Aspen Plus

Scaling Model: CO2-CaCO3-H2O

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Revision History
Version

Description

V7.2

First version

V7.3

Some parameters updated

V7.3.2

Databanks are updated, results are updated with V7.3.2

V8.0

Update the model to V8.0

Revision History

Contents
Revision History ......................................................................................................1
Contents..................................................................................................................2
Introduction ............................................................................................................3
1 Components .........................................................................................................4
2 Physical Properties...............................................................................................5
3 Reactions ...........................................................................................................10
4 Simulation Approach ..........................................................................................12
5 Simulation Results .............................................................................................14
6 Conclusion..........................................................................................................15
References ............................................................................................................16

Contents

Introduction

This file describes an Aspen Plus model for the scaling prediction of CO2CaCO3H2O ternary system at 398.15 K, and the scaling mineral CaCO3 is
included in this model. This model consists of a flash block to simulate the
liquid-solid equilibrium for CO2-CaCO3H2O at 398.15 K. The thermophysical
properties are studied intensively, wherever possible, model parameters have
been estimated and validated against experimental data from open literature.
The model includes the following key features:

Introduction

True species including ions

Unsymmetric electrolyte NRTL activity coefficient model[1-3] for liquid

phase nonideality and PC-SAFT equation of state for vapor phase

Thermodynamic equilibrium between solid and liquid phase

1 Components

The following components represent the chemical species present in the

process:

Table 1. Components Used in the CO2-CaCO3H2O Model

ID

Type

Name

Formula

CA+2

Conventional

CA++

CA+2

CO3-2

Conventional

CO3--

CO3-2

HCO3-

Conventional

HCO3-

HCO3-

H2O

Conventional

WATER

H2O

H3O+

Conventional

H3O+

H3O+

CO2

Conventional

CARBON-DIOXIDE

CO2

OH-

Conventional

OH-

OH-

CACO3(S)

SOLID

STRONTIUMCARBONATE

CACO3

1 Components

2 Physical Properties

The unsymmetric electrolyte NRTL method and PC-SAFT equation of state are
used to compute liquid and vapor properties respectively in this model. For
applying this model, the option code for model should be specified as follows:

Model ESPSAFT with 10 as the second option code should be used for
PHIVMX, DHVMX, DGVMX, DSVMX, VVMX. Model ESPSAFT0 with
10 as the second option code should be used for PHIV, DHV, DGV,
DSV, VV. That means the Copolymer PC-SAFT equation of state is
used to calculate the vapor fugacity coefficient, vapor molar enthalpy
departure, molar Gibbs free energy departure, molar entropy
departure, molar volume for both mixture and pure component. The
second option code 10 is implemented to find the true density at the
given condition of T, P, compositions regardless of the specified phase.

Note that, the specification of the databanks should be: ASPENPCD,

AQUEOUS, SOLID, INORGANIC, PURE27, PC-SAFT.
Henrys law is applied to CO2. Henrys constant parameters and BrelviOConnell characteristic volume parameters of CO2 required for pressure
correction of Henrys constant are identified against the experimental
solubility of CO2 in water[4-10]. The NRTL interaction parameters for the CO2H2O pair are set to zero, assuming the interactions between CO2 and water
are negligible.
Henrys constant can be calculated from the following equations:

1
H ij T , P H ij T , p j ,l exp
RT

ln H ij T , p j ,l Aij

Bij
T

V
dp
ij
,l

pw

C ij ln T Dij T

(1)

Eij
T

for

TL T TH

(2)

Where:

H ij T , P - Henrys constant of i in j at system temperature and pressure

H i j T , p j ,l - Henrys constant of i in j at system temperature and vapor

pressure of j

2 Physical Properties

Vij - Infinite dilution partial molar volume of i in solvent j obtained from the
Brelvi-OConnell model[11]
Aij, Bij, Cij, Dij, Eij, TL, TH - Correlation parameters
Table 2 shows the Henrys constant parameters of CO2 in water at system
temperature and water vapor pressure.

Table 2. Henrys Constant Parameters for CO2 in H2O (SI)

Component i

CO2

Component j

H2O

Aij

100.650

Bij

-6147.7

Cij

-10.191

Dij

-0.010

TLOWER

273

TUPPER

500

Eij

0.0

The general form of the Brelvi-OConnell model is expressed as:

Vij2 fcn Vi BO ,V jBO ,V j,l

(3)

Where:

Vi BO ,V jBO

- Characteristic volume for solute i and solvent j, respectively

V j,l - Liquid molar volume of solvent j

Brelvi and OConnell (1972)[11] presented the universal functions relating the
compressibility to the reduced density and the solute partial molal volume to
the reduced solvent density. Based on these empirical correlations, the
compressibility of a liquid and the partial molal volume of a solute at infinite
dilution in the solvent can be calculated with only the characteristic volumes
for the solute and the solvent being required. The characteristic volumes are
treated as temperature dependent with the following equation:

V BO v1 v 2T

(4)

Where:

v1 , v 2 - Correlation parameters for a solute or a solvent

Table 3 summarized the Brelvi-OConnell characteristic volume parameters
required in this model.

Table 3. Brelvi-OConnell characteristic volume

parameters (SI)

Component

Water[11]

CO2a

v1

0.0464

0.177

2 Physical Properties

v2
a

-3.42E-04

Parameters regressed.

Extended Antoine equation is used instead of a steam table for the calculation
of vapor pressure for water, because practice shows that the predictions from
steam tables at high temperatures are not accurate enough. To implement
this change, route PHIL04 should be used for property PHIL.
Because of the low ionization rate of CO2 in water and the minor solubility of
CaCO3, the interactions between species are negligible. So, zero is used for
the NRTL binary parameters between CO2 and H2O. The default values are
used for the NRTL parameters for electrolyte and electrolyte or molecule.
Based on the liquid activity coefficient, the enthalpy of aqueous solution can
be calculated from the following equations:

H m* x w H w xk H k H m* E
k

(5)

H w f H wig

ig
p ,w

dT H wv vap H w
(6)

298.15
T

H k f H k

p ,k

dT

298.15

H m*E RT 2 xi
i all

ln i*
T

(7)

(8)

Where:

C p ,,kaq
C igp ,w
H

- Infinite dilution aqueous phase heat capacity, J/kmol-K

- Ideal gas heat capacity of water, J/kmol-K

- Aqueous infinite dilution thermodynamic enthalpy, J/kmol

H m* E - Molar excess enthalpy defined with the asymmetrical reference state,

J/kmol

H w - Water molar enthalpy, J/kmol

f H wig

- Standard ideal gas enthalpy of formation for water, J/kmol

H wv

- Vapor phase enthalpy departure for water, J/kmol

vap H w

- Heat of vaporization of water, J/kmol

f H k

- Infinite dilution aqueous phase enthalpy of formation for ions and

molecules, J/kmol

2 Physical Properties

 i* - Liquid activity coefficient

The infinite dilution aqueous phase heat capacity (
following equation:

C p ,,kaq C1i C 2i T C 3i T 2

C p,,kaq

) is estimated by the

C 4 i C5i C 6 i
2
T
T
T for C 7i T C8i

(9)

Where: parameters C1i to C8i are equivalent to the CPAQ0/18 in Aspen Plus.
i indicated molecules, cations and anions.
Criss and Cobble (1964)[12] show that the Cp of ions changes little from
298.15 K to 473.15 K. That means considering the Cp of ions as a constant at
this temperature range is more reasonable than using the existing
specification in Aspen Plus. For this reason, we updated the CPAQ0 for anions
in this work as shown in Table 4.

Table 4. Heat Capacity Parameters Used in Eq. 9

Component

Ca++

CO2

H3O+

OH-

C1i

873.222

132230.718

75291

-148445.904

C2i

0.0

C3i

0.0

C4i

0.0

C5i

0.0

C6i

0.0

C7i

0.0

C8i

2000

2000

2000

2000

The estimated VLE behavior of CO2-H2O using the regressed equilibrium

constant parameters is plotted in Figure 1:

2 Physical Properties

175
150

Total P, MPa

125
100
75
50
25
0
0

0.02

0.04
0.06
CO2, mole fraction

0.08

Figure 1.CO2 Solubility in water. The symbols are experimental data[4-10], the
lines are model results: () 298.15 K; () 323.15 K; () 373.15 K; () 423.15
K; () 473.15 K.

2 Physical Properties

3 Reactions

The solid-liquid equilibrium chemistry and the equilibrium reactions between

CO2 and water have been represented as a CHEMISTRY model named Global.
The chemistry is specified to be Global on the Global sheet of the Properties
| Methods | Specifications form. This chemistry also can be used to
simulate the SLE for CaCO3-H2O binary systems at similar conditions.

A. Chemistry ID: SLE1

1

Equilibrium

H 2 O HCO 3 CO32 H 3 O

Equilibrium

2 H 2 O CO 2 HCO 3 H 3 O

Equilibrium

2 H 2 O OH H 3 O

Salt

CaCO3 ( s ) Ca 2 CO32

The built-in chemical equilibrium expression as follows is used for the

equilibrium reactions:

ln K A B / T C ln(T ) DT

(10)

Where: K is the equilibrium constant; A, B, C and D are adjustable

parameters; T is the temperature in Kelvin.
The parameters for the first three equilibrium reactions are retrieved from
Aspen Plus databank.
The parameters for the Salt reaction were regressed against Solid-Liquid
Equilibrium data for both binary CaCO3-H2O and CO2-CaCO3-H2O from open
literature[13-15], and the regressed parameters are given in Table 5.

Table 5. Parameters Required in Eq. 10

Reaction

CaCO3

289.994

-12626.5

-48.259

The parameters in Table 5 can be used to estimate the solubility of CaCO3(s) in

CO2-H2O at different pressures. That is because comparing to the pressure
effect on solubility product, the influence of CO2 concentration on the
solubility of carbonate minerals is more considerable. It means that the
dramatic increase of CaCO3 in CO2-H2O is caused by the reaction between

10

3 Reactions

dissolved CO2 and CaCO3(s). So, the influence of pressure on Ksp is ignored in
this model.
The predictions of the solubilities for CaCO3 in water and solutions saturated
with CO2 are plotted in Figures 2 and 3 along with the experimental data[13-15]:
9.0E-04
8.0E-04
7.0E-04

CaCO3, m

6.0E-04
5.0E-04
4.0E-04
3.0E-04
2.0E-04
1.0E-04
0.0E+00
273

323

373

423

473

523

573

623

T, K
Figure 2. Solubility of CaCO3(s) in water up to 573.15 K: () Linke (1958)[13];
the line is a prediction.

0.1

CaCO3, m

0.01

0.001

0.0001
1E-05

0.001

0.1

10

PCO2, MPa
Figure 3. Solubility of CaCO3(s) in CO2-H2O. The points are the data from Linke
(1958)[13] and Portier (2005)[15]: () 298.15 K; () 323.15 K; () 348.15 K; ()
373.15 K; () 398.15 K; () 423.15 K; () 448.15 K; () 473.15 K. The lines
are predictions.

3 Reactions

11

4 Simulation Approach

Because of the reaction between CO2 and CO3-2, the solubility of CaCO3(s) in
CO2-H2O is much greater than that in water at the same conditions. As there
are no industrial or pilot plant data available for barite precipitation
processes, we use the equilibrium model (flash calculations) to simulate the
scaling potential of the stable minerals. The scaling potential is estimated with
solubility index of a salt, and the solubility index can be expressed as:

SOLINDEX

Ip
K sp

(11)

Where:
Ip

Activity product in liquid phase

Ksp Solubility product.

Simulation Flowsheet In the following simulation flowsheet in Aspen Plus
(Figure 4), solid-liquid equilibrium for CO2-CaCO3H2O at 398.15 K is
simulated by a FLASH2 block.

Figure 4. CO2-CaCO3-H2O Solid-liquid Equilibrium Flowsheet in Aspen Plus

12

4 Simulation Approach

Unit Operations - Major unit operations in this model have been represented
by Aspen Plus blocks as outlined in Table 6.

Table 6. Aspen Plus Unit Operation Blocks Used in the

CO2-CaCO3-H2O Model
Unit Operation

Aspen Plus Block

SLE

Flash2

Comments / Specifications
1.Temperature is set at 398.15 K
2. Pressure is set at 1.5 MPa

Note that Gibbs is used as the flash convergence algorithm. It can be

specified on the Setup | Simulation Options | Flash Convergence form.
The Gibbs algorithm is based on Gibbs energy minimization, as in the RGibbs
unit operation model. It calculates mass and energy balances, true-species
chemistry (if applicable), and properties simultaneously. It is recommended if
the default inside-out algorithm exhibits convergence difficulties, especially
when solving three-phase problems, and almost all vapor electrolyte
chemistry with salts.
Streams - Feeds to SLE are the liquid stream CaCO3IN containing Ca+2, CO3-2
and H2O, and vapor stream CO2IN containing pure CO2. Feed conditions are
summarized in Table 7.

Table 7. Feed Specifications

Stream ID

CO2IN

CACO3IN

Temperature: K

398.15

398.15

Pressure: MPa

1.5

1.5

Substream: MIXED

Mole-Flow kmol/hr
CA+2

CO3-2

HCO3-

H2O

55.508

H3O+

CO2

0.5

OH-

CACO3(S)

Prop-Sets Two Prop-Set properties are used: SOLINDEX to monitor

precipitation of possible scaling minerals, and PPMX to report the partial
pressure of CO2 and H2O in the vapor phase.

4 Simulation Approach

13

5 Simulation Results

The simulation was performed using Aspen Plus V8.0. Key simulation results
are presented in Table 8. All the compositions are true compositions.

Table 8. Key Simulation Results

Stream ID

CO2IN

CACO3IN

GASOUT

LIQUIOUT

Temperature: K

398.15

398.15

398.15

398.15

Pressure: MPa

1.5

1.5

1.5

1.5

1.5981E-4

0.0037

1.2279E-06

1.2345E-07

1.5432E-4

0.0074

55.5083

0.0740

55.43073

0.9998

0.9963

8.1834E-09

5.9335E-06

0.5

4.2584E-06

0.3759

0.1204

1.6284E-4

2.7633E-07

0.5

56.5086

0.4499

56.5585

Substream: MIXED

Mole flow kmol/hr

CA+2
CO3-2
HCO3H2O
CACO3(S)
H3O+
CO2
OHTotal Flow kmol/hr
SOLINDEX
CACO3(S)

PPMX MPa
CO2
H2O

1.5

1.253
0.247

We can see from Tables 7 and 8 that about 0.376 kmol/h CO2 goes to the
vapor phase, which means the solution is saturated with CO2. And the
solubility of CaCO3(s) increases from 1.60E-04 molal to 3.7E-03 molal after
CO2 is bubbled into the solution. The results are consistent with the
experimental data[15].
The SOLINDEX in Table 8 shows that the streams CACO3IN and LIQUIOUT are
saturated with CaCO3(s).

14

5 Simulation Results

6 Conclusion

The CO2-CaCO3-H2O model provides a starting point for the potential

prediction of precipitation of carbonate minerals in CO2 aqueous solution. The
key features of this simulation model include electrolyte thermodynamics and
solution chemistry. Since the main factor influencing the solubility of
carbonate minerals is the solubility of CO2, just one set of parameters is used
to estimate the SLE at different pressures.
The model is meant to be used as a guide for modeling calcium carbonate
precipitation potential from the CO2-CaCO3-H2O ternary system at different
pressures and temperatures. This simple SLE model has been validated with
experimental solubility data for CaCO3-H2O and CO2-CaCO3-H2O up to 10 MPa
and 548.15 K. Further validation of this CO2-CaCO3-H2O model will be done
when industrial or pilot plant data become available.

6 Conclusion

15

References

[1] Y. Song, C.-C. Chen, Symmetric Electrolyte Nonrandom Two-Liquid

Activity Coefficient Model, Ind. Eng. Chem. Res., 48, 7788-7797, (2009)
[2] C.-C. Chen, L.B. Evans, A Local Composition Model for the Excess Gibbs
Energy of Aqueous Electrolyte Systems, AIChE Journal, 32, 444-454, (1986)
[3] 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)
[4] S. Takenouchi and G.C. Kennedy, The binary system H2OCO2 at high
temperatures and pressures. Am. J. Sci. 262, 10551074, (1964)
[5] K. Tdheide and E.U. Franck, Zeitschrift fur physikalische chemie neue
folge, BD. 37, S.387-401 (1963)
[6] W.S. Dodds, L.F. Stutzman and B.J. Sollami, "Carbon dioxide solubility in
water", industrial and engineering chemistry, 1 (1), 92-95, (1956)
[7] S.E. Drummond, Boiling and mixing of hydrothermal fluids: chemical
effects on mineral precipitation, Ph.D. Thesis, Pennsylvania State University,
(1981)
[8] A. Zawisza and B. Malesiska, Solubility of carbon dioxide in liquid water
and of water in gaseous carbon dioxide in the range 0.2-5 Mpa and at
temperature up to 473K" J. Chem. Eng. Data, 26, 388-391 (1981)
[9] R. Wiebe and V.L. Gaddy, The solubility of carbon dioxide in water at
various temperatures from 12 to 40 C and at pressures to 500 atm, J. Am.
Chem. Soc. 62, 815817, (1940)
[10] G. Houghton, A.M. Mclean, and P.D. Ritchie, "Compressibility, fugacity,
and water-solubility of carbon dioxide in the region 0-36 atm and 0-100 C",
Chemical engineering science, 6, 132-137 (1957)
[11] S.W. Brelvi and J.P. OConnell, Corresponding states correlations for
liquid compressibility and partial molal volumes of gases at infinite dilution in
liquids, AIChE J., 18, 1239-1243 (1972)
[12] C.M. Criss, J.W. Cobble, The Thermodynamic Properties of High
Temperature Aqueous Solutions. V. The Calculation of Ionic Heat Capacities
up to 200 . Entropies and Heat Capacities above 200 , J. Am. Chem. Soc.,
86, 5390-5393, (1964)

16

References

[13] W.F. Linke, Solubilities of inorganic and metal-organic compound, D.

Van Nostrand Company, Inc., Princeton, New Jersey (1958)
[14] O.I. Martynova, L.G. Vasina, S.A. Pozdnyakova, Determination of the
Solubility Product of Calcium Carbonate in the Temperature Range from 22 to
98 C, Dokl. Chem., 201, 1022-1024 (1971)
[15] S. Portier, Solubilite De CO2 Dans Les Saumures Des Bassins
Sedimentaires : Application au stockage de CO2 (gaz effet de serre),
Universite Louis Pasteur Strasbourg I, (2005)

References

17