kooperationsstelle hamburg, june 20021 substitution of hazardous chemicals in products and processes...

Kooperationsstelle Hamburg, June 2002 1

Substitution of Hazardous Chemicals in Products and Processes

Workshop 4

Metal Parts CleaningKlaus Kuhl

Hamburg, June 14, 2002


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



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)


Material composition (steel, cast, alu, alloys,...),

size, weight, geometry,narrow gaps, tiny holes,

blind holes


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



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)



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)



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



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)



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

-



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%



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



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)



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



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



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



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



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)



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



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.



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



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.



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

kooperationsstelle hamburg, june 20021 substitution of hazardous chemicals in products and processes...

Documents

painting cleaning

welding cleaning

final cleaning

automobile parts cleaning

metal parts cleaning

kooperationsstelle hamburg

properties of parts

frequency of parts type