L/O/G/O

單元操作(三)
Chapter 22
Introduction to
Multicomponent Distillation

化學工程學系 李玉郎
Calculation of equilibrium stage :
1. mass balance : for each component, for each stage , and for
the column.
2. enthalpy balance : for the column and for each stage.
3. vapor – liquid equilibria : more complex than for binary
system, temperature dependent
( changes from stage to stage)
Computer must be used with programs based squarely on the
following principles.

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Phase Equilibrium in Multicomponent Distillation
distribution coefficient, or K factor
mx
yie i  component i
Ki  (y=Kx)
xie e  at equilibrium
If Raoult’s law and Dalton’s law hold
Pi  xi Pi (22.2) Pi' : vapor pressure of pure liquid

Pi Pi : partial pressure of component i

yi  (22.3)
P P : total pressure
yi Pi P xi Pi P Pi Pi
Ki     (22.4) Ki 
xi xi xi P P
K factor  strongly temperature dependent
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 yi xi K i Pi
 ij    (22.5)
y j x j K j Pj
αij : relative volatility  change only moderately with temperature
Pi
when Raoult’s law applies ,  ij  (22.6)
Pj
 Bubble – point and dew – point calculation

Nc Nc
Bubble point  y  K x
i 1
i
i 1
i i  1 .0 (22.7)

Nc Nc
yi
Dew point  xi  
i 1 i 1 Ki
 1.0 (22.8)

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 Calculation procedure

(1) Bubble point : ( for liquid mixture , given : x1 , x2 , x3 ,…, P )

Pi
choose T find Pi' for each
component
Ki 
P
 y  K x
i i i

( choose a lower T )
∑ > 1  T too high No IF
∑ yi = 1
∑ < 1  T too low
( choose a higher T )
yes

T = Tb

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(2) Dew point : ( for gas mixture, given : y1 , y2 ,…, P )

( by published data )
choose T estimate Ki
( by Pi )
P

(choose a higher T )
∑ xi > 1  T too low No IF
∑ xi = 1
∑ xi < 1  T too high
(choose a lower T )
yes

T = Td

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 when summation is close to 1.0 , the yi can be determined by :
K i xi
yi  (22.9)  for liquid mixture
 K i xi
yi
Ki
similarity, xi   for vapor mixture
 Ki
yi

EXAMPLE 22.1. Find the bubble-point and the dew-point temperatures

and the corresponding vapor and liquid compositions for a mixture of 33
mole percent n-hexane, 37 mole percent n-heptane, and 30 mole percent n-
octane at 1.2 atm total pressure.
33% C6
37% C7 at P=1.2 atm
30% C8
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(1) Bubble point
choose T = 105oC
find Pi'

Hexane Pi' = 2.68 atm

Heptane Pi' = 1.21 atm
Octane Pi' = 0.554 atm
calculate Ki
Pi 2.68
Ki    2.23 …Hexane
P 1.2
calculate yi = Ki xi

y1 = 2.23  0.33 = 0.7359 … Hexane

y2 = K2  0.37 =

?
∑ yi = 1
 Bubble point. Choose T = 105oC, where the vapor pressure of heptane, the
middle component, is 1.2 atm.

Since ∑ yi is too large, try a lower temperature. Since the major contribution
comes from the Hexane, pick a temperature where Ki is lower by a factor 1/1.24.
Choose T = 96oC, where Pi' atm. ( P ' lower by a factor 1 )
2.68
 2.16
i 1.24
1.24

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 96oC ∑ = 0.983, 105oC ∑ = 1.248
By interpolation, the bubble point is 97oC, close enough to 96oC so
that the vapor compositions can be calculated using Eq. (22.9). – by
normalization

Dew point. The dew point is higher than the bubble point, so use 105oC as a
first guess.

PC8= 0.554 at 105 oC

 Select PC8 = 1.17  0.554 ≒ 0.64  T = 110oC

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 Since the sum is too high, choose a higher temperature. Pick T = 110oC,
where K3 is 17 percent higher.
Find
Select PC8 = 1.17  0.554 ≒ 0.64  T = 110oC

By extrapolation, the dew point is 110.5oC, and the composition of

the liquid in equilibrium with vapor is obtained by dividing the values of
yi / Ki by 1.0162.
110 C ∑ = 1.016
o

105oC ∑ = 1.169

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 Flash distillation of multicomponent mixtures

xF = f y + (1 – f ) x
1 f x
For flash distillation of binary mixture , Eq (21.2) y x F
f f
can be written as :
xFi 1 f
y Di   xBi (22.10)
f f
Eq (22.10)  yDi 1  xFi  (22.11)
 K i    f  1
xBi xBi f  xBi 
solve xBi xFi
xBi 
Nc Nc
f K i  1  1
xFi
then  xBi  1  
i 1 i 1 f K i  1  1 (22.12)
f (T)

 Eq(21.12) can be used to solve the temperature, and composition of

liquid ( xi ) and vapor ( yi ) products. The method is the same as that
for the dew – point calculation. 12
EXAMPLE 22.2. The mixture of Example 22.1 is subjected to a flash distillation
at 1.2 atm pressure, and 60 percent of the feed is vaporized. (a) Find the
temperature of the flash and the composition of the liquid and vapor products. (b)
To what temperature must the feed liquid be heated for 60 percent vaporization on
flashing ?

Solution :
xF1 ( Hexane ) = 0.33 , Tb = 97oC , Td = 110.5oC
xF2 ( Heptane ) = 0.37 , f = 0.6 , P = 1.2 atm
xF3 ( Octane ) = 0.30
flush temperature lie between Tb and Td , since f = 0.6
assume T = Tb + 0.6 ( Td – Tb ) = 105oC , then use Eq.(22.12) with f = 0.6
xFi
f K i  1  1

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 0.33 0.37 0.30
 xBi  0.62.23  1  1  0.61.01  1  1  0.60.462  1  1 xFi
f K i  1  1
= 0.190 + 0.368 + 0.443 = 1.001
yDi
since  K i , yDi = Ki xBi , flash T = 105oC
xBi

(b) Determine the temperature of feed before flashing ( liq. state , P > 1.2 atm )
use the enthalpy balance :
enthalpy after flashing ( Hvapor + Hliq. )105oC =
enthalpy before flashing ( Hliq )T ( T : to be determined )
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 reference Temp. = 105oC , require : heat of vaporization ΔHv at 105oC
heat capacity of liq. C P ( 105 ~ 200oC )

Based on liquid at 105oC , the enthalpies of the product are

Hvapor = 0.6 ( 0.424  6370 + 0.372  7510 + 0.204  8560 )
Hvapor = 4345 cal Hliquid = 0
For the feed , Hfeed = C P l ( T – 105 )
C P = 0.33  62 + 0.37  70 + 0.30  78 = 69.8 cal/mol·oC
69.8 ( T0 – 105 ) = 4345 T0 = 167oC = preheat temp.
For a more accurate answer , the liquid heat capacities could be reevaluated for the
range 105 to 170oC
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Fractionation of Multicomponent Mixture

Calculations are made by too methods:

1. Assume desired separation, choose reflux ratio ,
 calculate No. of plates above and below feed.
( used commonly for binary mixture )

2. Assume : No. of plates above and below feed.

choose reflux ( L ) and vapor rate from reboiler ( V )
 calculate separation of component.

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Key components

choose 2 components whose concentration in the distillate and bottom

products are a good index of the separation. C1
C2  LK
L  light key  more volatile
C3  HK
H  heavy key  less volatile C4
C5
 components lighter than the light key  nearly completely recovered in
the distillate components heavier than the heavy key  nearly completely
recovered in the bottom.
 small number are assigned to xB L ( light key in the bottom ) , or xD H ( heavy
key in the distillate )
 usually , L key and H key are adjacent in the rank order of volatility.
such a choice is call a sharp separation.
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Minimum number of plates ( total reflux , RD =  )

The Fenske equation (21.42)

n[( xDi xBi ) ( xDj xBj )]

N min  1 (22.13)
n  ij
applied to any 2 components , i and j , in a multicomponent system.

 ij  3  Dij Fij Bij (22.14)

αDij , αFij , αBij : relative volatility at temperature of distillate , feed

plate , and bottom respectively.

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Calculation of required reflux ratio and concentration profiles
Lewis – Matheson method  plate by plate calculation
 determine No. of ideal stage for a specified separation, at selected RD
xD , xB
V

y1,y2,y3 ….
L
Dew point calculation,
1, T1 T1, x1, x2, x3, …,.
x1, x2, x3
y1,y2,y3 …. Material balance: y2i V2 = L1 x1i + D xDi
y1,y2,y3 ….
2, T2
x1, x2, x3
y1,y2,y3 …. Dew point calculation,
T2, x1, x2, x3, …,.

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 specified : composition of distillate ( or vapor from top plate )
by trial
Dew point calculation  Temperature and xi on top plate
adjust the product composition

yi Eq (22.8)
∑xi = 1.0 = ∑ K
i

assume constant V , L ; if not , use enthalpy balance

Material balance equation  vapor composition from plate 2 , y2i
y2i V2 = L1 x1i + D xDi (22.31)

Dew point calculation  temperature and xi on top plate 2.

( until composition is close to that of feed )

feed plate  check compositions at the feed stage
similar procedure (bubble point calculation)
specified bottom composition
Calculation can be repeated for different RD at fixed No. of plate
20 and feed plate.
 Azeotropic and extractive distillation
complete separation may be impossible for :
(1) azeotrope ( K = 1 )
(2) components those have nearly the same boiling point.
Extractive distillation
liquid – liquid extraction with an added vapor phase
mixture of azeotrope + an additional component ( high – boiling liquid ,
or a solvent )

 to alter the relative volatility of the original components

 solvent : miscible with both key components, but is chemically more
similar to one of them, and the activity coefficient of the
similar component is decreased.

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 furfural (solvent)  permit the separation of butadiene from mixture
containing butane and butenes. lowers the activity of butadiene more than
it does for the others.

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Azeotropic distillation
Adding a solvent that forms an azotrope with one of the key component.
The azotrope is later separated into solvent and key component.
Entrainers (共沸劑，夾帶劑): the material added form a low boiling azeotrop
and is taken overhead.
Example :
separation of ( Ethanol + water ) + ( benzene, or heptane , or cyclohexane )

azeotrope 95.6% entrainer

 the low boiling azotrope formed: H2O – Et-OH – benzene
23.3 22.8 53.9

 feed : 95% Et-OH ( near middle of the dehydrating column )

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Example: Et-OH/H2O
Entrainer: Benzene

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珍惜 、 感恩
L/O/G/O

Thank You!

化學工程系 李玉郎