FI63441C - FOERFARANDE FOER FRAMSTAELLNING AV RAOKOPPAR FRAON KOPPARMALM ELLER -KONCENTRAT INNEHAOLLANDE SKADLIGA ELLER EKONOMISKT SINIFIKANTA MAENGDER ANDRA ICKE-JAERNMETALLER - Google Patents

Description

RS **] ΓΒΐ rtll NOTICE OF PUBLICATION, \ A A Λ IBJ (“) UTLAGGNINOSSKKIFT 004 41 fwlS C (45) Patent Issued 10 06 1933

Patent patent '(51) K ».Ht.3 / tata3 C 22 B 15/00 SUOM I — FI N LAN D pi) ^ uih ^ u.-760U55 (22) Halnmhplly · —AMMinIniatfag 23.02.76' '(23 ) Allcupaiv · —Glkfgtotttfag 23.02.76 (41) TuNuc JulkMcsI — ilMt offwidlg pj, Oo 77 1ft nhlitiilliilllttii 1. . 0 (44) NlhttvUulpanon J · kuLlulkalwn pvm.—, o n5

Fstent. och rVfirtMYtyrdMn '' AmWun utte | d och utJ.iki1ft «n puMIcorwl 2o.02.o3 (32) (33) (31) fyyfotr« uoHmui — ftgird priortttt (71) Outokumpu Oy, Outokumpu, FI; Töölönkatu 1 ;, 00100 Helsinki 10,

Finland-Finland (FI) (72) Olavi August Aaltonen, Pori, Jyrki Tapani Juusela, Harjavalta,

Heikki Pellervo Saari, Pori, Tapio Kalevi Tuominen, Pori,

Suomi-Finland (FI) (7M Berggren Oy Ab (5 * 0 'Method for the production of crude copper from copper ores or concentrates containing harmful or economically significant amounts of other non-ferrous metals - Förfarande för framställning av räkoppar frän kopparmalm eller -concentrat inneh & lland signifikanta mängder andra icke-järnmetaller

When pyrometallurgically producing crude copper from copper concentrates containing significant amounts of other metals, the anode copper generated at the end of the process must meet certain quality requirements. If the amount of impurities increases, it causes difficulties in the electrolytic cleaning of copper, whereby the quality of the cathode copper produced also suffers. In the case of economically significant quantities, these so-called side metals, it is by no means indifferent in what form and composition they are separated from copper. From the point of view of their post-treatment, it is advantageous if they are in a concentrated form and do not contain a lot of copper, since the separate removal of copper entails costs.

With the scarcity of raw materials, it is now increasingly necessary to explore the possibility of using non-convection concentrates also for the production of copper and, in general, for the most economical recovery of all the metals they contain.

When enrichment techniques, such as magnetic separation, flotation, etc., do not achieve a sufficiently selective result, various hydro- and pyrometallurgical methods have been studied. to process mixed concentrates.

According to our information, there is currently no so-called for impure sulfide copper concentrates, there is no operating economically advantageous hydro- or pyrometallurgical treatment process on an industrial scale.

A process based on the flame smelting method is already known (Finnish patent 22,694). In it, the concentrate is melted with fuel and preheated air (max. 550 ° C) in a flame melting furnace at a temperature of 1350-1550 ° C, the so-called in a neutral (fuel / air ratio) atmosphere, resulting in a low copper rock 40-50%

Cu, about H to Cu and Zn and 0.2-0.3% Pb to slag and to aerial dust, where most of the lead and zinc is. This air dust also contains 4.8% Cu, 20-25% Zn, 8-10% Pb and 7.8% S and 17% Pe. The amount of fly dust, calculated from lead, is about 640 kg / t of concentrate, so the enrichment in dust has not been particularly high. Besides, about 13% of the sulfur in air dust is mainly in the form of sulphates. When the shallow rock also contains about 22-23% sulfur and slag in equilibrium with it (1-2% S), there is thus sulfur in all three solid and melt phases and gases. The obtained air dust is by no means a preferred raw material, e.g. for a zinc plant, due to its low zinc content, high copper, sulfur and iron content.

Another attempt to treat mixed concentrates is a process in which the copper content in the concentrate is limited to 0-6% Cu, but the lead and zinc contents are high, so it can be considered mainly as a lead or zinc concentrate. How these different metals are separated is not known. Apparently, the process aims to evaporate lead and zinc and thus separate the copper, but the further processing of the relatively poor and dirty copper rock remains a problem.

The present invention for the treatment of mixed concentrates is based on Outokumpu Oy's flame smelting method, (Finnish patent 22,694). The flame smelting process has been found to be an energy-efficient and environmentally superior copper smelting process starting from sulphide concentrates (see, for example, Kellogg H.H., "Prospects for the Pyrometallurgy of Copper" Paper presented in 3 63441

Santiago, Chile 1973, and Carl-August Maelzer: "Fortschritte in der Pyrometallurgie", Neue HUtte. 20 Jg., Heft 3, March 1975) ·

Slag from flame smelting usually contains so many valuable metals that its post-treatment is worthwhile. It can be treated in known ways by slowly cooling, crushing, grinding and frothing and feeding the obtained flotation concentrate back to the furnace. Another treatment is to reduce it in an electric furnace to obtain either a stone or an alloy and to remove slag and air dust. The result depends on how the flame oven is run.

If, as mentioned above, an attempt is made only to carry out the smelting and to evaporate the lead and zinc in the concentrate into air dusts, an energy-efficient solution is reached. Smelting and evaporation have to be done almost exclusively using fuel at a relatively high temperature, so that the amount of gas per tonne of concentrate is high, as well as, of course, the so-called mechanical amount of dust, and, as already stated above, the dust obtained is not particularly advantageous for post-treatment. The resulting shallow rock requires a large conversion work and two dilute SOg gas streams are easily obtained.

The present invention for the treatment of mixed concentrates, the principle is that in a flame melting furnace the energy contained in the concentrate is used as efficiently as possible. The concentrate is oxidized to a high rock containing more than 70% Cu or directly to crude copper, depending on the amount of iron in the concentrate. In this case, especially by using process air preheating and / or oxygen enrichment, the flame melting furnace generally operates autogenously without additional fuel. All or part of the air dust is recycled. The slag, which contains 3-15% Cu, depending on the degree of oxidation, is fed directly hot to an electric furnace, where it is reduced with coke in a known manner. Whether more or less copper is present in the slag is not relevant to the energy requirement, as the reduction of Cu20 to metallic copper does not require much energy. In order to evaporate the zinc, the magnetite must be reduced and also part of the iron. This reduction and evaporation of zinc are the most energy-intensive reactions. A Cu-Pb-Fe alloy and air dust is obtained which is almost pure zinc and lead oxide containing less than 1% Cu. This is a first-class raw material for the production of zinc and lead. When the sulfur content of the slag is <. 1% S has been found to enter 4 63441 waste slag containing less precious metals than normal slag containing> 1% S. As the sulfur content decreases, the activities of the precious metals (Cu, Ni, Co, Pb, Zn, etc.) in the slag increase, resulting in a decrease in the concentrations. On the other hand, e.g. when copper settles from the slag, it happens faster, because in the case containing less sulfur, the difference in density is greater between the slag and the rock / metal. The raw copper or white stone from the flame furnace is cleaned together with the alloy of the electric furnace in the converter and anode furnace in the normal way. The slag and dust of these are fed back to the electric furnace. From the overall process (concentrate to anode copper) very high recoveries of more valuable metals are still obtained in an easy-to-handle form, 98-99% Cu, 88-90% Zn, 89-98% Pb. Other metals contained in the concentrate, such as Sn, Sb and Bi, are also enriched in electric furnace dust and are recovered during zinc and lead processing. If the concentrate contains economically significant amounts of cobalt and nickel, they are processed into an alloy during processing in an electric slag cleaning furnace in accordance with the present invention, whereupon treatment to recover cobalt and nickel is recommended. The precious metals Ag and Au, of course, go to the crude copper and are recovered from the electrolysis as an anode slurry.

The invention is described in more detail below with reference to the drawings, in which Figures 1-4 show flow diagrams of preferred embodiments of the invention, and examples obtained by performing flame melting furnace and electric furnace studies at about 1 t concentrate / h and conversion and anode furnace treatments at about 50 t copper / input.

Various concentrates have been used in the studies, which differ in terms of their coalition. Tables I, II, III and IV show, in different cases, the quantities of substances and the concentrations of the main components at different stages of the process, from 1000 kg of concentrate to the flame melting furnace (LSU). The presentation includes only converter and electric furnace (SU) treatments. Anode furnace treatment does not require any special treatment in all cases. The corresponding block diagrams I, II, III and IV showing the different stages of the process show the distributions of the main components in the different stages.

Example I

Here, a copper concentrate containing about 8% Zn and n.

4% Pb, Table I. It can be seen that LSU gave a rock containing 71.6% Cu 5 63441 with Zn 1.3% and Pb 1.8% 3 and slag with Cu = 2.8% and 0.23% S. When the stone was converted together with the stone obtained from the electric furnace, crude copper containing 0.2% Pb and 98.8% Cu was obtained, so that it was sufficiently pure for anode furnace treatment and further electrolytic purification. The slag from the converter, together with the LSU slag, was treated in an electric furnace to obtain a discardable slag containing 0.4% Cu, 0.1% Pb and 1.6% Zn. The dust from the electric furnace contained about 60% Zn and about 21% Pb and only 0.1% Cu, so it was suitable as a raw material for a zinc plant. The dust obtained from the converter, which contained about 79% Pb and about 10 f Zn and practically no copper at all, was a suitable raw material for the lead plant.

Figure 1 shows the distribution of the different components at different stages of processing. It is noted that 98.8% of the copper was obtained as crude copper and contained only 1.5% of lead. Correspondingly, the furnace dust contained 88.1% zinc and 65.4% lead and only 0.1% copper, and the converter dust contained 32.3% lead and 1.8% zinc and no copper at all. The rejectable electric furnace slag contained 1.2% copper, 1.8% lead and 10.1% zinc. Thus, the intakes of the major metals were

Cu 98.8% into a blister

Pb 97.7% Su and converter dust

Zn 89,9% - "-

In addition to copper, the intakes of lead and zinc were also very good and were almost pure metal oxides.

Example II

Here, a copper concentrate containing 5.8% Zn and 0.68% Pb was processed. The amounts and concentrations of substances are shown in Table II and the distributions of substances in Figure 2. They show that although the initial concentrations were lower than in the previous example, the metal yields were still good.

Cu 98.8% as crude copper

Pb 83.8% for Su and converter dusts

Zn 88,0% - "-

Example III

Here, a copper concentrate containing 1% Ni and 0.54%

C/o. The processing now included not only flame smelting and conversion, but also two separate electric furnace treatments (SY I and SU II). The amounts of substances 6 63441 and the concentrations are shown in Table III and the distributions of substances in Figure 3. The converter produces blister copper which is well suited for anode furnace treatment and electric furnace I an alloy which can be well treated in normal electrolysis as its own circuit. Electric furnace II produces an alloy suitable as a raw material for a cobalt plant. Waste slag losses are

Cu 0.6 / 6

Co 30%

Thus, although the initial contents of cobalt and nickel are relatively low, the process is obtained by applying not only first-class crude copper in good yield directly, but also remarkably low yields of cobalt and nickel to alloys that can be processed separately to recover these metals and improve overall copper yield.

Example IV

Here, a low-iron concentrate with a high copper content containing 2.4% cobalt was processed. The process was now preferably applied in such a way that crude copper was made directly in the flame smelting furnace by slagging iron and cobalt almost completely. The treatment of the slag took place in two stages, in the SU I and SU II electric furnaces, in the first stage a metal containing about 98% copper with 0.6% Co and 1.5% Fe was obtained. Further treatment of the slag from SU II again yielded a Co-Fe-Cu alloy and pure waste slag containing 0.2%

Cu and 0.3% Co. As such, the crude copper is suitable for anode furnace treatment and the copper metal obtained from SU I as its own circuit for electrolysis. The alloy obtained from SU II is a suitable raw material for the production of cobalt. The quantities and concentrations of substances and the distributions at the various stages of processing are shown in Table IV and Figure 4.

As can be seen from the above examples, according to the present invention, crude copper and anode copper can preferably be produced by the so-called impure copper ores or concentrates by using them in their smelting with high oxidation, either the so-called white metal or directly into crude copper, maximizing the thermal energy contained in the ores or concentrates in slurry smelting, and always combining conversion and anode treatments and slag cleaning, as appropriate, according to the principles of the examples, resulting in good recoveries of so-called for metals present as impurities.

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Claims (4)

63441 11 A process for the production of crude copper from harmful and / or economically significant amounts of other non-ferrous metals such as zinc and lead flame smelting stone and / or metal and slag using electric furnace reduction for slag purification and a converter for crude anode , characterized in that the slag containing less than 1% of sulfur is reduced in an electric furnace by means of coke at a temperature of 1300 to 1500 ° C to a copper content of less than 0.5% and mainly to a copper-lead-ferrous metal alloy. Rocks, crude metals and / or crude metal alloys containing 70-98% Cu are treated in the converter as crude copper, the slag containing less than 1% S in this treatment is passed together with the slag from the flame smelting furnace to a fly ash containing zinc and zinc and other non-ferrous metals, but of low copper, is fed as a raw material. metällinvalmistusprosessiin. A method according to claim 1, characterized in that the low-zinc, lead and other non-ferrous metal but low copper airborne dust generated in the electric furnace reduction of the flame melting furnace and converter slag is fed as a raw material. metal fabrication process. Process according to Claim 1, characterized in that when the concentrate and / or the ore contains economically significant amounts of cobalt and / or nickel, the alloy obtained from the slag cleaning electric furnace, which contains the majority of the concentrate from cobalt and nickel, is treated separately to recover these metals. Process according to Claim 1, characterized in that, where the concentrate and / or ore contains economically significant amounts of cobalt and / or nickel, the slag smelting of the flame melting furnace is carried out in two stages, first producing mainly copper-containing metal and finally less copper-containing and / or a nickel-containing metal alloy. 12 Patentkrav 63441