Equilibrium-Stage Separation

Processes
Rectification
EPFL
Master of Science in Chemical & Biochemical Engineering
Dr H. Randall

Rev1 11/2015

1
 Introduction
• Evaporation
– Separation of a non-volatile component from a volatile
one. (ex: water from salt). aAB=
• Distillation
– Single- or multi-stage separation of components of
different (but all>0) volatility without recycling of streams.
1<aAB<<
• Rectification
– multi-stage separation of components of different (but
all>0) volatility with recycling of streams. 1<aAB<<
 Simple binary distillation
Graphical solution 1
G, y1 L  L
Operating line: y1   x1  1   xF
G  G
F, xF
Equilibrium line

L, x1

3
Distillation: effect of relative
volatility G, y

F, xF

L, x

4
Distillation: effect of L/G
G, y

F, xF

L, x

5
 Simple binary distillation
Graphical solution 2
G, y1 L y1  xF b
Inverse lever rule:  
G xF  x1 a
F, xF

L, x1

6
 Multi-step distillation
Enriched in
most volatile
component
N

Feed 1
=heater

=condenser

Feed 1

N Enriched in
least volatile
component 7
 Multi-step distillation
y 4

y3

y2
x4
y1
x3

xF x2
y’2

y’3
x1
y’4
x’2

x’3

x4
8
 Multi-step distillation
Graphical solution 1
y4

y3

y2
x4
y1
x3
xF x2
y’2
y’3
x1
y’4
x’2
x’3
x’4

9
 Continuous rectification
y4

y3 All intermediate condensers and

4 heaters can be removed because
y2 Tdew>Tboil
3 x4
y1 Top stage still needs a condeser
2 x3 to produce a reflux
Bottom stage still needs a heater
xF x2
1 to produce a vapor stream
y’2 Stages above feed
2’ point=rectifying section (2-4 in this
y’3 case)
x1
3’ y’4 Stages below feed
x’2 point=stripping section (2’-4’ in this
4’ case)
x’3
x’4

10
 Batch Column (1)
VACUUM PUMP

CONDENSER VENT
WATER
GLYCOL

TRAP

REFLUX DISTILLATE
REFLUX VALVE
PRODUCT
COOLER

PISTON

STEAM

CONDENSATE
STILL 11
 Batch Column (2)
VACUUM PUMP

CONDENSER
TRAP

REFLUX VALVE

DISTILLATE
REFLUX
HEAT
EXCHANGER

PRODUCT
COOLER

12
 Continuous Column
CONDENSER
REFLUX
VALVE

DISTILLATE
REFLUX

PRODUCT
COOLER

FEED
HEAT
EXCHANGER

RESIDUE
13
 Rectification
G, xD
Total condenser

Rectifying
section
R, xD D, xD

F, xF
Stripping
section

B, xB

Partial reboiler 14
 External and internal reflux ratio
R
• External reflux rext 
D

L  C PL Tboil  Treflux
• Internal reflux rint   rext 1    rext
D  vH 
Drives the separation

G, Tsat
Tsat
Temperature

R, Treflux
D
Tboil
Treflux G

0 0.5 1
xA or yA
G+G L=R+G
 Operating lines
Mass balance envelope
G, xD for rectifying section
L  L
y x  1   x D
G  G
D, xD
G, y
R, xD
L, x

F, xF
Mass balance envelope
for stripping section
G’, y L’, x G’ L'  L' 
y x  1   x B
G'  G' 
L’
B, xB
16
 Operating lines
yN
Mass balance envelope yN-1
for rectifying section N D, xD
yj+1
M-1 xN
G, yj L  L
j+1 y  x  1   x D
y2
xN-1 G  G
j
y1 L, xj+1
2 xj
xF x2
1
y’2
2’ y’j
x1 G’, y’j+1
j’ L'  L' 
x’2 y x  1   x B
j+1’
y’N-1
G'  G' 
L’, x’j
N-1’ y’N
x’j+1
Mass balance envelope N’
for stripping section x’N-1
B, x’N=xB
17
Rectifying section operating line
L  L r 1 L
y  x  1   xD  x xD ; r  rint 
G  G 1 r 1 r D

L L
 1
G LD

18
Stripping section operating line
L'  L'  L' L  F q  1
y 
x  1   x B
G'  G'  G' G  qF

L' L'
 1
G ' L' B

19
 Constant molar overflow
• L/G and L’/G’ are constant in column if
– Equal latent heats of vaporization
– Sensible heat transport negligible compared to
heats of vaporization and condensation
– No heat of mixing in gas and liquid phase
– Adiabatic column

20
 Thermal condition of feed

G  G' hF  hL
G, y, hv L, x, hL q 
F hv  hL

F, xF, hF
Feed point Equation of q-line
(Locus of intersections of operating lines)

q 1 1
G’, y, hv L’, x, hL y x  xF
q q
See demo in pdf
 Thermal condition of feed
Feed=Saturated vapor Feed=between boiling Feed=Saturated liquid
and dew points

G L G L G L

F F F

G’ L’ G’ L’ G’ L’

G  G' G  G'
G  G ' F ; q   1 G '  G  G ' F ; 0  q  1 G  G' ; q  0
F F
q 1
q 1 0  ; L  L'  L  F q  1
 0; L  L' q  ; L'  L  F
q q
 Thermal condition of feed
Feed=super-saturated vapor Feed=liquid below boiling point

G L G L

F F

G’ L’ G’ L’

G  G' G  G'
G  G ' F ; q  1 G  G'; q  0
F F
q 1 q 1
0  1; L '  L  0; L'  L  F
q q
 Thermal condition of feed

Saturated liquid
y

y=x

Saturated vapor

xF

x
24
Estimation of q
 v H  C p , v TF  Tdew  hF  hL
1 q
v H vH
 v H  C p , v Tdew  Tdew 
1
a b v H

q  v H a
0  1; q 
v H ab
C p ,L Tboil  Tboil 
0
v H

C p ,L TF  Tboil 
0
v H

25
McCabe-Thiele construction
optimal feed location (1)

Fractional stage with EML=0.66

26
McCabe-Thiele construction
optimal feed location (2)
y4=yD
y3
y2
y1 x4
y'2
y'3 x3
y'4 x2
x1
y'5
x'2
y'6 x'3 x1 < xint < x2
x'4 xint
x'5

27
 McCabe-Thiele construction
optimal feed location (3)
y4=yD

y3 xD
y2
x4
y1
x3
xF x2
y’2
y’3
x1
y’4
x’2
x’3 y’5

x’4 y’6
Not at
equilibrium!
x’5 (frac. stage)
28
x’6
McCabe-Thiele construction
non-optimal feed location

29
McCabe-Thiele construction
non-optimal feed location

30
 Types of condensers
TOTAL PARTIAL

D, yD

R, xD D, xD

Can be considered
as 1 equilibrium
stage
 Minimum number of equilibrium stages
infinite reflux ratio
xD 1  xB 
ln
xB 1  xD 
N min 
ln a AB
FENSKE
 Minimum reflux ratio.
Pinch point on feed stage.
infinite number of stages

33
 Minimum reflux ratio.
Pinch point above feed stage
infinite number of stages

34
 Optimal reflux ratio

Total
Costs / kg product

Operational

Investment
Reflux ratio
1.2 rmin < ropt < 1.5 rmin

35
 Variables typically specified for
design or efficiency calculations
COLUMN DESIGN

• p, F, xF, hF , xD, xB, r, feed location

calculate N, D and B

COLUMN EFFICIENCY

• p, F, xF, hF , N, xD, r, feed location

calculate xB, D and B
High-purity specifications: combining McCabe
Thiele graphical method with Colburn eq.
High-purity specifications: combining McCabe
Thiele graphical method with Colburn eq.
N additional stages N additional stages
in stripping section in rectifying section

reboiler xF condenser
yAN+1 yBN+1
xA1
1 ... N N+1 ... F ... N+1 N ... 1 yB1
xAN+1 xBN+1
yA0 xB0
stripping section rectifying section

Red = specification
Purple = from McCabe-Thiele construction

y AN 1 y BN 1
KA  ; KB 
x AN 1 xBN 1
38
Column top: counter-current absorption
of heavy component B
Specification From McCabe-Thiele
yB1 yB2 yB3 yBj yBj+1 yBN G, yBN+1

B 1 B 2 B B j B B N B

L, xB0 xB1 xB2 xBj-1 xBj xBN-1 xBN

TOP BOTTOM

Liquid
from
condenser
 A 1 1  A
L
ln    K BG
 A f ' A
N  
A y B ,1  K B xB , 0 xB , 0  K B xB , 0
f 
'
A 
ln A y B , N 1  K B xB , 0 y B , N 1  K B xB39, 0
 Column bottom: counter-current
stripping of light component A
Specification From McCabe-Thiele
xA1 xA2 xA3 xAj xAj+1 xAN L’, xAN+1

A 1 A 2 A A j A A N A

G’, yA0 yA1 yAj-1 yAj yAN-1 yAN

BOTTOM TOP

Vapor from K AG '

reboiler S
 S 1 1  L'
ln    y A, 0 x A,1
S f' S x A,1  x A,1 
N  S  KA KA
f 
S
'

ln S y A, 0 x A,1
x A, N 1  x A, N 1 
KA K A40
Murphree efficiency in liquid phase
x j 1  x j a
EML  
x j 1  x * ( y j ) b

yj xj-1
b
yj
a Plate j

yj+1 xj
x
x*(yj) xj xj-1
Murphree efficiency in vapor phase
y j  y j 1 a
EMV  
y * ( x j )  y j 1 b
y

y*(xj) yj xj-1

yj b Plate j
a
yj+1

yj+1 xj
x
xj
Murphree efficiency line

43
Heterogeneous azeotropic distillation
A polar (ex. water); B less polar (ex. 1-butanol)

A is
most volatile Immiscibility zone

B is
most volatile

xaz1 xazxaz2

44
Heterogeneous azeotropic distillation:
column coupling

xaz1 < yD < xaz2 B+A xaz1 < y’D < xaz2
A+B
xaz1 xaz2
Decanter

Rectifyer Stripper
A+B

B A 45
Heterogeneous azeotropic distillation:
mass balances
2

yD y'D
xaz2

xaz1

G, y L, x
F, xF
3 G’’, y L’’, x

G’, y L’, x

1
B, xB S, xS
46
Heterogeneous azeotropic distillation:
operating lines
Column 1: rectifying

L  L L L
y  x  1   x S  1
G  G G LS
Column 1: stripping

L'  L'  L' L  F q  1 L' L'

y  x  1   x B   1
G'  G'  G' G  qF G ' L' B
Column 2: stripping

L' '  L' '  L' ' VB  1 G' '

y x  1   xS   1 VB 
G' '  G' '  G' ' VB S
47
Heterogeneous azeotropic distillation:
McCabe-Thiele construction
Rectifying op. line
column 1 (L/G)

y'D
yD Stripping op. line
column 2 (L’’/G’’)

q-line

Stripp. op. line col. 1 (L’/G’)

48
Heterogeneous azeotropic distillation:
Final design
y1=yD y’1=y’D

Fractional stage Fractional stage

xaz1
xaz2
1 1

x1 y2 x’1 y'2
xF 2 Rectifyer 2 Stripper

x2 y3 x'2 y'3
3 x3=xB 3
x'3 y'4
4 x'4=xS
49
Heterogeneous azeotropic distillation
Optimum L/G in both columns (I)
1. Determine (L’/G’)max and (L’’/G’’)max by increasing L’/G’ and L’’/G’’
until pinch points are obtained in both stripping sections

(L’’/G’’)max
Pinch points

q-line

(L’/G’)max

xB xF xaz1 xaz2 xS

50
Heterogeneous azeotropic distillation
Optimum L/G in both columns (II)

2. Compute minimum boilup ratios (G’/B)min and (G’’/S)min

3. Increase boilup ratios by multiplying them by an empirical
factor 1.2  Y  1.5
4. Determine working L’/G’ and L’’/G’’

51
 Reboiler heat duty

   
QB  G' y ( xB )V H A  1  y ( xB ) V H B
* *


G’, y*(xB)

Q B xB

52
 Condenser heat duty

Q C  GxD V H A  1  xD V H B 

G Q C
xD

53
 Azeotropic entrainment
aAB~1. Formation of a heterogeneous azeotrope
between A and water

Azeotrope
A / H2O (+B)

A (+H2O+B)
H2O
H2O (+A+B)

A+B

B 54
 Breaking a homogeneous azeotrope
A2=Hom. Azeotrope A3 A3
Ethanol / water
A3=Ternary het. azeotrope
Cyclohexane (C) / water / ethanol C / EtOH
(+H2O)
A2

C
H2O / EtOH
(+C)
EtOH / H2O

H2O / EtOH

H 2O EtOH 55
 Extractive distillation
aAB~1. Use of heavy solvent with greater affinity for B
gB decreases more than gA

A B

A+B

B+S S

Example: A=1-butene, B= isobutane, S=furfural 56

 Multiple feeds
D, xD

G, y L, x

F1, xF1, q1

G’’, y L’’, x

F2, xF2, q2
G’, y L’, x

B, xB
57
 Multiple feeds
Equations for operating lines
Rectifying section

r 1
y x xD
1 r 1 r
Intermediate section
L' ' D xD  F1 xF 1 L' '  L  F1 (1  q1 )
y x Where:
G' ' G' ' G' '  L' ' D  F1
Stripping section

L' B L'  L' ' F2 (1  q2 )

y x xB Where:
G' G' G'  L' B
58
 Multiple feeds
Graphical representation of operating lines
1
Stripping
section

Rectifying
section
0.5
y

q-line feed 1
Intermediate
section
q-line feed 2

0
xB xF2 xF1 xD
0 0.5 1
59
x
 Multiple feeds
McCabe-Thiele construction (optimum feed location)
1

0.5
y

Eq. stages:
1 in rect. section
3 in int. section
~2.8 in strip. section

0
xB xF2 xF1 xD
0 0.5 1
60
x
 Multiple feeds
Corresponding column scheme
y1

1 xD
y2 x1
xF1 2
y3 x2
3
y4 x3
4
y5 x4
xF2 5
y6 x5
6 Fractional stage
y7
x6 7 x7 = x B
61
 Side stream
D, xD

G, y L, x

P, xP Liquid side-stream

G’’, y L’’, x
F, xF, q

G’, y L’, x

B, xB
62
 Side stream
Equations for operating lines
Rectifying section

r 1
y x xD
1 r 1 r
Intermediate section
L' ' D xD  P xP L' '  L  P
y x Where: (Liquid side-stream)
G' ' G' ' G' '  G
Stripping section

L' B L'  L' ' F (1  q)

y x xB Where:
G' G' G'  L' B
63
 Side stream
q-line for side stream
Rectifying section Intermediate section

G y  L x  D xD 1 G' ' y  L' ' x  D xD  P xP 2

Intersection 1 - 2

G  G' ' y  L  L' ' x  P xP  y   L  L ' '

x
P
xP
G  G' ' G  G' '
Slope =  because G=G’’ for liquid side stream

x  xP  y 
L  L' '  P x  L  L' '  G  G ' '  L  L' ' x  x
G  G ' ' P G  G ' ' P P

 q-line for liquid side-stream is a vertical line going through xP

64
 Side stream
Graphical representation of operating lines
1
Stripping
Intermediate section
section

Rectifying
section
0.5
y

q-line
side stream

q-line
feed
0
xB xF xP xD
0 0.5 1
65
x
 Side stream
McCabe-Thiele construction (optimum feed location)
1 Frac.
stage

0.5
y

Eq. stages:
0.5 in rect. section
Frac. stage 2 in int. section
~3.9 in strip. section

0
xB xF xP xD
0 0.5 1
66
x
 Side stream
Corresponding column scheme
y1
Fractional stage
1 xD
y2 x1
2 xP = x 2
y3 x2
3
y4 x3
xF 4
y5 x4
5
y6 x5
6 Fractional stage
y7
x6 7 x7 = x B
67