Total reflux ratio

In distillation of a binary mixture A and B, the feed

conditions, distillate and bottoms compositions are
usually specified and the number of theoretical trays are
to be calculated. The number of theoretical trays depends
on the operating lines. To fix the operating lines, the
reflux ratio R = Ln/D at the top must be set.

Operating and optimum reflux ratio

The actual operating reflux ratio lies between the two
limits. To select the proper value of R requires a
complete economic balance on the fixed costs of the
tower and operating costs. By experience, the optimum
reflux ratio has been shown to be between 1.2Rm and
1.5Rm.

One limiting case is total reflux, R = , or D = 0. The

material balance becomes
Vn+1 = Ln
Vn+1yn+1 = Lnxn
Hence, the operating lines of both sections are on the 45o
line, yn+1 = xn.
Total reflux
is an extreme
case, the
number of
theoretical
trays required
is at its
minimum to
obtain the
given
separation of
xD and xB.
However, in
reality we
have no product at all, and the twoer diameter is infinite.
74

Example D4: Minimum reflux ratio and total reflux

ratio
For the rectification in Exanple D3, where a benzenetoluene feed is being distilled to give a distillate
composition of xD = 0.95 and a bottom product of xB =
0.10, calculate the following:
(a) Minimum reflux ratio Rm
(b) Minimum number of theoretical plates at a total
reflux
75

Solution:
(a) First draw the equilibrium line and the q line as we
did in Example D3. The operating line for minimum
reflux ratio is plotted as a dashed line and intersects the
equilibrium line at the same point the q line intersects.
Reading the values of x = 0.49 and y = 0.702, we have
0.95 0.702
0.539
0.95 0.49
1

Hence, the minimum reflux ratio is Rm = 1.17.

(b) The theoretical steps are drawn as shown between the

equilibrium line and the 45o line. The minimum number
of theoretical steps is 5.8, which gives 4.8 theoretical
trays plus a reboiler.

76

Special case for rectification

1. Stripping-column distillation.
In some cases the feed is added at the top of the stripping
column because we would like to have bottoms product
only. The feed is usually a saturated liquid at the boiling
point, and the overhead product VD is the vapor rising
from the top plate, which goes to a condenser with no
relux returned to the tower.

The bottoms product W usually has a high concentration

of the less volatile component B. Hence, the column
operates as a stripping tower, with the vapor removing
the more volatile A from the liquid as it flows downward.
Assuming constant molar flow rates, a material balance
of the more volatile component A around the dashed line
gives,
L
Wx
y m 1 m xm W
Vm 1
Vm 1
77

This stripping line is the same as that for a complete

tower. It intersects the y = x line at x = xW, and the slope
is constant at Lm/Vm+1.
If the feed is saturated liquid, then Lm = F. This is shown
in the figure. Starting at xF, the steps are drawn down the
tower.
If the feed is cold liquid below the boiling point, the q
line should should be used and q > 1: Lm = qF.
Example D5: Number of trays in stripping tower
A liquid feed at the boiling point of 400 kmol/h
containing 70 mol % benzene (A) and 30 mol % toluene
(B) is fed to a stripping tower at 101.2 kPa pressure. The
bottoms product flow is 60 kmol/h containing only 10
mol % A and the rest B. Calculate the kmol/h overhead
vapor, its composition, and the number of theoretical
steps required.
Solution
F = 400 kmol/h
xF = 0.70
W = 60 kmol/h
xW = 0.10
Plot the equilibrium
and diagonal lines.
Overall material
balance gives
F = W + VD
400 = 60 + VD
78

VD = 340 kmol/h
Component A balance gives
FxF = WxW + VDyD
400(0.70) = 60(0.10) + 340yD
yD = 0.806
For a saturated liquid, q=1, the q line is vertical. The
operating line is plotted through the point y = yW = 0.10
and the intersection of yD = 0.806 with the q line.
Alternatively, the slope of Lm/Vm+1 = 400/340 = 1.176
can be used. Stepping off the trays from the top, 5.3
theoretical steps or 4.3 theoretical trays plus a reboiler
are needed.
2. Enriching-column distillation
Enriching towers are also used at times, where the feed
enters the bottom of the tower as a vapor. The overhead
distillate is produced in the same way as in a complete
fractionating tower and is usually quite rich in the more
volatile component A. The liquid bottoms is usually
comparable to the feed in composition, slightly leaner in
A. If the feed is saturated vapor, the vapor in the tower
Vn = F.

79

Plate Efficiency

To translate ideal plates into actual plates

Applicable to both distillation & absorption

Types of plate efficiency

1.1 overall efficiency

number of ideal plates

number of actual plates

for the entire column

simple but the least fundamental

1.2 Murphree efficiency

y y
M n* n1
yn yn1
where
yn = actural concentration of vapor leaving plate n
yn+1 = actural concentration of vapor entering plate n
yn* = concentration of vapor in equilibrium with liquid
concentration xn leaving downpipe from plate n

for a single plate

in reality samples are taken of the liquid
on the plates, and the vapor compositions are
determined from a McCabe-Thiele diagram.

80

1.3 Local or point efficiency

y' y' n1
' n
y' en y' n1
where
y'n = concentration of vapor leaving a specific point in
plate n
y'n+1= concentration of vapor entering plate n at the
same location
y'en = concentration of vapor in equilibrium with liquid
at the same point (x'n)

for a specific location in a plate

2.

Relationship between efficiencies

2.1 Murphree & local efficiencies

In small columns, good mixing can be achieved so that
the concentration is uniform in the tray.
y'n = yn, y'n+1 =yn+1, and y'en = yn*. Therefore, ' M .
81

In large columns, incomplete mixing of the liquid occurs

in the tray. M is the integration of ' over the entire tray.

Fractional Distillation using

Enthalpy-Concentration Method

2.2 Murphree & overall efficiencies

ln1 M ( mV / L 1)
0
ln mV / L
where m is the slope of equilibrium line. When
mV/L=1.0 or M 1.0, M = 0.

molal flow rates need not to be constant

using enthalpy as well as material balances
When the operating lines are plotted with the
equilibrium curve on the x-y diagram, the McCabeThiele step-by-step construction can be used to compute
the number of ideal plates. However, unless Ln and Lm
are constant, the operating lines are curved and can be
plotted only if the change with concentration in these
internal streams is known. Enthalpy balances are
required in the general case to determine the position of
a curved operating line.

This relationship depends on the relative slopes of

equilibrium and operating lines.
M < 0 (stripping section)
M > 0 (enriching section)
M 0 for the whole column if the feed plate is near the
middle
3.

Use of Murphree efficiency

Draw an effective equilibrium line.
Use McCable and Thiele method between the
effective equilibrium line and the operating line.

4.

Factors influencing plate efficiency

Adequate and intimate contact between liquid and
vapor can enhance the efficiency; any excessive
foaming or entrainment, poor distribution, or shortcircuiting, weeping, or dumping of liquid, lowers
the plate efficiency.
Rate of mass transfer between liquid and vapor.

82

The enthalpy-concentration diagram requires the

following data at a constant pressure:
(1) heat capacity of the liquid as a function of
temperature, composition, and pressure.
(2) heat of solution as a function of temperature and
composition.
(3) latent heats of vaporization as a function of
composition and pressure or temperature.
(4) boiling point as a function of pressure, composition
and temperature.
The diagram at a given constant pressure is based on
arbitrary reference states of liquid and temperature,
which is usually taken as the boiling point of the lowerboiling component A.
83

The saturated liquid enthalpy is

H x x AC PLA Tb T0 (1 x A )C PLB Tb T0 H sol
(1)
Tb
= boiling temperature of mixture at xA
= reference temperature
T0
= liquid heat capacity of A
CPLA
CPLB
= liquid heat capacity of B
Hsol
= heat of mixing, usually ignored
The saturated vapor enthalpy is

H y y A HVA C PVA Td T0 (1 y A )HVB C PVB Td T0

(2)
Td
T0
CPVA
CPVB
HVA

= dew temperature of mixture at yA

= reference temperature
= vapor heat capacity of A
= vapor heat capacity of B
= latent heat of A at the reference
temperature T0 & calculated from that
at the normal boiling temperature TbA.

HVA CPLA TbA T0 HVAb CPVA TbA T0 (3)

HVB CPLB TbB T0 HVBb CPVB TbB T0 (4)
That is, the liquid is first changed from temperature T0 to
Tb and then evaporated at Tb , the vapor temperature is finally
changed back from Tb to T0.

Example D6. Enthalpy-concentration plot for

benzene-toluene

Prepare an
enthalpyconcentration plot
for benzenetoluene at 1 atm
pressure.
Equilibrium and
physical property
data are given.

Vapor pressure (kPa)

T (K)
353.3
358.2
363.2
368.2
373.2
378.2
383.8

Benzene
101.32
116.9
135.5
155.7
179.2
204.2
240.0

Component

Benzene (A)
Toluene (B)
84

Boiling
point
(oC)

80.1
110.6

Toluene
46.0
54.0
63.3
74.3
86.0
101.32

Mole fraction of
benzene at 101.325 kPa
xA
yA
1.000
1.000
0.780
0.900
0.581
0.777
0.411
0.632
0.258
0.456
0.130
0.261
0
0

Heat capacity
(kJ/kmol K)

Latent heat of
vaporization
Vapor (kJ/kmol)

Liquid
138.2 96.3
167.5 138.2
85

30820
33330

Solution.
We choose a reference temperature of T0=80.1oC so that
the liquid enthalpy of pure benzene (xA=1) at the boiling
point is zero.
For the first point, we select pure toluene (xA=0). For
liquid toluene at the boiling point of 110.6oC,
H x x AC PLA Tb T0 (1 x A )C PLB Tb T0 H sol
0 (1 0)(167.5)(110.6 80.1) 5109 kJ / kmol
For the saturated vapor enthalpy of pure toluene, we first
need to calculate HVB at T0=80.1oC:
HVB C PLB TbB T0 HVBb C PVB TbB T0

167.5(110.6 80.1) 33330 138.2(110.6 80.1)

34224 kJ/kmol
Hence, at xA = 0,

By the similar procedure,

at xA = 0.3 and yA = 0.3,
Hx = 2920 kJ/kmol and Hy = 36268 kJ/kmol
at xA = 0.8 and yA = 0.8,
Hx = 562 kJ/kmol and Hy = 32380 kJ/kmol

Enthalpy-concentration data for benzene-toluene mixture at 1 atm.

Saturated Liquid
Saturated Vapor
Enthalpy, Hx,
Enthalpy, Hy,
Mole
Mole
fraction, xA
(kJ/kmol)
fraction, yA
(kJ/kmol)
0
5109
0
38439
0.30
2920
0.30
36268
0.50
1820
0.50
34716
0.80
562
0.80
32380
1.00
0
1.00
30820

H y y A HVA C PVA Td T0 (1 y A )HVB C PVB Td T0

= 0 + (1-0)[34224+138.2(110.6-80.1)]
=38439 kJ/kmol
For pure benzene, xA = yA = 1, T = T0=80.1oC, Hx = 0,

H y y A HVA C PVA Td T0 (1 y A )HVB C PVB Td T0

=1[30820+96.3(80.1-80.1)] + 0 = 30820 kJ/kmol

Selecting xA = 0.5, the boiling point Tb = 92oC and the
dew point for yA = 0.5 is Td = 98.8oC from the T-x-y plot.
H x x AC PLA Tb T0 (1 x A )C PLB Tb T0
= 0.5(138.2)(92-80.1)+(1-0.5)(167.5)(92-80.1)
= 1820 kJ/kmol

H y y A HVA C PVA Td T0 (1 y A )HVB C PVB Td T0

= 0.5[30820+96.3(98.8-80.1)]
+(1-0.5)[34224+138.2(98.8-80.1)]
= 34176 kJ/kmol
86

Enthalpy-concentration plot for benzene-toluene mixture at 1 atm.

The tie line represents the enthalpies and composition of

the liquid and vapor phases in equilibrium.
87

Distillation in Enriching Section of Tower

Material balances
Vn 1 Ln D
(5)
Vn1 yn 1 Ln xn Dx D
(6)
By rearranging Eq. (6) we obtain the operating line
L
Dx
yn1 n xn D
(7)
Vn1
Vn1
Ln and Vn+1 may vary throughout the tower so Eq. (7)
will not be a straight line on an xy plot.

Making an enthalpy balance,

Vn1 H y,n1 Ln H xn DH xD qc
(8)
where qc is the condenser duty, kJ/h.
An enthalpy balance for the condenser only gives
qc V1 H y1 LH xD DH xD
(9)
88

Substitute Eq. (9) into Eq. (8) we have

Vn 1H y , n 1 Ln H xn V1H y1 LH xD
Vn 1 D H xn V1H y1 LH xD

(10)

Eqs. (7) & (10) are the final working equations for the
enriching section.
In order to plot the operating line Eq. (7), the terms Vn+1
and Ln must be determined from Eq. (10). If the reflux
ratio is set, V1 and L are know. The values of Hy1 and
HxD can be determined by Eqs. (1) & (2) or from an
enthalpy-concentration plot. If a value of xn is selected,
it is a trial-and-error solution to obtain Hy,n+1 since yn+1
is unknown. The steps to follow are given below.
1. Select a value of xn. Assume Vn+1 = V1 = L+D, then
Ln = Vn+1 - D.
2. Use Eq. (7) to calculate the approximate value of yn+1.
3. Using this yn+1 to obtain Hy,n+1 and xn to obtain Hxn .
Substitute these values into Eq. (10) and solve for the
new Vn+1. Obtain new Ln from Eq. (5)
4. Substitute the above values into Eq. (7) to get the new
yn+1.
5. If the newly calculated yn+1 the assumed value,
repeat steps 3-4. Usually one iteration is enough.
Assume another xn and repeat steps 2-5.
6. Plot the curved operating line for the enriching section.

89

Distillation in Stripping Section of Tower

Material balances
Lm Vm 1 B
Lm x m Vm 1 ym 1 Bx B
so that the operating line is
L
Bx
ym1 m x m B
Vm1
Vm 1

Example D7. Distillation Using EnthalpyConcentration Method

(11)
(12)
(13)

Making an enthalpy balance,

Vm 1H y,m1 Vm 1 B H xm BH xB qr (14)
where qr is the reboiler duty, kJ/h.
An enthalpy balance for the whole distiller gives
(15)
qr DH xD BH xB qc FH F
The final working equations are Eqs. (13) and (15).
Using a method similar to that of the enriching section to
solve the equations.
Component
Benzene
Toluene

Tb ( C)
80.1
110.6

CP (kJ/(kmol K)
Liquid
Vapor
138.2
96.3
167.5
138.2

Hvb
(kJ/kmol)
30820
33330

A liquid mixture of benzene-toluene is to be distilled in a

fractionating tower at 101.3 kPa pressure. The feed of
100 kmol/h is liquid, containing 45 mol % benzene and
55 mol % toluene, and enters at 54.4oC. A distillate
containing 95 mol % benzene and 5 mol % toluene and a
bottoms containing 10 mol % benzene and 90 mol %
toluene are to be obtained. The reflux ratio is 1.755. The
average heat capacity of the feed is 159 kJ/(kmol K) and
the average latent heat is 32099 kJ/kmol. Use enthalpy
balances to calculate the flow rates of the liquid and
vapor at various points in the tower and plot the curved
operating lines. Determine the number of theoretical
stages needed.

Solution:
F = 100 kg mol/h, xF = 0.45, xD = 0.95, xB = 0.10,
R = 1.5Rm = 1.5(1.17) = 1.755,
D = 41.2 kg mol/h, B = 58.8 kmol/h
The feed enters at 54.5oC so q = 1.195.
The flows at the top of the tower are calculated as
follows.
R = L/D = 1.755; L = 1.755D = 1.755(41.2) = 72.3;
V1 = L+D = 72.3+41.2 = 113.5
The latent heats of vaporization of benzene and toluene
at the reference temperature of 80.1oC are
HVA = HVAb = 30820 kJ/kmol

90

91

HVB CPLB TbB T0 HVBb CPVB TbB T0

= 167.5(110.6-80.1) + 33330 - 138.2(110.6-80.1)
= 34224 kJ/kmol
The saturation temperature (dew point) at the top of the
tower for y1 = xD = 0.95 is 82.3oC.
Hy1 = 0.95[30820+96.3(82.3-80.1)]
+(1-0.95)[34224+138.2(82.3-80.1)] = 31206 kJ/kmol
The boiling point of the distillate D is obtained as
81.1oC.
HxD = 0.95(138.2)(81.1-80.1)
+ (1-0.95)(167.5)(81.1-80.1) = 139 kJ/kmol

Step 1: select xn = 0.55 and guess yn+1 from Eq. (7)

yn1

Ln
Dx D 72. 3
41. 2
( 0. 55)
( 0. 95) 0. 695

xn
Vn1 113. 5
113. 5
Vn1

Step 2: using the Figure in Example D6 for xn = 0.55

obtain Hxn = 1590 and for yn+1 = 0.695, Hy,n+1 = 33240.
Substituting into Eq. (10)
Vn+1 (33240) = (Vn+1 - 41.2)1590
+113.5(31206) - 72.3(139)
Vn+1 =109.5
Using Eq. (5),
109.5=Ln +41.2 or Ln =68.3
Step 3: substituting into Eq. (7),
68. 3
41. 2
yn1
( 0. 55)
( 0. 95) 0. 700
109. 5
109. 5
92

This calculated value is close enough to the approximate

value of 0.695 so that no further trials are needed.
Select other values of xn and calculate the responding
yn+1, plot the curved operating line in the enriching
section.
The condenser duty is obtained from Eq. (9)
qc V1 H y1 LH xD DH xD

113. 5(31206) 72. 3(139) 41. 2(139) 3526100 kJ / h

For xB = 0.10, HxB = 4350 from the Figure in page 89.

The feed is at 54.5oC, using Eq. (1), we have
HF = 0.45(138.2)(54.5-80.1)
+ (1-0.45)(167.5)(54.5-80.1) = -3929 kJ/kg mol
Using Eq. (15),
qr = 41.2(139) + 58.8(4350) + 3526100 - 100(-3929)
= 4180500 kJ/h
Making a material balance below the bottom tray and
around the reboiler we have
(16)
LN B Vb
Enthalpy balance
Vb H yb Vb B H xN BH xB qr
(17)
From the equilibrium diagram we find that for xB = 0.10,
yB = 0.207, which is the vapor composition leaving the
reboiler.
For the equimolal overflow in the stripping section,
Lm Ln qF 72. 3 1.195(100 ) 191. 8
(18)
Vm 1 Vn 1 (1 q ) F 113. 5 (1 1.195)100 133. 0
93

Selecting ym+1 = yB = 0.207 and using Eq. (13), an

approximate value of xm = xN is obtained.
L
Bx
ym1 m x m B
Vm1
Vm 1
191. 8
58. 8
0. 207
xN
( 0.10 )
133. 0
133. 0
Solving xN =0.174. From the Figure in example D6 for
xN =0.174, HxN =3800, and for yB = 0.207, Hyb =37000.
Substituting into Eq. (17),
Vb (37000) Vb 58.83800 58.8(4350) 4180500
Solving Vb = 125.0. Using Eq. (16) we get LN = 183.8.
Substituting into Eq. (13) and solving for xN.
183. 8
58. 8
0. 207
xN
( 0.10 )
125. 0
125. 0
xN = 0.173
This value is quite close to the approximate value of
0.174.

Solid line: enthalpy-concentration method

Dashed line: constant molal overflow
The solid line is slightly above the dashed line.

Assuming other values of ym+1 and solving for xm using

the same procedure, the curved operating line for the
stripping section can be constructed.
The number of theoretical stages is determined to be
10.4, compared with 9.9 steps using the constant flow
method.

94

95

Ponchon and Savarit method

Rectifying section
We rearrange Eq. (8) as
Vn1H y,n1 Ln H xn DH xD qc DQ' (16)
DH xD qc
where Q'
D
The left hand side is the net rate flow of heat upwards
through the enriching section, while the right hand side
is constant. This means that the net rate of flow of heat
is constant and independent of the tray number in the
rectifying section.

Using Eq. (5) to eliminate Vn+1 in Eq. (6), we have

Ln D yn 1 Ln xn DxD
Ln y n 1 xn D x D y n 1
(17)
Hence,
Ln x D y n 1

internal reflux ratio

(18)
D y n 1 x n

This can be explained by the lever rule. A vapor of Vn+1

of composition y n+1 is separated into a distillate D of xD,
and a liquid Ln of xn. (Vn+1, yn+1) is at the fulcrum of a
beam, balanced by the distillate (D, xD) and liquid (Ln,
xn). In order for the beam to be balance, the moments
about the fulcrum must be equal. Hence, we have Eq.
(17).
A similar analysis for Eq. (16) gives
Ln D H y,n1 Ln H xn DQ'
Ln H y,n1 H xn D Q' H y ,n1
or
Q' H y ,n 1
Ln

internal reflux ratio (19)

H
D
H

y ,n 1

xn

Again this obeys the lever rule.

Combining Eqs. (18) & (19), we have

Q' H y,n1
Ln x D y n 1

(20)
D y n 1 x n H y ,n 1 H xn
On the H-x-y diagram, this is a straight line through the
points (Hy,n+1, yn+1) at Vn+1, (Hx,n, xn) at Ln, and (Q, xD)
at D as linked above and shown in the figure below. D
is termed the difference point.
96

97

Equilibrium data are used to determine the liquid and

vapor compositions leaving the first theoretical plate.
The graphical solution of Ponchon and Savarit is
continued using the equilibrium data and the H-x-y
diagram until the reboiler composition is reached. In the
following case, a total of 4 theoretical plates is shown, 3
in the column and 1 for the reboiler having an enthalpy
HR and composition xR.

Since the heat and mass balances apply to any tray, then
at the top plate, n = 0, we have
line length Q ' H y ,1
L
x y1 Q ' H y ,1
R 0 D

D y1 x D H y ,1 H xD line length H y ,1 H xD
The line length H y ,1 H xD is the latent heat of
vaporization at a distillate composition xD. If the reflux
ratio is specified, then the length of Q Hy,1 can be
calculated, and hence Q determined.

98

99

Stripping section
The same analytical techniques used in the rectifying
section can be applied to the stripping section and the
entire column.

tower) to B, intersects the saturated liquid enthalpy

curve at LZ, the liquid leaving the bottom plate. Vapor
VZ leaving the bottom plate is in equilibrium with the
liquid LZ and is located on the tie line Z.
The number of theoretical plates in the stripping section
can be determined from the H-x-y diagram by
alternatively constructing lines to B and tie lines. Each
tie line is a theoretical plate.
The complete column

We rearrange Eq. (14 ) as

Lm H xm Vm1H y,m1 BH xB qr BQ' '
where Q = HxB qr/B, by eliminating B (B=Lm Vm+1),

y x H y ,m1 Q"
Lm
m 1 B
xm xB H x,m Q"
Vm 1

(21)

On the H-x-y diagram, this is a straight line passing

throught (Hy,m+1, ym+1) at Vm+1, (Hx,m, xm) at Lm, and (Q,
xB) at B as shown in the figure above. B is also termed
the difference point. B is W in the figure.
Eq. (21) applies to every plate in the stripping section.
On the H-x-y diagram, this is a line from VZ+1 (vapor
leaving the reboiler and entering the bottom tray Z of the
100

101

The overall mass balance is

F=D+W
The more volatile component mass balance is
FxF = DxD + WxW
The heat balance is
FHF = QC + DHyD + WHxW QR = DQ+WQ
Eliminating F yields
D x F xW H F Q"

W x D x F Q ' H F
This is a straight line on the H-x-y diagram passing
through (Q, xD) at D, (HF, xF) at F, and (Q, xW) at W
and is shown in the above figure for a case of liquid feed
below its boiling point (cold liquid).
The procedure to determine the number of theoretical
plates is summarized below.
1. Locate the feed enthalpy and composition
2. Locate xD and xW
3. Locate D by computation of Q or for a specific
reflux ratio as R = L0/D
4. The line D, F is extended to x = xW and thus locates
W whose coordinates can be used to calculate QR.
5. The number of theoretical plates is then determined
by application of the straight line relationship on the
H-x-y diagram and the equilibrium data of the y-x
diagram.

102

Example D8. Distillation Using Ponchon Savarit

Method

Re-calculate the number of theoretical stages required

for example D7 using Ponchon Savarit method.
xF = 0.45, HF = -3929 kJ/kg mol
xD = 0.95, xB = 0.10
DH xD qc 41.2(139) 3526100

85724 kJ/kmol
Q'
41.2
D

Q = HxB qr/B =435 -4180500/58.8 = -66747 kJ/kmol

or in the H-x-y diagram, draw the line from D (xD=0.95,
Q=85724) through (xF=0.45, HF=-3929) to intersect
xB=0.10 gives Q = -66747 kJ/kmol from B.
The number of theoretical plates is then determined by
application of the straight line relationship on the H-x-y
diagram and the equilibrium data of the y-x diagram.
10.4 plates, or 9.4 plates plus 1 reboiler are needed. The
feed is at plate 6.

103

104

105

Multicomponent Distillation

need more than one distillation tower, for n

components, n-1 fractionators are required
Specification Limitations

The following are established at the beginning

1. Temperature, pressure, composition, and rate of
the feed.
2. Pressure of the distillation
3. Feed to be introduced on that tray which will
result in the least total number of trays
(optimum feed-tray location)
4. Heat loses (even if assumed to be zero)
Under these circumstances only three additional items of
the following list need to be specified, any other items
must be calculated.
1.
2.
3.

Total number of trays.

Reflux ratio
Reboil ratio (ratio of vapor produced by the
reboiler to residue withdrawn)
4. Concentration of one component in one product
(a maximum of two may be chosen)
5. Ratio of flow of one component in the distillate
to the flow of the same component in the
residue, or split of the component (a maximum
of two may be chosen)
6. Ratio of total distillate to total residue
106

Key components
The feed components are listed in order of their relative
volatility. The more volatile components are called light,
the less volatile are heavy. The components separated in
a tower are called light key (more volatile) and heavy key
(less volatile). Any components lighter than the light
key are called light components, while those heavier than
the heavy key are called heavy components.

In hydrocarbon systems, because of nonidealities, the

equilibrium data are often represented by
yA = KAxA, yB= KBxB, yC = KCxC, yD = KDxD
where KA is the vapor-liquid equilibrium constant or
distribution coefficient for component A. K is a function
of temperature and pressure, but is assumed to be
independent of composition, which is sufficiently
accurate for most engineering calculations. For an ideal
system, KA = PA*/PT = vapor pressure/total pressure.
The relative volatility in multicomponent distillation is
always computed with respect to the heavy key
K
y /x
(1)
j j je je
K hk yhke / x hke
The value of is greater than 1 for any component
lighter than the heavy key and less than 1 for any heavier
component.

107

 Bubble-point and dew-point calculations

These are required for a flash distillation and for each
stage of a multicomponent distillation, calculated by
trial-and -error.

For the bubble point,

NC

NC

i 1
NC

i 1
NC

yi Ki xi 1. 0

(2)

yi
1. 0
(3)
i 1
i 1 Ki
First a temperature is assumed and the values of Ki are
obtained from literature. If the summation 1 choose
another temperature.
For the dew point,

xi

Component Pi* at 105oC,

atm
1. Hexane 2.68
2. Heptane 1.21
3. Octane
0.554

2.23
1.01
0.462

yi=Kixi

0.33 0.7359
0.37 0.3737
0.30 0.1386
= 1.248

Since yi is too large, try a lower temperature. Since the

major contribution is from the first term, try a
temperature where Ki is lower by a factor of 1/1.24,
2.68/1.24=2.16. Choose T = 96oC, where P1* = 2.16 atm.
Component Pi* at
96oC, atm
1. Hexane 2.16
2. Heptane 0.93
3. Octane
0.41

Example D9. Find the

bubble-point and the
dew-point
temperatures and the
corresponding vapor
and liquid
compositions for a
mixture of 33 mole %
n-hexane 37 mole %
n-heptane and 30
mole % n-octane at 1.2
atm total pressure.
Solution. The logP vs
T plot is shown as
right.

Ki = Pi*/1.2 xi

Ki =
Pi*/1.2
1.8
0.775
0.342

xi

Kixi

0.33 0.5940
0.37 0.2868
0.30 0.1025
= 0.9833

yi
0.604
0.292
0.104
1.000

This is a liitle bit small. Try another T = 97oC, close

enough to 96oC so that y
.

Bubble point. Guess T = 105oC, this is based on the

vapor pressure of heptane, the middle component, is 1.2
atm.
108

Dew point. The dew point is higher than the bubble point,
so use 105oC as a first guess.
Component Ki
yi
yi / Ki
1. Hexane
2.23
0.33
0.148
2. Heptane
1.01
0.37
0.366
3. Octane
0.462
0.30
0.649
= 1.163
109

Since the sum is too high, try a higher temperature, T =

110oC.
Component Pi* at
yi /Ki xi
Ki =
yi
o
110 C
Pi*/1.2
1. Hexane 3
2.5
0.33 0.132 0.130
2. Heptane 1.38
1.15
0.37 0.3217 0.317
3. Octane
0.64
0.533 0.30 0.5625 0.553
= 1.0162 1.000
By extrapolation, the dew point is 110.5oC, and the
composition of the liquid in equilibrium with the vapor
/
/
is calculated by x
.

Flash distillation

Material balance for component i gives

x
f 1
yDi
(4)
x Bi Fi
f
f
where f=V/F is the fraction of the feed vaporized, yDi is
in equilibrium with xBi. So yDi Ki x Bi , substitute this
into Eq. (4) and solve for xBi.
x Fi
x Bi
(5)
f K i 1 1
The summation on xBi should be unity.
NC
NC
xFi
(6)
xBi 1
i 1
i 1 f K i 1 1
This equation is again solved by iteration. The final
values of T and Ki are used to calculate the composition
of the top and bottom product streams.
110

Example D10. The mixture of example D9 is subjected

to a flash distillation at 1.2 atm pressure, and 60% of the
feed is vaporized.
(a) Find the temperature of the flash and the
composition of the liquid and vapor products.
(b) To what temperature must the feed liquid be
heated for 60% vaporization on flashing?
Solution.
(a) The flash temperature must lie between the bubble
point (97oC) and the dew point (110.5oC).
Assume T = 97+0.6(110.5-97) = 105 oC.
From the figure in example D9, K1 =2.68/1.2=2.23,
K2 =1.21/1.2=1.01, K3 =0.554 /1.2=0.462.
The value of f is 0.6.

The right hand side of Eq. (6) becomes

.

=0.190+0.368+0.443=1.001

.
.

This is close to unity so the flash temperature is 105 oC.

The composition of the liquid product is 19% n-hexane,
36.8% n -heptane and 44.2% n -octane.
The composition of the vapor product is computed from
the values of K and x.
n-hexane, y = 0.190(2.23)
= 0.424
n heptane, y = 0.368(1.01)
= 0.372
n octane, y = 0.443(0.462)
= 0.204
1.000
111

(b) To determine the temperature of the feed before

flashing, an enthalpy balance is made using 105 oC as the
reference temperature. The heats of vaporization at 105
o
C and the average heat capacities of the liquid from 105
to 200 oC are obtained from the literature.
Cp, cal/(mol K)
Hv, cal/mol
n-hexane
62
6370
n heptane 70
7510
n octane 78
8560
Based on liquid at 105 oC, the enthalpies of the product
are
Hvapor = 0.6(0.424x6370+0.372x7510+0.204x8560)
= 4345 cal
Hliquid = 0
For the feed,
C
0.33x62

0.37x70 0.30x78
69.8 cal/ mol C
Hence, 69.8(T0 105) = 4345
T0 = 167oC = preheat temperature

Total Reflux for multicomponent distillation

(Minimum stages for total reflux)

For binary distillation, if the relative volatility of the two

components is approximately constant, we have the
following Fenske equation to calculate the minimum
number of theoretical steps when a total condenser and a
reboiler are used.
x
1 xB

ln D

x
x
1
D
B
Nm
1
(7)
ln AB
Similarly for any two components (i & j) in
multicomponent distillation,
x / x
ln Di Bi
x Dj / x Bj
(8)
Nm
1
ln ij
ij 3 Dij Fij Bij
(9)
The subscripts D, F and B in Eq. (9) refer to the
temperatures of the distillate, feed plate, and bottoms in
the column. Nm is the minimum number of equilibrium
stages excluding the reboiler, at total reflux.
The Fenske equation is derived as below. At total reflux,
D = B = 0, so V = L. Consider the equilibrium partial
reboiler for any two components A and B,

y
y

Rearrange to obtain
112

113

/x
/x

(10)

Material balances for these two components around the

reboiler are
VRyA,R = LNxA,N
(11a)
VRyB,R = LNxB,N
(11b)
Since VR = LN for total reflux (B = 0), we have
yA,R = xA,N, yB,R = xB,N (at total reflux) (12)
Combining Eqs. (10) and (12),

(13)

If we define AB as the geometric average relative

volatility,

/
(18)
Eq. (17) becomes

Solving Eq. (19) for Nm, we have

/
/

/
/

(14)

The mass balances around stage N simplify to

yA,N = xA,N-1 and yB,N = xB,N-1
Combining these equations to give

(15)

114

(21)

(22)

The fractional recovery of A in the bottoms is

FR
(16)

Repeating this procedure until we reach the top stage, we

have

FR
1

FR

(23)

Hence
Dx
Bx

Which relates the ratio of liquid mole fractions leaving

stage N-1 to the ratio in the reboiler.

(20)

The fractional recovery of A in the distillate is

Eqs. (13) and (15) can be combined to give

or

If we move up the column to stage N, the equilibrium is

(19)

FR
Fx
1 FR
Fx

(24)
(25)

The Fenske equation can also be written as

/
/

(17)
115

(26)

Example D11. A mixture with 33% n-hexane, 37% nheptane, and 30% n-octane is to be distilled to give a
distillate product with 0.01 mole fraction n-heptane and
a bottoms product with 0.01 mole fraction n-hexane.
The column will operate at 1.2 atm. 60% of the feed is
vaporized. Calculate the complete product compositions
and the minimum number of ideal plates at infinite
reflux.
Solution
light key (LK) heavy key (HK) heavy nonkey (HNK)
n-hexane
n-heptane
n-octane
Assume no n-octane and 0.99 mole fraction n-hexane in
the distillate. Take 100 mol/h of feed as the basis
overall M.B.
F = D + B = 100
hexane M.B.
FxF = DxD + BxB
100x0.33 = 0.99D+(100-D)(0.01)
D=32/0.98=32.65 mol/h; B=100-D = 67.35 mol/h
The composition of the bottoms product can be
calculated since this stream contains all the octane, all
but 0.01D of the heptane, 0.01 mole fraction of hexane.
FxF
LK
HK
HNK

n-C6
n-C7
n-C8

33
37
30

DxD

xD

BxB

xB

32.32 0.99
0.68
0.010
0.33
0.01
36.67 0.544
0
0
30
0.446
D=32.65
B=67.35

K at 105oC,
1.2 atm
2.23
1.01
0.462

Use the Fenske equation to obtain the minimum number

of plates. The relative volatility of the light key to the
heavy key is the ratio of their K factors. The K values at
116

the flash temperature were taken from the previous

example.
Lk,HK 2.23 / 1.01 2.21

Nm

x D,LK / x B,LK
0.99 / 0.01
ln

ln

/
x
x
D,HK B,HK
0.01 / 0.544

1
1
ln 2.21
ln LK , HK

10.8 1 9.8
So the minimum number of ideal stages is 9.8 plus a
reboiler.
A more accurate estimate of Nm can be obtained using a
mean relative volatility based on the values at the top,
middle, and bottom of the column. The top temperature
is about 75oC, the boiling point of n-hexane at 1.2 atm,
and the relative volatility is 2.53.
The bottom
o
temperature is about 115 C by using a bubble point
calculation for the bottoms product, giving a relative
volatility of 2.15.
LK , HK 3 2.53 2.21 2.15 2.29
Hence, Nm =9.4
To check our assumption of no octane in the distillate,
the Fenske equation can be applied to heptane and
octane using = K2/K3 = 1.01/0.462 = 2.19:
0.01 / 0.544
ln

x D3 / 0.446
N m 1 10.4
ln 2.19
from which xD3 = 2.4x10-6, which is negligible.
117

Minimum Reflux Ratio for

multicomponent distillation
At this reflux ratio, the desired separation is just
barely possible, but an infinite number of plates is
required. The desired separation is usually refers to
the amount of light key recovered in the distillate
and the amount of heavy key recovered in the
bottoms.
Since the only purpose of obtaining the minimum
reflux ratio is to estimate the product compositions
at RDm and to ensure that the specified RD is
reasonable, an exact value is not required. There
are two approximation methods in estimating RDm:

2. Underwood method
By using constant average s and assuming
constant molal overflow (L/V), the following
two equations are solved to obtain RDm:
1 q

i x Fi
i

(28)

Vmin
x
R Dm 1 i Di
i
D

where q is the moles of liquid to stripping section

of column per mole of feed, is a parameter to be
found from Eq. (28). The correct value of should
lie between the values of for the keys.

1. Treating the mixture as a pseudobinary

(light & heavy keys)

L min Dx D,LK / Fx F,LK LK,HK Dx D,HK / Fx F,HK

F
LK,HK 1
(27)

118

(29)

119

Example D12. A mixture with 4% n-pentane, 40%

n-hexane, 50% n-heptane, and 6% n-octane is to be
distilled at 1 atm with 98% of the hexane and 1% of
the heptane recovered in the distillate. What is the
minimum reflux ratio for a liquid feed at the boiling
point?

(a) By using the pseudobinary method, we have

L min 39.2 / 40 2.48(0.5 / 50)
0.645

F
2.48 1
R Dm

L min L min F
1

0.645
1.48
D
F D
0.437

(b) By using the Underwood method, the K values at 80

Solution
The light key is n-hexane and the heavy key is nheptane. The other components are sufficiently
different in volatility to be undistributed. The
known information is summarized below (assume
100 moles of feed).

LK
HK

n-C5
n-C6
n-C7
n-C8

n-C5
n-C6
n-C7
n-C8

xF
0.04
0.40
0.50
0.06

K80oC
3.62
1.39
0.56
0.23

KxF
0.145
0.556
0.280
0.014

FxF
4
40
50
6

DxD
4
39.2
0.5
0
D=43.7

xD
0.092
0.897
0.011
0

BxB
0
0.8
49.5
6
B=56.3

xB
0
0.014
0.879
0.107

The bubble point of the feed is

obtained by checking the
NC

NC

i 1

i 1

equation y Fi K i x Fi 1.0 , this

temperature is found to be 80 oC.

The corresponding LK, HK is 1.39/0.56 = 2.48.

120

C are converted to relative volatilities and the value

between 1 and 2.48 is found by trial. Since q=1 (feed at
the boiling point), we should have
x
i Fi 1 q 1 1 0
i

n-C5
n-C6
n-C7
n-C8

xFi

6.46
2.48
1.0
0.41

0.04
0.40
0.50
0.06

i x Fi
, =1.5
i

i x Fi
, =1.48
i

0.052
0.052
1.012
0.992
-1.00
-1.042
-0.023
-0.023
0.041
-0.021
By further trials or interpolation, =1.487, so
R Dm 1

i x Di 6.64(0.092) 2.48(0.897) 1(0.011)

i 6.64 1.487 2.48 1.487 1 1.487

= 0.119 + 2.24 - 0.023 = 2.336

RDm = 1.34, which is 10% less than the value
obtained using pseudobinary method.
121

Number of ideal plates at operating reflux

(Gilliland correlation)
Gilliland proposed a simple empirical method to
estimate the number of plates in multicomponent
distillation. The correlation requires knowledge
only of the minimum number of plates at total
reflux and the minimum reflux ratio.
The
correlation is given below.

Example D13. Estimate the number of ideal plates

required for the separation specified in Example
D11, if the reflux ratio is 1.5RDm.
Solution
From Example D11, the minimum number of ideal
stages is 9.4 plus a reboiler, or 10.4. The value of
RDm is obtained by the Underwood method.
xD
K
xF

LK n-hexane 0.33
0.99
2.23
2.21
HK n-heptane 0.37
0.01
1.01
1.0
n-octane 0.30
0
0.462 0.457
For a saturated liquid feed, q=1,

i x Fi
1 q 11 0
i

By trial, =1.45,
R Dm 1

i x Di 2.21(0.99) 1.0(0.01)

2.86
i 2.21 1.45 1 1.45

RDm = 1.86,

RD = 1.5x1.86 = 2.79

R D R Dm 2.79 1.86

0.245
2.79 1
RD 1

From the Gilliland correlation,

N N min
0.41
N 1

N is the total number of plates in the system,

including the reboiler. The same for Nmin.
122

N - 10.4 = 0.41N + 0.41

N = 10.81/0.59 = 18.3 stages, including the reboiler
123