Ch i l Engineering

Chemical
E i
i Operations
O
i
Distillation
Dr. A
D
Anand
dV
V. P
Patwardhan
t
dh
Professor of Chemical Engineering
Institute of Chemical Technology
Nathalal M
M. Parikh Road
Matunga (East), Mumbai-400019
av patwardhan@ictmumbai edu in; avpuict@gmail
av.patwardhan@ictmumbai.edu.in;
avpuict@gmail.com;
com; avpiitkgp@gmail.com
avpiitkgp@gmail com
1

REVIEW of the following BASICS of BINARY

distillation:
1 Vapour liquid equilibrium
1.
2 Relative volatility
2.
3. Enthalpy
Enthalpy-Concentration
Concentration Diagram
4. Application of enthalpy
enthalpy-concentration
concentration diagram to
FLASH distillation of a BINARY mixture
5. Steam distillation
6. Differential distillation / Rayleigh distillation

7. Continuous multistage fractionation of binary mixtures

(McCabe Thiele method)
(McCabe-Thiele
a) Material and energy balances
b) Determination of number of stages
c) Total reflux Fenske
Fenskess equation Minimum
number of stages
d) Minimum reflux ratio

8. Continuous multistage fractionation of binary mixtures

(Ponchon Savarit Method)
(Ponchon-Savarit
a) Determination of number of stages
b) Minimum reflux ratio
c) Total reflux

 Distillation: Technique of preferential separation of

MORE VOLATILE COMPONENT(s) from LESS
VOLATILE COMPONENT(s) by PARTIAL
VAPORISATION followed by condensation.
VAPORISATION,
condensation
Distribution of components in two phases = function of
(vapour-liquid equilibrium).
Distillation column consists of:
Column
C
having
i trays or packing
i and suitable
i
internals
i
Reboiler
Condenser
5

Functioning of distillation column:

Feed enters at a suitable point.
Reboiler partially vaporises the liquid received from
the column bottom.
bottom
Vapour flows UP through the trays (or packing),
packing) leaves
at the column top and enters into overhead condenser.
A part of the condensate is withdrawn as TOP
PRODUCT,, and the rest is fed back to the column as
REFLUX that flows down the trays (or packings).
6

 Intimate contact between UPFLOWING vapour and

DOWNFLOWING liquid
liq id occ
occurs
rs on the trays
tra s (or
packing).
EXCHANGE of mass takes place between the liquid
and vapour phases: M
M.V.C.
V C from liquid vapour;
L.V.C. from vapour liquid.

Typical
di till ti
distillation
column

Vapour
3
4

F
Feed

Steam
Condensate

Reflux
1

F: Feed (L, V, or a mixture of

L and V)
D: Distillate or top product
W: Bottom product
1: Distillation column
2: Feed preheater
3: Condenser
4: Reflux drum
5: Reboiler

5
W

Vapour-Liquid Equilibrium
Under a given set of conditions, the equilibrium vapour
composition is related to the liquid composition.
Gibb's Phase Rule
F
where C

number of components

number of phases

degrees of freedom

Example
Aqueous solution of C2H5OH in a closed vessel fitted
with a valve
Boiled for some time to expel the air contains only
H2O + C2H5OH
Vessel put in a constant temperature bath for sufficient
time
System
y
reaches equilibrium
q
L and V compositions,
p
,
and PT in the vapour space attain unique constant
values
10

Number of Components = 2 (C2H5OH and H2O)

Number of Phases = 2 (L and V)
Degrees of Freedom = 2
Total number of parameters = 4 (T, PT, L
composition V composition)
composition,
2 of these 4 parameters can be fixed to define
system COMPLETELY

11

 Accurate Vapour-Liquid Equilibrium (VLE) data are

essential for reliable design of a distillation column.
col mn
If the experimental data are not available
(multicomponent systems), a suitable predictive method
can be adopted
adopted, for example
example, UNIFAC method.
method
If data for prediction is also not available
available, conduct
experiments to determine the VLE.

12

TB
M1

Constant T & Constant P Binary V-L Equilibria

H
VAPOUR
N1
T-y
(dew point)

H1

M
G

Tx
T-x
(bubble point)

LIQUID

V
L1

zF

a
V1
TA

G1

Diagonal
y=x
Equilibrium (xy) diagram

(0, 0)

13

 At constant P: Boiling Temperature versus liquid

composition
iti T-x
T (bubble
(b bbl point)
i t) curve
At constant P: Boiling Temperature versus vapour
composition T-y (dew point) curve
Liquid at Point G heated gradually Point M
heating continued Liquid becomes progressively
POORER in A
Liquid
q
Boiling
g Point ((bubble p
point)) increases
Last liquid
q
droplet
p at M1
14

 Final VAPOUR at N1
further heating gives SUPERHEATED vapour
Same description can be given for LV, L1V1, G1H1

15

 F = amount of two-phase mixture, kmol (zF = mole

fraction)
L = amount of liquid,
liquid kmol (x = mole fraction)
V = amount of vapour,
vapour kmol (y = mole fraction)
Overall mole balance: F = L + V
Component A balance: F zF = L x + V y

y * z
L
length
g of section VF
F
Eli ti F :
Elimating

V
z x length of section FL
F
Lever Arm Rule
16

 Raoults Law: vapour-liquid equilibria for Ideal

Sol tions:
Solutions:
p

P v and p
A A
B

Total p
pressure

x Pv 1 - x Pv
A A
A B

Pv
B B

Mole fraction of A in vapour phase

P
A T

Pv
A A

1 - x

Pv
A B

PT

The above equation can is used to compute V-L

equilibrium data for IDEAL BINARY mixtures.
17

Deviation from Ideality and Formation of Azeotropes

POSITIVE deviation: a liquid mixture exerting an
equilibrium total vapour pressure more than that
computed by ideal equation.
NEGATIVE deviation: a liquid mixture exerting an
equilibrium total vapour pressure less than that
computed by ideal equation.

18

AZEOTROPES
LARGE POSITIVE deviation from ideality: vapour
pressures of A and B are not much different
different, the
TOTAL PRESSURE CURVE may have a MAXIMUM
at a certain liquid composition constant boiling
mixture minimum boiling AZEOTROPE.
x-PT and y-PT curves touch at Azeotropic Composition.
x-T and y-T curves pass through a common minimum.
The equilibrium curve crosses the diagonal line at the
azeotropic
p composition.
p
19

V-L Equilibria of a Minimum-Boiling Azeotrope (ethanol-benzene)

Equiliibrium prressure

x-PT curve
x-PB curve

x-PA curve
Ideal
behaviour

y
Azeotropic
point, x = y

(0, 0)

20

 LARGE NEGATIVE deviation from ideality: partial

press res of indi
pressures
individual
id al components are < ideal values,
al es
the TOTAL PRESSURE CURVE may have a
MINIMUM at a certain liquid composition constant
boiling mixture MAXIMUM boiling AZEOTROPE.
x-PT and y-PT curves touch at Azeotropic Composition.
x-T and y-T curves pass through a common minimum.
The equilibrium curve crosses the diagonal line at the
azeotropic
p composition.
p

21

RELATIVE VOLATILITY
Relative volatility of a component A in a mixture
indicates the EASE of its SEPARATION from another
component B.
y of A
Relative volatility

concentration of A concentration of B vapour

concentration of A concentration of B liquid

y 1 y y 1 x

AB x 1 x x 1 y
x
y
1 1 x
22

 For IDEAL binary solutions, can be expressed in

terms of vapour
apo r pressures
press res of the components:

p P
p P
y 1 y
A
T
B
T

x 1 x
p
Pv
p
Pv
A A
B B
P v vapour
p
p
pressure of A
A

v
vapour pressure of B
P
B

23

Equilibrium in a Multicomponent System

Hydrocarbons of a homologous series are nearly ideal
solutions.
For an IDEAL solution, we can write:
i

n
y P p x P v and P p
j T
j
j j
T
i
i 1
v
x P
p
j j
i
y

j P
i n
v
T
x
P

i i
i 1
where
h
P v = vapour pressure off pure componentt j
j

24

Since P v P v the above equation is rew ritten as:

ij
i
j
x
x
j
j
y

j
in

x
1 in
v
i ij
x
P

v
i1
i
i
Pj i 1

F hydrocarbon
For
h d
b mixtures,
i
a quantity
i called
ll d equilibrium

ilib i
vaporisation ratio is extensively used:
Pv
K i i
i x
P
i
T
y

25

Equilibrium in a nonideal system

At equilibrium, the FUGACILITIES of component i in
the vapour phase and in the liquid phase are EQUAL.

fV fL
i
i
V
V
L
L
0
f F y P and f F x P x g f
i
i i T
i
i i T
i i i
where,
F V fugacity coefficient of component i in vapour
i
g activity coefficient of component i in liquid
i
f 0 fugacity
g
y of component
p
i at standard state
i
26

 For low-to-moderate pressures, the fugacity at

standard state can be appro
approximated
imated to the vapour
apo r
pressure at the given temperature, that is:

L
v
f x P
i
i i i
Thus, at equilibrium : V y P x P v
i i T
i i i

27

ENTHALPY-CONCENTRATION DIAGRAM
Change in composition is accompanied by a change
in enthalpy. For a given T and concentration x of a
liquid, the molar enthalpy HL can be calculated using
the equation:

HL = cPS Mav (T T0) + HS

HL = molar enthalpy of solution at T, kJ/kmol
CPS = specific heat of solution, kJ/(kg K)
Mav = average molecular weight of solution
T0 = reference temperature, K
HS = heat
h t off solution
l ti att T0, kJ/kmol
kJ/k l
28

ENTHALPY-CONCENTRATION DIAGRAM
Since the heat of mixing of the vapour is negligible,
we can use the following equation to compute the
molar enthalpy of the saturated vapour HV at a
given T and y:

HV = y MA {cPA (T T0) + A}
+ (1 y) MB {cPB (T T0) + B}
cPA, cPB = specific heats of pure LIQUIDS A and B,
kJ/(kg K)
A, B = heats
h t off vaporisation
i ti off A and
d B att
temperature T, kJ/kg
29

ENTHALPY-CONCENTRATION DATA (Example)

Aceone (A)-Water (B) system at 1 atm total P. Integral heat of solution (15 0C) at
different concentrations
concentrations, specific heat of solutions and xx-yy data are given:
T, 0C

HS

cPS

56.5

0.54

57

0.95

0.963

0.56

57 5
57.5

09
0.9

0 935
0.935

10
10.55
55

0 56
0.56

58.2

0.8

0.898

23.88

0.61

58.9

0.7

0.874

41.11

0.66

59.5

0.6

0.859

60.3

0.7

60

0.5

0.849

83.56

0.75

60 4
60.4

04
0.4

0 839
0.839

121.5
121 5

08
0.8

61

0.3

0.83

171.7

0.85

62.2

0.2

0.815

187.7

0.9

66.6

0.1

0.755

159.7

0.96

75.7

0.05

0.624

106.8

0.98

91 7
91.7

0 01
0.01

0 253
0.253

22.2
22 2

100

Average specific heat of liquid

acetone = 0.57
0 57 kcal/(kg K)
Specific heat of water = 1
kcal/(kg K)
Heat of vaporisation of acetone =
A = 128.8 (T 0C 50), kcal/kg
Average heat of vaporisation of
water = B = 550 kcal/kg

30

x-y-H (Enthalpy-Concentration Diagram)

15000 kcal/mol

(HV)2

F
W

y HV curve
y-H

N
J

Tie Lines
(HV)1
x-HL curve

(a)

x y
x,

(b)

y
R
(0, 0)

31

ENTHALPY-CONCENTRATION DIAGRAM
The amount of vapour and liquid phases SEPARATED
can be determined by Lever Arm Rule
Rule.
Point R on x-y diagram corresponds to Tie Line WD.
WD
Point Q on x
x-y
y diagram corresponds to Tie Line IJ.
IJ
Consider 2 solutions whose states (H and x or y) and
amounts are given by M and N. After MIXING, the
resultant solution is P. Hence,,

32

Total material balance: M + N = P

Component A balance: M zM + N zN = P zP
Enthalpy balance: M HM + N HN = PHP
Eliminating P: M/N = (zN zP)/(zP zM)
Eliminating P: M/N = (HN HP)/(HP HM)
(HN HP)/(zN zP) = (HP HM)/(zP zM)
Slope of section NP = Slope of section MP
Points M, N, and P are collinear.

33

FLASH
di ill i
distillation
unit
Feed
F zF , HF
F,

Vapour

Baffles

Top product
D, xD = yD , HD
Flash drum

+Q

Bottom product
W, xW , HW
34

Flash vaporisation of a BINARY MIXTURE

If a sufficiently hot liquid is THROTTLED into a
vessel a part of it vaporises vapour will be richer in
vessel,
MVC partial separation.
The liquid is heated under Pressure, and throttled into
a vessel under Reduced pressure
pressure.
Let the Flow Rate, Composition, Enthalpy of FEED,
DISTILLALATE (TOP), and BOTTOM products be
((F,, zF, HF), (D,
( , xD, HD), (W,
( , xW, HW), and Q be the rate
of supply of heat exchanger:
35

Total material balance: F = D + W

Component A balance: F zF = D xD + W xW
(D + W) zF = D xD + W xW
Enthalpy balance : F HF + Q = D HD + W HW
Q

H H
x
z

D F F
W
D
F
Eliminating F :

Q
D x z

W
F H H
W F F

36

Flash Vaporisation of a Binary Mixture

En
nthalpy (H
HL, HV),
kcal/km
mol

15000 kcal/mol

y-HV

F (z
( F, HF + Q/F)

(a)

x-HL

W
F1

x y
x,

1
P

(b)

F (zF, zF)
x z
W
F
Slope =
D
x
z
D
W
F

(0, 0)

37

Flash vaporisation of a BINARY MIXTURE

Cold feed at F1 passes through preheater receives
Q heat energy hot feed F FLASHES into vapour
(D) and liquid (W) upon throttling into the flash drum.
The enthalpy and composition of vapour (D) and liquid
(W) streams are obtained by drawing TIE LINE
through F.
The point F(zF, zF) is located on the diagonal of x-y
p
plot.

38

 Point P is located on the equilibrium curve such that

the slope of the line FP = W/D.
W/D The line FP is the
operating line for flash vaporisation process.
By using the H-x-y and x-y curves, the amounts and
compositions of D and W can be calculated for a given
feed for given Q.
Alternatively, if the fraction of feed to be vaporised is
specified, the required Q can be computed.
The analysis
y can be extended to the case of a real stage
g
with a given value of stage efficiency (How ?).
39

STEAM
DISTILLATION
unit
it

Vapour

Receiver

Feed
B
(water)

Steam
coil
Open
steam

Steam
St
sparger
Residue

40

Steam Distillation
For an ideal binary solution, yA = pA/PT = (xA PAV)/PT
However, if A and B are IMMISCIBLE, their mixture
exerts a vapour pressure = (vapour pressures of
individual components).
Hence the BUBBLE POINT of such a mixture < boiling
point of either A and B.
Process: Live steam is p
passed through
g a liquid
q
A
vaporises leaves WITH steam condenser 2
y
((A and B)) separated
p
by
y decantation.
layers
41

Applications of steam distillation:

Separation of high boiling materials (decolourisation,
deodourisaion of vegetable oils,
oils purification of essential
oils).
Separation and purification of hazardous materials like
turpentine
Separation of thermally unstable materials
Separation
p
of volatile impurities
p
from waste water
(removal of ammonia, VOCs)
42

Separation of A immiscible with water

PT = PAV + PBV PBV = PT PAV
If mA moles of A are volatilised by putting in mB moles
of steam
steam, and if the system operates at equilibrium
equilibrium,

mA/mB = PAV/PBV = PAV/(PT PAV)

mA = mB PAV/(PT PAV)
However,, if the system
y
does not operate
p
at equilibrium,
q
,
pA < PAV
43

 A factor called vaporisation efficiency E is defined =

pA/PAV
mA = mB E PAV/(PT PAV)
The above equation can be used to compute the steam
requirement.
The vaporisation efficiency usually ranges from 60% to
90%.

44

BATCH DISTILLATION of a Binary Mixture

(Differential Distillation / Rayleigh
Ra leigh Distillation)

Cooling
water

L, LA, x
Kettle
(still)

yD,ave

Steam
45

 Equilibrium is assumed in the still.

Feed is charged to a still pot.
Heat is continuously supplied.
As boiling continues, MVC in liquid decreases with
time
Vapour is led to condenser
The condensate ((top
pp
product)) is collected in a receiver.
At the beginning,
g
g, the condensate is veryy rich in MVC.
46

 MVC in the condensate decreases with time.

Applicable when the components greatly differ in
volatility and when ultra
ultra-pure
pure products are NOT
required.

47

BATCH DISTILLATION of a Binary Mixture

Analysis is based on differential mass balance.
Let, at instance of time,

LA(t) = moles of A at any time t left in kettle liquid

LB(t) = moles of B at any time t left in kettle liquid
L = total moles of liquid left in kettle at time t, LA(t) +
), having
g mole fraction x
LB((t),
dL = moles of liquid
q
vapourised
p
between time t and t+dt
48

D = total accumulated moles of condensate up to time t

dD = moles of condensate accumulated between time t
and t+dt
x(t) = mole fraction of A remaining in kettle at time t
y(t) = instantaneous mole fraction of vapour produced

49

 Consider the vaporisation of liquid taking place

bet een time t and t + dt,
between
dt

dL = total moles evaporated

dD = dL
dL (total balance)
Moles of A evaporated can be given by
by,

dLA = d(x L) = x dL + L dx
The mole fraction of vapour
p
p
phase will be computed
p
as
follows, only on the basis of dLA, because y(t) =
p
p
produced,,
instantaneous mole fraction of vapour
50

moles of A vapourised between time t and t+dt

y
t t l moles
total
l vapourised
i d between
b t
ti
time t and t+dt
d Lx
xdL Ldx
y
y
ydL xdL Ldx
dL
dL
dL
dx
Ldx ydL xdL Ldx dL y x
dx
L
y x
If distillation starts with F moles of feed (xF), and
continues till the liquid reduces to W moles (xW),
) above
equation is integrated as:
x
W dL
W dx
dx

L
y

F
x
F
51

F dx
F
ln

... Rayleigh
a leigh eeq
quation
W x yx
W
If x-y data is available, the RHS can be solved
g p
graphically.
y

If y = f(x)
( ) is available, RHS can be solved analytically
y
y/
numerically.
If = Ave, then RHS can be solved analytically, as
follows:

52

W
F
dx
ln

x
W x
x
F 1 1 x

x 1 x
1 x
1
F
W
W

ln
ln
1 x
1 x
1 x
W
F
F

In a more convenient form,

Fx

F 1 x

F
F
ln
ln
Wx
W 1 x
W
W

53

 The above equation involves 4 quantities: F, W, xF, xW.

The AVERAGE composition of the ACCUMULATED
distillate is given be TOTAL and COMPONENT
material balances:
Total material balance: F = Dfinal + W
Component material balance:

FxF = DyD,Ave + WxW

54

Continuous Multistage
Fractional Distillation of
Binary Mixtures

55

Rec
ctifying
g
se
ection
Feed
F, zF , HF

Vapour
QC

1
n

Striipping
sec
ction

m
N

Ln
xn
HL,n

Vn+1
yn+1
HV,n+1

Envelope 1
Envelope 2

Top
pp
product
D, xD, HD

Lm Vm+1
xm
ym
m+11
HL,m HV,m+1

Envelope 3
Envelope 4

Vapour
+QB

Bottom product
W, xW , HW
56

MATERIAL AND ENERGY BALANCE EQUATIONS

The determination of number of stages is based on
steady state M & E B equations over the ENVELOPES
as shown in the Figure.
L & V: liquid and vapour flows ABOVE the feed
location.
location
L
L &V
V:: liquid and vapour flows BELOW the feed
location.
Ln & Vn = molar liquid and vapour flow rate LEAVING
nth stage.
g
57

 HL,n & HV,n = molar liquid and vapour enthalpy

LEAVING nth stage.
stage
L0 = flow rate of reflux to the top stage (suffix 0
signifies that the stream is as if coming from a
hypothetical 0th stage above top stage.
stage
QC = heat removal rate from overhead condenser.
condenser
QB = heat supply rate to reboiler (to vaporise a part of
the liquid leaving the bottom stage).
F = feed rate to the column.
58

 zF = mole fraction of MVC in feed.

D = rate of distillate removal from reflux drum.
xD = mole fraction of MVC in distillate.
W = rate of bottom product removal from reboiler.
xW = mole fraction of MVC in bottom product.
L0/D = R = reflux ratio.

59

Vapour: V1, y1, HV1

Stage 1

Reeflux: L0, x0, HL0

QC

Envelope 1

Top product:
D, xD, HD

60

ENVELOPE 1
( d
(condenser
+ reflux
fl drum)
d
)
Overall
O
ll balance:
b l
V1 = L0 + D = R D + D = D (R + 1)
Component A balance:
V1 y1 = L0 x0 + D xD
Enthalpy balance:
V1 HV1 = L0 HL0 + D HD + QC
QC = D { (R + 1) HV1 R HL0 HD }
Pl
Please
note:
t y1 = xD = x0 (for
(f ttotal
t l condenser)
d
)

61

Vapour

QC

Envelope 2

Rectifying
section

Stage n
Top product
D, xD, HD
Ln Vn+1
xn ynn+11
HL,n HV,n+1

62

ENVELOPE 2
(
(part
off rectifying
if i section
i + condenser)
d
)
Overall
O
ll balance:
b l
Vn+1 = Ln + D
Component A balance:
Vn+1 yn+1 = Ln xn + D xD
Enthalpy
E
th l b
balance:
l
Vn+1 HV,n+1 = Ln HL,n + D HD + QC
If you put n = 0, equations for Envelope 1 are obtained !
63

S
Stripp
ping
sectiion

Stage m
Lm Vm+1
xm ym+1
+1
HL,m HV,m+1

Envelope 3
Vapour
+QB

Bottom
B
tt
product
d t
W, xW, HW
64

ENVELOPE 3
(
(part
off stripping
i i section
i + reboiler)
b il )
Overall
O
ll balance:
b l
Lm = Vm+1 + W
Component A balance:
Lm xm = Vm+1 ym+1 + W xW
Enthalpy
E
th l b
balance:
l
Lm HL,m + QB = Vm+1 HV,m+1 + W HW

65

Vapour
Q
QC
Rectifying
section

Feed:
F,, zF, HF

Top product:
D xD, HD
D,

Feed
stage
Stripping
section

Envelope 4
Vapour
+QB

Bottom product
W, xW, HW
66

ENVELOPE 4
( i column
(entire
l
+ condenser
d
+ reboiler)
b il )
Overall
O
ll balance:
b l
F=D+W
Component A balance:
F zF = D xD + W xW
Enthalpy
E
th l b
balance:
l
F HF + QB = D HD + W HW + QC

67

 Above the FEED POINT: Vapour is enriched OR

p rified b
purified
by discarding the LVC into the
downflowing liquid MVC concentration in
vapour is more than that in the feed Rectifying
OR enriching section.
Below the FEED POINT: MVC is removed or
stripped out of the downflowing liquid MVC
concentration in vapour is less than that in the feed
stripping section.

68

 Flow rate, composition, state of FEED: T, P, phase, etc.

Feed ma
may be L,
L V,
V or V+L (two-phase).
(t o phase)
Required degree of separation: requirement of
QUALITY or PURITY.
Reflux ratio and the condition of the reflux: The ratio of
reflux FED BACK to the top and the top product
WITHDRAWN. Reflux may be SATURATED liquid or
SUB-COOLED
SUB
COOLED liquid.

69

 Operating pressure and allowable pressure drop across

the column:
col mn: operating press
pressure
re also determines the
TEMPERATURE of column.
P = f(type, number of hydraulic design of trays OR
type and size of packings)
packings).
P is very important if the column is run at
LOWER PRESSURES.
Tray / packings type: determine the efficiency of
separation.
p

70

Number of Trays: McCabe-Thiele Method

Developed in 1925: graphical solution of material
balance equations together with the equilibrium
relation x-y (or equilibrium data).
ASSUMPTIONS:

1. CONSTANT MOLAR OVERFLOW of liquid (and

vapour) from one tray to another over any section of
the distillation column, that is:
L0 = L1 = L2 = ... = Ln = L (RECTIFYING section);
Lm = Lm+1 = ... = LN = L (STRIPPING section) 71

AND
V1 = V2 = V3 = ... = Vn+1 = V (RECTIFYING section);
Vm+1 = Vm+2 = ... = VN+1 = V (STRIPPING section)
2. Heat loss from distillation column is negligible. (If
there are heat losses,
losses there will be NET condensation
within the column, leading to a corresponding variation
in the flow rates along the column.

72

Steps:
(1) Draw equilibrium curve using available x-y data
(2) Draw operating lines for the rectifying and the
stripping sections
(3) Draw the STEPS between the equilibrium curve
and the operating lines to find out the number of
IDEAL stages.

73

The RECTIFYING Section

ENVELOPE 2 (part of rectifying section + condenser)
Component A balance: Vn+1 yn+1 = Ln xn + D xD
L

L
0
Since R

D D

CMO: constant molar overflow

x
L
D
LD
x D
y
x x
n1 V n V D V D n V D
y n 1

xD
R

xn
R1
R1
74

 The above equation is a STRAIGHT line,

Slope = R/(R+1)
Y-intercept = xD/(R+1)
The line satisfied by xn = xD; yn+1 = xD
This equation is called the operating line for
RECTIFYING section
section..

75

The STRIPPING Section

ENVELOPE 3 (part of stripping section + reboiler)
Component A balance: L xm = V ym+1 + W xW
Since V L W
L
W
y

x
x
m 1 V m V W
L
W
y

x
x
m 1 L W m L W W

76

 The above equation is a STRAIGHT line,

Slope = L/(LW)
The line satisfied by xm = xW; ym+1 = xW
This equation is called the operating line for
STRIPPING section
section.

77

The FEED line

Consider the plate ON WHICH the feed is introduced
(feed plate).
plate)

L,, HL,f1
L f1 V, HV,f
Vf
F, zF,
HF

L, HL,f V, HV,f+1

78

Total material balance: F + L + V = L + V

Enthalpy balance:
F HF + L HL,f1 + V HV, f+1 = L HL,f + V HV,f
Assuming Uniform Enthalpy:
and HV,f+1
V f+1 HV,f
V f HV

HL,f1 HL,f HL

F HF + L HL + V HV = L HL + V HV
((L L)) HL = ((V V)) HV + F HF
79

Eliminating V and V,
L L H V H F

q say
F
H H
V
L
heat required to convert 1 mole of
FEED to saturated vapour
q
heat required to convert 1 mole of
SATURATED FEED to saturated vapour

heat required to convert 1 mole of

FEED to saturated vapour

molar heat of vaporisation

of the saturated liquid

80

 L L = increase in the liquid flow rate across the feed

stage as a res
result
lt of introd
introduction
ction of the feed

= Rate of LIQUID INPUT with the feed

LIQUID FRACTION in the feed

heat required to convert 1 mole of

FEED to
t saturated
t t d vapour
Also, q
molar heat of vaporisation
of the saturated liquid

Feed at its bubble point (saturated liquid): q = 1

Feed at its dew point (saturated vapour): q = 0
If feed is a two-phase mixture, q = fraction of liquid in
the feed (1 q) = quality of the feed

81

 If the point of intersection of RECTIFICATION

operating line and STRIPPING operating line is (x,
( y),
)
then:

V y = L x + D xD and V y = L x W xW
Subtracting the above equations, and using the equation
for component balance for the complete column (F zF =
D xD + W xW), we get:

(V V
V)) y = (L L
L)) x + (D xD + W xW) = (L L
L)) x + F zF
Total material balance on feed plate:
p

F + L + V = L + V
82

 Using the above two equations, and the definition of q,

wee get the equation
eq ation of FEED LINE:

z
q
y
x F , passing
i through
h
h z ,z
F F
q 1
q1
and the intersection of two
two ope
operating
rating lines

83

 The number of IDEAL STAGES are determined by step

(staircase) constr
construction
ction bet
between
een the equilibrium
eq ilibri m curve
c r e
and operating lines.
(xn, yn): on equilibrium curve.
(xn, yn+1): on operating line.
Construction may start from either D (xD) or W (xW).
When the FEED LINE is crossed, a CHANGEOVER
from one operating
p
g line to the other is done (that is, a
transition from RECTIFICATION to STRIPPING
section,, or vice versa).
)
84

1. If feed is Superheated Vapour: feed line has +VE slope

(q < 0): Explain.
2 If feed
2.
f d is
i Saturated
S t
t d Vapour:
V
f d line
feed
li is
i horizontal
h i
t l
(q = 0): Explain.
3. If feed is Liquid + Vapour: feed line has VE slope
(0 < q < 1): Explain.
Explain
4 If feed is Saturated Liquid: feed line is vertical
4.
(q = 1): Explain.
5. If feed is Subcooled Liquid: feed line has +VE slope
(q > 1): Explain.
85

Various Types of Feed Lines

4

3
Subcooled L
( ))
(+,

V+L
(, +)
2

Saturated L (, )

F
Saturated V ((0, +))

1
Superheated
S
h t dV
(+, +)

L L H V H F
q

F
H H
V
L
z
q
x F
Feed line: y
q1
q1
86

Feed Tray Location and Number of Ideal Trays

D
N

M
S
E

Feed =
S
Saturated
Liquid
i i

W
87

TOTAL REFLUX
If the liquid from overhead condenser is TOTALLY
recycled to the column (D = 0),
0) the column is said to
run at total reflux. Also no product is drawn from
the reboiler either there should not be any Feed.
Feed

R = L0/D = L0/0 =
Operating line for Rectifying section
x
R
D
y

x
n1 R 1 n R 1
When R , Slope 1, Y-intercept 0
Operating line coincides with DIAGONAL
88

 Naturally, the number of stages corresponding to

infinite R are minimum.
minim m
Total reflux is very often used during the startup of a
distillation column till the steady state is attained.
After this, continuous flow of feed, top product, and
bottom product withdrawal are
SIMULTANEOUSLY started.

89

Fenskes equation
Used to compute theoretically the minimum number of
trays if the relative volatility remains reasonably (more
or less) constant. It also assumes a total reboiler
(analogous to total condenser)
condenser).
If w is relative volatility of A at the reboiler
temperature, and xW, yW are Liquid and Vapour mole
fractions in the reboiler, then:
y
x
W
W
W 1 x
1 y
W
W
90

 The Vapour leaving the reboiler and entering the lowest

tra (Nm) has a mole fraction yW of component A
tray
A. The
Liquid leaving this tray has a composition xNm (xNm,
yW) lies on the Operating Line xNm = yW. Therefore,
Therefore
the above equation can be rewritten as:
x
x
Nm
W
W 1 x
1 x
Nm
W
Applying the same procedure to the case of tray number
Nm, we get:
y
x
x
Nm
Nm
W

Nm 1 x
Nm W 1 x
1 y
Nm
Nm
W
91

 Continuing the procedure up to the top tray (where y1 =

xD),
) wee get:
x
x
y
W
D
1 ...

1 2
Nm 1 Nm W 1 x
1 x
1 y
D
1
W
N 1 x
x

m
W
D

average
1 x
1 x

D
W

1
x
D
W
log
1 x
x
W
D

N 1
m

log

average
g

92

 The above equation is called the Fenskes equation,

which
hich is useful
sef l for the calculation
calc lation of MINIMUM
number of trays.

93

Minimum Reflux Ratio

This is exactly analogous to the (L/G)min for gas
absorption. This is based on the identification of
pinch point.

The following procedure is followed to determine Rm:

Locate the points D (xD, xD) and W (xW, xW) on the
DIAGONAL of the x-y diagram. These are the
terminal points of operating lines.
Draw the feed line through
g F from the known feed
composition zF, and feed quality (given by q); locate the
point of intersection of the feed line and the
p
equilibrium curve (x-y diagram). Call this point M. 94

 Join DM (operating line for rectifying section), and

e tend this line till the Y-axis.
extend
Y a is
Y
Y-intercept
intercept = E = xD/(Rm + 1).
1) Get Rm from the
intercept.
At Reflux Ratio = Rm, the number of stages for the
given separation are infinity (driving force becomes
ZERO at the PINCH POINT).

95

Minimum Reflux Ratio

D

M
F

Slope = Rm/(Rm + 1)

Yi t
Y-intercept
t = xD/(Rm + 1)

W
96

Sieve Tray

97

Tray Columns

98

Tray Deck

99

Reboilers

100

Reboilers
Bottom
Tray

Bottom
Tray
Heating
Medium

Heating
Medium

Bottoms
Product

Bottoms
P d t
Product
Circulating Pump

Forced Circulation

Vertical Thermosiphon
101

Reboilers
Bottom
Tray

Bottom
Tray
Heating
Medium

Bottoms
Product

Kettle

Heating
Medium
ed u

Bottoms
Product

Horizontal Thermosiphon
102

Feed Distributors

103

The Real
Real World

Fouled Structured Packing

Damaged Valve Tray

104

The Real
Real World

Plugged Distributor
Tray Blanking Strips

105

Valve Tray Deck

106

Major Tray Damage

107

Fouled Bubble Cap Tray

108

Structured Packings

Fair, J.R., Seibert, A.F., Behrens, M., Saraber, P.P., and Olujic, Z. Structured Packing
Performance Experimental Evaluation of Two Predictive Models, Industrial and
Engineering Chemistry Research 2000,
2000 39,
39 1788-1796.
1788-1796
109

Structured Packing Wetted Area

110

Ponchon Savarit Method (Number of Stages)

Calculations on an Enthalpy-Concentration (H-x-y)
diagram.
diagram
If the dew point and bubble point lines are more or less
straight and roughly parallel Latent heat of
vaporisation is basically constant with respect to
composition Prerequisite for constant molar
overflow, energy balances may be neglected.
If the saturation curves show significant
g
changes
g in
curvature constant molar overflow cannot be
assumed.
111

 H-x-y diagram is more general than a McCabe-Thiele

constr ction beca
construction,
because
se it takes direct account
acco nt of the
thermal effects and does not require an assumption of
constant equimolar overflow.
overflow
Feed and product points (F,
(F D,
D W) can be located on Hx-y diagram. The coordinates are their composition
and enthalpy
enthalpy.

112

Rec
ctifying
g
se
ection

Feed
F, zF , HF

Vapour
QC

1
n

Striipping
sec
ction

m
N

Ln
xn
HL,n

Vn+1
yn+1
HV,n+1

Envelope 1
Envelope 2

Top
pp
product
D, xD, HD

Lm Vm+1
xm
ym
m+11
HL,m HV,m+1

Envelope 3
Envelope 4

Vapour
+QB

Bottom product
W, xW , HW
113

MATERIAL AND ENERGY BALANCE EQUATIONS

The determination of number of stages is based on
steady state M & E B equations over the ENVELOPES
as shown in the Figure.
L & V: liquid and vapour flows ABOVE the feed
location.
location
L
L &V
V:: liquid and vapour flows BELOW the feed
location.
Ln & Vn = molar liquid and vapour flow rate LEAVING
nth stage.
g
114

 HL,n & HV,n = molar liquid and vapour enthalpy

LEAVING nth stage.
stage
L0 = flow rate of reflux to the top stage (suffix 0
signifies that the stream is as if coming from a
hypothetical 0th stage above top stage.
stage
QC = heat removal rate from overhead condenser.
condenser
QB = heat supply rate to reboiler (to vaporise a part of
the liquid leaving the bottom stage).
F = feed rate to the column.
115

 zF = mole fraction of MVC in feed.

D = rate of distillate removal from reflux drum.
xD = mole fraction of MVC in distillate.
W = rate of bottom product removal from reboiler.
xW = mole fraction of MVC in bottom product.
L0/D = R = reflux ratio.

116

Vapour: V1, y1, HV1

Stage 1

Reeflux: L0, x0, HL0

QC

Envelope 1

Top product:
D, xD, HD

117

ENVELOPE 1
( d
(condenser
+ reflux
fl drum)
d
)
Overall
O
ll balance:
b l
V1 = L0 + D = R D + D = D (R + 1)
Component A balance:
V1 y1 = L0 x0 + D xD
Enthalpy balance:
V1 HV1 = L0 HL0 + D HD + QC
QC = D { (R + 1) HV1 R HL0 HD }
Pl
Please
note:
t y1 = xD = x0 (for
(f ttotal
t l condenser)
d
)

118

Vapour

QC

Envelope 2

Rectifying
section

Stage n
Top product
D, xD, HD
Ln Vn+1
xn ynn+11
HL,n HV,n+1

119

ENVELOPE 2
(
(part
off rectifying
if i section
i + condenser)
d
)
Overall
O
ll balance:
b l
Vn+1 = Ln + D
Component A balance:
Vn+1 yn+1 = Ln xn + D xD
Enthalpy
E
th l b
balance:
l
Vn+1 HV,n+1 = Ln HL,n + D HD + QC
If you put n = 0, equations for Envelope 1 are obtained !
120

S
Stripp
ping
sectiion

Stage m
Lm Vm+1
xm ym+1
+1
HL,m HV,m+1

Envelope 3
Vapour
+QB

Bottom
B
tt
product
d t
W, xW, HW
121

ENVELOPE 3
(
(part
off stripping
i i section
i + reboiler)
b il )
Overall
O
ll balance:
b l
Lm = Vm+1 + W
Component A balance:
Lm xm = Vm+1 ym+1 + W xW
Enthalpy
E
th l b
balance:
l
Lm HL,m + QB = Vm+1 HV,m+1 + W HW

122

Vapour
Q
QC
Rectifying
section

Feed:
F,, zF, HF

Top product:
D xD, HD
D,

Feed
stage
Stripping
section

Envelope 4
Vapour
+QB

Bottom product
W, xW, HW
123

ENVELOPE 4
( i column
(entire
l
+ condenser
d
+ reboiler)
b il )
Overall
O
ll balance:
b l
F=D+W
Component A balance:
F zF = D xD + W xW
Enthalpy
E
th l b
balance:
l
F HF + QB = D HD + W HW + QC

124

Rectifying Section
ENVELOPE 2 (part of rectifying section + condenser)
Total material balance: Vn+1 = Ln + D
Component A balance: Vn+1 yn+1 = Ln xn + (Vn+1 Ln) zD
Ln / Vn+1 = (zD yn+1) / (zD xn)
Note: Reflux may be a sub-cooled liquid and hence the
composition
p
is denoted by
y zD.

125

Energy balance:
Vn+1 HV, n+1 = Ln HL,n + D (HD + QC/D) = Ln HL, n + D QD
where QD = Enthalpy removed from the TOP section of
the column per mole of distillate.
distillate
Substituting D = Vn+11 Ln :
Vn+1
QD
+1 HV,
V n+1
+1 = Ln HL,
L n + (Vn+1
+1 Ln) Q
Ln/Vn+1 = (Q
(QD HV,
(Q D HL,
V n+1))/(Q
L n)
The q
quantity
y Ln/Vn+1 is called internal reflux ratio.
126

 From the above two equations:

Q H
z y
D
V,n 1

D
n
1

z x
Q H
D n
D
L,n
Q H
Q H
D
Ln
L,n
D
V
V,n
n1

z x
z y
D n
D
n1
,
The 3 points z , Q , x , H

D
D n
L,n

and y
,H
, are COLLINEAR.

V,n 1
V,
n1
the points Ln , Vn 1 , and QD are COLLINEAR.

127

Point D (zD, QD) can be considered as a phase

obtained by
b subtracting
s btracting Ln from Vn+1.

Flow rate of phase D is also denoted by D = Vn+1 Ln.

However
However, NONE of the phases can have the
composition zD, and enthalpy QD = HD + QC/D.
The stream D is a fictitious stream defined for the
purpose of graphical construction.
D lies vertically
y above D,, because they
y have same
abscissa = zD.
128

 If D lies below H-x curve, D is sub-cooled liquid.

Put n = 0 D, D, V1 are collinear.
Point L1 (x1, HL1) is located by drawing a tie line from
V1.
L1D
D is joined to get point V2, and so on

129

Q H
Q H
V
D
V,n 1
D
L,n
n
n
1

Now:

V
Q H
L
Q H
n1
D
L,n
n
D
V,n 1
Q H
Q H
L
D

V
D
L,0
D
L,0
0
1
Put n 0

Q H
L
Q H
L
0
D
V
V,1
1
0
D
V
V,1
1
Q H
D
D
D
1

L
Q H
0
D
V,1
Q H
L
vertical distance DV
D
V,1
1
R 0

D H
H
vertical distance V D
D
V,1
1
L

130

 If the reflux ratio is given, the above relation is used

to locate D.
D
First
First, D (zD, HD) is located from the given state of the
distillate.
A vertical line through zD intersects the y-HV curve at
V1.
Then, obtain D
D so that the above relation for R is
satisfied.

131

Rectifying Section

HL , HV

y-HV curve
Vn+1

Vn

V3

V2 V1

x-HL curve
Ln

Ln1

L2

Tie lines

L1
D

Operating line SEGMENTS

00
0.0

x y
x,

zD 1.0
10
132

Stripping Section
ENVELOPE 3 (part of stripping section + reboiler)
Total material balance: Lm = Vm+1 + W
Component A balance:
Lm xm = Vm+1 ym+1 + (Lm Vm+1) xW
Ln / Vm+1 = (ym+1 xW) / (xm xW)

133

Energy balance:
Lm HL, m Vm+1 HV, m+1 = W HW QB = W (HW QB/W)
Lm HL, m Vm+1 HV, m+1 = W QW
where QW = Enthalpy supplied to the BOTTOM section
of the column per mole of bottom product.
product
Substituting D = L
Lm V
Vm+1
+1 :
Lm HL,
QW
L m Vm+1 HV,
V m+1 = ((Lm Vm+1) Q
Lm / Vm+1 = ((HV,
QW) / ((HL,
QW)
V m+1 Q
L mQ
134

 From the above two equations:

H
Q
y
x
V,m 1
W
m
1
W

x x
H
Q
m
W
L,m
W
Q
Q
H
H
V m1
V,m
W
L
L,m
m
W

y
x
x x
m1
W
m
W
,
The 3 points x , Q , x , H

W W m L,m

and y
,H
, are COLLINEAR.

,
m+1 V,m+1

that is, the points L , V

, and Q are COLLINEAR.
m m+1
W

135

 The flow rate of phase W is also denoted by W = Lm

Vm+1.
The stream W is a fictitious stream defined for the
purpose of graphical construction.
W lies vertically below W, because they have same
abscissa = xW.
V
V N+1 (reboiler vapour) should lie on the y
y-H
HV curve on
the tie line drawn from W.

136

 The line connecting VN+1 and W intersects x-HL curve

at LN (collinearity
(collinearit condition)
condition).
The tie line through LN intersects the y-H
y HV curve at
VN, and so on

137

Stripping Section

HL , HV

VN+1

VNV

N1

y-HV curve

V1

W L
N
x-HL curve
xW
0.0
W

x, y

D
zD 1.0

Tie lines
Operating
p
g line SEGMENTS
138

Feed Plate
A changeover from one section to the other is necessary
at the feed plate,
plate and hence feed line is required.
required
Consider the material and enthalpy balances over
envelope 4, that is, entire column + condenser +
reboiler.
reboiler
Component A balance:

((D + W)) zF = D zD + W xW ((D/W)) = ((zF xW) / (z

( D zF )

139

 Enthalpy balance:
(D + W) HF + QB = D HD + W HW + QC

D HF + W HF = D (HD + QC/D) + W (HW QB/W)

Q

H H C
F
D

H Q
D
D

F
Q
W
Q H
D
F
H B H
W W
F

z x
H Q
H Q
Q H
W F
W F
W D
F
F
z z
Q H
z x
z z
D F
D
F
F
W
D F
The 3 points W(xW, QW), F(zF, HF), and D(zD, QD)
are collinear.

140

 The intermediate point F(zF, HF) denotes the state of

feed in terms of composition and enthalp
enthalpy.
F(zF, HF) lies on the line joining D and W.
W
W
W:: a fictitious stream of flow rate W
W = L
Lm V
Vm+1.
D
D:: a fictitious stream of flow rate D
D = V
Vn+11 L
Ln.
F = D + W = D + W
Therefore, F, a real stream can be viewed as a stream
y mixingg the 2 fictitious streams D and W.
obtained by
The line DW is called feed line.
141

The steps (graphical) for obtaining the number of ideal

stages on H-x-y
H
diagram:
Data supplied (directly or indirectly): Concentrations
Concentrations,
Enthalpies, Flow Rates of Distillate, Bottom Product, as
well as Reflux Ratio.
Ratio
Points D,
D D
D, and F are located.
located
DF
D F is joined, and extended to meet the vertical line
{drawn through W(xW, HW)} at point W.
Stages can be constructed either from D or from W.
142

 A changeover has to be made after the feed line is

crossed.
crossed
The stage at which the changeover is made is feed
stage.
Construction continues till the other end point is
reached.
reached

143

The steps (graphical) for obtaining the number of ideal

stages on x-y diagram:
Draw the equilibrium curve (x-y
(x y diagram) using
separate axes below the H-x-y diagram using matching
scale.
scale
Locate (zD, zD) and (xW, xW) on the diagonal line.
line
Since any line starting from D
D and W
W intersects the H
Hx and H-y curves at xn and yn+1 respectively, the point
((xn, yn+1) is p
point on the operating
p
g line in the x-y
y
diagram.
144

 Several lines can be drawn from D and W, and for

each of these lines,
lines the point (x
( n, yn+1) is located on the
x-y diagram.
All these points are joined, giving rise to two curves;
these are the 2 operating curves,
curves namely,
namely rectifying
section operating curve and stripping section operating
curve.
curve
Since the flow rates in both these sections are not
constant (constant molar overflow is not applicable),
p
g lines are not straight.
g
the operating
Staircase construction g
gives the number of ideal stages.
g
145

Minimum Reflux Ratio

If a line through D or W coincides with tie line, the
corresponding (x,y)
(x y) values give a pinch point.
point
Reflux ratio is given by:
Q H
vertical distance DV
D
V,1
1
R 0

D H
H
vertical distance V D
V,1
D
1
L

The above relation indicates that the smaller the

V1 ((or the nearer the point
p
D to the H-x
distance DV
curve), the smaller is the reflux ratio.
146

 Most commonly, when the line DW coincides with the

tie line thro
through
gh the feed point,
point minimum
minim m reflux
refl ratio
occurs.
However, for some highly nonideal mixtures, it may
happen that a tie line through a point other than F
intersects the vertical line (drawn through zD) at the
smallest distance
distance. In that case
case, the same should be
taken as the true pinch point.
Once (D)min has been located on the H-x-y diagram,
p
using
g the
then the minimum reflux ratio is computed
above relation.
147

Total Reflux
In this case, the reflux ratio is infinite.
Naturally, the points D and W are located at infinity.
Therefore, all the lines through D and W are vertical
lines.
lines

The graphical construction involves:

Locate V1 vertically
y above zD, on the H-y
y curve.

148

 Draw a tie line from V1, which will intersect H-x curve
at L1.
Draw a vertical line from L1, which will intersect H-y
Hy
curve at V2.
Continue the above construction till xW is reached.
This (obviously) gives the minimum number of ideal
stages.

149