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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)

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

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

isotherm

L MV

V
LM

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

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?

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*

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

## 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

yB 1 yA
xB 1 xA

AB xA
yA
1 ( AB 1)xA

## Bubble point calculation

using relative volatility
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.

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