DOCUMENTATION OF DISTILLATION COLUMN DESIGN

Submitted to:
Dr. Nadeem Feroze

Submitted By:
Engr. Anees Ahmad

UNIVERSITY OF ENGINEERING AND TECHNOLOGY LAHORE

 CONTENTS

1.1 DEFINITION ................................................................................................................................... 3

1.2 TYPES OF DISTILLATION ........................................................................................................... 3
1.3 FOUNDATION ............................................................................................................................... 3
1.4 NON-REACTIVE DISTILLATION AND ITS CLASSIFICATION ............................................. 3
1.5 PHASE EQUILIBRIA[2] .................................................................................................................. 4
1.5.1 PHASE EQUILIBRIA FOR SINGLE COMPONENT ............................................................ 4
1.5.2 PHASSE EQUILIBRIA FOR TWO COMPONENTS (VAPOR-LIQUID EQUILIBRIA) ..... 5
Details of Vapor-Liquid Equilibria................................................................................................. 6
1.6 THE FUNDAMENTAL LAWS[1] ................................................................................................. 10
1.6.1 DALTON’S LAW ................................................................................................................... 10
1.6.2 RAOULT’S LAW ................................................................................................................... 10
1.6.3 HENRY’S LAW ..................................................................................................................... 10
1.7 THE FRACTIONATING COLUMN[1] ......................................................................................... 11
1.8 MATHEMATICAL MODELING OF THE DISTILLATION ..................................................... 15
1.8.1 MODELING AT STEADY STATE (STATIC BEHAVIOUR)[4].......................................... 15
Rectifying Section Operating Line ............................................................................................... 18
Stripping Section Operating Line ................................................................................................. 21
Feed Stage Considerations – The Equation of q-Line .................................................................. 24
1.8.2 MODELING AT UNSTEADY STATE (DYNAMIC BEHAVIOUR)[5] ............................... 30
1.8.3 DESIGN OF DISTILLATION COLUMN (METHOD OF MCCABE-THIELE) ................. 34
Condenser Type ............................................................................................................................ 37
Reboiler Type ............................................................................................................................... 38
Condenser and Reboiler Heat Duties............................................................................................ 39
 DISTILLATION

1.1 DEFINITION

Distillation is a unit operation which is used to separate the liquid mixtures into
its constituent species on the basis of difference in boiling points of each individual
species (or Relative Volatility).

1.2 TYPES OF DISTILLATION

Distillation is divided into two main types on the basis of occurrence of chemical
reaction.
1. Distillation (Not involving Chemical Reaction; Physical Distillation)
2. Reactive Distillation (Involving Chemical Reaction)
1.3 FOUNDATION

The foundation which is necessary to understand the process of distillation is the

Fundamentals of Thermodynamics and Chemical Kinetics. Basically, the depth
knowledge of the following two areas is necessary:
1. Phase Equilibrium
2. Chemical Equilibrium (It is not required for non-reactive distillation)
At Bachelor’s Level, only the understanding of NON-REACTIVE DISTILLATION is
necessary.

1.4 NON-REACTIVE DISTILLATION AND ITS CLASSIFICATION

Non-Reactive Distillation or only Distillation is further classified on the basis of:

1. Number of Components in the Feed Mixture
a. Binary Distillation
b. Multicomponent Distillation
2. Type of Column used for Distillation
a. Tray Column Distillation
b. Packed Column Distillation
 3. Mode of Operation
a. Differential Distillation
b. Flash or Equilibrium Distillation
c. Rectification
4. Phase of Feed
a. Distillation of Liquid Feed (Normal Distillation)
b. Cryogenic Distillation (e.g. Separation of Air)
The purpose of defining the types of distillation here is that reader should
understand that which type of distillation operation is discussed in this whole document.
In this document, we are dealing with the design of distillation column which are non-
reactive, having only two components in the feed stream (Binary Distillation), and the
process is occurring in the rectification column which is tray type. [1] So, only the
understanding of the PHASE EQUILIBRIA is needed for its design calculations.

1.5 PHASE EQUILIBRIA[2]

Phase Equilibria is also referred to as the PHASE EQUILIBRIUM and it has three types:
1. Phase Equilibria for Single Component
2. Phase Equilibria for Two Components
3. Phase Equilibria for Multicomponent
For the understanding of our desired distillation column only first two types of Phase
Equilibria will be discussed:

1.5.1 PHASE EQUILIBRIA FOR SINGLE COMPONENT

The phase equilibrium for pure components is illustrated in Figure-1 given below.
At low temperatures, the component forms a solid phase. At high temperatures and low
pressures, the component forms a vapor phase. At high pressures and high temperatures,
the component forms a liquid phase. The phase equilibrium boundaries between each of
the phases are illustrated in Figure-1. The point where the three phase equilibrium
boundaries meet is the triple point, where solid, liquid and vapor coexist. The phase
equilibrium boundary between liquid and vapor terminates at the critical point. Above
the critical temperature, no liquid forms, no matter how high the pressure is. The phase
equilibrium boundary between liquid and vapor connects the triple point and the critical
point, and marks the boundary where vapor and liquid coexist. For a, given temperature
on this boundary, the pressure is the vapor pressure. When the vapor pressure is 1 atm,
the corresponding temperature is the normal boiling point. If, at any given vapor
pressure, the component is at a temperature less than the phase equilibrium, it is
subcooled. If it is at a temperature above the phase equilibrium, it is superheated.
Various expressions can be used to represent the vapor pressure curve.

FIGURE-1

1.5.2 PHASSE EQUILIBRIA FOR TWO COMPONENTS (VAPOR-LIQUID

EQUILIBRIA)

Consider a simple process in which a binary component feed is allowed to

separate into a vapor and a liquid phase with the phases coming to equilibrium, as shown
in Figure-2 given below.

FIGURE-2

An overall material balance and component material balances can be written as:
The vapor–liquid equilibrium relationship can be defined in terms of K-values by:

Above equations can now be solved to give expressions for the vapor- and liquid-phase
compositions leaving the separator:

The vapor fraction (V / F) in above Equations lies in the range 0 ≤ V /F ≤ 1.

where NC is the number of components.

Details of Vapor-Liquid Equilibria

Figure-3 shows, as an example of the vapor–liquid equilibrium behavior for a
binary mixture of benzene and toluene. Figure-3a shows the behavior of temperature of
the saturated liquid and saturated vapor (i.e. equilibrium pairs) as the mole fraction of
benzene is varied (the balance being toluene). This can be constructed by calculating
the bubble and dew points for different concentrations. Figure-3b shows an alternative
way of representing the vapor–liquid equilibrium in a composition or x–y diagram.
 FIGURE-3
The x–y diagram can be constructed from the relative volatility. From the definition of
relative volatility for a binary mixture of Components A and B:

Rearranging gives:

By Checking:
𝛼𝐴𝐵 < 1 𝑁𝑜 𝑆𝑒𝑝𝑎𝑟𝑎𝑡𝑖𝑜𝑛
𝛼𝐴𝐵 = 1 𝑁𝑜 𝑆𝑒𝑝𝑎𝑟𝑎𝑡𝑖𝑜𝑛
𝛼𝐴𝐵 > 1 𝐺𝑜𝑜𝑑 𝑆𝑒𝑝𝑎𝑟𝑎𝑡𝑖𝑜𝑛
1
𝛼𝐴𝐵 = 𝑓(𝑇) 𝑎𝑛𝑑 𝛼𝐴𝐵 ∝
𝑇
Thus, by knowing αAB from vapor–liquid equilibrium and by specifying xA, yA
can be calculated. Figure-3a also shows a typical vapor–liquid equilibrium pair, where
the mole fraction of benzene in the liquid phase is 0.4 and that in the vapor phase is
0.62. A diagonal line across the x–y diagram represents equal vapor and liquid
compositions. The phase equilibrium behavior shows a curve above the diagonal line.
This indicates that benzene has a higher concentration in the vapor phase than toluene,
that is, benzene is the more volatile component. Figure-3b shows the same vapor-liquid
equilibrium pair as that shown in Figure-3a.
 Figure-3a can be used to predict the separation in a single equilibrium stage, given
a specified feed to the stage and a stage temperature. For example, suppose the feed is
a mixture with equal mole fractions of benzene and toluene of 0.5 and this is brought to
equilibrium at 95◦C (Point Q in Figure-3a). Then, the resulting liquid will have a mole
fraction of benzene of 0.4 and the vapor, a mole fraction of 0.62. In addition, the quantity
of each phase formed can be determined from the lengths of the lines PQ and QR in
Figure-3a.
Consider first, a binary mixture of two Components A and B; the vapor–liquid
equilibrium exhibits only a moderate deviation from ideality, as represented in Figure-
4a.

FIGURE-4
In this case, as pure A boils at a lower temperature than pure B in the temperature–
composition diagram in Figure 4.4a, Component A is more volatile than Component B.
This is also evident from the vapor–liquid composition diagram (x–y diagram), as it is
above the line of yA = xA. In addition, it is also clear from Figure-4a that the order of
volatility does not change as the composition changes. By contrast, Figure-4b shows a
more highly non-ideal behavior in which γi > 1 (positive deviation from Raoult’s Law)
forms a minimum-boiling azeotrope. At the azeotropic composition, the vapor and
liquid are both at the same composition for the mixture. The lowest boiling temperature
is below that of either of the pure components and is at the minimum-boiling azeotrope.
It is clear from Figure-4b that the order of volatility of Components A and B changes,
depending on the composition. Figure-4c also shows azeotropic behavior. This time, the
mixture shows a behavior in which γi < 1 (negative deviation from Raoult’s Law) forms
a maximum boiling azeotrope. This maximum-boiling azeotrope boils at a higher
temperature than either of the pure components and would be the last fraction to be
distilled, rather than the least volatile component, which would be the case with non-
azeotropic behavior. Again, from Figure-4c, it can be observed that the order of
volatility of Components A and B changes depending on the composition. Minimum
boiling azeotropes are much more common than maximum boiling azeotropes.
Some general guidelines for vapor–liquid mixtures in terms of their nonideality
are:
a) Mixtures of isomers usually form ideal solutions.
b) Mixtures of close-boiling aliphatic hydrocarbons are nearly ideal below 10
bar.
c) Mixtures of compounds close in molar mass and structure frequently do
not deviate greatly from ideality (e.g. ring compounds, unsaturated
compounds, naphthenes etc.).
d) Mixtures of simple aliphatics with aromatic compounds deviate modestly
from ideality.
e) Noncondensables such as CO2, H2S, H2, N2, and so on, that are present in
mixtures involving heavier components tend to behave nonideally with
respect to the other compounds.
f) Mixtures of polar and nonpolar compounds are always strongly non-ideal.
g) Azeotropes and phase separation into liquid–liquid mixtures represent the
ultimate in nonideality.
Moving down the list, the nonideality of the system increases.
1.6 THE FUNDAMENTAL LAWS[1]

1.6.1 DALTON’S LAW

𝑛

𝑃 = ∑ 𝑃𝑖
𝑖=1

𝑃𝐴 = 𝑦𝐴 𝑃
For Gaseous Phase (Ideal Gas or Vapors), only.
P = Total Pressure [Pa]
PA = Partial Pressure of A [Pa]
yA = Mole Fraction of A in the Vapor Phase

1.6.2 RAOULT’S LAW

Only for High Values of xA

For Ideal Solutions
𝑃𝐴 = 𝑃𝐴𝑜 𝑥𝐴
For Non-Ideal Solutions
𝑃𝐴 = 𝛾𝐴 𝑃𝐴𝑜 𝑥𝐴
PA = Partial Pressure of A [Pa]
γA = Activity Coefficient of A
PAo = Vapor Pressure of Pure A [Pa]
xA = Mole Fraction of A in the Liquid Phase

1.6.3 HENRY’S LAW

Only for Low Values of xA

𝑃𝐴 = Ԋ𝑥𝐴
PA = Partial Pressure of A [Pa]
 Ԋ = Henry’s Constant
xA = Mole Fraction of A in the Liquid Phase

1.7 THE FRACTIONATING COLUMN[1]

The operation of a typical fractionating column may be followed by reference to

Figure-5. The column consists of a cylindrical structure divided into sections by a series
of perforated trays which permit the upward flow of vapor.

FIGURE-5
 The liquid reflux flows across each tray, over a weir and down a downcomer to
the tray below. The vapor rising from the top tray passes to a condenser and then through
an accumulator or reflux drum and a reflux divider, where part is withdrawn as the
overhead product D, and the remainder is returned to the top tray as reflux R.
The liquid in the base of the column is frequently heated, either by condensing
steam or by a hot oil stream, and the vapor rises through the perforations to the bottom
tray. A more commonly used arrangement with an external reboiler is shown in Figure-
5 where the liquid from the still passes into the reboiler where it flows over the tubes
and weir and leaves as the bottom product by way of a bottoms cooler, which preheats
the incoming feed. The vapor generated in the reboiler is returned to the bottom of the
column with a composition ys, and enters the bottom tray where it is partially condensed
and then re-vaporized to give vapor of composition y1. This operation of partial
condensation of the rising vapor and partial vaporization of the reflux liquid is repeated
on each tray. Vapor of composition yt from the top tray is condensed to give the top
product D and the reflux R, both of the same composition yt. The feed stream is
introduced on some intermediate tray where the liquid has approximately the same
composition as the feed. The part of the column above the feed point is known as the
rectifying section and the lower portion is known as the stripping section. The vapor
rising from an ideal tray will be in equilibrium with the liquid leaving, although in
practice a smaller degree of enrichment will occur.
In analyzing the operation on each tray, it is important to note that the vapor rising
to it, and the reflux flowing down to it, are not in equilibrium, and adequate rates of
mass and heat transfer are essential for the proper functioning of the tray. The tray as
described is known as a sieve tray and it has perforations of up to about 12 mm diameter,
although there are several alternative arrangements for promoting mass transfer on the
tray, such as valve units, bubble caps and other devices as shown below. In all cases the
aim is to promote good mixing of vapor and liquid with a low drop in pressure across
the tray.[3]
FIGURE-6a (Bubble Cap Tray) FIGURE-6b (Dual Flow Tray)
Several types of baffle tray variations also exist as shown in Figure-7.

FIGURE-7
Figure-7a (Segmental)
Figure-7b (Disk and Doughnut)
Figure-7c (Multipass)
Figure-7d (Angle Irons)

On each tray the system tends to reach equilibrium because:

a. Some of the less volatile component condenses from the rising vapor into the
liquid thus increasing the concentration of the more volatile component (MVC)
in the vapor.
b. Some of the MVC is vaporized from the liquid on the tray thus decreasing the
concentration of the MVC in the liquid.
The number of molecules passing in each direction from vapor to liquid and in
reverse is approximately the same since the heat given out by one mole of the vapor on
condensing is approximately equal to the heat required to vaporize one mole of the
liquid. The problem is thus one of equimolecular counter diffusion. If the molar heats
of vaporization are approximately constant, the flows of liquid and vapor in each part
of the column will not vary from tray to tray. This is the concept of constant molar
overflow.
In the arrangement discussed, the feed is introduced continuously to the column
and two product streams are obtained, one at the top much richer than the feed in the
MVC and the second from the base of the column weaker in the MVC. For the
separation, of small quantities of mixtures, a batch still may be used. Here the column
rises directly from a large drum which acts as the still and reboiler and holds the charge
of feed. The trays in the column form a rectifying column and distillation is continued
until it is no longer possible to obtain the desired product quality from the column. The
concentration of the MVC steadily falls in the liquid remaining in the still so that
enrichment to the desired level of the MVC is not possible.
A complete unit will normally consist of a feed tank, a feed heater, a column with
boiler, a condenser, an arrangement for returning part of the condensed liquid as reflux,
and coolers to cool the two products before passing them to storage. The reflux liquor
may be allowed to flow back by gravity to the top plate of the column or, as in larger
units, it is run back to a drum from which it is pumped to the top of the column. The
control of the reflux on very small units is conveniently effected by hand-operated
valves, and with the larger units by adjusting the delivery from a pump. In many cases
the reflux is divided by means of an electromagnetically operated device which diverts
the top product either to the product line or to the reflux line for controlled time intervals.
1.8 MATHEMATICAL MODELING OF THE DISTILLATION

1.8.1 MODELING AT STEADY STATE (STATIC BEHAVIOUR)[4]

The steady state modeling of the distillation column is based on the Figure-8
shown below:

FIGURE-8
The purpose of the steady state modeling is to arrive at design equations so that
column can be designed and its number of trays or stages required can be found for
specified product quality specifications.
 Figure-8 shows a column containing the equivalent of N theoretical stages; a total
condenser in which the overhead vapor leaving the top stage is totally condensed to a
bubble point liquid distillate and a liquid reflux that is returned to the top stage; a partial
reboiler in which liquid from the bottom stage is partially vaporized to give a liquid
bottoms product and vapor boil up that is returned to the bottom stage; and an
intermediate feed stage. By means of multiple, countercurrent stages arranged in a two-
section cascade with reflux and boil up, a sharp separation between the two feed
components is possible unless an azeotrope exists, in which case one of the two products
will approach the azeotropic composition.
The feed, which contains a more volatile (light) component (the light key, LK),
and a less-volatile (heavy) component (the heavy key, HK), enters the column at feed
stage f. At feed-stage pressure, the feed of LK mole fraction zF may be liquid, vapor, or
a mixture of the two. The mole fraction of LK is xD in the distillate and xB in the bottoms
product. Mole fractions of the HK are (1 - zF), (1 - xD), and (1 - xB). The goal of
distillation is to produce a distillate rich in the LK (i.e., xD approaching 1.0), and a
bottoms product rich in the HK (i.e., xB approaching 0.0). Whether the separation is
achievable depends on relative volatility of the two components A and B. For
components with close boiling points, the temperature change over the column is small
and relative volatility is almost constant.
An equilibrium curve for the benzene–toluene system is shown in Figure-9,
where the fixed pressure is 1 atm, at which pure benzene and pure toluene boil at 176
o
F and 231oF, respectively.

FIGURE-9
 Thus, these two components are not close boiling. In 1925, McCabe and Thiele
published a graphical method for combining the equilibrium curve with mass balance
operating lines to obtain, for a binary-feed mixture and selected column pressure, the
number of equilibrium stages and reflux required for a desired separation of feed
components. Although computer-aided methods are more accurate and easier to apply,
the graphical McCabe–Thiele method greatly facilitates visualization of the
fundamentals of multistage distillation, and therefore the effort required to learn the
method is well justified.
Typical input specifications and results (outputs) from the McCabe–Thiele
construction for a single-feed, two-product distillation are summarized in the Table
(Nomenclature) below:

It is required that xB < zF < xD. The distillate can be a liquid from a total condenser,
or a vapor from a partial condenser. The feed-phase condition must be known at column
pressure, assumed to be uniform throughout the column. The type of condenser and
reboiler must be specified, as well as the ratio of reflux to minimum reflux. From the
specification of xD and xB for the LK, distillate and bottoms rates, D and B, are fixed by
material balance, since:
Component Mole Balance on Overall Process:
Overall Mole Balance on Overall Process:

The McCabe–Thiele method determines N, the number of equilibrium stages;

Nmin, the minimum number of equilibrium stages; Rmin = Lmin/D, the minimum reflux
ratio; and the optimal feed-stage location. Lastly, condenser and reboiler heat duties
are obtained from energy balances.
Besides the equilibrium curve, the McCabe–Thiele method includes a 45o
reference line, operating lines for the upper rectifying section and the lower stripping
section of the column, and a fifth line (the q-line or feed line) for the phase or thermal
condition of the feed.

Rectifying Section Operating Line

Figure-8, shows that the rectifying section of equilibrium stages extends from the
top stage, 1, to just above the feed stage, f. Consider a top portion of the rectifying
stages, including the total condenser, as shown by the envelope in Figure-10. A material
balance for the LK over the envelope for the total condenser and stages 1 to n is as
follows, where y and x refer, respectively, to LK vapor and liquid mole fractions.

Solving this equation for yn+1 gives the equation for the rectifying section operating line:

The following figure represents the system under consideration over which the
mole balance resulted the TOP OPERATING LINE.
 FIGURE-10
This equation relates LK compositions yn+1 and xn of passing streams Vn+1 and
Ln, respectively. For top operating line to be plotted as a straight line, y = mx + b, which
is the locus of compositions of all passing streams in the rectifying section, L and V
must not vary from stage to stage in the rectifying section.
This is the case if:
1. The two components have equal and constant molar enthalpies of vaporization
(latent heats).
2. Component sensible-enthalpy changes and heat of mixing are negligible
compared to latent heat changes.
3. The column is insulated, so heat loss is negligible.
4. Column pressure is uniform (thus, no pressure drop).
These are the McCabe–Thiele assumptions leading to the condition of constant
molar overflow in the rectifying section, where the molar flow rates remain constant as
the liquid overflows each weir from one stage to the next. Since a total mole balance for
the rectifying-section envelope in Figure-10 gives:

If L is constant, then V is also constant for a fixed D. Rewriting TOP OPERATING

LINE EQUATION as:
Thus, the slope of the operating line in the rectifying section is a constant L/V, with V
> L and L/V < 1, as in Figure-11.

FIGURE-11
In order to sketch TOP OPERATING LINE two points are needed which will lie on this
line and they are:
1. (xD , xD )
𝐷𝑥𝐷
2. (0, )
𝑉𝑛+1

For constant molar overflow in either the rectifying or the stripping section, only
material balances and an equilibrium curve are required. Energy balances are needed
only to determine condenser and reboiler duties. Liquid entering stage 1 at the top is the
external reflux rate, L0, and its ratio to the distillate rate, L0/D, is reflux ratio R. Because
of constant molar overflow:
𝐿
𝑅=
𝐷
is a constant in the rectifying section. Since:
𝑉 =𝐿+𝐷
the slope of the operating line is readily related to the reflux ratio:

Similarly, D/V:

Combining above equations produce the most useful form of the operating line for the
rectifying section:

If R and xD are specified. In order to sketch this useful form of TOP OPERATING
LINE; two points are needed which will lie on this line and they are:
1. (xD , xD )
𝑥𝐷
2. (0, )
𝑅+1
In Figure-11, the stages are stepped off. Starting from point (y1 = xD, x0 = xD) on
the operating line and the 45o line, a horizontal line is drawn to the left until it intersects
the equilibrium curve at (y1, x1), the compositions of the equilibrium phases leaving the
top stage. A vertical line is dropped until it intersects the operating line at (y2, x1), the
compositions of the passing streams between stages 1 and 2. Horizontal- and vertical-
line constructions are continued down the rectifying section to give a staircase
construction, which is arbitrarily terminated at stage 5. The optimal termination stage is
considered in later section of this article.
Stripping Section Operating Line

The stripping section extends from the feed to the bottom stage. In Figure-12,
consider a bottom portion of stripping stages, including the partial reboiler and
extending up from stage N to stage m + 1, below the feed entry f. A mole balance for
the LK over the envelope results in:
Solving for ym+1:

In order to sketch BOTTOM OPERATING LINE shown by last equation can be

plotted as a straight line using point and slope form which will lie on this line and they
are:
1. (xB , xB )
𝐿(𝑏𝑎𝑟)
2. Slope: 𝑚 =
𝑉(𝑏𝑎𝑟)

OR

FIGURE-12
where L(bar) and V(bar) are total molar flows (which may be different from L and V in
the rectifying section because of feed addition), subject to the constant-molar-overflow
assumption. The slope of this operating line for the compositions of passing steams in
the stripping section is L(bar)/V(bar). Because L(bar) > V(bar), L(bar)/V(bar) > 1, as in
Figure-13. This is the inverse of the flow conditions in the rectifying section.

FIGURE-13
Vapor leaving the partial reboiler is assumed to be in equilibrium with the liquid
bottoms product, B, making the partial reboiler an equilibrium stage. The vapor rate
leaving it is the boil up, , and its ratio to the bottoms product rate:

is the boil up ratio. With the constant-molar overflow assumption, VB is constant in the
stripping section. Since;
Combining the equations of stripping section will lead to the stripping-section
operating-line equation and that is:

If values of VB and xB are specified, then BOTTOM OPERATING LINE shown

by last equation can be plotted as a straight line using:
1. (xB , xB )
𝑉𝐵 +1
2. Slope =
𝑉𝐵

The stages are stepped off, in a manner similar to that described for the rectifying
section, starting from (y = xB, x = xB) on the operating and 45o lines and moving upward
on a vertical line until the equilibrium curve is intersected at (y = yB, x = xB), which
represents the vapor and liquid leaving the partial reboiler. From that point, the staircase
is constructed by drawing horizontal and then vertical lines between the operating line
and equilibrium curve, as in Figure-13, where the staircase is arbitrarily terminated at
stage m. Next, the termination of the two operating lines at the feed stage is considered.

Feed Stage Considerations – The Equation of q-Line

In determining the operating lines for the rectifying and stripping sections, it is
noted that although xD and xB can be selected independently, R and VB are not
independent of each other, but related by the feed-phase condition.

Figure-14 shows Possible Feed Conditions

14-a: Subcooled Liquid Feed
14-b: Bubble Point Liquid Feed
14-c: Partially Vaporized Feed
14-d: Dew-Point Vapor Feed
14-e: Superheated Vapor Feed
 FIGURE-14
Consider the five feed conditions in Figure-14, where the feed has been flashed
adiabatically to the feed-stage pressure. If the feed is a bubble-point liquid, it adds to
the reflux, L, from the stage above, to give L(bar) = L + F. If the feed is a dew point
vapor, it adds to the boil up, V(bar), coming from the stage below, to give V = V(bar) +
F. For the partially vaporized feed in Figure-14c, F = LF + VF, L(bar) = L + LF, and V =
V(bar) + VF. If the feed is a subcooled liquid, it will cause some of the boil up, V(bar),
to condense, giving L(bar) > L + F and V < V(bar). If the feed is a superheated vapor,
it will cause a portion of the reflux, L, to vaporize, giving L(bar) < L and V > V(bar) +
F.
 For cases (b), (c), and (d) of Figure-14, covering feed conditions from a saturated
liquid to a saturated vapor, the boil up V(bar) is related to the reflux L by the material
balance:

Alternatively, the reflux can be obtained from the boil-up by:

Although distillations can be specified by reflux ratio R or boil up ratio VB, by

tradition R or R/Rmin is used because the distillate is often the more important product.
For cases (a) and (e) in Figure-14, VB and R cannot be related by simple material
balances. An energy balance is necessary to convert sensible enthalpy of subcooling or
superheating into heat of vaporization. This is conveniently done by defining a
parameter, q, as the ratio of the increase in molar reflux rate across the feed stage to the
molar feed rate,

or by material balance around the feed stage,

Values of q for the five feed conditions of Figure-14 are:

For subcooled liquids and superheated vapors, a more general definition of q is:

For a subcooled liquid feed, this equation becomes:

For a superheated vapor feed, the same second last equation becomes:

where CPL and CPV are molar heat capacities, is the molar enthalpy change from
the bubble point to the dew point, and TF, Td, and Tb are, respectively, feed, dew-point,
and bubble-point temperatures at column operating pressure.
Instead of using the stripping-section operating-line equation to locate the
stripping operating line on the McCabe–Thiele diagram, it is common to use an
alternative method that involves the q-line, shown in Figure-15. The q-line, one point
of which is the intersection of the rectifying- and stripping-section operating lines, is
derived by combining Stripping-Section Operating Line equation with Rectifying-
Section Operating Line equation to give:
Stripping-Section Operating Line

Rectifying-Section Operating Line

However, overall,

and a total material balance around the feed stage gives:

Combining last four equations give the EQUATION OF q-LINE:

which is located on the McCabe–Thiele diagram of Figure-15

FIGURE-15
by noting that when x = zF, Equation of q-Line reduces to the point y = zF = x, which
lies on the 45o line.
Hence in order to plot the equation of q-Line on the equilibrium diagram the
following information is needed:
1. Point: (zF, zF)
2. Slope: m = q/(q-1)
In Figure-15, the q-line is constructed for a partially vaporized feed, where 0 < q
< 1 and -∞<[q/(q-1)]<0. Following placement of the rectifying-section operating line
and the q-line, the stripping-section operating line is located by drawing a line from the
point (x = xB, y = xB) on the 45o line to and through the intersection of the q-line and
rectifying-section operating line, as in Figure-15. The point of intersection must lie
somewhere between the equilibrium curve and the 45o line.
As q changes from > 1 (subcooled liquid) to < 0 (superheated vapor), the q-line
slope, q/(q-1), changes from positive to negative and back to positive, as shown in
Figure-16. For a saturated-liquid feed, the q-line is vertical; for a saturated vapor, the q-
line is horizontal. This figure shows the Effect of thermal condition of feed on slope of
the q-line.

FIGURE-16
1.8.2 MODELING AT UNSTEADY STATE (DYNAMIC BEHAVIOUR)[5]

The modeling of Distillation at unsteady state conditions is required for the

Distillation Column Process Control purposes. Because until dynamic model of
chemical process is not available it is impossible to design a CONTROLLER by making
its CONTROL LAW available to electronic engineers.
Consider a binary mixture of components A and B, to be separated into two
product streams using conventional distillation. The mixture is fed in the column as a
saturated liquid (i.e., at its bubble point), onto the feed tray f (Figure-17), with a molar
flow rate (mol/min) Ff and a molar fraction of component A, Cf. The overhead vapor
stream is cooled and completely condensed, and then it flows into the reflux drum. The
cooling of the overhead vapor is accomplished with cooling water. The liquid from the
reflux drum is partly pumped back in the column (top tray, N) with a molar flow rate FR
(reflux stream) and is partly removed as the distillate product with a molar flow rate FD.
Let us call MRD the liquid holdup in the reflux drum and xD the molar fraction of
component A in the liquid of the reflux drum. It is clear that XD is the composition for
both the reflux and distillate streams.

FIGURE-17
At the base of the distillation column, a liquid product stream (the bottoms
product) is removed with a flow rate FB and a composition xB (molar fraction of A). A
liquid stream with a molar flow rate V is also drawn from the bottom of the column and
after it has been heated with steam, it returns to the base of the column. The composition
of the recirculating back to column stream is xR. Let MB be the liquid holdup at the base
of the column.
The column contains N trays numbered from the bottom of the column to the top.
Let M, be the liquid holdup on the ith tray. The vapor holdup on each tray will be
assumed to be negligible. In Figure-18a we see the material flows in and out of the feed
tray. Similarly, Figure-18b and 18c show the material flows for the top (Nth) and bottom
(first) trays, while Figure-18d refers to any other tray.

FIGURE-18
To simplify the system, we will make the following assumptions:
1. Vapor holdup on each tray will be neglected.
2. The molar heats of vaporization of both components A and B are approximately
equal. This means that 1 mole of condensing vapor releases enough heat to
vaporize 1 mole of liquid.
3. The heat losses from the column to the surroundings are assumed to be negligible.
4. The relative volatility of the two components remains constant throughout the
column.
 5. Each tray is assumed to be 100% efficient (i.e., the vapor leaving each tray is in
equilibrium with the liquid on the tray).
The first three assumptions imply that:

and there is no need for energy balance around each tray.

The last two assumptions imply that a simple vapor-liquid equilibrium
relationship can be used to relate the molar fraction of A in the vapor leaving the ith tray
(yi) with the molar fraction of A in the liquid leaving the same tray (xi):

The final assumptions that we will make are the following:

1. Neglect the dynamics of the condenser and the reboiler. It is clear that these two
units (heat exchangers) constitute processing systems on their own right and as
such they have a dynamic behavior. Therefore, accurate modeling should include
the state equations, which describe the dynamic behavior of condenser and
reboiler.
2. Neglect the momentum balance for each tray and assume that the molar flow rate
of the liquid leaving each tray is related to the liquid holdup of the tray through
the Francis weir formula:

Let us now develop the state equations that will describe the dynamic behavior
of a distillation column. The fundamental quantities are total mass and mass of
component A. But the question is: What is the system around which we will make the
balances? From a practical point of view the boundary of the system of interest is
outlined by dashed lines in Figure-17. Such a boundary clearly identifies the inputs and
outputs of practical significance for the overall system. It is also evident that unless we
can describe how the concentrations and liquid holdups on each tray change with time,
we cannot find how the variables of practical significance, such as xD and xB, change
with time. Therefore, we are forced to consider the balances around each tray. Thus, we
have (see also Figure-18).
All the equations above are state equations and describe the dynamic behavior of the
distillation column. The state variables of the model are:
 To complete the modeling of the column, in addition to the state equations, we
need the following relationships:

When all the modeling equations above are solved, we find how the flow rates
and concentrations of the two product streams (distillate, bottom) change with time, in
the presence of changes in the various input variables.
The modeling steps outlined above indicate that the overall procedure may be
tedious and full of simplifying assumptions. At times the resulting model is
overwhelming in size and the solution of the corresponding equations may be
cumbersome. For the binary distillation column, we have to solve a system of:
a) N + 4 non-linear ordinary differential equations (state equations).
b) 2N + 1 algebraic equations (equilibrium, and hydraulic relationships).
Solution of these equations will lead to outputs=f(inputs) which is used to develop the
CONTROL LAW for CONTROLLER DESIGN.

1.8.3 DESIGN OF DISTILLATION COLUMN (METHOD OF MCCABE-THIELE)

Following construction of the equilibrium curve, the 45o line, the two operating
lines, and the q-line, all shown in Figure-15, the equilibrium stages required as well as
the location of the feed stage are determined by stepping off stages from the top down
or from the bottom up until a point of merger is found with the feed stage. An exact
integer number of stages is rare; usually fractions of stages arise. Normally the staircase
is stepped off from the top and continued to the bottom, starting from the point (x = xD,
y = xD) on the 45o line, as shown in Figure-19 for a partially vaporized feed. In that
figure, point P is the intersection of the q-line with the two operating lines. The feed-
stage location is the transfer point for stepping off stages between the rectifying-section
operating line and the equilibrium curve to stepping off stages between the stripping-
section operating line and the equilibrium curve.
The smallest (optimal) number of total equilibrium stages occurs when the
transfer is made at the first opportunity after a horizontal line of the staircase passes
over point P, as in Figure-19, where the feed stage is stage 3 from the top and a fortuitous
total of exactly five stages is required (four plus a partial reboiler).
 FIGURE-19
An example of distillation design calculations is given on the next page for
demonstration of concepts presented before.
Condenser Type

Types of condensers are shown in Figure-20. A total condenser is suitable for

reflux-drum pressures to 215 psia (1.48MPa). A partial condenser is appropriate from
215 psia to 365 psia (2.52 MPa) but can be used below 215 psia to give a vapor distillate.
A mixed condenser can provide both vapor and liquid distillates. A refrigerant is often
used as coolant above 365 psia when components are difficult to condense. A partial
condenser provides an additional stage, based on the assumption that liquid reflux
leaving the reflux drum is in equilibrium with the vapor distillate.

FIGURE-20
 a) Total Condenser
b) Partial Condenser
c) Mixed Condenser

Reboiler Type

Reboilers for industrial-size distillation columns are usually external heat

exchangers of either the kettle or the vertical thermosyphon type, shown in Figure-21.
Either can provide the large heat-transfer surface required. In the former case, liquid
leaving the sump (reservoir) at the bottom of the column enters the kettle, where it is
partially vaporized by transfer of heat from tubes carrying condensing steam or some
other heat-transfer fluid. The bottoms product liquid leaving the reboiler is assumed to
be in equilibrium with the vapor returning to the bottom tray. Thus, a kettle reboilers,
which is sometimes located in the bottom of a column, is a partial reboiler equivalent to
one equilibrium stage.
Vertical thermosyphon reboilers are shown in Figures-21b and 21c. In the former,
bottoms product and reboiler feed are both withdrawn from the column bottom sump.
Circulation through the reboiler tubes occurs because of a difference in static heads of
the supply liquid and the partially vaporized fluid in the reboiler tubes. The partial
vaporization provides enrichment in the exiting vapor. But the exiting liquid is then
mixed with liquid leaving the bottom tray, which contains a higher percentage of
volatiles. This type of reboiler thus provides only a fraction of a stage and it is best to
take no credit for it.
In the more complex and less-common vertical thermosyphon reboiler of Figure-
21c, the reboiler liquid is withdrawn from the bottom-tray downcomer. Partially
vaporized liquid is returned to the column, where the bottoms product from the bottom
sump is withdrawn. This type of reboiler functions as an equilibrium stage.
Thermosyphon reboilers are favored when (1) the bottoms product contains
thermally sensitive compounds, (2) bottoms pressure is high, (3) only a small deltaT is
available for heat transfer, and (4) heavy fouling occurs. Horizontal thermosyphon
reboilers may be used in place of vertical types when only small static heads are needed
for circulation, when the surface-area requirement is very large, and/or when frequent
tube cleaning is anticipated. A pump may be added to a thermosyphon reboiler to
improve circulation. Liquid residence time in the column bottom sump should be at least
1 minute and perhaps as much as 5 minutes or more. Large columns may have a 10-
foot-high sump.
 FIGURE-21

Condenser and Reboiler Heat Duties

For saturated-liquid feeds and columns that fulfill the McCabe–Thiele

assumptions, reboiler and condenser duties are nearly equal. For all other situations, it
is necessary to establish heat duties by an overall energy balance:
 Except for small and/or uninsulated distillation equipment, Qloss can be ignored.
With the assumptions of the McCabe– Thiele method, an energy balance for a total
condenser is:

Where:

For a partial condenser:

For a partial reboiler:

 REFERENCES

1. Richardson, J.F., Harker, J.H, Backhurst, J. R., Coulson and Richardson’s CHEMICAL
ENGINEERING Volume 2. 2002: p. 559-575.
2. Smith, R., Chemical Process Design and Integration. 2005: p. 59-67.
3. Green, D.W., Perry, R.H., Perry’s Chemical Engineers’ Handbook. p. 14-28, 14-35.
4. Seader, J.D., Henley, E.J., Roper, D.K., Separation Process Principles. 2011: p. 261-279.
5. Stephanopoulos, G., Chemical Process Control. p. 70-75.