International Journal of Greenhouse Gas Control 31 (2014) 121127

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International Journal of Greenhouse Gas Control

journal homepage: www.elsevier.com/locate/ijggc

Simulating the capture of CO2 from natural gas: New data and
improved models for methane + carbon dioxide + methanol
Thomas J. Hughes, Mohamed E. Kandil, Brendan F. Graham, Eric F. May
Centre for Energy, School of Mechanical and Chemical Engineering, University of Western Australia, Crawley, WA 6009, Australia

a r t i c l e

i n f o

Article history:
Received 11 April 2014
Received in revised form 25 August 2014
Accepted 22 September 2014
Available online 29 October 2014
Keywords:
Carbon capture
Rectisol process, Equations of state
Vapor liquid equilibrium
Binary interaction parameters
Methanol

a b s t r a c t
The simulation of carbon capture unit operations often involves predicting the vapor liquid equilibrium
(VLE) for mixtures containing polar, non-polar and quadrupolar compounds. In this work, we investigate how well a simple cubic equation of state (EOS) can predict the results of new low temperature,
high-pressure VLE measurements of the ternary methane + carbon dioxide + methanol system, which
is important to the Rectisol process used for capturing CO2 from natural gas. The ternary p, T, x measurements presented here are the rst such data for this system reported in the open literature. First,
predictions made with the Peng Robinson (PR) EOS as implemented in a commercial process simulator
were compared to binary p, T, x data measured in this work and also taken from the literature. Signicant deviations were found between the measured liquid mole fractions and those predicted with the
EOS using the default binary interaction parameters (BIP): the relative standard errors were 39%, 77%
and 17% for the methane + methanol, methane + carbon dioxide and methanol + carbon dioxide binaries,
respectively. Regression of the PR EOS to the binary VLE data by adjusting the BIPs improved the liquid phase mole fraction predictions for the ternary mixture data by a factor of about 2.5 for methane
and methanol. However, improvement by a factor of 4.4 in the carbon dioxide liquid mole fraction was
achieved by describing the carbon dioxide + methanol binary with an asymmetric composition and temperature dependent mixing rule and tuning the BIPs therein to VLE data for this binary over a wide
temperature range. This reduced the standard error in the liquid phase CO2 mole fractions predicted for
the ternary mixture using the optimized model by 79% relative to the default model.
2014 Elsevier Ltd. All rights reserved.

1. Introduction
Predicting the vapor liquid equilibrium (VLE) of systems containing non-polar, polar and quadrupolar components is important,
especially for processes intended to capture CO2 . One such process is the Rectisol process, jointly developed by Lurgi (Weiss and
Schrie, 2010) and Linde (2014), where methanol is used as a physical solvent at temperatures as low as 200 K for the removal of acid
gases from natural gas or syngas (Kohl and Nielsen, 1997). In this
process the CO2 content of the natural gas can be scrubbed down
to a few parts-per-million (ppm) and it is possible to separate H2 S
from the CO2 in addition to impurities generated during coal or
heavy oil gasication (Kohl and Nielsen, 1997). A further advantage of the process is that the gas is dehydrated and dosed with
methanol which is a hydrate inhibitor. An example of the use of the
Rectisol process to capture CO2 is the Great Plains Synfuel Plant in

Corresponding author. Tel.: +61 8 6488 2954; fax: +61 8 6488 1024.
E-mail address: Eric.May@uwa.edu.au (E.F. May).
http://dx.doi.org/10.1016/j.ijggc.2014.09.020
1750-5836/ 2014 Elsevier Ltd. All rights reserved.

North Dakota where coal is gasied (Dakota Gasication Company,

2013). The CO2 from this plant is piped to the Weyburn oil eld in
Saskatchewan, Canada where it is simultaneously sequestered and
used to enhance the recovery of the oil from the eld (Preston et al.,
2005).
The Rectisol process or similar variants could become increasingly important in projects where the production of liqueed
natural gas (LNG) is the goal because the cryogenic processing
capability is already available. Alternative emerging CO2 capture
processes for treating lean gases to pipeline specications, such
as the controlled freeze zone process (Denton and Valencia, 1985;
Fieler et al., 2010; Nichols et al., 2009) which also utilizes cryogenic
temperatures, could potentially be combined with an appropriately
sized Rectisol process to further remove CO2 to the 50 ppm LNG
specication (Rufford et al., 2012). New or adapted processes for
removing CO2 from natural gas are likely to be important to the
development of oating LNG applications (Pettersen et al., 2013).
Once removed, nding an environmentally-acceptable means of
disposing of the captured CO2 becomes important and, particularly
for FLNG applications where transport and sequestration options

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T.J. Hughes et al. / International Journal of Greenhouse Gas Control 31 (2014) 121127

are likely to be limited, re-injection of the captured CO2 into the

source formation to enhance the recovery of natural gas (EGR)
(Honari et al., 2013; Hughes et al., 2012) may be an increasingly considered solution. However, before economically-incentivized CO2
sequestration scenarios such as EOR and EGR can be developed and
seriously considered, reliable simulations of the capture process are
required to assess, for example, the quantity and potential impact
of impurities likely to be in the produced CO2 stream.
The CO2 capture process is most readily modeled in process simulators, such as AspenTech HYSYS (AspenTech, 2011). The industry
preferred equations of state (EOS) used in natural gas processing
simulations are the cubic Peng Robinson (PR) (Peng and Robinson,
1976) and SoaveRedlichKwong (SRK) EOS (Soave, 1972) These
EOS are usually considered to be decient for systems containing
polar components; however, in the Rectisol process methanol is
the only polar component present in a signicant quantity and it
may not be necessary to add complexity to the EOS to adequately
model the system. This papers objective is to demonstrate that
by using an improved mixing rule and optimized binary interaction parameters in a simple cubic like the PR EOS, it is possible to
describe adequately the low temperature VLE of the ternary system
methane (1) + methanol (2) + carbon dioxide (3) as is necessary for
simulations of the Rectisol and other similar industrial CO2 capture
processes.
To make this assessment, binary p, T, x VLE data calculated from
the PR EOS (as implemented in AspenTech HYSYS 7.3 generalized
cubic EOS) have been compared to low temperature binary p, T, x
VLE data from the literature and new data that we present in this
work for the methane (1) + methanol (2) binary. The liquid mole
fractions predicted with the simulator using the default values of
the EOSs binary interaction parameters (BIPs) are shown to be poor,
as has been found elsewhere, e.g. (Kandil et al., 2010, 2011). To
improve the calculated VLE, the BIPs for each cross-binary were
optimized (the optimization method is described below) using the
standard mixing rule, but the need for further improvement was
still evident. Accordingly, the use of an optimized asymmetric composition dependent mixing rule for the BIP to provide the most
accurate description of the VLE governing the Rectisol process is
demonstrated. Values for the ternary mixtures p, T, x VLE conditions predicted using the PR EOS with the default and optimized
BIPs are then compared to the new low temperature ternary data.
2. Materials and methods
The suppliers and supplier-analyzed purities of all components
used in this work are listed in Table 1. Our analysis of these components by gas chromatography indicated no detectable impurities.
The apparatus used for VLE measurements in this work has
been described in detail previously; (Kandil et al., 2010, 2011)
and improvements described by Kandil et al. (2011) for the
methane + hexane measurements were implemented in this work.
For the methane (1) + methanol (2) binary, one measurement was
made at a T = 200.10 K and p = 3.07 MPa and ve measurements
were made at T = 193.15 K and p between 0.55 and 2.88 MPa. For
the methane (1) + methanol (2) + carbon dioxide (3) ternary a total
of 20 measurements were made at isotherms of 183, 188, 193, 203,
213 and 323 K at p between 1.84 and 11.38 MPa. To ll the cell
Table 1
Material purities and suppliers.
Material

Supplier

Supplier mole fraction purity

Methane
Carbon dioxide
Methanol
2-Propanol

Air Liquide
BOC
Sigma-Aldrich
Sigma-Aldrich

0.99995
0.99995
0.999
0.999

with the binary mixture the cell was rst evacuated and ushed
with pure methane several times and was then lled close to the
desired pressure with methane. A high pressure liquid chromatography (HPLC) pump was then used to inject about 15 mL of degassed
methanol into the cell. To ll the cell with the ternary mixture, the
cell was rst evacuated and ushed with carbon dioxide several
times and was then charged with carbon dioxide to a higher pressure. Next the cell was charged with methane to close to the desired
pressure. The approximate relative mole fractions of carbon dioxide and methane were controlled by the lling pressures of each
of these gases. Methanol was then pumped into the cell using the
HPLC pump. After charging the cell, for both mixtures, the contents
were maintained isothermally and were mixed for a period of at
least 12 h. Up to ve samples of both the vapor and liquid phases
were then removed and analyzed by gas chromatography (GC). The
next measurement at a different pressure was made either by venting vapor or adding methane gas to the cell. Between each new p
and/or T the cell contents were mixed and the system was allowed
at least 12 h to equilibrate.
2.1. Gas chromatograph (GC) calibration
As described in our previous works (Kandil et al., 2010, 2011), to
rigorously quantify the uncertainty in composition measurements
by GC it is essential to perform a calibration of the GCs detectors.
The GC was equipped with both thermal conductivity detectors
(TCDs) and ame ionization detectors (FIDs). In this work only liquid mole fraction measurements are reported. Samples from the
equilibrium cell passed through a TCD before being sent to a FID.
Gas sample loops with volumes of 5, 25, 100 and 250 L were
used to obtain absolute response factors for methane on both the
FID and TCD, and for carbon dioxide on the TCD. A xed volume
(nominally 0.5 L) liquid sampling valve was used to obtain the
response factors for methanol. To nd the volume of the valve
more precisely the valve was rstly lled with methane and this
sample was sent to the GC. The area measured using the FID was
compared to the areas measured with the gas sample loops and
the volume of the liquid sampling valve was determined to be
0.43 0.01 L. The methanol FID response factor was then obtained
by passing pure methanol and two gravimetrically prepared solutions of methanol in 2-propanol (x2 = 0.1 and 0.5) from the sample
valve to the GC. Finally, relative response coefcients were determined for methanol relative to methane (FID) and carbon dioxide
relative to methane (TCD) (Kandil et al., 2010, 2011).
3. Optimization of equation of state binary interaction
parameters
The PR EOS (Peng and Robinson, 1976) relates the uids pressure, p, temperature, T. and molar volume, v:
p=

RT

vb

(1)

v (v + b) + b (v b)

The values of a for a pure component is related to the critical

temperature, critical pressure and accentric factor of the components and the value of b for a pure component is related to the
critical temperature and pressure. To apply the PR EOS to a mixture containing N components, effective values of a (amix ) and b
(bmix ) must be calculated using a mixing rule. The most commonly
used mixing rules and those used by default in AspenTech HYSYS
(AspenTech, 2011) are:
amix =

N
N


i

xi xj

ai aj 1 kij ,

(2)

T.J. Hughes et al. / International Journal of Greenhouse Gas Control 31 (2014) 121127

and

bmix =

standard error (SE) and relative standard error (RSE), dened as

follows:
N


xi bi

SE =

here xi is the mole fraction of component i in the mixture, and

kij is known as the binary interaction parameter (BIP). Although
Eqs. (1)(3) only relate p, T, v and x, such EOS can also be used to
calculate all other residual thermodynamic properties for the uid,
including the partial fugacities that govern phase equilibrium (Peng
and Robinson, 1976). The kij are adjustable parameters, which are
determined empirically by forcing agreement between observed
VLE data for binary mixtures and the EOS predictions. AspenTech
HYSYS has default values of these kij values which have presumably been obtained by tting to VLE data; however, it is uncertain
to what data and over what temperature range the kij values have
been tted. In this work we have re-t the kij values to VLE data
using the optimization method described in the next section. Additionally, AspenTech HYSYS offers the use of a mixing rule that is
composition dependent and has the functional form introduced by
Panagiotopoulos and Reid (1986, 1987) mixing rule for a:
N
N


i

 
2


xh xcalc,h


(3)

amix =

123

xi xj

ai aj 1 xi kij xi kji

(4)

This mixing rule was developed by Panagiotopoulos and Reid

(1986, 1987) to better t VLE data for mixtures containing
CO2 and polar components such as ethanol, acetone and water.
Panagiotopoulos and Reid (1986) note that a signicant improvement was observed in the representation of binary and ternary
phase equilibrium data for highly polar and asymmetric systems
and that ternary phase equilibrium data at high pressures were
successfully correlated using parameters regressed from binary
data only. In this work, this mixing rule has been tted to data for
the cross-binaries of the methane (1) + methanol (2) + carbon dioxide (3) ternary. We refer to the kij and kji from Eq. (4) as asymmetric
BIPs and to kij from Eq. (2) as the symmetric BIP. In addition to
temperature independent asymmetric BIPs, AspenTech Hysys also
allows for temperature dependence through the following equations:
(5)

and
kji = Aji + Bji T

RSE =


 

2
xh xcalc,h


xh

h

(8)

Nm

where m is the number of adjustable parameters, with m = 1 for

the symmetric mixing rule (Eq. (2)) and m = 2 for the asymmetric
mixing rule (Eq. (4)). In the case of temperature dependent BIPs,
individual isotherms were regressed to determine the kij and kji at
each temperature and these were then linearly regressed with temperature using Eqs. (5) and (6) to determine the optimized values
of Aij and Bij .
4. Results and discussion
4.1. Binary mixtures

kij = Aij + Bij T

and

(7)

Nm

(6)

3.1. Optimization method

For the binary mixtures, the Levenberg-Marquadt (Marquardt,
1963) non-linear least squares regression algorithm was implemented in Visual Basic for Applications (VBA) code to nd the
minimum of a user-dened objective function. In this work
that objective function was the sum of the squared deviations
(xh xcalc,h )2 , where xh is the measured liquid mole fraction and
xcalc,h is the liquid mole fraction calculated using the EOS (the
counter h represents a single measurement point). The code calculates numerical derivatives of the objective function with respect
to the BIP, using them to nd the objective functions minimum
rapidly and also to estimate the statistical uncertainty of the bestt BIP or kij value, u(kij ). In all cases the root mean squared (rms)
deviation of the model from the data was quantied through the

4.1.1. Methane (1) + methanol (2)

Our new p, T, x measurements of methane (1) + methanol (2)
measured at temperatures 193.15 K and 200 K are plotted on a p, x
(bubble point) diagram in Fig. 1a and are tabulated in Table 2. In this
gure the literature data of Hong et al. (1987) measured at a temperature of 200 K and Vetere (1986) measured at 213.15 K are also
plotted. The curves in Fig. 1a represent VLE data calculated using
the AspenTech Hysys PR EOS. The black curves were calculated
with the default BIP of k12 = 0.035 and the blue curves were calculated with an optimized symmetric BIP of k12 = 0.073. The VLE
calculated with the optimized BIP provides a signicantly better
description of the experimental data than that calculated with the
default BIP. However, the large scale of the ordinate deemphasizes
trends in deviations between the calculated and measured liquid
mole fractions. To emphasize these trends, and to help quantify
the deviation of the model, it can be more instructive to construct deviation plots, where the ordinate is the deviation of the
measured liquid mole fraction from the calculated liquid mole
fraction. Also, as the deviation plot displays data at different temperatures, it can be assessed whether BIP temperature dependence
would be benecial in improving the calculated VLE. In Fig. 1b
the deviations of the measured methane liquid mole fraction (x1 )
from that calculated using the PR EOS (x1,calc ) at the same T and
p with the a symmetric optimized BIP of 0.072 are plotted. The
same measured data are included as in Fig. 1a. Our data and those
of Hong et al. (1987) and Vetere (1986) display the same trend,
showing small deviations about the abscissa and the data show a
Table 2
Vaporliquid equilibrium measurements for the methane (1) + methanol (2) system.
T/Ka

p/MPab

x1

u(x1 )c

200.10
193.15
193.15
193.15
193.15
193.15

3.069
2.878
2.024
1.471
1.034
0.554

0.0607
0.0641
0.0464
0.0346
0.0252
0.0147

0.0003
0.0002
0.0002
0.0002
0.0002
0.0007

u(T) = 0.10 K.
u(p) = 0.005 p.
c
The u(x1 ) values include the effect of the propagated temperature and pressure
uncertainties on the measured compositions combined with the uncertainties of the
composition measurements.
b

124

T.J. Hughes et al. / International Journal of Greenhouse Gas Control 31 (2014) 121127

Table 3
Summary of the results of tuning the binary interaction parameters (BIP), kij , to binary mixture VLE data, in terms of the models standard error (SE) and relative standard
error (RSE) as dened in Eq. (7) and (8).
Methane (1) + methanol (2) (14 points)
Tmin /K
193.15

Tmax /K
213.15

pmin /MPa
0.554

pmax /MPa
6.910

x1,min
0.0147

x1,max
0.1118

Casea

k12

u(k12 )

k21

u(k21 )

SE

RSE

Default
Symmetric
Asymmetric

0.035
0.073
0.11

0.001
0.02

0.015

0.003

0.0275
0.0045
0.0040

0.387
0.050
0.050

Tmin /K
183.15

Tmax /K
210.15

pmin /MPa
3.407

pmax /MPa
5.788

x1,min
0.3175

x1,max
0.9993

Casea

k13

u(k13 )

k13

u(k13 )

SE

RSE

Default
Symmetric
Asymmetric

0.100
0.0917
0.0932

0.0009
0.0009

0.072

0.004

0.0173
0.0114
0.0095

0.77
0.74
0.75

Tmin /K
213.15

Tmax /K
247.12

pmin /kPa
98.1

pmax /kPa
1372.9

x3,min
0.0246

x3,max
0.47

Casea

k23

k32

SE

RSE

Default
Symmetric
Asymmetric
Symmetric temperature dependent

0.040
0.0547 0.0009
0.019 0.002
(0.13 0.02) +
(7.9 0.8) 104 T
(0.046 0.01) +
(3.0 0.5) 104 T

0.064 0.001

0.0778
0.0432
0.0154

0.170
0.162
0.055

Methane (1) + carbon dioxide (3) (35 points)

Methanol (2) + carbon dioxide (3) (34 points)

Asymmetric temperature dependent

(0.094 0.008) +
(6.5 0.3) 104 T

0.0324

0.134

0.0038

0.015

a
The Default case refers to the use of AspenTech HYSYS default BIP. The Symmetric and Asymmetric cases refer to the optimized BIPs using Eqs. (2) and (4)
respectively.

negligible temperature dependence (comparable in magnitude to

the uncertainty of the experimental data which is generally a mole
fraction of about 0.001), indicating that a temperature dependent
BIP is not necessary to describe this binary. Additionally in Fig. 1b,
lines are plotted which represent the methane liquid mole fraction calculated with the default AspenTech Hysys BIP minus the
methane liquid mole fraction calculated with the optimized BIP
(x1,calc ) for each isotherm of the data. It is apparent from these
lines that the deviation grows approximately linearly with x1 and
that our optimization process has both corrected for the offset as
well as the slope in the deviations. Also, it is apparent that the
lines, each for a different isotherm, overlap, again indicating that a
temperature dependent BIP is unnecessary. The SE and RSE of the
deviations, before optimization, using the Hysys default BIP were
0.0275 and 38.7%, respectively. The result of optimizing the symmetric BIP for the binary mixture pairs is summarized in Table 3.
The optimized symmetric BIP of 0.073 0.001 reduced the SE
and RSE of the model to 0.0044 and 5.0%, respectively, which is
over a ve-fold improvement. The optimized asymmetric BIPs of
k12 = 0.065 0.003 and k23 = 0.11 0.02 only resulted in a small
decrease in the SE to 0.0040 and an unchanged RSE of 5.0%, indicating that the use of the asymmetric mixing rule is unjustied for
this binary mixture.

curves. The solid curves represent the calculated p, x data using

the optimized symmetric BIP of 0.0917 0.0009. In Fig. 2b these
results are shown as a deviation plot. It is apparent that there is
structure to the deviations, with positive residuals in the ranges
0.3 < x1 < 0.6 and x1 > 0.95, and negative residuals between x1 0.6
and x1 0.95. As in Fig. 1b, the curves plotted in Fig. 2b represent
the methane liquid mole fraction calculated with the default
AspenTech Hysys BIP minus the methane liquid mole fraction
calculated with the optimized BIP for each isotherm of the data.
These curves, each for a different isotherm, overlap, indicating
that a temperature dependent BIP would not remove the structure
observed in the deviations. From these curves it can also be
observed that the maximum magnitude of the residuals is reduced
from a mole fraction of about 0.06 to about 0.02. The SE and RSE
of the deviations, before optimization, using the Hysys default BIP
were 0.0173 and 77%, respectively. The optimized symmetric BIP of
0.0917 0.0009 resulted in an improvement in both the SE and RSE
to 0.0114 and 74%, respectively, which is an improvement of about
34% in the SE. Optimized asymmetric BIPs of k13 = 0.09320 0.0009
and k31 = 0.072 0.004 were also obtained by regression; however,
this resulted in only a small further decrease in the SE to 0.0095
and a slightly worse RSE of 75%, indicating that the use of the
asymmetric mixing rule is unjustied for this binary.

4.1.2. Methane (1) + carbon dioxide (3)

For the methane (1) + carbon dioxide (3) binary, the literature
data of Mraw et al. (1978), measured at temperatures between
(183 and 210) K were used in the BIP optimization process. In
Fig. 2a each isotherm of Mraw et al.s (1978) data is plotted on a
p, x (bubble point) diagram. The calculated p, x data from the PR
EOS using the AspenTech Hysys default BIP are included as dashed

4.1.3. Methanol (2) + carbon dioxide (3)

For the methanol (2) + carbon dioxide (3) binary, the literature data of Shenderei et al. (1959) measured at temperatures
between 213 and 247 K were used in the BIP optimization process. In Fig. 3a each isotherm of Shenderei et al.s (1959) data
is plotted on a p, x (bubble point) diagram. The calculated p, x
data from the PR EOS using the AspenTech Hysys default BIP are

T.J. Hughes et al. / International Journal of Greenhouse Gas Control 31 (2014) 121127

8000

6000
5500
5000

p/kPa

p/kPa

6000
4000

4500
4000

2000

T= 186 K
T= 183 K

3500

0
0.00

0.02

0.04

0.06

x1
(a)

0.08

0.10

3000

0.12

0.3

0.4

0.5

0.6

0.3

0.4

0.5

0.6

0.06

0.06

x1
(a)

0.7

0.8

0.9

1.0

0.7

0.8

0.9

1.0

0.04

x1 - x1,calc

0.04

x1 - x1,calc

125

0.02
0.00

0.02
0.00

-0.02

-0.02

-0.04

-0.04

-0.06

-0.06
0.00

0.02

0.04

0.06

x1
(b)

0.08

0.10

0.12

Fig. 1. (a) Methane (1) + methanol (2) p, x diagram showing measured methane liquid mole fractions and those calculated with the AspenTech HYSYS PR EOS. , This
work T = 193 K; , this work T = 200 K; , Hong et al. (1987) T = 200 K; Vetere (1986)
T = 213 K. The black curves represent AspenTech Hysys liquid mole fractions calculated with default BIP of k12 = 0.035 and the blue curves represent AspenTech Hysys
liquid mole fractions calculated with the optimized (symmetric) BIP of k12 = 0.073
(, T = 193 K; - - -, T = 200 K, , T = 213 K). (b) Deviations between the measured
liquid mole fractions and those calculated (indicated by subscript calc) with the
AspenTech HYSYS PR EOS using the optimized symmetric BIP of 0.073 0.001
for methane (1) + methanol (2). The measured data are represented by the same
symbols as in part a. The curves represent the deviation between the liquid mole
fractions calculated with the default AspenTech Hysys BIP and with the optimized
(symmetric) BIP: , T = 193 K; - - -, T = 200 K, , T = 213 K. (For interpretation of the
references to color in this gure legend, the reader is referred to the web version of
this article).

included as dashed curves. The solid curves represent the calculated p, x data using an optimized asymmetric temperature
dependent
BIP
[A23 = 0.046 0.012,
A32 = 0.094 0.008,
B23 = (3.0 0.5) 104 , B32 = (6.5 0.3) 104 ]. It is apparent,
even from this p, x diagram, that the PR EOS does a signicantly
better job of representing the VLE data with the optimized BIP
rather than the default BIP, particularly at x3 greater than about
0.25. In Fig. 3b the results of Fig. 3a are shown as a deviation plot. It is
apparent that the PR EOS calculated carbon dioxide mole fractions
with the optimized temperature dependent asymmetric BIP lie
within a band of less than about 0.01 of the measured carbon
dioxide mole fractions and that there are no signicant trends
either with temperature or mole fraction (x3 ). Similarly to Figs. 1b
and 2b, the curves plotted in Fig. 3b represent the carbon dioxide
liquid mole fraction calculated with the default AspenTech Hysys
BIP minus the carbon dioxide liquid mole fraction calculated with
the optimized asymmetric temperature dependent BIP for each
isotherm of the data. Unlike for the other binary mixtures, these
lines for each isotherm do not overlap indicating the need to use
a temperature dependent BIP. It is also noted that the deviations
of the PR EOS using the default Aspen Hysys BIP become very
large at x3 greater than about 0.25 with deviations growing to a
mole fraction of 0.2 or more for two of the isotherms (see inset of
Fig. 3b). Before optimization the SE and RSE of the deviations from
predictions made using the Hysys default BIP were 0.0778 and 17%,
respectively. The optimized symmetric temperature dependent

x1
(b)

Fig. 2. (a) Methane (1) + carbon dioxide (3) p, x diagram showing measured methane
liquid mole fractions and those calculated with the AspenTech HYSYS PR EOS. ,
Mraw et al. (1978) T = 183 K; , Mraw et al. (1978) T = 186 K; , Mraw et al. (1978)
T = 193 K; , Mraw et al. (1978) T = 203 K; , Mraw et al. (1978) T = 210 K; - - -, curves
calculated with the default BIP of 0.010; , curves calculated with the optimized
symmetric BIP of 0.0917 0.0009. (b) Deviations between the measured liquid mole
fractions and those calculated (indicated by subscript calc) with the AspenTech
HYSYS PR EOS using the optimized symmetric BIP of 0.0917 0.0009 for methane
(1) + carbon dioxide (3). The measured data are represented by the same symbols as
in part a. The curves, which are largely superimposed on each other, represent the
deviation between the liquid mole fractions calculated with the default AspenTech
, T = 186 K, ,
Hysys BIP and with the optimized (symmetric) BIP: , T = 183 K;
T = 193 K; - - -, T = 203 K; , T = 210 K.

BIP resulted in a substantial improvement in both the SE and RSE

to 0.0038 and 1.5%, respectively, which is an improvement of about
95% in the SE. As shown in Table 3 alternative functional forms for
the BIP optimization were investigated. The use of an optimized
symmetric (non-temperature dependent) BIP only reduced the RSE
from 17.0% to 16.2%. The use of an asymmetric (non-temperature
dependent) BIP reduced the RSE to 5.5%. In comparison the use of
symmetric temperature dependent BIP reduced the RSE to 13.4%,
indicating that the use of a temperature dependent or asymmetric
BIP alone could not reduce the RSE as signicantly. Only by using
both an asymmetric and temperature dependent BIP could the RSE
be reduced to 1.5%.
4.2. Ternary mixture
The methane (1) + methanol (2) + carbon dioxide (3) ternary p, T,
x VLE measurements are listed in Table 4 and represent the rst data
published for this system. The additional degrees of freedom for the
ternary mixture mean that there are several ways of quantifying the
deviation of the model from the data. In Table 5 we report the SE
and RSE determined for the mole fractions of all three components
in the liquid phase for two cases, the rst using the default AspenTech Hysys BIPs (which we will refer to as the default case) and the
second using the best optimized BIPs (which we will refer to as the
optimized case). For the optimized case the BIPs for the methane
(1) + methanol (2) and the methane (1) + carbon dioxide (2) were
the symmetric optimized BIPs, and for methanol (2) + carbon dioxide (3) the asymmetric temperature dependent BIPs were used
(refer to Table 3).

T.J. Hughes et al. / International Journal of Greenhouse Gas Control 31 (2014) 121127

1400
1200
1000
800
600
400
200
0

Table 5
Comparison of model predictions with the measured data for the methane
(1) + methanol (2) + carbon dioxide (3) ternary mixture using the AspenTech Hysys
default BIPs and the optimized BIP values, in terms of the models standard error
(SE) and relative standard error (RSE) as dened in Eqs. (7) and (8).
Casea

Default Hysys
Optimized

0.0
0.04

x3 - x3,calc

x1

0.1

0.3
0.2
0.1
0.0
-0.1

0.02
0.00

0.2

x3
(a)

0.3

0.4

0.5

0.0 0.1 0.2 0.3 0.4 0.5

-0.02

-0.04
0.0

0.1

0.2

x3
(b)

0.3

0.4

0.5

Fig. 3. (a) Methanol (2) + carbon dioxide (3) p, x diagram showing measured carbon dioxide liquid mole fractions and those calculated with the AspenTech HYSYS
PR EOS. , Shenderei et al. (1959) T = 213 K; , Shenderei et al. (1959) T = 228 K; ,
Shenderei et al. (1959) T = 237 K; , Shenderei et al. (1959) T = 247 K; - - -, curves
calculated with the default BIP of 0.040; , curves calculated with the optimized
temperature dependent asymmetric BIP [Eqs (5) and (6) with A23 = 0.046 0.012,
A32 = 0.094 0.008, B23 = (3.0 0.5) 104 , B32 = (6.5 0.3) 104 . (b) Deviations
between the measured liquid mole fractions and those calculated (indicated by
subscript calc) with the AspenTech HYSYS PR EOS using the optimized temperature dependent symmetric BIP. The measured data are represented by the same
symbols as in part a. The curves represent the deviation between the liquid mole
fractions calculated with the default AspenTech Hysys BIP and with the optimized
temperature dependent symmetric BIP: , T = 213 K, - - -, T = 228 K; , T = 237 K;
, T = 247 K. The inset shows the full scale of the extent of the deviations between
the tuned and default models.

x2

x3

SE

RSE

SE

RSE

SE

RSE

0.0429
0.0186

0.496
0.194

0.0461
0.0186

0.054
0.022

0.0038
0.0008

0.111
0.025

a
The Default Hysys case used the AspenTech HYSYS PR EOS default BIPs. The
Optimized case includes binary optimized symmetric BIP values for methane
(1) + methanol (2) and methane (1) + carbon dioxide (3) and the binary optimized
asymmetric temperature dependent BIP values for methanol (2) + carbon dioxide
(3) (see Table 3 for the values of the BIPs).

The mole fraction deviations (xi xi,calc ) calculated for each component are plotted in Fig. 4. For the default case the xi,calc values
were predicted using the PR EOS with the default BIPs, and the
resulting deviations are plotted as red symbols. For the optimized
case, the x1,calc values were predicted using the PR EOS with the
optimized BIPs, and the deviations are plotted as black symbols. It
is clear that the optimization of the BIPs has improved the prediction of the liquid mole fractions of all the components. Of course, not
all the mole fractions shown in Fig. 4 are independent and clearly
a deviation trend in one component can result in a complementary
trend for another component. In Fig. 4, the results for x1 and x2
show this complementarity.

0.08

x1 - x1,calc

p/kPa

126

0.04
0.00

-0.04
-0.08

0.00

0.04

x1

0.08

0.12

for

the

methane

(1) + methanol

p/MPab

x1

u(x1 )

x2

u(x2 )

x3

u(x3 )

183.15
183.15
183.17
183.17
183.17
183.23
188.15
188.15
193.15
193.15
193.15
193.15
193.15
203.15
203.15
203.15
203.15
213.15
213.15
323.15

3.008
3.260
2.586
2.671
3.270
2.096
2.182
3.225
2.914
2.331
1.841
3.447
4.070
3.245
2.094
2.528
2.533
2.79
4.311
11.380

0.099
0.113
0.091
0.085
0.120
0.075
0.070
0.094
0.079
0.0614
0.0497
0.087
0.100
0.069
0.0461
0.0542
0.0543
0.0510
0.073
0.015

0.004
0.018
0.003
0.008
0.011
0.002
0.004
0.004
0.003
0.0002
0.0006
0.003
0.002
0.001
0.0004
0.0004
0.0004
0.0002
0.001
0.003

0.848
0.83
0.873
0.87
0.83
0.889
0.874
0.857
0.889
0.9072
0.9195
0.867
0.851
0.9027
0.9345
0.9235
0.9231
0.9087
0.893
0.984

0.004
0.02
0.005
0.01
0.01
0.002
0.006
0.005
0.004
0.0003
0.0009
0.004
0.002
0.0008
0.0005
0.0004
0.0006
0.0006
0.002
0.003

0.053
0.055
0.036
0.043
0.055
0.0355
0.057
0.049
0.0321
0.0314
0.0308
0.046
0.0489
0.0281
0.0194
0.0223
0.0226
0.0403
0.0339
0.0015

0.001
0.002
0.003
0.002
0.003
0.0003
0.002
0.001
0.0007
0.0001
0.0003
0.001
0.0004
0.0004
0.0002
0.0001
0.0003
0.0004
0.0006
0.0002

a
b

u(T) = 0.10 K.
u(p) = 0.005p.

0.04
0.00

-0.04

T/Ka

-0.08

0.80

0.85

0.90

x2

0.95

1.00

0.01

x3 - x3,calc

Table 4
Vaporliquid equilibrium measurements
(2) + carbon dioxide (3) system.

x2 - x2,calc

0.08

0.00

-0.01

0.00

0.02

x3

0.04

0.06

Fig. 4. Deviations (xi xi,calc ) for each component in the methane (1) + methanol
(2) + carbon dioxide (3) system (black symbols) plotted against the measured liquid
mole fraction of that component for the ternary mixture using the optimized BIPs
with the PR EOS (see Table 5). , T = 183 K; , T = 188 K; , T = 193 K; , T = 203 K;
T = 203 K. The red symbols are points where the default Hysys BIP with the PR EOS
has been used to calculated the xi ,calc value. (For interpretation of the references to
color in this gure legend, the reader is referred to the web version of this article).

T.J. Hughes et al. / International Journal of Greenhouse Gas Control 31 (2014) 121127

The RSEs of x1 , x2 and x3 for the default case were 49.6%, 5.4%
and 11.1%, respectively compared to optimized case with values of
19.4%, 2.2% and 2.5%. The optimized RSEs represent a 61%, 59% and
77% improvement in the calculation of x1 , x2 and x3 , respectively.
The SEs and RSEs of both case studies are summarized in Table 5.
These signicant improvements, particularly in the x3 , should allow
Rectisol plants to be simulated more accurately.
5. Conclusions
Predictions of the liquid phase mole fractions made for the
ternary mixture with the PR EOS using the default HYSYS BIPs were
found to be poor. A factor of about 2.5 improvement in the RSE
was achieved for x1 and x2 by instead using the symmetric BIPs
obtained from the optimization of the binary systems. The RSE in
x3 for the ternary was improved by a factor of about 4.4 by using
a temperature dependent asymmetric mixing rule with BIPs tuned
to binary VLE data. Tuning the binary systems to the simple temperature dependent asymmetric composition-dependent mixing
rule resulted in a signicant reduction in the RSE of the t for the
methanol (2) + carbon dioxide (3) from 17% to 1.5% (an improvement of 91%). However, no signicant improvement was observed
by applying the asymmetric mixing rule for the other two binaries.
This might be expected given that this mixing rule was initially
developed to improve EOS calculations of carbon dioxide + polar
component VLE. This result illustrates that a simple temperature
and asymmetric compositional dependent mixing rule can greatly
improve the predictions of a simple EOS for the carbon dioxide liquid mole fractions in a polar solvent and the use of the optimized
BIPs should improve the simulation of Rectisol plants.
Acknowledgment
The authors would like to thank Craig Grimm for constructing
and maintaining the apparatus.
References
Linde AG Engineering Division RECTISOL Wash. http://www.lindeengineering.com/en/process plants/hydrogen and synthesis gas plants/
gas processing plants/rectisol wash/index.html (accessed 29.01.14.).
AspenTech, 2011. Aspen HYSYS Process Simulator, v7.3. Aspen Technology, Inc.,
Cambridge, MA.
Dakota Gasication Company, 2013. Tap into the Future: Bakken Oil Report. DEL
communications Inc., Winnipeg, Canada, pp. 146.
Denton, R.D., Valencia, J.A., 1985. Method and apparatus for separating carbon dioxide and other acid gases from methane by the use of distillation and a controlled
freezing zone. Google Patents.

127

Fieler, E.R., Grave, E.J., Northrop, P.S., Yeh, N.K., 2010. Controlled freeze zone tower.
Google Patents.
Honari, A., Hughes, T.J., Fridjonsson, E.O., Johns, M.L., May, E.F., 2013. Dispersion
of supercritical CO2 and CH4 in consolidated porous media for enhanced gas
recovery simulations. Int. J. Greenh. Gas Control 19, 234242.
Hong, J.H., Malone, P.V., Jett, M.D., Kobayashi, R., 1987. The measurement and interpretation of the uid-phase equilibria of a normal uid in a hydrogen bonding
solvent: the methanemethanol system. Fluid Phase Equilib. 38, 8396.
Hughes, T.J., Honari, A., Graham, B.F., Chauhan, A.S., Johns, M.L., May, E.F., 2012. CO2
sequestration for enhanced gas recovery: new measurements of supercritical
CO2 CH4 dispersion in porous media and a review of recent research. Int. J.
Greenh. Gas Control 9, 457468.
Kandil, M.E., May, E.F., Graham, B.F., Marsh, K.N., Trebble, M.A., Trengove, R.D.,
Huang, S.H., 2010. Vaporliquid equilibria measurements of methane + 2methylpropane (isobutane) at temperatures from 150 to 250 K and pressures
to 9 MPa. J. Chem. Eng. Data 55, 27252731.
Kandil, M.E., Thoma, M.J., Syed, T., Guo, J., Graham, B.F., Marsh, K.N., Huang, S.H., May,
E.F., 2011. Vaporliquid equilibria measurements of the methane + pentane and
methane + hexane systems at temperatures from 173 to 330 K and pressures to
14 MPa. J. Chem. Eng. Data 56, 43014309.
Kohl, A.L., Nielsen, R., 1997. Gas Purication, 5th ed. Gulf Publishing Company, Houston, Tx.
Marquardt, D.W., 1963. An algorithm for least-squares estimation of nonlinear
parameters. J. Soc. Ind. Appl. Math. 11, 431441.
Mraw, S.C., Hwang, S.-C., Kobayashi, R., 1978. Vaporliquid equilibrium of the
methanecarbon dioxide system at low temperatures. J. Chem. Eng. Data 23,
135139.
Nichols, J.L.V., Friedman, B.M., Nold, A.L., McCutheon, S., Goethe, A., 2009. Processing
technologies for CO2 rich gas. In: Proceedings of the 88th Annual Convention of
the Gas Processors Association, San Antonio, TX.
Panagiotopoulos, A.Z., Reid, R.C., 1986. New mixing rules for cubic equations of
state for highly polar, asymmetric systems. In: Chao, K.C., Robinson Jr., R.L.
(Eds.), Equations of State: Theories and Applications. American Chemical Society,
Washington, D.C, pp. 571582.
Panagiotopoulos, A.Z., Reid, R.C., 1987. High-pressure phase equilibria in ternary
uid mixtures with supercritical component. In: Squire, T.G., Paulaitis, M.E.
(Eds.), Supercritical Fluids, Chemical and Engineering Principles and Applications. American Chemical Society, Washington DC, pp. 115129.
Peng, D.-Y., Robinson, D.B., 1976. A new two-constant equation of state. Ind. Eng.
Chem. Fundam. 15, 5964.
Pettersen, J., Nilsen, ., Vist, S., Giljarhus, L.E.N., Fredheim, A.O., Aasekjr, K., Neeraas,
B.O., 2013. Technical and Operational Innovation for Onshore and Floating LNG,
LNG 17, Houston, TX.
Preston, C., Monea, M., Jazrawi, W., Brown, K., Whittaker, S., White, D., Law, D., Chalaturnyk, R., Rostron, B., 2005. IEA GHG Weyburn CO2 monitoring and storage
project. Fuel Process. Technol. 86, 15471568.
Rufford, T.E., Smart, S., Watson, G.C.Y., Graham, B.F., Boxall, J., Diniz da Costa, J.C., May,
E.F., 2012. The removal of CO2 and N2 from natural gas: a review of conventional
and emerging process technologies. J. Pet. Sci. Eng. 9495, 123154.
Shenderei, E.R., Zelvenskii Ya., D., Ivanovskii, F.P., 1959. Solubility of carbon dioxide
in methanol at low temperature and high pressure. Khim. Prom-st. (4), 5053
(St. Petersburg, Russ. Fed.).
Soave, G., 1972. Equilibrium constants from a modied RedlichKwong equation of
state. Chem. Eng. Sci. 27, 11971203.
Vetere, A., 1986. Vaporliquid equilibria with supercritical gases calculated by the
excess Gibbs energy method. Fluid Phase Equilib. 28, 265281.
Weiss, M.M., Schrie, A., 2010. Rectisol and oxyclaus: mature processes still going
strong. In: Proceedings of the 10th European Gasication Conference, Amsterdam, The Netherlands.