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Natural gas properties

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Natural petroleum gases contain varying amounts of different (primarily alkane) hydrocarbon compounds and one or more inorganic compounds, such as hydrogen sulfide, carbon dioxide, nitrogen (N2), and water. Characterizing, measuring, and correlating the physical properties of natural gases must take into account this variety of constituents. This article discusses phase behavior, pressure volume temperature (PVT) behavior, gas density and formation volume factor (FVF), viscosity, determining reservoir fluid properties, retrograde behavior, and equations of state (EOS).

Types of gas reservoirs

A dry-gas reservoir is defined as producing a single composition of gas that is constant in the reservoir, wellbore, and lease-separation equipment throughout the life of a field. Some liquids may be recovered by processing in a gas plant. A wet-gas reservoir is defined as producing a single gas composition to the producing well perforations throughout its life. Condensate will form either while flowing to the surface or in lease-separation equipment. A retrograde-condensate gas reservoir initially contains a single-phase fluid, which changes to two phases (condensate and gas) in the reservoir when the reservoir pressure decreases. Additional condensate forms with changes in pressure and temperature in the tubing and during lease separation. From a reservoir standpoint, dry and wet gas can be treated similarly in terms of producing characteristics, pressure behavior, and recovery potential. Wellbore hydraulics may be different. Studies of retrograde-condensate gas reservoirs must consider changes in condensate yield as reservoir pressure declines, the potential for decreased well deliverability as liquid saturations increase near the wellbore, and the effects of two-phase flow on wellbore hydraulics.

Phase behavior of natural gas reservoirs

A widely accepted system for categorizing petroleum reservoir fluids is based on five classes:

  • Low-shrinkage (crude) oils
  • High-shrinkage (volatile) oils
  • Retrograde-condensate gases
  • Wet gases
  • Dry gases

Typical phase diagrams for the gas categories are shown in Figs. 1 through 3.

A retrograde-condensate fluid has a phase envelope such that reservoir temperature lies between the critical temperature and the cricondentherm (Fig. 1). As a result, a liquid phase will form in the reservoir as pressure declines, and the amount and gravity of produced liquids will change with time. Condensate liquids are generally "water white" or light in color (brown, orange, or greenish), with gravities typically between 40 and 60°API. Producing-liquid yields can be as high as 300 STB/MMscf. McCain[1] suggests that when yields are below approximately 20 STB/MMscf, even though phase-behavior considerations may show retrograde behavior, the amount of liquid dropout in the reservoir is insignificant. The primary difficulties in producing condensate reservoirs are as follows:

  • Liquid deposition near the wellbore causes a decrease in gas deliverability that can approach 100% in a reservoir with less than 50-md permeability
  • A large amount of the most valuable hydrocarbon components is left in the reservoir rather than produced

In a wet-gas reservoir, temperature is higher than the cricondentherm (Fig. 2). Therefore, a liquid phase never forms in the reservoir. Considerable liquid can still form (condense) at surface conditions or even in the wellbore. The term "condensate" is often applied to any light hydrocarbon liquid produced from a gas well. However, the term "condensate reservoir" should be applied only to situations in which condensate is actually formed in the reservoir because of retrograde behavior. Wet-gas reservoirs can always be treated as containing single-phase gas in the reservoir, while retrograde-condensate reservoirs may not. Wet-gas reservoirs generally produce liquids with gravities similar to those for retrograde condensates, but with yields less than approximately 20 STB/MMscf.[1]

In a dry-gas reservoir, the cricondentherm is much lower than the reservoir temperature (Fig. 3), resulting in little or no liquid production at the surface. A somewhat arbitrary cutoff liquid yield of 10 STB/MMscf is sometimes used to distinguish dry-gas reservoirs.

While the difference between retrograde-condensate and wet gases is notable, there is much less distinction between wet and dry gases. For both wet and dry gases, reservoir engineering calculations are based on a single-phase reservoir gas. The only issue is whether there is a sufficient volume of produced liquid to be considered in such calculations as material balance or wellbore hydraulics. Retrograde systems require more-complex calculations using equations of state (EOSs) and other advanced engineering methods.

Pressure/volume/temperature (PVT) behavior

The basis of gas PVT behavior is the ideal gas law, and by extension the real gas law:

Vol5 page 0983 eq 001.png....................(1)

The universal gas constant in practical units is

Vol5 page 0983 eq 002.png

Vol5 page 0984 eq 001.png....................(2)

For economic reasons, most (but not all) pressure gauges read zero pressure when pressure is equal to the ambient atmospheric pressure. Therefore, atmospheric pressure must be added to gauge pressures to convert them to an absolute basis. For most engineering purposes, atmospheric pressure is usually taken to be 14.7 psia (101 kPa). For precise scientific and engineering applications, actual atmospheric pressure (i.e., barometric pressure, which varies with both location and time) should be used. Standard temperature and pressure are set by different governmental agencies and should be determined for a specific field or reservoir to be sure that reserves and produced quantities are reported with the correct bases. The SPE standard temperature is 59°F (15°C), and the standard pressure is 14.696 psia (101.325 kPa).

Application of Eq. 1, in a practical sense, must consider how to determine the various factors for petroleum gases that are mixtures of several components. Such determinations would include apparent molecular weight and z (using pseudoreduced pressure and temperature and corrections for nonhydrocarbon components).

Gas density and formation volume factor

The density of a gas can be calculated from the real-gas law once a z factor has been determined. For pressure in psia and temperature in °R, density in lbm/ft3 is given by

Vol5 page 0984 eq 002.png....................(3)

For pressure in kPa, temperature in K, and density in kg/m3,

Vol5 page 0985 eq 001.png....................(4)

The gas formation volume factor is defined as the volume occupied by a gas at reservoir conditions divided by the volume at standard conditions:

Vol5 page 0985 eq 002.png....................(5)

The second and third lines of Eq. 5 give Bg using standard pressure of 14.696 psia and standard temperature of 60°F.

In SI units using SPE standard pressure and temperature,

Vol5 page 0985 eq 003.png....................(6)

Viscosity

Most gas viscosities range from 0.01 to 0.03 cp, making them difficult to measure accurately. Accurate determination of gas viscosities has low economic value. Instead, values are normally determined from one of two correlations.

The first one in common use today, from Lee et al.,[2] is given in equation form as

Vol5 page 0985 eq 004.png....................(7)

where Vol5 page 0985 inline 001.png, and Vol5 page 0985 inline 002.png

The gas density in Eq. 7 is in g/cm3 when p and T are in oilfield units (psia, °R). The equivalent formula for SI units (pressure and temperature in kPa and K, respectively) is

Vol5 page 0985 eq 005.png....................(8)

Fig. 4 shows gas viscosities generated from this correlation for a 0.80-gravity natural gas.

Another common correlation[3] entails a two-step graphical process and is cumbersome for computer applications. Because gas viscosities are seldom needed with great accuracy, the Lee et al.[2] correlation is most applicable for modern reservoir-engineering practice.

Determining reservoir-fluid properties

Condensation of liquids from wet-gas and retrograde-condensate fluids in the production system means that gas produced from separation equipment may be significantly different from the gas that flows into the wellbore from the reservoir. In general, separator gas will be lower in gravity and will have fewer high-molecular-weight hydrocarbons present in the mixture.

For proper laboratory measurements, a bottomhole sample should be collected. An alternative is a reconstituted sample that is created by mixing the separator-produced gas and liquid in proportion to their relative production rates. When the compositions of liquid and gaseous streams have both been measured, the composition of the mixture can be determined from

Vol5 page 0986 eq 001.png....................(9)

Note that

Vol5 page 0986 eq 002.png....................(10)

Vol5 page 0986 eq 003.png....................(11)

Relative molar amounts can be determined by converting measured produced volumes either to moles or to equivalent standard cubic feet. For a gas phase, conversion of a produced volume referenced to standard conditions to moles is

Vol5 page 0986 eq 004.png....................(12)

For a liquid, conversion of a volume to moles is

Vol5 page 0987 eq 001.png....................(13)

If liquid volume is measured at standard conditions, density can be calculated from specific gravity or API gravity. If liquid molecular weight is not measured, it can be approximated with the Gold et al.[4] correlation:

Vol5 page 0987 eq 002.png....................(14)

An alternative to converting measured volumes to moles is to convert all measured volumes to equivalent standard volumes because standard volume is directly proportional to moles (through the value of the standard molar volume). This procedure has the advantage that measured gas volumes need not be converted (this is necessary only for liquid volumes).

Liquid volumes are converted to equivalent gas standard volumes using a parameter called the gas equivalent of oil. This parameter represents the effective standard volume occupied by hydrocarbons that are liquid at surface conditions but are in the gas phase at downhole conditions. This parameter is calculated by

Vol5 page 0987 eq 003.png....................(15)

GEo is calculated with oilfield units in Mscf/STB (the second term below uses standard conditions of 14.696 psia and 60°F) by

Vol5 page 0987 eq 004.png....................(16)

In SI units, GEo in std m3/std m3 is (using standard conditions of 101.325 kPa and 15°C)

Vol5 page 0987 eq 005.png....................(17)

Liquid-production volumes are multiplied by GEo to determine the equivalent standard volume as gas in the reservoir; that is,

Vol5 page 0987 eq 006.png....................(18)

where Vol5 page 0987 inline 001.png is the actual oil volume measured at stock-tank conditions, and Vol5 page 0987 inline 002.png is the gas-equivalent volume of the oil.

These equations also can be used to determine the equivalent gas production of pure hydrocarbons separated from gas in a processing plant. Values of specific gravity and molecular weight for pure components can be found from standard sources such as the Gas Processors Suppliers Association (GPSA) Handbook.[5] In addition, if liquid production is measured at separator, rather than stock-tank, conditions, Eq. 16 or Eq. 17 can be used with separator temperature and pressure rather than standard temperature and pressure.

Relative volumes of gas and liquid phases can then be calculated as

Vol5 page 0988 eq 001.png....................(19)

When wellstream composition is unavailable, correlations must be used to determine gas properties, requiring the calculation of the wellstream (mixture) gravity on the basis of the gravity of the separator gas (often called dry gas) and the specific gravity of the produced liquid (condensate or oil):

Vol5 page 0988 eq 002.png....................(20)

where the subscript g refers to the separator-gas gravity, wg refers to the wellstream gas, and o refers to the produced condensate (oil). Y is the produced condensate yield. Gold’s correlation can be used to estimate condensate molecular weight.

In oilfield units with yield in STB/MMscf,

Vol5 page 0988 eq 003.png....................(21)

In SI units with yield in std m3/std m3,

Vol5 page 0988 eq 004.png....................(10.22)

Measuring retrograde behavior

When a liquid phase begins to form in the reservoir, the produced stream is no longer representative of the reservoir-fluid composition, but rather only the composition of the fluids entering the wellbore. Situations in which the liquid content of gases is high require the use of advanced laboratory tests and/or equation-of-state modeling to measure and predict these multiphase effects.

Laboratory measurements of the PVT behavior of condensate systems are similar to tests used for black oils; however, the primary interest becomes the measurement of relatively small amounts of condensed liquid. In general, systems with producing gas/oil ratios of 15,000 scf/STB (67 STB/scf) have a liquid dropout of approximately 4 to 6% by volume, while reservoirs with ratios around 50,000 scf/STB ordinarily have liquid dropouts of less than 1% by volume.[1]

Two types of tests are generally run on retrograde fluids: constant-composition expansion (CCE) and constant-volume depletion. For examples refer to Tables 1 through 3.

Table 1 gives the compositions of separator gas and liquid streams and other data used in making a recombined sample for analysis of reservoir-fluid composition.

A CCE using a visual cell furnishes the dewpoint of the reservoir fluid at reservoir temperature and the total volume of the reservoir fluid as a function of pressure. The volume of liquid formed at pressures below the dewpoint can also be measured. Table 2 shows the results of such a test. The term "relative volume" refers to the volume of gas plus liquid compared to the dewpoint volume. Retrograde-liquid volume is given as a percent of pore space, which essentially shows how the average condensate saturation changes with average reservoir pressure. Fig. 5 is a graphical representation of the relative condensate volume.

Visual cells also can be used to simulate pressure depletion. The validity of these tests is based on the assumption that the retrograde liquid that condenses in the reservoir will not be mobile. This assumption is valid except for very rich gas/condensate reservoirs. If significant retrograde liquid becomes mobile and migrates to producing wells, gas/liquid relative permeability data should be measured and used to adjust the predicted recovery.

Table 3 is an example of a visual-cell depletion study on the same retrograde gas for which properties are shown in Tables 1 and 2.

The depletion study begins by expanding the reservoir fluid in the cell until the first depletion pressure is reached (5,000 psig in this example). The fluid in the cell is brought to equilibrium, and the volume of retrograde liquid is observed. Gas is removed from the top of the cell while a constant pressure is maintained until the hydrocarbon volume of the cell is the same as when the test began. The gas volume removed is measured at the depletion pressure and reservoir temperature, analyzed for composition, and measured at atmospheric pressure and temperature.

The ideal-gas law can be used to calculate the "ideal volume" at the depletion pressure and reservoir temperature of the gas withdrawn from the cell. Dividing the ideal volume by the actual volume yields the deviation factor, z, for the produced gas. This is listed in Table 4 under z for the equilibrium gas. The actual volume of gas remaining in the cell at this point is the gas originally in the cell at the dewpoint pressure minus the gas produced at the first depletion level. Dividing the actual volume remaining in the cell into the calculated ideal volume remaining in the cell at this first depletion pressure yields the two-phase deviation factor shown. The two-phase z factor is an equivalent z factor that includes the total volume of gas plus liquid:

Vol5 page 0991 eq 001.png....................(23)

The two-phase z factor is the correct value to apply to such things as p/z analysis of retrograde-condensate reservoirs.

A series of expansions and constant-pressure displacements is repeated at each depletion pressure until an arbitrary abandonment pressure is reached. The abandonment pressure is considered arbitrary because no engineering or economic calculations have been made to determine this pressure for the purpose of the reservoir-fluid study.

At the final depletion pressure, the compositions of both the produced well stream and the retrograde liquid are measured. These data are included as a control composition in the event that the study is used for compositional material-balance purposes.

The composition data can be used with equilibrium constants (determined by either laboratory measurements or general correlations) to determine recovery at the various stages of pressure depletion represented by the laboratory measurements. In this case, initial condensate content was 181.74 STB/Mrcf (213 STB/Mscf), and the amount recovered from the dewpoint to 700 psig was 51.91 STB/Mrcf. The gas formation volume factor was determined to be 0.6472 RB/Mscf at initial conditions and 0.6798 RB/Mscf at the dewpoint. If a hydrocarbon pore space of 500 × 10 6 ft3 were determined from volumetric calculations, then from these data and those presented in Table 3, recoveries by pressure depletion would be

Vol5 page 0992 eq 001.png....................(24)

These calculations indicate the large amount of liquid remaining in the reservoir at depletion even with excellent drainage to the wells. Further reductions in recovery would be expected because of areas of the reservoir inadequately drained with existing wells.

To deal with such phase-behavior effects in more than an empirical manner requires the use of PVT simulators. These simulators are based on EOSs that describe the phase volumes and compositions of liquid and gaseous phases as functions of pressure and temperature. Because hydrocarbon molecules interact with each other in solution, the coefficients in an EOS are not always adequately known. PVT tests such as those described, along with the known composition of the original fluid, can be used to "tune" an appropriate EOS to achieve results that nearly match the measurements. Once this tuning process is complete, those coefficients can then be used to make predictions under differing operating conditions with some degree of reliability.

Equations of state

When the effects of complex phase behavior on phase compositions and physical properties cannot be calculated accurately with simple approaches, it is often desirable to use an equation of state (EOS). An EOS approach is often necessary when dealing with volatile oils and retrograde-condensate gases.

EOSs provide a numerical method for calculating both composition and relative amount for each phase present in the system. In reservoir simulation, EOS calculations are typically restricted to two hydrocarbon phases: a liquid (oleic) phase and a gaseous phase. However, there are situations in which an aqueous phase is included in the EOS calculations, or even in which a third hydrocarbon-containing phase may be present (e.g., in CO2 flooding). These are generally done in more advanced compositional simulators.

The two most common EOSs used in petroleum engineering applications are the Peng-Robinson and Soave-Redlich-Kwong equations, which historically were derived from van der Waals’ equation. These three equations are called "cubic" because they result in a cubic representation for the molar volume. The basic equations are as follows:

Ideal gas

Vol5 page 0993 eq 001.png....................(25)

van der Waals

Vol5 page 0993 eq 002.png....................(26)

Soave-Redlich-Kwong

Vol5 page 0993 eq 003.png....................(27)

Peng-Robinson

Vol5 page 0994 eq 001.png....................(28)

The parameters ac, α(T), and b are determined empirically from experimental data (for pure components, the data are critical temperature and pressure and a specified point on the vapor-pressure curve), α(T) being a function of temperature and having a value of 1 at the critical temperature. Note that the parameters have different values depending on the equation.

The reader is referred to texts such as those by Ahmed,[7] Pedersen et al.,[8] McCain,[1] and Whitson and Brule.[9]

Nomenclature

a = empirical constant
A = drainage area, reservoir area, L2
AOF = absolute open flow potential, std L3/t
b = empirical constant
B = formation volume factor, L3/std L3
Bgi = initial gas formation volume factor, L3/std L3
c = compressibility, Lt2/m
cf = pore-volume compressibility, Lt2/m
cw = water compressibility, Lt2/m
C = constant in gas-deliverability equation
CA = Dietz shape factor, dimensionless
D = non-Darcy-flow coefficient, t/std L3
Efw = cumulative formation and water expansion, L3
Eg = cumulative gas expansion, L3
ER = recovery efficiency, fraction
Et = total cumulative expansion, L3
Ev = volumetric sweep efficiency, fraction
F = cumulative reservoir voidage, L3
G = original gas in place, std L3
GE = gas equivalent, std L3/std L3
Gpc = cumulative gas production during a period of constant rate, std L3
h = average reservoir thickness, L
kg = measured gas permeability, L2
kl = effective liquid permeability, L2
K = parameter in Lee et al.2 viscosity correlation
m = real-gas potential, m/Lt2
M = molecular weight
n = number of moles of gas or exponent in gas-deliverability equation
nc = total number of components in gas mixture
nw = number of wells
Vol5 page 1033 inline 001.png = relative number of total moles in gaseous phase, fraction
Vol5 page 1033 inline 002.png = relative number of total moles in oil phase, fraction
Np = cumulative condensate production, std L3
p = pressure, m/Lt2
Vol5 page 1033 inline 003.png = average pressure, m/Lt2
Vol5 page 1033 inline 004.png = variable of integration in real-gas potential equation, m/Lt2
PI = productivity index, std L3/t/m/Lt2
q = production rate, std L3/t
qc = production rate during period of constant rate, std L3/t
qR = total reservoir gas production rate, std L3/t
r1 = radial distance at which pressure p1 is measured, L
r2 = radial distance at which pressure p2 is measured, L
R = universal gas constant, mL2/nt2T
t = time, t
tc = time of constant-rate production, t
T = temperature, T
u = volumetric flux ( q/A ), L3/t/L2
V = volume, L3
Vm = molar volume, L3/n
xj = mole fraction of component j in liquid phase
X = parameter in Lee et al.2 viscosity correlation
yj = mole fraction of component j in gaseous phase
Y = produced condensate yield, std L3/std L3
z = gas deviation factor, dimensionless
zj = mole fraction of component j in mixture
α = cubic equation-of-state parameter
αc = empirical constant
ρ = density, m/L3
ϕ = porosity, fraction
γ = specific gravity (air = 1.0 for gas)
μ = viscosity, cp

References

  1. 1.0 1.1 1.2 1.3 1.4 1.5 1.6 McCain, W.D. Jr. The Properties of Petroleum Fluids, PennWell, Tulsa (1990).
  2. 2.0 2.1 2.2 Lee, A.L., Gonzalez, M.H., and Eakin, B.E. 1966. The Viscosity of Natural Gases. J Pet Technol 18 (8): 997–1000. SPE-1340-PA. http://dx.doi.org/10.2118/1340-PA
  3. Carr, N.L., Kobayashi, R., and Burrows, D.B. 1954. Viscosity of Hydrocarbon Gases Under Pressure. J Pet Technol 6 (10): 47-55. http://dx.doi.org/10.2118/297-G
  4. Gold, D.K., McCain Jr., W.D., and Jennings, J.W. 1989. An Improved Method for the Determination of the Reservoir-Gas Specific Gravity for Retrograde Gases (includes associated papers 20006 and 20010 ). J Pet Technol 41 (7): 747-752. SPE-17310-PA. http://dx.doi.org/10.2118/17310-PA
  5. Engineering Data Book. 1987. Tulsa: Gas Processors Suppliers Association.
  6. 6.0 6.1 6.2 Katz, D.L. and Lee, R.L. 1990. Natural Gas Engineering—Production and Storage. New York City: McGraw-Hill.
  7. Ahmed, T. 1989. Hydrocarbon Phase Behavior. Houston: Gulf Publishing Co.
  8. Pedersen, K.S., Fredenslund, A., and Thomassen, P. 1989. Properties of Oils and Natural Gases. Houston: Gulf Publishing Co.
  9. Whitson, C.H. and Brule, M.R. 2000. Phase Behavior, Vol. 20. Richardson, Texas: Monograph Series, SPE.

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See also

Petrophysical properties of gas reservoirs

PEH:Gas Reservoirs