Aspen Plus

Rate-Based Model of the CO2 Capture Process by

Mixed PZ and MDEA Using Aspen Plus
Copyright (c) 2010-2014 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

V7.2 First version

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 3c.
Add two reactions into the kinetics.
V7.3.2 Update databank to PURE26.

Revision History 1
 Version Description

August Use ENRTL-RK method to replace ELECNRTL method; use PC-SAFT EOS
2012 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 Antoine equation parameters, heat of vaporization
parameters, ideal gas heat capacity parameters and PC-SAFT
parameters for MDEA.
Update the NRTL interaction parameters between MDEA and H 2 O, H2 O
and (MDEAH+, HCO3 - ), H2 O and (MDEAH+, CO3 -2 ), MDEA and (MDEAH+,
HCO3 - ), H2 O and (MDEAH+, HS- ) and those between MDEA and
(MDEAH+, HS- ).
Update the Henry’s constants of CO 2 and H2 S in H2 O and MDEA.
Update DGAQFM, DHAQFM and CPAQ0 of MDEAH+.
Update the interaction parameters, VLQKIJ, between MDEA and H2 O,
the Clarke model parameter, VLCLK/1, for (MDEAH +, HCO3 - ), (MDEAH+,
CO3 -2 ) and (MDEAH+, HS- ).
Update the Jones-Dole model parameters, IONMUB, for MDEAH+ and
HS- .
Update the NRTL parameters between PZ and MDEA, MDEA and (PZH+,
PZCOO- ), H2 O and (MDEAH+, PZ(COO- )2 and those between HPZCOO
and (MDEAH+, HCO3 - )
Update figures for properties.
Update kinetics.
Update flowsheet to Kaiserslautern Pilot Plant
V8.0 Update databank to PURE27.
V8.2 Update databank to PURE28.
Update the simulation results.
V8.6 Update databank to PURE32.
Update the simulation results.

2 Revision History
 Version Description

V10.0 Update GMENCC parameters between CO 2 and (PZH+, PZCOO- ), CO2

and (PZH+, PZCOO-2 ), CO2 and (PZH+, HCO3 - ), and those between CO2
and (PZH+, CO3 -2 ) to match the data of CO 2 activity coefficient.
Update GMENCC parameters between CO 2 and (MDEAH+, HCO3 - ), and
those between CO2 and (MDEAH+, CO3 -2 ) to match the data of CO 2
activity coefficient.
Update simulation results.

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

Contents..................................................................................................................4

Introduction ............................................................................................................5

1 Components .........................................................................................................6

2 Physical Properties...............................................................................................8

3 Reactions ...........................................................................................................22

4 Simulation Approach ..........................................................................................25

5 Simulation Results .............................................................................................29

6 Conclusions ........................................................................................................33

References ............................................................................................................34

4 Contents
Introduction

This file describes an Aspen Plus rate-based model of the CO2 capture process
by the aqueous solutions of mixed piperazine (PZ) and methyldiethanolamine
(MDEA). As there appear to be no public domain industrial or pilot plant data
available for aqueous MDEA/PZ/CO2 separations, the feed conditions and
column specifications in the model were loosely based on a pilot plant study
of CO2 capture with MEA performed at the University of Kaiserslautern [1]. The
flows, feed compositions, reboiler duty, and absorber and stripper packed
heights were adjusted so that the CO2 recovery was greater than 95% using
the HANLEY -STRUC mass transfer correlations. These variables would need to
be adjusted with the choice of different mass transfer correlations.
Thermophysical property models and reaction kinetic models are based on our
recent work and those of Bishnoi and Rochelle (2000, 2002) [2-3]. Transport
property models and model parameters have been validated against available
experimental data from open literature.
The model is meant to be used as a guide for modeling the CO 2 capture
process with mixed PZ and MDEA. Users may use it as a starting point for
more sophisticated models for process development, debottlenecking, plant
and equipment design, among others. Further validation of this PZ+MDEA
model will be done when industrial or pilot plant data become available.
The model includes the following key features:
 True species including ions
 Unsymmetric electrolyte NRTL activity coefficient model for liquid and PC-
SAFT equation of state for vapor
 Activity-based reaction kinetics
 Electrolyte transport property models
 Rate-based models for columns with structured packing

Introduction 5
1 Components

The following components represent the chemical species present in the

process:

Table 1. Components Used in the Model

ID Type Name Formula

MDEA Conventional METHYL-DIETHANOLAMINE C5H13NO2

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
HS- Conventional HS- HS-
S-2 Conventional S-- S-2
MDEAH+ Conventional MDEA+ C5H14NO2+
PZH+ Conventional PZH+ C4H11N2+
PZH+2 Conventional PZH+2 C4H12N2+2
*HPZCOO Conventional HPZCOO C5H1ON2O2
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

6 1 Components
 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 7
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 the
rate-based PZ+MDEA model. CO2, H2S, N2, O2, CO and H2 are selected as
Henry-components (solutes) to which Henry’s law is applied. Henry’s
constants are specified for these components with water, PZ and MDEA. 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
literatures (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) [4]

H2 S H2 O Zhang and Chen (1011) [5]
CO2 PZ Set to that of CO 2 in H2 O
H2 S PZ Set to that of H2 S in H2 O
CO2 MDEA Zhang and Chen (2011) [6]
H2 S MDEA Set to that of H2 S in H2 O

The PC-SAFT parameters of PZ are regressed from the vapor pressure data [7-
9]
, liquid heat capacity data[8, 10] and liquid density data[8].Those of MDEA are
regressed from the vapor pressure data[11-13], the liquid heat capacity data[14-
16]
and the liquid density data[17-18]. Those of H2O are obtained from Gross and
Sadowski (2002) [19], 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 [7-
9]
. 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.

8 2 Physical Properties
 The Antoine equation parameters of MDEA are regressed from the recently
available vapor pressure data[11-13]. The heat of vaporization (from 293 K to
473 K) generated with the regressed Antoine equation parameters through
the Clausius-Clapeyron equation are used to determine the DIPPR heat of
vaporization equation parameters for MDEA. The ideal-gas heat capacity
correlation parameters are obtained by fitting to the liquid heat capacity
data[14-16].
The characteristic volume parameters of H 2O for the Brelvi-O’Connell Model,
VLBROC, are obtained from Brelvi and O’Connell (1972) [20], those of CO2 are
obtained from Yan and Chen (2010) [2], and those of PZ, MDEA, H2S, N2, O2,
CO and H2 are defaulted to their critical volume in the Aspen Databank.
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 [21]. The
nonrandomness factor is fixed at 0.2.
The NRTL interaction parameters between PZ and H 2O are determined from
the regression with binary VLE data[22] and heat capacity data[10, 22]. Those
between MDEA and H 2O are determined from the regression with binary VLE
data[23-25], excess enthalpy data[14, 26-27] and heat capacity data[15-16, 28].
The interaction energy parameters between H 2O and (PZH+, HCO3-), H2O and
(PZH+, PZCOO-), and those parameters between H2O and (PZH+, PZ(COO-)2),
GMELCC, and the NRTL interaction parameters between H2O and HPZCOO,
are regressed using the VLE data[22, 29-32], heat of absorption data[22], heat
capacity data[22] and NMR speciation data[33] of the PZ-H2O-CO2 system and
the VLE data of the PZ-MDEA-H2O-CO2 system[34-37].
The interaction energy parameters between H2O and (MDEAH+, HCO3-), H2O
and (MDEAH+, CO3-2), and those between MDEA and (MDEAH +, HCO3-),
GMENCC, are regressed using the ternary VLE data [38-40], CO2 absorption heat
data[41-42], ternary heat capacity data[43] and liquid phase concentration data
of MDEA-H2O-CO2 system from NMR spectrum [44].
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[45-46].
The interaction energy parameters between H 2O and (MDEAH+, HS-) and
those between MDEA and (MDEAH +, HS-), GMENCC, are regressed with the
H2S solubility data in aqueous MDEA solution [46-49].
The NRTL interaction energy parameters between PZ and MDEA, and the
interaction parameters between MDEA and (PZH +, PZCOO-), H2O and
(MDEAH+, PZ(COO-)2) and those between HPZCOO and (MDEAH +, HCO3-),
GMENCC, are regressed with the VLE data of the PZ-MDEA-H2O-CO2
system [34-37].
The dielectric constants of nonaqueous solvents are calculated by the
following expression:

1 1
 T   A  B  (1)
T C 

2 Physica l Prope rties 9

 The parameters A, B and C for PZ are set to 4.25, 1532 and 298.15 and those
for MDEA in Aspen databanks are 21.9957, 8992.68 and 298.15.
The liquid molar volume model and transport property models have been
validated and model parameters regressed against available experimental
data from open literatures. 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[8], 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[50-
52]
and PZ-H2O-CO2[53]. The VLQKIJ parameter for MDEA and H2O is
regressed against the experimental MDEA-H2O density data from Bernal-
Garcia et al. (2003) [54]. The VLCLK/1 parameters are also regressed for
main electrolytes (MDEAH+, HCO3-) and (MDEAH+, CO3-2) against the
experimental MDEA-H2O-CO2 density data from Weiland (1998)[55], and
that of (MDEAH+, HS-) is regressed against experimental data of the
MDEA-H2O-H2S system from Rinker et al. (2000) [56].
 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+MDEA 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 H2O 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[50-52] and PZ-H2O-CO2[53]. MUKIJ and MULIJ parameters between
MDEA and H2O are regressed against experimental viscosity data of the
MDEA-H2O system [57]. IONMUB of MDEAH+ is regressed against MDEA-
H2O-CO2 viscosity data from Weiland (1998) [55]. That of HCO3- is regressed
against KHCO3-H2O viscosity data from Palaty (1992)[58], that of CO32- is
regressed against K 2CO3-H2O viscosity data from Pac et al. (1984) [59], and
that of HS - is regressed against experimental data of the MDEA-H2O-H2S
system from Rinker et al. (2000) [56].
 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 [60].The
DIPPR liquid surface tension parameters for HPZCOO are set to those of
PZ. The predictions of surface tension of the MDEA-H2O-CO2 system can
be in the range of the experimental data from Weiland (1996) [61].

10 2 Physical Properties
  For thermal conductivity, the Riedel electrolyte correction model, called
KL2RDL in Aspen Plus, is used. The DIPPR thermal conductivity
parameters 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 [62], 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[22], heat
capacity data[22], CO2 solubility data[22, 29-32] and liquid phase concentration
data[33]. DGAQFM, DHAQFM and CPAQ0 for MDEAH+ are regressed with heat
of absorption[41-42], VLE[38-40], heat capacity[43] and liquid phase concentration
data[44].
The estimation results of various transport and thermal properties are
summarized in Figures 1-10. Note that CO2 loading is defined as the ratio of
the moles of apparent CO2 to the moles of apparent amines. Apparent means
before reaction, so for example if 1 mole of PZ and 1 mole of MDEA are added
to 8 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+1)
= 0.15, regardless of the forms of CO2, PZ and MDEA after reacting. Weight
percent of amine is calculated without CO2, so in the above example, it is
calculated from the mixture of 1 mole of PZ, 1 mole of MDEA and 8 moles of
water. Since PZ has a molecular weight of 86.139, MDEA has a molecular
weight of 119.164, and water has a molecular weight of 18.015, this equals
86.139/(86.139+119.164+8*18.015) = 0.24652 or about 25 wt% PZ and
119.164/(86.139+119.164+8*18.015) = 0.34103 or about 34 % MDEA.

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 1a. Liquid Density of PZ-CO2-H2O at 293 K, experimental data from

Freeman (2011)[53], (○)PZ concentration is 2 m (15 wt%), (●)PZ

2 Physica l Prope rties 11

 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%)

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 MDEA

Figure 1b. Liquid Density of MDEA-CO2-H 2O at 298 K, experimental data from

Weiland (1998)[55], (□)MDEA concentration is 3.6 m (30 wt%), (◇)MDEA
concentration is 5.6 m (40 wt%), (△)MDEA concentration is 8.4 m (50 wt%),
(○)MDEA concentration is 12.6 m (60 wt%)

1.0E+00
Viscosity, Pa.S

1.0E-01

1.0E-02

1.0E-03
0 0.2 0.4 0.6 0.8 1

CO2 Loading, mol CO2/mol MDEA

Figure 2. Liquid Viscosity of MDEA-CO2-H 2O at 298 K. experimental data from

Weiland (1998)[55], (□)MDEA concentration is 3.6 m (30 wt%), (◇)MDEA
concentration is 5.6 m (40 wt%), (△)MDEA concentration is 8.4 m (50 wt%),
(○)MDEA concentration is 12.6 m (60 wt%)

12 2 Physical Properties
 0.1

0.08

Surface Tension, N/m 0.06

0.04

0.02

0
0 0.2 0.4 0.6 0.8 1

CO2 Loading, mol CO2/mol MDEA

Figure 3. Surface tension of MDEA-CO2-H 2O at 298 K, experimental data from

Weiland (1998)[55], (□)MDEA concentration is 3.6 m (30 wt%), (◇)MDEA
concentration is 5.6 m (40 wt%), (△)MDEA concentration is 8.4 m (50 wt%),
(○)MDEA concentration is 12.6 m (60 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 4a. Liquid Thermal Conductivity of PZ-CO2-H 2O 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 13

 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 MDEA

Figure 4b. Liquid Thermal Conductivity of MDEA-CO2-H2O at 298 K, (—)MDEA

concentration is 8.4 m (50 wt%), (—•—)MDEA concentration is 5.6 m (40
wt%), (——)MDEA concentration is 3.6 m (30 wt%)

100
Heat capacity, J/mol.K

90

80

70

60
300 320 340 360 380 400
Temperature, K

Figure 5a. Liquid Heat Capacity of PZ-CO2-H2O at 298 K, PZ concentration is 2

m (15 wt%), experimental data from Hilliard (2008)[22], (△)CO2 loading is
0.75, (○)CO2 loading is 0.32

14 2 Physical Properties
 120

100

Heat capacity, kJ/kmol.K

80

60

40

20

0
0 0.2 0.4 0.6 0.8 1

CO2 loading, mol CO2/mol MDEA

Figure 5b. Liquid Heat Capacity of MDEA-CO2-H2O at 298 K, experimental

data from Weiland (1997)[43], (□)MDEA concentration is 3.6 m (30 wt%), (◇
)MDEA concentration is 5.6 m (40 wt%), (△)MDEA concentration is 8.4 m (50
wt%), (○)MDEA concentration is 12.6 m (60 wt%)

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 6a. Differential CO2 absorption heat in aqueous PZ solution, PZ

concentration is 2.4m (17 wt%), experimental data from Hilliard (2008)[22],
(○)313 K, (△)353 K, (□)393 K; (—)313 K, (—•—)353 K, (——)393 K

2 Physica l Prope rties 15

 80

Absorption heat, kJ/mol

60

40

20

0
0 0.3 0.6 0.9 1.2 1.5

CO2 loading, mol CO2/ mol MDEA

Figure 6b. Integral CO2 absorption heat in aqueous MDEA solution, MDEA
concentration is 3.6 m (30 wt%), experimental data from Mathonat
(1995)[41], (○) 313 K, (△)353 K, (□)393 K; (—)313 K, (—•—)353 K, (——)393
K

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 7a. Differential H2S absorption heat in aqueous PZ solution, PZ

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

16 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 MDEA

Figure 7b. Differential H2S absorption heat in aqueous MDEA solution, MDEA
concentration is 3.6 m (30 wt%), experimental data from Oscarson and Izatt
(1990)[63], (○)300 K, (△)350 K, (□)400 K; (—)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 8a. VLE of PZ-CO2-H 2O, PZ concentration is 8 m (41 wt%), (□)313 K,

experimental data from Dugas (2009)[31], (◇)353 K, experimental data from
Dugas (2009)[31], (△)393 K, experimental data from Xu (2011) [32], (○)433 K,
experimental data from Xu (2011)[32]

2 Physica l Prope rties 17

 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 MDEA

Figure 8b. VLE of MDEA-CO2-H 2O, MDEA concentration is 8m (49 wt%),

(□)313 K, experimental data from Ermatchkov (2006) [40] and Jou (1982)[47],
(◇)353 K, experimental data from Ermatchkov (2006) [40], (△)393 K,
experimental data from Ermatchkov (2006)[40] and Jou (1982)[47], (○)433 K,
experimental data from Chakma (1987)[64]

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 + mol MDEA)

Figure 8c. CO2 Partial Pressure of PZ-MDEA-CO2-H 2O, PZ concentration is 2 m

(8 wt%) and MDEA concentration is 8 m (45 wt%), (□)313 K, experimental
data from Speyer (2010)[35] and Chen (2011)[36], (◇)353 K, experimental
data from Speyer (2006)[35] and Böttger (2009)[34], (△)393 K, experimental
data from Speyer (2006)[35] and Böttger (2009)[34], (○)433 K, experimental
data from Xu (2011)[37]

18 2 Physical Properties
 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 9a. VLE of PZ-H2S-H 2O, PZ concentration is 2m (15 wt%), (□)313 K,

experimental data from Xia (2003)[46] and Speyer (2011)[47], (◇)353 K,
experimental data from Xia (2003)[46], (△)393 K, experimental data from Xia
(2003)[46] and [46] and Speyer (2011)[46]

1.E+04
H 2S pressure, kPa

1.E+02

1.E+00

1.E-02
0 0.5 1 1.5 2 2.5

H2S loading, mol H2S/mol MDEA

Figure 9b. VLE of MDEA-H 2S-H 2O, MDEA concentration is 8.4 m (50wt%),
(□)313 K, experimental data from Jou (1982)[48] and Huang (1998)[66], (◇
)353 K, experimental data from Jou (1982)[48] and Huang (1998)[66], (△)393
K, experimental data from Jou (1982)[48] and Huang (1998)[66]

2 Physica l Prope rties 19

 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 10a. Speciation in PZ-CO2-H2O at 298 K, PZ concentration is 1.5 m (11

wt%), experimental data from Ermatchkov (2003)[33], (□), concentration of
PZ(COO-)2, (△), concentration of PZCOO - and HPZCOO, (○), concentration of
PZ and PZH +

1.0E-01
Speciation, mole fraction

1.0E-02

1.0E-03

1.0E-04
0 0.2 0.4 0.6 0.8 1

CO2 loading, mol CO2/mol MDEA

Figure 10b. Speciation in MDEA-CO2-H 2O at 293 K, MDEA concentration is 2.5

m (23 wt%), experimental data from Jokobsen (2005)[44], (□), concentration
of CO3-2, (◇), concentration of HCO 3-, (△), concentration of MDEAH +, (○),
concentration of MDEA

20 2 Physical Properties
 0.08

Speciation, mole fraction

0.06

0.04

0.02

0
0 0.2 0.4 0.6 0.8 1

CO2 loading, mol CO2/(mol PZ + mol MDEA)

Figure 10c. Speciation in PZ-MDEA-CO2-H 2O at 293 K, PZ concentration is 2.6

m (13 wt%) and MDEA concentration is 4.2 m (29 wt%), experimental data
from Böttinger (2008)[66], ], (□), concentration of HCO 3-, (■), concentration
of PZ(COO-)2, (△), concentration of PZCOO - and HPZCOO, (▲), concentration
of PZ and PZH+, (○), concentration of MDEA and MDEAH +

2 Physica l Prope rties 21

3 Reactions

PZ is a cyclic amine, as shown in Figure 11. It can associate with H + to form

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

Figure 11. PZ Molecular Structure

MDEA is a tertiary amine, as shown in Figure 12. It can associate with H + to

form an ion MDEAH+.

Figure 12. MDEA Molecular Structure

The electrolyte solution chemistry has been modeled with a CHEMISTRY

model with CHEMISTRY ID = P-M. 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 P-M. In addition, a
REACTION model called P-M-REA has been created. In P-M-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: P-M

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 2O  CO 32   H3O 

22 3 Reactions
 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 MDEAH   H 2 O  MDEA  H 3 O 
9 Equilibrium H 2 S  H 2 O  HS   H 3 O 

10 Equilibrium HS  H2O  S2  H3O

B. Reaction ID: P-M-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 MDEAH   H 2 O  MDEA  H 3 O 
6 Equilibrium H 2 S  H 2 O  HS   H 3 O 

7 Equilibrium HS  H2O  S2  H3O

8 Kinetic CO 2  OH   HCO 3
9 Kinetic HCO 3  CO 2  OH 
10 Kinetic PZ  CO 2  H 2 O  PZCOO -  H 3 O 
11 Kinetic PZCOO -  H 3 O   PZ  CO 2  H 2 O
12 Kinetic PZCOO -  CO 2  H 2 O  PZ (COO - ) 2  H 3 O 
13 Kinetic PZ(COO - ) 2  H 3 O   PZCOO -  CO 2  H 2 O
14 Kinetic MDEA  CO 2  H 2 O  MDEAH   HCO 3-
15 Kinetic MDEAH   HCO 3-  MDEA  CO 2  H 2 O
The equilibrium constants are calculated from the standard Gibbs free energy
change. DGAQFM. DHAQFM and CPAQ0 of MDEAH+, 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.
Power law expressions (T0 not specified) are used for the rate-controlled
reactions (reactions 8-15 in P-M-REA):

3 Reactions 23
   E  1 1  N
r  k T T0  exp     xi  i  i
n a
(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;
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 reactions 8 are taken from the work of Pinsent et
al. (1956)[67], and the kinetic parameters for corresponding reversible
reactons 9 are calculated by using the kinetic parameters of reaction 8 and
the equilibrium constants of the reversible reactions 8 and 9. The kinetic
parameters for reactions 10-13 in Table 3 are derived from the work of
Bishnoi and Rochelle (2000, 2002) [2-3], and those for reactions 14 and 15 are
derived from the work of Rinker et al. (1997) [68].

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

Reaction No. k E , cal/mol
8 1.33e+17 13249
9 6.63e+16 25656
10 1.70e+10 319
11 3.40e+23 14160
12 1.04e+14 8038.3
13 3.20e+20 8692
14 6.85e+10 9029
15 6.62e+17 22131

24 3 Reactions
4 Simulation Approach

The flowsheet is based off of the pilot plant study by Notz, Mangalapally and
Hasse (2012) [1] for CO2 capture by aqueous MEA solutions. The flowsheet has
been modified to accommodate a PZ/MDEA solvent. Table 4 represents the
operating conditions of the simulation.

Simulation Flowsheet – In the following simulation flowsheet in Aspen Plus

(Figure 13), CO2 is absorbed by mixed PZ and MDEA from a mixture of CO2,
H2O, N2, and O2 in an absorber.

Figure 13. PZ+MDEA Simulation Flowsheet in Aspen Plus

4 Simulation Approach 25
 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

mixed PZ and MDEA Model
Unit Aspen Plus Block Comments / Specifications
Operation

Absorber RadFrac 1. Calculation type: Rate-Based

2. 20 Stages
3. Top Pressure: 1.00bar
4. Reaction: Reaction ID is P-M-REA for all
stages
5. Packing Type: FLEXIPAC® 250Y
6. Diameter: .125m
7. Height: 15.42m
8. Wash Section Height: .42 m
9. Mass transfer coefficient method:
HanleyStruc (2010)[48]
10. Interfacial area method: HanleyStruc
(2010)[48]
11. Flooding method: Wallis [49]
12. Heat transfer coefficient method: Chilton
and Colburn
13. Film resistance options: Discrxn for liquid
film; Film for vapor film
14. Flow model: VPlug
15. Estimates: provide temperature at stages
1 and 20. These estimates are intended to
aid convergence.

26 4 Simulation Approach
 Unit Aspen Plus Block Comments / Specifications
Operation

Stripper RadFrac 1. Calculation type: Rate-Based

2. 20 Stages
3. Top Pressure: 2 bar
4. Reaction: Chemistry ID is P-M for
condenser and reboiler, Reaction ID is P-M-
REA for all other stages
5. Packing Type: FLEXIPAC® 250Y
6. Diameter: .125m
7. Height: 5.42m
8. Distillate Rate: 6.23 kg/hr
9. Reboiler Duty: 8.42 kW
9. Mass transfer coefficient method:
HanleyStruc (2010)[48]
10. Interfacial area method: HanleyStruc
(2010)[48]
11. Flooding method: Wallis [49]
12. Heat transfer coefficient method: Chilton
and Colburn
13. Film resistance options: Discrxn for liquid
film; Film for vapor film
14. Flow model: VPlug
15. Estimates: provide temperature at stages
3 and 20. These estimates are intended to
aid convergence.
HX1 HeatX 1. Calculation Type: Shortcut
2. Hot Outlet – Cold Inlet Temperature
Difference: 10 C
3. Cold Side Outlet Pressure: 2.9bar

HX2 Heater 1. Outlet Temperature: 50 C

2. Outlet Pressure: 2bar
3. Valid Phases: Vapor-Liquid

HX3 Heater 1. Outlet Temperature: 40 C

2. Outlet Pressure: 1.01bar
3. Valid Phases: Vapor-Liquid

Pump Pump 1. Discharge Pressure: 2.9bar

FLEXIPAC® is a registered trademark of Koch-Glitsch, LP

4 Simulation Approach 27
 Streams - Feeds to the absorber are gas stream FLUEGAS containing H2O,
CO2, N2 and O2 and liquid solvent stream LEANIN containing aqueous PZ and
MDEA solution loaded with some CO2. Feed conditions are summarized in
Table 5.

Table 5. Feed specifications

Stream ID FLUEGAS LEANIN
Substream: MIXED
Temperature: C 50 50
Pressure: bar 1.013 2
Total flow 76.2 kg/hr 249.9 kg/hr
Mass-Frac Mass-Frac
MDEA 0 0.208
PZ 0 0.045
H2O 0.061 0.742
CO2 0.081 0.005
N2 0.737 0
O2 0.121 0
CO2 Loading n/a .054 mol CO2 /mol MDEA+PZ

Balance Blocks – The water makeup stream flowrate was determined using
a standard balance block. The inlet stream was FLUEGAS and the water
makeup stream for the water balance. The outlet streams were GASOUT,
CO2OUT, and COND.
Because the amine can be lost in the stream COND in an ionized form,
makeup amine was calculated using a design specification block. The total
amine in COND was calculated using the WAPP property set for the total flow
of amine in all speciated forms. Amine was also lost through CO2OUT and
GASOUT.

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

PZ, MDEA and H2O in liquid streams. The Prop-Set MLLOAD was implemented
to display the CO2 loading of the amine, defined as the ratio of the apparent
moles of CO2 to the apparent moles of the total amines (MDEA and PZ).

28 4 Simulation Approach
5 Simulation Results

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

Table 6. Key Simulation Results

Variable Rate-Based PZ-MDEA Model

CO2 mole fraction in GASOUT .0046

CO2 Recovery 91.1%
Loading of RICHOUT, molCO2 /molMDEA+PZ 0.280
Stripper Reboiler Duty 8.42 kW
Specific Energy Requirement of the Reboiler 5.39 MJ/kgCO2
Excluding Heat Losses
Makeup Water 3.49 kg/hr
Makeup MDEA 0.0007 kg/hr
Makeup PZ 0.0004 kg/hr
Heat Recovery Exchanger Duty 16.2 kW

In this simulation the stripper operates at below 10% of predicted capacity.

The performance of public domain mass transfer correlations for predicting
column operation in this regime are untested.

5 Simulation Results 29
 65

60

Temperature, C

55

50 Hanley&Chen, L

Hanley&Chen, V

45
0 4 8 12 16

Packing height from top, m

Figure 14. Absorber Temperature Profiles

125

120
Temperature, C

115

Hanley&Chen, L
110
Hanley&Chen, V

105
0 1 2 3 4 5 6

Packing height from top, m

Figure 15. Stripper Temperature Profiles

30 5 Simulation Results
 0.30

CO2 loading, mol CO2/mol amine

0.25

0.20

0.15

0.10

0.05
Hanley&Chen

0.00
0 4 8 12 16

Packing height from top, m

Figure 16. Absorber Liquid Loading Profile

0.30
CO2 loading, mol CO2/mol amine

0.25

0.20

0.15

0.10

0.05 Hanley&Chen

0.00
0 1 2 3 4 5 6

Packing height from top, m

Figure 17. Stripper Liquid Loading Profile

5 Simulation Results 31
 0.030

0.025

CO2 mass fraction

0.020

0.015

0.010

0.005
Hanley&Chen

0.000
0 4 8 12 16

Packing height from top, m

Figure 18. Absorber CO2 Liquid Concentration Profile

0.030

0.025
CO2 mass fraction

0.020

0.015

0.010

0.005
Hanley&Chen

0.000
0 1 2 3 4 5 6

Packing height from top, m

Figure 19. Stripper CO2 Liquid Concentration Profile

The Hanleystruc (2010) correlation [48] is used to calculate the mass transfer
coefficient and interfacial area in the simulation. The Bravo (1985)
correlation[71] is an alternative for the mass transfer calculation. The results
will be changed if the Bravo (1985) correlation is applied.

32 5 Simulation Results
6 Conclusions

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

capture process by aqueous solutions of mixed PZ and MDEA with rigorous
electrolyte thermodynamics and solution chemistry and reaction kinetics for
the liquid phase reactions.

6 Conc lusions 33
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