Reliable Prediction of Aqueous Dew Points in CO2 Pipelines and New Approaches for

Control During Shut-in

Darren Rowland†, John A. Boxall‡, Thomas J. Hughes†, Saif Z.S. Al Ghafri†, Fuyu Jiao†, Xiong
Xiao† and Eric F. May†*

†Fluid Science & Resources Division, ARC Training Centre for LNG Futures, The University
of Western Australia, Crawley 6009, Australia

‡ Chevron Energy Technology Company Pty Ltd., Perth, Western Australia 6000, Australia

ABSTRACT

Accurate predictions and precise control of the allowable water content in CO2-rich fluids are
required in large-scale pipeline operations. Especially during transient shut-in and re-start
operations, the pressure decrease associated with cooling may cause the CO2-rich mixture to
pass through its dew point, producing an aqueous liquid phase. The pH of this liquid aqueous
phase will rapidly decrease as carbonic acid is formed, greatly accelerating the corrosion rate
of the carbon steel pipeline. The phase behaviour of CO2-rich fluid mixtures is qualitatively
different to that of hydrocarbons, and standard oil and gas property packages in process
simulation software may be inadequate for predicting dew points and other key properties. An
extensive literature survey reveals 37 data sets where water contents of CO2-rich fluids have
been measured near conditions relevant to CO2 pipelines. Following consistency tests, 26 data
sets were found to be of good quality and 11 data sets were found to be of poor quality. The
good-quality data were compared with predictions from 6 equations of state. Overall,
Multiflash’s RKS (Advanced) model was found to provide the best agreement with the aqueous
dew point data of CO2-rich fluid phases. A case study is presented wherein it is demonstrated
that the formation of a corrosive aqueous phase can be avoided during shut-in via introduction
of a relatively small volume of ethanol.

Keywords

CO2 pipelines
CO2 specification
Dew point control
Corrosion

* Corresponding author.
Tel: +61 8 6488 2954
Fax:+61 8 6488 1024
E-mail address: Eric.May@uwa.edu.au (E.F. May)

1
Introduction

Sequestration of produced carbon dioxide (CO2) is an increasingly important consideration in

the development of new oil and gas production facilities. The removal of CO2 from natural gas
is typically achieved via an amine contact process. The resultant wet CO2 stream is dried,
compressed, and transported via pipeline for injection. Under normal operating conditions the
CO2-rich fluid is expected to maintain high temperature and pressure throughout the pipeline.
However, under transient shut-in and re-start operations, fluid conditions may differ
substantially from those of normal operation. If excess water is present, changes to the fluid
condition may result in the mixture’s dew point being crossed, resulting in the formation of a
corrosive aqueous phase that could damage the pipeline. Preventing this from occurring is
essential for the continued safe use of the pipeline. Hence, predicting reliably dew point
conditions of CO2-rich fluids is of substantial importance, particularly in the presence of likely
impurities.

In the DNV’s ‘Recommended Practice: Design and Operation of CO2 Pipelines’ (DNV, 2010),
it is suggested that the mass density of overwhelmingly pure CO2 streams can be satisfactorily
obtained with the Peng Robinson equation of state (Peng and Robinson, 1976). However, the
important issue of predicting H2O solubility in the fluid is barely addressed: the DNV
recommendation is that designers and operators should tune their models to appropriate
experimental data relevant to their project-specific CO2-rich stream and its impurities. The
object of the present work is to assist designers with this step by (i) assessing critically the
quality of available aqueous dew point data relevant to the conditions of CO2 compression and
transportation in pipelines, (ii) testing the ability of popular thermodynamic equations of state
to predict aqueous dew points of CO2-rich mixtures, and (iii) investigating methods of
maintaining single-phase conditions within CO2 pipelines during shut-in situations.

Literature review

The data review considers the binary system CO2 + H2O and ternary systems consisting of CO2
+ H2O plus compounds likely to exist as impurities in the industrial CO2-rich mixture.
Chemical solvents likely to promote H2O solubility are also considered.

Binary system CO2 + H2O

An extensive review of the thermodynamic literature was conducted to identify data relating to
fluid-fluid equilibria of the CO2 + H2O binary system. In total, more than 130 references were
identified containing data on the solubility of CO2 in H2O-rich phase and/or the solubility of
H2O in CO2-rich phase. The majority of the data and references related to the composition of
the aqueous phase and are not relevant to the present work. However, approximately 750 data
points were found relating to the H2O content of the CO2-rich phase at equilibrium. The
locations of these data in the (p,T) plane are shown in Figure 1.

2
Figure 1. Pressure and temperature conditions of literature data for the solubility of H2O in the
CO2-rich phase for the binary CO2 + H2O system. The saturation pressure curve of pure CO2
is shown together with the hydrate boundary calculated using the software package Multiflash
(Infochem, 2014). The approximate (p,T) region corresponding to shut-in conditions is also
shown.

Once compressed to approximately 15 MPa, CO2-rich fluids are likely to enter the pipeline
network at temperatures near 330 K, although higher or lower temperatures may be
encountered depending on operating and environmental conditions. In the case of prolonged
shut-in, the pipeline will cool to ambient conditions that will vary geographically and
seasonally. From Figure 1, the risk of hydrate formation increases substantially below
approximately 280 K, so this temperature is taken as the lower limit of possible pipeline cooling
during shut-in. Therefore, a total of 36 literature references (Table 1) were classified as
containing data on the solubility of H2O in CO2-rich fluids relevant to pipeline conditions.

3
Table 1. Recommended and rejected data for the aqueous dew point of the CO2-rich phase in
the CO2 + H2O binary system (280 < T /K < 348, p < 15 MPa).
Recommended data Rejected data
Wiebe and Gaddy, 1941 Tödheide and Franck, 1963
Sidorov et al., 1953 Gillespie and Wilson, 1982
Coan and King, 1971 Sayegh and Najman, 1984
Verbrugge, 1979 Patel et al., 1987
Chrastil, 1982 Sako et al., 1991
Smith et al., 1985 Feng and Hou, 1993
Nakayama et al., 1987 Cai and Wu, 1996
Song and Kobayashi, 1987 Valtz et al., 2004
Briones et al., 1987 Hou et al., 2013 (dense phase)
Ohgaki et al., 1988 Jiang et al., 2014
D'Souza et al., 1988 Comak et al., 2016
King et al., 1992
Dohrn et al., 1993
Jackson et al., 1995
Bamberger et al., 2000
Jarne et al., 2004
Iwai et al., 2004
Koglbauer and Wendland, 2008
Seo et al., 2011
Kim et al., 2012
Wang et al., 2013
Hou et al., 2013 (vapour-phase)
Song et al., 2014
Foltran et al., 2015
Meyer and Harvey, 2015
Loring et al., 2017

Ternary systems CO2 + H2O + X

The likely impurities in CO2-rich streams generated from natural gas sources are predominantly
hydrocarbons from the produced reservoir fluid. This contamination is typically on the order
of (0.5 to 4) mole% and may include BTEX compounds up to 1000 ppm depending on the
current performance of the acid gas removal unit (AGRU). Nitrogen (N2) may also be present
in the feed stream and/or remain in the system after commissioning, which may affect the water
dewpoint of the CO2 rich stream.

The literature review located about 20 references with phase equilibrium data for ternary
mixtures containing CO2 + H2O with N2, alkanes or aromatic compounds (Table 2). The
number of relevant data for the aqueous dew points of CO2-rich phases is quite small. Many of
the available ternary data relate to the composition of the aqueous phase or to a phase rich in
hydrocarbon. Of the data related to the CO2-rich phase, many are at lower (e.g. Jarne et al.,
2004) or higher temperatures (e.g. Brandt et al., 2000; Forte et al., 2011; Al Ghafri et al., 2014;
Al Ghafri et al., 2015) than are relevant to CO2 pipeline conditions.

4
Table 2. Number of references and phase equilibrium data for ternary mixtures of CO2 + H2O
+ X, where X is N2 or a hydrocarbon compound.
Substance Reference # CO2- # Aqueous # Hydrocarbon-rich phase
(X) rich phase phase
N2 Zel'venskii, 1939 0 48 0
a
Liu et al., 2012 42 42 0
Foltran et al., 2015 14 0 0
CH4 Sharma, 1969 0 0 30
Song and 6 0 0
Kobayashi, 1990
Dhima, 1998 0 9 0
Servio et al., 1999 0 17 0
Jarne et al., 2004 51 0 81
Qin et al., 2008 0 21 0
Al Ghafri et al., 38 54 16
2014
Fouad et al., 2015 13 0 29
Chapoy et al., 2016 0 0 12
Loring et al., 2017 1 0 3
C2H6 Jarne et al., 2004 31 0 25
Fouad et al., 2015 21 0 0
C3H8 Gil et al., 2006 20 0 0
Forte et al., 2013 0 16 16
n-heptane Al Ghafri et al., 26 26 26
2015
n-decane Forte et al., 2011 40 40 40
Rocha et al., 2013b 0 0 0
Benzene Brandt et al., 2000 129 68 0
Toluene Pfohl et al., 1997 5 12 7
Pfohl, 1998 2 2 0
a
Composition given on ‘water-free’ basis
b
Sampling of phases not performed

Polar solvents may be beneficial for maintaining single phase conditions in pipelines by
enhancing the solubility of H2O in the CO2-rich stream. A literature survey was conducted for
ternary mixtures containing solvents including methanol, ethanol (EtOH), isopropyl alcohol
and acetone. Only the CO2 + H2O + EtOH ternary system was identified as having sufficient
numbers of available data near the conditions of interest to CO2 pipelines. A summary of the
data situation for the ternary system CO2 + H2O + EtOH is given in Table 3.

5
Table 3. Number of phase equilibrium data for the CO2 + H2O + Ethanol ternary system in the
literature.
Reference # CO2-rich phase # other phase
Kreim, 1983 20 20
Gilbert and Paulaitas, 1986 29 29
Takishima et al., 1986 7 13
Feng et al., 1988 17 17
Nagahama et al., 1988 7 22
Furuta et al., 1989 18 18
Inomata et al., 1989 41 41
de la Ossa et al., 1990 27 27a
Cho et al., 1991 74 74
Di Giacomo, 1991 27 0
Cho et al., 1993 27 27
Feng and Hou, 1993 5 5
Hirohama et al., 1993 15 15
Horizoe et al., 1993 20 10
Lim et al., 1994 108 108
Yao et al., 1994 15 15
Yoon et al., 1994 6 6
Lim et al., 1995 15 15
Zhou and Wang, 1996 0 29
Kim et al., 1997 12 12
Chen et al., 2000 9 9
Budich and Brunner, 2003 15 15
Yao et al., 2004 17 0
Dalmolin et al., 2006 0 124
de la Fuenta et al., 2007 0 11
Durling et al., 2007 38 38
Fornari et al., 2009 4 4
Bejerano et al., 2015 7 7
Maeta et al., 2015 4 4
a
CO2-free basis

Data assessment

The relatively large number of fluid phase equilibrium data available for the CO2 + H2O binary
system permits thorough assessment of their relative quality. These were analyzed using the
stringent consistency test developed by Heck and Hiza (1967), known as the method of
enhancement factors. The data relating to the diffuse and dense CO2-rich phases were assessed
by calculating the enhancement factor, f, defined in terms of the mole fraction of water in the
CO2-rich phase, 𝑦H2 O , the mixture pressure, p, and the saturation pressure of pure water at the
specified temperature 𝑝H𝑠𝑎𝑡
2O
:

𝑦H2 O 𝑝
𝑓=
𝑝H𝑠𝑎𝑡
2O

6
The nature of this definition means that as p  0, f  1; data which do not exhibit this limiting
behaviour can be excluded as being of low quality. The quality of the available data was
assessed by plotting f for several isotherms in the temperature range of interest (280 to 348) K.
Examples of the enhancement factor analysis are shown in Figures 2 and 3 for isotherms near
(298 and 323) K (figures for other temperatures are shown in the Supplementary Material).

70

60

50

40
f

30

20

10

0
10 20 30 40 50 60
p /MPa
Weibe, 1941 Coan, 1971 GPA RR-48 Nakayama, 1987
Song, 1987 Ohgaki, 1988 King, 1992 Valtz, 2004
Koglbauer, 2008 Kim, 2012 Hou, 2013

4.0

3.5

3.0

2.5

2.0
f

1.5

1.0

0.5

0.0
1 2 3 4 5 6 7
p /MPa
Weibe, 1941 Coan, 1971 GPA RR-48 Nakayama, 1987
Song, 1987 Ohgaki, 1988 King, 1992 Valtz, 2004
Koglbauer, 2008 Kim, 2012 Hou, 2013

Figure 2. Enhancement factor analysis for data measured near 298 K for the CO2 + H2O binary.
Dotted line is a guide consistent with 𝑓(𝑃 = 0) = 1.

7
 50

40

30
f

20

10

0
10 20 30 40 50 60
p /MPa
Wiebe, 1941 Sidorov, 1953 Toedheide, 1963 Coan, 1971
Chrastil, 1982 Smith, 1985 Briones, 1987 Patel, 1987
D'Souza, 1988 Dohrn, 1993 Jackson, 1995 Bamberger, 2000
Koglbauer, 2008 Hou, 2013 Song, 2014 Loring, 2017

10

6
f

0
4 8 12 16
p /MPa
Wiebe, 1941 Sidorov, 1953 Toedheide, 1963 Coan, 1971
Chrastil, 1982 Smith, 1985 Briones, 1987 Patel, 1987
D'Souza, 1988 Dohrn, 1993 Jackson, 1995 Bamberger, 2000
Koglbauer, 2008 Hou, 2013 Song, 2014 Loring, 2017

Figure 3. Enhancement factor analysis for data measured near 323 K for the CO2 + H2O binary.

Based on the analysis of enhancement factors, the available data for H2O solubility in CO2-rich
sub- and super-critical phases were categorised as either ‘Recommended’ (those having few or
minor inconsistencies) or ‘Rejected’ (those having many or large inconsistencies). Of 37 data
sets from 36 references, 26 data sets were recommended as being of good quality and 11 were
rejected as being of poor quality (Table 1). The relatively small number of relevant available
data for each ternary mixture prohibits meaningful consistency tests.
8
Results of comparisons with thermodynamic models

A range of thermodynamic models were chosen for comparison with the available experimental
aqueous dew point data in the binary system CO2 + H2O. The following six models were
selected either because they were thought likely to perform reasonably well in the description
of these properties and/or because they are widely used by industry and compatible with
dynamic simulations of the process:

 Multiflash RKS (Advanced) (‘Advanced’ Redlich-Kwong-Soave EOS) (Infochem,

2014)
 Multiflash CPA-Infochem (Cubic Plus Association EOS) (Infochem, 2014)
 AspenTech HYSYS Peng Robinson EOS (AspenTech, 2016)
 TREND 3.0 EOS-CG (combustion gas multi-parameter EOS) (Span et al., 2016;
Gernert and Span, 2016)
 NIST REFPROP 9.1 (GERG EOS) (NIST, 2013)
 PSE gPROMs SAFT--Mie (Statistical Associating Fluid Theory with Mie potential)
EOS (PSE, 2015)

Figures 4 and 5 show predictions of H2O solubility in CO2-rich phases from three of the
selected thermodynamic models near (298 and 323) K, respectively. Recommended data at
these conditions are also shown.

0.005

0.004

0.003
y(H2O)

0.002 CPA-Infochem
RKS Advanced
TREND 3.0 EOS-CG
0.001

0
0 5 10 15 20
p /MPa
Figure 4. Aqueous dew point predictions from thermodynamic models and recommended data
for the binary system CO2 + H2O near 298 K (Table 1).

9
Figure 5. Aqueous dew point predictions from thermodynamic models and recommended data
for the binary system CO2 + H2O near 323 K (Table 1).

The CPA(Infochem) model under-predicts systematically the solubility of H2O in the CO2-rich
phase, with deviations reaching approximately 30 % near 323 K and 15 MPa. The predictions
with the RKS (Advanced) implemented in the same software package also tend to be
conservative; however the magnitude of the deviations is considerably smaller than
CPA(Infochem). The EOS-CG results are the least conservative with the model marginally
over-predicting the solubility of H2O in the CO2-rich phase.

The other thermodynamic models that were tested gave less satisfactory results. The SAFT--
Mie model over-predicted the H2O solubility of the dense CO2 by (10 to 20) %. Deviations
with the HYSYS Peng-Robinson model were even larger: predicted H2O solubilities are up to
an order of magnitude too large. The multiparameter Helmholtz EOS based on the GERG-2008
equation of state implemented in REFPROP exhibited unacceptable convergence behaviour,
especially in the dense fluid-fluid region (i.e. at pressures above the critical pressure of pure
CO2).

Overall, the RKS (Advanced) model gives the best results. Its predicted aqueous dew points
are conservative but not overly so, which is beneficial for process design, and agreement with
data is highly satisfactory over the full temperature range of interest. For this reason, only RKS
(Advanced) –

10
 0.005

0.004 300 K (no CH4)

300 K

0.003 294 K
y(H2O)

288 K

0.002

0.001

0
0 5 10 15 20
p /MPa
Figure 6. Equilibrium H2O content of the ternary system CO2 + H2O + CH4, where the methane
mole fraction was 0.0531 at 300 K, 294 K and 288 K. The data were measured by Song &
Kobayashi (1987) and the solid curves were calculated with the RKS (Advanced) EOS in
Multiflash. The dashed curve corresponds to the calculated aqueous dew point of the CO2 +
H2O binary mixture at 300 K.

0.006
313 K (no N2)
0.005 5 mol% N2

0.004
10 mol% N2
y(H2O)

0.003

0.002

0.001

0
0 5 10 15 20
p /MPa
Figure 7. Equilibrium H2O content of the ternary system CO2 + H2O + N2 at 313 K where the
N2 mole fraction was 0 (blue symbols & dashed curve), 0.05 (orange symbols and curve) and
0.10 (green symbols and curve). The data were measured by Foltran et al. (2015) and the curves
were calculated with the RKS (Advanced) EOS in Multiflash.

11
The overall effects of CH4 and N2 on the solubility of H2O in CO2-rich fluids are similar. In
the low-pressure region, compared to the situation of pure CO2, the presence of 0.05 mole
fraction of impurity is not predicted to have significant effect on the solubility of H2O.
However, in the high-pressure region where density of the CO2-rich fluid is larger, the presence
of impurities causes the solubility of H2O to decrease considerably. Compared to pure CO2,
fractions of CH4 or N2 near 0.05 are predicted to decrease the solubility of H2O by (10 to 20) %.
These predictions are in good qualitative agreement with the experimental values of Song and
Kobayashi (1987) and Foltran et al. (2015).

Effect of polar solvents

Literature data for ternary systems of CO2 + H2O + polar solvent are also scarce. Sufficient
literature data for CO2-rich fluids were only identified for the CO2 + H2O + EtOH ternary
system. The impact of the addition of EtOH on the H2O dew point of the CO2-rich fluid has
been investigated by examining a selection of the available phase equilibrium data (Figure 8).

Figure 8(a) shows that the representation of the experimental data for this ternary by the
Multiflash RKS (Advanced) EOS is poor, as may be expected for a system containing two
strongly polar compounds. The two-phase region predicted by the Multiflash RKS (Advanced)
EOS is much larger than the experimental one. The experimental data in Figure 8(a) show that
if the mole fraction of EtOH is above 0.4, any mole ratio of CO2 and H2O will result in a single
phase fluid, whereas according to predictions made with the EOS, the fraction of EtOH
necessary to ensure single phase conditions is close to 0.6. Furthermore, the CO2 + EtOH binary
is erroneously predicted by the RKS (Advanced) EOS to be two-phase at some mole fractions.
Durling et al. (2007) suggest that the Peng Robinson EOS coupled with the Wong-Sandler
mixing rules could be used to correlate the experimental data well.

12
 CO2 + H2O + EtOH 0 1 Phase Boundary Curves:
T = 313 K 0.1 0.9
p = 10 MPa
(Dashed lines are tie lines
0.2 0.8 that correspond to these
phase boundary series)
0.3 0.7

0.4
Single Phase 0.6

0.5 0.5

0.6 0.4

0.7 0.3
Two Phase
0.8 0.2

0.9 0.1

1 0
0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1
(a) yCO2
0.08

0.07

0.06

0.05

0.04
yEtOH

0.03

0.02

0.01

yCO2
yH2O
(b)
Figure 8. (a) Ternary triangular phase equilibrium diagram for CO2 + H2O + EtOH at T =
313 K and p = 10 MPa. The thick blue curve is the measured phase boundary of Durling et al.
and the thin red curve is the phase boundary calculated using the Multiflash RKS (Advanced)
EOS. The dashed lines represent tie lines. (b) Inset of CO2-rich region: Literature data are
points (except the red and green filled points which are binary CO2 + H2O mixture dew points
calculated using the Multiflash RKS (Advanced) EOS at (313 and 333) K, respectively). The
green dashed line represents the addition of EtOH to a mixture of 0.99265 CO2 + 0.00735 H2O
(the H2O saturation mole fraction at T = 333 K and p =15 MPa). This dashed line intersects the
phase boundary (solid blue curve) at an EtOH mole fraction of about 0.041, suggesting that the
addition of this much EtOH would keep the mixture single phase, even as it cooled from (333
to 313) K. The experimental data of Lim et al (1994), Lim et al (1995) and Durling et al. (2007)
suggest that the required mole fraction of EtOH needed to keep the H2O in the CO2-rich phase
could be significantly less than 0.041.

13
Case Study: Dew Point Control in CO2 Pipelines

The experimental data in Figure 8(a) confirm that a sufficient dose of EtOH to a CO2-rich
stream can enhance H2O solubility and maintain single phase conditions. The minimum amount
of EtOH likely to be required to be dosed into an industrial pipeline for such an application is
investigated in the following case study.

Consider a pipeline containing a (water-saturated) binary mixture of 0.99265 CO2 + 0.00735

H2O at T = 333 K and p = 15 MPa. Under shut-in conditions, the confined fluid will cool
isochorically. Upon cooling to T = 313 K and p = 10 MPa (an approximately isochoric path),
the mixture is expected to split into two phases, as indicated by the location of the green point
in Figure 8(b). The green dashed line in Figure 8(b) signifies injection of EtOH into the CO2 +
H2O mixture. The point of intersection between the green line and the blue saturation curve
represents the amount of EtOH required to prevent phase separation. In the case of a mixture
with a H2O to CO2 molar ratio of 0.0074, the lines intersect at a required EtOH mole fraction
of 0.041. This calculation is based on the intersection of the green and blue curves, where the
blue saturation curve represents a ‘worst-case’ situation. If one were instead to use the
experimental data of Lim et al (1994), Lim et al (1995) and Durling et al. (2007), which suggest
that the water dew point is to the left of the solid blue curve in Figure 8(b), the amount of EtOH
required to keep the system single phase could be significantly less.

Assuming a pipeline volume of 1000 m3, estimates of quantities of ethanol required to maintain
single-phase states for CO2-rich fluids under different conditions have been calculated and are
shown in Table 4. The first situation (row) is based on the worst-case behaviour shown in
Figure 8(b), in which the system cools from an initial condition of T = 333 K and p = 15 MPa
to T = 313 K and p =10 MPa. The volume of EtOH required to be injected into the pipeline
network is approximately 35 m3, or 3.5 % of the volume of the network. In the next two rows
of Table 4, the same ratio of EtOH to H2O is assumed to keep the fluid single phase. In the
second row, the initial condition is T = 313 K and p =15 MPa, so the required amount of EtOH
increases because the amount of CO2 is larger. In the third row, the amount of water present
has been reduced to a level around 2000 mg / std m3 for an initial condition of T = 313 K and
p = 15 MPa. Under the assumption that the ratio of EtOH to H2O required to stay in a single
phase condition remains at 5.8, approximately 11.6 tonnes of EtOH would need to be injected
(only 1.5 % of the volume of the network).

Table 4. Estimated mass and volume of ethanol required to keep pipeline single-phase.
Tinit pinit Vpipe ρCO2 mCO2 yH2O yEtOH mEtOH VEtOH
3 -3
K MPa m kg·m tonne tonne m3
333 15 1000 604.1 604 0.007 0.041 27.2 34.6
313 15 1000 780.2 780 0.007 0.041 35.1 44.7
313 15 1000 780.2 780 0.0025 0.014 11.6 14.8

Discussion

The RKS (Advanced) EOS predicts the solubility of H2O in CO2-rich phases very well.
Inspection of the binary interaction parameters between the components CO2 and H2O in
Multiflash reveals the likely reason for this success: the binary interaction parameters are
represented by a temperature-dependent function having three tuned coefficients, viz

14
 kij = 1 – (0.1387397 + 0.000241538T – 1.95236×10-7T 2 )

This gives the RKS (Advanced) EOS significantly greater flexibility than the Peng-Robinson
equation implemented in HYSYS, which has a temperature-independent binary interaction
parameter between CO2 and H2O.

In addition to their well-known high computational cost, which already places them at
disadvantage compared to cubic EOS, it seems apparent from this investigation that
multiparameter Helmholtz EOS such as GERG-2008 and EOS-CG are not as well-suited for
use in process simulations due to convergence issues. This is despite the fact that these
multiparameter models ought to be able to represent the properties of mixtures such as CO2 +
H2O more accurately than simple cubic EOS. Multi-parameter Helmholtz EOS are in general
more accurate at representing the single-phase properties of mixtures for which they were
developed. While this is beyond the scope of this review, Efika et al. (2016) found that the
density predictions of the EOS-CG for saturated CO2 + H2O binaries were slightly better than
the predictions of the cubic EOS by Spycher and Pruess (2010) over the temperature range
(293 to 450) K and at pressures to 64 MPa.

Although not unexpected, one of the main disadvantages of the RKS (Advanced) equation of
state identified in this work was the inability to represent accurately the enhancing effect that
EtOH has on the solubility of H2O in the CO2-rich phase. It is likely that this deficiency could
be redressed by tuning temperature-dependent binary interaction parameters for the binary
subsystems CO2 + EtOH and H2O + EtOH based on data in the literature. This was beyond the
scope of the present work but represents an opportunity for future improvement.

Conclusions

The literature on the aqueous dew points in the CO2 + H2O binary system and related ternary
systems has been reviewed. Twenty-six data sets were found to be of good quality and are
recommended for the purposes of EOS development and process design at conditions relevant
to CO2 pipelines. The RKS (Advanced) EOS from Multiflash was best able to predict the
solubility of H2O in CO2-rich phases. Multiparameter Helmholtz EOS were problematic and
many issues related to convergence were encountered, especially for mixtures at high pressure
where dense fluid-fluid equilibria occur.

Acknowledgements

Financial support for this work was obtained from Chevron (project no. AES 17-P1ABU-149).

15
References

Al Ghafri, S.Z., Maitland, G.C., Trusler, J.P.M., 2014. Experimental and modeling study of the phase behavior of
synthetic crude oil + CO2. Fluid Phase Equilibria 365, 20-40.
Al Ghafri, S.Z., Forte, E., Galindo, A., Maitland, G.C., Trusler, J.P.M., 2015. Experimental and Modeling Study
of the Phase Behavior of (Heptane + Carbon Dioxide + Water) Mixtures. Journal of Chemical & Engineering
Data 60, 3670-3681.
AspenTech HYSYS, 2016. Version 9, Aspen Technology, Inc.
Bamberger, A., Sieder, G., Maurer, G., 2000. High-pressure (vapor + liquid) equilibrium in binary mixtures of
(carbon dioxide + water or acetic acid) at temperatures from 313 to 353 K. The Journal of Supercritical Fluids 17,
97-110.
Bejarano, A., López, P. I., del Valle, J. M., Juan, C., 2015. High-pressure (vapour + liquid) equilibria for ternary
systems composed by {(E)-2-hexenal or hexanal + carbon dioxide + water}: Partition coefficient measurement.
The Journal of Chemical Thermodynamics 89, 79-88.
Brandt, E., Franck, E. U., Wei, Y. S., Sadus, R. J., 2000. Phase behaviour of carbon dioxide–benzene–water
ternary mixtures at high pressures and temperatures up to 300 MPa and 600 K. Physical Chemistry Chemical
Physics 2, 4157-4164.
Briones, J. A., Mullins, J. C., Thies, M. C., Kim, B. U., 1987. Ternary phase equilibria for acetic acid-water
mixtures with supercritical carbon dioxide. Fluid Phase Equilibria 36, 235-246.
Budich, M., Brunner, G., 2003. Supercritical fluid extraction of ethanol from aqueous solutions. The Journal of
Supercritical Fluids 25, 45-55.
Cai, Z., Wu, Z., 1996. Measurement and correlation of vapor–liquid equilibrium with CO2 systems at high
pressure. Huaxue Gongcheng 24, 71-73.
Chapoy, A., Burgass, R., Terrigeol, A., Coquelet, C., 2016. Water content of CO2-rich mixtures: Measurements
and modeling using the cubic-plus-association equation of state. Journal of Natural Gas Engineering, 1, 85-97.
Chen, H.I., Chang, H.Y., Huang, E.T., Huang, T.C., 2000. A new phase behavior apparatus for supercritical fluid
extraction study. Industrial & Engineering Chemistry Research, 39, 4849-4852.
Cho, J.S., Lim, J.S., Kim, J.D., Lee, Y.Y., Chun, H.S., 1991. A study on concentration of ethanol by supercritical
fluids and salts (II)-High pressure vapor-liquid equilibria for CO2-C2H5OH-H2O System. Korean Chemical
Engineering Research 29, 487-487.
Cho, J.S., Lee, K.R., Lim, J.S., Kim, J.D., Choi, D.K., Lee, Y.Y., Chun, H.S., 1993. A study on concentration of
ethanol solution by supercritical CO2. Korean Chemical Engineering Research 31, 448-448.
Chrastil, J., 1982. Solubility of solids and liquids in supercritical gases. The Journal of Physical Chemistry 86,
3016-3021.
Coan, C.R., King Jr, A.D., 1971. Solubility of water in compressed carbon dioxide, nitrous oxide, and ethane.
Evidence for hydration of carbon dioxide and nitrous oxide in the gas phase. Journal of the American Chemical
Society 93, 1857-1862.
Comak, G., Foltran, S., Ke, J., Pérez, E., Sánchez-Vicente, Y., George, M.W., Poliakoff, M., 2016. A synthetic-
dynamic method for water solubility measurements in high pressure CO2 using ATR–FTIR spectroscopy. The
Journal of Chemical Thermodynamics 93, 386-391.
Dalmolin, I., Skovroinski, E., Biasi, A., Corazza, M.L., Dariva, C., Oliveira, J.V., 2006. Solubility of carbon
dioxide in binary and ternary mixtures with ethanol and water. Fluid Phase Equilibria 245, 193-200.
de la Fuente, J.C., Nunez, G., del Valle, J.M., 2007. Bubble-point measurements for the system CO2 + aqueous
ethanol solutions of boldo leaf antioxidant components (boldine and catechin) at high pressures, Fluid Phase
Equilibria 259, 77-82
Dhima, A., 1998. Solubility of natural gases in high pressure water, PhD, Univ. Claude Bernard - Lyon 1.
Di Giacomo, G., 1991. Supercritical fluid extraction of ethanol from dilute aqueous solutions, Chim. Ind. Milan
1, 2-6
DNV, 2010. Design and Operation of CO2 Pipelines, DNV-RP-J202, Det Nortske Veritas, Norway.
Dohrn, R., Bünz, A.P., Devlieghere, F., Thelen, D., 1993. Experimental measurements of phase equilibria for
ternary and quaternary systems of glucose, water, CO2 and ethanol with a novel apparatus. Fluid Phase Equilibria
83, 149-158.
D'Souza, R., Patrick, J.R., & Teja, A.S., 1988. High pressure phase equilibria in the carbon dioxide—n‐
Hexadecane and carbon dioxide—water systems. The Canadian Journal of Chemical Engineering 66, 319-323.

16
Durling, N.E., Catchpole, O.J., Tallon, S.J., Grey, J.B., 2007. Measurement and modelling of the ternary phase
equilibria for high pressure carbon dioxide–ethanol–water mixtures. Fluid Phase Equilibria 252, 103-113.
Efika, E.C., Hoballah, R., Li, X., May, E.F., Nania, M., Sanchez-Vicente, Y., Trusler, J.P.M., 2016. Saturated
phase densities of (CO2 + H2O) at temperatures from (293 to 450) K and pressures up to 64 MPa. The Journal
ia, M.
ofe J)T 841.92 Pr(f)8

17
Jarne, C., Blanco, S.T., Artal, M., Rauzy, E., Otı́, S., Velasco, I., 2004. Dew points of binary carbon dioxide +
water and ternary carbon dioxide + water + methanol mixtures: Measurement and modelling. Fluid Phase
Equilibria 216, 85-93.
Jiang, C., Wu, J., Sun, Z., Pan, Q., 2014. Solubility of water in supercritical CO2. Huaxue Gongcheng 42, 42-47.
Kim, J.K., Ju, D.P., Kim, C., 1997. Phase equilibrium study of supercritical CO2 - C2H5OH - H2O system, Hwahak
Konghak 35, 192-198.
Kim, S., Kim, Y., Park, B.H., Lee, J.H., Kang, J.W., 2012. Measurement and correlation of solubility of water in
carbon dioxide-rich phase. Fluid Phase Equilibria 328, 9-12.
King, M.B., Mubarak, A., Kim, J.D., Bott, T.R., 1992. The mutual solubilities of water with supercritical and
liquid carbon dioxides. The Journal of Supercritical Fluids, 5, 296-302.
Koglbauer, G., Wendland, M., 2007. Water vapor concentration enhancement in compressed humid nitrogen,
argon, and carbon dioxide measured by Fourier transform infrared spectroscopy. Journal of Chemical &
Engineering Data 53, 77-82.
Kreim, K., 1983. Separation of ethanol - water mixtures with gas extraction, PhD, TU Hamburg-Harburg.
Lim, J.S., Lee, Y.Y., Chun, H.S., 1994. Phase equilibria for carbon dioxide-ethanol-water system at elevated
pressures. The Journal of Supercritical Fluids 7, 219-230.
Lim, J.S., Lee, Y.W., Kim, J.D., Lee, Y.Y., Chun, H.S., 1995. Mass-transfer and hydraulic characteristics in spray
and packed extraction columns for supercritical carbon dioxide-ethanol-water system. The Journal of Supercritical
Fluids 8, 127-137.
Liu, Y., Hou, M., Ning, H., Yang, D., Yang, G., Han, B., 2012. Phase equilibria of CO2 + N2 + H2O and N2 + CO2
+ H2O + NaCl+ KCl+ CaCl2 systems at different temperatures and pressures. Journal of Chemical & Engineering
Data 57, 1928-1932.
Loring, J.S., Bacon, D.H., Springer, R.D., Anderko, A., Gopinath, S., Yonkofski, C.M., Thompson, C.J., McGrail,
B.P., Rosso, K.M., Schaef, H.T., 2017. Water solubility at saturation for CO2–CH4 mixtures at 323.2 K and 9.000
MPa. Journal of Chemical & Engineering Data 62, 1608-1614.
Maeta, Y., Ota, M., Sato, Y., Smith, R.L., Inomata, H., 2015. Measurements of vapor–liquid equilibrium in both
binary carbon dioxide–ethanol and ternary carbon dioxide–ethanol–water systems with a newly developed flow-
type apparatus. Fluid Phase Equilibria 405, 96-100.
Martinez de la Ossa, E.M., Brandani, V., Del Re, G., Di Giacomo, G., Ferri, E., 1990. Binary and ternary phase
behaviour of the system water-ethanol-carbon dioxide. Fluid Phase Equilibria 56, 325-340.
Meyer, C.W., Harvey, A.H., 2015. Dew‐point measurements for water in compressed carbon dioxide. AIChE
Journal 61, 2913-2925.
Nagahama, K., Suzuki, J., Suzuki, T., 1988. High pressure vapor–liquid equilibria for the supercritical CO2 +
ethanol + water system. In Proceedings of the First International Symposium on Supercritical Fluids 1, 143.
Nakayama, T., Sagara, H., Arai, K., Saito, S., 1987. High pressure liquid-liquid equilibria for the system of water,
ethanol and 1,1-difluoroethane at 323.2 K. Fluid Phase Equilibria 38, 109-127.
NIST REFPROP, 2013. Version 9.1, National Institute of Standards and Technology, USA.
Ohgaki, K., Nishikawa, M., Furuichi, T., Katayama, T., 1988. Entrainer effect of H2O and ethanol on alpha-
tocopherol extraction by compressed CO2. Kagaku Kogaku Ronbunshu 14, 342-346.
Patel, M.R., Holste, J.C., Hall, K.R., Eubank, P.T., 1987. Thermophysical properties of gaseous carbon dioxide-
water mixtures. Fluid Phase Equilibria 36, 279-299.
Peng, D.Y., Robinson, D.B., 1976. A new two-constant equation of state. Industrial & Engineering Chemistry
Fundamentals 15, 59-64.
Pfohl, O., Avramova, P., Brunner, G., 1997. Two- and three-phase equilibria in systems containing benzene
derivatives, carbon dioxide, and water at 373.15 K and 10–30 MPa. Fluid Phase Equilibria 141, 179-206.
Pfohl, O., 1998. Measurement and calculation of phase equilibria with almost critical and super-critical carbon
dioxide and associating components in the range of high pressure. PhD, TU Hamburg-Harburg.
PSE gSAFT, 2015. Version 3.2.1, PSE, London, UK.
Qin, J., Rosenbauer, R.J., Duan, Z., 2008. Experimental measurements of vapor–liquid equilibria of the H2O +
CO2 + CH4 ternary system. Journal of Chemical & Engineering Data 53, 1246-1249.
Rocha, I.C., Fialho, R.L., Marques, J.J., Dariva, C., Pessoa, F.L., 2013. Effect of water content on the equilibrium
pressure of (carbon dioxide + decane and + decalin) from T = (313.15 to 333.15) K. The Journal of Chemical
Thermodynamics 65, 11-17.

18
Sako, T., Sugeta, T., Nakazawa, N., Okubo, T., Sato, M., Taguchi, T., Hiaki, T., 1991. Phase equilibrium study
of extraction and concentration of furfural produced in reactor using supercritical carbon dioxide. Journal of
Chemical Engineering of Japan 24, 449-455.
Sayegh, S.G., Najman, J., 1984. CO2-SO2-Brine Phase Behavior Studies. Petroleum Recovery Institute.
Seo, M.D., Kang, J.W., Lee, C.S., 2011. Water solubility measurements of the CO 2-rich liquid phase in
equilibrium with gas hydrates using an indirect method. Journal of Chemical & Engineering Data 56, 2626-2629.
Servio, P., Englezos, P., 2001. Effect of temperature and pressure on the solubility of carbon dioxide in water in
the presence of gas hydrate. Fluid Phase Equilibria 190, 127-134.
Sharma, S. C., 1969. Equilibrium water content of gaseous mixtures. PhD, The University of Oklahoma.
Sidorov, I.P., Kazarnovskii, Y.S., Goldman, A.M., 1953. Solubility of water in compressed gases. Trudy
Gosudarstremogo Naučno-Issledovatel’skogo i Proektnogo Instituta Azotnoj Promyslennosti, Moskau, Russland,
1, 48-67.
Smith, R.D., Udseth, H.R., Wright, B.W, 1985. Micro-scale methods for characterization of supercritical fluid
extraction and fractionation processes. Process Technol. Proc. 3, 191-223.
Song, K.Y., Kobayashi, R., 1987. Water content of CO2 in equilibrium with liquid water and/or hydrates. SPE
Formation Evaluation 2, 500-508.
Song, K.Y., Kobayashi, R., 1990. The water content of a carbon dioxide-rich gas mixture containing 5.31 mol%
methane along the three-phase and supercritical conditions. Journal of Chemical and Engineering Data 35, 320-
322.
Song, W., Fadaei, H., Sinton, D., 2014. Determination of dew point conditions for CO2 with impurities using
microfluidics. Environmental Science & Technology 48, 3567-3574.
Span, R., Eckermann, T., Herrig, S., Hielscher, S., Jäger, A., Thol, M., 2016. TREND. Thermodynamic Reference
and Engineering Data 3.0. Lehrstuhl für Thermodynamik, Ruhr-Universität Bochum.
Spycher, N., Pruess, K., 2010. A phase-partitioning model for CO2–brine mixtures at elevated temperatures and
pressures: application to CO2-enhanced geothermal systems. Transport in porous media 82, 173-196.
Takishima, S., Saiki, K., Arai, K., Saito, S., 1986. Phase equilibria for the carbon dioxide–ethanol–water system.
J. Chem. Eng. Jpn 19, 48-56.
Tödheide, K., & Franck, E.U., 1963. Das zweiphasengebiet und die kritische kurve im system kohlendioxid–
wasser bis zu drucken von 3500 bar. Zeitschrift für Physikalische Chemie 37, 387-401.
Valtz, A., Chapoy, A., Coquelet, C., Paricaud, P., Richon, D., 2004. Vapour–liquid equilibria in the carbon
dioxide–water system, measurement and modelling from 278.2 to 318.2 K. Fluid Phase Equilibria 226, 333-344.
Verbrugge, P., 1979. Vapour-liquid equilibria of the ammonia-carbon dioxide-water system.
Wang, Z., Felmy, A.R., Thompson, C.J., Loring, J.S., Joly, A.G., Rosso, K.M., Schaef, H.T., Dixon, D.A., 2013.
Near-infrared spectroscopic investigation of water in supercritical CO2 and the effect of CaCl2. Fluid Phase
Equilibria 338, 155-163.
Wiebe, R., Gaddy, V.L., 1941. Vapor phase composition of carbon dioxide-water mixtures at various temperatures
and at pressures to 700 atmospheres. Journal of the American Chemical Society 63, 475-477.
Yao, S., Guan, Y., Zhu, Z., 1994. Investigation of phase equilibrium for ternary systems containing ethanol, water
and carbon dioxide at elevated pressures. Fluid Phase Equilibria 99, 249-259.
Yao, S.J., Guan, Y.X., He, W.Z., Qi, X.M., Zhu, Z.Q., 2004. Activities of several enzymes in ethanol + water at
elevated pressure of carbon dioxide. Journal of Chemical & Engineering Data 49, 1333-1339.
Yoon, J.H., Lee, H., Chung, B.H., 1994. High pressure three-phase equilibria for the carbon dioxide-ethanol-water
system. Fluid Phase Equilibria 102, 287-292.
Zel'venskii, Ya.D, 1939. Solubility of the gas-mixtures CO2 + N2 and CO2 + H2 in water under pressure, Zh. Prikl.
Khim. (S.-Peterburg, Russ. Fed.) 12, 1312-1329.
Zhou, J., Wang, C., 1996. Solubilities of carbon dioxide in ethanol-water mixed solvents, Huaxue Gongcheng 24,
63-67.

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