Chapter 4

4.4 Distillation with Reflux

4.4a Introduction: Distillation with reflux can be considered to be a process in which
equilibrium stages are arranged in a series in such a manner that the vapor and liquid product
from each stage flow counter-current to each other. Each stage receives the liquid flow from
the stage above and the vapor flow from the stage below. The liquid and vapor are mixed in
each stage and they are assumed to be in equilibrium when they leave a stage. Figure 4.4-1
shows the process flow diagram for a distillation tower containing sieve trays.
Condenser

Overhead
product

Reflux
Liquid

Vapor

Feed

Reboiler

Bottom
liquid
product

Figure 4.4-1 Process flow of a distillation tower containing sieve trays.

The feed is normally introduced into the distillation at a location between the top and the
bottom trays. For a total condenser, the vapor from the top tray is condensed and part of the
condensate is returned to the top of the column to provide liquid flow above the feed point.
Part of the liquid from the bottom tray is vaporized in the reboiler and returned to the bottom
of the column to provide the vapor flow.
4-15

4.4b McCabe-Thiele Method

v1

QC
L0

D, xD

plate n-1
L n-1

Vn

Ln

Vn+1

plate n
F, x F

plate n
plate n+1

feed plate
plate m-1
plate m

L m-1

Vm

Lm

Vm +1

plate m
plate m+1

QR

B, xB

Figure 4.4-2 Distillation column notations.

The McCabe Thiele method is a graphical procedure to solve alternately the equilibrium
relation and the material balance for binary distillation. Consider the distillation column
shown in Figure 4.4-2 with the tray above and below the feed tray using the index n and m,
respectively. The section of the column above the feed tray is the rectifying section and the
section below the feed tray is the stripping section. The two streams (Ln and Vn or Lm and Vm)
leaving a theoretical (or equilibrium) tray are in equilibrium. The two passing streams (for
example Ln-1 and Vn) are related by the material balance or operating line. A total material
balance for tray n gives
Vn+1 + Ln-1 = Vn + Ln

(4.4-1)

A component balance on the more volatile component, A, gives

yn+1Vn+1 + xn-1Ln-1 = ynVn + xnLn

(4.4-2)

In this expression, yn+1 is mole fraction of component A in Vn+1 and xn-1 is the mole fraction of
component A in Ln-1 and so on. The McCabe-Thiele method is valid when we have constant
molal overflow in both the rectifying and stripping sections of the distillation column. Hence
V1 = V2 = V3 = = Vn = Vn+1 = constant
L0 = L1 = L2 = = Ln-1 = Ln = constant
Vm-1 = Vm = Vm+1 = constant
4-16

Lm-1 = Lm = Lm+1 = constant

Even for CMO, Vn Vm and Ln = Lm. The constant molal overflow is justified if the heat of
mixing is negligible for the two components in the mixture (ideal solution) and the molar
heats of vaporization for the two components are almost the same.
Equations for rectifying section
Figure 4.4-3 shows the rectifying or enriching section which is the distillation tower section
above the feed. The vapor from the top tray with a composition y1 is condensed in the total
condenser so that the resulting liquid is at the boiling point. Part of the liquid is taken out as
the overhead product D and the remaining liquid is returned to the first tray with flow rate L0.

v1

QC

x0

y1

x1

y2

x2

y3

Ln, xn

L0

D, xD

Vn+1 , yn+1

Figure 4.4-3 Schematic of the rectifying section with a total condenser.

Making a balance over the top part of the tower (the dashed-line section) on component A
gives
yn+1Vn+1 = xnLn + xDD

(4.4-3)

Since CMO is assumed, Vn+1 = V = constant and Ln = L = constant. Eq. (4.4-3) can be written
as
yn+1 = xnL/V + xDD/V

(4.4-4)

From the total balance V = L + D D/V = 1 L/V. In terms of the reflux ratio R = L/D
L
L
L/D
R
=
=
=
V
L+D
L / D +1 R +1

4-17

D
D
1
1
=
=
=
V
L+D
L / D +1 R +1
Eq. (4.4-4) becomes
yn+1 =

R
1
xn +
xD
R +1
R +1

(4.4-5)

This equation which is the material balance for component A is called the operating line.
Given xD, xF, R, and the equilibrium data, the equilibrium stages can be determined by
successively solving the equilibrium relation and the material balance at each stage. Starting
at xD, y1 is evaluated, for a total condenser y1 = xD. The liquid composition x1 is then
determined form the equilibrium curve at y = y1. This is a dew point calculation with known
y1. Next y2 is determined from the mass balance or operating line
y2 =

R
1
x1 +
xD
R +1
R +1

x2 is again determined from the equilibrium curve and y3 is determined from

y3 =

R
1
x2 +
xD
R +1
R +1

This process continues until xn < xF. The number of equilibrium stages in the rectifying
section is n including the feed tray, n is the number of equilibrium calculations during the
process.

Example 4.4-1 ---------------------------------------------------------------------------------A distillation column receives a feed that is 40 mole % n-pentane and 60 mole % n-hexane.
Feed flow rate is 2,500 lbmol/hr and feed temperature is 30oC. The column is at 1 atm. A
distillate that is 97 mole % n-pentane is desired. A total condenser is used. Reflux is a
saturated liquid. The external reflux ratio is L0/D = 3. Bottoms from the partial reboiler is 98
mole % n-hexane. Determine the number of equilibrium trays and their compositions for the
rectifying section.
Data: Vapor pressure, Psat, data: ln Psat = A B/(T + C), where Psat is in kPa and T is in K.
Compound
A
n-pentane (1) 13.9778
n-hexane (2) 14.0568

B
2554.6
2825.42

C
36.2529
42.7089

Heat of evaporation for n-pentane, C5 = 11,369 Btu/lbmol, CpL,C5 = 39.7 Btu/lbmoloF

Heat of evaporation for n-hexane, C6 = 13,572 Btu/lbmol, CpL,C6 = 51.7 Btu/lbmoloF

Solution -----------------------------------------------------------------------------------------Overall material balance over the entire tower gives

4-18

D + B = 2,500
Material balance for n-pentane over the entire tower gives
0.97D + 0.02B = (0.4)(2,500) = 1,000 0.97(2,500 B) + 0.02B = 1,000
Solving for B and D from the above equations we have B = 1,500 lbmoles/hr and D = 1000
lbmoles/hr.

v1

QC
D, xD = 0.97
L0
L/D
=3
0

F = 2,500 lbmol/hr
T = 30o C
F, xF
P = 1 atm

feed plate

QR

B, xB = 0.02

Since the column has a total condenser, y1 = xD = 0.97. The liquid composition x1 is then
determined form the equilibrium curve at y = y1 = 0.97. The equilibrium curve y versus x for
n-pentane and n-hexane system is plotted in Figure E-1a where x and y are the mole fraction
of n-pentane in the liquid and vapor phase, respectively. The equilibrium curve is expanded
near the region x = 1 in Figure E-1b. At y = y1 = 0.97, x = x1 = 0.9107. We can also perform
a dew point temperature calculation with y = y1 = 0.97.
We start with the equation
x1 + x2 = 1

(E-1)

Substituting xi = yiP/Pisat into equation (E-1) yields

y1 P
y P
+ 2sat = 1
sat
P1
P2

(E-2)

With the numerical values for mole fractions and pressure, equation (E-2) becomes

4-19

.97101.325/exp(13.9778 2554.6/(T 36.2529))

+ 0.03101.325/exp(14.0568 2825.42/(T 42.7089)) = 1

(E-3)

Figure E-1a: Equilibrium curve for n-pentane and n-hexane system.

Figure E-1b: Equilibrium curve for n-pentane and n-hexane system near x = 1.

4-20

The dew point temperature should be between the boiling points of n-pentane and n-hexane
given by
T1boil =

2554.6
+ 36.2529 = 309.20 K
13.9778 ln(101.325)

T2boil =

2825.42
+ 42.7089 = 342.06 K
14.0568 ln(101.325)

The solution of the nonlinear algebraic equation (E-3) can be determined using Matlab
function fsolve with inline function as follows:

>>fun=inline('.97*101.325/exp(13.9778-2554.6/(T-36.2529))+
0.03*101.325/exp(14.0568 -2825.42/(T-42.7089))-1');
>> T=fsolve(fun,309.5,optimset('Display','off'))
T = 311.0479
The dew point temperature of the n-pentane and n-hexane mixture is 311.0479 K. At this
temperature, the vapor pressure of n-pentane is
P1sat = exp(13.9778 - 2554.6/( 311.0479 - 36.2529)) = 107.9228 kPa

The mole fraction of n-pentane in the liquid stream leaving state 1 is then
x1 =

y1 P
(0.97)(101.325)
=
= 0.9107
sat
107.9228
P1

Next y2 is determined from the mass balance or operating line

y2 =

R
1
3
1
x1 +
xD =
x1 +
xD = 0.75x1 + 0.25xD
R +1
R +1
3 +1
3 +1

y2 = (0.75)(0.9107) + (0.25)(0.97) = 0.9255

x2 is again determined from the equilibrium curve and y3 is determined from
y3 =

R
1
x2 +
xD
R +1
R +1

This process continues until xn < xF. The following Matlab program alternately solves the
equilibrium relation and material balance for the mole fraction of n-pentane leaving each
equilibrium stage:

4-21

------------------------ Table 4.4-1: Matlab program e2d4d1b -----------------------------% Example 4.4-1

%
A=[13.9778 14.0568];B =[2554.6 2825.42];C=[-36.2529 -42.7089];
xd=.97;xb=.02;xf=.4;R=3;
am=R/(R+1);bm=xd/(R+1);
P=101.325;pl=log(P);
Tb=B./(A-pl)-C;
dT=.01;
yi=xd;
for i=1:20;
% Assume a temperature for the dew point calculation
T=yi*Tb(1)+(1-yi)*Tb(2);
% Solve for the dew point temperature using Newton's method
for n=1:20;
f=P*(yi/exp(A(1)-B(1)/(T+C(1)))+(1-yi)/exp(A(2)-B(2)/(T+C(2))))-1;
T1=T+dT;f1=P*(yi/exp(A(1)-B(1)/(T1+C(1)))+(1-yi)/exp(A(2)-B(2)/(T1+C(2))))-1;
fp=(f1-f)/dT;eT=f/fp;T=T-eT;
if abs(eT)<0.001,break, end
end
% Solve for the mole fraction in the liquid phase using equilibrium relation for ideal
system
xi=yi*P/exp(A(1)-B(1)/(T+C(1)));
fprintf('Stage #%g x = %8.5f , y = %8.5f\n',i,xi,yi)
% Solve for the mole fraction in the vapor stream leaving a stage
yi=am*xi+bm;
if xi<xf, break, end
end
-------------------------------------------------------------------->> e2d4d1b
Stage #1 x =
Stage #2 x =
Stage #3 x =
Stage #4 x =
Stage #5 x =

0.91070 , y =
0.79889 , y =
0.63454 , y =
0.46085 , y =
0.32841 , y =

0.97000
0.92552
0.84167
0.71840
0.58814

4-22