Applied Technology Modeling High-Temperature Materials
Producing High-Grade Nickel
Sulfate with Solvent Displacement
Crystallization
Georgiana A. Moldoveanu and George P. Demopoulos
Solvent displacement crystallization
entails the addition of water-miscible
organic solvents to aqueous metallifer-
ous solutions to cause salt crystalliza-
tion. In this work, isopropanol is used to
produce well-grown and relatively pure
nickel-sulfate hexahydrate crystals from
industrial de-copperized electrolyte.
By proper selection of the organic-to-
aqueous ratio, the method of solvent
addition and seeding/product recycling,
nickel-sulfate crystals were produced
with at least an order of magnitude
higher purity than the ones convention-
ally produced by evaporative crystal-
lization. The processing and product
quality advantages of integrating
solvent displacement crystallization
with electrolyte purification in a copper
refinery context are discussed.
INTRODUCTION
Many inorganic salts are produced
industrially from aqueous solutions,
involving the crystallization of the
salt from solution. When the solubility
Figure 1. The influence
of isopropanol ratio on
nickel solubility at differ-
ent temperatures and acid
contents.
2002 January • JOM
of salts is minimally dependent on
temperature, evaporative crystallization
(EC) is used. With this method, water
is removed to increase the solute
concentration above its solubility.
Simple boiling is extremely expensive
since, typically, ~1.5 kg of water must
be evaporated to recover ~0.5 kg of salt,1
for salts whose solubility changes little
with temperature (depending, on the
specific salt). Moreover, the enthalpy
of vaporization of water is high (41.6
kJ/mol)2 and, therefore, the method is
energy intensive. A illustration of this
problem is the recovery of nickel as
crystalline nickel sulfate from copper
electrorefining spent electrolytes. 3,4
During electrolytic refining of copper,
the amount of soluble impurities from
the anodes can increase in the electrolyte
to a level that affects the quality of
the copper cathodes. The conventional
practice of impurity control consists of
continuously withdrawing electrolyte
(the “bleed-off”) from the circulation
system to recover its copper content (by
electrowinning) and to isolate/remove
the soluble impurities; nickel is recov-
ered as sulfate salt via evaporative
crystallization. Although effective,
this technique is expensive, presenting
some major disadvantages:
• The residual solutions are extremely
corrosive (>1,000 g/L H2SO4), result-
ing in high operating and maintenance
costs.
• The evaporation step required to
remove water is highly energy
intensive, increasing operating
costs.
• Due to the violent boiling, super-
saturation control cannot be applied,
so the final product is of poor quality
in terms of purity and crystal size.
Solvent displacement crystallization
(SDC) could serve as an alternative to
evaporative crystallization. It is well
documented that the addition of a water-
miscible organic solvent to an aqueous
solution can reduce the solubility of
some inorganic solutes5,6—this is the
well-known “salting out” phenomenon.
For salting-out to take place, the activity
coefficient of the solute (the inorganic
salt) has to increase or, inversely, the
water activity has to decrease. A general
explanation of this effect indicates that
there is a competition between the polar
organic molecules and inorganic ions for
the water molecules. Since the organic
solvent exhibits a higher affinity for
water (via similar-strength hydrogen
bonds), part of the hydration water
molecules are captured, causing salt
precipitation.5 This enables the separa-
tion of electrolytes from their aqueous
solutions via precipitation and filtration;
the solvent is recovered for reuse by
means of relatively inexpensive low-
temperature or vacuum distillation.
Figure 2. The homo-
geneous crystallization
of nickel sulfate (20°C,
250 g/L H2SO4).
49
 Solvent displacement crystallization concept of supersaturation control,10 and sulfuric acid needs to be known.
has found a wide range of applications has sought to define a process flow Some typical measured solubility
in fields such as specialty chemical sheet that yields clean, well-grown data for the industrial electrolyte are
production and pharmaceutical produc- crystals and achieves low final nickel presented in Figure 1.
tion, but has attracted very limited inter- concentration in the aqueous phase. As expected, the solubility (measured
est in inorganic processing and hydro- This objective was achieved via the as g/L nickel in the aqueous phase)
metallurgy, with the exception of some regulated mixing of the organic solvent decreases with increasing organic frac-
exploratory laboratory studies.1,7–9 with the electrolyte and the use of tion and sulfuric acid concentration and
Cohen was the first to recognize the seed/product recycling. (See sidebar for decreasing temperature. For a typical
potential of using this method to recover experimental procedures.) copper bleed-off solution containing
nickel sulfate from de-copperized 250 g/L H2SO4 and about 20 g/L nickel,
SOLVENT DISPLACEMENT
electrolyte.7 This paper will demonstrate it can be seen that a volumetric ratio of
CRYSTALLIZATION
the application of SDC to an industrial 2-propanol to aqueous phase (expressed
electrolyte. The outcome will be a high- For optimum design of the crystal- as O/A) of 1.5 reduces the solubility of
grade nickel sulfate that can potentially lization process, the solubility of the nickel to 6.65 g/L at 20°C or 3.8 g/L at
be sold to the electroplating industry. salt as a function of organic/aqueous 10°C. On the other hand, increasing the
In particular, this work, based on the ratios (O/A) for various temperatures sulfuric acid concentration to 400 g/L
from 250 g/L lowers the nickel content
EXPERIMENTAL PROCEDURES to 5.6 g/L as compared to 6.65 g/L. Once
the solubility lines were established,
The industrial electrolyte (courtesy of CCR-Noranda) employed throughout this work
had the following composition (in g/L): 18.7 Ni; 250 H2SO4; 0.11 Al; 0.99 As; 0.02 Bi; 0.39
the next step was to conduct SDC tests
Ca; 0.02 Co; 1.14 Cu; 0.29 Fe; 0.08 Mg; 0.11 Sn; and 0.14 Zn. Reagent-grade 2-propanol to determine the optimum experimental
(isopropanol) from Fisher Scientific was used as organic solvent. procedure for achieving low final nickel
Determination of Nickel Solubility (Precipitation Method) values in the aqueous phase and good
quality nickel sulfate crystals (both in
One hundred milliliter samples of industrial electrolyte (~ 19 g/L Ni, ~ 250 g/L H2SO4)
were mixed with isopropanol at different organic/aqueous (O/A) ratios and stirred at
terms of purity and crystal size).
20°C and 10°C for 24 h (6 h for 10°C) to reach complete equilibrium. Following this In a series of tests, 2-propanol (IP)
equilibration period, the crystals were separated by filtration and the nickel content in was added either all at once (high
solution was determined. A similar test was conducted at 20°C on a pre-evaporated sample supersaturation case) or gradually,
of electrolyte, with starting concentration of ~ 30 g/L Ni and ~ 400 g/L H2SO4. maintaining a low supersaturation. First,
In a typical SDC test, 200 mL industrial electrolyte was agitated while 2-propanol was
added to an organic/aqueous total ratio (O/A)total of 1.5 (meaning 300 mL of 2-propanol
the kinetics of homogeneous crystal-
were used in each SDC experiment). After each organic solvent addition, equilibration lization were assessed by monitoring
periods of 15 minutes were allowed, then the solution was sampled to monitor the aqueous nickel concentration after
nickel concentration. The duration of standard tests was 120–180 minutes, unless instantaneous addition of 2-propanol
otherwise mentioned. to give (O/A)total = 1.5. Crystallization
Homogeneous Crystallization kinetics under high supersaturation
To homogeneously precipitate nickel sulfate, the organic solvent was added either at conditions are moderate (Figure 2-curve
once (high supersaturation [S] case) or incrementally (low supersaturation [S] case) to i), requiring slightly over 120 min. to
the aqueous phase. The mixture was agitated for 120 minutes and samples were taken reach the final (equilibrium) value of
periodically for analysis. Samples taken by pipette were diluted ten times immediately with 7.7 g/L. The incremental addition of
5% HCl solution to prevent further precipitation within the sample.
isopropanol (low S, Figure 2-curve
Controlled Heterogeneous Crystallization ii) ensured that formation of colloidal
Low supersaturation was maintained via the slow addition of alcohol; in order to nickel sulfate was avoided, hence the
favor the secondary nucleation process and, hence, crystal growth, nickel-sulfate seed lower Niaq, final (i.e. 6.6 g/L nickel in 120
(obtained from previous tests) was provided to the system upon saturating the solution min. vs. 8.33 g/L).
with isopropanol. After a 15-min. equilibration period, alcohol addition was resumed in a Crystal growth is favored if crystalline
controlled, step-wise manner, followed by a 15-min. equilibration period, to maintain low
supersaturation throughout the whole experiment. seed is provided at low supersaturation
Upon completion of the precipitation tests, the crystals were separated by filtration, (S < S*cr, homo ,where Scr, homo signifies
washed with 2-propanol to displace water and sulfuric acid, air-dried at room temperature, the threshold above which spontaneous
weighted, and collected for further analyses. The nickel content in solution was determined homogeneous nucleation-crystallization
by atomic absorption spectrometry. Sulfuric acid concentrations at different stages of occurs.10) The advantages of producing
the experiments were monitored by titration with 1N NaOH and (EDTA)2Mg, according
to the method developed by Principe.11 The solids produced were characterized by well-grown crystals are obvious: better
x-ray diffraction, scanning electron microscopy and energy-dispersive spectroscopy, filterability and settling, less solution
the chemical composition was determined via digestion and inductively coupled retention, and lower uptake of impurities.
plasma analysis. As seed, 60 g/L of NiSO4◊6H2O crystals
The filtrate was measured and subjected to fractional distillation in order to recover the obtained from previous homogeneous
organic phase. Fractional distillation experiments were performed according to the procedure
described by Pavia et al.12 An azeotropic mixture was collected having the following SDC tests at low supersaturation were
composition: 87.8% IP, 12.2% H2O, wt/wt at a fixed boiling point, 80.4°C. used. The seed was added in the range
0.3 < O/A < 0.4 since, if added at

50 JOM • January 2002


Figure 3. The heterogeneous crystalliza-
tion of nickel sulfate (20°C, low S, 250
g/L H2SO4).
lower O/A, it would have dissolved.
A 30-minute equilibration time was
allowed after adding the seed, resulting in
a clear decrease in nickel concentration
in aqueous phase. Remaining solvent
was added in doses (Figure 3).
The final nickel concentration was
similar to that obtained with the low
S/homogeneous tests. However, in
terms of crystal size and properties,
seeding had a net beneficial dramatic
effect.
Further seeding tests, in combination
always with the controlled (low) super-
saturation procedure, were conducted,
this time involving the recycling (as
seed) of 50% of the produced crystals.
Five recycles were performed, resulting
in considerable crystal growth.
It is important to mention that while
performing SDC tests on the industrial
electrolyte, the premature precipitation
of a white, fine product later identified
as gypsum was observed. Most of the
gypsum crystallized before reaching
O/A = 0.3. To minimize contamination
of the final product with gypsum, the
latter will have to be filtered before
nickel-sulfate crystallization starts.
PRODUCT PROPERTIES
The solids density (SD) represents
a good semi-quantitative measure of
the growth process and an important
property in slurries/solids separation.
Because large crystals have a smaller
specific surface area, they retain less
solution. After the slurry was allowed
to settle, three samples of the solids
were collected from the settled mass
and weighed. They were dried under
ambient conditions and re-weighed. The
following calculation was performed to
check the solids density:
SD (%) = (dry sample mass)/
(wet sample mass) x 100 (1)
2002 January • JOM
The percentage of fines (F) was deter-
mined by filtering the mother liquor
that contained unsettled colloidal/fine
particles, allowing the crystals to dry,
and comparing their mass to the total
quantity of solids generated by the SDC
test, as follows:
F (%) = (mass of fines)/(total mass
of solids) x 100 (2)
The increasing trend in SD values
proves the growth process is enhanced
by the use of seed and product recycling
under low supersaturation (Figure 4).
It can be clearly seen that heteroge-
neous crystallization generates crystals
that have a superior percentage of solids
content and lower percentage of fines
than those obtained under homogeneous
conditions. The same results show that
extended recycling triggers particle
fragmentation since there appears to
be an increase in the content of fines
following the third recycling.
For equivalent solids loading, the
settling velocities offer another means
of evaluating the crystals. As expected,
low supersaturation and the use of
seed/product recycling (heterogeneous
crystallization) resulted in increased
settling velocities (Figure 5).
The small drop in settling velocity
after the third recycle is attributed again
to fragmentation: As the particles reach
a critical size, they apparently start
breaking, increasing the amount of
fines and causing a drop in settling
velocities.
An XRD analysis of the product
showed the crystals to be NiSO4◊6H2O.
The large number of crystallization
waters is due to the low temperature of
crystallization—this is in agreement with
literature.13,14 The product obtained via
evaporative crystallization (100–130°C)
has only two crystallization waters.
A SEM examination of the crystals
revealed crystal morphology and size to
depend on supersaturation magnitude
and on crystallization strategy (i.e.,
heterogeneous vs. homogeneous),
confirming the trends observed with
solids density and settling velocity.
Homogeneous tests conducted at high
supersaturation (Figure 6a) yielded fine,
irregular crystals with an average size
of less than 50 µm. On the other hand,
as can be seen from the SEM photo of
Figure 6b, heterogeneous crystallization
and product recycling produced well-
grown crystals of more than 100 µm
average size.
The SEM pictures of nickel sulfate
obtained via SDC and EC, respectively
(using the same de-copperized industrial
electrolyte), are compared in Figure 7
(equal magnification) to reveal major
differences. Nickel sulfate crystals
obtained industrially via EC (at T ~
130°C) are agglomerates of very fine
crystallites (~10 µm), indicating a
porous structure that is responsible
for solution retention and crystal
contamination. Their greenish-yellow
color is characteristic of low-hydration
nickel sulfate that forms at high
temperatures in the presence of dehydrat-
ing agents (e.g., sulfuric acid).13 In
contrast, the SDC-produced crystals
(deep-green color, with an average size
of ~200 µm) have a relatively regular
shape (Figure 7b).
The chemical composition of crystals
obtained by the two techniques was
determined by ICP analysis after dis-
solution in 5% HCl. The obtained data,
along with purity specifications for
electroplating-grade nickel sulfate, are
given in Table I.
The impurity content is, in general,
one order of magnitude lower for
certain elements in the case of crystals
produced via SDC in comparison
to the conventional product. Copper
Figure 4. The influence of crystallization
strategy on solids density and formation
of fines.
Figure 5. The influence of crystallization
strategy on settling velocity.
51
represents the major impurity in both
cases, most probably due to high initial
concentration in the aqueous solution
and lattice similarity. The most striking
difference between the two methods lays
in the sulfuric-acid content: While the
traditional EC method yields a product
containing 5% H2SO4, the precipitate
obtained via SDC contains only 0.5%.
Some upgrading of the product may
be required for meeting electroplating
quality specifications for NiSO4⋅6H2O.
PROCESS
CONSIDERATIONS
A simplified flowsheet of the solvent
displacement crystallization process
as applied to nickel recovery from
de-copperized electrolyte is shown
in Figure 8. For water balance, the
de-copperized feed electrolyte may be
pre-evaporated (it has been determined
that at least 50% of the water can be
removed by evaporation before reaching
the crystallization point), reducing the
volume of solution treated by SDC and,
consequently, lowering the required
solvent inventory. Alternatively, the
evaporation of excess water may be
a 100 µm
b 100 µm
52
Table I. Chemical Composition of Nickel Sulfate Crystals
Element NiSO4⋅6H2O NiSO4⋅2H2O Specifications for Electroplating-
(%) (SDC) (EC-Industrial) Quality NiSO4⋅6H2O
Ni 21.9 31.4 22
Cu 0.11 1.25 0.02
Fe 0.01 0.59 0.005
As <0.02 0.05 0.001
Sb 0.01 0.10
Bi 0.02 0.02
Al 0.02 0.26 0.002
Ca 0.1 0.72 0.025 (as Ca + Mg)
Mg — 0.16
Na 0.05 0.2 0.01
H2SO4 0.44 5.0
practiced on the de-nickelized acid prior the worst-case scenario), simulating
to recirculation to the tank-house. the transfer of isopropanol from the
Simple laboratory distillation tests nickel sulfate recovery section to the
at 80.4°C yielded 98% isopropanol tank-house,15 showed no adverse effects
recovery as azeotropic mixture (87.2% on copper deposition as long as additives
isopropanol, 12.2% H2O wt/wt). Based were used. Hence, the integration of
on vapor-liquid equilibrium data pre- SDC in a copper electrolytic refining
sented by Cohen,7 99.5% isopropanol plant should not cause metallurgical
recovery can be achieved in an eight quality problems. Another feature not
theoretical plate distillation column. shown in the simplified flowsheet is the
Cathodic polarization tests performed cooling of the feed electrolyte down to
with copper sulfate electrolyte contain- ~10°C to reduce the solvent inventory
ing up to 5 g/L isopropanol (representing requirements (refer to Figure 1).
Solvent displacement crystallization
not only has the potential to produce
high-grade nickel sulfate crystals, as
already discussed, but to do so at
a competitive energy cost with the
conventional submerged combustion/
evaporative crystallization method. The
data of Table II were generated for a
hypothetical refinery that produces 454 t
of nickel as nickel sulfate salt from a
de-copperized electrolyte with 20 g/L initial
nickel concentration. The respective
energy cost of the submerged combus-
tion crystallization method is estimated
at 0.9 × 105 million BTU. The estimates
are based on fractional distillation
performed to recover isopropanol as an
azeotrope that contains 88 wt% IP.7
It can be clearly seen that the energy
Figure 6. (a) Fine, irregular cost is equal to or lower than that of the
crystals, less than 50 µm, conventional process. Crystallization at
resulted from homogenous
tests conducted at high
10°C is, by far, the least energy-intensive
supersaturation. (b) Well- option due to the lower requirements
grown crystals more than in solvent. Option 3 is interesting as
100 µm average size
resulted from heteroge-
it allows for 50% water removal by
neous crystallization and pre-evaporation to satisfy water bal-
product recycling. ance requirements, plus SDC at lower
O/A ratio due to acid/nickel sulfate
pre-concentration.
In terms of maintenance cost, SDC
JOM • January 2002
 Table II. Energy Cost Estimates for Various SDC Options
(Basis—106 lbs Ni/year Production)
Option Conditions
I No pre-evaporation
SDC @20°C
II No pre-evaporation
SDC @ 10°C
III 50% pre-evaporation
SDC @ 20°C
* with reference to initial aqueous volume (i.e., prior to pre-evaporation)
with or without pre-evaporation is
expected to be significantly less costly
than evaporative crystallization. Typi-
cally, in the case of the latter, the
maintenance costs cause operating costs
to double. Furthermore, taking into
account the credit from the sales of
the high-grade nickel sulfate product
of the SDC process, the latter clearly
becomes a very attractive alternative to
the current technology.
CONCLUSIONS
This work confirmed 2-propanol to
be an effective salting out agent to
cause precipitation of NiSO 4⋅6H 2O
from industrial de-copperized bleed-off
a 100 µm
b 100 µm
2002 January • JOM
O/A* Energy Cost (106 BTU)
2 0.99 × 105
1.2 0.70 × 105
0.7 0.9 × 105
electrolyte solutions. When the SDC
and EC methods are compared, the
former method by far produces superior
quality nickel sulfate salt at an energy
cost similar or lower than that of the
conventional method.
ACKNOWLEDGEMENTS
The authors acknowledge with grati-
tude the funding received from the
National Sciences and Engineering
Research Council of Canada and the
technical support received from the
CCR Division of Noranda (in particular,
the feedback received from Vicken
Aprahamian, Jack Stafiej, and David
Tracy is much appreciated).
Figure 7. (a) Nickel sulfate
crystals obtained industri-
ally via EC. (b) Nickel-
sulfate crystals produced
via SDC.
Figure 8. A simplified SDC flowsheet.
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Georgiana Moldoveanu (PhD candidate) and
George P. Demopoulos (professor) are with the
Department of Mining, Metals and Materials
Engineering, McGill University.
For more information, contact G. Demopoulos,
McGill University, Department of Mining, Metals and
Materials Engineering, 3610, University St., Montreal,
PQ, H3A 2B2, Canada; (514) 398-2046; fax (514)
398-4492; e-mail george.demopoulos@mcgill.ca”.
53