Mass Transfer Operations I

Distillation
By
Prof. Bishnupada Mandal
Professor, Department of Chemical Engineering, IIT Guwahati
Email: bpmandal@iitg.ac.in
Note: Some of the materials of this handouts are copyrighted. Thus, you can use only for this
course.

Lecture 7
Pinch Points and Minimum reflux ratio
The intersection of an operating line and the equilibrium curve is called a pinch point. A simple
column will have two pinch points (because there are two operating lines). The points change when
the operating lines do. An existing column can "pinch" if its operating line is too close to its
equilibrium curve. This means that there are several stages doing very little separation and wasting
resources.

To cure a pinch, the most direct solution is to move the feed entry point. This is often an expensive
proposition. In such cases, the reflux and boilup ratios can be increased to change the operating
lines. This will increase operating costs and energy consumption, but may be the only realistic
option.

A pinch at the intersection of the feed line and the equilibrium curve indicates that the column is
operating at minimum reflux.

The minimum reflux condition represents the theoretical opposite of total reflux -- an infinite
number of ideal separation stages. In this case, the intersection of the operating lines lies on the
equilibrium curve itself. Thus, the distance between the equilibrium curve and the operating lines
is at its minimum, the stepping triangles become very small, there is no gap between the
equilibrium curve and the intersection point, so you cannot step past the feed point.

The determination of the minimum reflux ratio for distillation is based on identifying the pinch
point. Let us refer to Figure in which the equilibrium curve and the feed line are shown; D  xD , xD 
and W  xW , xW  are the terminal points of the operating lines. For a particular reflux ratio (R1, say),
PI1 is the enriching section operating line having a slope R1/(R1+1). It intersects the feed line point
P1; WP1is stripping section operating line. The number of theoretical trays required is obviously
finite. As the reflux ratio R1 decreases to R2, the slope of the upper operating line decreases, but
the intercept increases, i.e. the point I1moves to I2(say). The upper operating line is DP2; the
stripping section line is WP2; and they intersect at P2 on the feed line. Now the driving force is less
at all the points and the number of theoretical trays will be more. If the reflux ratio is gradually
reduced, a situation will appear when the upper operating line DP3intersects the feed line at the
point P3 that lies on the equilibrium curve. The driving force is zero at the point P3 it is pinch point.
The number of theoretical trays required to achieve the given separation becomes infinite. This
operating line DP3 corresponds to the minimum reflux ratio, because if the reflux ratio is further
reduced, the operating line will intersect the line at a point Rm, for the kind of equilibrium line
shown in Figure, the steps given below should be followed.

a) Locate the points D  xD , xD  and F  Z F , Z F  on the diagonal on the x  y plane.

b) Draw the feed line through F from the known feed composition Z F , and the feed quality
(given by q); locate the point P3.
c) Join DP3 and extend to intersect the y-axis at I3.Find out the ordinate of I3 and equate it
to xD / (Rm+1). Calculate the minimum reflux ratio, Rm.

equilibrium
curve

y P3
q-line
P2
I3 P1
°

I2 45 line

I1

yW

xW x=zF xD

Example:

A mixture of 45 mole % n-hexane and 55 mole % n-heptane is subjected to continuous fraction in

a tray column at 1 atm total pressure The distillation contains 95% n-hexane and the residue
contains 5% n-hexane. The feed is saturated vapor. The relative volatility of n-hexane in mixture
is 2.36. Determine the minimum reflux ratio for this separation.

Solution:

x
y  = 2.36
1    1 x
,
x 0 0.076 0.199 0.341 0.505 0.705 1
y 0 0.16255 0.3696 0.54979 0.709 0.8493 1
 xD
 0.26
Rm  1
0.95
 Rm   1  3.65  1  2.65
0.26

Equilibrium
curve
1
0.9
(0.95, 0.95)
Rectifying OL
0.8
0.7
0.6 q-line
y
0.5
°
0.4 45 line
0.3
xD/(Rm+1)
0.2
0.1
Stripping
(0.05, 0.05) 0 OL
0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1
xW x=zF xD
x

The minimum reflux rate can be determined mathematically from the endpoints of the rectifying
line at minimum reflux -- the overhead product composition point (xD,xD) and the point of
intersection of the feed line and equilibrium curve (xeq, yeq).
 q   z F  x
y   x   
q  1 q  1 1 x  1

y
yD yD  yeq Rmin

ye xD  xeq Rmin  1

°
45 line
yB

x x x=zF xD
W eq
Minimum reflux corresponds to a pinch at the intersection of the feed line and the equilibrium
curve. From its formula, the rectifying line has slope = Rmin/Rmin+1 and will connect the
intersection point (xeq, yeq) and (xD, xD). Consequently, we can express the slope in terms of "rise
over run" or (xD – yeq)/(xD - xeq)

Algebraic rearrangement gives the desired formula:

Rmin y  yeq xD  yeq

 D 
Rmin  1 xD  xeq xD  xeq
Rmin  1 xD  xeq
 
Rmin xD  yeq
1 x x
 1  D eq
Rmin xD  yeq
1 x x
  D eq  1
Rmin xD  yeq
1 x  x  x  yeq yeq  xeq
  D eq D 
Rmin xD  yeq xD  yeq
xD  yeq
 Rmin 
yeq  xeq

Clearly, this formula doesn't apply if there are more than two operating regions. In these cases, it
is probably smarter to calculate the reflux ratio from the ratio of the liquid and vapor flow rates.

One important thing to realize: the formula only applies when the feed line is the breakpoint for
the operating curve in the top portion of the column. If there are intermediate product draws
between the reflux and the feed, the formula does not apply. In this case, you must calculate the
liquid flow down the column at the pinch point, and then work it back up the column to find the
reflux flow at minimum reflux conditions.

The above strategy fails to some other shapes of equilibrium curve. If the equilibrium curve has
an inflection point, it may not be possible to construct a line between the overhead product point
and the feed/equilibrium intersection without passing outside the equilibrium envelope. Operating
curves must always intersect within the equilibrium envelope and cannot cross outside (in either
half of the column). In this case, minimum reflux occurs at a tangent pinch and the operating line
is tangent to the equilibrium curve. Calculations are based upon the intersection of the tangent
operating line and the feed point. This type of pinch point and the minimum reflux ratio can be
determined only graphically.
 Equilibrium
y curve

yW
xW x=zF xD

Example:

A mixture of 45 mole % A and 55 mole % B is subjected to continuous fraction in a tray column

at 1 atm total pressure. The distillatte contains 95% A and the residue contains 5% A. The feed is
saturated liquid. Determine the minimum reflux ratio for this separation. The equilibrium data for
the system is given below:

x 0 0.05 0.15 0.3 0.5 0.7 1

y 0 0.2 0.4 0.65 0.8 0.85 1

Solution:

Equilibrium
curve
1
(0.95, 0.95)
0.9
0.8

y 0.7
0.6
xD/(Rm+1) °
0.5 45 line
0.4
0.3 q-line
0.2
0.1
(0.05, 0.05) 0
0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1
xW x=zF xD
x
 xD
 0.55
Rm  1
0.95
 Rm   1  1.73  1  0.73
0.55

When designing columns, it is common to define the design reflux ratio as some multiple of the
theoretical minimum reflux. The cost optimum reflux ratio is typically in the 1.1Rm to 1.5Rm range
depending on energy costs, condenser coolant, and materials of construction. The rule of thumb
reported most often suggests that a reflux ratio of about 1.2 times the minimum is a good design
value.

Lecture 8
Reflux below its bubble point: Subcooled Reflux
It may also be necessary to distinguish between returned reflux (the reflux stream flowing from
the accumulator to the column) and the effective reflux flowing down the column. This is a concern
if the reflux is subcooled. In this case, the effective reflux will consist of the returned reflux plus
whatever additional liquid is condensed when the cold liquid contacts vapor on the reflux tray. It
is probably best to use effective reflux in minumum reflux calculations.

The vapour from the top tray may sometimes be condensed and then cooled below its bubble point
(Sub cooled) in the condenser. This is ‘cold reflux ‘. On entering the top tray, the ’cold reflux’
reaches its bubble point very quickly. The required energy is supplied by condensation of some of
the vapour on the tray. Thus, the vapour flow rate G1 from the top tray will be less than that at the
lower trays, and the liquid flow rate L in the rectifying section (see Figure) will be larger than the
reflux Lo feed to the column from the condenser. As a result, the ‘internal reflux ratio’,
Rint   L / D  , will be greater than the ‘external reflux ratio’, Rext   Lo / D . In order to calculate
the internal reflux ratio, Rint , we need to know the liquid flow rate L.
If TcR is the temperature of the cold reflux, and TbR is its bubble point, energy required for heating
the reflux,
Q L C M T  T 
Q  Lo CpR M R TbR  TcR  ; vapour condensed   o pR R bR cR ;
MR  MR 
Where
C pr = Specific heat of the reflux (KJ/Kg. oC)
Mr= its average molecular weight (this is the same as that of the vapour from the top tray)
 = latent heat of condensation of the vapour (KJ/Kg) .
Then the internal liquid flow rate,
Lo  C pR M R  TbR  TcR  L C T  T 
L  Lo   Lo  o pR bR cR
MR  
 L Lo Lo C pR TbR  TcR 
 
D D D 
L L
Rint  Rext  0
D and D
C T  T   C T  T  
Rint  Rext  Rext pR bR cR  Rext 1  pR bR cR 
   
R x
The Equation of the rectifying operating line ym1  int xn  D
Rint  1 Rint  1

Example:
A mixture of 45 mole % n-hexane and 55 mole % n-heptane is subjected to continuous fraction in
a tray column at 1 atm total pressure The distillation contains 95% n-hexane and the residue
contains 5% n-hexane. The feed is saturated liquid. The vapor leaving the top of the tower is
condensed and cooled below its bubble point. The reflux is return to the tower at 62oC and the
external reflux ratio of 2.0 is used. The relative volatility of n-hexane in mixture is 2.36. Determine
the number of ideal trays required for this separation using McCabe Thiele Method. The following
data were given:

Boiling point of 95% n-hexane reflux is 72oC

Heat of vaporization of top product (95% n-hexane): 7500 kcal/kmol
Heat capacity of n-hexane: 25 kcal/kmol K (over the temperature range)
Heat capacity of n-heptane: 30 kcal/kmol K (over the temperature range)
Solution:

Heat capacity of reflux:

CpR = 0.95*25+0.05*30 = 25.25 kcal/kmol K
TbR = 273+72 = 345 K
TcR = 273+62 = 335 K

We know that
 C T  T  
Rint  Rext 1  pR bR cR 
  
 25.25  345  335 
Rint  2.0 1    2.0 1  0.0337   2.07
 7500 
Given: xD = 0.95, xW = 0.05, saturate liquid feed, q=1, slope of q-line = infinite
R x
ym1  int xn  D
Rint  1 Rint  1
xD 0.95
  0.31
Rint  1 2.07  1
 Equilibrium
curve
1
1
0.9
2 (0.95, 0.95)
4
0.8
6
0.7 q-line
0.6 8
y
0.5
°
0.4 10
45 line
xD/(Rint+1) 0.3
0.2
12
0.1
(0.05, 0.05) 0
0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1
xW x=zF xD
x

Number of ideal plates = 12.5

Stage Efficiencies
Mass transfer limitations prevent the vapor leaving a tray from truly being in precise equilibrium
with the liquid on the tray; consequently, the assumption of ideal stages is only an approximation.

An efficiency is used to represent the deviation from equilibrium. There are three types of
efficiencies we will consider:

1. Overall efficiency
2. Local efficiency
3. Murphree efficiency

An overall efficiency is the simplest choice. It is the ratio of the number of ideal stages to the
number of actual stages.

A single efficiency can thus be used for the entire column, but is only accurate enough for
prelimary design. Some improvement can be achieved by using separate efficiencies for each
section of the column. Accuracy is limited because effectiveness of mass transfer is constrained
by geometry and design of the trays, flowrates and paths of all streams, compositions, etc. The
problem is really too complex to lump into a single parameter, so when overall efficiencies are
used they should be based on performance data from similar columns or laboratory tests.

The local efficiency is the most accurate option, but also the most difficult to use. It is defined at
only a single point on a specific tray.

It is most necessary on large diameter columns where position dependence is significant.

A Murphree efficiency is probably the most common choice, since it represents a workable
compromise between accuracy and ease of use. It has the same form as a local efficiency but is
based on tray average compositions.

yn  yn 1
EM 
yeq ,n  yn 1

Note that actual enrichment of the vapor over the nth tay is

yn  yn1  EM  yeq ,n  yn1 

A pseudo-equilibrium line is drawn such that its vertical distance from the operating line is EM
times the distance between the operating line and the equilibrium curve. Staircase construction
between the pseudo-equilibrium curve and the operating lines gives the number of real plates.

Equilibrium Pseudo-equilibrium
curve curve
P
N
S M
2
O

y 3

xW x=zF xD

Values between 0.6 and 0.75 are common for sieve trays. We know that the liquid leaving a tray
is not really the same as the tray average, so a Murphree efficiency effectively assumes perfect
mixing on the tray. In practice, we normally measure the liquid composition and get the vapor
composition from an equilibrium calculation or diagram. In the case of multicomponent systems,
the efficiencies are different for each component.

The overall efficiency and the Murphree efficiency are not directly related. You cannot use an
average Murphree efficiency in place of an overall value.
To use a local or Murphree efficiency with a graphical method, the true equilibrium curve is
replaced with an effective equilibrium curve located between the true curve and the operating
curves. The effective curve is used to count stages. Note, however, that the efficiency doesn't apply
to the reboiler, so the true equilibrium curve should be used for the last stage of the stripping
section.

To construct an effective equilibrium curve is not difficult. The effective curve is given by:

yeff  y  EM  yeq,n  y 

where y represents the operating curve. A plot of yeff will produce an interior line on the equilbrium
diagram construction.

Example:

A mixture of 45 mole % A and 55 mole % B is subjected to continuous fraction in a tray column

at 1 atm total pressure. The distillate contains 90% A and the residue contains 5% A. The feed is
saturated liquid. A reflux ratio of 2.5 is used. Determine the number of real trays required for this
separation if the Murphree efficiency is 75%. The equilibrium data for the system is given below:
x 0 0.05 0.10 0.20 0.40 0.70 1
y 0 0.25 0.40 0.60 0.80 0.92 1

Solution:

xD 0.90
  0.257
R  1 2.5  1

x 0 0.05 0.10 0.20 0.40 0.70 1

y 0 0.25 0.40 0.60 0.80 0.92 1
yeff 0 0.26 0.38 0.55 0.74 0.88 1
 Equilibrium Pseudo-equilibrium
curve curve
1 1
(0.95, 0.95)
0.9
q-line 2
0.8
3
0.7
0.6
y 4
0.5
°
0.4 45 line
5
0.3
xD/(R+1)=0.257
0.2
0.1
(0.05, 0.05)
0
0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1
xW x=zF xD
x

Number of real trays = 5.5

Open steam
In general, the heat to a distillation operation is supplied by reboiler and the steam does not come
into direct contact with the boiling solution. However, when separating an aqueous solution, if the
residue or bottom product of water and traces of the solute, sometimes it may be convenient to
feed live steam at the bottom of the tower. No reboiler is necessary.

The steam is injected as small bubbles into the liquid in the tower bottom. The vapor leaving the
liquid is then in equilibrium with the liquid if sufficient contact is obtained. The overall balance
on the tower and a component balance on A are as follows:

F  S  D W
FzF  SyS  DxD  WxW

Where GS = mol/h of steam, yS = 0 is the molfraction of A in the steam.

The operating line equation for the rectifying section remains the same as derived earlier, but that
for the stripping section is obviously different. The total mass balance and material balance of
component A over the stripping envelop is (assume that the inlet steam is saturated)
Lm  S  Gm1  W
Lm xm  S (0)  Gm1 ym1  WxW
Solving:
 Lm W
ym1  xm  xW
Gm1 Gm1
Since there is no reboiler, Lm  W and for saturated steam entering S  Gm1 . Therefore,
L L W W
ym1  xm  xW  xm  xW
Gm1 Gm1 S S
L W ym1
   Slope of the operating line
Gm1 S xm  xW

The determination of the number of ideal plates in a column using open steam is illustrated in
Example 7.18. When open steam used one or two more ideal trays are required for a separation,
but there is no reboiler cost.

There may be other practical situations which are not covered in the above discussion. Cases may
arise when heat loss from the column wall may occur causing some condensation of the vapour,
or the overhead vapour may be partially condensed and the top product may be with-drawn as a
vapour. In any such case, the operating lines have to be drawn on the basis of appropriate mass
and energy balance equations.

Example:

An aqueous solution of ethanol containing 60 mol% methanol is subjected to a fractionators at 1

atm total pressure. Open steam is used as the source of heat energy at a rate of 100 kmol/hr. The
top product contains 90% methanol and bottom product contains 5% methanol. The feed is
saturated liquid and a reflux ratio of 2.5 is used.

(a) Obtain the stripping section operating line

(b) Determine the number of ideal plates required for the given separation.
(c) The steam rate required for the for the separation.
The equilibrium data for the methanol-water system at 1 atm total pressure is given below:

x 0 0.04 0.10 0.40 0.60 0.80 1

y 0 0.23 0.42 0.73 0.83 0.92 1

Solution:
 Equilibrium curve
1
1
0.9 q-line (0.90, 0.90)
2
0.8
0.7
3
0.6
y °

0.5 45 line
0.4
0.3 4
xD/(R+1)=0.257
0.2 Slope of
Stripping OL =
0.1
1.11
(0.05, 0.05) 0
0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1
xW x=zF xD
x

Given
Distillate (xD, xD) is (0.90,0.90),
Feed mixture contains 60 mole % methanol, Feed (xF,xF) is (0.60,0.60)
Residue contains 5% mole of methanol (xW, xW) is (0.05,0.05)
Reflux ratio = 2.5

(a) Intercept of Rectifying OL = xD/R+1 = 0.90/(2.5+1) = 0.257

q-line is vertical at zF = 0.6 (since saturated liquid feed)

L L W W
ym1  xm  xW  xm  xW
Gm1 Gm1 S S

Slope of the stripping OL = 0.61/0.55 =1.11 = W/S

Intercept of stripping OL = 1.11*0.05 = 0.056

Equation for Stripping section OL: y = 1.11 x - 0.056

(b) By McCabe Thiele method the number of ideal stages = 4.0

(c) In order to calculate the steam rate we have to use the material balance

F  S  D W
 100  S  D  W
for saturated steam entering S  Gm1 .
 100  G  D  W (1)
FzF  SyS  DxD  WxW
100*0.6  S *0  D *0.90  W *0.05
60  D *0.90  W *0.05
(2)
W
 1.11
G
W
G
1.11 (3)

D =25 kmol
W = 750 kmol
G = 675 kmol/h = 12150 kg steam per hour
 Mass Transfer Operations I
Distillation
Lecture 9
Multiple feeds
If two feeds of different compositions are to be fractionated to give the same products, both can
be handled in the same fractionator and each feed should normally be introduced on the tray of
matching compositions.

Total condenser
Overhead
vapor Reflux drum
Reflux Distillate

Feed 1

Feed 2
Boilup
Partial reboiler
Bottoms

The MaCabe-Thiele diagram for two feed column is shown above. Each feed is considered
separately (as if neither ‘knew’ of the other’s presence).

Overhead I
vapor Reflux drum
Distillate
Reflux D, xD

F1, zF1 n
Feed 1 Ln Gn+1 II
xn yn+1
Feed 2 m
F2, zF2 Lm Gm+1 III
xm ym+1

Boilup
NP Partial reboiler
Bottoms
W, xw
The upper operating line is located as usual.

A total materials balance over the envelope:

G = L+D
Let us define reflux ratio: R = L/D

 G  RD  D  D( R  1)
G
  R 1
D

Equation that represents the material balance of component A over an envelope shown is written
below:

Gyn 1  Lxn  DxD

L D L D x
 yn1  xn  xD  xn  D
G G G D G D
R x
 yn 1  xn  D
R 1 R 1
 This is the equation of a straight line on the x-y plane with a slope R ( R  1) and an intercept
xD ( R  1) on the y-axis.

For Envelop II (including Feed 1)

L’ and G’ is calculated based on the condition of Feed 1.

Fz F  G ' y '  x L '  D xD

L' D xD  F z F
y ' x
G' G'

Section III (Stripping Section):

The lowermost operating line intersects the intermediate one at the q-line for the less rich feed.

With the constant molar overflow assumption, the material balance for component A over
envelope an envelope
Lxm  Gym 1  WxW

Putting G  L  W ,
L W L W
ym1  xm  xW  xm  xW
G G L W L W
This is the equation of the operating line for the stripping section. It has a slope of L ( L  W ) and
passes through the point  xW , xW  which lies on the diagonal. This line is also shown in Figure.

For the least number of stages at a given reflux ratio, the feed are each introduced at the stage
whose construction on the diagram straddles their q-line.
 Equilibrium
curve
Rectifying Section:
Operating Line with Constant Slope
y
Feed 1 introduced
Intermediate section:
Operating Line with Constant Slope
Feed 2 introduced
Stripping Section:
Operating Line with Constant Slope
yW

xW xD

The intermediate operating line, for the section between feeds, intersects the enriching line at the
q-line for richer feed and has a slope given by L and G quantities computed from the following
equations:

L G
F, zF

L G
G G LL
1  q
F F
Example: Feed 1 is a saturated liquid of composition zF1, and Feed 2 is a
saturated vapor of composition zF2

Equilibrium curve
Rectifying Section:
Operating Line Slope =L/G=R/R+1
y Saturated
liquid
Intermediate section:
 
Operating Line Slope = L /G

Stripping Section:
Operating Line Slope =L/G
yW Saturated
vapor

xW ZF ZF xD
2 1
Example

Two feeds were fed in a distillation column:

(i) 100 kmol/h, saturated liquid with 60 mol% n-hexane and 40 mol% n-heptane.
(ii) 150 kmol/h, saturated vapor with 50 mol% n-hexane and 50 mol% n-heptane.
The top product contains 96% n-hexane and residue contains 4% n-hexane. The reflux is a
saturated liquid and reflux ratio of 1.5 is used. The relative volatility of n-hexane in the mixture is
2.36.
(a) Find out the number of ideal trays required for the given separation.
(b) Identify the locations of feed trays.
Solution
Basis: 1 hour operation
F1  100 kmol hr , F2 150 kmol hr ,
Total material balance:
F1  F2  D  W
 100  150  D  W
 D  W  250  1
n-hexane balance:
F1 z F 1  F2 z F 2  D xD  W xW
100  0.6  150  0.5  D  0.96  W  0.04
 60  75  0.96 D  0.04 W
 0.96 D  0.04W 135   2
Putting W=(250-D ) from Eqn (1) in Eqn(2)
0.96 D  0.04  250 - D  135
 0.96 D  10  0.04 D 135
 0.92 D 135  10  125
 D  125 0.92  135.9
Now from Eqn(1)
135.9  W  250
W  250  135.9  114.1
The equilibrium diagram and the diagonal are drawn in Fig. the points
D  xD  0.96, xD  0.96 , W  xW  0.04 xW  0.04 , F  zF1  0.6, zF1  0.6 , F2  zF 2  0.5, zF 2  0.5
are located on the x-y plane.

Rectifying section operating line

The Reflux is saturate liquid.
R  L0 D  L0  R  D  1.5 135.9
 203.9
G1   R  1 D  2.5 135.9  339.75
Eqn of operating line:
R x 1.5 0.96
y n+1  xn  D  xn 
R 1 R  1 1.5  1 1.5  1
 0.6 xn  0.384
Section II
Liquid Rate = Liquid flow rate in section I
(Since the feed 1 introduced as saturated liquid)
L0  F1  203.9  100  303.9
Vapor rate = G1  339.8
303.9
Slope of the operating line =   0.894
339.8
Fz F  G ' y '  x L '  D xD
L' D xD  F z F
y ' x
G' G'
303.9 135.9  0.96  100  0.6
 x
339.8 339.8
 0.894 x  0.207
Section III Striping Section
Liquid rate  L  II  2 303.9
Vapor rate = G  339.8  F2  339.8  150  189.8
L W
 yn 1  xm  xW
G G
303.9 114.1
 xm   0.04
189.8 189.8
1.6 xm  0.024
 1
1
Equilibrium curve 2 (0.96, 0.96)
0.9
4
0.8
6
0.7
0.6 8
y °
0.5 10 45 line
xD/(R+1)=0.384 0.4
12
0.3

0.183 0.2 14
0.1 16
(0.04, 0.04)
0
0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1
xW zF2 zF1 xD
x
(a) The number of ideal trays required is 16
(b) The location of Feed 1 is 5th tray and for Feed 2 is 9th tray

Multiple product withdrawal or side streams

Similarly, a products stream of any intermediate composition may be withdrawn from the
appropriate tray. Withdrawal of side streams is done frequently in refinery column.

Total condenser
Overhead
vapor Reflux drum
Reflux Distillate

Ls Side Stream
Feed
Boilup
Partial reboiler
Bottoms

We may consider the column as consisting of three sections on the basis of the flow rates of the
liquid and the vapor phases. The number of such sections in a column is one less than the total
number of input and output streams. The liquid and vapor flow rates vary from one section to
another. The operating line for each section has a different slope. So, there will be as many
operating lines as the number of sections

How do we analyze this configuration?

Use the multiple mass balance envelopes and assume a constant molar overflow condition.
If we perform a material balance in the light key around the stages above the side stream including
the condenser:

Gn1 yn1  Ln xn  DxD

Which we can rearrange to find:

L D
yn1  n xn  xD
Gn1 Vn1

For L and G constant from stage to stage, then:

L D
y  x  xD Operating line above side stream
G G

Overhead
vapor Reflux drum
Reflux Distillate

Ls Side Stream
Feed
Boilup
Partial reboiler
Bottoms

If we perform a material balance in the light key around the stages above the side stream
including the side stream and condenser:

G y  L x  L x  Dx
n 1 n 1 n n s s D

Which we can rearrange to find:

L L x  DxD
yn1  n xn  s s
Gn 1 Gn 1
For L and G constant from stage to stage, then:
L' L x  DxD
y  x s s Operating line below side stream
G G
The two operating lines intersect at :
xx
s

Stripping Section:

With the constant molar overflow assumption, the material balance for component A over
envelope an envelope
Lxm  Gym 1  WxW
Putting G  L  W ,
L W L W
ym1  xm  xW  xm  xW
G G L W L W
This is the equation of the operating line for the stripping section. It has a slope of L ( L  W ) and
passes through the point  xW , xW  which lies on the diagonal. This line is also shown in Figure.

Side Stream:
y Liquid withdrawn
Rectifying Section:
Equilibrium
Operating line
curve
Slope=L/G=R/(R+1)
yN Intermediate section:
<1
Saturated liquid feed
Operating line
Slope=L/G
Stripping Section:
yw Operating line
Slope=L / G=(Gw+1) /Gw
xw x=zF x=xs xD

Determination of the minimum reflux ratio for such a column is a bit tricky. The pinch point may
occur at the intersection of a feed line or a side stream line, and the equilibrium curve. If the
equilibrium curve has any unusual curvature, a pinch point may have to be found out by drawing
an operating line that touches the equilibrium curve.

Example:

A mixture of 50 mole % n-hexane and 50 mole % n-heptane is subjected to continuous fraction in

a tray column at 1 atm total pressure at feed rate of 100 kmol/h. A liquid side stream of 70 mol%
n-hexane is to be withdrawn at a rate of 20 kmol/h. The top product contains 90% n-hexane and
the residue contains 5% n-hexane. The feed is saturated liquid. The reflux is a saturated liquid and
reflux ratio of 2.5 is used. The relative volatility of n-hexane in the mixture is 2.36.

(c) Find out the number of ideal trays required for the given separation.
(d) Identify the tray from which the side stream should be withdrawn.

Solution

Basis: 1 hour operation

F  100 kmol hr , R  2.5
 Overhead
vapor
Reflux drum
Reflux Distillate

Ls Side Stream
Feed
Boilup
Partial reboiler
Bottoms

Total material balance:

F  D  S W
 100  D  20  W
 D  W  80
Material balance
FzF  DxD  S xS  WxW
 100  0.5  D  0.9  20  0.7  W  0.05
 50  0.9 D  14  0.05W
 50  0.9 D  14  0.05W
 0.9 D  0.05W  36
putting w=  80-D  in Eqn(2)
0.9 D  0.05  80-D   36
 0.9 D  4  0.05 D  36
 0.9 D  32
 D  32 0.9  35.56
 From (1) W=80-D=80-35.56=44.44

Rectifying section (above side stream)

L
R 0  L0  R  D  2.5  35.56
D
 88.9
G1   R  1 D 124.46
R x
y n+1  xn  D  0.714 xn  0.257
R 1 R 1

Section II (including side stream)

Gn 1 yn 1  Ln xn  LS xS  DxD
Ln L x  DxD
 yn 1  xn  S S
Gn 1 Gn 1
 L' L x  DxD
y  xn  S S
G G
L '  L0  S  88.9  20  68.9
G  G1  124.46
68.9 20  0.7  35.56  0.9
y xn 
124.46 124.46
 0.554 xn  0.37

Section III: Striping section

Liquid Rate L  L  F  68.9  100
168.9
Vapor rate = G  G  G1  124.46
L W
ym 1  xn  xW
G G
168.9 44.44
 xm   0.05
124.46 124.46
 1.357 xm  0.018

1
Equilibrium curve 1
0.9 (0.9, 0.9)
2
0.8
0.7 4

0.6
y
0.5
6 °
0.4 45 line
0.37
0.3
xD/(Rint+1)=0.257
0.2
8
0.1
(0.05, 0.05) 0
0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1
xW zF xD
x

(a) The number of ideal trays required is 8

(b) The location of feed tray is 4th tray
Lecture 10
MULTISTAGE BATCH DISTILLATION WITH REFLUX
In single stage batch distillation (Rayleigh distillation), the purity of the product is practically
governed by the concentration of the feed and the fraction distilled out. However, if a batch of
liquid is distilled in a multistage column with reflux, a significantly higher product purity as well
as higher fractional recovery of the product can be achieved. A schematic of a multistage batch
distillation unit is shown in Figure.

Total condenser
Overhea
Reflux drum
d vapor Distillate
Reflux

Still pot

Steam Condensate

In the theoretical analysis given below we assume that: (a) Constant molar overflow occurs, i.e.
the vapor rate G and liquid rate L remain constant in the column; (b) liquid holdup on the plates is
negligible; (c) batch distillation is an unsteady state process, however, we assume that pseudo-
steady condition prevails; this means that the liquid and the vapor concentration profiles in the
column at any moment are the same as the steady-state profiles achievable under identical
conditions.

It is easy to understand that if the reflux ratio is held constant, the distillate concentration will
decrease as the distillation proceeds. So the column may be operated till the distillate quality
remains within the acceptable limit. This is called the constant reflux operation. Alternatively, the
reflux ratio is continuously increased so that the product concentration remains constant for some
time. This is called variable reflux operation. In practice, the constant reflux operation is more
common.

To use the Rayleigh equation when a column is refluxed, generally, one or more iterative
calculations are required. Typically, a McCabe-Thiele diagram is used to obtain some of the
information needed in the calculation.

Constant Reflux operation (Constant Reflux)

Let the amount of liquid in the still pot of the multistage unit at any moment be W mole at a
concentration xW . Over a small time, dD mole of distillate is withdrawn and the amount of the
liquid in the still pot decrease by dW mole. We can write:
d WxW   xD dD   WdxW  xW dW   xD dD Since dD   dW 
dW dxW
 
W xD  xW
If Wi and Wf are the initial and final amounts of liquid in the still pot, then on integration,
x
Wi
Wi dxW
ln  
W f xWf xD  xW

As distillation proceeds, x D and xW both keep on changing. The integral in the above Eq. can
now be evaluated graphically. This is explained in the example.

Of the four quantities Wi ,W f , xWi , xWf any one can be calculated by this way if the others are known.
The accumulated distillate composition can be found out by material balance.
Wi xWi  W f xWf
xD,av 
Wi  W f

Example

A 100 kmol mixture of 40% A and 60% B is subjected to batch distillation column at 1 atm total
pressure. The column has one tray, a stillpot and a total condenser. The final concentration of
residue is 5 mol% A. The reflux is a saturated liquid and a reflux ratio of 1.6 is used. Calculate the
composition and amount of distillate. The equilibrium data is given below:

x 0 0.05 0.10 0.20 0.40 0.7 1

y 0 0.25 0.40 0.60 0.80 0.82 1

Solution

The batch distillation is operation at constant reflux. Hence, the concentration of the vapor from
top try will decrease gradually. The procedure is as follows:
(i) Select a number of values of xD on the diagonal and draw the corresponding operating
lines (since the reflux rate is constant, the operating line will be parallel)
(ii) For each value of xD, determine the value of xW by drawing two stages (one tray and
the still pot) between the operating line and the equilibrium line. Thus, we shall have a
set of values of xD and xW with the concentration range xWi=0.4 (intial) and
xWf=0.05(final)
(iii) The integral of the following equation can then be evaluating graphically.

Wi xWi dxW
ln 
Wf xWf x  x
D W

The reflux ratio R=1.6

R 1.6
Slope    0.615
R  1 2.6
The Equilibrium line, two operating lines and the graphical construction are shown
in the figure.
 Equilibrium curve
1 1
2
0.9 (0.92, 0.92)
0.8 3
0.7
0.6
y 0.5
xD/(R+1)=0.35 °
0.4 45 line
0.3
0.2
0.1
(0.05, 0.05) 0
0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1
xW x=zF x xD

xD 0.90 0.80 0.70 0.60 0.50 0.40

xW 0.40 0.20 0.14 0.10 0.07 0.05

1/  xD  xW  2.00 1.67 1.79 2.0 2.33 2.86

2.5

2
1/ XD-XW

1.5

0.5

0
0 0.1 0.2 0.3 0.4 0.5
XW

Area under the curve = 0.722

Initial amount of liquid, Wi = 100 kmol, Now

Wi xWi dxW 100

ln   ln  0.722
Wf xWf x  x Wf
D W

W f  48.59

D  100  48.59  51.41

100*0.4  48.59*0.05
xD ,avg   0.731
51.41

Variable Reflux operation (Constant xD)

In a variable reflux operation, the reflux ratio is continuously increased in such a manner that the
distillate concentration remains unchanged despite the fall in concentration of the more volatile in
the still pot. If dG, dL and dD are the changes in the rates of vapour flow, liquid flow and distillate
withdrawal,
dG  dL  dD
 dD  1   dL / dG  dG
By material balance,
x x 
W xW  Wi xWi  Wi  W  xD  xD  Constant 
 W  Wi  Wi D 
 xW  xD 
Substituting for dD and W in the material balance Eq. and nothing that dD = - dW,
Wi  xWi  xD  dxw
dG 
 xD  xW  1  dL / dG 
2

Total amount of vapour generated,

Wi  xWi  xD  dxw
xWf xWi
dxw
G   Wi D
x  xWi  
xWi  xD  xW  1  dL / dG  xWf  xD  xW  1  dL / dG 
2 2

Example

A 100 kmol mixture of 40% A and 60% B is subjected to batch distillation column at 1 atm total
pressure. The column has three trays, a stillpot and a total condenser. The top product contains
96% A. The final concentration of residue is 4% A. The reflux is a saturated liquid. Calculate the
composition and amount of distillate.

(a) Calculate the amount of top and bottom products.

(b) What initial and final reflux ratios should be used?
(c) Determine the total moles of vapor to be generated to achieve the separation.

The equilibrium data is given below:

 x 0 0.05 0.10 0.20 0.40 0.7 1

y 0 0.25 0.40 0.60 0.80 0.82 1

Solution

(a) Total material balance:

F  D W
 100  D  W

Component balance
F z F  D xD  W xW
100  0.4  D  0.96  W  0.04
 40  0.96 D  0.04 W
 40  0.96 D  0.04 100  D 
 0.96 D  4  0.04 D
 36  0.92 D
D  36 0.92  39.13
From (1) W  100  39.13  60.87

This is a case of operating a batch still with variable reflux. The concentrating of more volatile (n-
hexane) in the still decreases gradually. But the reflux ratio has to be increase continuously until the
bottom liquid concentration (xwf) drops down to 4 % n-hexane while five ideal trays (from plates
and a re- boiler) are fitted between thr operating line and the equation. The overhead vapor
concentration should always be 96% n-hexane. The steps are:
(1) Draw the Equilibrium line on the x-y plane
(2) Locate the point (xD, xD) where xD=0.96
(3) Draw a bunch of operating lines origination from (0.96, 0.096) and having varying slopes.
(4) In each case, fit five ideal stages between the operating line and the equilibrium line and
determine the bottom concentration xW.
(5) Using the (xD, xW) data as well as the slopes of the bunch of operating line drawn evaluate the
integral of the following equation either numerically or graphically to get the total moles of vapor
generated during distillation.
 Equilibrium curve
1
(0.96, 0.96)
0.9
0.8 4

0.7
0.6
y
0.5
°
0.4 45 line
0.3 4
0.2
0.1
(0.04, 0.04) 0
0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1
xW x=zF xD
x

dxW
G  Wi  xD  xWi  
 xD  xW  1  
2 dL
 dG 
dL  L 0.417 0.521 0.656 0.781 0.9375
dG G

xW 0.5 0.26 0.17 0.11 0.04

1 8.106 4.261 4.658 6.320 18.903

 dL 
 xD  xW  1 
2

 dG 

20
1/(XD-XW)2(1-dL/dG)

15

10

0
0 0.2 0.4 0.6

XW

Area under the curve = 3.0

 Mass Transfer Operations I

Distillation

Lecture 11
THE PONCHON-SAVARIT METHOD

This method was developed by Ponchon and Savarit independently in 1921-22. Variations in
internal vapor and liquid flows inside a distillation column depend on the enthalpies of the
mixtures. Equimolal overflow assumes the rates are independent of the energy balance. To remove
the assumption we must consider the enthalpy balances explicitly. It is a more rigorous method
and is free from the assumption of 'constant molar overflow'. So the use of this method is suggested
if the enthalpy of a stream appreciably depends upon its composition.

The Ponchon-Savarit method is also a graphical method of solution of the material and energy
balance equations as well as the equilibrium relation taken together.

Rectifying Section
Refer to Figure given below:

QC
Overhead I
vapor Reflux drum
Distillate
Reflux D, xD, HD

II
n
Feed Ln Gn+1
xn yn+1
F, zF, HF H IV
LnHG,n+1
m
Lm Gm+1 III
x y
HmL,mHm+1
G,m+1
Boilup
NP Partial reboiler
W, xw+1, Hw Bottoms
QW

Consider the material and energy balance taken over envelope II:
Total material balance: Gn1  Ln  D (10.1)
Component A balance: Gn1 yn1  Ln xn  D xD (10.2)
Energy balance: Gn1 HG,n1  Ln HL,n  D HD  QC (10.3)

From eqs. (10.1) and (10.2) we have:

Ln x y
Gn1 yn1  Ln xn  Gn1  Ln  xD   D n1 (10.4)
Gn1 xD  xn

Here we assume that the reflux may be a sub-cooled liquid (i.e. below its bubble point) in general
and xD is the mole fraction of the more volatile in it.

The energy balance equation (10.3) can be rewritten as

 Q 
Gn1 HG,n1  Ln H Ln  D  H D  C   Ln H Ln  DQ 'd (10.5)
 D
Here Q'd  HD  QC D  thermal energy removed from the top section of the column per mole of
distillate. Putting D = Gn+l - Ln in the above equation:
Gn1 H G ,n1  Ln H Ln  (Gn1  Ln )Q 'd
Ln Q '  HG ,n1
  d
Gn1 Q 'd  H Ln (10.6)

The quantity Ln/Gn+1 is the internal reflux ratio.

From Eqs. (10.4) and (10.5),

xD  yn1 Q'd  HG ,n1 Q'd  H L,n Q'd  HG ,n1
 '   (10.7)
xD  xn Q d  H L,n xD  xn xD  yn1

Refer to the Figure xx on which the liquid and vapor enthalpy--concentration curves (x-HL and y-
HG) are plotted. A point on this diagram represents the composition and enthalpy of a phase (liquid,
vapour or mixed), and we denote this point by a term that also represents the flow rate of the
particular phase. Thus, the point Ln represents the liquid phase leaving the nth plate (and entering
the (n+1)th plate) at a rate Ln mole/h with enthalpy HL,n and concentration xn.

The right side of Eq. (10.7) is the slope of a line through the points (yn+l, HG,n+l) and (xD, Q’d), and
the left side is the slope of a line through the points (xn, HL,n) and (xD, Q’d) on the concentration--
enthalpy plane. So the points (xn, HLn) ,(yn+l, HG,n+l) and (xD, Q’d) are collinear. The point (xD, Q’d)
can be viewed as a phase obtained by subtracting Ln from Gn+l. We represent this point by V' in
Figure 7.30. The flow rate of the phase V' is also denoted by V' = Gn+l- Ln However, none of the
phases can have the concentration xD and enthalpy Q’d = HD + Qc/ D. So this stream V' is a
"fictitious stream" defined solely for the purpose of graphical construction.

The point V(xD, HD) and V'(xD, Q’d) are located on the enthalpy--concentration diagram, V' lying
vertically above V (because they have the same abscissa, xD). In Figure xx, the point V lies below
the x-HL curve. So, the reflux is a sub-cooled liquid here. If we put n = 0 in Eq. (10.7), it appears
that the vertical line joining the points V and V' should intersect the y-HG curve at (y1, HG) because
these points are collinear. The point (y1, HG) is denoted by G1 according to our convention. The
point L1 (x1,HLl) is now located by drawing a tie line through G1, because x1 and y1 are in
equilibrium for an ideal tray. Next, LV' is joined to get the point G2. The graphical construction
now proceeds from one tray to the next.

Now we consider Eq. (10.6), again. Inverting both sides and putting n = 0,
G1 Q 'd  H L 0
 ; We note that H L 0  H D ; G1  L0  D
L0 Q 'd  H G1
G1 L0  D D Q '  HD
  1   d
L0 L0 L0 Q 'd  H G1
L Q '  H G1 verticaldistance GV 1 '
 R 0  d 
D H G1  H D verticaldistance VG1 (10.8)
If the reflux ratio is given, Eq. (10.8) can be used directly to locate the point V'. First the point
V(xD, HD) is located from the known state (concentration xD, and enthalpy HD). A vertical line
through xD intersects the y-HG curve at G1. Then obtain V' so that Eq. (10.8) is satisfied.

The stripping section:

The material and energy balance equations for the stripping section (envelope III) are given by:
Total material balance: Lm  Gm1  W (10.9)

Component A balance: Lm xm  Gm1 ym1  W xW (10.10)

Energy balance: Lm H L,m  QW  G m1 HG,m1  W HW (10.11)

Putting W  Lm  Gm1 from Eq. (10.9) in Eq. (10.10),

 
Lm xm  G m1 ym1  Lm  G m1 xW (10.12)

Lm ym1  xW
  (10.13)
Gm1 xm  xW
We may write the energy balance Equation (10.11) as
Lm H Lm  G m1HG,m1 WHW  QW  W  HW  QW W 

 Lm H Lm  G m1HG,m1 WQ 'W ; Q 'W  HW  QW W (10.14)

puting W= Lm  G m1 ,
Lm HV ,m1  Q 'W
 
(10.15)
Lm H Lm V m1HV ,m1  Lm V m1 Q 'W  
V m1 H Lm  Q 'W

From eqs. (10.13) and 10.15)

HG,m1  Q 'W H Lm  Q 'W
 (10.16)
ym1  xW xm  xW

Extending the arguments put forward in the analysis of the rectifying section, we can say:
(a) The points Gm1  ym1, HG,m1  , Lm  xm , HLm  and M'(xw, Q’w), are collinear
(b) The point M' denotes a "fictitious stream" of concentration xw, enthalpy Q’w =Hw – QW/ W (=
the rate of enthalpy removal at the bottom, per mole of the bottom product), and flow rate
W'= Lm  Gm1

Now, let us see how to proceed with the graphical construction of stages for the stripping section,
The points M(xw, Hw) and M'(xw, Q’w), are located on the enthalpy--concentration plane. The
output stream or the bottom product, W, leaving the partial reboiler is in equilibrium with the vapor
generated in the reboiler and entering the bottom tray. If there is a total of Np trays in the column,
we may call the reboiler the (Np + 1 )th tray. So the flow rate as well as the state of the vapor from
the reboiler is denoted by GNP 1 ; GNP 1 should lie on the y-HG curve at the end of the tie line through
M. The line connecting G NP 1 and M' intersects the x-HL curve at LNp by virtue of the collinearity
condition given by Eq. (10.16). The tie line through LN identifies G on y-HG curve and thus the
construction for trays in the stripping proceeds.

The feed line

The procedures of graphical construction of ideal trays for the rectifying and for the stripping
sections have been discussed above. However, a changeover from one section to the other is
necessary at the feed tray and for this purpose we have to draw the 'feed line'. Consider the material
and energy balance equations over envelope-IV of the column in Figure as given below:
Total material balance: F  D  W (10.17)
Component A balance: F zF  D xD  W xW (10.18)
Energy balance: F H F  QW  D H D  W HW  QC (10.19)
Substituting for F from Eq. (10.17) in Eq. (10.18),
 D  W  zF  DxD  WxW (10.20)
xD denote the reflux or distillate concentration and these may be sub cooled liquids; the notation
 D zF  xW
  (10.21)
W zD  zF

Similarly, from Eqs. (10.17) and (10.19),

 D  W  H F  QW  DH D  WxW  QC
 DH F  WH F  D  H D  QC D   W  HW  QW W
D H   H D  QC D  H F  Q 'W
  F  (10.22)
W  HW  QB W   H F Q 'd  H F
From Eqs. (10.21) and (10.22),
H F  Q 'W Q 'd  H F
 (10.23)
zF  xW xD  zF

The above equation shows that the points M'(xw, Qw), F(zF' HF), and V'(xD, Q’d) are collinear. The
intermediate point F(zF' HF) denotes the state of the feed in terms of composition and enthalpy. It
lies on the line joining M' and V'. As stated before, M' represents a fictitious stream of flow rate
W '  Lm  Gm1  W and V' is another fictitious stream of flow rate D '  Gn1  Ln  D .
 F  D W  D 'W ' (10.24)
So, F, a real stream, can be viewed as a stream obtained by mixing the two fictitious streams M'
and V'. The line M'V' is called the feed line.
Lecture 12
Determination of the number of ideal stages using H-x,y diagram:
(a) Draw the H-x,y diagram
(b) Locate the points V and V' with the help of given data or material and/or energy balance
(c) Locate the feed point F(zF' HF)
(d) Join V'F and extend to meet the vertical line through M(xw, Hw) at the point M'
(e) Construct stages either from V' or from M'. A changeover has to be made after the feed
line is crossed. Proceeds construction till the other point is reached.

Determination of the number of ideal stages using H-x,y and x,y diagrams:
(a) Draw the equilibrium curve using separate axes below the H-x-y curves with matching scales.
(b) Locate (xD, xD) and (xw, xw) on the diagonal.
(c) It is obvious from Eq. (10.7) that any line emanating from V' (or M') intersects the H-x and H-
y curves at xn and yn+l, respectively. The point (xn, yn+l) is a point on the operating line in the lower
diagram. Several lines are now drawn from V' and M' and for each such line, the point (xn, yn+l) is
located on the x-y plane. All such points are joined by two continuous curves. These two curves
are the two operating lines. Because the flow rates in any of the sections are not constant (since
constant molar overflow is not applicable), the operating lines are not straight. Staircase
construction between the equilibrium line and the operating lines gives the number of ideal stages.

Minimum reflux ratio (Rm)

 If the reflux ratio is minimum, there must be a pinch point on the diagram.
 If a line through V' or M' coincides with a tie line, the corresponding (x, y) values give the pinch
point.
 The expression for the reflux ratio given by Eq. (10.8) indicates that the smaller the distance
G1V' (or the nearer the point V' is to the concentration axis), the smaller is the reflux ratio.
 For many liquid mixtures this happens when the line V'M' coincides with the tie line through
the feed point.
 But for some highly non-ideal mixtures, it so happens that a tie line through a point other than
F intersects the vertical line through xD at the smallest distance. This gives the true pinch point.
The minimum reflux ratio is calculated by Eq. (10.8) once the point (V')min is identified .

Total reflux
 Here the reflux ratio is infinite and the points D' and W' lie at infinity. So all the lines through
V' and M' are vertical lines.
 The construction involves drawing alternate tie lines and vertical lines starting at G1 to obtain
the number of plates at total reflux. This gives the minimum number of plates too.
 However, it is easier to find it by drawing steps between the equilibrium curve and the diagonal
on the x-y plane

Optimum reflux ratio

 While designing a new column (or even for using an existing column) for a given separation,
the designer has to choose a reflux ratio.
 From the foregoing discussion, it is clear that the number of plates required decreases as the
reflux ratio is increased. The column height decreases as a result.
 However, at a higher reflux, both the liquid and vapor flow rates are higher. This increases the
column diameter. But, on the whole, the cost of the column decreases with increasing reflux
ratio.
 On the other hand, a larger reflux ratio demands higher heat duty of both the reboiler (more
heat supply to the reboiler is necessary to maintain a larger supply of the vapor) and the
condenser (more heat is to be removed in the condenser).So the size, and therefore the capital
cost, of these equipment will be more.
 The operating cost will also be higher because of larger heat duty of the reboiler and the
condenser. So there are a number of opposing factors that govern the different types of cost.
 A simplified approach to determine the optimum reflux ratio is to plot the fixed cost of the
equipment taken together and also the operating cost versus the reflux ratio as shown in Figure
yy.
 The plot of the total cost shows a minimum which gives the optimum reflux ratio.
An important point needs attention in this context. The fixed cost has the unit of rupees, dollars,
etc. but the operating cost is based on unit time (rupee/year, dollar/year, etc.). How to calculate the
total cost, then? Without going into details, we can divide the fixed cost by the estimated "life" of
the equipment and then estimate the 'total annual cost'. A more realistic calculation should take
into account the interest rate on various cost items, if necessary.
 In actual practice, a reflux ratio of 1.2 to 1.5 times the minimum is common.

Example

A feed containing 50 mole% A and 50 mole% B is fed to a distillation column. A reflux ratio of
1.3 is maintained. The overhead product is 96% A and the bottoms 5% A. Find the number of
theoretical stages and the optimum feed stage. Assume that a total condenser is used. The column
is to operate at 1 atm. Equilibrium data is given as.

Equilibrium data at 1 atm

x 0.0 0.1 0.2 0.3 0.5 0.6 0.7 1.0
y 0.0 0.30 0.50 0.70 0.85 0.90 0.95 1.0
 Enthalpy-Concentration Data
Mole Fraction of A Enthalpy kcal/kmol
Sat. Liquid Sat. Vapor
0.0 6900 15,600
0.1 6200 15,100
0.2 5700 15,000
0.3 4900 14,600
0.4 4600 14,100
0.5 4000 13,800
0.6 3800 13,400
0.7 3500 12,800
0.8 3200 12,100
0.9 3000 11,400
1.0 2800 9,700

Distillation in Packed Towers

Distillation of a liquid mixture in a packed tower is preferred in the following cases: (a) vacuum
or low pressure operation, (b) low capacity or feed rate, (c) small allowable pressure drop, and (d)
corrosive service.

A packed tower for distillation is essentially similar to the one used for gas absorption. However,
the tower should be provided with a distributor for the feed at an appropriate location (this is in
addition to the distributor of the reflux at the top), besides a condenser, a reflux drum and a reboiler.

There are two methods for the determination of the height of packing: (a) from the height and
number of transfer units (HG and NG) and (b) from the HETP. To derive the design equations for
the calculation of the packed height based on HtG and NtG, refer to the following Figure.
 G, y2
Overhea
d vapor Reflux drum
Reflux Distillate
L0, xD D, xD
G L
y x
dz

Feed
F, zF

G,yW
Partial reboiler
L, xw Bottoms
W, xw

Rectifying Section:
Let us consider the rectifying section first. Constant molar overflow is assumed. The vapor and
liquid flow rates remain constant over a section. Let the flow rates (based on unit cross-section of
the tower) be G and L kmol/h m3. The individual mass transfer coefficient are kx and ky and the
specific interfacial area is a . It is to be noted that equimolar counter-diffusion of the components
occurs. If NA is the local flux at a height z from the bottom of the packed section, then
The interface surface = adz (11.1)
The quantity of substance A in the vapor
passing through the differential section = d (G y) (11.2)
Similarly, the rate of mass transfer in liquid = d (L x) (11.3)
Therefore, we may write the following differential mass balance equations for the more volatile
component.
Vapor phase: a.dz.N A  d  G y   Gdy  k ' y a  yi  y  dz  Gdy (11.4)
Liquid phase: a.dz.N A  d  L x   Ldx  k 'x a  x  xi  dz  Ldx (11.5)
Note that transport of the more volatile component occurs from the liquid to the vapor phase and
its concentration in the vapor as well as in the liquid phase increases with z. Rearranging Eq. (11.4)
and integrating over the rectifying section [from y = yF (at the feed point) to y = yl (top of the
tower)]
zr y2
Gdy Gdy
dz 
k ' y a  yi  y 
  dh 
0
 k ' a  y  y
yF y i
y2 (11.6)
G dy
 zr  
k ' y a yF yi  y
 zr  HtG NtG
Here zr, is the packed height of the rectifying section. The value of HtG can be calculated if the
individual volumetric mass transfer coefficient, ky’ a , is known; NtG can be obtained by numerical
or graphical evaluation of the integral in Eq. (11.6). The interfacial vapor concentrations, yi, for a
set of values of y (yF< y <yl) are required for the numerical integration. The procedure described
earlier can be followed for this purpose. From Eqs. (11.4) and (11.5), we can write
k 'x a y  yi
  (11.7)
k ' y a x  xi
The equation for the operating line for the rectifying section can be written for a given reflux ratio,
R. We take a point (x, y) on the operating line and draw a line of slope k 'x a k ' y a . This line meets
the equilibrium curve at (xi, yi). If the individual coefficients remain constant over a section (this
is quite reasonable because the flow rates do not vary over a section), such lines emanating from
different points on the operating line are parallel. Thus, for a set of points (x,y), the corresponding
interfacial concentrations (xi, yi) required for integration can be obtained.

Similar design equations can be written for the height and the number of individual liquid phase
transfer units.
rz 2x
Ldx Ldx
dz    dz  
k 'x a  x  xi  0 xF k 'x a  x  xi 
x (11.7)
L 2 dx
k 'x a xF x  xi
 zr   zr  HtL NtL

The packed height can also be determined using the overall coefficients k 'x a and k ' y a . The
design equations can be obtained by putting NA = Ky’(y* - y) in Eq. (11.4) or NA = Kx’(x – x*)
in Eq. (11.5).
dy dx
z  HtOG   HtOL 
y2 x2

;
yF y  y xF x  x

G L (11.8)
HtOG  and HtOL 
K 'y a K 'x a
We assume that the height of overall transfer units, HtOG and HtOL reasonably constant over the
section. The numbers of overall gas-phase or liquid-phase transfer unit are to be determined by
graphical integration. Corresponding to a point (x, y) on the operating line, y* is the ordinate of
the point vertically above it on the equilibrium curve; x* is the abscissa of a point on the
equilibrium line horizontally left to (x, y). Thus the values of y* for a set of values of y (yF< y <yl)
can be obtained and NtOG can be evaluated graphically or numerically.

Mass exchange between the vapor and the liquid phases in distillation is mostly controlled by the
vapor phase resistance. Thus, for the sake of accuracy, it is advisable to calculate the packed height
using the 'gas-phase coefficient'.
Following the procedure described earlier, it is possible to combine the heights of individual
transfer units to obtain the height of an overall transfer unit. Thus,
1 1 m
  (11.9)
K ' y k ' y k 'x
1 1 1
  (11.10)
K 'x mk ' y k 'x
mG
HtOG  HtG  HtG (11.11)
L
L
HtOL  HtL  HtG (11.12)
mG
m  m '  m '' = slope of straight equilibrium curve
A similar procedure is used to determine the packing height for the stripping section.
Example
A feed containing 50 mole% A and 50 mole% B is fed to a packed distillation column at 1 atm
pressure. The feed flow rate is 50kmol/h. The diameter of the column is 0.5m. The overhead
product is 96% A and the bottoms 5% A. The feed is a saturated liquid and a reflux ratio of 1.5 is
used. Find the packing height required for this separation. Rectifying section individual volumetric
mass transfer coefficients are k ' y a = 300 kmol/h m3 and k 'x a = 200 kmol/h m3. Stripping section
individual volumetric mass transfer coefficients are k ' y a = 400 kmol/h m3 and k 'x a = 300 kmol/h
m3. Equilibrium data is given below:
Equilibrium data at 1 atm
x 0.0 0.1 0.2 0.3 0.5 0.6 0.7 1.0
y 0.0 0.30 0.50 0.70 0.85 0.90 0.95 1.0
Lecture 13
Multicomponent Distillation
Nonideal systems of three components can be treated graphically, using triangular coordinates.
But for more than three components graphical treatment becomes very complicated.

Many of the multicomponent systems of industrial importance can be considered ideal in the liquid
phase for all practical purposes. In such cases, Roult’s law can be applied and the equilibria
calculated from the properties of the pure component.

But it is unsafe to predict detailed behavior of the multicomponent system from consideration of
pure component alone or even from knowledge of simple binary system. The complexities of these
systems make the digital computer helpful in dealing with the data.

The overall approach to solving multicomponent problems is the same in many respects as those
described for binary systems. There is one mass balance for each component and enthalpy balances
are similar to those for binary case. The equilibrium relationships are more complex for
multicomponent systems; in particular, the identity of the most volatile component may change
with temperature in the system. Equilibrium data are used to calculate multicomponent bubble and
dew points. The limiting cases of total and infinite reflux apply to multicomponent columns just
as they do to binary systems.

Rigorous computer methods for solving multicomponent distillation problems are available, but
the approximate, or "shortcut", methods described here are common for preliminary design,
examining the relationships between design parameters, process synthesis, etc.

Number of distillation tower

In a binary distillation, one tower was used to separate the components A and B into relatively
pure components. However, in multicomponent mixture of n components, n-1 fractionators will
be required for the separation. For example, for three-component mixture, two columns will be
needed.

Design calculation method

In a design, the conditions of the feed are generally known or specified (temperature, pressure,
composition, flow rate). Then, in most cases, the calculation procedure follows either of the two
general methods.

In the first method, the desired separation or split between two of the components is specified and
the number of theoretical stages is calculated for a selected reflux ratio. It is clear that with more
than two components in the feed, the complete compositions of the distillate and bottoms are not
then known, and trial and error procedures must be used.

In the second method, the number of stages in the enriching section and stripping section and the
reflux ratio are specified or assumed and the separation of the components is calculated using
assumed liquid and vapor flows and the temperatures for the first trial. This approach is often
preferred for computer calculations. In the trial and error procedures, the design method of Thiele
and Geddes, which is reliable, is often used to calculate resulting distillate and bottoms
compositions together with tray temperatures and compositions.

For the remainder of this section, the approximate, or "shortcut", methods described are common
for preliminary design, examining the relationships between design parameters, process synthesis,
etc.

Before discussing these methods, equilibrium relationships and calculation methods of bubble
point, due point, and flash distillation of multicomponent systems will be covered.

Equilibrium in multicomponent systems

Separation of multicomponent mixtures rather than binaries is much more common in the chemical
process industries. Experimental VLE data for the most multicomponent mixtures are not known
and have to be computed by using the available equations or correlations. The job becomes pretty
simple if we have an ideal multicopmponent system so that the Roult’s law is applicaple.
Hydrocarbons of a homologous series form nearly ideal solutions. For the ith component in an
ideal solution, we can write

n
y*j Pt  p*j  x j Pjv and Pt   pi* (12.1)
i 1

p*j x j Pjv
 y*j   n (12.2)
 pi*
Pt
i 1

where, Pjv = vapor pressure of component j at the given temperature

At a given temperature, the vapor pressures of the components, Pjv ’s are known. Therefore, for a
particular liquid composition (i.e., for given values of x1, x2, ….., xn), the vapor compositions (
y1* , y2* ,......, yn* ) can be calculated.

Pi v
Noting that ij  v
Pj

Eq.(12.2) can be rewritten:

xj xj x j  ji
 y*j  n
 n
 n (12.3)
(1/ Pjv ) xi piv (1/ Pjv )ij xi (1/ Pjv )ki xk
i 1 i 1 i 1

Once the equilibrium vapor phase mole fractions are known, the partial pressures and the total
pressures can be calculated from eq. (12.1).

For multicomponent systems, the equilibrium data is described by means of distribution

coefficient, m.
For component j:

y*j
 mj  (12.4)
xj
where in general, mj depends upon the temperature, pressure and composition of the mixture.
The relative volatility of component i w.r.t j in multicomponent mixture is defined by:
y*j / xi mi
 ij   (12.5)
y j / x j mj
For ideal solutions at moderate pressure, mj is independent of composition and depends upon the
temperature (as this affect vapor pressure) and the total pressure. Therefore,
Pjv
mj  (12.6)
Pt
Pi v
ij  (12.7)
Pjv

Bubble Point Calculations

For bubble point vapor,
y 
i 1.0
or mA xA  mB xB  mC xC  ..........  1.0

(12.8)
With component J as a reference component,

mA xA mB xB mC x 1.0
   ........... 
mJ mJ mJ mJ
1
or  AJ xA   BJ xB  CJ xC  .............  i , J xi 
mJ
(12.9)
The Equilibrium bubble point vapor composition is given by
i , J x
yi 
i, J xi (12.10)
The liquid composition and total pressure is fixed, the calculation of temperature is made by trial
and error to satisfy equation (8).Convergence is rapid since  ’s vary only slowly with changing
temperature.

Dew Point Calculations

For the dew point liquid,

 x i 1.0
yA y y
 B  C  ..........  1.0
mA mB mC
(12.11)
With component J, as a reference component,

mJ y A mJ yB mJ yC
   ...........  1.0
mA mB mC
or ,  AJ xA   BJ xB  CJ xC  .............  mJ
(12.12)
The dew point composition is given by,

yi  i , J
xi 
 yi i, J (12.13)

Example: A solution of hydrocarbons at a total pressure 350 kN/m2 has the analysis n-C3H8=5.0,
n-C4H10=30.0, n-C5H12=40.0, n-C6H14=25.0 mol %. Compute the bubble point and dew point.

Solution: values of m will be taken from nomograph, which assumed ideal liquid solutions.

Bubble point:
i
Col 1
xi mi
60oC
i ,C5
i,C xi
5
mi
56.8oC
i,C5
i,C xi
5
yi
Col 9
Col 2 Col 4 Col 5 Col 7 Col 8
Col 3 Col 6
n-C3 0.05 4.70 7.58 0.379 4.60 7.82 0.391 0.229
n-C4 0.30 1.70 2.74 0.822 1.60 2.72 0.816 0.478
n-C5 0.40 0.62 1.00 0.400 0.588 1.00 0.400 0.234
n-C6 0.25 0.25 0.403 0.1008 0.235 0.40 0.100 0.0586

 At the first estimate of bubble point, 60 oC is chosen. And col 3 list the corresponding m’s
at 60oC, 350 kN/m2.
 The reference component in chosen to be the pentane and Col4 list the relative volatility
C3 , C5  4.70/ 0.62  7.58 etc  .
  x  1.702 in Col5, whence (eq 8) mC5=1/1.702=0.588.
i ,C5 i

The corresponding temperature from the monograph in 56.8 oC.

 The calculations are repeated for this temperature in Col6 V to Col8.
 mC5=1/1.707=0.586, corresponding to t=56.7 oC, which is nearly equal to 56.8 (assumed)
 This is the bubble point temperature. And corresponding vapor composition is giving Col9
(0.391/1.707=0.229)
 Dew point

The procedure is similar to that of the bubble point

i
yi mi
80oC
i ,C 5
yi
 i ,C
mi
83.7oC
i ,C
5
yi
 i ,C
xi
5 5
Col1 Col2 Col3 Col4 Col6 Col7 Col9
Col5 Col8
n-C3 0.05 6.30 6.56 0.80762 6.60 6.11 0.00818 0.0074
n-C4 0.30 2.50 2.60 0.1154 2.70 2.50 0.120 0.1088
n-C5 0.40 0.96 1.0 0.400 1.08 1.00 0.40 0.3626
n-C6 0.25 0.43 0.448 0.558 0.47 0.435 0.575 0.5213

Assume 80oC, when y  i

i ,C5
= 1.081= mC5, T=83.7oC repetition lead to mC5=1.103

corresponding to 84oC, which in the dew point.

Multicomponent Flash Distillation

For a flash distillation, the process flow diagram is shown below:

Defining f  V F as the fraction of the feed vaporized and 1  f   L F as the fraction of the
feed remaining as liquid, and making a component i balance, the following is obtained:
f 1 x
yi  xi  iF
f f (12.14)
where yi is the composition of i in the vapor, in equilibrium with xi in the liquid after vaporization.

Because a flash is a single equilibrium stage, equilibrium fixes another relationship between y and
x. If this is represented by an equation, using distribution coefficients for instance, the two
equations (equilibrium and operating) can be combined and rearranged

For equilibrium, yi  Ki xi  Kci xi , when i  Ki Kc .Then Eq.(12.14) becomes

 f 1 x
yi  Kci xi  xi  iF
f f (12.15)
Solving for xi and summing for all components,
x
 xi  f  K iF 1  1  1.0
 c i (12.16)
This is solved by trial and error by first assuming a temperature if the fraction f vaporized has been
set. When the  xi values add up 1.0, the proper temperature has been chosen. The composition of
the vapor yi can be obtained from yi  Kci x or by a material balance.

The iteration procedure is similar as a bubble-point or dew-point calculation.

1. assume a flash temperature
2. determine K values at that temperature
3. compute the summation
4. if the summation is not equal to 1.0, adjust the temperature and repeat
The final values of T and the Ks are used to determine the product compositions.

"Key" Components

Fractionation of a multicomponent mixture in a distillation tower will allow separation only

between two components. For a mixture of A, B, C, D, and so on, a separation in one tower can
only be made between A and B, or Band C, and so on.

The first step in setting up multicomponent distillation problems is to select two components to
serve as the heavy key (identified by the subscript H) and the light key (L). Key components must
be present in both the overhead and the bottoms, so that by specifying the recovery of the keys,
you specify the extent of the split. The components more volatile than the light key are called light
components and will be present in the bottoms in small amounts. The components less volatile
than the heavy key are called heavy components and will be present in the distillate in small
amounts. The two key components are present in significant amounts in both the distillate and
bottoms.

Product specifications for these calculations are generally in the form of recovery specifications -
- for example, of the butane in the feed, 75% exits in the overhead -- rather than mole fractions,
since to calculate mole fractions requires prior knowledge of how all the components distribute
between the products.

Non-key components (everything but the keys) are classed as distributed if they occur in both
products, or non-distributed if they appear in only one product. Remember, keys must be
distributed. Non-keys may be distributed when they have volatilities very close to the keys or
between the keys, and when the desired separation is sloppy.

Minimum Stages

As in binary distillation, the Fenske equation can also be used for multicomponent system to
determine the minimum number of stages theoretically necessary to make a given separation at
total reflux. The equation can be written for any two components. Typically, initially apply the
equation to the key components and solve for the number of stages:
 log[( xLD D / xHD D)( xHWW / xLWW )
Nmin 
log( L,avg ) (12.17)

xLD = mol fraction of light key in distillate

xLW = mol fraction of light key in bottoms
xHD = mol fraction of heavy key in distillate
xHW = mol fraction of heavy key in bottoms

The mean relative volatility is used when alpha isn't constant -- normally a geometric mean value
is best. The following equation may be used:

 L,avg   LD LW
(12.18)

Once Nmin has been established, the same equation can be rearranged to determine the splits of the
other components in the mixture as given below:

xiD D x D
 ( L,avg ) Nmin HD
xiWW xHWW (12.19)

Minimum Reflux

Minimum reflux calculations are based on invariant zones around the feed where the compositions
stop changing. These are similar to the pinch point idea used for binary columns.

One way to determine an approximate minimum reflux ratio is to represent a multicomponent

mixture as a pseudobinary system. This is done by creating a hypothetical feed made up of the two
key components only. A McCabe-Thiele construction can then be used to determine the pinch and
minimum reflux. The accuracy of the approximation depends heavily on how large a portion of
the material is made up of the keys. Considering this limitation, and the amount of work required
to recast the calculations, other methods are usually preferred.

As in the case of binary distillation, the minimum reflux ratio Rm is that reflux ratio which will
require an infinite number of trays for the given separation of the key components. For binary
distillation, only one "pinch point" occurs where the number of steps becomes infinite, and that is
usually at the feed tray. For multicomponent distillation, two pinch points or zones of constant
composition occur: one in the section above the feed plate and another below the feed tray. The
rigorous plate-by-plate stepwise procedure for calculating Rm is trial and error and can be
extremely tedious for hand calculations.

Often, minimum reflux is estimated using the Underwood method. This assumes equimolar
overflow and defines relative volatilities for each component relative to some reference
component, usually the heavy key

Underwood's shortcut method for calculating Rm uses constant average  values and assumes
constant flows in both sections of the tower. This method provides a reasonably accurate value.
The two equations to be solved in order to determine the minimum
Reflux ratios are
 i xiF
1 q  
i   (12.20)
x
Rm  1   i iD
i   (12.21)
The values of xiD for each component in the distillate in Eq. (12.21) are supposed to be the values
at the minimum reflex. However, as an approximation, the values obtained using the Fenski total
reflux equation are used. Since each i may vary with temperature, the average value of i to use
in the preceding equations is approximated by using i at the average temperature of the top and
bottom of the tower. To solve for Rm, the value of  in Eq. (12.20) is first obtained by trial and
error. This value of  lies between the  value of the light key and the  value of the heavy key,
which is 1.0. Using this value of  in Eq. (12.21), the value of Rm is obtained directly.

The Underwood method assumes constant molar overflow and relatively constant relative
volatilities. If these do not apply, caution is necessary when applying the results.

Stages, Reflux for a Given Separation

Number of stages at operating reflux ratio

An important shortcut method for determining the theoretical number of stages required for an
operating reflux ratio R is the empirical correlation of Gilliland and should be considered as an
approximate method. Gilliland plots can be used to find the actual stages required for a given
reflux rate or vice versa. The plots relate two variables:
R  Rmin
X
R 1
(12.22)
which ranges from zero at R=Rmin to infinity at N=Nmin, and

N  Nmin
Y
N 1
(12.23)
which ranges from 1.0 at R=Rmin to zero at N=Nmin. The plots available on either linear or log axes.
To use them, calculate either X or Y, read the other from the graph, and get your answer.

Feed Tray location

Kirkbride has devised an approximate method to estimate the number of theoretical trays above
and below the feed which can be used to estimate the feed tray location. This empirical relation is
as follows:
NR  x  W  x 2 
log  0.206log  HF   LW  
NS  x LF  D  x HD  
(12.24)
Where NR is the number of theoretical stages above the feed tray and NS, the number of theoretical
stages below the feed plate.