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International Journal of Chemical and Environ mental Engineering
Abstrac t
Carbon dioxide content in natural gas can cause corrosion and environmental issues. M ost natural gas reserves in M alaysia contain 50
to 74 mol% of CO 2 . However, the capability of most existing acid gas treatment systems is limited to treat natural gas with CO2
content of 30 to 40 mol%. The purpose of this paper is to present preliminary study on the potential of an off-shore application of an
adsorption system using aminated resin to capture CO2 at the natural gas reserves. This system is intended to reduce the CO2 content
down to the capability of existing acid gas treatment. The flowsheet simulation based approach implemented in PETRONAS’ iCON
and HYSYS process simulators is used to study the effect of temperature, pressure, adsorbent concentration and flow rate on the CO 2
removal performance using the proposed system. For the assumed CO2 content of 70 mol% in the natural gas from reserves, the
developed iCON and HYSYS models predict reduction to 11.8 mol% and 14 mol% of CO 2 in the treated gas stream, respectively. The
preliminary economic study indicates positive economic potential. Thus, the results showed that the aminated resin can be used for
effective and efficient CO 2 removal process using the proposed off-shore system from the natural gas stream.
Reflux Makeup
Aminated resin-water water
mixture Regeneration Regenerator
Adsorber
feed
Reboiler.Q
Sour Natural gas Flash vapor
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contaminants which might be accumu lated over some Hence, the generalized equation governing the
run times are assumed to be removed fro m the cycle by reaction mechanism of CO2 with the aminated resin can
filtration process as appropriate. be summarized as follo ws:
4. Chemical Reaction Analysis CO2 H 2O R MDEA R MDEAH HCO3
Aminated resin is an amine functionalized resin in
(3)
which the active sites on the resin are amines capable of
capturing CO2 . The amine group selected is where R represents the resin (Fig.3).
methyldethanolamine (M DEA) known for its bulk CO 2
removal capacity. The tertiary amine, MDEA, has two As H2 S is among the contaminant gases in natural gas,
ethanol groups attached to the nitrogen atom along with a it also undergoes reaction with the MDEA on the resin
methyl group [18]. Fig.3 illustrates the simp le structures instantaneously with infinite reaction rate. In this wo rk, its
of the aminated resin. concentration is assumed to be constant. The overall
Active sites reaction of H2 S with the MDEA is summarized as
HOCH2 CH2
.. N CH3
follows:
HOCH2CH2
Resin
H 2 S R MDEA R MDEAH HS (4)
HOCH2 CH2
.. N
The resulting anions from the overall reaction
CH3
HOCH2CH2
equations 3 and 4 i.e. HCO3 and HS , would give off
Fig.3. Simple structure of the Aminated Resin
CO2 and H2 S when heated, respectively [22].
Since the resin is functionalized 1.1.2
with
methyldethanolamine, the resin itself is considered as a 5. Process Simulation
simp le inert solid. Hence, the reaction mechanis m of CO2 In the simulat ion using iCON, the MDEA flu id
with the MDEA on the resin’s active sites is assumed to package that supports a simp le inert solid is used.
be similar to CO2 with liquid MDEA. The reaction Meanwhile, in HYSYS a generalized package for amines
mechanis m of CO2 with liquid MDEA is readily availab le called amine fluid package is used instead as the
in various literatures [19] and [20]. simu lator does not have a fluid package designed
Three overall react ions, given in equations 1-3 are explicit ly meant for MDEA.
assumed to occur during the adsorption process. MDEA is The concentration of MDEA assumed is 38 wt% as
a tertiary amine and does not have hydrogen atom the tertiary amine, MDEA , is found to be efficient and
attached to the nitrogen, thus the reaction with CO 2 can effective for CO2 removal between the concentration
only occur after the CO2 dissolves in the water to form a range of 20–50 wt% [23]. Another assumption made is
bicarbonate ion [21]. that the tray efficiency of the adsorption column is
CO2 H 2O HCO3 H assumed as 15% and 80% for CO2 and H2 S [24]
(1) respectively. This is because H2 S can instantly react with
MDEA, and CO2 reacts more slowly. The number of trays
The bicarbonate ion format ion is slow and only occurs for the adsorption column is assumed to be 20.
in the liquid phase [20]. The bicarbonate ion then The simulations of the system imp lemented in ICON
involves in an acid-base reaction with the amine to yield and HYSYS process simulators are given in Figs.4 and 5,
an overall CO2 adsorption reaction. respectively.
CO2 H 2O MDEA MDEAH HCO3 (2)
P-1 E-2
M-1
MDEA_TO_PUMP
MDEA_TO_COOL MAKEUP_WATER
MDEA_TO_RECY
ADSORBER FLASH_VAP
REGEN_BTTMS
ACID_GAS
MDEA_TO_FLASH_TK
Vlv-1 DISTILLATION_COLUMN
GAS_TO_CONTACTOR RICH_TO_REGEN
FLASH_TANK
RICH_MDEA
SOUR_GAS
SEPARATOR
BOTTOMS_LIQUIDS
Fig.4. Simulation model for the off-shore CO 2 removal system using iCON process simulator.
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Fig.5. Simulation model the off-shore CO 2 removal system using HYSYS process simulator.
Table 2. Material balance for the off-shore CO2 removal system using Icon process simulator
Table 3. Material balance for the off-shore CO2 removal system using HYSYS process simulator
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Based on simu lations, the concentration of CO2 in
the treated natural gas stream labeled as “sweet gas” in 0.35
130.00, 0.24
most important parameters for the design of CO2 removal MDEA-resin Tem perature [F]
dimensional search i.e. not identify ing the best Fig.7 shows the acid gas concentration in the sweet gas
performance with respect to all parameters in relation to the MDEA-resin temperature at 38 wt%
simu ltaneously. MDEA. Based on Fig.7, belo w 130 ºF, the increase in
temperature enhances CO2 removal in the system. This is
6.1 Effect of Resin Flow Rate because high temperature improves the reaction kinetics
Fig.6 compares the CO2 removal performance for the to a greater extent and less viscosity i.e. higher
system at different adsorbent concentration of 38 wt% diffusivity. However, beyond 130 ºF, the decrease in
MDEA and 48 wt% MDEA when increasing the MDEA solubility of the CO2 becomes the overriding factor
flow rate. A similar trend to Fig.6 was also reported [12]: leading to less CO2 removal. A similar trend is also
when the circulation rate is increased for any given reported in the work by [24] and [26]. Based on the trend
column, the CO2 adsorption increases in a column of plotted in Fig.7 it can be concluded that the system
fixed diameter. Another observation is that high removes the highest amount of CO2 at 130 ºF.
concentration of MDEA favors the CO2 removal in the 6.3 Effect of Sour Gas Pressure
developed unit. The higher the quantity of reactive amine Fig.8 illustrates that both simulat ion models generate
present, the higher the quantity of CO2 removed. similar trends of sour gas pressure effect on CO2 removal.
Up to 1500 kPa, the increase in pressure shows
insignificant effect on the CO2 adsorption capacity of the
aminated resin. That is because the CO2 reaction is driven
by kinetics and it is less affected by lowered pressure.
However, Fig.8 indicates that high pressure, more than
CO2 mass fraction in Sweet Gas
0.26
4500 kPa, enhances CO2 removal. This can be exp lained
38 wt% MDEA
48 wt% MDEA
as with the increase of pressure carbon dio xide seems to
0.24
485.00, 0.24
interact stronger with the adsorbent [1].
485.00, 0.22
605.00, 0.22
0.22
765.00, 0.21 0.26
CO2 Mass Fraction in Sweet Gas
605.00, 0.21
765.00, 0.21
Using ICON
0.2 1150.00, 0.24 1900.00, 0.25
Using HYSYS
400 500 600 700 800
0.24
MDEA-resin flow rate [m 3/hr]
1100.00, 0.20
0.2
0 1000 2000 3000 4000 5000 6000 7000 8000
Fig.8. Effect of the sour natural gas pressure on CO2 amount at 38 wt%
MDEA using HYSYS and ICON process simulators (T = 30ºC)
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Deviation analysis for results for the effect of pressure results
was performed using equations 5, 6 and 7 [27]. Table 4
shows the detail of the calculat ion. MDEA- Simulator
2 Resin converged Simulation did not
N x
iCON x HYSYS circulation converge for various
RSS
rate
i 1
tries
xiCON
(5) 7. Preliminary Cost Analysis
RSS A preliminary cost analysis is performed to evaluate
MRSS economic potential level 1 of the system, given in
N
(6) equation 8.
Economic Potential 1 = Profit fro m Product – Cost of
Mean error MRSS
Reactant
(7) (8)
The calculation is performed based on the basis given
Table 4. Deviation between the results in Table 6. The price of the aminated resin is assumed to
D P CO2 (wt %) Deviation be 40 % and 16 % h igher than the price of the solvent
ata MDEA and a resin [28] and [29], respectively (Table 6).
(kP in treated gas
P a) A total of 330 operational days in a year is considered to
oint HYS IC RS M Mean obtain the estimate for the economic potential level 1.
YS ON S RSS error
1 100 0.24 0.2 Table 6. Price of Raw materials and products
05 Material Price Amount Total price
0.1 0.0 0.187 consumed/ ($ per year)
2 130 0.24 0.2 05 35 produced
0 06 (m3 /hr)
3 190 0.25 0.2 Aminated $0.70 per
0 11 resin lb* 273
26,872,673
Water
Table 5. Observation on simulators performance during parametric The economic potential is calculated to RM
study 697,959,485 per year. The positive value indicates the
economic v iability of the off-shore CO2 removal system.
Simulator
Parameter HYSYS ICON 8. Conclusion
Fluid Amine MDEA
package fluid package fluid package In this paper the use of MDEA functionalized resin
Pressure Simulator based CO2 removal system for off-shore application was
converged for each Simulator converged investigated according to the two simulation models
∆P attempted and for each ∆P
produced consistent attempted
created using iCON and HYSYS process simu lators. The
results features and capabilit ies of the simulat ion softwares are
However, also reported. From the simulat ion conducted, it was
the simulator did not observed that the increase in temperature of the MDEA -
converge for
P > 2000 kPa
resin of 38 wt% up to 130 °F enhances the CO2 removal
Temperat Simulator and the 130 °F is spotted being the best operating
ure converged for each Simulator did not condition. Moreover, introducing the sour gas at a
∆T attempted and converge for various pressure higher than 4.5 MPa is identified to bring better
produced consistent ∆T attempted performance to the system. Needless to say, the increase
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in flo w rate of the MDEA-resin imp roved the CO2 [13] S.A. Al-Sobhi, H.E. Alfadala and M.M. El-Halwagi. "Simulation
and energy integration of a Liquefied Natural Gas (LNG) plant," in
removal performance of the unit as the quantity of
Proceedings of the 1st Annual Gas Processing Symposium. 10-12
reactive amine present for CO2 removal is high. Hence, Jan, 2009, Qatar.
we concluded that the use of MDEA functionalized resin
is effective and economical for CO2 removal for off-shore [14] J.M. Douglas, "Conceptual design of chemical processes," New
York, McGraw-Hill, 1988.
application where the resin allows the amine to withs tand
high pressure. The work can further be improved by [15] Uniongas,
considering heat integration to make the system more http://www.uniongas.com/aboutus/aboutng/composition.asp, 2010
energy efficient.
[16] N.H. Darman and A.R.B. Harun, "Technical challenges and
solution on natural gas development in Malaysia, " in Proceedings
ACKNOWLEDGMENT of The Petroleum Policy and Management (PPM) Project - 4 th
Workshop of the China- Sichuan Basin Case Study, 30 May – 3
The authors are thankful to Universit i Teknologi June, 2006, China.
PETRONAS for providing research facilit ies to
accomplish the task. [17] H. Randy, "Contaminants in amine gas treating," GPA Houston
Regional Meeting, 2001. www.reclaim.com
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