PEE 314 Petroleum Production Engineering I 3 CREDIT

Properties of oil and Gas: Composition of oil and natural gas; classification of crude oil;
natural gas

PROPERTIES OF OIL AND GAS

Originally, hydrocarbon and water are sealed in reservoir rocks. Before the reservoir comes
on stream, the fluids in the reservoir are maintained under initial reservoir pressure and
temperature. After the production begins, fluids flow through reservoir and wellbore to
reach surface. During this process, the pressure and temperature decline, and the
properties of oil and gas also change with changing conditions.
Crude oil is a mixture of light to heavy hydrocarbons, plus some sulphur, oxygen, nitrogen
and metallic components. According to different structures, hydrocarbons are classified as
paraffin alkane, olefin alkene, naphthene and aromatics. Some examples of alkane series
are given in Fig.1. Alkane are open chain molecules with saturated bonds, they have the
generalized formula CnH2n+2. Each carbon atom has four open bonds, thus can join with four
other atoms.

Fig.1 Some examples of alkanes

Under standard conditions, methane, ethane, propane and butane are in gaseous state. The
density of alkanes increases with increasing carbon number. Under standard conditions, C5
to C17 remain in liquid state, while the C18 and higher compounds exist in wax-like solid
state. Alkanes from C1 to C40 typically appear in crude oil. They contribute up to 20% of
crude oil by volume.
Alkenes have at least one carbon-carbon double bond. The double bond makes alkenes
more reactive than alkanes. Naphthenes are ring structures with saturated bonds, while
aromatics are rings with double bonds, as shown in Fig 2.
 Fig.2 Examples of ring structures

PHASE BEHAVIOUR
Phase behaviour describes the phase in which a mass of fluid exists at given conditions of
pressure, volume and temperature PVT. The simplest way to start to understand this
relationship is by considering a single component, for example, water, under only two
variables: Pressure and temperature. Fig.3 shows the phase behaviour in the solid, liquid
and vapor states. Starting with the liquid phase at point A, as the temperature is increased,
the boiling point is reached, at which the water boils and turns to steam gas. Starting from
the situation of the gaseous phase at point B, if the temperature is reduced, the dew point
curve is reached, and the component changes from the gaseous phase to the liquid phase.
For a single component, the boiling point curve and the dew point curve are coincident, and
are known as the vapor pressure curve. The phase boundary between the liquid and solid
phases is the melting point curve. At the triple point, all three phases coexist. At critical
point, it is impossible to distinguish between liquid and gas phases. The compressed gas
exists in liquid state.

Fig.3 Phase behaviour of a pure component

Reservoir fluids may exist as vapor or liquid, even as solid phase. The change in phases can
be directly mapped on a pressure-temperature P-T diagram. While a reservoir produces
fluids, its pressure depletes, and its temperature remains relatively constant.
A typical P-T diagram is shown in Fig.4. The phase envelope is formed by connecting bubble
point curve and dew point curve. The bubble point curve separates liquid phase from the
two-phase region. Two phases coexist inside the envelope. The two curves converge at
critical point. The pressure and temperature at critical point are named critical pressure and
critical temperature. Cricondentherm refers to the maximum temperature beyond which
liquid cannot form regardless of pressure. Cricondenbar refers to the maximum pressure
beyond which gas cannot form regardless of temperature.
Different types of oil and gas reservoirs are defined based on their P-T diagrams.

OIL RESERVOIR: If the reservoir temperature is lower than the critical temperature of the
reservoir fluid, the reservoir is referred to as an oil reservoir. Oil reservoirs can be further
classified into three types as follows.
 Saturated reservoir: If the initial reservoir pressure is equal to the bubble point
pressure of reservoir fluid, the reservoir is referred to as saturated reservoir.
 Under saturated reservoir: If the initial reservoir pressure is higher than the bubble
point pressure of reservoir fluid, the reservoir is referred to as under saturated
reservoir.
 Gas cap reservoir: If the initial reservoir pressure is below the bubble point pressure
of reservoir fluid, the reservoir is referred to as gas cap reservoir. In this scenario, a
gas zone lies above the oil zone. The gas that exists in the gas cap is named free gas,
while that dissolved in the oil phase is named solution gas.
Crude oils can also be classified as volatile oil (high shrinkage oil) or black oil (low shrinkage
oil).
A volatile oil contains large fractions of light and intermediate component which vaporizes
easily. The colour is brown, orange or green. Large amount of gas is liberated with a small
drop in pressure below bubble point. It has an initial producing GOR 2000 and 3300 scf/bbl.

Black oils contain a lower fraction of light components, thus requiring a more significant
pressure drop below bubble point for gas to liberate from oil phase. It is usually black but
can have a greenish or brownish colour. It has an initial GOR of 2000 scf/bbl or less.
GAS RESERVOIRS: If the reservoir temperature is above the critical temperature of
hydrocarbon in the reservoir, the reservoir is classified as a gas reservoir. Gas reservoirs can
be further classified as three types.
 Dry gas reservoir: For dry gas reservoir, the produced gas always exists as vapor
phase, the only liquid produced is water.

 Wet gas reservoir: For this type of reservoir, its temperature is above the
cricondentherm, Hence the original hydrocarbon is in vapor state. However, while
the gas flows to surface, its pressure and temperature reduce and a liquid phase
begins to condense. This type of reservoir is classified as wet gas reservoir.
 Retrograde condensate reservoir: If the reservoir temperature lies between the
critical temperature and the Crinconderntherm of the reservoir hydrocarbon system,
the reservoir is classified as retrograde condensate reservoir. Retrograde
condensate demonstrates very unique thermodynamic behaviour, which is
illustrated in Fig.5. At point 1, the hydrocarbon exists as vapor phase. As pressure
decline, it expands in volume. While pressure further declines into the two-phase
region, it begins to condense rather than expand further. The condensate volume
reaches maximum at point 3. Afterwards, the condensate begins to vaporize while
pressure declines further point 4
 PROPERTIES OF CRUDE OIL
Under reservoir pressure, significant amount of hydrocarbon is dissolved in crude oil. When
oil is produced, pressure and temperature reduce, and gas is liberated from the oil phase.
Changes in pressure, temperature and dissolved gas lead to changes in oil properties. The
most important oil properties include oil density, solution gas oil ratio, oil formation volume
factor, and oil viscosity.
OIL DENSITY
Density of oil is defined as the mass of oil per unit volume, or lbm/ft3 in U.S. Field unit. It is
widely used in hydraulics calculations, e.g., wellbore flow and pipeline flow performance
calculations. Because of gas content, density of oil is pressure dependent. The density of oil
at standard condition (stock tank oil) is evaluated by API gravity.
The specific gravity of crude oil is defined as the ratio of the oil density over the density of
the water, both measured at the same reference temperature and pressure. Specific gravity
measurements are usually based on 60°F temperature. Crude oil specific gravity usually
ranges from 0.8 to 0.9.
Specific gravity has no units
𝜌 𝑠𝑡
𝛾 = (1)
𝜌
where,
γo = oil specific gravity; 1 for freshwater
ρo,st = density of stock tank oil, lbm/ft3
ρw = density of freshwater, 62.4 lbm/ft3
The specific gravity of oil is commonly expressed as API gravity. As defined by the American
Petroleum Institute, the API gravity is computed as follows:
141.5
𝐴𝑃𝐼 𝐺𝑟𝑎𝑣𝑖𝑡𝑦 = − 131.5 (2)
𝛾
Unit is degree °API
API gravity can range approximately from 40° for light crude oil to 10° for heavy crude oil.

SOLUTION GAS OIL RATIO (RS)

Solution gas oil ratio solution (GOR), or gas solubility is defined as the amount of gas that
evolves from oil as pressure is reduced or the amount of gas dissolved in oil at reservoir
temperature and pressure. It often carries the unit of scf/stb (standard cubic feet per stock
tank barrel) or scm/t (standard cubic meter per metric ton).
 𝑣𝑜𝑙 𝑜𝑓 𝑑𝑖𝑠𝑠𝑜𝑙𝑣𝑒𝑑 𝑔𝑎𝑠 𝑖𝑛 𝑟𝑒𝑠𝑒𝑟𝑣𝑜𝑖𝑟, 𝑠𝑐𝑓
𝑅 = (1)
𝑟𝑒𝑑𝑢𝑐𝑒𝑑 𝑣𝑜𝑙 𝑜𝑓 𝑜𝑖𝑙 𝑓𝑜𝑙𝑙𝑜𝑤𝑖𝑛𝑔 𝑙𝑖𝑏𝑒𝑟𝑎𝑡𝑖𝑜𝑛 𝑜𝑓 𝑔𝑎𝑠, 𝑆𝑇𝐵
It’s behaviour versus pressure is expressed in fig 6 below where Pb is the bubble point
pressure

When pressure reduces but still above bubble point pressure, no gas is liberated and the
initial solution GOR (Rsi) remains constant. After pressure drops below the bubble point
pressure, gas begins to liberate and solution GOR is reduced. In fact, any pressure below
original bubble point pressure is also a new bubble point pressure, since oil is still saturated
with gas at this point.
If the reservoir pressure remains above the bubble point, then any gas liberated from the oil
must be released in the tubing and the separators, and will therefore appear at the surface.
In this case, the producing GOR is equal to solution GOR, that is every stock tank barrel of oil
produced liberates Rs standard cubic ft of gas at surface.
If the reservoir pressure drops below the bubble point, then gas is liberated from oil in the
reservoir. The liberated gas may flow towards the producing wells due to the lower pressure
at the well, or it may migrate upwards to form a secondary gas cap under the influence of
the buoyancy force. Consequently, the producing GOR differs from solution GOR.
In a saturated oil reservoir containing an initial gas cap, the producing GOR may be
significantly higher than the solution GOR of the oil, as free gas in the gas cap is produced
through the wells via a coning mechanism. Free gas is the gas existing in the gas cap as a
separate phase, distinct from solution gas which is dissolved in the oil phase.
Gas solubility below bubble point pressure can be predicted by various correlations. Such as
Standing correlation
.
𝑃 10 . ( )
𝑅 =𝛾 .
(2)
8 10
where,
P = system pressure, psia;
T = system temperature, ºF;
γg = specific gravity for solution gas;
API = API gravity of oil.

OIL FORMATION VOLUME FACTOR

The Oil formation volume factor oil FVF or Bo is defined as the ratio of the volume of oil
containing solution gas at the prevailing pressure and temperature, to the volume of oil at
standard conditions.
𝑣𝑜𝑙 𝑜𝑓 𝑜𝑖𝑙 𝑎𝑡 𝑟𝑒𝑠𝑒𝑟𝑣𝑜𝑖𝑟 𝑐𝑜𝑛𝑑𝑖𝑡𝑖𝑜𝑛 𝑉
𝐵 = (1)
𝑣𝑜𝑙 𝑜𝑓 𝑜𝑖𝑙 𝑎𝑡 𝑠𝑢𝑟𝑓𝑎𝑐𝑒 𝑐𝑜𝑛𝑑𝑖𝑡𝑖𝑜𝑛 𝑉
When system pressure declines from initial reservoir pressure, oil first expands and oil
formation volume factor increases. After gas is liberated below the bubble point pressure,
oil shrinks and Bo decreases. The value of oil formation volume factor depends on the fluid
type and reservoir conditions. The value can vary from 1.1 for a black oil to 2.0 for very
volatile oil. A few correlations are available for prediction of oil formation volume factor
under saturated conditions.
. .
𝛾
𝐵 = 0.9759 + 0.00012 𝑅 + 1.25𝑇 (2)
𝛾
where,
T = temperature, ºF;
γo = specific gravity of stock tank oil;
γg = specific gravity of solution gas.
OIL VISCOSITY
Viscosity is an empirical parameter used for describing the resistance to flow of fluid.
Viscosity of oil indicates how easily it will flow in the reservoir. It is a measure of the internal
resistance to flow. The unit of viscosity is the centipoise.

Viscous crude would require more energy to flow towards the wellbore than low viscosity
oil. The heaviest and most viscous of hydrocarbon deposits usually require unconventional
methods of recovery.

Oil viscosity is strongly affected by oil composition, pressure, temperature, and gas
solubility. Oil viscosity is reduced at high temperature. Solution gas lightens oil and leads to
a reduction in oil viscosity. As oil is produced and reservoir pressure declines, oil viscosity
reduce somewhat as long as no gas evolves from the liquid phase. However, once the light
components are liberated with further decline in pressure below the bubble point, oil
becomes more viscous.

OIL COMPRESSIBILITY
Oil compressibility is a measure of change in volume as a result of change in prevailing
pressure. It is defined as the rate of change in the volume of crude oil per unit change in
pressure divided by the volume of oil. Compressibility of oil at a given pressure and
temperature can be expressed mathematically by:

𝐶=− (1)

Using this equation, the compressibility of oil is measured at a reference temperature, T.

where
C = fluid compressibility, psi−1;
V = oil volume, bbls;
p = fluid pressure, psi.
Oil is slightly compressible. As reservoir pressure declines, oil undergoes slight expansion in
volume as long as volatile hydrocarbons are not liberated from the liquid phase. The unit of
oil compressibility is the inverse of pounds per square inch (psi−1).
Values of oil compressibility can typically range from 5 × 10−6 psi−1 to 12 × 10−6 psi−1 or more.
If one million barrels of oil in a reservoir are found to have a compressibility of 12 × 10−6
psi−1 and a drop of 100 psi in reservoir pressure occurs, the volume of oil would expand by
1200 barrels. The result would be obtained by:
𝑐ℎ𝑎𝑛𝑔𝑒 𝑖𝑛 𝑜𝑖𝑙 𝑣𝑜𝑙
= 𝑜𝑟𝑖𝑔𝑖𝑛𝑎𝑙 𝑜𝑖𝑙 𝑣𝑜𝑙 × 𝑜𝑖𝑙 𝑐𝑜𝑚𝑝𝑟𝑒𝑠𝑠𝑖𝑏𝑖𝑙𝑖𝑡𝑦 × 𝑐ℎ𝑎𝑛𝑔𝑒 𝑖𝑛 𝑟𝑒𝑠𝑒𝑟𝑣𝑜𝑖𝑟 𝑝𝑟𝑒𝑠𝑠
The total compressibility of the system accounts for the compressibility of the fluid phases
present in the system as well as the formation compressibility.
𝐶 =𝐶 +𝐶 𝑆 +𝐶 𝑆 +𝐶 𝑆
Example:
A reservoir oil is under 3000 psia and 200ºF. The bubble point pressure is 2500 psia. Oil
specific gravity is 0.8, and gas specific gravity is 0.7. Predict oil solution gas ratio and oil
formation volume factor at 1000 psia and 100ºF.
 PROPERTIES OF NATURAL GAS
Natural gas is a naturally occurring hydrocarbon gas mixture consisting primarily of
methane, but commonly includes varying amounts of other higher alkanes, and sometimes
a small percentage of carbon dioxide, nitrogen, hydrogen sulfide, or helium. Natural gas is
primarily composed of light hydrocarbons compared to oil. Due to the low viscosity of
natural gas, it is produced with relative ease from gas and gas condensate reservoirs. Oil
reservoirs with a gas cap or the reservoirs that are operating under bubble point pressure
also produce natural gas along with oil. Natural gas is an important source of energy for
heating, cooking, and electricity generation. It is also a major feedstock for production of
plastics and fertilizers.

GAS EQUATION OF STATE

When a gas is stored at ambient pressure and temperature, it behaves like an ideal gas.
When pressure and temperature increase, its behaviour deviates from ideal gas. The ideal
gas law is given below:
𝑃𝑉 = 𝑛𝑅𝑇 (1)
where,
P = pressure, psi;
V = volume of gas, ft3;
T = absolute temperature, ºR;
n = number of pound moles of gas, lb-mol;
R = universal gas constant (10.73 for the above units).
It is clear that
𝑛= (2)

where,
m = the mass of gas, g;
M = the gas molecular weight, g/mol.
Therefore,
𝑃𝑉 = . 𝑅𝑇 (3)

And the Density of gas can be expressed as:

𝜌 = = (4)

or

𝜌 = (5)
where ρg is gas density and m is mass of gas. Taking air molecular weight 29 and R=
10.73psia-ft3mole-1°R-1, equation 5 can be rearranged to yield
.
𝜌 =

Natural gas is a mixture of components. The apparent molecular weight of the mixture
depends on the molecular weight of each component and its fraction:
𝑀 =∑ 𝑦𝑀 (6)
where,
Ma = apparent molecular weight of a gas mixture;
Mi = molecular weight of a component in the mixture;
yi = mole fraction of a component in the mixture.

The Specific gravity of gas is defined as the ratio of gas density to air density.

𝛾 = (7)

Incorporating the density, the specific gravity of gas can be expressed as:

𝛾 = (8)

Under reservoir conditions with high pressure and temperature, real gas volume may
deviate significantly from that of the ideal gas. Hence, the ideal gas law is modified by
introducing gas compressibility factor or gas deviation factor (gas Z factor).
The real gas law is expressed as:
𝑃𝑉 = 𝑍𝑛𝑅𝑇 (9)
where,
R = universal gas constant.
The value of gas constant is 10.73 73 psi.ft3/lb-mole°R with the field units.

The gas compressibility factor can be expressed as follows:

𝑎𝑐𝑡𝑢𝑎𝑙 𝑣𝑜𝑙 𝑜𝑓 𝑔𝑎𝑠 𝑎𝑡 𝑠𝑝𝑒𝑐𝑖𝑓𝑖𝑐 𝑝𝑟𝑒𝑠𝑠𝑢𝑟𝑒 𝑎𝑛𝑑 𝑡𝑒𝑚𝑝
𝑧=
𝑣𝑜𝑙 𝑝𝑟𝑒𝑑𝑖𝑐𝑡𝑒𝑑 𝑏𝑦 𝑖𝑑𝑒𝑎𝑙 𝑔𝑎𝑠 𝑙𝑎𝑤 𝑎𝑡 𝑠𝑎𝑚𝑒 𝑡𝑒𝑚𝑝 𝑎𝑛𝑑 𝑝𝑟𝑒𝑠𝑠𝑢𝑟𝑒

Compressibility characteristics are also dependent on its composition

Pseudo-reduced pressure and temperature can be calculated when the pressure and
temperature data of a hydrocarbon component at the critical point are available. The vapor
and liquid phases of a pure substance at the critical point are indistinguishable. Pseudo-
reduced pressure and temperature is determined following these steps:
Calculate
𝑃
𝑃𝑝𝑟 = (10)
𝑃𝑝𝑐

𝑇
𝑇𝑝𝑟 = (11)
𝑇𝑝𝑐

where,
P = system pressure, psia;
T = system temperature, ºR;
Ppc = pseudo-critical pressure, psia;
Tpc = pseudo-critical temperature, ºR;
Ppr = pseudo-reduced pressure, psia;
Tpr = pseudo-reduced temperature, ºR.
The pseudo-critical properties can be gotten as:

𝑃 = 𝑦𝑃 (12)

𝑇 = 𝑦𝑇 (13)

Where;
Where, 𝑦𝑖, is the mole ratio of the gas component i
𝑃𝑐𝑖, is the critical pressure of the gas component i
𝑇𝑐𝑖, is the critical temperature of the gas component i

If the gas composition is unknown, the pseudo-critical properties can be estimated by the
following equations and charts
Ppc = 677 +15γg − 37.5γg2
Tpc =168 + 325γg −12.5γg2
GAS COMPRESSIBILITY
Gas compressibility is defined as the change in volume per unit volume for a unit change in
pressure. Gas compressibility is high, because gas is very compressible. The gas
compressibility is expressed as:

𝐶 =− (1)

Recall gas equation of state (PV = ZnRT), therefore,

𝑉= (2)

Differentiating the gas equation of state with respect to pressure gives;

= 𝑛𝑅𝑇 − (3)

Substituting the derivative we get,

𝐶 = − (4)

Since the second term in the right-hand side is usually small, gas compressibility is
approximately equal to the reciprocal of pressure.

1
𝐶 ≈𝑃

GAS FORMATION VOLUME FACTOR (FVF, BG)

Gas formation volume factor is defined as the ratio of gas volume at reservoir condition to
the gas volume at standard condition (60°F and 14.7psia). Gas formation volume factor is
the volume of gas in a reservoir barrel, rb divided by volume of gas under standard
conditions, scf. Where the unit of formation volume factor is ft3/scf.
𝑉 𝑃 𝑇𝑍 𝑧𝑇
𝐵 = = = 0.0283
𝑉 𝑃𝑇 𝑍 𝑃
If expressed in rb/scf, it takes the form

𝑧𝑇
𝐵 = 0.00504
𝑃
where

Bg = gas formation volume factor, rb/Mscf;

z = gas compressibility factor;

T = reservoir temperature, °R;

P = reservoir pressure, psia.

As the above equation suggests, the formation volume is a direct function of gas
compressibility factor and varies inversely with reservoir pressure. Since the gas formation
volume is a very small number, it is conveniently expressed in rb/Mscf rather than rb/scf.

Gas formation volume factor is frequently used in mathematical modeling of gas well-
inflow performance relationship (IPR).

Another way to express this parameter is to use gas expansion factor defined, in scf/ft3, as

1 𝑃
𝐸= = 35.3
𝐵 𝑧𝑇
Or

1 𝑃
𝐸= = 198.32
𝐵 𝑧𝑇
in scf/rb. It is normally used for estimating gas reserves.

VISCOSITY OF NATURAL GASES

Viscosity is a measure of the internal resistance to flow. The unit of viscosity is the
centipoise. Due to considerably less viscosity than oil, gas will flow at a significantly higher
rate than oil in porous media.

Dynamic viscosity (μg) in centipoises (cp) is usually used in petroleum engineering.

Kinematic viscosity (vg) is related to the dynamic viscosity through density (ρg),

𝜇
𝑣 =
𝜌
Kinematic viscosity is not typically used in natural gas engineering.

Direct measurements of gas viscosity are preferred for a new gas. If gas composition and
viscosities of gas components are known, the mixing rule can be used to determine the
viscosity of the gas mixture:

∑ 𝜇 𝑦 𝑀𝑊
𝜇 =
∑ 𝑦 𝑀𝑊
Viscosity of gas is very often estimated with charts or correlations developed based on the
charts. Gas viscosity correlation of Carr et al., 1954 involves a two-step procedure: The gas
viscosity at temperature and atmospheric pressure is estimated first from gas-specific
gravity and inorganic compound content. The atmospheric value is then adjusted to
pressure conditions by means of a correction factor on the basis of reduced temperature
and pressure state of the gas.

EXAMPLE
A natural gas under 3500 psia and 200°F contains 85% Methane, 10% Ethane, and 5%
Propane.
i. Find the apparent molecular weight and specific gravity for the gas mixture.
ii. Find the Z factor for this gas mixture under the system conditions
iii. Calculate gas formation volume factor and gas density under system conditions.
Take
Molecular weight of methane = 16
Molecular weight of ethane = 30
Molecular weight of propane = 44