Vapour metallurgical separation of metals from sulphide materials

Abstract

A system comprising a chlorination reactor with three reaction zones and methods using the reactor for the extraction and separation of iron, sulphur, copper and manganese from a feed material containing sulphides of iron, nickel, cobalt, copper, silver, gold and platinum group metals (PGM) and further for separation of these metals in the form of volatile chloride complexes from nickel, cobalt, silver, gold and platinum group metals. In the method, sulphur and iron are converted to volatile chlorides by the treatment of the feed material with gaseous chlorine at elevated temperature and pressure and extracted. Metal chlorides of manganese and copper are reacted in situ with ferric chloride vapours to form volatile complexes. These volatile complexes are removed from the reactor together with disulphur dichloride and ferric chloride and are separated by distillation and fractional desublimation. Disulphur dichloride is recycled to the reactor and removed as sulphur.

Description

Vapour Metallurgical Separation of Metals from Sulphide MaterialsTECHNICAL FIELD

[0001] This invention relates to a system and process for chlorination and selective extraction of at least copper, sulphur, manganese, and / or iron from a sulphide concentrate which may further contain nickel, cobalt, silver, gold and platinum group metals (PGM).BACKGROUND

[0002] Copper, nickel, cobalt, silver, gold and platinum group metals (PGM) containing sulphide ores, concentrates and metallurgical products may have significant amounts of iron. Conventionally, a refining process includes the production of a flotation concentrate with concentrations of nickel and copper between 1 and 20 wt%, and a combined content of iron and sulphur between 10-90 wt%. When a significant amount of copper is present, a flotation concentrate may be separated into nickel and copper flotation concentrates, sometimes with a significant loss of metals in the process. Moreover, the conventional nickel extraction process from sulphide ores does not realize the value for iron in such materials and extracts only nickel, cobalt, PGM and copper. In addition, a typical process includes a step of high- temperature roasting with the release of significant amounts of SO2. If significant amounts of manganese are present, the metal may report to a waste stream.

[0003] US Patent 3,537,961 PROCESS OF TREATING COPPER ORES describes a chlorination process of copper sulphide concentrate at between 350°C and 600°C to volatilize the sulphur and iron constituents and to yield a water-soluble copper chloride residue. It has been found that a very limited amount of the ferric chloride is formed in the presence of an excess of chlorine at temperatures between 300°C and 700°C. Produced ferric chloride, together with the evolved sulphur, was recovered from the chlorine retort. The chlorination residue was leached with water. The leach solution dissolved 47-59% of the copper originally charged into the chlorine reactor. Another 6% had volatilized in afurnace and therefore was unavailable for leaching. The leach solution contained small amounts of soluble iron, which was easily removed by aerating the solution overnight to oxidize the iron to ferric oxide, which was then filtered out. Copper was recovered by electrolysis.

[0004] US Patent 5,104,445A describes a process for recovering metals from refractory ores. It involves the chlorination of an ore concentrate in the presence of solid salt at a temperature between 300°C and 650°C. Sulphur and iron trichloride is produced in the process. The oxidation step can be used to convert iron chloride to iron oxide, and a gas mixture of oxygen and chlorine is recycled back to the chlorination reactor.

[0005] US Patent 1,406,595 teaches purification of Ni / Co concentrate containing As and Fe by treating the concentrate with dry chlorine at a temperature between 500-550°C to remove As and Fe chlorides without volatilization of Nickel and Cobalt.

[0006] In US patent 2,733,983, FeCF is used for chlorinating roasted ore to convert Ni and Co to solid chlorides. Vacuum sublimation is used for extracting these chlorides from ore at 850°C and 1 cm of Hg pressure. The same process is used for the separation of Co and Ni chlorides. The patent states that C0CI2 was volatile at 400°C and NiCh at 650°C at the same reduced pressure.

[0007] US patent 1,238,298 relates to chlorination of complex nickel-bearing ore with chlorine gas at temperature 225-275°C and dissolving resulting metal chlorides in water and hydrometallurgical separation of Ni, Cu, Co, Fe and PM chlorides.

[0008] In US patent 3,466,167, chlorination takes place with dry gaseous chlorine gas followed by treatment with CI2 in slurry. It is reported that Ni was separated from Cu, Co, PGM, Fe and As by selective chlorination of these elements by limiting the amount of chlorine during the dry chlorination and maintaining the temperature of chlorination below 325°C as well by maintaining a redox potential of plus 525 millivolts during chlorination of slurry. In contrast, the temperature of the slurry was kept at room temperature.

[0009] Therefore, there remains the need in the field for extraction systems and methods which can be used to selectively extract and separate all or almost all valuable materials from metal concentrates, including sulphur and iron, and thereby improvingutilization of ores. In addition, it is highly desirable to develop a method in which the release of toxic sulphur dioxide (SO2) is minimized or even completely avoided. Finally, conventional processes rely on extraction reactions requiring a significant use of energy, while it is advantageous to develop systems and methods which would be using a lesser amount of energy.SUMMARY

[0010] These and other needs are addressed at least partially by systems and extraction methods provided in this disclosure. This invention relates to a system and method for vapour metallurgical separation of iron, copper, sulphur and manganese from a sulphide concentrate which further contains nickel, cobalt, silver, gold and PGM. Advantageously, separation may be achieved without toxic SO2 emissions. Further technical advantages of the present systems and methods include, but are not limited to, separation of all or almost all materials from ores, including separation of sulphur and iron from metal concentrates. Additionally, the present methods and systems require a lesser amount of energy and therefore, they improve the utilization of intrinsic energy contained in the feed material.

[0011] In one aspect, this disclosure relates to a method of vapour metallurgical separation of iron, copper, sulphur and manganese from a feed material comprising a sulphide of one or more of the following metals: iron, copper, sulphur, manganese, nickel, cobalt, silver, gold and platinum group metals (PGM), the method comprises: a) reacting the feed material comprising metal sulphides with chlorine in the presence of nitrogen at a temperature in the range between 350 and 750°C and a pressure in the range from 3 to 5 Bar in a chlorination zone of a reactor and producing a gaseous mixture comprising disulphur dichloride and one or more of the following volatile metal chlorides: ferric chloride, cupric chloride (CuCh), manganese chloride and any mixture thereof, and a solid material comprising copper (II) chloride, nickel and cobalt chlorides, silver, gold and platinum group metals (PGM);b) passing the solid material produced in step “a” to a copper volatilization zone of the reactor and treating the solid material with a gas mixture containing chlorine, nitrogen and ferric chloride at a temperature ranging between 550 and 350 °C and a pressure in the range from 3 to 5 Bar and producing a gaseous mixture comprising volatile disulphur dichloride, ferric chloride and cupric chloride (CuCb), and a solid residue comprising nickel, cobalt, silver, gold and platinum group metals (PGM); c) passing the gaseous mixture obtained in step a) and the gaseous mixture obtained in step b) through a first condenser / desublimator operating at a pressure ranging between 3 and 5 Bar and at a temperature ranging between 550-450°C, and after that through a second condenser / desublimator operating at a pressure ranging between 3 and 5 Bar and at a temperature ranging between 450-320°C, and after that through a third condenser / desublimator operating at a pressure ranging between 3 and 5 Bar and at a temperature ranging from 320 to 120°C, and fractionally precipitating ferric chloride liquid from the gaseous mixture together with manganese chloride into a first product in the first condenser / desublimator, ferric chloride liquid from the gaseous mixture together with copper chloride, gold chloride and silver chloride into a second product in the second condenser / desublimator and ferric chloride liquid into a third product in the third condenser / desublimator, thereby depleting the gaseous mixture of volatile metal chlorides and obtaining a remaining volatile mixture which comprises S2CI2, nitrogen and small amounts of unreacted chlorine; d) passing the remain volatile mixture obtained in step c) which comprises S2CI2, nitrogen and small amounts of unreacted chlorine but is depleted of ferric chloride (FeCh) through a sulphur recovery zone of the reactor operating at a temperature ranging from 120 to 250°C and a pressure ranging from 1 to 3 Bar and producing elemental sulphur;e) performing fractional distillation at elevated pressure on the first product obtained in the first condenser / desublimator and recovering manganese chloride separated from ferric chloride; f) performing fractional distillation at elevated pressure on the second product obtained in the second condenser / desublimator and separating ferric chloride and produce copper concentrate; g) performing distillation at elevated pressure on the third product obtained in the third condenser / desublimator and producing high-purity ferric chloride and further oxidizing purified FeCh to metal iron or iron oxide; and h) collecting the residue obtained in step b), the residue comprising nickel II chloride, cobalt II chloride and platinum group metals (PGM).

[0012] In some embodiments, step b) may be performed together with step a).

[0013] Preferably, the feed material may be one or more of the following: sulphide ore, flotation concentrate, furnace matte or converter matte, preferably materials comprising from about 2 wt% to about 80 wt% metals, and more preferably from about 10 to about 70 wt% metals. Preferably, the method may further comprise: further oxidizing one or more metal chlorides in steps e), f) and / or g), and recycling chlorine gas hydrochloric acid (HC1) produced during reduction of metal chlorides.

[0014] In some embodiments, the method may further comprise: recycling chlorine gas produced during oxidation of ferric chloride in steps e), f) and / or g).

[0015] In particularly preferred embodiments, steps a), b) and d) may be performed in a chlorination reactor operating at 3 different reaction zones: zone I, zone II and zone III and wherein, zone II is used for performing step a), zone I is used for performing step b) and zone III is used for performing step d).

[0016] In another aspect, this disclosure relates to a system for extracting of one or more of iron, sulphur, copper, manganese, nickel, cobalt silver, gold and / or platinum group metals from a material containing sulphides of one or more of the metals and separating nickel and cobalt from sulphur, iron, copper, manganese, gold and silver the system comprising:- a chlorination reactor having three different reaction zones: copper volatilization I, chlorination reaction zone II, and sulphur recovery zone III, wherein the chlorination reactor is a chamber having a volume enclosed by a wall and having a length (L) from a bottom to a top of the chamber, and wherein the three reaction zones are located along the length (L) of the reactor, one after another, the copper volatilization zone I being the closest to the bottom of the reactor, followed by the chlorination reaction zone II in the middle and the sulphur recovery zone III being located after zone II, the sulphur recovery III being the closest to the top of the reactor chamber;- three or more condensers / desublimators;- one or more sulphur condensers; and- and a gas scrubber.

[0017] Preferably, the system may further comprise two or more liquid storage tanks for collecting and storing liquid ferric chloride / manganese chloride, one or more liquid storage tanks for ferric chloride / copper chloride mixture and one or more liquid storage tanks for liquid ferric chloride. In particularly preferred embodiments, the chlorination reactor may contain one or more inlets for receiving the feed material and wherein the inlets may be located at or near the top of the reactor and wherein the system may further include a conveyor (50) capable of moving the feed material from the top to the bottom of the reactor. In embodiments of the system, the reactor may include an exhaust line which can be connected to an outlet gas nozzle of the reactor, the exhaust line connecting to the reactor to three or more condensers / desublimators, the exhaust line being used for removing a gaseous mixture that comprises ferric chloride (FeCh), manganese chloride (MnCh), copper (II) chloride (CuCh) which may be referred to in this disclosure as cupric chloride, disulphur dichloride (S2CI2) and nitrogen with trace amounts of unreacted chlorine from the Zone II (16) of the reactor (12) to three or more condensers / desublimators. Preferably, the system may further include an exhaust line for connecting an outlet from the condensers / desublimators to the gas inlet below zone III ofthe reactor, the exhaust line being suitable for passing a ferric chloride depleted gaseous mixture from the condensers / desublimators to the sulphur recovery zone of the reactor.

[0018] In particularly preferred embodiments of the system, the chlorination reactor (12) may further comprise one or more of the following elements:- at least three inlets, a first inlet being located at or near the bottom of the chlorination reactor, the first inlet being suitable for supplying a gas mixture comprising chlorine (Ch), nitrogen (N2) and ferric chloride (FeCh) to the chlorination reactor, and a second inlet being located at or near the bottom of zone II for supplying additional chlorine / nitrogen gas mixture and a third inlet being located at or near the bottom of zone III (18) for introducing a gaseous mixture containing disulphur dichloride to sulphur recovery zone;- at least two outlet gas nozzles, a first outlet gas nozzle being located in or after the chlorination main reaction zone II, but before the sulphur recovery zone III, the first outlet gas nozzle being connectable to the exhaust line, the first outlet gas nozzle (20) being used for removing a gaseous mixture that comprises manganese chloride (MnCh), copper chloride (CuCh), disulphur dichloride (S2CI2) and nitrogen from the chlorination main reaction Zone II of the chlorination reactor to three or more desublimators / condensers; and a second outlet gas nozzle being located at or near the top of the chlorination reactor for removing sulphur vapours, the second outlet gas nozzle being connectable to a sulphur condenser;- a feed material hopper for feeding an ore, concentrate or metallurgical product to the chlorination reactor; and / or- a removal system eg. a screw conveyor for removing residue from the chlorination reactor.

[0019] In some embodiments of the system, the three or more desublimators / condensers may include a heat exchange unit and a bottom storage space for storage of ferric chloride and / or of a mixture of metal chlorides in liquid or crystal form. In any of the embodiments of the system, the sulphur condenser may include a storage tankfor storing liquid sulphur. Preferably, the system may include means for withdrawing the residue containing nickel (II) chloride, cobalt (II) chloride, silver, gold and PGM from the bottom of the reactor.

[0020] In embodiments of the methods according to this disclosure, the residue may be further treated by one of the following methods:- washing the residue with water and producing a solution comprising metal chlorides;- removing iron from the solution by oxidation or other methods;- precipitating metals as hydroxides, carbonates and / or sulphides or sulphates; and / or- reducing the residue and removing nickel, iron and cobalt as carbonyls.

[0021] In yet another aspect, this disclosure relates to a use of the system for performing the following method:- continuously feeding solid pellets to the chlorination reactor from the feed bin at the top of the reactor;- moving feed pellets downward through three zones of the reactor: sulphur recovery, chlorination main reaction and copper volatilization;- introducing a gas mixture of Q2 / N2 through the inlets and chlorinating feed material pellets in the chlorination main conversion zone;- introducing a gas mixture of Ch / FeCF through the inlets from the bottom of the reactor and producing volatile complexes of FeCF with CuCl2;- withdrawing a gaseous mixture containing iron, sulphur, copper and manganese chlorides from a gas outlet located above the chlorination main conversion zone;- passing the gaseous mixture through three or more desublimators / condensers and liquifying or precipitating solid ferric chloride / metal chlorides mixtures;- condensing a FeCh / MnCh mixture in a desublimator / condenser and discharging the FeCh / MnCh mixture into a storage tank;- condensing FeCh / CuCh mixture in a desublimator / condenser and discharging FeCh / CuCh mixture into a storage tank;- condensing FeCh in a desublimator / condenser and discharging FeCh into a storage tank;- collecting a remaining gaseous mixture which comprises disulphur dichloride from the outlet of the third desublimator / condenser and returning the remaining gaseous mixture which comprises disulphur dichloride back to the reactor through the inlet into the sulphur recovery zone of the reactor;- passing the remaining gaseous mixture which comprises disulphur dichloride through a heated feed material in the sulphur recovery zone of the reactor and removing elemental sulphur to the sulphur condenser;- evaporating the FeCh / MnCh mixture from the storage tank through a purification column to produce pure MnCh and FeCh;- evaporating the FeCh / CuCh mixture from the storage tank through a purification column to produce CuCh and separately FeCh;- evaporating crude FeCh from the storage tank through a purification column to produce pure FeCh; and- removing the residue containing nickel chloride, cobalt chloride and silver, gold and PGMs from the outlet of the reactor and treating the residue by one or more of the following methods:- washing the residue with water and producing a solution comprising metal chlorides;- removing iron from the solution by oxidation and / or other methods;- precipitating metals as hydroxides, carbonates and / or sulphides or sulphates; and / or- reducing the residue and removing nickel, iron and cobalt as carbonyls.BRIEF DESCRIPTION OF THE DRAWINGS

[0022] Fig. 1 is a schematic one embodiment of a system according to this disclosure and comprising a chlorination reactor.

[0023] Fig. 2 is a block diagram of one embodiment of a process according to this disclosure.DETAILED DESCRIPTION

[0024] In this disclosure, the term “about” means plus / minus 10% of the value. For example, “about 100” means 100±10 and “about 200” means 200±20.

[0025] In this disclosure the term “wt%” means percentage by weight.

[0026] In one aspect, this disclosure provides a system for efficient extraction of iron, sulphur, copper, manganese, nickel, cobalt, silver, gold and platinum group metals (PGM) from a feed material containing one or more of these metals in the form of metal sulphides and also separating nickel, cobalt, silver, gold and PGM from sulphur, iron, copper and manganese. Suitable feed materials for the system include metal ores, preferably copper containing ores, floating concentrates and metallurgical products and more preferably, containing nickel and copper between 1 and 20 wt%, and a combined content of iron and sulphur between 20-90 wt%.

[0027] Referring to Fig. 1, one embodiment of a system according to this disclosure, generally (10), is shown. The system (10) comprises a chlorination reactor (11) which includes a chamber (12) having a volume enclosed by a wall and having a length (L) from a bottom (12B) to a top (12T) of the chamber (12). The chlorination reactor (11) has at least three reaction zones (14, 16 and 18) located along the length (L) of the reactor chamber (12), one after another.

[0028] The first zone which may be referred in this disclosure as “Zone I” is the copper volatilization zone (14) is the closest to the bottom (12B) of the reactor chamber (12).

[0029] The second zone which may be referred in this disclosure as “Zone II” is the chlorination reaction zone (16) located in the middle of the reactor chamber (12).

[0030] The third zone which may be referred in this disclosure as “Zone III” is the scrubbing zone or sulphur recovery zone (18) located after the chlorination zone (16), being the closest to the top (12T) of the reactor chamber (12).

[0031] The reactor chamber (12) contains an outlet gas nozzle (20) located within and / or just above the chlorination reaction zone (16), relative to the top (12T) of the reaction chamber (12). A gas mixture generated in the chlorination reaction zone (16) and comprising ferric chloride (FeCh), manganese chloride (MnCb), copper chloride (CuCb), disulphur dichloride (S2CI2) and nitrogen with trace amounts of unreacted chlorine may be removed from the reactor chamber (12) through the outlet gas nozzle (20) which is connectable through an exhaust line (22) to three or more condensers / desublimators (24, 26 and 28) connectable consecutively in the exhaust line (22) and configured for receiving the gas mixture from the gas nozzle (20). Preferably, each of the condenser / desublimator (24, 26 and 28) may be operated at a different temperature, preferably decreasing from the condenser / desublimator (24) to the condenser / desublimator (26) and then preferably further decreasing to a third temperature in the condenser / desublimator (28). The condenser / desublimator (24) is the first condenser / desublimator that the gas mixture reaches after being removed from the outlet gas nozzle (20).

[0032] The condenser / desublimator (24) may be operated at a temperature in the range sufficient for selective condensation of liquid ferric chloride / manganese chloride, while copper chloride (CuCb) and disulphur dichloride (S2CI2) may remain in a gaseous form and are passed as a remaining gas mixture from the condenser / desublimator (24) to the condenser / desublimator (26) via the exhaust line (22). Preferably, the condenser / desublimator (24) may be connectable to a storage tank (25) in which liquid ferric chloride / manganese chloride from the condenser / desublimator (24) may be stored.

[0033] The second in line, condenser / desublimator (26) may be operated at a temperature lower than the temperature of the condenser / desublimator (24) and the temperature of the condenser / desublimator (26) being lowered such that copper chloride may be collected as liquid. Preferably, the condenser / desublimator (26) may beconnectable to a storage tank (27) in which liquid ferric chloride / copper chloride (CuCh) from the condenser / desublimator (26) may be stored.

[0034] The third in line, condenser / desublimator (28) may be operated at a temperature lower than the temperature of the condenser / desublimator (26) and the temperature of the condenser / desublimator (28) being lowered such that ferric chloride may be collected as liquid. Preferably, the condenser / desublimator (28) may be connectable to a storage tank (29) in which liquid ferric chloride from the condenser / desublimator (28) may be stored.

[0035] In some embodiments, additional condensers / desublimators may be added to the exhaust line (22) if separation and collection of other metal chlorides, e.g., lead and / or zinc from the gas mixture coming through the exhaust line (22) is needed.

[0036] In embodiments, the condensers / desublimators (24, 26 and / or 28) may include one or more heat exchange units (not shown) such that the heat removed in the condenser / desublimators (24, 26 and / or 28) is recycled back into the system (10) for example, for operating the reactor chamber (12).

[0037] The exhaust line (22) may further comprise a portion (23) suitable for collecting a gas mixture from the condenser / desublimator (28) through an outlet (52), the gas mixture being depleted of ferric chloride, but sill comprising disulphur dichloride gas. The exhaust line portion (23) is connectable to an inlet (30) located in the wall of reactor chamber (12) at the sulphur recovery zone (18), the inlet (30) being also located above the outlet (20), such that the disulphur dichloride gas can be recycled from the condensers / desublimators (24, 26 and / or 28) back into the sulphur recovery zone (18) of the reactor chamber (12) wherein the disulphur dichloride gas may be converted into sulphur which can be released from the reactor chamber (12) through one or more of outlet nozzles (32) located at or above the sulphur recovery zone (18) and above the inlet (30), relative to the top (12T) of the reactor chamber (12).

[0038] The outlet nozzle (32) is connectable with an exhaust line (33) to a sulphur condenser (34) in which gaseous sulphur that was released from the outlet (32) may be converted into liquid sulphur. The sulphur condenser (34) may be equipped with a storagetank (not shown) for storing liquid sulphur which can be sent to gas scrubbing (46). This addresses the technical need for not producing or producing only insubstantial amounts of sulphur oxide(s), which is toxic.

[0039] The system (10) may further comprise a feed material hopper (36) suitable for feeding an ore, concentrate, matte or any other feed material into the reactor chamber (12) through an inlet (48) located at or near the top (12T) of the reactor (12). The feed material hopper (36) is preferably located at or near the top (12T) of the reactor chamber (12). The feed material hopper (36) is connectable to a movable conveyer (50) located inside the chamber (12) and configured for moving the feed material through the length (L) of the reaction chamber (12) to the bottom (12B) of the reaction chamber (12).

[0040] The reactor chamber (12) may be further equipped with one or more of outlets (38) located at or near the bottom (12B) of the reactor chamber (12), the outlet (38) being configured for removing a solid residue from the reactor chamber (12). The system (10) may further comprise a screw conveyor, or other removal device (39) connectable to the outlet (38) and suitable for removing the residue from the reactor chamber (12) and into a residue storage bin (40). The residue may comprise nickel chloride, cobalt chloride and PGM, silver and gold which after being withdrawn from the outlet (38) can be then further treated in order to produce separated nickel, cobalt, silver, gold and PGMs.

[0041] One or more of the following methods can be used in order to treat the residue after its removal from the reactor chamber (12): 1) washing the residue with water and producing a solution comprising metal chlorides; 2) removing iron from the solution by oxidation or other methods; 3) precipitating metals from the solution as hydroxides, carbonates and / or sulphides; and / or 4) reducing the residue and removing nickel, iron and cobalt as carbonyls.

[0042] The reactor chamber (12) may further comprise one or more inlets (42) located at or near the bottom (12B) of the reactor chamber (12) through which a gas mixture comprising chlorine, nitrogen and ferric chloride may be supplied to the reactor chamber (12) for reactions with metal sulphides. Preferably, the reactor chamber (12) may further comprise one or more additional inlets (54) at or near the bottom of Zone II (16), relativeto the reactor chamber bottom (12B), the additional inlets (54) being suitable for supplying additional chlorine / nitrogen gas mixture into the Zone II (16) of the reactor chamber (12). The system (10) may further comprise one or more ferric chloride condensers (44).

[0043] As is shown in Fig. 1, the chlorination reactor (12) has three reaction zones, Zone I (14) Zone II (16) and Zone III (18). The copper volatilization zone I (14) is located at the bottom (12B) of the reactor (12). A chlorine / nitrogen gas mixture containing small amounts of ferric chloride enters the reactor (12) through inlets (42) and passes through Zone I (14) in order to maximize copper chloride (CuCh) volatilization. The zone I (14) is preferably kept at temperature in the range from about 550 and about 350°C and a pressure ranging from about 3 to about 5 Bar.

[0044] The main reaction zone II (16) is located in the middle of the reactor (12). A chlorine / nitrogen gas mixture enters the reactor (12) through inlets (54) and is passed through the reaction bed to convert metal sulphides to metal chlorides and disulphur dichloride. A gas withdrawal outlet (20) may be located at the top of this zone (16). A gaseous mixture of volatile metal chlorides and disulphur dichloride exits the reactor (12) through the outlet (20) and may be passed through at least 3 or more condensers (24, 26 and 28).

[0045] The chlorination reactor (12) may be heated to 200-400°C using an external heat source to initiate the chlorination reaction. After the chlorination reaction is initiated, the reaction bed may be kept at 350-750°C, and more preferably at 450-650°C. The reaction is exothermic and confined in the middle of the reaction bed. After the reaction reaches the steady state, the feed rate may be preferably kept constant to keep the reaction zone (16) in the middle of the chlorination reactor (12).

[0046] The manganese chloride fraction is collected in the first condenser (24) with traces of nickel and cobalt chlorides. The second condenser (26) is designed to remove the copper chloride (CuCb) mixture from the gas stream. Ferric chloride liquid is condensed in the third condenser (28). A remaining gas mixture which contains disulphur dichloride exits the third condenser (28) through an outlet (52) and this gas mixture may be passed back via an exhaust line portion (23) to the sulphur recovery zone III (18) of to thechlorination reactor (12), where S2CI2 reacts with metal sulphides of the feeding material, producing elemental sulphur. The zone (III) (18) may be preferably kept at a temperature ranging from 120 to 250°C and a pressure ranging from 1 to 3 Bar.

[0047] Elemental sulphur exits the reactor (12) through an outlet (32) and is condensed in a heated sulphur condenser (34). The remaining gases, mainly nitrogen, are removed from the sulphur condenser (34) through an outlet (56) and are treated to remove traces of chlorine species in a gas scrubber (46).

[0048] The first desublimator / condenser (24) temperature is preferably kept at a temperature in the range between 550-450°C and a pressure ranging from 3 to 5 Bar to desublimate mostly volatile mamganese metal chloride complexes and thereby produced crystals may be transferred to a storage tank (25) for future treatment.

[0049] The second desublimator / condenser (26) temperature may be kept at a temperature ranging between 450-350°C and a pressure ranging from 3 to 5 Bar to desublimate mostly volatile Cu metal chloride complexes and thereby produced crystals may be transferred to a storage tank (27) for future treatment.

[0050] The third desublimator / condenser (28) temperature is preferably kept above the boiling point of disulphur dichloride at 138°C and more preferably at a temperature ranging 150-250 °C and a pressure ranging from 3 to 5 Bar. Depending on the system’s pressure, FeCE may be collected as solid or liquid and thereby produced ferric chloride may be transferred to a storage tank (29).

[0051] The remaining gas mixture may be directed to a sulphur recovery part (18) of the reactor chamber (12) where S2CI2 may be reacted with metal sulphides in the feed material and thereby produced elemental sulphur vapours may be directed to a heated condenser (34) to recover sulphur as a liquid. Crude sulphur may be collected in a liquid storage tank for future purification (46).

[0052] In some preferred embodiments, the crude metal chloride mixture from the first (24) and second desublimator / condenser (26) may be purified by sublimation / distillation at 3 and 5 Bar pressure in order to remove ferric chloride as a liquid.The sublimation process may be performed using constant chlorine gas concertation in the gas mixture to prevent formation of FeCh.

[0053] For the MnCh / FeCh mixture, pure manganese dichloride may be collected as a solid and can be directly used as high-purity material for example in a battery-grade manganese (Mn) salt.

[0054] Purified by distillation, solid CuCh may be further purified by a hydrometallurgical method.

[0055] Ferric chloride (FeCh) may be purified by distillation at a pressure between 3 and 5 Bars. Purified FeCh may be used directly or converted to iron oxide or metal iron powders. Recovered chlorine or HC1 gas mixture may be used to recycle chlorine gas back to the reactor (12).

[0056] The chlorination reactor (12) may be equipped with a feed bin (36) with a metering valve that regulates addition of pellets to the reaction zone (16) of the reactor (12). The reaction gas mixture (104) may be introduced through the side ports (42) close to the bottom (12B) of the reactor (12) at a pressure between 1 and 5 Bar. Depending on the composition of the feed material (102), chlorine / nitrogen gas mixture may be passed over heated crude ferric chloride to enrich the feed material with FeCh, which increases the extraction yield of copper.

[0057] In the main reaction zone (16) of the reactor (12), sulphur and iron are converted to volatile chlorides by treatment of a feed material with gaseous chlorine at elevated pressure and extracted. In the process, nickel, cobalt, manganese and copper are converted to metal chlorides. Metal chlorides of Mn, Cu are reacted in situ with ferric chloride vapours to form volatile complexes.

[0058] In the main reaction zone (16), copper sulphide is converted to copper chloride (CuCh) together with iron, nickel and other sulphides. Some of the copper chloride (CuCh) reacts with produced ferric chloride (FeCh) and is volatilized, but some remains as a solid comprising CuCh. Additional ferric chloride may be suppled to Zone (I) (14) to increase volatilization of copper as CuCh.

[0059] These volatile chloride complexes are removed from the reactor (12) as gas together with disulphur dichloride and ferric chloride and are separated from the nonvolatile material containing nickel, cobalt, silver, gold and PGM by distillation and fractional desublimation.

[0060] Manganese ferric chloride is desublimated in the first fraction with traces of nickel and cobalt chlorides. Copper volatile complexes with ferric chloride are desublimated in the second fraction and ferric chloride is in the third fraction. FeCb is removed from the first and second fractions by distillation at elevated pressure, producing a mixture of MnCb and CuCb. After most of the high boiling point components of the exhaust gas mixture are removed, the remaining stream containing S2CI2 may be passed through the sulphur recovery part (18) of the reactor (12), where disulphur dichloride is converted to elemental sulphur by reacting with metal sulphides. Sulphur is separated from the exhaust gas stream in the condenser (34) and recovered.

[0061] In the reactor (12), the remaining nickel, cobalt chlorides, silver, gold and PGM with a small amount of copper (II) chloride, are passed to the copper volatilization section (14) of the reactor (12) and treated with chlorine / nitrogen mixture containing small amounts of gaseous ferric chloride to remove remaining Cu in the form of copper chloride (CuCb) / ferric chloride volatile complexes which are then removed from the reactor (12) together with other volatile chloride complexes.

[0062] The remaining copper-depleted residue which comprises nickel, cobalt, silver, gold and PGM may be removed by using a screw conveyer or other removal means (39) connected to the bottom (12B) of the reactor (12). The residue containing Ni, Co, Fe and other metals, including PGM, may be further treated to recover these metals, preferably by using methods such as water leach and precipitation of a mixture of metal hydroxide with lime or soda, or reduction of chlorinated residue and extraction of Ni and Co by carbonylation processes.

[0063] In the water leach method, the residue may be washed with water, and the resulting solution of metal chlorides may be aired to remove iron as iron oxide. After this,the remaining metals may be precipitated as metal hydroxides or carbonates to produce a mixed hydroxide concentrate.

[0064] Alternately, the residue may be reduced with hydrogen and subjected to a carbonyl process to remove Ni, Fe and Co in the forms of volatile metal carbonyls. After the carbonyl treatment, the residue contains a reduced metal mixture and metal oxides. This residue may be subjected to gravity and magnetic separation to recover silver, gold and PGM and other metals. The PGM-containing fraction may be sold directly to a PGM refinery without future purifications.

[0065] In yet another aspect, this disclosure relates to a method of selective extraction and separation of valuable materials from metal concentrates, including sulphur and iron, one embodiment of which, generally (100) is shown in Fig. 2. The method (100) provides substantial technological advantages in improving utilization of resources. In addition, the method (100) minimizes or even eliminates completely the release of SO2 and produces elemental sulphur instead. The method may recycle energy for extraction and refining of metals. In embodiments of the method, chlorine gas can be produced by electrolysis using solar power. Because the chlorination reaction is exothermic, no additional energy may be needed to extract iron and sulphur and produce manganese, copper and nickel and cobalt metal chlorides fractions.

[0066] With reference to a block diagram of Fig. 2, the method (100) of vapour metallurgical separation of iron, copper, sulphur and manganese from a feed material comprising sulphides of one or more of the following metals: iron, copper, sulphur, manganese, nickel, cobalt and platinum group metals (PGM) comprises:- reacting (104) the feed material comprising metal sulphides (102) with a gas mixture containing chlorine (160), preferably a chlorine / nitrogen gas mixture, and most preferably in a 1:2 ratio, respectively, preferably at a temperature in the range from about 350 to about 750°C and a pressure in the range from about 3 to about 5 Bar (162) and producing a mixture comprising volatile metal chlorides (106) and a solid material comprising copper (III) chloride and nickel, cobalt and platinum group metals (PGM) (108);- passing the solid material (108) to a copper volatilization zone and treating (110) the solid material (108) with a gas mixture containing chlorine, nitrogen and ferric chloride (164), preferably at a temperature ranging from about 550 to about 350 °C (166) and a pressure ranging from about 3 to about 5 Bar and producing a volatile mixture comprising copper (II) chloride (CuCb) and ferric chloride complexes (112) and a solid residue comprising nickel, cobalt and platinum group metals (PGM) (114);- collecting (120) the volatile mixture (106) and collecting (120) the volatile mixture (112), preferably as a combined volatile mixture (122);- sending (124) the volatile mixture (122) into a first condenser / desublimator (126), preferably operating at a pressure ranging from about 3 to about 5 Bar and at a temperature ranging 550-450°C in order to separate (148) from the volatile mixture (122) ferric chloride liquid together with manganese chloride into a first product (150) in the first condenser / desublimator (126), and then optionally, performing a fractional distillation at elevated pressure on the first product (150) to separate manganese chloride from ferric chloride;- passing (128) a volatile mixture which is now depleted of manganese chloride from the first condenser / desublimator (126) to a second condenser / desublimator (130) which preferably operates at a pressure ranging from about 3 to about 5 Bar and at a temperature ranging between 450-320°C and condensing (152) ferric chloride liquid together with copper chloride, gold chloride and silver chloride in a second product (154) in the second condenser / desublimator (130), and then optionally, performing fractional distillation at elevated pressure on the second product (154) to separate copper, silver, and gold concentrate from ferric chloride;- passing (132) the remaining volatile mixture from the second condenser / desublimator (130) to a third condenser / desublimator (134) which preferably operates at a pressure ranging from about 3 to about 5 Bar and ata temperature ranging between 320-120°C and condensing (156) ferric chloride liquid into a third product (158) in the third condenser / desublimator (134), and thereby sequentially depleting the volatile mixture (122) of volatile metal chlorides;- collecting (136) a remaining volatile mixture which comprises S2CI2, nitrogen and small amounts of unreacted chlorine (138) from the third condenser / desublimator (134);- passing (140) the volatile mixture (138) which comprises S2CI2, nitrogen and small amounts of unreacted chlorine but is depleted of ferric chloride (FeCF) through a sulphur recovery zone at a temperature ranging from about 120 to about 250°C and a pressure ranging from about 1 to about 3 Bar to produce (140) crude elemental sulphur (142) which can be then further treated (144) to remove traces of chlorine species in order to produce purified elemental sulphur (146);- collecting the residue (114) and processing (116) the residue (114) in order to produce separated nickel, iron and cobalt and PGMs (118).

[0067] The extraction and separation method (100) according to this disclosure can be performed with the system (10), one embodiment of which is shown in Fig. 1.

[0068] Additionally, present methods may recycle chlorine by converting ferric chloride to iron oxide and chlorine or reducing ferric chloride with hydrogen and converting released HC1 to chlorine. Other methods of chlorine recycling according to this disclosure include converting disulphur dichloride to elemental sulphur and chlorine.

[0069] The methods according to this disclosure may further include a recycling of ferric chloride vapours to chlorine streams in order to maximize extraction of copper, silver, gold and manganese. In addition, the methods may include production of elemental sulphur by reacting disulphur dichloride with metal sulphides in the sulphur recovery part (18) of the reactor (12).

[0070] In a further aspect, present disclosure relates to a method for producing and separating disulphur dichloride (S2CI2) and ferric chloride (FeCF) in a moving bedchlorinator reactor by reacting chlorine with iron sulphide, iron oxide or a mixture of the two and removing volatile compounds in gaseous form from the reactor. In an embodiment, the method may include formation and volatilization of complexes of chlorides of copper, silver, gold and manganese with ferric chloride from a concentrate and removing these complexes as a gas mixture from the reactor. In particularly preferred embodiments, the methods may include separating manganese chloride fraction and copper, silver, gold chlorides and ferric chloride fractions by fractional desublimation. In addition, the method according to this disclosure may produce iron-free metal chloride fractions described above by removing ferric chloride, preferably by low-temperature sublimation at elevated pressure.Example 1

[0071] A flotation concentrate with the composition shown in Table 1 was pelletized using 5% sulphur as a binder and dried. 100g of pellets was placed into a batch chlorination reactor.Table 1 - Feed Material Analysis Before Pelletization

[0072] The chlorination reactor was purged with nitrogen to remove air. The chlorination reactor was heated to 250°C using an internal thermocouple as an indicator. The heat was discontinued, and a chlorine / nitrogen gas mixture with a 1:2 ratio was introduced into the chlorination reactor. The bed temperature rose to above 600°C for 10- 15 minutes and then was stabilized at 550°C. The exhaust gas mixture was passed through four desublimators / condensers with temperatures 550, 450, 320 and 130°C.

[0073] After about 30 minutes, the temperature inside the reaction bed reduced to below 450 °C, and the heaters were turned on to keep the temperature inside the reaction bed at approximately 450°C. The reaction was completed after 1 hour, and the system was cooled down and depressurized. The collected residue and products were analyzed. The residue contained most of the nickel, cobalt and platinum group metals (PGM) as well as14.3% of copper and 4.4 % of iron from the total amount present in the feed material. 86.7% of copper, 95.9% of iron and 98.5% of sulphur were extracted as gases. The first desublimator / condenser contained very little material, and the second desublimator / condenser had a mixture of copper and iron chlorides with correspondent concentrations of 17.3 and 82.7%. About 85% of total copper reported to the second desublimator / condenser. The third desublimator / condenser contained the most iron and a small amount of copper with correspondent concentrations of 99.4 and 0.6%. The crystalline material from the third desublimator / condenser was distilled at 5 Bar and 320°C in a stream of 2% chlorine in nitrogen. The purity of distilled ferric chloride was 99.95%. The residue comprised iron and copper chlorides with close to a 2 to 1 -ratio. This residue was combined with the product from the second desublimator / condenser and distilled at 5 Bar and 320°C in a stream of 2% of chlorine in nitrogen. After most of the ferric chloride was removed, the distillation temperature was increased to 350°C, and the remaining ferric chloride was removed from the copper (II) chloride. The resulting copper (II) chloride had a small amount of gold with a concentration of 12 ppm.

[0074] The residue was washed with warm 40°C water. The filtrate composition was 12.11% nickel, 3.58% of copper, 9.91% iron and 0.26% cobalt. After washing, the residue comprised 24.67% magnesia, 23.99% silica, 7.63% iron, 4.12% alumina, 0.45% copper and 0.75% of sulphur. The filtrate was aerated for 20 minutes, and precipitated iron oxide was filtered out. The remaining metals were precipitated as hydroxides (21.3% Ni, 6.3% Cu, 0.46% Co and 0.04% Fe). The overall yield of nickel was 99%, copper (including both fractions) 99.5% and Co 99.9%.Example 2

[0075] A flotation concentrate with the composition shown in Table 2 was pelletized using 5% sulphur as a binder and dried. 1 Kg of pellets was placed into a batch chlorination reactor.Table 1 Feed Material Analysis Before Pelletization.Analysis % 36.40 1.94 18.36 1.84 16.50 0.10 0.12 0.17 3.69 4.09 0.00 11.40

[0076] The chlorination reactor was purged with nitrogen and pressurized to 5 Bar. The chlorination reactor was heated to 250 °C using an internal thermocouple as an indicator. The heat was discontinued, and a chlorine / nitrogen gas mixture with a 1:2 ratio was introduced into the chlorination reactor. The bed temperature rose to above 600°C for 10-15 minutes and then was stabilized at 550°C. The exhaust gas mixture was passed through four desublimators / condensers with temperatures 550, 450, 320 and 130°C.

[0077] After about 30 minutes, the temperature inside the reaction bed fell below 450 °C, and the heaters were turned on to keep the temperature inside the reaction bed at 450°C. The reaction was completed after 1 hour, and the system was cooled down and depressurized. The residue was washed with water at 40°C and analyzed together with filtrate and products. The residue contained mostly silica and magnesia (Table 3).Table 2 Final Residue Analysis.Approximately 22.5% of the copper from the total amount reported to the filtrate, 2.2% in the washed residue and 66.6% in the second desublimator. Close to 99.1% of nickel reported to the filtrate, 0.5% remained in the washed residue and 0.3% was found in the first desublimator. Distribution was for cobalt was 78.2% in the filtrate, 2.2% in the washed residue, with no cobalt detected in the first desublimator. 84.8% of the manganese was detected in the first desublimator. The total extraction yields were 98.9% for iron, 99.1% for nickel and 97.8 for copper. Based on residue analysis total extraction yield of cobalt was 97.8%, but mass balance wasn’t completed due to small amounts of the metal.Example 3

[0078] The feed material composition shown in Table 4 before palletization.Table 3 Feed Material Analysis Before Pelletization.

[0079] The extraction procedure was the same as in previous examples, but FeCb was recycled through the reactor to increase yield of copper. The residue was washed and analyzed together with filtrate and products. The composition of the washed residue is presented in Table 5.Table 4 Final Residue Analysis.

[0080] About 0.3% of the copper from the total amount was in the filtrate, 0.4 % in the washed residue and 1.3% in the first desublimator and the rest, 98% in the second desublimator. Total extraction yield for copper was 99.6%. The total extraction yields were 99.9% for sulphur, 99.8% for iron, 99.7% for nickel and 99.1 for cobalt.Example 4

[0081] To test behavior of gold, palladium and platinum a concentrate with low concertation of these metals was used (Tables 6).Table 5 Precious Metals distribution.

[0082] The test was performed as in Example 2. The washed residue contained most of the PGM and no PGM were found in the volatile product collected in all de sublimators. The total grade of PGM in the starting was 13.89 ppm, which was upgraded to 25.88 ppm in the final residue.Example 5

[0083] To test behavior of gold and platinum group metals a concentrate with high concertation of these metals was used (Tables 7).Table 6 Precious Metals distribution.

[0084] The test was performed as in Example 3. The washed residue contained most of the PGM and no PGM were found in the volatile product collected in all de sublimators. The total grade of PGM in the starting was 85.2 ppm, which was upgraded to 177.5 ppm in the final residue.

Claims

CLAIMSWe claim:Claim 1. A method of vapour metallurgical separation of iron, copper, sulphur and manganese from a feed material comprising a sulphide of one or more of the following metals: iron, copper, sulphur, manganese, nickel, cobalt and platinum group metals (PGM), the method comprises: a) reacting the feed material comprising metal sulphides with chlorine in the presence of nitrogen at a temperature in the range from 350 to 750°C and a pressure in the range from 3 to 5 Bar in a chlorination zone of a reactor and producing a gaseous mixture comprising disulphur dichloride and one or more of the following volatile metal chlorides: ferric chloride, manganese chloride, cupric chloride and any mixture thereof, and a solid material comprising and nickel and cobalt chlorides, silver, gold and platinum group metals (PGM); b) passing the solid material produced in step “a” to a copper volatilization zone of the reactor and treating the solid material with a gas mixture containing chlorine, nitrogen and ferric chloride at a temperature ranging from 550 to 350 °C and a pressure ranging from 3 to 5 Bar and producing a gaseous mixture comprising volatile disulphur dichloride, ferric chloride and cupric chloride, and a solid residue comprising nickel, cobalt and platinum group metals (PGM); c) passing the gaseous mixture obtained in step a) and the gaseous mixture obtained in step b) through a first condenser / desublimator operating at a pressure ranging between 3 and 5 Bar and at a temperature ranging between 550-450°C, and after that through a second condenser / desublimator operating at a pressure ranging between 3 and 5 Bar and at a temperature ranging between 450-320°C, and after that through a third condenser / desublimator operating at a pressure ranging between 3 and 5 Bar and at a temperature ranging between 320-120°C, and fractionally precipitating ferric chloride liquid from the gaseous mixture togetherwith manganese chloride into a first product in the first condenser / desublimator, ferric chloride liquid from the gaseous mixture together with copper chloride into a second product in the second condenser / desublimator and ferric chloride liquid into a third product in the third condenser / desublimator, thereby depleting the gaseous mixture of volatile metal chlorides and obtaining a remaining volatile mixture which comprises S2CI2, nitrogen and small amounts of unreacted chlorine; d) passing the volatile mixture obtained in step c) which comprises S2CI2, nitrogen and small amounts of unreacted chlorine but is depleted of ferric chloride (FeCF) through a sulphur recovery zone of the reactor at a temperature ranging from 120 to 250°C and a pressure ranging from 1 to 3 bar to produce elemental sulphur; e) performing fractional distillation at elevated pressure on the first product obtained in the first condenser / desublimator and recovering manganese chloride separated from ferric chloride; f) performing fractional distillation at elevated pressure on the second product obtained in the second condenser / desublimator and separating ferric chloride and produce copper; g) performing distillation at elevated pressure on the third product obtained in the third condenser / desublimator and producing high-purity ferric chloride and further oxidizing purified FeCF to metal iron or iron oxide; and h) collecting the residue obtained in step b), the residue comprising nickel II chloride, cobalt II chlorides and platinum group metals (PGM).Claim 2. The method of claim 1, wherein the feed material is one or more of the following: ore, flotation concentrate or metallurgical product comprising nickel and copper between 1 and 20 wt%, and a combined content of iron and sulphur between 20- 90 wt%.Claim 3. The method of any one of claims 1-2 wherein the method further comprises: further oxidizing one or more metal chlorides in steps e), f) and / or g), andrecycling chlorine gas from hydrochloric acid (HC1) which was produced during reduction of metal chlorides.Claim 4. The method of any one of claims 1-2 wherein the method further comprises: recycling chlorine gas produced during oxidation of ferric chloride in steps e), f) and / or g).Claim 5. The method of any one of claims 1-4, wherein steps a), b) and d) are performed in a chlorination reactor operating at 3 different reaction zones: zone I, zone II and zone III and wherein, zone II is used for performing step a), zone I is used for performing step b) and zone III is used for performing step d).Claim 6. A system for extracting of one or more of iron, sulphur, copper, manganese, nickel, cobalt, silver, gold and / or PGM from a material containing sulphides of one or more of these metals and separating nickel and cobalt from sulphur, iron, copper, manganese, the system comprising:- a chlorination reactor (11) having three different reaction zones: copper volatilization I (14), chlorination reaction zone II (16), and sulphur recovery zone III (18), wherein the chlorination reactor is a chamber (12) having a volume enclosed by a wall and having a length (L) from a bottom (12B) to a top (12T) of the chamber (12), and wherein the three reaction zones (14, 16 and 18) are located along the length (L) of the reactor (11), one after another, the copper volatilization zone I (14) being the closest to the bottom (12B) of the reactor (12), followed by the chlorination reaction zone II (16) in the middle and the sulphur recovery zone III (18) being located after zone II (16), the sulphur recovery III (18) being the closest to the top (12T) of the reactor chamber (12);- three or more condensers / desublimators (24, 26 and 28);- one or more sulphur condensers (34); and- and a gas scrubber (46).Claim 7. The system of claim 6, wherein the system further comprises two or more liquid storage tanks for collecting and storing liquid ferric chloride / manganese chloride (25), one or more liquid storage tanks for ferric chloride / copper mixture (27) and one or more liquid storage tanks for liquid ferric chloride (29).Claim 8. The system of claim 6 or 7, wherein the chlorination reactor (12) contains one or more inlets (48) for receiving the feed material and wherein the inlets (48) are located at or near the top (12T) of the reactor (12) and wherein the system (10) further includes a conveyor (50) capable of moving the feed material from the top (12T) to the bottom (12B) of the reactor (12).Claim 9. The system of any one of claims 6-8, wherein the reactor (12) includes an exhaust line (22) which can be connected to an outlet gas nozzle (20) of the reactor (12), the exhaust line (22) connecting to the reactor (12) to three or more condensers / desublimators (24, 26 and 28), the exhaust line (22) being used for removing a gaseous mixture that comprises ferric chloride (FeCh), manganese chloride (MnCh), copper chloride (CuCh), disulphur dichloride (S2CI2) and nitrogen with trace amounts of unreacted chlorine from the Zone II (16) of the reactor (12) to three or more condensers / desublimators (24, 26 and 28).Claim 10. The system (10) of any one of claims 6-9, wherein the system further includes an exhaust line (23) for connecting an outlet (52) from the condensers / desublimators (24, 26 and 28) to the gas inlet (30) below zone III (18) of the reactor (12), the exhaust line (23) being suitable for passing a ferric chloride depleted gaseous mixture from the condensers / desublimators (24, 26 and 28) to the sulphur recovery zone (18) of the reactor (12).Claim 11. The system of any one of claims 6-10, wherein the chlorination reactor (12) further comprises one or more of the following elements: at least three inlets, a first inlet (42) being located at or near the bottom (12B) of the chlorination reactor (12), the first inlet (42) being suitable for supplyinga gas mixture comprising chlorine (CI2), nitrogen (N2) and ferric chloride (FeCh) to the chlorination reactor (12), and a second inlet (54) being located at or near the bottom of zone II (16) for supplying additional chlorine / nitrogen gas mixture and a third inlet (30) being located at or near the bottom of zone III (18) for introducing a gaseous mixture containing disulphur dichloride to sulphur recovery zone (18);- at least two outlet gas nozzles, a first outlet gas nozzle (20) being located in or after the chlorination main reaction zone II (16), but before the sulphur recovery zone III (18), the first outlet gas nozzle (20) being connectable to the exhaust line (22), the first outlet gas nozzle (20) being used for removing a gaseous mixture that comprises manganese chloride (MnCb), copper chloride (CuCb), disulphur dichloride (S2CI2) and nitrogen from the chlorination main reaction Zone II (16) of the chlorination reactor (12) to three or more desublimators / condensers (24, 26 and 28); and a second outlet gas nozzle (32) being located at or near the top of the chlorination reactor (12) for removing sulphur vapours, the second outlet gas nozzle (32) being connectable to a sulphur condenser (34);- a feed material hopper (36) for feeding an ore to the chlorination reactor (12); and / or- a screw conveyor (39) for removing residue from the chlorination reactor (12).Claim 12. The system of any one of claims 6-11, wherein three or more desublimators / condensers (24, 26 and 28) include a heat exchange unit and a bottom storage space (25, 27 and 29) for storage of ferric chloride and / or of a mixture of metal chlorides in liquid or crystal form.Claim 13. The system (10) of any one of claims 6-12, wherein the sulphur condenser (34) includes a storage tank for storing liquid sulphur.Claim 14. The system (10) of any one of claims 6-13, wherein the reactor (12) includes means for withdrawing the residue containing nickel (II) chloride, cobalt (II) chloride and silver, gold and PGM from the bottom (12B) of the reactor (12).Claim 15. The method of any one of claims 1-5, wherein the residue is further treated by one of there, following methods:- washing the residue with water and producing a solution comprising metal chlorides;- removing iron from the solution by oxidation;- precipitating metals as hydroxides, carbonates and / or sulphates; and / or- reducing the residue and removing nickel, iron and cobalt as carbonyls.Claim 16. A use of the system according to any one of claims 6-14, for performing the following method:- continuously feeding solid pellets to the chlorination reactor (12) from the feed bin (36) at the top (12T) of the reactor (12);- moving feed pellets downward through three zones of the reactor: sulphur recovery (18), chlorination main reaction (16) and copper volatilization (14);- introducing a gas mixture of Q2 / N2 through the inlets (54) and chlorinating feed material pellets in the chlorination main conversion zone (16);- introducing a gas mixture of Ch / FeCh through the inlets (42) from the bottom (12B) of the reactor (12) and producing volatile complexes of FeCB with CuCh;- withdrawing a gaseous mixture containing iron, sulphur, copper and manganese chlorides from a gas outlet (20) located above the chlorination main conversion zone (16);- passing the gaseous mixture through three or more desublimators / condensers (24, 26 and 28) and liquifying or precipitating solid ferric chloride / metal chlorides mixtures;- condensing a FeCh / MnCh mixture in a desublimator / condenser (24) and discharging the FeCh / MnCh mixture into a storage tank (25);- condensing FeCh / CuCh mixture (containing silver and gold chlorides) in a desublimator / condenser (26) and discharging FeCh / CuCh mixture into a storage tank (27);- condensing FeCh in a desublimator / condenser (28) and discharging FeCh into a storage tank (29);- collecting a remaining gaseous mixture which comprises disulphur dichloride from the outlet (52) of the third desublimator / condenser (28) and returning the remaining gaseous mixture which comprises disulphur dichloride back to the reactor (12) through the inlet (30) into the sulphur recovery zone (18) of the reactor (12);- passing the remaining gaseous mixture which comprises disulphur dichloride through a heated feed material in the sulphur recovery zone (18) of the reactor (12) and removing elemental sulphur to the sulphur condenser (34);- evaporating the FeCh / MnCh mixture from the storage tank (25) through a purification column to produce pure MnCh and FeCh;- evaporating the FeCh / CuCh mixture which also contains silver and gold chlorides from the storage tank (27) through a purification column to produce CuCh containing silver and gold chlorides and separately FeCh;- evaporating crude FeCh from the storage tank (29) through a purification column to produce pure FeCh; and- removing the residue containing nickel and cobalt chlorides and PGM from the outlet (38) of the reactor (12) and treating the residue by one or more of the following methods:- washing the residue with water and producing a solution comprising metal chlorides;- removing iron from the solution by oxidation or other methods;- precipitating metals as hydroxides, carbonates and / or sulphides; and / or- reducing the residue and removing nickel, iron and cobalt as carbonyls.

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