Schwefelemissionen am stärksten gesunken - Feinstaub bleibt das Sorgenkind Die Emissionen von Luftschadstoffen in Deutschland sind seit 1990 teilweise drastisch gesunken: Bei Schwefelverbindungen (SO2) war 2010 ein Rückgang von 91,5 Prozent gegenüber 1990 zu verzeichnen, beim Staub 85,6 Prozent und beim Kohlenmonoxid 73,1 Prozent (jeweils im gleichen Zeitraum). Auch Schwermetalle und persistente organische Schadstoffe gelangen deutlich weniger in die Umwelt. Dies zeigt eine neue Erhebung des Umweltbundesamtes (UBA). Der gesundheitsschädliche Feinstaub und weitere Problemschadstoffe trüben aber weiter das insgesamt positive Gesamtbild: Die Feinstaubemissionen sinken zwar deutschlandweit, allerdings ist der Rückgang mit nur 30 Prozent gegenüber 1990 deutlich geringer als bei anderen Luftschadstoffen. Immer noch zu hoch sind auch die Emissionen der Stickstoffoxide und des Ammoniaks (minus 54,2 Prozent beziehungsweise minus 20,8 Prozent). UBA-Präsident Jochen Flasbarth drängt deshalb zu weiteren Anstrengungen: „Die Luftreinhaltung in Deutschland kennt zahlreiche Erfolgsgeschichten. Was uns beispielsweise beim Schwefeldioxid an großartigen Minderungen gelungen ist, müssen wir nun bei Feinstaub, Stickoxiden und Ammoniak fortsetzen.“ Den Grundstein für gesunde Luft in Europa legte die Genfer Luftreinhalte-Konvention, ein internationales Abkommen, das sich bereits 1979 über den „Eisernen Vorhang“ hinweg grenzüberschreitend wirkenden Luftschadstoffen annahm. Die EU-weite Festlegung nationaler Emissionshöchstmengen und der Umbau des Wirtschaftssystems in Osteuropa nach 1990 waren weitere Meilensteine. Zunehmend wurde auch die schwefelhaltige Braunkohle durch emissionsärmere Brennstoffe wie Steinkohle und Erdgas ersetzt - Kraftwerke wurden mit einer Abgasreinigung ausgestattet. Strengere Grenzwerte gab es auch für die Emissionen aus Industrieanlagen. Beim Straßenverkehr konnte die Festlegung sogenannter Euro-Normen (1 bis 5 für Pkw und I bis V für Lkw) die Emissionen aus Fahrzeugabgasen deutlich verringern. Für die Zukunft sind hier weitere Maßnahmen vorgesehen - etwa die Euro 6/VI-Norm für Personen- und Lastkraftwagen - die die Stickstoffoxidemissionen zusätzlich senken werden. Der Verkehr spielte auch bei der Abnahme der Schwermetallemissionen eine entscheidende Rolle. War 1990 verbleites Benzin noch an jeder Tankstelle zu haben, so ist seit dem Verbot des Verkaufs 1998 eine signifikante Reduktion der Emissionsmengen zu beobachten; zwischen 1990 und 2010 sanken die Bleiemissionen in Deutschland um nahezu 91 Prozent. Damit die Ammoniakemissionen aus der Landwirtschaft sinken, ist eine konsequente Anwendung der guten fachlichen Praxis nötig, also Einhaltung der Ausbringungsvorschriften für Düngemittel, sowie bei der Lagerung von Wirtschaftsdünger. Helfen können auch die Verbraucher, indem sie weniger Fleisch konsumieren. Die Emission schädlicher Schwermetalle wie Cadmium und Quecksilber ist mit minus 69 Prozent und minus 67 Prozent stark rückläufig. Die Trendverläufe für persistente organische Schadstoffe zeichnen ein ähnlich erfreuliches Bild - die Bandbreite reicht hier von ebenfalls minus 91 Prozent für Dioxine über minus 78 Prozent bei Benzo-a-Pyren (das durch unvollständige Verbrennung organischer Stoffe wie Holz oder Kohle entsteht) bis zu minus 35 Prozent für Hexachlorbenzol (dieses entsteht als unerwünschtes Nebenprodukt bei der Verbrennung organischer Materialien in Gegenwart von Chlorverbindungen). Das UBA aktualisiert seine Emissionsinventare für Luftschadstoffe jährlich. In diesem Jahr liegen erstmals Informationen für die gesamten zwei Dekaden seit der Wiedervereinigung vor. Hintergrund ist die Berichterstattung im Rahmen der Genfer Luftreinhaltekonvention. In diesem Rahmen werden die Emissionsfreisetzungen berechnet und an die internationalen Organisationen berichtet. Diese beinhalten dabei für den Zeitraum von 21 Jahren über 20 verschiedene Schadstoffe aus allen relevanten Emissionsquellen - von großen Kraftwerken über den Verkehr, Konsumprodukten bis hin zur Viehhaltung und Abfallwirtschaft.
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 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 processing of nickel-rich materials (GLO): Based on typical current technology. technologyComment of smelting and refining of nickel concentrate, 16% Ni (GLO): Extrapolated from a typical technology for smelting and refining of nickel ore. MINING: 95% of sulphidic nickel ores are mined underground in depths between 200m and 1800m, the ore is transferred to the beneficiation. Widening of the tunnels is mainly done by blasting. The overburden – material, which does not contain PGM-bearing ore – is deposed off-site and is partially refilled into the tunnels. Emissions: The major emissions are due to mineral born pollutants in the effluents. The underground mining operations generate roughly 80 % of the dust emissions from open pit operations, since the major dust sources do not take place underground. Rain percolate through overburden and accounts to metal emissions to groundwater. Waste: Overburden is deposed close to the mine. Acid rock drainage occurs over a long period of time. BENEFICIATION: After mining, the ore is first ground. In a next step it is subjected to gravity concentration to separate the metallic particles from the PGM-bearing minerals. After this first concentration step, flotation is carried out to remove the gangue from the sulphidic minerals. For neutralisation lime is added. In the flotation several organic chemicals are used as collector, frother, activator, depressor and flocculant. Sometimes cyanide is used as depressant for pyrite. Tailings usually are led to tailing heaps or ponds. As a result, nickel concentrates containing 7 - 25% Ni are produced. Emissions: Ore handling and processing produce large amounts of dust, containing PM10 and several metals from the ore itself. Flotation produce effluents containing several organic agents used. Some of these chemicals evaporate and account for VOC emissions to air. Namely xanthates decompose hydrolytically to release carbon disulphide. Tailings effluent contains additional sulphuric acid from acid rock drainage. Waste: Tailings are deposed as piles and in ponds. Acid rock drainage occurs over a long period of time. METALLURGY AND REFINING: There are many different process possibilities to win the metal. The chosen process depends on the composition of the ore, the local costs of energy carrier and the local legislation. Basically two different types can be distinguished: the hydrometallurgical and the pyrometallurgical process, which paired up with the refining processes, make up five major production routes (See Tab.1). All this routes are covered, aggregated according to their market share in 1994. imageUrlTagReplace00ebef53-ae97-400f-a602-7405e896cb76 Pyrometallurgy. The pyrometallurgical treatment of nickel concentrates includes three types of unit operation: roasting, smelting, and converting. In the roasting step sulphur is driven off as sulphur dioxide and part of the iron is oxidised. In smelting, the roaster product is melted with a siliceous flux which combines with the oxidised iron to produce two immiscible phases, a liquid silicate slag which can be discarded, and a solution of molten sulphides which contains the metal values. In the converting operation on the sulphide melt, more sulphur is driven off as sulphur dioxide, and the remaining iron is oxidised and fluxed for removal as silicate slag, leaving a high-grade nickel – copper sulphide matte. In several modern operations the roasting step has been eliminated, and the nickel sulphide concentrate is treated directly in the smelter. Hydrometallurgy: Several hydrometallurgical processes are in commercial operation for the treatment of nickel – copper mattes to produce separate nickel and copper products. In addition, the hydrometal-lurgical process developed by Sherritt Gordon in the early 1950s for the direct treatment of nickel sulphide concentrates, as an alternative to smelting, is still commercially viable and competitive, despite very significant improvements in the economics and energy efficiency of nickel smelting technology. In a typical hydrometallurgical process, the concentrate or matte is first leached in a sulphate or chloride solution to dissolve nickel, cobalt, and some of the copper, while the sulphide is oxidised to insoluble elemental sulphur or soluble sulphate. Frequently, leaching is carried out in a two-stage countercurrent system so that the matte can be used to partially purify the solution, for example, by precipitating copper by cementation. In this way a nickel – copper matte can be treated in a two-stage leach process to produce a copper-free nickel sulphate or nickel chloride solution, and a leach residue enriched in copper. Refining: In many applications, high-purity nickel is essential and Class I nickel products, which include electrolytic cathode, carbonyl powder, and hydrogen-reduced powder, are made by a variety of refining processes. The carbonyl refining process uses the property of nickel to form volatile nickel-carbonyl compounds from which elemental nickel subsides to form granules. Electrolytic nickel refineries treat cast raw nickel anodes in a electrolyte. Under current the anode dissolves and pure nickel deposits on the cathode. This electrorefining process is obsolete because of high energy demand and the necessity of building the crude nickel anode by reduction with coke. It is still practised in Russia. Most refineries recover electrolytic nickel by direct electrowinning from purified solutions produced by the leaching of nickel or nickel – copper mattes. Some companies recover refined nickel powder from purified ammoniacal solution by reduction with hydrogen. Emissions: In all of the metallurgical steps, sulphur dioxide is emitted to air. Recovery of sulphur dioxide is only economic for high concentrated off-gas. Given that In the beneficiation step, considerable amounts of lime are added to the ore for pH-stabilisation, lime forms later flux in the metallurgical step, and decomposes into CO2 to form calcite. Dust carry over from the roasting, smelting and converting processes. Particulate emissions to the air consist of metals and thus are often returned to the leaching process after treatment. Chlorine is used in some leaching stages and is produced during the subsequent electrolysis of chloride solution. The chlorine evolved is collected and re-used in the leach stage. The presence of chlorine in wastewater can lead to the formation of organic chlorine compounds (AOX) if solvents etc. are also present in a mixed wastewater. VOCs can be emitted from the solvent extraction stages. A variety of solvents are used an they contain various complexing agents to form complexes with the desired metal that are soluble in the organic layer. Metals and their compounds and substances in suspension are the main pollutants emitted to water. The metals concerned are Cu, Ni, Co, As and Cr. Other significant substances are chlorides and sulphates. Wastewater from wet gas cleaning (if used) of the different metallurgical stages are the most important sources. The leaching stages are usually operated on a closed circuit and drainage systems, and are therefore regarded as minor sources. In the refining step, the combustion of sulphur leads to emissions of SO2. Nitrogen oxides are produced in significant amounts during acid digestion using nitric acid. Chlorine and HCl can be formed during a number of digestion, electrolytic and purification processes. Chlorine is used extensively in the Miller process and in the dissolution stages using hydrochloric acid and chlorine mixtrues respectively. 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. Large quantities of effluents contain amounts of metals and organic substances. Waste: Regarding the metallurgical step, several co-products, residues and wastes, which are listed in the European Waste Catalogue, are generated. Some of the process specific residues can be reused or recovered in preliminary process steps (e. g. dross, filter dust) or construction (e. g. cleaned slag). Residues also arise from the treatment of liquid effluents, the main residue being gypsum waste and metal hydroxides from the wastewater neutralisation plant. These residuals have to be disposed, usually in lined ponds. In the refining step, quantities of solid residuals are also 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 (ironhydroxide, 60% water, cat I industrial waste). References: Kerfoot D. G. E. (1997) Nickel. In: Ullmann's encyclopedia of industrial chemis-try (ed. Anonymous). 5th edition on CD-ROM Edition. Wiley & Sons, London. technologyComment of smelting and refining of nickel concentrate, 7% Ni (CN): The nickel concentrate (6.78% beneficiated - product of the mining and beneficiation processes) undergoes drying, melting in flash furnace and converting to produce high nickel matte. The nickel matte undergoes grinding-floating separation and is refined through anode plate casting and electrolysis in order to produce electrolytic nickel 99.98% pure. Deng, S. Y., & Gong, X. Z. (2018). Life Cycle Assessment of Nickel Production in China. Materials Science Forum, 913, 1004-1010. doi:10.4028/www.scientific.net/MSF.913.1004 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 ethylene oxide production (RER): Ethylene is directly oxidized with air or oxygen in the presence of a catalyst to ethylene oxide (EO). About 40% of all European EO production is converted into glycols, globally the figure is about 70%. Usually, EO and MEG are produced together at integrated plants. Industrial production started in 1937 with a union Carbide process based on ethylene and air. In 1958 oxygen rather than air was instroduced by Shell Development Company, and today most processes are based on oxygen. Total European production was 3.4 million tons per year in 1997, while the US produced 5.2 million tons per year. Further production capacity of at least 1.2 million tons is reported from Saudi Arabia, Kuwait, Japan and South Korea giving a total of at least 9.8 million tons of ethylene oxide production worldwide. Ethylene oxide is a hydrocarbon compound made from ethylene and oxygen. Major manufacturers include Hoechst Celanese, Shell Chemical, and Union Carbide, among many others. EO is produced by passing a mixture of ethylene and oxygen over a solid silver-containing catalyst. Selectivity is improved by the addition of chlorine compounds such as chloroethane. Reaction conditions are temperatures of about 200 - 300 °C and a pressure of 10 – 30 bar. The main by-products are carbon dioxide and water, formed when ethylene is fully oxidised or some of the EO is further oxidised. Ethylene glycols are formed when the reactor gases are absorbed into chilled water. C2H4 + 1/2 O2 C2H4O (1) C2H4 O + H2O HO-C2H4-OH (2) C2H4 + 3 O2 2 CO2 + 2 H2O (3) (1) production of ethylene oxide (2) production of MEG from EO and water (3) production of carbon dioxide and water from oxidation of ethylene The carbon dioxide is removed from the scrubber by absorption with hot aqueous potassium carbonate, the resulting solution is steam stripped to remove the carbon dioxide, which is vented to air. The potassium carbonate is regenerated. The carbon dioxide can be reused for inerting, or is sold, or is vented to atmosphere. References: IPPC Chemicals, 2002. European Commission, Directorate General, Joint Research Center, “Reference Document on Best Available Techniques in the Large Volume Organic Chemical Industry”, February 2002. Wells, 1999. G. Margaret Wells, “Handbook of Petrochemicals and Processes”, 2nd edition, Ashgate, 1999
technologyComment of Mannheim process (RER): Production of sodium sulfate and HCl by the Mannheim process. This process can be summarized with the following overall stoechiometric reaction: 2 NaCl + H2SO4 → Na2SO4 + 2 HCl technologyComment of allyl chloride production, reaction of propylene and chlorine (RER): based on industry data in the US and Europe technologyComment of benzene chlorination (RER): Clorobenzenes are prepared by reaction of liquid benzene with gaseous chlorine in the presence of a catalyst at moderate temperature and atmospheric pressure. Hydrogen chloride is formed as a by-product. Generally, mixtures of isomers and compounds with varying degrees of chlorination are obtained, because any given chlorobenzene can be further chlorinated up to the stage of hexa-chlorobenzene. Because of the directing influence exerted by chlorine, the unfavoured products 1,3-dichlorobenzene, 1,3,5-trichlorobenzene and 1,2,3,5-tetrachlorobenzene are formed to only a small extent if at all. The velocity of chlorination for an individual chlorine compound depends on the compound's structure and, because of this, both the degree of chlorination and also the isomer ratio change continuously during the course of reaction. Sets of data on the composition of products from different reactions are only comparable if they refer to identical reaction conditions and materials having the same degree of chlorination. By altering the reaction conditions and changing the catalyst, one can vary the ratios of different chlorinated products within certain limits. Lewis acids (FeCl3, AlCl3, SbCl3, MnCl2, MoCl2, SnCl4, TiCl4) are used as principal catalysts. The usual catalyst employed in large scale production is ferric chloride, with or without the addition of sulfur compounds. The ratio of resulting chlorobenzenes to one another is also influenced by the benzene:chlorine ratio. For this reason, the highest selectivity is achieved in batch processes. If the same monochlorobenzene:dichlorobenzene ratio expected from a batch reactor is to result from continuous operation in a single-stage reactor, then a far lower degree of benzene conversion must be accepted as a consequence of the low benzene:chlorine ratio). The reaction is highly exothermic: C6H6 + Cl2 --> C6H5Cl + HCl ; delta H = -131.5 kJ/mol Unwanted heat of reaction can be dissipated either by circulating some of the reactor fluid through an external heat exchanger or by permitting evaporative cooling to occur at the boiling temperature. Circulation cooling has the advantage of enabling the reaction temperature to be varied in accordance with the requirements of a given situation. Evaporative cooling is more economical, however. Fractional distillation separates the products. Iron catalyst is removed with the distillation residue.Unreacted benzene is recycled to the reactor. technologyComment of hydrochloric acid production, from the reaction of hydrogen with chlorine (RER): HCl can be either directly prepared or generated as a by-product from a number of reactions. This dataset represents the production of HCl via the combustion of chlorine with hydrogen gas. The process involves burning hydrogen gas and chlorine in a gas combustion chamber, producing hydrogen chloride gas. The hydrogen chloride gas then passes through a cooler to an absorber where process water is introduced, producing aqueous hydrochloric acid. H2 + Cl2 -> 2 HCl (exothermic reaction) References: Althaus H.-J., Chudacoff M., Hischier R., Jungbluth N., Osses M. and Primas A. (2007) Life Cycle Inventories of Chemicals. ecoinvent report No. 8, v2.0. EMPA Dübendorf, Swiss Centre for Life Cycle Inventories, Dübendorf, CH. technologyComment of tetrafluoroethylene production (RER): The production of fluorochemicals and PTFE monomers can be summarized with the following chemical reactions (Cedergren et al. 2001): CaF2 + H2SO4 -> CaSO4 + 2HF (1) CH4 + 3Cl2 -> CHCl3 + 3HCl (2) CHCl3 + 2HF -> CHClF2 + 2HCl (3) 2 CHClF2 + heat -> CF2=CF2 + 2 HCl (4) This dataset represents the last reaction step (4). Parts of the production are carried out at high pressure and high temperature, 590 ºC – 900 ºC. The first reaction (1) takes place in the presence of heat and HSO3 - and steam. The inventory for the production of hydrogen fluoride can be found in the report (Jungbluth 2003a). Reaction (2) is used to produce trichloromethane. Reaction 3 for the production of chlorodifluoromethane takes place in the presence of a catalyst. The production of PTFE (4) takes place under high temperature pyrolysis conditions. Large amounts of hydrochloric acid (HCl) are generated as a couple product during the process and are sold as a 30% aqueous solution. A large number of other by-products and emissions is formed in the processes (benzene, dichloromethane, ethylene oxide, formaldehyde, R134a, and vinyl chloride) and small amounts of the highly toxic perfluoroisobutylene CF2=C(CF3)2. The by-products in the production of monomers can harm the processes of polymerisation. Because of this, the refinement of the production of monomers has to be very narrow. This makes the process complex and it contributes to a high cost for the PTFE-laminates. (Cedergren et al. 2001). References: Althaus H.-J., Chudacoff M., Hischier R., Jungbluth N., Osses M. and Primas A. (2007) Life Cycle Inventories of Chemicals. Final report ecoinvent data v2.0 No. 8. Swiss Centre for Life Cycle Inventories, Dübendorf, CH.
Polychlorierte Biphenyle PCB Formel: C12H10-xClx Erläuterung: Persistente und toxische Chlorverbindungen
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