Schulze, Tobias; Ricking, Mathias; Schröter-Kermani, Christa; Körner, Andrea; Denner, Hans-Dietrich; Weinfurtner, Karlheinz; Winkler, Andreas; Pekdeger, Asaf Journal of Soils and Sediments 7 (2007), 6, 361-367 Goal, Scope and Background. The European Water Framework Directive implies a risk based sediment management. In this approach sediments are recognised as secondary sources of contaminants, and suspended particulate matter (SPM) as the carrier. For that reason the concept of the German Environmental Specimen Bank (ESB) includes the establishment of these specimens. The ESB is characterised by a high quality assurance system of standard operation procedures (SOP) to preserve the integrity of the specimens under cryogenic conditions for transportation, storage and handling. The aim of this study was (1) the development and validation of SOPs for the collection of sediment and SPM, and (2) the adaptation and standardisation of sampling techniques for the ESB. This paper provides information about sediment and SPM as new specimens in the ESB. Methods. A redesigned freeze-coring device was tested and applied to collect unconsolidated sediments at the fresh water sampling sites of the German ESB. Liquid nitrogen was used as a cooling agent. Sediment cores were cut on site using a stainless steel saw or an angle grinder with a diamond blade, stored in stainless steel containers and transported to the depot of the ESB inside a nitrogen vapour freezer. SPM was collected using passive sedimentation boxes (SBs). The SBs were installed permanently in surface waters or monitoring stations. Sampling of SPM was performed monthly and the SPM was subsequently frozen on site, stored in stainless steel containers and transported to the depot of the ESB in a nitrogen vapour freezer. At two locations the comparability of this method with sampling using a continuous-flow centrifuge Padberg Z61 was investigated. Results and Discussion. The sediments at almost all fluvial sampling sites of the ESB are sapropel or Gyttja type. The use of a freeze-coring device allowed sampling of these unconsolidated sediments under the conditions of ESB. The device was not applicable at two locations due to tidal influence and fine-grained sediments, respectively due to the depth in case of Lake Belau (~28 m). In these cases piston corers were used for sediment sampling. The collection of time-integrated SPM samples using SBs achieves the approach of the ESB. In comparison, the Padberg Z61 provides only samples, which are representative for the short collection period of 8-10 h (snapshot). A shortcoming of SBs is a possible alteration of SPM during the sampling period of about 4 weeks. However, alteration of the samples is not as evident as shorter collection periods and usage of a Padberg Z61 causes technical and economic difficulties. Conclusions. The modified freeze-coring device and the sedimentation boxes are applicable for the collection of sediment and SPM samples within the framework of the ESB. The chosen sampling and handling techniques attain the requirements of the ESB. Consequently, routine collection and storage of sediment cores and SPM started in 2005. According to our knowledge, the German ESB is the first of all specimen banks worldwide that routinely collects and stores SPM and that applies in situ freeze-coring to collect sediment cores. Perspectives. The collection and storage of sediments and SPM as new specimens in the ESB enhances the possibilities to control the efficacy of the European Water Framework Directive, REACh, and similar regulations and to take further action. doi: 10.1065/jss2007.08.24
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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.
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 gold-silver mine operation with refinery (PG): 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 recovery processes of the Misima Mine are cyanide leach and carbon in pulp (CIP). 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: The recovery process in the Porgera Mine is pressure oxidation and cyanide leach. 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. WATER SUPPLY: For Misima Mine, process water is supplied from pit dewatering bores and in-pit water. Potable water is sourced from boreholes in the coastal limestone. For Porgera Mine, the main water supply of the mine is the Waile Creek Dam, located approximately 7 kilometres from the mine. The reservoir has a capacity of approximately 717, 000 m3 of water. Water for the grinding circuit is also extracted from Kogai Creek, which is located adjacent to the grinding circuit. The mine operates four water treatment plants for potable water and five sewage treatment plants. ENERGY SUPPLY: For Misima Mine, electricity is produced by the mine on site or with own power generators, from diesel and heavy fuel oil. For Porgera Mine, electricity is produced by the mine on site. Assumed with Mobius / Wohlwill electrolysis. Porgera's principal source of power is supplied by a 73-kilometre transmission line from the gas fired and PJV-owned Hides Power Station. The station has a total output of 62 megawatts (“MW”). A back up diesel power station is located at the mine and has an output of 13MW. The average power requirement of the mine is about 60 MW. For both Misima and Porgera Mines, an 18 MW diesel fired power station supplies electrical power. Diesel was used in the station due to the unavailability of previously supplied heavy fuel oil. technologyComment of gold-silver mine operation with refinery (CA-QC): One of the modelled mine is an open-pit mine and the two others are underground. technologyComment of gold-silver mine operation with refinery (RoW): The mining of ore from open pit mines is considered. 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 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 silver-gold mine operation with refinery (CL): 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. BENEFICIATION: The processing plant consists of primary crushing, a pre-crushing circuit, (semi autogenous ball mill crushing) grinding, leaching, filtering and washing, Merrill-Crowe plant and doré refinery. The Merrill-Crowe metal recovery circuit is better than a carbon-in-pulp system for the high-grade silver material. Tailings are filtered to recover excess water as well as residual cyanide and metals. A dry tailings disposal system was preferred to a conventional wet tailings impoundment because of site-specific environmental considerations. technologyComment of silver-gold mine operation with refinery (RoW): Refinement is estimated with electrolysis-data. technologyComment of treatment of crust from Parkes process for lead production (GLO): Processing of Parkes desilvering crust by hot pressing, dezincing (vacuum distillation), cupellation of lead and moebius electrolysis (electrowinning) 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 technologyComment of treatment of waste x-ray film (GLO): None
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.
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 natural gas production (CA-AB): Canadian data completed with german data. The uncertainty has been adjusted accordingly. Data used in original data contains no information on technology. technologyComment of natural gas production (DE): Data in environmental report contains no information on technology. technologyComment of natural gas production (RoW): The data describes an average onshore technology for natural gas to 13% out of combined oil gas production. Natural gas is assumed to 20% sour. Leakage in exploitation is estimated at 0.38% and production 0.12%. It is further assumed that about 30% of the produced water is discharged in surface water. Water emissions are differentiated between combined oil and gas production and gas production. technologyComment of natural gas production (RU): The data describes an average onshore technology for natural gas with a share of 4% out of combined oil gas production and 96% from mere natural gas production. Natural gas is assumed to 20% sour. It is assumed that about 30% of the produced water is discharged in surface water. Water emissions are differentiated between combined oil and gas production and gas production. technologyComment of natural gas production (US): US data (NREL) for emissions completed with german data. Emissions from NREL include combined production (petroleumm and gas) and off-shore production. The uncertainty has been adjusted accordingly. Data used in original data contains no information on technology. technologyComment of petroleum refinery operation (CH): Average data for the used technology. 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 rare earth oxides production, from rare earth oxide concentrate, 70% REO (CN-SC): This dataset refers to the separation (hydrochloric acid leaching) and refining (metallothermic reduction) process used in order to produce high-purity rare earth oxides (REO) from REO concentrate, 70% beneficiated. ''The concentrate is calcined at temperatures up to 600ºC to oxidize carbonaceous material. Then HCl leaching, alkaline treatment, and second HCl leaching is performed to produce a relatively pure rare earth chloride (95% REO). Hydrochloric acid leaching in Sichuan is capable of separating and recovering the majority of cerium oxide (CeO) in a short process. For this dataset, the entire quantity of Ce (50% cerium dioxide [CeO2]/REO) is assumed to be produced here as CeO2 with a grade of 98% REO. Foreground carbon dioxide CO2 emissions were calculated from chemical reactions of calcining beneficiated ores. Then metallothermic reduction produces the purest rare earth metals (99.99%) and is most common for heavy rare earths. The metals volatilize, are collected, and then condensed at temperatures of 300 to 400°C (Chinese Ministryof Environmental Protection 2009).'' Source: Lee, J. C. K., & Wen, Z. (2017). Rare Earths from Mines to Metals: Comparing Environmental Impacts from China's Main Production Pathways. Journal of Industrial Ecology, 21(5), 1277-1290. doi:10.1111/jiec.12491 technologyComment of scandium oxide production, from rare earth tailings (CN-NM): See general comment. technologyComment of sulfur production, petroleum refinery operation (Europe without Switzerland): The technology level in Europe applied here represents a weighted average of BREF types II (62%), III (29%), IV (9%) refineries; API 35; sulfur content 1.03%. technologyComment of sulfur production, petroleum refinery operation (PE): The technology represents BREF type II refinery; API 25; sulfur content 0.51% technologyComment of sulfur production, petroleum refinery operation (BR): The technology represents BREF type II refinery; API 25; sulfur content 0.57% technologyComment of sulfur production, petroleum refinery operation (ZA): The technology represents a weighted average of BREF types II and III refineries; API 35; sulfur content 0.7% technologyComment of sulfur production, petroleum refinery operation (CO): The technology represents a weighted average of BREF types II and IV refineries; API 35; sulfur content 0.56% technologyComment of sulfur production, petroleum refinery operation (IN): The technology represents a weighted average of BREF types II and IV refineries; API 35; sulfur content 1.39% technologyComment of sulfur production, petroleum refinery operation (RoW): This dataset represents the prevailing technology level in Europe, this is a weighted average of BREF complexity types II (62%), III (29%), IV (9%) refineries (see BREF document, European Commission, 2015); API 35; sulfur content 1.03%. Reference(s): European Commission (2015) Best Available Techniques (BAT) Reference Document (BREF) for the Refining of Mineral Oil and Gas, Industrial Emissions Directive 2010/75/EU Integrated Pollution Prevention and control, accessible online at http://eippcb.jrc.ec.europa.eu/reference/BREF/REF_BREF_2015.pdf, February 2019 technologyComment of synthetic fuel production, from coal, high temperature Fisher-Tropsch operations (ZA): SECUNDA SYNFUEL OPERATIONS: Secunda Synfuels Operations operates the world’s only commercial coal-based synthetic fuels manufacturing facility of its kind, producing synthesis gas (syngas) through coal gasification and natural gas reforming. They make use of their proprietary technology to convert syngas into synthetic fuel components, pipeline gas and chemical feedstock for the downstream production of solvents, polymers, comonomers and other chemicals. Primary internal customers are Sasol Chemicals Operations, Sasol Exploration and Production International and other chemical companies. Carbon is produced for the recarburiser, aluminium, electrode and cathodic production markets. Secunda Synfuels Operations receives coal from five mines in Mpumalanga (see figure attached). After being crushed, the coal is blended to obtain an even quality distribution. Electricity is generated by both steam and gas and used to gasify the coal at a temperature of 1300°C. This produces syngas from which two types of reactor - circulating fluidised bed and Sasol Advanced SynthoTM reactors – produce components for making synthetic fuels as well as a number of downstream chemicals. Gas water and tar oil streams emanating from the gasification process are refined to produce ammonia and various grades of coke respectively. imageUrlTagReplacea79dc0c2-0dda-47ec-94e0-6f076bc8cdb6 SECUNDA CHEMICAL OPERATIONS: The Secunda Chemicals Operations hub forms part of the Southern African Operations and is the consolidation of all the chemical operating facilities in Secunda, along with Site Services activities. The Secunda Chemicals hub produces a diverse range of products that include industrial explosives, fertilisers; polypropylene, ethylene and propylene; solvents (acetone, methyl ethyl ketone (MEK), ethanol, n-Propanol, iso-propanol, SABUTOL-TM, PROPYLOL-TM, mixed C3 and C4 alcohols, mixed C5 and C6 alcohols, High Purity Ethanol, and Ethyl Acetate) as well as the co-monomers, 1-hexene, 1-pentene and 1-octene and detergent alcohol (SafolTM).
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.
technologyComment of titanium production (GLO): Primary titanium metal is produced mainly by Kroll process. In this batch process, titanium tetrachloride (TiCl4) is reduced with magnesium under inert atmosphere creating a sponge like titanium metal solid which is refined by vaccum arc remelting. The Kroll process is characterized by multiple steps for which many are energy and labor intensive. Main steps include batch reduction, processing, vaccum distillation and remelting. Main batch reduction takes place in a steel reactor filled with argon where the magnesium is melt at temperature between 850°C-950°C. The titanium chloride (TiCl4) is fed, or blown in as vapor, into the reactor. The reduction is a highly exothermic reaction, thus little energy input is required for it to take place. Reaction is as follow: TiCl4(l or g) + 2 Mg(l) = Ti(s) + 2 MgCl2(l). During the processing the reaction by-product, molten magnesium chloride (MgCl2), is remove from the reator periodically during the reaction. The magnesium and clhoride from this by-product are recovered using electrolysis and re-used. Main product from the process is a sponge like titanium (Ti(0)). Vaccum distillation is then use to purified the crude sponge removing residual metal chlorides and magnesium. This process takes place at temperature between 900°C and 1000°C. The residuals are recovered by condensation. The purified titanium sponge is refined using vacuum arc remelting.
technologyComment of aluminium alloy production, AlLi (CA-QC, RoW): No comment present technologyComment of aluminium alloy production, Metallic Matrix Composite (CA-QC, RoW): No comment present 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 copper production, cathode, solvent extraction and electrowinning process (GLO): Oxide ores and supergene sulphide ores (i.e. ores not containing iron) can be recovered most easily by hydro-metallurgical techniques, such as SX-EW. The general steps of mining and refining are identical to those of copper mine operation and primary copper production, respectively. The difference lies in that the beneficiation and smelting stages are by-passed and substituted with a leaching stage followed by cementation or electro-winning. technologyComment of electrorefining of copper, anode (GLO): Based on typical current technology. 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 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 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 copper cake (GLO): 'The ore is pre-treated, reduced and refined according to the country specific mix of process alternatives: reverberatory furnace 23.7%; flash smelting furnaces 60.7%; other 6.2%.; SX-EW 9.4%. An overall abatement for sulphur dioxide of 45.4% was estimated.' as cited in original dataset. technologyComment of treatment of copper scrap by electrolytic refining (RoW): In three different stages different types of copper scrap and 10% of the feed of blister copper are refined to copper cathodes. Waste water is led to a communal treatment plant. technologyComment of treatment of copper scrap by electrolytic refining (RER): 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 technologyComment of treatment of metal part of electronics scrap, in copper, anode, by electrolytic refining (SE, RoW): Production of cathode copper by electrolytic refining. 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). technologyComment of treatment of non-Fe-Co-metals, from used Li-ion battery, pyrometallurgical processing (GLO): Based on technology that treats anode slime by pressure leaching and top blown rotary converter. technologyComment of treatment of used cable (GLO): Shredder, followed by a modern grinding machine with current separation technology
technologyComment of cyclohexane production (RER, RoW): Over 90 % of all cyclohexane is produced commercially by hydrogenation of benzene. A small amount is produced by superfractionation of the naphtha fraction from crude oil. Naturally occurring cyclohexane can be supplemented by fractionating methylcyclopentane from naphtha and isomerizing it to cyclohexane. Hydrogenation of benzene: Benzene can be hydrogenated catalytically to cyclohexane in either the liquid or the vapor phase in the presence of hydrogen. Several cyclohexane processes, which use nickel, platinum, or palladium as the catalyst, have been developed. Usually, the catalyst is supported, e.g., on alumina, but at least one commercial process utilizes Raney nickel. Hydrogenation proceeds readily and is highly exothermic (Δ H500K = – 216.37 kJ/mol). From an equilibrium standpoint, the reaction temperature should not exceed 300 °C. Above this, the equilibrium begins to shift in favor of benzene so that high-purity cyclohexane cannot be produced. As a result of these thermodynamic considerations, temperature control of the reaction is critical to obtaining essentially complete conversion of benzene to cyclohexane. Temperature control requires economic and efficient heat removal. This has been addressed in a number of ways by commercial processes. The earlier vapor-phase processes used multistage reactors with recycle of cyclohexane as a diluent to provide a heat sink, staged injection of benzene feed between reactors, and interstage steam generators to absorb the exothermic heat of hydrogenation. In the 1970s processes have been developed that use only one reactor or a combination of a liquid-and a vaporphase reactor. The objectives of the later processes were to reduce capital cost and improve energy utilization. However, all of the commercial processes have comparably low capital cost and good energy efficiency. In the vapor-phase process with multistage reactors in series, the benzene feed is divided and fed to each of the first two reactors. Recycled cyclohexane is introduced to the first reactor along with hydrogen. The recycled cyclohexane enables higher conversion in the reactors by absorbing part of the heat of hydrogenation. Steam generators between the reactors remove the heat of hydrogenation. The outlet temperature of the last reactor is controlled to achieve essentially 100 % conversion of benzene to cyclohexane. The effluent from the last reactor is cooled, and the vapor and liquid are separated. Part of the hydrogen-rich vapor is recycled to the first reactor, and the rest is purged to fuel gas or hydrogen recovery facilities. The liquid from the separator goes to a stabilizer where the overhead gas is sent to fuel gas; the remaining material is cyclohexane product, part of which is recycled to the first reactor. In the process with liquid- and vapor-phase reactors, benzene and hydrogen are fed to the liquid-phase reactor, which contains a slurry of finely divided Raney nickel. Temperature is maintained at 180 – 190 °C by pumping the slurry through a steam generator and by vaporization in the reactor. Roughly 95 % of the benzene is converted in this reactor. The vapor is fed to a fixed-bed reactor where the conversion of benzene is completed. The effluent from the fixed-bed reactor is processed as described previously for the vapor-phase process. Benzene hydrogenation is done typically at 20 – 30 MPa. The maximum reactor temperature is limited to ca. 300 °C so that a typical specification of < 500 mg/kg benzene and < 200 mg/kg methylcyclopentane in the product can be achieved. This is necessary because of the thermodynamic equilibrium between cyclohexane – benzene and cyclohexane – methylcyclopentane. Actually, equilibrium strongly favors methylcyclopentane, but the isomerization reaction is slow enough with the catalysts employed to avoid a problem if the temperature is controlled. The hydrogen content of the makeup hydrogen has no effect on product purity but it does determine the makeup, recycle, and purge gas rates. Streams with as low as 65 vol % hydrogen can be used. Carbon monoxide and sulfur compounds are catalyst deactivators. Both can be present in the hydrogen from catalytic naphtha reformers or ethylene units, which are typical sources of makeup hydrogen. Therefore, the hydrogen-containing stream is usually passed through a methanator to convert carbon monoxide to methane and water. Prior to methanation, hydrogen-containing gas can be scrubbed with caustic to remove sulfur compounds. Commercial benzene contains less than 1 mg/kg sulfur. In some cases, the recycle gas is also scrubbed with caustic to prevent buildup of hydrogen sulfide from the small amount of sulfur in the benzene. With properly treated hydrogen and specification benzene, a catalyst life in excess of three years can be achieved easily in fixed-bed reactors that use noble-metal catalysts supported on a base. The catalyst in the process that uses Raney nickel in suspension is reported to have a typical life of about six months before it must be replaced. Reference: Campbell, M. L. 2011. Cyclohexane. Ullmann's Encyclopedia of Industrial Chemistry.
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