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Markt für Zink

technologyComment of gold mine operation and refining (SE): OPEN PIT MINING: The ore is mined in four steps: drilling, blasting, loading and hauling. In the case of a surface mine, a pattern of holes is drilled in the pit and filled with explosives. The explosives are detonated in order to break up the ground so large shovels or front-end loaders can load it into haul trucks. ORE AND WASTE HAULAGE: The haul trucks transport the ore to various areas for processing. The grade and type of ore determine the processing method used. Higher-grade ores are taken to a mill. Lower grade ores are taken to leach pads. Some ores may be stockpiled for later processing. HEAP LEACHING: The ore is crushed or placed directly on lined leach pads where a dilute cyanide solution is applied to the surface of the heap. The solution percolates down through the ore, where it leaches the gold and flows to a central collection location. The solution is recovered in this closed system. The pregnant leach solution is fed to electrowinning cells and undergoes the same steps as described below from Electro-winning. ORE PROCESSING: Milling: The ore is fed into a series of grinding mills where steel balls grind the ore to a fine slurry or powder. Oxidization and leaching: Some types of ore require further processing before gold is recovered. In this case, the slurry is pressure-oxidized in an autoclave before going to the leaching tanks or a dry powder is fed through a roaster in which it is oxidized using heat before being sent to the leaching tanks as a slurry. The slurry is thickened and runs through a series of leaching tanks. The gold in the slurry adheres to carbon in the tanks. Stripping: The carbon is then moved into a stripping vessel where the gold is removed from the carbon by pumping a hot caustic solution through the carbon. The carbon is later recycled. Electro-winning: The gold-bearing solution is pumped through electro-winning cells or through a zinc precipitation circuit where the gold is recovered from the solution. Smelting: The gold is then melted in a furnace at about 1’064°C and poured into moulds, creating doré bars. Doré bars are unrefined gold bullion bars containing between 60% and 95% gold. References: Newmont (2004) How gold is mined. Newmont. Retrieved from http://www.newmont.com/en/gold/howmined/index.asp technologyComment of primary zinc production from concentrate (CA-QC): Hydrometallurgical process Sulphide concentrates are roasted first in fluidized bed roasters to produce zinc oxide (calcine) and sulphur dioxide. Roasting is an exothermic process and no additional fuel is used to sustain the reaction, the heat generated is recovered to produce steam. Calcine is then sent to the leaching step. Roaster gases are treated in hot electrostatics precipitators to remove dust. The remaining dust and volatile metals such as mercury and selenium are removed in the wet section of the acid plant through a cooling tour, a mist precipitator and a mercury tower (Boliden mercury removal processs). The sulphur dioxide is then converted to sulphuric acid in a conventional recovery system (converted and absorbing tower). Leaching of the calcine is carried out in a number of successive stages using a gradually increasing strength of hot sulphuric acid. The initial stages dissolve the major part of the zinc oxide and the other stages dissolve the zinc ferrite (ZnO.Fe2O3) and convert iron into Jarosite (sodium Jarosite). Zinc sulfate (ZnSO4) entering the electrolysis stage produce electrolyte (H2SO4) that is returned to leaching plant. Other metals are also dissolved during the process and are removed after leaching. Iron is the major impurity, which is precipitated in the form of Jarosite. Overall waste: The production of metals is related to the generation of several by-products, residues and wastes. Relatively large quantities of iron based solids, depending on the iron content, are generated by the leaching process (6.14E-1 kg Jarosite/kg zinc). Cement is added to the Jarosite to produce Jarofix (an inert waste). Solid residues also arise as the result of the liquid effluents treatment. The main waste stream is gypsum (CaSO4) and metal hydroxides that are produced at the wastewater neutralization plant. Mercury and selenium residues arise from the weak acid bleed treatment from the acid plant. Selenium can be recovered from these residues depending on the market demand for this metal. Overall emissions: The emissions to air can either be stack emissions or fugitive emissions. Stack emissions are normally monitored continuously (SO2) or periodically (other emissions) and reported. The main emissions to air from zinc production are sulphur dioxide (SO2) and particulate matters including metals. Main emissions to water are metals and their compounds. The monitored metals are zinc, cadmium, lead, mercury, selenium, copper and arsenic. technologyComment of primary zinc production from concentrate (RoW): The technological representativeness of this dataset is considered to be high as smelting methods for zinc are consistent in all regions. Refined zinc produced pyro-metallurgically represents less than 5% of global zinc production and less than 2% of this dataset. Electrometallurgical Smelting The main unit processes for electrometallurgical zinc smelting are roasting, leaching, purification, electrolysis, and melting. In both electrometallurgical and pyro-metallurgical zinc production routes, the first step is to remove the sulfur from the concentrate. Roasting or sintering achieves this. The concentrate is heated in a furnace with operating temperature above 900 °C (exothermic, autogenous process) to convert the zinc sulfide to calcine (zinc oxide). Simultaneously, sulfur reacts with oxygen to produce sulfur dioxide, which is subsequently converted to sulfuric acid in acid plants, usually located with zinc-smelting facilities. During the leaching process, the calcine is dissolved in dilute sulfuric acid solution (re-circulated back from the electrolysis cells) to produce aqueous zinc sulfate solution. The iron impurities dissolve as well and are precipitated out as jarosite or goethite in the presence of calcine and possibly ammonia. Jarosite and goethite are usually disposed of in tailing ponds. Adding zinc dust to the zinc sulfate solution facilitates purification. The purification of leachate leads to precipitation of cadmium, copper, and cobalt as metals. In electrolysis, the purified solution is electrolyzed between lead alloy anodes and aluminum cathodes. The high-purity zinc deposited on aluminum cathodes is stripped off, dried, melted, and cast into SHG zinc ingots (99.99 % zinc). Pyro-metallurgical Smelting The pyro-metallurgical smelting process is based on the reduction of zinc and lead oxides into metal with carbon in an imperial smelting furnace. The sinter, along with pre-heated coke, is charged from the top of the furnace and injected from below with pre-heated air. This ensures that temperature in the center of the furnace remains in the range of 1000-1500 °C. The coke is converted to carbon monoxide, and zinc and lead oxides are reduced to metallic zinc and lead. The liquid lead bullion is collected at the bottom of the furnace along with other metal impurities (copper, silver, and gold). Zinc in vapor form is collected from the top of the furnace along with other gases. Zinc vapor is then condensed into liquid zinc. The lead and cadmium impurities in zinc bullion are removed through a distillation process. The imperial smelting process is an energy-intensive process and produces zinc of lower purity than the electrometallurgical process.

Markt für Palladium

technologyComment of platinum group metal mine operation, ore with high palladium content (RU): imageUrlTagReplace6250302f-4c86-4605-a56f-03197a7811f2 technologyComment of platinum group metal, extraction and refinery operations (ZA): The ores from the different ore bodies are processed in concentrators where a PGM concentrate is produced with a tailing by product. The PGM base metal concentrate product from the different concentrators processing the different ores are blended during the smelting phase to balance the sulphur content in the final matte product. Smelter operators also carry out toll smelting from third part concentrators. The smelter product is send to the Base metal refinery where the PGMs are separated from the Base Metals. Precious metal refinery is carried out on PGM concentrate from the Base metal refinery to split the PGMs into individual metal products. Water analyses measurements for Anglo Platinum obtained from literature (Slatter et.al, 2009). Mudd, G., 2010. Platinum group metals: a unique case study in the sustainability of mineral resources, in: The 4th International Platinum Conference, Platinum in Transition “Boom or Bust.” Water share between MC and EC from Mudd (2010). Mudd, G., 2010. Platinum group metals: a unique case study in the sustainability of mineral resources, in: The 4th International Platinum Conference, Platinum in Transition “Boom or Bust.” technologyComment of treatment of automobile catalyst (RoW): After collection and transportation to the intermediary dealer, the scrap is ground in a mill. The resulting material is fed to specialised refineries. The metallurgical step consists of an arc-furnace. Same refining process as in primary production assumed (selective precipitation) technologyComment of treatment of automobile catalyst (RER): The production process consists of three steps: Collection, Beneficiation and Refining. COLLECTION: Spoiled automotive catalysts are bought by specialised enterprises from different origins. Part of it originates from scrap dealer recycling end-of-life cars. Further more during the cars operating phase, defective catalysts are exchanged in garages. The third sources is the production waste, i. e. defective catalysts which do not reach market. In most cases, there are fix agreements between the different supplier and the intermediary trade. Although the trade with PGM containing scrap is risky. Motor car manufacturer built up their own internal recycling systems with their contractor garages and gained access to exchanged catalysts. Emissions: Emissions during collection are gases from transportation and dust from dismantling. Also in this step the combustion leads to emissions of SO2. No serious water emissions are reported. BENEFICIATION: The catalysts are dismantled and then sold to refining companies. Refineries too have long-term contracts with the intermediary trade. Emissions: Emissions during beneficiation are gases from transportation and dust from dismantling. Also in this step the combustion leads to emissions of SO2. No serious water emissions are reported. REFINING: The scrap first is shredded and then pyrometallurgicaly processed: The scrap is smelted in an electric arc furnace, and the ceramic wafer is slagged. The PGMs are concentrated in the collector metal, usually copper. Low-content PGM scrap is often smelted together with other non-ferrous metal matte. This is cheap, but effects a high loss in PGM. The collector matte from the furnace then is treated hydrometallurgically by re-precipitation. In this step usually production scrap from other industries (glass, chemical laboratories) is joined. The overall PGM-yield is 98 % for platinum and 85 % for rhodium. Emissions: Dust and metals are generally emitted from incinerators and furnaces. VOC can be emitted from solvent extraction processes, while organic compounds, namely dioxins, can be emitted from smelting stages resulting from the poor combustion of oil and plastic in the feed material. All these emissions are subject to abatement technologies and controlling. Effluents from refining contain considerable amounts of metals and organic substances. Waste: Solid residues from pyrometallurgical step are usually re-used in copper facilities, final residues generally comprise hydroxide filter cakes. References: Hagelücken C. (2001b) Die Märkte der Katalysatormetalle Platin, Palladium und Rhodium. In: Autoabgaskatalysatoren, Vol. 612. pp. 95-115. Expert Verlag, Renningen. Online-Version under: http://www.dmc-2.de/pmc_eng/Veroeffentlichungen_2/Die%20M%C3%A4rkte%20der%20Katalysatormetalle%20Pt%20Pd%20Rh.pdf. technologyComment of treatment of precious metal from electronics scrap, in anode slime, precious metal extraction (SE, RoW): Anode slime treatment by pressure leaching and top blown rotary converter. Production of Silver by Möbius Electrolysis, Gold by Wohlwill electrolysis, Palladium to further processing

Markt für Rhodium

technologyComment of platinum group metal mine operation, ore with high palladium content (RU): imageUrlTagReplace6250302f-4c86-4605-a56f-03197a7811f2 technologyComment of platinum group metal, extraction and refinery operations (ZA): The ores from the different ore bodies are processed in concentrators where a PGM concentrate is produced with a tailing by product. The PGM base metal concentrate product from the different concentrators processing the different ores are blended during the smelting phase to balance the sulphur content in the final matte product. Smelter operators also carry out toll smelting from third part concentrators. The smelter product is send to the Base metal refinery where the PGMs are separated from the Base Metals. Precious metal refinery is carried out on PGM concentrate from the Base metal refinery to split the PGMs into individual metal products. Water analyses measurements for Anglo Platinum obtained from literature (Slatter et.al, 2009). Mudd, G., 2010. Platinum group metals: a unique case study in the sustainability of mineral resources, in: The 4th International Platinum Conference, Platinum in Transition “Boom or Bust.” Water share between MC and EC from Mudd (2010). Mudd, G., 2010. Platinum group metals: a unique case study in the sustainability of mineral resources, in: The 4th International Platinum Conference, Platinum in Transition “Boom or Bust.” technologyComment of treatment of automobile catalyst (RoW): After collection and transportation to the intermediary dealer, the scrap is ground in a mill. The resulting material is fed to specialised refineries. The metallurgical step consists of an arc-furnace. Same refining process as in primary production assumed (selective precipitation) technologyComment of treatment of automobile catalyst (RER): The production process consists of three steps: Collection, Beneficiation and Refining. COLLECTION: Spoiled automotive catalysts are bought by specialised enterprises from different origins. Part of it originates from scrap dealer recycling end-of-life cars. Further more during the cars operating phase, defective catalysts are exchanged in garages. The third sources is the production waste, i. e. defective catalysts which do not reach market. In most cases, there are fix agreements between the different supplier and the intermediary trade. Although the trade with PGM containing scrap is risky. Motor car manufacturer built up their own internal recycling systems with their contractor garages and gained access to exchanged catalysts. Emissions: Emissions during collection are gases from transportation and dust from dismantling. Also in this step the combustion leads to emissions of SO2. No serious water emissions are reported. BENEFICIATION: The catalysts are dismantled and then sold to refining companies. Refineries too have long-term contracts with the intermediary trade. Emissions: Emissions during beneficiation are gases from transportation and dust from dismantling. Also in this step the combustion leads to emissions of SO2. No serious water emissions are reported. REFINING: The scrap first is shredded and then pyrometallurgicaly processed: The scrap is smelted in an electric arc furnace, and the ceramic wafer is slagged. The PGMs are concentrated in the collector metal, usually copper. Low-content PGM scrap is often smelted together with other non-ferrous metal matte. This is cheap, but effects a high loss in PGM. The collector matte from the furnace then is treated hydrometallurgically by re-precipitation. In this step usually production scrap from other industries (glass, chemical laboratories) is joined. The overall PGM-yield is 98 % for platinum and 85 % for rhodium. Emissions: Dust and metals are generally emitted from incinerators and furnaces. VOC can be emitted from solvent extraction processes, while organic compounds, namely dioxins, can be emitted from smelting stages resulting from the poor combustion of oil and plastic in the feed material. All these emissions are subject to abatement technologies and controlling. Effluents from refining contain considerable amounts of metals and organic substances. Waste: Solid residues from pyrometallurgical step are usually re-used in copper facilities, final residues generally comprise hydroxide filter cakes. References: Hagelücken C. (2001b) Die Märkte der Katalysatormetalle Platin, Palladium und Rhodium. In: Autoabgaskatalysatoren, Vol. 612. pp. 95-115. Expert Verlag, Renningen. Online-Version under: http://www.dmc-2.de/pmc_eng/Veroeffentlichungen_2/Die%20M%C3%A4rkte%20der%20Katalysatormetalle%20Pt%20Pd%20Rh.pdf.

Markt für Selen

technologyComment of processing of anode slime from electrorefining of copper, anode (GLO): Based on typical current technology. Anode slime treatment by pressure leaching and top blown rotary converter. Production of Silver by Möbius Electrolysis, Gold by Wohlwill electrolysis, copper telluride cement and crude selenium to further processing. technologyComment of selenium production (RER, RoW): Production from selenium is based on simplified roasting process with sodium carbonate. The inventory is based on stoechiometric calculations, according to the following equations: 2 X-Se + 2 Na2CO3 + 3 CO2 -> 2 Na2O4Se + 2 CO2 + 2 X (with X = compounds that were connected to Se - e.g. Cu2, CuAg, ....) 2 Na2O4Se + 4 HCl -> 2 H2O3Se + 4 NaCl + O2 2 H2O3Se + 2 SO2 -> 2 Se + 2 H2SO4 + O2 A surplus input of 25% is assumed. The air emissions occurring from the process are estimated to 0.2% of the raw material input. The remaining amount of unreacted raw materials is assumed to leave the production process to 95% as a solid waste and to 5% in the wastewater. Further it is assumed that this wastewater is treated in an internal wastewater plant. The carbonate is dissolved in the water and not shown anymore in the dataset. Sodium and chloride are assumed to be neutralized within the waste water treatment plant, leading to emissions of Cl- and Na+ in the water outflow. Sodium dioxide will be reacted into sulphuric acid and therefore leads to emissions of SO42- in the water outflow.

Aufbereitung von Kupferschrott durch elektrolytische Raffination

Secondary copper consists of various types of scrap. Prompt scrap is directly reused in foundries and is not further processed. Old scrap has to be treated in a secondary copper smelter, where a variety of metal values are recuperated. Depending on the chemical composition, the raw materials of a secondary copper smelter are processed in different types of furnaces, including: - blast furnaces (up to 30% of Cu in the average charge), - converters (about 75% Cu), and - anode furnaces (about 95% Cu). A scheme of the process considered is given in Fig 1. The blast furnace metal (“black copper”) is treated in a converter; then, the converter metal is refined in an anode furnace. In each step additional raw material with corresponding copper content is added. In the blast furnace, a mixture of raw materials, iron scrap, limestone and sand as well as coke is charged at the top. Air that can be enriched with oxygen is blown through the tuyeres. The coke is burnt and the charge materials are smelted under reducing conditions. Black copper and slag are discharged from tapholes. The converters used in primary copper smelting, working on mattes containing iron sulphide, generate surplus heat and additions of scrap copper are often used to control the temperature. The converter provides a convenient and cheap form of scrap treatment, but often with only moderately efficient gas cleaning. Alternatively, hydrometallurgical treatment of scrap, using ammonia leaching, yields to solutions which can be reduced by hydrogen to obtain copper powder. Alternatively, these solutions can be treated by solvent extraction to produce feed to a copper-winning cell. Converter copper is charged together with copper raw materials in anode furnace operation. For smelting the charge, oil or coal dust is used, mainly in reverberatory furnaces. After smelting, air is blown on the bath to oxidise the remaining impurities. Leaded brasses, containing as much as 3% of lead, are widely used in various applications and recycling of their scrap waste is an important activity. Such scrap contains usually much swarf and turnings coated with lubricant and cutting oils. Copper-containing cables and motors contain plastic or rubber insulants, varnishes, and lacquers. In such cases, scrap needs pre-treatment to remove these non-metallic materials. The smaller sizes of scrap can be pre-treated thermally in a rotary kiln provided with an after-burner to consume smoke and oil vapours (so-called Intal process). Emissions and waste: Elevated levels of halogenated organic compounds may arise, such as TCDD. Slags are usually used in construction. Waste water is led to a communal treatment plant. References: EEA, 1999. imageUrlTagReplacef2b602ec-dc47-48e3-88a7-ab8ec727bd33

Markt für Blei

technologyComment of gold mine operation and refining (SE): OPEN PIT MINING: The ore is mined in four steps: drilling, blasting, loading and hauling. In the case of a surface mine, a pattern of holes is drilled in the pit and filled with explosives. The explosives are detonated in order to break up the ground so large shovels or front-end loaders can load it into haul trucks. ORE AND WASTE HAULAGE: The haul trucks transport the ore to various areas for processing. The grade and type of ore determine the processing method used. Higher-grade ores are taken to a mill. Lower grade ores are taken to leach pads. Some ores may be stockpiled for later processing. HEAP LEACHING: The ore is crushed or placed directly on lined leach pads where a dilute cyanide solution is applied to the surface of the heap. The solution percolates down through the ore, where it leaches the gold and flows to a central collection location. The solution is recovered in this closed system. The pregnant leach solution is fed to electrowinning cells and undergoes the same steps as described below from Electro-winning. ORE PROCESSING: Milling: The ore is fed into a series of grinding mills where steel balls grind the ore to a fine slurry or powder. Oxidization and leaching: Some types of ore require further processing before gold is recovered. In this case, the slurry is pressure-oxidized in an autoclave before going to the leaching tanks or a dry powder is fed through a roaster in which it is oxidized using heat before being sent to the leaching tanks as a slurry. The slurry is thickened and runs through a series of leaching tanks. The gold in the slurry adheres to carbon in the tanks. Stripping: The carbon is then moved into a stripping vessel where the gold is removed from the carbon by pumping a hot caustic solution through the carbon. The carbon is later recycled. Electro-winning: The gold-bearing solution is pumped through electro-winning cells or through a zinc precipitation circuit where the gold is recovered from the solution. Smelting: The gold is then melted in a furnace at about 1’064°C and poured into moulds, creating doré bars. Doré bars are unrefined gold bullion bars containing between 60% and 95% gold. References: Newmont (2004) How gold is mined. Newmont. Retrieved from http://www.newmont.com/en/gold/howmined/index.asp technologyComment of primary lead production from concentrate (GLO): There are two basic pyrometallurgical processes available for the production of lead from lead or mixed lead-zinc-sulphide concentrates: sinter oxidation / blast furnace reduction route or Direct Smelting Reduction Processes. Both processes are followed by a refining step to produce the final product with the required purity, and may also be used for concentrates mixed with secondary raw materials. SINTER OXIDATION / BLAST FURNACE REDUCTION: The sinter oxidation / blast furnace reduction involves two steps: 1) A sintering oxidative roast to remove sulphur with production of PbO; and 2) Blast furnace reduction of the sinter product. The objective of sintering lead concentrates is to remove as much sulphur as possible from the galena and the accompanying iron, zinc, and copper sulphides, while producing lump agglomerate with appropriate properties for subsequent reduction in the blast furnace (a type of a shaft furnace). As raw material feed, lead concentrates are blended with recycled sinter fines, secondary material and other process materials and pelletised in rotating drums. Pellets are fed onto sinter machine and ignited. The burning pellets are conveyed over a series of wind-boxes through which air is blown. Sulphur is oxidised to sulphur dioxide and the reaction generates enough heat to fuse and agglomerate the pellets. Sinter is charged to the blast furnace with metallurgical coke. Air and/or oxygen enriched air is injected and reacts with the coke to produce carbon monoxide. This generates sufficient heat to melt the charge. The gangue content of the furnace charge combines with the added fluxes or reagents to form a slag. For smelting bulk lead-zinc-concentrates and secondary material, frequently the Imperial Smelting Furnace is used. Here, hot sinter and pre-heated coke as well as hot briquettes are charged. Hot air is injected. The reduction of the metal oxides not only produces lead and slag but also zinc, which is volatile at the furnace operating temperature and passes out of the ISF with the furnace off-gases. The gases also contain some cadmium and lead. The furnace gases pass through a splash condenser in which a shower of molten lead quenches them and the metals are absorbed into the liquid lead, the zinc is refined by distillation. DIRECT SMELTING REDUCTION: The Direct Smelting Reduction Process does not carry out the sintering stage separately. Lead sulphide concentrates and secondary materials are charged directly to a furnace and are then melted and oxidised. Sulphur dioxide is formed and is collected, cleaned and converted to sulphuric acid. Carbon (coke or gas) and fluxing agents are added to the molten charge and lead oxide is reduced to lead, a slag is formed. Some zinc and cadmium are “fumed” off in the furnace, their oxides are captured in the abatement plant and recovered. Several processes are used for direct smelting of lead concentrates and some secondary material to produce crude lead and slag. Bath smelting processes are used: the ISA Smelt/Ausmelt furnaces (sometimes in combination with blast furnaces), Kaldo (TBRC) and QSL integrated processes are used in EU and Worldwide. The Kivcet integrated process is also used and is a flash smelting process. The ISA Smelt/Ausmelt furnaces and the QSL take moist, pelletised feed and the Kaldo and Kivcet use dried feed. REFINING: Lead bullion may contain varying amounts of copper, silver, bismuth, antimony, arsenic and tin. Lead recovered from secondary sources may contain similar impurities, but generally antimony and calcium dominate. There are two methods of refining crude lead: electrolytic refining and pyrometallurgical refining. Electrolytic refining uses anodes of de-copperised lead bullion and starter cathodes of pure lead. This is a high-cost process and is used infrequently. A pyrometallurgical refinery consists of a series of kettles, which are indirectly heated by oil or gas. Over a series of separation processes impurities and metal values are separated from the lead bouillon. Overall waste: The production of metals is related to the generation of several by-products, residues and wastes, which are also listed in the European Waste Catalogue (Council Decision 94/3/EEC). The ISF or direct smelting furnaces also are significant sources of solid slag. This slag has been subjected to high temperatures and generally contains low levels of leachable metals, consequently it may be used in construction. Solid residues also arise as the result of the treatment of liquid effluents. The main waste stream is gypsum waste (CaSO4) and metal hydroxides that are produced at the wastewater neutralisation plant. These wastes are considered to be a cross-media effect of these treatment techniques but many are recycled to pyrometallurgical process to recover the metals. Dust or sludge from the treatment of gases are used as raw materials for the production of other metals such as Ge, Ga, In and As, etc or can be returned to the smelter or into the leach circuit for the recovery of lead and zinc. Hg/Se residues arise at the pre-treatment of mercury or selenium streams from the gas cleaning stage. This solid waste stream amounts to approximately 40 - 120 t/y in a typical plant. Hg and Se can be recovered from these residues depending on the market for these metals. Overall emissions: The main emissions to air from zinc and lead production are sulphur dioxide, other sulphur compounds and acid mists; nitrogen oxides and other nitrogen compounds, metals and their compounds; dust; VOC and dioxins. Other pollutants are considered to be of negligible importance for the industry, partly because they are not present in the production process and partly because they are immediately neutralised (e.g. chlorine) or occur in very low concentrations. Emissions are to a large extent bound to dust (except cadmium, arsenic and mercury that can be present in the vapour phase). Metals and their compounds and materials in suspension are the main pollutants emitted to water. The metals concerned are Zn, Cd, Pb, Hg, Se, Cu, Ni, As, Co and Cr. Other significant substances are fluorides, chlorides and sulphates. Wastewater from the gas cleaning of the smelter and fluid-bed roasting stages are the most important sources. References: Sutherland C. A., Milner E. F., Kerby R. C., Teindl H. and Melin A. (1997) Lead. In: Ullmann's encyclopedia of industrial chemistry (ed. Anonymous). 5th edition on CD-ROM Edition. Wiley & Sons, London. IPPC (2001) Integrated Pollution Prevention and Control (IPPC); Reference Document on Best Available Techniques in the Non Ferrous Metals Industries. European Commission. Retrieved from http://www.jrc.es/pub/english.cgi/ 0/733169 technologyComment of primary zinc production from concentrate (RoW): The technological representativeness of this dataset is considered to be high as smelting methods for zinc are consistent in all regions. Refined zinc produced pyro-metallurgically represents less than 5% of global zinc production and less than 2% of this dataset. Electrometallurgical Smelting The main unit processes for electrometallurgical zinc smelting are roasting, leaching, purification, electrolysis, and melting. In both electrometallurgical and pyro-metallurgical zinc production routes, the first step is to remove the sulfur from the concentrate. Roasting or sintering achieves this. The concentrate is heated in a furnace with operating temperature above 900 °C (exothermic, autogenous process) to convert the zinc sulfide to calcine (zinc oxide). Simultaneously, sulfur reacts with oxygen to produce sulfur dioxide, which is subsequently converted to sulfuric acid in acid plants, usually located with zinc-smelting facilities. During the leaching process, the calcine is dissolved in dilute sulfuric acid solution (re-circulated back from the electrolysis cells) to produce aqueous zinc sulfate solution. The iron impurities dissolve as well and are precipitated out as jarosite or goethite in the presence of calcine and possibly ammonia. Jarosite and goethite are usually disposed of in tailing ponds. Adding zinc dust to the zinc sulfate solution facilitates purification. The purification of leachate leads to precipitation of cadmium, copper, and cobalt as metals. In electrolysis, the purified solution is electrolyzed between lead alloy anodes and aluminum cathodes. The high-purity zinc deposited on aluminum cathodes is stripped off, dried, melted, and cast into SHG zinc ingots (99.99 % zinc). Pyro-metallurgical Smelting The pyro-metallurgical smelting process is based on the reduction of zinc and lead oxides into metal with carbon in an imperial smelting furnace. The sinter, along with pre-heated coke, is charged from the top of the furnace and injected from below with pre-heated air. This ensures that temperature in the center of the furnace remains in the range of 1000-1500 °C. The coke is converted to carbon monoxide, and zinc and lead oxides are reduced to metallic zinc and lead. The liquid lead bullion is collected at the bottom of the furnace along with other metal impurities (copper, silver, and gold). Zinc in vapor form is collected from the top of the furnace along with other gases. Zinc vapor is then condensed into liquid zinc. The lead and cadmium impurities in zinc bullion are removed through a distillation process. The imperial smelting process is an energy-intensive process and produces zinc of lower purity than the electrometallurgical process. technologyComment of treatment of electronics scrap, metals recovery in copper smelter (SE, RoW): Conversion of Copper in a Kaldo Converter and treatment in converter aisle. technologyComment of treatment of scrap lead acid battery, remelting (RoW): The referred operation uses a shaft furnace with post combustion, which is the usual technology for secondary smelters. technologyComment of treatment of scrap lead acid battery, remelting (RER): The referred operation uses a shaft furnace with post combustion, which is the usual technology for secondary smelters. Typically this technology produces 5000 t / a sulphuric acid (15% concentration), 25’000 t lead bullion (98% Pb), 1200 t / a slags (1% Pb) and 3000 t / a raw lead matte (10% Pb) to be shipped to primary smelters. Overall Pb yield is typically 98.8% at the plant level and 99.8% after reworking the matte. The operation treats junk batteries and plates but also lead cable sheathing, drosses and sludges, leaded glass and balancing weights. From this feed it manufactures mainly antimonial lead up to 10% Sb, calcium-aluminium lead alloys with or without tin and soft lead with low and high copper content. All these products are the result of a refining and alloying step to meet the compliance with the designations desired. The following by products are reused in the process: fine dust, slag, and sulfuric acid. References: Quirijnen L. (1999) How to implement efficient local lead-acid battery recycling. In: Journal of Power Sources, 78(1-2), pp. 267-269.

Markt für Magnesium

technologyComment of magnesium production, electrolysis (RoW, IL): Electrochemical processes to make magnesium are based on salts containing chloride which can be found naturally or are transformed from other raw materials like serpentine, magnesite, bischofite or carnallite. The magnesium chloride salts are dried with various processes in order to receive anhydrous MgCl2. The raw material for magnesium production in this activity is an anhydrous carnallite (MgCl2-KCl). In the process, KCl represents the electrolyte. In the course of the MgCl2 decomposition, the KCl content increases until the (spent) electrolyte is partly pumped out and replaced with new carnallite. Finally, two by-products are produced: liquefied chlorine (Cl2) and KCl-rich salt (70% KCl). Magnesium oxide (MgO) is formed as an impurity during dehydration. Concerning the CO2/CO equilibrium in the calcination process, there are numerous reactions that take place in the chlorination chambers and the carbon can be consumed by reaction with MgO, air, water, sulfates and other impurities. Theoretically, the predominant reactions are those in which carbon dioxide is formed. Thus, it is assumed that the carbon is entirely converted to CO2. The CO2 emissions from graphite anode consumption are expected to contribute less than 1 % of the overall emissions and are neglected in the module. In practice, the off gases are not released to the atmosphere as is, as they are treated in wet alkali scrubbers. That is that some of the CO2 (be it from the reaction or from the ambient dilution air) is converted to calcium carbonate. The input of petroleum coke contributes less than 1 % to the overall GWP results and is excluded from this datasets for reasons of confidentiality. technologyComment of magnesium production, pidgeon process (CN): The Pidgeon process includes the following process steps: calcination, grinding & mixing, briquetting, reducion and refining. Coal as energy source is only used in for the calcination process. For other process steps, coke oven, semi coke oven, producer or natural gas are used. The use of these fuels is calculated according to the weighted average in terms of annual magnesium output per fuel. The production of producer (coal) gas is included in this module. A main influencing factor for the emissions from fuel combustion is the composition of the fuel itself. Due to the different origins of the fuel gases used in the Pidgeon process, the composition of the gases varies considerably. For semi coke and coke oven gas, a large variation in gas composition can be observed. As the data base for these compositions is restricted to few measurements, no statistical average can be determined.

Markt für Mangan

technologyComment of manganese production (RER): The metal is won by electrolysis (25%) and electrothermic processes (75%). ELECTROLYSIS OF AQUEOUS MANGANESE SALTS The production of manganese metal by the electrolysis of aqueous manganese salts requires at first a milling of the manganese ore. Milling increases the active surface and ensures sufficient reactivity in both the reduction and the subsequent leaching steps. After milling the manganese ore is fed to a rotary kiln where the reduction and calcination takes place. This process is carried out at about 850 - 1000 ºC in a reducing atmosphere. As a reducing agent, several carbon sources can be used e.g. anthracite, coal, charcoal and hydrocarbon oil or natural gas. The cal-cined ore needs to be cooled below 100 ºC to avoid a further re-oxidation. The subsequent leaching process is carried out with recycled electrolyte, mainly sulphuric acid. After leaching and filtration the iron content is removed from the solution by oxidative precipitation and the nickel and cobalt are removed by sulphide precipitation. The purified electrolyte is then treated with SO2 in order to ensure plating of γ-Mn during electrolysis. Electrolysis is carried out in diaphragm cells. The cathode is normally made of stainless steel or titanium. For the anode lead-calcium or lead-silver alloy can be used. After an appropriate reaction time the cathodes are removed from the electrolysis bath. The manganese that is deposited on the cathode starter-sheet is stripped off mechanically and then washed and dried. The metal is crushed to produce metal flakes or powder or granulated, depending on the end use. ELECTROTHERMAL DECOMPOSITION OF MANGANESE ORES The electrothermal process is the second important process to produce manganese metal in an industrial scale. The electrothermal process takes place as a multistage process. In the first stage manganese ore is smelted with only a small amount of reductant in order to reduce mostly the iron oxide. This produces a low-grade ferro-manganese and a slag that is rich in Mn-oxide. The slag is then smelted in the second stage with silicon to produce silicomanganese. The molten silicomanganese can be treated with liquid slag from the fist stage to obtain relatively pure manganese metal. For the last step a ladle or shaking ladle can be used. The manganese metal produced by the electrothermal process contains up to 98% of Mn. Overall emissions and waste: Emissions to air consist of dust and fume emissions from smelting, hard metal and carbide production; Other emissions to air are ammonia (NH3), acid fume (HCl), hydrogen fluoride (HF), VOC and heavy metals. Effluents are composed of overflow water from wet scrubbing systems, wastewater from slag and metal granulation, and blow down from cooling water cycles. Waste includes dust, fume, sludge and slag. References: Wellbeloved D. B., Craven P. M. and Waudby J. W. (1997) Manganese and Manganese Alloys. In: Ullmann's encyclopedia of industrial chemistry (ed. Anonymous). 5th edition on CD-ROM Edition. Wiley & Sons, London. IPPC (2001) Integrated Pollution Prevention and Control (IPPC); Reference Document on Best Available Techniques in the Non Ferrous Metals Industries. European Commission. Retrieved from http://www.jrc.es/pub/english.cgi/ 0/733169 technologyComment of manganese production (RoW): The metal is won by electrolysis (assumption: 25%) and electrothermic processes (assumption: 75%). No detailed information available, mainly based on rough estimates. technologyComment of treatment of non-Fe-Co-metals, from used Li-ion battery, hydrometallurgical processing (GLO): The technique SX-EW is used mainly for oxide ores and supergene sulphide ores (i.e. ores not containing iron). It is assumed to be used for the treatment of the non-Fe-Co-metals fraction. The process includes a leaching stage followed by cementation or electro-winning. A general description of the process steps is given below. In the dump leaching step, copper is recovered from large quantities (millions of tonnes) of strip oxide ores with a very low grade. Dilute sulphuric acid is trickled through the material. Once the process starts it continues naturally if water and air are circulated through the heap. The time required is typically measured in years. Sulphur dioxide is emitted during such operations. Soluble copper is then recovered from drainage tunnels and ponds. Copper recovery rates vary from 30% to 70%. Cconsiderable amounts of sulphuric acid and leaching agents emit into water and air. No figures are currently available on the dimension of such emissions. After the solvent-solvent extraction, considerable amounts of leaching residues remain, which consist of undissolved minerals and the remainders of leaching chemicals. In the solution cleaning step occur precipitation of impurities and filtration or selective enrichment of copper by solvent extraction or ion exchange. The solvent extraction process comprises two steps: selective extraction of copper from an aqueous leach solution into an organic phase (extraction circuit) and the re-extraction or stripping of the copper into dilute sulphuric acid to give a solution suitable for electro winning (stripping circuit). In the separation step occurs precipitation of copper metal or copper compounds such as Cu2O, CuS, CuCl, CuI, CuCN, or CuSO4 • 5 H2O (crystallisation) Waste: Like in the pyrometallurgical step, considerable quantities of solid residuals are generated, which are mostly recycled within the process or sent to other specialists to recover any precious metals. Final residues generally comprise hydroxide filter cakes (iron hydroxide, 60% water, cat I industrial waste).

Markt für Platin

technologyComment of platinum group metal mine operation, ore with high palladium content (RU): imageUrlTagReplace6250302f-4c86-4605-a56f-03197a7811f2 technologyComment of platinum group metal, extraction and refinery operations (ZA): The ores from the different ore bodies are processed in concentrators where a PGM concentrate is produced with a tailing by product. The PGM base metal concentrate product from the different concentrators processing the different ores are blended during the smelting phase to balance the sulphur content in the final matte product. Smelter operators also carry out toll smelting from third part concentrators. The smelter product is send to the Base metal refinery where the PGMs are separated from the Base Metals. Precious metal refinery is carried out on PGM concentrate from the Base metal refinery to split the PGMs into individual metal products. Water analyses measurements for Anglo Platinum obtained from literature (Slatter et.al, 2009). Mudd, G., 2010. Platinum group metals: a unique case study in the sustainability of mineral resources, in: The 4th International Platinum Conference, Platinum in Transition “Boom or Bust.” Water share between MC and EC from Mudd (2010). Mudd, G., 2010. Platinum group metals: a unique case study in the sustainability of mineral resources, in: The 4th International Platinum Conference, Platinum in Transition “Boom or Bust.” technologyComment of treatment of automobile catalyst (RoW): After collection and transportation to the intermediary dealer, the scrap is ground in a mill. The resulting material is fed to specialised refineries. The metallurgical step consists of an arc-furnace. Same refining process as in primary production assumed (selective precipitation) technologyComment of treatment of automobile catalyst (RER): The production process consists of three steps: Collection, Beneficiation and Refining. COLLECTION: Spoiled automotive catalysts are bought by specialised enterprises from different origins. Part of it originates from scrap dealer recycling end-of-life cars. Further more during the cars operating phase, defective catalysts are exchanged in garages. The third sources is the production waste, i. e. defective catalysts which do not reach market. In most cases, there are fix agreements between the different supplier and the intermediary trade. Although the trade with PGM containing scrap is risky. Motor car manufacturer built up their own internal recycling systems with their contractor garages and gained access to exchanged catalysts. Emissions: Emissions during collection are gases from transportation and dust from dismantling. Also in this step the combustion leads to emissions of SO2. No serious water emissions are reported. BENEFICIATION: The catalysts are dismantled and then sold to refining companies. Refineries too have long-term contracts with the intermediary trade. Emissions: Emissions during beneficiation are gases from transportation and dust from dismantling. Also in this step the combustion leads to emissions of SO2. No serious water emissions are reported. REFINING: The scrap first is shredded and then pyrometallurgicaly processed: The scrap is smelted in an electric arc furnace, and the ceramic wafer is slagged. The PGMs are concentrated in the collector metal, usually copper. Low-content PGM scrap is often smelted together with other non-ferrous metal matte. This is cheap, but effects a high loss in PGM. The collector matte from the furnace then is treated hydrometallurgically by re-precipitation. In this step usually production scrap from other industries (glass, chemical laboratories) is joined. The overall PGM-yield is 98 % for platinum and 85 % for rhodium. Emissions: Dust and metals are generally emitted from incinerators and furnaces. VOC can be emitted from solvent extraction processes, while organic compounds, namely dioxins, can be emitted from smelting stages resulting from the poor combustion of oil and plastic in the feed material. All these emissions are subject to abatement technologies and controlling. Effluents from refining contain considerable amounts of metals and organic substances. Waste: Solid residues from pyrometallurgical step are usually re-used in copper facilities, final residues generally comprise hydroxide filter cakes. References: Hagelücken C. (2001b) Die Märkte der Katalysatormetalle Platin, Palladium und Rhodium. In: Autoabgaskatalysatoren, Vol. 612. pp. 95-115. Expert Verlag, Renningen. Online-Version under: http://www.dmc-2.de/pmc_eng/Veroeffentlichungen_2/Die%20M%C3%A4rkte%20der%20Katalysatormetalle%20Pt%20Pd%20Rh.pdf.

Markt für Kobalt

technologyComment of cobalt production (GLO): Cobalt, as a co-product of nickel and copper production, is obtained using a wide range of technologies. The initial life cycle stage covers the mining of the ore through underground or open cast methods. The ore is further processed in beneficiation to produce a concentrate and/or raffinate solution. Metal selection and further concentration is initiated in primary extraction, which may involve calcining, smelting, high pressure leaching, and other processes. The final product is obtained through further refining, which may involve processes such as re-leaching, selective solvent / solution extraction, selective precipitation, electrowinning, and other treatments. Transport is reported separately and consists of only the internal movements of materials / intermediates, and not the movement of final product. Due to its intrinsic value, cobalt has a high recycling rate. However, much of this recycling takes place downstream through the recycling of alloy scrap into new alloy, or goes into the cobalt chemical sector as an intermediate requiring additional refinement. Secondary production, ie production from the recycling of cobalt-containing wastes, is considered in this study in so far as it occurs as part of the participating companies’ production. This was shown to be of very limited significance (less than 1% of cobalt inputs). The secondary materials used for producing cobalt are modelled as entering the system free of environmental burden. technologyComment of primary zinc production from concentrate (RoW): The technological representativeness of this dataset is considered to be high as smelting methods for zinc are consistent in all regions. Refined zinc produced pyro-metallurgically represents less than 5% of global zinc production and less than 2% of this dataset. Electrometallurgical Smelting The main unit processes for electrometallurgical zinc smelting are roasting, leaching, purification, electrolysis, and melting. In both electrometallurgical and pyro-metallurgical zinc production routes, the first step is to remove the sulfur from the concentrate. Roasting or sintering achieves this. The concentrate is heated in a furnace with operating temperature above 900 °C (exothermic, autogenous process) to convert the zinc sulfide to calcine (zinc oxide). Simultaneously, sulfur reacts with oxygen to produce sulfur dioxide, which is subsequently converted to sulfuric acid in acid plants, usually located with zinc-smelting facilities. During the leaching process, the calcine is dissolved in dilute sulfuric acid solution (re-circulated back from the electrolysis cells) to produce aqueous zinc sulfate solution. The iron impurities dissolve as well and are precipitated out as jarosite or goethite in the presence of calcine and possibly ammonia. Jarosite and goethite are usually disposed of in tailing ponds. Adding zinc dust to the zinc sulfate solution facilitates purification. The purification of leachate leads to precipitation of cadmium, copper, and cobalt as metals. In electrolysis, the purified solution is electrolyzed between lead alloy anodes and aluminum cathodes. The high-purity zinc deposited on aluminum cathodes is stripped off, dried, melted, and cast into SHG zinc ingots (99.99 % zinc). Pyro-metallurgical Smelting The pyro-metallurgical smelting process is based on the reduction of zinc and lead oxides into metal with carbon in an imperial smelting furnace. The sinter, along with pre-heated coke, is charged from the top of the furnace and injected from below with pre-heated air. This ensures that temperature in the center of the furnace remains in the range of 1000-1500 °C. The coke is converted to carbon monoxide, and zinc and lead oxides are reduced to metallic zinc and lead. The liquid lead bullion is collected at the bottom of the furnace along with other metal impurities (copper, silver, and gold). Zinc in vapor form is collected from the top of the furnace along with other gases. Zinc vapor is then condensed into liquid zinc. The lead and cadmium impurities in zinc bullion are removed through a distillation process. The imperial smelting process is an energy-intensive process and produces zinc of lower purity than the electrometallurgical process. technologyComment of treatment of used Li-ion battery, hydrometallurgical treatment (GLO): Shredder, followed by a chemical treatment in order to separate the various fractions produced technologyComment of treatment of used Li-ion battery, pyrometallurgical treatment (GLO): Crushing of the batteries, followed by a neutralization and a processing step.

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