AU2007215378A1

AU2007215378A1 - Processing of laterite ore

Info

Publication number: AU2007215378A1
Application number: AU2007215378A
Authority: AU
Inventors: John Joseph Andreazza
Original assignee: Andreazza Consulting Pty Ltd
Current assignee: Andreazza Consulting Pty Ltd
Priority date: 2006-02-15
Filing date: 2007-02-14
Publication date: 2007-08-23
Also published as: CA2640550A1; WO2007092994A1; US20090217786A1

Description

WO 2007/092994 PCT/AU2007/000149 TITLE "PROCESSING OF LATERITE ORE" The present invention relates the processing of laterite ore. 5 BACKGROUND TO THE INVENTION Processing of nickel laterite ore is complicated due to the mineralogically and chemically complex nature of the ore. A technique called high-pressure acid leaching (HPAL) is usually used. The process involves the preparation of the ore into a slurry. The slurry is then contacted with sulfuric acid at temperatures of 250 0 C - 280 0 C and under high 10 pressure for 60 minutes. This process leaches the nickel, cobalt and iron into solution. The resultant nickel cobalt liquor is recovered and processed by solvent extraction to produce separate nickel and cobalt products. The processing of nickel laterites by the above method is complex, costly, time 15 consuming and involves high energy consumption. The present invention attempts to overcome at least in part the aforementioned disadvantages SUMMARY OF THE INVENTION According to one aspect of the present invention there is provided a process for the 20 leaching of metals from highly oxidised laterite ores by admixing the ore and an acidic aqueous medium and treating the resulting mixture with a sulfur reducing agent at ambient temperature and pressure so as to reduce mineral species containing cobalt, nickel or manganese, the reduced mineral species being dissolved and subsequently recovered. 1 WO 2007/092994 PCT/AU2007/000149 DETAILED DESCRIPTION OF THE INVENTION Naturally occurring nickel laterites are derived from peridotite rocks containing olivine and serpentine. Under favorable conditions and with abundant rainfall various acids, such 5 as humic and others, are produced as a result of decaying organic matter. These acids leach out the magnesium and silica values, while enriching the residue with iron and nickel. These laterite deposits can be divided into three zones at increasing depth from the 10 surface. The three zones are the limonite zone, the serpentinite zone, and the garnierite zone. The zone of interest in this invention is the limonite zone. Limonite zones are typically highly oxidised and preferably contain asbolite type materials such as asbolane. Asbolane 15 has the general formula: (Co,Ni) 1l-y(MnO 2 )2-x(OH)2-2y+2x-n(H20). The present invention proposes that highly oxidised laterite ores, preferably containing 20 asbolane, are treated by the reduction of the mineral species by a sulfur reducing agent in an aqueous acidic medium. The present invention is envisaged to be used where the asbolane ore is preferably made up of between 0.1-10 per cent cobalt by weight, 40-80 per cent manganese oxide by weight and 0.1-20 per cent nickel by weight. More preferably the asbolane ore is made up of between 2-5 per cent cobalt by weight, 50-70 2 WO 2007/092994 PCT/AU2007/000149 per cent manganese oxide by weight and 5-15 per cent nickel by weight. The ore may preferably be ground to a particle size in the range of 50 to 600 mesh, more preferably 100 mesh. This ground ore is admixed with, such as by being added to, an 5 aqueous medium. Preferably the aqueous medium may be a dilute solution of mineral acid, more preferably a dilute solution of sulfuric acid. Preferably the medium has a low pH, more preferably a pH less than 2.0. The sulfur reducing agent may be added directly to the medium in the form of gaseous 10 sulfur dioxide, or an aqueous solution thereof. The amount of sulfur dioxide is preferably in the range of 0.8 to 3.2 mol SO 2 / kg of ore. The sulfur dioxide may be added incrementally or all at once. More preferably the sulfur reducing agent is generated in situ by the reduction of an alkali 15 metal sulfite salt, preferably sodium sulfite through the reaction:

SO

3 2 - + 2H + S 0 2 + H 2 0 The amount of sulfite salt may preferably be in the range of 10 to 40 per cent by weight 20 of the ore. The sulfite salt may be added to the medium containing the asbolane ore either incrementally or all at once. The nickel, cobalt and manganese in the ore are solubilised in the aqueous medium as a 3 WO 2007/092994 PCT/AU2007/000149 result of a reduction of the mineral components by the sulfur reducing agent. Copper, iron and aluminium may not be leached to an appreciable level and 'remain in the solid residue. 5 The treatment time may be in the range of 20 minutes to 20 hours, preferably in the range of 30 minutes to 10 hours. The treatment temperature may preferably be in the range of 20 to 50 0 C. Preferably the pressure is less than 2 atmospheres, more preferably the pressure is ambient. 10 The process of the present invention may be performed in sealed reactors designed to contain sulphur dioxide or any other off gases from venting to atmosphere. The reactors preferably contain a stirring mechanism to maintain the slurry in suspension. Also, the reactors may contain baffles to reduce bypass or short circuiting' the reactor residence volume. 15 The nickel, cobalt and manganese can then be recovered by known processes. For example, the soluble metal salts may be recovered by ionic exchange to produce nickel sulphate hexahydrate, cobalt suylphate hexahydrate and manganese sulphate. 20 In an alternative embodiment of the present invention the sulfur reducing agent may preferably be generated in situ by the reduction of an alkali metal metabisulfite salt, preferably sodium metabisulfite through the reaction: 4 WO 2007/092994 PCT/AU2007/000149

S

2 0o 5 2 + 2H+ . 2S02 + H 2 0 The amount of metabisulfite salt may preferably be in the range of 5 to 30 per cent by weight of the ore. The metabisulfite salt may be added to the medium containing the 5 asbolane ore either incrementally or all at once. The present invention will now be described with reference to the following examples. 10 In the following examples the ore used had the following composition of elements of interest. The percentage of cobalt, manganese, nickel and iron in the highly oxidised laterite ore sample was 0.688, 4.35, 0.996 and 38.1 per cent by weight respectively. Example 1 15 This example illustrates the rate of leaching over a 24 hour period. 50 g of asbolane ore was admixed with 500 mL of 0.2 M sulfuric acid and 15 g of Na 2

SO

3 added incrementally. The experiment was conducted at 25 0 C and ambient pressure. Samples were taken at 0, 6, 9 and 24 hours and analysed for their cobalt, nickel, iron and manganese concentrations. 20 An analysis of the samples taken at six hours showed that 76.7 per cent of the cobalt, 67.4 per cent of the manganese, 43.2 per cent of the nickel and 0.8 per cent of the iron had been recovered. An analysis of the samples taken at nine hours showed that 79.9 per cent 5 WO 2007/092994 PCT/AU2007/000149 of the cobalt, 70.5 per cent of the manganese, 45.2 per cent of the nickel and 0.9 per cent of the iron had been recovered. An analysis of the samples taken at twenty four hours showed that 83.0 per cent of the cobalt, 72.6 per cent of the manganese, 47.4 per cent of the nickel and 1.4 per cent of the iron had been recovered. 5 From the data it may be seen that the optimal contact time is under 10 hours. Example 2 This example illustrates the effect of increasing temperature and decreasing amounts of 10 Na 2

SO

3 in the reaction with respect to Example 1. 50 g of asbolane ore was admixed with 500mL of 0.2M sulfuric acid and 10 g of Na 2

SO

3 added incrementally. The experiment was conducted at 40 0 C and ambient pressure. Samples were taken at 0, 3, 6, 9 and 24 hours and analysed for their cobalt, nickel, iron and manganese concentrations. 15 An analysis of the samples taken at three hours showed that 62.9 per cent of the cobalt, 50.1 per cent of the manganese, 35.1 per cent of the nickel and 0.7 per cent of the iron had been recovered. An analysis of the samples taken at 6 hours showed that 74.8 per cent of the cobalt, 65.6 per cent of the manganese, 43.0 per cent of the nickel and 1.0 per cent of the iron had been recovered. An analysis of the samples taken at nine hours 20 showed that 81.1 per cent of the cobalt, 69.7 per cent of the manganese, 47.8 per cent of the nickel and 1.5 per cent of the iron had been recovered. An analysis of the samples taken at twenty four hours showed that 80.8 per cent of the cobalt, 69.6 per cent of the manganese, 47.3 per cent of the nickel and 2.2 per cent of the iron had been recovered. 6 WO 2007/092994 PCT/AU2007/000149 From this data it may be seen that the optimal contact time for extraction of the metal values is around 10 hours. After twenty four hours the recovery rates for cobalt and nickel were greater in Example 5 1 than in Example 2. In the same period the amount of nickel recovered was very similar. The amount of iron however was 1.4 per cent in Example 1 compared with 2.2 per cent in Example 2. Example 3 10 This example illustrates the effect of the concentration of reducing agent on the extraction efficiency. 25 g samples of asbolane ore were admixed with 500 mL of 0.2M sulfuric acid. These samples were then treated with differing concentrations of sulfur dioxide, namely approximately 1.8, 7.2, 10.8, 12.6 and 14.4 mmol/g. The samples were leached for 45 minutes at 25 0 C and ambient pressure. At the completion of the leaching 15 period the pulps were filtered dried and analysed. An analysis of the sample treated with 1.8 mmol/g SO 2 showed that 16.2 per cent manganese, 8.0 per cent nickel, 16.0 per cent cobalt and 4.0 per cent iron by weight had been recovered from the ore. An analysis of the sample treated with 7.2 mmol/g SO 2 20 showed that 62.6 per cent manganese, 48.6 per cent nickel, 25.0 per cent cobalt and 4.0 per cent iron by weight had been recovered from the ore. An analysis of the sample treated with 10.8 mmol/g SO 2 showed that 82.1 per cent manganese, 76.6 per cent nickel, 30.0 per cent cobalt and 5.8 per cent iron by weight had been recovered from the ore. An analysis of the sample treated with 12.6 mmol/g SO 2 showed that 88.6 per cent 7 WO 2007/092994 PCT/AU2007/000149 manganese, 88.6 per cent nickel, 52.1 per cent cobalt and 5.8 per cent iron by weight had been recovered from the ore. An analysis of the sample treated with 14.4 mmol/g SO 2 showed that 92.6 per cent manganese, 92.0 per cent nickel, 88.0 per cent cobalt and 5.8 per cent iron by weight had been recovered from the ore. 5 It may be seen from Example 3 that a selective recovery of nickel, manganese and cobalt may be achieved by leaching with sulfur dioxide in an acid medium. The efficiency of the leaching increased with the increasing concentration of sulfur dioxide. The quantities of iron leached were minimal and appeared independent of the concentration of sulfur 10 dioxide when leached in this way. Example 4. This example illustrates the effect of adding Na 2

SO

3 all at once at the start of the reaction rather than incrementally during the reaction, as performed in Example 1. 50 g of 15 asbolane ore was admixed with 500 mL of 0.2M sulfuric acid and 10 g ofNa 2

SO

3 , adding all the Na 2

SO

3 at the start of the reaction. The experiment was conducted at 25 0 C and ambient pressure. Samples were taken at 0, 30, 60, 110, 150, and 190 minutes and analysed for their cobalt, nickel, iron and manganese concentrations. 20 An analysis of the samples taken at thirty minutes showed that 59.6 per cent of the cobalt, 61.4 per cent of the manganese, 28.2 per cent of the nickel and 0.4 per cent of the iron had been recovered. An analysis of the samples taken at sixty minutes showed that 67.3 per cent of the cobalt, 71.3 per cent of the manganese, 33.3 per cent of the nickel and 0.5 per cent of the iron had been recovered. An analysis of the samples taken at one hundred 8 WO 2007/092994 PCT/AU2007/000149 and ten minutes showed that 72.3 per cent of the cobalt, 76.0 per cent of the manganese, 37.1 per cent of the nickel and 0.5 per cent of the iron had been recovered. An analysis of the samples taken at one hundred and fifty minutes showed that 73.7 per cent of the cobalt, 78.6 per cent of the manganese, 37.7 per cent of the nickel and 0.5 per cent of the 5 iron had been recovered. An analysis of the samples taken at one hundred and ninety minutes showed that 74.2 per cent of the cobalt,78.5 per cent of the manganese, 39.1 per cent of the nickel and 0.6 per cent of the iron had been recovered. It is evident from the data in Example 4 that the optimal contact time is approximately 10 1 hour when the Na 2

SO

3 is added all at once at the start of the reaction. This reaction time is significantly lower than times used in examples 1 and 2, however the recoveries achieved in this example were slightly lower. Example 5 15 This examples illustrates the effect that the particle size of the ore has on the efficiency of the leaching process. Samples of the asbolane ore were crushed and separated into sizes ranges, namely 75- 104 i, 104 - 152 t, 152 - 211 t, 211 - 295t, 295 - 422pt, 422 - 599g. Samples of the ore from each size fraction were then admixed with 500 mL of 0.2M sulfuric acid and 10 g ofNa 2

SO

3 .The samples were then leached for 45 minutes at 25 0 C 20 and ambient pressure. At the completion of the leaching period the pulps were filtered dried and analysed. An analysis of the 75 - 104g ore fraction showed that 75.3 per cent nickel, 85.6 per cent cobalt, 88.0 per cent manganese and 5.8 per cent by weight of iron had been recovered. 9 WO 2007/092994 PCT/AU2007/000149 An analysis of the 104 - 152[t ore fraction showed that 70.9 per cent nickel, 80.1 per cent cobalt, 86.0 per cent manganese and 5.8 per cent by weight of iron had been recovered. An analysis of the 152 - 211 R ore fraction showed that 68.1 per cent nickel, 76.4 per cent cobalt, 84.7 per cent manganese and 5.9 per cent by weight of iron had been recovered. 5 An analysis of the 211 - 295R ore fraction showed that 59.0 per cent nickel, 69.4 per cent cobalt, 76.2 per cent manganese and 7.6 per cent by weight of iron had been recovered. An analysis of the 295 - 422t ore fraction showed that 53.2 per cent nickel, 59.8 per cent cobalt, 60.6 per cent manganese and 5.9 per cent by weight of iron had been recovered. An analysis of the 422 - 599k ore fraction showed that 47.9 per cent nickel, 55.6 per cent 10 cobalt, 60.2 per cent manganese and 5.7 percent by weight of iron had been recovered. It may be seen from this example that the efficiency of the leaching process decreased with the increase in size fraction of the ore. The quantities of iron leached were minimal and appeared independent of the particle size of the ore when leached in this way. 15 Modifications and variations as would be apparent to a skilled addressee are deemed to be within the scope of the present invention 10

Claims

2. A process as defined in claim 1, wherein the highly oxidised laterite ore contains asbolane.
3. A process as defined in claim 2, wherein the highly oxidised laterite ore comprises 5 cobalt in the range of 0.1 to 10 per cent by weight, manganese in the range of 40 to 80 per cent by weight and nickel in the range of 0.1 to 20 per cent by weight.
4. A process as defined in claim 3, wherein the highly oxidised laterite ore comprises cobalt in the range of 2 to 5 per cent by weight, manganese in the range of 50 to 70 o per cent by weight and nickel in the range of 5 to 15 per cent by weight.
5. A process as defined in any one of claims 1 to 4, wherein the sulfur reducing agent is provided in the form of an aqueous solution of sulfur dioxide 11 WO 2007/092994 PCT/AU2007/000149
6. A process as defined in any one of claims 1 to 5, wherein the sulfur dioxide is generated in situ by the reduction of an alkali metal sulfite.
7. A process as defined in claim 6, wherein the sulfur dioxide is generated in situ by 5 the reduction of sodium sulfite.
8. A process as defined in any one of claims 5 to 7, wherein the amount of sulfur reducing agent added provided is in the range of 0.8 to 3.2 mol SO 2 / kg of the ore. 0 9. A process as defined in any one of the preceding claims, wherein the pH of the aqueous medium is less than 2.0.
10. A process as defined in claim 9, wherein the source of acid is a mineral acid. 5 11. A process as defined in claim 10, wherein the mineral acid is sulfuric acid.
12. A process as defined in any one of the preceding claims, wherein the treatment temperature is in the range of 20'C to 50°C. o 13. A process as defined in any one of the preceding claims, wherein the treatment pressure is less than 2 atmospheres.
14. A process as defined in any one of the preceding claims, wherein the ore is crushed to a size in the range of 50 to 600 mesh. 12 WO 2007/092994 PCT/AU2007/000149
15. A process as defined in claim 14, wherein the ore is crushed to a size in the range of 90 to 110 mesh 13