PETE 310

Lecture # 29

Chapter 14
Equilibrium Ratio Correlations
(K-values)
Gas-Liquid Equilibrium
Non Ideal Behavior
When evaluating VLE we use models for the equilibrium
ratios (Ki-values)

Simpler models Ki = f (P,T)

low pressure applications
explicit

More complex models Ki = f(P,T,xi,yi) use equations of state

EOS (current), or convergence pressure methods (earlier)
apply lo low and high pressures
implicit, highly iterative
Whats a low or a high pressure?

Separator pressures for a black oil are

usually considered low
Reservoir pressures considered high are >
1000 psia, but this limit depends upon type
of fluid
For black oils simple K-value correlations do a
good job
Volatile oils and gas condensates have a more
complex behavior
K-values
Compositionally independent correlations assume
that k-values depend upon pressure and temperature
only
In fact Ki values depend upon the type and
proportions of other molecules in the mixture
Example: Your behavior is different when you are
surrounded by people of your same age than when you are
surrounded by professors, or potential employers
 Statement of Equilibrium
Only component
yi xi K i 3 has a vapor
pressure for the
selected T 2 & 1
are supercritical
1

P 2 3
P3
T
 Bubble Point & Dew Point
Evaluations
The bubble point pressure at a given T is

yi zi K i pbp ,T ,...) 1 zi K i pbp ,T ,...

The dew point pressure at a given T is

yi xi K i
zi x i K i ( pdp ,T ,...)
Flash Calculations
Objective function (flash function) is

zi K i
F ( fv ) 1 0
1 fv K i fv
One of the Models for Equilibrium
Ratios
Requires critical properties & acentric
factors

pci Tci
Ki exp 5.37 1 i 1
p T

We need other models for higher pressures

For higher pressures and temperatures

Equilibrium ratio charts for different

convergence pressures
Tedious but
Illustrate fundamental concepts
Equations of State (mainly cubic)
Tedious by hand
Suitable for computers
More in later lectures
Convergence Pressure Equilibrium Ratio
Charts
Plot Ki vs p in a log-log
scale
K-values converge to a
unique pressure called
convergence pressure
But this convergence
pressure depends upon
type of fluid
Black oils have convergence
pressures of about 10000
psia
Observed experimental
behavior (see Fig. 14-1 and
14-2) of text book
Convergence Pressure Highlights
Is a property that takes into account the compositional effect
When the mixture is a volatile oil the K-values of their
components have convergence pressures of about 7000 psia
When the mixture is a gas condensate the K-values of their
components have convergence pressures of about 5000 psia
Book contains only charts for convergence pressure (pk) of
5,000 psia
90 Convergence pressure charts are tabulated for pks of 800,
1000, 1500, 2000, 3000, 5000, and 10000
Convergence Pressure Highlights
Convergence pressure is found iteratively
Some interpolation may be needed among charts
Charts have not been digitized and no publicly available
equations have been generated from these charts (GPSA
have computer codes at a cost)
Procedure is lengthy and tedious
For repetitive computations (reservoir simulation), Equations
of State (EOS) have replaced this methodology
Still a good approach for few calculations
Other Uses of Convergence Pressure
Charts

To determine the pressure range of ideal

behavior
To have a quick comparison among K-values
of different components
To estimate vapor pressures
Convergence Pressure Equilibrium Ratio
Charts

Note the slope for low pressures

Errors: Black Oil at Surface Conditions
Errors: Black Oil at Surface Conditions

What would be the percent error in the

evaluated liquid produced at 65 psia and
120 oF if the K-value for methane is
15% higher than the actual value
15% lower than the actual value
How about the effects of the other components
in the mixture?
Errors: Retrograde Gas at Reservoir
Conditions
Errors: Retrograde Gas at Reservoir
Conditions

What would be the percent error in the

evaluated liquid volume at 2650 psia and
195 oF if the K-value for C7+ is
15% higher than the actual value
15% lower than the actual value
Which are the most influential
components
Equilibrium Ratios for Methane
Convergence Pressure = 5000 psia

Note the
slope and
dotted lines
Equilibrium Ratios for Ethane
Convergence Pressure = 5,000 psia

Given a
temperature
lower than the Tc
of C2, How can
we estimate the
vapor pressure
of C2 from this
chart?
Equilibrium Ratios for Octane
Convergence Pressure = 5,000 psia

According to this
chart, what is the
pressure range for
which we could have
used the Raoults law
model for KC8 as a very
good approximation?
Standings K-value Correlation
(SPE 7903)

Correlation good for

Pressures up to 1000
psia
Observed behavior

F is a component
characterization factor

Number in chart
indicates compound
Standings K-value Correlation
(SPE 7905, JPT - September 1979)
Is the normal boiling
Correlation is T
bi point temperature
of the component
a cF
10
Ki
p
With
pci
log
1 1 14.7
F bi bi
Tbi T 1 1
Tbi Tci
(T in oR and p in psia)
Standings K-value Correlation
(SPE 7905, JPT - September 1979)

Correlation is (F already defined)

a cF
10
Ki
p
With
4
a 1.2 4.5 10 p 15 10 8 p 2
4
c 0.89 1.7 10 p 3.5 10 8 p 2
Values for bi and Tb (from SPE paper)
For heptanes and heavier we can use

We will use the following approach

KC 0.15 KC7
7

Other approaches include using an equivalent

carbon number that determines a normal boiling
point for the heavy fraction (paper)
Modified Homework
Use the data from problem 14-1 and determine the K-value
for each component at T = 160oF and p = 1500 psia
Compare the K-values with the K-values provided in the book
Indicate the % differences
Calculate the initial oil composition if the fraction of gas
produced with the old K-values is 10%
Use the recently obtained reservoir composition with the
new K-values, run a flash and determine the new gas
fraction.
Compare with the previously reported one and discuss