SIMULTANEOUS HEAT AND

MASS TRANSFER
(SHMT)
7th Semester,
B.Sc. Chemical Engineering
Session 2016

Delivered by:
Dr. Usman Ali

Department of Chemical Engineering

University of Engineering & Technology, Lahore
 Introduction to Multicomponent Distillation

 Equilibrium Data

 Feed and Product Composition

 Degree of Freedom Analysis

 Vapor-liquid Equilibria
 Equilibrium Data
 Relative Volatility
 K Values

DePriester chart
 Vapor-liquid Equilibria
 Phase equilibria
 Types of phase equilibria
 Bubble point calculations
 Dew point calculations
 Flash calculations
 Degree of Freedom for
Multicomponent Distillation
 Separation Principles
 Phase creation.
 Phase addition.
 Barrier separation.
 Solid-agent separation.
 Separation by gradient.
 Measures of Separation
 Split fraction.
 Split ratio.
 Separation power/factor.
 Fractional recovery.
 Multicomponent Distillation (MCD) – The Problem
 Off-the-Shelf Solutions
 Key Components
 Light key
 Heavy key
 Non Keys
 Non Key component splits
 How to determine the keys (LK, HK, NK)
 Missing Keys
 Number and sequencing of columns
 In multicomponent distillations it is not possible to obtain more than one pure
component, one sharp separation, in a single column.
 If a multicomponent feed is to be split into two or more virtually pure products,
several columns will be needed.
 Impure products can be taken off as side streams; and the removal of a side stream
from a stage where a minor component is concentrated will reduce the concentration
of that component in the main product.
 For separation of Nc components, with one essentially pure component taken
overhead, or from the bottom of each column, (Nc — 1) columns will be
needed to obtain complete separation of all components.
 For example, to separate a mixture of benzene, toluene and xylene two
columns are needed , Benzene is taken overhead from the first column and the
bottom product, essentially free of benzene, is fed to the second
column. This column separates the toluene and xylene
 Sequence of Ordinary Distillation Column
 Multicomponent mixtures are often separated into more
than two products. Although one piece of equipment of
complex design might be devised to produce all the
desired products, a sequence of two product separators is
more common.
 For nearly ideal feeds, such as hydrocarbon mixtures and
mixtures of a homologous series, the most economical
sequence will often include only ordinary distillation
columns.
 Heuristics for Determining Favorable
Sequences of Columns
 The relative volatility between the two selected key components for the
separation in each column is > 1.05.
 The reboiler duty is not excessive. An example of an excessive duty occurs in the
distillation of a mixture with a low relative volatility between the two key
components.
 The tower pressure does not cause the mixture to approach its critical
temperature.
 The overhead vapor can be at least partially condensed at the column pressure to
provide reflux without excessive refrigeration requirements.
 The bottoms temperature at the low pressure is not so high that chemical
decomposition occurs.
 Azetropes do not prevent the desired separation.
 Column pressure drop is tolerable, particularly if operation is under vacuum.
Heuristics for Determining Favorable Sequences
of Columns

 Remove thermally unstable, corrosive, or chemically reactive components early

in the sequence.
 Remove final products one by one as distillates( the direct sequence).
 Sequence separation points to remove, early in the sequence, those components
of greatest molar percentage in the feed.
 Sequence separation points in the order of decreasing relative volatility so that
the most difficult splits are made in the absence of the other components.
 Sequence separation points to leave last those separations that give the highest-
purity products.
 Sequence separation points that favour near equimolar amounts of distillate and
bottoms in each column.
 Summary: Heuristics for Determining Favorable
Sequences of Columns

Do the most difficult separation last.

Favor the direct sequence.
Large fraction components should be
removed first.
Favor equimolar splits.
 Sequencing of Columns

Separation points in the Sequence = P-1

Number of different Sequences:

Five Sequences of Four Component Feed
Five Sequences of Four Component Feed
 Costs Considerations
 The order in which the components are separated will determine the
capital and operating costs.

 Where there are several components the number of possible

sequences can be very large; for example, with five components the
number is 14, whereas with ten components it is near 5000.

 When designing systems that require the separation of several

components, efficient procedures are needed to determine the
optimum sequence of separation.
 Tall and vacuum columns
 Where a large number of stages is required, it may be
necessary to split a column into two or more separate
columns to reduce the height of the column, even
though the required separation could, theoretically,
have been obtained in a single column.
 This may also be done in vacuum distillations, to
reduce the column pressure drop and limit the
bottom temperatures.
 MCD Calculation Procedure
 The normal procedure for a typical problem is to solve the MESH
(Material balance, Equilibrium, Summation and Heat) balance
equations stage-by-stage, from the top and bottom of the column toward
the feed point.
 For such a calculation to be exact, the compositions obtained from both
the bottom-up and top-down calculations must mesh at the feed point
and mesh the feed composition.
 The calculated compositions will depend on the compositions
assumed for the top and bottom products at the commencement of the
calculations.
 Though it is possible to match the key components, the other
components will not match unless the designer was particularly
fortunate in choosing the trial top and bottom compositions.
 MCD Calculation Procedure
 For a completely rigorous solution the compositions must be
adjusted and the calculations repeated until a satisfactory match
at the feed point is obtained by iterative trial-and-error
calculations.
 Clearly, the greater the number of components, the more difficult
the problem.
 For other than ideal mixtures, the calculations will be further
complicated by the fact that the component volatilities will be
functions of the unknown stage compositions.
 If more than a few stages are required, stage-by-stage
calculations are complex and tedious.
Exact Stage By Stage Calculation Methods – Rigorous Procedures
 Rigorous Solution Procedure: Basic Steps
The basic steps in any rigorous solution procedure will be .
 Specification of the problem; complete specification is essential
for computer methods.
 Selection of values for the iteration variables; for example,
estimated stage temperatures, and liquid and vapour flows (the
column temperature and flow profiles).
 A calculation procedure for the solution of the stage equations.
 A procedure for the selection of new values for the iteration
variables for each set of trial calculations.
 A procedure to test for convergence; to check if a satisfactory
solution has been achieved.
 Rigorous Solution Procedure – Available
Methods

Lewis-Matheson method.
Thiele-Geddes method.
Relaxation method.
Linear algebra method.
 Lewis-Matheson Method
 The method proposed by Lewis and Matheson (1932) is essentially
the application of the Lewis-Sorel method to the solution of
multicomponent problems.
 Constant molar overflow is assumed and the material balance and
equilibrium relationship equations are solved stage by stage starting
at the top or bottom of the column.
 To define a problem for the Lewis-Matheson method the following
variables must be specified, or determined from other specified
variables;
 Feed composition, flow rate and condition.
 Distribution of the key components.
 One product flow.
 Reflux ratio.
 Column pressure.
 Assumed values for the distribution of the non-key components.
 Lewis-Matheson Method
 Calculation procedure follow use of equilibrium relationship and
operating lines.
Equilibrium relation:

Top operating line:

Bottom operating line:

 Thiele-Geddes Method
Like the Lewis-Matheson method, the original method of
Thiele and Geddes (1933) was developed for manual
calculation.
It has subsequently been adapted by many workers for
computer applications.
The variables specified in the basic method, or that must
be derived from other specified variables, are:
 Reflux temperature.
 Reflux flow rate.
 Distillate rate.
 Feed flows and condition.
 Column pressure.
 Number of equilibrium stages above and below the
feed point.
 Thiele-Geddes Method
 Consider Enriching Section:
 For nth tray;
1

 For feed tray;

2

 Consider Enriching Section:

 For mth tray;

 For feed tray;

4
Thiele-Geddes Method
5

7
 Relaxation Method
 With the exception of this method, all the methods described solve
the stage equations for the steady-state design conditions.
 In an operating column other conditions will exist at start-up, and
the column will approach the "design" steady-state conditions after
a period of time.
 The stage material balance equations can be written in a finite
difference form, and procedures for the solution of these
equations will model the unsteady-state behaviour of the column.
 Relaxation methods are not competitive with the "steady-state"
methods in the use of computer time, because of slow convergence.
However, because they model the actual operation of the column,
convergence should be achieved for all practical problems.
 The method has the potential of development for the study of the
transient behaviour of column designs, and for the analysis and
design of batch distillation columns.
 Linear Algebra Method
 The Lewis-Matheson and Thiele-Geddes methods use a stage-by- stage
procedure to solve the equations relating the component
compositions to the column temperature and flow profiles.
 However, the development of high-speed digital computers with large
memories makes possible the simultaneous solution of the complete
set of MESH equations that describe the stage compositions
throughout the column.
 If the equilibrium relationships and flow-rates are known (or
assumed) the set of material balance equations for each component is
linear in the component compositions.
 With the aim of a numerical method these equations are solved
simultaneously and the results used to provide improved estimates of the
temperature and flow profiles.
 Linear Algebra Method
 The set of equations can be expressed in matrix form and solved
using the standard inversion routines available in modern computer
systems. Convergence can usually be achieved after a few
iterations.
 It is possible to include and couple to the distillation program, some
thermodynamic method for estimation of the liquid-vapour
relationships (activity coefficients) as the UNIFAC method
 This makes the program particularly useful for the design of
columns for new processes, where experimental data for the
equilibrium relationships are unlikely to be available.
Short-cuts Methods
 “Short-cut" Methods

 Before the advent of the modern digital computer, various "short-

cut" methods were developed to simplify the task of designing
multicomponent columns.
 Though computer programs will normally be available for the
rigorous solution of the MESH equations, short-cut methods are
still useful in the preliminary design work, and as an aid in defining
problems for computer solution.
 Intelligent use of the short-cut methods can reduce the computer
time and costs.
 “Short-cut" Methods
The short-cut methods available can be divided into two classes:
 Simplifications of the rigorous stage-by-stage procedures to
enable the calculations to be done using hand calculators, or
graphically.
 Typical examples of this approach are the methods given by
Hengstebeck , and the Smith-Brinkley method.
 Empirical methods, which are based on the performance of
operating columns, or the results of rigorous designs.
 Typical examples of these methods are Gilliland's
correlation, and the Erbar-Maddox correlation.
 Pseudo-binary Systems
 If the presence of the other components does not significantly
affect the volatility of the key components, the keys can be
treated as a pseudo-binary pair.
 The number of stages can then be calculated using a McCabe-
Thiele diagram, or the other methods developed for binary
systems.
 This simplification can often be made when the amount of the non-
key components is small, or where the components form near-ideal
mixtures.
 Where the concentration of the non-keys is small, say less than
10%, they can be lumped in with the key components.
 For higher concentrations the method proposed by Hengstebeck
(1946) can be used to reduce the system to an equivalent binary
system.
 Hengstebeck's Method
 For any component i the Lewis-Sorel material balance equations and
equilibrium relationship can be written in terms of the individual
component molar flow rates; in place of the component composition:
For the rectifying section: For the stripping section:

where ln,i = the liquid flow rate of any component i from stage n,
vn,i = the vapour flow rate of any component i from stage n,
di = the flow rate of component i in the tops,
bi = the flow rate of component i in the bottoms,
Kn,i = the equilibrium constant for component i at stage n.
The superscript ' denotes the stripping section.
V and L are the total flow-rates, assumed constant.
 Hengstebeck's Method
 To reduce a multicomponent system to an equivalent
binary it is necessary to estimate the flow-rate of the
key components throughout the column.
 Hengstebeck considers that in a typical distillation the
flow-rates of each of the light non-key components
approaches a constant, limiting, rate in the rectifying
section; and the flows of each of the heavy non-key
components approach limiting flow-rates in the stripping
section.
 Hengstebeck's Method
 Putting the flow-rates of the non-keys equal to these
limiting rates in each section enables the combined
flows of the key components to be estimated.
For the rectifying section: For the stripping section:
Lighter Heavier
species species

where Ve and Le are the estimated flow rates of the combined keys,
li and vi are the limiting liquid and vapour rates of components lighter than the keys in the
rectifying section,
li' and vi’ are the limiting liquid and vapour rates of components heavier than the keys in the
stripping section.
 Hengstebeck's Method
 The method used to estimate the limiting flow-rates is
that proposed by Jenny. The equations are:
For the rectifying section: For the stripping section:

where αi relative volatility of component i, relative to the heavy key (HK),

αLK = relative volatility of the light key (LK), relative to the heavy key.
di and bi = corresponding top and bottom flow rate of component i.
 Hengstebeck's Method
 Estimates of the flows of the combined keys enable operating lines
to be drawn for the equivalent binary system.
 The equilibrium line is drawn by assuming a constant relative
volatility for the light key:

where y and x refer to the vapor and liquid concentrations of the light
key.
Minimum Reflux Ratio -
Underwood’s Method
Number of Plates at Total Reflux –
Fenske’s Method
Relation Between Reflux Ratio and Number
of Plates – Gilliland Correlation

𝑁 − 𝑁𝑚 1+54.4 Ψ Ψ −1 𝑅 − 𝑅𝑚
= 1 − exp where Ψ =
𝑁+1 11+117.2 Ψ Ψ0.5 𝑅+1
Erbar-Maddox Correlation
 Feed-point Location – Kirkbride Equation
 A limitation of the Erbar-Maddox, and similar empirical methods, is that they do not give the
feed-point location.
 An estimate can be made by using the Fenske equation to calculate the number of stages in
the rectifying and stripping sections separately, but this requires an estimate of the feed-
point temperature.
 An alternative approach is to use the empirical equation given by Kirkbride :

where Nr = number of stages above the feed, including any partial condenser,
Ns = number of stages below the feed, including the reboiler,
B = molar flow bottom product,
D = molar flow top product,
xf,HK = concentration of the heavy key in the feed,
xf,LK = concentration of the light key in the feed,
xd,HK = concentration of the heavy key in the top product,
xb,LK = concentration of the light key if in the bottom product.
 Distribution of Non-key Components -
Graphical Method
 The graphical procedure proposed by Hengstebeck , which is based on the
Fenske equation, is a convenient method for estimating the distribution of
components between the top and bottom products.
 Hengstebeck and Gedde have shown that the Fenske equation can be
written in the form:

 Specifying the split of the key components determines the constants A and C
in the equation.
 The distribution of the other components can be readily determined by
plotting the distribution of the keys against their relative volatility on log-log
paper, and drawing a straight line through these two points.
 Summary of Empirical Methods
Data: feed composition and thermal condition, operating pressure.
 Choose LK and HK and fix their distribution on top and bottom
product.
 Estimate overall top and bottom flow rate compositions (assume
light non-key components in top and heavy non-key component in
bottom as first attempt).
 Estimate dew and bubble points on top, bottom and feed:

(where, Ki taken from De Priest chart).

 Summary of Empirical Methods
 Estimate relative volatility with respect to the HK of all comps. at the Tdew
(top) and Tboiling (bottom):
and calculate average volatilities αi, avg= (αi,top*αi,bot)0.5
 Recalculate overall top and bottom flow rate compositions on the basis of
the Hengstebeck and Geddes equation:

by plotting on log-log diagrams knew points relevant to LK and HK

(assume first trial relative volatilities)
 Please note that A=log(dHK/bHK) and C=[log(dLK/bLK) - ]/logαLK
 Check first attempt composition and go back to step 3 to update
Tdew and Tboiling and recalculate relative volatilities if necessary
 Summary of Empirical Methods
 Estimate the minimum number of stages for the separation Nm
using Fenske eq.:

where A = LK and B = HK.

 Estimate the minimum reflux ratio Rm using Underwood eq.:

q = (LR-LS)/F

where θ is the root of eq., and remember that 1 < θ < αLK.
 Summary of Empirical Methods
 Choose an operative reflux ratio R and calculate the number of
(ideal) stages N with the
 Erbar-Maddox diagram
or
 with Gilliland Correlation:
𝑁 − 𝑁𝑚 1+54.4 Ψ Ψ −1 𝑅 − 𝑅𝑚
= 1 − exp where Ψ =
𝑁+1 11+117.2 Ψ Ψ0.5 𝑅+1

 Calculate the feed stage position using Kirkbride eq.:

Azeotropic & Extractive Distillation
 Azeotropic Mixture

Ethanol-Water system (upto 96 %)

Minimum boiling Azeotrope

Maximum boiling Azeotrope

 Examples of Azeotropic Mixture

Water – nitric acid

Water – hydrochloric acid
Water – alcohols
Acetone – chloroform
Acetone – carbon disulfide
 Low Relative Volatility

For nearly pure product

 High Reflux Ratio

 Large No. of plates

 n-heptane – methyl cyclohexane system

 R.V = 1.08
 Large No. of plates are required
Principles of Azeotropic & Extractive
Distillation

Phase addition
 To increase the Relative Volatility
 Azeotropic Distillation

A component of high volatility is added called ENTRAINER

MSA is used which forms a azeotrope with one of the
components in the mixture.
Principle of separation: boiling point differences caused by
formation of a azeotropic mixture.
Separating agent: liquid entrainer (MSA) and heat transfer
(ESA)
Low boiling azeotrope is obtained at top of the column.
Mostly Entrainer is added at feed plate.
 Azeotromism

Homogeneous Azeotropic Distillation

Heterogeneous Azeotropic Distillation

Homogenous Azeotropic Distillation

If at these two conditions, a single liquid phase is in

equilibrium with the vapor phase, the azeotrope is
homogeneous.
Homogenous Azeotropic Distillation
Homogenous Azeotropic Distillation
Hetrogenous Azeotropic Distillation

If multiple liquid-phase behavior is exhibited at the

azeotropic condition, the azeotrope is heterogeneous.

For heterogeneous azeotropes, the vapor-phase

composition is equal to the overall composition of
the two (or more) liquid phases
Hetrogenous Azeotropic Distillation
Hetrogenous Azeotropic Distillation
 Properties of Entrainer

Cheap
Readily available
Chemically stable
Non reactive
Non corrosive
Non toxic
Low latent heat of vaporization
Low freezing pt. to facilitate storage & handling
Low viscosity
 Extractive Distillation

A component of low volatility is added called SOLVENT

MSA is used which forms Low volatile mixture with one or
more components in the mixture.
Low volatile mixture is obtained at the bottom of the
column.
Separating agent: liquid entrainer (MSA) and heat transfer
(ESA)
Mostly Solvent is added at top plate.
Extractive Distillation
Extractive Distillation
 Choice of Entrainer & Solvent

Satisfactory Selectivity
Satisfactory volatility
Ease of Separation
Miscibility Relationships
Miscellaneous properties
 Chemical stability
 Thermal stability
 Non-toxic
 Non- corrosive
 Cost
 Availability
 Choice of Entrainer & Solvent
Should enhance significantly the natural relative volatility of
the key component.
Should not require an excessive ratio of solvent to nonsolvent
Should remain soluble in the feed components and should not
lead to the formation of two phase.
Should be easily separable from the bottom product.
Should be inexpensive and readily available.
Should be stable at the temperature of the distillation and
solvent separation.
Should be nonreactive with the components in the feed
mixture.
Should have a low latent heat.
Should be noncorrosive and nontoxic.
Naturally no single solvent or solvent mixture satisfy all the
criteria, and compromises must be reached.