Umweltbundesamt begrüßt Fortschritte im internationalen Chemikalienmanagement und mahnt weiter zur Wachsamkeit Am 03. Dezember 1984 ereignete sich in der indischen Stadt Bhopal in einem Betrieb der Union Carbide India Ltd ein folgenschwerer Chemieunfall. Wegen zahlreicher Mängel, Fehler und nicht funktionierender Sicherheitseinrichtungen, gelangte eine Gaswolke aus 20 bis 30 Tonnen des sehr giftigen Zwischenproduktes Methylisocyanat in die Atmosphäre. In der ersten Woche starben mindestens 2.500 Menschen und 500.000 wurden zum Teil schwer verletzt. Noch Jahre später waren bis zu 50.000 Menschen in Folge des Unfalls behindert und die Sterblichkeitsrate in der Bevölkerung erhöht. In Bhopal lebten zum Zeitpunkt des Unglücks etwa 700.000 Menschen, davon ca. 130.000 in unmittelbarer Nähe zum Betrieb. Das Unglück ist die bis heute schlimmste Chemiekatastrophe. „Der Preis für Industriekatastrophen wie in Bhopal ist so hoch, dass die Lehren daraus nicht in Vergessenheit geraten dürfen. Auch in Deutschland und Europa müssen wir immer wieder kritisch prüfen, ob wir genug für die Sicherheit unserer chemischen Anlagen tun”, sagte Jochen Flasbarth, Präsident des Umweltbundesamtes (UBA). Das Bhopal-Unglück löste weltweit Aktivitäten aus, chemische Betriebe sicherer zu machen. Bereits aufgrund früherer Störfälle, wie dem in der italienischen Stadt Seveso 1976, schuf Deutschland 1980 mit der Störfall-Verordnung und 1982 die EU in der Seveso-Richtlinie ein übergreifendes Anlagensicherheitsrecht. Die Störfall-Verordnung fordert ein stringentes Sicherheitskonzept, um Störfälle zu verhindern oder deren Auswirkungen zu begrenzen. Systematische sicherheitsanalytische Untersuchungen industrieller Produktionsverfahren und Anlagen sind heute Standard. Unterstützt werden diese Fortschritte durch Informationspflichten nach der europäischen Chemikalienverordnung REACH , wonach Chemikalienhersteller auch Zwischenprodukte bei der Europäischen Chemikalienagentur registrieren müssen. Methylisocyanat, das in Bhopal zur Katastrophe führte, ist ein Beispiel dafür. Unternehmen in Industriestaaten müssen auch Verantwortung für die Sicherheit ihrer Chemieanlagen in weniger entwickelten Ländern übernehmen. Sicherheitsstandards dürfen nicht geringer als in Europa oder Nordamerika sein. Dafür wurden von der Organisation für Ökonomische Zusammenarbeit und Entwicklung ( OECD ) und der Wirtschaftskommission für Europa der Vereinten Nationen ( UNECE ) Leitfäden erarbeitet. Diese fordern bei dortigen Investitionen gleiche Sicherheitsniveaus wie in Industriestaaten. Dies gilt auch für deutsche Unternehmen. Ob die Empfehlungen immer befolgt werden, ist bisher nicht geprüft. Die zunehmende Vernetzung der internationalen Chemikalienproduktion demonstriert, wie wichtig internationale Sicherheitsstandards in der Chemikalienproduktion sind. Geringere Standards dürfen kein Wettbewerbsvorteil sein. Internationale Übereinkommen zum Chemikalienmanagement nehmen dazu auch die Industriestaaten in die Pflicht: So dürfen nach dem Rotterdamer Übereinkommen (Prior Informed Consent Procedure = PIC) gefährliche Chemikalien nur mit Informationen zu ihren Wirkungen auf die menschliche Gesundheit und die Umwelt und nicht ohne vorherige Zustimmung durch das Empfängerland exportiert werden. Das Umweltbundesamt unterstützt durch Fachinformationen die Fortentwicklung dieses Übereinkommens. Das Umweltbundesamt ist der Meinung, dass die Sicherheit der Chemikalienproduktion noch weiter verbessert werden muss. Erkenntnisse aus der Katastrophe in Bhopal sollten noch mehr beachtet werden, indem man zum Beispiel:
Aus der amerikanischen Pestizidfabrik Union Carbide Corporation in Bhopal (Indien) entweicht aus einem lecken Tank Methylisocyanat. Die Folgen sind 3 400 Tote und ca. 200 000 Schwerverletzte.
technologyComment of manganese production (RER): The metal is won by electrolysis (25%) and electrothermic processes (75%). ELECTROLYSIS OF AQUEOUS MANGANESE SALTS The production of manganese metal by the electrolysis of aqueous manganese salts requires at first a milling of the manganese ore. Milling increases the active surface and ensures sufficient reactivity in both the reduction and the subsequent leaching steps. After milling the manganese ore is fed to a rotary kiln where the reduction and calcination takes place. This process is carried out at about 850 - 1000 ºC in a reducing atmosphere. As a reducing agent, several carbon sources can be used e.g. anthracite, coal, charcoal and hydrocarbon oil or natural gas. The cal-cined ore needs to be cooled below 100 ºC to avoid a further re-oxidation. The subsequent leaching process is carried out with recycled electrolyte, mainly sulphuric acid. After leaching and filtration the iron content is removed from the solution by oxidative precipitation and the nickel and cobalt are removed by sulphide precipitation. The purified electrolyte is then treated with SO2 in order to ensure plating of γ-Mn during electrolysis. Electrolysis is carried out in diaphragm cells. The cathode is normally made of stainless steel or titanium. For the anode lead-calcium or lead-silver alloy can be used. After an appropriate reaction time the cathodes are removed from the electrolysis bath. The manganese that is deposited on the cathode starter-sheet is stripped off mechanically and then washed and dried. The metal is crushed to produce metal flakes or powder or granulated, depending on the end use. ELECTROTHERMAL DECOMPOSITION OF MANGANESE ORES The electrothermal process is the second important process to produce manganese metal in an industrial scale. The electrothermal process takes place as a multistage process. In the first stage manganese ore is smelted with only a small amount of reductant in order to reduce mostly the iron oxide. This produces a low-grade ferro-manganese and a slag that is rich in Mn-oxide. The slag is then smelted in the second stage with silicon to produce silicomanganese. The molten silicomanganese can be treated with liquid slag from the fist stage to obtain relatively pure manganese metal. For the last step a ladle or shaking ladle can be used. The manganese metal produced by the electrothermal process contains up to 98% of Mn. Overall emissions and waste: Emissions to air consist of dust and fume emissions from smelting, hard metal and carbide production; Other emissions to air are ammonia (NH3), acid fume (HCl), hydrogen fluoride (HF), VOC and heavy metals. Effluents are composed of overflow water from wet scrubbing systems, wastewater from slag and metal granulation, and blow down from cooling water cycles. Waste includes dust, fume, sludge and slag. References: Wellbeloved D. B., Craven P. M. and Waudby J. W. (1997) Manganese and Manganese Alloys. In: Ullmann's encyclopedia of industrial chemistry (ed. Anonymous). 5th edition on CD-ROM Edition. Wiley & Sons, London. IPPC (2001) Integrated Pollution Prevention and Control (IPPC); Reference Document on Best Available Techniques in the Non Ferrous Metals Industries. European Commission. Retrieved from http://www.jrc.es/pub/english.cgi/ 0/733169 technologyComment of manganese production (RoW): The metal is won by electrolysis (assumption: 25%) and electrothermic processes (assumption: 75%). No detailed information available, mainly based on rough estimates. technologyComment of treatment of non-Fe-Co-metals, from used Li-ion battery, hydrometallurgical processing (GLO): The technique SX-EW is used mainly for oxide ores and supergene sulphide ores (i.e. ores not containing iron). It is assumed to be used for the treatment of the non-Fe-Co-metals fraction. The process includes a leaching stage followed by cementation or electro-winning. A general description of the process steps is given below. In the dump leaching step, copper is recovered from large quantities (millions of tonnes) of strip oxide ores with a very low grade. Dilute sulphuric acid is trickled through the material. Once the process starts it continues naturally if water and air are circulated through the heap. The time required is typically measured in years. Sulphur dioxide is emitted during such operations. Soluble copper is then recovered from drainage tunnels and ponds. Copper recovery rates vary from 30% to 70%. Cconsiderable amounts of sulphuric acid and leaching agents emit into water and air. No figures are currently available on the dimension of such emissions. After the solvent-solvent extraction, considerable amounts of leaching residues remain, which consist of undissolved minerals and the remainders of leaching chemicals. In the solution cleaning step occur precipitation of impurities and filtration or selective enrichment of copper by solvent extraction or ion exchange. The solvent extraction process comprises two steps: selective extraction of copper from an aqueous leach solution into an organic phase (extraction circuit) and the re-extraction or stripping of the copper into dilute sulphuric acid to give a solution suitable for electro winning (stripping circuit). In the separation step occurs precipitation of copper metal or copper compounds such as Cu2O, CuS, CuCl, CuI, CuCN, or CuSO4 • 5 H2O (crystallisation) Waste: Like in the pyrometallurgical step, considerable quantities of solid residuals are generated, which are mostly recycled within the process or sent to other specialists to recover any precious metals. Final residues generally comprise hydroxide filter cakes (iron hydroxide, 60% water, cat I industrial waste).
technologyComment of chromium production (RoW): Metallic chromium is produced by aluminothermic process (75%) and electroylsis of dissolved ferrochromium (25%) technologyComment of chromium production (RER): Metallic chromium is produced by aluminothermic process (75%) and electroylsis of dissolved ferrochromium (25%) ALUMINOTHERMIC PROCESS The thermic process uses aluminium as a reducing agent for chromium hydroxide. The charge is weighed and loaded into a bin, which is taken to an enclosed room to mix the contents. The firing pot is prepared by ramming refractory sand mixed with water around a central former. After ramming the firing pot, the inner surface is coated with a weak binder solution and dried under a gas fired hood before being transferred to the firing station. The raw material mix is automatically fed at a controlled rate into the firing pot, where the exothermic reaction takes place. When the metal has solidified following the reaction, the firing pot is removed and transferred by crane to a cooling conveyor. On removal from the cooling conveyor (by crane), the firing pot is placed on a stripping bogie for transferral to a stripping booth. Inside the closed booth, the pot casing is hoisted off the solidified metal/slag. The slag is separated from the Chromium metal “button” and sent to a despatch storage area. Water is used to reduce button temperature to below 100 ºC. After cooling the metal button is transferred to other departments on site for cleaning, breaking, crushing and grinding to achieve the desired product size. ELECTROLYTIC PROCESS In the electrolytic process normally high carbon ferrochrome is used as the feed material which is then converted into chromium alum by dissolution with sulphuric acid at temperatures at about 200 ºC. After several process steps using crystallisation filtration ageing, a second filtration and a clarifying operation the alum becomes the electrolyte for a diaphragm cell. Chromium is plated onto stainless steel cathodes until it attains a thickness of ca. 3 mm. The process is very sensitive. The additional de-gassing (heating at 420 °C) stage is necessary because the carbon content of the electrolytic chromium is sometimes too high for further industrial applications. The cooled chromium metal is fragmented with a breaker prior to crushing and drumming. The generated slag can be reused as refractory lining or sold as abrasive or refractory material. Overall emissions and waste: Emissions to air consist of dust and fume emissions from smelting, hard metal and carbide production; other emissions to air are ammonia (NH3), acid fume (HCl), hydrogen fluoride (HF), VOC’s and heavy metals. Emissions to water are overflow water from wet scrubbing systems, wastewater from slag and metal granulation, and blow down from cooling water cycles. Solid waste is composed of dust, fume and sludge, and slag. References: 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 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
Das Projekt "Commercial process outline for crystalline silicon thin film solar cells and modules" wird vom Umweltbundesamt gefördert und von Fraunhofer-Institut für Solare Energiesysteme durchgeführt. General Information: Thin film technologies to fabricate solar cells offer a high potential for a breakthrough in production cost since they consume less materials and ease the introduction of mass production techniques, as compared to the currently dominating wafer-based silicon technology. One of the most promising of these thin film approaches is the crystalline silicon thin film cell. A consortium has been formed by partners from industry and from research organisations to investigate the potential of the new technology. The main goals are: - to define a cell concept appropriate to an industrial product - to show the feasibility of essential process steps - to perform a careful economic process evaluation In this project, only the high temperature approach for the silicon deposition will be discussed, and for economic reasons only chlorosilanes are discussed as silicon source. This limits the substrate materials to those that can withstand temperatures of higher than 1000 C, and which are chemically stable in contact with silicon at this high temperature. Furthermore, it has been decided to focus mainly on substrate materials based on silicon. This can be silicon itself, crystallised in form of sheets, or it can be a ceramic material based on silicon oxides, nitrides, or carbides. Expected achievements are the demonstration of: - an appropriate substrate and a low-cost fabrication technique - a fast and cost-effective deposition technique for silicon films - a cell technology which is compatible with mass fabrication - interconnection and encapsulation schemes for these new cells. An important feature of the research is the inclusion of a thorough economic evaluation. The Consortium is confident to be able to deliver data for an in-depth comparison of the new technology with other thin-film options, but also with the conventional thick silicon technique. It is the intention of this proposed work to direct research and development in the field of the crystalline silicon thin film solar cells towards the industrial perspectives. Prime Contractor: Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V., Institut für Solare Energiesysteme; Freiburg im Breisgau; Germany.
Das Projekt "Silicon kerf loss recycling (SIKELOR)" wird vom Umweltbundesamt gefördert und von Helmholtz-Zentrum Dresden-Roßendorf e.V., Institut für Sicherheitsforschung durchgeführt. Solar energy direct conversion to electricity is expanding rapidly to satisfy the demand for renewable energy. The most efficient commercial photovoltaic solar cells are based on silicon. While the reuse of feedstock is a severe concern of the photovoltaic industry, up to 50% of the valuable resource is lost into sawdust during wafering. Presently, the majority of silicon ingots are sliced in thin wafers by LAS (loose abrasive sawing) using slurry of abrasive silicon carbide particles. The silicon carbide is not separable from the silicon dust in an economical way. The newer FAS (fixed abrasive sawing) uses diamond particles fixed to the cutting wire. It is expected that FAS will replace LAS almost completely by 2020 for poly/mono-crystalline wafering. The intention of the proposed project is to recycle the FAS loss aiming at a sustainable solution. The main problem is the large surface to volume ratio of micron size silicon particles in the kerf loss, leading to formation of SiO2 having a detrimental effect on the crystallisation. The compaction process developed by GARBO meets the requirements of a reasonable crucible-loading factor. Overheating the silicon melt locally in combination with optimised electromagnetic stirring provides the means to remove SiO2. The technology developed by GARBO removes the organic binding agents, leaving about 200 ppm wt diamond particle contamination. If untreated, the carbon level is above the solubility limit. Formation of silicon carbide and precipitation during crystallisation is to be expected. The electromagnetic mixing, in combination with the effective means to separate electrically non-conducting silicon carbide and remaining SiO2 particles from the silicon melt by Leenov-Kolin forces and the control of the solidification front, is the proposed route to produce the solar grade multi-crystalline silicon blocks cast in commercial size in a unified process.
Das Projekt "High density power electronics for FC- and ICE-Hybrid Electric Vehicle Powertrains (HOPE)" wird vom Umweltbundesamt gefördert und von Siemens AG durchgeführt. Objective: The project HOPE is addressing power electronics. It is based on previous EU research projects like the recently finished FW5 HIMRATE (high-temperature power modules), FW5 PROCURE (high-temperature passive components), and MEDEA+ HOTCAR (high-temperature control electronics) and other EU and national research projects. The general objectives of HOPE are: Cost reduction; meet reliability requirements; reduction of volume and weight. This is a necessity to bring the FC- and ICE-hybrid vehicles to success. WP1 defines specifications common to OEM for FC- and ICE-hybrid vehicle drive systems; Identification of common key parameters (power, voltage, size) that allows consequent standardisation; developing a scalability matrix for power electronic building blocks PEBBs. The power ranges will be much higher than those of e.g. HIMRATE and will go beyond 100 kW electric power. WP2 works out one reference mission profile, which will be taken as the basis for the very extensive reliability tests planned. WP3 is investigating key technologies for PEBBs in every respect: materials, components (active Si- and SiC switches, passive devices, sensors), new solders and alternative joinings, cooling, and EMI shielding. In WP4 three PEBBs will be developed: HDPM (high density power module) which is based on double side liquid cooling of the power semiconductor devices; IML (power mechatronics module), which is based on a lead-frame technology; and SiC-PEBB inverter (silicon carbide semiconductor JFET devices instead of Si devices). WP5 develops a control unit for high-temperature control electronics for the SiC-PEBBs. Finally WP6 works on integrating the new technologies invented in HOPE into powertrain systems and carries out a benchmark tests. All the results achieved in HOPE will be discussed intensively with the proposed Integrated Project HYSIS where the integration work will take place. It is clear from the start that many innovations are necessary to meet the overall goal.
Das Projekt "Teilprojekt B" wird vom Umweltbundesamt gefördert und von Leibniz-Institut für Katalyse e.V. an der Universität Rostock durchgeführt. Ziel des Verbundprojektes ist die Entwicklung eines chemisch-biotechnischen Verfahrens zur Herstellung von Phenol aus Biogas. In einem ersten Schritt sollen aus Biogas chemokatalytisch Benzol und die Nebenprodukte Ethen und Naphthalin hergestellt werden. In einem zweiten biotechnologischen Schritt sollen Benzol in Phenol sowie die Nebenprodukte in die Wertstoffe Ethylenoxid und Naphthol umgesetzt werden. Die Ziele des Teilprojekts sind: i) Aufbau einer Testanlage, ii) Einsatzfähige Single-Site Katalysatoren sowie iii) Produktion von Phenol, Naphthol und Ethylenoxid aus Biogas durch Kopplung von Chemo- und Biokatalyse. Für letzteres Ziel optimiert LIKAT drei Klassen von Katalysatoren auf maximale Selektivität für Benzol bei höchstmöglichem Umsatz von Biogas bzw. Methan. MLU stellt eine lösliche Methanmonooxygenase zur Verfügung und screent nach weiteren Benzol und Naphthalin oxidierenden Enzymen, welche rekombinant gewonnen werden sollen. IGB ist zuständig für das Screening nach weiteren Ethen oxidierenden Enzymen, die Untersuchung und Optimierung der Ganzzellkatalyse durch methanotrophe Mikroorganismen, sowie Aufbau und Betrieb einer Versuchsanlage zur Herstellung aller Endprodukte. Danach sollen die in den Teilprojekten erreichten Ergebnisse in der Versuchsanlage durch Kopplung der Chemo- und Biokatalyse vereinigt werden. Die Arbeitsplanung von LIKAT umfasst im Einzelnen folgende Arbeitspakete: 1) Aufbau des Teststandes für die Methanaromatisierung; 2) Synthese geeigneter Single-Site-Katalysatoren, wie Fe, Mo und vergleichbare, auf Trägermaterialien, wie SiO2, SiC, Kohlenstoffallotrope, Zeolithe; 3) Katalysatorcharakterisierung (XRD, BET, TG/DSC, XPS, UV-vis, IR/Raman, Chemisorption, TEM, XANES/EXAFS); 4) Katalysatortests im breiten Parameterraum 5) Optimierung von Katalysatorsynthese und Austestung sowie 6) Chemo- und Biokatalytische Kopplung.
Das Projekt "Synthese von neuen Prozessgasen fuer die Abscheidung von amorphem Silicium(carbid) a-Si(C)" wird vom Umweltbundesamt gefördert und von Technische Universität München, Anorganisch-Chemisches Institut durchgeführt. Amorphes Silicium fuer photovoltaische Zwecke wird nach konventionellen Methoden aus Silangas hergestellt, dem zum Zwecke der Dotierung in kleinen Mengen Fremdgase zugemischt werden. Wenn zur Veraenderung der elektronischen Eigenschaften Legierungen mit Kohlenstoff oder anderen Elementen abgeschieden werden sollen, dann wird zusaetzlich ein Kohlenstofftraeger zugegeben, zB Methan oder Acetylen. Diese Trennung von Silicium- und Kohlenstoffquelle bringt viele Nachteile mit sich, so dass hier und an vielen anderen Stellen schon frueh erwogen worden ist, Gase einzusetzen, die von vornherein alle notwendigen Komponenten enthalten. Das so thematisch vorgegebene Forschungsprogramm hat die Darstellung neuer Prozessgase zum Ziel, aus denen sich unter geeigneten Bedingungen amorphe Schichten von Siliciumcarbid gewinnen liessen, die in ihren Eigenschaften mindestens den Materialien entsprechen, die nach etablierten Verfahren erhalten werden. Im einzelnen gelten die laufenden Aktivitaeten der Herstellung von Polysilylmethanen, -ethenen und -ethinen mit hohem Siliciumgehalt. Schon entwickelte Verfahren sollen weiter optimiert und neue Verfahren sollen gefunden werden. In einer begleitenden Versuchsreihe werden darueberhinaus Vorstufen fuer amorphes Siliciumnitrid hergestel, um auch verbesserte Moeglichkeiten zur Abscheidung von sog Plasmanitrid zu eroeffnen. Die neuen Prozessgase muessen den Anforderungen entsprechend in Reinstform erhalten und analytisch spezifiziert werden. Es sind Verfahren zu ihrer Handhabung zu entwickeln, wobei die geringere Empfindlichkeit gegen Luft und Feuchtigkeit wichtige Vorteile bringen sollte. Polysilylmethane sind naemlich in der Regel nicht selbstentzuendlich.
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