Distillation

Equilibrium (Review)
Flash Distillation
Multistage Distillation
07/03/2013
MRB
Single Equilibrium Stage
Ethanol-Water, P = 1 atm
Vapor
Liquid
F,
z
EtOH
V,
y
EtOH

L,
x
EtOH

F is the total moles of ethanol and water fed to the stage.
V is the total moles in the vapor stream exiting the stage.
L is the total moles in the liquid stream exiting the stage.
z
EtOH
is the mole fraction of ethanol in the feed.
y
EtOH
is the mole fraction of ethanol in the vapor stream.
x
EtOH
is the mole fraction of ethanol in the liquid stream.
Feed Mole-Fraction Relationships

Note that a feed mole-fraction, z
F
,can be a
subcooled liquid, a saturated liquid, a two-phase
mixture, a saturated vapor, or a superheated vapor.

The feed phase is dependent upon the temperature,
pressure, and the composition (mole fraction).

z
F
and x,y Relationships
Assuming that the equilibrium stage is at the same temperature and
pressure of the feed:
If z
F
is a subcooled liquid, then z
F
is simply x
F
and there is no y.
If z
F
is a superheated vapor, z
F
is y
F
and there is no x.
If z
F
is a saturated liquid, z
F
is essentially x
F
with a single vapor
bubble formed of new mole fraction y.
If z
F
is a saturated vapor, z
F
is essentially y
F
with a single liquid drop
formed of new mole fraction x.
If z
F
is in the two-phase region, the system will separate into a liquid
and vapor of new mole fractions x and y, respectively. z
F
is not equal
to either x or y, but x and y be determined from the T vs. x,y data or
plot.

Mass Balance Lever Rule
Vapor
Liquid
F, z
A
V, y
C

L, x
B

Mass Balance Lever Rule
Let
F = the moles of feed of composition z
A

L = the moles of liquid of composition x
B

V = the moles of vapor of composition y
C

Then the mass balances before and after separation are

C B A
Vy Lx Fz + =
Eq. (2-6)
and

V L F + =
Eq. (2-7)

Mass Balance Lever Rule
Substituting Eq. (2-7) into Eq. (2-6) and rearranging yields


B A
A C
x z
z y
V
L

=
Eq. (2-8)

where L/V is the ratio of liquid to vapor.

Comparing the numerator and denominator with the two-
phase diagram indicates that the distance between points A
and C and points A and B are equivalent to the magnitudes
of the liquid-phase and vapor-phase quantities,
respectively.

Graphically, this is
BA
AC
V
L
=
:

Mass Balance Lever Rule
Temperature-Composition Diagram
for Two-Phase System
75
80
85
90
95
100
0.0 0.2 0.4 0.6 0.8 1.0
x or y

T
(
o
C
)
Superheated Vapor Phase
Subcooled Liquid Phase
Isotherm
y
C
x
B
Two Phase
T
sy s
B A C
z
A

L


V

Mass Balance Further Relationships

From inspection, other useful relationships can be
determined:

Fraction feed remaining as liquid


B C
A C
x y
z y
F
L
V L
L
q

= =
+
=


Fraction feed vaporized


B C
B A
x y
x
F
V
V L
V
f

= =
+
=
z


Note for a Two-Phase Mixture

At vapor-liquid equilibrium, the temperatures of the vapor and liquid are
equal.

When a two-phase mixture separates at vapor-liquid equilibrium
conditions, the vapor phase will be at saturated vapor conditions and
the liquid phase will be at saturated liquid conditions.

We will use this assumption when we do our multi-stage solutions the
vapor and liquid streams exiting a stage will be assumed to be at
saturated conditions.

Thus, the liquid fed from one stage to another stage can be assumed to
be a saturated liquid and the vapor feed to another stage can be
assumed to be a saturated vapor.



Enthalpy vs. Composition
Ponchon-Savarit Plot
Presents the temperature equilibrium relationship for enthalpy vs.
x and y.
Pressure is constant.
Enthalpy will be required in future problems utilizing energy
balances.
Note the units of concentration!



For a non-ideal system, where the molar latent heat is no longer constant and where
there is a substantial heat of mixing, the calculations become much more tedious.
For binary mixtures of this kind a graphical model has been developed by
RUHEMANN, PONCHON, and SAVARIT, based on the use of an enthalpy-
composition chart.
It is necessary to construct an enthalpy-composition diagram for particular binary
system over a temperature range covering the two-phase vapor-liquid region at the
pressure of the distillation.

Enthalpy vs. Composition Ponchon-Savarit Plot
What is the enthalpy of a (two phase) feed stream at 1 kg/cm2
pressure, 82C, 0.6 wt% ethanol?

Enthalpy vs. Composition
Enthalpy Determination

The major purpose of an enthalpy diagram is to determine
enthalpies.

We will use enthalpies in energy balances later.

For example, if one were given a feed mixture of 35% ethanol
(weight %) at T = 92
o
C and P = 1 kg/cm
2
and the mixture was
allowed to separate into vapor and liquid, what would be the
enthalpies of the feed, vapor, and liquid?

Lecture 5 14
Enthalpy vs. Composition
Enthalpy Determination
425
295
90
Equilibrium Data How to Handle?

Tabular Data
Generate graphical plots
Generate analytical expressions (curve fit)

Graphical
y vs. x (P constant) McCabe-Theile Pot
T vs. x,y (P constant) Saturated Liquid, Vapor Plot
Enthalpy vs. composition (P constant, T) Ponchon-Savarit Plot

Analytical expressions
Thermodynamics: Equations of state/Gibbs free energy models
Distribution coefficients, K values
Relative volatility
DePreister charts
Curve fit of data
Analytical Expressions for Equilibrium

There are several disadvantages to using graphical techniques:
One cannot readily plot multi-component systems graphically
(maximum is typically three).
Separator design often has to be done using numerical methods;
thus, analytical expressions for equilibrium behavior are needed.
We will now look at other representations for handling equilibrium
data analytically





Other Equilibrium Relationships
Distribution Coefficient
Another method of representing equilibrium data is to
define a distribution coefficient or K value as:


A A A
/ x y K = Eq. (2-10)

K
A
is typically a function of temperature, pressure, and
composition.

The distribution coefficient K is dependent upon
temperature, pressure, and composition. However, for a
few systems K is independent of composition, to a good
approximation, which greatly simplifies the problem.
p) K(T, K
A
= Eq. (2-11)

Other Equilibrium Relationships
DePriester Charts

One convenient source of K values for
hydrocarbons, as a function of temperature and
pressure (watch units), are the DePriester charts

The DePriester plots are presented over two
different temperature ranges.
Using DePriester Charts
Boiling Temperatures of Pure Components

One can determine the boiling point for a given component and
pressure directly from the DePriester Charts one can then
determine which component in a mixture is the more volatile
the lower the boiling point, the more volatile a component is.

For a pure component, K = 1.0.

Assume one wishes to determine the boiling point temperature of
ethylene at a pressure of P = 3000 kPa


Lecture 5
T
bp
= - 9.5
o
C
Question DePriester Charts
What are the equilibrium distribution coefficients, K,
for a mixture containing:

Ethylene
n-Pentane
n-Heptane

at T = 120
o
C and P =1500 kPa?

Lecture 5
Answer DePriester Charts
The equilibrium distribution coefficients, K,
are:
K
Ethylene 8.5
n-Pentane 0.64
n-Heptane 0.17

at T = 120
o
C and P =1500 kPa.
Question Volatility
What can one say about the volatility of
each component from the K values?
K
Ethylene 8.5
n-Pentane 0.64
n-Heptane 0.17

Answer Volatility
What can one say about the volatility of each component from the K values?
K T boiling
Ethylene 8.5 -35.5
o
C
n-Pentane 0.64 153
o
C
n-Heptane 0.17 >200
o
C



The boiling point temperatures of the pure components at P = 1500 kPa have
also been determined from the DePriester charts for K = 1.0 for each
component (n-heptanes is off the chart).

From the K values and the boiling point temperature of each pure component,
one can say that the volatility follows the trend that ethylene>n-pentane>n-
heptane.



A A A
/ x y K =
Other Equilibrium Relationships
DePriester Equation
While the DePreister charts may be used directly, they have
been conveniently fit as a function of temperature and
pressure:


p
a
p
a
a a
T
a
T
a
2
p3
2
p2
p1 T6
T2
2
T1
p ln K ln + + + + + = Eq. (2-12)

where T is in
o
R and p is in psia. Table 2.4 (p. 26, Wankat)
contains the K fit constants along with their mean errors
(again, watch units!).

Eq. (2-12) provides an analytical expression which can be
used in numerical analyses. We will use this later for
bubble and dew-point temperature calculations.

Other Equilibrium Relationships
Mole Fraction Vapor Pressure Relationship
If one does not have equilibrium data, K can be approximated
using other more common thermodynamic data quantities such as
vapor pressures.

From Raoults law for ideal systems:


A A A
(VP) x p = Eq. (2-14)

where p
A
is the pressure due to component A in the mixture and
(VP)
A
is the vapor pressure of pure component A, which is
temperature dependent.

From Daltons law of partial pressures:


p
p
y
A
A
= Eq. (2-15)

Combining Eqs. (2-15) and (2-14) and rearranging yields:


p
(VP)
x
y
A
A
A
= Eq. (2-16)

Other Equilibrium Relationships
Distribution Coefficient Vapor Pressure Relationship
The left-hand side of Eq. (2-16) is the definition of the distribution coefficient K; thus,


p
(VP)
K
A
A
= Eq. (2-17)

Eq. (2-17) allows one to obtain Ks from the vapor pressures of the pure components, which can be
readily found for many chemical species using the Antoine equation:


C T
B
A ln(VP)
A
+
= Eq. (2-18)

where A, B, and C are constants, which can be found in many thermodynamic texts for many
chemical species. Vapor pressure correlations can also be found in The Properties of Gases and
Liquids (5
th
Ed. Poling, Prausnitz, OConnell)

Caution must be used when applying this K relationship since many systems are non-ideal.

Actually, systems are often less ideal in the liquid phase because of the intimate contact of the
chemical species, and these are handled by the liquid-phase activity coefficient,
A
:


p
(VP)
K
A A
A

= Eq. (2-19)

The activity coefficient can be obtained from correlations, e.g, Van Laar, Wilson, etc. (see
thermodynamic texts).

Other Equilibrium Relationships
Relative Volatility
K values are strongly dependent on temperature; however, this temperature behavior maybe
somewhat similar, especially for similar chemical species, over certain temperature ranges.
Consequently, if one takes the ratio of the Ks for two components, the temperature dependence
will be less (see HW problem 2-D5).

This ratio, defined as the relative volatility,
AB
, for a binary system is:


B B
A A
B
A
AB
/x y
/x y
K
K
= = o Eq. (2-20)

If the temperature dependence for the K values is identical, then
AB
will be independent of
temperature. However, for all but the most ideal situations,
AB
will have some temperature
dependence.

Why is it termed relative volatility? Because, if Raoults law is valid:


B
A
AB
(VP)
(VP)
= o Eq. (2-21)

Thus, if (VP)
A
> (VP)
B
, component A is the more volatile and
AB
> 1. Likewise, K
A
> K
B
; thus,
one can determine the more volatile component by comparing Ks. If A is more volatile, its K
value will be greater than Bs K value.

Other Equilibrium Relationships
Relative Volatility
It will be convenient later on in separation problems to express the relative volatility in terms of the
mole fractions and vice-versa

For binary systems, the mole fractions are related by


A B
y 1 y = and
A B
x 1 x = Eq. (2-4)

and substituting these into Eq. (2-20) yields:


A A
A A
AB
)x y (1
) x (1 y

= o Eq. (2-22)

or
A
A
A AB
y 1
x 1
K

= o

Solving Eq. (2-22) for y
A
and x
A
yields:


A AB
A AB
A
x ) 1 ( 1
x
y
+
=
o
o
Eq. (2-23)
and

A AB AB
A
A
y ) 1 (
y
x

=
o o


Flash Distillation

Flash distillation is the simplest method of separation.

A feed stream is flashed into a chamber or flash drum and the liquid and
vapor are allowed to separate under equilibrium.

It is flashed by throttling the feed stream through a nozzle or valve into the
chamber the pressure drops through the valve.

The more volatile component will be concentrated in the vapor stream the less
volatile in the liquid stream.

The system is very close to a single equilibrium stage.

Separation is usually not very high for a single equilibrium stage.


Flash Distillation Solution

Flash distillation problems can be solved using
three sets of equations:
Equilibrium relationship
Mass balance
Energy balance
Flash Distillation
Equilibrium Parameters
Feed Composition z
Vapor-Phase Composition y
Liquid-Phase Composition x
Upstream Feed Temperature T
1
Feed Temperature T
F
Drum Temperature T
d
Upstream Feed Pressure P
1
Feed Pressure P
F
Drum Pressure P
d
Flash Distillation
Mass Parameters
Feed Flow Rate F
Vapor Flow Rate V
Liquid Flow Rate L
Feed Composition z
Vapor-Phase Composition y
Liquid-Phase Composition x






Flash Distillation
Energy Parameters
Heater Input Q
H
Flash Drum Heat Input Q
flash

Feed Enthalpy h
F
Vapor Enthalpy H
V
Liquid Enthalpy h
L
Upstream Feed Temperature T
1
Feed Temperature T
F
Drum Temperature T
d






Flash Distillation Mass Balances

Overall mass balance


Component mass balance




L V F + =
Lx Vy Fz + =
Flash Distillation Operating Line

Solving the overall mass balance for y yields



which is termed the operating line. It relates the
composition of the streams leaving the stage or
drum.
z
V
F
x
V
L
y + =
Common problem specifications.

Liquid to vapor ratio
L/V
Fraction of feed vaporized
f = V/F
Fraction of feed remaining as liquid
q = L/F
Operating Line Form
Fraction Vaporized
From the overall mass balance



then




f
f 1
V/F
V/F 1
V
V F
V
L
=

=
z
f
1
x
f
f - 1
y + =
Operating Line Form
Fraction Remaining as Liquid
or


and


q - 1
q
L/F - 1
L/F
L - F
L
V
L
= = =
z
q 1
1
x
q - 1
q
y
|
|
.
|

\
|

+ =
Operating Lines Linear!
Slope


y Intercept


x intercept
q 1
q
f
f 1
V
L

=
z
q - 1
1
z
f
1
z
V
F
= =
z
q
1
z
f - 1
1
z
L
F
= =
So How Do Solve?
We often know all of the system parameters except
the compositions of the vapor and liquid leaving the
stage or flash drum two unknowns, y and x.

We have two equations:
Equilibrium Relationship
Mass Balance (Operating Line)

With two equations and two unknowns we can solve
the problem!

McCabe-Thiele Analysis
Flash Distillation
Typical Problem

One will usually be given the feed stream, F, or it can be assumed.

One will usually be given the feed composition, z, in mole or weight fraction.

One will also typically be given one of the following: x, y, T
d
, f = V/F, q = L/F,
L/V, or T
F
.

One will usually be given the pressure, P
d
, in the flash drum, or it will be chosen
such that the feed is above its boiling point at T
d
, so that some of it vaporizes.

What is given in the problem determines the type of problem and the method of
solution.





Flash Distillation
Problem Type 1a: Sequential Solution
If one of the equilibrium conditions x, y, or T
d
in the drum is specified, then the other
two can be found from the equilibrium relationships using:
Equilibrium data and plots or
K values or
Relative volatility relationships

Once we have x and y, we can then solve for the streams F, V, and L using:
Overall mass balance and
Component mass balance

We can then solve the energy balances to determine Q
H
, T
F
, and T
1
(Q
flash
= 0, since we
typically assume an adiabatic drum) using enthalpies from:
Heat capacities and latent heats of vaporization or
Enthalpy-composition plots

This method of solution is known as a sequential solution method since the energy
balance is decoupled from the equilibrium and mass balances.



Flash Distillation
Problem Type 1b: Sequential Solution
If the stream parameters are specified, usually as fraction of feed vaporized
f = V/F or the fraction of feed remaining as liquid q = L/F , then the
problem can be solved for x, y, T
d
, F, V, and L by a simultaneous solution
using:
Equilibrium relationships and
Mass balances

We can then solve the energy balances to determine Q
H
, T
F
, and T
1
using
enthalpies from:
Heat capacities and latent heats of vaporization or
Enthalpy-composition plots

This method of solution is also known as a sequential solution method since
the energy balance is still decoupled from the equilibrium and mass
balances.



Flash Distillation
Problem Type 2: Simultaneous Solution

If the temperature, T
F
, of the feed is given, then the problem requires
a simultaneous solution for all of the other parameters using:
Equilibrium relationship and
Mass balance and
Energy balance

This method of solution is known as a simultaneous solution method
since the energy balance is not decoupled from the equilibrium and
mass balances.


Flash Distillation
Pressures
The pressure, P
d
, in the flash drum is chosen such that the feed is
above its boiling point at T
d
, so that some of it vaporizes.

The pressure, P
1
, is chosen such that the upstream feed is below its
boiling point and remains liquid at T
1
.

Likewise, the feed pressure, P
F
, must be chosen so that the feed is
below its boiling point and remains liquid.

The pump and heater assist in adjusting the required pressures and
temperatures of the system.

If the feed is already hot enough, the heater may not be needed, and if
the pressure of the flash drum is low enough, the pump may not be
needed.





Column Distillation

Flash distillation provides a method of separation, but
the amount of separation obtained is limited.

What if we need to have a greater separation to obtain
essentially pure components?

We could place flash drums in series or as a cascade
Lecture 9
Flash Drums in Cascade
Flash Drums in Cascade
One can obtain a high level of separation using cascading flash
drums.

The problem with this arrangement is that we generate a large
number of intermediate liquid and vapor streams, which would
need to be separated.

One could feed these intermediate streams to another flash drum
cascade, but even more intermediate streams are formed, and
so on and so on.

Lets look at what we can do with the intermediate streams


Lecture 9
Flash Drums in Counter-Current Cascade
Use of Intermediate Steams
Flash Drums in Counter-Current Cascade
Isobaric Operation
Lecture 9
Flash Drums in Counter-Current Cascade
Reflux and Boilup
Lecture 9
Flash Drums in Counter-Current Cascade
Intermediate Heat Exchange
Lecture 9
Distillation Column
Lecture 9
Distillation Column External Balance
Column Distillation
Typical Specified Variables

Column pressure, P
c
.

Feed flow rate, F.

Feed composition, z.

Feed temperature, T
F
; enthalpy, h
F
; or quality, q = L/F.

Reflux temperature,T
R
; or enthalpy, h
D
.

Reflux ratio, L/D; or distillate composition, x
D
.

Bottoms composition, x
B
.
Column Distillation
Tools for Solution

Equilibrium relationships

Mass balances

Energy balances
Column Distillation
Methods of Solution
External column balances
Overall
Condenser
Reboiler

Internal column balances
Stage-by-stage calculations