1[1 − (ΦK)s] KK (13-46)

Example 2: Calculation of Kremser Method For the simple absorber specified in Fig. 13-35, a rigorous calculation procedure as described below gives the results in Table 13-7. Values of Φ were computed from component

TABLE 13-7 Results of Calculations for Simple Absorber of Fig. 13-35 N = 6 (rigorous method) (lb⋅mol)/h Component C1 C2 C3 nC4 nC5 Absorber oil Totals

NOTE:

N = 12 (Kremser method) (lb⋅mol)/h (Φi)S (Ai)e 0.0772 0.2541 0.5692 1.3693 3.6 0.9997 0.0003 (Si)e (vi)12 147.64 275.98 103.46 0.16 0 0.05 527.29 ( i)1 12.36 94.02 136.54 24.84 5.0 164.95 437.71 (Φi)A 0.9228 0.7459 0.4311 0.0063 0.0 0.9997 (Φi)S

(vi)6 147.64 276.03 105.42 1.15 0.0015 0.05 530.29

( i)1 12.36 94.97 134.58 23.85 4.9985 164.95 435.71

(Φi)A 0.9228 0.7460 0.4393 0.0460 0.0003

To convert pound-moles per hour to kilogram-moles per hour, multiply by 0.454.

3. The degree of stripping of the absorber oil is essentially unchanged. (13-41). Use the Kremser method to estimate component product rates if N is doubled to a value of 12. [W. somewhat increased amounts of absorption occur. and (13-39) gives the results in the last four columns of Table 13-7. Edmister. . (13-40) and (13-41) with N = 6. Application of Eqs. and corresponding effective absorption and stripping factors were obtained by iterative calculations in using Eqs. Overall.] product flow rates. only an additional 0. Assume that values of Ae and Se will not change with a change in N. C. 13-34 Absorption and stripping factors.. Because of its small value of Ae. For the other components. AIChE J. (13-40).APPROXIMATE MULTICOMPONENT DISTILLATION METHODS 13-29 FIG. the extent of absorption of C1 is unchanged.5 percent of absorption occurs. The greatest increase in absorption occurs for n-C4. to the extent of about 4 percent. 165–171 (1957).

two-product columns). and supercritical extraction. 13-36b. S stands for mole fraction summation equations. nearly always operate away from equilibrium. and H refers to the heat or enthalpy balance equations. thus rV = j c i=1 (13-47) (13-49) xi. A complete separation process is modeled as a sequence of these equilibrium stages. In recent years it has become possible to simulate distillation and absorption as the mass-transfer rate-based operations that they really are. 4 of this handbook) • Degrees-of-freedom analysis • Solution of large linear and strongly nonlinear systems of equations These are the topics we consider in what follows. as shown in Fig. 13-36a. petroleum distillation. requires us to address the following topics: • Formulation of the model equations • Physical property data and calculations (see Sec. The M equations are the material balance equations. using what have become known as nonequilibrium (NEQ) or rate-based models [Taylor et al. Vapor from the stage below and liquid from a stage above are brought into contact on the stage together with any fresh or recycle feeds. Real distillation processes. it has been used to model a wide variety of distillation-like processes. There are two types of material balance: the total material balance Vj +1 + Lj −1 + Fj − (1 + r V)Vj − (1 + r L)Lj = 0 j j and the component material balance Vj +1 yi. EQUILIBRIUM-STAGE MODELING A schematic diagram of an equilibrium stage is shown in Fig. We also discuss the use of simulation tools in the modeling of real distillation columns. multiple-product columns). CEP (July 28. 13-35 Specifications for the absorber example. j = 1 (13-50) The enthalpy balance is given by L Vj+1HV + Lj−1Hj−1 + FjHF − (1 + rV)VjHV − (1 + r L)LjHL − Qj = 0 (13-51) j+1 j j j j j The superscripted H′s are the enthalpies of the appropriate phase. 2003)]. complex distillation (multiple-feed. j − (1 + rV)Vj yi. j = 0 (13-48) j j In the material balance equations given above. j +1 + Lj −1 xi. SIMULATION OF DISTILLATION PROCESSES Chemical engineers have been solving distillation problems by using the equilibrium-stage model since 1893 when Sorel outlined the concept to describe the distillation of alcohol.13-30 DISTILLATION FIG. The MESH Equations (the 2c 3 Formulation) The equations that model equilibrium stages often are referred to as the MESH equations. however. liquid-liquid extraction. including simple distillation (single-feed. rj is the ratio of sidestream flow to interstage flow: Uj Wj rL = j Vj Lj Mole fractions must be forced to sum to unity. j = 1 c i=1 yi. E stands for equilibrium equations. absorption. Since that time. j − (1 + r L)Lj xi. The computer simulation of distillation processes. j −1 + Fj zi. extractive and azeotropic distillation. The vapor and liquid streams leaving the stage are assumed to be in equilibrium with each other. .. whether done using equilibrium or nonequilibrium models. j = 1 c i=1 zi. stripping.

The total number of variables appearing in these equations is 3c + 10. The table below shows how we may need to solve hundreds or even thousands of equations. j (13-52) The Ki. we assume that these two streams are in equilibrium with each other. The remaining variables.SIMULATION OF DISTILLATION PROCESSES Vj yi. j Lj−1 yi. j. There are 2c + 4 equations per stage. one of these equations must be ignored in a (computer-based) method to solve the equations. Thus. c – 1 mole fractions in the feed (the last is then computed directly from the feed mole fraction summation equation. an alternative is to combine the vapor and liquid mole fraction summation equations (as was done for flash calculations by Rachford and Rice. Thus. however. The quantities for stage j that appear in these equations are summarized in Table 13-9. cit. j Vj−1 Uj−1 Fj−1 Stage j −1 Uj Vj Lj−1 Wj−1 Fj Uj+1 Fj+1 Uj+2 Fj+2 Stage j Vj+1 Lj Wj Stage j +1 Vj+2 Lj+1 Wj+1 only 2c + 3 are independent.). j Stage j Wj xi. Degrees-of-Freedom Analysis and Problem Formulation Table 13-8 summarizes the equations for a single equilibrium stage (in a sequence of stages). it is usual to add equations that relate the compositions of the two streams leaving the stage. In the standard model of a distillation column. pressure. op. j = Ki. TABLE 13-9 Variables for an Equilibrium Stage Variable Symbol Vj Lj Fj Wj Uj yi. (b) Multistage column. For a column of N stages. and composition. that need to be specified are the stage pressure Pj. j Uj yi. the subsection Degrees of Freedom below in which this topic is revisited in greater detail). the mole fractions in the exiting streams are related by the familiar equations of phase equilibrium: yi. the latter “belong” to the equation set for adjacent stages (see. j Vj+1 yi. j. quantities that do appear in the table of variables. Thermodynamic properties are functions of temperature. and the sidestream flows Uj and Wj. j are the equilibrium ratios or K values for species i on stage j. nor are equations for their estimation included in the list of equations. temperature and pressure of the feed. which was not included in the equations for stage j in Table 13-8). the stage heat duty Qj.j Tj Pj Qj Number 1 1 1 1 1 c c c 1 1 1 1 1 3c + 10 Vapor flow rate Liquid flow rate Feed flow rate Vapor sidestream flow Liquid sidestream flow Vapor-phase mole fractions Liquid-phase mole fractions Feed composition Stage temperature Stage pressure Feed temperature Feed pressure Stage heat duty To complete the model. the c liquid mole fractions xi.j xi. the stage temperature Tj. j xi. c 2 3 5 10 40 N 10 20 50 30 100 N(2c + 3) 70 180 650 690 8300 Stage j +2 Wj+2 Lj+2 (b) FIG. In some methods we disregard the total material balance. 13-36 (a) The equilibrium stage. Note that the mole fraction summation equations for the feed are omitted here. as are the mole fraction summation equations for interstage vapor and liquid traffic. of which . c + 7 in number (the difference between the number of variables and the number of independent equations). It is important to recognize that the other flows and composition variables appearing in the MESH equations are associated with the equivalent equations for adjacent stages. The 2c + 3 unknown variables normally determined by solving the MESH equations are the c vapor mole fractions yi. j−1 TABLE 13-8 Equations for an Equilibrium Stage Equation Total mass balance Component mass balances Total energy balance Mole fraction summation equations Equilibrium equations Equation no. the feed flow rate. we must solve N(2c + 3) equations. Note that the K values and enthalpies that also appear in the MESH equations are not included in the table of variables. (13-47) (13-48) (13-51) (13-50) (13-52) 13-31 Number 1 c 1 2 c 2c + 4 Fj zi. and the vapor and liquid flow Vj and Lj. j+1 (a) Lj xi.j zi.

for a total condenser and the reflux stream splitter at the top of a distillation column. cit. Tearing methods in which the equations are divided into groups and each group is solved separately 2. and continuation method. the K values depend on the vapor-phase composition). op. For a partial condenser (with no 1 stream splitter needed) the vapor product is V1 and the reflux ratio R = L1/V1. cit. Collocation methods 7. such methods have largely been replaced by the inside-out methods that now are standard in all major (and many less widely used) flow sheet simulation programs. Condenser and Reboiler The MESH equations given above apply to all the interior stages of a column. It is less useful if vapor-phase nonideality is important (and. any reboiler and condenser must be considered. and modeled by the appropriate balance equations (see the section below on Degrees of Freedom where we address this topic in greater detail). from the late 1950s to the early 1990s hardly a year passed without the publication of at least one (and usually many more than one) new algorithm for solving these equations (Seader. j = 0 j j (13-55) and from the summation equation c i=1 Ki. It is possible to make the case that it was the equilibrium model that brought computing into chemical engineering in the first place! One of the incentives for this activity has always been a desire to solve problems with which existing methods have trouble. There are two key steps in the development of an algorithm for solving systems of nonlinear equations: • The selection of particular numerical methods • The selection of the order in which the equations are to be solved We may identify several classes of methods for numerically solving the MESH equations: 1. simultaneous convergence methods. In such cases it is necessary to specify either the actual temperature of the reflux stream or the difference in temperature between the reflux stream and the bubble point of the condensate. In this variation. j xi. insideout methods. therefore. j −1 + fi. cit. the vapor-phase mole fractions no longer are independent variables but are defined by Eq. cit. Optimization methods The methods for solving the MESH equations that are used most widely fall into categories 1 through 3 and 5—tearing methods. Seader and Henley.13-32 DISTILLATION For a total condenser. Simultaneous convergence (SC) methods in which all the equations are solved at the same time simultaneously by using Newton’s method (or a variant thereof) 4. op.g. we make use of the component flow defined by vij = Vj yij lij = Lj xij fij = Fj zij (13-53) In terms of the component flow. It often happens that the temperature of the reflux stream is below the bubble point temperature of the condensed liquid (subcooled condenser). therefore. and the form of the model equations being solved. pressure. In addition. • Computer-based methods. j +1 xi. j +1 + li. In computer-based methods for solving the MESH equations. Following the sections on each of these three classes of method. Some graphical methods retain their value for a variety of reasons and were discussed at length in a prior subsection. the development of mathematical techniques that can be exploited. Even homotopy methods (sometimes considered to belong The 2c + 1 Formulation An alternative form of the MESH equations is used in many algorithms. Note that an equilibrium stage with a sidestream is considered here to be a single unit in essentially the same way. the number of equations and variables per stage has been reduced by 2 to 2c + 1. King. cit. In this formulation of the MESH equations. Holland. These methods were the subject of the immediately preceding subsection. (13-52).. In these a great many simplifying assumptions are made to obtain solutions of the model equations. the summation equations and total mass balance equation are satisfied automatically. 1992)].). j +1 + Lj−1 xi. the sum of the component flow rates of the respective phases.) has written an interesting history of equilibrium-stage simulation. Continuation methods 6.. j − (1 + rV)vi. the bottoms flow rate is LN... a total condenser may be followed by a reflux accumulator and a stream divider. for a partial reboiler at the base of a column. op. Haas (in Kister op. For many years the older tearing methods formed the backbone of sequential modular flow sheet simulation programs. The accumulator does not add any equations to a steady-state model (but it is important to consider in an un-steady-state model). A condenser/splitter device unit that provides both vapor and liquid products is given by a combination of these two units. j = 1 (13-56) This equation is familiar to us from bubble point calculations. it is possible to calculate them from the energy balances after all the other model equations have been solved. Inside-out (IO) methods 3. These methods were developed before modern computer methods became widely adopted. Seader (op. . The c + 3 Formulation The number of unknown variables per stage can be reduced to only c + 3 if we use the equilibrium relations to eliminate the vapor-phase mole fractions from the component mass balances Vj +1Ki. Simultaneous convergence methods also now are available in many of these systems. j = 0 j j (13-54) Since the total vapor and liquid flow rates are. In practice the condenser and reflux splitter often are modeled as a single combined unit. The evolution of algorithms for solving the stage model equations has been influenced by. j − (1 + r L)li. the availability (or lack) of sufficient computer storage and speed. For example. and the MESH equations described above may be used to model these stages with only some minor modifications. it is common to replace the energy balance of the condenser (with or without the associated stream splitter) and reboiler with a specification equation. We continue with a brief discussion of computer-based methods. the component material balance becomes vi. among other things. Thus. The MESH equations form a set of nonlinear. j − (1 + rV)VjKi. Relaxation methods in which the MESH equations are cast in unsteady-state form and integrated numerically until the steady-state solution has been found 5. the liquid distillate is U1 and the reflux ratio R = 1/r L. In addition. These vapor mole fractions are not used in the component mass balances since there is no vapor stream from a total condenser. This formulation of the MESH equations has been used in quite a number of algorithms. be solved by some iterative process. algebraic equations (in the sense that no derivatives or integrals are involved) and must. op. Solution of the MESH Equations We may identify several classes of methods of solving the equilibrium-stage model equations: • Graphical methods. Possible specifications include • The flow rate of the distillate/bottoms product stream • The mole fraction of a component in either the distillate or bottoms product stream • Component flow rate in either the distillate or bottoms product stream • A reflux/reboil ratio or rate • The temperature of the condenser or reboiler • The heat duty to the condenser or reboiler If the condenser and/or reboiler heat duties are not specified. but the stream splitter is a separate unit with its own temperature. j xi. many computerbased methods are discussed at length in a number of textbooks [see. Finally. the vapor composition used in the equilibrium relations is that determined during a bubble point calculation based on the actual pressure and liquid compositions found in the condenser. j − (1 + r L)Lj xi. and heat loss. Readers interested in complete details of the methods discussed should consult the references cited below. by definition. On an actual plant. we discuss homotopy continuation methods. • Approximate methods. j−1 + Fj zi. e. Indeed. the complexity of physical property (K value and enthalpy) correlations. cit.

) who used matrix inversion to solve equations. intermediate. 13. Eng. Billingsley and Boynton. 2. 16. implement such a technique. 52. 14.and composition-dependent physical properties are used. Chem. Matrix techniques were first used in separation process calculations by Amundson and Pontinen [Ind. 901 (1990)] developed a modified SR method that is capable of solving problems involving narrow. e. 86 (8). op. Despite their essential simplicity and appeal.g. Eng. having a locally quadratic convergence rate in the case of Newton’s method.. Other possible drawbacks (at least in some cases) include the number of times physical properties must be evaluated (several times per outer loop iteration) if temperature. Seader and Henley (op. Jelinek [Comput. Eng. (20). we may use continuation . 50. cit.. Chem. tearing methods may be analyzed in the following terms: • The order in which the equations are grouped • The order in which each group of equations is solved • The selection of which variables are to be computed from which equation Subsequent issues are • The method(s) used to solve the M and E equations • The method of calculating the new stage temperatures • The method of calculating the new flow rates Vj and Lj Most tearing methods are based on keeping all the equations of a given type together. For example. of equations. Other problems can arise if any of the iteration loops are hard to converge. The “torn” set of equations is then solved for the “tear” variables. The development of methods for solving all the equations at the same time was tackled independently by a number of investigators. Simultaneous convergence procedures have shown themselves to be generally fast and reliable. 135 (1980).. 23. cit. Engng. by Savarit. 105 (1984). 496 (1932)] and Thiele and Geddes [Ind.. Many others have since employed Newton’s method or a related method to solve the MESH equations.) have combined some of these ideas with the “theta method” of convergence acceleration. 229 (1970)]. To start the calculations. Sujuta used the 2c + 1 version of the MESH equations in his work and the tridiagonal system of combined M + E equations was written in terms of the component flow rates in the liquid phase.. and Chem. Ser. Process Des. Chem. A great many tearing methods for solving the MESH equations have been proposed. Dev. the vapor and liquid flow rates are computed directly from the summation equations and the stage temperatures determined from the energy balances. Thesis. however. The two best-known papers are those of Goldstein and Stanfield [Ind. Engng.D. In the sum rates (SR) method. the BP methods are more successful for distillation. Similar methods are described by Holland (op. 9. however. our remarks above on modified BP and SR methods). the process starts over and is repeated until all the equations are satisfied simultaneously. Chem. 195 (1988)]. 45–54 (1990)]. University of Manchester Institute of Science and Technology (1964)] (see Stainthorp and Whitehouse [I.. 2. In these methods. 12. Successive groups of equations and variables are torn or decoupled from the full set of equations and variables until all the variables have been updated. Eng. the liquid flow rates follow from the total material balances [Tierney and coworkers. 8. most often for simulating systems for which tearing and inside-out methods are less successful (typically those that involve strongly nonideal mixtures). Eng. 148 (1971)]. 556 (1967). Inside-Out Methods First proposed by Boston and Sullivan [Can.. Engr. Symp. 90. 15. Chem. x. V. and since modeling a column could require hundreds. 290 (1933)] represent the first attempts at solving the MESH equations for multicomponent systems numerically (the graphical methods for binary systems discussed earlier had already been developed by Ponchon. Three quite different approaches to the problem of computing the flow rates and temperatures have evolved: 1. or Q on any stage. and wideboiling mixtures alike. the S + E equations are used to determine the stage temperatures from a bubble point calculation. 13. 40(12). Chem.. Interlinked systems of columns and nonideal solutions could be dealt with even though no examples of the latter type were solved by Whitehouse. Prog. 24. 78 (1970)] and Naphtali and Sandholm [AIChE J. stage-to-stage calculation procedures are not used now as often as they used to be. 163 (1967)] incorporated the Thomas algorithm in their implementation of the SR method. L. y are replaced by variables within the simple models that are relatively free of interactions with each other. No. The vapor and liquid flow rates are computed from the energy balances and total material balances. Chem. Chem. their very widespread use in many commercial simulation programs demands that they be granted a category all to themselves. Holland and coworkers (Holland. E. 17. The classic papers by Lewis and Matheson [Ind.). A significant improvement in the BP method was introduced by Wang and Henke [Hydrocarbon Process. AIChE J. Inside-out methods have replaced many of the older algorithms in commercial simulation programs.. cit. cit. the modified version of Russell [Chem.. 109 (1978).. Such methods have become standard in commercial process simulation programs. Seader (Sec. 337 (1991)]. for all the stages at once. Eng.. cit.. 1986) discusses the design of simultaneous convergence methods.. therefore. 155 (1966)] who used a form of Gaussian elimination known as the Thomas algorithm that can be used to solve a tridiagonal system very efficiently. 897 (1969). 730 (1958)] who demonstrated that the combined M + E equations (the c + 3 formulation) could be conveniently written in tridiagonal matrix form. Eng. complicated equilibrium and enthalpy expressions are replaced by simple models. it was necessary to divide the MESH equations into smaller subsets if hand calculations were to be feasible. T. Chem. only a corresponding number of variables.) in a classic paper analyzing the reasons why other algorithms fail. At that time the computer had yet to be invented. 7th ed.. Sridhar and Lucia [Comput. however. It is the physical properties calculations that generally dominate the computational cost of chemical process simulation problems. They did not. Engng. 15. Chem. Whitehouse’s code allowed for specifications of purity. AIChE J. ACS Symp. the bubble point equations and energy balances are solved simultaneously for the stage temperatures and vapor flow rates. Comput. 25. J. 17. Continuation Methods (for Really Difficult Problems) For those problems that other methods fail to solve. 53 (1983)] being the basis for some of them. and Simandl and Svrcek [Comput. 124. 65 (1971)]. 13-33 3. According to Friday and Smith (1964). and the SR-type methods are considered better for mixtures that exhibit a wide range of (pure-component) boiling points (see.. The SR algorithm was due originally to Sujuta [Hydrocarbon Process. the latter providing more details of an application of Newton’s method described by Naphtali at an AIChE meeting in May 1965. Among other things. At this point... V. A method to solve all the MESH equations for all stages at once by using Newton’s method was implemented by Whitehouse [Ph. Perry’s Chemical Engineers’ Handbook. 46(10). Burningham and Otto [Hydrocarbon Process. and these methods are much less sensitive to difficulties associated with nonideal solutions than are tearing methods. the “tear” variables. Simultaneous solution of all the MESH equations was suggested as a method of last resort by Friday and Smith (op. In solving any subset of the complete set of equations.SIMULATION OF DISTILLATION PROCESSES to the domain of specialists) are finding increasing use in commercial software. cit. the M equations or the H equations. Tearing Methods Equation tearing involves breaking a system of nonlinear equations into small groups and solving each group of equations in turn.. Series. 52 (1974)] and further developed by Boston and coworkers [Comput. Simultaneous Convergence Methods One drawback of some tearing methods is their relatively limited range of application.. Chem. 137 (1961)] and Friday and Smith (op. In the bubble point (BP) method.) and by Tomich [AIChE J. 45(8). Engng. In the Newton-Raphson methods. it is necessary to assume values for the remaining variables. and by McCabe and Thiele). possibly thousands. can be determined.) provide complete details of the somewhat lengthy algorithm. inside-out methods really belong in the group of tearing methods. assuming that the values assigned to all other variables are correct. 181 (1967)]). The BP method was introduced by Amundson and Pontinen (op. and the iteration variables T.

. Sci. [Chem. that the curves that represent the mole fractions of the keys in the overhead and bottoms appear to flatten. We can identify the following categories of continuation method that have been used for solving the equilibrium-stage MESH equations: 1. Tex. thesis. Eng. The reflux ratio or bottoms flow rate has been used in parametric solutions of the MESH equations [Jelinek et al. Comput. 81. Key papers are by Rose. The Peng-Robinson equation of state was used to estimate K values and enthalpy departures [as opposed to the De Priester charts used in Example 1 and by Seader (ibid. 36. Engng. AIChE Monograph Series.. Eng. 1986). the path exists and can be followed. 11. The lines in the diagram have similar significance as would be expected from our knowledge of McCabe-Thiele diagrams for binary systems discussed earlier in this section... Sci. the triangles correspond to equilibrium stages.. the heat loss from the reflux divider is zero. Ball (AIChE National Meeting. Los Angeles. indicated in Fig. A drawback is that convergence is generally a very slow process. A simultaneous convergence method was used for the calculations reported below.. the method is used (only) for problems which are very difficult to converge or for situations in which a knowledge of how the steady state is achieved is important. Bryne and Baird [Comput. AIChE. slowing even more as the solution is approached. A pseudobinary McCabe-Thiele diagram for this multicomponent system is shown in Fig. Eng. New York. 17. 29. The axes are defined by the relative mole fractions: X= xlk xlk + xhk Y= ylk ylk + yhk where the subscripts lk and hk refer to light and heavy key. 1141 (1993)]. [Comput. For this reason.58 (calculated from the results of the simulation).. Physical continuation methods in which the nature of the equations being solved is exploited in some way The first to use the Newton homotopy for separation process problems were Hlavacek and coworkers [Chem. Sweeney. 593 (1987)] used the Newton homotopy for solving distillation problems involving highly nonideal mixtures. 40. The fact that the staircase of triangles visible in Fig. 32. They are a simple distillation In addition. AIChE J. New Orleans. Mathematical methods which place the MESH equations into a homotopy equation of purely mathematical origin 2. 15. these diagrams can only be computed from the results of a computer simulation.. accompanied by an increase in both the operating cost. 40. It is worth asking what can be done to improve the separation obtained with this column. An example of a method in this category is that of Lucia and Wang [Comput.. In the category of physical continuation methods are the thermodynamic homotopies of Vickery and Taylor [AIChE J. 1989) has combined several continuation methods to solve problems that involved nonstandard specifications and multiple liquid phases. Foundations of Computer-Aided Process Design. Parametric continuation methods may be considered to be physical continuation methods. 34. 32. however. 1555 (1973)]. we have assumed that the pressure of the reflux divider is the same as the pressure of the condenser. 35 lb mol/h 120 psia 0 Pj = 120 psia Qj = 0 V2 = 175 lb⋅mol/h D = 48. 1369 (1994). 13-39 by the increase in reboiler duty.9 lb⋅mol/h methods. temperatures. Chem. maintaining all other specifications at the values . however. 11. 737 (1958)]. and mole fractions). 813 (1994)]. The specifications for this problem are summarized below and in Fig. For detailed descriptions of homotopy methods in chemical engineering..13-34 DISTILLATION column. 409 (1985)]. Engng.. In most cases the results here differ only very slightly from those obtained by Seader (almost certainly due to small differences in physical property constants). In most cases. Chem.. 270 (1983). The operating lines are not straight because of heat effects and because the feed is not in the best location. interstage vapor and liquid flow rates and compositions. Engng. 49. 13-37.. Sci. Chem. Chem. Other Methods Relaxation techniques differ from both tearing algorithms and simultaneous convergence methods in that the relaxation techniques do not solve steady-state problems. 165 (1984)].. Cho and Joseph [AIChE J. 13-38. collocation methods have not become part of the mainstream of equilibrium-stage simulation. Collocation methods are widely used for solving systems of partial differential equations. and a product flow rate (or reflux flow). 593 (1985)] describe the use of proprietary continuation methods. 13-37. Sci.. 1599 (1981). 28.D. University of Cambridge. 2541 (2004)]. 1832 (1986)]. For systems with more than two components. Further improvement in product purity can best be made by changing a different specification. These methods begin with a known solution of a companion set of equations and follow a path to the desired solution of the set of equations to be solved. 1971). Second Intern. and mole fractions). Figure 13-39 shows how the mole fraction of i-pentane in the overhead and of n-butane in the bottom product changes with the reflux ratio. Eng. Convergence of the computer algorithm was obtained in just four iterations. and capital cost. Kovach and Seider [Comput. and the reflux temperature is the boiling point of the condensed overhead vapor.. temperatures.. Thermodynamic continuation has also been used to find azeotropes in multicomponent systems by Fidkowski et al. Commun. Conf. Methods that have been developed for finding the optimal solution(s) to engineering models have also been used to solve difficult equilibrium-stage separation process problems. The computer program that was used for these exercises automatically generated initial estimates of all the unknown variables (flows. 20. Woodman (Ph. showing that product purity will not increase indefinitely as the reflux ratio increases. and a reboiled stripper. Note. the reflux ratio. Eng. 8. and Ketchum [Chem. an absorber. 28. Miami Beach.) method]. Chem. 765–862 (1984). 50. Eng. It is clear that increasing the reflux ratio has the desired effect of improving product purity. The appeal of the relaxation methods lies in their extreme stability.. CACHE. The equations are then integrated from some initial state (guess) until successive values of the variables do not change. Examples In what follows we illustrate possible column specifications by considering four examples from Seader (Perry’s Chemical Engineers’ Handbook. 25. 7th ed.) who solved this problem by using the Thiele-Geddes (op. Rather. In papers of considerable significance Wayburn and Seader [Comput. Engng. 28.. Eng. and Schrodt [Ind. 81. Engng. 9. Example 3: Simple Distillation Column Compute stage temperatures. at least one set of the MESH equations is cast in an unsteady-state form. For the base case considered above. With 11 stages and 5 components the equilibrium-stage model has 143 equations to be solved for 143 variables (the unknown flow rates. Swartz and Stewart [AIChE J. Chem. Engng. 7–25 (1987). cit. see Seader [Computer Modeling of Chemical Processes. Chem. 387 (1979)]. respectively. 547 (1986)] and a related method due to Frantz and Van Brunt (AIChE National Meeting. Chem. 261. Figure 13-40 shows the tradeoff in product purities when we change the specified distillate flow rate. a more complicated distillation column. and reboiler and condenser duties for the butane-pentane splitter studied in Example 1. AIChE Monograph Series 15. Verneuil and Oleson (ACS National Mtg. 1997). Despite their considerable potential for certain types of equilibrium-stage simulation problems. This improvement in purity is. because a larger column would be needed to accommodate the increased internal flow. (1985)]. 81 (1984)]. 15 (1985)] used the Newton homotopy in their solution of the MESH equations for interlinked distillation columns. Proc. Sci. 13-38 fails to come close to the corners of the diagram where X = Y = 1 and X = Y = 0 shows that the separation is not especially sharp. Key papers are by Stewart et al.. Austin. Chem. The parameters that have a significant effect on the separation are the numbers of stages in the sections above and below the feed. and Seferlis and Hrymak [Chem. Computed product flows are shown in Fig. the reflux ratio is 2. 1961). No. The specifications made in this case are summarized below: Variable Number of stages Feed stage location Component flows in feed Feed pressure Feed vapor fraction Pressure on each stage including condenser and reboiler Heat duty on each stage except reboilers and condensers Vapor flow to condenser (replaces heat duty of reboiler) Distillate flow rate (replaces heat duty of condenser) Total Number 1 1 c=5 1 1 N = 11 N−2=9 1 1 31 Value 11 6 5..

7 48. The temperature increases from top to bottom of the column. we obtain the following products: Mole flows.19 19. Flows are in poundmoles per hour. This is normally the case in distillation columns (exceptions may occur with cold feeds or feeds with boiling points significantly lower than that of the mixture on stages above the feed stage).03 45. lb⋅mol/h Propane Isobutane N-Butane Isopentane N-Pentane Total Feed 5. The McCabe-Thiele diagram for this configuration. On increasing the number of stages to 26. 13-37 Specifications and calculated product stream flows for butane-pentane splitter.00 0. At lower distillate flow rates the mole fraction of heavy key (i-C5) in the distillate is small.8 YC4−iC5 0.9 Feed: saturated liquid at 120 psia C3 i-C4 n-C4 i-C5 n-C5 5 15 25 20 35 100 6 P = 120 psia = 827 kPa 11 C3 i-C4 n-C4 i-C5 n-C5 0 0. 13-38 Multicomponent McCabe-Thiele diagram for butane-pentane splitter in Fig.6 specified in the base case.SIMULATION OF DISTILLATION PROCESSES 13-35 Total condenser V2 =175 lb·mol/h 1 Saturated liquid reflux D = 48.00 20. The composition profiles also are as expected. In most cases.4 0.00 15. 13-42. the flow rate of the light key (n-butane) and all components with a higher volatility is 45 lb⋅mol/h.6 22.00 25.1 16.97 55. The components more volatile than the light key (n-butane) are . From this result we see that the “best” overall product purities are obtained when the distillate rate is in the vicinity of 45 lb⋅mol/h. and at higher distillate flow rates the mole fraction of light key (n-C4) in the bottoms is small. On reflection this should not come as a surprise.1 FIG.00 100. However. 13-41. shows that the product purities have improved significantly.2 0 0 0.9 lb·mol/h C3 i-C4 n-C4 i-C5 n-C5 5 14. Both cannot be small simultaneously. and decreasing the distillate rate to 45 lb⋅ mol/h.4 2. The temperature and liquid phase composition profiles for this final case are shown in Fig.6 XC4−iC5 0.7 2.84 34.4 0. 13-37.00 Bottom 0.00 0. shown in Fig.81 0. increasing the number of stages will improve the separation.3 51.9 3. with the feed to stage 12. even with the distillate flow rate set to 45 lb⋅mol/h there remains room for improvement in the separation. 1 0.3 32.16 0. increasing the overhead vapor flow to 195 lb⋅mol/h.00 15. The other key design specifications here are the total number of stages and the location of the feed stage.00 0.2 0.00 Top 5.8 1 FIG.00 24.00 35.

a vapor sidestream rich in n-C4.4 0. 13-39 Product mole fractions and reboiler heat duty as a function of the reflux ratio for butane-pentane splitter in Fig. interstage vapor and liquid flow rates and compositions.8 C4 in bottoms i-C5 in distillate Heat duty 1 0.13-36 0.1 DISTILLATION 0. The slight (in this case) curvature in the flow profiles is due to enthalpy changes. 5 lb mol/h 260 psia 0 Pj = 250 psia Qj = 0 L1 = 150 lb⋅mol/h D = 23 lb⋅mol/h 13 37 lb⋅mol/h vapor 0. 0. 20.2 FIG. The specifications were selected to obtain three products: a vapor distillate rich in C2 and C3.6 Mole fraction 0. The specifications made in this case are summarized below: Variable Number of stages Feed stage location Component flows in feed Feed pressure Feed vapor fraction Pressure on each stage including condenser and reboiler Heat duty on each stage except reboilers and condensers Reflux rate (replaces heat duty of reboiler) Distillate flow rate (replaces heat duty of condenser) Sidestream stage Sidestream flow rate and phase Total Number 1 1 c=5 1 1 N = 17 N − 2 = 15 1 1 1 2 46 Value 17 9 3.04 0.3 YC4-iC5 0.04 0. Had the feed been partially vaporized. 0. 13-37. we would have observed changes in both vapor and liquid flows around the feed stage.02 38 FIG. as summarized in the table below. and the reflux temperature is the boiling point of the condensed overhead vapor. 35. 13-42c.1 C4 in bottoms i-C5 in distillate 0. 13-43.8 1 concentrated above the feed. 13-41 profile. The mole fractions of the two keys exhibit maxima. 37.5 0. The decrease in the mole fraction of light key over the top few stages is necessary to accommodate the increase in the composition of the lighter compounds.2 0 0 0.08 Heat duty (MW) 0.6 0. 13-40 40 42 44 46 48 50 52 Distillate flow rate (lb·mol/h) Product mole fraction duty as a function of the distillate rate for butane-pentane splitter in Fig. those compounds less volatile than the heavy key (i-pentane) are concentrated below the feed. Note the step change in the liquid flow rate around the feed stage. FIG. As in Example 3. and reboiler and condenser duties for the light hydrocarbon distillation column shown in Fig. Flow profiles are shown in Fig.02 1 2 3 4 Reflux ratio 5 6 7 0.6 0.2 0.06 0.08 Mole fraction Example 4: Light Hydrocarbon Distillation Compute stage temperatures. Similar arguments pertain to the decrease in the mole fraction of the heavy key over the stages toward the bottom of the column.8 0. we have assumed that the pressure of the reflux divider is the same as the pressure of the condenser. and a saturated vapor feed would significantly change only the vapor flow Multicomponent McCabe-Thiele diagram for butane-pentane splitter after optimization to improve product purities. the heat loss from the reflux divider is zero. . How might the separation be improved? This more complicated example features a partial condenser (with vapor product) and a vapor sidestream withdrawn from the 13th stage. The SRK equation of state may be used for estimating the K values and enthalpy departures for thermodynamic properties. and a bottoms rich in n-C5 and n-C6.7 0.4 XC4-iC5 0.06 0. the light key above the feed stage and the heavy key below the feed stage. 13-37.4 0.

Mole flows.00 Convergence of the simultaneous convergence method was obtained in five iterations.0 Top 3.8 4. lb⋅mol/h Ethane Propane N-Butane N-Pentane N-Hexane Total molar flow Feed 3.6 25. with the feed to stage 7 and the sidestream removed from stage 17. lb⋅mol/h Ethane Propane N-Butane N-Pentane N-Hexane Total Feed 3.61 40.00 37.7 9.00 20. we increase the .46 27.93 4.0 0. 13-42 160 200 Flows (lb·mol/h) 240 (a) Composition..00 Top 3.00 100.54 0.8 25 120 140 160 180 200 Temperature (°F) 220 240 (c) 5 10 Stage 15 20 Vapor Liquid 25 120 FIG.2 0.00 5.4 Mole fraction 0.00 100.00 37.0 23.07 0.7 0. Further improvement in the purity of the sidestream as well as of the other two products could be obtained by increasing the reflux flow rate (or reflux ratio) and the number of stages in each section of the column.0 Bottom 0.0 Sidestream 0. e.00 0.54 29.46 0. we obtain the following: Mole flows.5 37.5 40.0 1.3 1.SIMULATION OF DISTILLATION PROCESSES (a) 5 5 13-37 (b) 10 Stage 15 Propane Isobutane n-butane Isopentane n-pentane 10 Stage 15 20 20 25 0 0.00 35.g.00 7.0 0.6 25.0 9.00 19. and (c) flow profiles in butane-pentane splitter.00 18.00 0.39 37.0 Sidestream 0.6 0.00 7.00 23.0 Bottom 0.0 number of stages to 25 (including condenser and reboiler in this total).00 0. If.2 0.00 35.00 5. (b) temperature.00 20.

. 135 lb⋅mol/h 1 400 psia 1 80°F 1 8 c = 6 360. 2. The oil may be taken to be n-dodecane.2 n-C6 0. 3. The temperature profile shows the rise in temperature toward the bottom of the column that is typical of gas absorption processes. 13-44.0 Secondary oil 13.0 10. The computed product flows are summarized below: Example 5: Absorber Compute stage temperatures and interstage vapor and liquid flow rates and compositions for the absorber specifications shown in Fig. the curvature in the flow profiles is due to enthalpy changes.0 15.6 n-C4 25.0 5.3 32. Thermodynamic properties may be estimated by using the Grayson-Streed modification of the Chao-Seader method.2 0.0 0. The specified bottoms rate is equivalent to removing most of the nC5 and n-C6 in the bottoms. As was the case in Example 3. note the step changes due to both the feed and the sidestream. 5.0 250. The Peng-Robinson equation of state was used to estimate K values and enthalpy Example 6: Reboiled Stripper Compute stage temperatures and interstage vapor and liquid flow rates and compositions and reboiler heat duty for the reboiled stripper shown in Fig. .0 0.0 164. Flows are in pound-moles per hour.5 37 C2 0 0 C3 n-C4 9.0 0.0 25.0 250. 0. 5. Note that a second absorber oil feed is used in addition to the main absorber oil and that heat is withdrawn from the seventh theoretical stage. . 13-48. . The specifications made in this case are summarized below: Variable Number of stages Location of feed 1 Component flows in feed 1 Pressure of feed 1 Temperature of feed 1 Location of feed 2 Component flows in feed 2 Pressure of feed 2 Temperature of feed 2 Location of feed 3 Component flows in feed 3 Pressure of feed 3 Temperature of feed 3 Pressure on each stage Heat duty on each stage Total Number Value(s) Mole flows. j = 1. 0.6 n-C5 25. . 40. j = 1.0 135.7 0.0 549.0 4. . showing that the feed is to the optimum stage.42 MMBtu/h FIG. 4.7 10. The flow profiles are shown in Fig. .5 40 17 1.) who solved this problem by using the SR method. 0.7 n-C5 0 n-C6 0 23 1 Reflux flow = 150 lb·mol/h Feed: saturated liquid at 260 psia C2 C3 n-C4 n-C5 n-C6 3 20 37 35 5 100 9 P = 250 psia 13 Vapor sidestream: 37 lb·mol/h 0 C2 C 3 1.0 0.0 40. The liquid flow profile exhibits a step change due to the secondary oil feed at the midpoint of the column. 13-47.6 Rich oil 69.000 Btu/h 44 The energy withdrawn from stage 7 has the effect of slightly increasing the absorption of the more volatile species in the rich oil leaving the bottom of the column.0 Rich gas 360.0 0. 15.13-38 DISTILLATION Vapor distillate 23 lb·mol/h 0.0 15. The specifications made in this case are summarized in Fig.3 n-C4 1. .4 1 8 1 1 c=6 0. 10 lb⋅mol/h 1 400 psia 1 80°F N=8 Pj = 400 psia.0 4. 13-46.0 Lean gas 303.7 n-C5 9. 25. 15.0 450. 13-48 and in the table below. 1345. lb⋅mol/h Methane Ethane Propane N-Butane N-Pentane N-Dodecane Total molar flow Lean oil 0. 8.0 314.0 3. 8 N = 8 Qj = 0.0 0.0 385.0 0. The bottom of the column is where the bulk of the absorption takes place. and the temperature rise is a measure of the heat of absorption. 7th ed. . Temperature and flow profiles are shown in Fig. 250 lb⋅mol/h 1 400 psia 1 80°F 1 4 c=6 13. The simultaneous solution method solved this example in four iterations. Q7 = 150. 0.3 28.8 19.8 n-C6 4. departures and by Seader (Perry’s Chemical Engineers’ Handbook. The McCabe-Thiele diagram for this design. 2. is shown in Fig. 6.91 MMBtu/h C2 3 C 3 18. 13-43 Specifications and calculated product stream flows and heat duties for light hydrocarbon still.

05 FIG.4 XC3 -C4 0.01 0 0 0.4 0.SIMULATION OF DISTILLATION PROCESSES 1 13-39 0.6 YC3 .C4 0.C4 0.6 0.04 0.03 0.03 YC3 . 13-43. 13-44 Multicomponent McCabe-Thiele diagram for the hydrocarbon distillation in Fig.02 XC3 -C4 0.2 0 0 0.05 0.2 0. .04 0.8 1 0.01 0.02 0.8 0.

0 Oil 385 8 300 Flows (lb·mol/h) 400 500 600 FIG.3 C 2 32.0 n-C5 15.0 n-C5 0.000 Btu/h Rich oil C 1 69. 13-47 (a) Temperature and (b) flow profiles in absorber in Fig.0 Stage 2 Vapor Liquid 1 4 (b) Secondary oil 80oF.2 n-C4 0. 400 psia C 1 360 C2 40 C3 25 n-C4 15 n-C5 10 4 P = 400 psia throughout 6 7 8 150. 13-46. 13-43. 13-46 Specifications and calculated product stream flows and heat duties for absorber.13-40 DISTILLATION 1 Vapor Liquid 4 2 3 Stage 8 4 Stage (a) 5 12 6 7 16 120 160 200 240 8 84 88 92 96 100 Flows (lb·mol/h) FIG. Flows are in pound-moles per hour.7 C 3 0. 400 psia 250 lb·mol/h C 1 304 C 2 10. 400 psia C1 13 C2 3 C3 4 n-C4 4 n-C5 5 Oil 135 Rich gas 90oF.3 C 3 28.8 n-C4 19. 13-45 Temperature (oF) Flow profiles in hydrocarbon distillation in Fig.0 Oil 0. . Lean gas Lean oil 80oF. FIG.

Vapor and liquid flow rates for n-C4 change dramatically from stage to stage.50 29. 8 Qj = 0.10 0.8 F.22 33.10 26. .4 67. 173.838 18.1 13. The column has 74 valve trays. Mole flows.33 lb.00 8011 Bottom 0. j = 1.20 1.20 0 0 0. the design details of which can be found in Example 11. Eng.51. multiple sets of plant measurements should be obtained at different operating conditions.22.00 0. and composition). Condenser and reboiler heat duties should be known (or available from the appropriate energy balance) whenever possible. Ideally.22 59.2 150. Note how the C4 olefins are assigned to isobutene and 1-butene. University of Lapeenranta.13 44.30 93.22 58..8°F Pj = 150 psia.24 Computed temperature.59 Overhead 0. 35.67 10.09 13. it is necessary to know all feed and product conditions (flow rate. The feed was introduced onto tray 37.22 173.99 30. 73.6 0.63 lb⋅mol/h 150 psia 40.00 0.30 98. Flows. The measured compositions and flow rates of the feed and products for the C4 splitter are summarized in the table below. 33.94 7 C2 C3 n-C4 8 4.2 58.02 59. kPa Feed pressure.SIMULATION OF DISTILLATION PROCESSES Variable Number of stages Component flows in feed Pressure of feed Temperature of feed Pressure on each stage Heat duty on each stage (except reboiler) Bottom product flow rate Total Number 1 c=7 1 1 N=8 N–1=7 1 26 Value(s) 8 0.20 0.47 892. are not of the shapes that might have been expected.51 73.22 33. 153. It may be necessary to obtain additional samples of these streams to determine Example 7: An Industrial i-Butane/n-Butane Fractionator Rarely.80 0. kg/h Feed 1.00 0. thesis.69 C1 C2 C3 1 n-C4 n-C5 n-C6 0. 4579 (1996)] and Ilme (Ph. lb⋅mol/h Nitrogen Methane Ethane Propane N-Butane N-Pentane N-Hexane Total Feed 0.00 0. .63 N2 C1 P = 150 psia throughout o 0.mol/h FIG. Chem. .51 73.20 1.94 99.33 Other measured parameters are as follows: Other Details of the i-Butane/n-Butane Fractionator Reflux flow rate. pressure. Klemola and Ilme [Ind. shown in Fig.51 73.D. Finland.06 23. . The computed product flows and reboiler duty are shown alongside the specifications in Fig. cit.57 153. 13-49. .99 30. Measured Feed and Product Flows and Compositions (Mass %) for i-Butane/n-Butane Fractionator (Ilme op. are provided below.57 153.2. °C Column top pressure. j = 1.23 2.2.5 0. and vapor-phase mole fraction profiles.10 0. and pressures often are available from standard instrumentation.22 59.26 Bottoms 0.20 0. .234 Top 5.1 0.63 551. Flows are in pound-moles per hour.) Species Propane Isobutane n-Butane C4 olefins Neopentane Isopentane n-Pentane Total flow. 59. are plant data in exact material balance. .23 2. kPa Boiler duty. 150 psia N2 C1 C2 C3 n-C4 n-C5 n-C6 0. and this is a case in point.50 0. as adjusted by Ilme so that they satisfy material balance constraints.00 0.51 73.57 153. temperature. and it will be necessary to reconcile errors in such measurements before continuing. kPa Pressure drop per tray. The feed and product compositions.887 Convergence in this case was obtained after four iterations.10 17. kg/h Reflux temperature. temperatures. 58.22. flow rates.13 44. N2 Overhead vapor Feed: 40.16 150.7 0.2 173. Such sampling should be scheduled as part of a plant trial to ensure that measured data are consistent.38 MMBtu/h n-C5 n-C6 Bottoms flow = 99.69 452.02 59. 7 99. Measurements should be taken over a time interval longer than the residence time in the column and time-averaged to avoid a possible mismatch between feed and product data.33 lb⋅mol/h 13-41 their composition. MW 92.57.00 0. To properly model an existing column. 13-48 Specifications and calculated product stream flows and reboiler heat duty for a reboiled stripper.5 658. 13-48 and in the table below. .06 23. 1997) report data from an industrial i-butane/n-butane fractionator that is used here as the basis for this example.57 153. and care should be taken to ensure that operating data are obtained at steady state since a steady-state model can only be used to describe a column at steady state. .

122 Top 4. (b) flow.00 0. Instead.10 0.17 1.4 0. Upon computing the bubble point of the overhead product.11 17.8 1 Mole fraction FIG.1 0.13 0.00 0.94 94.20 0.00 8123 Bottom 0.00 0. the liquid portion to the stage below and the vapor portion to the stage above.13-42 1 DISTILLATION 1 (a) 2 (b) 2 3 3 4 4 Stage Stage Vapor Liquid 5 5 6 6 7 7 8 120 160 200 240 280 8 400 Temperature (oF) Flows (lb·mol/h) (c) 500 600 2 4 Methane Ethane Propane n-butane n-pentane n-hexane Stage 6 8 . To proceed with building a model of this column.5 67.08 26.77 0. we find that the measured reflux temperature is well below the estimated boiling point. and we provide just a single feed to stage 38. 13-48. we choose the subcooled condenser model.20 0. In this particular illustration the feed is (assumed to be) saturated liquid.2 0.08 0. we specify the number of stages equal to the number of trays plus condenser and reboiler (N = 76).) Species Propane Isobutane n-Butane Isobutene 1-Butene Neopentane Isopentane n-Pentane Total flow. The common arrangement of locating the actual feed between stages may require modeling as two separate feeds. but not for dynamic models.11 0.54 29.2 0. kg/h Feed 1. Thus. We assume a partial reboiler.6 0.23 0. and (c) vapor mole fraction profiles in reboiled stripper in Fig. Adjusted Feed and Product Compositions (Mass %) and Flows for i-Butane/ n-Butane Fractionator (Ilme op. The subcooled condenser is a convenient work-around for steady-state models (as is needed here). the condenser is in vapor-liquid equilibrium with the vapor augmented by a blanket of noncondensable gas (that has the effect of lowering the dew point of the overhead vapor). cit. 13-49 (a) Temperature.41 0. The steady-state concept of the “subcooled” condenser often does not exist in practice.999 .3 98.7 0.12 0.

20. 960–964 (1925)] being by far the most widely used in separation process calculations: yi. Sci. MV Here Ei. 595 (1953)]. Holland and McMahon [Chem. they are not widely used and have not (yet) been included in any of the more widely used commercial simulation programs. Eng. the Antoine equation for vapor pressures.999 kg/h).16 1.) for a review of the literature]. 331 (1978).. indeed.588 B = 17. 25.). The pressure of the condenser is not known here. The Taylor-Baur-Krishna (TBK) efficiency has just one value per stage regardless of the number of components in the mixture. and there are sound theoretical reasons as well as experimental evidence for not assuming the individual component efficiencies to be alike. [Chem. Eng.00 0. Finally.89 0. For example.47 kPa). in the absence of further information.. operate at equilibrium despite attempts to approach this condition by proper design and choice of operating conditions. 1105 (1979)]. (As an aside. Standart [op. Other types of efficiency include that of Hausen [Chemie Ingr. with some tearing methods). but we do have sufficient information to allow us to compute the reflux ratio from plant flow data (R = 11.e.12 0.. 41 (1989)] summarizes the shortcomings of efficiencies.) had earlier used the UNIFAC model for liquid-phase activity coefficients.J is the Murphree vapor efficiency for component i on stage j. 3134 (2004)] proposed the following efficiency for multicomponent systems: Finally. Chem. they may be greater than 1. In this case we do not know the set points used for controlling the column. 34. 26.. or even possible. Also described in Sec.11 0. cit. among others. Baur. it is possible that a column simulation might involve the specification of the reflux ratio and bottoms flow rate because such specifications are (relatively) easy to converge. the bottom product flow is specified as equal to the adjusted value reported above (17. (op. cit. For binary systems in tray columns the TBK average efficiency simplifies to the Murphree efficiency [Taylor. it is the ratio of the length of the actual composition profile (in mole fraction space) to the length of the composition profile given by the equilibrium-stage model. op. Chem.68 0. the temperature of tray 48). we must select appropriate methods of estimating thermodynamic properties. j+1 i.47 kPa Qj = 0 R = 11.j liquid. Thus. We return to this point later. This efficiency has a simple and appealing physical significance. Eng.. The fact that component efficiencies in multicomponent systems are unbounded means that the arithmetic average of the component Murphree efficiencies is useless as a measure of the performance of a multicomponent distillation process. Taylor. cit. and y* is the composition of the vapor in equilibrium with the i.13 0.. Murphree efficiencies are easily incorporated within simultaneous convergence algorithms (something that is not always easy. 611 (1965)]. Sci.36 0. 14.j)2 The agreement with the adjusted material balance (tabulated previously) appears to be quite good.73 0.53 97. cit.. It is quite likely that the column may be controlled by using the temperature at some specific location (e. 431 (1972)].54 29.. with that of Murphree [Ind. Tech. Eng. we make the condenser pressure equal to the top tray pressure (knowing that in practice it will be lower). 50.00 8123. cit. j+1 EMV = (13-58) i y* j − yi.67 0. although they cannot be less than 0. it can never be negative. kg/h Feed 1. There is by no means a consensus on which is best. note that vaporization . whereas Klemola and Ilme (op.. Chem. and Krishna [AIChE J. Sci. and Krishna (op. This specification should be used in building the model. The pressures of all trays below the top tray can then be fixed from the knowledge of the pertray pressure drop (0. Computed product compositions and flow rates are shown in the table below. cit. 33. cit. and to a first approximation it seems that we have a good model of the column. only two are present in significant amounts. It is usually relatively straightforward to match product compositions in processes involving only two different species simply by adjusting the number of equilibrium stages. For this exercise we used the Peng-Robinson equation of state.6).6 kPa). Eng. and the SRK equation for vapor-phase fugacities only. There are many different definitions of stage (or tray) efficiency. Specified Feed and Computed Product Compositions (Mass %) and Flows for i-Butane/n-Butane Fractionator (Ilme op.95 93. 85(10).08 26. 17.29 0. and generalized Hausen [Standart.65 K 13-43 The overall column efficiency is defined by Eo = NEQ Nactual (13-57) where NEQ is the number of equilibrium stages.) Compound Propane Isobutane n-Butane Isobutene 1-Butene Neopentane Isopentane n-Pentane Total flow.01 Bottom 0. Eng.j) i Efficiencies In actual operation the trays of a distillation column rarely.6 kPa 0. vaporization (see Holland. Seader [Chem. The Murphree (and Hausen) efficiencies of both components in a binary mixture are equal. It is advisable to use the plant set points in building a model.12 17. those with more than two components) there are c – 1 independent component efficiencies. A table of typical values of Murphree tray efficiency can be found in Sec. and Medina et al.. Baur.49 67. Sci. Arguments for and against various types are presented by. Progress. Note that although this column is distilling a mixture containing at least eight identifiable compounds. is never used in industrial practice.999 kg/h 291.)]. 747–750.77 0.999 c (∆yi. Possibly the most soundly based definition. Component efficiencies are more likely to differ for strongly nonideal mixtures. they may take values between plus and minus infinity.j − yi. For multicomponent systems (i. The specifications made to model this column are summarized below: Variable Number of stages Feed stage location Component flows in feed Feed pressure Feed vapor fraction Pressure at the top of the column Pressure drop per stage Heat duty on each stage except reboilers and condensers Reflux ratio (replaces heat duty of condenser) Bottoms flow rate (replaces heat duty of reboiler) Temperature of reflux Total Number 1 1 c=8 1 1 1 N – 1 = 75 N – 2 = 74 1 1 1 165 Value N = 76 39 See previous table 120 psia 0 658. 14 are methods for estimating Murphree efficiencies when they are not known. cit. Ilme (op. εj = i=1 c i=1 (13-59) 2 (∆y*.00 0. The usual way of dealing with departures from equilibrium in multistage towers is through the use of stage and/or overall efficiencies.06 0.13 0.122 Top 4.20 0.00 0. 985 (1971)].SIMULATION OF DISTILLATION PROCESSES The pressure of the top stage is specified (at 658.g. and therefore this is essentially a binary separation. the generalized Hausen efficiency of Standart (op. if ever.). 25.) used the SRK equation of state to model this column. While models exist for estimating efficiencies in multicomponent systems [see chapter 13 in Taylor and Krishna.

along with the number of equilibrium stages in each section of the column (between feed and product takeoff points). the overall column efficiency for this model is 114 percent. composition. These methods are very effective at solving difficult problems involving standard specifications (in which the reflux ratio and bottoms flow rate are specified). This corresponds to an overall column efficiency of 82/74 = 111 percent. For vanishingly small stage efficiencies the column performs no separation. we find the product mass fractions that are in excellent agreement with the plant data. This many adjustable parameters may lead to a model that fits the data very well. is shown in Fig. The McCabe-Thiele (Hengstebeck) diagram for this case. 10 20 Propane Isobutane n-butane Isobutene 1-butene Neopentane Isopentane n-pentane 30 Stage 40 50 60 70 1E-005 0. Ilme (op. Note that the mole fractions are shown on a logarithmic axis so that all the composition profiles can easily be seen.g. Unfortunately. It is also unwise to employ Murphree efficiencies for trays with a vapor product since any Murphree efficiency less than 1 will necessarily lead to the prediction of a subcooled vapor. 12. we find that 84 stages are needed (while maintaining the feed to the center stage as is the case here). assembled from the results of the simulation.D. 13-51. Ph. Example 8: The Industrial i-Butane/n-Butane Fractionator (Again) With the material on efficiencies in mind.2 0 0 0. of species with significant concentrations.13-44 DISTILLATION 1 efficiencies are very easily incorporated in all computer algorithms. this corresponded to an overall efficiency of 119 percent. Thesis in Chem. the Antoine equation for vapor pressures.) used the UNIFAC model for liquid-phase activity coefficients. University of Porto.) The Murphree-stage efficiency also makes a good continuation parameter for cases that are hard to converge. when a product stream purity is specified). cit. ETH Zurich. we return to the model of the C4 splitter that we developed in Example 7. it is not at all easy to include the more fundamentally sound TBK efficiencies in a computer method for equilibrium-stage simulations. Efficiencies are often used to fit actual operating data. 99 (1988)].8 0. however. process temperatures. The performance of a packed column often is expressed in terms of the height equivalent to a theoretical plate (HETP) for packed columns. At the other extreme. 13-50 McCabe-Thiele diagram for C4 splitter. 74 in this case (plus condenser and reboiler). Ph.. indeed. the overall efficiency defined by Eq. cit.e. As an alternative to varying the number of stages. 13-51 Liquid-phase mole fraction profiles for i-butane/n-butane frac- tionator. The maximum number of these efficiencies is the number of independent efficiencies per stage (c – 1) times the number of stages—potentially a very large number. Vickery.4 0.01 0. A compromise often used in practice is to use just one value for all components and all stages in a single section of a column..6 YiC4-n C4 0. Efficiencies should not be used to model condensers and reboilers. cannot describe how the column will behave when something changes).1 1 Mole fraction FIG. It must be remembered that this is essentially a binary separation and that it is usually relatively straightforward to match product compositions in processes involving only two different species. it is usually safe to assume that they are equilibrium devices. (13-57) is just a single parameter that can improve the robustness of the model and speed of convergence. This fact can be exploited in a simple continuation method for solving difficult equilibrium-stage separation process problems [Muller. Using the Peng-Robinson equation of state and a Murphree stage efficiency of 116 percent. and the SRK equation for vapor-phase fugacities only and found that 88 ideal stages were needed. Engng. Sereno. Chem. Comput. and Taylor. but has no predictive ability (i.. The differences between these efficiencies are not large in this case. we may prefer to maintain a one-to-one correspondence between the number of stages and the number of actual trays. With the Peng-Robinson equation of state for the estimation of thermodynamic properties.6 0. Engng.2 0. but the important point here is that efficiencies—all types—depend on the choice of model used to estimate the thermodynamic properties. it will likely be necessary to vary both the number of stages and the component efficiencies to match plant data.0001 0. We do not recommend adjusting thermodynamic model parameters to fit plant data since this can have unfortunate consequences on the prediction of product distributions. Thesis in Chem. and temperature as the combined feeds to the stage. The HETP is related to the height of packing H by H HETP = (13-60) NEQ . they cannot easily handle problems involving nonstandard specifications (e. Ferrari. Composition profiles computed from this model are shown in Fig. 13-50. It is possible to estimate the overall efficiency for a column such as this one simply by adjusting the number of equilibrium stages in each section of the column that is needed to match the mass fractions of i-butane in the distillate and n-butane in the bottoms. Caution must therefore be exercised when one is using efficiencies determined in this way to predict column performance. 1979. a fact that has helped to prolong the use of these quantities in industrial practice despite the lack of any convenient way to relate them to the fundamental processes of heat and mass transfer.4 0. Engng.001 0. and/or pressures. with the feed to tray 38.. Using the SRK equation of state for estimating thermodynamic properties. Klemola and Ilme (op.8 1 XiC -n C 4 4 FIG. In other cases involving a greater number 0.D. but it may be difficult to match actual temperature and/or composition profiles since there is unlikely to be a one-to-one correspondence between the model stages and actual trays.) found that 82 equilibrium stages (plus condenser and reboiler) and the feed to stage 38 were required.. 1985. and the streams leaving the stage have essentially the same flow rates.

9 83. 93. to lessen the degree of nonideality by reducing the interaction parameters sufficiently to make the problem easy to solve. There is always (at least) one solution if the reflux ratio and bottoms flow rate are specified (the so-called standard specifications)..5 2655. along with suggestions on what might make the problem more amenable to solution. each time using the solution converged by using the previous set of parameter values as the starting point. It is all too easy to specify a desired product purity or component flow rate that simply cannot be attained with the specified column configuration.0 0.2 0.0 0. The principal cause of convergence failures is generally a poor initial estimate of the variables being computed. 633 (1970)] presented the results of field tests on a packed absorber in a gas plant.1 5. Large heat effects can lead to convergence difficulties. It is not even possible to match the exit flows by using the Chao-Seader model combined with a stage efficiency as low as 0. Sci. Bassyoni. The key idea is to modify the problem that is difficult to solve as posed into one that is easy to solve—essentially to provide an improved initial estimate that is more likely to lead to convergence. Using the stage efficiency as a continuation parameter also is useful for such cases. It is possible. however.7 188.5 17. We have avoided detailed discussion of such systems in this section because special algorithms are needed for these cases. and the source of the convergence difficulties often encountered with such systems. we choose an appropriate thermodynamic model that will be used to estimate K values and enthalpies. something not available in all programs.2 4. Once the behavior of the column is . In other cases the iterations may take the estimates of temperature and composition into regions where the equation of state can provide only one mathematically real root for density or compressibility. First solving an equivalent ideal system that omits entirely the activity coefficient model (i.9 Rich gas 807 0 14. temperatures. will lead to constant molar flows from stage to stage (within each separate section of the column).9 0. In this case the reason for the unrealistic estimate of the HETP has nothing to do with the packing.5 1. It is likely that an activity coefficient model is part of the model used to describe the thermodynamics of these systems. if the simulator includes a constant-enthalpy model.1 0. the degree of difficulty increases with increasing nonideality. A measure of the nonideality of the system is given by the magnitude of the interaction parameters for the activity coefficient model..0 0.2 54.0 0. at least in part) to solve those problems with which the algorithm at hand may have trouble.5 50. a condition often approached in many real distillation (but not absorption) columns. Use of a constant-enthalpy model in distillation calculations. Thus. The packed section was 23 ft in height. for example. The solution to the “easy” problem may then be used as a starting point for the more difficult problem whose solution is desired. Nevertheless. °F Mole flows. and Holland [Chem. serving merely as an aid to convergence.0 0. Very large numbers of stages can pose their own kind of convergence difficulty. cit. Note that most simulators allow a calculation to be restarted from an older converged solution. It turns out not to be possible to match the plant data with the Chao-Seader method since even one equilibrium stage overpredicts the separation by a very significant amount. Other specifications that can cause difficulties for similar reasons include specifying temperatures and compositions anywhere in the column and specifying condenser and/or reboiler heat duties. it is possible to obtain reasonable agreement with the measured overall product flows by using precisely one equilibrium stage! This suggests that the HETP for this column is 23 ft. it is the extreme sensitivity of the simulation to the thermodynamic model. and mole fractions for any added stages. A possible remedy is to make the system “less” nonideal. Nonstandard specifications are very likely to be the source of convergence difficulties. the section on azeotropic distillation and. a value much higher than any HETP ever published by a packing vendor.8 199. and the column was 3 ft in diameter and filled with 2-in metallic Pall rings.SIMULATION OF DISTILLATION PROCESSES In this case NEQ is the number of equilibrium stages (theoretical plates) needed to accomplish the separation that is possible in a real packed column of height H. High pressure adds to the difficulties of converging simulation models.9 3. The parameters may then be increased in size in a series of steps until the desired values are reached. With the Peng-Robinson equation of state. It is generally not straightforward to modify enthalpies in a simulator because no adjustable parameters exert their influence over the enthalpy in a way comparable to that of the interaction parameters in the activity coefficient model. emphasizing the need for caution when one is using efficiencies and HETPs to model some absorption (and distillation) processes. Stream Pressure.1 10. By doing this we are employing a form of continuation (albeit executed manually.00001. It is essential that the parameters return to their correct values in the final step because intermediate solutions have no meaning. For such systems it is the enthalpies that are the source of the nonlinearity that leads to convergence failures. In some cases the column may operate close to the critical point at which the densities of both phases approach each other. Engng.5 61. therefore. Interpolation will have to be used to estimate values of the flows. It is likely that an equation of state will be used to estimate fugacity coefficients and enthalpy departures in such systems. this technique may not be of sufficient help.) for entry points to the literature. since many simulators use ideal solution thermodynamic models in any self-initialization method. Simultaneous convergence methods are often recommended for simulating strongly nonideal systems (as opposed to tearing or inside-out methods).2 19. which is likely to converge easily. provided that the simulation employs standard specifications (more on this topic below). As a rule. at times such methods fail to converge. however. but even SC methods can experience difficulties with strongly nonideal systems. A way to circumvent this kind of difficulty is first to obtain a converged solution for a case involving standard specifications. As a first step. Using a Simulator to Solve Distillation Problems Computerbased methods for solving distillation (and related) column simulation problems now are reasonably reliable. lb⋅mol/h Carbon dioxide Nitrogen Methane Ethane Propane Isobutane n-Butane Isopentane n-Pentane n-Hexane n-Heptane n-Octane n-Nonane n-Decane Total molar flow Lean oil 807 2. psia Temperature. For such systems we suggest reducing the pressure until the problem becomes easy to solve. Example 9: HETP of a Packed Absorber McDaniel. However.2 13-45 Determine the number of equilibrium stages needed to match the lean gas product flow for this column (2721. Below we discuss some of the reasons that a simulation might be difficult to converge.4 0. Mixtures become increasingly nonideal as the pressure is raised. Occurrences of this behavior often are a source of convergence difficulties.1 lb·mol/h.0 0.2 0.0 0. The measured feeds are summarized in the table below.0 2994. if available. then this can be used to obtain a converged solution that may provide a good starting point for the problem with a more realistic enthalpy model. Either the Chao-Seader method or the Peng-Robinson equation of state could be considered for this system.e.6% methane). using Raoult’s law) may provide a converged solution that may be an adequate starting point for the nonideal system of interest. This solution can then be used as the starting point for a problem with more stages.0 0. The most strongly nonideal systems are those that may exhibit two liquid phases. chapter 8 of Doherty and Malone (op. 25. see.5 0. A possible remedy is to reduce the number of stages until a converged solution can be obtained. A converged solution obtained in this way may be used as the starting point for subsequent calculations at increasingly higher pressures (up to that desired).

3). Engng. and others. having been studied. and Wayburn [Ind. Gaubert et al. 46.7 kPa Feed Ethanol Water Benzene Total kmol/h 85. 20. For cases such as this. the three solutions exist over a narrow range of ethanol feed flows. 93 (1996)] found complex-valued solutions to the MESH equations for values outside this range. this column is modeled by ignoring the condenser and decanter. ideal and near-ideal multicomponent vapor-liquid mixtures. cit.] FIG. The goal of the distillation is to recover high-purity ethanol in the bottom stream from the column by using benzene as a mass separating agent. Chem.. Fundam. in common with others. Chem. 4 in Kister (op. 13-53b is rather more difficult to obtain. Guttinger. Seader.. however. The numerical results are very sensitive to the choice of activity coefficient model and associated parameters. in one form or another. Parametric continuation has been used to detect multiple solutions of the MESH equations [Ellis et al. Example 10: Multiple Steady States in Distillation This example is one of the most famous in the entire literature on distillation column modeling. 10. In fact. Indeed. Cambridge University. The highpurity solution in Fig. there is no substitute for trial and error. 566 (1986)] used homotopy methods to find multiple solutions for some systems of interlinked columns.. 13-53.. and pressure to the top of the column. Symp. The UNIQUAC method was used for estimating the activity coefficients. Series. Chem. Thesis in Chem. This is by no means an exhaustive list of the reasons that computerbased simulations fail.). again using an old converged result as a starting point. and Lucia [Comput. Columns in which temperature and/or compositions change over a wide range in a limited number of stages pose their own particular difficulties. Taylor. Achuthan. with parameters given by Prokopakis and Seider. Sci. have proved to be quite adequate for binary and closeboiling. as a starting point. is easily obtained from an ideal solution starting point (but with severe restrictions on the maximum allowed temperature change per iteration). Køggersbol et al.3 kPa Reflux Ethanol Water Benzene Total kmol/h 103. and the literature on this topic is quite extensive. temperature. 1992] offers some additional insight on using simulators to solve distillation column models.. [Comput.7. 12.8 56. Haas [chap. Chem.. Kovach and Seider (op. Prokopakis and Seider [AIChE J. it will be possible to make sensible nonstandard specifications. understood. The intermediate profile in Fig. [Chem. 25. Chavez. and Morari [AIChE J. E. One liquid phase is sent to a second column.. Multiple solutions for this column have been reported by many authors (including the three cited above).D. Engng. 955 (2000)]. the behavior illustrated below is typical of many systems. 20. [Ind. 13-52 . containing a large amount of water in the bottom product. In fact. for the specifications considered here. 2691 (1995)]. Res.3 375. The low-purity profile in Fig. cit. The column simulated here is adapted from the work of Prokopakis and Seider and shown in Fig.6 14. Some highly nonideal systems exhibit this kind of behavior (see Example 11 below). Chem. and problems with this cause are not the source of convergence difficulties that they once were. 13-53a. Chem. Engng.. In those cases it may be necessary to combine several of the strategies outlined above to solve the simulation problem. Chem. containing very little water in the bottom product. Engng.2 215. Reflux is simulated by a feed of appropriate composition.).. Engng. 56 (1979)]. [I. and Venkataraman and Lucia [Comput. That real distillation columns can possess multiple steady states has been confirmed by the experimental work of Kienle et al.0 P1 = 101.0 100. in many cases it is a combination of more than one of the above factors that leads to difficulty. Comput. and the other is returned to the main column as (cold) reflux. however. Reflux: 298 K and 101. Eng. NONEQUILIBRIUM MODELING Although the widely used equilibrium-stage models for distillation. it is wise to limit periteration changes to temperature and composition. 433 (1986).4 0. 2914 (2001)].8 kPa B = 83. S835 (1996)]. by many investigators including Magnussen et al. Eng. Here. 1986]. 49 (1983)]. Burton. 55 (1988)]. cit. 29.. 13-53c. 13-52. Multiple steady-state solutions of the MESH equations have been found for many systems. Engng. with the parameters used here. a profile that had been converged at a stage efficiency of 0.5 5 Feed: 311 K and 102. The ethanol-benzenewater ternary system actually splits into two liquid phases when the overhead vapor is condensed and cooled below its bubble point. 50. described above. [After Prokopakis and Seider (op.0 kmol/h Azeotropic distillation tower for distillation of an ethanol-water mixture using benzene as a mass separating agent. qualitatively. Ph. Most modern computer methods will do this as a matter or course.13-46 DISTILLATION This system is considered difficult because convergence of the MESH equations can be difficult to obtain with any algorithm.3 kPa 41 P41 = 112. We were able to find it by using.). Often. An introduction to the literature is provided by Bekiaris. the composition profiles are shown in Fig. 40. is also easily obtained from an initial profile calculated by assuming that the stage efficiency is quite low (0. there are no less than three solutions..

4 0.. Kooijman. Chem. Walter and Sherwood [Ind.2 0. with some values less than 10 percent.2 0. pointed out clearly their deficiencies for multicomponent mixtures and when efficiencies are small. 33. (c) High-purity profile. and avoid entirely the (a priori) use of concepts such as efficiency and HETP [Krishnamurthy and Taylor. (a) Low-purity profile.4 0. Even Murphree (op.8 1 Mole fraction FIG. (b) Intermediate-purity profile.. In recent years a new approach to the modeling of distillation and absorption processes has become available: the nonequilibrium or rate-based models.8 1 20 30 30 40 40 0 0. 205–217 (1994)]. 449–465 (1985).2 0. 198 (1957)] predicted that the Murphree vapor efficiencies in some multicomponent systems could cover the entire range of values from minus infinity to plus infinity. 493 (1941)] showed that experimentally measured efficiencies could cover an enormous range. Toor [AIChE J. Eng. AIChE J.8 1 Mole fraction Mole fraction (b) 10 Stage 20 30 Ethanol Benzene Water 40 0 0.. A schematic diagram of a nonequilibrium (NEQ) stage is given in Fig. and Hung. 13-53 Liquid-phase mole fraction profiles for ethanol-benzene-water distillation. 13-54. This NEQ stage may represent (part of) the two phases on . a result that was verified experimentally by others. who formulated the widely used plate efficiencies that carry his name. their deficiencies for general multicomponent mixtures have long been recognized.6 0. Taylor. 18.6 0.SIMULATION OF DISTILLATION PROCESSES (a) 13-47 (c) 10 10 Ethanol Benzene Water Stage 20 Stage Ethanol Benzene Water 0 0. These models treat these classical separation processes as the mass-transfer rate governed processes that they really are. 31.6 0. cit.4 0. Chem. Engng. 3.. Comput.).

The material balances for each species in the vapor and liquid phases on an arbitrary stage j are (1 + rV)Vj yi. In a nonequilibrium model. to account for mass transfer from bubbles in the froth on a tray as well as to entrained droplets in a spray. It is worth emphasizing that Eqs. j − N L j = 0 i. j is the rate of mass transfer across the phase interface (with units of moles per second or equivalent). j and p E j . The energy balance is treated in a similar way. j i. we need summation equations for the mole fractions in the vapor and liquid phases. However. xi. the equation used in the equilibrium-stage model. j L (1 + r L)Lj xi. In addition. A material balance around the interface yields L N V j = N i. a completely comprehensive model for estimating mass-transfer rates in all the possible flow regimes does not exist at present. j−1 − f i.j Vj Lj−1 xi. a tray or within a section of a packed column. 13-54 Liquid film Schematic diagram of a nonequilibrium stage. j where Ej is the rate of energy transfer across the phase interface in phase p and is defined by Ej = p p E j da a p (13-67) where a is the interfacial area and E is the energy flux across the interface from/to phase p. and simpler approaches are used. the equipment design. the column operation. and x iI and yiI are the mole fractions of species i at the phase interface. j+1 − f V j + N Vi. and N i. Formally. This illustration is intended only to aid in understanding the basic principles of nonequilibrium modeling. at least in principle. f p is the external feed flow rate of species i in i. and kiV and kiL are the mass-transfer coefficients for . yV is the mole fraction in the bulk vapor phase. split into two parts— one for each phase.13-48 DISTILLATION yi. the actual flow patterns and the shape of the phase boundary are very complicated and depend upon. p i. we may write N p j = N p j daj i.j−1 Vapor Ni. and the physical properties of the system. (1 + r )Vj H − Vj +1H V j V j V j +1 (13-70) −F H +E +Q =0 V j VF j V j V j (13-65) (13-66) (1 + r )LjH − Lj−1H L j L j L j−1 −F H −E +Q =0 L j LF j L j L j In these equations c and c are the molar densities of the superscripted phases. among other things. j − Vj+1 yi. (13-49). as well as transport between the phases flowing over and through the elements of packing in a packed column.j Ej Liquid Interface mole fractions I I yi. With a mechanistic model of sufficient complexity it is possible. j (13-63) where N is the molar flux in phase p [with units of mol/(m2⋅s) or equivalent] at a particular point in the two-phase dispersion and daj is the portion of interfacial area through which that flux passes. NL = c LkL(xI − x L) + x LNL i t i i i i t V t L t (13-64) (13-69) The sum of the phase and interface balances yields the component material balance for the stage as a whole. cit. The simplest approach is to say that the molar fluxes at a vaporliquid interface may be expressed as NV = cVkV(yV − yI) + yVNV i t i i i i t with a similar expression for the liquid phase.j Vapor film FIG.).j. separate balance equations are written for each distinct phase. j = 0 i.j phase p to stage j.j yi. A review of early applications of NEQ models is available in chapter 14 of Taylor and Krishna (op. An energy balance at the phase interface yields EV=EL j j (13-68) p j (13-61) (13-62) where rV and r L are the ratios of sidestream to interstage flows and are j j defined by Eqs. (13-61) to (13-68) hold regardless of the models used to calculate the interphase transport rates N i. j − Lj−1 xi. j+1 Vj+1 Lj xi. xiL is i the mole fraction in the bulk liquid phase. i. each part containing a term for the rate of energy transfer across the phase interface. Also Np is the total molar t flux in phase p. The wavy line in the middle of the box represents the phase interface.

The 6c + 5 variables for each stage determined during the solution of the nonequilibrium model equations are the vapor and liquid flow Vj and Lj. respectively. We may. as summarized in Table 13-12. (13-64). The energy fluxes are related by c c EV = qV + NV H V = E = qL + NL HL = EL (13-71) i i i i i=1 i=1 13-49 TABLE 13-11 Variables for a Nonequilibrium Stage Variable Vapor and liquid flow rates Sidestream flow rates Vapor-phase bulk composition Liquid-phase bulk composition Vapor interface composition Liquid interface composition Component feed flow rates Feed pressure and temperature Vapor-phase temperature Liquid-phase temperature Interface temperature Stage pressure Heat loss from vapor phase Heat loss from liquid phase Mass-transfer rates in the vapor phase Mass-transfer rates in the liquid phase Symbol Vj. therefore. pressure. McGraw-Hill. the bulk phase mole fractions that appear in the rate equations (13-69) and (13-70) vary with position and should not automatically be assumed to be equal to the average exit mole . Although it appears that the number of degrees of freedom is higher for this more complicated model.(and heat-) transfer coefficients means that nonequilibrium models are rather more demanding of physical property data than are equilibrium-stage models. and the K values are evaluated at the composition of the two exiting streams and the stage temperature (usually assumed to be the same for both phases). 5th ed. Physical Properties The only physical properties needed for an equilibrium-stage simulation are those needed to estimate K values and enthalpies. the interface state is assumed uniform on the stage. It is important to recognize that we have not included mass. these same properties are needed for nonequilibrium models as well.and heat-transfer coefficients in the table of variables.j (c). fL i. These coefficients may depend on a number of other physical properties. It is important to recognize that the other flows and composition variables appearing in the nonequilibrium-stage model equations are associated with the equivalent equations for adjacent stages. heat-transfer. The additional variables that are specified here take into account that there is one additional heat duty (one per phase) and that the feed is split into vapor and liquid fractions. Methods for estimating physical and transport properties are described in Sections 4 and 5 of this handbook [see also Poling et al. Lj Uj. It is important to recognize that efficiencies are not used in a nonequilibrium model. we have not included the feed mole fraction summation equation.j i. the interface mole fractions and temperature yi. Note i.j NL i. this is misleading. respectively. and the mass-transfer rates N i.j (this reduces the number of variables being computed). the composition and temperature at the interface vary with position in two-phase dispersion that exists on a tray or within the confines of a packed bed. thus.j (c). These quantities are considered analogous to the thermodynamic properties of the equilibrium-stage model and are functions of other variables (as discussed in greater detail below). The variables appearing in these equations are summarized in Table 13-11. the model of a single stage includes one set of mass-transfer.j xi. Enthalpies are required for the energy balance equations. (13-69) and (13-70) is not often important in distillation (its neglect is equivalent to the assumption of equimolar counterflows in the column). It is common in almost all treatments of mass transfer across a phase boundary to assume that the mole fractions in the vapor and liquid phases at the interface are in equilibrium with each other. Strictly speaking. (13-61) (13-62) (13-64) Number c c c 1 1 (13-65) (13-66) (13-73) (13-69) (13-70) (13-71) 1 1 c c−1 c−1 1 1 1 Total 6c + 5 per stage. the vapor and liquid temperatures I TV and TL. therefore. Eq. The remaining variables. and composition would be specified.SIMULATION OF DISTILLATION PROCESSES the vapor and liquid phases (with units of velocity). 2c + 7 in number. Wj yi. they may.j TV j TL j TI j Pj QV j QL j Number 2 2 c c c c 2c 2 1 1 1 1 1 1 c c 8c + 12 Specified Yes Yes Yes with qV = hV(TV − TI) qL = hL(TI − TL) (13-72) where hV and hL are the heat-transfer coefficients in the vapor and liquid phases. be calculated from the results obtained by solving the model equations.j xI i. The need for mass.j f V.j yI i.. the compositions of the leaving streams are related through the assumption that they are in equilibrium (or by use of an efficiency equation). Methods for estimating mass-transfer coefficients in distillation processes are discussed briefly below and at greater length in Section 5 of this handbook. however. In most NEQ models. Flow Models In a real column the composition of the vapor and liquid phases changes due to flow across a tray or over and around packing. the bulk vapor mole fractions. yi. the bulk liquid mole fractions xi. say. The second term on the right-hand sides of Eqs. be computed during a nonequilibrium column simulation. As with the equilibrium-stage model discussed above. that need to be specified. but can be quite significant in gas absorption. There are 6c + 5 independent equations TABLE 13-10 Equations for a Nonequilibrium Stage Equation Vapor-phase component balance Liquid-phase component balance Interface material balance Vapor bulk mole fraction summation equation Liquid bulk mole fraction summation equation Vapor-phase energy balance Liquid-phase energy balance Equilibrium at the interface Mass transfer in the vapor phase Mass transfer in the liquid phase Energy balance at phase interface Summation equation for vapor mole fractions at phase interface Summation equation for liquid mole fractions at phase interface Equation no.j Total 2c + 7 where the superscript I denotes the interface compositions and K i is the vapor-liquid equilibrium ratio (or K value) for component i. respectively.j j j I V (c).j (c) and N L (c). respectively. and TjI. the overall feed flow. N i. and the vapor and liquid component flows in the feed determined from an adiabatic flash. are identified in Table 13-11. The interface composition and temperature must.j that the interface material balance. temperature (or vapor fraction). The Properties of Gases and Liquids. xi. In equilibrium-stage calculations. means that only one set of mass-transfer rates really needs to be counted in the set of variables for this stage. use the very familiar equations from phase equilibrium thermodynamics to relate the interface mole fractions yI = K i x I i i (13-73) Yes Yes Yes NV i. the equilibrium equations are used to relate the composition of the streams leaving the stage. The inclusion in the model of the mass and energy transport equations introduces the mole fractions and temperature at the interface. (2001)]. In practice.j (c in number). In nonequilibrium models the K values are evaluated at the interface composition and temperature by using exactly the same thermodynamic property models as that used in equilibrium-stage simulations. Degrees of Freedom Table 13-10 summarizes the equations for a single nonequilibrium stage. Thus. In equilibrium-stage models. or those for the vapor and liquid streams coming from adjacent stages. vapor-liquid equilibrium ratios are needed for the calculation of driving forces for mass and heat transfer. and phase equilibrium equations.

op. Kister. m2 hL = clear liquid height on tray..and liquid-phase residence times.143 m. Engng. the diffusion coefficients of all binary pairs in the mixture would be expected to have similar values. AIChE DL (0. cit. For many years this work represented the only such procedure available in the open literature.86 m2 Downcomer area center Tray spacing Hole diameter Total hole area Outlet weir height Tray thickness Number of valves per tray Free fractional hole area 0. m2/m3 a These areas are related to the interfacial area per unit volume of froth a by 1 = a a′ = a (13-76) 1−a α where α = hL/hf is the relative froth density. Ind. There are three flow models in general use: mixed flow. cit. presented the first comprehensive procedure for estimating the numbers of transfer units in distillation. The vapor-phase Schmidt number ScV is defined by ScV = µV/(ρVDV). cit.8QL W ScV L V = kL a tL = k ahf Z QL W L = (13-79) (13-75) = 19.885 m 0.) and Kooijman and Taylor [Chem. In this model the number of transfer units is given by 0. op. Engng.). which here takes the value V Sc = 0. cit. op.). noting that the correlation was not developed specifically for valve trays (few methods were).776 + 4.4Fs + 0.g.6 m 39 mm 0. 57.061 m3/s.0 800 × 10−9 Liquid 550 520 1.0 × 10−9 0. it is necessary to estimate the mass-transfer coefficients for each of the binary pairs.). 14 of this handbook for summaries and references to what is available in the open literature. tallest column).700 where hf = froth height. cit. 14 of this handbook—see also Lockett.0 1.17)tL (13-80) In the expressions above hw is the weir height (m). polarity). cit. mol/s Density.67 s. The liquid-phase residence time is tL = hLZWl /QL = 4. For systems similar to this one.35 × 10−4 58. Column height Column diameter Number of trays Weir length.967 m per pass 4. cit. side 51. The key design parameters for the valve trays are given in the table below (from Klemola and Ilme. m a′ = interfacial area per unit volume of vapor.014 We use the AIChE correlation to illustrate the general approach. For further discussion of the importance of flow models and the equations used to estimate average compositions.7 (kg ms)1 2. 1986. The mass-transfer performance of trays often is expressed by way of a dimensionless group called the number of transfer units [see Lockett (op. side Weir length.. Sci.).57 hw − 0. .859 m 2. 23.). The most realistic model is dispersion flow (see Lockett. Chan and Fair. and Sec. Chem. m/s ct Abub Abub = bubbling area of tray. cit. The diffusivities used in this example were for the light key–heavy key pair of components. cit. we assume a flow pattern for the vapor and liquid phases. m Z = liquid flow path length.. N/m2 Molecular weight. kg/m3 Viscosity. Tray Efficiencies in Distillation Columns.922 m2 51 mm 2 mm 772 18. Example 11: Mass-Transfer Coefficient in a Tray Column Consider again the C4 splitter that formed the basis of Examples 7 and 8. Lockett (op. 814. J. 1992) to be hf = 0. m3/s ct V us = V = superficial vapor velocity. Engng.45 and for the liquid phase from Eq. m W = weir length.8 8. enthalpies K values Enthalpies.9 m2 0. 14 for additional background]. a parameter with which they frequently are combined) may be computed from empirical correlations or theoretical models. N/m 590 16. (13-79) as V = 2. Kister (op. m2/m3 = interfacial area per unit volume of liquid. Klemola and Ilme (op.33.. The products of the vapor. In practice.42 m/s. This is the simplest (and an often used) approach that leads to the most conservative simulation (lowest mass-transfer rates. Des. t The froth height on the tray is estimated (by using the methods in Sec. and this allows us to determine appropriate average mole fractions for use in the rate equations.82% TABLE 13-12 Physical Property Needs of Equilibrium and Nonequilibrium Models Property K values Enthalpy Activity coefficient Fugacity coefficients Vapor pressure Heat capacity Mass-transfer coefficients Heat-transfer coefficients Density Diffusion coefficients Viscosity Surface tension Thermal conductivity EQ model Yes Yes Yes Yes Yes Yes NEQ model Yes Yes Yes Yes Yes Yes Yes Yes Yes Yes Yes Yes Yes Used for Driving forces Energy balances K values. published in 1958 [see also Gerster et al.). enthalpies K values. 820 (1984)].). For these more highly nonideal mixtures. size. but this model is not included in most computer implementations of NEQ models as it is quite complicated. If both phases are assumed well mixed.238Fs + 104. the work of organizations such as Fractionation Research Incorporated (FRI) was available only to member companies.9 m 74 1. and Sec. 37. heat-transfer coefficient Mass-transfer rate equations Energy-transfer rate equation Mass-transfer coefficients Mass-transfer coefficients Mass-transfer coefficients Mass-transfer coefficients Heat-transfer coefficients fractions that appear in the material balance equations. center Liquid flow path length Active area Downcomer area. then the average mole fractions are indeed equal to the mole fractions in the exit streams. In practice this is not a concern since it is the mass-transfer rates that are needed rather than the fluxes and the product suffices for NEQ model computations. Dev. This will not be the case for mixtures of components that differ sharply in their fundamental properties (e. Readers are referred to Kister (op. defined by tV = (1 − α)hf us (13-77) Z hLZW tL = = (13-78) uL QL The AIChE Bubble Tray Design Manual. 1441 (1982). s t Here Fs is the so-called F factor and is Fs = uV ρV = 1. A flow model needs to be identified for each phase. at the opposite extreme is plug flow.86 m2 0. m L QL = L = volumetric liquid flow rate.). plug flow. These dimensionless numbers are defined by kVahf V = kVa′tV = (13-74) uV s L Estimate the mass-transfer coefficients for tray 7 where the flow and physical properties are estimated to be as summarized below: Gas/vapor Flow.. 177 (1995)]. Chem. and dispersion flow (Lockett.13-50 DISTILLATION (1958)].8 m 2. kmol/kg Diffusivity. (13-80) as L = 2.6 × 10−6 58. Proc. Other comprehensive procedures for trays appeared in the 1980s [Zuiderweg. The superficial velocity is computed next from uV = V/(cV Abub) = 0. see Taylor and Krishna (op. Also tV and tL are the vapor.640. The volus metric liquid flow is QL = L/cL = 0. Note that it is not possible with these correlations to separate the mass-transfer coefficient from the interfacial area. m2/s Surface tension.and liquid-phase mass-transfer coefficients and the interfacial area follow directly from the second parts of the same equations. The number of transfer units follows for the vapor phase from Eq. Mass-Transfer Coefficients Mass-transfer coefficients (and the equally important interfacial area.

42 m/s t and uL = L/(cL At) = 0. Res. Finally. a nonequilibrium model of a column has many more equations than does an equivalent equilibrium-stage model.) and continuation methods [Powers et al.2 98. The agreement is quite good. the value in the table below is an average of that computed for each tray from the simulation results using Eq. This is not true. we note that the strategies outlined above for helping to converge equilibrium-stage simulation may prove equally useful when simulating distillation operations using the nonequilibrium models described here. while providing the very significant advantage of allowing nonequilibrium or rate-based models to be used at all stages of process simulation. that means selecting vapor and liquid flow models and correlations to estimate the mass-transfer coefficients in each phase. Nevertheless. and ap is the specific surface area of the packing.9 4. both of which are modeled as equilibrium stages.6 × 10−9 number of model equations and the associated overhead in evaluating a greater number of physical properties.0017 m/s. The flows and physical properties are estimated to be as summarized below. by Wang et al. 1986). kmol/kg Diffusivity.0 TBK efficiency.8 100 × 10−9 Liquid 37 266 705 2.0021 m/s. Eng. 44.. % 90. 5 of this handbook. a = 96.9 n-C4 in bottoms. Gulf Pub.0508 m). The liquid-phase mass-transfer coefficient is given by kL = 0. It is necessary to choose models that allow for the estimation of the rates of interphase mass transfer. this is so because the efficiencies are greater than 100 percent.17 × 10−5 16.2 1. All operating specifications are the same as for the corresponding equilibrium-stage model and are given in Examples 7 and 8. (13-58) vary more widely from stage to stage and from component to component than might be expected for a system such as this. Example 12: Mass-Transfer Coefficients in a Packed Column Estimate the mass-transfer coefficients at the top of the packed gas absorber in Example 9. cit.. Temperature. the interfacial area per unit volume is given by a′ = ap 1 − exp −1. weir height of trays).. the estimation of mass-transfer coefficients and interfacial areas from empirical correlations nearly always requires us to know something about the column design. A = 5. Example 13: A Nonequilibrium Model of a C4 Splitter Consider.33 (apdp)−2 (13-85) where dp is the nominal packing size (2 in = 0. the internal temperature profile can often be as useful provided that it is known to which phase a measured temperature pertains. does not change by more than a few percentage points over the height of the column. Vapor flow model Mixed Plug Plug Liquid flow model Mixed Mixed Dispersion i-C4 in distillate.0051 ρL µLg −1/3 uL a′µL 2/3 µL ρLDL 1/2 (ap dp)0. and in Sec.6 62. as described above]. The specific surface area of this packing is 112 m2/m3. as discussed above.2 63. This need for more or less complete equipment design details suggests that nonequilibrium models cannot be used in preliminary process design (before any actual equipment design has been carried out). % 96. Also A is a constant that has the value 2 if nominal packing size is less than 0. Engng. 14) to estimate the mass-transfer coefficients.. otherwise. It is often relatively easy to match even a simple model only to product compositions. The predicted component Murphree efficiencies computed with Eq. The importance of the flow model is clear from the simulation results tabulated below.2 (13-87) Internal vapor and/or liquid composition data rarely are available. one such method is illustrated below. The height of a transfer unit (HTU) is defined as uV H V = V = V (13-83) k a′ L = H L = uL kLa′ (13-84) Methods of estimating numbers and/or heights of transfer units and mass-transfer coefficients and interfacial areas in packed columns are reviewed by Ponter and Au Yeung (in Handbook of Heat and Mass Transfer. In the absence of composition profiles. Column design methods are available in the literature as well in most process simulation programs. Equipment Design As we have already seen. the model column includes 74 model trays with the feed to tray 38 [plus a (subcooled) condenser and a reboiler.). 1229 (1988)].2 93.g. [Ind. % 63 78 106 0. For a nonequilibrium column these diagrams can only be constructed from the results of a computer simulation. a is the interfacial area per unit volume.75 ρLuL apµL 0.43 × 10−4 87. mol/s Temperature. In this case the AIChE correlations were used.17 × 10−4 m/s. Chem. m2/s Surface tension. The vapor-phase coefficient is given by kV apDV =A ρVuV µVap 0. and 11. It is known that this method is more conservative than others (i.2 m2/m3.23. (see Sec.. At the very least we need to know the diameter and type of internal column (although usually we need to know more than that since most empirical correlations for mass-transfer coefficients have some dependency on equipment design parameters. Note that the triangles that represent the stages extend beyond the curve that represents the equilibrium line. When we create a nonequilibrium model of this—or any—column. op. t (13-85) to (13-87) gives kV = 0. 12. and kL = 3. Solving the NEQ Model Equations In general. Comput. °C Tray 9 65 74 Measured 47.e.05 u2LρL apσL 0.5 62. and it is straightforward to carry out equipment sizing calculations at the same time as the stage equations are being solved (Taylor et al. Substituting the values provided above into Eqs. 13-55. N/m2 Molecular weight.1 2 apuL g 0.45 σc σL 0.012 m. This does not add significantly to the difficulty of the calculation.. 8. again the C4 splitter that formed the basis of Examples 7. . kg/m3 Viscosity. (13-59). op. we do not need to guess how many stages to use in each section of the column. The column has 23 ft of 2-in metallic Pall rings and is 3 ft in diameter. Convergence of a nonequilibrium model is likely to be slower than that of the equilibrium model because of the greater A portion of the McCabe-Thiele diagram for the simulation involving plug flow of vapor and dispersion flow of the liquid is shown in Fig.0085 We will use the well-known correlation of Onda et al. The TBK efficiency.4 (13-86) Finally. however.1 The vapor and liquid velocities are calculated to be uV = V/(cV At) = 0. K Density. the predicted efficiencies are lower). Chem. we use may essentially the same computational approaches to solve the nonequilibrium model equations: simultaneous convergence (Krishnamurthy and Taylor.2 Predicted 48. cit.7 µV ρVDV 0. with Ac the cross-sectional area of the column. but such data are the best possible for model discrimination and validation. 8715 (2005)]. on the other hand..3 97.SIMULATION OF DISTILLATION PROCESSES The number of transfer units for packed columns is defined by kVa′H V = (13-81) uV L 13-51 = kLa′H uL (13-82) where uV =V/(cV Ac) and uL = L/(cLt Ac) are the superficial vapor and liqt uid velocities. The real column had 74 valve trays. The table below compares the few available measured tray temperatures with those computed during the simulation. N/m 332 267 51. e.2 92. Gas/vapor Flow.5 63.

88 4 Operating line Equations (13-88) for ideal gas mixtures may be derived by using nothing more complicated than Newton’s second law: The sum of the forces acting on the molecules of a particular species is directly proportional to the rate of change of momentum. involve more than two different chemical species. If. di is termed the generalized driving force.13-52 DISTILLATION For a nonideal fluid. The most fundamentally sound way to model mass transfer in multicomponent systems is to use the Maxwell-Stefan (MS) approach (Taylor and Krishna. 13-55 Expanded view near upper right corner of McCabe-Thiele diagram for C4 splitter. unlike the equilibrium-stage model simulations. 14 in the seventh xi xk(ui − uk) Dik (13-88) where Dik is the Maxwell-Stefan diffusion coefficient for the binary i-k pair of components. leading to a simple difference approximation to the MS equations ∆xi = − xi Nk − xkNi ctκ i.84 0. therefore.) for a more complete derivation]. (13-91) are independent. cit. are not shown.). That is not to say. the resistance to mass transfer in the liquid phase is negligible. and the distillate is to contain at least 99 mol % methanol but no more than 50 ppm water.84 xi Nk − xkNi ctDik (13-91) 0. The reason for the similarity is that. The rate of change of momentum between different species is proportional to the concentrations (mole fractions) of the different species and to their relative velocity [see also Taylor and Krishna (op.5 mol % methanol. Equation (13-88) is more familiar in the form di = − c k=1 YiC -nC 4 0. Only c − 1 of Eqs.k k=1 c (13-92) In this particular case the converged composition and temperature profiles have the same shape as those obtained with the equilibrium-stage model (with specified efficiency) and. (13-69) and (13-70) does not change the number of independent model equations or the number of degrees of freedom. Following Doherty and Malone (op. In Eq.88 0. cit. In principle. (13-69) and (13-70) are valid only for describing mass transfer in binary systems under conditions where the rates of mass transfer are low. then the MS equations for the liquid phase can safely be replaced by ∆xi = xI − xL = 0 i i (13-94) The use of the MS equations in place of the simpler Eqs.8 0.). the mole fraction of the last component is obtained by the mole fraction summation equations for both phases.92 di = Equilibrium line xi dµi RT dz (13-90) 0. 10 mol/s isopropanol. Example 14: The Need for Rigorous Maxwell-Stefan-Based NEQ Models Design a distillation column to separate a feed of 20 mol/s methanol. cit. as noted above. Solving the MS equations can be quite involved (see Taylor and Krishna. where κi. where we have replaced the velocities by the molar fluxes Ni = ciui (see Section 5). For an ideal gas mixture the driving force is related to the partial pressure gradient and the mole fraction gradient as follows: di = dxi 1 dpi = P dz dz (13-89) . this choice provides a consistent basis for the comparison of different models. the nonequilibrium model predicted how the column would perform. As a first step we attempt to design the column by using the equilibriumstage model. the mass-transfer coefficients and interfacial area (or parameters in the equations used to estimate them) can be tuned to help the model better fit plant data. op.). The important point here is that. cit.8 0. however.) (see also Section 5 of this handbook and Poling et al. (13-88). Doherty and Malone estimate the minimum reflux as 5.. For a nonideal fluid the driving force is related to the chemical potential gradient di = xi dµi RT dz (13-93) MAXWELL-STEFAN APPROACH Strictly speaking. we used a value 50 percent higher in this example and specified the bottoms product rate at 30 mol/s.). and 20 mol/s water. Eqs. Most industrial distillation and absorption processes. no parameters were adjusted to provide a better fit to the plant data. op. that NEQ models cannot be used to fit plant data. Methods for estimating these coefficients are discussed by Taylor and Krishna (op. Most often a simple film model solution of Eqs. Efficiencies of alcohol-water and alcohol-alcohol systems obtained experimentally in sieve tray columns vary from 60 to 100 percent (Sec. cit. as often is assumed to be the case (not always with justification). this is basically a binary separation of very similar compounds. The number of stages and the location of the feed were varied until a column configuration was obtained that met the desired product purity: 80 total stages (including total condenser and partial reboiler) with the feed to stage 16. op. the NRTL model was used for the activity coefficients and the Antoine equation for the vapor pressures. cit. (13-91) is used. of course. The bottom product is to contain no more than 0. the driving force is related to the chemical potential gradient 0. The Maxwell-Stefan mass-transfer coefficients can be estimated from existing correlations for mass-transfer coefficients using the binary MS diffusion coefficients.92 XiC4-nC4 FIG.k is the mass-transfer coefficient for the binary i-k pair of components. The MS equation for diffusion in a mixture with any number of different species can be written as di = − c k=1 The difference approximation of this expression is somewhat more involved since we have to include the derivative of the activity (or fugacity) coefficient in the approximation.

% active Downcomer area. that for the trays above the feed is summarized in the table below. After specifying an average efficiency of 80 percent.8 1 130 140 150 160 170 180 190 Mole fraction Flows (mol/s) 20 Stage 40 60 Liquid Interface Vapor (c) 80 64 68 72 76 80 84 Temperature (oC) FIG. we find that 99 total stages with the feed to stage 21 were needed to get the distillate product below 50 ppm water. m Weir height. If we use the nonequilibrium model to design a sieve tray column.3 5 12 Segmental 1.76 2. m Liquid flow path length.75 91. m2 Number of flow passes Tray spacing. .43 2 0. 13-56 Composition. % total Total hole area. mm Weir type Combined weir length. m Total tray area. The computer simulation also provided a preliminary tray design.6 0. flow. The reflux ratio and bottoms flows were maintained at the values employed for the equilibrium-stage design. it is found that a column with 84 trays (plus condenser and reboiler) and with the feed to tray 21 (stage 22) will produce an overhead product of the desired purity. and the vapor and liquid phases were assumed to be in plug flow. m Active area. Column diameter.55 50 13-53 20 Methanol Isopropanol Water 20 Stage Stage 40 40 60 60 (b) (a) Vapor Liquid 80 80 0 0. % total Hole diameter.2 0.SIMULATION OF DISTILLATION PROCESSES edition of this handbook).6 0. mm Hole pitch. The AIChE method was used for estimating the masstransfer coefficient–interfacial area products. mm 1.4 14 4. and temperature profiles in nonideal distillation process. The pressure was assumed constant in the column (an assumption that would need to be relaxed at a later stage of the design exercise).4 0.

McCabe-Thiele diagram for nonideal distillation column. Clearly. 13-57 is a measure of the efficiency of that tray. Engng. is it possible that the nonequilibrium model suggests that the column needs only 6 trays more than the number of equilibrium stages? It is. all models lead to essentially the same results. 2367 (1994)].8 1 0. For further discussion of this example.g. Res. Design.. cit. Eng. in nonideal systems and in processes where trace components are a concern. Chem. 77. 13-58. 2021 (2004)]. cannot be reliably predicted..2 0. to determine the appropriate location for a sidestream decanter).. 40. 561 (1999)]. 413 (2003)]. An extended bibliography is available at www. This example demonstrates the importance of masstransfer models for nonideal systems. Chem. 13-57 Efficiency FIG. flow. e. Note that nonequilibrium models will not always lead to a design with fewer trays than might be suggested by a constant-efficiency model. E. It is possible to develop nonequilibrium models for systems with more than two phases. Chem. 13-56. Process. it was necessary first to solve the problem at a much lower reflux ratio R = 2 and then increase R in steps until the desired value of 7. although Müller and Marquardt [Ind. a model based on the assumption of equilibrium on every stage cannot hope to be able to predict column performance. Engng. Thus. we find an overall efficiency of 93 percent. The limited experimental data available suggest that efficiencies are low and highly variable with between 25 percent and 50 percent being not uncommon.4 0. Chem. 13-58. [Comput. the constant value of 80 percent used above appears to be appropriate. 29. Trans. while that of water is close to 90 percent in the bulk of the column before falling off on the bottom few trays. The TBK average efficiency.8 20 YMeOH-iPrOH 0. [Chem. The length of the vertical section of each step in Fig.chemsep. (13-59).org/publications. Chem. Experimental work that can be used to evaluate these models is scarce. 13-57.) and Baur et al. Eng. 854 (2005)]. All component efficiencies are found to be lower in the rectifying section.6 0.5 was reached. then. see Doherty and Malone (op. 25. The McCabe-Thiele diagram for this column is shown in Fig. is close to the Murphree efficiency of methanol and varies from 60 percent in the top of the column to 78 percent. A brief review of other applications follows. Eckert and Vane [Comput. Note that in this case the triangles that represent the stages do not touch the equilibrium line. There is now an extensive literature on using nonequilibrium models for reactive distillation.7 0.. 36.) and Springer et al. in fact. 235 (2001).6 Stage 40 TBK average Methanol Isopropanol Water 60 0. 36.4 0. ˘k Eng. however. For ideal or nearly ideal systems.8 0.. as well as the TBK average efficiency defined by Eq. Three-phase distillation remains relatively poorly understood compared to conventional distillation operations involving just a single liquid phase. The component Murphree efficiencies calculated from the simulation results and Eq. 13-58 Component Murphree efficiencies and TBK average efficiency [defined by Eq. also shown in Fig.. 5410 (1997)] find that an efficiency modified EQ stage model to be perfectly adequate for their column for the dehydration of ethanol using cyclohexane. It is worth noting that there exists extensive experimental evidence for mass-transfer effects for this system. are shown in Fig. cit. The liquid composition. 5392 (1997) and Chem.6 0. Baur et al. especially when trace components are a concern. Engng. Cairns and Furzer [Ind. The efficiency of methanol in the stripping section is seen to be around 80 percent. and Higler et al. because the efficiency of water is so much higher than that of the alcohols that leads to a column design that can produce high-purity methanol while producing the 50-ppm methanol bottom product in so few extra stages. Res.g.. To converge the nonequilibrium model at the specified reflux ratio. 81. In this particular system the vapor and liquid temperatures estimated by the rate-based model are quite close (as often is the case in distillation operations). that of isopropanol to be approximately 75 percent. Simulation methods currently in use for three-phase systems and systems involving chemical reaction employ the equilibrium-stage model [Doherty and Malone (op. 33. as shown by Lao and Taylor [Ind.. Res. I. 603 (2001)]. it is just as likely for the mass-transfer rate-based model to predict that more stages will be needed—it all depends on the differences between the component efficiencies. and are low and/or highly variable.)]. 5392 (1997)] explicitly warn against incorporating Murphree efficiencies into the equlilibrium-stage model for three-phase systems. Chem. Individual component efficiencies can vary as much as they do in this example only when the diffusion coefficients of the three binary pairs that exist in this system differ significantly. 28. [AIChE J. Ind. a figure that is quite at odds with the values of the individual component efficiencies seen in Fig. Cairns and Furzer (op. 51.9 XMeOH-iPrOH FIG. Res. How.. Res. and it is known that nonequilibrium models accurately describe the behavior of this system. 13-58. the column designed with the constant-efficiency model required no less than 99 stages (97 trays)! With 84 trays as opposed to 78 equilibrium stages (not counting condenser and reboiler in either case). . and temperature profiles are shown in Fig.2 80 0 0 0. see. Eng. Eng. whereas equilibrium models (and equal-efficiency models) sometime predict completely erroneous product compositions [Pelkonen et al. see. and yet..13-54 1 DISTILLATION 0. It is important to be able to correctly predict the location of the stages where a second liquid phase can form (e. cit. (13-59)] for nonideal distillation. Nonequilibrium models should be preferred to equilibrium models when efficiencies are unknown. Taylor and Krishna [Chem. There is a rapidly growing body of literature on nonequilibrium modeling of distillation and absorption processes. Chem. Engng.. (13-58).

SOFTWARE FOR DISTILLATION COLUMN SIMULATIONS Computer software for equilibrium-stage and nonequilibrium column models is available from a number of suppliers. Eng.. [Chem. and Klöcker et al. For such systems the chemical reaction influences the efficiencies to such an extent that the concept loses its meaning. 2085 (2001)]. Res.bre. a design solution is possible if the number of independent equations equals the number of unknowns Ni = Nv − Nc (13-95) where Nv is the total number of variables (unknowns) involved in the process under consideration. [Chem. Pressures 4. and Kenig et al. Chem.. if the column is not at steady state.) An alternative is to write C − 1 component balances and one overall mass balance.g. Sci. 157 (2003)].g..com www. e. Stream flow rates 5. that is. but only two are independent.. Sci.. The concept of degrees of freedom in this context is similar to the same concept that appears in the Gibbs phase rule. The fifth is neither an intensive nor an extensive variable but is a single degree of freedom that the designer uses in specifying how often a particular element is repeated in a unit. 55. 58. For example. Engng..aspentech. 1852 (1995)]. Eng. Baur et al. 5195 (1999)]. (13-1). 6139 (2000)]. and as many repetition variables exist as there are sections. Gunaseelan and Wankat [Ind. Noeres et al. Chem. In vapor-liquid systems. Even at steady state. For the analysis here. Chemical equilibrium The inherent restrictions are usually the result of definitions and take the form of identities. Processing. without in any way claiming that this list is exhaustive or providing an endorsement of any particular package. Nr = 2. equilibriumstage models with efficiencies should not be used to model the dynamic behavior of distillation and absorption columns. 44. 26. Energy balance 4. The fourth is an extensive variable that is not considered in the usual phase rule analysis. Eng. Nc is the number of restricting relationships among the unknowns (independent equations).psenterprise.DEGREES OF FREEDOM AND DESIGN VARIABLES TABLE 13-13 Selected List of Suppliers of Column Simulation Software Supplier Aspen Tech Bryan Research & Engineering ChemSep Chemstations Deerhaven Technical Software Honeywell Process Systems Engineering ProSim SimSci-ESSCOR VMG Website www. 41. Stream concentrations (e. then efficiencies also must vary with time as a result of changes to flow rates and composition inside the column. In Table 13-13 we list several suppliers of column simulation models that are available commercially. Eng.com www. The phase distribution restrictions reflect the requirement that f V = f L i i at equilibrium where f is the fugacity. Sci.. 56. see. Wiley-VCH. 37.honeywell.prosim. The mass balance restrictions are the C balances written for the C components present in the system.. DEGREES OF FREEDOM AND DESIGN VARIABLES DEFINITIONS In the models described in previous subsections. 41. If the distillation column contains more than one section (such as above and below a feed stage). Repetition variables Nr The first three are intensive variables. [Chem. Nonequilibrium models for studying column dynamics are described by. 2671 (2003)]. 1245 (1980)]. where Np is the number of phases present. 631 (2003)]. each chemical compound present is a phase rule component. the forms in which the restricting relationships are expressed are unimportant. Eng. The variables Ni with which the designer of a separation process must be concerned are 1. Peng et al. the number of restricting relationships due to the distribution phenomenon will be C (Np − 1). Many other models have been implemented primarily for research purposes and are not available commercially. 4107 (1998)]. Technol. [Chem.. Thus. The degrees of freedom is the number of design variables that must be specified to define one unique operation (solution) of the process. [Chem. For separation processes.simsci-esscor. Thus. (Since we will deal with only nonreactive mixtures. 42.g. Phase distribution 5. This may be expressed by Eq. Only the number of such restrictions is important.com virtualmaterials. [Chem. each component will have three such restrictions. Mass balance 3. and when the designer specifies the number of stages that the section contains.com www. Temperatures 3. Gas absorption accompanied by chemical reaction for a long time has been modeled by using masstransfer rate-based concepts. 35. e.com EQ model Yes Yes Yes Yes Yes Yes Yes Yes Yes Yes NEQ model Yes Yes Yes Yes Yes Yes 13-55 Sci. . The simulations described in this subsection were carried out with ChemSep.chemsep.com www. Res.deerhaventech. 5775 (2002)]. it should always be recognized that all components appear in both phases to some extent and there will be such a restriction for each component in the system.chemstations. when all components exist in all phases.net www. the concept of the equilibrium stage involves the inherent restrictions that TV = TL and PV = PL where the superscripts V and L refer to the equilibrium exit streams. In general. Cornelisse et al.com www. and a review by Kenig et al.. Kooijman and Taylor [AIChE J. Inherent 2.com www. a distillation column section is composed of a series of equilibrium stages. Sci.. We recommend that users interested in any of these (or other) packages carry out an independent evaluation that focuses on the ability of the package to tackle the simulation problems of direct interest. Processing. 617 (2005)]. 54. mole fractions) 2. and Ni is the degrees of freedom that must be specified for there to be exactly the same number of unknowns as there are independent equations in the model. Sundmacher and Kienle (Reactive Distillation: Status and Future Directions. We now develop a general approach to the topic. Pacheco and Rochelle [Ind. [Chem. 2003). The various restricting relationships Nc can be classified as 1. he or she uses the single degree of freedom represented by the repetition variable (Nr = 1. we have determined the degrees of freedom on a case-by-case basis. efficiencies vary from component to component and with position in a column.net www.0). Eng. the number of stages in each section must be specified. Engng. In vapor-liquid-liquid systems. Eng.. For example.

13-59 Stream divider. McGraw-Hill. Details of the analyses are given by Smith (Design of Equilibrium Stage Processes. Wiley. New York. The divider is permitted to operate nonadiabatically if desired. The independent restrictions are as follows: e Nc The results of the analyses for all the various elements commonly encountered in distillation processes are summarized in Table 13-14. A simple equilibrium stage (no feed or sidestreams) is depicted in Fig. which shows the division of the condensed overhead liquid Lc into distillate D and reflux LN+1. but then have to include as a restriction. Our strategy will be to analyze all elements that appear in a separation process and to determine the number of design variables associated with each. the “heat leak” q. but an energy stream has only its rate q as a variable. Of course allowance must be made for the connecting streams (interstreams) whose variables are counted twice when elements or units are joined. ANALYSIS OF UNITS A unit is defined as a combination of elements and may or may not constitute the entire process. Four mass streams and a heat leak (or heat addition) stream provide the following number of variables: e Nv = 4(C + 2) + 1 = 4C + 9 (13-99) There are no restricting relationships when the stream is considered only at a point. Consider Fig. These two inherent identities when added to C-component balances. The unit may be all or only part of an operation or the entire process. Henley and Seader (Equilibrium-Stage Separation Operations in Chemical Engineering. and the C phase distribution relationships give e Nv = 2C + 3 (13-100) (13-101) (13-102) Then N =N −N e i e v e c or i yi = 1 (13-96) = (4C + 9) − (2C + 3) = 2C + 6 These design variables can be used as follows: Specifications Specification of Ln +1 stream Specification of Vn −1 stream Pressure of either leaving stream Heat leak q Nie C+2 C+2 1 1 2C + 6 A stream divider simply splits a stream into two or more streams of the same composition. the ratio LN +1/D.). The appropriate elements can then be quickly combined to form the desired units and the various units combined to form the entire process. respectively. The simplest element is a single homogeneous stream. Three mass streams and one possible “energy stream” are involved. 13-59. 13-60. 0 2C + 2 C+1 C+1 C+1 C+1 C+1 C+1 2C + 3 2C + 3 2C + 3 2C + 3 3C + 4 2C + 3 2C + 3 . 1967) and in a somewhat different form by Henley and Seader (op. xi = 1 i Vapor and liquid streams Vn and Ln. 13-60 Simple equilibrium stage. cit. 1981) count all C compositions as variables. and the pressure of either stream leaving the divider uses these design variables and defines one unique operation of the divider. so e Nv = 3(C + 2) + 1 = 3C + 7 (13-97) Each mass stream contributes C + 2 variables.13-56 DISTILLATION ANALYSIS OF ELEMENTS An element is defined as part of a more complex unit. By definition Nu = Nr + v i T and P identities between LN+1 and D Composition identities between LN+1 and D Mass balances Energy balance 2 C−1 C 1 2C + 2 The number of design variables for the element is given by e Ne = Nv − Ne = (3C + 7) − (2C + 2) = C + 5 i c Ne i u c (13-103) (13-104) (13-98) and N =N −N u i u v e Specification of the feed stream Lc (C + 2 variables). one energy balance. The variables necessary to define it are Ne v Compositions Temperature Pressure Flow rate C−1 1 1 1 C+2 FIG. are in equilibrium with each other by definition and therefore are at the same T and P. TABLE 13-14 Design Variables N i for Various Elements Element Homogeneous stream Stream divider Stream mixer Pump Heater Cooler Total condenser Total reboiler Partial condenser Partial reboiler Simple equilibrium stage Feed stage Sidestream stage Adiabatic equilibrium flash Nonadiabatic equilibrium flash Ne v C+2 3C + 7 3C + 7 2C + 5 2C + 5 2C + 5 2C + 5 2C + 5 3C + 7 3C + 7 4C + 9 5C + 11 5C + 11 3C + 6 3C + 7 e Nc Nfe C+2 C+5 2C + 6 C+4 C+4 C+4 C+4 C+4 C+4 C+4 2C + 6 3C + 8 2C + 7 C+3 C+4 FIG. New York.

13-61 is analyzed here to illustrate the procedure. the two units of N − (M + 1) and M − 1 stages are treated just as elements. and a partial reboiler. C + 2 new restricting relationships must be counted for each interstream in the combination of elements to prevent redundancy. The variables Nu v that must be considered in the analysis of the entire process are just e the sum of the Ni ’s for these six elements since here Nr = 0. where Ncu refers to new restricting relationships (identities) that may u arise when elements are combined. Here Nc does not include any of the restrictions considered in calculating the N ie’s for the various elements. It includes only the stream identities that exist in each interstream between two elements. Nu = Nu − Nu = Nr + i v c i a partial reboiler. 13-60. There i are 2(N − 1) interstreams. Therefore. and . and therefore 2(N − 1)(C + 2) new identities (not previously counted) come into existence when elements are combined. the v design variables that must be specified. a total condenser. Ne = 1 + N(2C + 6) i (13-105) since Ne = 2C + 6 for a simple equilibrium stage in Table 13-14. Nine interstreams are created by the combination of elements. 13-62 Distillation column with one feed. so Nu = 9(C + 2) = 9C + 18 c The number of design variables is Nu = C + 2N + 9Nu = (10C + 2N + 27) − (9C + 18) i v = C + 2N + 9 (13-110) (13-111) (13-109) A more complex unit is shown in Fig. Dotted lines encircle the six connected elements (or units) that constitute the distillation operation. we get the following: Element (or unit) Total condenser Reflux divider N − (M + 1) equilibrium stages Feed stage M − 1 equilibrium stages Partial reboiler Nu = v i Ne i Ne − N u i c (13-106) (13-107) (13-108) = [1 + N(2C + 6)] − 2[(N − 1)(C + 2)] = 2C + 2N + 5 These might be used as follows: Specifications Two feed streams Number of stages N Pressure of either stream leaving each stage Heat leak for each stage Nu i C+4 C+5 2C + 2(N − M − 1) + 5 3C + 8 2C + 2(M − 1) + 5 C+4 10C + 2N + 27 2C + 4 1 N N 2C + 2N + 5 Here. This unit consists of a series of simple equilibrium stages of the type in Fig. a total condenser. Subtraction of these restrictions from Nu gives Niu. 13-61 Simple absorption column. 13-62. which is a schematic diagram of a distillation column with one feed.DEGREES OF FREEDOM AND DESIGN VARIABLES 13-57 FIG. The simple absorber column shown in Fig. Specification of the number of stages N uses the single repetition variable and Nu = Nr + c i FIG. The interstream variables (C + 2) were counted in each of the two elements when their respective Ne ’s were i calculated. Using Table 13-14.

and heat integration. Eng. Smith and Linhoff [Chem. 40. Res. “Remove corrosive components first. Eng. add C + 3 degrees of freedom for each additional feed (C + 2 to define the feed and 1 to designate the feed stage) and 2 degrees of freedom for each sidestream (1 for the sidestream flow rate and 1 to designate the sidestream-stage location). and 5 percent of C in the feed stream. For example. Therefore. Interestingly. including distillation. Direct split. However. assuming that columns are connected by a liquid stream in both cases. More exact.. More recently. Marques. 421 (1985)] discussed methods for synthesis of distillation systems that include sharp splits. Glinos.” Since heuristics are just rules of thumb. Tedder and Rudd proposed a design method for various column networks.). Des. 27. 49. DISTILLATION SYSTEMS Distillation systems for the separation of nonazeotropic mixtures are discussed in this subsection. Also separation of streams that are later mixed (blended) should be avoided. 13-2. 49. In other approaches. Eng. most of which are shown in Fig.. the system using more energy requires bigger heat exchangers and larger column diameters. McGraw-Hill. Moreover. The indirect split requires 58 percent more energy than the direct split. The total energy of separation has been identified as the major component of the total separation system cost and energy-saving distillation schemes for light hydrocarbons with high levels of flexibility and operability.” “Remove most plentiful components first. They proposed several heuristics to compare various configurations. The components contained in streams recycled into the process (e. 2260 (2001)]. thermal linking. there are at least two possible ways of separating a ternary mixture of components A. The separation system needs to be optimized together with the entire plant. Many heuristics are intuitive. They evaluated several rank order functions that allow for comparison of various configurations without detailed cost calculations. algorithmic synthesis methods and cost optimization should be used in practice. Stephanopoulos. and C into pureproduct streams (where A is the most volatile and C the least volatile component): 1. the direct split configuration would clearly be a better choice in this case. Whenever we desire to separate a mixture into multiple products. unreacted reactants recycled to the reactor) usually do not have to be separated from each other.. it does not mean that all C products are necessary. OTHER UNITS AND COMPLEX PROCESSES In Table 13-15. including conventional and complex columns—a detailed discussion of these systems is given below. Eng... 66.g. one of the rank order functions used successfully to compare various systems was the total minimum vapor flow. Nishida. were discussed by Petterson and Wells [Chem. various combinatorial possibilities of column arrangements are feasible and the optimal (usually the least expensive) column configurations are sought. either simultaneously or in a hierarchical approach. 84.. Engng. where they compared eight distillation systems for the separation of ternary mixtures and determined the regions of economic optimality (with respect to feed compositions and relative volatilities). as described by Douglas (The Conceptual Design of Chemical Processes. 9. Agrawal [AIChE J. An alternative method for determining the degrees of freedom for equipment and processes is given by Pham [Chem. 2507 (1994)]. B. 321 (1981)] presented a comprehensive review of process synthesis. they sometimes conflict with one another and may provide wrong answers even if they are not in conflict among themselves [Malone. New York. Although a mixture may consist of C components. and αC = 1 containing 90 percent of A. Any number of elements or units can be combined to form complex processes. 683 (1985)].g. Further examples are given in Henley and Seader (op. (20). αB = 2. which increase the capital investment costs. 379 (2003)] presented a method for systematic generation of distillation configurations.. 303 (1978)]. . & Chem... & Chem. Heuristic methods have been widely used for synthesis of distillation sequences to avoid lengthy calculations. where C is removed first (AB/C) and then mixture AB is distilled The difference in energy required for these splits can be assessed by simply comparing the total minimum vapor flows (summed over all the columns) for each column sequence. but not condenser. e. 13-1 or 13-2 that involve additional feeds and/or sidestreams. No new rules beyond those developed earlier are necessary for the analysis. where component A is separated from BC first (A/BC split) and then mixture BC is distilled to separate B from C 2. One of the most important factors that determines the column configuration is the formulation (or goals) of the separation task with respect to the total flow sheet.. 1977]. the number of design variables is summarized for several distillation-type separation operations. Nu* i C + 2N + 9 C + 2N + 6 2C + 2N + 5 C + 2N + 3 2C + 2N + 5 C + 2N + 3 2C + 2N + 6 2C + 2N + 9 2C + 2N + 12 One set of specifications that is particularly convenient for computer solutions is the following: Specifications Pressure of either stream leaving each stage (including reboiler) Pressure of stream leaving condenser Pressure of either stream leaving reflux divider Heat leak for each stage (excluding reboiler) Heat leak for reflux divider Feed stream Reflux temperature Total number of stages N Number of stages below feed M Distillate rate D/F Reflux ratio LN+1/D Nu i N 1 1 N−1 1 C+2 1 1 1 1 1 C + 2N + 9 Other specifications often used in place of one or more of the last four listed are the fractional recovery of one component in either D or B and/or the composition of one component in either D or B. Example calculations were performed for a mixture with relative volatilities αA = 4. Minimum vapor flow will also be used to compare various distillation systems presented here. cit. 311 (1985)] proposed an optimization algorithm based on maximum thermodynamic efficiency. They developed a pinch method based on the temperature–heat duty diagram to accomplish this task. and Westerberg [AIChE J. Sci. in the third part of their paper. Res. 31. Gomez-Munoz and Seader [Comp. Many of the results extend also to azeotropic mixtures when the desired splits do not attempt to break azeotropes or cross a distillation boundary. Tedder and Rudd presented a three-part paper [AIChE J. AIChE J. nonsharp splits. Westerberg [Comp. 195 (1988)] pointed out the importance of a simultaneous design of the separation network and the rest of the process. and Douglas. 1988). 5 percent of B. Finally. 9. 78. Eng. Chem. 24..13-58 DISTILLATION TABLE 13-15 Design Variables N u for Separation Units i Unit Distillation (partial reboiler-total condenser) Distillation (partial reboiler-partial condenser) Absorption Rectification (partial condenser) Stripping Reboiled stripping (partial reboiler) Reboiled absorption (partial reboiler) Refluxed stripping (total condenser) Extractive distillation (partial reboiler–total condenser) *N includes reboiler.” or “Remove the lightest component first. if possible. Indirect split. For columns not shown in Figs. Sorting through the alternatives and selecting the low-cost systems can be quite tedious and are best done with computer-aided optimization strategies such as those proposed by Caballero and Grossmann [Ind.

52. C) in the network. AB/BC—Component B distributes between both product streams. . and C as indicated by the dashed envelope in Fig. PanABC 2 BC 4 C A 1 1 3 B ABC 2 BC 6 C AB 3 A 4 5 B ABC 2 1 AB 13-59 3 4 A B C (a) FIG. 6) connecting the nodes. we obtain the side rectifier arrangement. 13-64. (b) Prefractionator system. and Sargent [Comp. AIChE J. and c). The combinatorial possibilities for separating a three-component mixture ABC into two product streams in which the most volatile component and the least volatile component do not distribute between the top and bottom product are 1. C. Systems containing simultaneously simple and complex distillation columns are considered. and configuration (3) is called the indirect split (see Fig. complex columns have multiple feeds and/or multiple product streams. In the prefractionator system the binary columns separating components AB and BC may be stacked together.742]. The ternary mixtures resulting from these splits may be separated in one of the three possible ternary splits. multiple streams) are not specified. 13-67a (the column containing sections 1 and 2) we obtain a thermally coupled system. we obtain a partially thermally coupled system [Agrawal and Fidkowski.. The total energy of separation can be minimized for the direct split if the two columns have a liquid connection. . Side stripper configurations can be obtained from the indirect split in an analogous way (Fig. 36. sharp splits (none of the components distribute) in cases (1) and (3). Note that all these three configurations can be represented by one state-task network. Reboilers and condensers are deliberately not shown in Fig. if we eliminate only the reboiler (or only the condenser) from the prefractionator column in Fig. are shown in Fig. as explained in detail in the subsection below on thermally coupled systems. & Chem. AIChE J. shown in Fig. U. Therefore. 13-63 (b) C (c) Basic column configurations. The arrows on the flow sheets symbolize the net material flow. vapor. all these three systems are topologically equivalent to the same basic column configuration represented by the STN in Fig. b. An alternative side rectifier arrangement is seen more clearly in Fig. and products) are represented by the nodes (ABC. and Slavinskii. 1275 (1990)]. and for the prefractionator system if the top connection is vapor and the bottom connection is liquid. When we add binary separations. or two-phase mixtures. if we take into account reboilers and condensers. 13-65b and c) are topologically equivalent. 3. Platonov. shown in Fig.. 13-65c. side rectifier. B. 13-64 (b) (c) State-task networks. 13-67a. AB/C—Top product AB is separated from bottoms C. (c) Indirect split. 22. intermediate mixtures. (c) Indirect split. the states (feeds. There are six possible types of splits for a quaternary mixture. 13-63). A. 13-63. forming one column with three products A. 555 (1965)]. Side stripper. Components are named A. 13-64a. In other instances.. Table 13-16 summarizes the resulting number of possible basic column configurations. . Chem. 13-66a. Simple columns are the conventional columns with one feed stream and two product streams. Res. telides. Eng. For simplicity. This STN representation was used by Sargent to represent distillation systems [Comp. 13-65a. B. AB. and Petlyuk systems can also be built as divided wall columns. The numbers used to represent the column sections in this figure correspond to the numbers used to represent the tasks in the STN (Fig.. Originally STNs were introduced by Kondili. A complete direct split configuration. Patent 5. By eliminating the reboiler from the first column in Fig.. D. . These systems are called the basic column configurations. because for some types of interconnecting streams they are not necessary. BC. . 2. 13-65a and supplying the boil-up from the second column. Eng. we see that only the two side rectifier configurations (Fig. also known as a Petlyuk system. the column configuration corresponding to split (1) is known as the direct split. Interconnecting streams may be liquids. where arrows denote the net flow of material. This number does not account for the various possible types of interconnecting streams. 13-64a). for the indirect split it is minimized if the columns have a vapor connection. but the types of streams connecting the columns (liquid. See Fidkowski and Krolikowski [AIChE J. and they are listed in the order of decreasing volatility (or increasing boiling temperature). B. Ind. Chem. (b) Prefractionator system. 13-64a and the column arrangement in Fig. where the stripping section of the binary BC column (section 4) has been moved and lumped with the first column. In each configuration in Fig. 2. two-phase. Basic column configurations are configurations in which the types of interconnecting streams are not defined. 45. 38. 5. 13-67b [Petlyuk. the column configuration corresponding to split (2) is called the prefractionator system. 31 (1998)] and has been widely used ever since. These separations are also frequently referred to as splits. called state-task networks (STNs). Eng. one may significantly increase the thermodynamic efficiency of the direct split and the indirect split if a portion of the interconnecting stream is vaporized and fed to the second column below the liquid connection [Agrawal and Fidkowski. as described above. (a) Direct split. . shown in Fig. 13-63a. A/BC—Top product A is separated from bottom product BC.970. 13-65. . 485 (1999). There are many other possible ternary column systems that have different interconnecting streams between the columns. 211 (1993)] for representing batch processes. Symbolic-network representations of these separation systems. For example. feed ABC is separated in section 1 to get component A and in section 2 to get mixture BC. 643 (1987). 13-63b. A A AB A ABC AB B B ABC ABC B B BC BC C C (a) FIG. is shown in Fig.DISTILLATION SYSTEMS POSSIBLE CONFIGURATIONS OF DISTILLATION COLUMNS This subsection describes how to generate the feasible combinatorial possibilities of distillation column configurations for separation of mixtures that do not form azeotropes. In this representation. including reboilers and condensers. 2098 (2006)] is very similar to the methods . This method of generating various column configurations [Fidkowski. we consider only separations where final products are relatively pure components. (a) Direct split. & Chem. and a nonsharp split in case (2).S. We limit our considerations to splits where the most volatile (lightest) component and the least volatile (heaviest) component do not distribute between the top and bottom product. 13-65b. By eliminating the reboiler and condenser in the prefractionator column in Fig. 17.. However. and the tasks (separations) are depicted as lines (1. 2065 (1999)]. Then mixture BC is further separated in section 3 to give component B and in section 4 to produce C.. 33. Eng. Int. vapors.

and Slavinskii [Int. etc. two-phase. 20. Platonov.S. Wright. The only difference is that in addition to sharp splits. one can analyze possible splits for a five-component mixture. Two columns are thermally coupled if a vapor (liquid) stream is sent from the first column to the second column and then a return liquid (vapor) stream is implemented between the same locations. and Turunen. 5. [Rong. The development of thermally coupled systems started with attempts to find energy-saving schemes for the separation of ternary mixtures into three products. Five of these configurations consist of only sharp splits. 42. see. if a sidestream is withdrawn from the rectifying section. see Fig. e.. 13-65 (a) Direct split configuration. provide (at least partial) reflux or boil-up to this column. the nonsharp splits are included here. The prefractionator and the main product column are built in one shell. and Powers [AIChE J. (b). Res. controllability and operability. Eng. a sidestream is contaminated to an appreciable extent by either the light or the heavy component. It consists of the prefractionator which accepts the ternary feed stream followed by the main column that produces the products (product column). The side stripper configuration followed naturally. the side rectifier (Fig. By combining the two we obtain the fully thermally coupled system of Petlyuk.882 (1933). however. used previously for conventional systems. In some cases it is possible to achieve high purity of the intermediate component in the sidestream of a distillation column. U. (c) Side rectifier configurations. vapor. Rathore. separated by a dividing wall (Fig. These splits create quaternary and ternary products that can be further separated by one of the column configurations discussed above. which results in each distributing component appearing in product streams from two different locations. 13-68. as in thermally linked columns. Similarly. it must contain not only the intermediate component but also some of the most volatile component. 555 (1965)]. Van Wormer. see Fig. These streams. Eng. Kraslawski. when introduced at the top or bottom of a column. The dividing wall column is topologically equivalent to the fully thermally coupled system (Fig. In many applications. For example. There might also be several alternatives for column stacking.134. and extension to more than three components. This contamination problem can be eliminated by adding a dividing wall that prevents the most volatile component (and the heaviest component) from entering the zone where the intermediate component is withdrawn. which increases the number of possible configurations even further.13-60 DISTILLATION A A A B ABC 1 2 3 B ABC 1 2 3 B ABC 1 2 3 BC 4 BC C 4 4 BC C (b) C (c) (a) FIG. Eng. The dividing wall column was invented as a way of producing three pure products from a single column [Monro. 20. 13-67b). 940 (1974)]. 4258 (2001)]. 13-65c) and side stripper (Fig. (b). Chem. 1204 (2003)] to generate all the possible quaternary thermally coupled configurations. (c) . Chem. 13-69a A AB A A AB 3 4 3 3 4 AB 4 ABC 1 2 ABC B 1 2 ABC B 1 2 B C C C (a) FIG. One of the first industrial applications was the side rectifier configuration for air separation. Res. THERMALLY COUPLED SYSTEMS AND DIVIDING WALL COLUMNS In recent years there has been significant interest in thermally coupled systems and dividing wall columns for ternary mixtures. experimental and industrial experience. Similar methods were proposed by Rong et al.. 13-69c). U.471. 13-66 (b) (a) Indirect split configuration. Ind. 13-69. their energy requirements. Patent 2. The corresponding dividing wall columns are shown in Fig. The basic column configurations for all 22 quaternary distillation systems are shown in Fig. Subsequently. hence each species appears in only one product stream. 13-67b. 491 (1974).. the interconnecting streams could be liquid.. 40. which leads to unconventional systems. design and optimization methods.S.134 (1949)]..g. 13-66c) configurations can be built in one shell as dividing wall columns [Agrawal. Chem. In this subsection we discuss such column arrangements. Patent 2. This is possible when the sidestream is withdrawn above the feed as a liquid or below the feed as a vapor and when relative volatilities of components differ significantly. Ind. or two-way liquid and vapor. (c) Side stripper configurations. Seventeen of the configurations have at least one nonsharp split. Again.

and b. These include those by Stupin and Lockhart [Chem. 35. and Marquardt [AIChE J.. 236 (2001)]. 537 (1986)]. 13-68 C BCD D C Basic column configurations for separation of a four-component mixture. 13-65 to 13-67. The fully thermally coupled system uses less energy than any other ternary column configuration [Fidkowski and Krolikowski. AIChE J. Eng. Annakou and Mizsey [Ind. 32. Watzdorf. Chem. 45.. Eng. Eng. Various design. Chem. Kim [J.. 811. Chem. 13-67 A 3 Liquid split B 4 ABC 1 2 4 5 BC liquid Vapor split 6 C BC vapor (b) (a) Prefractionator system. and evaluation methods have been developed for the distillation systems shown in Figs. Eng. 71 (1972)]. 45. 643–653 (1987)]. 537 (1986)] (`d) A AB (e) AB B B A (a) A ABCD B C BCD CD D (c) A ABCD BC B (b) A ABCD BC C BCD CD D C CD D (f) B B ABCD BC AB A B ABCD B B C ABCD BC C BCD CD D C BCD BCD D FIG.DISTILLATION SYSTEMS 13-61 A AB vapor 3 AB vapor AB liquid B ABC 1 2 5 BC liquid 6 C (a) FIG. 1877 (1996)]. respectively [Agrawal and Fidkowski. 118 (1992)]. Triantafyllou and Smith [Trans. The corresponding sections in the thermally coupled systems and the dividing wall columns have exactly the same numbers and perform exactly the same separation tasks... 27. Fidkowski and Krolikowski [AIChE J... 33. depending on the feed composition and volatilities of the components. & Chem. Eng. Chem. indicating that the column arrangements are topologically equivalent. Eng. 34.. 38. (1988)]. Eng. respectively. Japan. Rudd [Distillation Supplement to the Chemical Engineer. Res. (b) Thermally coupled system. Similar energy savings are possible in partially thermally coupled columns. (1992)].... AIChE J. Bausa. Hernandez and Jimenez [Comp. Part A. Inst. 1615 (1999)]. Prog. S14. 162 (1999)].. 1005 (1999)]. Res. 485 (1999)]. The energy savings may be on the order of 30 to 50 percent. 23. 68 TABLE 13-16 Number of Basic Column Configurations for Separation of a Four-Component Mixture Split 1 2 3 4 5 6 Distillate/bottoms A/BCD AB/BCD AB/CD ABC/BCD ABC/CD ABC/D Total Number of configurations 3 3 1 3×3=9 3 3 22 (10). Fidkowski and Krolikowski [AIChE J. 32. 10. simulation. Purif. 70. where only one connection (top or bottom) between the columns is thermally coupled and the other is just a single liquid or vapor stream together with an associated condenser or reboiler. Chem. Nikolaides and Malone [Ind. 169 (1996)]. Finn [Gas Sep. Eng. Dunnebier and Pantelides [Ind. .

13-62 DISTILLATION A (h) AB ABCD B C CD A D B BC BC C ABCD (j) ABC BC BC C BCD CD D (g) A ABC B BC B BCD CD C C ABCD (k) ABC AB A (l) B ABC B BC B BCD CD C C A AB ABC ABCD BC BC C B B BCD CD ABCD BC BC AB A B B ABCD C C (i) ABC ABCD A D B (m) D D BCD C BCD D D A (n) ABC ABCD C B BCD CD D ABCD C A (p) ABC C BC BCD D C AB B B BCD CD ABCD AB B ABC C BC (o) AB A (q) ABC A A B BC C C CD A D (s) ABC ABCD C C CD D AB CD B D ABCD (r) ABC BC C C AB B B B B ABCD C C D (t) ABC ABCD A A B BC C D D A (v) ABC ABCD C AB B ABCD (u) ABC BC C AB B B D FIG. 13-68 (Continued) .

But the pressure at the bottom of section 3 in the main column must be lower than the pressure at the top of section 1 in the prefractionator. Zeglam. they may even be such that vapor flows in the wrong direction. 3957 (1999)]. In the new Agrawal and Fidkowski configuration. Although invented long ago. Chem. Liquid split control is easier to realize in practice. One is shown in Fig. These pressure drops depend on the height of these sections.e. main column) becomes equal to the minimum vapor flow for the side rectifier system (i. At β = 0 it corresponds to the A/BC split and at β = 1 to the AB/C split. 39. 2565 (1998). Hernandez and Jimenez [Ind.106. solved analytically the optimization problem for the minimum vapor boil-up rate from the reboiler in the main column for the fully thermally coupled system (shown in Fig. Halvorsen and Skogestad [Comp. however. yB and xB are corresponding mole fractions of component B. the prefractionator. see. Coincidentally. The minimum vapor flow for each column in the system is shown in Fig. 44.. This is the reason why dividing wall columns usually work well without tight control of the vapor or liquid split between both sides of the partition. these pressure drops cannot be easily controlled in the configuration shown in Fig. Chem. Therefore. 76. Agrawal and Fidkowski [AIChE J. (c) thermally coupled system. the values of these two minimum vapor flows are always the same: (VSR)min = (VSS)min. 319 (1998)]. 13-70.. For β = 0 the minimum vapor flow for the entire thermally coupled system (i. The solution depends on the splits of vapor and liquid between the main product column and the prefractionator [or between both sides of the dividing wall (Fig. 13-67b. which also corresponds to the minimum vapor flow for the entire system since all the vapor for the total system is generated by this reboiler.. 2001. column section 6 is just shifted from the product column to the . 13-67b and retains its energy advantage. the pressure in the main column at the top of section 6 must be higher than the pressure in the prefractionator at the bottom of section 2. How much vapor flows straight up the main column and how much vapor splits off to the prefractionator depends on the pressure drops in the middle sections of the main column (sections 4 and 5 in Fig. 13-70 as a function of β. and fB denotes the molar flow of component B in the feed stream. There is a minimum in the minimum vapor flow in the prefractionator for β = βP. and liquid flows. Res. 13-67b. Eng.. 13-67b. and Smith [Trans. The major objections concerned controllability and operability. The upper line in Fig. The minimum vapor flow for the entire thermally coupled system is flat over a wide range of β: βP ≤ β ≤ βR. 1301(1993)]. 13-65b or c) (VSR)min. The lower line in Fig. Inst. 13-67b). dividing wall columns and fully thermally coupled distillation systems were not implemented in practice until the late 1980s. 21. The optimally designed fully thermally coupled system should operate with a fractional recovery of B in the top product of the prefractionator placed somewhere between points P and R. chaps. the minimum vapor flows for separations A/B and B/C are equal. A major control problem was attributed to inability to set the vapor split between the main column and prefractionator due to conflicting pressure drop requirements between sections 6 and 2. βP can be calculated as βP = αB − αC αA − αC (13-113) where the α’s are relative to any reference component. and it is not a recommended design point for normal operation because process disturbances may move the operating point outside the optimal section PR shown in Fig. Chem.. see Fig. 13-69 6 C (b) B (c) C Dividing wall columns equivalent to (a) side rectifier configuration. U. the so-called transition split. see Fig. 4 and 5).674] proposed robustly operable two-column configurations that cleverly overcome this design and control problem. Suppl. 13-69c)].DISTILLATION SYSTEMS 13-63 A B 3 1 3 A 3 A ABC 2 ABC 1 4 2 1 4 ABC 2 5 B 4 C (a) FIG. moreover. This new configuration is topologically equivalent to the original thermally coupled configuration in Fig.e. assuming constant molar overflow and constant relative volatilities among the components. several papers have shown that control of these systems is possible. type of packing or stages...e. and Malone [AIChE J. Eng. 13-70 is the minimum vapor flow leaving the reboiler of the main column. i. For β = βR the main column is pinched at both feed locations.g.. Patent 6. as well as sections 1 and 3 in Fig. S249 (1997)]. The transition split divides direct-type splits from indirect-type splits as discussed by Doherty and Malone (Conceptual Design of Distillation Systems.. e. overflows. For the BC vapor to flow from section 6 to section 2. Mutalib. Eng. 13-71. also see Fidkowski. Recently. between the interconnecting streams) and in the prefractionator.. Doherty. or else the AB vapor stream will not flow from the prefractionator to the main column. 38. 13-66b or c). or pumps. 13-70 is the minimum vapor flow in the first column. The transition split P is located at one end of the optimal section PR. main column of the siderectifier system. (b) side stripper configuration. where the parameter β is defined as the fractional recovery of the distributing component B in the top product of the prefractionator β= V1yB − L1xB fB (13-112) where V1 and L1 are the vapor and liquid flows at the top of the prefractionator (section 1).S. for β = 1 it is equal to the minimum vapor flow of the entire side stripper system (VSS)min (which is the sum of the vapor flows from both the reboilers in this system. by using liquid collectors.

The Agrawal and Fidkowski thermally coupled systems are expected to have higher investment cost than dividing wall columns. W. Chem. 13-73.6 DISTILLATION (VSR )min/F (V )min/F SS 1. L. 13-71 operates at a slightly higher pressure than the second column.34.4 0. αC = 1. and Smith [Trans. The basic configurations for these five sharp-split systems are shown in Fig. 42 are owned by BASF (Parkinson. All the multicomponent thermally coupled configurations have a corresponding dividing wall column equivalent. 13-72).. Fidkowski and Agrawal [AIChE J. Technol. and the relative flows of the vapor streams can be changed by using a valve on one of them. Eng. 13-72) perform transition splits. p. 40. They analyzed the quaternary fully thermally coupled system in detail (there are many equivalent column configurations. 78. They also concluded that the optimized quaternary fully coupled system always requires less energy than the five sharp-split conventional systems (where each column performs a sharp split and has one feed. 267) presented a natural extension of the Petlyuk column sequence to multicomponent systems. bottom curve. 2260 (2001)]. separating three.33. 13-72) and both ternary columns (the two middle columns in Fig. Experimental tests of dividing wall columns were carried out by Mutalib. Res. Eng. and v. Eng. two products. 35. Res. 40. The first column (with sections 1. 2.6 βR 0. Eng. 76. . p.0 and feed mole fractions zA = 0. Academic Press. Chem. 13-70 Minimum vapor flows in the thermally coupled system. t. Inst. CEP. 10. 4258 (2001)] presented several examples of quaternary columns with partitions and multiple reboilers and condensers. thus the two interconnecting vapor streams flow in the same direction. which is 10.e. one of the configurations is shown in Fig. the interval PR may be short) and dividing wall columns may not be able to operate at the optimum. However. αB = 2.4 Main Column 1. all with the minimum number of column sections. Zeglam. 319 (1998)]. as well as one reboiler and one condenser. On the other hand. the energy optimum in Fig. ed. 13-68a. and zC = 0. c. One of these examples is shown in Fig..4 0.2 P R 1 Vmin/F 0. minimum vapor flow in prefractionator. 92 (1987)] has shown examples of columns with multiple dividing walls. Chem.1 0. and one condenser). the Agrawal and Fidkowski configurations are able to operate at the optimum because of better control. one reboiler. Keibel [Chem. 454 (2000)] presented a method for generating an even more complete superstructure from which all the known column configurations (including thermally coupled systems) can be derived. Thermally coupled systems can also be devised for multicomponent mixtures. Dixon.3 0. and six components. Res. Inst. minimum vapor flow from the reboiler of the main column (total minimum vapor flow for entire system) for αA = 6.25. 10.8 Prefractionator 0.33. Agrawal [Ind.5. Chem. and 6) in Fig. C. 2713 (2001)] presented a method for calculating the minimum vapor flows in multicomponent thermally coupled systems.8 0. and the same investment cost as a Petlyuk thermally coupled system.2 0.9 1 β FIG. This is so because the two columns are built in separate shells which may contain more stages in one of the shells than could be accommodated in the corresponding side of the dividing wall column. Trans. for certain feed compositions and volatilities. Selecting the best thermally coupled column configuration can be tedious without computer-aided tools such as the disjunctive programming approach developed by Caballero and Grossmann [Ind. 1059 (1996). zB = 0. 1976. Eng.2 βP 0 0 0.. Sargent and Gaminibandara (Optimization in Action.7 0. Also the Agrawal and Fidkowski configurations are useful in cases where high-purity products (especially B) are required. 47. Chem. Eng..6 Transition Split 0..5 0. 13-70 may be narrow (i. July 2005). top curve. They showed that one of the optimum solutions (with the minimum value of the total minimum vapor flow rate from the single reboiler in the system) occurs when the quaternary feed column (far left column in Fig. four. Today there are about 60 dividing wall columns in operation.... as shown in the figure. Agrawal [Ind. bottom of prefractionator. g.13-64 1. London.

Patent 6. Often. or total vapor rate) for comparing alternative column configurations. as discussed by Agrawal and Fidkowski [Ind. 37. 13-74. The fully thermally coupled system can only accept heat at the temperature of the highest-boiling component (boiling point of C) and reject heat at the lowest temperature (condensation temperature of A). .. 38. This conclusion gave rise to new. Chem. more thermodynamically efficient thermally coupled configurations. A AB 3 7 8 ABC B 4 9 A BC ABCD B ABCD 1 BC 2 5 10 C BCD 6 C BCD CD 11 12 CD D FIG. 13-71 THERMODYNAMIC EFFICIENCY Thermodynamic efficiency can be a useful figure of merit (in place of total cost. FIG. multieffect distillation of binary mixtures. 3444 (1998)]. FIG. This is especially true for cryogenic distillations where very low temperatures are needed and highly efficient “cold box” designs are needed for achieving them. and multieffect distillation for thermally coupled configurations. HEAT INTEGRATION In this subsection we describe heat pumps. U. synthesis of multicomponent distillation systems with heat integration. Thermodynamic efficiency of thermally coupled and other distillation systems for the separation of ternary mixtures was analyzed by Agrawal and Fidkowski [Ind. Res.S. the efficiency of the direct split or the indirect split is better than the efficiency of thermally coupled systems. Feed composition regions for column configurations with the highest thermodynamic efficiency are shown in Fig. 13-73 D One possible dividing wall column for separation of a quaternary mixture.116. Eng. 2065 (1999). Res.051]. This is primarily due to the ability of these configurations to accept or reject heat at the intermediate boiling or condensing temperatures of the binary submixtures.DISTILLATION SYSTEMS 13-65 A 3 VAPOR AB LIQUID AB ABC 1 4 B 5 2 VAPOR BC LIQUID BC 6 C Agrawal and Fidkowski thermally coupled system (topologically equivalent to the Petlyuk system shown in Fig. Chem. 13-72 One configuration of a fully thermally coupled system for separation of a quaternary mixture. 13-67b).. Eng.

moreover. to increase the temperature of the condenser.6 DS 0.0. and αC = 1. Air is compressed (typically to about 6 bar) and fed in the bottom of the high-pressure column.2 0. 13-75c). Another heat pump (Fig. DS—direct split. and more stages and energy may be required. 13-76). If the condenser temperature is too low. which is compressed and condensed in the reboiler and then returned to the top of the column as reflux. through the material stream connecting the columns. FC—fully thermally coupled. or heat exchange between a (hot) column feed and a reboiler. (a) External fluid heat pump. it is possible to heat-integrate these streams via a heat exchanger and reuse the heat rejected from the condenser. which is let down in pressure and vaporized in the condenser. (c) Heat pump using column bottoms.4 0. since the process is more thermodynamically reversible. the reboiler and condenser from the same column may be heat-integrated by using a heat pump. 13-75b) uses column overhead vapor. A third possibility is to use the column bottoms. as discussed by Null [Chem. 58 (1976)]. Higher-pressure columns need hotter external heating utilities that are more expensive.6 0. However. The other heat exchangers considered for heat integration might be feed preheaters and product coolers. 1 B 0. Two columns are heat-integrated when they exchange heat indirectly through a heat exchanger. The objective of heat integration in distillation systems is to save energy. However. For example. and the sizes of the reboiler and condenser. When the temperature of the condenser becomes higher than the temperature of some other column reboiler. It reduces the consumption of both hot and cold utilities. Heat integration is realized by matching heat sources (usually condensers) with heat sinks (usually reboilers). Separation in higher-pressure columns is more difficult (because relative volatilities tend to decrease with increasing pressure). In multiple-column systems. since the overall dimensions decrease with pressure. Example for αA = 4. αB = 2. 13-74 A 0. This is called secondary reflux and vaporization (SRV) distillation.8 0.4 IS 0. The entire rectifying section can be pressurized. capital cost is increased by additional intermediate heat exchangers. 13-75 (b) (c) Heat pumps transfer heat from the top to the bottom of the column. SS—side stripper. Typical examples of heat integration schemes are heat transfer from a condenser to a reboiler. A heat pump may use an external fluid which is vaporized in the condenser.. where the heat exchange between columns is direct. Eng. Nitrogen is condensed at the top of the high-pressure column. 72(7).0. This is different than in thermally linked configurations. one may increase the condensing pressure or use a heat pump. 13-75a). although this is not always certain. The required heat-transfer area in the integrated exchangers needs to be increased due to smaller temperature differences between the process streams than would normally exist when hot and cold external utilities are used to provide boil-up and condensation. possibilities for heat integration may be created by increasing the pressure in one of the columns. the opportunity for the match is straightforward.2 SR FC SS 0 C 0 FIG. Prog. SR—side rectifier. then compressed and condensed in the column reboiler (Fig. . higher-pressure column shells and piping may be more expensive. then compressed and fed back to the bottom of the column as boilup (Fig. One of the first industrial applications of heat-integrated distillation was a double column for air separation. If the temperature of the heat source (a) FIG. there are several drawbacks to this procedure. IS—indirect split. Finally. (b) Heat pump using column overhead.8 1 Feed composition regions of column configurations with highest thermodynamic efficiency. it requires more stages to achieve the desired separation.0. developed by Linde in the beginning of the 20th century (Fig.13-66 DISTILLATION (condenser) is sufficiently higher than the temperature of the heat sink (reboiler). and the heat can be transferred between any desired stages of the rectifying and stripping sections.

Niida. but without vapor interconnecting streams. Also. He developed heuristics to devise a feasible system.K. the thermally coupled system with heat integration is even more energy-efficient than the dividing wall column. Sloppy first bottom split. This design method is the recommended starting point for heat integration studies. see Siirola [Adv. and the configuration is still thermodynamically equivalent to the original thermally coupled system (Fig. Wankat [Ind. and adding sections 3x and 6x (analogous to sections 3 and 6 in the product column). thicker walls of high-pressure equipment. 13-77 A 3 B 3 4 5 B C 6 (a) Configuration equivalent to thermally coupled system. There is a significant cost associated with heat integration (e. 46. with large feed and product flow rates. 20. higher cost of high-temperature utilities) which is why such configurations are not widely used.. The heat of condensation provides boil-up to the low-pressure column. Andrechowich and Westerberg [AIChE J. second column pressurized. Split feed configuration. were not considered. These cases have the potential to save a lot of energy due to heat integration. Several alternative designs were evaluated. Therefore.. and Shiriko [AIChE J. Chem. which is very expensive. 491 (1974) and 20. To achieve heat integration without compressors. high-pressure column is further separated in the low-pressure column These heat-integrated systems were economically advantageous because of the large feed flow rate. Van Wormer.. 940 (1974)] presented an algorithmic synthesis method for multicomponent separation systems with energy integration. However. Sloppy first bottom split.g. as discovered by Agrawal [AIChE J. 1 (1996)]. 13-77b). taller columns with more stages. it makes sense to reuse the expensive refrigeration. multiple columns may be required to process a given feed anyway.. for heat pump compressors. 894 (1993)] analyzed 23 different multieffect distillation systems obtained by dividing a single column into two or three columns and operating them at various pressures or compositions. the vapor connections between the columns must be eliminated.g. It is now possible to heatintegrate the columns by pressurizing one of them and allowing heat transfer from the high-pressure condenser to the low-pressure reboiler (Fig. in which the bottoms from the first. Rathore. 2211 (2000)]. This is shown in Fig. Linhoff and coworkers (A User Guide on Process Integration for the Efficient Use of Energy. in which the bottoms from the first column is further separated in the highpressure column 3. .. 423 (1979)] published a thermodynamic approach to heat integration in distillation systems based on pinching heat source and heat sink curves on the temperature–heat duty diagram. with some components present in very small amount (e. in which the feed is split between the high-pressure and the low-pressure columns 2. 13-77a. Umeda. Thermally coupled systems. Engng. 1461 (1985)] presented a simple conceptual design approach wherein temperature-enthalpy diagrams are used to select the best column stacking. 13-76 Double-column arrangement for air separation. Even thermally coupled systems can be heat-integrated. less than 2 percent). Another industrial example of heat integration occurs in the large-scale methanol-water separation in the production of methanol from synthesis gas. U. Eng. The five-component separation problem was solved by decomposing it into all the possible sharp splits and then examining all the possible integrations of heat exchangers. Because of the large feed rate. first column pressurized. most successfully.. But.. to obtain the temperatures necessary for heat integration. Typical applications where heat-integrated systems are preferred include • Cryogenic separation. The last configuration was built. 1982) developed the very successful pinch technology approach. The operational flexibility of a heat-integrated system also becomes more constrained. The thermally coupled system and dividing wall column are equally energy-efficient. Rugby. 23. feed compositions are far from equimolar.DISTILLATION SYSTEMS NITROGEN LOW– PRESSURE COLUMN OXYGEN 13-67 HIGH– PRESSURE COLUMN AIR FIG. by vaporizing oxygen in the sump located above the nitrogen condenser. Design heuristics and computer-aided design methods for heatintegrated distillation systems have been developed in numerous publications. and the regions of superior cost were developed on volatility-feed composition diagrams. only liquid interconnecting streams remain.. Therefore. heat-integrated systems can be quite economical for some applications. In these cases the top or bottom product flow rate is less than 2 percent of the feed flow rate.. (b) Heat-integrated thermally coupled system. pressurizing some equipment in these large-scale processes allows for decreased equipment sizes or increased production rate at a fixed equipment size. and Powers [AIChE J. Institution of Chemical Engineers. The design for imbalanced feeds may include • Various column diameters • Intermittent pumping of heavies from the reboiler • Intermittent firing up a specially devoted column to purify the dirty product made at a small rate • In a continuous operation an overrefluxed section (to keep the column diameter the same over the height of the column) • Producing an impure product to be purified later or discarded A A 3x LIQUID AB ABC 1 2 LIQUID BC 6x C 6 C ABC 4 5 A 3x 1 2 6x (a) (b) C FIG. Res. 13-67b). however. commonly used for heat exchanger synthesis and heat integration of entire plants. where very low-temperature cooling utilities do not exist and need to be created. By balancing heat duties. 32. The configuration is constructed by extending the prefractionator to a full column with a reboiler and condenser. Three heat-integrated designs were better than a single column: 1. 31. • Very large-scale processes. 25. IMBALANCED FEEDS In many practical cases. Chem.

38. shown in Table 13-17. 2d ed.13-68 DISTILLATION ENHANCED DISTILLATION In distillation operations. does not guarantee that the azeotrope will be heterogeneous since the azeotropic composition may not necessarily fall within the composition range of the two-liquid phase region. In sufficiently nonideal systems. and Walas (Phase Equilibria in Chemical Engineering. 110. London.g. cyclohexane (n.. 8. 4th ed. 17. Extractive distillation and salt distillation. As the boiling point difference between the components increases.e. Washington. Chem. Azeotropic distillation and pressure-swing distillation. 1967. Additional general information on the thermodynamics of phase equilibria and azeotropy is available in Malesinski (Azeotropy and Other Theoretical Problems of Vapour-Liquid Equilibrium. All these special techniques are ultimately based on the same differences in the vapor and liquid compositions as ordinary distillation. and the minimum-boiling azeotrope between methyl acetate (n.. 1977). a compendium of published experimental VLE data. the azeotrope is homogeneous. AZEOTROPY At low to moderate pressure ranges typical of most industrial applications. Thus. Smith and Van Ness (Introduction to Chemical Engineering Thermodynamics. 969 (1983)]. y diagram when the deviations from Raoult’s law are positive (Fig.800 systems involving 1700 compounds. or in any combination). Conceptual Design of Distillation Systems. but not necessarily equal (see Prigogine and Defay. Frankfort. London. 4901 (1999)]. c (13-115) and the system is said to form an azeotrope (from the Greek word meaning “to boil unchanged”). Methods that use chemical reaction to modify the composition of the mixture or. 3. 1975). at these two conditions.. heterogeneous. Swietoslawski (Azeotropy and Polyazeotropy. and no separation by simple distillation is possible. and perhaps also in the vicinity close to the Bancroft point [e. Malone.7°C) and benzene (n. Rowlinson. Robbins [Chem. 13-6) and a maximum in the T vs. x. Mixtures of components whose boiling points differ by more than about 50°C generally do not exhibit azeotropes distinguishable from the pure components even if large deviations from Raoult’s law are present.b. In many situations. and NRTL equations.. as is the case for the methyl acetate–water and tetrahydrofuran-water systems.p. the azeotrope occurs at the temperature and pressure where the curves cross. A computational method for determining the temperatures and compositions of all homogeneous azeotropes of a multicomponent mixture. Eng. 1963). Interscience. maximum-boiling azeotropes (γi < 1) are never heterogeneous. Butterworths. the vapor-phase composition is equal to the overall composition of the two (or more) liquid phases (Fig. Reactive distillation.p. and toward the higher-boiling pure component for maximum-boiling azeotropes). These conditions are consequences of the general definition of an azeotrope in any kind of mixture (i. London. 13-8). Horsley (Azeotropic Data-III. App. separation results from differences in vaporand liquid-phase compositions arising from the partial vaporization of a liquid mixture or the partial condensation of a vapor mixture. reactive. Pergamon. 80. Another source for azeotropic data and activity coefficient model parameters is the multivolume Vapor-Liquid Equilibrium Data Collection (DECHEMA..b. Fla. 5.9°C) and water (n. 56. 13-7. a system is said to show negative deviations from Raoult’s law if γi < 1 and. and 13-8. New York. The fact that immiscibility does occur. 64. use existing vapor-liquid differences between reaction products and reactants to enhance the performance of a reaction.p. and the liquid-phase activity coefficient of each component i in the mixture: yiP = xiγiP sat i (13-114) In systems that exhibit ideal liquid-phase behavior. Liquids and Liquid Mixtures.b. 1969. New York. Most of the data have been tested for thermodynamic consistency and have been fitted to the Wilson. London. however. since two liquid phases may form when deviations from Raoult’s law are large and positive. the activity coefficients γi are equal to unity and Eq. but. The method was generalized to determine all homogeneous and heterogeneous azeotropes by Wasylkiewicz. Prog. If. and for systems exhibiting azeotropic behavior.. entitled Azeotropic Data by Gmehling et al. alternatively. 58 (1980)] developed a matrix of chemical families.. from liquid-phase activity coefficient correlations. 13-7). and Doherty [Computers and Chem. 1985). Eng.1°C) form an almost ideal mixture yet exhibit a minimum-boiling azeotrope with roughly equal proportions of each component]. The vapor phase becomes enriched in the more volatile components while the liquid phase is depleted of those same components. Margules. Doherty and Malone. the change in composition between the vapor and liquid phases in equilibrium becomes small (so-called pinched condition). Deerfield Beach. homogeneous. For nonideal liquid-phase behavior. because of the formation of an azeotrope. which indicates expected deviations from Raoult’s law. the equilibrium vapor and liquid compositions are identical. and a large number of successive partial vaporizations and partial condensations are required to achieve the desired separation.p. Alternatively. (13-114) simplifies to Raoult’s law. 1967). ideal or nearly ideal mixtures) may form an azeotrope but only if the saturated vapor pressure curves of the two pure components cross each other (such a point is called a Bancroft point). 1965). as shown in Figs. Doherty.. Wizniak [Chem.5°C) and toluene (n. conversely. These enhanced techniques can be classified according to their effect on the relationship between the vapor and liquid compositions: 1. Van Winkle (Distillation. C). American Chemical Society.6°C) occurs at 90 mol % methanol. 2001. the composition of the azeotrope shifts closer to one of the pure components (toward the lower-boiling pure component for minimumboiling azeotropes. In such a situation. · · · . Since strong positive deviations from Raoult’s law are required for liquid-liquid phase splitting.b. the minimum-boiling azeotrope between methanol (n. 13-6. chaps. the fundamental composition relationship between the vapor and liquid phases in equilibrium can be expressed as a function of the total system pressure. 2. the vapor and liquid phases may have identical compositions. McGraw-Hill.b. At such maxima or minima. McGraw-Hill.. . Boston. y diagram when the deviations from Raoult’s law are negative (Fig. however. Van Laar. in addition. Mixtures with only small deviations from Raoult’s law (i. As a qualitative guide to liquid-phase activity coefficient behavior.. the azeotrope is heterogeneous. Azeotropic systems show a minimum in the T vs. 80. An extensive two-volume compilation of azeotropic data for 18. yi = xi for all i = 1. 1983) compiled an extensive list of experimental azeotropic boiling point and composition data for binary and some multicomponent mixtures. If multiple-liquid-phase behavior is exhibited at the azeotropic condition. Eng. Eng..e. positive deviations from Raoult’s law if γi > 1.b. The formation of two liquid phases within some boiling temperature range is generally an indication that the system will also exhibit a minimum-boiling azeotrope. the vapor pressure of each pure component. 1141 (1993)]. and Malone [Ind. a single liquid phase is in equilibrium with the vapor phase. Methods that cause or exploit azeotrope formation or behavior to alter the boiling characteristics and separability of the mixture. Res. Methods that primarily modify liquid-phase behavior to alter the relative volatility of the components of the mixture. Butterworths. Chemical Thermodynamics.p. they rely on some additional mechanism to further modify the vapor-liquid behavior of the key components. Several enhanced distillation-based separation techniques have been developed for close-boiling or low-relative-volatility systems. For heterogeneous azeotropes. Sci. UNIQUAC.p. x. For example. 100°C) occurs at 90 mol % methyl acetate. McGraw-Hill. Longmans Green and Co. 38. the deviations may be so large that the temperature-composition phase diagrams exhibit extrema. which is as follows: An azeotropic state is one in which mass transfer occurs between phases in a closed system while the composition of each phase remains constant. by a differential arclength homotopy continuation method is given by Fidkowski. was published in 1994 by VCH Publishers. 76(10).

sulfoxide Ester. travels toward and then away from the hexane vertex. nitrate. halogen aromatic. not all residue curves originate or terminate at the same two compositions.. for four components. nitrite. and terminates at the heptane vertex. Eng. (13-116) both forward and backward in time [Doherty and Perkins. phosphine oxide Tertamine Secamine Priamine. relative-volatility information is not represented on an RCM. the boundary is a surface. A residue curve map (RCM) is generated by varying the initial composition and integrating Eq. as exemplified for the ideal normal-paraffin system of pentane-hexane-heptane. The steady states therefore correspond to all the pure components and all the azeotropes in the mixture. Distillation boundaries are related to the existence of azeotropes. carbon disulfide 0 0 − 0 0 0 − 0 − − 0 + 0 0 + 0 − − + − − − 0 − − 0 − − − 0 − − − 0 − − − 0 − − − − − 0 − − − − 1 2 3 4 5 6 7 8 9 10 11 12 5 6 7 8 9 10 − − − − − − − − 0 0 0 0 + 0 − − + + − − − − − − 0 + + + + + + 0 + + 0 + − − 0 0 0 0 − − 0 0 − − − 0 0 − 0 − + + 0 + + 0 − 0 0 − 0 − − 0 − − − − 11 + + + 0 + 0 0 − 0 + 0 0 12 SOURCE: + + + + + 0 + + + + 0 0 Robbins.. then residue curve maps contain exactly the same information as the corresponding phase equilibrium diagram for the mixture. Composition changes taking place in simple batch distillation can be described mathematically by the following ordinary differential equation dxi = xi − yi dξ for all i = 1. carbonate. amide with 2H on N Ether. the system is simple enough that vapor-phase information can be included with liquid-phase information without confusion. For three components. 58–61 (1980). .. and so on. A. Chem. and quaternary azeotropes are placed at the appropriate compositions on the edges and/or interior of the triangle and tetrahedron. a T vs. similar to that used in liquid-liquid extraction. nitrile. . 13-78a. water Active-H on multihalo paraffin H-acceptor Ketone. monohalo paraffin Non-H-bonding Paraffin. Unlike a binary y-x plot. The trajectory of liquid compositions starting from some initial composition is called a residue curve. . but can be pictured graphically only up to four components. c. it is difficult to determine the ease of separation from a residue curve map alone. or a maximumboiling azeotrope. the distillation boundary is a point (the azeotropic composition). Four-component systems can be plotted in a three-dimensional tetrahedron. Chem. 5]. olefin. For binary mixtures. Arrows are usually added to these curves. the collection of all such curves for a given mixture is called a residue curve map. Prog. Eng. The residue curve that divides two distillation regions in which adjacent residue curves originate from different compositions or terminate at different compositions is called a simple batch distillation boundary or separatrix. 281 TABLE 13-17 Solute-Solvent Group Interactions Solute class 1 2 3 4 (1978). The steady states of Eq. 33. chap. amide with no H on N. For ternary mixtures. (13-116) are the constant-composition trajectories corresponding to dxi /dξ = 0 for all i = 1. multihalo paraffin without active H. phosphate. integrating them backward in time leads to the more volatile compositions which would produce a residue curve passing through the specified initial composition. Residue curve maps can be constructed for mixtures of any number of components. y diagram or a y-x diagram suffices. In the composition space for a binary system. is illustrated in Fig. e. for many systems. Solvent class Group H-donor Phenol Acid. · · · . ternary. Doherty and Malone. which corresponds to increasing temperature. by permission. The vertices of the triangular diagram or tetrahedron represent the pure components. aldehyde. Because the vapor is richer in the more volatile components than the liquid. This last composition may be a pure-component species. Any binary. Therefore.ENHANCED DISTILLATION RESIDUE CURVE MAPS AND DISTILLATION REGION DIAGRAMS The simplest form of distillation involves boiling a multicomponent liquid mixture in an open evaporation from a single-stage batch still.g. 76(10). . liquid-phase compositions are plotted on a triangular diagram. and it may depend on the initial composition of the mixture charged to the still. and decreasing volatility. Each of the infinite number of possible residue curves originates at the pentane vertex. sulfone. ammonia. the vapor generated is removed from contact with the liquid as soon as it is formed. Such systems will have more than one distillation region. intramolecular bonding. Sci. As the liquid is boiled. thiol Alcohol. such that the escaping vapor is in phase equilibrium with the residual liquid. If the liquid is well mixed and the vaporization is slow. cit. pointing in the direction of increasing time.. c (13-116) 13-69 where ξ is a dimensionless nonlinear time scale. L. Systems that do not involve azeotropes have only one region—the entire composition space. the distillation boundary is a curve. using a right-triangle diagram. x. o-nitro phenol Aromatic. The simplest form of ternary RCM.. Maps for all other nonazeotropic ternary mixtures are qualitatively similar. but they represent it in a way that is much more useful for understanding distillation systems. the composition and boiling temperature of the liquid remaining in the still change continuously over time and move progressively toward less volatile compositions and higher temperatures until the last drop is vaporized. Normally. op. However. Integrating these equations forward in time leads to the less volatile final compositions. yi and xi are related by an isobaric VLE model. The family of all residue curves that originate at one composition and terminate at another composition defines a distillation region. . oxide.

however.). all of which are four-sided and share the ternary azeotrope as the low-boiling node. Adjacent regions may share some (but not all) nodes and saddles. but never at pure component saddles—distillation boundaries can be calculated by using the method proposed by Lucia and Taylor [AIChE J. 13-78c Residue curve map: MEK-MIPK-water system at 1 atm containing two minumum-boiling binary azeotropes. 13-78b FIG. Distillation boundaries always originate or terminate at saddle azeotropes.). In this ternary system. 205 (1957)] for a ternary mixture with a ternary saddle azeotrope (reproduced as fig.. The high-boiling node of region I is pure water. the high.13-70 DISTILLATION component or a minimum-boiling azeotrope. Trans. However. the most volatile composition on the boundary (either a pure FIG. Both methylethylketone (MEK) and methylisopropylketone (MIPK) form minimum-boiling homogeneous azeotropes with water (Fig. Pure components and azeotropes are labeled as nodes and saddles as a result of the boiling points of all the components and azeotropes in a system. respectively. All pure components and azeotropes in a system lie on region boundaries. In region II. The boundaries of the composition diagram (e. Chem. FIG. 52. If one species is removed. (Azeotropic Data. Ternary saddle azeotropes are particularly interesting because they are more difficult to detect experimentally (being neither minimum-boiling nor maximum-boiling). 13-78a Residue curve map: Nonazeotropic pentane-hexane-heptane system at 1 atm. All other pure components and azeotropes are called intermediate-boiling saddles. have a different number of saddles—one in region I and two in region II. Within each region. USSR (Engl.. The first ternary saddle azeotrope to be detected experimentally was reported by Ewell and Welch [Ind. their presence in a mixture implies the existence of distillation boundaries which may have an important impact on the design of a separation system. Eng. and the origin of all residue curves in that region) is called the low-boiling node. the labeling of all remaining pure components and azeotropes.and low-boiling nodes are MIPK and the MEK-water azeotrope. 1994).9 in Doherty and Malone. Residue curve map: Ethanol-cyclohexane-water system at 1 atm containing four minimum-boiling azeotropes (three binary and one ternary) and three distillation regions. 13-78b). More ternary saddle azeotropes are reported in Gmehling et al. Appl. . cit. 30. 37. 13-78c) has three boundaries and three regions. 582 (2006)]. and a particularly comprehensive set of experimental residue curves were reported by Bushmakin and Kish [J. Chem. while region II has four sides. a distillation boundary connects the binary azeotropes and divides the RCM into two distillation regions. This leads to region I having three sides. I and II. The more complicated cyclohexane-ethanol-water system (Fig. op. while the lowboiling node is the MEK-water azeotrope.. the edges of a composition triangle) also form region boundaries since they divide physically realistic residue curves with positive compositions from unrealistic curves with negative compositions. particularly those that were saddles. The leastvolatile composition on the boundary (either a pure component or a maximum-boiling azeotrope. 5. may change. and the terminus of all residue curves in that region) is called the high-boiling node. These two regions.g. 1224 (1945)].

which is situated in a different distillation region than the desired product. These DRDs are indexed in Table 13-18 according to a temperature profile sequence of position numbers. 30. Applications include 1. Positions 2. 24. and methanol (64.. Control analysis/design.. All three of these temperature profiles correspond to DRD 107. Consider the recovery of MIPK from an MEK-MIPK-water mixture. the correct diagram for a system must be determined from residue curves obtained from experimental or calculated data. 474 (1985). Methanol forms minimum-boiling azeotropes with both acetone (54. the stage-to-stage liquid compositions (along with the distillate and bottoms compositions) of a single-feed. Also note that some combinations of binary azeotropes require the existence of a ternary saddle azeotrope. However. Material balances for mixing or continuous separation operations are represented graphically on triangular composition diagrams such as residue curve maps or distillation region diagrams by straight lines connecting pertinent compositions. Ind. However. Res. Eng. 4.. Ind. such as extraction and decantation. and 5 are the pure components in order of decreasing volatility. pure MIPK cannot be obtained at all. Therefore. 3. Doherty and Caldarola. reflux. Table 13-18 also indicates that the pure-component and binary azeotrope data are consistent with three temperature profiles involving a ternary saddle azeotrope. Since residue curves do not cross simple batch distillation boundaries. If a RCM distillation boundary exists in a system. defined in a keyed triangular diagram at the bottom of the table. arranged by increasing boiling point. 2364 (1991)]. suggest the existence of a ternary saddle azeotrope and DRD 107 as the correct approximation of the distillation regions. and acetone-chloroform forms a maximum-boiling azeotrope (64. particularly when combined with other information such as liquid-liquid binodal curves. Assuming no ternary azeotrope. 39. 2345 (1992)] and Fidkowski. and overall feed compositions must lie on the same straight line. and determination of initial estimates of column parameters including feed-stage location. Also some temperature profiles are consistent with more than one DRD. Res. to a first approximation. examination of composition profiles. 6. 1224 (1945)] confirmed experimentally such a ternary saddle at 57.5°C). Positions 1. 36. which from Table 13-18 is consistent with DRD 040 and DRD 042. [Ind. Chem. Evaluation of laboratory data. Schematic DRDs are particularly useful in determining the implications of possibly unknown ternary saddle azeotropes by postulating position 7 at interior positions in the temperature profile. As an example. Eng. Ind. [Ind. Both types of boundaries correspond exactly at all pure components and azeotropes. J. Chem. Eng. Calculated residue curve trajectories for the acetone-chloroform-methanol system at 1-atm pressure. a corresponding continuous distillation boundary will also exist.. 38. Res. the temperature profile for this system is 461325. 13-81). Mass balance lines for mixing and for other separations not involving vapor-liquid equilibria. Eng. with the upper edge of the bow tie region along the MEK-MIPK (water-free) face of the composition triangle and part of the lower . and 4613725. 13-80. 10. The precise boundaries of these distillation regions are a function of reflux ratio. Analysis of column balances and profiles to aid in control system design and operation... considerable information on system behavior can still be deduced from a simple qualitative sketch of the RCM distillation boundaries based only on pure-component and azeotrope boiling point data and approximate azeotrope compositions. Figure 13-79 illustrates all the 125 possible DRDs for ternary systems [see Peterson and Partin. The straight lines are exact representations of the compositions due to the lever rule. Eng. Japan. as explained by Wahnschafft et al. 36. 24. and 6 are binary azeotropes at the positions shown in the keyed triangle.g. and tracking of trace impurities with implications for corrosion and process specifications. Feed F2 is more favorable. Azeotropes are schematically depicted generally to have equimolar composition. (13-116) if equation-of-state or activitycoefficient expressions are available (e. Process modeling. The approximate bow tie regions of product compositions for three different feeds are shown in Fig 13-81. Chem. feasible products. 1799 (1997)].. 1799 (1997)]. but they are closely approximated by the RCM distillation boundaries. and such combinations have been excluded from the index. for systems with distillation boundaries and multiple regions. Res. Chem. 31. and product compositions. and Malone [AIChE J. it is generally not possible to obtain a saddle product (pure component or azeotrope) from a simple distillation column. 181 (1977). Azeotrope position numbers are deleted from the temperature profile if the corresponding azeotrope is known not to exist. Chem. Experimentally there are no data for maximum. The exact shape of the reachable product composition regions involves replacing two of the straight-line segments of the bow tie with a locus of pinch points. Residue curves can be constructed from experimental data or can be calculated by integrating Eq. For ternary systems containing no more than one ternary azeotrope and no more than one binary azeotrope between each pair of components. number of stages in the stripping and enriching sections. For example. Peterson and Partin. Chem. Fundam. Chem.2°C). The bottoms. AIChE J. 125 such DRDs are mathematically possible [Matsuyama and Nishimura. azeotropes. 454 (1985)]. Doherty. As is evident from the index. Eng. Since residue curves are deflected by saddles. although only a dozen or so represent most systems commonly encountered in practice. Fundam. Eng. and liquid-liquid regions.4°C). a single-feed. APPLICATIONS OF RCM AND DRD Residue curve maps and distillation region diagrams are very powerful tools for understanding all types of batch and continuous distillation operations.7°C) at 1-atm pressure.ENHANCED DISTILLATION The liquid composition profiles in continuous staged or packed distillation columns operating at infinite reflux and boil-up are closely approximated by simple distillation residue curves [Van Dongen and Doherty. Ind. A more accurate approximation involves replacing two of the straight-line segments of the bow tie with the residue curve through the feed composition [Stichlmair and Herguijuela. distillation boundaries are shown as straight lines. Overall flow rates are found by the inverse-lever-arm rule. and redesign or modification of existing process flow sheets. 2. Eng. twoproduct.5°C.. 1303 (1993)]. and position 7 is the ternary azeotrope. From feed F3. the distillate and bottoms compositions must be in the same distillation region with the mass balance line intersecting a residue curve in two places. distillation regions. Process synthesis. namely. some DRDs are consistent with more than one temperature profile. Identification of infeasible or problematic column specifications that could cause simulation convergence difficulties or failure. 4617325. 37. Distillation material balance lines are governed by two constraints: 1. distillation composition profiles are constrained to lie in specific regions. In such cases. chloroform (61. Note that not every conceivable temperature profile corresponds to a thermodynamically consistent system. The bow tie shaped set of reachable product compositions for a simple distillation column is roughly bounded by the (straight) material balance lines connecting the feed composition to the sharpest direct separation and the sharpest indirect separation possible (see Fig. Residue curves are also indicative of many aspects of the general behavior of continuous columns operating at more practical reflux ratios. as 13-71 shown in Fig. distillate. continuous distillation column lie on the same residue curve. The bottoms and distillate compositions must lie (to a very close approximation) on the same residue curve. are of course not limited by distillation boundaries. Rules for constructing such qualitative distillation region diagrams (DRDs) are given by Foucher et al. 4671325.. and the arrows on the distillation boundaries indicate increasing temperature.6°C) and chloroform (53. 2.. two-product distillation column (simple column) can be designed with sufficient stages. Wilson binary-interaction parameters. 4.or minimum-boiling ternary azeotropes for this mixture. and material balance control to produce separations ranging from the direct-split mode of operation (low-boiling node taken as distillate) to the indirect-split mode (high-boiling node taken as bottoms). consider the system acetone (56. Location and confirmation of saddle ternary azeotropes and a thermodynamic consistency check of data. UNIFAC groups). 5. Ewell and Welch [Ind. 3. Location of distillation boundaries. For a given multicomponent mixture. Chem. Concept development. Process trouble shooting. System visualization. 760.5°C). Analysis of separation system operation and malfunction. construction of flow sheets for new processes. 1523 (1992)]. reflux ratio.

13-72 DISTILLATION (a) FIG. . 13-79 Distillation region diagrams for ternary mixtures.

13-79 (Continued) .Next Page ENHANCED DISTILLATION 13-73 (b) FIG.

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