CH 12
CH 12
CH 12
135
manganese. In addition, the contained water is lower than hydroxide precipitates, which makes it more economical to transport sulfides to distant refineries.
12.2. FLOWSHEET
The flowsheet for the precipitation of the mixed nickel-cobalt sulfide from the hot slurry leaving the autoclave was shown in Figure 10.1. The process is continuous. It entails the following steps: (a) cooling the slurry;
(b) neutralization of the slurry;
(c) solidlliquid separation and residue washing; (d) further neutralization of the solution to remove impurities like aluminum, chromium, iron and silicon by precipitation together with their associated solidlliquid separation; (e) removal of zinc and copper by sulfide precipitation; and finally, (f) precipitation of the mixed nickel-cobalt sulfide. The product of this process, the mixed nickel-cobalt sulfide precipitate, is then sent to a local or distant refinery for releaching and metal production. The details of various industrial operations are given in Tables 12.1-12.3. Steps (a) and (c) in this process are discussed in Appendices D and E. Steps (b), (d), (e) and (f) are discussed here.
CaS04.2H20(s)
precipitated gypsum
+ CO2(g)
(12.1)
in limestone slurry
The neutralization is performed in a stirred vertical tank with a residence time of about 48 minutes, and then the flocculants are added. A portion of the leach residue is recycled to the tank to ensure sufficient growth of gypsum particles so that they can settle rapidly in the subsequent counter-current decantation circuit. The rate of the addition of limestone is controlled to prevent excessive production of carbon dioxide gas. The neutralized slurry is transferred to solidliquid separation and residue washing in the counter-current decantation circuit. The solution from the counter-current decantation circuit is pumped to solution reneutralization.
(g
\
TABLE 12.1 Compositions of the Leach Solution Feed to Industrial NickelLCobalt Sulfide Precipitation Circuits. The nickel concentration is controlled by dilution
Concentration, g/L Component
Ni
co
Fe
0.4
0.3
0.5
0.6 27
O.OOSa
so',cu
Zn
Cr
1.6
0.001 0.07
Ca Al
1.6 0.03
Si
Mg Mn
1.93 1.4
0.9 2.9
"Ni+ Co concentration controlled to < 4.8g/L to avoid sulfide pellet formation. Cu concentration controlled to less than 0.008 g/L to avoid excessively fine precipitate (Chalkley& Toirac, 1997).
3CaC03(s)
in limestone slurry
9H20((1) (12.2)
6 0 " '
2Fe(OH)3(s)
+ 3(CaS04.2H20)(s) + 3co2(g)
precipitates
The neutralization is performed in a stirred vertical tank. Flocculants and recycle leach residue are added so that the precipitates that are formed will
TABLE 12.2 Compositions of Nickel-Cobalt Sulfide Precipitates from Industrial Laterite Leach Plants.
The similarity of the nickel and sulfur contents are noteworthy. Particle sizes are 10-50 p m
Concentration, % Element
Ni
co
Fe
cu
Zn
Cr
1.6 0.1
0.4
Ca Al
0.2 <0.01 S.
Si
Precipitate from the Murrin-Murrin (Australia) plant contains -51% Ni, 5% Co and36%
settle rapidly in the subsequent thickening step. Air is often bubbled into the tank to ensure that iron is present mostly as Fe3+. The slurry is transferred to solidliquid separation. The solution is pumped to zinc and copper removal.
a
\
Location
Startup date Precipitation vessels
Temperature, "C
95
120 2 -2.5
80 3-3.5 2
10
-1
-1
co
Precipitation efficiency, Ni
0.4
98.5-99.5 98-99
Recycle precipitation product Recycle precipitation product
>99
co
Precipitation seed
Some
(Continued
Location
Reaction vessel exit method Precipitate composition, O h Ni
57 5
55 5
57 4.5 0.4
co
Fe
-1
35 -50
-80
-1 0 60
-1 50
"The new Toarnasina plant plans to precipitate in a stirred vertical tank at 105C and2-bar H2S pressure.
(c) they are harmful to nickel-cobalt sulfide precipitation or to subsequent nickel and cobalt refining (Kofluk & Freeman, 2006; Molina, 2009; Nakai, Kawata, Kyoda, & Tsuchida, 2006). Fortunately, zinc and copper can be removed from the leach solution (with negligible nickel and cobalt precipitation) by adding hydrogen sulfide to the solution at low pressure and temperature (Molina, 2009). This is because the solubility products for zinc and copper sulfides are lower than those for nickel or cobalt sulfide. Operating conditions for zinc and copper removal (Nakai et al., 2006; Tsuchida, Ozaki, Nakai, & Kobayashi, 2004) are given in Table 12.4. The concentration of zinc in solution after this treatment is less than 0.001 g/L. The concentration of copper is even lower.
@ )
\
TABLE 12.4 Typical Conditions for the Precipitation of Zinc and Copper
Value
<60"C
3.0-3.4 4 . 1 bar
From gas space above agitated solution in a baffle tank -60 min Mixed Zn-Cu sulfide precipitate
The nickel and cobalt losses during the precipitation of zinc and copper from solution as sulfides are less than 0.1% and less than 0.3%, respectively. The resulting slurry is filtered. The zinc and copper sulfide precipitate is discarded. The filtrate is sent to nickel and cobalt precipitation.
H2S(g)
80-120C 80-120C
NiS(s)
in sulfide precipitate
+
+
H2S04(aq)
sulfuric acid to neutralization
(12.3)
CoS04(~q)
in purified pregnant solution
H2S(g)
CoS(s)
in sulfide precipitate
H2S04(aq)
sulfuric acid neutralization
(12.4)
As shown in Table 12.1, the purified feed solutions to the sulfide precipitation typically contain 5 g/L Ni and 0.4 g/L Co. These solutions are less concentrated in nickel and cobalt than the solution leaving the autoclave due to the addition of water during slurry washing.
c
80C & 2 bai pressure purified pregnant solutionlrecycle precipitatemocculant slurry
I
>
3 3 3
H2Sgas
FIGURE 12.1 Sketch of nickel-cobalt sulfide precipitation vessel. The process is continuous. The product slurry is settled and filtered. The barren solution is used for washing of leaching residue or is discarded. The nickel-cobalt sulfide precipitate is washed and sent to an adjacent refinery or washed, dried and bagged then sent to a distant refinery for metal production. The input solution typically contains 5 g/L Ni and 0.4 g/L Co. The product precipitate typically contains 55% Ni and 5% Co. Precipitation is also done in horizontal autoclaves.
The product composition is given in Table 12.2. It typically contains 56% Ni, 5% Co, and 1% Fe. The remainder of the material is sulfur. About 99% of the nickel and the cobalt in the leach solution are precipitated.
(g
12.8. APPRAISAL
Production of concentrated solutions of pure nickel and cobalt by precipitation of mixed nickel-cobalt sulfide and later releaching it in a refinery seems awkward and costly. However, there is no denying its efficacy.
(g
Solvent extraction would seem to be a better process, but high impurity levels, particularly calcium, in autoclave exit solutions have delayed its adoption. However, the operation at Goro, New Caledonia, planned to use solvent extraction to (i) extract nickel and cobalt from its purified pregnant solution; and then, (ii) produce separate nickel and cobalt solutions from which it will make NiO and CoCO3 (Okita, Singhal, & Perraud, 2006). Due to problems in commissioning, Goro currently produces a mixed hydroxide precipitate that is processed at Yabulu, Queensland.
12.9. SUMMARY
Most currently operating laterite leaching plants precipitate nickel and cobalt from solution as a mixed nickel-cobalt sulfide. This sulfide typically contains 56% Ni, 5% Co, and 0.5%-1% Fe, with the remaining mass made up of sulfur. The mixed nickel-cobalt precipitate is produced by contacting purified pregnant leach solution with hydrogen sulfide gas at temperatures of 80- 120C and partial pressures of hydrogen sulfide of between 2 and 10 bar. The recovery of the nickel and the cobalt to precipitate is approximately 99%. Rapid precipitation is promoted by recycling large quantities of product precipitate (sometimes finely ground) to the precipitation tank. This also prevents scale formation on the reactor walls, extending campaign life and minimizing maintenance costs. The mixed-sulfide precipitate is an intermediate product that is redissolved to make concentrated solutions of nickel and cobalt suitable for high-purity metal production, which is discussed in Chapter 23.
REFERENCES
ChaMey, M. E., & Toirac, I. L. (1997). The acid pressure leach process for nickel and cobalt laterite. In W. C. Cooper & I. Mihaylov (Eds.), Nickel/cobalt 97, Vol. I, Hydrometallurgy and rejining o f nickel and cobalt (pp. 341-353). CIM. Collins, M. J., Barta, L. A., Buban, K. R., et al. (2005). Process development by Dynatec for the Ambatovy nickel project. CIM Bulletin, 98, 90. Collins, M. J., Buban, K. R., Holloway, P. C., et al. (2009). Ambatovy laterite ore preparation plant and high pressure acid leach pilot plant operation. In J. J. Budac, R. Fraser & I. Mihaylov, et al. (Eds.), Hydrometallurgy o f nickel and cobalt 2009 (pp. 499-510). CIM. Donegan, S. (2006). Direct solvent extraction of nickel and Bulong operations. Minerals Engineering, 19, 123&1245. Hayward, K. (2008). Murrin Murrin leads the way. Sulfuric Acid Today, 14, 7-10. Kofluk, R. P., & Freeman, G. K. W. (2006). Iron control in the Moa Bay laterite operation. In J. E. Dutrizac & P. A. Riveros (Eds.), Iron control technologies (pp. 573-589). CIM. Molina, N. (2009). Nickel and cobalt sulphide precipitation, a proven method of selective metal precipitation in laterite process flowsheets. In J. J. Budac, R. Fraser & I. Mihaylov, et al. f nickel and cobalt 2009 (pp. 27 1-281). CIM. (Eds.), Hydrometallurgy o
Nakai, O., Kawata, M., Kyoda, Y., & Tsuchida, N. (2006). Commissioning of Coral Bay nickel project. In ALTA 2006 nickel/cobalt conference proceedings. ALTA Metallurgical Services. Okita, Y., Singhal, A., & Perraud, J.-J. (2006). Iron control in the Goro nickel process. In J. E. Dutrizac & P. A. Riveros (Eds.), Iron control technologies (pp. 573-589). CIM. Tsuchida, N., Ozaki, Y., Nakai, O., & Kobayashi, H. (2004). Development of process design for Coral Bay nickel project. In W. P. Imrie, D. M. Lane & S. C. C Barnett et al. (Eds.), International laterite nickel symposium 2004, process development for prospective projects (pp. 152-160). TMS.
SUGGESTED READI NG
Lewis, A. E. (2010). Review of metal sulfide precipitation. Hydrometallurgy, 104, 222-234. Molina, N. (2009). Nickel and cobalt sulphide precipitation, a proven method of selective metal precipitation in laterite process flowsheets. In J. J. Budac, R. Fraser, I. Mihaylov, V. G. Papangelakis & D. J. Robinson (Eds.), Hydrometallurgy o f nickel and cobalt 2009 (pp. 271-281). CIM. Matos, R. R. (1997). Industrial experience with the NiKo sulphide precipitation process. In W. C. Cooper & I. Mihaylov (Eds.), Nickel/cobalt 97, Vol. I, Hydrometallurgy and rejning o f nickel and cobalt (pp. 371-378). CIM.