Thesis Blast Plasma

Chemical Modeling of Ammoniacal Solutions
in Ni/Co Hydrometallurgy
by
Sam Roshdi
A thesis submitted in conformity with the requirements

for the degree of Master of Applied Science
Department of Chemical Engineering and Applied Chemistry
University of Toronto
Copyright by Sam Roshdi 2011
Chemical Modeling of Ammoniacal Solutions

in Ni/Co Hydrometallurgy
Sam Roshdi
Master of Applied Science
Department of Chemical Engineering and Applied Chemistry
University of Toronto
2011
ABSTRACT
Chemical modeling has become an important subject of research in applied thermodynamics for
designing, developing, optimizing and controlling of different industrial processes. In this work,
a new database for successful modeling of solid and aqueous phase equilibria in specific
hydrometallurgical processes was developed using the Mixed Solvent Electrolyte (MSE(H3O+))
model of the OLI Systems software. The ionic interaction parameters between dominant species
in the solution were determined by fitting available binary and ternary experimental data such as
mean activity, heat capacity and solubility data and then these interaction parameters were
validated in multi-component systems.
A chemical model was also developed to predict the phase behaviour in ammoniacal solutions
containing cobalt, nickel, copper, and zinc. The developed model was shown to accurately
predict the chemistry of the Copper Boil process in ammonia leach process. As it is not practical
to measure solubility data under all possible conditions, because of the large number of
components involved, chemical modeling becomes a valuable tool for assessing the process
chemistry for a wide variety of complex aqueous processing streams.
ii
Also, ammonium nickel sulphate hexa hydrate double salt solubility was measured within its
stability temperature range and used as new sets of data to validate the accuracy of developed
model. Using HSC 6.1 software, the copper boil processes was simulated. This simulation was
linked with thermodynamic results of MSE model to successfully predict the chemistry of the
Copper Boil process as well as provide some practical recommendations for the optimum process
operation.
iii
Acknowledgments
I would like to express my sincere gratitude to all those who have helped make this thesis
possible.
Many thanks are due to my supervisor, Professor Vladimiros G. Papangelakis for his support,
guidance and supervision.
Also, special and sincere thanks go to my Supervisory Committee, Professor Donald Kirk, and
Professor Honghi Tran for their advice, feedback and commitments.
In addition, I would like to acknowledge and thank the OLI Systems Inc., Sherritt International
Corp., Ontario Graduate Scholarships in Science and Technology, and CONNAUGHT
scholarship for their contributions, and the financial support provided for this project.
Many thanks to the Aqueous Process Engineering and Chemistry group members during my
study especially, Ghazal Azimi, Ilya Perederiy, Matthew Jones, Ming Huang, Haixia Liu,
Srinath Garg ,Samouel Peters, Ramapal Seini and Dr. Li.
I wish to pay a very special thank to my family, in particular, my very best friend and my wife,
Azadeh, for her continuous support, motivation, inspiration and love as well as my father for his
endless encouragement and belief in me, without whom none was possible.
iv
Table of Contents
Acknowledgments.......................................................................................................................... iv
Table of Contents ............................................................................................................................ v
List of Tables ................................................................................................................................ vii
List of Figures .............................................................................................................................. viii
List of Appendices .......................................................................................................................... x
1 INTRODUCTION...................................................................................................................... 1
1.1 Objectives ........................................................................................................................... 2
1.2 The Chemistry of the Copper Boil ....................................................................................... 3
2 METHODOLOGY ..................................................................................................................... 8
2.1 Chemical Modeling Methodology ....................................................................................... 8
2.1.1
Chemical Equilibria and Thermodynamic Framework........................................... 8
2.1.2
Model Parameter Evaluation................................................................................. 10
2.2 Experimental Methodology................................................................................................ 11

3 RESULTS AND DISCUSSION ................................................................................................ 15
3.1. Binary Systems.................................................................................................................. 15
3.2. Ternary Systems ................................................................................................................ 24
3.3. Nickel-Ammonia Complexation ....................................................................................... 29
3.4. Experiment Results. .......................................................................................................... 32
4 SIMULATION OF THE COPPER BOIL PROCESS USING THE HSC 6.1 SOFTWARE .. 35
4.1 Prediction of ammonia mole fraction in the vapor phase measured by Sherritt ................ 37
5 CONCLUSIONS........................................................................................................................ 40
6 REFERENCES .......................................................................................................................... 42
APPENDICES .............................................................................................................................. 45
Appendix 1: Density Tables.......................................................................................................... 45
v
Appendix 2: HSC results .............................................................................................................. 47
vi
List of Tables
Table 1. Experimental data used for model parameter estimation
Table 2. MSE middle range ion interactions parameters
Table 3. The dissociation reaction, standard state Gibbs free energy and entropy of formation of
the solid
Table 4. The stability constant of nickel and cobalt ammine complexes
Table 5. The Comparison of outflow compositions of the Copper Boil pots calculated by the
HSC Chemistry simulation with available Industrial data. Concentrations are in molality [mol/kg
water]. (H2O= 55.51 mol/kg water)
Table 6. The composition of different pots in the Copper Boil process of Sherritt
vii
List of Figures
Fig 1. The Sherritt nickel/cobalt refinery process
Fig 2. The Copper Boil process flowsheet
Fig 3. Schematic view of the reaction vessel for solubility measurements
Fig 4. NH3-H2O equilibrium curves: Mole fraction of ammonia in both vapour phase and liquid
phase at equilibrium state. using the MSE (H3O+) default database prediction ;experimental data
from [22]
Fig 5. The solubility of ammonium sulphate in water, experimental data from Terres and
Schmidt [31], Ishikawa and Murooka [32], and Linke and Siedel [22] and MSE (H3O+) default
data base are used. Solid phase is ammonium sulphate
Fig 6. The solubility of the CoSO4 in water. Experimental data are from [22, 32, 34]. The curve
is the fitted model.
Fig 7. The Cp of the CoSO4 in water vs. temperature. Data points are from [26]. The curve is the
fitted model.
Fig 8. The mean activity coefficient of the CoSO4 in water. Data points are from [26]. The curve
is the fitted model.
Fig 9. The solubility of ZnSO4 in Water Experimental data are from [22, 36]. The curve is the
fitted model. Solid phase at low temperature is ZnSO4.7H2O and after 42C it is ZnSO4.6H2O
and at high temperatures ZnSO4.H2O forms a solid phase.
Fig 10. The solubility of the NiSO4 in water. Experimental data are from [22, 23]. The curve is
the fitted model. Solid phase at low temperature is NiSO4.7H2O and after 31.4C it is
NiSO4.6H2O and at temperatures higher than 100.1C NiSO4.H2O forms a solid phase.
Fig 11. The solubility of (NH4)2SO4 in NiSO4- H2O, The curve is the fitted model and
experimental data from [22]. T=25 C.
Fig 12. NiSO4 solubility vs. CoSO4 concentration. Data points are from [22,30]. Lines are fitted
model results.
Fig 13. (NH4)2Ni(SO4)2.6H2O solubility in water. Data points are from [37,38]. Lines are fitted
model results.
Fig 14. Solubility of Ni(OH)2 in ammonia solution. Lines are model predictions and
experimental data are from [ 43-36].
viii
Fig 15. Total pressure vs. ammonia molality in solution of 2 molal ammonium sulphate. Solid
lines are fitted model result where dotted line shows the default model prediction. Experimental
data are from [38, 39]
Fig 16. Total pressure vs. ammonia molality in solution of 4 molal ammonium sulphate. Solid
lines are fitted model result where dotted line shows the default model prediction. Experimental
data are from [38, 39]
Fig 17. Speciation of nickel ammine complexes in NiSO4-(NH4)2SO4-NH3 solution
Fig 18. Experimental set up for solubility measurements. A. Jacketed reactor, B. Temperature
controller, C. Temperature-controlled circulating heater, D. Sampling line, E. stirring speed
controller, F. Stirrer
Fig 19. Ammonium Nickel Sulphate Hexa Hydrate solubility in water. Diamond and dash dots
show this works experiments. Star dots show literature values. Solid line is a model prediction.
Fig 20. The Copper Boil process Flowsheet from the HSC Simulation
Fig 21. Ammonia mole percentage in the vapor phase vs. ammonia:metal mole ratio. Dots are
MSE model calculated results; the curve is lab test results from the Sherritt plant.
Fig 22. The Comparison of total pressure in the Copper Boil pots obtained from the MSE model
with that from plant data
ix
List of Appendices
Appendix 1: Density Tables

Appendix 2: HSC Results
INTRODUCTION
Chemical modeling, a powerful tool for predicting and understanding the behaviour of complex
aqueous processing systems, is used to study the ammoniacal solutions existing in Ni/Co
hydrometallurgy. Electrolyte thermodynamics plays an important role in the simulation and
optimization of hydrometallurgical processes where multicomponent electrolyte solutions exist
under diverse operating conditions. The Copper Boil process in the Sherritt Refinery (Corefco)
is an ammonia distillation process for nickel and cobalt recovery. The presence of metal ions,
ammonium sulphate and ammonia in the process solution affects the solution properties in a nonstraightforward manner. This is due to the formation of metal ammonium complexes which
makes the speciation in the solution more sophisticated. The presence of mixed electrolytes in
aqueous solutions leads to the deviation of solution properties and strong nonideality. Therefore,
developing an appropriate methodology to predict solid-liquid-vapour equilibria has become an
important field of research.
In this work, the Mixed Sovent Electrolyte (MSE) model of the OLI software (OLI ESP 8.2) is
used. It is proposed to correlate ion interaction parameters of the MSE model with temperature
and solution composition from literature data such as mean activity, heat capacity and solubility
of binary and ternary systems containing metal sulphates and ammonia. Calculating the model
parameters makes it possible to predict the thermodynamic properties of the systems for which
data are not available in the literature or cannot be measured experimentally. The results
obtained in this study can be applied in different industrial fields including hydrometallurgical
processes.
Developing a chemical model which can predict the solution chemistry in the Copper Boil
process is one of the main goals of this work. For developing such a model, first the
thermodynamic properties of binary and ternary solutions containing the electrolytes of interest
such as NiSO4, CoSO4, (NH4)2SO4, etc. should be used to regress the model parameters. Then,
the parameters obtained in the fitting step can be applied to predict the phase behaviour of mixed
multicomponent solutions in the ammonia recovery process. By using this model, the effect of
changing the feed composition on the amount of ammonia to be recovered can be determined.
Available experimental data for electrolyte systems containing NiSO4, NH3, (NH4)2SO4, CoSO4,
etc. was used to estimate the model parameter through the OLI built-in regression facility. Since
complexation has a substantial effect on the behaviour of electrolytes in the ammoniacal nickel
sulphate solutions. The concentration of the free nickel ion in solution is significantly reduced by
the formation of nickel ammine complexes, Ni(NH3)n2+, (n=1-6). Similar to nickel in
ammoniacal solutions, both Co(II) and Co(III) form complexes in the presences of NH3 ligands.
Therefore, Ni(NH3)n2+-H2O system, Co(NH3)n2+-H2O system, and Co(NH3)63+-H2O system are
effectively developed into the OLI database,(n=1-6).
To develop a comprehensive model with the ability to predict multicomponent solutions under
various conditions in ammoniacal solutions, more experimental data are needed which are either
not available or available in a narrow range of conditions. The solubility data for ammonium
nickel sulphate hexahydrate is available in literature only from 20 to 60 C which does not cover
the industrial temperature range; this salt is stable up to 96 C. Therefore, solubility of this
double salt alongside with other double salts of picromerite series needed to be measured with
dissolution procedure. Results of these measurements are used to fit interaction parameters of
these salts into the database.
Furthermore, thermodynamic equilibrium data from the established chemical model is used to
modify the simulation database. Using the modified database, HSC Chemistry Software (HSC
6.1) is used to simulate the Copper Boil process. This makes it possible to find the best operating
conditions for the ammonia recovery process. It also provides insight regarding sulphuric acid
and steam consumption of the Copper Boil process.
1.1 Objectives
One of the objectives of this work is to develop a reliable database for chemical modeling of the
ammoniacal hydrometallurgical systems using the OLI software. Using this chemical model
makes it possible to predict the solution chemistry in the ammonia recovery stage of the Copper
Boil process. This can be done by using the MSE model implemented in the OLI software and fit
the MSE model interaction parameters in the systems for which experimental data are available
in the literature. The result of this work would be a dedicated thermodynamic database to predict
the chemistry in this process.
One of the main advantages of the ammonia pressure leach process is that a large amount of
ammonia is recovered from the vapour phase in the circuit to be used again. It is evident that any
significant increase in the capacity of the refinery leads to redesign of the leaching stage as well
as the nickel-cobalt separation stage. The ammonia recovery system will also be affected.
Having a model to predict the influence of these changes on the percent of ammonia to be
recovered would be very advantageous. Using such a model makes it possible to discover
whether the current capacity of the ammonia recovery circuit can handle the changes in feed
composition and flow rate.
Another objective of this study is to measure and produce new experimental data which are
useful for validating the chemical model developed. As well, the new data will be measured
under relevant industrial conditions, so they can be used in different research fields or by
different industries, since it is not practical to do these measurements under all different
conditions. Three different types of measurements of interest in this work are to study the SolidLiquid Equilibria (SLE) which is to study the solubility of a solid in a solution; to study the
Solid-Vapour-Liquid Equilibria (SLVE) which is to study the solubility of a gas and solid in a
solution; to study the ammonia complexation and speciation in a nickel sulphate solutions.
1.2 The Chemistry of the Copper Boil

The Sherritt refining process has been in operation since 1954. The original process was
described in details by Boldt and Queneau (1967) [1]. There were only minor changes to the
original process f1owsheet from 1954 to 1991. After 1991, some modifications were made in the
refinery according to the feed change [2-6].
The nickel/cobalt sulphides containing 55% Ni, 5% Co, 0.8% Fe, 35% S and 10% moisture are
produced from limonitic laterite ores by pressure acid leaching (PAL) in Cuba (by Moa Nickel
S.A.) and are shipped to the Corefco nickel-cobalt refinery, located in Fort Saskatchewan,
Alberta, as the feed [6-8].
The Sherritt process is an excellent classical approach for treating nickel concentrate. This
process is based on an ammoniacal oxygen pressure leach and subsequent recovery of nickel by
hydrogen reduction. A schematic diagram of the process is shown in Figure 1. The ammoniacal
oxygen pressure leach is very efficient at rejecting most impurities to the leach residue mainly
iron as hematite. Then cobalt enriched solution separated is fed to the cobalt refining circuit. The
cobalt-depleted nickel ammine solution is configured to produce sufficient partially reduced
sulphur species to precipitate the copper as copper sulphide in the Copper Boil where free
ammonia is removed, causing the copper to precipitate. Nickel is preferentially reduced during
hydrogen reduction until the nickel:cobalt ratio reaches approximately one. The remaining
nickel and cobalt are then precipitated as a mixed sulphide by H2S gas [9].
Fig 1. The Sherritt nickel/cobalt refinery process
The filtered leach liquor from leaching stage is treated with anhydrous ammonia to precipitate a
large portion of cobalt as cobalt(III)-nickel(II) hexamine complexes, which forms the feed to the
cobalt refining circuit. On the other hand, the cobalt-depleted nickel ammine solution is fed to
the Copper Boil process to recover most of the ammonia, while concentrating nickel solution and
quantitatively precipitating copper as copper sulphide, by reacting with sulphur dioxide and
elemental sulphur. The ammoniacal copper-free nickel solution is adjusted to give the
ammonia:nickel mole ratio of around 2, which is required by the nickel reduction process.
The Copper Boil Process is an ammonia distillation process. In this process, some of the
ammonia that is not complexed with metal ions in the solution is stripped in the Boil Feed
Stripper. The rest is distilled in the Nickel Boil with steam, and the ammonia that is complexed
with metal ions is removed by boiling in the Copper Boil pots and reacted with sulphuric acid in
the reboiler. Besides, adding elemental sulphur and sulphur dioxide to the second pot forces the
copper to precipitate as copper sulphide. Therefore ammonia can be recovered to be used in the
leach circuits and the copper sulphide precipitate is shipped to copper refineries [7].
The ammonia and copper removal circuit consists of three stages. The first stage is an air
stripping column, in which the compressed air and the pre-heated high ammonia content feed
solution enter counter-currently. The second stage is a packed distillation column with a steam
heated thermosyphone reboiler, known as the nickel boil, which reduces the ammonia:metal
mole ratio from about 8:1 to 5:1. The third stage is the original copper boil distillation train,
consisting of four pots and one reboiler. These four pots arranged in cascade, and feed the
solution by gravity into the steam heated reboiler. The vapour phase consists of steam which
flows counter-currently to the liquid phase and striped the ammonia from the solution in each
stage.
Copper precipitates in the form of copper sulphide as the ammonia concentration
decreases. Copper reacts with unsaturated sulphur species such as thiosulphate and dithionate to
form insoluble copper sulphide. Sulphuric acid is added into the reboiler to neutralize part of the
residual ammonia in order to adjust the ammonia:metal mole ratio of about 2:1. The following
three reactions take place in the Copper Boil pots and the forth one occurs in the reboiler:
Ni ( NH 3 ) 62+ Ni ( NH 3 ) 22+ + 4 NH 3
(1)
Co( NH 3 ) 36+ Co( NH 3 ) 32+ + 4 NH 3
(2)
Cu ( NH 3 ) 24+ Cu 2+ + 4 NH 3
(3)
2 NH 3 + H 2 SO4 ( NH 4 ) 2 SO4 + heat
(4)
Figure 2 shows the process flowsheet of the Copper Boil stage. The feed solution to this stage in
the original process contained 130 to 140 g/L NH3, corresponding to a mole ratio in the range
from 6:1 to 9:1. With the introduction of the new cobalt separation process, the feed solution
increased in ammonia content to the range 175 to 185 g/L, corresponding to mole ratios in the
range 10:1 to 14:1. However current average mole ratio is in range of 9:1 to 11:1. The existing
copper boil circuit proved to have insufficient distillation and condensing capacity to handle the
increased ammonia load [6, 7].
Copper sulphide precipitation occurs only in the copper boil circuit following the addition of
elemental sulphur and sulphur dioxide in the second pot. Sulphuric acid is still required to adjust
the ammonia: metal mole ratio to 2:1 in the reboiler.
S + SO2 + 2 NH 4OH ( NH 4 )2 S 2O3 + H 2 O
(5)
Cu ( NH 3 )4 SO4 + ( NH 4 )2 S 2 O3 + H 2 SO4 CuS + 3( NH 4 )2 SO4
(6)
Ni ( NH 3 )4 SO4 + H 2 SO4 Ni ( NH 3 )2 SO4 + ( NH 4 )2 SO4
(7)
The copper sulphide precipitate, which includes a significant amount of unreacted elemental
sulphur, is thickened in a lamella thickener. A portion of the underflow is recycled to the
leaching circuits to provide soluble copper, while the balance as precipitated copper sulphide is
filtered on a conventional vacuum drum filter [9]. The copper free overflow solution is filtered to
be sent to the high temperature oxydrolysis step.
In addition to removing the excess ammonia from the nickel solution, the three ammonia
removal steps also remove a substantial amount of water, resulting in a significant increase in
metal and ammonium sulphate concentrations. The overall solution volume reduction
corresponds to 15 to 20%, and as a result, the nickel concentration increases by about 10 g/L e.g.
from 55 to 65 g/L. The copper-free nickel diammine liquor, outflow of the Copper Boil Process,
typically contains 65 to 70 g/L Ni, 3 g/L Co, less than 1 mg/L Cu, 35 to 40 g/L NH3 and 320 to
340 g/L (NH4)2SO4 [6].
NH3
NH3, Steam, Air
T=85 oC
Co/Ni
Separation
Nickel Pregnant
Solution
MR=9-11
MR=6-8
Boil
Feed
Stripper
Ni
Boil
Steam
Condensate
NH3 vapour
T=82 oC
Compressed Air
(P=120 psi)
~ 2.8 psi
T=96 oC
MR=5-5.5
T=99 oC
~ 4.0 psi
~ 4.4 psi
Steam
o
T=112 C
~ 4.9 psi
Sulphur
Steam
~ 6.0 psi
SO2
H2SO4
Reboiler
MR=2
Copper free solution
containing mainly NiSO4
To Oxydrolysis
Thickener
Filter
Solids
containing CuS & Cu2S
Containing
(NH4)2SO4
Cu2S & CuS
NiSO4
trace CoSO4
to
Drum filter
Fig 2. The Copper Boil process flowsheet
According to the chemistry of the Copper Boil process, there are different electrolytes in the
solution which are important for chemical modeling of the process. Among them, (NH4)2SO4,
NiSO4, CoSO4, CuSO4, ZnSO4 , Na2SO4, H2SO4, nickel ammine complexes, and cobalt ammine
complexes are important to be studied. Cupric and cuprous sulphides exist as precipitate in the
solution. There is also ammonia and water in the vapour phase.
METHODOLOGY
2.1 Chemical Modeling Methodology

2.1.1
Chemical Equilibria and Thermodynamic Framework
To obtain the equilibrium constant of a reaction at temperature T and pressure P, the standard
state chemical potentials of products and reactants should be determined. The HKF model,
developed by Helgeson and coworkers [10], is embedded in the OLI to calculate standard state
thermodynamic properties at high temperatures and pressures up to 1000C and 5 kbar.
For a general chemical reaction that may involve solid, aqueous species, gas or vapour species,
the following equation can show the equilibrium:
aA + bB + .... cC + dD + ...
(8)
The equilibrium constant of the reaction at temperature T and pressure P is defined as:
K T ,P =
aCc a Dd ... mCc m Dd ... Cc Dd ...

=
a Aa a Bb ... m Aa m Bb ... Aa Bb ...
(9)
where a is the activity, m is the molality concentration of an aqueous species, and is the activity
coefficient. For pure and crystalline solid phases, a is equal to 8. The value of the equilibrium
constant KT,P is determined from following equation:
ln K T , P =
GT0, P
RT
With GT0, P = i i0
(10)
(11)
where G is the Gibbs free energy of the reaction, i0 is the standard-state chemical potential of
species i, i is the stoichiometric coefficient of species i in the above reaction , and R is the gas
constant (8.314 J K-1 mol-1) [11-13].
To obtain the equilibrium constant of a reaction at temperature T and pressure P, the standard
state chemical potentials of products and reactants should be determined. The HKF model,
developed by Helgeson and coworkers [10], is embedded in the OLI to calculate standard state
thermodynamic properties at high temperatures and pressures up to 1000C and 5 kbar. The
general equation is as follows:
X T0, P = X T , P, a1 , a 2 , a 3 , a 4 , c1 , c 2 ,
(12)
where X denotes a thermodynamic function such as chemical potential (), partial molal enthalpy
( H ), entropy ( S ), heat capacity ( C p ), and volume ( V ); a1, a2, a3, a4, c1, c2, are HKF
parameters.
The most important parameter to account for the non-ideality of electrolyte solutions is the
activity coefficient, which results from the relation with the excess Gibbs free energy of the
solution:
GE
RT
ln i =
ni
T , P ,n j i
(13)
where ni is the mole number of species i, and j is any other species (excluding i). The pursuit of
an expression for GE to calculate has been ongoing for decades. Numerous models have been
proposed and some of them have also been incorporated into commercial software and applied in
industry [14].
The recently developed Mixed Solvent Electrolyte (MSE) model [11-13] is capable of describing
systems of electrolyte solutions by means of calculating the thermodynamic properties of
electrolyte solutions from infinite dilution to the fused salt state, as well as electrolytes in mixed
solvents. Capability and accuracy of this model in predicting multicomponent solutions in
hydrometallurgy has been proven where the MSE model in the OLI software was applied into
complex solutions [14-17].
In this work, the MSE model is used in the OLI software to calculate activity coefficients in
order to establish a chemical model to investigate chemistry and equilibria of ammonia recovery
system. In the MSE model, the excess Gibbs energy consists of three terms [13]:
10
GE
E
E
E
G SR
G LR
GMR
=
+
+
RT
RT
RT
RT
(14)
E
where G LR
represents the long-range electrostatic interactions which is expressed by the PitzerE
Debye-Hckel formula, GSR
is the short-range interaction term counting primarily for
E
interactions between neutral molecules and is calculated by the UNIQUAC model, and G MR
accounts for the middle-range ionic interactions (i.e., ion-ion, ion-molecule) that are not included
in the long-range term. It is a second virial coefficient-type term for the remaining ionic
interactions and is given by:
E
GMR
= ni xi x j Bij (I x )
RT
i
i j
(15)
where x is the mole fraction of species, and Bij is a binary interaction parameters between species
i and j (ion or molecule), and is also a function of ionic strength as following:
Bij (I x ) = bij + cij . exp I x + 0.01
(B
ij
= B ji )
(16)
bij = BMD0 + BMD1 T +
BMD2
+ BMD3 T 2 + BMD4 ln T
T
(17)
cij = CMD0 + CMD1 T +
CMD2
+ CMD3 T 2 + CMD 4 ln T
T
(18)
where BMDk and CMDk (k =0,,4) are adjustable parameters between species i and j that can be
obtained by fitting available experimental data such as mean activity coefficient, activity of
water, heat capacity, solubility, etc.[14,15].
2.1.2
Model Parameter Evaluation
Regression of experimental data ensures the thermodynamic consistency among those data. It is
essential for reliable process modelling and simulation to ensure consistency with experimental
observations. The pursuit for model reliability results in the generation of new thermodynamic
data and parameters, or the modification of existing data. A successful regression involves
11
selecting the right model and appropriate parameters, and regressing the data with using as few
adjustable parameters as possible.
The OLI-Systems Software needs well tuning of its available default database to manage the
modeling of complex multicomponent systems of our interest. This software provides an
efficient built-in regression facility as well as a databank which facilitates to obtain equilibrium
constants.
The validation of model parameters is a necessary final step in process modelling and simulation
to ensure that the regressed parameters produce results consistent with experimental data that
were not used in the regression step. This is accomplished by comparing the model results with
experimental data beyond the range of available data used for parameterization, i.e., at different
temperatures and in more complicated multi-component systems, or even in real
hydrometallurgical or chemical process solutions. This prevents excessive fitting that has no
chemical foundation. Process modelling without parameter validation can produce serious
deviation from experimentally known chemical behaviour.
2.2 Experimental Methodology

The new measurements are meant to produce new experimental data to be used either for
validating the chemical model developed so far or for regressing interaction parameters in the
chemical model. As well, the new data are measured under relevant industrial conditions, so they
will be useful in different research fields or by different industries, since it is not practical to do
these measurements under all different conditions. The solubility of solid in solution and
ammonia measurements will be discussed further.
Relevant industrial conditions are in the following ranges. The feed solution to the Copper Boil
process contained 175 to 185 g/L, corresponding to mole ratios in the range 10:1 to 14:1[18, 19].
After removing the excess ammonia from the nickel solution, the three ammonia removal steps
also remove a substantial amount of water, resulting in a significant increase in metal and
ammonium sulphate concentrations. The overall solution volume reduction corresponds to 15 to
20%, and as a result, the nickel concentration increases by about 10 g/L e.g. from 55 to 65 g/L.
The copper-free nickel diammine liquor, outflow of the Copper Boil Process, typically contains
12
65 to 70 g/L Ni, 3 g/L Co, less than 1 mg/L Cu, 35 to 40 g/L NH3 and 320 to 340 g/L (NH4)2SO4
[18]. Temperature is varying from 85 to 115 C and pressure is in the range of 14.7 to 20 psia.
Since nickel and ammonia are two dominant species in the Copper Boil process, the prediction of
their chemistry is crucial to predict the whole solution chemistry. To obtain the interaction
parameters between Ni2+ and NH4+ ions, the solubility data of the double salt of ammonia nickel
sulphate hexahydrate, (NH4)2SO4.NiSO4.6H2O, in NiSO4-(NH4)2SO4-H2O system is required.
The solubility of this double salt in water has been measured by Sue et al. [20] up to 60 C. Their
data were used in this work to regress the Gibbs free energy and entropy of the double salt and
the new data were added into the OLI database. But it is necessary to measure the solubility of
this double salt in water up to the double salt stable temperature of 96.6 C to make sure the
fitting can cover the condition of the Copper Boil process.
Also, there are some other solid phases for which solubility data are either missing or are at
lower temperature ranges up to 50 C and it is necessary to measure their solubilities. Cobalt
ammonium sulphate hexahydrate double salt ((NH4)2SO4.CoSO4.6H2O), and Cobalt(III)-nickel
hexammine sulphate complex salts are examples for which solubilities need to be determined.
The latter is the salt which precipitates in the nickel leach solution and dissolves in water to set
nickel free. This is the key factor for nickel and cobalt separation process.
There are two methods for measuring the solubility of solid phases: dissolution method and
precipitation method. Reliability and feasibility of the dissolution method is higher, since the
complicated formation of intermediate phases is avoided [21]. However, in some studies,
solubility of a known solid was measured during heating and subsequent cooling. If the results
obtained from heating are similar to those obtained from cooling, it shows that there was no
intermediate metastable phase formation.
To study the solubility of a solid phase, a 2L flanged jacketed glass reaction vessel (ACE Glass)
with stirrer is used (Figure 3). A temperature-controlled circulating heater with oil is used to heat
the solution to 0.2 C of the desired temperature. Also, a calibrated thermometer, conductivity
meter, condenser, and sampling line are positioned in the vessel. The reaction vessel is filled
with water or a solution of known composition with an excess amount of solid phase for example
ammonium nickel sulphate hexahydrate double salt (ANSH) is added in excess beyond its
solubility at highest temperature.
13
The charged reactor is heated to a known temperature while stirring takes place. Then, the
solution reaches to equilibrium over time; equilibrium is reached when conductivity and
solubility reaches a constant value. This equilibrium time is established for lowest temperature
where kinetic is slow to ensure that at higher temperatures equilibrium is reachable. Using
preheated syringe, samples are taken at the temperature of the experiment and prepared for
analysis. Inductively coupled plasma (ICP-EOS) analysis is used for the concentration of Ni, Co,
Zn, Cu, and S in the solution. X-ray diffraction (XRD), scanning electron microscopy (SEM),
and thermo gravimetric analysis (TGA) can be used for solid phase sample analysis to analyze
the morphology of solid particles, solid phase characterization and amount of hydrate,
respectively.
This experiment is repeated at different temperature intervals for instant from 20 C up to 120 C
with 10 C intervals. Highest temperature is limited for some solids due to the dehydration
temperature or instability of that solid for instance ANSH is only stable up to 96.6 C.
Furthermore, to investigate the possibility of the formation of any intermediate metastable solid
phase, precipitation method is conducted. Same experiment procedure is repeated starting from
the highest temperature to the lowest one with the same temperature intervals. Consistency
between the results obtained from ICP and XRD analysis confirms the solubility of the same
solid phase is measured through both dissolution and precipitation method. However, in case of
discrepancy in results of heating and cooling method, further investigation is due to analyze the
nature of new meta-stable solid phase and related solubility mechanism.
14
Pressure gauge
Stirrer
Sampling line
Stirring speed
controller
2L Glass reaction vessel
Flange
Temperature controller
Jacket heater
2L Flanged jacketed reactor

Fig 3. Schematic view of the reaction vessel for solubility measurements
15
3 RESULTS AND DISCUSSION

3.1. Binary Systems
There are some experimental data available for electrolyte systems containing NiSO4, NH3,
(NH4)2SO4, CoSO4, etc. This work focuses on binary and ternary systems of the mentioned
electrolytes. The model parameter estimation was performed through the OLI built-in regression
facility from collected experimental data. A list of experimental data sources used for model
parameter estimation is presented in Table 1. Literature data type includes various
thermodynamics properties including but not limited to solubility data, mean activity coefficient,
heat capacity, activity coefficient of water, and stability constant of complex. BMDs and CMDs
are the MSE ion interaction parameters between dominant species in studied systems. Table 2
shows these ion interaction parameters and the database that is developed with these new ion
interaction parameters.
Table 1. Experimental data used for model parameter estimation
System
Data type
Temperature range (C)
Reference
CoSO4-H2O
Solubility, , Cp
0-200
[22-26]
Ni(NH3)n2+-H2O
n, (n=1,,6)
25
[27]
Co(NH3)n2+-H2O
n, (n=1,,6)
25
[27]
Co(NH3)63+-H2O
n, (n=5,6)
25
[27]
(NH4)2Ni(SO4)2-H2O
Solubility
20-60
[22,28, 29]
NiSO4-CoSO4-H2O
Solubility
17-90
[22,30]
n=stability constant of the complex
16
Table 2. MSE middle range ion interactions parameters

Temp.
Species
Species
BMD0
BMD1
BMD2
CMD0
CMD1
CMD2
range(C)
Database
CoSO4-H2O
Co2+
SO42-
-76.43047
-0.0381
20551.6
-49.3487
0.44399
0-200
Niboil
NiSO4-CoSO4-
Co2+
Ni2+
266.2736
-0.8961
-235328.9
978.051
0.23133
17-90
Niboil
NiSO4-H2O
Ni2+
SO42-
-62.81981
0.131417
-110727.55
29.09487
0.0107966
32862.21
0-300
Niboil
NiSO4-H2O
Ni2+
HSO4-
-228.2051
0.505456
151.6307
-0.227221
0-300
Niboil
NiSO4-H2O
Ni2+
SO42-
-257.629
0.335022
31865.56
301.1285
-0.239186
-31179.97
0-300
MSE
NiSO4-H2O
Ni2+
HSO4-
-123.997
0.452732
-14193.98
267.8592
0.870478
0-300
MSE
(NH4)2SO4-H2O
NH4+
SO42-
526.427
-1.38466
-69253
-1151.25
2.99106
153609
(NH4)2SO4--
NH4+
NH3
-2.17
0.01472
-1501
29.99
-0.05427
-4751
Systems
H2O
MSE
0-160
NH3-H2O
The standard state Gibbs free energy (Gf) and entropy of formation (Sf) should be adjusted
since the reaction equilibrium constant is the exponent function of the Gibbs free energy of
formation; the reaction equilibrium constant directly affects the solubility calculations.
Therefore, the standard state Gibbs free energy (Gf) and entropy of formation (Sf) of several
solids of studied systems were adjusted by fitting the experimental solubility data over the entire
range of temperature to obtain the optimum solubility product of those solids. Table 3 shows the
regressed values of the standard state Gibbs free energy (Gf) and entropy of formation (Sf) of
the studied solids. First column of Table 3 shows the dissociation of these solids in water and the
dissociation reaction is defined in the database. It should be noted that formation reaction which
is the formation of one mole of a compound from its elements is different from dissociation
reaction.
Niboil
17
Table 3. The dissociation reaction, standard state Gibbs free energy and entropy of formation of the solid
Gf
Sf
(kcal/mol)
(cal/K/mol)
CoSO4.7H2O=Co2++SO42-+7H2O
-591.2
106.9
0-43.3
-534.5
89.1
43.3-64.2
-250.4
12.8
64.2-200
CoSO4=Co2++SO42-
-191.3
-55.4
0-200
(NH4)2Ni(SO4)2.6H2O=2NH4++Ni2++SO42-+6H2O
-752.8
117.9
20-60
NiSO4.7H2O=Ni2++SO42-+7H2O
-588.5
95.8
0-31.4
-531.8
80.7
31.4-100.1
-244.8
30.9
100.1-250
NiSO4=Ni2++SO42-
-185.5
22.1
0-250
Dissociation reaction
Temperature range, C
Figure 4 shows how well the MSE model can predict the thermodynamic properties. Mainly,
solubility of vapor or solid is shown which is of interest. Ammonia and water equilibria is
predicted well by default model as shown in Figure 4. Mole fraction of ammonia in ammoniawater mixture is predicted very well in both liquid and vapour phase over a wide range of
temperature and pressure. This prediction is very important in the Copper Boil process since the
majority of vapour phase is consist of ammonia and water vapour, however due to the existence
of other electrolytes in solution, prediction of vapour pressure over multi-component solution of
the studied process is complex.
Absolute average relative deviation is used as a statistical measure to show the deviation of
experiment or literature value from calculated value from the modeling results.
AARD =
1
N
exp_ value calculated _ value
n =1
exp_ value
18
The solubility of ammonium sulphate in water was studied by Terres and Schmidt [31], Ishikawa
and Murooka [32], and compiled by Linke and Siediel [22]. The OLI default database is capable
of predicting ammonium sulphate solubility in water very well using MSE model. As can be seen
in Figure 5, the solubility is high. This graph also shows the well prediction with AARD of 2.7%
over the temperature range of interest in the studied process. No additional fitting was carried out
in these two systems.
1.2
Exp (Linke & Siedel) x NH 3
OLI (M SE) xNH 3
Exp (Linke & Siedel) y NH 3
OLI (M SE) yNH 3
xNH and yNH

3
3
1.0
0.8
0.6
0.4
0.2
0.0
-0.2
-100
P atm =0.2 0.5 1 2
-50
50
100
4 6 8 10
150
200
Temperature ( C)
Fig 4. NH3-H2O equilibrium curves: Mole fraction of ammonia in both vapour phase and liquid phase at
equilibrium state. using the MSE (H3O+) default database prediction ;experimental data from [22]. Lower lines
and square dots illustrated the mole fraction of ammonia in liquid phase and upper lines and circles show the
mole fraction of ammonia in vapour phase.
19
8
OLI ( default databas-MSE)
Exp data (Linke and Siedel)
(NH4)2SO4 ,mol/kg water
Exp data (Ishikawa and Murooka)

Exp dara (Terres and Schmidt)
AARD%=2.7
5
0
20
40
60
80
100
Temperature (C)
Fig 5. The solubility of ammonium sulphate in water, experimental data from Terres and Schmidt [31],
Ishikawa and Murooka [32], and Linke and Siedel [22] and MSE (H3O+) default data base are used. Solid phase
is ammonium sulphate.
The solubility of CoSO4 in water has been measured by Bruhn et al. [33], Bursa [34] and was
sited by Linke and Seidell [22]. There are also experimental data available on the mean activity
coefficient and the heat capacity of CoSO4 in water [26,35] and activity of water. These
experimental were used in this work to fit the MSE middle-range interaction parameters between
Co2+ and SO42- ions, as well as to adjust the standard state Gibbs free energy and entropy of
formation of the solids, CoSO4.7H2O, CoSO4.6H2O, and CoSO4.1H2O, as a function of
temperature.
Therefore, Cobalt sulphate and its solid phases, namely CoSO4.7H2O,
CoSO4.6H2O and CoSO4.1H2O, were added in the Niboil database of the OLI software.
Solubility of CoSO4 in water is shown over a wide range of temperature in Figure 6 where solid
phase change temperature is shown and well fitted model is shown by solid line compared to
experimental points as dots in the figure.
20
6.0
Linke & Seidell (1958)
CoSO4, mol/kg water
5.0
Bruhn (1965)
Bursa (1980)
CoSO4.6H2O
4.0
Fitted model results
3.0
T=64.2 oC
CoSO4.1H2O
T=43.3 oC
2.0
CoSO4.7H2O
1.0
AARD%=5.2
0.0
0
50
100
150
200
Temperature, C
Fig 6. The solubility of the CoSO4 in water. Experimental data
are from [22, 32, 34]. The curve is the fitted model.
The fitted parameters and the adjusted values for the Gibbs free energy and entropy of formation
are presented in the Tables 2 and 3, respectively. Figures 6 to 8 show the fitted results for the
solubility, and Cp values compared with experimental data and as can be seen the fit is very
good. Absolute average relative deviation of 5.2% is a collective measure for all
thermodynamics properties used in cobalt sulphate and water system.
21
4.5
3
2.5
2
1.5
Asseyev (1996), T=25 C
1
0.5
Asseyev (1996), T=95 C
Fitted Model results, T=25 C
Fitted Model results, T=95 C
0
0
0.5
1.5
CoSO4, mol/ kg water

Fig 7. The heat capacity (Cp ) of the CoSO4 in water vs. temperature.
Data points are from [26]. The curve is the fitted model. AARD%=5.2
1.0
0.9
Mean activity coefficient
Cp , J/kg/K
4
3.5
Francesco (1999)
0.8
0.7
0.6
0.5
0.4
0.3
0.2
0.1
0.0
0.0
0.2
0.4
0.6
0.8
1.0
CoSO4 , mol/kg water

Fig 8. The mean activity coefficient of the CoSO4 in water. Data points are from [26].
The curve is the fitted model. AARD%=5.2
ZnSO4, mol/kg water
22
AARD%=4.3
Fig 9. The solubility of ZnSO4 in Water, Experimental data are from [22, 36]. The curve is the fitted model.
Solid phase at low temperature is ZnSO4.7H2O and after 42C it is ZnSO4.6H2O and at high temperatures
ZnSO4.H2O forms a solid phase.
The solubility of ZnSO4 in water is predicted using default database and compared by measured
data from Rudolph [36], and Link and Siedel [22] as shown in Figure 9. The OLI default
database was tested using the mean activity coefficient, activity of water, and the solubility of
aqueous solution of zinc sulphate that was shown to be adequate to describe this system
compared with experimental data. There is only 4.3 % deviation which is in an acceptable range.
Results obtained from the OLI default database for the solubility of NiSO4-H2O is shown in
Figures 10. Within the studied range of temperature, both Ni2+and NiSO4-aq are dominant
species. The fitted parameters and the adjusted values for the Gibbs free energy and entropy of
formation are presented in the Tables 2 and 3, respectively. Figures 10 shows the fitted results of
this work for the solubility compared with experimental dada and as can be seen the fit is very
good with AARD of 3.9%. It should be noted that previously adjusted parameters and recent
parameters in the updated database, both predicting the NiSO4 behavior very well. Therefore, it
23
was decided to be consistent with the new version of software and use the updated new version
of database. Nickel ion is the most dominant species in electrolyte solution in the Copper Boil
process, so predicting the behavior of nickel sulphate and its speciation in water and multicomponent solution is of great importance. It can be noted from this figure that nickel sulphate
hexa hydrate could be the possible precipitation within the process temperature range providing
that it reaches its solubility limits.
7
Exp Data, Linke & Siedel 1965,
Brune 1965
NiSO44, (mol/kg
water)/
NiSO
mol/kg water
Fitted model result

5
NiSO4.6H2O
4
NiSO4.7H2O
NiSO4.1H2O
3
2
1
AARD%=3.9
Ice
0
-10
AARD%=3.9
40
90
140
190
240
Temperature ( C)
Fig 10. The solubility of the NiSO4 in water. Experimental data are from [22, 23]. The curve is the fitted model.
Solid phase at low temperature is NiSO4.7H2O and after 31.4C it is NiSO4.6H2O and at temperatures higher than
100.1C NiSO4.H2O forms a solid phase.
24
3.2. Ternary Systems

Since most of binary systems were predicted well over the condition range of interest, ternary
systems were investigated. The solubility of NiSO4 in ammonium sulphate solution at 25C was
measured and data collected by Linke and Siedel [22]. The OLI default database can predict the
solubility behavior of this system very accurately at 25C. However there is a lack of
experimental data for this important system that requires measurements. Figure 11 shows the
solubility of (NH4)2SO4 in NiSO4 where a double salt NiSO4.(NH4)2SO4.6H2O forms as a solid
phase.
6
Exp. data ( Linke & Siedel)
(NH4)2SO4, mol/kg water
(NH
4) 2SO 4 molality
OLI (Default database-MSE)
(NH4)2SO4.NiSO4.6H2O
AARD%=1.2
0.5
1
1.5
NiSO 4 molality
2.5
Ni SO4, mol/kg water

Fig 11. The solubility of (NH4)2SO4 in NiSO4- H2O, where (NH4)2SO4.NiSO4.6H2O is forming as a solid phase. The
curve is the fitted model and experimental data from [22]. T=25 C.
25
The solubility of NiSO4 in CoSO4 was measured from 17 to 90C by Benarth [30] and also was
sited by Linke and Seidell [22]. These data were used again in this work to adjust the interaction
parameters between Ni2+ and Co2+ ions. Figure 12 shows the experimental solubility of NiSO4 in
CoSO4 solution and the fitted model results at different temperatures. As it is clear, the fitting is
very good. The error between the experimental data and the fitted results is 2 % very close to
previous work. The parameters between Co2+ and SO42- are those obtained in this work. The
system of NiSO4 in water is decided to use the updated default database rather than previously
regressed parameters. Since, cobalt ion is the second dominant metal ion in the Copper Boil
process solution, its interaction with nickel ion plays an important role for understanding of the
chemistry of electrolyte solution in the process. In general, these interactions are also crucial to
analyze the behavior of ammonia pressure leach stage and nickel-cobalt separation process.
7.0
Benrath (1934), 17.5 C
NiSO44, ,mol/kg
water
NiSO
mol/Kg
H2 O
6.0
Benrath (1934), 30 C
NiSO4.1H2O
5.0
NiSO4.6H2O
4.0
3.0
Model, 17.5 C
Model, 30 C
2.0
Model, 50 C
NiSO4.7H2O
1.0
Model, 70 C
Model, 90 C
AARD%=2
0.0
0
10
15
20
25
30
CoSO,4mol/kg
, mol/Kg
H2 O
CoSO
water
4
Fig 12. NiSO4 solubility vs. CoSO4 concentration. Data points
are from [22,30]. Lines are fitted model results.
Ammonium nickel sulphate hexahydrate (ANSH) is one of the picromerite series of double salts.
The picromerite series of double salts includes a large number of compounds formed from
26
sulphates of divalent metals such as Mg, Ni, Co and Zn with alkali metals such as K, Rb and
NH4. These crystallize from water as hexahydrates and show resemblances in many properties.
In ammoniacal nickel sulphate media, the double salt of (NH4)2SO4.NiSO4.6H2O or
(NH4)2Ni(SO4).6H2O precipitates as the solid phase. So in order to model this system, it was
necessary to add this solid to the OLI database. There are some data available for the solubility
of ANSH in water in the literature [28, 29]. These experimental data were used to fit the Gibbs
free energy and the entropy of formation of this solid. The fitted values are reported in Table 3.
Figure 13 shows the fitted model results compared with experimental data. As it is clear the fit
was very good with a relative error of 2.75%.
ANSH solubility, mol/ kg water
0.8
Su (2002), Hill (1940) Exp data
0.7

0.6
0.5
Solid: (NH4)2Ni(SO4)2.6H2O
0.4
0.3
0.2
0.1
AARD%=2.7
0.0
10
20
30
40
50
60
70
Temperature, C
Fig 13. (NH4)2Ni(SO4)2.6H2O solubility in water. Data points are from [37,38]. Lines are fitted model
results.
The solubility of nickel hydroxide in ammonia solution was measured by Arkhipov [37],
Bonsdorff[38], Paris [39], Ziemniak[40] at different concentrations and temperatures in the range
of 16-60C. Model can predict the solubility of Ni(OH)2 in ammonia solution well as shown in
27
Figure 14. However there is space for further investigation to narrow the error range and obtain
better agreement by manipulating interaction parameters of Ni2+ ion and NH3(aq).
0.6
MSE, T=16C
MSE,T=20C
0.5
MSE, T=25C
Ni(OH)2, mol/kg water
MSE, T=40C
MSE, T=60C
0.4
Arkhipov et al. 1950, T=20C

Arkhipov et al. 1950,T=20C
dilution
Bonsdorff 1904, T=25C
0.3
Bonsdorff 1904, T=25C

0.2
Muendel et al. 1961, T=40C

Muendel et al. 1961, T=60C
Paris 1951, T=16C
0.1
Ziemniak and Goyette 2004
0
0
10
15
20
25
NH 3, mol/kg water
Fig 14. Solubility of Ni(OH)2 in ammonia solution. Lines are model predictions and experimental data are
from [ 37-40]
The behaviour of ammonia over an aqueous solution containing studied species is an important
issue to understand very well and investigate. Rumpf and Maurer [41, 42] measured solubility of
ammonia in aqueous solutions of sodium and ammonium sulphate at temperatures from 60 to
160 C and pressures up to 3 MPa. Figures 15 and 16 present total ammonia pressure versus
ammonia molality in solution while the molality of ammonium sulphate is fixed at two levels of
2 and 4 molal. The solubility of ammonia in an aqueous solution of ammonium sulphate is not
predicted well by using the OLI default database therefore interaction parameters between
dominant species which are ammonia and ammonium ion are regressed and reported in Table 3.
Solid lines in both figures represent the fitted model results showing a good agreement between
28
the fitted model and experimental data at both 2 and 4 molal ammonium sulphate solution.
Deviation of fitted model result from the experimental data is 2.1 and 3.3 % for 2 and 4 molal
ammonium sulphate solution, respectively.
Since ammonium sulphate molality is changing from 1.3 to 2.9 within the Copper Boil process
and temperature range of 85 to 115 C, these two figures provide a rough estimate about total
pressure above solution. For instance, ammonia molality is changing between 2 and 7 molal
(Table 5). In reboiler where molality of both ammonia and ammonium sulphate is around 2
molal, total pressure can be read from figure 15 to be around 1 atm which is close to actual plant
data. However, in this example the effect of other metal sulphate electrolytes were neglected
which creates an error into final calculation.
Furthermore, dashed lines in figures 15 and 16 show the prediction of MSE model with default
database without the contributions of this work to clearly illustrate the benefits and accuracy of
fitted model resulted from this work.
35
T=60 C, regression
T=60 C, exp data
T=160 C, regression
(NH 4)2SO4= 2 mol/kg water
Total Pressure, atm
30
25
T=160 C, exp data

T=60 C, default database
T=120 C, regression
T=160 C
20
T=120 C, exp data

15
T=120 C
10
T=60 C
AARD%= 2.1
0
0
10
15
20
NH3, mol/kg water
25
30
Fig 15. Total pressure vs. ammonia molality in solution of 2 molal ammonium sulphate. Solid lines are
fitted model result where dotted line shows the default model prediction. Experimental data are from [38,
39]
29
30
(NH4)2SO4=4 mol/kg water
T=160 C
25
Total Pressure, atm

20
T=140 C
T=60 C, regression
T=80 C, regression
15
T=120 C, regression
T=120 C
10
T=140 C, regression
T=160 C, regression
T=60 C,exp data
T=80 C,exp data
T=80 C
T=120 C,exp data

T=140 C,exp data
T=160 C,exp data
T=60 C
0
0
10
15
20
25
NH3 mol/kg water
30
35
AARD%= 3.3
Fig 16. Total pressure vs. ammonia molality in solution of 4 molal ammonium sulphate. Solid lines are
fitted model result where dotted line shows the default model prediction. Experimental data are from [38,
39]
3.3. Nickel-Ammonia Complexation

Complexation has a substantial effect on the behaviour of electrolytes in the ammoniacal nickel
sulphate solutions. The concentration of the free nickel ion in solution is significantly reduced by
the formation of nickel ammine complexes, Ni(NH3)n2+, (n=1-6).
The role of ammonia is to increase the solubility of the nickel in the reduction solution by
forming complexes and on the other hand to neutralize the acid which forms during the reduction
[43].
2+
Niaq
+ nNH 3( aq ) = Ni ( NH 3 ) 2n+
(19)
H 3O + + NH 3( aq ) = NH 4+ + H 2O
(20)
30
The stability constants of complexes for reaction 19 were collected from the literature [27] and
entered into the OLI database. These data are presented in Table 4. There is no data available on
the entropy or enthalpy of formation of these complexes.
The amount of each complex can be measured using different technologies such as Raman
spectroscopy. This is beyond the scope of this work however it is of interest to check whether the
speciation based on the new complexation data added to the OLI meet the real world or not. If
not, those data to be measured can be used to introduce the complexes more properly to the OLI
database. In other words, there is lack of literature data for the speciation of complextion to
validate the accuracy of model prediction except the model overall performance.
Figure 17 shows the speciation of different nickel amine complexes versus NiSO4 concentration
in a solution containing 3.5 m ammonium sulphate and 3.5 m ammonia at 112C which is near
the condition in the Copper Boil process.
100
2+
2+
Ni(NH3)4
Ni
2+
Ni(NH3)
T=112 C
[NH3]=3.5 molal
80 [(NH4)2SO4]=3.5 molal
2+
Ni(NH3)5
2+
2+
Ni(NH3)2
Ni(NH3)6
Ni Speciation, %
2+
Ni(NH3)3
60
40
20
0
NiSO4, mol/kg water

Fig 17. Speciation of nickel ammine complexes in NiSO4-(NH4)2SO4-NH3-H2O solution
31
Similar to nickel in ammoniacal solutions, both Co(II) and Co(III) form complexes in the
presences of NH3 ligands. So, stability constants of these complexes were found in the literature
[27] and were added into the OLI database. These data are presented in Table 4. There is no data
in the literature to shows the speciation of these complexes versus temperature or composition.
Table 4. The stability constant of nickel and cobalt ammine complexes
Reaction
Log n
T (C), Medium
Reference
Ni2++NH3=NiNH32+
2.67
30, Dilute
[27]
Ni2++2NH3=Ni(NH3)22+
4.79
30, Dilute
[27]
6.4
30, Dilute
[27]
7.47
30, Dilute
[27]
8.1
30, Dilute
[27]
8.01
30, Dilute
[27]
Co2++NH3=CoNH32+
1.99
30, Dilute
[27,44]
Co2++2NH3=Co(NH3)22+
3.5
30, Dilute
[27,44]
4.43
30, Dilute
[27,44]
5.07
30, Dilute
[27,44]
5.13
30, Dilute
[27,44]
4.39
30, Dilute
[27,44]
29.51
25, Dilute
[44]
33.66
25, Dilute
[18]
n=stability constant of the comple
32
3.4. Experiment Results.

As discussed in the introduction, the solubility of ammonium nickel sulphate hexa hydrate in
water is of importance due to its role in the Cupper Boil chemistry. Solubility of picromerite salts
are described in detail in the experiment methodology. Ammonium nickel sulphate hexa hydrate
was used as reagent chemical grade from Fisher with 99.9% purity. A solution of known
composition with an excess amount of ANSH solid beyond its solubility at highest temperature is
prepared. To ensure the existence of only one solid phase for solubility measurement, both
dissolution and precipitation methods were used. To study the solubility of a solid phase, a 2L
flanged jacketed glass reaction vessel from ACE Glass with magnetic controllable stirrer was
used. A temperature-controlled circulating heater with oil is used to heat the solution to 0.2 C
of the desired temperature. Also, a calibrated thermometer, conductivity meter, condenser, and
sampling line are positioned in the vessel. The reaction vessel is filled with the prepared solution.
Figure 18 shows the actual experiment set-up for solid-liquid equilibria measurements.
The charged reactor was heated to a known temperature starting at room temperature while
stirring took place. Then, the solution reached to equilibrium over time; equilibrium was reached
when conductivity and solubility reached a constant value (plateau). This equilibrium time was
established for the lowest temperature where kinetic is slow to ensure that at higher temperatures
equilibrium is reachable within that time. For sampling, a syringe was preheated to the
experiment temperature. Samples were withdrawn by syringe at the temperature of the
experiment through a filter to prevent any solid withdrawal into the solution. Also, tight sealed
were used to prevent solution evaporation and maintain the same solution concentration.
Withdrawn solution samples were diluted with 5% HNO3 and stored in sealed plastic test tubes at
room temperature prepared for analysis. The concentration of nickel was measured by
inductively coupled plasma ICP-EOS analysis using the 231.604, 221.648, and 232.008 nm
emission lines. The X-ray diffraction (XRD), scanning electron microscopy (SEM), and thermo
gravimetric analysis (TGA) can be used for solid phase sample analysis to analyze the
morphology of solid particles, solid phase characterization and amount of hydrate, respectively.
This experiment is repeated at different temperature intervals for instant 10 C up to 96 C which
is limited due to the dehydration temperature and instability of ANSH. After each temperature
increase, 0.5 h was allocated to reach thermal equilibrium. Time allowed to reach a chemical
33
equilibrium depends on the dissolution rate of the solid phase at the experiment conditions. For
ANSH solubility measurement, around 12 h was the equilibrium time at lowest temperature.
However this time is shorter at higher temperatures due to faster dissolution rate at higher
temperatures, the same 12 h was allowed for each repeated experiment to satisfy the chemical
equilibrium.
Then precipitation method is conducted by cooling from the highest temperature to the lowest
one with the same temperature intervals to investigate the possibility of the formation of any
intermediate metastable solid phase. The consistency between the results obtained from ICP
analysis of both methods confirmed that the solubility of same solid phase is measured through
both dissolution and precipitation method.
D
B
A
A
A
Fig 18. Experimental set up for solubility measurements.

A. Jacketed reactor, B. Temperature controller, C. Temperature-controlled circulating heater, D. Sampling line, E.
stirring speed controller, F. Stirrer
Figure 19 shows the results of experiments carried out in this work extending to ANSH stability
temperature of 96.6 C beyond available literature experimental data. Diamond dots show the
results carried out in dissolution (heating) method and dash dots shows the results obtained in
34
precipitation (cooling) method. Star dots presenting limited available literature data. Also using
enhanced database in OLI software, ammonium nickel sulphate solubility is well predicted over
a wide range of temperature with absolute average relative deviation of 4.8 percent. Appendix 1
shows a density table of ANSH which can be used to convert g/100 ml to mol/ kg water.
40
35
ANSH (g/100 ml)
30
25
20
15
Dissolution method results

Precipitation method results
10
Sue et al data
MSE model prediction
5
0
0
20
40
60
80
100
Temperature (C)
Fig 19. Ammonium Nickel Sulphate Hexa Hydrate solubility in water. Diamond and dash dots show this works
experiments. Star dots show literature values. Solid line is a model prediction.
35
SIMULATION OF THE COPPER BOIL PROCESS USING

THE HSC 6.1 SOFTWARE
To understand the behavior of the process chemistry, its important to simulate the Copper Boil
process with simulation software to use the industrial data and connect thermodynamic modeling
to the real world. The HSC Chemistry 6.1 is simulation software designed based on independent
chemical reactions and process units including metal-refining unit operations. The newly added
HSC-Sim module consisting of flowsheet and spreadsheet type processes increases the ability of
the software to be applied to a real process. The HSC Add-In functions are used to turn these
independent calculation units into small HSC engines for thermodynamic applications. The
HSC-Sim module is used to create a simple but still powerful simulation tool to simulate the
Cupper Boil process. This simulation is based on known chemical reactions, known inflows, and
conditions to determine the amount of chemical compounds all around the process.
The industrial data are categorized into two groups: stream and unit operation conditions such as
flow rates, temperature, pressure, etc., and stream composition data. The former is available from
plant data all over the process like Table 6, but the latter data is sparse. Therefore another goal of
using simulation is to find these data. Calculated composition data can be used to validate the
chemical model against industrial data. Therefore, the data from the HSC Chemistry model can
be used in the model developed to simulate the chemistry of the process. As well,
thermodynamic equilibrium model from the OLI provides more detailed and concise
thermodynamic relationship between species which can be used in HSC simulation. This back
and forth approach continues until both the process simulation and the thermodynamic model
become consistent regarding to experimental data and industrial data validation.
The flowsheet of the Copper Boil process is shown in Figure 20. All streams and unit operation
data were gathered during the visit of the Sherritt plant (Corefco) in Fort Saskatchewan, Alberta.
Data used in the simulation are the average of daily values From May-1-2007 to October-112007. Then species that are not included in HSC database such as nickel ammine sulphates and
cobalt ammine sulphates were added to the database using their enthalpy, entropy and heat
capacity values. Furthermore, controllers are used to adjust the mole ratio of ammonia to metals
to the desired amounts by changing the extent of reactions occurring in the process. The most
important mole ratio to be adjusted is 2:1 in the outflow of the reboiler.
A new equilibrium function was built to correlate ammonium ion concentration to H2SO4
concentration in the reboiler. This correlation is confirmed by thermodynamic modeling as well.
36
NH3
NH3
Gas
Gas
Feed from
Co/Ni Separation
Boil
Ni
Feed
Boiler
Stripper
Compressed
NH3 gas output
Steam
air
pot #1 ~2.8psi
coppper boiler
Steam
Steam
copper boiler
pot #2 ~4.0psi
Steam
SO2
copper boiler
pot #3 ~4.4psi
To Oxydrolysis
copper boiler
pot #4 ~4.9psi
Reboiler
Containing NH4SO4
Cu2S & CuS NiSO4
Thickener
Filter
Steam
Steam
H2SO4
Solids containing
Cu(I) & Cu(II)
Fig 20. The Copper Boil process Flowsheet from the HSC Simulation
Using the composition of pot #1 as an inflow to pots and other available flow conditions from
the plant, the Copper Boil pots were simulated and the outflow of four pots and the reboiler were
obtained. Table 5 shows the composition of different species in molality obtained from the HSC
compared to industrial data. Calculated data from HSC are very close to the actual data from
37
Sherritt plant. It should be noted that measured data were in g/L and using density of solution,
they were converted to molality as shown in the following table (*).
Table 5. The Comparison of outflow compositions of the Copper Boil pots calculated by the HSC Chemistry
simulation with available Industrial data. Concentrations are in molality [mol/kg water]. (H2O= 55.51 mol/kg water)
Species
Measured Data from Sherritt Plant *
Simulated Data by HSC Chemistry
Pot #1
Pot #2
Pot #3
Pot #4
Reboiler
Pot #1
Pot #2
Pot #3
Pot #4
Reboiler
NH3
7.062
5.595
4.913
4.176
2.051
6.302
2.768
1.746
1.719
1.698
(NH4)2SO4
1.314
1.302
1.320
1.325
2.905
1.333
1.328
1.328
1.848
1.838
NiSO4
1.068
1.018
1.019
1.038
1.175
1.059
1.059
1.059
1.063
1.059
CoSO4
0.0475 0.0451 0.0163 0.0464
0.0525
0.0386 0.0386 0.0386 0.00387
0.0386
CuSO4
0.0203 0.0157 0.0364 0.0147
0.00
0.0098 0.0096 0.0094 0.00094
0.0059
ZnSO4
0.0383 0.0452 0.0452 0.0371
0.0415
0.0342 0.0342 0.0342
0.0342
0.0342
4.1 Prediction of ammonia mole fraction in the vapor phase measured

by Sherritt
The model developed in this work based on the new parameters that were added to the OLI
database, was checked against the data provided by Sherritt company to see whether the results
from the model is comparable to the test results obtained in the plant. Figure 21 shows the mole
percentage of ammonia in the vapour phase versus different ammonia:metal mole ratio.
38
Table 6. The composition of different pots in the Copper Boil process of Sherritt
Solution Analysis
unit
Pot #1
Pot # 2
Pot #3
Pot #4
Reboiler
Ni
g/L
62.67
59.74
59.84
60.90
68.95
Co
g/L
2.80
2.66
2.67
2.74
3.10
Cu
g/L
1.29
1.00
1.03
0.94
0.00
Zn
g/L
2.50
2.37
2.38
2.42
2.72
g/L
80.50
77.46
77.72
78.86
133.74
(NH4)2SO4
g/L
173.73
172.08
172.84
175.09
383.89
NH3 (titratable)
g/L
120.33
95.33
83.72
71.17
34.94
5.73
5.03
4.41
3.69
1.62
NH3:TM*
Molar Ratio
Operating Conditions
Pressure
atm
1.19
1.27
1.31
1.35
1.36
Temperature
77.92
93.60
97.19
100.91
113.60
TM= Total Metals, MR=Molar Ratio of titratable ammonia to total metals
In order to obtain this figure, the pot composition presented in Table 6 was used. These data
were measured in the Sherritt plant under real process conditions. The line in Figure 21 presents
the lab test work conducted in Sherritt which is the distillation of ammonia over a solution with
similar composition to the one in pot no. 1. Using measured data from Sherritt plant presented in
Table 6, the mole per cent of ammonia vs. NH3:metal molar ratio was calculated by using the
new model. These results are shown as dots in the figure 21. Figure 22 also shows the calculated
total pressure in pots compared to the measured total pressure in pots in the Copper Boil process.
Since the condition in pot #2 and pot #3 is closer to lab test condition, better predictions were
observed.
39
Lab test results from Sherritt
% NH3 in vapour phase
50
Model result prediction

40
30
20
10
0
1.0
1.5
2.0
2.5
3.0
3.5
4.0
4.5
5.0
5.5
NH3: Metal Mole Ratio

Fig 21. Ammonia mole percentage in the vapor phase vs. ammonia:metal mole ratio.
Dots are MSE model calculated results; the curve is lab test results from the Sherritt plant.
3.00
Total Pressure (atm)
2.50
Model result prediction

Sherritt plant data
2.00
1.50
1.00
0.50
0.00
Pot #1
Pot #2
Pot #3
Pot #4
Pot #5
Fig 22. The Comparison of total pressure in the Copper Boil pots obtained from the MSE model
with that from plant data
40
5 CONCLUSIONS
The chemistry of the Copper Boil process was studied in this work, and a chemical model for
predicting the phase behaviour in ammoniacal solutions containing cobalt, nickel, copper, and
zinc was investigated. The OLI software with the MSE (H3O+) model was used, and the ionic
interaction parameters between dominant species in the solution were determined by fitting
available binary and ternary experimental data, and then these interaction parameters were
validated in multicomponent systems. This approach proves the predictability and consistency of
the chemical model. Using the chemical model makes it possible to predict the solution
chemistry in the ammonia recovery stage of the Copper Boil process. Therefore the results of this
work would be a dedicated thermodynamic database to predict the chemistry of the Copper Boil
process and assess the solubility of nickel sulphate in a wide variety of complex aqueous process
units in Ni/Co Hydrometallurgy.
Using experimental data available for electrolyte systems containing NiSO4, NH3, (NH4)2SO4,
CoSO4, etc., the model parameter estimation was performed through the OLI built-in regression
facility. Since complexation has a substantial effect on the behaviour of electrolytes in the
ammoniacal nickel sulphate solutions. The concentration of the free nickel ion in solution is
significantly reduced by the formation of nickel ammine complexes, Ni(NH3)n2+, (n=1-6).
Similar to nickel in ammoniacal solutions, both Co(II) and Co(III) form complexes in the
presences of NH3 ligands. Therefore, Ni(NH3)n2+-H2O system, Co(NH3)n2+-H2O system, and
Co(NH3)63+-H2O system are added to OLI database,(n=1-6).
To develop a comprehensive model with the ability to predict multi-component solutions under
various conditions in ammoniacal solutions, more experimental data are needed which are either
not available or available in a narrow range of conditions. The available literature data for the
solubility data of ammonium nickel sulphate hexa hydrate is limited and does not cover the
industrial temperature range of interest. A comprehensive solubility measurement of this double
salt was carried out through both dissolution and precipitation method. MSE model with
developed database predict the behaviour of this solid liquid equilibria very well.
41
Furthermore, thermodynamic equilibrium data from the established chemical model was used to
modify the simulation database. Using the modified database, HSC Chemistry Software (HSC
6.1) was used to simulate the Copper Boil process. This simulation provided some insight on the
ability of the developed model to well predict the chemistry of the Copper boil. Also, it shed
some light on possibility of finding the optimum operating condition for the ammonia recovery
process to minimize the use of sulphuric acid reagent and steam consumption of the Copper Boil
process while maintaining mole ratio of 2 at the end of this process.
42
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fuer Anorganische und Allgemeine Chemie, 1965, 337, no. 1-2, 68-79.
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,1974-c1977, v. 4. inorganic complexes.
45
APPENDICES
Appendix 1: Density Tables

Following tables show density of ammonium nickel sulphate hexa hydrate which can be used for
the conversion calculation of g/ml to molality.
g ANSH/ 100 ml
H2O
T
C
34
39.5
44.5
49
54
59
13.8723
15.63828125
17.43928125
19.219425
21.3743
23.715425
density
1.0798
1.08744
1.09535
1.10343
1.11155
1.11958
Solubility
molality
0.325257
0.364087
0.403086
0.440978
0.486838
0.536287
Density table:
Ammonium Nickel Sulphate Hexa Hydrate
Temp Visc, abs Aq
Density, Aqueous
C
cP
g/ml
0
5
10
15
20
25
30
35
40
45
50
55
60
65
70
75
80
85
90
95
100
1.94499
1.67073
1.46022
1.29481
1.16229
1.05434
0.965124
0.890485
0.827361
0.773444
0.726957
0.68651
0.65099
0.619495
0.591277
0.565708
0.542251
0.520443
0.499879
0.480206
0.46112
1.02801
1.03192
1.03577
1.03962
1.0435
1.04742
1.05138
1.05538
1.05938
1.06337
1.06729
1.0711
1.07476
1.0782
1.08135
1.08416
1.08654
1.08842
1.08971
1.09032
1.09016
46
Molar mass of mostly mentioned components are listed in the following table:
Component
H2SO4
NiSO4
CoSO4
CuSO4
(NH4)2SO4
NH3
FeSO4
Na2SO4
ZnSO4
molar mass
g/mol
98.09
154.74
155
159.62
132.17
17.04
151.92
142.05
161.46
47
Appendix 2: HSC results

Following figures show better illustration of species in the Copper Boil pots and comparison of
the HSC Chemical calculations results versus plant data.
Metals and Ammonia Concetration in Pots

450.0
Concentration (g/l)
400.0
350.0
Ni (g/l)
300.0
Co (g/l)
250.0
Cu (g/l)
200.0
Zn (g/l)
150.0
NH3 titrable (g/l)

(NH4)2SO4 9g/l)
100.0
50.0
0.0
0
pot no.
Composition in pots (inflow to OLI)
8
Ammonia
mol/Kg W
ammonium
sulphate
NiSO4
4
CoSO4
3
2
CuSO4
ZnSO4
0
0
4
pot no.
48
Comparison of Industrial data and

simulated data for the reboiler
8.00
Sherritt plant
data
mol/ kg water
7.00
6.00
Calculated
data by HSC
Chemistry
5.00
4.00
3.00
2.00
1.00
N
H
(N
3
H
4)
2S
O
4
N
iS
O
4
C
oS
O
4
C
uS
O
4
Zn
SO
4
0.00
AARD%=17.98
Comparison of Industrial data and

simulated data for pot #1
8.00
Sherritt plant
data
6.00
5.00
4.00
Calculated data
by HSC
Chemistry
3.00
2.00
1.00
0.00
N
H
(N
3
H
4)
2S
O
4
N
iS
O
4
C
oS
O
4
C
uS
O
4
Zn
SO
4
mol/ kg water
7.00
AARD%= 13.45

Thesis Blast Plasma

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Chemical Modeling of Ammoniacal Solutions

A thesis submitted in conformity with the requirements

Copyright by Sam Roshdi 2011

Chemical Modeling of Ammoniacal Solutions

Chemical Equilibria and Thermodynamic Framework........................................... 8

Model Parameter Evaluation................................................................................. 10

2.2 Experimental Methodology................................................................................................ 11

Appendix 2: HSC results .............................................................................................................. 47

Appendix 1: Density Tables

1.2 The Chemistry of the Copper Boil

Fig 1. The Sherritt nickel/cobalt refinery process

Copper precipitates in the form of copper sulphide as the ammonia concentration

Co( NH 3 ) 36+ Co( NH 3 ) 32+ + 4 NH 3

2 NH 3 + H 2 SO4 ( NH 4 ) 2 SO4 + heat

Cu ( NH 3 )4 SO4 + ( NH 4 )2 S 2 O3 + H 2 SO4 CuS + 3( NH 4 )2 SO4

Ni ( NH 3 )4 SO4 + H 2 SO4 Ni ( NH 3 )2 SO4 + ( NH 4 )2 SO4

NH3, Steam, Air

Fig 2. The Copper Boil process flowsheet

2.1 Chemical Modeling Methodology

Chemical Equilibria and Thermodynamic Framework

aCc a Dd ... mCc m Dd ... Cc Dd ...

Bij (I x ) = bij + cij . exp I x + 0.01

bij = BMD0 + BMD1 T +

cij = CMD0 + CMD1 T +

Model Parameter Evaluation

2.2 Experimental Methodology

2L Glass reaction vessel

2L Flanged jacketed reactor

3 RESULTS AND DISCUSSION

Table 1. Experimental data used for model parameter estimation

Temperature range (C)

n=stability constant of the complex

Table 2. MSE middle range ion interactions parameters

exp_ value calculated _ value

Exp (Linke & Siedel) x NH 3

OLI (M SE) xNH 3

Exp (Linke & Siedel) y NH 3

OLI (M SE) yNH 3

xNH and yNH

P atm =0.2 0.5 1 2

(NH4)2SO4 ,mol/kg water

Exp data (Ishikawa and Murooka)

Therefore, Cobalt sulphate and its solid phases, namely CoSO4.7H2O,

Fitted model results

Asseyev (1996), T=25 C

Asseyev (1996), T=95 C

Fitted Model results, T=25 C

Fitted Model results, T=95 C

CoSO4, mol/ kg water

CoSO4 , mol/kg water

ZnSO4, mol/kg water

Fitted model result

3.2. Ternary Systems

OLI (Default database-MSE)

Ni SO4, mol/kg water

ANSH solubility, mol/ kg water

Fitted model results

Ni(OH)2, mol/kg water

Arkhipov et al. 1950, T=20C

Bonsdorff 1904, T=25C

Muendel et al. 1961, T=40C

Ziemniak and Goyette 2004

(NH 4)2SO4= 2 mol/kg water