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Thermal Properties of Petroleum and Gas-to-liquid Products

Article  in  Petroleum Science and Technology · April 2007

DOI: 10.1080/10916460500294556

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Petroleum Science and Technology, 25:415–425, 2007
Copyright © Taylor & Francis Group, LLC
ISSN: 1091-6466 print/1532-2459 online
DOI: 10.1080/10916460500294556

Thermal Properties of Petroleum and

Gas-to-liquid Products

D. K. Das, S. Nerella, and D. Kulkarni

Department of Mechanical Engineering, University of Alaska Fairbanks,
Fairbanks, Alaska, USA

Abstract: There are many locations in the world where natural gas is abundant,
but isolated from the transportation infrastructure. Research is currently underway to
develop methods to convert the gas to liquid (GTL) and transport it to the market. For
safe and efficient transportation of this GTL, researchers and engineers must know its
properties. This article presents several correlations for viscosity, specific heat, and
thermal conductivity of this GTL. Researchers are also considering transportation of
GTL commingled with crude oil. Therefore, the properties of this commingled mixture
are presented here as well. Data on how these properties vary with temperature is also
presented in graphs; this information would be very useful for designing a method of
transportation in extremely cold regions.

Keywords: gas-to-liquid, mixture properties, specific heat, thermal conductivity,

viscosity

1. INTRODUCTION

There has been a great deal of interest in recent years in converting natural gas
to liquid products, called gas-to-liquid (GTL), via the Fisher-Tropsch process,
and this topic has been the focus of much research in Alaska. Alaska has
about 35 trillion cubic feet of proven reserve of natural gas at the North Slope.
A pilot plant has been built in Nikiski, Alaska (at a cost of $86 million) to
produce 300 barrels per day of GTL from 3 million cubic feet of natural gas.
Gas-to-liquid resembles a clean diesel fuel, without sulfur and nitrogen, and
it produces much cleaner products after combustion. Hence its development
has strong merit from a clean air point of view. Several research projects
addressing various aspects of GTL have been undertaken at the University
of Alaska Fairbanks (UAF). These projects have culminated in three theses
dealing with economic consideration of oil and GTL transportation, their

Address correspondence to Debendra K. Das, Department of Mechanical Engi-

neering, University of Alaska, 327 Duckering Bldg., Fairbanks, AK 99775. E-mail:
ffdkd@uaf.edu

415
416 D. K. Das et al.

properties, fluid dynamic studies in a pipeline environment, and computation

of heat transfer that affects transportation of fluid through the Trans Alaska
Pipeline System (TAPS). Oil flow has been declining, from 2 million barrels
per day (BPD) through TAPS in early years to about 1 million BPD at
the present time. To keep operation of the pipeline economical and viable,
there is serious consideration in converting the vast reserve of natural gas
at Alaskan North Slope to GTL and in transporting it through TAPS. The
other alternative, building a new natural gas pipeline, bears an estimated cost
of $20 billion. In order to ascertain that GTL can be transported properly
through the existing TAPS, its fluid dynamic and thermal characteristics must
be known accurately. Successful transportation technology requires careful
evaluation of heat loss from the pipeline as the liquid travels 800 miles from
Prudhoe Bay, on the North Slope of Alaska, to the Valdez terminal where
the liquid can be loaded on tankers for shipment.
Northern Alaskan temperatures are harsh; in winter they can hover around
−40◦ F (−40◦ C) for extended periods. Occasionally the temperature may dip
down to −60◦ F (−51◦ C) for a short period of time. In this environment it is
very important to know the thermal behavior of liquids being pumped through
the pipeline. If they lose too much heat and become extremely viscous, they
require uneconomically high pumping power. In the worst case scenario, un-
der extreme cold conditions, the liquid may become gel and resist any attempt
at pumping. Knowing the thermal properties, such as thermal conductivity,
specific heat, viscosity, and density of GTL, will allow engineers to properly
evaluate if this liquid can be transported safely in the pipeline. If not, then
what design modifications would be necessary to overcome existing prob-
lems? However, there is a lack of data on GTL and GTL-oil mixtures. This
article presents some results and equations to calculate the properties of pure
GTL and GTL-oil mixtures and should be useful to researchers.
Two modes of shipping GTL are being investigated: (1) pure slugs of
GTL in-between oil flow and (2) a commingled mixture of GTL with oil in
various proportions. Nerella et al. (2003) present some analysis of heat loss
of GTL transportation.

2. THEORY

Heat loss from crude oil or GTL and pumping power required are the two
major issues. The heat transfer rate is dependent on the Nusselt number
(Nu = hd/k), which is a function of the Reynolds number (Re = V dρ/µ)
and the Prandtl number (Pr = cp µ/k), where h is the convective heat transfer
coefficient, d is inside pipe diameter, k is the thermal conductivity, V is the
velocity, ρ is the density, µ is the viscosity, and cp is the specific heat of the
liquid flowing in the pipe. The fluid properties required in determining Nu,
Re, and Pr are sensitive to temperature change. Let us discuss the equations
that govern these properties.
Thermal Properties 417

2.1. Viscosity of Liquids

The Heat Exchanger Design Handbook by Edwards et al. (1983) presents

Souders’ equation for determining viscosity of liquids:
J
log(log η + 4) = ρX10−3 − 2.9. (1)
M
Values of J can be read from Edwards et al. (1983) and η is the viscosity in
Ns/m2 , M is the molecular mass in kg/kmol, and ρ in kg/m3 .
These authors suggest another equation:

  
η 1
log 8,600 1 = θ −1 (2)
ρ2 Tr

where θ is available from Edwards et al. (1983) and Tr is the reduced tem-
perature.

2.1.1. Temperature Dependency of Viscosity of Liquids

Generally the viscosity of liquids decreases with temperature. Andrade’s

equation presented in Edwards et al. (1983), good for organic and inorganic
liquids, is
1
η = 10−6 Aρ 3 ecρ/T (3)

where A and c are constants listed in Edwards et al. (1983).

2.1.2. Viscosity of Oil

From the work of Amin and Maddox presented by Edwards et al. (1983), the
viscosity-temperature behavior for crude oil fractions is
B
υ = A exp (4)
T
where υ = kinematic viscosity in centistokes, A = (223Tb−0.568 − 4.038)
K/B, K = Watson characterization factor, B = exp(4.924+0.00454Tb ), and
Tb = 50% boiling point in K and T in K.

2.1.3. Pressure Dependency of the Viscosity of Liquids

The viscosity of all liquids generally increases with pressure. Andrade’s re-
lationship is
 1/6
 1/2
ηp ρp ko
= ec(ρp −ρo )/T (5)
ηo ρo kp
418 D. K. Das et al.

where subscripts “p” and “o” denote high pressure and low pressure condi-
tions, k  is the isothermal compressibility, and other variables are defined above.

2.2. Specific Heat

According to research by the American Petroleum Institute (API) cited in

Edwards et al. (1983), the isobaric heat capacity of liquid petroleum fraction
can be estimated from
cp = A1 + A2 T + A3 T 2 (6)
where cp is the isobaric heat capacity in Btu/lb◦ F.
(1.14982 − 0.046535K)
A3 = −1.17126 + (0.023722 + 0.024907SG)K +
SG
 
0.27634
A2 = 10−4 (1.0 + 0.82463K) 1.12172 −
SG
 
0.70958
A1 = 10−8 (1.0 + 0.82463K) 2.9027 −
SG
where T = temperature in ◦ R, K = described earlier, and SG = specific
gravity = density of oil at 60◦ F/density of water at 60◦ F. Over a temperature
range 293 < T < 423 K, specific heat is calculated by Cragoe cited in
Edwards et al. (1983):
cp = 4,200A(ρ + )−1/2 + 3.78(T − 288) J/kg K. (7)
Fortsh and Whitman’s equation from Edwards et al. (1983) is
cp = [1,450 + 3.72(T − 273)](2.1 − ρ + ) J/kg K (8)
where ρ + is the dimensionless density with respect to water at T = 288 K,
A for paraffin oils = 0.425, for mixed oils = 0.415, and for nephtenic oils =
0.405.

2.3. Thermal Conductivity of Oil

Empirical formulas for thermal conductivity for the temperature range 273 <
T < 423 K, are presented by Cragoe:
k = 0.118ρ −1 [1 − 0.00054(T − 273)] ∗ 103 W/m K (9)
and Smith in Edwards et al. (1983):
k = 0.137ρ −1 [1 − 0.00054(T − 273)] ∗ 103 W/m K (10)

where ρ is in kg/m3 at 288 K.

Thermal Properties 419

2.4. Prandtl Numbers of Liquids

The Prandtl number of any liquid can be determined by knowing cp , µ,

and k. When exact values of these properties are not available, the Gambill
equation presented in Edwards et al. (1983) can be used, which is claimed
to be valid for all practical purposes:

Hv
log Pr = 0.0270 − 1.80 (11)
T
where Hv is change in total enthalpy (at T ) in kJ/kmol, and T in K. For
GTL, Prandtl number data is generally not available.

2.5. Properties of GTL and Mixture

Currently, researchers are also asked to evaluate the viability of transporting

a mixture of crude oil and GTL called a commingled mixture. Therefore, to
explore different scenarios, we must determine the property variation of pure
oil, pure GTL, and the commingled mixture.
Thermal properties of various types of oils have been adequately reported
in the literature. For example, Thomas (1993) presents the following equa-
tions for 30◦ API oil, citing data from the Standards of Tubular Exchanger
Manufacturers Association:

ρ = (871 − 0.565T ) kg/m3 , T in ◦ C. (12)

cp = (1.79 + 0.00428T ) kJ/(kg ◦ C), T in ◦ C. (13)

k = (0.137 − 8.73 ∗ 10−5 T ) W/(m ◦ C), T in ◦ C. (14)

µ = 0.1 exp(1.35 − 0.0855T + 0.00032T 2 )

kg/(m s) 0◦ C < T < 80◦ C. (15)

µ = 0.1 exp(−0.243 − 0.0478T + 9.72 ∗ 10−5 T 2 )

kg/(m s) 80◦ C < T < 610◦ C. (16)

For Alaskan crude oil, actual measurements of oil properties and fitting
the measured data to empirical relations have resulted in the following thermal
properties equations presented by Chrisman (2001):

µ = exp(exp(31.52 − 4.9 ∗ ln(T + 460))) centipoises, T in ◦ F. (17)

SG = 0.8997 − 0.000458 ∗ T , T in ◦ F. (18)

420 D. K. Das et al.

The curve-fit Eqs. (17) and (18) were based on test results obtained from
samples taken at Pump Station 1 on the Trans-Alaska Pipeline in September
2000. The equations were curve-fitted from measurements between −20◦ F
to 140◦ F at 10◦ F intervals. Hence, the above equations should be valid only
in this temperature range.

2.5.1. Density of a Mixture

Density of the crude oil varies with temperature, and the variation is given
by Chrisman (2001):

ρ = (0.885044 − 0.0008244 ∗ T ) ∗ (1,000) kg/m3 , T in ◦ C (19)

The measured density of GTL is correlated as a function of tempera-

ture (T in ◦ C) and crude oil composition by volume (x, in fraction). The
experimental data were correlated using a nonlinear regression technique de-
scribed in a research article by Ramakrishnan et al. (2003). The density data
is correlated as shown below:

ρ = aT 2 + bT + c (20)

where a = a1 x 2 + b1 x + c1 , b = a2 x 2 + b2 x + c2 , c = a3 x 2 + b3 x + c3 . The
values of the coefficients are given by

a1 = 1.48633 ∗ 10−5 b1 = 1.83177 ∗ 10−5 c1 = 1.29317 ∗ 10−5

a2 = −0.00146545 b2 = 0.00188374 c2 = −0.00159337
a3 = −0.0581009 b3 = 0.207453 c3 = 0.770151

where, for example, x = 0.75 for a crude oil and GTL mixture in which oil
to GTL is 3:1 by volume. The density of pure GTL will correspond to no
crude oil (x = 0). For different temperatures, density is given by

ρ = 1.29317 ∗ 10−5 ∗ T 2 − 0.00159337 ∗ T + 0.770151

(21)
(ρ in g/cc and T in ◦ C).

Let us illustrate determination of commingled mixture properties as an

example. Consider a commingled flow where crude oil and GTL are mixed in
the volumetric ratio of 3:1, respectively. The volume of the mixture is equal
to the sum of the volume of GTL and the volume of crude oil and can be
written as V = Vg + Vo . Therefore,

m mg mo
= + . (22)
ρmix ρg ρ0
Thermal Properties 421

Figure 1. Variation of density of three fluids with temperature.

Using the 3-to-1 volumetric mix and densities of oil and GTL evaluated
at an average temperature between Pump Station 1 (117◦ F) and the Valdez
terminal (58◦ F), it was computed that 1 kg of mixture contains 0.7789 kg of
crude oil and 0.2210 kg of GTL. Based on this proportion, the density of the
commingled mixture is determined for different temperatures. The variation
of density of crude oil, GTL, and commingled mixture (3:1) with temperature
is shown graphically in Figure 1.

2.5.2. Thermal Conductivity of a Mixture

Thermal conductivity variation with temperature for crude oil and GTL are
obtained by curve-fitting data obtained from the thesis prepared by Rama-
krishnan (2000) at UAF:

ko = −6E–07T 2 − 0.0002T + 0.1516 W/m K (23)

kg = 4E–06T 2 − 0.0005T + 0.1451 W/m K (24)

422 D. K. Das et al.

Figure 2. Variation of thermal conductivity of three fluids with temperature.

The thermal conductivity of the mixture can be determined by the volume

average method

νg k g + ν o k o
kmix = (25)
νo + ν g

where subscript g is for GTL, subscript o is for oil, and ν is the specific
volume.
The variation of thermal conductivity of crude oil, GTL, and the com-
mingled mixture (3:1) with temperature is shown in Figure 2.

2.5.3. Viscosity of a Mixture

Experimental data of viscosity variation with temperature for GTL is pre-

sented by Ramakrishnan (2000). This data was curve-fitted to the following
equation:
Thermal Properties 423

µ = [0.00009286T 2 − 0.02273T + 1.712]

(26)
∗ 10−3 kg/ms, T in ◦ C.

The viscosity of the commingled mixture is determined by the volume

average method:

νg µg + νo µo
µmix = . (27)
νo + ν g

The variation of viscosity of crude oil, GTL, and the commingled mixture
(3:1) with temperature is shown graphically in Figure 3. Any other mixture
proportion of crude oil and GTL can easily be determined following the
procedure just illustrated for a case of 3:1 mixture.

Figure 3. Viscosity variation of three fluids with temperature. Note different scale
for GTL.
424 D. K. Das et al.

White (1991) presents the general rule: (a) for liquids, viscosity decreases
rapidly with temperature; (b) for gases at low pressure, viscosity increases
with temperature; and (c) viscosity always increases with pressure.

2.6. Temperature Dependencies

Numerous data analyses presented in Edwards et al. (1983) show that the
thermal conductivity k and density ρ decrease with increase in temperature,
whereas the specific heat cp increases with temperature for oils. This depen-
dency for GTL is not thoroughly investigated thus far.

2.7. Polymer Additives

In order to reduce drag, additives are added to oil during transportation

through TAPS, which affect thermal properties. Very little published data
is available on the properties of such mixtures. We recommend that research
be undertaken in this area for GTL and its mixtures.

3. CONCLUSIONS

Thermal properties of crude oil are well researched and understood. Many
equations are available to determine them, and some of these have been sum-
marized in this article. However, for new fluids like GTL and its mixture with
oil, variation of properties with temperature is not found in the literature. We
have presented a few equations in this article. It is recommended that broad
experimental programs be undertaken to determine the thermal properties of
GTL and the commingled mixture of GTL and oil. Although the thermal
properties are strong functions of temperature and weak functions of pres-
sure, experiments must still be conducted to ascertain that this general rule
is applicable for GTL.

REFERENCES

Chrisman, K. (2001). Systems Engineering Oil Property Data Sheet; Alyeska

Pipeline Service Company. Fairbanks, Alaska.
Edwards, D. K., Liley, P. E., Maddox, R. N., Matavosian, R., Pugh, S. F.,
Schunck, M., Schwier, K., and Shulman, Z. P. (1983). Heat Exchanger
Design Handbook, Vol. 5. Washington, DC: Hemisphere Publishing Cor-
poration.
Nerella, S., Das, D. K., Chukwu, G. A., Dandekar, A. Y., Khataniar, S., and
Patil, S. L. (2003). Heat transfer analysis for gas-to-liquids transportation
through Trans Alaska Pipeline. Petrol. Sci. Tech. 21:1275–1294.
 Thermal Properties 425

Ramakrishnan, H. (2000). Experimental and Economic Evaluation of GTL

Fluid Flow Properties and Effect on TAPS. M.S. Thesis, University of
Alaska, Fairbanks.
Ramakrishnan, H., Khataniar, S., Dandekar, A. Y., Patil, S. L., Chukwu,
G. A., Kamath, V. A., Haslebacher, W. F., and Hackworth, J. H. (2003).
Characterization of gas-to-liquids (GTL) and Alaska North Slope Crude
(ANSC) oil blend properties for flow through the Trans Alaska Pipeline
System (TAPS) by density and viscosity measurements. J. Petrol. Sci.
Eng. 21:301–314.
Thomas, L. C. (1993). Heat Transfer. Englewood Cliffs, NJ: Prentice Hall.
White, F. M. (1991). Viscous Fluid Flow, 2nd ed. New York, NY: McGraw-
Hill.

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