kooperationsstelle hamburg, june 20021 substitution of hazardous chemicals in products and processes...
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Kooperationsstelle Hamburg, June 2002 1
Substitution of Hazardous Chemicals in Products and Processes
Workshop 4
Metal Parts CleaningKlaus Kuhl
Hamburg, June 14, 2002
Kooperationsstelle Hamburg, June 2002 2
Workshops 4: Metal Parts Cleaning
Application
Metal cleaning is an unavoidable step in many manufacturing processes:
Cleaning in the mechanical production
Intermediate 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 repairCar repair, maintenance, paint stripping
Kooperationsstelle Hamburg, June 2002 3
Workshops 4: Metal Parts Cleaning
Application IICleaning 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)
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Material composition (steel, cast, alu, alloys,...),
size, weight, geometry,narrow gaps, tiny holes,
blind holes
Workshops 4: Metal Parts Cleaning
Technological PrinciplesEnterprises have to choose among a vast variety of cleaning agents, equipment and processes.
Propertiesof parts
Amount, frequencyof parts
Type and amountof dirt
Further processing;degree of cleanliness
Cleaning agent
Cleaning equipment
Auxiliary equipment
Cleaning process
Cleaning support
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Workshops 4: Metal Parts Cleaning
Chemical Scope
Others5%
HC (chlorinated)
25%Aqueous
65%
HC (fp > 55°C)5%
„Others“ include e.g.:
•HC fp < 55°C•Blasting•Plasma•Burning•Brushing
Source: DGO, 1999Estimation!
Market share of processes in Germany(D)
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Workshops 4: Metal Parts Cleaning
Chemical 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)
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Workshops 4: Metal Parts Cleaning
Toxicity, environmental impactChlorinated solventsPoor 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
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Workshops 4: Metal Parts Cleaning
Toxicity, environmental impact IIHydrocarbonsOzone 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)
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Workshops 4: Metal Parts Cleaning
Toxicity, environmental impact IIIAqueous cleaners
Ingredients Function Eco Tox Human tox
Biocides Biological stability Toxic impact on organisms and microorganisms
Toxic impact depending on type of biocide
Corrosion inhibitors
Corrosion protection
Toxic impact on organisms and microorganisms
Toxic impact depending on type of corr. inhibitor
Antifoaming agents
Cleaning efficiency
Low biodegradability in water
Skin irritation
Surfactants Cleaning activation
Low biodegradability in water
Skin irritation
Emulsifiers, demulsifiers
Degreasing, cleaning
Biodegradability in water Skin irritation
Builders Over fertilization -
Complexing agents
Keep heavy metals in solution
Low biodegradability in sediments
-
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Workshops 4: Metal Parts Cleaning
Political LevelChlorinated solventsPublic 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%
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Workshops 4: Metal Parts Cleaning
Political Level IIProduction and sales figures TRI and PER western Europe
0
20
40
60
80
100
120
1990 1993 1994 1995 1996 1997 1998 1999 2000
TRI
PER
Source: ECSA, Solvents Digest 20, Brussels, April 2000
Met
ric to
ns in
thou
sand
s
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Workshops 4: Metal Parts Cleaning
Political Level IIIHydrocarbonsRestrictions 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)
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Workshops 4: Metal Parts Cleaning
EnterprisesChlorinated solvents
Pro substitution Contra substitution Main actor
Cleaning efficiency Industrial users, especially producers of high quality products
More advanced & expensive cleaning equipment available, to reduce emissions acc. to stricter regulations
Equipment producers
More advanced & expensive cleaning equipm. necessary against fire & explosion
Industrial users
Use of less cleaning agents through improved machinery design
Industrial users, Cleaning equipment producers
Risks of spilling and soil contamination, storage obligations
Industrial users, insurances, authorities
Prices for sludge (waste), contaminated with chl. solv.
Industrial users, authorities
Health hazards Less potential conflicts with authorities, workers, neighbours and the public
Health hazards by stabilising additives and spontaneous risks by decomposition
Industrial users, technicians and HSE
hydrocarbons
Kooperationsstelle Hamburg, June 2002 14
Workshops 4: Metal Parts Cleaning
Enterprises IIAqueous cleaners
Pro substitution Contra substitution Main actor
Cleaning efficiency Industrial users (technical and quality view)
Drying problems (time, quality),
corrosion Industrial users (technical and quality view)
Fire and explosion risk Industrial users
More advanced & expensive waste water equipment
Industrial users (economic view)
Difficult sharpening of the cleaning agent
Industrial users (process handling)
Energy and water consumption Industrial users (environmental view)
Less risks of spilling and soil Industrial users (environmental view)
Less health hazards Authorities, workers, public, neighbours
Hydrocarbons
Kooperationsstelle Hamburg, June 2002 15
Workshops 4: Metal Parts Cleaning
SubstitutionChlorinated solvents
Carbontetra-chloride (CCL4)(1850 to 1940)
Trichloroethylene(1920 to today, loosing market share towards PER)
Perchloro-ethylene(1930 to today)
Chlorofluoro-carbons CFC’ s (1940 to 1980)
Hydrochlorofluoro-carbons (HCFC’s) (1975 to today)
1,1,1,Trichloroethane and similar chlor. solv. (1920 to a very limited use today)
Hydrofluoroether HFE’s and Perfluorocarbons (PFC’s) (1975 to today)
MINOR USE AND ROUTE OF SUBSTITUTION
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Workshops 4: Metal Parts Cleaning
Substitution IIHydro carbons
CRUDE SOLVENT MIXTURES OF ALL TYPES MAINLY ALKANES CONTAINING AROMATES
SOLVENT MIXTURES without aromates(from 1980)
SOLVENT MIXTURES with a lower VP and without aromates(from 1990)
Alcohols, Ketones, Esters, Ethers, acetates, all other hydrocarbon based alternatives
SOLVENT MIXTURES with less impurities and without benzene(from 1960)
SEMI-AEQUEOUS CLEANERS
MINOR USE AND ROUTE OF SUBSTITUTION
MAJOR USE AND ROUTE OF SUBSTITUTION
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Workshops 4: Metal Parts Cleaning
Substitution IIIAqueous cleaners
WATER WITH CAU-STIC SODA OR SOAP for special purposes(from 1850)
MAJOR USE AND ROUTE OF SUBSTITUTION
WATER WITH BETTER BIODEGRADABLE and LESS TOXIC COMPONENTS(from 1985)
WATER WITH EFFECTIVE DETERGENTS(from 1975)
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Workshops 4: Metal Parts Cleaning
Substitution IVOther cleaning alternatives
CLEANING WITH SUPERCRITICAL CARBONDIOXIDE
CHANGE OF PRODUCTION PROCESSES AVOIDING DIRT LIKE CUTTING WITHOUT CUTTING FLUIDS
PLASMA, LASER, NANO CLEANING
HC AND CHLORINATED SOLVENTS
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Workshops 4: Metal Parts Cleaning
Implications for BusinessesThe 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.
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Workshops 4: Metal Parts Cleaning
Implications for Businesses II
Example 1Aluminium 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 2Spray can cleaning in vehicle repair
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Workshops 4: Metal Parts Cleaning
ConclusionsRisk 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.
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Workshops 4: Metal Parts Cleaning
Conclusions IISingle important factors overview Economics
Costs for investments in new cleaning equipment hinder substitution
Economics/costs hindrance to substitution
Technical functionality
Supposed less functional effectiveness hinder substitution efforts
Technical functionality/process integration hindrance to substitution
Social factors
Increasing importance of environmental and health aspects
Social factors/communication B2B support for substitution
Risk assessment
Complex water based alternatives need complicated risk assessments
risk assessment/RA of alternatives/shift of risks hindrance to substitution
Regulation
Regulation support substitution for large installations but not in SME´s
concerning large enterprises strong support for substitution
concerning small and medium enterprises no influence
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