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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?

Vapor-liquid equilibrium
(VLE)

Consider a binary (i.e., 2-component) system with 2-phases:


What do we know?
Tvap, Pvap
yA , yB

yA + yB = 1

xA + xB = 1

yA xA
Tliq, Pliq
xA , xB

At equilibrium:
Tvap = Tliq
Pvap = Pliq

ibbs Phase Rule:


degrees of freedom = # components (C) - # phases (P) + 2

or a binary, 2-phase system:

22+2=2

e can specify only 2 intensive variables (all others are fixed, by VLE)

Specify P and T
2 graphs in one:
T vs. xA
T vs. yA

superheated vapor
2-phase
region

saturated liquid line

TA

saturated vapor line

A subcooled liquid
feed of composition
zA, heated to
temperature TA, will
separate
spontaneously into
2 phases,
Figure 2-3 Temperature-composition diagram
for of
xA and
From Separation Process Engineering, Third Edition by Phillipcomposition
C. Wankat
ethanol-water
(ISBN: 0131382276) Copyright 2012 Pearson Education, Inc. All
reserved.
yrights
A
zA

subcooled liquid
yA
xA

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.

dew point
boiling
range
bubble point
xE,initial

yE,initial

1. Consider a subcooled binary liquid


that is 40 mol%
ethanol.
What is its bubble
point?
What is the
composition
2. Consider aof the
first
bubble? binary
superheated
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?

Figure 2-3 Temperature-composition diagram for


ethanol-water
From Separation Process Engineering, Third Edition by Phillip C. Wankat
(ISBN: 0131382276) Copyright 2012 Pearson Education, Inc. All rights reserved.

Useful definitions
Boiling/bubble point Tbp: 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 < Tbp, by evaporation

Saturated liquid: a liquid at its boiling/bubble point


Dew point Tdp: 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?
F, L and V are extensive
variables
mass balance method OR
total mass balance (TMB):
F=L+V
component mass balance
(CMB):
F zA = L xA + V yA
L yA zA

rearrange:V zA xA

inverse lever-arm metho

isotherm

L MV

V
LM

For a given F, we can now compute L

Specify P and one composition (x A)

E
VL

e
lin

cr.
n
i
T

K = yE/xE

y=

For a binary
system at
constant P, if
one
composition (xA
or yA) is
VLE:
chosen, all
K = yA/xA
others are
fixed:
mole balance:
xA + xB = 1
yA + yB = 1

VLE line always lies


above y=x line if
plotted for the more
volatile component

volatility = K = K(T,
P, zi)
K(T)
azeotrope: K =
1.0

Figure 2-2 McCabe-Thiele diagram for


ethanol-water

From Separation Process Engineering, Third Edition by Phillip C. Wankat


(ISBN: 0131382276) Copyright 2012 Pearson Education, Inc. All rights reserved.

how can we
break an
azeotrope?

Specify two of (P, T,


volatility)
pure compound
T

P0
P*

Tbp

K = 1.0

K<1

DePriester Chart

temperature

total
pressure

K>1

Consider a pure compound:


for a given P, find Tbp (i.e., K = 1)
for a given T, find P0 (i.e., K = 1)
for a given P, T, find K
K > 1 prefers vapor phase
K < 1 prefers liquid phase

T*

Dont extrapolate beyond the range of


the chart.

Figure 2-11 Modified DePriester chart (in S.I. units) at low


temperatures
volatility

(D. B. Dadyburjor, Chem. Eng. Prog.,85, April 1978; copyright 1978, AIChE; reproduced by permission of the American Institute of Chemical
Engineers)

At 2000 kPa, what is


the boiling point of
ethane?
At 15 C, what is
the saturated vapor
pressure of
isobutane?
At 0 C and 500
kPa, what is the
volatility of nhexane?

From Separation Process Engineering, Third Edition by Phillip C. Wankat


(ISBN: 0131382276) Copyright 2012 Pearson Education, Inc. All rights reserved.

Using data from vapor pressure


tables
vapor pressure

Raoults Law
0
P

x
P
(T )
ideal liquid:
A
A A
non-ideal liquid:

PA A xAPA0 (T )
activity coefficient

Daltons Law
ideal gas:
non-ideal gas:

yA

PA
PTOTAL

yA

PA
APTOTAL

fugacity coefficient

yA
PA0 (T )
PA0 (T )
KA

xA APTOTAL PTOTAL

Bubble point calculation


for multi-component mixtures

Trial-and-error method
Given the composition of a subcooled liquid and P TOTAL,
find Tbp and (yi)bp
VLE:

yi K i xi

mole balance:

1.0

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

How to pick a temperature? How to pick the next

To achieve rapid
convergence:
T ziTi (K i 1)
Initial guess:
i
(weighted average of boiling points of pure
components)

Next guess:
pick a reference
component (A)
K A (Tnext )

K A (Tprev )

(y )

i prev

find Tnext 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 Tdp and (xi)dp
VLE:

mole

xi

yi
Ki

Algorithm:

1. Pick a temperature T and find the


corresponding Ki(T) values for
balance:
each component
2. Calculate the xi value for each
Ki(T)
xi 1.0
3. Check to see if xi = 1
i
4. If not, pick a new temperature and
repeat
K A (Tprev )

K A (Tnext )

(x )

i prev

Relative volatility
yA
KA
K A (T )
xA

volatility

yA

relative volatility

AB

KA
xA

K B yB
xB

strong function of
temperature

not a strong
function of
temperature; often
assumed
independent

for a binary system, substitute and rearrange:


yB 1 yA
xB 1 xA

AB xA
yA
1 ( AB 1)xA

Bubble point calculation


using relative volatility
yi

definition of relative volatility:

solve for yi:

sum:

Ki
xi
i

K ref K ref

yi i xi K ref

y 1.0 x K
i

solve for Kref:

K ref

ref

i xi
i

Algorithm:
given a solution composition (xi values), find relative volatilities (i values), then
1. guess Tinitial
2. calculate Kref
3. find T = T corresponding to K

Ex.: Finding Tbp using relative


volatilities
Find the bubble point of a mixture of n-pentane (x P = 0.3), n-hexane
(xX = 0.3) and n-heptane (xH = 0.4), at 1 atm total pressure. Find the
composition of the first vapor bubble.

Tinitial xiTi (K i 1) 0.3(36) 0.3(68) 0.4(99) 71C


i

esignate n-pentane as the reference. At 71 C, KP = 2.8.

XP

K
1.2
X
0.43
K P 2.8

K P (Tbp )

HP

K H 0.45

0.16
KP
2.8

1
1

2.0
i xi 0.3(1) 0.3(0.43) 0.4(0.16)
i

Tbp corresponding to KP = 2.0 (read from DePriester Chart):

yi i xi K ref

Tbp = 58 C

yP 0.3(1)(2.0) 0.60
yX 0.3(0.43)(2.0) 0.26
yH 0.4(0.16)(2.0) 0.14

Check:

1.0