Lecture 4: Phase Equilibrium in Flowing Systems

1
Lecture 4: Phase Equilibrium in Flowing Systems
In this lecture well show:

How to apply thermodynamics to flowing systems
Energy and entropy balances in flowing systems
Availability and lost work
Gibbs Phase Rule for flowing systems and system specification
How data of mixture compositions are sometimes tabulated graphically.
Graphical determination of vapor-liquid equilibrium of hydrocarbon systems
Last lecture primarily focused on the thermodynamics of separations.
We covered:

Phase Stability and the Gibbs phase rule.
A simple separation based on a vapor-liquid phase diagram.
The lever rule.
Equilibrium ratios (K-values, distribution coefficients, etc.).
The activity, and activity coefficients.
Measures of separations.
Lecture 4: Phase Equilibrium in Flowing Systems
2
Separation System Flows
Streams in
We can use the tools of entropy, energy, availability and mass balances to analyze
any separations system:

...
...
...
...
Streams out
Heat in and heat out
Work in and work out
n, z
i
, T, P, h, s, b, v
For each stream:
n: molar flow rate
z
i
: composition variables
T: temperature
P: pressure
h: enthalpy
s: entropy
b: availability
v: specific volume
(w
s
)
in
(w
s
)
out
Q
in
Q
out

n, z
i
, T, P, h, s, b, v
T
0

Lecture 4: Phase Equilibrium in Flowing Systems
3
Balances and Availability
Energy balance:
nh +Q+W
s
( )
out
nh +Q+ W
s
( )
in
= 0
Entropy balance:

ns +
Q
T
s
|
\


|
.
|
|
out
ns +
Q
T
s
|
\


|
.
|
|
in
= AS
irr
Availability balance:

nb + Q 1
T
0
T
s
|
\


|
.
|
|
+ W
s




(

(
(
in
nb +Q 1
T
0
T
s
|
\


|
.
|
|
+ W
s




(

(
(
out
= LW
b = h T
0
s
Availability:
Availability balance: Combine entropy balance, and energy balance
with the definitions for lost work and availability.
Lost work:
LW = T
0
AS
irr
Minimum work:
nb
out
nb
in
= W
min
The minimum work for a separation is
the change in availability carried by the
feed and product streams.
Availability: the energy available in the system
for conversion to shaft work.
Lecture 4: Phase Equilibrium in Flowing Systems
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Gibbs Phase Rule
F = C t + 2
The number of thermodynamic conditions that can be specified for a system with C components
with t phases in equilibrium.

Variables: Equations:
P
T t
C t (composition of each phase) C(t-1)
C t+2 C(t-1) + t
X
i
i
= 1
k
i
o,|
=
X
i
o
X
i
|
Note that the Gibbs phase rule does not deal
with flow variables or extensive variables.
K-values are equations
determined by
thermodynamic
equilibrium
To extend the Gibbs Phase Rule to flow systems requires
Adding: Feed stream and extensive variables
Adding: Independent equations relating variables
Lecture 4: Phase Equilibrium in Flowing Systems
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Gibbs Phase Rule
F = Ct + 2
The number of thermodynamic conditions that can be specified for a system with 3 components
with 3 phases in equilibrium.

Variables: Equations:
T, P,
X
1
, X
2
, X
3
Y
1
, Y
2
, Y
3
Z
1
, Z
2
, Z
3

X
i
i
= 1
Y
i
i
= 1
Z
i
i
= 1
k
1
v, L
=
Y
1
v
Z
1
L
k
2
v, L
=
Y
2
v
Z
2
L
k
3
v, L
=
Y
3
v
Z
3
L
k
1
v, S
=
Y
1
v
X
1
S
k
2
v, S
=
Y
2
v
X
2
S
k
3
v, S
=
Y
3
v
X
3
S
Mole Fractions Equilibrium Conditions
Lecture 4: Phase Equilibrium in Flowing Systems
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Gibbs Phase Rule for a Flowing System
The number of thermodynamic conditions that can be specified for a system with 3 components
with 3 phases in equilibrium.

Variables: Equations:
T, P,
X
1
, X
2
, X
3
...

Y
1
, Y
2
, Y
3
...
Z
1
, Z
2
, Z
3
...


X
i
i
= 1
Y
i
i
= 1
Z
i
i
= 1
}
t
C
F, Z
i
, T
F
, P
F

V, L, ...
Q

} t
C
C+4+t
Ct +2
Additional
Original
k
i
o,|
=
X
i
o
X
i
|
C t 1 ( )
F
zi
= V
yi
+L
xi
+...
C
F
hf
+Q=V
hv
+ L
hl
+...
1
Ct C+t
t
C+1
F =Ct +2
AF =t +3
F = C+ 5
For a flow system:
O
r
i
g
i
n
a
l

A
d
d
i
t
i
o
n
a
l

}
Lecture 4: Phase Equilibrium in Flowing Systems
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Determination of Unspecified Variables
F, T, P, T
F
, P
F
, Z
i


F =C+5 If variables are used to specify
Then remaining C + 1 ( )t +1
variables must be found from
A) mole fraction summations
B) K-Value relationships
C) Mass balances
D) Energy balance
t
t 1 ( )C
C
1
Lecture 4: Phase Equilibrium in Flowing Systems
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DePriester
In order to carry out an analysis of a separation which uses differences in
K-values between two phases to cause a separation, we need a source of
K-values.




A lot of equilibrium (K-Value) information for binary systems is
often contained in vapor-liquid phase diagrams.
For hydrocarbon systems, interactions between molecules are very similar,
and consequently, the K-Values will not be a function of composition. K-Values
at different pressures and temperatures for hydrocarbons can thus be graphed
for multicomponent systems.

One type of these graphs is called DePriester charts.

Another type showing vapor-liquid equilibria for a multicomponent hydrocarbon
system is shown in Figure 2.8 of the text.
Lecture 4: Phase Equilibrium in Flowing Systems
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DePriester Charts: Low T
Lecture 4: Phase Equilibrium in Flowing Systems
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DePriester Charts: High T
Lecture 4: Phase Equilibrium in Flowing Systems
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DePriester Charts: High T
Lecture 4: Phase Equilibrium in Flowing Systems
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DePriester
Lecture 4: Phase Equilibrium in Flowing Systems
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Summary
In this lecture we discussed:
How to carry out energy and entropy balances in flowing systems
Availability and lost work
Gibbs Phase Rule for flowing systems and system specification


How to use DePriester charts to determine k-values for hydrocarbon vapor-liquid systems
F =C+5
Next Lecture will focus on:
Isothermal Flash calculations
Derivation of the Rachford-Rice Equations
Use of Newtons Iterative method to solve the RR equations
An example using the RR procedure with Newtons method
and DePriester charts to describe equilibrium