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State and directions for development of non-ferrous ores enrichment and metallurgy in Poland Professor Zbigniew Śmieszek

1. Introduction Industrial deposits of copper ore in the copper area of Legnicko-Głogowski Okręg Mie dziowy (LGOM) are estimated at about 1,5 billion Mg. The average copper content in the ore is 1,0 – 2.5% and the basic copper bearing minerals are sulphides: chal cocite – Cu2S, bornite – Cu5FeS4 and chalcopyrite – CuFeS2. The main copper bearing mi nerals also carry accompanying elements (isomorphous admixtures). Some accompany ing metals occur also in a native form or in a form of minerals. Average contents of the basic accompanying metals are as follows: Pb ~ 0,15%, Zn ~ 0,05%, Ag ~ 45ppm, Ni ~ 45 ppm, Co ~ 50 ppm. Copper ore is composed of three main lithologic forms: sandstone ore, carbonate ore and shale ore. Diversification of the individual types of ores, with referen ce to the mineralogy-petrography and to physico-chemical properties, determines the character of the possibility for their enrichment and necessity for diversif ication of the applied technologies of enrichment. Currently used technologies a re based on flotation process and their main objective is maximum recovery of co pper and silver. Copper concentrates which are produced at the ore beneficiation plants contain 1 7-30% of Cu and 400-1000 ppm of Ag. The concentrates are processed in 3 metallurgical plants, where the following te chnologies are used: flash smelting in a direct process into blister copper, imperial smelting of concentrates. The final products of the copper smelters are: electrolytic copper, silver, prec ious metals, lead bullion, technical selenium, nickel sulphate and zinc dusts of high metallic content. The total capacity of copper smelters is currently about 500 thousand Mg of elec trolytic copper and about 1200 Mg of silver per annum. Zinc-lead resources are large, but geological and mining conditions and current low zinc price give grounds for assumption that economical exploitation in the p eriod of 10-15 years should be about 2,5 million Mg of ore per annum. The current exploitation of Zn-Pb ore in Poland is higher and amounts to about 4 ,5 million Mg of ore per annum, but in the following several years, in the resul t of depleting of resources, closing down of one of the currently operating mine s is expected. Average zinc content in the ore is at the level of ~ 4%, while lead is at the le vel of ~ 1,8%. The technologies for Zn-Pb ores treatment cover processes of gravity separation and flotation. In the process of Zn-Pb ores enrichment the following concentrates are produced: zinc blende of Zn content at 55 ÷ 64% sedimentary galena of Pb content at about 79% flotation galena of Pb content at 64 – 72% collective concentrate of Zn content at about 50% and Pb at 10%. Zinc concentrates are processed in zinc electrolysis plant at ZGH Bolesław, and co llective zinc and lead concentrates as well as part of zinc blende and of galena in shaft furnace by Imperial Smelting method. The total capacity of metallurgical plants is about160 thousand Mg of zinc per y ear and about 70 thousand Mg of lead per year, where about 45% comes from proces sing of battery scrap. For battery scrap processing, a separation technology by Engitec Impianti method is used, followed by smelting of the metallic fractions in rotary furnaces and refining of lead bullion for production of commercial grades of refined lead and for manufacture of battery alloys. 2. Current technology and directions for development in non-ferrous ores en

richment 2.1. Copper ores enrichment

Copper ore of LGOM becomes enriched at three ore beneficiation plants i.e. ZWR L ubin, ZWR Polkowice and ZWR Rudna. The ore delivered to each of these plants com es from separate exploitation areas and varies in lithologic composition, minera lisation, grain distribution of copper bearing minerals and in different charact eristics of enrichment. At ZWR Lubin and ZWR Rudna sandstone-carbonate ore is processed, while at ZWR Po lkowice it is dolomite-shale ore (table 1). Table 1 Average lithologic composition of copper ore Beneficiation plant sandstone ZWR Lubin 70 ZWR Polkowice 15 ZWR Rudna 60 Lithologic composition of ore in % carbonate shales 20 10 70 15 32 8

The sandstone-carbonate ore undergoes separation into sandstone and carbonate fr actions in the preliminary stage of enrichment process by selective breaking up and screening, as well as by washing up (soft grinding) and classification in th e first stage of the grinding. The separated fractions of the ore are subjected to selective processing in autonomous sections of enrichment, which comprise gri nding, flotation and a system for cleaning of concentrates. Flowsheet for dolomite-shale ore enrichment is basically similar to the technolo gy for enrichment of the separated carbonate fraction. Figure 1 presents a simplified flowsheet of copper ore enrichment.

Some characteristic data of beneficiation plants and reached average results of copper ore enrichment are listed in the Table 2. Table 2. Characteristic data and results of copper ore enrichment (average) Parameter Unit Plant ZWR Lubin ZWR Polkowice ZWR Rudna Processing capacity thous. Mg/day 22,5 24,0 43,5 Metals content in the feed: Cu % 1,28 2,0 2,2 Ag ppm 70 37 49 Metals content in the concentrate Cu % 19 27,2 29 Ag ppm 950 480 620 Metals yields into the concentrates Cu % 88,5 87,8 90 Ag % 85,0 84,5 87 2.2. Directions for development of copper ores enrichment

The basic criterion for modernisation and optimisation of a technology f or copper ore enrichment is maximisation of copper and silver recovery, while at the same time maintaining high quality of concentrates and simultaneous reducti on of processing costs.

Improvement in copper ore enrichment will cover in the first place: • Reconstruction of systems for preparation of ore for flotation, comprising break ing up, grinding and classification for increase in selectivity of ores separati on in relation to lithologic composition and reduction in energy and material co nsumption of the system, especially during breaking up and grinding operations. • Introduction of crude ore washing up and separation of 60-70% of fraction with g rain size below 0.3mm. • Application of flash flotation in autonomous sections of mills output enrichment , with separation of 25-30% of copper minerals in a form of a final concentrate, with a use of flotation machines of special construction. • Application of new types of flotation machines, adjusted to the capacity of indi vidual production cycles, of cell size up to 60m3, of low operation costs, espec ially in the scope of energy consumption and costs of repairs. (Institute of Non-ferrous Metals has developed many types of flotation machines of various capacity which confirmed their usefulness in industrial practice in v arious stages of copper ore flotation, as well as in coal flotation and in moder nised Zn-Pb ores processing flowsheet). • Modernisation of flotation flowsheets mainly for increase in metals yields by, a mong others, introduction of reagents which can facilitate selection of flotatio n and increase concentrates quality. • Modernisation of internal transport systems for reaching technological effect of ore bedding and for more precise control of initial material properties.

• Automation in monitoring of enrichment processes and their control by: changing into system of automatic retrieval of data on process conditions, development an d implementation of indices for process evaluation, which will take into conside ration elements of economical evaluation, introduction of optimising and stabili sing control into individual blocks of the technological system. A perspective direction for development of copper ores enrichment seems to be th e separate processing of recycled products in chemical-flotation operations. It could free usable minerals bound in carbonate rocks and, through flotation, tran sfer them into a form of usable concentrates. Economical use of the flotation tailings is a very important problem. One of the potential methods for their utilisation is to convert them into a product which can be used for filling in mining industry. 2.3. Technology and directions for development of zinc-lead ores enrichment.

Technology of Zn-Pb ores enrichment (Fig. 2 and 3) covers the following basic op erations: breaking up and screening the ore, initial enrichment of the ores of grain size 15-60 mm in heavy suspension liquid s and separation in that operation ~ 35% of dolomite with low content of metals (Zn ~ 0,7%, Pb ~ 0,05%). The material is fully utilised as an aggregate in road constructions, railroads and in other engineering works, flotation of galena and blende as well as collective flotation, at the processing plant ZG Trzebionka magnesium removal from zinc blende is perf ormed, by adding sulphuric acid to the blende, and flotation for gypsum removal , which lead to increase of zinc content in the blende concentrate from ~ 56% to ~ 64%. Additionally, because of the higher Pb content in the ore at the ZG Trzebionka, fraction smaller than 2 mm after breaking up and initial screening becomes enric hed on a concentrating table, for separation of high quality galena concentrate.

Improvement and modernisation of technology for ores enrichment is expected only in the Mechanical Processing Plant „Pomorzany”, which belongs to the ZGH Bolesław, be cause there are some perspectives for that plant to operate for at least some do zen years. The directions for technology development are mainly related to reduction in cos ts of processing and to improvement in concentrate quality. In that area the fol lowing improvements are expected in the first place: optimisation of flowsheet for galena flotation with application of modern flotat ion machines developed in IMN, magnesium removal from zinc blende and reduction of MgO content in the concentra te from about 1,8% to about 0,1% and increase of Zn content in that concentrate from ~ 55 to ~ 60%. 3. State of technology and directions for development in non-ferrous metals metallurgy 3.1. Copper metallurgy.

Polish copper concentrates (Table 3) when compared with widely processed in the world chalcopyrite concentrates have different chemical and mineralogical compos ition, and different physico-chemical properties. The copper occurs mainly in a form of chalcocite (Cu2S). The concentrates have significantly lower sulphur and iron contents, high level of organic parts content and a large volume of silty minerals, which amounts to 24-30% wt. The basic metallic impurities in the coppe r concentrates are lead, of content usually below 2,5%, and arsenic, of content up to 0,3%. Table 3 Typical chemical composition of copper concentrates Beneficiation plant Content of components in % wt. Cu Ag Al2O3 K „Lubin” 19 0,095 6,4 1,3 „Polkowice” 27 0,048 5,5 1,6 „Rudna” 29 0,062 5,5 1,4 Pb Na 1,9 0,18 1,2 0,25 2,1 0,25 As Zn 0,27 0,30 0,20 0,35 0,10 0,60 Fe S Corg SiO2 CaO MgO



















Copper concentrates are processed by two smelting methods: (Figures 4 and 5) smelting of briquetted concentrates in shaft furnaces with receiving of copper m atte, direct smelting of concentrates into blister copper in a flash smelting furnace.

Converting of copper matte is performed in Hoboken type converters. Slag from th e flash smelting furnace, which contains ~ 14% of Cu, is subjected to a process of copper removal in an electric furnace into Cu-Pb-Fe alloy which contains 70-8 0% of Cu. That alloy is then processed in converters into converter copper, whic h is directed for fire refining in anode furnaces. Fire and electrolytic refining processes are typical, commonly used in copper me tallurgy throughout the world. Anode slime from the electrorefining process, whi ch contains 35-45% of Ag, is processed into refined silver and precious metals. The produced electrolytic copper – in a form of cathodes – meets the requirements of London Exchange for the „Grade A”, while the refined silver is registered by the LB MA as „Good delivery”. Table 4 Some characteristic parameters of metallurgical processes in copper concentrates processing Parameter Unit Flash-smelting process Shaft process Efficiency of concentrate smelting in 1 furnace unit Mg of conc/hour 94 64 Cu yield into electrolytic copper % 98,1 96,0 Ag yield into anode slime % 96,5 94,8 Cu content in waste slag % 0,57 0,46 Content of impurities in blister and converter copper Pb % 0,3 0,24 As % 0,12 0,16 Content of impurities in anodes Pb % 0,20 0,16 As % 0,09 0,12 Dusts emission kg/Mg of electr. Cu 0,16 0,35 Emission of sulphur compounds converted into SO2 kg/Mg of electr. Cu 3,4 14,6 Index of manhours necessary for production of 1 Mg of copper lectr. Cu 10 21

manhour./Mg of e

Electrolytic copper produced from anodes from flash-smelting and shaft processes is of high quality and is usually classified as „Grade A”. Technological parameters of both processes are advantageous and in most cases co mparable. Also the basic indices for impurities emission both for flash smelting process and for the shaft process, after providing the installation with a syst em for sulphur removal from off-gases, can be treated as most advantageous and c omparable with those reached by the leading copper manufacturers in the world. However, the costs of copper production in the shaft process are over 100 USD hi gher when compared to the costs in the flash smelting process. There are several basic reasons for such a situation: significantly larger amount of aggregates in the shaft process and consequently higher labour consumption, lower degree of mechanisation and automation of the shaft process, laborious and expensive methods of charge preparation for the melting process, necessity for sulphur removal from gases arising in process of concentrates melt ing after their burning in power boilers (SO2 content in gases after burning is about 0,5% vol.). Sulphur removal from gases is a costly operation and significa

ntly increases the costs of metallurgical processing of copper concentrates. 3.2. Directions for development in copper metallurgy

The basic direction for development in copper metallurgy is replacement of the s haft process with a new flash smelting furnace, which will make possible to repl ace 6 currently operating melting units with a one melting unit. In the result further reductions in pollutants emission into atmosphere would fo llow, at least at the same degree as is reached by currently used flash smelting process. The directions for development in copper metallurgy cover also the following iss ues: reduction in costs of copper concentrates drying by implementation of installati ons using the heat generated in smelters, i.e. steam resulting from heat recover y from technological gases, reduction in costs of copper removal from slag by introduction of combined metho d of copper removal: reduction-flotation. The method also gives possibility for more advantageous separation of lead and arsenic impurities from copper, intensification of copper electrorefining process by increase in the current den sity and reduction of distances between electrodes, while maintaining high quali ty of cathodes, better use of accompanying metals: lead, nickel, cobalt, selenium, rhenium and z inc as well as production of highly processed chemical compounds of those metals . 3.3. State and directions for development in zinc and lead metallurgy

Zinc and lead metallurgical plants currently operating in Poland can be classifi ed as a medium size, i.e.: installation for zinc and lead production of capacity about 87 thousand Mg of zi nc per annum, zinc electrolysis plant of capacity about 75 thousand Mg of zinc per annum. The plants was modernised, especially in the area of refining and rectification of zinc from the Imperial Smelting process and from leaching process, and in cle aning solutions and some of the components of tank hall in the process of zinc e lectrolysis. That has led to production of high quality zinc used in manufacture of high qual ity zinc alloys for zinc plating of steel products, for casting alloys, for prod uction of rolled sheets, wires and zinc anodes. Lead bullion, beside its production from IS shaft furnace, is also produced from battery scrap and from lead bearing semi-products and waste, mainly from copper metallurgy. The technology for battery scrap processing covers: separation of full batteries together with electrolyte by Engitec Impianti metho d, remelting of metal bearing fractions of the battery waste in rotary furnaces, eq uipped with installations for enriching air with oxygen, lead fire refining and production of alloys for starting batteries. Lead bearing semi-products from copper metallurgy (dusts and slimes from dedusti ng systems of copper smelters) are processed into lead bullion in rotary-rocking furnaces, equipped with burner installations for enrichment of air with oxygen. Zinc bearing waste (dusts from steelmaking processes and slimes after leaching o f blende roasted for zinc electrolysis process) is processed in rolldown furnace s for obtaining of zinc oxide which contains about 50% of Zn and15% of Pb. The directions for development in lead and zinc metallurgy cover the following b asic issues: further intensification and reduction of the costs of zinc production in the Imp erial Smelting process by enrichment of air with oxygen and by treatment of powd ery zinc bearing materials introduced through nozzles into the shaft furnace,

further intensification and reduction of the costs of electrolytic zinc producti on, by processing of zinc blende after magnesium removal, widening of assortment and range of zinc alloys manufactured both from rectified and from electrolytic zinc, complete management of lead bearing semi-products and waste from copper metallur gy, widening of assortment of lead alloys, mainly for battery industry. 4. Conclusions

The developments in technologies for non-ferrous ores enrichment and metallurgy are aimed towards reaching the level necessary for operation in the competitive world market. It is related to the three basic areas of activity: quality of commercial products, fabrication costs, environmental protection. In the area of ores enrichment, the technological development is directed toward s optimisation of ore deposits exploitation, and maintaining or even increasing the quality of concentrates. Reduction in fabrication costs is specifically important, especially by: modernisation of systems of ore preparation for flotation, introduction of new types of flotation machines developed by IMN, of low energy consumption and low operation costs, modernisation of dewatering systems for elimination of concentrates thermal dryi ng, separate processing of difficult in enrichment semi-products, including methods for chemical-flotation treatment, better management of flotation tailings. There has to be mentioned that currentl y ~ 20% of the total volume of the tailings is separated in the result of classi fication in a form of thick grained sandstone fraction and is used for formation of settling tanks. That results in limitation of natural resources used for sub structure of the settling tanks. In the area of non-ferrous metals metallurgy the basic objective for technologic al development is reduction of fabrication costs, while simultaneously maintaini ng high quality of production as well as maintaining or improving the positive i ndices of pollutants emission into the natural environment. The first priority task in copper metallurgy is replacement of shaft process wit h a modern process of obtaining copper directly from sulphide concentrates in a flash smelting furnace. The other objectives are focused mainly on reductions in costs of metallurgical processing of copper concentrates and are related to: reductions in costs of charge preparation for smelting, by use of the heat recov ered in boilers in a form of steam, modernisation of a technology for copper removal from slag, intensification of copper electrorefining process, more efficient utilisation of accompanying metals in copper ores. The development in the area of zinc-lead metallurgy is mainly related to intensi fication of production and reduction of fabrication costs as well as to widening the scope and assortment of zinc and lead alloys.