Minerals Engineering, Vol. 5. No. 9, pp. 1061-1068, 1992 0892-6875/92 $ 5 . 0 0 + 0 .

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TECHNICAL NOTE
A THERMODYNAMIC APPROACH FOR THE SULPHURIC ACID
PRESSURE LEACHING OF NICKELIFEROUS LATERITES

F.T. DA SILVA

Department of Metallurgy and Materials Science, Federal University of Rio de Janeiro,

COPPE/UFRJ, P.O. Box 68505 - CEP 21945 - Rio de Janeiro, Brazil
(Received 2 December 1991; revision accepted 1 April 1992)

ABSTRACT

This work introduces a thermodynamic approach for the sulphuric acid pressure
leaching of nickeliferous laterites. The results obtained are used to interpret
the leaching and hydrolytic reactions, including crust formation, that may occur
inside the autoclave.

Keywords
Nickeliferous laterites; pressure leaching

INTRODUCTION

The extraction of nickel and cobalt from nickeliferous laterites (limonites) is usually carried
out through sulphuric acid pressure leaching processes, such as at AMAX and Moa-Bay.

In Moa-Bay, the lateritic ore with granulometry less than 830 /~m, is leached with a
sulphuric acid solution in an autoclave at approximately 523K under intense agitation. The
use of such high temperatures, however, results in undesirable side reactions, while nickel
and cobalt remain preferentially as Ni 2+ and Co 2+ ions in equilibrium with HSO,'. These
side reactions are mainly due to hydrolysis reactions of the iron and aluminum ions,
producing a residue composed of basic iron and aluminum sulphates and hematite.

Studies carried out at AMAX Extractive Research and Development Inc., Golden, Colorado
[1], showed that the addition of garnieritic ore at a pre-determined leaching step, was
effective in reducing crust formation. The magnesium sulphate precipitated at high leaching
temperature, tend to inhibit alunite scaling. According to Marshall and Slusher [2], the
inverse solubility of magnesium sulphate with temperature, favours the magnesium
dissolution and hematite liberation during autoclave cooling. According to Chou et al [3],
crust formation can be minimized by combining acid addition, agitation and high leaching
temperature. In respect to nickel and cobalt recoveries, it was observed that higher nickel
extractions were obtained at leaching temperature in the range 493-543K. At higher
temperatures, however, nickel and cobalt extraction was decreased.

This study analyses the thermodynamic feasibility of leaching and hydrolytic reactions using
solubility data for sulphates and the Eh-pH diagrams of the Me-S-H20 systems
(Me=Ni,Co,Fe,A1,Mg) at high temperatures. These data together with the stability diagrams
for the different hydrolysis products, give valuable information concerning sulphuric acid
pressure leaching of nickeliferous laterites.

1061
1062 Technical Notes

THERMODYNAMIC ANALYSIS OF LEACHING REACTIONS

Data on the free energy of formation of solids at high temperature were taken from Barin
and Knacke [4], Pankratz [5,6], Chavez and Ibarra [7] and Chavez, R.M.A. [8]. The data
concerning the free energy of formation of ions at high temperatures were calculated using
the Criss and Coble method according to Barner and Sheuerman [9].

The Eh-pH diagrams of the Ni-S-H20, Co-S-HzO, Fe-S-H2, A1-S-H20 and Mg-S-H20
systems, were constructed based upon the chemical composition of the lateritic ore, as well
as on the usual composition of the leach liquors resulting from the processing of these ores.

Ni-S-H20 and Co-S-H20 Systems

In order to characterize which nickel and cobalt solid hydrated sulphates are
thermodynamically stable at the leaching temperatures, Figure 1 and 2 show the evolution
of the dehydration of nickel and cobalt sulphates with temperature. In Figure 1, the most
stable phase up to 373K is NiSO4.6H20. At higher temperatures up to 573K, the stable
phase is NiSO4.H20. In the case of cobalt, Figure 2 shows that up to 330K, the most stable
phase is COSO4.6H20. At higher temperatures up to 573K, the COSO4.H20 becomes the
stable phase.

4.0 000
NiS04.H20(s)-, NiS04(s

20 000
I

<I
-20 000

-40 000
300 400 500 600
Temp. (K)
Fig. 1 Stability diagram of nickel sulphates

The Eh-pH diagrams of the Ni-S-H20 and Co-S-H20 systems at 573K, for metal and
sulphur molar concentrations of 10 "1 and 1.0 M, respectively, are shown in Figures 3 and
4. It can be seen that at high leaching temperatures, the precipitation of solid hydrated
metal sulphates in sulphuric acid media is thermodynamically feasible at low pH and high
oxidizing potentials.

Fe-S-H~O, AI-S-H20 and Mg-S-H2K) Systems

It has been verified for metal and sulphur molar concentrations of 10 "1 and I.OM,
respectively, that the precipitation of anhydrous aluminum and iron sulphates at 573K, is
 Technical Notes 1063

not thermodynamically feasible. The precipitation of the hydrated aluminum and iron
sulphates were not investigated due to the lack of thermodynamic data.

40 000

I
20 ooo
©

0 ~ _ j Co2+ > CoS04.H 20(s)

r~
<3
-20 ooo--

-40 ooo
300 400 500 600
Temp. (K)

Fig.2 Stability diagram of cobalt sulphates

In terms of basic sulphates, Chavez and Ibarra [7] reported the thermodynamic feasibility
of the formation of iron and aluminum basic sulphates at lower leaching temperatures. An
increase in temperature would promote the thermal hydrolysis of the iron basic sulphate
precipitating hematite and regenerating sulphuric acid. In terms of the aluminum basic
sulphates, the hydrolysis reactions producing AI(OH) 3 and regenerating sulphuric acid, are
hindered by increasing leaching temperature. In these conditions, the presence of solid basic
aluminum sulphate may be expected in the leaching residue, being the main constituent of
the alunite crusts.

For magnesium and sulphur molar concentrations of 10 "1 and 1.0M, respectively, Figure
5 shows that the precipitation of MgSO4.HzO is thermodynamically feasible for temperatures
above 473K.

MATERIALS AND METHODS

The chemical composition of the lateritic ore from Vermelho-Carajas(Para State) Brazil, is
shown in Table 1. According to Viera [10], the main constituents of the ore are goethite
and antigorite. Nickel oxide is mainly distributed between both minerals and cobalt oxide
is mainly associated to goethite.

The ore comminuted at - 8 3 0 # m , was leached in a 500 ml Parr autoclave under constant
agitation for 60 minutes, for different temperatures (493-543K), acid/ore ratios (0.26-0.30)
and solid/liquid ratios (0.12-0.30). Immediately after the end of the experiment, a sample
was taken at the leaching temperature in order to determine the nickel and cobalt
concentrations in the liquor.
1064 Technical Notes

- 2-
HS0, S0 4
I
1.5
O
>
1.0
z2 /
L 0 ......... .....
Lr2
,~5"Ni2+ iiil i -
.5
c~ ~N i 0

HNiO 2
-.5
f -~...~.NiS
-1.0 A_

-1.5 H S ' S 2-
Ni <" i
i
i
-2.0 I

-2 0 £ 4 6 8 10 12 14 16
pH

Fig.3 Eh-pH diagram of the Ni-S-H20 system at 523K. [ Ni 2÷ [ = 10-2M and ] S [ = 1.0M.
The thicker lines bound the water stability domain. The shaded areas correspond to the
stability domain of solids from the Ni-HeO system. The hatching area corresponds to the
stability domain of the NiSO4.HzO(s)

TABLE 1 Chemical composition of nickeliferous laterite of Vermelho-Carajas (Brazil)

OXIDES % (BY WEIGHT)

FeOOH 61.70
NiO 1.96
CoO 0.14
Cr20s 1.69
Si02 £5.55
MgO 6.02
AI20s 2.59
 Technical Notes 1065

2-
HSO 4 SO,
< , >
i

©
>
v

-2 0 2 4 6 8 i0 12 14 i6
pH

Fig.4 Eh=pH diagram of the Co=S=H20 system at 523K. I C°2+ ] = 10"2M and ] S ] = 1.0M.
The thicker lines bound the water stability domain. The shaded areas correspond to the
stability domain of solids from the Co-H20 system. The hatching area corresponds to the
stability domain of the CoSO4.H20(s )

RESULTS AND COMMENTS

Table 2 shows nickel and cobalt recoveries for the different Aeaching tests. The plus (+)
and minus (-) signs correspond to the upper and lower limits of the selected variables in the
factorial designed experiments. It can be seen that nickel and cobalt recoveries are greatly
affected by the leaching temperature. At the selected temperature range, the nickel and
cobalt extractions decreased with increasing leaching temperature.

In spite of the low nickel and cobalt concentrations in solution, an increase in temperature
tends to favour the precipitation of hydrated sulphates. According to Derry [11], " the
solubility of metallic sulphates starts to decrease at temperatures near the critical
temperature of water, while for temperatures in the range 423=523K it has a magnitude of
only a few grams per liter". Data on the solubility limits of nickel and cobalt sulphates in
water, confirmed the tendency of the decrease in the solubility of both sulphates with
increasing temperature. Under high acidic conditions, the solubility of the sulphates
increases sharply. Therefore for a pH around 2.0 and oxidizing conditions, the Ni 2+ and
Co z+ prevails in equilibrium with HSO4".

According to Queneau et al [1], the precipitation of nickel sulphates during leaching at

543K is associated with the co-precipitation of magnesium sulphate. Depending on the
amount of MgO in the ore and the leaching temperature, the formation of (Mg,Ni)SO4.H20
can become thermodynamically feasible.
1066 Technical Notes

2-
HSO
/
/

1.5
©

1.0
Mg(OH)
~\..5

t
0

-.5 -L t~¢. 2

-1.0 Mg z+ i ~ . ,

-1.5 __ H S [ c~
t
, Mg(0H)~
-2.0 I

-2 0 2 4 6 8 10 12 14 16
pH

Fig.5 E h - p H diagram of the Mg-S-H20 system at 523K. [ Mg 2÷ I = 10-2M and I S I = 1.0M.

The thicker lines bound the water stability domain. The shaded areas correspond to the
stability domain of solids from the M g - H 2 0 system. The hatching area corresponds to the
stability domain of the MgSO4.H20(s)

The presence of magnesium and nickel sulphates in the leaching residue (identified by
infrared spectroscopy and chemical analysis), was an indication that the assumption
proposed by Queneau et al [1] may be the main reason for the apparent decrease in nickel
and cobalt extraction on increasing leaching temperature. It is important to point out that
in those systems where the conditions exist for precipitation of hydrated sulphates at high
temperatures, those precipitates will tend to redissolve on cooling.

In spite of the thermodynamic feasibility of the formation of basic aluminum sulphate

(alunite) [7], their presence in the leaching residue was not identified by any method of
analysis. Duyvesteyn et al [12] found out that the formation of alunite was strongly
dependent on agitation and acid distribution inside the autoclave. Since in the present work,
the pulp was kept fully agitated and the distribution of sulphuric acid was homogeneous,
the precipitation of the basic sulphate was not favoured. It is important to note that on
industrial operations, where agitation and pH cannot be so closely controlled, the
precipitation of basic aluminum sulphate is possible.

CONCLUSIONS

. High nickel and cobalt recoveries of 91.2 and 92.3%, respectively, were obtained
under the following conditions: leaching temperature - 493K; acid/ore ratio-- 0.26;
solid/liquid ratio - 0.30.
. The lower nickel and cobalt recoveries after leaching at 543K, were probably due to
precipitation of complex magnesium mono-hydrated sulphates containing nickel and
 Technical Notes 1067

cobalt. During cooling those sulphates would tend to redissolve in the liquor, thus
minimizing nickel and cobalt losses.
. In spite of the thermodynamic feasibility of the formation of solid basic aluminum
sulphate, its presence at the leaching residue was not identified. High leaching
temperature, high acidic solution and intense agitation minimized its formation.
. The thermodynamic analysis carried on in the present work was based on equilibrium
conditions. Care must be taken when using these data under non-equilibrium
conditions.

TABLE 2 Nickel, cobalt and iron extraction after sulphuric acid

pressure leaching of nickeliferous laterites

VARIABLES NICKEL COBALT IRON

ID
AND LIMITS EXTRACTION EXTRACTION EXTRACTION
{*) (z)

A B C R1 R2 R1 R2 R1 R2

1 38.8 40.3 ;4 7 49.0 0.4 0.4

? 32.2 35.5 56. ~ 36.1 0.5 0.5

3 -- ÷ --
65.8 64.2 79.2 73.2 0.7 0.6

4 + -I- -- 43.7 39.5 52.2 49.2 0.6 0.7

5 _ _ -{-
53.8 46.7 62.8 62.8 0.7 0.7

6 + - + 55.7 49.0 536 49.4 0.7 0.7

7 -- -4- -I- 91.3 85.7 92.6 89.8 0.9 1.0

8 68.4 69.1 67.5 64.2 1.1 1.2

q ~ A - temperature (K) 493(-)ond 543(-t-)

B - s o l i d / l i q u i d ratio (%): t 2 ( - ) and 3 0 ( + )
C - a z i a / o r e ratio: 0 . 2 6 ( - ) and 0 . 5 7 ( + )

AKNOWLEDGEMENTS

To the National Research Council of Brazil(CNPq) and to the Federal University of Rio de
Janeiro(UFRJ) for the financial support. To Luis Antonio Pretti for the experimental data
obtained from his M.Sc. thesis at COPPE/UFRJ.

REFERENCES

. Queneau, P.B.; Doane, R.E.; Coperrider, M.W.; Bergren, M.H. & Rey, P., Control of
Autoclave Scaling during Acid Pressure Leaching of Nickeliferous Laterite Ore
Metallurgical Trans. B., 15B, 433 (1984).
2. Marshall, W.L. & Slusher, R., J. Chem. Eng. Data, 10, 353 (1965).
1068 Technical Notes

. Chou, E.C., Queneau,P.B. & Rickard, R.S., Sulphuric Acid Pressure Leaching of
Nickeliferous Limonites Met. Trans. B., lIB, 547 (1977).

. Barin, I. & Knacke, O., Thermochemical Properties of Inorganic Substances,

Springer Verlag, 1973 Supplement (1977).

. Pankratz, L.B., Thermodynamic Properties of Elements and Oxides U.S. Bureau of

Mines Bulletin 672, (1982).

. Pankratz L.B., Stuve, J.M. & Gokcen, N.A., Thermodynamic Data for Mineral
Technology U.S. Bureau of Mines Bulletin 677, (1984).

. Chavez, R.M.A. & Ibarra, O.G., Analisis Termodinamico de Reacciones Secundarias

en la Lixiviacion Acida de Minerales Lateriticos Tecnologia Quimica, Cuba, 23
(1985)

. Chavez, R.M.A., Genesis de la Formacion de Incrustaciones en la Lixiviacion Acida

de los Minerales Lateriticos Tesis de Doctorado en Ciencias Quimicas , Universidad
de Oriente, Cuba, (1985).

. Barner, M.E. & Scheurman, R.V., Handbook of Thermochemical Data for Compounds
and Aqueous Species John Wiley and Sons, (1978).

I0. Viera, E.V., Concentracao por Metodos Fisicos de Lateritas Niqueliferas Limoniticas
do Vermelho Carajas (Para) Tese de M.Sc., COPPE/UFRJ, (1989).

11. Derry, R., Pressure Hydrometallurgy: A Review Minerals Science Engineering, 4,

3 (1972).

12. Duyvesteyn, W.P.C., Wicker, G.R. & Doane, R.E., An Omnivorous Process for
Laterite Deposits Proc. Int. Laterite Symp., Soc. Min. Eng. and American Inst. Min.
Met. Petroleum Eng., New Orleans, 553 (1979)