IOP Conference Series: Materials Science and Engineering

PAPER • OPEN ACCESS You may also like

- Disk Evolution Study through Imaging of
Phase identification of natural gas system with Nearby Young Stars (DESTINYS): A
Panchromatic View of DO Tau’s Complex
high CO2 content through simulation approach Kilo-astronomical-unit Environment
Jane Huang, Christian Ginski, Myriam
Benisty et al.
using Peng-Robinson model
- Analysis of SRK S.A. mining rescue costs
Piotr Mocek
To cite this article: Ali Qasim et al 2018 IOP Conf. Ser.: Mater. Sci. Eng. 458 012068
- Electrical, thermal and thermoelectric
transport in open long-range Kitaev chain
Averi Banerjee, Sayeda Rafisa Rahaman
and Nilanjan Bondyopadhaya

View the article online for updates and enhancements.

This content was downloaded from IP address 5.117.75.102 on 15/11/2023 at 17:27

ICPEAM2018 IOP Publishing
IOP Conf. Series: Materials Science and Engineering 458 (2018) 012068 doi:10.1088/1757-899X/458/1/012068

Phase identification of natural gas system with high CO2 content

through simulation approach using Peng-Robinson model

Ali Qasim, Azmi Mohd Shariff, Suriati Sufian, Muhammad Ayoub, Bhajan Lal*
Department of Chemical Engineering, Universiti Teknologi PETRONAS, 32610 Seri
Iskandar, Perak, Malaysia.

*bhajan.lal@utp.edu.my

Abstract: The phase behavior for natural gas mixtures with high CO 2 content and heavier
hydrocarbons up to pentane for cryogenic separation has been obtained through simulation using
Peng-Robinson (PR) model. The bubble point and dew point curves which define the liquid-vapor
and solid-vapor domains for separation are obtained by generating the pressure-temperature phase
diagram. The simulations are performed using Aspen HYSYS. The validation for the use of PR
model is done by comparing the results of CO 2 freeze-out temperature predictions for PR and
Soave-Redlich-Kwong (SRK) model with the experimental data available in the literature.

1. Introduction
The energy consumption and demand throughout the world is increasing. Also the increase in population
calls for an increase in energy usage. Natural gas serves as a clean and sustainable source of energy, so
for this reason it is widely employed in industrial and household applications [1, 2]. It was reported in
2010 that natural gas fulfills almost a quarter of the world’s total energy requirements [3]. Although
natural gas is considered a clean fuel in comparison with the fossil fuels but raw natural gas contains
impurities such as CO2, water and other hydrocarbons. Regarding natural gas reservoirs, it is estimated
that almost 33% of these reservoirs are acrid. In Malaysia, some of the reserves contain more than 70% of
CO2 in natural gas [4, 5]. In these impurities, removal of CO2 is of utmost importance as it significantly
decreases the calorific content of natural gas and causes erosion in delivery pipelines [6, 7].
In order to predict the phase behavior of natural gas mixture, a number of equation of states are used
for modeling and simulation purposes such as Peng-Robinson (PR), Soave-Redlich-Kwong (SRK) and
Benedict-Webb-Rubin-Starling (BWRS). Among these equations, Peng-Robinson equation of state model
is suitable to be used in oil, gas and petrochemical applications. It is extensively used to model VLE
behavior of natural gas in cryogenic gas processing systems. Peng-Robinson equation of state also holds
high degree of efficiency and reliability for its use in low pressure and higher temperature conditions [8,
9]. The cryogenic separation method, among the other CO2 removal processes, is a resourceful technique
for CO2 capture. Cryogenic separation method involves the removal of CO2 impurity at lower
temperatures of up to -120°C or below [10]. In hybrid cryogenic separation technique, conventional
distillation columns and packed beds are incorporated and separation of the components can be performed
in both liquid-vapor and solid-vapor regions of the phase [11].

Content from this work may be used under the terms of the Creative Commons Attribution 3.0 licence. Any further distribution
of this work must maintain attribution to the author(s) and the title of the work, journal citation and DOI.
Published under licence by IOP Publishing Ltd 1
ICPEAM2018 IOP Publishing
IOP Conf. Series: Materials Science and Engineering 458 (2018) 012068 doi:10.1088/1757-899X/458/1/012068

In this work, the phase behavior of two natural gas mixtures with high CO2 content is determined
through simulation using the suitable equation of state that predicts it more accurately, which in this case
is PR equation of state. The investigation of phase behavior is done to determine the vapor, liquid and
sold boundaries for cryogenic based separation. Simulations are performed in Aspen HYSYS. The phase
behavior obtained through the use of PR and SRK equations of states for binary gas mixture containing
CO2 and CH4 are compared with the experimental data for validation.

2. Methodology
The composition of the natural gas feed gas mixtures is shown in Table 1. It is based on the maximum
available amount of higher hydrocarbons that exists in Malaysian wells [12]. Also, in both mixtures, more
than half of the total amount of gas constitute of CO2.
Table 1. Natural gas feed streams composition [12].
Composition (Mol %)
Component
Gas Mixture 1 Gas mixture 2
CH4 30 20
CO2 60 70
C2H6 5 5
C3H8 2.8 2.8
C4H10 1.2 1.1
C5H12 1 1
The VLE behavior of gas mixtures has been predicted through the generation of pressure-temperature
phase diagram using Aspen HYSYS 8.0. Bubble point and dew point curves along with the CO2 freeze
out line construe the boundaries for liquid-vapor and solid-vapor regions. Figure 1 shows the simulation
environment where the feed enters the separator and is separated in vapor and liquid states.

Figure 1. HYSYS simulation for phase identification.

In order to determine the accuracy of the software and suitability of the equation of state, the Solid-
Liquid-Vapor (SLV) locus is obtained through simulation for both the PR and SRK models. It is obtained
at the same pressure and temperature conditions that were used experimentally in previous study.
Donnelly et al. had reported the experimental data for SLV locus of CO2-CH4 binary gas mixture which is

2
ICPEAM2018 IOP Publishing
IOP Conf. Series: Materials Science and Engineering 458 (2018) 012068 doi:10.1088/1757-899X/458/1/012068

available in literature [13]. The comparison between the predicted and experimental SLV locus is
reported in Table 2 of the next section along with the discussion.

3. Results and discussion

The simulation results for phase separation of the selected compositions of natural gas mixtures are
obtained by using PR and SRK equation of states. In case of gaseous mixture composed of hydrocarbons,
previous studies suggest the use of PR equation of state for the accurate prediction and description of
vapor-liquid, vapor-solid and liquid-solid phase behavior [14, 15]. Some studies also involved SRK
model to investigate the thermodynamic behavior of natural gas for the optimization of a cryogenic
system in a large scale natural gas processing plant [16]. In this work, for validation purposes, the SLV
locus predicted by these equilibrium relationships through simulation is compared with the available
experimental data. The experimental range of pressure at which the CO2 freeze out temperatures and SLV
locus are determined vary from 9 bar to 38 bar. Donnelly et al. determined experimentally the three phase
locus describing the equilibria wherein solid CO2 came in coexistence with the liquid and vapor phases.
Their experimental setup consisted of a glass-windowed pressure cell in an alcohol bath used to confine
the system [13]. For validation, Table 2 shows the comparison between experimental set of values at
which CO2 freeze out occurs and the phase exists in liquid, vapor and solid states with the predicted
values for SLV locus considering both the PR and SRK equation of states.
Table 2. Comparison of experimental and predicted CO2 freeze out temperatures [13].
PR Model SRK Model AAE for
Experimental AAE for PR
P (bar) Predicted Predicted SRK Model
Temp ( °C) Model (%)
Temp ( °C) Temp ( °C) (%)
9 -57.7 -60 -57.4 3.846 0.602
10.7 -58.3 -57.8 -57.8 0.914 0.928
12.8 -57.5 -58.2 -58.2 1.217 1.163
18 -59.1 -59.3 -59.3 0.225 0.205
24.3 -59.7 -60.6 -60.6 1.47 1.48
29.7 -60.5 -61.7 -61 1.89 0.706
31.2 -61.1 -62.1 -61 1.618 0.208
32 -61.3 -62.3 -61 1.484 0.659
38 -61.3 -63.7 -61 3.765 0.654
39.5 -61.6 -64 -61 3.784 1.1
40.2 -62.2 -64.2 -61 3.179 1.983
41.8 -63 -64.6 -61 2.449 3.277
44.2 -62.7 -65.4 -61 4.177 2.847
44.6 -63 -65.5 -61 3.877 3.275
44.9 -64.1 -65.6 -61 2.234 4.949
46.9 -64.7 -66.3 -61 2.438 5.764
47.8 -66.9 -66.7 -61 0.365 8.891
46.4 -69.7 -67.8 -61 2.678 12.522
44.7 -71.1 -69.7 -61 1.909 14.232
43 -72.7 -71.6 -61 1.507 16.197
37.5 -78.6 -78.1 -61 0.578 22.419
MAE=2.172% MAE=4.955%

3
ICPEAM2018 IOP Publishing
IOP Conf. Series: Materials Science and Engineering 458 (2018) 012068 doi:10.1088/1757-899X/458/1/012068

The average absolute error in terms of percentage for the predicted temperature values for both the
models is calculated and mean absolute error (MAE) is also determined. The mean absolute error for SRK
model is about 5 % while for PR model, it is only 2.172 %. The comparison between the results predicted
by PR model and SRK model clearly shows that the ability of PR model to predict the actual phase
behavior is much better as compared to that of SRK model. The results also show the imprecision of SRK
model to predict the phase behavior and the actual CO2 freeze out temperatures at higher pressures and
the model is not suitable to simulate the phase behavior for natural gas in high pressure applications. So
the phase identification for the feed gas mixtures mentioned in Table 1 is done by using PR equation of
state and the Figure 2 shows the boundaries of liquid, vapor and solid phases for both the gas mixtures.

Figure 2. Phase regions for natural gas mixtures.

From the above figure it can be noticed that the liquid-vapor (L-V) region starts from about 0°C to
around -60°C and solid-vapor (S-V) domain lies in the temperature range starting from about -60°C to -
120°C. Bubble point and dew point curves are obtained in order to determine the phase behavior.
Figure 2 also indicates that from the temperature range of 40°C to 0°C, the gas mixture is in vapor
state. It is also be noticed that the vapor-liquid region lies between the temperature range of 0 to -60°C
and beyond -60°C, the phase enters into solid-vapor region. The solid-vapor region has been worked upon
by Davis et al. and it is reported that in this region only CO2 exists in solid form while CH4 is all vapor as
the freezing point of methane is much lower than that of CO2 [17]. At very low temperatures as -120°C
and at both lower and higher pressures, phase enters into solid-liquid region. It is feasible to do separation
in liquid-vapor and solid-vapor regions. The energy requirements for separation in liquid-solid region is
high as more energy is needed to lower the temperatures to enter this region. Also the solidification of
methane is avoided in this region as it is possible at very lower temperatures therefore it is not
recommended to separate CO2 in solid-liquid region.

4. Conclusion
The liquid-vapor and solid-vapor phase regions are identified for natural gas systems with high CO2
content through simulation using PR model. These domains are determined in order to separate natural
gas components at lower temperatures for cryogenic applications. PR equation of state was selected due
to more accurate prediction of the phase behavior of natural gas with the data available in literature in

4
ICPEAM2018 IOP Publishing
IOP Conf. Series: Materials Science and Engineering 458 (2018) 012068 doi:10.1088/1757-899X/458/1/012068

comparison to that of SRK model. PR model predicts the VLE phase behavior and CO 2 freeze out
temperatures more accurately.

Acknowledgement
The authors would like to acknowledge Universiti Teknologi PETRONAS grant YUTP-0153AAE16 for
providing the necessary facilities and financial support for this research project work.

References
[1] Fantazzini D, Höök M and Angelantoni A 2011 Global oil risks in the early 21st century Energy
Policy 39 7865
[2] Speight J G Natural gas: a basic handbook 2007 Elsevier
[3] Rufford T, Smart S, Watson G, Graham B, Boxall J and Da Costa J D 2012 The removal of CO2
and N2 from natural gas: a review of conventional and emerging process technologies J. Petrol.
Sci Eng. 94 123
[4] Partoon B, Sabil K M, Roslan H, Lal B and Keong L K 2016 Impact of acetone on phase boundary
of methane and carbon dioxide mixed hydrates Fluid Phase Equilib. 412 51
[5] Khan M S, Bavoh C B, Partoon, Lal B, Bustam M A and Shariff A M 2017 Thermodynamic effect
of ammonium based ionic liquids on CO2 hydrates phase boundary J. Mol. Liq. 238 533
[6] Parrish W R and Kidnay A J 2006 Fundamentals of natural gas processing CRC Press Taylor &
Francis Group
[7] Abdullah M Z and Qasim A 2016 Parametric analysis of carbon dioxide adsorption on
nanoporous activated carbon using computational approach Procedia Eng. 148 1416
[8] Hart A and Gnanendran N 2009 Cryogenic CO2 capture in natural gas Energy Procedia 1 697
[9] Xu G, Li L, Yang Y, Tian L, Liu T and Zhang K 2012 A novel CO2 cryogenic liquefaction and
separation system Energy 42 522
[10] Song C, Kitamura Y and Li S 2014 Optimization of a novel cryogenic CO2 capture process by
response surface methodology (RSM) J. Taiwan Inst. Chem. Eng. 45 1666
[11] Maqsood K, Mullick A, Ali A, Kargupta K and Ganguly S 2014 Cryogenic carbon dioxide
separation from natural gas: a review based on conventional and novel emerging technologies
Rev. Chem. Eng. 30 453
[12] AbulHassan A 2015 Study on desublimation based cryogenic packed beds for CO2 removal from
natural gas PhD, Universiti Teknologi Petronas
[13] Donnelly H G and Katz D L 1954 Phase equilibria in the carbon dioxide–methane system Ind. Eng.
Chem. 6 511
[14] Williams C A, Zana E N and Humphrys G E 1980 Use of the Peng-Robinson equation of state to
predict hydrocarbon phase behavior and miscibility for fluid displacement in SPE/DOE
Enhanced Oil Recovery Symposium
[15] Wu J and Prausnitz J M 1998 Phase equilibria for systems containing hydrocarbons, water, and
salt: An extended Peng− Robinson equation of state Ind. Eng. Chem. Res. 37 1634
[16] Cavenati S, Grande C A and Rodrigues A E 2006 Separation of CH4/CO2/N2 mixtures by layered
pressure swing adsorption for upgrade of natural gas Chem. Eng. Sci. 61 3893
[17] Davis J A, Rodewald N and Kurata N F 1962 Solid-liquid-vapor phase behavior of the
methane-carbon dioxide system American Inst. Chem. Eng. 8 537