2.

1 PVT Analysis and Its Importance

the importance of PVT analysis was stressed for relating observed volumes of gas production at
the surface to the corresponding underground withdrawal. For gas this relationship could be
obtained merely by determining the single or two phase Z−factor, and using it in the equation of
state. The basic PVT analysis required to relate surface production to underground withdrawal
for an oil reservoir is necessarily more complex due to the presence, below the bubble point
pressure, of both a liquid oil and free gas phase in the reservoir.

2.1.1 Definition of the Basic Pvt Parameters:

The Pressure−Volume−Temperature relation for a real gas can be uniquely defined by the simple
equation of state

Pv=ZnRT Eq . 2.1

in which the Z−factor, which accounts for the departure from ideal gas behaviour, Using this
equation, it is a relatively simple matter to determine the relationship between surface volumes
of gas and volumes in the reservoir as

( )
P T SC 1 P scf
E= × × =35.37 Eq .2.2
P SC T Z ZT scf

Unfortunately, no such simple equation of state exists which will describe the PVT properties of
oil. Instead, several, so-called, PVT parameters must be measured by laboratory analysis of
crude oil samples. The parameters can then be used to express the relationship between surface
and reservoir hydrocarbon volumes, equivalent to Eq. (2.2).

The complexity in relating surface volumes of hydrocarbon production to their equivalent

volumes in the reservoir can be appreciated by considering fig. 2.1.

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Fig. 2.1 Production of reservoir hydrocarbons (a) above bubble point pressure, (b) below bubble
point pressure

Above the bubble point only one phase exists in the reservoir − the liquid oil. If a quantity of this
undersaturated oil is produced to the surface, gas will separate from the oil as shown in fig.
2.1(a), the volume of the gas being dependent on the conditions at which the surface separation is
effected. In this case, it is relatively easy to relate the surface volumes of oil and gas to volumes
at reservoir conditions since it is known that all the produced gas must have been dissolved in the
oil in the reservoir. If the reservoir is below bubble point pressure, as depicted in fig. 2.1(b), the
situation is more complicated. Now there are two hydrocarbon phases in the reservoir, gas
saturated oil and liberated solution gas. During production to the surface, solution gas will be
evolved from the oil phase and the total surface gas production will have two components; the
gas which was free in the reservoir and the gas liberated from the oil during production. These
separate components are indistinguishable at the surface and the problem is, therefore, how to
divide the observed surface gas production into liberated and dissolved gas volumes in the
reservoir.

3
Below bubble point pressure there is an additional complication in that the liberated solution gas
in the reservoir travels at a different velocity than the liquid oil, when both are subjected to the
same pressure differential. the flow velocity of a fluid in a porous medium is inversely
proportional to the fluid viscosity. Typically, gas viscosity in the reservoir is about fifty times
smaller than for liquid oil and consequently, the gas flow velocity is much greater. As a result, it
is normal, when producing from a reservoir in which there is a free gas saturation, that gas will
be produced in disproportionate amounts in comparison to the oil. That is, one barrel of oil can
be produced together with a volume of gas that greatly exceeds the volume originally dissolved
per barrel of oil above bubble point pressure. Control in relating surface volumes of production
to underground withdrawal is gained by defining the following three PVT parameters which can
all be measured by laboratory experiments performed on samples of the reservoir oil, plus its
originally dissolved gas.

Rs − The solution (or dissolved) gas oil ratio, which is the number of standard cubic feet
of gas which will dissolve in one stock tank barrel of oil when both are taken down to the
reservoir at the prevailing reservoir pressure and temperature (units − scf. gas/stb oil).

Bo − The oil formation volume factor, is the volume in barrels occupied in the reservoir,
at the prevailing pressure and temperature, by one stock tank barrel of oil plus its dissolved gas
(units – rb (oil + dissolved gas)/stb oil).

Bg − The gas formation volume factor, which is the volume in barrels that one standard
cubic foot of gas will occupy as free gas in the reservoir at the prevailing reservoir pressure and
temperature (units − rb free gas/ssf gas.

Both the standard cubic foot (scf) and the stock tank barrel (stb) referred to in the above
definitions are defined at standard conditions, which in this text are taken as 60°F and one
atmosphere (14.7 psia). It should also be noted that Rs and Bo are both measured relative to one
stock tank barrel of oil, which is the basic unit of volume used in the field. All three parameters
are strictly functions of pressure, as shown in fig. 2.5, assuming that the reservoir temperature

4
remains constant during depletion. Precisely how these parameters can be used in relating
measured surface volumes to reservoir volumes is illustrated in figs. 2.2 and 2.3.

Fig. 2.2 Application of PVT parameters to relate surface to reservoir hydrocarbon volumes;
above bubble point pressure.

Fig. 2.2 depicts the situation when the reservoir pressure has fallen from its initial value pi to
some lower value p, which is still above the bubble point. As shown in the P−T diagram (inset)
the only fluid in the reservoir is undersaturated liquid oil. When this oil is produced to the
surface each stock tank barrel will yield, upon gas oil separation, Rsi standard cubic feet of gas.
Since the oil is undersaturated with gas, which implies that it could dissolve more if the latter
were available, then the initial value of the solution gas oil ratio must remain constant at Rsi
(scf/stb) until the pressure drops to the bubble point, when the oil becomes saturated, as shown in
fig. 2.5(b). Figure 2.2 also shows, in accordance with the definitions of Bo and Rs, that if Rsi scf
of gas are taken down to the reservoir with one stb of oil, then the gas will totally dissolve in the
oil at the reservoir pressure and temperature to give a volume of Bo rb of oil plus dissolved gas.
Figure 2.5(a) shows that Bo increases slightly as the pressure is reduced from initial to the
bubble point pressure. This effect is simply due to liquid expansion and, since the

5
compressibility of the undersaturated oil in the reservoir is low, the expansion is relatively small.
Typical values of Bo and Rs above the bubble point are indicated in fig. 2.5, these are the plotted
results of the laboratory analysis presented in table 2.4. The initial value of the oil formation
volume factor Boi is 1.2417 which increases to 1.2511 at the bubble point. Thus initially, 1.2417
reservoir barrels of oil plus its dissolved gas will produce one stb of oil. This is a rather
favourable ratio indicating an oil of moderate volatility and, as would be expected in this case,
the initial solution gas oil ratio is also relatively low at 510 scf/stb. Under less favourable
circumstances, for more volatile oils, Boi can have much higher values. For instance, in the
Statfjord field in the North Sea, Boi is 2.7 rb/stb while the value of Rsi is approximately 3000
scf/stb. Obviously the most favourable value of Boi is as close to unity as possible indicating that
the oil contains hardly any dissolved gas and reservoir volumes are approximately equal to
surface volumes. The small oil fields of Beykan and Kayaköy in the east of Turkey provide good
examples of this latter condition having values of Boi and Rsi of 1.05 and 20 scf/stb respectively.
Below the bubble point the situation is more complicated as shown in fig. 2.3.

Fig. 2.3 Application of PVT parameters to relate surface to reservoir hydrocarbon volumes;
below bubble point pressure
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In this case each stock tank barrel of oil is produced in conjunction with R scf of gas, where R
(scf/stb) is called the instantaneous or producing gas oil ratio and is measured daily. As already
noted, some of this gas is dissolved in the oil in the reservoir and is released during production
through the separator, while the remainder consists of gas which is already free in the reservoir.
Furthermore, the value of R can greatly exceed Rsi, the original solution gas oil ratio, since, due
to the high velocity of gas flow in comparison to oil, it is quite normal to produce a
disproportionate amount of gas. This results from an effective stealing of liberated gas from all
over the reservoir and its production through the relatively isolated offtake points, the wells. A
typical plot of R as a function of reservoir pressure is shown as fig. 2.4.

Fig. 2.4 Producing gas oil ratio as a function of the average reservoir pressure for a typical
solution gas drive reservoir

The producing gas oil ratio can be split into two components as shown in fig. 2.3, i.e.

R=Rs +(R−Rs)Eq . 2.3

The first of these, Rs scf/stb, when taken down to the reservoir with the one stb of oil, will
dissolve in the oil at the prevailing reservoir pressure to give Bo rb of oil plus dissolved gas. The
remainder, (R − Rs) scf/stb, when taken down to the reservoir will occupy a volume

7
 ( ) ( )
scf rb
( R−RS ) stb × B g scf =( R−R S ) B g (rb−free gas) Eq .2.3

and therefore, the total underground withdrawal of hydrocarbons associated with the production
of one stb of oil is

(Underground withdrawal)/stb=Bo+( R−Rs) Bg (rb /stb)Eq .2 .5

The above relationship shows why the gas formation volume factor has the rather unfortunate
units of rb/scf. It is simply to convert gas oil ratios, measured in scf/stb, directly to rb/stb to be
compatible with the units of Bo. While Bg is used almost exclusively in oil reservoir engineering
its equivalent in gas reservoir engineering is E, the gas expansion factor, which was introduced
in the previous chapter and has the units scf/rcf. The relation between Bg and E is therefore,

Bg ( stbrb )= 5.6151 × E Eq .2.6

thus Bg has always very small values; for a typical value of E of, say, 150 scf/rcf the value of Bg
would be .00119 rb/stb

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Fig. 2.5 PVT parameters (Bo, Rs and Bg), as functions of pressure, for the analysis presented in
table 2.4; (pb = 3330 psia).

The shapes of the Bo and Rs curves below the bubble point, shown in fig. 2.5(a) and (b), are
easily explained. As the pressure declines below pb, more and more gas is liberated from the
saturated oil and thus Rs, which represents the amount of gas dissolved in a stb at the current
reservoir pressure, continually decreases. Similarly, since each reservoir volume of oil contains a

9
smaller amount of dissolved gas as the pressure declines, one stb of oil will be obtained from
progressively smaller volumes of reservoir oil and Bo steadily declines with the pressure.

2.2 Equations of State and PVT Models

An equation of state (EOS) is an analytical expression relating the pressure, p, to the

temperature, T, and the volume, V. A proper description of this PVT relationship for real
hydrocarbon fluids is essential in determining the volumetric and phase behavior of petroleum
reservoir fluids and predicting the performance of surface separation facilities; these can be
described accurately by equations of state. In general, most equations of state require only the
critical properties and acentric factor of individual components. The main advantage of using an
EOS is that the same equation can be used to model the behavior of all phases, thereby assuring
consistency when performing phase equilibria calculations.

The best known and the simplest example of an equation of state is the ideal gas equation,
expressed mathematically by the expression

RT
P= Eq .2 .7
V

where

V = gas volume in ft3 per 1 mol of gas, ft3 /mol.

The PVT relationship is used to describe the volumetric behavior of hydrocarbon gases at
pressures close to the atmospheric pressure for which it was experimentally derived. However,
the extreme limitations of the applicability of Eq. (2.7) prompted numerous attempts to develop
an equation of state suitable for describing the behavior of real fluids at extended ranges of
pressures and temperatures.

A review of recent developments and advances in the field of empirical cubic equations of state
are presented next, along with samples of their applications in petroleum engineering. Four
equations of state are discussed here:

 van der Waals.

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  Redlich-Kwong.

 Soave-Redlich-Kwong.

 Peng-Robinson.

2.2.1 The Van der Waals Equation of State “VdW EOS” :

In developing the ideal gas EOS, two assumptions were made:

 The volume of the gas molecules is insignificant compared to the total volume and distance
between the molecules.
 There are no attractive or repulsive forces between the molecules.

Van der Waals (1873) attempted to eliminate these two assumptions in developing an empirical
equation of state for real gases. In his attempt to eliminate the first assumption, van der Waals
pointed out that the gas molecules occupy a significant fraction of the volume at higher pressures
and proposed that the volume of the molecules, denoted by the parameter b, be subtracted from
the actual molar volume, V, in Eq. (2.7), to give

RT
P= Eq .2 .8
V −b

where the parameter b is known as the covolume and considered to reflect the volume of
molecules. The variable V represents the actual volume in ft3 per 1 mol of gas. To eliminate the
second assumption, van der Waals subtracted a corrective term, denoted by a/V2 , from this
equation to account for the attractive forces between molecules. In a mathematical form, van der
Waals proposed the following expression:

RT a
P= − Eq.2 .9
V −b V 2

where

P = system pressure, psia.

T = system temperature, °R.

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 R = gas constant, 10.73 psi-ft3 /lb-mol, °R .

V = volume, ft3 /mol.

a = “attraction” parameter.

b = “repulsion” parameter.

The two parameters, a and b, are constants characterizing the molecular properties of the
individual components. The symbol a is considered a measure of the intermolecular attractive
forces between the molecules. Eq. (2.9) shows the following important characteristics:

1. At low pressures, the volume of the gas phase is large in comparison with the volume of the
molecules. The parameter b becomes negligible in comparison with V and the attractive forces
term, a/V2 , becomes insignificant; therefore, the van der Waals equation reduces to the ideal gas
equation [Eq. (2.8)].

2. At high pressure (ie, p → ∞) the volume, V, becomes very small and approaches the value b,
which is the actual molecular volume, as mathematically given by

lim V ( p )=b
p→∞

2.2.2 Redlich-Kwong’s Equation of State “RK EOS” :

Redlich and Kwong (1949) observed that the van der Waals a/V2 term does not contain the
system temperature to account for its impact on the intermolecular attractive force between the
molecules. Redlich and Kwong demonstrated that by a simple adjustment of the van der Waals’
a/V2 term to explicitly include the system temperature could considerably improve the prediction
of the volumetric and physical properties of the vapor phase. Redlich and Kwong replaced the
attraction pressure term with a generalized temperature dependence term, as given in the
following form:

RT a
P= − Eq .2.10
V −b V ( V + b ) √ T

in which T is the system temperature, in °R. Redlich and Kwong noted that, as the system
pressure becomes very large (ie, p → ∞) the molar volume, V, of the substance shrinks to about
26% of its critical volume, Vc , regardless of the system temperature. Accordingly, they
constructed Eq. (2.10) to satisfy the following condition:

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 b=0.26 V c Eq.2 .11

Imposing the critical point conditions on Eq. (2.10) and solving the resulting two equations
simultaneously, gives

2 2.5
R Tc
a=Ωa Eq .2.12
Pc

RTc
b=Ωb Eq .2.13
Pc

where

Ωa = 0.42747.

Ωb = 0.08664.

It should be noted that by equating Eq. (2.13) with (2.11) gives

RTc
0.26 V c =Ω b Eq .2 .14
Pc

Arranging the above expression:

Pc V c =0.33 R T c Eq.2 .15

Eq. (2.14) shows that the RK EOS produces a universal critical compressibility factor (Zc ) of
0.333 for all substances. As indicated earlier, the critical gas compressibility ranges from 0.23 to
0.31 for most of the substances, with an average value of 0.27.

Replacing the molar volume, V, in Eq. (2.10) with ZRT/p and rearranging gives

Z3 −Z 2+ ( A−B−B2 ) Z −AB=0 Eq.2 .16

Where

ap
A= 2 2.5
Eq .2.17
R T

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 bp
A= Eq .2.18
RT

As in the van der Waals EOS, Eq. (2.16) yields one real root in the one-phase region (gas-phase
region or liquid-phase region) and three real roots in the two-phase region. In the latter case, the
largest root corresponds to the compressibility factor of the gas phase, Zv , while the smallest
positive root corresponds to that of the liquid, ZL .

2.2.3 Soave-Redlich-Kwong Equation of State “SRK EOS” :

One of the most significant milestones in the development of cubic equations of state is
accredited to Soave (1972) with his proposed modification of the RK EOS attraction pressure
term. Soave replaced the explicit temperature term (a/T 0.5) in Eq. (2.10) with a more generalized
temperaturedependent term, denoted by [a α (T)]; that is

RT aa
P= − Eq .2.19
V −b V ( V + b ) √T

where α(T) is a dimensionless parameter that is defined by the following expression

α (T )=[1+ m(1−√ T /T c )] Eq .2.20

2

or equivalently in terms of reduced temperature “Tr”:

α (T )=[ 1+ m ( 1−√ T r ) ] Eq.2 .21

2

Soave imposed the following conditions on the a dimensionless parameter α(T):

 α(T)=1 when the reduced temperature Tr , = 1; that is, α(T=Tc )=1 when T/Tc=1.

 At temperatures other than the critical temperature, Soave regressed on the vapor pressure
of pure components to develop a temperature correction parameter “m” that correlated with
the acentric factor “ω” by the following relationship:

2
α (T )=0.480+1.74 ω−0.176 ω Eq .2 .22

where

Tr = reduced temperature, T/Tc

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ω = acentric factor of the substance

T = system temperature, °R

For simplicity and convenience, the temperature-dependent term “α(T)” is replaced by the
symbol “α” for the remainder of this chapter. For any pure component, the constants “a” and “b”
in Eq. (2.19) are found by imposing the classical van der Waals’s critical point constraints on Eq.
(2.19) and solving the resulting two equations, to give

2 2.5
R Tc
a=Ωa Eq .2.23
Pc

RTc
b=Ωb Eq .2.24
Pc

where

Ωa = 0.42747.

Ωb = 0.08664.

2.2.4 The Peng-Robinson Equation of State :

Peng and Robinson (1976a) conducted a comprehensive study to evaluate the use of the SRK
equation of state for predicting the behavior of naturally occurring hydrocarbon systems. They
illustrated the need for an improvement in the ability of the equation of state to predict liquid
densities and other fluid properties, particularly in the vicinity of the critical region. As a basis
for creating an improved model, Peng and Robinson (PR) proposed the following expression:

RT aa
P= − Eq .2 .25
V −b ( V + b )2 cb2

where a, b, and α have the same significance as they have in the SRK model, and parameter c is a
whole number optimized by analyzing the values of the terms Zc and b/Vc as obtained from the
equation. It is generally accepted that Zc should be close to 0.28 and b/Vc should be
approximately 0.26. An optimized value of c = 2 gives Zc = 0.307 and (b/Vc ) = 0.253. Based on
this value of c, Peng and Robinson proposed the following equation of state (commonly referred
to as PR EOS)

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 RT aa
P= − Eq .2 .26
V −b V ( V + b ) +b(V −b)

Imposing the classical critical point conditions on Eq. (2.26) and solving for parameters a and b
yield
2 2.5
R Tc
a=Ωa Eq .2.27
Pc

RTc
b=Ωb Eq .2.28
Pc

where

Ωa = 0.42747.

Ωb = 0.08664.

2.3 Previous Studies on Reservoir Fluid Simulation

2.4 Advances in PVT Simulation Software

2.5 Summary of Key Findings

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