Aspen Plus

Rate-Based Model of the CO2 Capture Process by

NaOH using Aspen Plus
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Revision History
Version Description

V7.0 First version.

V7.1 Re-verified simulation results using Aspen Plus V7.1.
V7.1 CP1 Add CO and H2 to the model as Henry components.
V7.2 Updated results for V7.2
V7.3 Update databank to PURE25.
Add the definition of acid gas loading and Na2CO3 weight fraction
convention.
V7.3.2 Update databank to PURE26.
V8.0 Update databank to PURE27.
V8.2 Update databank to PURE28.
V8.6 Update databank to PURE32.

Revision History 1
Contents
Introduction ............................................................................................................3

1 Components .........................................................................................................4

2 Process Description..............................................................................................5

3 Physical Properties...............................................................................................6

4 Reactions ...........................................................................................................11

5 Simulation Approach ..........................................................................................13

6 Simulation Results .............................................................................................15

7 Conclusions ........................................................................................................17

References ............................................................................................................18

2 Contents
Introduction

This document describes an Aspen Plus rate-based model of the CO2 capture
process by NaOH (sodium hydroxide) from a gas mixture of N2, O2, H2O, and
CO2. The model consists of an absorber. The operation data from a pilot
plant[1] were used to specify feed conditions and unit operation block
specifications in the model. The reaction kinetic models are based on the
works of Pinsent et al. (1956)[2]. The thermophysical property model and
transport property models and model parameters have been validated against
experimental data from open literature.
The model presented here includes the following key features:
 True species including ions
 Electrolyte NRTL method for liquid phase properties and RK equation of
state for vapor phase properties
 Concentration-based reaction kinetics
 Electrolyte transport property models
 Rate-based models for absorber with packing

Introduction 3
1 Components

The following components represent the chemical species present in the

process:

Table 1. Components Used in the Model

ID Type Name Formula

H2O Conventional WATER H2O

CO2 Conventional CARBON-DIOXIDE CO2
NA2CO3 Conventional SODIUM-CARBONATE NA2CO3
H3O+ Conventional H3O+ H3O+
OH- Conventional OH- OH-
HCO3- Conventional HCO3- HCO3-
CO3-2 Conventional CO3-- CO3-2
NA+ Conventional NA+ NA+
NAOH Conventional SODIUM-HYDROXIDE NAOH
N2 Conventional NITROGEN N2
O2 Conventional OXYGEN O2
NAHCO3 Conventional SODIUM-BICARBONATE NAHCO3
CO Conventional CARBON-MONOXIDE CO
H2 Conventional HYDROGEN H2

4 1 Components
2 Process Description

The flowsheet for the pilot plant[1] for CO2 capture by NaOH includes an
absorber. Table 2 represents typical operation data:

Table 2. Data of the pilot plant

Absorber
Diameter 0.1 m
Packing Type and Size 0.5 inch ceramic Berl Saddles
Packing Height 6.6 m

Feeds and Products

Sour Gas to Absorber 0.495 kmol/hr

Lean NaOH solution to Absorber 106.0 l/hr
CO2 in Feed (Gas) 15.4(Vol %)
CO2 in Outlet (Gas) 0.0(Vol %)

2 Process Description 5
3 Physical Properties

The electrolyte NRTL method is used for computing liquid phase properties
while RK equation of state is used for computing vapor phase properties in
this Rate-based NaOH model. The electrolyte pair parameters in the
electrolyte NRTL model for (H2O, NaOH) were taken from the works of Aspen
Technology (1985)[3]; those for (H2O, Na2CO3) were regressed in this work
against vapor pressure data from Taylor (1955)[4] and osmotic coefficient data
from Khvorostin et al. (1975)[5] and Goldberg et al. (1981)[6] of the Na2CO3-
H2O system; and those for (H2O, NaHCO3) were also regressed in this work
against CO2 solubility data in Na2CO3-H2O system from Knuutila et al.
(2006)[7].
CO2, N2, CO, H2 and O2 are selected as Henry-components to which Henry’s
law is applied and the Henry’s constants are retrieved from Aspen Plus
databanks for these components with water. In the reactions calculations, the
activity coefficient basis for the Henry’s components is chosen to be Aqueous.
Therefore, in calculating the unsymmetric activity coefficients (GAMUS) of the
solutes, the infinite dilution activity coefficients will be calculated based on
infinite-dilution condition in pure water, instead of in mixed solvents.
The liquid molar volume model and transport property models have been
updated and model parameters regressed from literature experimental data.
Specifications of the transport property models include:
 For liquid molar volume, the Clarke model, called VAQCLK in Aspen Plus,
is used with option code of 1 to use the quadratic mixing rule for solvents.
The Aspen Plus built-in databank values for the Clarke model parameter
 
VLCLK/1 of some main electrolytes (Na+, OH ), (Na+, HCO 3 ) and (Na+,
2
CO 3 ) are used.
 For liquid viscosity, the Jones-Dole electrolyte correction model, called
MUL2JONS in Aspen Plus, is used with the mass fraction based ASPEN
liquid mixture viscosity model for the solvent. There are three models for
electrolyte correction and the NaOH model Breslau and Miller equation
instead of Jones and Dole equation when electrolyte concentration
exceeds 0.1. The three option codes for MUL2JONS are set to 1 (mixture
viscosity weighted by mass fraction), 0 (use Breslau and Miller equation
instead of Jones and Dole equation when electrolyte concentration
exceeds 0.1 M), and 2 (ASPEN liquid mixture viscosity model),
respectively. The electrolyte correction model parameters, IONMUB, for
HCO3- is regressed against KHCO3-H2O viscosity data from Palaty (1992)[8];

6 3 Physical Properties
 2
and that of CO 3 is regressed against K2CO3-H2O viscosity data from Pac et
al. (1984)[9]. For Na+, IONMOB and IONMUB were regressed against
viscosity data from Klochko et al. (1959)[10] and Vargaftik (1972)[11] of the
NaOH-H2O system. For the other ions, Aspen Plus built-in databank values
are used.
 For liquid surface tension, the Onsager-Samaras model, called SIG2ONSG
in Aspen Plus, is used with its option codes being -9 (exponent in mixing
rule) and 1 (electrolyte system), respectively.
 For thermal conductivity, the Riedel electrolyte correction model, called
KL2RDL in Aspen Plus, is used. The model parameter IONRDL for Na+,
CO3-2, and HCO3- was regressed in this work against data from Riedel
(1951)[12], Vargaftik et al. (1956)[13], Vargaftik (1972)[11] and Cederberg
(1965)[14], Chernen'kaya et al. (1973)[15], Chernen'kaya et al. (1972)[16].
 For binary diffusivity, the Nernst-Hartley model, called DL1NST in Aspen
Plus, is used with option code of 1 (mixture viscosity weighted by mass
fraction).
In addition to the updates with the above transport properties, the heat
2
capacity at infinite dilution (CPAQ0) for CO 3 and HCO3- are adjusted to keep
constant with the rate-based amines models, and that of Na+ was regressed
in this work against the heat capacity data from Puchkov et al. (1978)[17] and
Chernen'kaya (1971)[18] together with the vapor pressure data from Taylor
(1955)[4] and osmotic coefficient data from Khvorostin et al. (1975)[5] and
Goldberg et al. (1981)[6] of the Na2CO3-H2O system.
The estimation results of the transport and thermal properties are
summarized in Figures 1-6. Note that CO2 loading is defined as the ratio of
the moles of apparent acid gas to the moles of apparent Na2CO3. Apparent
means before reaction, so for example if 1 mole of Na2CO3 is added to 9
moles of water, and then 0.3 moles of CO2 is added to this mixture at
sufficient pressure to dissolve all the CO2, then the CO2 loading is 0.3/1 = 0.3,
regardless of the forms of CO2 and Na2CO3 after reacting. Weight percent of
Na2CO3 is calculated without CO2, so in the above example, it is calculated
from the mixture of 1 mole of Na2CO3 and 9 moles of water. Since Na2CO3 has
a molecular weight of 105.989 and water has a molecular weight of 18.015,
this is 105.989/(105.989+9*18.015) = 0.39530 or about 40 wt% Na2CO3.

3 Physical Properties 7
 1140
EXP 298.15K
1120 EST 298.15K
EXP 348.15K
1100
EST 348.15K
Density, kg/m3 1080

1060

1040

1020

1000

980
0 0.02 0.04 0.06 0.08 0.1 0.12
NaOH Mass Fraction

Figure 1. Liquid Density of NaOH-H2O, experimental data from Herrington et

al. (1986)[19]

10
EXP Klochko59 298.15K
EST 298.15K
EXP Klochko59 348.15K
EST 348.15K
1 EXP Klochko59 373.15K
EST 373.15K
EXP Vargaftik72 293.15K
EXP Vargaftik72 303.15K
Viscosity, PaS

0.1 EXP Vargaftik72 313.15K

0.01

0.001

0.0001
0 0.2 0.4 0.6 0.8
NaOH Mass Fraction

Figure 2. Liquid Viscosity of NaOH-H2O, experimental data from Klochko et al.

(1959)[10] and Vargaftik (1972)[11]

8 3 Physical Properties
 0.1

0.09

Surface Tension, N/m

0.08

0.07
EXP NAOH 5WT%
EST NAOH 5WT%
0.06 EXP NAOH 10WT%
EST NAOH 10WT%
EXP NAOH 15WT%
EST NAOH 15WT%
0.05
290 300 310 320 330 340 350
T, K

Figure 3. Surface Tension of NaOH-H2O, experimental data from Gel'perin et

al. (1969)[20]

0.9
Thermal COnductivity, Watt/m-K

0.8

0.7

0.6

0.5
0.4
EXP Riedel51 293.15K
0.3 EXP Vargaftik56 293.15K
0.2 EXP Vargaftik72 293.15K
EXP Cederberg65 293.15K
0.1 EST 293.15K

0
0 0.1 0.2 0.3 0.4 0.5 0.6
NaOH Mass Fraction

Figure 4. Liquid Thermal Conductivity of NaOH-H2O, experimental data Riedel

(1951)[12], Vargaftik et al. (1956)[13], Vargaftik (1972)[11] and Cederberg
(1965)[14]

3 Physical Properties 9
 6000

5000

H eat Capac ity , J /k g- K

4000

3000
EXP Conti88 325K EST 325K
EXP Conti88 373K EST 373K
2000
EXP Conti88 422K EST 422K
EXP Conti88 470K EST 470K
1000 EXP Conti88 521K EST 521K

0
0 0.01 0.02 0.03 0.04 0.05 0.06
NaO H Mas s F r ac tion

Figure 5. Liquid Heat Capacity of NaOH-H2O at 1atm, experimental data from

Conti et al. (1988)[21]

100

10
P CO2, kPa

0.1
EXP 80C EXP 60C
EXP 40C EST 80C
EST 60C EST 40C
0.01
0.1 1
CO2 loading

Figure 6. CO2 partial pressure of Na2CO3-CO2-H2O (Na2CO3 mass fraction =

0.08), experimental data from Knuutila et al. (2006)[7]

10 3 Physical Properties
4 Reactions

The electrolyte solution chemistry has been modeled with a CHEMISTRY

model with the CHEMISTRY ID = CAUSTIC. This CHEMISTRY ID is used as the
global electrolyte calculation option in the simulation by specifying it on the
Global sheet of the Properties | Specifications form. Chemical equilibrium
is assumed with all the ionic reactions in CHEMISTRY CAUSTIC. In addition, a
kinetic REACTION model called CAUST-R has been created, which is used in
calculations of the absorber by specifying it in the Reaction part of the
absorber specifications. In CAUST-R, all reactions are assumed to be in
chemical equilibrium except the reactions of CO2 with OH-.

A. Chemistry ID: CAUSTIC

1 Equilibrium
CO 2  2H 2 O  H 3 O   HCO 3

2 Equilibrium
HCO 3  H 2 O  H 3 O   CO 32

3 Equilibrium 2H 2 O  H 3 O   OH 
4 Dissociation NaOH  Na   OH 
5 Dissociation Na 2 CO 3  2Na   CO 32
6 Dissociation NaHCO 3  Na   HCO 32

B. Reaction ID: CAUST-R

1 Equilibrium 2H 2 O  H 3 O   OH 
2 Equilibrium HCO 3  H 2 O  H 3 O   CO 32
3 Kinetic CO 2  OH   HCO 3
4 Kinetic HCO 3  CO 2  OH 
The equilibrium expressions for the reactions are taken from the work of
Aspen Technology (1985)[3]. The power law expressions are used for the rate-
controlled reactions (reactions 3-4 in CAUST-R) and the general power law
expression is:

4 Reactions 11
   E  1 1  N
r  k T T0  exp     C i i
n a
(1)
 R  T T0  i 1
Where:
r = Rate of reaction;
k = Pre-exponential factor;
T = Absolute temperature;
T0 = Reference temperature;
n = Temperature exponent;
E = Activation energy;
R = Universal gas constant;
N = Number of components in the reaction;
Ci = Concentration of component i;
ai = The stoichiometric coefficient of component i in the reaction equation.
If T0 is not specified, the reduced power law expression is used:

E N
r  kT n exp (  ) C i i
a
(2)
RT i 1
In this simulaiton, the reduced expressions are used. In equation (2), the
concentration basis is Molarity, the factor n is zero, k and E are given in
Table 3. The kinetic parameters for reaction 3 are taken from the work of
Pinsent et al. (1956)[3], and the kinetic parameters for reaction 4 are
calculated by using the kinetic parameters of reaction 3 and the equilibrium
constants of the reversible reactions 3 and 4.

Table 3. Parameters k and E in Equation (2)

Reaction No. k E (cal/mol)
2 4.32e+13 13249
3 2.83e+17 29451

12 4 Reactions
5 Simulation Approach

Case 12 for the absorber of the pilot plant[1] for CO2 capture by NaOH are
used in this study.
Simulation Flowsheet – The pilot plant has been modeled with the following
simulation flowsheet in Aspen Plus, shown in Figure 7.

GASOU T

LEANIN

ABSORBER

GASIN

R IC HOUT

Figure 7. Rate-Based NaOH Simulation Flowsheet in Aspen Plus

5 Simulation Approach 13
 Unit Operations - Major unit operations in this model have been represented
by Aspen Plus Blocks as outlined in Table 4.

Table 4. Aspen Plus Unit Operation Blocks Used in the

Rate-Based NaOH Model
Unit Operation Aspen Plus Block Comments / Specifications

Absorber RadFrac 1. Calculation type: Rate-Based

2. 18 Stages
3. Top Pressure: 101.15 kPa
4. Reaction condition factor: 0.9
5. Film discretization ratio: 5
6. Reaction: Reaction ID is CAUST-R for all stages; when
calculation type is equilibrium stages, Liquid Holdup is used,
and in this file, the Liquid Holdup = 0.0003 cum
7. Packing Type: GENERIC, 0.5-IN, CERAMIC, BERL
8. Packing height: 6.6 m and Section diameter: 0.1m
9. Mass transfer coefficient method: Onda et al (1968)
10. Interfacial area method: Onda et al (1968)
11. Interfacial area factor: 2
12. Heat transfer coefficient method: Chilton and Colburn
13. Holdup correlation: Stichlmair et al. (1989)
14. Film resistance options: Discrxn for liquid film, and Film
for vapor film
15. Additional discretization points for liquid film: 5
16. Flow model: Mixed

Streams - Feeds to the absorber are gas stream GASIN containing N2, O2,
H2O, and CO2 and liquid solvent stream LEANIN containing aqueous NaOH
solution. Feed conditions are summarized in Table 5.

Table 5. Feed specifications

Stream ID GASIN LEANIN
Substream: MIXED
Temperature: C 20 21
Pressure: kPa 103.15 103.15
Total flow 0.138 mol/sec 0.106 cum/hr
Mole-Frac Mole-Conc
H2O 0.03
CO2 0.155
NAOH 0 1.9 kmol/cum
N2 0.65
O2 0.165

14 5 Simulation Approach
6 Simulation Results

The simulation was performed using Aspen Plus. The measured versus
calculated absorber liquid temperature and concentration profiles are
presented in Figures 8-10.

45

Experimental
40
Rate-Based NaOH Model
35
Temperature, C

30

25

20

15
0 2 4 6 8
Distance from top, m

Figure 8. The Absorber Temperature Profile

6 Simulation Results 15
 0.2
Experimental

CO2 concentration, mole fraction

0.16 Rate-Based NaOH Model

0.12

0.08

0.04

0
0 2 4 6 8
Distance from top, m

Figure 9. The Absorber CO2 Concentration Profiles in Vapor Phase

2
OH- conncentration, mol/l

1.6

1.2

0.8

Experimental
0.4
Rate-Based NaOH Model

0
0 2 4 6 8
Distance from top, m

Figure 10. The Absorber OH- Concentration Profiles in Liquid Phase

16 6 Simulation Results
7 Conclusions

The Rate-Based NaOH model provides a rate-based rigorous simulation of the

process. Key features of this rigorous simulation include electrolyte
thermodynamics and solution chemistry, reaction kinetics for the liquid phase
reactions, rigorous transport property modeling, rate-based multi-stage
simulation with Aspen Rate-Based Distillation which incorporates heat and
mass transfer correlations accounting for columns specifics and hydraulics.
The model is meant to be used as a guide for modeling the CO2 capture
process with NaOH. You may use it as a starting point for more sophisticated
models for process development, debottlenecking, plant and equipment
design, among others.

7 Conclusions 17
References

[1] R. Thiele, R. Faber, J.-U. Repke. “Design of Industrial Reactive Absorption

Processes in Sour Gas Treatment Using Rigorous Modelling and Accurate
Experimentation”, Chemical Engineering Research and Design, 85, 74-
85(2007)
[2] B.R. Pinsent, L. Pearson, F.J.W. Roughton, “The Kinetics of Combination of
Carbon Dioxide with Hydroxide Ions”, Trans. Faraday Soc., 52, 1512-1520
(1956)
[3] Aspen Technology, (1985)
[4] C.E. Taylor, “Thermodynamics of Sodium Carbonate in Solution”, J. Phys.
Chem., 59, 653-657(1955)
[5] Khvorostin, S. Yu., V.K. Filippov, L.I. Reshetova, “Isopiestic determination
of the activity coefficients of sodium carbonate solutions at 25 C”, Russ. J.
Phys. Chem., 49, 5, 743-744(1975)
[6] R.N. Goldberg, “Evaluated Activity and Osmotic Coefficients for Aqueous
Solutions: Thirty-Six Uni-Bivalent Electrolytes”, J. Phys. Chem. Ref. Data, 10,
671-764(1981)
[7] H. Knuutila, M. Anttila, E. Børresen, O. Juliussen, H.F. Svendsen, “CO2
capture with sodium carbonate”, paper presented at the 8th International
Conference on Greenhouse Gas Control Technologies, Trondheim, Norway,
19-22 June 2006
[8] Z. Palaty, “Viscosity of diluted aqueous K2CO3/KHCO3 solutions”, Collect.
Czech. Chem. Commun., 57, 1879(1992)
[9] J.S. Pac, I.N. Maksimova, L.V. Glushenko, “Viscosity of Alkali Salt
Solutions and Comparative Calculation Method”, J. Appl. Chem. USSR., 57,
846(1984)
[10] M.A. Klochko, M.M. Godneva, “Electrical conductivity and viscosity of
aqueous solutions of NaOH and KOH”, Russ. J. Inorg. Chem., 4, 964-
968(1959)
[11] N.B. Vargaftik, “Dictionary of Thermophysical Properties of Gases and
Liquids”, Moskva, (1972)
[12] L. Riedel, "The Thermal Conductivity of Aqueous Solutions of Strong
Electrolytes", Chem. Ing. Tech., 23, 59-64(1951)

18 References
 [13] N.B. Vargaftik, Y.P. Os'minin, "Thermal Conductivity of Aqueous
Solutions of Salts, Acids and Alkalis", Teploenergetika, 3, 11-15(1956)
[14] N.V. Cederberg (Ed.), "Thermal Conductivity of Gases and Liquids. X.
Thermal Conductivity of Aqueous Electrolyte Solutions", Edward Arnold;
London Pub., 223-233(1965)
[15] E.I. Chernen'kaya, G.A. Vernigora, "Experimental Determination and
Calculation of Thermal Conductivity of Liquors of the Ammonia-Soda Process",
J. Appl. Chem. USSR, 46, 1306-1309(1973)
[16] E.I. Chernen'kaya, G.A. Vernigora, “Experimental Determination of
Thermal Conductivities of Aqueous Solutions of Salts and Ammonia at 25 and
50 C”, J. Appl. Chem. USSR, 45, 1779-1782(1972)
[17] L.V. Puchkov, R.P. Matveeva, I.S. Dankova, “Heat capacity of aqueous
solutions of lithium, sodium, and potassium sulfate and of sodium and
potassium carbonate at temperatures up to 350 C”, Deposited Doc. 1978
NIITEKHIM N1716/78 dep. 14 pp. Avail. CHEMIE BERLIN, 14(1978)
[18] E.I. Chernen'kaya, “Experimental Determination of the Specific Heats of
Aqueous Solutions of NH4HCO3, NaHCO3, Na2CO3, NH3, and of Liquors of
the Soda Industry at 25 C”, J. Appl. Chem. USSR, 44, 1562-1566(1971)
[19] N.M. Herrington, A.D. Pethybridge, M.G. Roffey, “Densities of Aqueous
Lithium, Sodium, and Potassium Hydroxides From 25 to 75 C at 1 Atm”, J.
Chem. Eng. Data, 31, 31-34(1986)
[20] N.I. Gel'perin, B.M. Gurovich, K.K. Dubinchik, “The Relation between the
Surface Tension of Aqueous Solutions of Inorganic Substances and
Concentration and Temperature”, J. Appl. Chem. USSR, 42, 190-192(1969)
[21] G. Conti, P. Gianni, A. Papini, E. Matteoli, “Apparent Molar Heat Capacity
and Relative Enthalpy of Aqueous NaOH between 323 and 523 K”, J. Solution
Chem., 17, 487-491(1988)

References 19