Goal 1: Design a flash drum

How big should the drum be?

What height should the nozzle be?
What T and P should the drum be?
What T and P should the feed be?
Vapor-liquid equilibrium (VLE)
Consider a binary (i.e., 2-component) system with 2-phases:
T
vap
, P
vap
y
A
, y
B

T
liq
, P
liq
x
A
, x
B

What do we know?

y
A
+ y
B
= 1 x
A
+ x
B
= 1

y
A
x
A

At equilibrium: T
vap
= T
liq
P
vap
= P
liq
Gibbs Phase Rule:
degrees of freedom = # components (C) - # phases (P) + 2

For a binary, 2-phase system: 2 2 + 2 = 2
We can specify only 2 intensive variables (all others are fixed, by VLE)
Specify P and T
From Separation Process Engineering, Third Edition by Phillip C. Wankat
(ISBN: 0131382276) Copyright 2012 Pearson Education, Inc. All rights reserved.
Figure 2-3 Temperature-composition diagram for ethanol-water
superheated vapor
subcooled liquid
2-phase
region
saturated vapor line
saturated liquid line
2 graphs in one:
T vs. x
A
T vs. y
A
A subcooled liquid feed
of composition z
A
,
heated to temperature
T
A
, will separate
spontaneously into 2
phases, of composition
x
A
and y
A

T
A
x
A

y
A

z
A

From Separation Process Engineering, Third Edition by Phillip C. Wankat
(ISBN: 0131382276) Copyright 2012 Pearson Education, Inc. All rights reserved.
Figure 2-3 Temperature-composition diagram for ethanol-water
bubble point
dew point
x
E,initial
y
E,initial
boiling
range
1. Consider a sub-cooled
binary liquid that is 40
mol% ethanol.
What is its bubble point?
What is the composition of
the first bubble?
2. Consider a superheated
binary vapor that is 40
mol% ethanol.
What is its dew point?
What is the composition of
the first drop?
3. What is the boiling range
of this mixture?
Boiling point, dew point, bubble point
Pure liquids have a
boiling point; mixtures
have a boiling range,
delimited by their
bubble point and dew
point.
Useful definitions
Boiling/bubble point T
bp
: temperature at which the average
liquid molecule has just enough kinetic energy to escape from
the surface of the liquid into the gas phase
Recall that kinetic energy follows a Boltzmann distribution, so
molecules with higher than average kinetic energy can still escape
from the surface at T < T
bp
, by evaporation
Saturated liquid: a liquid at its boiling/bubble point
Dew point T
dp
: temperature at which the average vapor
molecule has just enough kinetic energy to condense
Saturated vapor: a vapor at its dew point
Vapor pressure: pressure at which the liquid and vapor phase
are in equilibrium at a given temperature
Azeotrope: a constant-boiling mixture, i.e., a mixture that
behaves like a single component


How much liquid and vapor
will the flash drum produce?
mass balance method

total mass balance (TMB):
F = L + V
component mass balance (CMB):
F z
A
= L x
A
+ V y
A

rearrange:

L
V

y
A
z
A
z
A
x
A
OR inverse lever-arm method
F, L and V are extensive variables

L
V

MV
LM

L

M

V
isotherm
For a given F, we can now compute L and V.
From Separation Process Engineering, Third Edition by Phillip C. Wankat
(ISBN: 0131382276) Copyright 2012 Pearson Education, Inc. All rights reserved.
Figure 2-2 McCabe-Thiele diagram for ethanol-water
K = y
E
/x
E

volatility = K = K(T, P, z
i
)
K(T)


azeotrope: K = 1.0

how can we break
an azeotrope?
Specify P and one composition (x
A
)
For a binary system
at constant P, if one
composition (x
A
or
y
A
) is chosen, all
others are fixed:

VLE:
K = y
A
/x
A

mole balance:
x
A
+ x
B
= 1
y
A
+ y
B
= 1
VLE line always lies above
y=x line if plotted for the
more volatile component
Specify two of (P, T, volatility)
t
o
t
a
l

p
r
e
s
s
u
r
e

t
e
m
p
e
r
a
t
u
r
e

K = 1.0
DePriester Chart
for a given P, find T
bp
(i.e., K = 1)
for a given T, find P
0
(i.e., K = 1)
for a given P, T, find K
K > 1 prefers vapor phase
K < 1 prefers liquid phase
Dont extrapolate beyond the range of the chart.
T
bp
P
0

pure compound
Consider a pure compound:
T

P

K > 1
T*

P*

K < 1
Figure 2-11 Modified DePriester chart (in S.I. units) at low temperatures
(D. B. Dadyburjor, Chem. Eng. Prog.,85, April 1978; copyright 1978, AIChE; reproduced by permission of the American Institute of Chemical Engineers)
From Separation Process Engineering, Third Edition by Phillip C. Wankat
(ISBN: 0131382276) Copyright 2012 Pearson Education, Inc. All rights reserved.
At 2000 kPa, what is the
boiling point of ethane?
volatility
At 15 C, what is the
saturated vapor pressure
of isobutane?
At 0 C and 500 kPa,
what is the volatility of
n-hexane?
Using data from vapor pressure tables
Raoults Law
ideal liquid:
non-ideal liquid:
Daltons Law
ideal gas:
non-ideal gas:
P
A
x
A
P
A
0
(T)
P
A

A
x
A
P
A
0
(T)
y
A

P
A
P
TOTAL
y
A

P
A

A
P
TOTAL
K
A

y
A
x
A

P
A
0
(T)

A
P
TOTAL

P
A
0
(T)
P
TOTAL
activity coefficient
fugacity coefficient
vapor pressure
Bubble point calculation
for multi-component mixtures
Trial-and-error method
Given the composition of a subcooled liquid and P
TOTAL
,
find T
bp
and (y
i
)
bp


VLE:


mole balance:

y
i
K
i
x
i
y
i
i
1.0
Algorithm:

1. Pick a temperature T and find the
corresponding K
i
(T) values for each
component
2. Calculate the y
i
value for each K
i
(T)
3. Check to see if Sy
i
= 1
4. If not, pick a new temperature, repeat

How to pick a temperature? How to pick the next temperature?
To achieve rapid convergence:
Initial guess:
(weighted average of boiling points of pure components)
T z
i
T
i
i
(K
i
1)
K
A
(T
next
)
K
A
(T
prev
)
(y
i
)
prev
i
Next guess:
pick a reference component (A)
find T
next
using DePriester Chart
Dew point calculation
for multi-component mixtures
Trial-and-error method
Given the composition of a superheated vapor and P
TOTAL
,
find T
dp
and (x
i
)
dp


VLE:


mole balance:

x
i

y
i
K
i
x
i
i
1.0
Algorithm:

1. Pick a temperature T and find the
corresponding K
i
(T) values for each
component
2. Calculate the x
i
value for each K
i
(T)
3. Check to see if Sx
i
= 1
4. If not, pick a new temperature and repeat

K
A
(T
next
)
K
A
(T
prev
)
(x
i
)
prev
i
Relative volatility
volatility
K
A

y
A
x
A
K
A
(T)

AB

K
A
K
B

y
A
x
A
y
B
x
B
strong function of
temperature
not a strong function of
temperature; often
assumed independent
relative volatility
for a binary system, substitute and rearrange:
y
A


AB
x
A
1+(
AB
1)x
A
y
B
1 y
A
x
B
1 x
A
Bubble point calculation
using relative volatility
K
ref

1

i
x
i
i

i

K
i
K
ref

y
i
x
i
K
ref
definition of relative volatility:
solve for y
i
:
y
i

i
x
i
K
ref
solve for K
ref
:
sum:
y
i
i
1.0
i
x
i
( )
i
K
ref
Algorithm:
given a solution composition (x
i
values), find relative volatilities (a
i
values), then
1. guess T
initial
2. calculate K
ref
3. find T = T
bp
corresponding to K
ref

Ex.: Finding T
bp
using relative volatilities
Find the bubble point of a mixture of n-pentane (x
P
= 0.3), n-hexane (x
X
=
0.3) and n-heptane (x
H
= 0.4), at 1 atm total pressure. Find the
composition of the first vapor bubble.
T
initial
x
i
T
i
i
(K
i
1) 0.3(36) +0.3(68) +0.4(99) 71C
Designate n-pentane as the reference. At 71 C, K
P
= 2.8.

XP

K
X
K
P

1.2
2.8
0.43
K
P
(T
bp
)
1

i
x
i
i

1
0.3(1) +0.3(0.43) +0.4(0.16)
2.0
Find T
bp
corresponding to K
P
= 2.0 (read from DePriester Chart): T
bp
= 58 C
y
P
0.3(1)(2.0) 0.60
y
i

i
x
i
K
ref
y
X
0.3(0.43)(2.0) 0.26
y
H
0.4(0.16)(2.0) 0.14
y
i
i
1.0
Check:

HP

K
H
K
P

0.45
2.8
0.16