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Substitution of Hazardous Chemicals in Products and Processes Workshop 4 Metal Parts Cleaning Klaus Kuhl Hamburg, June

Substitution of Hazardous Chemicals in Products and Processes Workshop 4 Metal Parts Cleaning Klaus Kuhl Hamburg, June 14, 2002. Workshops 4: Metal Parts Cleaning Application. Metal cleaning is an unavoidable step in many manufacturing processes:

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Substitution of Hazardous Chemicals in Products and Processes Workshop 4 Metal Parts Cleaning Klaus Kuhl Hamburg, June

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  1. Substitution of Hazardous Chemicals in Products and ProcessesWorkshop 4Metal Parts CleaningKlaus KuhlHamburg, June 14, 2002 Kooperationsstelle Hamburg, June 2002

  2. Workshops 4: Metal Parts CleaningApplication Metal cleaning is an unavoidable step in many manufacturing processes: • Cleaning in the mechanical productionIntermediate and final cleaning after cutting, forming and welding • Cleaning for surface treatmentCar bodies, casings, galvanizing, enamelling, painting • Cleaning for heat treatmentCog wheels, pistons, automobile parts • Cleaning for maintenance and repair Car repair, maintenance, paint stripping Kooperationsstelle Hamburg, June 2002

  3. Workshops 4: Metal Parts CleaningApplication II Cleaning process is the main term for the removal of not desired substances from surfaces • Physically adhering substances (oil, dust, chips,..) • Chemically adhering substances ( rust, scales, …) Industries: Construction, car repair, servicing, food processing, electronics, optics, … We will focus on: • Mechanical engineering, car and steel industry • Removal of processing fluids (drawing, cutting, rolling oils, lubricants) Kooperationsstelle Hamburg, June 2002

  4. Workshops 4: Metal Parts CleaningTechnological Principles Enterprises have to choose among a vast variety of cleaning agents, equipment and processes. Propertiesof parts Cleaning agent Material composition (steel, cast, alu, alloys,...), size, weight, geometry,narrow gaps, tiny holes,blind holes Amount, frequencyof parts Cleaning equipment Auxiliary equipment Type and amountof dirt Cleaning process Further processing;degree of cleanliness Cleaning support Kooperationsstelle Hamburg, June 2002

  5. Workshops 4: Metal Parts CleaningChemical Scope Market share of processes in Germany(D) • „Others“ include e.g.: • HC fp < 55°C • Blasting • Plasma • Burning • Brushing • Source: DGO, 1999 • Estimation! Kooperationsstelle Hamburg, June 2002

  6. Workshops 4: Metal Parts CleaningChemical Scope II • Hydro carbonsAliphates, aromates, alcoholes, ketones, glycoles, acetates, ethers, esters, terpenes • Chlorinated solventsTrichloroehylene, tetra(per)chloroethylene, dichloromethane • Aqueous cleanersAlkaline, neutral, acid, usually containig surfactantsand additives (builders, sequestering agents, ..) • Semi-aqueous cleanersCombination of surfactants and hydrocarbons (emulsions) Kooperationsstelle Hamburg, June 2002

  7. Workshops 4: Metal Parts CleaningToxicity, environmental impact Chlorinated solvents Poor biodegradability High evaporation rate, breathing in of small amounts may cause headaches, lung irritation, dizziness, poor coordination, and concentration difficulties; during longer periods: nerve, kidney, and liver damage. Skin contact for short periods may cause skin rashes. In 1995 the International Agency for Research on Cancers has classified TRI and PER as "probably carcinogenic to humans” (Class 2A). In 2001 the classification of TRI under the EU Dangerous Substances Directive was changed from carcinogenous category 3 (R40 –possible risks of irreversible effects) to category 2 (R45 – may cause cancer) Stabilisers (zinc, alu, sodium hydroxide) epichlorohydrine, epoxybutane Kooperationsstelle Hamburg, June 2002

  8. Workshops 4: Metal Parts CleaningToxicity, environmental impact II Hydrocarbons Ozone through photochemical oxidation (summer smog) Depletion of stratosphaeric ozone layer (some hc). Water and soil contamination. Explosion and fire risks. Solvents, their vapours and mists enter the body by inhalation, by swallowing and through the skin. The most probable exposure route depends on the volatility and fat-solubility of the solvent Many have a narcotic effect, causing fatigue and dizziness. High doses may lead to unconsciousness and death, large doses may slow reaction time and affect rational judgement. Some solvents irritate the eyes and the respiratory tract. Many defat the skin, a very common cause of skin disorders and dermatitis. They penetrate the skin and enter the blood circulation, damaging the liver, kidneys, heart, blood vessels, bone marrow and the nervous system Content of aromatics (high cleaning efficiency) Kooperationsstelle Hamburg, June 2002

  9. Workshops 4: Metal Parts CleaningToxicity, environmental impact III Aqueous cleaners Kooperationsstelle Hamburg, June 2002

  10. Workshops 4: Metal Parts CleaningPolitical Level Chlorinated solvents Public awareness started in the seventies (stratospheric ozone layer, Seveso) Use is limited and regulated in many ways (1,1,1-trichloroethane and CFC-113 banned). Indirectly many national laws e.g. for ground water protection, waste disposal etc. contributed significantly to the reduction of the use of chlorinated solvents. For metal cleaning in the EU today only the two solvents remain:TRI and PER (methylenchloride mainly used for paintstripping) Strictly regulated is the storage and the maintenance of the storage systems. European directives and regulations as e.g. in the context of waste or disposal to water (as e.g. Council Directives EC/86/280 or EC/90/415) influenced the use of chlorinated solvents Europe-wide. Additionally a number of national regulations contributes to reductions in the use of TRI and PER. Sweden prohibited TRI 96, exemptions possible. Germany set the emission levels so low that chlorinated solvents can only be used in closed loop circle machinery. France accepts chlorinated solvents as reasons for occupational diseases. Spain enforced national storage, transport and emission regulations. Permits or licences for emissions to the water are common in the Member States. Norway has put a tax on PER, which leads to a price increase of app. 500% Kooperationsstelle Hamburg, June 2002

  11. Workshops 4: Metal Parts CleaningPolitical Level II Production and sales figures TRI and PER western Europe Metric tons in thousands Source: ECSA, Solvents Digest 20, Brussels, April 2000 Kooperationsstelle Hamburg, June 2002

  12. Workshops 4: Metal Parts CleaningPolitical Level III Hydrocarbons Restrictions regarding aromatics content Restrictions concerning fire and explosion risks. Occupational health regulations (starting in DK in the eighties). OELs for widely used typical hydrocarbons and mixtures were enforced for the first time. Studies on how to reduce VOCs started in several member states. Hydrocarbons are still the dominating cleaning agents. 1999 VOC directive (1999/13/EC) sets emission limit values and fugitive emission values for certain industries. It will trigger much stricter emission control measures and by this also support indirectly substitution. Eco label (Nordic Svan) Government-industry agreements Covenants (Netherlands) Kooperationsstelle Hamburg, June 2002

  13. Workshops 4: Metal Parts CleaningEnterprises Chlorinated solvents hydrocarbons Kooperationsstelle Hamburg, June 2002

  14. Workshops 4: Metal Parts CleaningEnterprises II Hydrocarbons Aqueous cleaners Kooperationsstelle Hamburg, June 2002

  15. Workshops 4: Metal Parts CleaningSubstitution Chlorinated solvents Perchloro-ethylene(1930 to today) 1,1,1,Trichloroethane and similar chlor. solv. (1920 to a very limited use today) Carbontetra- chloride (CCL4) (1850 to 1940) Trichloroethylene(1920 to today, loosing market share towards PER) MINOR USE AND ROUTE OF SUBSTITUTION Chlorofluoro- carbons CFC’ s (1940 to 1980) Hydrochlorofluoro-carbons (HCFC’s) (1975 to today) Hydrofluoroether HFE’s and Perfluorocarbons (PFC’s) (1975 to today) Kooperationsstelle Hamburg, June 2002

  16. Workshops 4: Metal Parts CleaningSubstitution II Hydro carbons MAJOR USE AND ROUTE OF SUBSTITUTION SOLVENT MIXTURES with a lower VP and without aromates (from 1990) SOLVENT MIXTURES with less impurities and without benzene (from 1960) SOLVENT MIXTURES without aromates(from 1980) CRUDE SOLVENT MIXTURES OF ALL TYPES MAINLY ALKANES CONTAINING AROMATES MINOR USE AND ROUTE OF SUBSTITUTION Alcohols, Ketones, Esters, Ethers, acetates, all other hydrocarbon based alternatives SEMI-AEQUEOUS CLEANERS Kooperationsstelle Hamburg, June 2002

  17. Workshops 4: Metal Parts CleaningSubstitution III Aqueous cleaners MAJOR USE AND ROUTE OF SUBSTITUTION WATER WITH BETTER BIODEGRADABLE and LESS TOXIC COMPONENTS(from 1985) WATER WITH EFFECTIVE DETERGENTS(from 1975) WATER WITH CAU-STIC SODA OR SOAP for special purposes (from 1850) Kooperationsstelle Hamburg, June 2002

  18. HC AND CHLORINATED SOLVENTS CLEANING WITH SUPERCRITICAL CARBONDIOXIDE CHANGE OF PRODUCTION PROCESSES AVOIDING DIRT LIKE CUTTING WITHOUT CUTTING FLUIDS PLASMA, LASER, NANO CLEANING Workshops 4: Metal Parts CleaningSubstitution IV Other cleaning alternatives Kooperationsstelle Hamburg, June 2002

  19. Workshops 4: Metal Parts CleaningImplications for Businesses The large operators are switching or have already switched to automatic and relatively closed installations using all three types of chemicals. All these types of cleaning agents need a detailed control of practical handling and risk reduction measures. These necessary organisational efforts have been made or are intended, if cleaning from process fluids plays an important role for the business. Other users in companies, where cleaning is still seen as a minor task in the whole process, seem to tackle the cleaning issue without a strategic background. They use the products and technologies, which are available on the market and are not connected with too much regulative restrictions. Larger strategic considerations about substitution are rare. A general opinion in all companies seems to be, that the regulative restrictions and the quality demands will become stricter. For suppliers of larger companies as the car industry the demands from the quality or environmental management systems of their customers play a growing role. Kooperationsstelle Hamburg, June 2002

  20. Workshops 4: Metal Parts CleaningImplications for Businesses II Example 1 Aluminium heat exchangers for engine coolers and air conditioners: Company considered all possible equipment and agents and in the end choose an airtight steam degreaser; problem: lamellar distances of 0.6 mm and avoidance of fogging effect. Drying would have taken too long with aqueous or AII/AIII agents. Another company selected in a similar problem steam degreasing with a modified alcohol. Example 2 Spray can cleaning in vehicle repair Kooperationsstelle Hamburg, June 2002

  21. Workshops 4: Metal Parts CleaningConclusions Risk discussion Discussion on chlorinated solvents and later all types of organic solvents resulted in a broad variety of different cleaning technologies and cleaning chemicals. Which in turn results in reduced transparency. Main actors User companies, the HSE-administration, the workers, the equipment producers and the chemical suppliers. The role of consumers of the final products is very weak. Choice of the user companies still depends mainly on functionality, but strategic choices and trade discussions about cleaning agents have can be seen more and more. Quality and health and environment aspects have become more important. Risk assessment Very difficult due to the complex influence factors. Often shifts of risks have to be considered. Kooperationsstelle Hamburg, June 2002

  22. Workshops 4: Metal Parts CleaningConclusions II Single important factors overview Economics Costs for investments in new cleaning equipment hinder substitution Economics/costshindrance to substitution Technical functionality Supposed less functional effectiveness hinder substitution efforts Technical functionality/process integrationhindrance to substitution Social factors Increasing importance of environmental and health aspects Social factors/communication B2Bsupport for substitution Risk assessment Complex water based alternatives need complicated risk assessments risk assessment/RA of alternatives/shift of riskshindrance to substitution Regulation Regulation support substitution for large installations but not in SME´s concerning large enterprisesstrong support for substitution concerning small and medium enterprisesno influence Kooperationsstelle Hamburg, June 2002

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