FI119774B - Process for the treatment of cobalt-containing copper concentrate - Google Patents

Description

METHOD FOR TREATMENT OF COBOLTIC COPPER CONCENTRATION

FIELD OF THE INVENTION

The invention relates to a process for the recovery of cobalt and copper in a pyrometallurgical treatment process of cobalt-containing copper concentrate. In the suspension melting furnace and / or the converter, the raw copper is formed and fed to the anode furnace, and the resulting slag is fed with the reducing agent into the slag purification furnace. The slag purification furnace yields raw copper which is also fed to the anode furnace to produce anode copper. The slag from the slag cleaning furnace is led to a cobalt recovery furnace, where sulfide-containing material is introduced in addition to the reducing agent. The cobalt is recovered from the stone in the cobalt recovery furnace.

BACKGROUND OF THE INVENTION

When pyrometallurgically producing copper from a copper sulphide concentrate, the concentrate is introduced into a melting furnace, which is preferably a suspension melting furnace, such as a flame smelting furnace. At the melting stage, the furnace comprises at least two layers of melt: · · · ·: the upper is a slag layer and below it a stone and / or: T: 20 crude copper layer. If the concentrate is directly smelted into crude copper (V * copper), it is conveyed directly to the anode furnace without conversion, where it is desulphurized and any impurities oxidized. The residual oxygen ·· * * ·· is removed with a suitable reducing agent and the pure copper is poured into If stone is formed in the smelting furnace, it is processed either in a flame converter or other suitable converter, such as a Pierce-Smith converter from which the raw copper is fed to the anode furnace.

• · • · • ♦ ·

In addition to pure copper concentrates, concentrates containing precious metals other than copper will also be processed. CA-A-1085620: ***: 30 discloses a method of recovering other precious metals of copper concentrate from the slag of a suspension smelting furnace. The slag is fed to at least one electric furnace, whereby the zinc and lead are mainly recovered from the fly dust of the electric furnace 2. If the concentrate contains significant amounts of nickel and cobalt, the slag treatment is carried out in two electric furnaces. The first furnace then produces a metal containing mainly copper and slag which is fed to the second electric furnace. The product of the second furnace is mainly an alloy containing 5 cobalt and / or nickel and discarded slag.

The method of CA 0885620 is otherwise workable, but the disadvantage of the process is that the base metal formed during the cobalt recovery step is quite high, of the order of 1350 ° C. Since the melting point of the slag is always higher, the temperature of the second electric furnace must be kept very high. Furthermore, the further treatment of the alloy produced in the second electric furnace is very difficult, since the metal phase is a material that is very difficult to grind.

15 PURPOSE OF THE INVENTION

The object of the present invention is to eliminate the difficulties encountered in the prior art in the pyrogenetic treatment of cobalt-containing copper sulphide concentrate and in particular in the recovery of cobalt. The invention relates to a process for treating cobalt-containing copper sulphide concentrate pyrometallurgical: T: 20, wherein the slag formed in the slurry melting furnace and the converter is first treated in a slag purification furnace and the slag produced therein is led to a cobalt recovery furnace. The conditions for the cobalt recovery furnace j * ·· are adjusted to operate at the lower temperatures of the prior art technology and thus save energy. At the same time, a cobalt-containing stone is formed which does not cause further processing.

The process according to the invention also provides for the subsequent treatment of the · · · crude copper produced at different stages in a uniform manner and not as separate processing steps as in the description of the prior art.

• · · · · · · · · ·

. · **. 30 SUMMARY OF THE INVENTION

The invention relates to a process for the recovery of cobalt and copper in a process. The concentrate, the oxygen-containing gas and the slag-forming agent are fed into a slurry melting furnace, where the raw materials are reacted to form copper crude and / or copper rock. Copper stone is processed in the converter into raw copper. The crude copper is fed to the anode furnace, and the cobalt-containing slag formed in the slag melting furnace and converter is fed to the slag purification furnace. In the slag purification furnace, the copper is formed with the aid of a reducing agent and the slag is fed to the cobalt recovery furnace. A reducing agent and a sulphide-containing material are also introduced into the cobalt recovery furnace and the slag is processed there into cobalt-containing copper shale and waste slag.

According to the method, the crude copper produced in the slag purification furnace is fed to the anode furnace for cleaning together with the crude copper formed in the slurry melting furnace and / or the converter.

15

Preferably, both the slag purification furnace and the cobalt recovery furnace are electric furnaces.

·: ··: According to an embodiment of the invention, the reducing agent for the slag purification furnace and the: T: 20 cobalt recovery furnace is coke. In another embodiment of the invention,] *, a fine reducing agent, such as carbon dust, is used as the reducing agent, which is injected into a furnace.

• t • · • · · · · ·

According to the method, the sulphide-containing material fed to the cobalt recovery furnace is in the form of a dew, preferably copper sulphide concentrate, or pyrite in the form of lump. According to an alternative to the process, the sulphide-containing material is a rock of a suspension melting furnace.

• · · · · · · · · ·

The cobalt-containing copper stone 30 formed in the cobalt recovery furnace is preferably cooled by granulation.

• · · • • • 4 ·

According to one embodiment of the invention, the converter is a flame converter. According to another embodiment of the invention, the converter is a Pierce-Smith type converter.

An embodiment of the invention is a process for the recovery of cobalt and copper in a pyrometallurgical treatment process of a cobalt-containing copper sulphide concentrate. The concentrate, the oxygen-containing gas, and the slag-forming agent are fed into a slurry melting furnace, where the raw materials are reacted to form a crude copper. The crude copper is fed to the anode furnace, and the slag formed in the suspension melting furnace containing cobalt is fed to the slag purification furnace. In the slag purification furnace, by means of a reducing agent, crude copper is fed to the anode furnace and slag is fed to the cobalt recovery furnace. A reducing agent and a sulphide-containing material are also introduced into the cobalt recovery furnace and the slag is processed there into cobalt-containing copper rock and waste slag.

Another embodiment of the invention is a process for recovering cobalt and copper in a pyrometalluric *: ** treatment process of a cobalt-containing copper sulfide concentrate. The concentrate, the oxygen-containing gas, and the slag v: 20 substance are fed into a slurry melting furnace, where the raw materials are reacted into copper rock. Copper stone is processed into ··· raw copper. The crude copper is fed to the anode furnace, and the cobalt-containing slag formed in the slag melting furnace and converter is fed into the slag purification furnace. The slag purification furnace uses a reducing agent to form crude copper, which is fed to the anode furnace, and slag that is • ♦: ”fed to a cobalt recovery furnace. Reducing agent and sulphide-containing material are also fed into the cobalt recovery furnace and are then processed into cobalt-containing copper rock and waste slag.

The essential characteristics of the invention will be apparent from the appended claims.

♦ ·

»· I

• · * • · 5

LIST OF FIGURES

Figure 1 is a schematic diagram of a preferred embodiment of the invention, Figure 2 is a schematic diagram of another method of the invention, Figure 3 is a schematic diagram of a third method of the invention, Figure 4 is impact on refining energy.

DETAILED DESCRIPTION OF THE INVENTION

The method according to the invention is described below with reference to the principle diagram according to Fig. 15. The copper sulphide concentrate 1 is fed with an oxygen-containing gas such as oxygen enriched air or oxygen 2 and a slag-forming agent 3 into a suspension melting furnace such as a flame smelting furnace 4.

Reactions between the concentrate and the oxygen-containing gas take place in the reaction pit 5 of the flame ·: ··: melting furnace. If required, additional fuel can also be fed into the reaction pit: T: 20. The reaction products melt and settle on the set ·: · set section 6 of the oven.

The reactions leading to the formation of crude copper, or blister, continue to occur in the melt bath of the lower furnace (settler). Similarly, slag reactions 25 also occur in the lower furnace. According to the method, the conditions of the flame smelting furnace are adjusted so that the copper-containing phase formed is of crude copper, thus avoiding a separate conversion step. The resulting crude copper descends to the bottom of the bottom furnace and slag over it. The oxidation state of the reaction shaft defines the sulfur content of the raw copper formed and the copper content of the 30 slags. The optimum ratio of copper to slag • · · copper content is adjusted by adjusting the ratio of concentrate to oxygen fed to the furnace (Nm3 (See Concentrate).

• · 6

Almost all of the cobalt in the concentrate ends up in the slag. The gases from the flame smelting furnace are led to a waste heat boiler for heat recovery and dust separation. The final dust removal takes place in an electric filter. The airborne dust is recycled back to furnace 5 (not shown in detail).

The raw copper 7 formed in the suspension melting furnace is further fed to the anode furnace 8, which in the example shown in the figure is three pieces, but the amount may vary as needed. The anode furnace copper 9 from the anode furnace is pure copper (99.9%) which is cast on the anode casting table 10 into anodes which are further processed into electrolytically pure cathode copper (99.999%).

The slag 11 formed in the suspension melting furnace is preferably led along the chutes 15 to the slag purification furnace 12, which is an electric furnace. The furnace is also fed with a reducing agent such as metallurgical coke 13, and the slag is reduced to crude copper 14 and slag phase 15, the copper content of which is adjusted to be in the order of 2.5 to 4%. In this case, significant amounts of iron from the slag have not yet been reduced to raw copper. Formed, so-called. the other 20 copper copper 14 is also fed to the anode furnace 8. Thus, the slag purification copper: in the furnace is not treated separately but simultaneously with the crude copper in the slurry furnace. The advantage of co-treatment is that there is no need for separate oxidation to remove sulfur and iron and to slag iron:.

Preferably, the cobalt-containing slag 15 formed in the slag cleaning furnace 12 is preferably led moltenly into a cobalt recovery furnace 16, which is also an electric furnace. The slag is reduced in the furnace by means of a reducing agent such as coke 17 which is fed therein. It can also be used as a reducing agent. 30 finely divided reducing agents, e.g., carbon dust, which are added to the furnace by injection.

• · · either alone or mixed with a sulfurizer. A sulphide-containing material 18 is also introduced into the furnace, which can be added, for example, with or without the reducing agent. The melting point of the cobalt-containing copper-iron rock produced by the sulphide-containing material is 50-60 ° C lower than without the introduction of the sulfur-containing material. Preferred sulphide-containing materials include, for example, copper sulphide concentrate, lump pyrite, and molten slurry furnace stone, if available or in powder form. After the addition of the sulphide-containing material, the melting point of the cobalt-containing copper rock is of the order of 1300 ° C and the resulting slag is somewhat higher. Because the supply of sulphide-containing material lowers the melting temperature of the stone, it also ensures sufficient fluidity of the rock phase. The cobalt content of the stone is proportional to the amount of iron in the stone and thus the ratio of the iron content of the stone to the copper and cobalt content of the formed waste slag is controlled by the ratio of reducing agent and slag fed to the furnace. The batch dwell time is another parameter used to control the reduction result in a cobalt treatment furnace. The copper-cobalt-iron stone 19 discharged from the furnace 15 is led to the recovery of the cobalt. The resulting slag 20 is a waste slag.

Sulfurization in the cobalt recovery furnace ensures that when the stone is rapidly cooled, preferably by granulation, the sulfur and metal phases do not separate in the stone structure, but are distributed evenly within the stone structure. The result is a brittle, easy to · · · · · · · · · · · · · · · · kiv kiv kiv kiv kivaasiasiasiasiaaaaaasiasiaaaaaasiasiasiaaaaasiasiasiaaaaasiasiasiaaaasiasiasiaaaasiasiasiasiasi, jonka jonka jonka jonka jonka jonka jonka jonka jonka jonka jonka,,, jonka, jonka, jonka jonka jonka jonka jonka jonka jonka jonka jonka.

The amount of sulfur in the stone depends on the process temperature, which is determined by the melting temperature of the · · · * ·· higher temperature melting phase, i.e., the slag. The melting point of the completely sulfur-free metal system is about 1380 ° C. As shown in Figure 4, with a sulfur content of about 8%, i.e., · · · metal / sulfur ratio of 11.5, the melting point of the stone is slightly below 1300 ° C, ···. 30, which can be considered as the normal operating temperature for copper production.

• · • · ·: By increasing the sulfur content of the stone, lowering the metal / sulfur ratio,

• S

further decreasing the melting temperature of the stone. However, the temperature of the stone 8 must be in a suitable proportion to the slag temperature, in practice 20-50 ° C lower than the slag temperature. If the operating temperature is significantly higher than the melting point of the stone, the stone will be reactive and fluid (low viscosity) due to overheating. This can cause problems when 5 stones are lowered out of the oven. It also accelerates the wear of furnace masonry and drainage materials.

The Cu-Fe-Co stone formed in the cobalt recovery furnace is granulated and finely ground for hydrometallurgical treatment of the stone. The sulfur content of the stone ίο has an effect on the energy consumed by grinding the granulated stone. The graph of Figure 5, where the solid line represents the measured results and the dashed line extrapolated, shows that as the sulfur content decreases, energy consumption increases. The dependence is assumed to be linear in the range of 1 to 13% sulfur, but it is likely that energy consumption 15 will increase more strongly at low sulfur concentrations. At a sulfur content of> 0%, the material is not milled at all. According to the dependence shown in the graph, energy consumption increases by about 25% as the S content of the stone decreases from 8 to 1%.

The principle diagram of Figure 2 illustrates another embodiment of the invention in which the slag melting furnace 4 is not formed of raw copper, but the furnace conditions are controlled in a known manner to form copper stone in the furnace. , which is further processed into the reaction shaft 23 of the flame converter 22. The flame converter is the same type of furnace solution 25 as the flame smelting furnace, but the input is stone which is converted into crude copper under furnace conditions. In addition to copper shale, the flame converter is typically supplied with a slag-forming substance and: an oxygen-containing gas. The · · · raw copper 7 formed in the bottom furnace 24 of the flame converter is fed to the anode furnace 8 and the resulting slag 25. The remainder of the process operates as shown in Figure 1, that is, the raw copper produced in the slag cleaning furnace is fed to · · 9 the anode furnace 8 and the slag to the cobalt recovery furnace 16, where copper-cobalt-iron rock 19 and waste slag 20 are formed.

The application of Figure 3 is otherwise in accordance with Figure 2, but incorporates conventional Pierce-Smith type converters 26 as the converter.

EXAMPLES Example 1:

The process described above was applied to the processing of cobalt-containing Cu concentrate by melting the concentrate directly into a blister copper in a Direct Blister Flash Smelting Furnace (DBF) by slagging the concentrate iron and cobalt almost completely. The precious metals of the slag from the flame smelting furnace were recovered in two stages by reduction in coke in electric furnaces. The slag was passed from a flame smelting furnace to a Slag Cleaning Furnace (SCF) 15, where the degree of reduction and residence time were adjusted to obtain more than 99% copper-containing metal with a Fe content of 0.03% and a Co content of 0.18%. At this point, efforts were made to avoid the reduction of iron and cobalt to Cu-methyl. The metal, together with the blister copper from the flame smelting furnace, was subjected to • · 20 further treatment in the anode furnace. More detailed results are shown in Table 1 below.

··· ····: * ··; The slag purification furnace slag with a Cu content of 3% was charged to a subsequent furnace, the Cobalt Recovery Furnace (CRF), which was subjected to a higher reduction (coke addition, longer residence time) to recover copper and slag contained in the slag as closely as possible to the Cu-Fe-Co stone formed in the furnace. The metal content of the slag from this '·' / · step is so low that; the slag goes to waste.

··· • · · · · · · ···. ···. 30 Because of the extremely low sulfur content of the slag entering the cobalt recovery furnace CRF, the DBF concentrate alloy was fed there to sulfurize the resulting alloy. The concentrate mixture was fed to · ·· 10 slag melt near the rock boundary by injection with carrier gas. The purpose of sulfurization was to lower the melting temperatures of the metal melt to an appropriate level relative to the melting heat of the slag.

Example 2 (Comparative Example):

Otherwise, the method described was applied in the same manner as in Example 1, but no Titching was carried out in the cobalt recovery furnace, so that the resulting alloy had an S content of 1%. The relationship between the sulfur content of the rock and the melting heat is shown in the diagram in Figure 5. In order to ensure the fluidity of the stone, the operating temperature had to be raised by 60 ° C. This translates into an almost 9% increase in electricity consumption in the slag reduction furnace. More detailed results are shown in Table 2.

From the foregoing examples, it is apparent that the process of the present invention has significant improvements over the prior art process in terms of controlling operating temperatures and product quality in the cobalt recovery step. This results in significant energy savings in the slag treatment process itself and in the further processing of Cu-Fe-Co slate.

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Claims (14)

A process for recovering copper and cobalt in a pyrometallurgical treatment process of a cobalt-containing copper sulfide concentrate, wherein the concentrate (1) is fed to a slurry furnace (4) with an oxygen-containing gas (2) and a slag-forming agent (3) (21); the copper stone is introduced into the converter (22, 26) and the raw copper formed in the slurry melting furnace and / or the converter is fed to the anode furnace (8); the cobalt-containing slag (11, 25) generated in the slurry melting furnace and the converter is fed with the reducing agent (13) into the slag purification furnace (12), characterized in that crude copper (14) is formed in the slag purification furnace (12) and (16) fed with a reducing agent (17) and a sulfide-containing material (18) to produce a cobalt-containing copper rock (19) and a waste slag (20). The process according to claim 1, characterized in that: • · · · 20 the raw copper (14) • · · formed in the slag cleaning furnace (12) is fed to the anode furnace (8) for cleaning together. • · • · ·: · formed in a suspension melting furnace and / or converter. with crude copper (7). • · · · · · · · · · A method according to claim 1, characterized in that the cobalt-containing copper stone (19) is cooled by granulation. • · Ml • · • · · · · ♦. ·· ♦. A process according to claim 1, characterized in that the sulfide-containing material to be introduced into the cobalt recovery furnace (16) is a sulfide concentrate. * · # • · ··· • · · Method according to Claim 4, characterized in that the sulfide-containing material (18) to be fed to the cobalt recovery furnace (16) is a copper sulfide concentrate. Method according to Claim 1, characterized in that the sulfide-containing material (18) introduced into the cobalt recovery furnace (16) is a piece of sacred material. A method according to claim 1, characterized in that the sulfide-containing material (18) introduced into the cobalt recovery furnace (16) is a slurry furnace stone. A method according to claim 1, characterized in that the reducing agent (13,17) of the slag purification furnace (12) and the cobalt recovery furnace (16) is coke. A process according to claim 1, characterized in that the reducing agent (13,17) of the slag cleaning furnace (12) and the cobalt recovery furnace (16) is a finely divided reductant, such as carbon dust, which is injected into the furnace. • · · • · · · · ·. ···. A method according to claim 1, characterized in that the slag purification furnace (12) and the cobalt recovery furnace (16) are: ···. electric arc furnaces. • · · 25 A method according to claim 1, characterized in that the converter is a flame converter (22). • · · · · · · · · · · Method according to claim 1, characterized in that the converter 30 is a Pierce-Smith type converter (26). • • • • • • Iff A process for recovering copper and cobalt in a pyrometallurgical treatment process of a cobalt-containing copper sulphide concentrate, wherein the concentrate (1) is fed to a slurry furnace (4) with an oxygen-containing gas (2) and a slag-forming agent (3) (8), and as a cobalt-containing slag (11) fed with a reducing agent (13) to the slag cleaning furnace (12), characterized in that the slag cleaning furnace (12) is formed with raw copper (14) and fed to the anode furnace (8). ), which is fed to a cobalt recovery furnace (16) fed with a reducing agent (17) and a sulfide-containing material (18) to produce a cobalt-containing copper rock (19) and a waste slag (20). A process for recovering copper and cobalt in a pyrometallurgical treatment process of a cobalt-containing copper sulphide concentrate, wherein the concentrate (1) is fed to a suspension melting furnace (4) with an oxygen-containing gas (2) and a slag-forming agent (3). with reacting in a slag smelting furnace • · 20 into copper rock (21); the copper stone is fed to the converter (22.26) and the raw copper (7) formed in the converter is fed to the anode furnace [··· m (8); the slag (11.25) containing cobalt from the slag melting furnace and converter is fed with the reducing agent (13) • ♦ ·! ···. slag purification furnace (12), characterized in that the slag purification furnace (12) forms a crude copper (14) which is fed to the anode furnace (8) and a slag (15) which is fed to the cobalt • ·. ···. a recovery furnace (16) fed with a reducing agent (17) and a sulfide-containing material (18) to produce a cobalt-containing copper rock (19) and a waste slag (20). • «30 ·· · • · • • • • • • • • • • • • • • • if i?