Reservoir Fluids & Thermodynamics

A reservoir is most commonly an enlarged natural or artificial lake created using

a dam to store fresh water.

Reservoirs can be created in a number of ways, including controlling a watercourse that

drains an existing body of water, interrupting a watercourse to form an embayment within it,
through excavation, or building any number of retaining walls or levees.

Defined as a storage space for fluids, reservoirs may hold water or gasses,
including hydrocarbons.

Tank reservoirs store these in ground-level, elevated, or buried tanks. Tank reservoirs for
water are also called cisterns.

Most underground reservoirs are used to store liquids, principally either water or petroleum,
below ground.
A petroleum reservoir or oil and gas reservoir is a subsurface accumulation
of hydrocarbons contained in porous or fractured rock formations.

Such reservoirs form when kerogen (ancient plant matter) is created in

surrounding rock by the presence of high heat and pressure in the Earth's crust.

Petroleum reservoirs are broadly classified

as conventional and unconventional reservoirs.

In conventional reservoirs, the naturally occurring hydrocarbons, such as crude

oil or natural gas, are trapped by overlying rock formations with lower permeability,
while in unconventional reservoirs, the rocks have high porosity and low
permeability, which keeps the hydrocarbons trapped in place, therefore not
requiring a cap rock.

Reservoirs are found using hydrocarbon exploration methods.

Thermodynamics, science of the relationship between heat, work, temperature,
and energy.

In broad terms, thermodynamics deals with the transfer of energy from one place to another
and from one form to another.

The key concept is that heat is a form of energy corresponding to a definite amount of
mechanical work.
The zeroth law of thermodynamics. When two systems are each in thermal
equilibrium with a third system, the first two systems are in
thermal equilibrium with each other.

This property makes it meaningful to use thermometers as the “third system”

and to define a temperature scale.

The first law of thermodynamics, or the law of conservation of energy.

The change in a system’s internal energy is equal to the difference between heat
added to the system from its surroundings and work done by the system on its
surroundings.
The second law of thermodynamics. Heat does not flow spontaneously from a colder
region to a hotter region, or, equivalently, heat at a given temperature cannot be converted
entirely into work.

Consequently, the entropy of a closed system, or heat energy per unit temperature,
increases over time toward some maximum value.

Thus, all closed systems tend toward an equilibrium state in which entropy is at a
maximum and no energy is available to do useful work.
The third law of thermodynamics :
The entropy of a perfect crystal of an element in its most stable form tends to
zero as the temperature approaches absolute zero.

This allows an absolute scale for entropy to be established that, from

a statistical point of view, determines the degree of randomness or disorder in a
system.
 CLASSIFICATION OF RESERVOIR FLUIDS
The typical phase diagram of a reservoir hydrocarbon system can be used conveniently to
describe various types of reservoir fluids.
A reservoir contains gas if its temperature is higher than the fluid critical temperature,
otherwise it contains oil.

The depletion of reservoir will result in retrograde condensation in the reservoir if the
reservoir temperature lies between the critical temperature and the cricondentherm, whereas
no liquid will form if it is above the cricondentherm.

The oil in a reservoir with a temperature close to its critical point is more volatile than that at
a lower temperature.

A small reduction of pressure below the bubble point, in a reservoir with a temperature just
below the fluid critical temperature, may vaporize half the oil volume.

It is evident, therefore, that the location of reservoir temperature on the phase diagram can be
used to classify reservoir fluids.
The temperature of a reservoir is determined by its depth.
The phase behaviour of a reservoir fluid is determined by its
composition.

Typical compositions of various classes of reservoir

hydrocarbon fluids are given in Table. Critical temperatures
of heavy hydrocarbons are higher than those of light
compounds.

Therefore, the critical temperature of hydrocarbon mixtures

predominantly composed of heavy compounds is higher than
the normal range of reservoir temperatures, and these fluids
behave liquid-like, i.e., oil.

Whereas the temperature of a reservoir mainly composed of

methane, with a critical temperature of 190.6 K, will be
higher than the mixture critical temperature.
When the reservoir pressure falls below the saturation
point, the phase diagram of the original reservoir fluid
is no longer valid.

Gas and liquid phases are produced at a ratio different

to that in the original combined state, resulting in
changes of the overall composition.

The gravitational segregation of the two phases with

different densities will also inhibit the contact between
the phases, hence preventing the achievement of
equilibrium throughout the reservoir.
In a hydrocarbon reservoir consisting of a gas cap and
an oil column two separate phase diagrams, one for
each phase can be considered.
The two phases are both saturated, with the saturation
pressures ideally equal to the reservoir pressure at the
gas-oil contact as shown in Figure. Hence, when a
saturated gas reservoir is discovered, an oil column
below it is generally expected. Similarly a saturated
oil reservoir may strongly indicate the presence of a
gas cap.
The reservoir fluid is produced and measured at the
surface as the stock tank oil and gas at standard
conditions, as shown schematically in Figure.

As the material balance equations relate the produced

fluids to those in the reservoir, the initial producing gas
to liquid volumetric ratio is considered as the most
important indicator of the class of a reservoir fluid.

The gas to oil ratio, GOR, is most commonly defined as

the number of cubic feet of the associated gas produced
at standard conditions per barrel of stock tank oil in the
Field units.

For gas condensate fluids, where the produced fluid is

predominantly gas, the inverse of the above definition,
known as the condensate to gas ratio, CGR, is often
used.
The stock tank oil gravity generally varies significantly
for different classes of fluids, hence it can also be used
as an indicator.

The gravity is expressed as API degrees in field units,

where So is the stock tank oil specific gravity, or

relative density, to water at 60°F ~ (288 K).
The concentration of heavy fraction, C7+ , in reservoir
fluid correlates reasonably well with GOR.

As the stock tank oil is mostly comprised of this

fraction, it can also be used as an indicator of the
reservoir fluid type.

Figure shows that an initial producing GOR of 570

v/v (3,200 SCF/STB) and 12.5 mole% C7+ are valid
boundaries for gas and oil systems [19], as shown in
Figure 1.20.
Dry gases are predominantly composed of methane
and non-hydrocarbons such as nitrogen and carbon
dioxide.

Figure shows the phase diagram of a dry gas.

The phase envelope is relatively tight and mostly

located below the ambient temperature.

Note that the gas remains single phase from the

reservoir to the separator conditions.

Water, however, may condense at the surface

conditions due to the gas cooling. PVT tests in the
laboratory are limited to the gas compressibility
measurement.
A wet gas is mainly composed of methane and
other light components with its phase envelope
located entirely over a temperature range below
that of the reservoir.

A wet gas, therefore, will not drop-out

condensate in the reservoir during depletion, (1)
to (2), as shown in Figure.

The separator conditions lie, however, within

the phase envelope, producing some condensate
at the surface.
As no condensate is formed in the reservoir, material balance equations for a dry gas are
equally suitable for a wet gas.

The only PVT test required at the reservoir conditions is the gas compressibility measurement.

Separator tests are generally conducted to determine the amount and properties of the
condensed phase at the surface conditions.

A wet gas reservoir is commonly produced by simple blow-down, similar to a dry gas, as no
condensate is formed in the reservoir.

Producing gas to condensate ratios are typically above 10,000 v/v (50,000 SCF/STB) and
remain constant during the entire life of the reservoir.

The condensate colour is usually water-white with a low specific gravity which remains
unchanged during the reservoir production life.
Gas condensate Reservoir

A typical gas condensate phase diagram is shown in Figure. The presence of heavy
hydrocarbons expands the phase envelope relative to a wet gas, hence, the reservoir
temperature lies between the critical point and the cricondentherm.

The gas will drop-out liquid by retrograde condensation in the reservoir, when the pressure
falls below the dew point, from (1) to (2) in Figure. Further condensation from the produced
gas also occurs at separator conditions due to cooling.

The amount of potentially condensable hydrocarbons in the reservoir increases with the
richness of the gas, as heavy compounds shift the critical temperature towards the reservoir
temperature.

Whereas a gas with a cricondentherm near the reservoir temperature will behave very much
like a wet gas.
Gas to liquid ratios range between 570 to 30,000 v/v (3,200 to 150,000 SCF/STB).
For practical purposes a gas condensate reservoir with a GOR of above 10,000 v/v (50,000 SCF/STB) can
be treated as a wet gas.

The producing GOR initially remains constant until the reservoir pressure falls below the dew point and
increases thereafter.

For gases with GOR of above 20,000 v/v (100,000 SCF/STB), the condensation in reservoir has negligible
effect on the properties of produced gas, but it can noticeably reduce the gas recovery rate.
The concentration of heptanes plus is generally less than 12.5 mole% in gas condensate fluids as fluids containing
more than that almost always behave liquid like in the reservoir.

Exceptional cases with condensates as high as 15.5 mole% and oils with as low as 10 mole% of heptanes plus
have also been reported.

The condensate colour can be water-white or dark. Dark condensates usually have relatively high specific gravity
and are associated with high dew point gases.

Condensate specific gravity ranges between 0.74 and 0.82 (60 to 40 oAPI), although values as high as 0.88 (as
low as 29oAPI have been reported.

Material balance equations developed for dry gases can be used for a gas condensate reservoir as long as its
pressure remains above the dew point.

It is commonly assumed that the condensate formed in reservoir remains immobile due to its low saturation, and
is mostly non-recoverable.

Recent result, however, have indicated that the condensate can flow even at very low saturations.
 Figure shows a common characteristic of gas
condensate fluids.
The liquid drop-out reaches a maximum and
then decreases by vaporisation during pressure
depletion.

This behaviour may imply that when the

reservoir pressure decreases sufficiently, the
condensate will be recovered by revaporisation.

However, by the time the pressure falls below

the dew point, the original phase diagram is no
longer valid as the system composition changes
during the production period.

Condensation and loss of valuable compounds

Liquid drop-out behaviour of gas condensate. in reservoirs could be avoided by maintaining
the reservoir pressure above the fluid dew point
by gas recycling.
In practice, however, this is very seldom carried out because of shortage of gas.

Partial pressure maintenance is more common to minimise the losses of condensate, where it is
economical to do so.

In recycling operations intermediate and heavy compounds of the produced fluid are separated
and the remaining lean gas is injected back into the reservoir.

The recycled gas which is predominantly methane, not only reduces the pressure decline rate,
but also makes the system leaner.

The removal of a sufficient amount of heavy hydrocarbons from a gas condensate reservoir
may ideally shift the entire phase diagram farther away from the reservoir temperature to form
a wet gas reservoir.
The reservoir can then be produced by blow down without much loss of valuable
liquid. But the lack of complete displacement and mixing of the recycled gas
with the in-situ fluid limits the success of the above operation. However, the
liquid loss by depletion will be lower after recycling.
 Volatile oils have many common features with gas
condensates, but as they contain more heavy
compounds they behave liquid-like at reservoir
conditions.

The phase envelope of a volatile oil is relatively

wider than that of a gas condensate, with a higher
critical temperature due to its larger concentration
of heavy compounds.

A typical volatile oil phase diagram is shown in

Figure. The reservoir temperature is near the
critical temperature, hence, volatile oils are referred
to as near-critical oils. Note that iso-volume lines
are tighter and closer near the bubble point curve.

A small reduction of pressure below the bubble

point vaporises a significant fraction of the oil,
hence the name "volatile oil".

Phase diagram of a volatile oil. Separator conditions typically lie on low quality
(iso-volume) lines.
Initial producing gas to liquid ratios (GOR) of volatile oils typically range between about 310
and 570 v/v (1,750-3,200 SCF/STB.

The GOR increases when the reservoir pressure falls below the bubble point during the reservoir
life.

The stock tank liquid is coloured with a specific gravity usually lower than 0.82 (higher than 40 oAPI).

The specific gravity decreases during production below the bubble point, particularly at high
producing GOR, as a significant liquid production is due to condensation of the rich associated
gases.

Saturation pressures of volatile oils are high. Gases produced below the bubble point, therefore,
are quite rich and behave as retrograde gases.

The amount of liquid recovered from the gas constitutes a significant portion of the total oil
recovery. Compositional material balance methods should be applied generally to study volatile
oil reservoirs.
 Black oils, or ordinary oils, are the most common type of
oil reserves.

The name does not reflect the colour, but to distinguish it

from the volatile oil.

The oil is generally composed of more than about 20

mole% heptanes and heavier compounds.

Its phase envelope, therefore, is the widest of all types of

reservoir fluids, with its critical temperature well above
the reservoir temperature.

A typical black oil phase diagram is shown in Figure.

The quality lines are broadly spaced at reservoir

conditions with separator conditions lying on relatively
high quality lines.
Phase diagram of a black oil.
The above characteristics lead to a low shrinkage of oil
when produced.
Initial producing GOR's are less than about 310 v/v (1,750 SCF/STB).

The GOR may decrease initially when the reservoir pressure falls below the bubble point, as
the evolved gas remains immobile at very low saturations.

The GOR, then increases sharply as the gas to oil mobility ratio within the reservoir varies
inversely with the viscosity ratio, which is typically of two orders of magnitude.

In fractured reservoirs, however, where the fractures provide a good conduit for the gas to rise
by gravity, the GOR declines throughout the producing life of the field, as long as the pressure
keeps declining and no gas coning takes place.

The stock tank liquid is dark with a specific gravity higher than 0.80 (lower than 45 oAPI).
The variation of the specific gravity is relatively small, in comparison with that of volatile
oils, during the reservoir production life.

The saturation pressure of black oils is relatively low.

Contribution of heavy compounds present in evolved gases in reservoir to the total liquid
recovery is not significant.

Hence, volumetric material balance equations, which treat the reservoir fluid as a two
component system, i.e., oil and gas, may be sufficient for some reservoir studies.

Indeed, as there is no definite boundary between black and volatile oils, the acceptability of
results obtained by the volumetric method is a practical criterion for distinguishing between
the two types.
 Reservoir fluids properties

Petroleum reservoirs may contain any of the three fluid phases—water (brine), oil, or gas.

The initial distribution of phases depends on depth, temperature, pressure, composition,

historical migration, type of geological trap, and reservoir heterogeneity (that is, varying rock
properties).

The forces that originally distribute the fluids are gravity, capillary, molecular diffusion,
thermal convection, and pressure gradients.

It is generally assumed that reservoir fluids are in a static state when discovered or, more
correctly, that fluids are moving at a very slow rate relative to the time required to extract the
fluids (10 to 50 years).

Clearly the fluids may still be in a dynamic state in terms of geological time.
Because gravity is the dominant force in distributing fluids through geological time,
hydrocarbons migrate upward and are trapped against impermeable cap rock.

Gas overlies oil, which overlies water.

However, because the reservoir pores are usually saturated completely by water before
[[hydrocarbon migration]] and because capillary forces acting to retain water in the smallest
pores exceed gravity forces, an initial (connate) [[water saturation]] will always be found in
hydrocarbon-bearing formations.

The connate water saturation may vary from 5 to 50% with the hydrocarbons still having
sufficient mobility to produce at economical rates.

Connate water is water trapped in the interstices of sedimentary rock (subsequently

buried by younger sediments) or igneous rock when it was deposited.
 Fluid Properties

Formation volume factor (FVF)

The ratio of a phase volume (water, oil, gas, or gas plus oil) at reservoir conditions, relative to
the volume of a surface phase (water, oil, or gas) at standard conditions resulting when the
reservoir material is brought to the surface. Denoted mathematically as Bw(bbl/STB),
B0 (bbl/STB), Bg (ft3/SCF), and Bt (bbl/STB).

Solution gas-oil ratio (GOR)

The amount of surface gas that can be dissolved in a stock tank oil when brought to a specific
pressure and temperature. Denoted mathematically as Rs (SCF/STB).

Solution oil-gas ratio (OGR)

The amount of surface condensate that can be vaporized in a surface gas at a specific pressure
and temperature; sometimes referred to as liquid content. Denoted mathematically
as rs (STB/MMSCF).
Liquid specific gravity
The ratio of density of any liquid measured at standard conditions (usually 14.7 psia and 60
°F) to the density of pure water at the same standard conditions. Denoted mathematically as
γo (where water = 1).

API specific gravity

Another common measure of oil specific gravity, defined by γAPI = (141.5/γO) –131.5, with
units in °API.

Gas specific gravity

The ratio of density of any gas at standard conditions (14.7 psia and 60 °F) to the density of
air at standard conditions; based on the ideal gas law (pV = nRT), gas gravity is also equal to
the gas molecular weight divided by air molecular weight (Mair = 28.97). Denoted
mathematically as γg (where air = 1).

Bubble point pressure

At a given temperature, this condition occurs when an oil releases an infinitesimal bubble of
gas from solution when pressure drops below the bubble point.
Retrograde dew point pressure
At a given temperature, this condition occurs when a gas condenses an infinitesimal drop of oil from
solution when pressure drops below the dew point.

Saturation pressure
An oil at its bubble point pressure or a gas at its dew point pressure.

Critical point
The pressure and temperature of a reservoir fluid where the bubble point pressure curve meets the
retrograde dew point pressure curve (see Figures 1 and 2), representing a unique state where all
properties of the bubble point oil are identical to the dew point gas.

Composition or feed
Quantifies the amount of each component in a reservoir mixture, usually reported in mole fraction.
Typical components in petroleum reservoir mixtures include the nonhydrocarbons N2, CO2, and H2S
and the hydrocarbons C1 C2, C3iC4nC4, iC5, nC5, C6, and C7+ (C7+, or “heptanes-plus,” includes many
hundreds of heavier compounds, such as paraffins, napthenes, and aromatics). Asphaltenes are also
found in reservoir oils.
Saturated condition
A condition where an oil and gas are in thermodynamic equilibrium, that is, the chemical
force exerted by each component in the oil phase is equal to the chemical force exerted by
the same component in the gas phase, thereby eliminating mass transfer of components from
one phase to the other.

Undersaturated condition
A condition when an oil or a gas is in a single phase but not at its saturation point (bubble
point or dew point), that is, the mixture is at a pressure greater than its saturation pressure.
 Reservoir water
The water found in petroleum reservoirs is usually a brine consisting mostly of sodium chloride (NaCl)
in quantities from 10 to 350 ppt (‰); seawater has about 35 ppt (parts per thousand).

Other compounds (electrolytes) found in reservoir brines include calcium (Ca), magnesium (Mg),
sulfate (SO4), bicarbonate (HCO3), iodide (I), and bromide (Br). Brine specific gravity increases with
salinity in units of about 0.075 per 100 ppt.

At reservoir conditions, the brine that is sharing pore space with hydrocarbons always contains a limited
amount of solution gas (mainly methane), from about 10 SCF/STB at 1000 psia to about 35 SCF/STB at
10,000 psia for gas-water systems and slightly less for oil-water systems.

Increasing salinity decreases gas in solution. Water compressibility ranges from 2.5 to 5 × 10–6 psi–1,
decreasing with increasing salinity.

Water viscosity ranges from about 0.3 cP at high temperatures (>250°F) to about 1 cP at ambient
temperatures, increasing with increasing salinity. Finally, reservoir brines exhibit only slight shrinkage
(<5%) when produced to the surface.
McCain, W.D. Jr.: McCain, W.D. Jr. 1990. The Properties of Petroleum Fluids, second edition. Tulsa,
Oklahoma:PennWell Books.
In this figure, we can see that the reservoir is an undersaturated oil reservoir.
The initial reservoir pressure, pi, is greater than the bubble-point pressure.

If this reservoir were to undergo pressure depletion from oil production, then
the average reservoir pressure would decline over time, and the pressure would
eventually reach the bubble-point pressure.

During this time period, the volume of gas in solution in the crude oil remains
constant at the initial value of R .
Once the reservoir pressure reaches the bubble-point pressure, p, gas begins to come out of
solution.

As the gas comes out of solution and evolves into Free Gas, the volume of gas remaining in
solution, R, must decrease.

This is the behavior observed in Figure 3.09.

The volume of free gas liberated from the original stock tank barrel can be calculated as
(R – R) in SCF/STB or MSCF/STB.
The laboratory procedure for determining the solution gas-oil ratio was discussed in terms of
the differential liberation test.

The R values are calculated by summing the appropriate gas volumes obtained during the
differential test and dividing by the final oil volume.

When this is done, all volumes need to be corrected back to the reference volumes of STB
and SCF to get to the appropriate R curve.

When laboratory derived R data are unavailable, then Equation 3.41 and Equation 3.42 can
be used to estimatethe solution gas-oil ratio.

This is done by placing an assumed pressure into Equation 3.42 and using Equation 3.41 to
calculate the pressure associated with that assumed R value (not the bubble-point pressure as
explicitly writtenin the equation).
 Fluid property correlations

Relatively accurate correlations are available for estimating the key fluid properties of
reservoir systems. Standing and McCain give useful reviews of property correlations for oil
and gas, and other correlations are available. Note, however, that for specific producing
provinces (such as the Gulf Coast or the [[North Sea]]) more accurate correlations may exist.

Gas Oil and water

Pseudocritical properties Bubblepoint pressure
Z factor Solution GOR
Bubblepoint
Density
Isothermal compressibility
Viscosity
K values
Interfacial tension
Diffusion coefficients
Equations of state (EOS) are now commonly used to calculate phase and volumetric behavior
of reservoir mixtures.

In particular, EOS are useful for predicting phase behavior of miscible and immiscible
displacement processes resulting from the injection of gases such as carbon dioxide, nitrogen,
and lean or enriched natural gas in oil and gas condensate reservoirs.

EOS do not usually predict phase and volumetric behavior of reservoir mixtures accurately,
thereby requiring adjustment of component properties to match experimental PVT data.
 Laboratory pressure-volume-temperature (PVT) experiments

Experimental PVT measurements are usually obtained for (1) large oil and gas fields, (2)
volatile oil and gas condensate reservoirs, and (3) reservoirs where gas injection is a potential
EOR ([[enhanced oil recovery]]) method.

Two types of fluid samples can be taken during production, or when a well is shut-in:
•Bottomhole samples, preferred for oils
•Separator samples, which must be recombined at the producing GOR during sampling

Recombined separator samples are standard for gas condensate fluids, but they may also be
used for oil reservoirs.

Bottom hole sampling is preferred for oils if the reservoir is under saturated (that is, the initial
pressure is higher than the bubble point pressure).
Standard PVT experiments include compositional gas chromatography (GC) analysis through
heptanes-plus (C7+), constant composition expansion, differential liberation expansion,
constant volume depletion, and multistage surface separation.

Other PVT measurements include true boiling point (TBP) distillation of the C7+ material and
multicontact gas injection experiments. Table summarizes these experiments, indicating when
they are performed and on what types of reservoir fluids.

Compositional analyses are used to describe the reservoir fluid makeup on a component basis,
including calculation of British thermal unit (BTU) (energy content) of gases, optimization of
separator conditions for liquid yield, and characterization of an EOS for compositional
simulation.
Differential liberation and constant volume depletion experiments are designed to provide
quantitative information about the volumetric behavior of oil and gas condensate
reservoirs during pressure depletion.

The multistage separator test is used together with differential liberation and constant
volume depletion data to calculate black oil properties Rs, Bo, Bg, and rs.

Multicontact gas injection experiments provide important volumetric and compositional

data that can be used to “tune” an equation of state (or alternative) model for simulation
of gas injection processes.
 Laboratory Analysis Oils Condensates
Bottomhole sample * +
Recombined composition + *
C7+ TBP distillation + +
C7+ simulated distillation + +
Constant composition expansion * *
Multistage surface separation * +
Differential liberation * -
Constant volume depletion + *
Multicontact gas injection + +

Key: * standard, + can be done, – not done