Gas Properties: PNGE 461 FALL 2011-2012

Gas Properties
PNGE 461
FALL 2011-2012
Dr. Çağlar Sınayuç

Gas Formation Volume Factor, Bg
•  Gas formation volume factor is
Volume of gas at reservoir conditions
Bg =
Volume of gas at surface conditions
o  If we define the surface conditions as P=14.7 psia, T=520 °R
zT
Bg = 0.02827
p
o  Unit is rcf/scf

COMPRESSIBILITY OF NATURAL GASES
Knowledge of the variability of fluid compressibility with pressure

Compressibility of Natural Gases
and temperature is essential in performing many reservoir engineering
calculations. For a liquid phase, the compressibility is small and usually
assumed to be constant. For a gas phase, the compressibility is neither
•  For nor
small a liquid
constant.phase, the compressibility is small and
usually assumed
By definition, to be
the isothermal constant. For
gas compressibility is the a gasinphase,
change vol-
thepercompressibility
ume
60
60 unit volumeReservoir
a unit ischange
forReservoir neither small
in pressure
Engineering
Engineering or, innor
Handbook
Handbook constant.
equation form:
1 ∂V
  gas compressibility,
cg = isothermal gas compressibility, 1/psi
where
c
where =c =
− isothermal
 
g c = isothermal
g 1/psi. 1/psi.
gas compressibility, (2-44)
g V  ∂p  T
From the real gas equation-of-state:
From the real gas equation-of-state:
•  FromnRTz
the real gas equation of state:
V=
nRTz
V= p
p
Differentiating the above equation with respect to pressure at constant
Differentiating
•  temperature T gives: the equation
Differentiating the above abovewith
equation gives:at constant
respect to pressure
temperature T gives:

 ∂V  1  ∂z  z 
  = nRT    − 2
 ∂p  T  p  ∂p  p 
 ∂V   1  ∂z  z 
  = nRT Equation − 2
  2-44
∂
 T
Substituting
p into p ∂
   p produces
p  the following generalized
relationship:
Substituting into Equation 2-44 produces the following generalized
temperature T gives:
 ∂V   1  ∂z  z 
  = nRT    − 2 
∂∂Vp T  1 p∂z ∂
 p  z p 
  =Compressibility of Natural Gases
nRT    − 2 
 ∂p  T  p  ∂p  p 
•  Substituting into compressibility equation produces the
relationship:
relationship: equation.
following
1 1  ∂z 
c g 1 −1  ∂ z  
= (2-45)
c g = p− z ∂p T (2-45)
p z  ∂p  T
Foran
anideal
idealgas,
gas, z =and (∂z/∂p)T( ∂z
1 and
z = 1z=1
(∂z/∂p) =therefore:
T∂p
= 0, )0,T =therefore:
•  For
Foran ideal gas, and 0
=11
ccgg= (2-46) (2-46)
pp
ItIt should
shouldbebepointed
pointed outout
thatthat
Equation
Equation2-462-46
is useful in determining
is useful the
in determining the
expected
expectedorderorderofofmagnitude
magnitude of the isothermal
of the gas compressibility.
isothermal gas compressibility.
Equation
Equation2-45 2-45cancanbe be
conveniently
conveniently expressed in terms
expressed of the of
in terms pseudo-
the pseudo-
reduced pressure and temperature by simply replacing
reduced pressure and temperature by simply replacing p with p with (p p ), or:p ), or:
pc pr(p
pc pr
1 1 ∂z 
cg = 1 − 1  ∂z  
c g =p pr p pc −z  ∂( p pr p pc )  Tpr 
p p
pr pc z  ∂ ( p pr p pc )  Tpr
g = 
cFor    2 (2-46)
 ∂pan
 p  ∂p  p
p Tideal gas,z = 1 and (∂z/∂p)
 T = 0, therefore:
ItSubstituting
should
1 be pointed out that 2-44
Equation 2-46 is
theuseful in determining the
cg
expected
= Compressibility of Natural Gases
into Equation produces following generalized
(2-46)
porder of magnitude of the isothermal gas compressibility.
relationship:
Equation 2-45 can be conveniently expressed in terms of the pseudo-
It should
reduced be
1 pointed
1pressure ∂zand out that Equation
 temperature by 2-46 isreplacing
simply useful in determining
p with (p the
p(2-45)
− of magnitude pc pr), or:
c g = order
expected  of the isothermal gas compressibility.
p z  ∂p  T
Equation 2-45 can be conveniently expressed in terms of the pseudo-
The
• reduced 1
above
pressure equation
and ∂z can
1  temperature  bybe conveniently
simply expressed
replacing p with in terms
(ppc ppr), or:
g = an ideal −
cFor gas, z = 1 and (∂z/∂p) = 0, therefore:
of the p pc z  ∂ ( p pr p pc ) pressure
p pr pseudoreduced Tpr
T
and temperature
1 1 ∂z 
cg = 1 − 
c g = p pr p pc z  ∂ ( p pr p pc )  Tpr (2-46)
Multiplying the above equation by p
p pc yields:
•  Multiplying the above equation by ppc yields:
It should bethe
Multiplying pointed
aboveout that Equation
equation 2-46 is useful in determining the
by ppc yields:
expected order of 1  ∂z of
1 magnitude  the isothermal gas compressibility.
c g p pc = c pr = −   (2-47)
Equation 2-45p1prcan1zbe  ∂∂conveniently
Reservoir-Fluid
p
z pr  Tpr expressed in terms of the pseudo-61
Properties
reduced = c pr = and
c g p pc pressure − temperature
  by simply replacing p with (p(2-47)
pc ppr), or:
p pr z  ∂ p pr  T
The term
•  The termccprprisis called
calledthe the
pr isothermal
isothermal pseudo-reduced
pseudo-reduced compressibility
andcompressibility
cis =defined1 by1the
−
 and ∂z is defined
relationship:  by the relationship:
p pr p pc z  ∂ ( p pr p pc )  Tpr
g
cpr = cg ppc (2-48)

cpr = isothermal
where
Multiplying the abovepseudo-reduced compressibility
equation by ppc yields:
For an ideal gas, z = 1 and (∂z/∂p)T = 0, therefore:
1 1  ∂z 
c g = −   (2-45)
p z ∂p T
Estimation of Compressibility of Natural Gases
cg =
1
p
For an ideal gas, z = 1 and (∂z/∂p)T = 0, therefore:
•  Assuming an ideal gas behavior, It should be pointed out that Equation 2-46 is useful in de
1 expected order of magnitude of the isothermal gas compress
cg = (2-46)
Equation 2-45 can be conveniently expressed in terms o
p
reduced pressure and temperature by simply replacing p with
•  ItAssuming
should be pointed
a realout thatbehavior,
gas Equation 2-46 is useful
(using in determining
Standing and the
Katz chart)
expected order of magnitude of the isothermal 1 gas1 compressibility.
 ∂z 
1.  Calculate Tpc and ppc c = −
Equation 2-45 can be conveniently g expressed in terms of the pseudo-
2.  Compute T and p p pr p pc z  ∂ ( p pr p pc )  Tpr
reduced pressure and pr temperature
pr by simply replacing p with (ppc ppr), or:
3.  Determine the z-factor
4.  Calculate 1 the
1  slope ∂z ⎡⎣∂z ∂p Multiplying
⎤ usingthe Standing
above equation andbyKatzppc yields:
chart
pr ⎦ T Reservoir-Fluid Properties
cg = −
p pc cprz by
∂ ( papplying)  pr
5.  Solve p pr for p
pr pc  Tpr
1 1  ∂z 
pc = c pr =
c g pcalled −  
The term cpr is thep prisothermal
z  ∂ p pr  T pseudo-reduced compre
Multiplying the above equation by ppc yields:
and is defined by the relationship: pr
6.  Calculate cg
1 cpr1 = c∂gz ppc
c g p pc = c pr = −   (2-47)
p pr z  ∂ p pr  T
where cpr = isothermal pseudo-reduced compressibility
pr
cg = isothermal gas compressibility, psi−1

ppc = pseudo-reduced pressure, psi
Estimation of Compressibility of Natural Gases
•  Assuming a real gas behavior, (using Trube (1957) graphs)
1.  64 Find cpr Reservoir
using Trube’s pseudo-reduced compressibility
Engineering Handbook
for natural
Reservoir-Fluid Properties 63
gases graph.

force per unit area to the local velocity gradient. Viscosities are
expressed in terms of poises, centipoise, or micropoises. One poise
equals a viscosity of 1 dyne-sec/cm2 and can be converted to other field
Viscosity of Natural Gases
units by the following relationships:
•  The = 100 centipoises

viscosity
1 poise of a fluid is a measure of the internal
= 1 × 10
fluid friction 6 micropoises
(resistance) to flow.
= 6.72 × 10−2 lb mass/ft-sec
•  Viscosity is expressed in terms of poises, centipoise
= 2.09 × 10−3 lb-sec/ft2
or micropoise.
•  OneThe gas viscosity
poise equalsis not
a commonly
viscosity measured in the laboratory
of 1 dyne-sec/cm 2. because
it can be estimated precisely from empirical correlations. Like all inten-
•  Like all intensive properties, viscosity of a natural gas
sive properties, viscosity of a natural gas is completely described by the
is completely
following function:described by the following function:
µg = (p,T,yi)
where µg = the viscosity of the gas phase. The above relationship simply
states that the viscosity is a function of pressure, temperature, and com-
position. Many of the widely used gas viscosity correlations may be
viewed as modifications of that expression.
Calculation of Viscosity of Natural Gases
•  The gas viscosity is not commonly measured in the
laboratory because it can be estimated precisely
from emprical correlations.
•  Two popular methods that are commonly used in
the petroleum industry are:
o  Carr-Kobayashi-Burrows Correlation Method
o  Lee-Gonzalez-Eakin Method

critical properties for the presence of the nonhydrocarbon gases
(CO2, N2, and H2S) should be made if they are present in concen-
trations greater than 5 mole percent.
Step 2. Obtain the viscosity of the natural gas at one atmosphere and the
temperature of interest from Figure 2-5. This viscosity, as denoted
•  Carr-Kobayashi-Burrows Correlation Method (1954)
by µ1, must be corrected for the presence of nonhydrocarbon
1.  Calculatecomponents
ppc, Tpc andby Musing
a the inserts of Figure 2-5. The nonhydrocar-
2.  Obtain gas bonviscosity
fractionsattend
one toatmosphere and at Tofusing
increase the viscosity thephase.
the gas Carr’sThe
atmosphericeffectgas viscosity correlation.
of nonhydrocarbon Calculated
components value should
on the viscosity of the be
nat-
correcteduralforgas
thecan
presence of nonhydrocarbon
be expressed mathematically by components
the followingusing
rela-
the insertstionships:
and by the following relationships:
µ1 = (µ1)uncorrected + (∆µ)N2 + (∆µ)CO2 + (∆µ)H2S (2-57)

3.  Calculatewhere
the ppr andµ1T=pr “corrected” gas viscosity at one atmospheric
4.  µg µ1 and
Obtain the viscosity ratio pressure from Carr’s temperature,
reservoir viscosity ratio
cp
correlation. (∆µ)N2 = viscosity corrections due to the presence of N2
5.  µgCOat
The gas viscosity(∆µ) = viscosity corrections due to the presence of CO
2 the pressure and temperature of interest is2
µ1 by corrections
(∆µ)H2 S = viscosity
calculated by multiplying the viscosity
dueratio.
to the presence of H2S
(µ1)uncorrected = uncorrected gas viscosity, cp
Step 3. Calculate the pseudo-reduced pressure and temperature.

Step 4. From the pseudo-reduced temperature and pressure, obtain the
Figure 2-5.Dr. Carr’s

Çağlaratmospheric Carr’s atmospheric gas viscosity correlation
Sınayuç gas viscosity correlation. (Permission to publish by the Society of Petroleum Engineers of AIME. Copy-
right SPE-AIME.)
Dr. Çağlar Sınayuç Carr’s viscosity ratio correlation

Figure 2-6. Carr’s viscosity ratio correlation. (Permission to publish by the Society of Petroleum Engineers of AIME. Copyright SPE-
Heating Value
•  The heating value of natural gas is the heat liberated
when the gas is burned under specified conditions.
•  A British Thermal Unit, BTU is a unit of measurement for
the quantity of heat that must be added to 1 lb of pure
water to raise its temperature from 58.5 to 59.5 °F under
standard pressure.
•  Total or gross heating valve, is the number of BTU’s
evolved by the complete combustion of 1 SCF of gas
with air at 14.7 psia with the temperature of the gas, air
and products of combustion at 60 °F, and all water
formed by combustion reaction condensing to the liquid
state.

Heating Value
•  The chemical reaction for the combustion of 1 lb
mole of methane is BTU
•  The latent heat of water at 60 °F and 14.7 psia is

1060 BTU/lb, for 2 lb moles of water, this is
•  Which means that there is an extra 38160 BTU of

heat energy hidden in 2 lb of water vapor. Thus we
can write;

Heating Value
•  The quantity 382778-38160 = 344618 BTU is the net heat gain
after the complete combustion of 1 lb mole of methane with
air at STP with the produced 2 lb moles of water is at the vapor
state.
•  Thus we can define a net heating value using the same
definition except that the water formed remains in the vapor
state.
•  Therefore the difference between the gross and net heating
values are due to the latent heat of condensation of the
water. The difference between gross and net heating values
for most gases are around 7-10%. Remember that the heat
liberated from the complete combustion of 1 lb mole of
methane at STP was 382778 BTU, with water condensed to
liquid phase.

Heating Value
•  To calculate the gross heating value we need to find the
volume of 1 lb mole of methane at STP.
•  At 14.7 psia and 520 R, taking z as 0.998
•  For CH4
•  Gross heating value is
•  To calculate the heating value of a natural gas we multiply

the gross (or net) heating value of each component with its
mole fraction and add the results.

Heating values for some gases
Component Net Heating Value (BTU/SCF) Gross Heating Value (BTU/SCF)
Methane 911 1010
Ethane 1631 1763
Propane 2353 2557
n-‐‑Butane 3101 3369
i-‐‑Butane 3094 3354
n-‐‑Pentane 3709 4009
i-‐‑Pentane 3698 4001
n-‐‑Hexane 4404 4756
n-‐‑Heptane 5101 5503
n-‐‑Octane 5797 6250
H2S 621 672
CO2 0 0
N2 0 0
Heating Value
•  If only gas gravity is available;
o  Gross heating value = 215 + 1500*γg , BTU/SCF
o  Net heating value = 155 + 1415*γg , BTU/SCF

Hydrates
What is hydrate?

What is hydrate?
•  Hydrate is a term used in organic and inorganic
chemistry to indicate that a substance contains
water.
•  Gas hydrates are clathrate hydrates: water ice with
gas molecules trapped within.
•  Clathrate hydrates are crystalline water-based
solids physically resembling ice, in which small non
polar molecules (typically gases) are trapped inside
“cages” of hydrogen bond water molecules.
•  Clathrate hydrates are cage compounds in which
the host molecule is water and the guest molecule
is typically a gas.

What is hydrate?
•  Most low molecular
weight gases
o  (including O2, H2, N2, CO2,
CH4, H2S, Ar, Kr, and Xe),
o  as well as some higher
hydrocarbons and
o  freons will form hydrates at
suitable temperatures and
pressures
•  Without the support of
the trapped molecules,
the lattice structure of
hydrate clathrates would
collapse into
conventional ice crystal
structure or liquid water.
Natural gas hydrates
•  In combination with water, many of the
components commonly found in natural gas form
hydrates.
•  Water is often associated with natural gas.
o  In the reservoir, water is always present. Thus produced natural
gas is always saturated with water.
o  In addition formation water is occasionally produced along with
the gas.
o  Furthermore, water is often involved in processing natural gas. The
process to sweeten natural gas often employs aqueous solutions.
The most common of these processes involve aqueous solutions
of alkanolamines. The sweet gas (i.e., the product of the
sweetening process) from these processes is saturated with water.
•  This association of water and natural gas means
that hydrates are encountered in all phases of the
production and processing of natural gas.

Natural gas hydrates
•  One of the problems in the production, processing,
and transportation of natural gas and liquids
derived from natural gas is the formation of
hydrates;
o  gas was produced and delivered at relatively low pressure
in the early era, thus hydrates were never encountered.
o  In the twentieth century, with the expansion of the natural
gas industry, the production, processing, and distribution of
gas became high-pressure operations. Under pressure, it
was discovered that pipelines and processing equipment
were becoming plugged with what appeared to be ice,
except the conditions were too warm for ice to form.
o  In the 1930s, Hammerschmidt (1934) demonstrated that the
“ice” was actually gas hydrates.

Why water molecules form cages?
•  Water has an anomalously
high boiling point.
•  The hydrogen compounds
of the column 6A elements
are
o  water (hydrogen oxide),
o  hydrogen sulfide,
o  hydrogen selenide,
o  and hydrogen telluride.
•  Normal boiling point of
water is 100°C.

•  Water has a fairly large
enthalpy of vaporization,
even in comparison to other
polar substances.
•  It takes significantly more
energy to boil 1 kg of water
than it does to boil any of
the hydrocarbons listed in
the table.

•  The density of ice (917 kg/
m3 or 57.2 lb/ft3) is less than
that of liquid water
(1,000kg/m3 or 62.4 lb/ft3) at
the freezing point.
•  Another unusual property of
water is that it expands
upon freezing.
•  The reason for this expansion
is that the water atoms
arrange themselves in an
ordered fashion, and the
molecules in the crystal
occupy more space than
those in the liquid water.

•  Virtually all of the unusual properties of water noted earlier can
be explained by the shape of the water molecule and the
interactions that result from its shape.
•  The water molecule consists of a single
atom of oxygen bonded to two
hydrogen atoms.
•  Because of the induced electrostatic
charges on the molecule (denoted δ+
for the positive charge and δ- for the
negative), the water molecules will tend
to align, with a hydrogen molecule
lining up with an oxygen molecule.
•  This aligning of the hydrogen and
oxygen atoms is called a hydrogen
bond.

•  When the water molecules line up, they form a hexagonal
pattern. This is the hexagonal crystal structure discussed earlier.
•  The hexagonal pattern of the water molecules is not planar.
•  It is a result of the hydrogen bond that water can form
hydrates. The hydrogen bond causes the water molecules to
align in regular orientations. The presence of certain
compounds causes the aligned molecules to stabilize, and a
solid mixture precipitates.
•  No bonding exists between the guest and host molecules.

Formation of hydrates
•  The formation of a hydrate requires the following
three conditions:
1.  The right combination of temperature and pressure.
Hydrate formation is favored by low temperature and
high pressure. The exact temperature and pressure
depends on the composition of the gas; however,
hydrates form at temperatures greater than 0°C (32°F),
the freezing point of water.
2.  A hydrate former. Hydrate formers include methane,
ethane, and carbon dioxide.
3.  A sufficient amount of water—not too much, not too little.

•  Other phenomena that enhance hydrate formation
include the following:
•  Turbulence
o  High velocity. Hydrate formation is favored in regions
where the fluid velocity is high. This makes choke valves
particularly susceptible to hydrate formation. First, there is
usually a significant temperature drop when natural gas is
choked through a valve because of the Joule-Thomson
effect. Second, the velocity is high through the narrowing
in the valve.
o  Agitation. Mixing in a pipeline, process vessel, heat
exchanger, and so on enhances hydrate formation.
•  Nucleation sites

•  Other phenomena that enhance hydrate formation
include the following:
•  Turbulence
•  Nucleation sites
o  In lay terms, a nucleation site is a point at which a phase
transition is favored, and in this case the formation of a
solid from a fluid phase. Nucleation sites for hydrate
formation include an imperfection in the pipeline, a
weld spot, a pipeline fitting (e.g., elbow, tee, valve),
and so on. Silt, scale, dirt, and sand all make good
nucleation sites as well.

Hydrate types and formers
•  Hydrates are classified by the arrangement of the
water molecules in the crystal, and hence the
crystal structure.
•  There are two types of hydrates commonly
encountered in the petroleum business. These are
called Type I and Type II, sometimes referred to as
Structure I and II. A third type of hydrate that may
also be encountered is Type H (Structure H), but it is
much less common.

Hydrate types and formers

Type I Hydrate
•  The simplest of the hydrate structures is the Type I.

•  Type I hydrates consist of 46 water molecules.
•  Typical formers:
o  CH4, C2H6, H2S, CO2

Type II Hydrate
•  The structure of the Type II hydrates is significantly more

complicated than that of the Type I.
•  The Type II hydrate consists of 136 molecules of water.
•  The Type II hydrates are also constructed from two types
of cages.
•  Typical formers:
o  N2, C3H8, i-C4H10

Type H Hydrate
•  Type H hydrates are much less common than either
Type I or II.
•  In order to form, this type of hydrate requires a small
molecule, such as methane, and a Type H former.
•  Type H formers include the following hydrocarbon
species:
o  2-methylbutane, 2,2-dimethylbutane, 2,3-dimethylbutane,
2,2,3-trimethylbutane, 2,2-dimethylpentane, 3,3-
dimethylpentane, etc.
•  These components are not commonly found in
natural gas.
•  The Type H hydrates are constructed from three
types of cages.

Size of the guest molecule
•  Von Stackelberg (1949)
discovered the
relationship between
the size of a molecule
and the type of
hydrate formed. He
plotted a chart,
showing the nature of
the hydrate based on
the size of the guest
molecule.

Hydrate-‐‑forming conditions
•  Experimental investigations have been performed
for almost all of the common components in natural
gas.
•  These results are summarized in the book by Sloan
(1998).
o  Sloan, E.D. (1998). Clathrate Hydrates of Natural Gases, 2nd
ed. New York: Marcel Dekker.

Hydrate-‐‑forming conditions for Methane
•  Methane is found in
following phases for a
given pressure and
temperature
o  LA: Aqueous liquid
o  V: Vapor
o  H: Hydrate

Hydrate forming conditions
•  Figure shows the hydrate
loci for several
components found in
natural gas.
•  At quadruple point the
phases are in equilibrium.
•  Methane has no
quadruple, because it
does not liquefy at
conditions required to
form such a quadruple
point.
Hydrate forming conditions for mixtures
•  Mixtures of the Same Type
o  If the gas mixture contains hydrate formers of only one type,
then the hydrate formed is of that type. For example, a
mixture of methane, hydrogen sulfide, and carbon dioxide, all
Type I formers, will form a Type I hydrate.
•  Type I Plus Type II
o  The type formed by the mixture is the one that is
thermodynamically stable.
o  Type II hydrate predominates. Whenever there is only a small
amount of Type II former present, the resultant hydrate is Type
II.
o  This change from Type I to Type II can have a significant effect
on the hydrate-forming pressure. For example, pure methane
forms a Type I hydrate at 15°C and 12.8MPa. The presence of
only 1% propane, a Type II former, results in a mixture that
forms a Type II hydrate. This mixture is estimated to form a
hydrate at 15°C and 7.7MPa.

Hydrate forming conditions – Hand
calculation methods
•  Hand calculation methods are useful for rapid
estimation of hydrate formation conditions since less
information is required as input.
•  Unfortunately, the drawback to these methods is
that they are not highly accurate; however, these
methods remain quite popular.
o  Gas gravity method
o  K-factor
o  Baillie and Wichert method

Gas gravity method
•  Developed by Katz and
co-workers in the 1940s.
•  This method does not
indicate the
composition or type of
the hydrate.
•  This chart is an
approximation and
should only be used as
such.

K-‐‑Factor method
•  This method originated with Carson and Katz (1942).
•  The K-factor is defined as the distribution of the
component between the hydrate and the gas:
where yi and si are the mole fractions of component i in the

vapor and hydrate, respectively. These mole fractions are on a
water-free basis, and water is not included in the calculations. It is
assumed that sufficient water is present to form a hydrate.
•  A chart is available for each of the components commonly
encountered in natural gas that is a hydrate former: methane,
ethane, propane, isobutane, n-butane, hydrogen sulfide, and
carbon dioxide.
•  The recommended ranges for application of the K-factor
method are 0 < T < 20°C and 0.7 < p < 7 MPa

K-factor chart for Methane K-factor chart for Ethane

K-factor chart for CO2 K-factor chart for H2S

•  The K-charts are usually used in three methods:
1.  given the temperature and pressure, calculate the
composition of the coexisting phases;
2.  given the temperature and vapor composition, calculate the
pressure at which the hydrate forms and the composition of
the hydrate; and
3.  given the pressure and vapor composition, calculate the
temperature at which the hydrate forms and the composition
of the hydrate.

1.  given the temperature and pressure, calculate the
composition of the coexisting phases;
The objective function to be solved, in the Rachford-Rice-form, is:
•  where zi is the composition of the feed on a water-free basis.

An iterative procedure is used to solve for the vapor phase
fraction, V, such that the function equals zero. Once you have
calculated the phase fraction, the vapor phase compositions
can be calculated as follows:
•  and from the vapor phase, the composition of the solid is

calculated from:

2. given the temperature and vapor composition, calculate the
pressure at which the hydrate forms and the composition of the
hydrate; and
3. given the pressure and vapor composition, calculate the
temperature at which the hydrate forms and the composition of
the hydrate.
Iterative method
1.  Input the temperature, T.
2.  Input the vapor composition, yi.
3.  Assume a value for the pressure, P.
4.  Set the K-factors for all nonformers to infinity.
5.  Given P and T, obtain K-factors from the Katz charts for the
hydrate-forming components in the mixture.
6.  Calculate the summation:

2. given the temperature and vapor composition, calculate the
pressure at which the hydrate forms and the composition of the
hydrate; and
3. given the pressure and vapor composition, calculate the
temperature at which the hydrate forms and the composition of
the hydrate.
Iterative method
7.  If the summation equal unity the convergence is reached.
8.  If not update the pressure estimate

o  If the sum is greater than 1, reduce the pressure.
o  If the sum is less than 1, increase the pressure.

Hydrate forming conditions – Computer
methods
•  The bases of these computer programs are the
rigorous thermodynamic models found in the
literature.
•  Phase Equilibrium
o  The criteria for phase equilibrium, which were established
more than 100 years ago by Gibbs, are that (1) the
temperature and pressure of the phases are equal; (2) the
chemical potentials of each of the components in each of
the phases are equal; and (3) the global Gibbs free energy
is a minimum.
•  Van der Waals and Platteeuw, Parrish and Prausnitz,
Ng and Robinson are examples of phase equilibrium
models.

Hydrate forming conditions – Computer
methods
•  Commercial Software Packages
•  Several software packages that are dedicated to
hydrate calculations are available.
•  Such as:
o  EQUI-PHASE Hydrate from D.B. Robinson and Associates in
Edmonton, Alberta,
o  CSMHYD from Professor E.D. Sloan

Hydrate control through water removal
•  Except in arctic conditions, the maximum water
content of gas is specified as 4 lbm/MMSCF;
typically the water content is 2.25 lbm/MMSCF.
•  After the free water is separated from the gas
stream, two processes are commonly used to lower
the dew point by removing dissolved water.
o  In the first process, contacting the gas with a compound,
typically tri-ethylene glycol (TEG), which removes water
through hydrogen bonding, lowers the water
concentration.
o  In the second process, the gas is contacted with a solid,
such as molecular sieve, alumina or silica gel, which
selectively adsorbs water.

Hydrate control through use of chemicals
•  Frequently inhibitors are injected into processing
lines as a means of hydrate control by both the
breakage of hydrate hydrogen bonds and the
competition for available water molecules.
•  The more frequently used inhibitors are strong polar
fluids, such as methanol, the ethylene glycols, and
ammonia, arranged in order of decreasing usage
frequency.
o  While ammonia is more than twice as effective as
methanol, it is only used in cases of severe hydrate
blockage, due to the reaction of NH3 with CO2 in the gas
to form plugs of solid ammonium carbonate, bicarbonate
and carbamate.

Hydrate control through use of chemicals
•  Hammerschmidt proposed the first empirical equation to find
the required concentration of an inhibitor X, in an aqueous
solution, for lowering the hydrate formation temperature by a
given amount,
•  ΔT: °F, X: weight %
•  Experimentally determined values of K and molecular weights

of inhibitors are given in the following Table.

Gas Properties: PNGE 461 FALL 2011-2012

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Gas Properties

Dr. Çağlar Sınayuç

Dr. Çağlar Sınayuç

Knowledge of the variability of fluid compressibility with pressure

cpr = cg ppc (2-48)

cg = isothermal gas compressibility, psi−1

Dr. Çağlar Sınayuç

• The = 100 centipoises

Dr. Çağlar Sınayuç

µ1 = (µ1)uncorrected + (∆µ)N2 + (∆µ)CO2 + (∆µ)H2S (2-57)

Step 3. Calculate the pseudo-reduced pressure and temperature.

Figure 2-5.Dr. Carr’s

Dr. Çağlar Sınayuç Carr’s viscosity ratio correlation

Dr. Çağlar Sınayuç

• The latent heat of water at 60 °F and 14.7 psia is

• Which means that there is an extra 38160 BTU of

Dr. Çağlar Sınayuç

Dr. Çağlar Sınayuç

• Gross heating value is

• To calculate the heating value of a natural gas we multiply

Dr. Çağlar Sınayuç

o Gross heating value = 215 + 1500*γg , BTU/SCF

o Net heating value = 155 + 1415*γg , BTU/SCF

Dr. Çağlar Sınayuç

Dr. Çağlar Sınayuç

Dr. Çağlar Sınayuç

Dr. Çağlar Sınayuç

Dr. Çağlar Sınayuç

Dr. Çağlar Sınayuç

Dr. Çağlar Sınayuç

Dr. Çağlar Sınayuç

Dr. Çağlar Sınayuç

Dr. Çağlar Sınayuç

Dr. Çağlar Sınayuç

Dr. Çağlar Sınayuç

Dr. Çağlar Sınayuç

Dr. Çağlar Sınayuç

Dr. Çağlar Sınayuç

• The simplest of the hydrate structures is the Type I.

Dr. Çağlar Sınayuç

• The structure of the Type II hydrates is significantly more

Dr. Çağlar Sınayuç

Dr. Çağlar Sınayuç

Dr. Çağlar Sınayuç

Dr. Çağlar Sınayuç

Dr. Çağlar Sınayuç

Dr. Çağlar Sınayuç

Dr. Çağlar Sınayuç

Dr. Çağlar Sınayuç

where yi and si are the mole fractions of component i in the

Dr. Çağlar Sınayuç

Dr. Çağlar Sınayuç

Dr. Çağlar Sınayuç

Dr. Çağlar Sınayuç

• where zi is the composition of the feed on a water-free basis.

• and from the vapor phase, the composition of the solid is

Dr. Çağlar Sınayuç

Dr. Çağlar Sınayuç

8. If not update the pressure estimate

Dr. Çağlar Sınayuç

Dr. Çağlar Sınayuç

Dr. Çağlar Sınayuç

Dr. Çağlar Sınayuç

•  The = 100 centipoises

•  The latent heat of water at 60 °F and 14.7 psia is

•  Which means that there is an extra 38160 BTU of

•  Gross heating value is

•  To calculate the heating value of a natural gas we multiply

o  Gross heating value = 215 + 1500*γg , BTU/SCF

o  Net heating value = 155 + 1415*γg , BTU/SCF

•  The simplest of the hydrate structures is the Type I.

•  The structure of the Type II hydrates is significantly more

•  where zi is the composition of the feed on a water-free basis.

•  and from the vapor phase, the composition of the solid is

8.  If not update the pressure estimate

•  ΔT: °F, X: weight %

•  Experimentally determined values of K and molecular weights