ARTICLE

pubs.acs.org/IECR

Wax Solubility in Gaseous System: Thermodynamic Consistency

Test of Experimental Data
Amir H. Mohammadi,*,†,‡ Ali Eslamimanesh,† and Dominique Richon†
†
nerg
etique et Proc
ed
es (CEP/TEP), 35 Rue Saint Honor
e, 77305 Fontainebleau, France
MINES ParisTech, Centre E
‡
Thermodynamics Research Unit, School of Chemical Engineering, University of KwaZulu-Natal, Howard College Campus, King
George V Avenue, Durban 4041, South Africa

ABSTRACT: Wax deposition from natural gas can cause severe problems in production, transmission and processing operations.
Accurate knowledge of wax solubility in natural gas system is required to avoid operating problems. Unfortunately, experimental
measurements of solubilities of these compounds in gaseous systems are quite challenging. This is partly because concentrations of
these solid substances in the gas phase are extremely low; this generally may result in generation of highly uncertain experimental
data. In this paper, we present a thermodynamic consistency test based on the Gibbs-Duhem equation to determine the reliability
of experimental solubility data of paraffin waxes (n-C24H50 to n-C33H68) available in the open literature. This test uses the Peng-
Robinson equation of state and two-fluid van der Waals (vdW2) mixing rules to represent the solubilities of solid waxy compounds
in supercritical CO2 and ethane. The results show that all the investigated experimental data that are well represented by the applied
thermodynamic model seem to be thermodynamically consistent.

’ INTRODUCTION ’ THERMODYNAMIC CONSISTENCY TEST

An ever-growing demand for natural gas has made it one of the
significant products of the petroleum industry. Natural gas is
considered to be an environmentally friendly clean fuel, offering
important environmental benefits when compared to other fossil
fuels.1 It is also a relatively safe source of energy when trans-
ported, stored, and used.1
Certain pressure and temperature variations in some natural gas
production fields may result in precipitation/deposition of some
heavy hydrocarbons, which are normally extracted by supercritical
components of natural gases in the reservoirs. One important
fraction, which has great deposition potential during production,
transmission, and processing, is wax. Paraffin waxes are mixtures of
alkanes normally in a homologous series of chain lengths, typically
in the range n-C15-n-C50.2-4 Wax deposition in oil systems has
been the subject of many experimental and theoretical studies.4,5
Wax precipitation from gas condensates has been investigated by a
few researchers.3,6-8 Consequently, there is indeed very limited
information on wax deposition/solubility in natural gas systems.9
The deposition of waxy compounds in natural gases is of interest
in the development of production from some gas reserves such as
deep wells or acid gas fields.9 Failure to account for the presence of
these compounds can lead to significant increases in operating
costs, lost production, or failure of piping systems.9 Overdesign of
facilities to account for waxy compounds can bring about higher
capital and operating costs, and may prevent the development of
otherwise economic natural gas resources.9 Accurate experimental
data and reliable thermodynamic models on solubility of wax in
natural gas system are required to avoid the stated problems.
In this work, we focus on modeling the solubilities of paraffin
waxes in supercritical CO2 and ethane and investigating the
reliability of the iterature data applying a thermodynamic con-
sistency test. It is expected that the current study provides a
better understanding of wax solubility in natural gas systems.
The thermodynamic relationship that is frequently used
to analyze thermodynamic consistency of experimental phase
equilibrium data is the fundamental Gibbs-Duhem equa-
tion.10-12,14,15 This equation, as presented in the literature,
interrelates the activity/fugacity coefficients of all components
in a given mixture. If this equation is not obeyed within the
defined criteria, then the data are declared to be thermodynami-
cally inconsistent. This means that this relation imposes a
constraint on the activity/fugacity coefficients that is not satisfied
by the experimental data.10-12 This is due to various errors
occurring during experimental works, especially those dealing
with high pressure and very low solubilities.13
The ways in which the Gibbs-Duhem equation10-12,14,15 is
arranged and applied to the experimental data have resulted in the
origination of several “consistency test methods”, most of them
designed for low-pressure data. Among these are the “slope test”,
the “integral test”, the “differential test”, and the “tangent-inter-
cept test”.10-12,14-17 Good reviews of these methods are given
elsewhere.14,15
In the past decade, Valderrama and co-workers17-21 have
investigated the applications of numerical thermodynamic con-
sistency methods to various systems including incomplete phase
equilibrium data of high-pressure gas-liquid mixtures,17 high-
pressure ternary mixtures of compressed gas and solid solutes,18
high-pressure gas-solid solubility data of binary mixtures,19 vapor-
liquid equilibrium data for mixtures containing ionic liquids,20
and high-pressure gas-liquid equilibrium data including both
liquid and vapor phases.21 Recently, Eslamimanesh et al.12,22,23
Received: November 1, 2010
Accepted: February 14, 2011
Revised: February 5, 2011
Published: March 18, 2011

r 2011 American Chemical Society 4731 dx.doi.org/10.1021/ie1022145 | Ind. Eng. Chem. Res. 2011, 50, 4731–4740
Industrial & Engineering Chemistry Research ARTICLE

have applied almost the same approach for performing the This equation can be written in terms of the composition of
thermodynamic consistency test on significant systems encoun- paraffin wax in the gas phase. If the latter compound is considered
tered in oil and gas industries, e.g., the water content of methane as species 2 in the binary mixture of paraffin wax þ supercritical
in equilibrium with gas hydrate, liquid water, or ice,12 the sulfur CO2/ethane, the latter equation becomes12,17-23
content of hydrogen sulfide,22 and the solubility data of carbon
1 dP y2 dðln j2 Þ 1 - y2 dðln j1 Þ
dioxide and methane with water inside and outside the gas ¼ þ ð3Þ
hydrate formation region.23 P dy2 Z - 1 dy2 Z - 1 dy2
A method based on rewriting the Gibbs-Duhem equa- or in integral form:
tion10-12,14,15 in terms of fugacity coefficients,24 has been used Z Z Z
in this work. The consistency method employed here can be 1 1 1 - y2
dP ¼ dj2 þ dj ð4Þ
considered as a modeling procedure. This is because a thermo- Py2 ðZ - 1Þj2 y2 ðZ - 1Þj1 1
dynamic model that can accurately represent the experimental
data (i.e., the average deviations of the model results from j1, j2, and Z can be calculated using an equation of state and
experimental values are within the acceptable range according suitable mixing rules (thermodynamic model).
to the studied system and for a desired purpose) must be used to In eq 4, the left-hand side is designated by Ap and the right-
apply the consistency test.12,22,23 The fitting of the experimental hand side is designated by Aj, as follows:12,17-23
data requires the calculation of some model parameters using a Z
1
defined objective function that must be minimized.12 Ap ¼ dP ð5Þ
Py2
As stated by Valderrama and Alvarez17 and Eslamimanesh
et al.,12,22,23 a good consistency test method to analyze high-
pressure data must fulfill 10 basic requirements:12,17,22,23 Aj ¼ Aj1 þ Aj2 ð6Þ
(i) It must use the Gibbs-Duhem equation.10-12,14,15 Z
(ii) It must use the fundamental equation of phase 1 - y2
Aj1 ¼ dj ð7Þ
equilibrium. y2 ðZ - 1Þj1 1
(iii) It must use for testing all the experimental P-T-y
(pressure-temperature-gas phase composition) data Z
1
available. A j2 ¼ dj ð8Þ
ðZ - 1Þj2 2
(iv) It does not necessarily require experimental data for the
whole concentration range and be applicable for data in Thus, if a set of data is considered to be consistent, Ap should
any range of concentration. be equal to Aj within acceptable defined deviations. To set the
(v) It must be able to correlate the data within acceptable margins of errors, a percent area deviation (ΔAi%) between
limits of deviations, deviations that must be evenly experimental and calculated values is defined as12,17
distributed. " #
(vi) It requires few additional calculated properties. Aji - Api
ΔAi % ¼ 100 ð9Þ
(vii) It must be able to detect erroneous experimental points. Api
(viii) It makes appropriate use of necessary statistical
parameters. where i refers to given experimental data. The maximum values
(ix) It must be simple to be applied, with respect to the accepted for these deviations regarding the proposed systems are
complexity of the problem to be solved. calculated using appropriate mathematical procedure.
(x) It must be able to conclude about consistency with regard Thermodynamic Model. For phase equilibrium calculations,
to defined criteria. the equality of the fugacity of pure solute to its fugacity in
Equations. The Gibbs-Duhem10-12,14,15 equation for a binary supercritical fluid has been assumed, i.e.26
homogeneous mixture at constant temperature can be written pure solid supercritical
as12,17-25 fi ¼ fi ð10Þ
" # where f refers to the fugacity and i stands for the ith component in
vE the mixture. In this study, the derivation of the required
dP ¼ y1 dðln γ1 Þ þ y2 dðln γ2 Þ ð1Þ equations is based on the following assumptions:26
RT
1. The supercritical fluid is assumed to be insoluble in the
solid (solute-containing) phase.
where vE is the excess molar volume, T represents temperature, R
2. The fugacity of pure solid i stands for the fugacity of the
stands for the universal gas constant, γ is the activity coefficient,
solute i in the mixture.
y represents the solute mole fraction, P stands for pressure, and “d”
3. The molar volume of the solute is pressure-independent.
is the derivative symbol. In this equation, subscripts “1” and “2”
4. The solid phase is incompressible.
refer to components 1 and 2 in the present phases, respectively.
5. The fugacity coefficient of the solute at saturation is unity.
Equation 1 is rewritten in terms of fugacity coefficients as
follows:12,17-23 Therefore, eq 10 is rewritten as
s 
  vi ðP - Pisat Þ
Z-1 sat
Pi exp ¼ yi j i P ð11Þ
dP ¼ y1 dðln j1 Þ þ y2 dðln j2 Þ ð2Þ RT
P
where vs is the solid molar volume, superscript “sat” stands for
where Z is the compressibility factor and j stands for the fugacity saturation conditions, and yi and ji are the mole fraction and
coefficient in the related phase. fugacity of the solute i in supercritical phase, respectively.
4732 dx.doi.org/10.1021/ie1022145 |Ind. Eng. Chem. Res. 2011, 50, 4731–4740
Industrial & Engineering Chemistry Research ARTICLE

Table 1. Experimental Data Ranges Used for the Consistency Test in This Work

range of data

system Na T (K) P (MPa) y2  106 (mole fraction)c refb

mixtures with supercritical CO2

n-C24H50 9 310 8.85-26.06 544-1090 9
n-C25H52 8 308-313 10.36-20.75 215-1000 9
n-C28H58 13 308-318.15 7.52-22 10.1-435 9, 31
n-C29H60 6 308 7.57-21.51 11.4-66.2 9
mixtures with supercritical ethane
n-C28H58 6 308.1 6.57-20.20 1890-15200 9
n-C29H60 5 308.1 6.47-16.67 2320-14200 9
n-C30H62 10 308.1-313.1 6.57-20.20 594-3200 9
n-C32H66 16 308.1-319.1 6.57-20.20 149-2180 9
n-C33H68 16 308.1-318.1 6.47-20.20 183-2970 9
a
Number of data points. b Reference of experimental data. c Wax solubility

To accurately evaluate the fugacity coefficient of the solute,
reliable equations of states are needed. The cubic equations of
state (CEoSs) have been widely used in phase equilibrium
calculations due to their application simplicity. It was previ-
ously shown9 that the Peng-Robinson (PR)27 equation of state
(EoS) with two-fluid van der Waals (vdW2) mixing rules28 leads
to reliable results for calculation of the solubility of paraffin wax in
supercritical CO2 and ethane.
Methodology. The following algorithm is applied for the
thermodynamic consistency test:12,17,22,23
1. Determine Ap from eq 5 using the experimental P-T-y
data. Use a numerical integration for this purpose. In this work,
Simpson’s 3/8 rule29 was used. Valderrama and Alvarez17 have
demonstrated that the deviations between the calculated values
of the integrals by the simple trapezoidal integration rule and a
fitted polynomial function are below 2%. Therefore, a simple
numerical integration method, e.g., the trapezoidal rule, can be
applied for the cases when there are only two available experi-
mental data points.12,22,23
2. Evaluate Aj by eqs 6-8 using the obtained values for j2 and
Z from the thermodynamic model for the proposed system and
y2 from experimental data.
3. For every set of the experimental data, determine an
absolute percent area deviation (ΔAi%) between experimental
and calculated values using eq 9.
Consistency Criteria. First and perhaps most important is
the fact that the thermodynamic model should lead to the
average absolute deviations of the results from experimental
values to be within the acceptable range.12 In this work, the
accepted deviations in gas-phase mole fraction calculations
(defined by the following equation), are considered to lie
between 0 and 25%:18
exp
jycal
i - yi j
AD% ¼ 100 exp
yi
where superscripts “cal” and “exp” refer to calculated and
experimental values, respectively.
For determination of the acceptable percentages of the two
evaluated areas deviations from each other, the error propagation
was performed on the existing experimental data. This was done
using the general equation of error propagation,31 considering
the temperature and mole fraction of paraffin wax in supercritical
CO2 and ethane phase as the independent measured variables.17
The calculated individual area (Aj) is the dependent variable of
interest. The error in the calculated areas, EA and the percent
error EA% are calculated as follows:12,19,22,23
" # " #
DAjj DAjj
EA ¼ ΔT þ Δy ð13Þ
DT Dy
2  3
E 
 A
EA % ¼ 1004 5 ð14Þ
Ajj 
where subscript j refers to the jth calculated area. We assume
maximum uncertainties of 0.3 K for the experimental tempera-
ture and 5% for the experimental solubility data.9 However,
these uncertainties depend on the method of experimental
measurements; e.g., the method used by Teja and co-workers9
is based on dynamic method. The maximum acceptable
errors are much dependent on the uncertainty of solubility
measurements, and one can also neglect the first right-hand-side
term of eq 13. However, the uncertainty for the measurement
of the solubility of paraffin wax is high, and that is why it is
justified to perform our thermodynamic consistency test on
such data.
The partial derivatives of the two preceding equations have
been evaluated using the central finite difference29 method. It
results in the relative average absolute deviations range between 0
and 22% for the data of solubilities of investigated compounds in
supercritical CO2 and ethane. Therefore, the range [0, 22]% is
established as the maximum acceptable error for the areas ([Ai])
of the left- and right-hand sides of eq 6.
Regarding these facts, the thermodynamic consistency test
ð12Þ criteria are applied through the following instructions:12,17-23
1. Check the percentage Δy2 to see that it is not outside the
margins of errors [0, 25]%. If it is, change the thermo-
dynamic model or eliminate the weak predictions until the
absolute deviations of the results from experimental values
are within the acceptable range. In this work, we have not
changed the thermodynamic model as it is demonstrated to
bring about accurate calculation results for most of the
investigated data.
4733 dx.doi.org/10.1021/ie1022145 |Ind. Eng. Chem. Res. 2011, 50, 4731–4740
Industrial & Engineering Chemistry Research ARTICLE

Table 2. Sublimation Pressures of the Investigated Paraffin Table 4. Acentric Factor (w) and Critical Properties (Tc and
Waxes at Different Temperatures9 Pc) of the Investigated Pure Compounds9
substance T (K) sublimation press. (MPa) compound Tc (K) Pc (MPa) ω
-11
n-C24H50 310 4.90  10 C2H6 305.32 4.872 0.099
n-C25H52 308 1.58  10-11 CO2 304.19 7.382 0.2276
313 5.39  10-11 n-C24H50 809.96 1.0496 1.032
n-C28H58 308 1.71  10-13 n-C25H52 818.56 1.0256 1.066
318 2.67  10-12 n-C28H58 842.11 0.9694 1.163
325 1.68  10-11 n-C29H60 849.29 0.9549 1.195
n-C29H60 308 1.14  10-13 n-C30H60 856.17 0.9421 1.226
n-C30H66 308 1.50  10-14 n-C32H66 869.12 0.9208 1.287
313 6.46  10-14 n-C33H68 875.22 0.9119 1.317
n-C32H66 308 1.02  10-15
experimental data sets have been investigated for the consistency
313 4.74  10-15
-14
test. Table 1 summarizes the ranges of the data along with the
318 2.12  10 references. The sublimation pressures and solid molar volumes
319 2.86  10-14 of the paraffin waxes are reported in Tables 2 and 3, respectively.
n-C33H68 308 1.15  10-15 Table 4 shows the acentric factor and critical properties of the
313 5.43  10-15 compounds investigated in this study.
318 2.44  10-14
’ RESULTS AND DISCUSSION
Table 3. Solid Molar Volumes (vs) of the Paraffin Waxes9
The results of calculations of solubilities of investigated paraffin
solute vs  103 (m3/mol) waxes in supercritical CO2 and ethane are shown in Table 5. The
tuned binary interaction parameters using the proposed thermo-
n-C24H50 0.4238
dynamic model are also reported in Table 5. It is inferred that the
n-C25H52 0.4513
applied model is able to represent many of the experimental
n-C28H58 0.4894 solubility values within the acceptable absolute deviation range of
n-C29H60 0.5058 approximately [0, 25]% requested for a successful consistency test.
n-C30H66 0.5222 Table 6 reports the results of the thermodynamic consistency
n-C32H66 0.5550 test for solubilities of investigated paraffin waxes in supercritical
n-C33H68 0.5714 CO2 and ethane. It should be noted that the data sets for which the
proposed thermodynamic model does not lead to the deviations
2. If the model correlates the data within the acceptable error within the acceptable range are ignored for the consistency test.
ranges of the calculations and the area test is fulfilled for all The results show that all of the studied experimental data that
points in the data set, the proposed model is reliable and the are well represented by the applied thermodynamic model seem
data are thermodynamically consistent. to be thermodynamically consistent. This fact demonstrates the
3. In the case that the model acceptably correlates the data, capability of the experimental procedure to measure these
which are not proved yet to be thermodynamically con- solubilities using the dynamic method in spite of several difficul-
sistent, and the area test is not accomplished for most of the ties in such measurements. Another element inferred from the
data set (more than 75% of the areas), the applied model is test results is that these measurements have been done with
conclusive but the experimental data are considered to be careful calibration of the measuring devices such as pressure
thermodynamically inconsistent. transducers and temperature probes by the group of Prof. Teja.
4. In the case that the model acceptably correlates the data and Furthermore, the results of such a test introduce a procedure
some of the area deviations (e25% of the areas) are outside to select the experimental data by which a thermodynamic model
the error range [0,22]%, the applied method declares the is supposed to be tuned and optimal values of the model
experimental values as being not fully consistent. parameters are supposed to be obtained. Thermodynamically
5. The determined data in the previous step could be further inconsistent data (sometimes not fully consistent data) used for
analyzed to check, if after eliminating some points, the tuning of the models will bring about inaccurate predictions of
remaining data fulfill the criteria described before and these the model in further applications and the cause of such deviations
remaining data are consistent or inconsistent. may not be easily determined.
Experimental Data. We have reviewed the existing data The final point to consider is that the data on which the
related to solubilities of paraffin waxes in supercritical natural proposed thermodynamic consistency test was applied should
gas fluids. Most of the data (alkanes from n-C24 to n-C33) have be reported as isotherms because the main assumption in the
been reported in GPA Research Report 1719 by Prof. Teja’s development of eqs 1-8 is similar to that assumed in developing
group of the Georgia Institute of Technology. It should be noted the original Gibbs-Duhem equation10-12,14,15 at constant tem-
that there are some other data sets such as solubilities of perature. This fact assigns some limitations to choosing the
triacontane and n-C36H68 in supercritical carbon dioxide,9,31 experimental data sets for the consistency test by the applied
which are not used in this study due to lack of the required procedure (constant temperature) especially for scarce data of
experimental properties for modeling including solid molar the solubilities of paraffin waxes in natural gas systems. One way
volumes and sublimation pressures. Eighteen (isothermal) of solving this problem of few data is to generate more data in a
4734 dx.doi.org/10.1021/ie1022145 |Ind. Eng. Chem. Res. 2011, 50, 4731–4740
Industrial & Engineering Chemistry Research ARTICLE

Table 5. Results of Tuning the Thermodynamic Model

2  10
yexp 2  10
6
ycalc 6

system T (K) P (MPa) (mole fraction) (mole fraction) kijc lijc ARDa (%) refb

mixtures with supercritical CO2

n-C24H50 310 8.85 544.0 620.7 0.118 0.267 14.1 9
11.03 572.0 651.5 13.9
14.31 806.0 918.4 13.9
15.74 863.0 985.5 14.2
17.53 926.0 1053.4 13.8
19.18 999.0 1139.0 14.0
22.62 1008.0 1149.0 14.0
24.41 996.0 1132.3 13.7
26.06 1090.0 1242.6 14.0
14.0
n-C25H52 308 10.36 215.0 236.2 0.184 0.438 9.9 9
12.68 383.0 422.1 10.2
15.20 574.0 629.4 9.7
20.23 602.0 663.3 10.2
313 10.34 321.0 324.3 0.200 0.400 1.0
13.79 659.0 715.3 8.5
16.82 1000.0 1086.5 8.7
20.75 952.0 1043.8 9.6
n-C28H58 308 7.52 10.1 11.1 0.118 0.308 9.7 9
10.00 39.0 42.7 9.5
14.98 52.3 57.0 9.0
17.51 64.7 70.9 9.6
19.98 68.9 75.1 8.9
21.51 72.4 79.9 10.3
318 11.96 172.0 189.8 0.112 0.284 10.4 9
12.67 207.0 227.9 10.1
15.65 240.0 263.9 10.0
16.58 307.0 336.5 9.6
17.69 390.0 428.2 9.8
20.24 435.0 439.5 1.0
n-C28H58 308.15 8.00 12.3 1.9 0.035 -0.031 84.2 31
9.00 34.5 46.4 34.6
10.00 51.7 73.2 41.5
11.00 54.6 82.3 50.8
12.00 59.1 81.2 37.4
15.00 68.3 56.2 17.7
18.00 81.3 31.8 60.9
20.00 93.6 20.7 77.9
22.00 99.0 13.2 86.7
318.15 10.50 39.6 42.7 0.036 -0.033 7.7 31
11.00 76.0 69.3 8.8
12.50 127.8 129.6 1.4
13.50 179.0 146.6 18.1
n-C29H60 308 7.57 11.4 15.0 0.118 0.308 32.0 9
10.07 19.8 25.1 27.0
12.65 31.4 40.8 30.0
17.51 38.1 50.7 33.0
20.03 45.5 60.1 32.0
21.51 66.2 87.1 31.6
mixtures with supercritical ethane
n-C28H58 308.1 6.57 1890.0 2234.0 -0.006 0.190 18.2 9
10.10 3380.0 3985.7 17.9

4735 dx.doi.org/10.1021/ie1022145 |Ind. Eng. Chem. Res. 2011, 50, 4731–4740

Industrial & Engineering Chemistry Research ARTICLE

Table 5. Continued
2  10
yexp 2  10
6
ycalc 6

system T (K) P (MPa) (mole fraction) (mole fraction) kijc lijc ARDa (%) refb
12.02 6430.0 7716.0 20.0
13.64 7530.0 8985.2 19.3
16.67 10080.0 12092.0 20.0
20.20 15200.0 18237.0 20.0
n-C29H60 308.1 6.47 2320.0 2767.1 0.016 0.123 19.3 9
10.20 4320.0 5178.4 19.9
12.12 8290.0 9840.2 18.7
13.64 9910.0 11786.0 18.9
16.67 14200.0 16969.0 19.5
n-C30H62 308.1 6.57 549.0 667.0 -0.048 0.024 21.5 9
10.10 1240.0 1483.7 19.7
12.02 1450.0 1744.1 20.3
13.64 1710.0 2066.4 20.8
16.67 2240.0 2706.8 20.8
20.20 3200.0 3852.5 20.4
313.1 6.57 486.0 610.8 -0.079 -0.111 25.7 9
10.10 1450.0 1801.0 24.2
12.02 1450.0 1832.8 26.4
13.64 1710.0 2171.4 27.0
n-C32H66 308.1 6.57 216.0 258.4 -0.083 -0.067 19.7 9
10.10 713.0 855.6 20.0
12.02 801.0 962.9 20.2
13.64 959.0 1140.5 18.9
16.67 1260.0 1527.1 21.2
20.20 1810.0 2184.7 20.7
313.1 6.57 177.0 208.9 0.111 -0.218 18.0 9
10.10 933.0 1110.1 19.0
12.02 1150.0 1370.8 19.2
13.64 1440.0 1709.7 18.7
16.67 1730.0 2062.2 19.2
20.20 2180.0 2581.1 18.4
319.1 6.57 149.0 196.8 -0.154 -0.455 32.1 9
10.10 1280.0 1675.1 30.9
12.02 1440.0 1889.3 31.2
13.64 2140.0 2818.0 31.7
n-C33H68 308.1 6.47 371.0 441.4 -0.026 -0.029 19.0 9
10.20 963.0 1155.6 20.0
12.12 1140.0 1359.7 19.3
13.64 1360.0 1627.1 19.6
16.67 1640.0 1966.9 19.9
20.20 2370.0 2846.4 20.1
313.1 6.47 288.0 344.4 -0.032 -0.080 19.6 9
10.20 1540.0 1844.9 19.8
12.12 1470.0 1754.9 19.4
13.64 1720.0 2062.1 19.9
16.67 2240.0 2658.2 18.7
20.20 2930.0 3508.4 19.7
318.1 6.47 183.0 239.2 -0.048 -0.159 30.7 9
10.20 1540.0 2005.1 30.2
12.12 1960.0 2565.6 30.9
13.64 2970.0 3890.7 31.0
2 - y2 |)/y2 ]. References of experimental data. Binary interaction parameter.
a exp b c
ARD = 100[(|ycalc exp

4736 dx.doi.org/10.1021/ie1022145 |Ind. Eng. Chem. Res. 2011, 50, 4731–4740

Industrial & Engineering Chemistry Research ARTICLE

Table 6. Detailed Results of Thermodynamic Consistency Test on the Experimental Data of Solubilities of Paraffin Waxes in
Supercritical CO2 and Ethane
system T (K) P (MPa) Z jG
1 jG
2 Ap Aj ΔA (%) test resulta

mixtures with supercritical CO2

n-C24H50 310 8.85 0.276 0.598 1 2.66  10-7 1229.556 1337.910 8.8 TC
11.03 0.278 0.510 0 1.65  10-7
14.31 0.319 0.42 2.21  10-7
15.74 0.340 0.398 7 2.75  10-7
17.53 0.366 0.371 9 3.73  10-7
19.18 0.390 0.351 5.04  10-7
22.62 0.440 0.319 2 9.93  10-7
24.41 0.46 0.306 2 1.44  10-6
26.06 0.489 0.295 2.00  10-6
n-C25H52 308 10.36 0.264 0.521 0 1.21  10-6 1844.934 1559.377 15.5 TC
12.68 0.292 0.450 3 1.80  10-6
15.2 0.327 0.397 4 3.06  10-6
20.23 0.401 0.331 1.01  10-5
n-C25H52 313 10.34 0.292 0.552 7 3.65  10-6 1117.351 1028.382 8.0 TC
13.79 0.32 0.452 5 5.77  10-6
16.82 0.361 0.397 1 1.08  10-5
20.75 0.417 0.349 3 2.81  10-5
n-C28H58 308 7.52 0.453 0.653 3 2.68 10-6 24187.923 23265.347 3.8 TC
10 0.262 0.534 1.08  10-8
14.98 0.32 0.401 1.78  10-8
14.98 0.325 0.401 1.78  10-8
17.51 0.362 0.362 2.93  10-8
19.98 0.397 0.333 7 5.00  10-8
21.51 0.420 0.319 7.07  10-8
318 11.96 0.329 0.527 4 4.19  10-8 2132.006 1925.925 9.7 TC
12.67 0.331 0.507 3.80  10-8
15.65 0.361 0.441 9 4.30  10-8
16.58 0.372 0.426 1 4.79  10-8
17.69 0.386 0.409 3 5.58  10-
20.24 0.420 0.377 7 8.69  10-8
318.15 10.5 0.343 0.576 5.96  10-9 3125.123 2876.067 8.0 TC
11 0.334 0.558 6 3.50  10-9
12.5 0.333 0.512 1.65  10-9
13.5 0.339 0.487 3 1.35  10-9
mixtures with supercritical ethane
n-C28H58 308.1 6.57 0.243 0.528 7 6.78  10-11 256.507 221.806 13.5 TC
10.1 0.319 0.389 1 2.19  10-11
12.02 0.362 0.348 1 1.63  10-11
13.64 0.400 0.322 3 1.67  10-11
16.67 0.474 0.288 3 2.01  10-11
20.2 0.565 0.263 3 2.88  10-11
n-C29H60 308.1 6.47 0.241 0.534 8 7.77  10-11 143.561 138.305 3.7 TC
10.2 0.323 0.386 7 2.50  10-11
12.12 0.369 0.346 6 1.81  10-11
13.64 0.408 0.322 7 1.82  10-11
16.67 0.488 0.289 1 2.09  10-11
n-C30H62 308.1 6.57 0.251 0.528 2 4.54  10-12 884.162 841.806 4.8 TC
10.1 0.325 0.388 7 8.77  10-13
12.02 0.368 0.34 7.02  10-13
13.64 0.405 0.321 1 6.62  10-13
16.67 0.475 0.286 7.25  10-13
20.2 0.555 0.261 0 9.91  10-13

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Industrial & Engineering Chemistry Research ARTICLE

Table 6. Continued
system T (K) P (MPa) Z jG
1 jG
2 Ap Aj ΔA (%) test resulta
n-C32H66 308.1 6.57 0.254 0.528 2 2.61  10-13 1757.077 1558.892 11.3 TC
10.1 0.326 0.388 3.34  10-14
12.02 0.369 0.346 2.41  10-14
13.64 0.406 0.321 2.14  10-14
16.67 0.474 0.286 2.15  10-14
20.2 0.554 0.261 0 2.77  10-14
n-C33H68 308.1 6.47 0.251 0.534 3 1.56  10-12 1196.326 1135.358 5.1 TC
10.2 0.328 0.386 1 2.44  10-13
12.12 0.372 0.345 1.96  10-13
13.64 0.407 0.321 1 1.86  10-13
16.67 0.475 0.286 2.06  10-13
20.2 0.555 0.261 0 2.83  10-13
313.1 6.47 0.279 0.563 1.27  10-13 1067.608 929.362 12.9 TC
10.2 0.337 0.410 1 6.50  10-13
12.12 0.379 0.367 1 4.85  10-13
13.64 0.413 0.341 8 4.35  10-13
16.67 0.482 0.305 7 4.46  10-13
20.2 0.561 0.278 4 5.85  10-13
a
TC, thermodynamically consistent data.

statistical form using statistical software. The generated data are In eq A1, Z represents compressibility factor and, a and b are
treated as pseudoexperimental. However, it is not recommended attractive and repulsive parameters of the equation of state, res-
to generate data based on doubtful data which are not yet pectively, and subscript i refers to ith components in mixture.26
thermodynamically tested.12,22,23 Therefore, one has to perform  
Dðnam Þ
such a test by the used procedure with the existing experimental ^ai ¼ ðA2Þ
Dðni Þ T , P, nj6¼i
data, even if only two isothermal data points are available.12,22,23
 
’ CONCLUSIONS ^bi ¼ Dðnbm Þ ðA3Þ
Dðni Þ T , P, nj6¼i
In this work, a thermodynamic consistency test was applied
on the related 12 isothermal experimental data sets. The PR pffiffiffi
EoS27 with vdW2 mixing rules28 was applied to calculate σ ¼ 1- 2 ðA4Þ
the solubilities of the investigated compounds in supercritical pffiffiffi
CO2 and ethane. The consistency test was based on the area ε ¼ 1þ 2 ðA5Þ
test approach derived from the original Gibbs-Duhem bm P
equation10-12,14,15 at constant temperature.12,17-24 The results β¼ ðA6Þ
show that 100% of the investigated experimental data of solubi- RT
lities, which are well represented by the applied model, seem
to be thermodynamically consistent. In addition, the results
am ¼ ∑i ∑j yi yj aij ðA7Þ
indicated that the measurements of such data must be done
accurately and deliberately to be able to use them in tuning of bm ¼ ∑i ∑j yi yj bij ðA8Þ
future models for prediction/representation of such solubilities
in natural gas systems. The presented test also leads to pffiffiffiffiffiffiffiffi
better understanding of the importance of solubilities of solid aij ¼ aii ajj ð1 - kij Þ ðA9Þ
compounds in natural gas fluids produced in the petroleum
industry. bi þ bj
bij ¼ ð1 - lij Þ ðA10Þ
2
’ APPENDIX where kij and lij are interaction parameters between the ith and
The following equation has been used to evaluate the fuga- jth compounds in the mixture, and n is the mole number of
city coefficients of species in the mixture using the PR EoS27 and compounds. Applying eqs A2 and A3 yields the following relations:26
vdW2 mixing rules:28   N
Dðnam Þ
^bi am =ðbm RTÞ
^ai ¼
Dðni Þ T , P, nj6¼i
¼2
j¼1
yj aij ∑ ðA11Þ
lnðji Þ ¼ ðZ - 1Þ - lnðZ - βÞ -
bm σ-ε
" #    
^ai ^bi Z þ σβ N
1þ - ln ðA1Þ ^bi ¼ Dðnbm Þ ¼2 yj bij∑ ðA12Þ
am bm Z þ εβ Dðni Þ T , P, nj6¼i j¼1

4738 dx.doi.org/10.1021/ie1022145 |Ind. Eng. Chem. Res. 2011, 50, 4731–4740

Industrial & Engineering Chemistry Research ARTICLE

’ AUTHOR INFORMATION 1 = refers to supercritical CO2 or ethane

2 = refers to paraffin wax
Corresponding Author
*E-mail: amir-hossein.mohammadi@mines-paristech.fr Tel.: Superscripts
þ (33) 1 64 69 49 70. Fax: þ (33) 1 64 69 49 68. calc = calculated
E = excess property
exp = experimental
’ ACKNOWLEDGMENT s = solid
The financial support of the ANR (Agence Nationale de la G = gas
Recherche) and OSEM (Orientation Strat
egique des Ecoles des sat = saturation (sublimation) pressure (MPa)
Mines) is gratefully acknowledged. A.E. wishes to thank MINES
ParisTech for providing a Ph.D. scholarship. The authors are
grateful to Prof. Jos
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