SEPARATION PROCESS

CHAPTER 2:

DISTILLATION

1
 LEARNING OUTCOME

The student should be able to:

◼ Define and explain the fundamental concepts of VLE & distillation.
◼ Define and apply relative volatility, α, in distillation process
◼ Explain azeotrope and the limit imposed by system having azeotrope point
◼ Determine the composition at equilibrium for batch distillation by using Rayleigh eq
◼ Explain rectification and stripping process in distillation
◼ Sketch and label appropriate diagram
◼ Solve for continuous distillation problems :
Calculate the flowrates and mole fractions
◼ Apply McCabe-Thiele method to :
 Identify and formulate the respective operating line equations for continuous distillation
process
 Determine the no. of theoretical stages
 Describe assumptions made in this method
 Calculate and apply the minimum reflux ratio in determining the optimized design
consideration
 Calculate minimum number of stages at total reflux
◼ Explain the concepts of total and minimum reflux ratio
◼ Explain and apply overall plate efficiency in distillation

2
Chapter 2
Distillation
2.1 Definition and general description of the process
2.2 Physical concepts of distillation
2.3 Vapor-liquid equilibrium relationship
2.4 Relative volatility
2.5 Batch distillation
2.5.1 Rayleigh equation
2.6 Continuous distillation
2.6.1 Rectification and stripping: definition and description of process
2.6.2 Reflux ratio
2.6.3 Number of theoretical stages for binary mixtures: McCabe-Thiele
method
2.6.4 Overall plate efficiency
2.6.5 Minimum reflux ratio
2.7 Multi component distillation (MCD)
2.7.1 Boiling Point and Dew Point
2.7.2 Number of theoretical stages for multicomponent mixture

Activity: Rotary Evaporator Lab, Pilot plant visit, CDIO Activities, Asignment 1

3
2.1 DISTILLATION

◼ A feed of two or more components is separated into two or more

products – an overhead distillate and a bottoms as a residual
◼ The feed is a liquid or a vapor-liquid mixture
◼ The bottoms product is almost always a liquid
◼ The distillate may be a liquid or a vapor or both
◼ Mixtures can be separated with distillation if the components of the
mixture have different boiling points.
◼ The substance in the mixture with the lowest boiling point
vaporizes first, collecting the vapors and then condensing them to
attain the original components.

4
2.2 PHYSICAL CONCEPT OF DISTILLATION

5
6
2.3 Vapor Liquid Equilibrium(VLE)

•Liquid in a closed container evaporates

•Resulting vapor molecules accumulate inside the container

•The vapor cannot go anywhere.

•When sufficient amount of vapor molecules accumulated

•A portion of the vapor begin to change back to its original liquid states condensation

•While the liquid still evaporates

•Now 2 process evaporation and condensation occur.

• In sufficient time rate evaporation = rate of condensation → equilibrium state

7
 Vapor Liquid Equilibrium

Rate Evaporation A = Rate condensation A

Rate Evaporation B = Rate condensation B

XA and YA constant

8
 Vapor Liquid Equilibrium

Vapor-liquid equilibrium data has done by experiments

and established data has been tabulated in Perry’s
chemical engineer’s handbook

Vapor-liquid equilibrium data also can be predict by

calculating using Roult’s law and Dalton’s law.

9
Table 1: Vapor liquid Table 2: Vapor liquid equilibrium data
equilibrium data for hexane- for benzene-toluene system
octane system

T(K) xA yA T(K) xA yA
371.6 1.00 1.00 353 1 1
374 0.82 0.90 358 0.78 0.9
377 0.65 0.78 363 0.581 0.777
380 0.50 0.67 368 0.411 0.632
383 0.39 0.56 373 0.258 0.456
386 0.29 0.45 375 0.26 0.38
389 0.20 0.34 376 0.27 0.3
392 0.13 0.24 377 0.150 0.28
395 0.07 0.13 378 0.13 0.260
398.8 0.00 0.00 383 0 0

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VAPOR-LIQUID EQUILIBRIUM (VLE)

xA + xB = 1 ; yA + yB = 1

PT = pA + pB
bubble point yA

xA
dew point

0% A
100% B 100% A
0% B

Figure 1: Boiling point diagram for benzene (A) – toluene (B) at 101.3 kPa (1 atm) total pressure

11
bubble point - when the liquid starts to boil,

dew point - when the vapour starts to condense.

dew point

bubble point

12
VLE COMPOSITION FOR BINARY MIXTURE
1.1.1 Raoult’s law
pA = xA PA

Where:
pA = partial pressure of A in vapor phase
xA = mol fraction of A in liquid phase
PA = vapor pressure of pure A at certain Temp

1.1.2 Dalton’s law

pA = yA PT ; PT = pA + pB

Where:
yA = mol fraction of A in vapor phase
PT = total pressure of the system
pA/B = partial pressure of A/B in vapor phase Figure 2: Equilibrium diagram for benzene (A)
– toluene (B) at 101.3 kPa (1atm) total pressure
by manipulating above equations,
composition of each component can be obtain as follows:

xA = (PT – PB) ………. (1) ; yA = xAPA ………..(2)

(PA – PB) PT
13
 =
(P − PB )
(P )
T
xA
A − PB

x A PA x B PB
yA = yB =
PT PT Eq..2

Hence, if we know the system total pressure (PT) and the vapor
pressure of pure A (PA) and pure B (PB)at various temperature, the
equilibrium composition of the vapor (yA) and the liquid (xA) at the
temperature can be calculated.

14
2.4 RELATIVE VOLATILITY OF MIXTURE
In order to separate a binary mixture using distillation process, there must be a differences in
volatilities of the components.

The greater the difference, the easier it is to do so. A measure for this is termed the relative volatility.

- Relative volatility of A to B ( AB) – indication of how much A volatile than B

-   : good separation; while   : poor separation

yA yA
xA xA
 AB = =  AB x A
- yB (1 − y A ) / (1 − x A ) eq 3 rearrange to give yA =
1 + ( AB − 1)x A
xB

- Substituting eq .2 into eq. 3

PA
 AB = Note:
PB
 AB (ideal solution) = constant vs temp.
 AB (non-ideal solution) = varies vs temp. 15
RELATIVE VOLATILITY OF MIXTURE

When α = 1.0, no separation is possible:

both component-A and component-B are

equally volatile.

They will vaporize together when heated.

α = 1.0, we obtain: y = x.

The larger the value α - above 1.0,

the greater the degree of separation.

From the equilibrium curve,

the greater the distance between the
equilibrium curve and the diagonal line
(where y = x), the greater the difference in liquid and vapour compositions and
therefore the easier the separation by distillation.

16
EXERCISE 2.1
A liquid mixture is formed by mixing n-heptane (A) & n-octane (B) in a closed
container at constant pressure of 1 atm (101.3kPa).
i. Calculate the equilibrium compositions of vapor & liquid
ii. Plot a boiling point diagram for the system. Determine the boiling point for a
mixture which having xA = 0.5
iii. Plot an equilibrium curve for the system
iv. Calculate the AB
v. What is the condition of the mixture? Ideal solution or Non ideal solution?
The table below shows the vapor pressure for pure n-heptane & n-octane at
various temperature.

17
ANSWER:
PT = 101.3 kPa
xA =
(P − P )
T B
yA =
x A PA
 AB =
PA
(P − P )
A B PT PB

T(K) PA PB xA yA  AB
371.6 101.3 - 1.00 1.00 -
374 110.8 56.9 0.82 0.90 1.95
yA yA
xA xA
377 122.6 62.3 0.65 0.78 1.97
 AB = =
380
383
134.4
146.2
67.6
73
0.50
0.39
0.67
0.56
1.99
2.00
yB (1 − y A ) / (1 − x A )
386 158 78.4 0.29 0.45 2.02 xB
389 169.8 83.8 0.20 0.34 2.03
392 181.6 89.1 0.13 0.24 2.04
395 193.5 94.5 0.07 0.13 2.05
398.8 - 101.3 0.00 0.00 -

405 1.0
400 0.9
0.8
395
0.7
390
0.6
T(K)

385 0.5

yA
380 0.4
0.3
375
0.2
370 0.1
0.00 0.20 0.40 0.60 0.80 1.00 1.20 0.0
xA or yA 0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0

xA

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 EXERCISE 2.2
A liquid mixture is formed by mixing butane (A) & pentane (B)
in a closed container at constant pressure of 1 atm
(101.3kPa). The relative volatility of butane to pentane is 2.3.
i. Calculate the equilibrium compositions of vapor & liquid
ii. Plot an equilibrium curve for the system

19
ANSWER
 AB = 2.3

 AB x A
yA =
1 + ( AB − 1) x A
1
pg. 15
0.8
xA yA
0 0 0.6

yA
0.1 0.20
0.2 0.37 0.4

0.3 0.50
0.4 0.61 0.2
0.5 0.70
0.6 0.78 0
0.7 0.84 0 0.2 0.4 0.6 0.8 1
0.8 0.90 xA
0.9 0.95
1 1

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Azeotropic Mixture

◼ Departures from Raoult’s law frequently manifest themselves in the

formation of azeotropes .
◼ Vapor and liquid compositions are identical at the azeotropic
composition, xA =yA ; thus relative volatility αAB =1, and no separation of
species can take place
◼ Two types of azeotropes are known: positive azeotrope and negative
azeotrope

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Positive Azeotrope

◼ A positive azeotrope is one in which the boiling point is lower than any of its components.
◼ Also called minimum-boiling azeotrope
◼ An example is a water-ethanol mixture, composed of 95.63% ethanol and 4.37% water by weight.
This azeotrope boils at 78.2 ºC which is lower than that of water (100 ºC) or ethanol (78.4 ºC).
This azeotrope is also called a minimum boiling mixture

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Negative Azeotrope

◼ azeotrope is negative, if its boiling point is higher than any of its

components. An example of this, is hydrochloric acid 20.2% and 79.8%
water (by weight). The boiling point of this azeotrope is 110 ºC, which is
higher than that of water as well as hydrogen chloride.
◼ Negative azeotropes are also called maximum boiling azeotrope

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Azeotrope Distillation Process

azeotropic distillation usually refers to the specific technique of adding

another component to generate a new, lower-boiling azeotrope that is
heterogeneous (e.g. producing two, immiscible liquid phases), such as the
example below with the addition of benzene to water and ethanol.

To split up the azeotrope, a material separation agent or entrainer is added,

which basically 'breaks' the azeotrope.

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Example ;

◼ Water and ethanol form a binary, minimum-boiling azeotrope containing 95.6 wt%
ethanol, 4.6 wt% water and boiling at 78.2 C at 101.3 kPa.

◼ Thus it is impossible to obtain pure ethanol (boiling point pure ethanol=78.4C)

◼ The addition of benzene to ethanol-water mixture results in the formation of

minimum boiling, heterogeneous ternary, azeotrope containing by weight 18.5%
ethanol, 74.1% benzene, 7.4% water boiling at 68.45C

◼ Upon condensation, the ternary azeotrope separates into two liquid layer

◼ Top layer – 14.5% ethanol, 84.5% benzene, 1% water

◼ Bottom layer - 53% ethanol, 11% benzene, 36% water

◼ The benzene rich layer is return as reflux and other layer sent to a second
distillation column for recovery and recycling
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 DISTILLATION
Involves the production of a vapor by boiling the liquid
mixture to be separated in a single stage and
condensing the vapors. No liquid is allowed to return to
the single-stage still to contact the rising vapors.
Simple Distillation
Flash
Distillation
e.g: flash, simple batch(differential and steam)
Involves the returning of a portion of the condensate
to the still. The vapor rise through a series of stages/
trays , and part of the condensate flow downward
through the series of stages/ trays countercurrent to
the vapors
Fractional Continuous
Distillation or Rectification
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 2.5 BATCH DISTILLATION
FLASH/ EQUILIBRIUM DISTILLATION

- Occurs in single stage , where a liquid mixture is partially vaporized.

- The vapor is allowed to come to equilibrium with the liquid , and then
the vapor and liquid phases are separated.
- It can be done either by batch or continuous.
V
y* F = feed (mol/h)
xF = initial mol fraction of A in feed
V = equilibrium vapor (mol/h)
Vapor region y* = equilibrium mol fraction of A in the vapor
FEED STREAM SEPARATOR
F L = equilibrium residual liquid (mol/h)
xF Liquid region
x* = equilibrium mol fraction of A in the residual liquid
HEAT EXCHANGER
= diagram’s boundary
L
x*

Schematic diagram of flash/ equilibrium distillation.

27
PREDICTION OF AN EQUILIBRIUM COMPOSITION FOR BINARY MXTURE
- When the system has attained its equilibrium, the material balance for the diagram’s boundary can be
written as:-

Overall mass balance : F = V + L

Mass balance on more volatile comp. i.e A : FxF = Vy* + Lx*
xF = y*V + x*L ……(4)
F F
Remarks: * denote at the state of equilibrium
Assumption: f denote to the fraction of feed which has been vaporized where f = V/F
Substitute f into overall m/balance : 1 = V/F + L/F
 L/F = 1 - f ……(5)
V
y* xF = y*f + x*(1-f) Substitute (5) into (4)
y* = (f-1)x* + xF ……(6)
f f
Vapor region
FEED STREAM SEPARATOR
F
Liquid region
xF OPERATING LINE
HEAT EXCHANGER
y = m x + c
L
x* 28
 EQUILIBRIUM CURVE
45O DIAGNOL LINE
OPERATING LINE
y* = (f-1)x* + xF
y*
f f

Where: xF = y*

xF
x*

Determination of equilibrium composition in flash distillation by graphical method

29
Exercise 2.3
A liquid mixture containing 70 mol% n-heptane (A) and 30 mol % n-
octane at 30oC is to be continuously flash at the standard atmospheric
pressure vaporized 60 mol% of the feed. What will be the
compositions of vapor and liquid and the temperature of the separator
for an equilibrium stage? The table below shows the vapor pressure
for pure n-heptane & n-octane at various temperature.

30
 ANSWER
x AF = 0.7 PT = 101.3 kPa
xA =
(P
T
)
− PB
yA =
x A PA
f= 0.6 (P
A
−P )
B PT
y* = (f-1)x* + xF
f f T(K) PA PB xA yA
y = -0.67 x + 1.167 371.6 101.3 - 1.00 1.00
374 110.8 56.9 0.82 0.90
x y 377 122.6 62.3 0.65 0.78
0.7 0.7 380 134.4 67.6 0.50 0.67
0.4 0.9 383 146.2 73 0.39 0.56
386 158 78.4 0.29 0.45
389 169.8 83.8 0.20 0.34
392 181.6 89.1 0.13 0.24
395 193.5 94.5 0.07 0.13
398.8 - 101.3 0.00 0.00

405 1.0
0.9
400
0.8
395 0.75
0.7
390 0.6
T(K)

0.5

yA
385
0.4
380 377.5 K
0.3
375 0.2
370 0.61 0.1
0.00 0.10 0.20 0.30 0.40 0.50 0.60 0.70 0.80 0.90 1.00 0.0
0.61
xA or yA 0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0

xA
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SIMPLE BATCH DISTILLATION
- Also known as differential distillation which only one vaporization stage involved.
- It is done by boiling a liquid mixture in a steam jacketed kettle/ pot and the vapor
generated is withdrawn and condensed as fast as it formed so that the vapor and
liquid do not have sufficient time to reach its equilibrium.
CONDENSE
CONDENSE R
R DISTILLATE
DISTILLATE

Change infinitesimal time lapse ( t) STEAM

STEAM y
 L x t2 = t1 + t JACKET
JACKET

L L - L
x x - x
STEAM IN STEAM IN

Figure 5: Schematic diagram of simple batch distillation.

L = number of moles of liquid mixture in the pot

x = mol fraction of more volatile component i.e. A
L = infinitesimal change number of moles in liquid mixture
x = infinitesimal change of mol fraction A 32
 L1 – L2,
yav

L1,,X1 L2,,X2
33
2.5.1 RALEIGH EQUATION FOR IDEAL/ NON IDEAL BINARY MIXTURE
- Consider a binary mixture to be separated by a flash distillation as shown in Fig. 5.
- A material balance on A can be made, where:-
ORIGINAL AMOUNT = AMOUNT OF RESIDUAL LIQUID + AMOUNT OF VAPOR
Mass balance on more volatile comp. i.e A will yield:-
xL = (x - x)(L – L) + y (L) Where:
xL = xL - xL - Lx + xL + y L L1 = number of moles of liquid at t1
negligible L2 = number of moles of liquid at t2
Lx = - xL + y L x1 = mol fraction of A in liquid at t1
Lx = ( y - x )L x2 = mol fraction of A in liquid at t2
L = x .
L (y- x)
Integrating both sides within limits initial (t1) to final (t2):-
x1
x
L1
L 2
L =
L
ln L1
L2
=
2
1 x
(y- x)
……(7)
RAYLEIGH EQUATION
x1
The term x 2
1 x must be evaluated graphically by determining an area under the graph of
(y –x)
1
(y –x) vs x between the limit x 1 and x2.
The average composition of total material distilled, y av can be obtained:

L1 x1 = L2 x2 + (L1 − L2 ) yav
34
EXERCISE 2.4
A liquid mixture of acetone-water containing 50 mol% acetone is distilled under differential batch condition at
atmospheric pressure, until 10 mol% of acetone remained in the still-pot. The vapor-liquid equilibrium data for
the acetone-water mixture is given below :

Determine the fraction of acetone in the distillate, yav.

35
ANSWER
xA 0.05 0.1 0.15 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 0.95
yA 0.64 0.73 0.77 0.79 0.81 0.83 0.84 0.85 0.87 0.89 0.93 0.96
1/(y-x) 1.69 1.59 1.61 1.69 1.96 2.33 2.94 4.00 5.88 11.11 33.33 100.00

7.00

6.00

5.00

4.00
1/(y-x)

3.00

2.00

1.00

0.00
0 0.2 0.4 0.6 0.8

xA

Area under the graph = 0.81

ln(L1/L2) = 0.81
Assume L1 = 100 mol
L2 = 44.5 mol
L1 x1 = L2 x2 + (L1 − L2 ) yav
36
yav = 0.82
Exercise 2.5
A mixture of 100 mol containing 50 mol% n-pentane and 50 mol% n-heptane is
distilled under differential condition at 101.3 kPa until 40 mol is distilled. What
is the average composition of the total vapor distilled and the composition of
the liquid left? The equilibrium data are as follows:

xA 0 0.059 0.145 0.254 0.398 0.594 0.867 1.000

yA 0 0.271 0.521 0.701 0.836 0.925 0.984 1.000

1/3 Simpson Rule

 f (x A1 ) + 4 f (x Ai ) + f (x A 2 ) 
1. Guess xAi and xA2, calculate the A. A = (x A1 − x A2 ) 
2. If the A is smaller than the A should be, change the  6 
xA2.
3. If the A is larger than the A should be, change both xAi
and xA2.
4. Do ‘try and error’ to obtain the A is same as A should
be.
37
ANSWER
xA 0 0.059 0.145 0.254 0.398 0.594 0.867 1
yA 0 0.271 0.521 0.701 0.836 0.925 0.984 1
1/(y-x) - 4.72 2.66 2.24 2.28 3.02 8.55 -

L1 = 100 mol 5.00

L2 = 60 mol 4.50
x A1 = 0.5 4.00
3.50
ln (L1/L2)= 0.511 3.00

1/(y-x)
First Trial 2.50
x A1 = 0.5 f(x A1) = 2.6 2.00

Assume x Ai = 0.4 f(x Ai) = 2.3 1.50

1.00
x A2 = 0.3 f(x A2) = 2.2
0.50
 f ( x A1 ) + 4 f ( x Ai ) + f ( x A 2 ) 
A = ( x A1 − x A 2 )  0.00
 6 
A= 0.467 (compare with ln (L1/L2)) 0 0.1 0.2 0.3 0.4 0.5 0.6 0.7

xA
Second Trial
x A2 = 0.25 f(x A2) = 2.3
A= 0.588

Third Trial
x A2 = 0.28 f(x A2) = 2.2
A= 0.513 (same with ln(L1/L2))

x A2 = 0.28

L1 x1 = L2 x2 + (L1 − L2 ) yav

yav = 0.83
38
 2.5 FRACTIONAL/ CONTINUOUS DISTILLATION
- In a multi stage fractional distillation process, the vapor and liquid are brought into
continuous and counter-current contact inside the a column as shown in Figure 6.

VAPOR

FEED LIQUID DISTILLATE

(F, xF) (D, xD)

BOTTOM
(B, xB)
Schematic diagram of a fractionating distillation.
39
40
41
- The feed enters somewhere in in the middle of the column (Fig. 6). The portion
above the feed stream is known as enriching section, while the bottom is known as
stripping section.
- If the feed is liquid, it flows down to a stage/tray. Vapor enters the tray and bubbles
through the liquid on this tray as the entering liquid flows across.
- The vapor and liquid leaving the tray are essentially in equilibrium.
- The vapors continues up to the next tray, where it is again contacted with the down-
flowing liquid. In this case the concentration of more volatile component i.e A is
being increased in the vapor from each stage going upward and decreased in the
liquid from each tray going downward.
- The final vapor product coming overhead is condensed in a condenser and a
portion of the liquid product (distillate) is removed, which contains a high
concentration of A. The remaining liquid from the condenser is refluxed (returned)
as a liquid to the top tray.
- The liquid leaving the bottom tray enters the reboiler, where it is partially vaporized
and the remaining liquid, which is rich in B is withdrawn as bottom liquid product.
The vapor from the reboiler is sent back to the bottom tray.

42
 McCABE –THIELE METHOD: CALCULATION FO THEORITICAL STAGES/ TRAYS
EQUATIONS FOR ENRICHING SECTION

1
y 2
n
Figure 7: Material 2

balance and operating

line for enriching
section.
n-1 xD
xD
n
Vn+1, yn+1 Ln,
n+1 xn

x
1

- The upper part of the column above the feed entrance is called enriching section. Since the
entering feed of binary components A and B is enriched in this section, so that the distillate
is richer in A than B.
- Assumption: i. column operates at steady state condition
ii. constant molal overflow in the column 43
- The material balance for the diagram’s boundary in Fig 6 can be written as:-

Overall mass balance : F = D + B ……(8)

Mass balance on comp. A : FxF = DxD + BxB ……(9)

The m/balance over the red dashed line section in Fig 7,

Overall mass balance : Vn+1 = Ln + D ……(10)
Mass balance on comp. A : Vn+1yn+1 = Lnxn + DxD ……(11)
Solving for y n+1, the enriching operating line is:-

yn+1 = Ln xn + DxD ……(12)

Vn+1 Vn+1

44
 Since
Vn+1 = Ln + D; R=L/D

yn+1 = Ln xn + DxD
Vn+1 Vn+1

yn+1 = Ln xn + DxD
Ln +D Ln +D

yn+1 = Ln/D xn + D/D xD

Ln/D +D/D Ln/D +D/D

yn+1 = R xn + xD
ENRICHING
R+1 R+1 OPERATING
LINE
Where R = L n/D = reflux ratio = constant value
45
EQUATIONS FOR STRIPPING SECTION

m
Vm +1, ym +1 L m , xm
m+1

N
m
m+1 BOILER
yM+1
N SLOPE = L m/ Vm+1
yB

BOTTOM
xM ( B, xB )

xB

Figure 8: Material balance and operating line for stripping section.

46
The m/balance over the red dashed line section in Fig 8 for the stripping section of the column below the
feed entrance
Overall mass balance : Vm+1 = Lm - B ……(14)
Mass balance on comp. A : Vm+1ym+1 = Lmxm - BxB ……(15)

Solving for y m+1, the stripping operating line is:-

ym+1 = Lm xm - BxB ……(16)

STRIPPING OPERATING LINE
Vm+1 Vm+1

- Since equimolar flow is assumed, L m = LN = constant & Vm+1 = VN = constant; eq. 16 is a straight line
when plotted as y vs. x in Fig. 8, with a slope of Lm/Vm+1.
- It intersects the y = x line at x = xB. The intercept at x = 0 is y = -BxB/ Vm+1.
- Again the theoretical trays for the stripping section are determined by starting at x B going up
to yB, and then across to the operating line and so on.

47
EFFECT OF FEED CONDITIONS
◼ The condition of the feed stream (F) entering the column determines the relation
between the vapor Vm in the stripping section and Vn in the enriching section as
well as between Lm and Ln.
◼ q represents fraction of liquid in the feed flowing down the stream.
◼ The condition of the feed is representing by q, which
◼ defined as:-

q = heat needed to vaporise 1 mol of feed at entering conditions

Molar latent heat of vaporization of feed
q = HV - HF ……(18)
Hv - HL

Where:
HV = enthalpy of the feed at dew point
q = L/F
HL = enthalpy of the feed at the boiling point
HF = enthalpy of the feed at its entrance conditions
48
 Refer to Figure 11.4-6 page 711
q OPERATION LINE
Vn = Vm + (1 − q )F
Vm − Vn = ( q − 1) F − − − 1

Lm = Ln + qF
Lm − Ln = qF − − − 2

Vn y = Ln x + Dx D − − − 3
Vm y = Lm x − Bx B − − − 4
3− 4
(Vn y − Vm y ) = (Ln x − Lm x ) + (Dx D + Bx B )
(Vm − Vn ) y = (Lm − Ln ) − (Dx D + Bx B ) − − − 5

FxF = Dx D + Bx B − − − 6
Subsitute 1, 2 and 6 into 5
( 1-q)Fy = qFx-FxF
(1 − q ) y = qx − xF
q 1
y= x− xF 49
1− q 1− q
- The q operating line is given by:-
q xF
y = x - ……(19)
q OPERATING LINE
q-1 q-1

- It is locus of the intersection of the 2 operating lines.

- Setting y = x in eq. 19, the intersection of the q-line equation with the 45o line is y = x = xF, where
xF is the overall composition of the feed. The q-line is plotted for various feed condition in Fig. 9.

Where:-
q<0 : superheated vapor
q=0 : saturated vapor (DEW POINT)
0<q<1: mixture of liquid + vapor
q=1 : saturated liquid (BUBBLE/BOILING POINT)
q>1 : cold liquid

Location of the q-line for various feed conditions. 50

 q op. line enriching Equilibrium curve
1.2
operating line

1
Stripping op. line
0.8

0.6

0.4

0.2

0
0 0.2 0.4 0.6 0.8 1 1.2

XB XF XD

51
STEP 1
Draw the equilibrium curve from equilibrium data (xA , yA)

STEP 2
Find the value of XF, XD, XB

STEP 3
Draw the enriching operating line, start from the X D yn+1 = R xn + xD
R+1 R+1

STEP 4
q xF
Draw the q operating line, start from the X F y = x -
q-1 q-1
STEP 5
Draw the stripping line, start from the X B to the intersection of (q line-----enriching line)
53
FEED
FIRST OPPORTUNITY AFTER PASSING
THE OPERATING LINE INTERSECTION

54
OVERALL TRAY EFFICIENCY
◼ Define as the ratio of the number of
theoretical or ideal trays needed in an
entire tower to the number of actual trays
used:
Number of ideal trays
EO =
Number of actual trays

55
Exercise 5
A continuous rectifiying column handles a mixture consisting of 40 mol% of benzene
and 60 mol% of toluene at a rate of 150 kmol/h and separates it into a top product
containing 97 mol% of benzene and a bottom product containing 98 mol% toluene.
Give the q value is 0.6.

Table 1 Vapor-liquid equilibrium data for benzene-toluene mixture

xA 0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0

yA 0 0.22 0.38 0.51 0.63 0.7 0.78 0.85 0.91 0.96 1

a) Draw the schematic diagram for this system.

b) Determine the molar flow rate of distillate and bottom.
Ans; D=60 kmol/h; B=90 kmol/h
c) Determine the number of theoretical plates if the reflux ratio is 3.0.
Ans; 14 steps, 13 plates/stages
d) Determine the position of the feed plates.
Ans; 7 from the top
e) Determine the actual plates number if the efficiency is 82%
Ans; 15.85 plates/stages

56
Exercise 6
A liquid of benzene-toluene mixture is to be distilled in fractionating tower at 101.3 kPa. The feed of
100 kg-mol/h liquid contains of 45 mol% benzene and 55 mol% toluene enters at 327.6 K. A distillate
contains 95 mol% benzene and a bottoms containing 10 mol% benzene are to be obtained. The reflux ratio
is 4:1. The average heat capacity of the feed is 159 kJ/kg-molK and the average latent heat 32099 kJ/kg-
mol. The boiling point of the feed is 366.7 K. The equilibrium data for this mixture is given below.

Determine:
a) The distillate and bottom product in kg-mol/h.
b) The q value.
c) The number of theoretical tray.
e) The position of feed tray.
f) The number of actual tray if the overall efficiency is 73% .

57
xA 1 0.78 0.58 0.41 0.26 0.13 0
yA 1 0.9 0.78 0.63 0.46 0.26 0

F= 100 kgmol/h 1 1
x AF = 0.45
0.9 2
x AD = 0.95 3
0.8 Feed tray
x AB = 0.1 4
R= 4 0.7
Cp = 159 kJ/kgmol.K 0.6
5
HV - HL = 32099 kJ/kgmol
Tin = 327.6 K
0.5
ANSWER
0.4 6
Tb = 366.7 K
F=D+B 0.3
7
Fx AF = Dx AD + Bx AB 0.2
7.3
0.1
D+B= 100
D= 100 - B 0
45 = (100 - B)0.95 + 0.1B 0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1
45 = 95 - 0.95B + 0.1 B
0.85B = 50
B= 58.82353 kgmol/h Enriching Operating Line: Number of ideal trays
D= 41.17647 kgmol/h
yn+1 =
R
xn + xD EO =
q = HV - HF
R+1 R+1 Number of actual trays
y= 0.8 x + 0.19
Hv - HL x y
HV - HF = (HV - HL) + (HL - HF)
HL - HF = Cp (TB - TF)
0.95
0.3
0.95
0.43
0.73 = 6.3/Actual trays
q = (HV - HL) + Cp (TB - TF) No. of Actual trays is 8.63
Hv - HL q Operating Line:
q = 32099 + 159 (366.7 - 327.6) q - xF
plus a reboiler.
y = x
32099
q= 1.194 q- 1 q- 1
y= 6.163184 x - 2.323433
x y
0.45 0.45
0.5 0.758159

The number of theoretical tray is 6.3 plus a reboiler.

The feed is introduced on tray 4 from the top.
58
 TOTAL REFLUX
◼ R = , yn+1 = R xn + xD
◼ Enriching operating line, R+1 R+1
the slope will become 1.0 and both section operating lines coincide with the 45
diagonal line.
◼ Minimum number of trays
◼ Required infinite sizes of condenser, reboiler and tower diameter for a given feed
rate.
◼ The minimum number of theoretical steps, Nm when a total condenser is used:

59
 Minimum Reflux Ratio, Rm
◼ Require an infinite number of trays for the given desired separation.

◼ Minimum vapor flow in the tower, minimum reboiler and condenser sizes.

◼ R is decreased, the slope of the enriching operating line is decreased and the
intersection of this line and the stripping line with the q line moves farther from the
45 line and closer to the equilibrium line, a ‘pinch point’ happen when two
operating lines touch the equilibrium line.

Rm xD
y= +
R m +1 R m +1

x
slope D = c ( int er sec tion)
Rm +1
Rm xD − y '
=
Rm + 1 x D − x '
60
Operating & Optimum Reflux Ratio
◼ Total reflux: minimum number of plates but tower diameter
is infinite.

◼ Minimum reflux: infinite number of trays.

◼ Actual operating reflux ratio lies between these two limits

◼ The optimum reflux ratio to use for lowest total cost per
year is between Rm and total reflux.
Design
consideration
◼ Operating reflux ratio between 1.2 Rm and 1.5 Rm
61
EXERCISE
A saturated liquid feed of 200 mol/h at the boiling point containing 42 mol% heptanes and 58
mol% ethyl benzene is to be fractionated at 101.32 kPa abs to give a distillate containing 97
mol% heptanes and a bottoms containing 10 mol% heptanes. The equilibrium data are given
below at 101.32 kPa abs pressure for the mole fraction n-heptane.

Table 1 Equilibrium data for heptane-ethyl benzene system

Mol fraction of n-heptane in liquid

0 0.08 0.25 0.485 0.79 1
phase (xA)
Mol fraction of n-heptane in vapor
0 0.23 0.514 0.73 0.904 1
phase (yA)
a) Determine the minimum reflux ratio, Rm .
Ans 1.115
a) Determine the number of theoretical plates at minimum reflux ration.
Ans infinite
a) Determine the minimum number of theoretical plates at total reflux.
Ans 5.5 steps and 4.5 trays/stages
a) The reflux ratio used is 2.27Rm , determine:
i. The distillate and bottoms flow rate in mol/h.
Ans D=73.56 mol/h B=126.44 mol/h
i. The theoretical number of trays.
Ans y=0.7167x +0.27 ; 8.5 steps and 7.5 stages/trays
b) Determine the feed tray number
Ans 6 from the top

62