CHAPTER TWO

Distillation
 Distillation

Joe is doing
distillation.
Can you explain
what’s going on?

Distillation has been practiced since long…

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Alchemy distillation apparatus

3
 Alchemy distillation apparatus

Distillation columns have changed a lot. However, the basic

principles remain the same.
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 Different types of distillation

• Flash distillation
• Batch distillation
• Steam distillation
• Continuous distillation
• Vacuum distillation
• Extractive distillation

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 Flash distillation
A flash is a single-equilibrium stage distillation in which a feed is
partially vaporized to give a vapor richer in the most volatile
components than the remaining liquid .

• Adiabatic flash: A liquid feed is

heated under pressure and flashed
across a valve adiabatically to a lower
pressure resulting in the creation of a
vapor phase that is separated from the
liquid in the flash drum.

• Isothermal flash: The valve is omitted

and a low pressure liquid can be
partially vaporized in the heater and
then separated in the flash drum.

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 Flash distillation

➢ Alternatively, a vapor can be cooled and partially condensed, with

phase separation in a flash drum as in figure (4.10b, Seader), to give a
liquid that is richer in the less volatile components.
➢ In both cases, if the equipment is properly designed, the vapor and
liquid leaving the drum are in equilibrium
 Application: Flash distillation

• Used for separating components that boil at widely different

temperatures.

• Because of single equilibrium stage, the degree of separation

achievable is poor unless the relative volatility is very large.

• Usually used as an auxiliary operation to prepare streams for

further processing.

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Flash distillation

9
 Flash distillation

Operating Line Equation : Operating Line :

1− f L F
y=−
1
x+ z y = − x+ z
f f V V

Commonly given specifications :

• If you know f and z you can draw the V
operating line. f =
F
Slope of the operating line :
• Notice that for all values of f , the operating
line goes through the point x = y = z. L 1− f
− =−
V f
• So you can locate the point x = y = z and
y intersept :
with the slope or the intercept you can draw F= L + V
the operating line. F 1
z= z F/V= L/V + 1
V f 1/f= L/V + 1
L/V= 1/f –f/f = ((1-f)/f)

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Typical flash calculation problems

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Information we get
Operating Line :
L F
y = − x+ z
V V

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Solution

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 Flash distillation: Example

• A flash distillation operating at an atmospheric pressure is separating an

ethanol-water mixture. The feed mixture is 40% mole ethanol, if half of the
feed is vaporized, what is the vapor composition.

f=2/3,,,,,,, y= - ½ x+ 0.6
Operating Line Equation :
1− f 1
y=− x+ z F= 0.5,,,,,,,, Y= - x + 0.8
f f y = 0.65,,,,,, x= 0.21

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Flash distillation: example

line

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Flash distillation: example

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Flash distillation: example

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Ref: McCabe & Smith

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 Batch Distillation

• Liquid mixture is charged in a still or

reboiler and heat is supplied to bring the
liquid to its boiling point and then vaporize
part of the batch.

• The vapor formed is continuously removed

and taken to a condenser.

• The vapor leaving the still at any time is in

equilibrium with the liquid in the still.

• The composition of both the remaining liquid and distillate changes with time;
there is no steady state.
• The still temperature increases and the relative amount of the lower boiling
components remaining in the still decreases as distillation proceeds.

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 Applicability of batch distillation

• Small capacity does not warrant continuous operation.

• Separation is to be done only occasionally.

• Separation is preparative to produce a new product.

• Upstream operations are batchwise or feedstocks vary with time or

from batch to batch.

• Feed materials are not appropriate for a continuous flow system.

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Batch distillation nomenclature

• D = instantaneous distillate rate

• y = yD = xD = instantaneous distillate
composition, mole fractions

• W = moles of liquid left in the still

• x = xW = composition of liquid left in the

still, mole fraction

• 0 subscript referring to t = 0

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Batch distillation: mole balance

• Overall mass balance:

 rate of change 
Instantane ous   
  = of moles of liquid in 
 distillate rate   
 still 
dW
D=−
dt

• Component mole balance:

Rate of change of  Rate of change of 

   
 component = component 
 in distillate   
   in still 
d (Wx)
Dy = −
dt

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 Batch distillation: mole balance

d (Wx) dx dW
=W +x
dt dt dt
dx dW
Dy = −W −x
dt dt

y ( Ddt ) = −Wdx − xdW

Now, as Ddt = − dW

− ydW + xdW = −Wdx

dx dW
=
y−x W

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 Batch distillation: Rayleigh equation

If the initial charge conditions areW0 and x0, integration from

the initial condition gives

dx dW x dx W dW W
=
y−x W
 
x0
=
y − x W0 W
= ln( )
W0

This equation is called the Rayleigh equation.

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 Batch distillation: Rayleigh equation

Rayleigh equation

x dx W
x0 y−x
= ln( )
W0

Solutions depends on how y is expressed in terms of x

1. Using a constant K value

2. Using constant relative volatility α

3. Using graphical or tabular relation of y and x

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 Rayleigh equation: Using constant K value

x dx W
Rayleigh equation 
x0 y−x
= ln( )
W0

Assumptions:

• The pressure is constant

• The temperature change in the still pot is relatively small (close boiling mixture)

• K -values are composition independent and constant

Then we have y = Kx

x dx W 1 x W
x0 ( K − 1) x = ln(
W0
) ln( ) = ln( )
( K − 1) x0 W0

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Rayleigh equation: Using constant α-value

Assumptions:

• The relative volatility is constant

x
y=
1 + x( − 1)

dx W x dx W

x
x0 y−x
= ln( )
W0 x0
(

− 1) x
= ln(
W0
)

1 + x( − 1)

W 1   x   1− x 
ln( ) = ln  −  ln  

 − 1   x0 
W0   1 − x0 

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 Rayleigh equation: Using equilibrium x-y data

1
• Tabulate data using x and y data
y−x

x dx
• Numerically integrate x0 y−x
e.g. using Trapezoidal rule :

x dx  1 

x0

y − x  y − x  avg
x

x dx W
x0 y−x
= ln( )
W0

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 Rayleigh equation: Solutions
x dx W
Rayleigh equation x0 y−x
= ln( )
W0
Solutions depends on how y is expressed in terms of x

1. Using a constant K value 1 x W

ln( ) = ln( )
( K − 1) x0 W0

2. Using constant relative volatility α

W 1   x   1− x 
ln( ) =  
ln   −  ln   

 − 1   x0  
W0  1 − x0  
3. Using graphical or tabular relation of y and x

x dx  1 
x0

y − x  y − x  avg
x

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 Examples: Batch distillation

Problem statement:

A liquid contains 50 mole% of n-heptane (A) in n-octane (B). 60 mole% of the

initial charge is distilled using batch distillation technique. Calculate the
composition of the distillate (average composition) and the residue.

Following equilibrium data is given for the binary system:

x dx W
 x0 y−x
= ln( )
W0

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 Examples: Batch distillation

x dx W 40
Basis: W0=100 moles
x0 y−x
= ln( ) = ln(
W0 100
) = −0.916

x0=0.5
D=60 moles, W=100-D=40 moles x dx
Using Rayleigh equation: 
0 .5 y−x
= −0.916

1/(y-x) avg= 5.41

x dx  1 

x0

y − x  y − x  avg
x  xW = 0.33
Mole balance : 100  (0.5) = 40(0.33) + 60( y D )
5.41*(0.50-0.33)=0.919  y D = 0.614

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Another example using graphical solution

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 Examples: Batch distillation

Problem statement: A 30 mol% feed of benzene in toluene is to

be distilled in a batch operation. A product having an average
composition of 45 mol% benzene is to be produced. Calculate
the amount of the residue, assuming α = 2.5 and W0 = 100.

Xo=0.3,yD=0.45, Wo=100, α =2.5, find W and also x

W 1   x   1− x 
ln( )= ln   −  ln   

 − 1   x0  
W0  1 − x0  

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 Examples: Batch distillation

x0=0.30
Product (yD)ave=0.45
α = 2.5 and W0 = 100
W=?

W 1   x   1− x   100  2   0.30   1 − x 
ln( ) =  
ln   −  ln    ln   = ln   + 2.5 ln   (1)

 − 1   x0         
W0  1 − x0   W 3 x 0 .70

(100  (0.30) − Wx)

0.45 =
(W0 x0 − Wx) 100 − W
( x D ) ave = ( y D ) ave = 45 − 0.45W = 30 − Wx
W0 − W
15 = W (0.45 − x)
15
x = 0.45 − (2)
Solve the two non-linear equations to W
get W = 57.9 moles.

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 Batch distillation: Pros & Cons

Pros Simple to
Cons Small
make & amount for
operate high purity

Large
Cheap
amount for
component
low purity

Energy
Flexible
intensive

How to Slow
improve ?

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Batch distillation: Improvements

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Flash distillation: revisited

y ???

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 Examples: Multistage flash separation

• Consider a binary system of benzene (A) and toluene (B).

• If 100 moles of a feed mixture containing 40% A is vaporized to

produce 25 moles of vapor, what will be the vapor composition?

• If instead of vaporizing 25 moles, in the first step 50 moles are

vaporized and the vapor is condensed. In the second step, if 25
moles from the condensate is vaporized, what will be the
composition of the resulting vapor?

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Examples: Multistage flash separation

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Examples: Multistage flash separation

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Examples: Multistage flash separation

(0.58, 0.35) (0.4, 0.4)

M= (0.4-0.58)/(0.4-0.35)=(-0.18/0.05)=- 3.6
Y= -3.6 x + c
0.4= - 1.44 + c
C= 1.84

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Examples: Multistage flash separation

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Examples: Multistage flash separation

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Examples: Multistage flash separation

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Separation in partial evaporation and partial condensation

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Basic principle of stage separation

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Stage equilibrium

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 Details of a tray
http://www.youtube.com/watch?v=D0H9FWsk_Ck

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 Details of a tray
http://www.youtube.com/watch?v=D0H9FWsk_Ck

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Vapor liquid contact in a tray

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 Where do we get the liquid from?

More details are seen in the next Chapter

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Batch distillation with reflux

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 FLASH CALCULATION, multi components

➢ Isothermal flash calculations

In this process an entering stream (a liquid at high pressure) flash as it
comes into a vessel that is at lower pressure. Significant quantities of
both liquid and vapor phases are formed.

V= vapor flow rate (moles/ time)

L= Liquid flow rate (moles/ time)
F= Feed flow rate (moles/ time) TV=TL
zi,xi,yi= mole fraction of PV=PL
component i in the feed,
liquid, and vapor streams
respectively.
 FLASH CALCULATION, multi components

➢ In a typical isothermal flash calculation,

Given: F , zi , T and P in the vessel.
unknown: V , L, yi , and xi.

We have (C) component balances, C more equations are required. They

are obtained from phase equilibrium.

Total mass balance (1 eqn )

F = L +V (1)
 FLASH CALCULATION

Component mass balance (C) equation:

Fzi = Lxi +Vyi (2)

Phase equilibrium (C) equation: γ :Activity coefficient
yi Pisat iL
= Ki = (3)
xi P
(3) and (1) are substituted in (2 ):

Fz i = ( F − V ) xi + VK i xi (4)
Solving for xi:
zi F
xi = (5)
F − V + VKi
 FLASH CALCULATION

Dividing numerator and denominator by F yields

zi
xi = (6)
1+ (V / F )[ Ki −1]
If the system is ideal, iL= 1.0, Ki =Pisat/P

zi
xi = (7)
Pisat
1+ (V / F )[ −1]]
P
Equations 6,7 can be written for each of the (C) components in the system

i =C

i =C
zi 

i =1
xi =   
i=1  1+ (V / F )[ Ki −1] 
= 1.0
 FLASH CALCULATION

zi K i
If yi = K i xi and yi =
1 + (V / F )[ Ki − 1]

i =C i=C  zi K i 
Then 
i =1
y i =   
i=1  1+ (V / F )[ Ki −1] 
= 1.0

A flash calculation is an iterative trial and error procedure where the

problem is to guess (V/F) ratio until:
i =C
 xi = 1.0
i=1
 FLASH CALCULATION

➢ Flash calculation iteration for ideal systems

➢ The first thing to do in any flash calculation is to make sure that something
will flash (there is liquid and vapor phases).
➢ If we are in a region where nothing flashes P of the system must higher
than the bubble point P of the feed at the specific T.
sat sat
zi Pi i=n
z i Pi

Saturated liquid line
yi = , = 1.0 T= constant
P i=1 P Sub-cooled x
i=n PBP liquid y
PBUB =  z i Pi
Saturated

Pressure
sat
P vapor line
i=1 1 PDP

 z P 
i =C
sat
P BUB= i i
Superheated
i =1 Vapor
If P>PBUB, nothing will flash, V/F=0 0 xDP x1 z y1 yBP 1.0
and xi=zi x,y
 FLASH CALCULATION

i=n i=n

 xi = 
zi P
Dew point sat
= 1.0
i =1 i =1 Pi
1
PDew = i =C PDew =
1
 sat 
 z i/ P  i=n sat 
 i i 
i  z / P
 i =1 
 i =1 

If P< PDew, every thing flashes, V/F=1 and yi=zi

Once we know that two phases will be present, equation (7) must be
solved for (V/F).
 FLASH CALCULATION
Example: A liquid feed stream containing 40 mole perercent benzene,
35 mole percent toluene and 25 mole percent o-xylene is flashed
to 110°C and 760 mm Hg (14.7psia). Determine the flow rates and
compositions of the vapor and liquid streams after the flash for 100
kg-mole/hr of feed. The VLE relationships can be assumed to be
ideal. i.e the system obeys Raoult's Law.

30 mole perercent benzene, 40 mole percent toluene and 30 mole

percent o-xylene
Solution

The first thing to do in any flash calculation is to check whether the actual
pressure P is between the bubble point and dew point pressures of the feed at
the operating temperature.

The vapor pressures at 110°C (230°F) are read from the Cox chart.
 FLASH CALCULATION

V=?
Pisat at 110 oC from Cox chart. y1= ?
y2=?
Benzene (1) = P1sat = 33 psia y3=?
F
Toluene (2)= P2sat = 14 psia . 100 kgmole/hr
TV=TL=110 oC
PV=PL= 1 atm
O-Xylene (3)= P3sat = 5.6 psia z = 0.4
1

z2=0.35 L=?
x1= ?
z3=0.25
PBUB =  zi Pi sat 
i =C x2=?
x3=?
i=1
1
PDew =
i=C sat 
 i i 
( z / P
 i =1 

PDew < P=14.7 psia < PBUB So there are two phases in the drum (vap. and liq. phases
 FLASH CALCULATION

Guess: V/F = 0.5, 0.7 and 0.65

zi
xi = xi Pisat
1+ (V / F )[i
Psat
−1]
yi = Raoult's law
P P

V/F=0.5 V/F=0.7 V/F=0.65 yi

Component zi Pjsat xi xi xi (at V/F=0.65)
Benzene 0.4 33 0.247 0.214 0.22 0.496
Toluene 0.35 14 0.359 0.362 0.36 0.344
O-xylene 0.25 5.6 0.362 0.441 0.42 0.159
Total 1.000 0.968 1.017 1.00 0.999
 FLASH CALCULATION

V =(V/F)* F =0.65 * 100= 65 kg mole/ hr

L= F - V = 100 - 65 = 35 kg mole/hr