SEPARATION PROCESSES (CHE 246)

DISTILLATION
JUPLIN KINTI
FACULTY OF CHEMICAL ENGINEERING
UiTM SARAWAK
 OBJECTIVE

CO2: Explain and distinguish the concept, application and

equipment design for distillation.

CO3: Evaluate the concept, application and equipment design

for distillation
 LEARNING OUTCOMES
Student should be able to:

 Define distillation, Rayleigh equation and reflux ratio

 Explain the physical concepts of distillation, including
vapour-liquid equilibrium and relative volatility
 Distinguish batch and continuous distillation
 Calculate the number of theoretical stages in a
distillation column using McCabe-Thiele method, the
overall plate efficiency and minimum reflux ratio
1. VAPOR-LIQUID EQUILIBRIUM (VLE)
- Fundamentally govern by evaporation and condensation process.
 Open system
 Closed system
- Factor derived by volatility of component ( )

xA + x B = 1 ; y A + y B = 1
PT = pA + pB
Raoult’s law:-
p A = xA P o A
Where:
pA = partial pressure of A in vapor phase
xA = mol fraction of A in liquid phase
PoA = vapor pressure of pure A at
certain Temp

Figure 1: Boiling point diagram for benzene (A) – toluene (B) at 101.3 kPa (1 atm) total pressure
CHE 347: UNIT OPERATION
(CHAPTER 1 )
1.1 VLE COMPOSITIN FOR BINARY MIXTURE
1.1.1 Raoult’s law
pA = xA PoA

Where:
pA = partial pressure of A in vapor phase
xA = mol fraction of A in liquid phase
PoA = 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 liquid 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 – PoB) ………. (1) ; yA = x A Po A ………..(2)

(PoA – PoB) PT
CHE 347: UNIT OPERATION
(CHAPTER 1 )
1.2 RELATIVE VOLATILITY OF MIXTURE
- Definition – the ratio of the concentration of A in the vapor to the concentration of A in
the liquid divided by the ratio of the concentration of B in the vapor to the
concentration of B in the liquid.
- Separations of components for distillation process depend on the differences in volatilities of
that leads to solution to be distilled.
-   : good separation; while   : poor separation
- Relative volatility of A to B (AB) – indication of how much A volatile than B

AB = yA / xA = y Ax B ……….(3)
yB / xB y Bx A

or AB = PoA ……….(4)

PoB
Then, x
y 
ab A

1  x   1
A
A ab

CHE 347: UNIT OPERATION

(CHAPTER 1 )
Exercise 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
iii. Plot an equilibrium curve for the system
iv. Calculate the AB
v. What is the condition of the mixture?
Use the following list if vapor pressure for pure n-heptane & n-octane at various temperature.

(ANSWER)
CHE 347: UNIT OPERATION
(CHAPTER 1 )
 Answer E1

Fig. 3: Boiling point diagram for n-heptane/ n-octane mixture at 1atm Fig. 4: Equilibrium diagram for n-heptane/ n-octane mixture at 1atm

CHE 347: UNIT OPERATION

(CHAPTER 1 )
Definition & General Description

 Distillation :
separation by mass transfer process in
which the components of feed stream are
separated based on their distribution
between the vapor and liquid phases by
thermal means.
1.3 DISTILLATION
- Is known as a method for separating various components of a liquid solution which depends upon the
distribution of these components between a vapor phase and a liquid phase.
- Classified into 2 main methods in practice i.e:-

1. 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.

i.e. : FLASH; SIMPLE BATCH; SIMPLE STEAM DISTILLATIONS

2. 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.

i.e. : FRACTIONAL/ CONTINUOUS DISTILLATION; RECTIFICATION

CHE 347: UNIT OPERATION

(CHAPTER 1 )
 1.3.1 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*
Where;

F = feed (mol/h)
Vapor region xF = initial mol fraction of A in feed
FEED STREAM SEPARATOR
F V = equilibrium vapor (mol/h)
xF Liquid region y* = equilibrium mol fraction of A in the vapor
HEAT EXCHANGER L = equilibrium residual liquid (mol/h)
x* = equilibrium mol fraction of A in the residual liquid
L = diagram’s boundary
x*

Figure 3: Schematic diagram of flash/ equilibrium distillation.

CHE 347: UNIT OPERATION

(CHAPTER 1 )
1.3.1.1 PREDICTION OF AN EQUILIBRIUM COMPOSITION FOR
BINARY MXTURE
- Consider a binary mixture to be separated by a flash distillation as shown in Fig. 3.
- 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)

Substitute (5) into (4) : xF = y*f + x*(1-f)

y* = (f-1)x* + xF ……(6)
f f
OPERATING LINE
y = m x + c
CHE 347: UNIT OPERATION
(CHAPTER 1 )
 EQUILIBRIUM CURVE

45O DIAGNOL LINE

OPERATING LINE
y* = (f-1)x* + xF
y* f f
Where: xF = y*

xF
x*

Figure 4: Determination of equilibrium composition in flash distillation by graphical method

CHE 347: UNIT OPERATION

(CHAPTER 1 )
Exercise 2
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?

* Use the previous table of the vapor pressure for pure n-heptane & n-octane at various temperature.

CHE 347: UNIT OPERATION

(CHAPTER 1 )
 1.3.2 SIMPLE BATCH / DIFFERENTIAL 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.
CONDENSER CONDENSER

DISTILLATE DISTILLATE

STEAM STEAM
Change infinitesimal time lapse (t)
JACKET L x y JACKET
t2 = t1 + t

L L - L
x x - x
STEAM IN STEAM IN

Figure 5: Schematic diagram of simple batch distillation.

Where,
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 CHE 347: UNIT OPERATION
x = infinitesimal change of mol fraction A (CHAPTER 1 )
1.3.2.1 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 yeild:-
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)
RALEIGH EQUATION
x1
- The term  (y –x) must be evaluated graphically by determining an area under the graph of
1 x
x2
1
(y –x) vs x between the limit x1 and x2.
CHE 347: UNIT OPERATION
(CHAPTER 1 )
- The average composition of the total material distilled yav, can be obtained by material balance :

L1 x1 = L2x2 + (L1 - L2)(yav)

Exercise 3
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:
a) The fraction of acetone in the distillate
b) Average composition of the distillate CHE 347: UNIT OPERATION
(CHAPTER 1 )
1.3.3 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)
Figure 6: Schematic diagram of a fractionating distillation. CHE 347: UNIT OPERATION
(CHAPTER 1 )
- 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.

CHE 347: UNIT OPERATION

(CHAPTER 1 )
1.3.3.1 McCABE –THIELE METHOD: CALCULATION FOR NO. OF
THEORITICAL STAGES/ TRAYS

1.3.3.1.1 INTRODUCTION & ASSUMPTION

- A mathematical-graphical method for determining the no. of theoretical trays needed for a given
separation of a binary mixture of component A and B.
- Assumption: constant molal overflow in the column

1.3.3.1.2 EQUATIONS FOR ENRICHING SECTION

- 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
- 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)

CHE 347: UNIT OPERATION

(CHAPTER 1 )
 1
2
y2 n

n-1
xD
xD
n
Vn+1, yn+1 Ln, xn
n+1

x1

Figure 7: Material balance and operating line for enriching section.

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)
CHE 347: UNIT OPERATION
(CHAPTER 1 )
 Solving for yn+1, the enriching operating line is:-

yn+1 = Ln x + DxD ……(12) ENRICHING OPERATING LINE

n
Vn+1 Vn+1

Since Vn+1 = Ln + D; Ln/Vn+1 = R/ (R+1) and eq. 12 becomes:-

yn+1 = R x + xD ……(13) ENRICHING OPERATING LINE

n
R+1 R+1

Where R = Ln/D = reflux ratio = constant value

- Eq. 13 is a straight line on a plot of vapor composition (y) vs liquid composition (x) as depicted in Fig. 7.
- It intersects the 45o diagonal line at x= xD.
- The interception of the operating line at x = 0 is y = xD/(R+1)
- The theoretical trays are determined by starting at xD and stepping off the first plate to x1. Then
y2 is the composition of the vapor passing the liquid x1.
- In similar manner, the other theoretical trays are stepped off down the column in the enriching
section to the feed tray.

CHE 347: UNIT OPERATION

(CHAPTER 1 )
1.3.3.1.3 EQUATIONS FOR STRIPPING SECTION

m
Vm+1, ym+1 Lm, xm
m+1

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

BOTTOM
xM ( B, xB )

xB

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

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) CHE 347: UNIT OPERATION
(CHAPTER 1 )
 Solving for ym+1, the stripping operating line is:-

ym+1 = Lm x - BxB ……(16)

m STRIPPING OPERATING LINE
Vm+1 Vm+1

- Since equimolar flow is assumed, Lm = 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 xB going up
to yB, and then across to the operating line and so on.

1.3.3.1.4 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.
- The condition of the feed is representing by q, which defined as:-
q = heat needed to vaporise 1 mol of feed at entering conditions ……(17) @ q = HV - HF ……(18)
Molar latent heat of vaporization of feed
Hv - H L
Where:
HV = enthalpy of the feed at dew point
HL = enthalpy of the feed at the boiling point
HF = enthalpy of the feed at its entrance conditions CHE 347: UNIT OPERATION
(CHAPTER 1 )
- 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
0<q<1: mixture of liquid + vapor
q=1 : saturated liquid
q>1 : cold liquid

Figure 9: Location of the q-line for various feed conditions. CHE 347: UNIT OPERATION
(CHAPTER 1 )
Reflux for McCabe-Thiele Method
 Definition-the quantity of Distillate product that is being
condensed and returned to the top of the column
 2 categories : Internal & External reflux ratio
i) Rv = L/V = reflux ratio Internal
ii)RD = L/D = reflux ratio External
-Total reflux
Minimum num. of trays, infinite sizes of condenser, reboiler and
tower diameter
-Minimum reflux
Infinite num. of trays
-Optimum reflux
Theoretical num. of stages
Many cases – operating reflux ratio between 1.2Rm and 1.5Rm
 Reflux (R) is a measure how much of material going up the
top of the column is returned back to the column { R = L/D}

y y
Pinch point
y’
yN yN yN

yB yB yB

xB x=zF xD xB x’ x=zF xD

Total Reflux ~ condition represents with no Minimum Reflux ratio, Rm ~ infinite of

product removal. trays for given desired separation of xD and
xw.
~ Reflux ratio is infinite and operation line
is 45 degree lines. ~ (Rm / Rm + 1) = ( XD –y’) / (XD – x’)
~ Number of stages is minimum
Summary : Construction Lines for McCabe-
Thiele Method

y
Rectifying Section:
Equilibrium Operating line
curve Slope=L/V=R/(R+1)<1
q-line L D
yN  q   z F  y x  xD
y   x    V V
q  1 q 1
Stripping Section:
Operating line
45° line Slope=L/V=(VB+1) /VB
L B
yB y x  xB
V V
xB x=zF xD

Lecture 12: McCabe Thiele

 Construction for the McCabe-Thiele Method
1. equilibrium 2. equilibrium
Step 1: Plot equilibrium curve and 45 degree line.
curve curve
45° line Step 2: Plot given compositions (F, B, and D)
y y Step 3: Draw q-line from LF and VF
Step 4: Determine Rmin from intersection of the
rectifying section OL and the equilibrium curve.
45° line Step 5: Determine R from R/Rmin
Step 6: Draw OL for Rectifying section
Step 7: Draw OL for Stripping section
xB x=zF xD
x

5. and 6. 7.
3. 4.
equilibrium equilibrium equilibrium
equilibrium
curve curve curve
curve

y y y y

xB xD xB x=zF xD xB x=zF xD xB x=zF xD

x=zF

Rmin/(Rmin+1) R/(R+1)

Lecture 12: McCabe Thiele

 Example: Determination of N and xB for McCabe-Thiele
Given:
100 kmol/hr of a feed of 60% benzene and 40% heptane is to be separated by distillation. The distillate is to be 90%
benzene and the bottoms 10% benzene. The feed enters the column as 30mol% vapor. Use R 1.5 times the
minimum. Assume a constant relative volatility of of 4 and that the pressure is constant throughout the column at
1atm.
Construction:
Step 1: Plot equilibrium curve and 45 degree line.
1 The equilibrium curve is found using:
0.9 x
y
0.8 1  x   1
0.7 Step 2: Plot given compositions (F, B, and D)
Step 3: Draw q-line from LF and VF. Use
0.6
L  L L  LF  L LF
y 0.5 q    0.7
F F F
0.4
to find q. Then plot the q-line using:
0.3
 q   z F 
0.2 y   x     2.333x  2
0.1
q  1 q 1

0 Step 4: Determine Rmin from intersection of the

0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1 rectifying section OL and the equilibrium curve.
This happens at a slope of about .25
x
Rmin
0.25   Rmin  0.333
Lecture 12: McCabe Thiele Rmin  1
 Example: Determination of N and xB for McCabe-Thiele
Given:
100 kmol/hr of a feed of 60% benzene and 40% heptane is to be separated by distillation. The distillate is to be 90% benzene and
The bottoms 10% benzene. The feed enters the column as 30mol% vapor. Use R 3 times the minimum. Assume a constant relative
Volatility of of 4 and that the pressure is constant throughout the column at 1atm.

Construction:
Step 5: From Rmin=0.333 and R=3Rmin we have R=1
And the slope of rectifying section OL is 0.5
1
Step 6: Draw the line with slope 0.5 which is the rectifying
0.9 section OL.
Step 7. Draw the stripping section operating line from the
0.8
Bottoms composition to the intersection of the rectifying section
0.7 OL and the q-line.
0.6
Solution:
y 0.5 Step 1: From xD locate x1 and y1 drawing a horizontal line
to the equilibrium condition for stage 1.
0.4
Step 2: Find y2 drawing a vertical line to the rectifying OL
0.3 locate the mass balance condition between x1 and y2.
Step 3: From y2 draw a horizontal line to the equilibrium
0.2
condition for stage 2 to locate x2.
0.1 Step 4: Return to step 2 and cycle through steps 2 and 3 until
xi <zF.
0
0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1
Results:
x Feed at stage between 2 and 3.
5 stages (minimum stages = 3.2)
xB=0.05% benzene
Exercise 4
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 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%.

CHE 347: UNIT OPERATION

(CHAPTER 1 )
Tray Efficiencies (Eo)
-McCabe-Thiele Method – theoretical trays / stages

-Due too time of contact and degree of mixing on tray are insufficient,
the stream are not be in in equilibrium. Hence, the efficiency of the
stage will not to be 100%.

Eo = Number of ideal/theoretical trays x 100%

Number of actual trays

-Most cases, number of actual trays less than 25

Lecture 12: McCabe Thiele