Rüdel, Heinz; Müller, Josef; Jürling, Heinrich; Bartel-Steinbach, Martina; Koschorreck, Jan Environ Sci Pollut Res 18 (2011), 9, 1457-1470 Samples from the German Environmental Specimen Bank (ESB) covering particularly the years 1994-1996, 2000-2002, and 2006-2009 were analyzed for perfluorinated compounds (PFC; mainly C4-C13 carboxylic and sulfonic acids) to gain an overview on current PFC levels and patterns in marine, limnetic, and terrestrial biota; to assess their concentrations in different trophic levels; and to investigate whether risk management measures for PFC are successful. Specimens, either standardized annual pooled samples (blue mussels, eelpout liver, bream liver, pigeon eggs) or individual single samples (cormorant eggs, rook eggs), were collected for the German ESB program from representative sampling sites according to documented guidelines. After appropriate extraction, PFC were quantified under ISO/IEC 17025 accreditation by HPLC/MS-MS with isotopically labeled internal standards. Limits of quantification (LOQs) were 0.2-0.5 ng/g. Data are reported on a wet weight basis. In most samples the predominant PFC was perfluorooctane sulfonic acid (PFOS). However, in marine mussels from North and Baltic Seas, PFOS levels were mostly below the LOQ, but low residues of PFOS amide were found which declined in recent years. Livers of eelpout showed maximum concentrations of 15-25 ng/g PFOS in the period 2000-2002 and low amounts of perfluoropentanoate in all years. Beside PFOS (median 48 ng/g) several PFC could be determined in cormorant eggs sampled in 2009 from a Baltic Sea site. For a freshwater ecosystem, current PFC burdens for cormorant eggs were even higher (median 400 ng/g PFOS). Livers of bream from rivers showed concentrations of 130-260 ng/g PFOS, but for bream from a reference lake levels were only about 6 ng/g. In contrast to cormorants, eggs of rook and feral pigeon from terrestrial ecosystems displayed only low PFC burdens (up to 6 ng/g PFOS). Generally, PFC levels were lower in marine than in freshwater biota. PFC burdens were higher in biota from the ESB-North Sea sites than in Baltic Sea organisms. Levels of PFC were quite high especially in top predators of both limnetic and marine ecosystems. Only low PFC levels were detected in eggs of terrestrial birds. A decrease of PFOS levels from maximum values around the year 2000 observed at least in North Sea biota may be a result of a production cease and shifts in marketing pattern. doi:10.1007/s11356-011-0501-9
Am 1. Juni 2013 kam der "Club der Energiewende-Staaten" zu seinem Gründungstreffen in Berlin zusammen. Gründungsmitglieder sind China, Dänemark, Deutschland, Frankreich, Indien, Marokko, Südafrika, Tonga, die Vereinigten Arabischen Emirate, das Vereinigte Königreich sowie der Generaldirektor der IRENA, Adnan Amin. Gemeinsames Ziel ist, den Ausbau der erneuerbaren Energien weltweit voranzutreiben.
Am 7. Oktober 2011 wurde von Bundesumweltminister Dr. Norbert Röttgen und Adnan Z. Amin, der Generaldirektor der Internationalen Organisation für Erneuerbare Energien (IRENA),das Innovations- und Technologiezentrum (IITC) von IRENA in Bonn eröffnet. Die von der Bundesregierung geförderte Beratungseinrichtung soll wissenschaftliche Szenarien zur Förderung erneuerbarer Energien erarbeiten und in Zusammenarbeit mit dem IRENA-Hauptsitz in Abu Dhabi zum weltweiten Umstieg auf Ressourcen schonende Technologien beitragen.
technologyComment of epoxy resin production, liquid (RER): Commercial epoxy resin can be produced by reacting bisphenol-A and epichlorohydrin in presence of a base catalyst (here represented by sodium hydroxide) (Guichon Valves n.d. and Pham and Marks 2005). Epoxy resins are in liquid form if n is from 0 to 1. When n is larger than 1 the resin in solid (Licare and Swanson, 2011). As the product here representes epoxy resin in liquid form, n is set to 1. 2C15H16O2 + 3C3H5ClO + 3NaOH -> C39H44O7 + 3Na+ + 3Cl- + 3H2O Pham, H.Q. and Marks, M.J. 2005. Epoxy Resins. In Ullmann's Encyclopedia of Industrial Chemistry, Electronic Release, Vol.13, pp.155-244. Wiley-VCH, Weinheim. Guichon Valves, n.d. Epoxy resins – Manufacturing process of Epoxy resins. Retrieved from: http://guichon-valves.com/faqs/epoxy-resins-manufacturing-process-of-epoxy-resins/, accessed 13th February 2017 For more information on the model please refer to the dedicate ecoinvent report, access it in the Report section of ecoQuery (http://www.ecoinvent.org/login-databases.html) The process is carried out in a reactor where a solution of sodium hydroxide is added (20 to 40% concentration). The product is brought to boiling temperature and a solvent is added. Solvents are not included in the inventory as it is assumed that solvents are closed-loop recycled. The unreacted epichlorohydrin is collected and recycled back into the system. The epoxy resin in then washed; this gives the final product in liquid form. Epoxy resin can also be produced in solid form. To do so, curing with, for example secondary amines, is necessary. Epoxy resins can have different characteristics, these depend on additional products that can be added to the liquid resin. The required characteristics depend on the final use of the product (Guichon Valves n.d.) This inventory representing production of a particular chemical compound is at least partially based on a generic model on the production of chemicals. The data generated by this model have been improved by compound-specific data when available. The model on production of chemicals is using specific industry or literature data wherever possible and more generic data on chemical production processes to fill compound-specific data gaps when necessary. The basic principles of the model have been published in literature (Hischier 2005, Establishing Life Cycle Inventories of Chemicals Based on Differing Data Availability). The model has been updated and extended with newly available data from the chemical industry. In the model, unreacted fractions are treated in a waste treatment process, and emissions reported are after a waste treatment process that is included in the scope of this dataset. For volatile reactants, a small level of evaporation is assumed. Solvents and catalysts are mostly recycled in closed-loop systems within the scope of the dataset and reported flows are for losses from this system. The main source of information for the values for heat, electricity, water (process and cooling), nitrogen, chemical factory is industry data from Gendorf. The values are a 5-year average of data (2011 - 2015) published by the Gendorf factory (Gendorf, 2016, Umwelterklärung, www.gendorf.de), (Gendorf, 2015, Umwelterklärung, www.gendorf.de), (Gendorf, 2014, Umwelterklärung, www.gendorf.de). The Gendorf factory is based in Germany, it produces a wide range of chemical substances. The factory produced 1657400 tonnes of chemical substances in the year 2015 (Gendorf, 2016, Umwelterklärung, www.gendorf.de) and 740000 tonnes of intermediate products. Reference(s): Hischier, R. (2005) Establishing Life Cycle Inventories of Chemicals Based on Differing Data Availability (9 pp). The International Journal of Life Cycle Assessment, Volume 10, Issue 1, pp 59–67. 10.1065/lca2004.10.181.7 Gendorf (2016) Umwelterklärung 2015, Werk Gendorf Industriepark, www.gendorf.de Licari, J.J. and Swanson, D.W. 2011. Chemistry, Formulation, and Properties of Adhesives. In Adhesives Technology for Electronic Applications (Second Edition), 2011
Production mix technologyComment of decarboxylative cyclization of adipic acid (RER): decarboxylative cyclization of adipic acid technologyComment of formic acid production, methyl formate route (RER): The worldwide installed capacity for producing formic acid was about 330 000 t/a in 1988. Synthesis of formic acid by hydrolysis of methyl formate is based on a two-stage process: in the first stage, methanol is carbonylated with carbon monoxide; in the second stage, methyl formate is hydrolyzed to formic acid and methanol. The methanol is returned to the first stage. Although the carbonylation of methanol is relatively problem-free and has been carried out industrially for a long time, only recently has the hydrolysis of methyl formate been developed into an economically feasible process. The main problems are associated with work-up of the hydrolysis mixture. Because of the unfavorable position of the equilibrium, reesterification of methanol and formic acid to methyl formate occurs rapidly during the separation of unreacted methyl formate. Problems also arise in the selection of sufficiently corrosion-resistant materials Carbonylation of Methanol In the two processes mentioned, the first stage involves carbonylation of methanol in the liquid phase with carbon monoxide, in the presence of a basic catalyst: imageUrlTagReplacea0ec6e15-92c8-4d44-82bb-84e90e58b171 As a rule, the catalyst is sodium methoxide. Potassium methoxide has also been proposed as a catalyst; it is more soluble in methyl formate and gives a higher reaction rate. Although fairly high pressures were initially preferred, carbonylation is carried out in new plants at lower pressure. Under these conditions, reaction temperature and catalyst concentration must be increased to achieve acceptable conversion. According to published data, ca. 4.5 MPa, 80 °C, and 2.5 wt % sodium methoxide are employed. About 95 % carbon monoxide, but only about 30 % methanol, is converted under these circumstances. Nearly quantitative conversion of methanol to methyl formate can, nevertheless, be achieved by recycling the unreacted methanol. The carbonylation of methanol is an equilibrium reaction. The reaction rate can be raised by increasing the temperature, the carbon monoxide partial pressure, the catalyst concentration, and the interface between gas and liquid. To synthesize methyl formate, gas mixtures with a low proportion of carbon monoxide must first be concentrated. In a side reaction, sodium methoxide reacts with methyl formate to form sodium formate and dimethyl ether, and becomes inactivated. The substances used must be anhydrous; otherwise, sodium formate is precipitated to an increasing extent. Sodium formate is considerably less soluble in methyl formate than in methanol. The risk of encrustation and blockage due to precipitation of sodium formate can be reduced by adding poly(ethylene glycol). The carbon monoxide used must contain only a small amount of carbon dioxide; otherwise, the catalytically inactive carbonate is precipitated. Basic catalysts may reverse the reaction, and methyl formate decomposes into methanol and carbon monoxide. Therefore, undecomposed sodium methoxide in the methyl formate must be neutralized. Hydrolysis of Methyl Formate In the second stage, the methyl formate obtained is hydrolyzed: imageUrlTagReplace2ddc19c0-905f-42c3-b14c-e68332befec9 The equilibrium constant for methyl formate hydrolysis depends on the water: ester ratio. With a molar ratio of 1, the constant is 0.14, but with a water: methyl formate molar ratio of 15, it is 0.24. Because of the unfavorable position of this equilibrium, a large excess of either water or methyl formate must be used to obtain an economically worthwhile methyl formate conversion. If methyl formate and water are used in a molar ratio of 1 : 1, the conversion is only 30 %, but if the molar ratio of water to methyl formate is increased to 5 – 6, the conversion of methyl formate rises to 60 %. However, a dilute aqueous solution of formic acid is obtained this way, and excess water must be removed from the formic acid with the expenditure of as little energy as possible. Another way to overcome the unfavorable position of the equilibrium is to hydrolyze methyl formate in the presence of a tertiary amine, e.g., 1-(n-pentyl)imidazole. The base forms a salt-like compound with formic acid; therefore, the concentration of free formic acid decreases and the hydrolysis equilibrium is shifted in the direction of products. In a subsequent step formic acid can be distilled from the base without decomposition. A two-stage hydrolysis has been suggested, in which a water-soluble formamide is used in the second stage; this forms a salt-like compound with formic acid. It also shifts the equilibrium in the direction of formic acid. To keep undesirable reesterification as low as possible, the time of direct contact between methanol and formic acid must be as short as possible, and separation must be carried out at the lowest possible temperature. Introduction of methyl formate into the lower part of the column in which lower boiling methyl formate and methanol are separated from water and formic acid, has also been suggested. This largely prevents reesterification because of the excess methyl formate present in the critical region of the column. Dehydration of the Hydrolysis Mixture Formic acid is marketed in concentrations exceeding 85 wt %; therefore, dehydration of the hydrolysis mixture is an important step in the production of formic acid from methyl formate. For dehydration, the azeotropic point must be overcome. The concentration of formic acid in the azeotropic mixture increases if distillation is carried out under pressure, but the higher boiling point at high pressure also increases the decomposition rate of formic acid. At the same time, the selection of sufficiently corrosion-resistant materials presents considerable problems. A number of entrainers have been proposed for azeotropic distillation. Reference: Gräfje, H., Körnig, W., Weitz, H.-M., Reiß, W.: Butanediols, Butenediol, and Butynediol, Chapter 1. In: Ullmann's Encyclopedia of Industrial Chemistry, Sev-enth Edition, 2004 Electronic Release (ed. Fiedler E., Grossmann G., Kersebohm D., Weiss G. and Witte C.). 7 th Electronic Release Edition. WileyInterScience, New York, Online-Version under: http://www.mrw.interscience.wiley.com/ueic/articles/a04_455/frame.html technologyComment of oxidation of butane (RER): The liquid-phase oxidation of hydrocarbons is an important process to produce acetic acid, formic acid or methyl acetate. About 43 kg of formic acid is produced per ton of acetic acid. Unreacted hydrocarbons, volatile neutral constituents, and water are separated first from the oxidation product. Formic acid is separated in the next column; azeotropic distillation is generally used for this purpose. The formic acid contains about 2 wt % acetic acid, 5 wt % water, and 3 wt % benzene. Formic acid with a content of about 98 wt % can be produced by further distillation. Reference: Gräfje, H., Körnig, W., Weitz, H.-M., Reiß, W.: Butanediols, Butenediol, and Butynediol, Chapter 1. In: Ullmann's Encyclopedia of Industrial Chemistry, Sev-enth Edition, 2004 Electronic Release (ed. Fiedler E., Grossmann G., Kersebohm D., Weiss G. and Witte C.). 7 th Electronic Release Edition. WileyInterScience, New York, Online-Version under: http://www.mrw.interscience.wiley.com/ueic/articles/a04_455/frame.html
technologyComment of trimethylamine production (RER): Production from vaporised methanol and ammonia with a process yield of 95%. After the process reaction excess ammonia and amine is recycled amine and trimethylamine is recovered in a distilling column. The inventory bases on stoechiometric calculations. The emissions to air (0.2 wt.% of raw material input) and water were estimated using mass balance. Treatment of the waste water in a internal waste water treatment plant assumed (elimination efficiency of 90% for C, 70% for NH4-N and 50% for N-tot). The used reaction catalysts in the process (aluminium silicate or phosphate) were neglected.
Um den wachsenden Anforderungen an Handelsmärkte gerecht zu werden, hat die EU schrittweise eine Reihe von Regelungen im Bereich der Marktaufsicht angepasst und erweitert, die sich auch auf den EU-Emissionshandel auswirken. Die bedeutendste Änderung für den EU-Emissionshandel ist dabei die Einordnung von Emissionsrechten1 unter den Begriff der Finanzinstrumente. Dadurch wird der Emissionshandel in Zukunft grundsätzlich den in der europäischen Finanzmarktrichtlinie (MiFID II; Markets in Financial Instruments Directive) festgelegten Regularien der Finanzmarktordnung unterfallen. Neben MiFID II wurden auch die Regelungen gegen Marktmissbrauch (CRIM-MAD/MAR; Directive on Criminal Sanctions for Market Abuse/Regulation on Market Abuse) sowie Regelungen zur Verhinderung von Geldwäsche und Terrorismusfinanzierung (sogenannte 4. Anti-Geldwäsche Richtlinie) überarbeitet. Zudem wurde mit dem Erlass der Verordnung über OTCDerivate, zentrale Gegenparteien und Transaktionsregister (EMIR; European Market Infrastructure Regulation) ein umfangreiches Regelwerk zur Regulierung des Derivate-Markts geschaffen. Bis auf die 4. Anti-Geldwäsche Richtlinie sind alle Regelwerke bereits in Kraft getreten. Soweit möglich, werden die neuen Regelungen sowie ihre potentiellen Auswirkungen auf die einzelnen Marktteilnehmer und Marktplätze in diesem Papier zusammenfassend dargestellt, diskutiert und vorläufig bewertet. Die konkrete Ausgestaltung einiger insbesondere auch für den Emissionshandel relevanter Punkte der MiFID II sowie der MAR befindet sich derzeit noch in einem Konsultations- und Gesetzgebungsprozess unter Koordination der ESMA (European Securities and Markets Authority), weshalb eine abschließende Beurteilung der Änderungen des regulatorischen Rahmens in diesem Papier nur bedingt möglich ist. Die Vorschriften der MiFID II werden ab 2017 europaweit Geltung finden. Quelle: Forschungsbericht
Das Projekt "Verbesserung der Qualitaet von Biogas mit dem Ziel der Erhoehung seines Heizwertes auf Heizgasstandard" wird vom Umweltbundesamt gefördert und von Landeshauptstadt Stuttgart, Tiefbauamt durchgeführt. Objective: To construct a plant for the purification of biogas produced in a sewage treatment plant and to upgrade its calorific value. A projected 10 000 m3 of biogas will be processed daily. General Information: The biogas, which contains a high percentage of CO2, has a calorific value of 7.45 Kwh/m3. In addition, for final use H2S should be eliminated from the biogas. In order to reach the prescribed calorific value of 11.2 Kwh/m3 it may be necessary to add some hydrocarbons such as propane. The CO2 and H2S are removed in a regenerative alcanolamin process (MEA) for which the required steam of the MEA-lye is obtained from the sludge incineration plant. The condensate is conveyed back to the boiler on the sludge incineration plant. For purification the sewage gas has to go through the following process: - removal of CO2 and H2S by means of regenerative alcanolamine scrubbing; - drying, compression and absorption on activated aluminium oxide; - analysis of the CO2 content and dew point of the purified gas; - odorization with a pungent substance added by metering pump; - conditioning of the purified gas with LPG, to comply with the prescribed calorific value for fuel gas. Achievements: Experimental operation of the plant carried out from 5/9 to 11/9/1985 with the agreement of the Public Works Department and the City Gas Company was successfully completed. During this period approx. 40000 m3 purified sewage gas of natural gas quality were fed into the city's mains gas supply. The plant was thus deemed to be accepted and was transferred to the authority of the Public Works Department on 12/9/1985. Output Data of the plant were the following: Crude gas approx. 606 Nm3/h CO2 approx. 36 - 38 per cent vol. H2S approx. 270 - 320 mg/Nm3 N2 + 02 approx. 0.6 - 1.8 per cent vol. t approx. 20 deg. C. Purified gas max. 369 Nm3/h min. 128 Nm3/h. From commissioning in September 1985 until the end of 1988 3.8 million m3 of purified gas have been produced. This is equivalent to 3.7 million litres or 3.2 million kg of heating oil. The guaranteed performance of the plant is exceeded and the consumption of operating materials falls below the stated values. Despite increased output the guaranteed composition of purified gas is below the required levels. Operating costs of the main sewage plant are slightly reduced by sewage gas processing.
Das Projekt "Revision der Einstufung und Kennzeichnung von 250 Stoffen des Anhang I der Richtlinie 67/548/EWG" wird vom Umweltbundesamt gefördert und von Baum, E. durchgeführt. Erstellung einer Stoffliste durch Abgleich der Vorschlagsliste der Bundesanstalt fuer Arbeitsschutz ,Sehr giftige Stoffe' mit den Listen in Norwegen gekennzeichneten Stoffe und den in der EG zur Umstufung von ,Reizend' nach ,Aetzend' vorgeschlagenen Aminen.
Das Projekt "Measurements of N-nitroso compounds (N-nitrosamines) in ambient air of workplaces and near coke works and steel shops" wird vom Umweltbundesamt gefördert und von DMT-Gesellschaft für Forschung und Prüfung mbH durchgeführt. Objective: The main objectives of the project are: 1 Determination of the nitrogen compounds which can lead to the formation of N-nitrosamines in coking plants and steelworks. 2 Investigation of artefact formation during sampling. 3 Development of new sampling and analysis techniques and evaluation of whether existing methods of analysis are suitable for N-nitrosamines. 4 Harmonisation (differences, correlations) of the procedures developed by each of the participating institutes and establishing of a standard procedure for use in all countries. 5 First measurements of N-nitrosamines to obtain tenable results which can serve as a basis for EC legislation. The focus will be on measurements at workstations in different types of plant in the coal and steel industries of the participating countries. General Information: Nitrosamines are known carcinogens. They are formed by reaction of preferentially secondary amines with nitro sating agents, both of which may occur at workplaces as undesirable by-products or emissions. Nitrosamines have so far been identified in the ambient air in the metal processing, rubber and leather industries. Bituminous coals used in the coking industry contain 1-2 per cent nitrogen, most of which ends up either in the tar fraction or, following gas scrubbing, as ammonium sulphate. However, coke oven leaks (from charging lids, doors and ascension pipes) may lead to uncontrolled emissions of mainly aromatic amines, which in the presence of nitrous gases (NO and NO2) may be transformed into N-nitrosamines. Formation of N-nitrosamines must also be expected in the steel industry, originating from cooling lubricants containing nitrogen and hardeners used in foundries. A major problem in the measurement of nitrosamines is artefact formation during the sampling process. It has been shown that in this case amines are also retained which react with NOx traces in the ambient air to form N-nitrous amines though only when they reach the substrate. This phenomenon is observed particularly in the presence of aromatic amines, which is specifically the case in coking plants. The pollutant concentrations identified should not be associated with a particular pollution source, as they are caused entirely by artefact formation as a result of subsequent notarisation on the sampling medium. In order to protect workers and the population from the toxicological effects of N-nitrosamines, it is necessary to act upon the conditions favouring the formation of these noxious substances in the environment. To be able to do this it is necessary to have information on concentrations, types of compound and sources of emission of N-nitrosamines and amines (their precursors). The planned research and development project is concerned with the problem of N-nitrosamines in the environment of steelworks and associated coking plants.
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