Method of continuously processing nickel-containing copper sulphide materials

Abstract

A method of continuously processing nickel-containing copper sulphide materials into blister copper, waste slag, and copper-nickel alloy includes oxidizing smelting along with SiO2 and CaO-containing fluxes and coal in a conversion furnace for conversion to produce blister copper, gases with concentration of SO.sub.2, and slag with an SiO2:CaO concentration ratio of 0.4:1 to 3:1, in which the sum of the iron, nickel, and cobalt is not more than 30 wt. %, at a specific oxygen consumption in the range of 150-240 Nm.sup.3 per ton of dry sulphide material, and depleting the slag in a separate reduction furnace, using a mixture of an oxygen-containing gas and a hydrocarbon fuel at an oxygen consumption coefficient (α) in a range of 0.5 to 0.9, while supplying coal in an amount of up to 15% of weight of the slag produced by the oxidizing smelting, to produce a waste slag and a copper-nickel alloy.

Claims

1. A method of continuously processing nickel-containing copper sulphide materials, the method comprising: oxidizing smelting of a dry nickel-containing copper sulphide material along with SiO.sub.2 and CaO-containing fluxes and coal at a specific oxygen consumption in a range of 150-240 Nm.sup.3 per ton of the dry nickel-containing copper sulphide material in a conversion furnace for conversion to produce blister copper, gases with a concentration of SO.sub.2, and a first slag with a sum of iron, nickel, and cobalt that is not more than 30 wt. %, wherein the first slag contains SiO.sub.2:CaO in a concentration ratio of 0.4:1 to 3:1; depleting the first slag by reduction in a separate reduction furnace, using a mixture of an oxygen-containing gas and a hydrocarbon fuel at an oxygen consumption coefficient (α) in a range from 0.5 to 0.9, while supplying coal in an amount of up to 15% of weight of the first slag produced by the oxidizing smelting, wherein $\alpha =\frac{V_{O_2}.Math.\%O_2+V_{\mathrm{air}}.Math.0.21}{Q_{\mathrm{CxHy}}.Math.K_{\mathrm{CxHy}}},$  wherein V.sub.O.sub.2 is an oxygen consumption in the reduction furnace, Nm.sup.3/hr., % O.sub.2 is a volume fraction of oxygen in the oxygen-containing gas, V.sub.air is an airflow to a recovery zone of the reduction furnace, Nm.sup.3/hr., Q.sub.CxHy is a consumption of the hydrocarbon fuel, Nm.sup.3/hr., and K.sub.CxHy is a coefficient characterizing complete combustion of the hydrocarbon fuel; and scavenging molten slag within 17-35 minutes from start of the depleting the first slag, in order to produce a second slag and a copper-nickel alloy.

2. The method of claim 1, wherein the second slag comprises less than or equal to 3.06 wt. % of nickel and less than or equal to 6.85 wt. % of copper from twenty-first minute of scavenging.

Description

BRIEF DESCRIPTION OF THE DRAWINGS

(1) The preferred embodiments of the present invention, as well as other objects, features, and advantages of this invention, will be apparent from the accompanying drawings wherein:

(2) FIG. 1 is a side perspective view of two single-zone Vanyukov furnaces that are used in the present invention;

(3) FIG. 2 is a graph illustrating the changes in composition of the slag over time with respect to the copper and nickel contents during the reduction stage;

(4) FIGS. 3A and 3B are graphs illustrating the changes in contents of copper and nickel in the slag with respect to increase in a content of nickel in the copper-nickel alloy; and

(5) FIG. 4 is a graph illustrating changes in contents of nickel and copper in the copper-nickel metal alloy versus the time of scavenging the molten slag using a reduction gas mixture.

DETAILED DESCRIPTION

(6) The claimed method of continuously processing nickel-containing copper sulphide materials in a continuous processing complex comprising two separate furnaces, namely two Vanuykov furnaces, is illustrated in FIG. 1. Nickel-containing copper sulphide materials are added along with SiO.sub.2 and CaO-containing fluxes to a Vanuykov conversion furnace 1 of the continuous processing complex. An oxygen-air mixture and a gaseous fuel are added to Vanuykov furnace 1 through furnace tuyeres 2. Blister copper formed during the smelting process in a first furnace of the continuous processing complex, namely Vanuykov conversion furnace 1, is continuously released into a mixer 3, and a slag with a high content of copper, nickel, and iron passes to a second furnace of the continuous processing complex, namely to Vanuykov reduction furnace 4, where the slag is depleted by reduction gas-air mixture along with coal to produce a waste slag and a copper-nickel alloy. The reduction gas-air mixture is formed as a result of natural gas combustion in an oxygen-air mixture under oxygen shortage conditions. A temperature of the oxidation and reduction processes is maintained at a level of 1350° C.

(7) Smelting products of the conversion furnace 1 (blister copper) and of the reduction furnace 4 (waste slag and copper-nickel alloy) are assumed to be released continuously. To release the smelting products, siphon-type devices (not shown in the drawings), located at the opposite ends of furnaces 1 and 4, are provided. Continuity of the proposed process in a form of a continuous processing complex comprising two Vanuykov furnaces 1 and 4 paves the way for maintaining constant levels of the slag and the blister copper in the Vanuykov conversion furnace 1, and waste slag and the copper-nickel alloy in the Vanuykov reduction furnace 4, which is an important advantage of this process. Blister copper is continuously released through a siphon-type device into the mixer 3 designed for it, and is then sent to anodic refining to produce copper anodes. A specific of the slag composition resulting from the oxidizing stage of the new method is that the slag contains copper and nickel in a ratio of 4:1-5:1, which is favorable for producing valuable copper-nickel alloy, for instance a ‘Melchior’ alloy. Copper-nickel alloy with some iron, which is a basis for producing commercial products, is produced as a result of deep reduction of the aforementioned slag to spoil standards. This copper-nickel alloy can be converted in pyrometallurgical nickel production, or directed to a stage of oxidizing refining in order to remove the iron and produce commercial products, the composition of which is determined for Russia by the State standard (‘melchior’ alloy, ‘neusilber’, etc.).

(8) An important feature of the developed processing method is the fact that, in a case of converting materials containing precious, platinum group metals in the Vanuykov conversion furnace 1, these metals are almost completely recovered to blister copper and are not transferred to the slag, which is then fed to the Vanuykov reduction furnace 4 for depletion by reduction. This provides a production of copper-nickel alloy that is almost free from precious, platinum group metals in the Vanuykov reduction furnace 4.

(9) It is obvious that it is more preferable to supply the copper-nickel alloy of the Vanuykov reduction furnace 4 to a customer as a commercial product after refining and casting operations.

(10) Slag produced in the Vanuykov reduction furnace 4 is the waste slag. The chemical composition allows the waste slag to be used in the building industry or for the stowing of mines.

(11) All sulphur contained in nickel-containing copper sulphide materials passes to a gaseous phase of the Vanuykov conversion furnace 1.

(12) Since the oxidation stage of the continuous conversion process, conducted in the Vanuykov conversion furnace with production of blister copper has passed extensive studies and currently is sufficiently investigated (Tsymbulov L. B., Knyazev M. V., Tsemekhman L, Sh. A method for processing copper sulphide materials to blister copper //The patent of the Russian Federation Russian Patent No. 2359046 of Sep. 1, 2008. Pigarev S. P. Structure and features of slag melts of the continuously converting nickel-containing copper sulphide materials. Abstract of PhD dissertation St-Petersburg. 2013. 21 p.), the proposed invention is based on data of experimental studies of the reduction stage of the new processing method, coupled with a search for conditions resulting in the production of a waste slag and a copper-nickel alloy, which is a basis for producing commercial products, for instance ‘Melchior’ alloy, which is widely used nowadays in industries as the alloy with high anticorrosion properties, and also for producing household products and jewelry.

(13) The methodology of the experimental studies was as follows. Into a laboratory furnace there were placed an alundum reactor having inside an alundum crucible, which contained an initial slag, namely an oxidative stage slag, with a following composition, wt. %: Cu—17.9; Ni—5.6; Fe—23.1; Co—0.135; SiO.sub.2—27.5; CaO—11.9; Al.sub.2O.sub.3—3.1; and MgO—0.79. The furnace was then run, changing voltage of an inductor, and was heated to an operating temperature of 1350° C.

(14) After the smelting of the slag, a melt was scavenged via a beryllium oxide tube with a reduction gas mixture of the following composition, vol %: CO—44; CO.sub.2—38; H.sub.2—18. Partial pressure of the oxygen in the reduction gas mixture corresponded to partial pressure of the oxygen in a mixture produced during natural gas combustion at the ‘alpha’ value (α)=0.6.

(15) In laboratory experiments, duration of melt scavenging using the gas mixture was varied from 0 to 50 mins. A flow rate of the gas mixture was 0.8 l/min After completion of scavenging, the melt was allowed to settle for 15 minutes, and the furnace was then turned off. Thereafter, the crucible with the melt was removed out of the furnace and cooled, and the slag was separated from the metal alloy.

(16) After appropriate sample preparation, the slag and the metal alloy were analyzed by methods of atomic absorption spectrometry and inductively coupled plasma atomic emission spectrometry.

(17) The chemical compositions of the metal alloy and the slag, produced as a result of the conducted experimental studies, are presented hereinbelow in TABLE 1.

(18) At first, we consider changes in the slag composition according to copper and nickel content, when changing a time of scavenging the molten slag using the reduction gas mixture. This dependency is presented in FIG. 2.

(19) As illustrated in FIG. 2, with the increase of time of scavenging the molten slag using the reduction gas mixture, there is a sharp decrease in copper content in the molten slag, and starting from the 17.sup.th minute of scavenging, there is also a substantial decrease in nickel content in the molten slag in view of the decreasing copper content. After the 35.sup.th minute of scavenging the molten slag, the decrease in copper and nickel concentrations in the slag becomes extremely insignificant.

(20) As illustrated in FIGS. 3A and 3B, a decrease of copper content (FIG. 3A) and nickel content (FIG. 3B) in the slag is accompanied by an increase of a nickel content in the metal alloy, reaching a maximum nickel content at a level of 21.5% at copper and nickel concentrations in the slag at levels of 0.8% and 0.4%, respectively. Further decreases in the content of copper and nickel in molten slag to standard values is characterized by a decrease of nickel content in metal alloy, being associated with a start of active iron recovery and transfer of iron to the metal alloy. This will be described hereinbelow in greater detail.

(21) As the proposed new method of continuously processing nickel-containing copper sulphide materials assumes simultaneous production of, on the one hand, an alloy with a certain ratio of copper and nickel and a certain standard content of iron, and on the other hand, a waste slag, it is necessary to choose optimum technological parameters in realizing the implementation of the proposed new method.

(22) Accordingly, the dynamics of the changes in the compositions of the slag and the copper-nickel alloy should be considered during scavenging using a reduction gas mixture (FIG. 4).

(23) As illustrated in FIG. 4, the changes in the contents of nickel and iron in the metal alloy depend on the time of scavenging the molten slag using the reduction gas mixture. FIG. 4 also illustrates the changes in the contents of copper and nickel in the slag depending on time of scavenging the molten slag using the reduction gas mixture.

(24) It is important to emphasize in FIG. 4, a correlation between the contents of copper and nickel in waste slag and the contents of nickel and iron in the metal alloy, produced as a result of the reduction. There is a significant decrease in the concentrations of both copper and nickel in the slag during active nickel reduction from 5.sup.th to 30.sup.th minutes of scavenging, but residual contents of copper and nickel are still rather high (Cu—0.8%; Ni—0.4%), and the resulting slag cannot be considered a waste slag.

(25) Only when active iron reduction starts, does it become possible to decrease the concentrations of copper and nickel in the slag to spoil standards.

(26) Accordingly, on the one hand, in order to obtain a standard iron content in the copper-nickel alloy, particularly, in ‘Melchior’ (Fe≤0.5%), it is necessary to strive for a minimal degree of iron reduction from the slag during the depletion process.

(27) On the other hand, deep reduction to the contents of copper and nickel in the slag is only possible when producing a copper-nickel alloy with an iron concentration of 5% or more, requiring additional expenditures at an additional stage of refining to produce trademark copper-nickel alloys. In this regard, it is recommended to conduct the depletion process until the iron concentration in the copper-nickel alloy reaches ˜6%. In this case, a waste slag with the following composition will be obtained, wt. %: Cu—0.45; Ni—0.17; Fe—30.3; SiO.sub.2—37.5; CaO—16.2; Al.sub.2O.sub.3—5; MgO—1. A composition of copper-nickel alloy will be as follows, wt. %: Cu—73.2; Ni—20.5; Fe—6.1.

(28) In order to produce commercial products from this alloy, for instance in a form of ‘Melchior’ alloy, it is necessary to carry out the aforementioned stage of refining, with which iron content in the copper-nickel alloy can be decreased to standard values. The ratio of Cu:Ni in the resulting refined metal alloy will be in range of 4:1-5:1, matching a composition of commercial products. The slag, formed during the oxidative refining process, the base of which are iron oxides, is supplied to a continuous conversion complex, namely to an oxidative stage of the process at the Vanuykov conversion furnace 1. It is possible to produce other types of products, the composition of which is determined for conditions of Russia by the State standard. A specific feature of the developed method, as indicated above, is fact that precious, platinum group metals, presented in the raw material, are almost completely transferred into blister copper at the converting stage, and production of new types of products will not cause additional losses of these metals.

(29) The developed method has a significant advantage—the possibility of producing new commercial products according to a shorter technological scheme, which in general substantially reduces a metallurgical plant's expenses for the production of the commercial products.

(30) TABLE-US-00001 TABLE 1 No Duration of Content in alloy, wt % Content in slag, wt % exp. scavenging, min Cu Ni Fe Ni Cu Fe.sub.general SiO.sub.2 CaO Al.sub.2O.sub.3 MgO 1 5 98.97 0.89 0.01 5.11 17.26 23.0 27.1 11.7 3.6 0.82 2 10 98.90 1.05 0.01 5.09 12.12 24.8 28.9 12.5 3.9 0.88 3 15 95.62 4.24 0.02 4.40 10.60 25.4 29.6 12.8 4.0 0.90 4 21 92.85 7.00 0.03 3.06 6.85 26.9 31.3 13.5 4.2 0.95 5 25 90.87 8.99 0.04 1.49 5.19 27.5 32.1 13.8 4.3 0.97 6 27 87.70 12.18 0.05 1.32 4.29 28.4 33.1 14.3 4.4 1.01 7 29 80.46 17.79 0.49 0.40 1.54 30.5 38.7 15.4 4.7 1.09 8 30 76.72 21.50 1.72 0.42 0.82 30.9 36.4 15.8 4.9 1.11 9 31 75.68 21.49 2.73 0.29 0.67 30.8 36.9 15.9 4.9 1.12 10 32 74.93 21.37 3.68 0.23 0.58 30.7 37.2 16.0 5.1 1.13 11 35 74.06 21.20 4.72 0.19 0.52 30.5 37.4 16.1 4.9 1.14 12 37 73.30 21.02 5.66 0.16 0.48 30.3 37.6 16.2 5.3 1.14 13 40 72.82 20.26 6.27 0.15 0.25 30.2 37.7 16.3 5.4 1.21 14 45 70.03 20.24 9.61 0.11 0.43 29.4 38.4 16.5 5.3 1.18 15 50 67.95 19.67 12.37 0.09 0.40 28.72 39.1 16.3 5.6 1.23