Hydrocarbon Liquid
Properties
This chapter outlines and describes properties and parameters important to the design and operational issues related to pipelines transporting hydrocarbon liquids. It
describes various liquid property terms and provides either data for use or equations
for predicting/calculating such properties.
31
1. Light density hydrocarbon liquids (including pure liquids; ethylene and propylene, mixture of light components such as ethane, propane, normal butane, and
iso-butane). These may contain small amounts of other hydrocarbon liquids;
e.g., ethane stream (>90% of ethane, and small amounts of propane, carbon
dioxide, etc.);
2. medium density/mixed light products (including Natural Gas Liquids (NGL),
natural gas condensate, natural gasoline, and Liquid Petroleum Gas (LPG);
3. heavy hydrocarbon products (include conventional, heavy crude, waxy crude
and bitumen).
The petroleum product properties are reflected in the pipeline system designs and
operations.
In the mixed light/medium density hydrocarbon liquids, NGL is a light hydrocarbon mixture extracted from natural gas and includes propane, butane, pentanes+ and
also may include traces amount of ethane. NGLs generally are classified according to
their vapor pressure as:
Condensate (composed of pentanes, hexane, heptanes, and a small amount of
heavier hydrocarbons);
Natural gasoline (composed of pentanes+ plus and some amounts of butanes); and
Liquefied petroleum gas (LPG-composed of propane, normal and iso-butane).
The vapor pressure of condensate is low, natural gasoline intermediate, and LPG
high. Natural gasoline has an intermediate vapor pressure between condensate and LPG.
Condensate is typically recovered from field separation facilities (has a gravity of
about 80API) and has a low vapor pressure but the highest density among the three
types of NGLs.
While the vapor pressure of condensate is lower than that of natural gasoline, the
density of condensate is similar to but tends to be higher than that of natural gasoline,
GPSA [1].
LPG (with typical gravity of around 120API) is liquefied under pressure that is
higher than its vapor pressure. LPG can be extracted from NGL and is often used as
fuel and chemical feedstock.
The medium density products may include light or medium crudes, refined products such as gasoline and diesel, naphtha, condensate, etc. The changes in the density
and viscosity of these products are relatively insensitive to temperature and pressure.
Heavy hydrocarbon products include conventional heavy crude, waxy crude, and
bitumen.
f P, V , T , ak , k = 1, np = 0
(2 1)
f P, V , T , ak , k = 1, np = 0
(2 1)
Liquids are much less compressible than gasses. Even when a liquid is described
with an equation similar to a gas equation, the constants in the equation will result in
much less dramatic changes in volume with a change in temperature. Also, at constant
volume, a temperature change will result in a much larger pressure change than would
be the case for gases.
A common equation of state used for both liquids and solids is [4, 5]:
Vm = C1 + C2T + C3T 2 - C4 p - C5 pT
(2 2)
where
Vm = molar volume
T = temperature
p = pressure
C1, C2, C3, C4, C5 = empirical constants
where the empirical constants are all positive and specific to each substance.
For constant pressure processes, this equation is often shortened to
Vm = Vmo 1 + AT + BT 2
(2 3)
where
Vm = molar volume
Vmo = molar volume at 0C
T = temperature
A, B = empirical constants
Note: A and B are positive constants.
The equation of state created by Peng and Robinson has been found to be useful
for both liquids and real gasses, particularly for phase equilibrium calculations.
(2 4)
where
p = pressure
a = empirical constant
Vm = molar volume
R = ideal gas constant
b = empirical constant
T = temperature
However, for liquid pipeline applications for light hydrocarbons (such as ethane
or propane) where the compositions of a fluid are known, Benedict, Webb, Rubin and
P = RT + B0 RT A0 02 + 30 04 2 + bRT a 3
T
T
T
T
d
c3
+ a + 6 + 2 + 2 exp 2
T
T
) (
(2 5)
r ( P, T ) = r ( Pb , Tb ) * Exp ( P - Pb ) / K * Exp -a * (T - Tb )
(2 6)
where
r(P,T) = density or specific gravity at pressure P and T
r(Pb,Tb) = density or specific gravity at Pb and Tb
K
= bulk modulus of the liquid
a
= thermal expansion coefficient
P
= flowing pressure
Pb
= reference or base pressure
T
= flowing temperature
Tb
= reference or base temperature
Bulk modulus K and thermal expansion coefficient a depend on pressure (P) and
temperature (T). The magnitude of change is small for heavier hydrocarbon liquids
and can thus be treated as a constant. However, they are relatively large for lighter
hydrocarbon liquids such as propane and ethane.
The following equation is often used for volume correction, particularly for custody transfer to a base condition [8]:
r( P,T ) = rb CT Cp
(2 7)
where
rb
= density at base pressure and temperature (gm/cm3 or 0.001 kg/m3)
d
d
CT = e[a T (1 + 0.8 a T)]
T
= difference between the flowing temperature and base temperature
a
= coefficient of thermal expansion at base temperature
= (Ko + K1* rb)/rb2
Ko, K1 = product dependent constants, see Figure 2-3 above.
CP
= 1/(1 Cf*P)
P
= difference between the flowing pressure and base pressure (normally the
base pressure is zero)
Cf
= Exp [1.62080 + 0.00021592*Tf + (0.87096/rb2) + (0.0042092*Tf/
r2b)]*106
This equation is valid for those petroleum products whose density is greater than
635 kg/m3 or API gravity is up to 90API.
Since the density of light hydrocarbon liquids are highly sensitive to pressure
and temperature, the equation of state is complex. For custody transfer of high vapor
pressure liquids, whose density ranges from 350 kg/m3 to 635 kg/m3 or greater than
91API, API bulletin 11.2.2 can be used [8].
Mass, or Volume
Density, compressibility or bulk modulus, and thermal expansion
Specific gravity and API gravity
Viscosity (Viscosity (cP), or kinematic viscosity (cSt))
Blending/diluting Ratio of hydrocarbon liquids (if applicable)
Vapor pressure
Heat capacity and thermal conductivity
Pour point/Cloud Point
Flash point (safety issues only)
K = (1/ PP )( V/V )
(2 8)
where
K = bulk modulus elasticity
d
P = differential change in pressure
d
V = differential change in volume
V = initial volume
Or Bulk Modulus of Elasticity can be alternatively expressed as
K = dr/ (d r/r)
(2 9)
where
dr = differential change in density
r = initial density
An increase in the pressure will decrease the volume. A decrease in the volume
will increase the density
The SI unit of the bulk modulus elasticity is N/m2 (Pa or kPa)
The imperial unit is lbf/in2 (psi) = 6.895 103 N/m2 (Pa) or 6.895 kPa
A large Bulk Modulus (K) indicates a relatively incompressible fluid.
The value obtained for the bulk modulus in Eq. (2.8) is negative because the volume shrinks due to the increased pressure.
2.3.3.2 Bulk Modulus K: as shown above bulk modulus is the inverse of compressibility and is more frequently used than compressibility for liquid pipeline applications. Bulk modulus therefore defines the compressibility of a liquid. The higher
the bulk modulus, the stiffer the liquid. Even though the liquid compressibility is
generally small for heavier hydrocarbon liquids, it is the main cause of pressure
surge in pipeline systems. Refer to Chapters 3 and 5 for a detailed discussion of surge
phenomena.
Table 2-1. Comparison of bulk modulus of some liquids
SI Units
Imperial Units
Bulk Modulus K
Mercury
Crude oil
Oil (range)
Bitumen-condensate
Gasoline
Motor oil (SAE 30)
Seawater
Water
28.5
1.66
1.4
1.53
1.071.49
1.5
2.34
2.15
41.4
2.41
2.03
2.22
1.552.16
2.2
3.39
3.12
K = -d P(V/dV ) = d P (r/ dr )
(2 10)
a = -(1/ dT ) d r/r
(2 11)
where
a = coefficient of thermal expansion
r = density, dr = change in density
d
T = temperature change
Thermal expansion coefficient is a function of fluid pressure and temperature. It
does not change very significantly for heavy hydrocarbon liquids over the range of
temperatures that are in common use in pipelines. However, it changes significantly
for light hydrocarbon liquids.
The thermal expansion coefficient can be estimated from the temperature correction term of the API equation.
Figure 2-5 shows typical bulk modulus and thermal expansion coefficients of various crude oils and lighter products. The values of bulk modulus and thermal expansion
Figure 2-5. B
ulk modulus and thermal coefficient of expansion for typical hydrocarbon liquids
transported through pipelines
r = rb
)]
1+
P - Pb
- a (T - Tb )
K
(2 12)
where
rb = density at base condition
Pb = pressure at base condition
Tb = temperature at base condition
a = liquid temperature coefficient of density
K = bulk modulus
For isobaric conditions (i.e., at constant pressure)
be rewritten as:
r - rb
d
r
rb
-a =
=
T - Tb rb dT
P Pb
= 0, and Eq. (2-12) can
K
(2 13)
where
d
r = r rb = change in density
If the liquid temperature coefficient of density a is known, it is possible to compute liquid densities at different pressures.
For isothermal conditions (i.e., at constant temperature), T Tb = 0, so Eq. (12-12)
can be rewritten as follows:
r = rb 1 +
P - Pb
K
(2 14)
or
K=
d
d
P
rb
p
(2 15)
where
d
P = P Pb change in pressure
Example: Calculate the bulk modulus and liquid coefficient of density for liquid
CO2 if the pressure drop across a pipeline segment is 3100 kPa. The inlet pressure is
13100 kPa. The density at base pressure and temperature is 968.5 kg/m3.
Solution: Given the density at inlet (13100 kPa) is 1073.5 kg/m3 and the density at
the outlet (1000 kPa) is 1064 kg/m3. Then, Dr = 1073.5 to 1064.0 = 9.5 kg/m3.
K=
(2 16)
(2 17)
where
K = Bulk Modulus in psig, T = Temperature F
Another example is the use of Caragoe equation as shown below:
(2 18)
The bulk modulus of a heavier hydrocarbon liquid can be estimated by either using
the pressure correction term of the API equation given above or the Arco correlation
as follows:
(2 20)
Conversely, the specific gravity of hydrocarbon liquids can be derived from the
API gravity value as
(2 21)
For example, oil with a specific gravity of 1.0 (i.e., with the same density as pure
water at 60F) would have an API gravity of:
There are also methods that provide adjustments for temperature. ASTM [11]
describes the methodology for temperatures corrections. Alternatively the following
correction factors can be used to allow for temperature effects (for crude oils relative
to 15C (59F). They are divided into 3 ranges:
All temperatures are in expressed in C.
For temperatures less than 3.98C:
(2 22)
(2 23)
It may be noted that an older version of the scale for liquids heavier than water, at
a reference temperature of 15.5C (59.9F), uses 144.32 rather than 145.
The relationship between API Gravity, Specific Gravity and Density (at 60F) is
summarized in Figure 2-6.
Densities and API gravities for some hydrocarbon liquids typically transported
through pipelines are shown in Table 2-2.
(2 24)
where
SGb = specific gravity of the blended liquid
Vi = volume of each product
Qi = flow rate of each product
SGi = specific gravity of each product
Figure 2-6. API gravity, specific gravity, and density (at 60F)
API
669.0
832.0850.0
775.0840.0
713.0767.0
<870
870.8920.0
865.4870.8
920.61000
1000.71029.1
80.0
35.038.6
51.037.0
52.067.0
>31.1
22.331.0
31.132.0
10.022.2
6.09.9
The above method cannot be directly applied when the gravities are expressed
in API. The API values must be first converted to specific gravities before applying
Eq.(2-24).
= ( u/y)
(2 25)
Figure 2-7. N
ewtonian and non-Newtonian fluids typical shear rate vs. shear stress relationships (adapted from [15])
When transporting non-Newtonian fluids such as bitumen and heavy oils, the viscosity has to be carefully considered. Since the shear rate changes with different fluid
velocities, the viscosity curve of a specific fluid must be determined at a known fluid
velocity along the fluid temperature profile of a pipeline.
Viscosity characteristics of a typical Bitumen/Bitumen Diluent Blend are shown
in Figure 2-8.
(2 26)
where
Vcur = current volume
SGc = current SG
SGt = target SG
New SG from current SG, current volume, and target volume
(2 27)
where
SGc = current SG
Vcur = current volume
Vtar = target volume
2.5.2.2 (B) Viscosity Blending Calculation
When two or more liquids are blended, it is also important that the viscosity of the
blend is determined to assess pipeline transportation options such as the location of
blending and/or injections and as well proper system capability determination. For
this purpose, the Refutas viscosity blending index is generally used by the industry.
This equation requires input of mass fractions. Often, in error, volume fractions are
used which will provide substantially incorrect results if the densities of the two blend
crudes are dissimilar.
Calculating the viscosity blending index of a liquid consisting of two or more
liquids having different viscosities (using the Refutas equation [16]) is a two step
procedure. The first step involves calculation of the Viscosity Blending Index (VBI) of
each component of the blend using the following equations:
(2 28)
(2 29)
REFERENCES
[1] GPSA (Gas Processor Suppliers Association), 1994, Engineering Data Book, Tulsa, OK, USA.,
Vol. II.
[2] Ahmed, T., 2000, Reservoir Engineering Handbook, 2nd edition, Gulf Professional Publishing,
Houston TX, USA.
[3] Mohitpour, M., Seevam, P., Botros, K. K., Rothwell, B., and Ennis, C., 2011, Pipeline Transportation of Carbon Dioxide Containing Impurities, ASME Press, New York, NY, USA.
[4] Young, D., 1998, Equations of State, http://www.ccl.net/cca/documents/dyoung/topics-orig/
eq_state.html.
[5] Young, D., 2001, Computational Chemistry: A Practical Guide for Applying Techniques to
Real World Problems, John Wiley, ISBN: 978-0-471-33368-5, http://ca.wiley.com/WileyCDA/
WileyTitle/productCd-0471333689.html.
[6] ESI (Energy Solutions International), 2012, Pipeline Studio Version 3.3.1 Liquid Pipeline Simulator TLNET, http://www.energy-solutions.com/products/pipelinestudio/.
[7] Starling, K. E., 1973, Fluid Properties for Light Petroleum Systems, Gulf, Publishing Company,
USA.
0.819
D2.28
API
where
Sv = volumetric shrinkage, as percent of total mixture ideal volume
C = concentration in liquid volume percent of light component
DAPI = gravity difference, in API
(1/DL 1/DH) = inverse density difference of light (DL) and heavy (DH) components, in m3/kg
The above equation is only applicable to a pressure range of 100 to 700 kPag (7 to
100 psig), and 15C (60F) temperature.
(2 35)
where
u = kinematic viscosity, stoke or m2/s (Centistoke (mm2/s) mostly used in liquid
pipeline industry)
m = absolute viscosity, Pascal-s
r = fluid mass density
For Newtonian fluids, if the viscosities at two different temperatures are known,
the viscosity at another temperature can be estimated.
Two viscosity correlations that are often used are the Andrade and the ASTM
method. The Andrade correlation shows that the variation of viscosity with temperature is logarithmic:
Ln ( u) = A - B T
(2 36)
where
u = viscosity of liquid, cSt
T = absolute temperature, K
A, B = constants
60 oF
0.0065
0.0085
1.3
0.00004
70 oF
80 oF
90 oF
0.009
0.012
0.016
0.021
0.011
0.017
2.4
1.6
1.1
0.00006 0.00011 0.0001
100 oF
0.022
0.029
2.7
0.00019
Figure 2-9. V
apor pressure of hydrocarbon liquids commonly transported through pipelines
(Source: [18, 19])
Figure 2-10. Scale comparison of true vapor pressure (TVP) and Reid vapor pressure (RVP)
Generally, pipeline standards have sections related to the design of high vapor pressure pipeline systems. For example, CSA Z662-2011 defines an HVP pipeline system as
a pipeline transporting hydrocarbons or hydrocarbon mixtures in the liquid or quasi-liquid
state with a vapor pressure greater than 110 kPa absolute at 38C, as determined using the
Reid method. The high vapor pressure (HVP) products include ethylene, ethane, propylene, propane, normal, and iso-butane since pipe flow is almost an isenthalpic process.
Flash point (FPT ) = 1/ - 0.014568 (2.84947 T10 ) 0 001903 log (T10 ) (2 37)
The heat capacity of a hydrocarbon liquid (at constant pressure) can be estimated
as a function of specific gravity and temperature as follows:
Cp = (1.685 + 0.003391 T ) / SG
(2 38)
where
Cp = heat capacity of the liquid at constant pressure (Isobaric), temperature
T (kJ/kg C)
SG = specific gravity of the liquid at 15C
T = temperature of the liquid (C)
Cp = A1 + A2T + A3T 2
(2 39)
where
Cp = Isobaric Heat Capacity for Liquid petroleum fraction (BTU/ lb. R)
A1 = 1.17126 + (0.023722 + 0.024907 SG) KW + [(1.14982 to 0.046535 KW)/
SG]
A2 = (104) (1.0 + 0.82463 KW) (1.12172 to 0.27634/SG)
A3 = (108) (1.0 + 0.82463 KW) (2.9027 to 0.70958/SG)
Tr = reduced temperature, T/Tpc
T = temperature in Rankine
Tpc = pseudocritical temperature in Rankine
KW = Watson characterization factor
SG = specific gravity 60F/60F
The Watson characterization factor (KW) denotes the paraffinic fraction of petroleum hydrocarbon fractions [23, 24], and, as such, can be expressed as:
(2 40)
where
Tb = the mean average boiling point in degrees Rankine (R)
This is valid from approximately 0.4 < Tr 0.85, requires significant property
knowledge to be applied in practice.
The above approach is indicated to yield significantly improved heat capacity estimates as only the elemental analysis of a material needs to be available to provide
accurate heat capacities on a unit mass basis [22].
Liquid
Gas or vapor
Dense phase or supercritical, and
Two-phase
salient properties are summarized in Table 2-4 for crude oils, refined products and
condensate/LPG.
REFERENCES
[1] GPSA (Gas Processor Suppliers Association), 1994, Engineering Data Book, Tulsa, OK, USA.,
Vol. II.
[2] Ahmed, T., 2000, Reservoir Engineering Handbook, 2nd edition, Gulf Professional Publishing,
Houston TX, USA.
[3] Mohitpour, M., Seevam, P., Botros, K. K., Rothwell, B., and Ennis, C., 2011, Pipeline Transportation of Carbon Dioxide Containing Impurities, ASME Press, New York, NY, USA.
[4] Young, D., 1998, Equations of State, http://www.ccl.net/cca/documents/dyoung/topics-orig/
eq_state.html.
[5] Young, D., 2001, Computational Chemistry: A Practical Guide for Applying Techniques to
Real World Problems, John Wiley, ISBN: 978-0-471-33368-5, http://ca.wiley.com/WileyCDA/
WileyTitle/productCd-0471333689.html.
[6] ESI (Energy Solutions International), 2012, Pipeline Studio Version 3.3.1 Liquid Pipeline Simulator TLNET, http://www.energy-solutions.com/products/pipelinestudio/.
[7] Starling, K. E., 1973, Fluid Properties for Light Petroleum Systems, Gulf, Publishing Company,
USA.