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A comprehensive model for calculating phase equilibria and thermophysical properties of electrolyte systems

P. Wang, A. Anderko * , R.D. Young and R.D. Springer OLI Systems Inc. 108 American Road Morris Plains, NJ 07950, USA

ABSTRACT

A thermodynamic model has been developed for calculating phase equilibria and other properties of multicomponent electrolyte systems. The model has been designed to reproduce the properties of both aqueous and mixed-solvent electrolyte systems ranging from infinite dilution to solid saturation or pure solute limit. The model incorporates formulations for the excess Gibbs energy and standard-state properties coupled with an algorithm for detailed speciation calculations. The excess Gibbs energy model consists of a long-range interaction contribution represented by the Pitzer-Debye-Hückel expression, a second virial coefficient-type term for specific ionic interactions and a short-range interaction term expressed by the UNIQUAC equation. The accuracy of the model has been demonstrated for common acids and bases and for multicomponent systems containing aluminium species in various environments.

* Author to whom correspondence should be addressed. E-mail: aanderko@olisystems.com

INTRODUCTION

Electrolyte thermodynamics is of great importance for the simulation and optimization of hydrometallurgical processes. In many processes, multicomponent electrolyte solutions are encountered at high concentrations under diverse conditions of temperature and pressure. Such solutions are challenging for computational models because of their complex chemical behaviour and strong nonideality.

Various models for electrolyte solutions have been reviewed by Zemaitis et al. (1), Pitzer (2), Rafal et al. (3), Loehe and Donohue (4) and Anderko et al. (5). A characteristic feature of electrolyte systems is the fact that phase equilibria and other thermodynamic properties are often inextricably linked to speciation equilibria, which may be due to ion pairing, acid-base reactions, complexation and other phenomena. In many industrial processes, speciation-related properties such as pH, oxidation-reduction potential, distribution of complexed or hydrolyzed species, etc., are of primary importance. Thus, self-consistent treatment of speciation and phase equilibria is of utmost importance for realistic simulation of electrolyte systems.

Recently, a general, speciation-based thermodynamic model has been developed for mixed-solvent electrolyte solutions (6). This model was shown to reproduce simultaneously vapor-liquid equilibria, solid-liquid equilibria, speciation, caloric and volumetric properties of electrolytes in water, organic, or mixed solvents. The model is valid for salts from infinite dilution to the fused salt limit and for various completely miscible inorganic systems (such as acid-water mixtures) over a full concentration range. Also, the model is capable of representing phase equilibria in multicomponent inorganic systems containing multiple salts, acids, and bases (7). Complex phase behavior such as formation of multiple hydrated salts, double salts, or the presence of eutectic points can be accurately represented. The model is referred to as the mixed-solvent electrolyte (MSE) model because it is equally valid for classical aqueous systems, those with more than one distinct solvent and mixtures in which a given component may continuously vary from being a solute to being a solvent (e.g., in acid-water mixtures).

In this study, we examine the applicability of this model to selected systems that are related to hydrometallurgical processes. Rather than focusing on particular processes, we select systems that provide a stringent test for the model. First, the model is used to represent the properties of fundamentally important acid-water and base-water solutions. Then, it is applied to systems containing aluminum in various aqueous environments.

THERMODYNAMIC MODEL

The thermodynamic framework has been developed (6) by combining an excess Gibbs energy model for mixed-solvent electrolyte systems with a comprehensive treatment of chemical equilibria. In this framework, the excess Gibbs energy is expressed as

G

ex

=

G

ex

LR

+

G

ex

MR

+

G

ex

SR

RT

RT

RT

RT

(1)

where

represents the contribution of long-range electrostatic interactions,

represents specific, primarily ionic (i.e., ion-ion and ion-molecule) interactions and

is a short-range contribution resulting from intermolecular interactions. For brevity,

is referred to as the middle-range term. Activity coefficients are obtained from eq. (1) by differentiation following standard thermodynamic definitions. The derivation of eq. (1) was discussed in detail by Wang et al. (6) and, therefore, only the basic features of the model are summarized here.

G

ex

LR

G

ex

MR

ex

G

SR

G

ex

MR

The long-range interaction contribution is calculated from the Pitzer-Debye- Hückel formula (8, 9) expressed in terms of mole fractions and symmetrically normalized, i.e.,

 

G

ex

DH

4A

 

= − 

 

i

n

x

I

x

RT

i

ln

ρ

1

I

1 2

+ x

ρ

0

1 2

x

i

[1

+ )

ρ

(

I

x,i

]

i


(2)

where the sum is over all species, I x is the mole fraction-based ionic strength, I x,i 0 denotes the ionic strength when the system composition reduces to a pure component i, i.e., I x,i =½ z i 2 ; ρ is related to the hard-core collision diameter (ρ = 14.0) and A x is given by

0

A

x

=

1

3

(

2

N

π

A

d

s

)

1 2

e

2

4

πε ε

0

s

k

B

T

3 2

(3)

where d s and ε s are the molar density and the dielectric constant of the solvent, respectively.

For the short-range interaction contribution to the excess Gibbs energy, the UNIQUAC equation (10) is used.

G

ex

G

ex

G

ex

UNIQUAC

=

combinatorial

+

residual

 

RT

RT

RT

(4)

with the combinatorial and residual terms expressed as:

G

ex

combinatorial

= 

 

 

ln

φ

i

+

Z

i

q

x

ln

θ

i

RT

i

i

x

i

2

i

i

φ

i

i

n

i

x

(5)

where

G

ex

residuall

RT

= − 

i

n

i

 

i

q

i

x

i

ln

j

θ τ

j

θ

i

φ

i

τ

ji

=

q

i

x

i

j

q

j

x

j

=

r x

i

i

r

j

j

x

j

=

exp

a

ji

RT

 

ij

(6)

(7)

(8)

(9)

where q i and r i are the surface and size parameters, respectively, for the species i; Z is a constant with a value of 10; a ij is the binary interaction parameter between species i and j (a ij a ji ). The UNIQUAC model has been extensively verified for systems composed of neutral molecules.

The middle-range interaction contribution is calculated from an ionic strength- dependent, symmetrical second virial coefficient-type expression (6):

where

B

ij

()

I

x

= B

ji

()

I

x

G

ex

MR

RT

= − 

,

B

B

ij

ii

(

=

I

x

B

jj

)

=

i

=

b

ij

n

i

0

∑ ∑

i

j

x x

i

j

B

ij

(

I

x

)

and the ionic strength dependence of

+

c

ij

exp(

I + a ) x 1
I
+
a
)
x
1

B

ij

(10)

is given by

(11)

where

parameters

b

ij

and

b

ij

c

ij

are adjustable parameters and

a 1 is set equal to 0.01. In general, the

and c are calculated as functions of temperature as

ij

b

c

ij

ij

=

=

b

c

0,

0,

ij

ij

+

+

b

c

1,

1,

ij

ij

T

T

+

+

b

c

2,

2,

ij

ij

/

T

(12)

/

T

(13)

In practice, the middle-range parameters are used to represent ion-ion and ion- neutral molecule interaction. The short-range parameters are used primarily for interaction between neutral molecules. For electrolyte systems encountered in hydrometallurgy, the middle-range contribution is by far the most important.

Speciation effects due to the formation of ion pairs and complexes are explicitly taken into account using chemical equilibria. Chemical equilibrium calculations require the standard-state chemical potential, µ i 0 , for all species together with activity coefficients. Thus, for a chemical reaction:

aA + bB +

= cC + dD +

(14)

the equilibrium conditions can be determined from

with

G

0

= ln

x

c

C

x

d

D

c

γ C

γ

d

D

RT

x

a

A

x

b

B

a

γ A

γ

b

B

0

0

G

= ∑

ν µ

i

i

⋅ 

i

(15)

(16)

where

participating in the chemical reaction, and ν is the stoichiometric coefficient of species i in Eq. (14) with positive values for the species on the right-hand side of the equation and negative values for those on the left-hand side.

0 is the standard-state chemical potential of species i, the sum is over all species

µ

i

i

The standard-state chemical potentials for aqueous species are calculated as functions of temperature and pressure using the Helgeson-Kirkham-Flowers equation of state (11). The parameters of this model are available for a large number of aqueous species including ions, associated ion pairs, and neutral species (12-15). It should be noted that standard-state properties calculated from the model of Helgeson et al. are based on the infinite-dilution reference state and on the molality concentration scale. At the same time, the activity coefficients obtained from eq. (1) are symmetrically normalized and based on the mole fraction scale. To make the speciation calculations consistent, the following conversions are performed: (i) the activity coefficients calculated from Eq. (1) are converted to those based on the unsymmetrical reference state, i.e. at infinite dilution in water, as described by Wang et al. (6), and (ii) the molality-based standard-state chemical potentials are converted to a corresponding mole fraction-based quantity.

Evaluation of model parameters

The parameters of the model are determined on the basis of various kinds of experimental data. In particular, data of the following type may be included in the regression of model parameters:

1. Vapor-liquid equilibria

2. Osmotic coefficients (or activity of water) in aqueous solutions and activity coefficients, especially in completely dissociated systems;

3.

Solubility of salts in water and other solvents

4. Properties of electrolytes at infinite dilution, such as acid/base dissociation and complexation constants

5. Data that reflect ionic equilibria in solutions, such as pH measurements

6. Densities

7. Heats of mixing and dilution

8. Heat capacities.

Among these types of data, vapor-liquid equilibria and salt solubilities are of paramount importance. Whereas vapor-liquid equilibrium data directly constrain the excess Gibbs energy, solid-liquid equilibrium data can be used to constrain both the excess Gibbs energy and the properties of solid phases that are in equilibrium with the liquid phase. The use of multiple data types is important to ensure the accuracy of model parameters. For example, caloric data (heat of mixing or dilution and heat capacities) are useful to determine the temperature dependence of model parameters. This makes it possible to make reliable predictions of solubilities well outside of the temperature range of experimental solubility data.

The experimental data cover the concentration ranges from infinite dilution in water to the solubility or fused salt limit, whichever applies. The combined model is typically applicable for temperatures up to 0.9T c , where T c is the critical temperature of the mixture. This is due to the fact that the excess Gibbs energy model is valid only for liquid-like systems and, therefore, cannot approach the critical locus too closely. Thus, the properties of relatively dilute aqueous systems can be represented up to ca. 300 °C. In concentrated electrolyte systems, the critical temperature is typically higher and the model may be valid well beyond 300 °C. For example, the model has been successfully applied up to 500 °C for concentrated sulfuric acid solutions as described below.

RESULTS AND DISCUSSION

In this study, we first apply the model to fundamental systems that often determine the electrolyte environment in practical hydrometallurgical systems. Figure 1 shows vapor-liquid equilibria for the system HCl – H 2 O at various temperatures. At low and moderate temperatures, this system shows liquid phase splitting, which is indicated by horizontal lines. The horizontal lines connect the compositions of two coexisting phases and show the equilibrium pressure of a three-phase liquid-liquid-vapor system. Below the three-phase pressure, Figure 1 shows the compositions of coexisting vapor and liquid phases. The correct representation of vapor-liquid and liquid-liquid equilibria demonstrates that the model accurately predicts the nonideality of hydrochloric acid solutions.

Figure 2 shows vapor-liquid equilibria in the sulfuric acid – water – sulfur trioxide system. Unlike in the case of hydrochloric acid, the volatility of sulfuric acid is very small and the partial pressure of water in this system is close to the total pressure. In

Figure 2, the mole fraction of sulfur trioxide is used as a concentration variable. This allows us to show the behavior of oleum mixtures (SO 3 – H 2 SO 4 ) in addition to that of sulfuric acid (H 2 SO 4 – H 2 O) on one plot. In view of the stoichiometric relation SO 3 + H 2 O = H 2 SO 4 , pure H 2 SO 4 corresponds to x(SO 3 ) = 0.5 in Figure 2. It is noteworthy that the model accurately reproduces the behavior of the system ranging from pure water to pure sulfur trioxide at temperatures from 0 °C to approximately 300 °C. At temperatures between ca. 300 °C and 500 °C, the model correctly reproduces the phase behavior of concentrated solutions.

Figure 3 shows solid-liquid equilibria in the system NaOH – H 2 O as a function of temperature. In this case, multiple hydrated solid phases are observed. The model accurately predicts the topology of the phase diagram, including eutectic points (e.g., the ice - NaOH7H 2 O eutectic) and congruently melting solid hydrate phases (e.g., NaOH3.5H 2 O and NaOHH 2 O) at temperatures ranging from ca –40 °C to 300 °C. It should be noted that the model reproduces other properties such as vapor-liquid equilibria, enthalpies of dilution and heat capacities in addition to solid-liquid equilibria.

After verifying the performance of the model for fundamental electrolyte systems, calculations have been made for a large number of binary and multicomponent systems containing aluminum. Figure 4 shows the solubility behavior of mixed systems containing aluminum oxides or hydroxides (expressed as weight % of Al 2 O 3 ), sodium hydroxide (expressed as weight % of Na 2 O) and water. The characteristic solubility maximum in this system is due to a transition between the stability of aluminum hydroxide or oxyhydroxide solid phases at lower alkalinities and sodium aluminate at higher alkalinities. The model accurately reproduces this behavior for temperatures ranging from 0 °C to at least 200 °C (which is the upper limit of experimental data).

While Figure 4 illustrates the solubility behavior of aluminum at strongly alkaline conditions, Figure 5 shows a solubility diagram for aluminum species at pH values ranging from 1 to 11. At the conditions shown in this figure, boehmite (AlOOH) is the stable phase. The pH effect on the phase behavior is of particular interest here because of a shift in the pH dependence as the temperature is increased from ca. 100 to 290 °C. Both the temperature and pH dependence of solubility are accurately reproduced by the model.

A particular advantage of the model is its ability to reproduce the properties of multicomponent systems on the basis of a limited amount of data. Of particular interest is the prediction of solubilities in systems containing multiple salts. An example of such calculations is shown in Figures 6 and 7. Figure 6 shows the solubility of solid phases in the binary system Al 2 (SO 4 ) 3 – H 2 O. The parameters obtained by fitting the thermodynamic properties of this system and the Na 2 SO 4 – H 2 O binary were further used to calculate the solubility behavior of the ternary mixture Al 2 (SO 4 ) 3 – Na 2 SO 4 – H 2 O. The results are shown in Figure 7. It is noteworthy that the ternary phase diagram shows the presence of a solid phase that does not occur in either of the binary subsystems (i.e., AlNa(SO 4 ) 2 ). Such double salts are common in many mixed electrolyte systems and can be accurately predicted by the model.

100 10 -20C -10C 5C 15C 25C 35C 45C 1 0.1 0.01 0.001 0.0001 0
100
10
-20C
-10C
5C
15C
25C
35C
45C
1
0.1
0.01
0.001
0.0001
0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
1
Pressure, atm

x (HCl)

Figure 1 - Calculated and experimental vapor-liquid equilibria in the HCl – H 2 O
Figure 1 - Calculated and experimental vapor-liquid equilibria in the HCl – H 2 O system.
The horizontal lines at high pressures connect the compositions of two
coexisting liquid phases. Experimental data are from references (16-22).
1.0E+03
500ºC
1.0E+02
400ºC 300ºC
200ºC
1.0E+01
100ºC
1.0E+00
50ºC
25ºC
1.0E-01
0ºC
1.0E-02
1.0E-03
1.0E-04
1.0E-05
1.0E-06
1.0E-07
1.0E-08
0.0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
1.0
P, atm

x SO 3

Figure 2 - Calculated and experimental vapor-liquid equilibria in the sulfuric acid/oleum system as a function of the mole fraction of SO 3 . Literature data are taken from Gmitro and Vermeulen (23), Brand and Rutherford (24), Schrage (25), and Giazitzoglou and Wuster (26).

100 90 NaOH 80 70 NaOH.H 2O 60 50 40 NaOH.2H2 O NaOH.3.5H 2 O
100
90
NaOH
80
70
NaOH.H 2O
60
50
40
NaOH.2H2 O
NaOH.3.5H 2 O
30
NaOH.4H 2O
20
NaOH.7H 2 O
10
Ice
0
-40
-20
0
20
40
60
80
100
120
140
160
180
200
220
240
260
280
300
%thiegw,HONa

Temperature, C

Figure 3 – Calculated and experimental solubility of NaOH in aqueous solutions as a function of temperature. Experimental data are taken from references (27) and

(28).

45 40 200 C 35 Al(OH) 3 (s) or AlOOH(s) 30 Na 2 O.Al 2
45
40
200 C
35
Al(OH) 3 (s)
or AlOOH(s)
30
Na 2 O.Al 2 O 3 .2.5H 2 O
110C
25
20
95C
15
50C
10
30C
5
25C
0
0
10
20
30
40
50
60
70
Al 2 O 3 wt%

Na 2 O wt%

Figure 4 - Representation of solubilities of solids in the ternary system Al 2 O 3 – Na 2 O – H 2 O. The experimental data are from references (29-36).

1.E+01 1.E+00 150 C 203.3 C 1.E-01 1.E-02 250 C 101.5 C 1.E-03 1.E-04 290.2
1.E+01
1.E+00
150 C
203.3 C
1.E-01
1.E-02
250 C
101.5 C
1.E-03
1.E-04
290.2 C
1.E-05
1.E-06
1.E-07
1.E-08
1.E-09
1.E-10
0
1
2
3
4
5
6
7
8
9
10
11
12
m (AlOOH)

pH

Figure 5 – Representation of the solubility of boehmite (AlOOH) in 0.03 m NaCl as a function of pH. The experimental data are from references (37) and (38).

60 50 40 Al 2 (SO 4 ) 3 .16H 2 O 30 20 ice
60
50
40
Al 2 (SO 4 ) 3 .16H 2 O
30
20
ice
10
0
-20
-10
0
10
20
30
40
50
60
70
80
90
100
110
120
wt% Al 2 (SO 4 ) 3

t/C

Figure 6 – Calculated and experimental solubilities of aluminum sulfate as a function of temperature. The experimental data are from references (27) and (39-43).

40 Al 2 (SO 4 ) 3 .16H 2 O 35 30 25 AlNa(SO 4
40
Al 2 (SO 4 ) 3 .16H 2 O
35
30
25
AlNa(SO 4 ) 2 .12H 2 O
20
Na 2 SO 4
15
30C
25C
10
0C
5
Na 2 SO 4 .10H 2 O
0
0
5
10
15
20
25
30
35
wt% Al 2 (SO 4 ) 3

wt%-Na 2 SO 4

Figure 7 – Calculated and experimental solubility of solids in the system Al 2 (SO 4 ) 3 Na 2 SO 4 – H 2 O. The experimental data are from Linke and Seidell (27).

CONCLUSIONS

A recently developed comprehensive mixed-solvent electrolyte model has been applied to calculate phase equilibria in multicomponent systems containing salts, acids and bases in wide concentration and temperature ranges. The model is based on a combination of an excess Gibbs energy formulation with a treatment of standard-state properties and an algorithm for comprehensive speciation calculations. The model is valid for aqueous systems ranging from infinite dilution to molten salts or pure acids at temperatures from the freezing point to 300 °C. In favorable cases, the model can be extended to even higher temperatures (up to 500 °C) as long as the system of interest is subcritical. In particular, the model has been shown to be very useful for reproducing complex solid-liquid equilibrium diagrams, which may involve multiple hydrates, eutectic points formed by salt hydrates and ice, double salts, congruently melting solid phases, etc. The model has been verified for a large number of systems including common acids, bases and salts of first- and second-group elements, aluminum, tin, and iron. It is also applicable to organic and organic – salt mixtures. Work is in progress on developing model parameters for a large class of systems that are of interest in hydrometallurgy.

ACKNOWLEDGEMENT

The work reported here was supported by Alcoa, Chevron, DuPont, Mitsubishi Chemical, Rohm & Haas and Shell.

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