Sodetyof Petrokurl En#leers

SPE 28589
A Comparison of Equation of State Tuning Methods
R.C. Merrill, BP Exploration; K.J. Hartman, Mobil E&P Technical Center; and J.L. Creek,
Chevron Petroleum Technology Co.
SPE Members

@@@

19%

SocietY of petroleum Engineem, Inc.

Thii paper was prepared for prewntaticm at the SPE Wth Annual Technical Conferet?-caand Exhibition held in New Orleats, IA, U.S.A., 2S-28 September 1994.
This paper was aebcted for presentation by an SPE Program Commmee following review of infmmetion contelned in en ~act
submitted by the authods). Conienff! of the ~-,
= w~t$d,..nc!.M@ad
by tha Soctety of Petrc4eum Enginecm and am 8ub@t to cormtion by the autf!cds).The material, as presented, does ml necessarily refbti
. .-... LU- ,--1.
1=,+*.i.lr.l)uniltOQ~Qf!@ S.xbty
any poaitbn of the Society of Penobum Engineem, its officer% o! membrs, P8parepreeentedet SPE mwtingn w subjea w pwmak, ,*..y . . ... . . . . . ........
d~m
E@~.
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of when and by WIIOM ma WIPW ~ Pm8snted. Write Libmrim, SPE, P.O. Sox 83S826, RMwdsIM ,7X 7YX3.W2S, U.S.A. Talex, 162245 SPEUT.

Abstract
Equations of state find widespread use for their
--.-:ability to describe a wide variety of reservcm
fiuid behaviour. However, this description is not
predictions.
usually obtained through a-priori
The parameters of the equation of state (EoS) often
need adjusting (tuning) before yielding usable
reservoir
predictions.
During tuning,
the
parameters of the EoS are adjusted to make the
predictions match a variety of experimental data.
As part of an industrial joint-venture,
three
Peng-Robinson equation of state models were
developed to describe a single set of phase
behaviour and PVT data. The EoS models were
developed
independently,
and their variety
illustrates the different techniques available for
This paper concentrates on: the
this purpose.
differences in each of the development processes,
the resulting match, and the effect this has on aThe paper
priori
slim-tube
predictions.
examines the rationale behind the choices made
during development.

consistency in the application of a technique is

more important than the technique itself.
The co-operative nature of this work serves as a
..----- $..1:lliie**m*ifin
Suuufzaalul
Illu=lllallwll 0,f ps w- inhnront
......... ctrrmrrth
.. -..-... of
joint ventures. The participating companies have
used this cross-fertilisation
to ensure the
technical integrity of their methods.
Introduction
Cubic equations of state (EoS) have found
widespread acceptance as tools which permit the
convenient and flexible calculation of the phase
They facilitate
behaviour of reservoir fluids.
calculations of the complex behaviour associated
with rich condensates, volatile oils and gas
injection processes.
Despite their flexibility (or perhaps because of
their flexibility)
the parameters
of a cubic
equation of state often need adjusting prior to
application to a particular oil field fluid. A priori
phase property predictions are difficult because:

The three methods share many similarities in

their execution,
however,
there are some
pronounced differences.
These differences are
most obvious in the treatment given to the
different classes of experimental data during EoS
development. Despite these differences, the models
were all suitable for reservoir development
purposes, which leads to the conclusion that

1)

References, tables and illustrations at end of paper

259

The character in terms of paraffinic,

napthenic and aromatic molecules of the oil
is not generally known. It is difficult to
assign
an
appropriate
boiling
specific
gravity,
and
temperature,
molecular weight to components of the
plus part of the oil.

A COMPARISONOF EQUATIONOF STATETUNINGM~HODS

2
~~e
~)

.f~aw#

-f *ha
UI Ill=

state also come

circumstances.

c.irvlnlc,

mlllplc

into

n, *N-

Uuulu

play

an, ,mtinn fif

=Ufuallull
WI

Data

in certain

The data forms the core of any equation of state

tuning process. This study is primarily concerned
with volatile oil data measured as part of a gas
injection study. Table 1 lists the experiments and
the measured quantities available.

Adjusting the parameters to overcome these

limitations is called tuning or characterizing
an equation of state. Many methods have been
proposed for this process. Most involve changing
the description of the heavy end or C 7+ portion
of the fluid, while others alter other parameters
(for example see references J213 and others).
More recently, there have been discussions
regarding what sort of data should be used in the
tuning process.4
Our paper has different objectives, and these are
three-fold:
1)

SPE 28589

Investigate how three different companies

would approach the tuning process for a
common set of data.

2)

Describe the choices made in the course of

the tuning processes.

3)

Compare the final results of the processes

and decide
whether
the different
radically
different
approaches
give
predictions
for
answers for a-priori
which there are no data.

In order to achieve these objectives it was

important to maintain the independence of the
three investigators; prior discussions regarding
the !echniques would have obviated the point of the
study. We used the following procedure:
1)

A single data set was chosen and distributed

to the participants by a third party.

2)

The investigators developed their EoS

models independently, using their own
techniques.

3)

The final results were collated and

discussed only after the models were
devebped.

The ?u~ing ef an eq~a!i~n nf

-. ctata
... . k
. a
- midti.den
...... ----~
process.
To avoid confusing the reader each
company will be treated in a single subsection;
contrasts
between the approaches
will be
performed in a later section.

During the EoS comparison different philosophies

of data treatment were immediately apparent.
Company A proceeded directly to the tuning step,
expecting that possible problems with the dataset
would be revealed during the tuning. Company B
.- ...4 Illule
---b:
. . --:AA.:-- um
b.* uata
A-4- uca~i
b-n 4..-:-mile wimluelulg
LUIIUIg
Spelll
the equation of state. Company C used an extended
EoS model to assess the data prior to the tuning
step.
Co. B Cheds
Neither the sixteen stage differential liberation
(DL) nor the separator test data contained gas
gravity data. This made a rigorous mass material
balance check impossible to carry-out.
It also
in tha
ti ininfi
etrataau
mm-ne=;i-+n~
- nhanma
llGuGsallaLGu9
Wtbalayu111111s2
LuD191e~
-sbutw~y lean
~-ww
below). The four stage differential liberation data
did not contain sufficient information to perform a
material balance, but it did have sufficient data to
Hoffman
construct
plotss of Ln[KP] vs.
characterisation factor.
These are similar to
that shown in Figure 11. Hoffman plots are not
particularly sensitive checks, but they are useful
to identify trends in the data. These plots suggested
that the compositional data become less reliable
This result is hardly unexpected;
past C14+.
quantification
of the higher carbon numbers,
particularly in a gas, is often elusive.
Full material balance information was provided
for the contact data. Graphical interpretations of
the two experiments are provided in Figures 1
and 2. The forward contact experiments show an
excellent material balance throughout the series.
The backward contact experiments show a good
material balance for the first contact, this
deteriorates for the second and third contacts. The
lab noted problems for the second and third
contacts, where the material balance error climbs
from <2.5Y0 for contact 1 to over 9% for
From the error in the methane
contact 2.
balance, it appears that more methane was added
than was recorded.
Those experiments which did not contain enough
information for a complete material balance were

260

R. C. MERRILL, K. J. HARTMAN AND J. L. CREEK

SPE28589

14.7 to 1,000 psia and 100~50 F.

If the
equation of state predicts a bubble point pressure
for the separator liquid in excess of the separator
pressure
at separator
temperature,
the
composition is in error or the samples are
mnsidered to be of lesser quality. The calculated
composition of the gas in equilibrium with the
separator liquid at the bubble point pressure of
the separator liquid should agree with the
separator gas composition.

sense-checked
by plotting
the data and
There was nothing
comparing to experience.
unusual about either the separator or the
differential
liberation
tests when taken in
isolation, however, when compared to each other
the DLs GOR was 42% higher than that obtained in
the separator test. Although large differences
between the DL and separator GOR are not
gn~~mrnon, particularly
for volatile oils, this
seemed excessive, particularly for a reported oil
gravity of 43.1 API. The overall gas gravity for
the separator test was backed-out using the
empirical relationship provided by McCain:6
~.= (% -0.01357R,7)

Company C built a 23 component model from the

experimental data. The composition was input and
the simple match of the bubble point pressure
made. Figures 3 and 4 compare the experimental
and estimated results.

(1)

Pinif

The separator test scaled against the volume of

reservoir fluid are shown in Table 2. The gas-oil
ratio agreement is satisfactory.
The volumetric
data are not satisfactory. The calculated residual
oil gravity was 42.45 API compared with the
experimental value of 43.1 APL

This relationship yielded a gravity of 0.55, which

is less than that of methane. On the basis of this
analysis, we decided to omit the separator data
from further consideration.
An exception to this
blanket omission was the density of the stock tank
The reported density of 810 kg/m3 is
oil.
consisieni with the C7+ density (837 k@n3)
which was determined by the experimental fluid
characterisation. We decided, therefore, to leave
it in the experimental data-set.

The data seem satisfactory ior ine work ai hand.

Note the high uncertainty in the Z values for the
differential and the poor agreement between
predicted and measured volumes for the separator
test.

Co. cchras

The laboratory PVT and fluid composition data are

checked with the equation of state to establish the
consistency
of the composition
with the
experimental data. The extended analysis of the
C7+ cut is used to construct a large model (23
components in this case). The boiling point, and
density of the heaviest hypothetical component are
adjusted so the reservoir fluid density is matched
-.. a#.A...Th.
mn+iA
lllc :n*a.
abtlvst
1111=1
at the ~atu~aihii IJIe=WJie.
parameters of the hypothetical components are
adjusted as a group to match the saturation
pressure of the reservoir fluid. The fluid density
is computed with the chain of rotators or volume
shifted Peng-Robinson equation of state.7 The
initial property estimates for the hypothetical
components are taken from Riazi and Daubert.8g

Equation of State Tuning Methods

Q). A
This problem was approached as a straightforward
tuning to static data so as to form a basis for
comparison to other companies tuning methods.
Our most typical equation of state application is
. .
c.;rnt,lmti-m
nlthniifih
~,~~
CG~pOSiii

GPi G!

al$iiutatlwlt,

altllwu~bl

applications to surface facility design are growing

in number and complexity.
Compositional
simulation was regarded as the destination of these
model parameters.
We use the Peng-Robinson (1978) equation of
Densities are predicted using a third
state. 10
shift parameter as reported by Pen610ux, et. al.
and Jhaveri and Youngren.l 1~12

Company C uses cumulative experience with the

equation of state as a sense test of the PVT data
An example of this is
from the imposition.
checking the composition of the separator liquid
and gas at separator conditions.

We commonly, but not always, characterise the

C7+ fraction with a iumping/splitting procedure
This
based on that proposed by Whitson.313
method assumes that the component distribution in
a fluid can be represented by a mntinuous, three
parameter, gamma probability function.
The

The Peng-Robinson equation of state generally

under predicts the K value for methane from

261

A COMPARISONOF EQUATIONOF STATETUNINGMETHODS

distribution function is fitted to available fluid

imposition
data to obtain model parameters
specific to that fluid. The continuous probability
function is then discretised using a modified
Gaussian quadrature technique to seiect ine besi
lumping scheme for the number of components
specified by the user. The user can override this
feature and pick the starting carbon numbers of
the lumped fractions.
In this case, we used the C7+ splitting/lumping
package, and tried from two to five C7 +
components. We carried these cases through the
multi-dimension regression step described below.
The two-component C7+ fraction characterisation
had the best match of the static data. It was chosen
for the comparison for that reason, and not because
it had the minimum number of components.
n.----:

-- rJI
-z *LnuIe
U7+ CG~pNK?RiS ii~~ iV3Si~fiWi
using a variation on Twus correlation. 14 This
method provides
smoothly
varying
critical
properties for paraffinic hydrocarbon components
with carbon numbers up to about one hundred.
These properties are modified for the aromatic
mntent of the fluid based on molecular weight and
If no specific gravity data are
specific gravity.
supplied, a typical distribution
is assigned
which assumes
increasing
aromaticity
with
increasing molecular weight.
An aromaticity
factor, A, is defined in the following manner:
rrwpwmrs

s.g.~

(2)

bfl_par-b
barm

where A =

bn_par

O
.575
1
>1

Tuning
is done with a multi-dimensional
regression scheme.
A rotational discrimination
method is used to calculate parameter changes in
the non-linear regression so as to minimise the
objeciive
of ine
error
funciion.
we
simultaneously perturb the regression parameters
and evaluate the Jacobean coefficient matrix
through numerical derivatives.
In this case, three regression parameters were
used. The C 7+ critical properties and acentric
factor were adjusted by regressing
on the
aromaticity parameter.
All binary interaction
parameters
between
the light and heavy
hydrocarbon components were varied together,
with the relationship between methane and the
heaviest component
controlling.
The shift
parameters of the C7+ components were also
regressed together, so that changes within the C7+
I---.,
_- .-----. .-.--.,rracuon
were syslemauc.
All of the static data (not the multi-contact data)
were used, with all points having equal weight.
Limited attempts
were made with various
weighting schemes, but none significantly affected
the resulting match. The comparison of the tuned
model to the data and the other models is discussed
later.
CO.B
Equations of State are customarily used to model
the detailed phase behaviour of a process. One
particular use of the EoS is to permit the transfer
i~~
rnearunir.,,
nnminaarinfi
anrt
of rlata
M. hatwnan
. ..,,
,,
.. ~.. .~ . . ..~
..
facilities engineering disciplines.
This usage
requires a detailed equation of state with individual
components in the C6. region and a fairly detailed
If compositional simulation is required, a
C7+.
reduced component equation of state is developed
using a suitable technique.

V=~=a(MW)+b

A=

SPE 28589

n-paraffins
naphthenes
aromatics
multi-ring.

Critical properties are assigned based on the value

of A.
,.....L.
mmal nyarocarbon binary inieraciion parameters
are set using an in-house correlation between
methane and the heaviest hydrocarbon component.
All other non-zero hydrocarbon BIPs are then
.-l,. *:---L.:A..A..AAL..-...A UI
-.. I IIL.:UGI IVGU uaarm
Ii= I matkn
ISI IqJ.

262

We use a Peng-Robinson (1978) equation of state.

Densities are predicted using the Pen610ux shift
technique.
A modification of Whitsons 1989
technique is used to develop the pseudocomponents.
In this modification the r-function is replaced by
an exponential decline. The exponential decline is
applied to the appropriate
portion of the
mrnerimr=mtai
data (in
this C2SQ tha
C +~ . \
--v--.. . . . . . . . . ---. .. . . . ..w -=-w
. ..v
-117/.

Thgj ~.~

to CI o components are lumped by hand into

appropriate
pseudocomponents.
The exact
distribution can vary from model to model, but the
nftcm
mncmtcuf
hu
tcinn
~rnp~neni~ ar~
---. ..,.. RI
--=~.-J I.
oo~ Whitcnnlc
. . . ... . . .
r-function.

SPE 28589

R. C. MERRILL, K. J. HARTMAN AND J. L. CREEK

The Twu correlation is used to determine the

individual
properties
of
the
critical
pseudocomponents. The characterisation factor (as
defined by Whitson) is kept constant for all
-.-,
mAAm*mnnnnnte fineaeinnallu
/stthnl
mh nd
in
Ww--r.
.,..,
,- . . ..~!.
...
.. .
pmuuwwlllpnlwalk-.

After the mass and molar properties are matched,

the volumetric are adjusted by altering the shift
parameters of methane and the C6+ components. A
regression is used to match the reported densities.

this case), the Kesler-Lee correlations

instead. 5

suggested by Jhaveri and Youngren.

Thn

,,,e

are used

Compositions are @wavs dealt with in weight

fraction.
This facilitates changing the C7 +
molecular weight (M. W.) which is used as the
primary tuning parameter. It also permits us to
Many
change the M.W. basis of the fluid.
laboratories report compositions based on nalkane M.W., however, for EoS tuning purposes we
usually use the M.W. suggested by Katz and
Firoozabadi.l 6
Binary interaction parameters are determined
using a modified Chueh-Prausnitz relationship:

(3)

The adjustment of C7+ M.W. and exponent p are

We find this faster than
performed by hand.
deciding upon the correct weights to use in a
If we are unable to achieve a
regression.
reasonable fit using these parameters, we will use
In this regression the
a limited regression.
critical properties of the C7+ are adjusted as a
group:

.4)

naramatnre
~-r ..!..

~~~

rnlatd
, ,-.

by

?h~

fl
trmtinn
. ..,.-..

The lack of gas gravity data necessitated an

alteration to our tuning procedure. We could not
use the incremental mass of either the separator
or DL experiments as a guide for our tuning
process. Instead, we replaced the DL mass and
molar properties by the ~
GOR and the
relative volume, both relative to saturated
conditions. There are two reasons for choosing the
-...---- _l----------- -l!.?---sawralea rererence mnaumns:
1)

The DL process is a reservoir process and

thus should be referenced to reservoir
renditions.

2)

The last stage of a DL process (reduction to

atmospheric pressure) is often difficult to
simulate. Often the bulk of the error in a
fit occurs in this step. In our opinion, it
is unreasonable to bias the rest of the fit to
a point which is not relevant to the
reservoir depletion process.

For the volatile oil, it was necessary to lower the

C 7+ molecular
weight
from 202 g/gmol
(reported) to 190 (-6.3%). If this change were
greater than 107., we would have reconsidered the
experimental data and/or the tuning process.
ac
OrWT-In9nW
P
tiene
Wwlllpllly
w UG9G0

anrf
watirm . nrcww
.
. eatt
. .....-.
~. ------ Ire=
---

37:

~+

The fit is then tested for internal consistency with

itself and general consistency with the data.

The pre-multiplier Ai was set to zero for i2C4.

The exponent p was the second tuning parameter.
We normally
start our tuning process by
calculating
the material
balance for each
The material balance calculations
experiment.
serve two purposes, 1) they serve as a quality
check of the data and 2) The equation of state is
tuned to match the incremental mass values of V/F
determined for the differential liberation, contact
and separator experiments (V/F = mass fraction of
vapour from a flash).
Other areas considered
important are the gas gravity of effluent vapour

C -.

II Imnad
,, ,yw

marlalc
,S,, e fnr
).

a unriatu
M
.-! ..,

nf
.

process and reservoir problems. The first step

after data validation is to examine the C7+ fluid
composition by plotting the mole fraction of each
component versus carbon number. This linear
portion
of this plot reveals
where semicontinuous
thermodynamics
is applicable.
Component C7, C8, C9, and CI o were assigned
properties from the fluid analysis provided. The
C I I + was split into two additional hypothetical
Behrens-Sandler
with
the
components
technique.17
Minor adjustments are made manually to obtain an
approximate match with the density and saturation
The constants Qa and fZb for each
pressure.

. .
u.Y
c J-r<i.i

263

A COMPARISONOF EQUATIONOF STATETUNINGMETHODS

hypothetical component are optimised. Normally

ine mnsiani composition expansion ciaia wiih iiquia
volumes are the preferred data for regression.
The problem was simplified
here by only
optimizing on the hypothetical component Qb
values. The differential liberation data was chosen
because of previous success with volatile oil
samples using these data.
Similar results are
obtained regardless of whether the differential
liberation or the constant composition expansion
data are used for regression.
The constant
composition expansion are the more reliable data
--11
-, -- - -. --,-, :- -_----- z.- .L - -L--since no ma[erlai IS removeu worn me pnase GWI
during the experiment and the experimental steps
are easier to execute. The optimised f2b values
were mnverted to optimised Tc and Pc values by
solving

c
bc=Q,~

(5)

PC=

and assuming the f2a = 0.45724, that ac and b have

ennetsnt
-...U.

mc
. . uah
.-.

that dlOW K2b

component.

and finrfinn
u..
....,..~

tha
,..

ual
me
.U, Iw

nf Tand
,
. ~ u..-

is even more striking when the relative volume is

. . . .-.
-,....
alsplayeci in iis more usual Iormal (Figure $)j.
The underlying cause of this improvement in the
volumetric fit is due to the treatment of density.
The densities
predicted
by model A are
significantly less than those predicted by either
model B or model C. The residual density of this fit
is 772 kg/m3, for the B and C the values are 864
kg/m3 and 838 kg/m3. It should be recalled that
a residual oil density was not reported, however
the stock tank density from the separator test was
The initial reservoir densities of all
810 kg/m3.
three equations are similar, but the density
changes far more rapidly during depletion for
models B and C.
A second reason (largely dwarfed by the density
effect) lies in the mass of gas liberated in the last
(lowest pressure) DL step.
Model A liberates
approximately 30% more gas than either Models B
Qrc.

(RTC)2
ac=

SPE 28589

P8~

At reasonable reservoir conditions (>500 psia),

the models give similar depletion behaviour, as
illustrated in the first figures of this series.
Turning io ine aeiaiiea composiiionai aaia oi ine
4 stage differential liberation, we see that all
equations yield similar K-values over the entire
pressure range measured (Figures 10 and 11).
The EoS models are closer to each other than to the
original data, and tend to predict lower K-values
than those observed.

0.07780 for each hypothetical

We find that volatile oil data are difficult to fit

because the data are difficult to obtain since
experimentally one is near a critical point and
because of the equation of state is extremely
composition sensitive in the near critical region.

.MI
....iltinle
y.

Cnntcmt
-,
#..#.

The final fit was checked for internal consistency

and match to the data.

Figures 12 and 13 illustrate the models fit to

Figures 14
the forward contact experiments.
and 15 do likewise for the backwards contacts.

Data Fit

All of the equations of state yield similar results.

The K-value results are qualitatively similar to
those obtained for the 4 stage DL experiments.
Each model tends to underpredict the K-values of
the system. The bulk results, in terms of mass of
each phase, are predicted similarly, although
Model A appears to consistently underpredict the
density of the condensed phase, which leads to
difference in the equilibrium volumes.

Constant Composition Expansion

The three models give indistiguishable fits to the

CCE relative volume data. Figure 5 displays the
fit to the liquid saturation measurements.
The
..l.
.-J.. ..... .L.. J.
iiiree niodeis give similar prealcuons 10mls aaIa.
Diffetentia/ Liberation

Separator Test

The differential liberation fits are displayed in

Figures 6 to 9. The data are displayed relative to
saturated conditions.
Co. As fit to this data is
quantitatively superior to the other two fits; this

264

The differences
in the predictions
for the
separator
test experiment
are provided
in

SPE28589

R. C. MERRILL, K. J. HARTMAN AND J. L. CREEK

It should be remembered
Table 3.
Models B and C discounted this data.

interesting; Co. C remariieo on ine size of Co. A and

Co. Bs parameters, whilst A and B were suqxised
by the smallness of Co. Cs. To some extent, it is
believed that the larger methane interaction
coefficients used by Co. B compensate for the
lowered molecular weight of the fluid.

that both

Discussion
The three models were developed using remarkably
similar procedures, despite the independent nature
of the work. As a consequence, the models have
very similar critical property trends, as shown in
Figures 16 and 17. The largest differences occur
in the selection of the C7+ pseudocomponents. The
Semi-continuous thermodynamic approach seems
to be widely
implemented,
although
each
These
implementation
has minor variations.
techniques result in the selection of properties
with similar trends.

Corrskferations 0/ Fit

..
The single most important difference in tie modeis
is in the treatment of the experimental densities.
This is reflected in the Pen610ux shift parameters.
Co. B had the largest, and these were obtained by
regressing SXlieiyagjairiSi CMWty CHa. Ca. A% w~ie
the smallest, and were obtained during a general
regression which included all the data points and
two other regression parameters (aromatidty and
binary interaction parameters).
All three models capture the decrease in volume
and release of gas when viewed from a reservoir
However, models B and C fail to
perspective.
capture the behaviour when viewed from a more
traditional reference point of residual conditions.
This is illustrated in Figure 9. This figure also
shows the effect of turning off the volumetric shift
This matches the separator data
parameters.
(within
3%) and improves
the initial
DL
formation volume factor. It has the unfortunate
effect of leaving one with a 70API oil at stock
tank conditions.
Removing the shiff parameters
also adversely affects the relative volumes from a
reservoir perspective, due no doubt to mismatching the densities.
Interestingly, it is possible to duplicate the same
effect by increasing the shiff parameters of the
heaviest components to the unrealistic values of
+0.4.
The results are similar to those just
described,
including
a residual density of
It is clear that arbitrary
=730 kg/m 3).
regression of these shift parameters is a trap for
the unwary.
The largest differences in the parameters which
govern pure phase behaviour occur in the binary
interaction parameters. The discussion here was

285

Company A felt that good matches were obtained for

the DL and the CCE data. The separator match of
GOR, formation volume factor and stock tank
density shows the compromise that the regression
routine made with these three diverging data
points. Since all points had equal weight, and there
were more relative volume data, that data was then
weighted more heavily than the separator data.
The MCV experiment was not regressed against.
- .,
-,. L rosslrxy, me compromise iii density fiiaich caused
by regressing against the separator data may have
influenced the liquid volumes predicted for the
MCV. The overall match was acceptable, although
t., cwa
if +hie
*~~@m
#s. atsa
hnwina
nnlw
a
einaln
uaaG,
llavlvl~
vtlr~
u
otll~mw
1111= WGI=
6
fluid sample would have been regarded as risky,
especially considering the volatile nature of the
fluid.
Companies B and C were disappointed
goodness of their respective fits.

in the

Company B was concerned with the validity of the

separator test. The sensibility check revealed
that there was some evidence that the separator
test was flawed. If this had been the case with an
operating asset additional data would be collected,
or increased reliance would be placed on other PVT
samples. The uncertainty in the B. value would
not be acceptable for reservoir planning purposes.
On the whole model B was deemed a good match to
the reservoir data.
Company C was also concerned with the separator
data, although satisfied with the match to
reservoir data (which was characterised
as
fair). Company C believed that the fault might
lie with the data since our model usually
underpredicts the formation volume factor and
separator GOR. This last comment was met with
interest by B, since the default values for model B
usually overpredict the separator GOR and B. by 4
-870.
During the after-action discussion, Co. C pointed
out that one could perform a material balance
check on the separator in molar units.
This
material balance check was quite good (=0.5Yo).

SPE 28589

A COMPARISONOF EQUATIONOF STATETUNINGMETHODS

This is not consistent with the unusual gas gravity

calculated
from the mass material balance
equation. This leads to the possibility that the feed
composition is incorrect. Feed compositions are
usually determined via a singie stage fiash,
where the overall composition is determined by
mathematically recombining the liquid and vapour
An error in this step would be
compositions.
difficult to detect but would lead to the observed
inconsistencies between the EoS predictions and
laboratory measurements.

Doint.
the measured bubble ,
Similar critical
volume vs. molecular weight relationships were
used for all three models and the Lohrenz-Bray Clark correlation was used to predict viscosity.20
Pressure drop profiies for the three cases were
very similar.
Figure 18 shows the recovery in
pore volumes produced and the associated gas/oil
ratio at standard conditions. Figure 19 shows the
mole fraction of C7+ components in the produced
vapour phase (Yc7+) at reservoir conditions. The
figures are divided into regions 1,2,3 and 4.

Equation (1) can be used to back-calculate any of

the parameters. All of the EoS models predict a
surface gas gravity of =0.73. If one uses this
value to back-calculate the stock tank gravity, one
This is
obtains a density of 735 kg/m3.
significantly
less than the reported value of
810 kg/m3.

Region 1 runs from O pore volumes injected (PVI)

to gas breakthrough. This occurs at 0.49 PVI for
the A and B models and slightly later, 0.53 PVI,
for the C model. For all three cases, production
after breakthrough consists almost entirely of
fluid which is vapour at reservoir conditions and
liquid at stock tank conditions.

With the separator

data in question,
and
deliberately omitted from some of the fits, the
final results must be judged on the basis of the
reservoir information.
On this basis, there is
little to choose between the models. Model A
provides a slightly better match to the volumetric
depletion data whilst models B and C perform a bit
better for the volumetric contact data.

The first shoulder (0.50 to 0.85 PVI) in the GOR

and YC7+ curves is Iabelled Region 2. It is the
result of equilibrium conditions between the
injected methane and the initial reservoir fluid.
Model B shows a somewhat different equilibrium
balance with Yc7+= 0.069 vs. 0.052 for the A and
C models.

A-Priori Displacement Study

We have sofar discussed tuning and quality of EOS
models using static PVT data. We also examined the
performance of the three EOS models under flowing
conditions. Because we had no such data available,
we could only examine differences in predictions,
rather than quality of fit.
We modelled a slim tube displacement using an inhouse compositional simulator.
The slim tube
model was based on an actual
system.
Experimental and simulation results, including
relative permeability, using this displacement rig
and simulator
model have been reported
previously.18 119 We conducted this study both
with and without
a correction
factor for
relative
interracial
tension
effects
on
While recovery was somewhat
permeability.
higher with IFT effects included, the effect of the
EOS models on the results was not significantly
different.
Five hydrocarbon pore volumes of methane were
injected into a 100V0 volatile oil filled slim tube
Tb.:-.---, ,.- la:- awul
-hAl.*
=n
mei A.,=I 111s pGaaule
dv
pal
WV8=1
~i 5112
@~.

286

Region 3 (0.85 to 1.20 PVI) on Figures 18

and 19 is a smooth extraction of the remaining
C2-C6 components from the liquid phase. This
extraction takes place very smoothly for all three
models because of the numerous components. The
YC7+ decreases as the solvent effect added by these
light ends is dissipated as they themselves are
completely extracted and produced.
Region 4 (1.2 to 5 PVI) shows the extraction of
the C 7+ components and reflects the various C7+
splits of the three models. Model A, with only two
components and a maximum mol. wt. of 333, shows
the C7+ fraction extracted in a large lump. This is
why the model A recovery curve is accelerated
over that of models B and C. Model B, with five
components and a maximum mol. wt. of 540, also
demonstrates some stepwise extraction of the .C7+
components. Model C has six C7+ components. In
addition, the extractable intermediates are treated
as individual components C7, Ca andc9. Model c
shows the smoothest performance, with the least
stepwise extraction in the GOR and YC7+.
Figure 20 shows the recovery
When
reservoir
conditions.
mnneiAnrnA

s#vllalu

GIGu

nn

ZJ rnean~nir

Wll a

hseie

8s70s71 WWkncaa#s?,

C%

and GOR at
recovery
is
A w,,
and
n

f%
.

-R

give very similar results. The breakthrough for

Co. C was delayed by 0.04 PVI. Contrarily, in
n ..-..I 0 e.- m-.+ eimilnr Iettandsrd

dh(?~

irIS~~~@~

i31 IU

UIG

IIIW

I IIICU

I~,CU WA!

7)

II, ~a~~
~~p!~@Qn~
fQr
cer:mgy
field-scale simulation of gas injection into volatile
Field-scale
compositional
simulations
oils.
frequently require minimisation of the number of
Premature
recovery may be
components.
predicted with a model that has too few C7+
components. It is suggested that sensitivity studies
be conducted prior to ensure that the required
If slim tube data are
detail is maintained.
available, the EoS should be confirmed.
-

This work has provided information regarding the

current state of the art in equation of state tuning,
by illustrating and comparing tuning methods
three different companies.
The following points
era
al nr.
al
~ ~leal.
1)

The equation of state tuning process is

highly dependent upon high quality data.
When even one item of suspect data is
included it can bias the entire fit.

~-Q~~O~~

of
different
C7 +
was clearly seen during

D~~di!2ik)r!

displacement. data may be

sensitivities to
!Qrnps.

-#..-, ,i*e
I GSult=

Conclusions

The
effect
characterisations
an
CL..

condition recoveries, and GORS ) or A and C are

most alike (Yc7+ in Region 2).
7L..
I IIGW

R. C. MERRILL, K. J. HARTMAN AND J. L. CREEK

SPE28589

Q!

2!

Sii!ll

iub~

to actual slim
-Tuning

tube

necessary, as well as
number and type of C7+

Acknowledgements
The authors gratefully acknowledge the permission
of B.P. Exploration, Chevron, and Mobil to present
this work.
We also acknowledge the crucial role played by
Heriot-Watt University (Edinburgh, Scotland) for
providing both the data and the forum for this
exercise.

Symbols and Abbreviations

Pstk

Formation volume factor, rb/stb

m---:... -$ bk- -*-.-L += Ir VII,
Al ~hdfis
UID
w,. .
Uel Iblly VI ~1l= ~LuGm Lanm

Pinit

Density of the reservoir oil, Ibm/f@.

Bo

M- c, -fWI tha
rslidO=- q~n
~~!!
=Ainipantc
IWun=
111=p=,
.Iwl ----- .-,
scale regression packages. In those cases
where regression was used, it was limited
wtihhl
narrow
io ceriain parmeiws
bounds (e.g. aromaticity, C7+ Mw, C7 +

Gas gravity (Air=l .0)

pseudo-molar volume, g/gmol, eqn 2
molecular weight
siope in equation 2

intercept in equation 2

barom

~b).

bn-par

3)

Semi-continuous thermodynamics appears

to have been generally adapted for
petroleum industry usage.

S9
A

intercept in equation 2 for aromatic

components
intercept in equation 2 for normal
paraffin components
specific gravity, 60/60.
Aromaticity, dimensionless
Premultiplier, eqn 3

4)

All of the equation of state models provided

reasonable descriptions of the reservoir
behaviour.

v
MW

~)

5)

The equation of states strength lies in its

ability to match the compositional paths in
mass or molar units.

6)

The EoSS ability to predict densities is

still a problem area.
Although the
Pen6ioux
shift
paraiiieiers
provide
?ie~~biii!~. ?he~ rnak~
judge the quality of experimental data on
an a-priori basis.
ii

irn~~~~ihi~

Critical volume, m3/mol

exponent in Equation 3
An EoS parameter, eqn 4
regression factor eqn 4
Pen610ux
shift
parameter,
dimensionless.
molar volume defined in equation 2
Heptanes plus in vapour
CnQ

!O

267

References

!Pariarpdarc
---...

10

COMPARISONOF EQUATIONOF STATETUNINGMETHODS

1.
Coats, K. H. and Smart, G. T., Applicationof a
Regression Based EoS PVT Program to Laboratory
Data, SPE Reservoir Engineering, May 1984, 277-

SPE 28589

of State to Improve Volumetric

Predictions,
SPE
13118, presented at the 59th Annual SPE Meeting,
Sept 16-19, 1984.

299.
2.

Thomassen, P. and
Pedersen,
K. S.,
Fredenslund, Aa., Thermodynamics of Petroleum
Mixtures Containing Heavy Hydrocarbons. 1. Phase
Envelope Calculations by Use of the Soave-RedlichKwong Equation of State, Ind. Eng. Proc. Des. Dev.,
B, 1964,946-54.
3.

Whitson, C. H., Characterizing

Hydrocarbon
Plus Fractions: SPEJ, 23, 1983,663-64.

4.

Merrill, R. C. and Newley,

T. M. J., A
Systematic Investigation into the Most Suitable Data
for the Development
of Equations
of State for
Petroleum Reservoir Fluids. Fluid Phase Equil, 82,
1993, 101-110.

5
Hoffman, A. E., Crump, J. S. and Holcott, C. R.
Equilibrium Constants for a Gas Condensate System,

13.
Whitson, C. H., Anderson, T. F. and Sareide,
l., C7+ Characterisation of Related Equilibrium Fluids
using the Gamma
Distribution,
in G7+ Fractim
.
.
CharacterIs@
Chorn and Mansoori, ads., Taylor
& Francis, (New York, 1989), 35-56.
14

Twu,
C.
H.,
An Internally
Consistent
Correlation for Predicting the Critical Properties and
Molecular Weights of Petroleum and Coal-Tar Liquids,
Fluid Phase Equilibria, 16, 137-150.
15.
Kesler,
M. G. and Lee, B.
Prediction
of Enthalpy
Fraction,
Processing, 55, 1976,153-8.

L, Improve
Hydrocarbon

16.

Katz, D. L. and Firoozabadi, A. Predicting

Phase Behaviour of Condensate/Crude-Oil
Systems
Using Methane Interaction Coefficients, J. Pe& Tech.
(Nov. 1978) 1649-1655, Trans AIME, 265.

Tians. AIME (1953) 198,1-10.

17
6.
-,

McCain, W. D., Ih,e

Pro-

of Petr-

2nd cd., Pennwell Books, 1990, p 318.

Ikhranc
,,,,!,

, ..

. .,

and
...

Rant+lnr
.-.-.,

v-.

.Q

-.

.. .

Tha
. . ..

I--lea

nf
a
. . .

Semicontinuous Description to Model the C7+ Fraction

in Equation of State Calculations, SPE Reservoir
Engineering, 1041 (August 1988).

7.

Chien, M.C.H.
and Monroy, M. Two New
Density
Correlations,
SPE 15676,
61st Annual
Technical Conference of the SPE, New Orleans, LA.
October 5-8, 1986.

18.

Bette, S., Hartman, K.J. and Heinemann, R. F.,

Compositional Modelling of Interracial Tension Effects
-.. .,. .. .-. .. . ..-
.- , -.
in fvtiscibie wlsplacemem processes, J. rer. acI. eng.,
June 1991, 1-14.

8.

Riazi, M.R. and Daubert, T. E., Prediction of

the Composition of Petroleum Fractions, Ind & Eng
ChenrPmcDev.(1980),
19,289-294.
9,

Riazi, M.R. and Daubert, T.

Property
Predictions,
Hydrocarbon
(1 980)115.

E., Simplify
Proc.
April

100
Robinson, D. B. and Peng, D.-Y., 1978, The
Characterisation of the Heptanes and Heavier Fractions
for the GPA PengRobinson Programs, Gas Processors
Association Research Report 28.
110

Pen610ux, A. Rauzy, E. and Fr6ze, R. A

Consistent
Correction
for Redlich-Kwong-Soave
Volumes, Fluid Phase Equilibria, 8, 1982,7-23.
12.
Jhaveri, B. S. and Youngren, G. K. Three
Parameter Modification of the Peng-Robinson Equation

19

Hartman, K.J., Culiick, A. S., Oil Recovery by

Gas Displacement at Low Interracial Tension, J. Pet.
Sci. Eng., JFeb 1994, 197-210.

20,

Lohrenz, J., Bray, B. G. and Clark, C. R.,

Calculating Viscosities of Reservoir Fluids from their
Compositions, JPT (Ott 1964), 1171-1176,
Trans.
AlME, 231.

R. C. MERRILL, K. J. HARTMAN AND J. L. CREEK

SPE28589

11

Table 1
Data Used for Comparison
1)

Reservoir

Fluid

2)

Constant

3)

Differential

4)

Four Stage DL:

5)

Forward

6)

Backwards contact experiment

Mole fractions,
component
molecular weights.

Composition

Composition

Relative
Volumes
(V/Vsat),
liquid
saturation pressure, saturation density.

Expansion:

Liberation

contact

densities,

component

saturations,

Solution gas-oil ratio, Relative

relative volume, Gas Z-Factor.

oil volume,

Vapour compositions, equilibrium

volumes, equilibrium gas density.

vapour

and liquid

Equilibrium vapour and fiquid compositions,

and densities (4 contacts with methane).

experiment:

same as (5). (3 contacts with methane).

For the CCE and DL experiments, the values are reported vs. depletion pressure.
In the
contact experiments the values are reported vs. contact number and for the separator test
the values are either by stage or overall.
In a backward contact experiment, the oil from the previous contact is brought into contact
In the forward contact experiment, the gas from a previous contact is
with fresh gas.
brought into contact with fresh oil. These processes are meant to simulate the front and
back regions of a displacement front.

Table 2
Company C Checks Vs. Separator Experiment
Pressure
psia
5,065.0
764.0
114.5
14.6
14.7

Source

Temperature
F

Rs
SCF/RESBBL

Expt Rs

so

SCF/RESBBL

Expt BO

VoO/[RESBBL] Vo/V[RESBBL]

212.0
66.9

939.6

909.81

1.0000

1.0000

719.6

715.26

0.6101

0.6421

68.9

156.3

141.24

66.9
60.0

63.7

53.32

0.5397
0.5024

0.5893
0.5695

0.0

0.0

0.4993

0.5869

Overall GOR
SCF/stb

Formation Volume Factor

rblstb

Stock Tank Density

kglm3

Experiment

1604

1.764

810

Model A
Mode!Et
ModelC

1766
1934

1.920
2.042
1.980

754
832
808

1878

Total

volumes,

SPE 28589

A COMPARISONOF EQUATIONOF STATETUNINGM~ODS

12

Gas-Oil Ratio, Rs

gog~
0

SCF/STB
-

N
0
N

0
0

Gee-Oil

Rob,

Rs

SCF/BTB

l- -:--- :-.. -:---: ----: ----.i

.0

g.

4
-:0
wA)

O1/A

270

.0

OWIOAWO1AmBIOM

R. C. MERRILL, K. J. HARTMAN AND J. L. CREEK

by-.

8;;:
Q/..

I:*

lWAd

271

- Z

4.0

2.8

EIpt

o ti, A

3.0

0 rxE
2.2

A tic

2.0

.*:*

4
>

.**8

1.0

.*

-1

-2.0

-3,0

1.0

-5,0

5100

31025

2550
Pressure, peia

1275

! . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ...!

Figur4

9.

Differential

Liberation

Formation

Volume

Flgura

factor

4.0

Eapt

&.A
CQ.

10.

Four Staga

D.L.:2S

MPa K-values

45

2.0

3.0

40

Cc.
tie
---cc.

35

Ca.
CO.

BB

***

vs. component

7 ~L
8*

A Cac

0.0

1.0

0.0

2.0

-1,0

-3.0

-3.0

C4mrac!erisat ion Factor: b (1 / 1.-1 / T)

-1
N

-40

Erot Vepouf
A
c
EXF4Lquid
A
B

---*C

30

25
20

-4.0
15

-6.0

J.

10

-8.0
3.0

.2.0

-1.0
C4mracteriserbn

FIgUra 11.

0.0

1.0

2.0

3.0

Four Step D.L: 4MPe KIvalbaa w6.coImponafd

3
Conlaol

Factor: b (l/T--l/T)

Flgura 12.

Forward

Number

Contacte,

Phaee

Maes

Cn

2
M
m

ul

0.60

-.

_=

--

0.55
}

ExprVepow
Cc.
A
CQB

D
---ac

Ce.
can

Exps1.iqui4
A

---sac

0.35

!
-

0.30

025

~-----

-.
<-.
.
----4
.

m
a

70

e----

e-.

e---

---

.,.--=--=

--

-5
1-

&

COnSWS
N
-4
u

Flguro 13.

4
Contact Number

Number
Figure

Forward Contact Experiment, Phase Densitiee

14.

Backwards

Contecte,

Phaaa

MaSS

b.

>

0.70
m
A
0.40

~ 0.40

0.30

CO. A

(%8

0.20

0.10
1

2
COIIWI Nuntmr

F19UW IS. Backward Contact Experiment, PlhaeeDenaitiee

200

100

Figure

16.

300
Molesulw Wsieht

400

EoS Perametere, Critical Temparatura

500

600

I&

,07

30

/
.

-- -_...
.

20
-.=
. -5

r_...
-

J
-

Co. A

-CO. B

10

000

----.

4..~

200

100

400

300
Mol*cular

Figure

0.07

Acentric

17:

FacIIor

and

0.06

Figure

\3

&e
Pressure

[r ~ ;
1

----.

. .

CO. C

.,..:]
10>

Soo

500

Wdghl
Critical

18:

-CO.B
g

Injauad

4
. . . . . . . . ..-

CO. C

Production
at S2andard
Condtions

o.a

Co.A

Vdumm-

10

0,5

---------

. . . . . . . . .. . . . . .

..-

0.05
8

0.4

.s

0.04

!!
0.3
0.03

L
. .
!

0.02
1.
&

0.01

0.00

- .
f..

!.

.,

7
. . . ---------------------

2
Pore Vdumss

Fiaure

19: Vsmorisad C-,. at

Co. A

~ 0.1

----.

.-t~,

0.2

.:

3
Injaded

Raaarvoir
Conditions

.4%.0

0.0
0

Pc4e Voluma6 lr-IJaasd

Figure 20: Production

at Reservoir
Condidona

CO.C