SEPARATION OF NICKEL FROM COPPER IN AUTOCLAVE

Abstract: A process for separating nickel from copper contained in solid particles of ground sulphidic matte or alloy comprises subjecting a slurry of the particles in an acidic chloride sol­ ution to a leach treatment, preferably with additional chlor­ ine, in an autoclave at an above atmospheric pressure and at a temperature greater than 110°C, and a redox potential which favours the dissolution of nickel over copper, to form a nickel enriched leach solution including a nickel im­ poverished solid residue containing copper sulphide, adding fresh unleached solid particles to the leach solution (either at atmospheric pressure or at above atmospheric pressure) to precipitate dissolved copper from the solution, separating the solid residue from the solution and treating them re­ spectively to recover copper and nickel. Cobalt may also be recovered from the solution, and precious metals may also be recovered from the residue.

Description: This invention relates to the hydrometallurgical treatment of solid particles selected from sulphidic matte and alloys, more particularly to the selective leaching of nickel from predominantly copper and nickel-containing sulphidic matte and alloys, and subsequently to recovering copper and precious metals from the residue. Mattes are the products of smelting sulphidic ores. The sulphidic ores and concentrates usually contain nickel, cobalt, iron, copper, other non-ferrous metals and some precious metals. During the smelting process, which often includes a converting step as well, most of the iron and silicate-containing gangue is slagged off, and the underlaying matte contains most of the copper, nickel and cobalt originally present in the ore and concentrate, mainly in the form of sulphides together with minor amounts of oxides,some retained iron and other non-ferrous metals as impurities, and all the precious metals initially combined with copper and nickel in the concentrate or ore. The present invention is directed to extracting copper, nickel and precious metals from sulphidic matte and alloy particles by hydrometallurgical methods solubilizing nickel, and cobalt if present, selectively as chloride and retaining copper and precious metals in the form of sulphides in the residue. The recovery of copper and precious metals is carried out by conventional means and processes subsequently, and do not form part of the present process description. Chlorine leaching of sulphidic particles in acidic chloride solutions at atmospheric pressure is described in U.S. patents 3,880,653 and 3,975,189 (inventor Hougen). The above process is carried out in two stages: In the first stage the ground matte slurried in a chloride ion bearing solution, is leached with chlorine gas at a redox potential range of 200 to 500 mV measured against SCE (saturated calomel electrode), which is maintained by controlling the feeding of both the solids and the chlorine gas to the slurry. In the second stage, untreated nickel rich sulphides are added to the agitated slurry obtained in the first stage to preferentially recover nickel into the solution and precipitate copper as sulphide. The second stage is often referred to as a cementation step. In the atmospheric chlorine leaching at the required redox potential range, a large portion of the nickel contained in the matte will dissolve and also a small portion of the copper. The residue in the first stage of the leaching is composed of partially leached sulphides and retained elemental sulphur. In the second stage excess nickel bearing sulphides will precipitate or cement out the copper in solution as sulphide, with more nickel going into solution as chloride. The precipitation is enhanced by the reaction with elemental sulphur, which is also present in the slurry. Ideally in the second leaching stage of the process the copper is cemented out while all the nickel in the solids go into solution. In practice, however, the incompletely leached particles and the freshly added nickel rich sulphide particles become coated with copper sulphide and thus the dissolution process is slowed down. Hence the total extraction of nickel into the solution and elimination of copper from the solution are not attained in commercially economical residence times and temperatures of this atmospheric leaching process. Prior processes have attempted to complete the selective dissolution process of nickel from matte by the use of autoclave leaching, thereby increasing the reaction temperature and hence the rate of the reaction. The process of U.S. patent 3,652,265 (Marschik et al.) utilizes an oxidative acidic pressure leach by treating ground matte and sulphur together with oxygen injection in an autoclave. This process, however, produces sulphuric acid and the nickel is dissolved in the form of sulphates, together with substantial amounts of highly soluble copper sulphates. Another process is described in U.S. patent 4,384,940 (inventors D.L. Jones et al.) which subjects nickel, cobalt and iron containing sulphidic matte slurried in hydrochloric acid to oxygen-pressure leaching in an autoclave, and the separated residue is subsequently chlorine leached under atmospheric condition. Any copper present initially in the matte is co-dissolved with the nickel, and requires separation by other purification steps subsequently. Yet another process utilizing pressure leaching a copper-nickel containing matte for selective extraction of nickel is described in U.S. 4,323,541 under oxidative conditions; this process, however, is directed totally to sulphate extractive process technology. It is the object of the present invention to selectively leach most of the nickel, and cobalt if present, contained in copper and nickel bearing sulphidic matte and similar sulphidic alloy particles in a chloride solution, and subsequently to recover the nickel and cobalt from the separated nickel containing solution by electrowinning, solvent extraction or other known methods; while retaining substantially all the copper and precious metals in the residue, for treatment in separate copper and precious metal recovery process steps. According to the invention there is provided a process for the separation of nickel from copper contained in solid particles of a copper- and nickel-containing ground sulphidic matte or sulphidic alloy, wherein said particles, after being slurried in an acidic solution, are chlorine leached at ambient atmospheric pressure to provide a chlorine leached slurry of sulphidic particles in a chloride solution, additional unleached solid particles of copper- and nickel-containing ground sulphidic matte or sulphidic alloy are added to the chlorine leached slurry to cement out copper dissolved in the chloride solution, the copper depleted chloride solution is separated and the residue treated for copper recovery, characterized in that the process includes the step of subjecting the chlorine leached slurry to a second leaching conducted in an autoclave at over-atmospheric pressure, in the presence of chlorine gas and air, at a pH less than 4 and at a temperature higher than 110°C, providing nickel impoverished copper sulphide containing particles slurried in a nickel enriched chloride solution. Preferably, the separated chloride solution is treated for nickel recovery. In one embodiment of this process the second chlorine leaching step is conducted before the cementation step, the fresh sulphidic particles being added in the cementation step to the nickel-enriched chloride solution obtained by the second chlorine leaching to cement out at atmospheric pressure any copper co-dissolved with nickel in said solution. In another embodiment of the process the cementation of dissolved copper in the chloride solution by fresh sulphidic particle addition is conducted in an autoclave at over-atmospheric pressure and at a temperature higher than 110°C. According to one feature of the process the second leaching at over-atmospheric pressure in an autoclave is conducted in the presence of chlorine gas. In yet another embodiment of the process the second leaching at over-atmospheric pressure is conducted with chlorine and oxygen injections into the autoclave. In yet another embodiment of the process the second chlorine leaching at over-atmospheric pressure is followed by cementation of copper onto fresh sulphidic particles added to the nickel-enriched chloride solution slurry from the second chlorine leaching step, said second chlorine leaching and said cementation being conducted in separate autoclaves. The invention will now be described with reference to preferred embodiments and the accompanying drawings, in which: Figures 1/a and 1/b show plots of nickel leach rate studies at above atmospheric pressure; Figure 2 shows a schematic flow diagram of a conventional atmospheric leaching process; and Figures 3 to 4 show schematic flow diagrams of preferred embodiments of the process in accordance with the invention. It is the object of most hydrometallurgical processes to convert the valuable metals present in ores, concentrates or heat treated intermediates such as mattes, into a water soluble form and to extract these in a pure form by further treatment steps. If all the valuable metals are dissolved together their respective subsequent separation can however, be very costly. Hence a selective dissolution process such as chlorine leaching of nickel-copper sulphidic mattes and alloys conducted at well controlled redox potentials have great advantages. The different embodiments of the present invention combine the pressure leaching of copper-nickel containing sulphidic matte or sulphidic alloys obtained by smelting, in a chloride ion-containing aqueous slurry in the presence of residual or additionally injected chlorine, with the known methods of atmospheric chlorine leaching of such sulphidic mattes and alloys. As already discussed above, the selective leaching of matte and other sulphidic alloys aims at combining the maximum dissolution of nickel, and cobalt if present, consistent with minimum copper content in solution, with the substantially complete retention of copper and attendant precious metals in the residue. The objectives of dissolving nickel in the solution and retaining copper in the residue, that is, the separation of these metals, are better obtained at elevated temperatures and pressures. While the improvements may be partially due to faster reaction rates at elevated temperatures, they are also the results of an unexpected, increased differential between the respective solubilities of nickel and copper sulphides at such elevated temperatures. Thus, the process steps embodying the present invention are conducted in an autoclave, and these steps are inserted between the process steps of the conventional atmospheric chlorine leaching process. The autoclave pressure leaching of the previously chlorine leached sulphidic particles may be conducted directly after the particles have been atmospherically chlorine leached, or optionally after they have already been purified by cementation under atmospheric conditions. In the latter case the autoclave pressure leaching step may be followed by further cementation of dissolved copper onto freshly added ground sulphidic particles, and this further cementation step may be conducted at above atmospheric pressure in an autoclave. For the purposes of this invention an autoclave is described as a vessel appropriately lined, which can be sealed to withstand above-atmospheric internal pressures with or without gas injection, and simultaneously the contents of the vessel can be heated to temperatures in the region of 100-300°C. The first two of the following examples are included to show the beneficial effects of utilizing over-atmospheric pressure leaching in selectively extracting nickel contained in copper-nickel matte. Examples 4 to 9 show the various embodiments of the present process wherein the pressure leaching conducted in an autoclave is incorporated at various stages with atmospheric chlorine leaching. These embodiments will be further illustrated by the appropriate flow sheets. Example 1 Laboratory experiments were conducted to show the improvement in nickel dissolution from ground copper nickel matte when the leaching is conducted at above atmospheric pressure and at elevated temperatures. The leaching experiments were carried out in a 6 litre titanium lined autoclave, having a chlorine atmosphere above the leach solution slurried with the ground matte. The solution at the start of the experiments had the following compositions: Ni ions 185 g/L Cu ions 25 g/L The leach temperature was controlled at 150±1°C; other conditions of the tests are tabulated in TABLE 1 below. The rate of nickel removal by leaching is shown in Figure 1a where the nickel content of the matte is plotted against the duration of leaching in the tests shown in TABLE 1. Fig. 1b indicates how the amount of nickel dissolved during leaching is effected by the amount of chlorine absorbed during leaching at elevated temperature. The beneficial effects of increased leach temperature and chlorine additions on the nickel dissolution from ground copper-nickel matte are clearly illustrated. Example 2 Laboratory autoclave leaching tests were conducted for selectively leaching nickel from a copper-nickel matte which was obtained by smelting copper concentrate. The matte was ground, slurried with a solution and leached in an autoclave at 135°C, having a two hour residence time. Chlorine together with air were injected into the autoclave during the leaching and the gas composition in the autoclave above the slurried matte was as follows: Chlorine 50 vol. % Oxygen 10 vol. % Nitrogen 40 vol. % The slurrying solution had the following initial and final compositions in grams per litre: The solids fed into the autoclave and leached, were analyzed, and were found to have the following initial and final composition in weight %. It can be seen that most of the nickel was leached in the autoclave leaching step but the copper concentration in the solution also increased, and a subsequent cementation step would be required to derive the full benefit of autoclave leaching of copper-nickel matte. Example 3 An atmospheric leaching process is shown schematically in Fig. 2 which is conducted according to conventional methods. Ground, untreated matte was fed through line (3) together with chlorine gas (1) and an acidic chloride solution (2) to a vessel at atmospheric pressure. The feeding of matte, and chlorine were coordinated so that the redox potential of the slurry was maintained at 360 to 380 mV, measured against S.C.E. The residence time of the matte was around 3 hours with constant agitation. The slurry temperature was close to the boiling point about 105-110°C. The feed solution was spent nickel electrolyte, but other nickel and copper chloride bearing solutions would serve as well. The feed solution was acidic, containing 2-5g per litre hydrochloric acid. The leached slurry was transferred (4) to an atmospheric cementation vessel, with fresh untreated matte added through line (5). The duration of the cementation step was around three hours, after which the slurry was removed (6) and subjected to liquid-solid separation. The filtrate or overflow was removed (7) for nickel recovery by electrowinning, solvent extraction or similar known processes. The residue or solids in the underflow was further treated for copper and precious metal recovery by conventional methods. TABLE 3 summarizes solution and solid compositions including slurries of solids in solution; as fed at various intermediate stages of the process and after the final liquid-solution separation. It is clear that the initial 39 wt.% nickel content in the matte was considerably reduced and the copper content was increased by the two stage atmospheric leaching process. The nickel content of the residue however was still around 15% and the copper, although increased was only 48.9% in the separated residue, requiring further selective extraction treatment. Example 4 The process described in this example illustrates the selective leaching of nickel from copper-nickel matte with an autoclave pressure leach step incorporated in the process. The first stage of the atmospheric chlorine leach as shown in Example 3 and in Fig. 2, was followed by an autoclave leach and subsequently by an atmospheric cementation process step. The schematic flow sheet is shown in Fig. 3. The slurry from the atmospheric chlorine leach was taken by a line (4) to an autoclave to be pressure leached at 4 atmospheres pressure with agitation for 3 hours and at a temperature range of 140-150°C. The gas phase in the autoclave above the slurry was air. The redox potential of the slurry in the pressure leaching autoclave was found to be in the range of 240-290mV. The pressure leached slurry from the autoclave was fed (5) to an atmospheric cementation vessel with the addition of fresh untreated matte (3). The retention time in the cementation vessel was 1.5 hours; at 70°C, and the redox potential of the slurry ranged between 80-120mV measured against S.C.E. The composition of the slurries, solutions and solids in the various streams of Fig. 3 are shown in TABLE 4. It can be seen that the nickel concentration in the residue when obtained by the process of the embodiment depicted in this example is reduced to 5 wt.%, while the copper has increased to 54.1%. The amount of copper retained in the solution to be treated for nickel and cobalt recovery is negligible, and hence requires no further separation treatment. Example 5 The process of this example is another variation of the embodiment described in Example 4. The matte was subjected to atmospheric chlorine leaching and cementation as has been described in Example 3, and treated in a first liquid solid separation step. The filtrate was treated for nickel recovery in a conventional manner, but as discussed above, the residue still retained 15 wt.% nickel, and hence was treated in a second atmospheric chlorine leach step. The flow sheet of the process of Example 5 is shown in Fig. 4. The thickened slurry of the residue was fed (7) to an atmospheric chlorine leach vessel, with chlorine gas (1) and water (8) additions. The second atmospheric chlorine leach with agitation was conducted at 105°C for a period of 2 hours. The second chlorine leach slurry was fed through line (9) to an autoclave to be pressure leached at 3-4 atmospheres and 150°C for further two hours. The slurry redox potential ranged between 180-200mV measured against S.C.E. The pressure-leach slurry was fed (10) to a liquid-solid separating equipment. The separated filtrate (11) was returned to the first atmospheric leaching vessel through line (2). The separated solids (12), high in copper sulphides, were treated for copper and precious metal recovery. The compositions of the slurries, solutions and the solids in the respective streams are tabulated in TABLE 5. It can be seen that the separated residue was substantially depleted of nickel. The filtrate from the first liquid-solid separation step still contained some copper, which could be removed if required by a relatively inexpensive process step before recovering nickel from the solution. The filtrate from the second liquid-solid separation (11) had a relatively high nickel and copper concentration which was utilized by recycling to the first chlorine leach vessel. Example 6 In the embodiment shown in Example 6, the pressure leaching step is conducted between the atmospheric chlorine leaching and the atmospheric cementation steps. The flow sheet of this process is schematically shown in Fig. 5 . The atmospheric leach was carried out shown in the first stage of Example 3, at a temperature range of 105-115°C, and the redox potential being controlled between 340-380 mV against S.C.E., with agitation, and in three hours residence time. The slurry was then fed (4) together with matte (3) to a pressure cementation autoclave. The slurry was agitated in the autoclave with the pressure being held at 4 atmospheres and the temperature between 140-150°C. The slurry residence time was three hours and the redox potential in the autoclave had a range of 230-300 mV measured against S.C.E. The slurry from the autoclave cementation was fed (5) to an atmospheric cementation vessel for a further 1.5 hours residence with matte additions (3) and agitation. The redox potential ranged between 80-120 mV against S.C.E. during the cementation and temperature was 70°C. The compositions of the various streams of slurries, solids and solutions are shown in TABLE 6, together with matte feed rates to the cementation vessels. It can be seen that the copper content of the solution from the liquid-solid separation stage has a very low copper content and thus could be directly treated for nickel recovery. The separated residue was very high in copper, 55.9 wt.%, and retained only about 6 wt.% of nickel and cobalt in total, which is an economically acceptable degree of separation. Example 7 The improved separation of nickel from copper contained in sulphidic matte particles described in this example incorporates an autoclave leaching step with chlorine gas injection into the atmospheric chlorine leach process. The process is shown schematically in Fig. 6. The two stages of the atmospheric chlorine leaching and cementation were conducted as described in Example 3, followed by a liquid-solid separation step. The solution from the liquid-solid separation through line (7) was taken for nickel recovery as was conducted in Example 3; the solids which were still high in nickel (15 wt.%) were fed (8) to an autoclave to be pressure leached at 4 atmospheres pressure with chlorine additions (1) and agitation. The temperature in the pressure leach step was 140-150°C. The duration of the pressure leach was two hours. The slurry from the autoclave was fed through line (9) to a second liquid-solid separation stage. The solution obtained (10) was returned to the atmospheric chlorine leach stage, a diluted bleed stream being taken to the chlorine- pressure leach autoclave to form a slurry with the solid residues from the first liquid-solid separation step. The residue from the chlorine-pressure leach (11) was treated for copper and precious metal recovery. The composition of the solution and the residues fed to and obtained from the chlorine pressure leach autoclave are shown in TABLE 7. The residue obtained in the autoclave leach step was low in nickel and high in copper and was further treated for copper and precious metal recovery. The separated solution was relatively high in copper and hence was returned to the atmospheric chlorine leach stage. The high copper content may be due to the relatively high acidity and sulphate content formed during the chlorine pressure leaching stage. Example 8 This process was a variation on the process described in Example 7, wherein the autoclave chlorine pressure leach stage followed directly the atmospheric chlorine leach and cementation stages without a liquid solid separation step. The autoclave chlorine pressure leach was followed by an autoclave cementation step and an atmospheric cementation step. The flow sheet of this process is shown in Fig. 7. The atmospheric chlorine leach and atmospheric cementation-I stages were conducted in a manner similar to Example 7. The slurry from the first cementation stage was fed through line (6) to an autoclave for a chlorine pressure leach step, with chlorine injection and agitation, at 4 atmospheres pressure and at a temperature range of 140-150°C. The redox potential in the autoclave was held between 300-320 mV measured against S.C.E. The slurry for the chlorine pressure leach was fed (8) to an autoclave cementation step with agitation, together with fresh untreated matte (7). Residence time in both autoclaves was 1.5 hours. The temperature in the second autoclave was also between 140-150°C and the pressure was 4 atmospheres. The redox potential measured against S.C.E. was found to be 230-360 mV. The autoclave cementation was followed by atmosphpric cementation-II, by feeding the autoclave cemented slurry through line (9) to an open cementation vessel. Untreated matte (7) was added at the same rate as in the autoclave cementation. The temperature of the slurry in the atmospheric cementation was 70°C. The redox potential was between 80-120 mV (S.C.E.) and the residence time was 1.5 hours. The slurry for the atmospheric cementation vessel was fed (10) to liquid-solid separation. The solution (11) was treated for nickel recovery and the residue (12) for copper and precious metal recovery. TABLE 8 shows the composition of the various slurries fed to the autoclaves and to the second atmospheric cementation vessel, as well as the matte composition and its feed rate. The compositions of the separated solution and the separated residue are also shown. It can be seen that the solution could be treated directly for nickel and cobalt recovery after the iron having been removed if desired, as the copper content was negligible. The residue had high copper content with the total nickel and cobalt retained being less than 6 wt.%. Example 9 A simplified process based on the embodiment described in Example 8 is shown in Fig. 8. In this process, nickel and copper containing chloride solution was fed through line (2) to an autoclave with matte particles added (3) and leached in the presence of chlorine gas. The pressure inside the autoclave was 3-4 atmospheres and the temperature was between 140-150°C. The redox potential was controlled at 310-320 Mv (S.C.E.); the slurry had a residence time of 2 hours. The slurry was subsequently taken through line (4) to an autoclave cementation stage and then to an atmospheric cementation vessel through line (6). Untreated matte was added to both cementation stages through lines (5) and (7) respectively. The autoclave cementation was conducted at 3-4 atm. pressure, at the range of 140-150°C. The redox potential ranges of the slurry was 240-250 mV (S.C.E.) and the duration of the autoclave cementation was around 2 hours. The atmospheric cementation was carried out in an open vessel for 1.5 hours at 80°C and in a redox potential range of 50-110 mV (S.C.E.). The slurry from the atmospheric cementation (8) was subjected to liquid-solid separation, yielding a solution (9) with negligible copper content and a residue (10) with high copper content, and total nickel and cobalt content less than 6 wt.%. The composition of the slurries in the various streams together with a final solution and residue compositions, are shown in TABLE 9. The various embodiments of combining autoclave leaching with atmospheric chlorine leach and cementation process steps for the improved separation of nickel and cobalt, from copper contained in particles of sulphidic matte and sulphidic alloys, are described above. The objective of obtaining a solution to be treated for nickel and cobalt recovery with very low copper content can be attained in all the embodiments described. The nickel and cobalt retained in the separated copper and precious metals containing residue can be varied between 1-6 wt.% according to the requirements dictated by market conditions and extraction process costs. Further embodiments will be readily apparent to those skilled in the art, the scope of the invention being defined in the appended claims.

Claims: 1. A process for the separation of nickel from copper contained in solid particles of a copper- and-nickel-containing ground sulphidic matte or sulphidic alloy, wherein said particles, after being slurried in an acidic solution, are chlorine leached at ambient atmospheric pressure to provide a chlorine leached slurry of sulphidic particles in a chloride solution, additional unleached solid particles of copper- and nickel-containing ground sulphidic matte or sulphidic alloy are added to the chlorine leached slurry to cement out copper dissolved in the chloride solution, the copper depleted chloride solution is separated and the residue treated for copper recovery, characterized in that the process includes the step of subjecting the chlorine leached slurry to a chlorine leaching conducted in an autoclave at over-atmospheric pressure, in the presence of chlorine gas and air, at a pH less than 4 and at a temperature higher than 110°C, providing nickel impoverished copper sulphide containing particles slurried in a nickel enriched chloride solution. 2. A process according to claim 1, wherein the separated chloride solution is treated for nickel recovery. 3. A process according to claim 1 or claim 2, wherein said solid particles also contain precious metals which are subsequently recovered from the leach residue. 4. A process according to claim 1, wherein the cementation of the dissolved copper in the chloride solution onto freshly added particles is carried out in an autoclave at over-atmospheric pressure and at a temperature higher than 110°C. 5. A process according to claim 2, wherein said solid particles also contain cobalt, which is dissolved together with said nickel in said chloride solution, and is subsequently recovered from said solution. 6. A process according to claim 1, wherein a chlorine and oxygen bearing gas is injected into said autoclave during the second chlorine leaching of said slurry at over-atmospheric pressure. 7. A process according to claim 2 conducted in a batch mode. 8. A process according to claim 2 conducted in a continuous mode. 9. A process for the separation of nickel from nickel- and copper-containing solid particles of ground sulphidic matte or sulphidic alloy comprising the steps of slurrying, in an acidic solution, material containing ground sulphidic matte or sulphidic alloy containing nickel and copper, thereafter leaching solid particles so obtained in the presence of gaseous chlorine at atmospheric pressure at a redox potential selected to be within the range favouring dissolution of nickel over copper in said acidic solution, maintaining said redox potential by controlling the feed rate of said ground sulphidic solid particles in conjunction with the addition of said chlorine gas, subjecting the chlorine leached particles slurried in a predominantly nickel chloride-containing solution to further chlorine leaching in an autoclave at above-atmospheric pressure, at a pH less than 4 and at a temperature in excess of 110°C, reacting the chlorine pressure leached slurry from said autoclave with additional unleached solid particles of ground sulphidic matte or sulphidic alloy containing nickel and copper to cement out copper dissolved in the nickel chloride- containing solution of said slurry, subjecting the slurry of sulphidic particles in the copper depleted nickel chloride-containing solution to liquid-solid separation to obtain a purified nickel chloride-containing solution and a residue containing copper sulphide and residual nickel sulphide, and treating the separated nickel chloride-containing solution for nickel recovery and said copper sulphidic residue for copper recovery. 10. A process according to claim 9, wherein unleached ground solid particles containing nickel and copper, are added to the chlorine pressure leached slurry in said autoclave for cementing out copper dissolved in said nickel chloride containing solution at over-atmospheric pressure and at a temperature higher than 110°C. 11. A process for the separation of nickel from nickel- and copper-containing solid particles of ground sulphidic matte or sulphidic alloy, comprising the steps of slurrying in an acidic solution solid particles of ground sulphidic matte or sulphidic alloy containing nickel and copper, thereafter first leaching said particles, in the presence of chlorine gas at atmospheric pressure, at a redox potential selected to be within the range favouring dissolution of nickel over copper in said acidic solution, maintaining said redox potential by controlling the addition of said chlorine gas in conjunction with the feed rate of said sulphidic solid particles, thereafter adding additional unleached nickel- and copper-containing ground solid sulphidic particles to said first leached slurry and obtaining leached nickel impoverished sulphidic particles slurried in a first predominantly nickel chloride-containing solution, separating the nickel chloride-containing solution and recovering nickel from said solution, transferring the nickel impoverished sulphidic particles separated from said first nickel chloride-containing solution to an autoclave and adding a second acidic solution thereto to form an aqueous slurry, subjecting said aqueous slurry in said autoclave to a second leaching with additions of chlorine gas at above-atmospheric pressure, at a pH less than 4 and a temperature in excess of 110°C, to yield a slurry of substantially nickel-free copper sulphide containing particles in a second nickel chloride-containing solution, separating the second nickel chloride-containing solution and returning it to said first atmospheric leaching step, and treating the substantially nickel-free copper sulphide containing residue for copper recovery. 12. A process for the separation of nickel from nickel and copper-containing solid particles of ground sulphidic matte or sulphidic alloy, comprising the steps of first leaching solid particles of ground sulphidic matte or sulphidic alloy containing nickel and copper, slurried in an acidic solution, in the presence of chlorine gas at atmospheric pressure, at a redox potential selected to favour nickel dissolution over copper dissolution in said acidic solution, maintaining said redox potential by controlling the addition of said chlorine gas with respect to the feed rate of said sulphidic solid particles, thereafter adding a second charge of unleached nickel- and copper- containing ground solid sulphidic particles to cement out copper dissolved in the solution in said first atmospheric chlorine leaching, thereby obtaining nickel impoverished sulphidic particles slurried in an acidic predominantly nickel chloride-containing solution, subjecting the slurry obtained in the cementation step to a second leaching with further injection of chlorine gas in an autoclave at above-atmospheric pressure, at a pH less than 4 and a temperature in excess of 110°C to provide a chlorine-pressure leached slurry, thereafter adding a third charge of unleached nickel- and copper-containing ground solid sulphidic particles to said chlorine-pressure leached slurry and reacting the resulting mixture at above-atmospheric pressure, at a pH less than 4, and at a temperature in excess of 110°C, to yield pressure-treated sulphidic particles impoverished in nickel and slurried in a nickel enriched chloride solution, reacting said nickel impoverished pressure treated sulphidic particles slurried in nickel enriched chloride solution with a fourth charge of unleached nickel- and copper-containing ground sulphidic particles at atmospheric pressure to cement dissolved copper onto said unleached ground solid sulphidic particles, subjecting the slurry to liquid-solid separation to obtain a purified nickel chloride-containing solution and a residue containing copper sulphide, treating said purified nickel chloride-containing solution for the recovery of nickel, and treating said residue for the recovery of copper. 13. A process according to any one of claims 9 to 12, wherein the nickel and copper containing sulphidic particles also contain cobalt which is dissolved with the nickel and is retained in, and subsequently recovered from the separated nickel chloride-containing solution. 14. A process according to any one of claims 9 to 12, wherein the nickel and copper containing sulphidic particles also contain precious metals which are retained in, and subsequently recovered from the separated copper sulphide containing residue.

Inventors: KOSTOL, CARL, STENSHOLT, ERLING, THOMASSEN, THOMAS, ZACHARIANSEN, HANS
Applicants: FALCONBRIDGE LIMITED
Application year: 1987
Main classification: C22B3
IPC codes: C22B15, C22B3, C22B23, C22B11