Aspen Plus

Rate-Based Model of the CO2 Capture Process by

PZ using Aspen Plus
Copyright (c) 2008-2014 by Aspen Technology, Inc. All rights reserved.

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This software includes NIST Standard Reference Database 103b: NIST Thermodata Engine Version 7.1

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Revision History
Version Description

V7.1 First version

V7.1 CP1 1. Add O2 , CO and H2 to the model as Henry components
2. Two corrections in the model:
(1) ID of the Henry Comp group: PZ-MEA (V7.1)  PZ(V7.1 CP1)
(2) VLQKIJ was missed in V7.1 and now it’s added
V7.2 Update Henry’s constant of CO 2 in H2 O by fitting VLE data of Takenouchi
(1964), Tödheide(1963), Dodds (1956), Drummond (1981), Zawisza
(1981), Wiebe (1940) and Houghton (1957).
Update NRTL parameters between PZ and H2 O by fitting VLE data of
Wilson (1994), Kamps (2003) and Hilliard (2008), and heat capacity
data of Hilliard (2008).
Determine DGAQFM, DHAQFM, CPAQ0 of PZH+, PZCOO- , PZ(COO- )2 and
HPZCOO by fitting VLE data of Ermatchkov (2006) and Hilliard (2008),
absorption heat data of Hilliard (2008) and heat capacity data of Hilliard
(2008) together with the interaction energy parameters between H 2 O
and (PZH+, HCO3 - ) and those between H2 O and (PZH+, PZCOO- ).
Update the figures for properties.
Calculate chemical equilibrium constants from Gibbs free energy,
Update kinetics.
Update Simulation results.
Update figure 3 for surface tension and update reference for PZ surface
tension data from Moerke (1982).
V7.3 Update databank to PURE25.
Add missing transport properties parameters in the bkp file to be
consistent with the documentation.
Add the definition of acid gas loading and amine weight fraction
convention.
Update Figure 3b.
V7.3.2 Update databank to PURE26.

Revision History 1
 Version Description

V8.0 Use ENRTL-RK method to replace ELECNRTL method; use PC-SAFT EOS
to model vapor-phase fugacity coefficient for its ability to model at high
pressure.
Treat HPZCOO as a zwitterion.
Update the PC-SAFT parameters, Antoine equation parameters and
DIPPR heat of vaporization parameters for PZ.
Update the NRTL parameters between PZ and H2 O, HPZCOO and H2 O,
H2 O and (PZH+, HCO3 - ), H2 O and (PZH+, PZCOO- ), H2 O and (PZH+,
PZ(COO-)2 ), H2 O and (PZH+, HS- ) and those between H2 S and (PZH+,
HS- ).
Update the DGAQFM, DHAQFM, CPAQ0 of PZH+, PZCOO- , PZ(COO- )2 and
HPZCOO.
Update the dielectric constants for PZ.
Update the DIPPR liquid density parameters for PZ and HPZCOO, the
interaction parameters, VLQKIJ, between PZ and H 2 O and those
between HPZCOO and H2 O, the Clark model parameters, VLCLK/1 for
(PZH+, HCO3 - ), (PZH+, PZCOO- ) and (PZH+, PZ(COO- )2 ).
Update the DIPPR liquid viscosity parameters for PZ, the interaction
parameters, MULIJ and MUKIJ, between PZ and H2 O and those between
HPZCOO and H2 O, the Jones-Dole parameters, IONMUB, for PZH+,
PZCOO- and PZ(COO- )2 .
Update the DIPPR liquid surface tension parameters for PZ.
Update the Henry’s constants of CO 2 and H2 S in H2 O and PZ.
Update figures for properties.
Update kinetics.
Update databank to PURE27.
V8.2 Update databank to PURE28.
V8.6 Update databank to PURE32.
V10.0 Update GMENCC parameters between CO 2 and (PZH+, PZCOO- ), CO2
and (PZH+, PZCOO-2 ), CO2 and (PZH+, HCO3 - ), and those between CO 2
and (PZH+, CO3 -2 ) to match the data of CO 2 activity coefficient.
Update simulation results.

2 Revision History
Contents
Revision History ......................................................................................................1

Contents..................................................................................................................3

Introduction ............................................................................................................4

1 Components .........................................................................................................5

2 Physical Properties...............................................................................................6

3 Reactions ...........................................................................................................13

4 Simulation Approach ..........................................................................................16

5 Simulation Results .............................................................................................18

6 Conclusions ........................................................................................................19

References ............................................................................................................20

Contents 3
Introduction

This file describes an Aspen Plus rate-based model of the CO2 capture process
by aqueous piperazine (PZ) solution. As there are no industrial or pilot plant
data publicly available for the CO2 capture process using aqueous PZ, a flash
model is used to test the feasibility of CO2 absorption from a gas stream
containing CO2 and N2 by PZ. Thermophysical property models and reaction
kinetic models are based on our recent work and those of Bishnoi and
Rochelle (2000, 2002) [1-2]. Transport property models and model parameters
have been validated against available experimental data from open literature.
The model includes the following key features:
 True species including ions
 Unsymmetric electrolyte NRTL method for liquid and PC-SAFT equation of
state for vapor
 Activity-based reaction kinetics
 Electrolyte transport property models

4 Introduction
1 Components

The following components represent the chemical species present in the

process:

Table 1. Components Used in the Model

ID Type Name Formula

PZ Conventional PIPERAZINE C4H10N2

H2O Conventional WATER H2O
CO2 Conventional CARBON-DIOXIDE CO2
H2S Conventional Hydrogen Sulfide H2S
H3O+ Conventional H3O+ H3O+
OH- Conventional OH- OH-
HCO3- Conventional HCO3- HCO3-
CO3-2 Conventional CO3-- CO3-2
PZH+ Conventional PZH+ C4H11N2+
PZH+2 Conventional PZH+2 C4H12N2+2
*HPZCOO Conventional HPZCOO C5H10NO2
PZCOO- Conventional PZCOO- C5H9N2O2-
PZCOO-2 Conventional PZCOO-2 C6H8N2O4-2
N2 Conventional NITROGEN N2
O2 Conventional OXYGEN O2
CO Conventional CARBON-MONOXIDE CO
H2 Conventional HYDROGEN H2

* HPZCOO is treated as a zwitterion: A zwitterion will be declared as

“Conventional” similar to solvents but is distinguished from solvents with a
value of unity for the parameter ZWITTER; all other components in Aspen
Plus default to zero for ZWITTER. The zwitterion interactions with other
molecular species are accounted for with NRTL binary interaction parameters.
The activity coefficient for the zwitterions is calculated as a molecular solute.
The contributions from the zwitterion to the solution enthalpy and Gibbs free
energy are calculated as molecular solutes using the aqueous phase Gibbs
free energy and heat of formation at infinite dilution and 25°C, DGAQFM and
DHAQFM, and the infinite dilution heat capacity, CPAQ0. PLXANT/1 is set
to -1E20 for zwitterions so that they are non-volatile.

1 Components 5
2 Physical Properties

The unsymmetric electrolyte NRTL method (ENRTL-RK) and PC-SAFT equation

of state are used to compute liquid and vapor properties, respectively, in this
rate-based PZ model. CO2, H2S, N2, O2, CO and H2 are selected as Henry-
components to which Henry’s law is applied. Henry’s constants are specified
for these components with water. In the reaction 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 Henry’s constant parameters of CO2 and H2S are obtained from the
literature (see Table 2). The other Henry’s constants are retrieved from the
Aspen Databank.

Table 2. Henry’s constants

Solute Solvent Source

CO2 H2 O Yan and Chen (2010) [3]

H2 S H2 O Zhang and Chen (1011) [4]
CO2 PZ Set to that of CO 2 in H2 O
H2 S PZ Set to that of H2 S in H2 O

The PC-SAFT parameters of PZ are regressed from the vapor pressure data [5-
7]
, liquid heat capacity data[6, 8] and liquid density data[7]. Those of H2O are
obtained from Gross and Sadowski (2002) [9], and those of the other
components are retrieved from the Aspen Databank.
The Antoine equation parameters of PZ are fitted to the vapor pressure data [5-
7]
. The DIPPR heat of vaporization parameters of PZ are determined from the
heat vaporization data generated from the PC-SAFT equation of state. The
ideal-gas heat capacity correlation parameters of PZ are retrieved from the
Aspen Databank.
The characteristic volume parameters of H 2O for the Brelvi-O’Connell Model,
VLBROC, are obtained from Brelvi and O’Connell (1972) [10], those of CO2 are
obtained from Yan and Chen (2010) [3], and those of PZ, H2S, N2, O2, CO and
H2 are defaulted to their critical volume in the Aspen Databank.

6 2 Physical Properties
 Unless specified otherwise, all molecule-molecule binary parameters and
electrolyte-electrolyte binary parameters are defaulted to zero. All molecule-
electrolyte binary parameters are defaulted to (8, -4), average values of the
parameters as reported for the electrolyte NRTL model [11]. The
nonrandomness is fixed at 0.2
The NRTL interaction parameters between PZ and H2O are determined from
the regression with binary VLE data[12] and heat capacity data[8, 12].
The interaction energy parameters between H 2O and (PZH+, HCO3-), H2O and
(PZH+, PZCOO-), and those parameters between H 2O and (PZH+, PZ(COO-)2),
GMELCC, and the NRTL interaction parameters between H 2O and HPZCOO,
are regressed using the VLE data[12, 13-16], heat of absorption data[12], heat
capacity data[12] and NMR speciation data[17] of the PZ-H2O-CO2 system and
the VLE data of the PZ-MDEA-H2O-CO2 system[18-21].
The interaction energy parameters between H 2O and (PZH+, HS-) and those
between H2S and (PZH+, HS-), GMENCC and GMENCD, are regressed with the
H2S solubility data in aqueous PZ solution [22-23].
The dielectric constants of nonaqueous solvents are calculated by the
following expression:

1 1
 T   A  B  (1)
T C 
The parameters A, B and C for PZ are set to 4.25, 1532 and 298.15.
The liquid molar volume model and transport property models have been
validated and model parameters regressed when literature experimental data
are available. Specifications of the transport property models include:
 For liquid molar volume, the Clarke model, called VAQCLK in Aspen Plus,
is used with option code 1 to use the quadratic mixing rule for solvents.
The DIPPR liquid density parameters for PZ are fitted to the liquid density
data of PZ[6], and those parameters for HPZCOO, the interaction
parameter VLQKIJ for the quadratic mixing rule between PZ and H2O, and
those between HPZCOO and H 2O, the Clark model parameters VLCLK/1 for
the main electrolytes (PZH +, HCO3-), (PZH+, PZCOO-) and (PZH+, PZ(COO-
)2) are also regressed against the experimental density data of PZ-H2O[24-
26]
and PZ-H2O-CO2[27].
 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 PZ model always uses the Jones-Dole
correction model. The three option codes for MUL2JONS are set to 1
(mixture viscosity weighted by mass fraction), 1 (always use Jones and
Dole equation when the parameters are available), and 2 (Aspen liquid
mixture viscosity model), respectively. The DIPPR liquid viscosity
parameters for PZ are fitted to the data retrieved from NIST Databank,
those parameters for HPZCOO, the interaction parameters in the ASPEN
liquid mixture viscosity model, MUKIJ and MULIJ, between PZ and H 2O and
those between HPZCOO and H 2O, the Jones-Dole parameters, IONMUB,
for PZH+, PZCOO- and PZ(COO-)2, are regressed against the viscosity data
of PZ-H2O[24-26] and PZ-H2O-CO2[27].

2 Physica l Prope rties 7

  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. The parameters of the
DIPPR liquid surface tension equation for PZ are regressed with the pure
PZ surface tension experimental data from Moerke and Roscher [28]. The
DIPPR liquid surface tension parameters for HPZCOO are set to those of
PZ.
 For thermal conductivity, the Riedel electrolyte correction model, called
KL2RDL in Aspen Plus, is used. The DIPPR parameters of liquid thermal
conductivity for HPZCOO are set to those of PZ.
 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 aqueous
phase Gibbs free energy and heat of formation at infinite dilution and 25°C
(DGAQFM and DHAQFM) of PZH+ are determined from the dissociation
constant of PZ [29], DGAQFM and DHAQFM of HPZCOO, PZCOO- and PZ(COO-)2,
and heat capacity at infinite dilution (CPAQ0) for PZH+, HPZCOO, PZCOO- and
PZ(COO-)2 are determined by fitting the CO2 absorption heat data[12], heat
capacity data[12], CO2 solubility data[12, 13-16] and liquid phase concentration
data[17].
The estimation results of various transport and thermal properties are
summarized in Figures 1-8. Note that CO2 loading is defined as the ratio of
the moles of apparent CO2 to the moles of apparent PZ. Apparent means
before reaction, so for example if 1 mole of PZ 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 PZ after reacting. Weight percent of PZ is calculated without
CO2, so in the above example, it is calculated from the mixture of 1 mole of
PZ and 9 moles of water. Since PZ has a molecular weight of 86.1369 and
water has a molecular weight of 18.015, this is 86.1369/(86.1369+9*18.015)
= 0.34694 or about 35 wt% PZ.

8 2 Physical Properties
 1300

1250

1200

Density, kg/cum
1150

1100

1050

1000

950
0 0.2 0.4 0.6 0.8 1 1.2

CO2 loading, mol CO2/mol PZ

Figure 1. Liquid Density of PZ-CO2-H 2O at 293 K, experimental data from

Freeman (2011)[27], (○) PZ concentration is 2 m (15 wt%), (●) PZ
concentration is 5 m (30 wt%), (□) PZ concentration is 7 m (38 wt%), (■)
PZ concentration is 10 m (46 wt%), (△) PZ concentration is 20 m (63 wt%)

0.6
Thermal conductivity, Watt/m.K

0.5

0.4

0.3

0.2

0.1

0
0 0.2 0.4 0.6 0.8 1

CO2 loading, mol CO2/mol PZ

Figure 2. Liquid Thermal Conductivity of PZ-CO2-H2O at 298 K, (—) PZ

concentration is 8 m (41 wt%), (—•—) PZ concentration is 4 m (26 wt%),
(——) PZ concentration is 2 m (15 wt%)

2 Physica l Prope rties 9

 100

Heat capacity, J/mol.K

90

80

70

60
300 320 340 360 380 400
Temperature, K

Figure 3. Liquid Heat Capacity of PZ-CO2-H2O at 298 K, PZ concentration is 2

m (15 wt%), experimental data from Hilliard (2008)[12], (△) CO2 loading is
0.75, (○) CO2 loading is 0.32

120

100
Absorption heat, kJ/mol

80

60

40

20

0
0 0.2 0.4 0.6 0.8 1

CO2 loading, mol CO2/mol PZ

Figure 4. Differential CO2 absorption heat in aqueous PZ solution, PZ

concentration is 2.4m (17 wt%), experimental data from Hilliard (2008)[12],
(○) 313 K, (△) 353 K, (□) 393 K; (—) 313 K, (—•—) 353 K, (——) 393 K

10 2 Physical Properties
 60

50

Heat of absorption, kJ/mol

40

30

20

10

0
0 0.5 1 1.5 2 2.5
H2S loading, mol H2S/mol PZ

Figure 5. Differential H2S absorption heat in aqueous PZ solution, PZ

concentration is 2.4 m (17 wt%), (—) 300 K, (—•—) 350 K, (——) 400 K

1.0E+04
CO 2 pressure, kPa

1.0E+02

1.0E+00

1.0E-02
0 0.2 0.4 0.6 0.8 1

CO2 loading, mol CO2/mol PZ

Figure 6. VLE of PZ-CO2-H 2O, PZ concentration is 8 m (41 wt%), (□) 313 K,

experimental data from Dugas (2009)[15], (◇) 353 K, experimental data from
Dugas (2009)[15], (△) 393 K, experimental data from Xu (2011) [16], (○) 433 K,
experimental data from Xu (2011)[16]

2 Physica l Prope rties 11

 1.0E+04

H 2S pressure, kPa
1.0E+02

1.0E+00

1.0E-02
0 0.5 1 1.5 2 2.5

H2S loading, mol H2S/mol PZ

Figure 7. VLE of PZ-H2S-H 2O, PZ concentration is 2m (15 wt%), (□) 313 K,

experimental data from Xia (2003)[22] and Speyer (2011)[23], (◇) 353 K,
experimental data from Xia (2003)[22], (△) 393 K, experimental data from Xia
(2003)[44] and [22] and Speyer (2011)[23]

1.6
Speciation, kmol/cum

1.2

0.8

0.4

0
0 0.2 0.4 0.6 0.8 1

CO2 loading, mol CO2/ mol PZ

Figure 8. Speciation in PZ-CO2-H2O at 298 K, PZ concentration is 1.5 m (11

wt%), experimental data from Ermatchkov (2003) [17], (□) concentration of
PZ(COO-)2, (△) concentration of PZCOO- and HPZCOO, (○) concentration of
PZ and PZH +

12 2 Physical Properties
3 Reactions

PZ is a cyclic amine, as shown in Figure 9. It can associate with H 3O+ to form

an ion PZH+, and can also react with CO2 to form a carbamate ion PZCOO-
and a dicarbamate ion PZ(COO-)2.

Figure 9. PZ Molecular Structure

The electrolyte solution chemistry has been modeled with a CHEMISTRY

model with CHEMISTRY ID = PZ. 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 the CHEMISTRY PZ. In addition, a
REACTION model called PZ-REA has been created. In PZ-REA, all reactions
are assumed to be in chemical equilibrium except those of CO 2 with OH- and
CO2 with PZ and PZCOO-.

A. Chemistry ID: PZ
1 Equilibrium 2H 2 O  H 3 O   OH 
2 Equilibrium CO 2  2H 2 O  HCO 3  H 3 O 
3 Equilibrium HCO 3  H 2 O  CO 32  H 3 O 
4 Equilibrium PZH   H 2 O  PZ  H 3 O 
5 Equilibrium PZ  HCO 3-  PZCOO -  H 2 O
6 Equilibrium HPZCOO  H2O  PZCOO -  H 3 O 
7 Equilibrium 
PZCOO -  HCO 3-  PZ COO - 
2  H 2O
8 Equilibrium H 2 S  H 2 O  HS   H 3 O 

9 Equilibrium HS  H2O  S2  H3O

3 Reactions 13
 B. Reaction ID: PZ-REA
1 Equilibrium 2H 2 O  H 3 O   OH 
2 Equilibrium HCO 3  H 2 O  CO 32  H 3 O 
3 Equilibrium PZH   H 2 O  PZ  H 3 O 
4 Equilibrium HPZCOO  H 2 O  PZCOO   H 3 O 
5 Equilibrium H 2 S  H 2 O  HS   H 3 O 

6 Equilibrium HS  H2O  S2  H3O

7 Kinetic CO 2  OH   HCO 3
8 Kinetic HCO 3  CO 2  OH 
9 Kinetic PZ  CO 2  H 2 O  PZCOO -  H 3 O 
10 Kinetic PZCOO -  H 3 O   PZ  CO 2  H 2 O
11 Kinetic PZCOO -  CO 2  H 2 O  PZ (COO - ) 2  H 3 O 
12 Kinetic PZ(COO - ) 2  H 3 O   PZCOO -  CO 2  H 2 O
The equilibrium constants are calculated from the standard Gibbs free energy
change. DGAQFM, DHAQFM and CPAQ0 of PZH+, PZCOO-, PZ(COO-)2 and
HPZCOO, which are used to calculate the standard Gibbs free energy, are
determined in this work. The DGAQFM (or DGFORM), DHAQFM (or DHFORM)
and CPAQ0 (or CPIG) parameters of the other components can be obtained
from the databank of Aspen Plus.
The power law expressions (T0 not specified) are used for the rate-controlled
reactions (reactions 7-12 in PZ-REA):

  E  1 1  N
r  k T T0     xi  i  i
n a
exp  (2)
 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;
xi = Mole fraction of component i;
γi = Activity coefficient of component i;

14 3 Reactions
 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 (  )  xi  i  i
a
(3)
RT i 1
In this work, the reduced expression is used. In equation (3), the
concentration basis is mole fraction, the factor n is zero, k and E are given
in Table 3.
The kinetic parameters for reaction 7 are taken from the work of Pinsent et al.
(1956)[30] , and the kinetic parameters for reaction 8 are calculated by using
the kinetic parameters of reaction 7 and the equilibrium constants of the
reversible reactions 7 and 8. The kinetic parameters for reactions 9-12 in
Table 3 are derived from the work of Bishnoi and Rochelle (2000, 2002) [1-2].

Table 3. Parameters k and E in Equation (1)

Reaction No. k E , cal/mol
7 1.33e+17 13249
8 6.63e+16 25656
9 1.70e+10 319
10 3.40e+23 14160
11 1.04e+14 8038.3
12 3.20e+20 8692

3 Reactions 15
4 Simulation Approach

As we are unable to find industrial or pilot plant data publicly available for the
aqueous PZ Separation process, we use a single equilibrium stage model
(flash calculations) to simulate the CO2 absorption by PZ.
Simulation Flowsheet – In the following simulation flowsheet in Aspen Plus
(Figure 10), CO2 is absorbed by PZ from a mixture of CO2 and N2 in an
absorber.

GASOUT

LEANIN
ABSORBER

GASIN

RICHOUT

Figure 10. PZ Simulation Flowsheet in Aspen Plus

16 4 Simulation Approach
 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 PZ

Model
Unit Aspen Plus Block Comments / Specifications
Operation
Flash Flash2 1. Temperature is set at 40 °C
2. Pressure is set at 1 atm

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

Table 5. Feed specifications

Stream ID GASIN LEANIN

Substream: MIXED
Temperature: °C 40 40
Pressure: atm 1 1
Flow rate mole/hr mole/hr
H2O 0 32000
PZ 0 3000
CO2 1500 150
H2S 1500 150
N2 27000 0

Prop-Sets – Prop-Set XAPP is used to report apparent mole fraction of CO 2,

H2S, N2, PZ and H2O in liquid streams

4 Simulation Approach 17
5 Simulation Results

The simulation has been run successfully in Aspen Plus. Key simulation results
are presented in Table 6. Here the RICHOUT compositions are the mole
fraction of apparent components.

Table 6. Key Simulation Results

Stream ID GASOUT RICHOUT

Substream: MIXED
Temperature: °C 40 40
Pressure: psig 0 0
Total flow 30317 mol/hr 33463 mol/hr
Mole-Frac Mole-Frac
H2O 0.066 0.858
PZ 4e-6 0.086
CO2 0.004 0.043
H2S 0.039 0.014
N2 0.891 8e-6

18 5 Simulation Results
6 Conclusions

The Rate-Based PZ model provides a simple simulation of the CO 2 capture

process using aqueous PZ solutions with rigorous electrolyte thermodynamics
and solution chemistry and reaction kinetics for the liquid phase reactions.
The model is meant to be used as a guide for modeling the CO 2 capture
process with PZ. Users may use it as a starting point for more sophisticated
models for process development, debottlenecking, plant and equipment
design, among others. This simple PZ model has been validated with limited
experimental thermophysical and transport properties data. Further validation
of this PZ model will be done when industrial or pilot plant data become
available, as well as more transport property data.

6 Conc lusions 19
References

[1] S. Bishnoi, G. Rochelle, “Absorption of Carbon Dioxide into Aqueous

Piperazine: Reaction Kinetics, Mass Transfer and Solubility”, Chemical
Engineering Science, 55, 5531-5543 (2000)
[2] S. Bishnoi, G. Rochelle, “Absorption of Carbon Dioxide into Aqueous
Piperazine/Methyldiethanolamine”, AIChE Journal, 48, 2788-2799 (2002)
[3] Y. Yan, C. –C. Chen, “Thermodynamic Modeling of CO2 Solubility in
Aqueous Solutions of NaCl and Na2SO4”, J. of Supercritical Fluids, 55, 623-634
(2010)
[4] Y. Zhang, C. –C. Chen, ”Modeling Gas Solubilities in the Aqueous Solution
of Methyldiethanolamine”, Ind. Eng. Chem. Res., 50, 6436-6446 (2011)
[5] H. L. Wilson, W.V. Wilding, “Vapor-Liquid and Liquid-Liquid Equilibrium
Measurements on Twenty-Two Binary Mixtures”, Experimental Results for
DIPPR 1990-91 Projects on Phase Equilibria and Pure Component Properties,
DIPPR Data Series No. 2, 63-115 (1994)
[6] W. V. Steele, R. D. Chirico, S. E. Knipmeyer, A. Nguyen, N. K. Smith,
“Thermodynamic Properties and Ideal Gas Enthalpies of Formation for
Dicyclohexy Sulfide, Diethylenetriamine, Di-n-octyl Sulfide, Dimethyl
Carbonate, Piperazine, Hexachloroprop-1-ene, Tetrakis (dimethylamino)
ethylene, N, N’-Bis-(2-hydroxyethyl)ethylenediamine, and 1,2,4-Triazolo [1,
5-a]pyrimidine”, J. Chem. Eng. Data, 42, 1037-1052 (1997)
[7] D. M. VonNiederhausern, G. M. Wilson, N. F. Giles, J. Chem. Eng. Data,
“Critical Point and Vapor Pressure Measurements for Four Compounds by a
Low Residence Time Flow Method”, 51, 1986-1989 (2006)
[8] Y. –R. Chen, A. R. Caparanga, A. N. Soriano, M. –H. Li, “Liquid heat
capacity of the solvent (piperazine + n-methyldiethanolamine + water)”, J.
Chem. Thermodyn., 42, 4-59 (2010)
[9] J. Gross, G. Sadowski, “Application of the Perturbed-Chain SAFT Equation
of State to Associating Systems”. Ind. Eng. Chem. Res., 41, 5510-5515(2002)
[10] S. W. Brelvi, J. P. O’Connell, “Corresponding States Correlations for
Liquid Compressibility and Partial Molar Volumes of Gases at Infinite Dilution
in Liquids”, AIChE J., 18, 1239-1243(1972)
[11] C.-C. Chen, H.I. Britt, J.F. Boston, L.B. Evans, “Local Composition Model
for Excess Gibbs Energy of Electrolyte Systems. Part I: Single Solvent, Single
Completely Dissociated Electrolyte Systems”. AIChE J., 28, 588-596(1982)

20 References
 [12] M.D. Hilliard, "A Predictive Thermodynamic Model for an Aqueous Blend
of Potassium Carbonate, Piperazine, and Monoethanolamine for Carbon
Dioxide Capture from Flue Gas", Ph.D. Dissertation, University of Texas at
Austin, (2008)
[13] Á. P. -S. Kamps, J. Xia, G. Maurer, “Solubility of CO2 in (H 2O +
Piperazine) and in (H 2O + MDEA + Piperazine)”, AIChE J., 49, 2662-2670
(2003)
[14] V. Ermatchkov, Á. P. -S. Kamps, D. Speyer, G. Maurer, “Solubility of
Carbon Dioxide in Aqueous Solutions of Piperazine in the Low Gas Loading
Region”, J. Chem. Eng. Data, 51, 1788-1796 (2006)
[15] R. E. Dugas, “Carbon Dioxide Absorption, Desorption, and Diffusion in
Aqueous Piperazine and Monoethanolamine”, Ph.D. Dissertation, University of
Texas at Austin, (2009)
[16] Q. Xu, G. Rochelle, “Total Pressure and CO2 Solubility at High
Temperature in Aqueous Amines”, Energy Procedia, 4, 117-124 (2011)
[17] V. Ermatchkov, Á. P. -S. Kamps, G. Maurer, “Chemical Equilibrium
Constants for the Formation of Carbamates in (Carbon Dioxide + Piperazine +
Water) from 1H-NMR-spectroscopy”, J. Chem. Thermodynamics, 35, 1277-
1289 (2003)
[18] A. Böttger, V. Ermatchkov, G. Maurer, “Solubility of Carbon Dioxide in
Aqueous Solutions of N-Methyldiethanolamine and Piperazine in the High Gas
Loading Region”, J. Chem. Eng. Data, 54, 1905-19-9 (2009)
[19] D. Speyer, V. Ermatchkov, G. Maurer, “Solubility of Carbon Dioxide in
Aqueous Solutions of N-Methyldiethanolamine and Piperazine in the Low Gas
Loading Region”, J. Chem. Eng. Data, 55, 283-290 (2010)
[20] X. Chen, “Carbon Dioxide Thermodynamics, Kinetics, and Mass Transfer
in Aqueous Piperazine Derivatives and Other Amines”, Ph.D. Dissertation,
University of Texas at Austin, (2011)
[21] Q. Xu, “Thermodynamics of CO2 Loading Aqueous Amines”, Ph.D.
Dissertation, University of Texas at Austin, (2011)
[22] J. Xia, A. P. –S. Kamps, G. Maurer, “Solubility of H2S in (H2O +
Piperazine) and in (H 2O + MDEA + Piperazine)”, 207, Fluid Phase Equilibria,
23-34 (2003)
[23] D. Speyer, G. Maurer, “Solubility of Hydrogen Sulfide in Aqueous
Solutions of Piperazine in the Low Gas-Loading Region”, J. Chem. Eng. Data,
56, 763-767 (2011)
[24] A. Mhuammad, M. I. A. Mutalib, T. Murugesan, A. Shafeeq,
“Thermophysical Properties of Aqueous Piperazine and Aqueous (N-
Methyldiethanolamine + Piperazine) Solutions at Temperatures (298.15 to
338.15) K”, J. Chem. Eng. Data, 54, 2317-2321 (2009)
[25] A. Samanta, S. S. Bandyopadyay, “Density and Viscosity of Aqueous
Solutions of Piperazine and (2-Amino-methyl-1-propanol + Piperazine) from
298 to 333 K”, J. Chem. Eng. Data, 51 467-470 (2006)
[26] G. Murshid, A. M. Shariff, L. K. Keong, M. A. Bustam, “Physical
Properties of Aqueous Solutions of Piperazine and (2-Amino-2-methyl-1-

Re fere nces 21
 propanol + Piperazine) from (298.15 to 333.15) K”, J. Chem. Eng. Data, 56,
2660-2663 (2011)
[27] S. A. Freeman, G. T. Rochelle, “Density and Viscosity of Aeuqous
(Piperazine + Carbon Dioxide) Solutions”, J. Chem. Eng. Data, 56, 574-581
(2011)
[28] Moerke, K, Roscher, T, “Determination of the surface tension of some
ethyleneamines”, Leuna protocol, 9101 (1982)
[29] E. S. Hamborg, G. F. Versteeg, “Dissociation Constants and
Thermodynamic Properties of Amines and Alkanolamines from (293 to 353)
K”, J. Chem.. Eng. Data, 54, 1318-1328(2009)
[30] 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)

22 References