7th Offshore South East Asia
Conference, Singapore
SPE 17685
OSEA 88174
Enhancing the Evaluation of PVT Data
by J.K. Drohm and W.H. Goldthorpe, Woodside Offshore Petroleum Pty. Ltd.,
and R. Trengove, Murdoch U. (Australia)
This paper was prepared for presentation at the 7th Offshore South East Asia Conference held in Singapore,
2-5 February 1988. This paper was selected for presentation by a programme committee following review of information in an
abstract. Contents of the paper have not been reviewed by OSEA and are subject to correction by the author(s).
ABSTRACT
A procedure for evaluating the quality and
consistency of PVT data is presented. This
procedure uses the material balance and the
associated error analysis for investigating
experimental accuracy, and to identify the
sources of erratic data. The use of this method
to 'correct' erratic data is illustrated for a
near-critical or volatile oil and a gas-
condensate.
INTRODUCTION
The need for sampling of petroleum reservoir
fluids and the subsequent experimental
determination of their properties has grown in
the last decade with the increased cost and
complexity of recovering hydrocarbons. Reservoir
recovery mechanisms relying on compositional
effects (such as COz flooding or gas cycling),
and the construction of more elaborate surface
processing plants (e.g. LNG and LPG) have
created a situation where engineers must now use
mathematical models to understand and predict
phase behaviour in a whole range of
circumstances. It has therefore become
imperative that the experimental data used for
generating a mathematical description of a
particular fluid be of the highest quality.
Despite development in the theory and use of
equations of state (EOS) over the last twenty
years, the commercial experiments performed on
fluids to understand their behaviour have hardly
changed. The gulf that now exists between the
accuracy of some experiments and the accuracy
actually required can result in erroneous
predictions from equations of state, however
good they may be.
Traditionally the more sophisticated experiments
carried out on naturally occurring hydrocarbon
mixtures have been closely allied to the
anticipated behaviour of the originating
reservoir as the pressure declines. Reservoir
engineers have used this data 'for global
material balance calculations and also for
characterising the fluid with an equation of
state(EOS). This EOS characterisation is
References and illustrations at end of paper
626
2-5 February 1988
subsequently used to predict the fluid phase
behaviour in numerical reservoir simulations,
which can provide insight into the effects of
different production strategies. In contrast to
this, EOS characterisations in the field of
process engineering are often primarily (if not
solely) based on an extended compositional
analysis (sometimes up to C4o) of the fluid.
Considering the number of degrees of freedom in
process design, it is not surprising that few
experiments are conducted. Nevertheless, because
equations of state are relied on so heavily, it
should be recognised that a compositional
analysis alone i~ insufficient to furnish a
reliable characterisation. The experiments of.
the reservoir engineer are therefore a good
source ot additional data.
In this paper we review the conventional PVT
experiments used by reservoir engineers: the
constant composition expansion, the differential
liberation and the constant volume depletion.
The data obtained from these experiments can be
used in many different calculations, and
should form the basis of EOS characterisations.
Our main aim is to demonstrate an improved
'methodology' for evaluating the quality of the
data, whether it is needed within or outside the
reservoir engineering environment. The method
makes use of material balance calculations and
an error analysis coupled with a new variation
of the black oil PVT representation, recently
presented by Drohm and Goldthorpe 1 •
The application of the material balance
calculations to experimental PVT for the
calculation of fluid properties was first
outlined by Reudelhuber and Hinds 2 in 1957.
However their treatment never achieved wide
acceptance. In 1983 Whitson and Torp 3 presented
the work of Reudelhuber and Hinds in a clear and
usable manner, using current SPE nomenclature.
In addition they coupled this treatment to a
method for calculating black oil PVT parameters
first suggested by Dodson, Goodwill and Mayer 4 ·
in 1953. However, Whitson and Torp advocated the
use of equations of state rather than the
complicated sampling procedure favoured by
Dodson et. al. Drohm and Goldthorpe reformulated
the black oil PVT representation so that, whilst
improving the accuracy of numerical reservoir
2 ENHANCING THE EVALUATION OF PVT DATA
simulations, the PVT parameters can be obtained
directly from the experimentally determined
properties. As a consequence these parameters
not only reproduce the data exactly but also
reflect all the errors and inaccuracies that
occur in that data. In- particular erratic and
sometimes even nonphysical values of the
parameters result.
It will be shown that, although it is not always
possible to trace back and repair
irregularities, quite often the sources of
observed unexpected or nonphysical behaviour can
be identified. This .will depend to a certain
extent on the particular fluid under
consideration. Nevertheless, it will become
obvious that additional measurements, not
included in the standard experimental procedures
can improve the quality of the data, or at least
provide an independent crosscheck. The standard
practice of smoothing experimental data by most
PVT laboratories in order to obtain
'consistency' is to be avoided since it masks
the real quality of the data, and sometimes can
actually create erratic phase properties upon
the application of the material balance.
We first briefly describe the standard PVT
experiments. Subsequently the material balance
is treated. The black oil mass PVT represen-
tation is summarised. Using the error analysis,
extensively treated in the appendix, two
examples are worked through. The paper concludes
with recommendations.
STANDARD PHASE BEHAVIOUR EXPERIMENTS FOR
HYDROCARBON RESERVOIR FLUIDS
Laboratory experiments on hydrocarbon fluids can
in principle be tailored to investigate many
different aspects of phase behaviour, including
PVT relations and compositional analyses in both
the single and two phase states. -Over the years
some particularly useful experiments have been
standardised and offered to the petroleum
industry by commercial PVT laboratories. The
most common of these for phase behaviour studies
are:
constant composition expansion (CCE)
- constant volume depletion (CVD)
- differential liberation (DLB)
If we subdivide the types of hydrocarbon
reservoir fluids into non-critical (black,
heavy) oils, near-critical (volatile, light)
oils, gas-condensates and dry gas, then the
above experiments are applied as follows :
- non-critical oil CCE, DLB
- near-critical oil CCE, DLB, CVD
- gas-condensate CCE, CVD
- dry gas CCE
The common feature of these experiments is the
use of a high pressure PVT cell. This cell is
fillerl with reservoir fluid (obtained eith~~
from bottom-hole sampling or recombining
separator oil and gas) at a pressure equal to
the reservoir pressure (CCE) br the saturation
pressure (DLB,CVD). A series of discrete
pressure reduction steps allowing vapour liquid
equilibrium to be attained is then performed.
627
88174
Th·e only difference between each experiment is
the amount of vapour removed from the cell after
each step, before the next pressure depletion
step is performed. In the CCE no vapour is
removed at all (constant composition), in the
CVD the vapour volume in excess of the original
total cell volume is removed, and for the DLB
all vapour is removed.
The CCE is applied to all reservoir fluids to
determine the saturation pressure and fluid
compressibility above that pressure. If the
experiment is conducted in a blind cell so that
the volumes of liquid and vapour in equilibrium
at each pressure cannot be measured the result
is called a PV relation. Note that the above
experiments could be carried out at different
temperatures other than the reservoir
temperature in order to gain extra information
on the two phase states of a fluid.
The common practice of not measuring, or at
least not reporting, the amount and composition
of the produced vapour in the DLB experiments
prevents the application of a component material
balance. This severely curtails its use beyond
the derivation of conventional black oil PVT
parameters as outlined by Moses~. Reports on DLB
experiments should contain all information found
in CVD reports.
THE COMPONENT MATERIAL BALANCE
Consider the contents of a PVT cell at pressure
step k in a standard experiment which started
with a.unit mass of fluid. The mass of component
j in the liquid in the cell equals the mass
fraction of that component in the initial fluid
minus the produced fraction of the initial
. amount minus the fraction remaining in the
vapour phase in the cell:
Here quantities with a hat denote component mass
fractions _( :!: iJ = 1 ) . For readers' convenience
the more famlliar component ~Q!~ balance is
desribed in appendix A. With a view to future
usage we continue with the mass formulation.
The total mass in the cell at step k after
production is given by:
1 - "~
I "· 1
n1 •••••••••••••••••••••••• (2)
The total liquid mass can be obtained from
equation (1).
s p~
Mt J ~1 X.n = 1 - I="
~ n1 -
1
(1 - s~ > (3)
Po
and the liquid density becomes
88174 J.K. DROHM, W.H. GOLDTHORP£ AND R.D. TRENGOVE 3

Po
= (1 - s~ » ... . (4 > •••••••••••••••••••••••••••••••• ( 8)
Po
and
The vapour densities can he obtained from the
reported vapour compressibility factors by i •••••••••••••••••••••••••••••••• (9)
applying the real gas law y~

The "formation volume factors"· are now inverted

·v partial densities:
Mt Pk
= •••••••••••••••••••••••••• (5)
z: RT VL
••••••••••••••••••••••••••••••• (10)
where K:
indicates the molecular weight of the
vapour at pressure Pk. For an initial mass of
fluid M0 , equation (3) can therefore he expanded
to ••••••••••••••••••••••••••••••• (11)

k-1
- 1=1
%
zr R T where yL and v' denote the volumes of the
phases "in the PVT cell. The equations relating
these quantities to the conditions in the cell
are
(V~- V~) •••••••••• (6)

vL Bo
M'
~
rs ~ •••••••••••••• (12)

v: represents the produced volume from the PVT 1. Rs rs

cell, V~ represents· the total cell volume and v~
represents the total liquid volume in the cell,
at step k. This equation provides insight into v' Bsr
~ Ra M'~
••••••••••••• (13)
the errors associated with the material balance 1 - Rs rs
calculations. ·These ~re discussed in Appendix B.
1 + R8
TBE BLACK OIL MASS PVT REPRESENTATION L
•••••••••••••••••••••• (14)
p
In reservoi~ engineering black oil PVT is an
often used representation of phase
behaviour. Recently Drohm and Goldthorpe1 1 + r8
v
proposed an adapted version in which the primary p = •••••••••••••••••••••• (15)
quantities are masses of two pseudo-components Bsr
instead of surface volumes of oil and gas. This
adap.tation allows for the direct use of where M' and M' indicate the total mass of the
experimental PVT data in the calculation of light a~d heav~ pseudo-component in the cell.
black oil parameters, while at the same time By way of .~xample the total liquid mass is given
providing insight into the eventual short- by
comings of that data. Interpolation and, if
necessary, smoothing of data is facilitated by ML = PL yL
this formulation.
1 + R8 ) ••••••••• (16)
Pseudo-components are obtained by grouping the 1 - R8 r 8
real components in a fluid. A pseUdo-component
mass fraction is simply given by the sum of mass Note that the split in ~ and ~ is arbitrary hut
fractions of the contributing real components the parameters R8 , r 8 , B0 and Bsr must he
positive irrespective of the actual grouping.
ZCI = JfCI iJ • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • (7)
EVALUATION OF PVT DATA
We denote by the mass fraction of
i
pseudo-componen~ u, and the summation is over In the conventional PVT experiments described in
the real components j in pseudo-component u. An this paper, the liquid phase properties
arbitrary hut convenient way of splitting a (composition, mass and density) are all
fluid into two pseudo-components is by grouping calculated from the material balance using
all light physical components into a light equations (1), (3) and (4). Renee, the errors in
pseudo-component indicated by ~, with the the experimentally determined quantities
remaining components making u~ the heavy pseudo- appearing on the right side of these equations
component ~. We then define are compounded to produce errors in the derived
liquid quantities. Identification of the reasons
for erratic or nonphysical data from an -
experiment is simplified by a consideration of

628
4 ENHANCING THE EVALUATION OF PVT DATA
the various contributing error sources. We have
therefore provided an error analysis and
description in Appendix B.
The analysis of a large number of fluids
has shown that erratic data derived from the
. component balance arise primarily from
measurements of the extensive parameters n1 and
s~, that is the produced quantity of vapour
and the liquid saturation at each pressure step.
Of course the errors resulting from an
experiment may be manifested in obvious ways,
e.g. negative component mole fractions, and
negative liquid masses. Consequently we
recommend that a material balance calculation be
performed concurrently with a CVD or DLB
experiment to determine if measurements at a
pressure step will at least give physically real
data. It may also be possible to check
productions and liquid saturations if the data
is amiss.
In the event that the material balance gives
non-negative compositions, our experience has
been that the liquid density is the most
sensitive parameter in the system. It picks up
and amplifies virtually every irregularity in
the other parameters (Appendix B, equation B.3).
Another useful parameter is the pseudo-component
mass R8 which can reflect compositional
irregularities in the liquid arising from
incorrect productions or liquid saturations.
Based on these observations, the following
procedure can be adopted for evaluating the
conventional CVD and DLB experiments after they
have been completed
1) Perform a component material balance and
check for nonphysical compositions.
2) Calculate the liquid densities and pseudo-
component R8 values, and plot as functions
of pressure.
If CCE data is also available over the
pressure range to the first CVD or DLB step,
then additional liquid densities can be
determined by interpolating vapour densities
and using measured saturations. Additional R8
values can be calculated by interpolating r 8
and inverting equation (16).
3) Identify pressures at which irregularities
occur in pL and/or R8 •
4) Determine whether the most likely cause of
the irregularity is an error in the produced
vapour mass and/or an error in the liquid
saturation. This will generally depend on the
fluid type (see Appendix B). · balance). Clearly there is a 'kink' in the
5) Make modifications to the produced vapour
mass and/or the liquid saturation that remove
the irregularities in pL and/or R8 • Repeat
the material balance calculations. This step
will always require some trial and error.
6) The magnitude of the modifications in step 5
will give an indication of whether an experi-
ment should be repeated. For example an
erroneous produced vapour mass may point to a
need for better chromatography and molecular
weight determination. If an incorrect liquid
saturation is found, this 1may imply a need
for longer equilibration times.
Alternatively, it may not be possible to
improve the liquid volume measurement due to
equipment limitations (e.g. dead volumes,
88174
liquid films, very small liquid volumes). In
that case there would be no g.ain from further
experimental work, and the "repaired data
11
should be used in preference to the original
data.
It is important to realise that in no case can
the modifications made in step 5 be proven to be
either unique or correct, mainly because the
measured data do not allow for an independent
consistency check. Nevertheless they indicate
where close investigation of reported data is
required. ·
EXAMPLES
We provide two examples that serve to illustrate
the evaluation procedure. In addition we will
see that
- for obviously erroneous data, common sense
is often enough to make repairs, and
- if the irregularities are only mild, then
repairing the data becomes tricky and is often
incomplete.
The first example is the CVD experiment on an
oil described in the original paper on
constant volume depletions Reudelhuber and
Hindsz. It shows that an irregularity can not
always be attributed to an error in any
one single parameter, but at least it points to
a weak spot in the data.
The second example is a CVD experiment on a
near-critical gas-condensate from a paper by
· MosesB on the use of PVT in reservoir
engineering applications. The liquid saturations
had to be obtained from elsewhere6 , despite the
author's viewpoint that they form an essential
part of the experimental data set. We also give
the CCE data of the same fluid, also not
provided by Moses.
Volatile oil example
Table 1 gives the quantitative experimental data
available from the Reudelhuber and Rinds paper.
Figure 1 shows the extensive parameters, liquid
saturation, fractional mass production, and
independently determined vapour density, which
all look very reasonable. Figure 2 shows the
liquid density as obtained from the balance
calculation. (solid line). The initial density is
determined independently (ie not from material
density curve, for which two reasons can be
suggested
- wrong liquid saturations. This is unlikely
in view of their big~ values, although with a
volatile oil it is not imp~ssible that
insufficient equilibration times cause the
measured liquid saturations to be in error.
- irregularities in the production. This would
leave the initial density unchanged and only
change the densities at lower pressure.
Since the kink in the density curve already
occurs at P1 , n1 may be the cause of the
problem. Reudelhuber and Rinds in their paper
also graphically display the results of the PV
629
88174 J.K. DROHM, W.H. GOLDTHORPE AND R.D. TRENGOVE
relation. This indicates that the volume
increas~ at P1 could be as much as 15' w.r.t.
the voluae at saturation pressure. Using the
measured vapour density, this corresponds
to a mass fraction recovery of
[ ~··· ] Po
:IS 0.095
whilst the one obtained from the CVD is as low
as 0.060. Repeating the material balance on the
CVD using the 'corrected' production curve
(Figure 2 dashed) gives new liquid densities
(Figure 2 dashed). The kink is still there
although not as marked as before. Admittedly the
recovery curve now also shows a kink, so the
conclusion must be that its correction is at
most a partial solution. The liquid saturation
may also be in error by up to 5' due to
inadequate equilibration times because of the
near-critical nature of the fluid. The main
message however, is that an irregularity in the
liquid density was able to cast doubt on the
recovery data that otherwise looked completely
regular. Nevertheless the experiment is
generally of reasonable quality and one could
accept the kink in the liquid density.
Gas-condensate example
Tabl~ 2.shows all experimental ·data available
from the CVD and CCE experiments on this near-
critical gas-condensate. Figure 3 shows the
usual liquid saturation curve, recovery curve
and the vapour density curve. Also indicated are
the CCE liquid saturations (crosses). They
indicate a strong 'tail-like' shape of the
saturation curve close to the dewpoint. Figure 4
shows the liquid density as obtained from the
material balance on the experimental data. Again
a kink is very apparent and accompanies liquid
density trends in contrast with the near~
critical nature of the gas condensate. Using
interpolated vapour densities from the CCE data,
the resulting liquid densities become
nonphysical, ranging up to 3600 kg/m 3 • The R8 -
curve ( C4 _, C5 + pseudo-component split) in
Figure 5 also appears to indicate an erroneous
composition at pressure P1 • _
The obvious candidate for the cause of the
problems is the liquid saturations. If we impose
a new density on the liquid at P1 (34575 kPa) by
linear extrapolation· from the lower pressures
(see Figure 4 dashed line) equation (4) can be
inverted to yield a new S~ which moves from 8'
to about 15' of the initial cell volume, almost
double. If we now linearly interpolate these
liquid saturations (Figure 4 dashed) and apply
them to the CCE data, the resulting liquid
densities only range from 580 to 610 kg/m 3 ,
instead of up to 3600 kg/m 3 •
Putting them on the extrapolated liquid density
curve would make the liquid saturation curve
slightly steeper close to the dewpoint.
630
5
Therefore one may conclude, through common
sense, that liquid volumes close to the dewpoint
can be orders of magnitude out. Figure 5 shows
two very acceptable curves for B0 and R8 (dashed).
The final picture now looks fairly consistent.
CONCLUSIONS AND RECOMMENDATIONS
the standard practice of smoothing
experimental data by most PVT laboratories
in order to obtain 'consistency' is to be
avoided
reports on differential liberation
experiments should contain all information
found in constant volume depletion
experiments
material balance calculations should be
performed concurrently with a constant
volume depletion or differential liberation
experiment in order to check data and take
corrective action if possible
'smoothness' and common sense are often
enough to at least trace if not improve
experimental data problems
liquid density is a very useful parameter for
the screening of PVT data quality since it is
affected most by inaccuracies in the
productions and liquid saturations, which
are most prone to inaccuracies anyway.
apply or develop non-destructive techniques
to measure the insitu liquid (and vapour)
density in the cell itself. With this
capability CCE experiments could already
provide most.information needed for
the conventional black oil PVT description
(see reference 7 Appendix C for example)
Nomenclature
reservoir liquid formation volume
factor
reservoir vapour formation volume
factor
total mass of fluid in the cell at
pressure step k
mass of liquid in the cell at
p_ressure step k
molecular weight of the vapour at
pressure step k
total mass of the pseudo-component a
in the cell
~Jk number of moles of component j in the
liquid in the cell at pressure step k
number of moles of liquid in the cell
at _pressure step k
number of moles of component j in the
vapour in the cell at pressure step k
number of moles of vapour in the cell
llvk
at pressure step k
pressure at pressure step k
universal gas constant
gas-oil ratio of reservoir liquid
oil-gas ratio of reservoir vapour
liquid saturation in the cell at
pressure step k
temperature
volume of the cell at pressure step k
volume of the liquid phase in the PVT
cell
6 ENHANCING THE EVALUATION OF PVT DATA
vr1
volume of vapour produced from the
cell at pressure step i
vrk total cell volume at pressure step k
vv volume of the vapour phase in the PVT
cell
XJk mass (or mole fraction} of component j
in the liquid at pressure step k
- mass of the pseudo-component a in the
xa
liquid
YJk mass (or mole fraction) of component j
in the vapour at pressure step k
iJ1 - mass fraction'of component j in the
produced vapour at pressure step i
mass of the pseudo-component a in the
Ya
vapour
zvk Z-factor of the vapour in the PVT
cell at pressure step k
za - mass fraction of pseudo-component a
in the cell
ZJk mass (or mole fraction) of component
in the cell at pressure step k
zJk - mass fraction of component j in the
cell at pressure step k
4np1 number of moles of vapour produced at
pressure step i
111 - mole percent of initial fluid in the
cell, of produced vapour at pressure
step i.
density of the liquid p·hase in the PVT
cell at pressure step k
density of vapour in the cell at
pressure step k
Po density of fluid initially present in
the cell
Subscripts and superscripts
i,k ~elate to the pressure step
j relates to the component
o relates to the initial cell fluid
L relates to the liquid phase
V relates to the vapour phase
T indicates the total in the cell
a,~,X - relate to the pseudo-components with
A and ~ 4esignating the light and
heavy pseudo-components respectively
ACKNOWLEDGEMENTS
The authors wish to thank the Joint Venture
Participants and the Management of Woodside
Offshore Petroleum Pty. Ltd. for permission to
present this paper. The participants in the
Domestic Gas Phase of the North West Shelf Joint
Venture are Woodside Petroleum Ltd. (through
subsidiaries), B.P. Developments Australia
Limited, California Asiatic Oil Company, Shell
Development (Australia) Pty. Ltd. and B.H.P.
Petroleum Pty. Ltd.
Note that the views contained within this paper
are those of the authors and are not necessarily
those of all Participants of the Joint Venture.
R.D. Trengove gratefully acknowledges the
support of a National Research Fellowship, under
which this work was carried out.
631
88174
REFERENCES
1. Drohm, J.K. and Goldthorpe, W.H., 'Black Oil
PVT Revisited - The Use of Pseudo-Component Mass
for an Exact Material Balance' submitted SPE
Reservoir Engineering, SPENo. 17081.
2. Reudelhuber, F.O. and Hinds, R.F., 'A
Compositional Material Balance Method for
Prediction of Recovery from Volatile Oil
Depletion Drive Reservoirs' Petroleum
Transactions, AIME, 1957, 210 19-26.
3. Whitson, C.H. and Torp, S.B., 'Evaluating
Constant-Volume Depletion Data' Journal of
Petroleum Technology, March 1983, 35 610-620.
4. Dodson, C.R., Goodwill, D. and Mayer, E.H.,
'Application of Laboratory PVT Data to Reservoir
Engineering Problems' Petroleum Transactions,
AIME, 1953, 198 287-298.
5. Moses, P.L., 'Engineering applications of
Phase behaviour of Crude Oil and Condensate
Systems' Journal of Petroleum Technology, July
1986, 38 715-723.
6. 'A Course in the Phase Behaviour of
Hydrocarbon Reservoir Fluids' Reservoir Fluid
Analysis Department, Core Laboratories, Inc.
7. Coats, K.H., 'Simulation of Gas Condensate
Reservoir Performance' Journal of Petroleum
Technology, October 1985, 17 1870-1886.
APPENDIX A
The component mass balance for a standard PVT
experiment starting with unit mass of reservoir
fluid at the saturation pressure was presented
in the text. Normal practice, however, is to
report experimental data in terms of moles and
mole fractions. We therefore provide component
mole balance equations using current SPE
nomenclature. Assume the PVT cell is filled with
one mole of fluid at the saturation pressure
(pressure stage k = 0). Let zJk be the total
mole fraction of component j in the cell at
pressure step k, xJk the mole fraction in the
liquid phase, and yJk the mole fraction in the
vapour phase. The.number of moles of component j
in the liquid at step k is given by (cf equation
(1)) :
k
ZJo -~~~tl~t YJI - nvkYik •••• (A.1)
where nL k , llv k are the number of moles of liquid
and vapour respectively, and tlnP 1 is the number
of moles of vapour removed from the cell at
pressure step i.
Denote nLJk xJk nLk anrl uVJk yJk n\. 1,.
Equation (A.l) can be expanded using the real
gas law to give
k pk V~ ll I I
nLlk= ZJo- ~ tln".tYJt- Y11 - - - (1- SLd
1 1 Z~;RT
(i\.2)
where Pk is the pressure at step k, Zk is the
v~po~r compres~ibility factor,c:?~ S1 k 1s the
llqu1d satur~.H?n, s.. k= V~_k/ V0 • For a gas-
condensate v~· can be found at the saturation
88174 J.K. DROHM, W.H. GOLDTHORPE AND R.D. TRENGOVE 7

pressure from the real gas law and hence M: represents the cumulative produced mass up
to and including step k, ie
k pk zo k
~Jk= ZJo-1~14~1 yJ1- YJk (1- SLk) (A.3) MPk Mo 1 ~1 n1 ••••••••••••••••••••••••• (B. 4)
zk Po

For a differential liberation experiment all the
vapour is removed so equation (A.3) reduces to
k We can observe the following from equations
~Jk = ZJo -1:14~1YJ1 •••••••••••••••••••(A.4)
APPENDIX B
In order to appreciate the error sources in the
calculation of the liquid mass and density in a
CVD or DLB experiment, we reproduce equation (6)
which includes the main quantities determined
during the experiment. The equation is no longer
on a unit mass basis as there is sometimes an
error introduced in obtaining the initial mass.
Suppose the measured initial volume of the PVT
cell filled with a reservoir fluid at the
saturation pressure is V0 , and that the density
of the fluid has been determined as p0 • The
initial mass in the cell is simply p0 V0 • The
mass of liquid that would actually be in the
cell at pressure step k is given by
k-1
K~ = - l:
1=1
zr R T
~v
Kk pk
(V~- V~)
z: R T
~ represents the produced volume from the
PVT cell, V~ represents the total cell volume
and V~ represents the liquid volume in the cell,
at step i or k respectively. The liquid density
is given by K~ I V~ •
Equation (B.l) clearly indicates the quantiti~s
that are obtained during an experiment. Some of
these must be derived after a series of
measurements is made, e.g. Mv and zv. Before
discussing the contributions to the errors in ML
and pL, however, it is expedient to write the
total error in ~ and pL as a combination of
the errors in the primary parameters used in our
evaluation procedure, namely masses, densities
and saturations •.
Consider the total differentials of the liquid
mass K~ and density p~ at pressure step k (we
assume that the initial cell volume has
negligible error):
d~ = dK 0 - dK= - V0 (1ooS~)dp: - V0 p: dS~
dM0 dK/
dp~
s~ V0 s~ V0
TI
(1-S~) (p: - (Kk I V0
dp:-
SLk < s~
The first two differentials in equation (8.2)
and (8.3) represent the error in the total mass
in the cell at step k.
(8.2) and (8.3) :
- for experiments where liquid saturations ~re
large (DLB and near-critical oil CVD) errors in
the liquid mass and density will be influenced
primarily by errors in the produced vapour
masses
- for experiments where the liquid saturations
are low (lean gas-condensate CVD) the error in
the liquid density will be influenced primarily
by the error in the measured liquid saturation.
The error in the total mass in the PVT cell at
step k is due to a combination of uncertainties
in a number of measured quantities. In the first
instance, the initial mass of fluid in the cell
at saturation pressure is determined from the
measured composition and component molecular
weights. Significant errors can arise in
obtaining the molecular weight and mole fraction
of the lumped heavy component (e.g. C7 +), and
therefore in calculating the initial fluid mass.
Secondly, the mass of vapour produced at each
pressure step is subject not only to the
composition related errors but also to the
uncertainty in the number of produced moles.
This later quantity is calculated from the
measurement of a gas volume at standard
•••••••• (8.1) conditions and application of the ideal gas law,
plus the measurement of a liquid mass and
average molecular weight. Combining these into
the produced moles at the pressure step
introduces the error in the produced mass.
The density of the vapour in the PVT cell is
determined using the real gas law. Errors in the
measurement of pressure and temperature can
effectively be ignored. The total error in the
vapour density is therefore caused by the
uncertainties in the molecular weight of the
vapour· (essentially the error in the lumped
heavy fraction molecular weight), and the
vapour compressibility factor. This is
calculated from the number of moles of vapour
produced at pressure step k, its volume at cell
conditions, and the temperature and pressure.
Thus, all errors in the produced moles are
carried through to the compressibility factors.
The remaining source of uncertainty in the
calculation of liquid mass or density results
from the measurement of the liquid saturation,
at cell conditions. This uncertainty is
(8.2) dependent on the amount of liquid in the cell
and the time allowed for the two phases to reach
thermodynamic equilibrium. The measured liquid
volume will not include any liquid film on the
cell walls, or liquid trapped by surface tension
in 'dead' volumes. For non-critical and near-
critical oils this effect is small. In the case
))
of gas-condensates (particurlarly lean fluids)
dS~ (8.3) large errors may result. The problem of
>z insufficient equilibration times can occur with
all fluids.

632
 TIBLI 1 - IJPEIIKIITIL DATA FROB VOLlTILI OIL CO.STAIT VOLUKI DEPLITIOII AT T = 374.8 I

Pressure fkPa)
33162 27611 21475 16028 9823 4859

Vapour Coaposition
(aole '~
liz 0.24 0.27 0.28 0.29 0.29 0.28
COz 0.27 0.27 0.27 0.28 0.29 0.32
C1 66.83 75.94 79.34 80.87 80.74 77.75
Cz 8.28 8.23 8.29 8.44 8.85 9.90
C:a 5.15 4.59 4.41 4.35 4.65 5.69
i - c.. 1.04 0.90 0.77 0.75 0.77 0.94
.D - c.. 2.27 1.93 1.73 1.57 1.61 2.08
i - Ca 1.00 0.78 0.64 0.55 0.54 0.64
.D -Ca 1.04 0.84 0.67 0.57 0.57 0.70
c. 1.85 1.24 0.90 0.72 0.65 ,0. 73
C7+ 12.03 5.01 2.70 1.61 1.04 0.97

C7+ aolecular
weight 182 144 123 115 112 112

Vapour z factor 1.042 0.924 0.848 0.845 0.879 0.929

Cuaaulative
Production (aole ') 0.0 9.054 22.100 36.318 55.083 70.880
Liquid saturation
(' of cell voluae) 100.00 50.35 45.80 42.50 37.93 34.50

TIBLI 2 - BIPBRIKIITIL DlTl FROB GlS-COIDBISlTI CO.STAIT VOLUIB DEPLITIOII lT T = 397.6 I

Pressure lkPa~
*
41539 41125 40780 40091 38712 36643 34575 27680 20786 14580 8375 4928
Vapour Coapo•ition
iaole 'l
•z 0.11 0.12 0.12 0.13 0.13 0.12 0.11
COz 0.01 0.01 0.01 0.01 0.01 0.01 0.01
C1 68.93 70.69 73.60 76.60 77.77 77.04 75.13
Cz 8.63 8.67 8.72 8.82 8.96 9.37 9.82
c. 5.34 5.26 5.20 5.16 5.16 5.44 5.90
i- c.. 1.15 1.10 1.05 1.01 1.01 1.10 1.26
.D- c.. 2.33 2.21 2.09 1.99 1.98 2.15 2.45
i - Ca 0.93 0.86 0.78 0.73 0.72 0. 77 0.87
.D - Ca 0.85 0.76 0.70 0.65 0.63 0.68 0.78
c. 1. 73 1.48 1.25 1.08 1.01 1.07 1.25
C7+ 9.99 8.84 6.48 3.82 2.62 2.25 2.42
C7+ aolecular
weight 158 146 134 123 115 110 109
Vapour Z factor 1.140 1.015 0.897 0.853 0.865 0.902 0.938
Cuaaulative
Production (aole ') 0.0 6.624 17.478 32.927 49.901 68.146 77.902
Liquid saturation
'' of cell voluae) 0.0 trace 0.1 0.2 0.5 2.0 7.8 21.3 25.0 24.4 22.5 21.0
Total Cell Voluae 1.00 1.0034 1.0076 1.0138 1.0267 1.0481 1.0749
I
+ CCE data point only (see reference 6)
* CCE and CVD data points

633
 -.s 11.-ooucnoN (~ON) M.QS P"<)OUCTION (~ON)
,OQ ,10 .ao .150 .oo ,10 .20 .~ .40 ,150
?+-------~------~------~------~------_,
UQUIO ....TU-TION (l"'''ttiCTTCIN)
.oo .20 ,40 .eo 1,00
?+-------~------~------~~------._------~

[/
,1'
\ ,I' /I
\ /
\ // I
,/
\ / / I
\ / / I
~ / / I
/
I '' / /
/
I
I
I
~
' /
"\
/

1/
/
I
I
;;

/
/ "" /
/
I
I
I '\.

I
/ ", '\.
/
/
I
I

;' '\. / I
I' '\. / I
I / '\. / I
i I '\. / I
'\.
fi // ' ,I
/
I
J

I I

I
/1
1/ / I
,/ '/ b

i+----~--r--~----,..---r-----1
0, 110, I 00, 1 110. 200. 2150, .10Q,
~~--~--~--~--~--~
2110. DO. ..0, 1180, 8110, 7110.
V~OU" OEN&I'IY (1<0/M~) UQUID DENSITY (loCO/M.8)

Fig. 1 Volatile ollllqukluturetlon, frectiOMI mMI production end Vllpour denllty. Fig. 7 Volatile oil liquid denllty end m... production; original end modltled.

,.,... II"<)OUcnON (~ON)

.oo ,10 .ao .40 ,110 .150

UQUIO ....TU-TION (I"''UUCTION)

.oo .oe ,to .us .2o .211
?+-----~----~------._----~----~----~

:I

\
\
\
\
\
\
\

100, aoo. ~o. 400. 1500.

V~U" DEN811Y (1<0/M~) Fig. 3 Gacondenutellqulcl..turatlon (CCEend CVD), maeprocludlon
end Vllpour denllty.

634
 I..IOUIO S.TU"AT10N ("IIIACT10N)
.oo .oo ,10 ,10 .ao .ao •.10
P+-------~------~----~------_. _______.______~

!
i
~
~
III
I

I: 'i~
§i
00 I
!~
~
~ ....

i) I
~

\
eeo. 100. 110. 700.
1..101.110 DENIIT"'' (ICO/Nol) Fig. 4 Gal conden•t• liquid den1lty and liquid •turaUon; original and
modified.

.0 ("II, Wol/ICO)
P+-----------._
.0010 .ooao
__________ .ooae
.___________ ._________.00.10 ~

I
I
s
l
j

j +---....-....-.----..-------.,.--.-l
.oo .10 .ao •.10 .40 .eo .eo
"I (MO/ICO) Fig. 5 G•• conden•t• black otl parametel"' 8 0 and R,; original and
modified.

635