Proceedings of the 6th International Conference on Process Systems Engineering (PSE ASIA)

25 - 27 June 2013, Kuala Lumpur.

Rate-based simulation of DEA promoted potassium

carbonate process
Tohid Nejad Ghaffar Borhani, Vahid Akbari, Mohd. Kamaruddin Abd. Hamid,
Zainuddin Abdul Manan*

Process Systems Engineering Center (PROSPECT), Faculty of Chemical Engineering,

Universiti Teknologi Malaysia, 81310 UTM Johor Bahru, Johor, Malaysia.

Abstract
An industrial diethanolamine (DEA) promoted hot potassium carbonate process was
simulated and validated against the industrial data from literature. By implementing the
industrial data the absorber unit of CO2 capturing using hot potassium carbonate
solution promoted by DEA, was simulated using rate based approach in Aspen Plus.
Acceptable agreements between simulation and the measured industrial data have been
interpreted. Further, the sensitivity analysis and finding the optimal operation points
were performed using the rate based model.

Keywords: CO2 capturing, potassium carbonate process, rate-based modeling,

sensitivity analysis, optimal operation points.

1. Introduction
Among the processes for CO2 capturing, the amine promoted hot carbonate process is
appropriate in economical and efficiency aspects. The Benfield process has been applied
in more than 700 plants worldwide for carbon dioxide and hydrogen sulfide removal
from streams like ammonia synthesis gas, crude hydrogen, natural gas, and town gas
(Kohl and Nielson, 1997). CO2 absorption process has been subject of some studies
using commercial softwares such as Aspen software. Hilliard used the Electrolyte
Nonrandom Two Liquid (NRTL) Activity Coefficient model within Aspen Plus to
develop a rigorous thermodynamic representation of an aqueous piperazine (PZ) and
potassium carbonate (K2CO3) mixed solvent electrolyte system for the application of
carbon dioxide (CO2) absorption/stripping from power plant flue gas (Hilliard, 2004).
Zhang and co-workers simulated the CO2 capture with MEA solution by rate based
modeling using the Aspen Plus. They illustrated that the rate-based model provides
excellent predictive capability and it should be very useful for design and scale up of
CO2 capture processes (Zhang et al., 2009). Niu and co-workers, on the other hand,
performed a rate-based simulation of CO2 absorption with aqueous ammonia solutions
and compared the results with experimental data of a pilot plant at laboratory scale (Niu
et al., 2012).
Using today's technology the separation models are generally based upon two
approaches: the equilibrium stage model and the non equilibrium (Rated based) stage
model. In the equilibrium stage model, vapor and liquid are assumed to enter a tray or
cross section of packing in a column, exchange matter and energy and leave in
equilibrium with each other and thermodynamic equilibrium is assumed to exist
between the vapor and liquid streams leaving each stage (Seader et al., 2010). In fact,
distillation and absorption are, by their nature, non-equilibrium processes: mass and
2 T.N.G Borhani et al

energy are transferred across the fluid interface at rates which depend upon the extent to
which the phases are NOT in equilibrium with each other. Historically, this departure
from equilibrium conditions has led to the use of efficiencies (for Tray columns) and the
Height Equivalent to a Theoretical Plate (HETP) (for packed columns).
In this study the experimental data provides the validity of rate-based modeling of CO2
capture process by hot promoted carbonate process. Finally sensitivity analysis and
optimizing the operating condition of Benfield process has been studied in this research.

2. Methodology
2.1. Process simulation
For process simulation in this study the Aspen Plus was used. To build the process flow
diagram, the composition of streams, and a proper thermodynamic model are needed.
The characteristics of column, natural gas stream, and potassium carbonate solution are
illustrated in Table 1.
Table 1: Characteristics of natural gas stream, potassium carbonate solution, and column
(Rahimpour and Kashkooli, 2004).
Name Sour Gas Lean Solution Column Chractristics
Temperature (K) 388.20000 401 Diameter (meter): 4
Total Molar Flow (kmol/hr) 8459 46259.60000 Number of trays: 13
Mole fraction of CO2 0.17150 0 Type of contactor: Glitsch Ballast
Mole fraction of CH4 0.00187 0 Weir height (mm): 60
Mole fraction of CO 0.00376 0 Column Pressure (kPa): 6000
Mole fraction of H2 0.57510 0 Flow Model: Mixed
Mole fraction of N2 0.18590 0 Calculation type: Rate-Based
Mole fraction of Ar 0.00217 0
Mole fraction of H2O 0.05970 0.92943
Mole fraction of K2CO3 0 0.03663
Mole fraction of KHCO3 0 0.02527
Mole fraction of DEA 0 0.00722
Mole fraction of KVO3 0 0.00145

2.2. Process chemistry

In a reactive absorption process, the effects of reactions on mass transfer should be
accounted for and there are differences between mass transfer coefficients in the
presence and absence of chemical reactions. Then, at first for solution containing
K2CO3, DEA, H2O, and CO2, one CHEMISTRY model with chemical equilibrium
relations is assumed with all the ionic reactions and this CHEMISTRY model is used as
a global electrolyte calculation option in the simulation. In addition, for the K2CO3,
DEA, H2O, and CO2 solution a REACTION model has been created, which is used in
calculations of the absorber by specifying it in the reaction section of the absorber
column (Table 2).
It should be noted that often in potassium carbonate solutions vanadium salts are used
as corrosion inhibitors. As V2O5 converts to KVO3, the KVO3 was used in the
component list of Aspen Plus. The chemical equilibrium expression for the chemical
equilibrium reactions is as follow.
ln = + + ln +
(1)
( )

Where the parameters A, B, C, and D are extracted from various literature (Austgen,
1989, Austgen et al., 1991). For the kinetic reactions the reaction rate expressions was
considered as power law form:
1 1 (2)
= exp − −
Rate-based simulation of DEA promoted potassium carbonate process 3

Where r is the rate of reaction, k pre-exponential factor, T absolute temperature, E

activation energy, R gas low constant. In this equation the concentration basis is
Molarity. The k and E were derived from the various works (Pinsent et al., 1956, Rinker
et al., 1996).
Table 2: Reaction models for K2CO3-DEA-H2O-CO2 system
CHEMISTRY model Reaction Type Reaction No.
CO + 2H O HCO + H O Equilibrium (R.1)
HCO + H O CO + H O Equilibrium (R.2)
2H O OH + H O Equilibrium (R.3)
K CO → 2K + CO Dissociation (R.4)
KHCO → K + HCO Dissociation (R.5)
DEAH + H O DEA + H O Equilibrium (R.6)
DEACOO + H O DEA + HCO Equilibrium (R.7)
REACTION model
HCO + H O CO + H O Equilibrium (R.2)
2H O OH + H O Equilibrium (R.3)
DEAH + H O DEA + H O Equilibrium (R.6)
CO + OH → HCO Kinetic (R.8)
HCO → CO + OH Kinetic (R.9)
DEA + CO + H O → DEACOO + H O Kinetic (R.10)
DEACOO + H O → DEA + CO + H O Kinetic (R.11)

2.3. Process thermodynamic and physical property models

In this work the ELECNRTL thermodynamic model was used for liquid phase and SRK
has been considered for gas phase. CO2, CH4, CO, H2, N2, and Ar are selected as Henry-
components. The Henry s constants are retrieved from the Aspen Plus databanks for
these components with water. The required Henry s constants and NRTL parameters for
CO2 with H2O, regressed against the binary VLE data of Takenouchi et al. (Takenouchi
and Kennedy, 1964), Tödheide et al. (Tödheide and Franck, 1963), Dodds et al. (Dodds
et al., 1956), Drummond et al. (Drummond, 1981), Zawisza et al. (Zawisza and
Malesiska, 1981), Wiebe et al. (Wiebe and Gaddy, 1940) and Houghton et al.
(Houghton et al., 1957). For CO2 with DEA, regressed against CO2 solubility data from
Maddox et al. (Maddox, 1987, Maddox and Elizondo, 1989). The column
hydrodynamics are considered using appropriate hold up correlations, interfacial area
relations, pressure drop equations, and mass transfer coefficients (Aspen Technology,
2001a).
2.4. Process optimal operating analysis
In order to perform the optimization, the first step is the sensitivity analysis. In fact, an
effective method to optimize and adjust an operational condition in an operating process
is to evaluate the performance indexes of the unit during the changing of operational
conditions. The sensitivity analysis was performed in these sequences. At first the
controllable or decision variables should be determined. In addition the most important
operational conditions of the process which might be changed during the production
(manipulated variables or operation parameters) must be identified. Then by altering
each of the manipulated variables the behaviour of process indexes can be observed
(Aspen Technology, 2001b).

3. Results and discussion

3.1. Simulation results
The simulation results for Potassium carbonate promoted by DEA are shown in Table 3.
As can be seen the simulated and experimental data of the treated gas which leave the
4 T.N.G Borhani et al

top of the absorber are compared to each other. Small differences between calculated
and industrial data are observed and the experimental data provides the verification of
rate-based Benfield process. Rahmipour and Kashkooli used the simple model presented
by Astrita et al. (Astarita et al., 1983) while in the present work the Electrolyte NRTL
model was used where showed the better results.
Table 3: Comparison of simulated results of Aspen model with experimental data and calculated
results in the work of Rahimpour and Kashkooli (Rahimpour and Kashkooli, 2004).
Stream name Treated Gas Experimental Treated Gas calculated by Treated Gas
data in the work of Rahimpour and Kashkooli simulated in this
Rahimpour and Kashkooli work
Temperature (K) 343.2 357.2 354.6
Mole Flow (kmol/hr) 6660 6576.60 6545.91
Mole Fraction
CO2 0.00197 0.00199 0.00198
CH4 0.00241 0.00241 0.00241
CO 0.00483 0.00484 0.00479
H2 0.73910 0.73964 0.74119
N2 0.23850 0.23910 0.24029
Ar 0.00285 0.00288 0.00283
H2O 0.01081 0.01002 0.00989

Fig. 1 shows the temperature profile of gas and liquid along the column. As can be seen
the temperature is reached to a maximum and then decrease. By flowing down the
liquid through the column, the acid gas is absorbed continually. This absorption is
accompanied by a heat of reaction, which cause the liquid to continue to rise. The
temperature drop at the bottom of the column results from the colder gas entering the
bottom and contacting the hot liquid flowing downwards.

Fig.1: Temperature profile of the liquid and Fig.2: The effect of column pressure on the
gas vs. stage number in the hot carbonate process CO2 amount in treated gas.
promoted by DEA.
As in this study the aim is to separate CO2 from natural gas, one would like to find how
the CO2 amount in treated gas would vary if the operating conditions of the system were
to change from its design value. The effect of the column pressure on the CO 2 amount
in treated gas is shown in Fig. 2.
3.2. Optimal operating results
The CO2 and H2O values in treated gas were selected as decision variables. It was found
that the system is sensitive to the mole flow of DEA in lean solution, temperatures of
natural gas stream and lean liquid. Thus, these variables were considered as manipulated
variables.
3.2.1. Optimal concentrations
Effects of DEA amount in lean solution on CO2 and H2O mole fraction in treated gas is
illustrated in Fig. 3. It can be seen that the concentration of DEA in potassium carbonate
solution plays an important role on the CO2 removal from natural gas stream. With
increasing the DEA amount in lean solution, the CO2 mole fraction in treated gas
Rate-based simulation of DEA promoted potassium carbonate process 5

decrease continually and after DEA flow rate around 700 kmol/hr keeps a stable value.
The H2O shows strange and different behavior in the treated gas; it reaches to a
minimum amount in flow rate 648 kmol/hr and then increases moderately. Thus, when
the DEA flow rate of lean solution is 600-800 kmol/hr, the CO2 and H2O amounts in
treated gas reaches to their lowest value. By increasing DEA mole flow, the temperature
of rich solution increases sharply.

Fig.3: Effects of DEA mole flow in lean solution on CO2 and H2O mole fraction in treated gas.
3.2.2. Optimal temperature
In potassium carbonate process, temperature is a significant parameter which has effect
on reaction kinetics, heat, mass, and diffusion rates. Effects of the gas and liquid
temperatures on CO2 and H2O amount in treated gas is demonstrated in Fig. 4. As
shown in the figure, when the temperature of natural gas stream increases the CO 2 and
H2O values in treated gas grow rapidly. From these results it can be realized that the
inlet gas temperature should be small as possible which for the described system in this
study the gas temperature 360-380 K obtain acceptable CO2 removal. It can be seen that
CO2 reaches to the lowest value at the liquid temperature of 372 K. In addition in the
liquid temperature range 370 to 390 K the water mole fraction is reasonable.

Fig.4: Effects of the gas and liquid temperatures on CO2 and H2O amount in treated gas

4. Conclusions
A promoted potassium carbonate unit was simulated using a rate based rigorous model
in Aspen Plus software and required physical properties and parameters were regressed
against the experimental data from various literature. The results of simulation show the
acceptable agreement with the experimental data which is related to the strength of
Electrolyte NRTL model. CO2 mole fraction and temperature profiles along the stages
of the column were obtained. It was found that CO2 in treated gas decreases with
increasing the column pressure. Further, optimal operating analysis was carried out by
considering DEA and CO2 mole flows in lean solution and natural gas stream. When the
DEA flow rate of lean solution is 600-800 kmol/hr, the CO2 and H2O amounts in treated
gas reaches to their lowest value. In order to meet the specification in treated gas, the
CO2 flow rate in natural gas 1600-1800 kmol/hr is acceptable. About the optimal
6 T.N.G Borhani et al

temperature it was found that the gas temperature 360-380 K obtains acceptable CO2
capturing. When temperature of liquid solution is 370-390 K the CO2 and H2O amounts
in treated gas are desirable.

Acknowledgements

The authors would like to thank the MOHE (Ministry of Higher Education) of Malaysia
and UTM for providing the research fund under Vote No. Q.J13.2544.03H55

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