Dichloromethane substitution
CAS 75-09-2
synonyms Methylene Chloride DCM
TOXICITY
Dichloromethane has been classified H 351, which can cause cancer according to the criteria of Annex 1 of Regulation (EC) No 1272/2008.
Occupational exposure limit values in workplace air have been set at 50 ppm art R 4412-149 of the Labour Code.
While carcinogenic effects of Dichloromethane have not been proven in humans, precautionary measures are required. However, the inhalation of small amounts (between 250 and 750 ppm) causes a depression of the central nervous system (fatigue, drowsiness). Inhalation of large concentrations causes serious, sometimes fatal, poisoning.
Dichloromethane has an acute toxicity when ingested, it is a moderate skin irritant, the vapours up to 100 ppm do not cause eye irritation, but projections of liquid induce conjunctivitis and keratitis.
Dichloromethane decomposes easily, especially in the presence of water, light or heat; it is therefore always stabilised with phenolic, amine, amylene, cyclohexane, or epoxide compounds.
REGULATION RELATED TO THE ENVIRONMENT
SOLVENT MANAGEMENT PLAN (SMP)
Material report on the entry/exit of solvents to an installation. Installation is understood to mean an industrial site. Its objective is to evaluate the total emissions (directed and diffused) of volatile organic compounds (VOCs) in order to verify compliance with emission limits.
references
www.ineris.fr how to establish a solvent management plan
www.installationsclassees-developpement-durable.gouv.fr annual declaration of polluting emissions
VOC EMISSIONS
French regulations on the reduction of VOC emissions, to date, under the ICPE regulation of 1 June 2015 SEVESO III. Industrial plants falling under the 4330 nomenclature are required to establish a Solvent Management Plan (SMP) to reduce their VOC emissions.
Definition of a VOC
A compound that may be in a gaseous form in the atmosphere which has direct or indirect impact on animals or nature.
Any substance or organic mixture, which is in a gaseous state or evapourates easily under the standard conditions of temperature and pressure, is therefore a VOC when used. Solvents are therefore primarily concerned if they have a vapour pressure greater than 0.01 Kpa at a temperature of 293K (20°).
Dichloromethane with a vapour pressure of 47.400kPa is 100% VOC.
MONITORING OF INDUSTRIAL WASTE
The Framework Directive of the Ministry of the Environment 2008/98/CE sets out the main objectives as well as the prioritisation of actions, in matters of industrial waste
1 Waste prevention
2 Reuse
3 Recycling
4 Recovery
5 Disposal (incineration)
6 Final waste management
"Every producer or holder of industrial waste is responsible under the law for its waste, and the conditions in which it is collected, transported, disposed of or recycled. It is the producer or keeper's principle of responsibility, who must be able to justify the final destination of their waste, and their method of disposal. "
The classification of industrial waste is the subject of a nomenclature (6-digit code) included in the environmental code R 541-7 to R 541-11 and annexes R 541-8
This nomenclature has been updated to be consistent with the CLP regulation and is applicable from 1st June, 2015.
The CLP regulation defines a hazard class for a substance, a preparation, but also for a waste product, which depends on all the products that make up this waste. If the product is classified as hazardous, then the waste is also classified in the same way, and entails the obligation to issue a Waste Management Schedule . The waste must then be taken back by an authorised centre.
The ICPE classification for industrial waste is different.
Sections 4000 on Storage and Stored Quantity
Sections 3000 on the waste itself (IED sections)
Sections 2700 on activities
Industrial waste generated by the use of solvents, degreasers and cleaning agents is included in the nomenclatures
070 101 aqueous cleaning agents
070 103 halogenated solvents (chlorine, bromine, fluorine
070 104 non-halogenated solvents
160 504 pressurised containers (aerosols) which contained solvents, degreasing agents or cleaning agents
OBLIGATION OF RETENTION
Regulatory context
The obligation to store or not to store is subject to two regulations:
- Labour Code - Article R4412 chemical hazard prevention applicable to labeled products.
- ICPE environmental code, law of 19 July 1976 which states "Any storage of a liquid likely to cause the pollution of water or soil must be associated with secondary containment"
Pollution risk
Refer to the chapter on the Water or Soil Pollution.
WATER and SOIL POLLUTION
This includes all industrial establishments that store, use, process or distribute chemicals that are hazardous in terms of flammability or toxicity.
Pollution of water (groundwater, water courses, sewerage networks) or soils, may be caused by a deliberate release, especially in the event of an intrusion on a site, an accidental release, case of a leak at after a hardware failure, fire or explosion.
In the latter case, which is unfortunately the most common, different types of accidents are possible:
- Fire with release of toxic fumes and heat dissipation
- UVCE Unconfined Vapour Cloud explosion, explosion of an unconfined cloud of flammable vapours
- BLEVE Boiling Liquid Expanding vapour Explosion, which generally concerns the explosion of a tank following an increase in temperature and pressure
- BOIL OVER a phenomenon that can occur when there is a film of water in a hydrocarbon storage tank that it is heated during heat dissipation
- DOMINO EFFECT causing one or more other incidents
Water and soil pollution is therefore always highly likely after an incident. If the establishment is subject to declaration or authorisation, a test by the DREAL (Departnent of the Environment, Development and Housing) is then automatically enacted.
In this matter, the DREAL is considered to be the Water Police. It enforces article L 210 of the environmental code "water is part of the common heritage of the nation". Decree 93-743 of 29 March 1993 established the nomenclature of all operations and industrial activities subject to declaration or authorisation. The decree of 11 May 2015, called SEVESO III , set the new reporting threshold at 20L when the halogenated solvents bear the hazard statement H 341 (item ICPE 2564 modified by decree 2013-1301).
In terms of soil pollution, whatever its origin or reason, the regulation is simple and is established on the basis of "the polluters are the payers". However, if soil analysis is made extremely easy by current analytical methods, the costs of soil remediation can be enormous.
The density of dichloromethane, its low solubility in water, and its persistence make it a major risk solvent.
Water agencies have just made a declaration of activity mandatory for companies using halogenated solvents, such as dichloromethane (CERFA No. 5131.03) in order to establish a fee to finance the modernisation of collection networks.
Refer to the chapter on News.
30,000 checks are regularly made each year in France. The DDT, water agencies, ONEMA, as well as the gendarmerie and town halls are empowered to report infractions.
FIRE and EXPLOSION RISK
Dichloromethane is not flammable under normal conditions of use. Its vapours can present a risk of explosion but only at extreme pressures, temperatures or in the presence of a large source of energy.
However, the presence of Dichloromethane in a fire, generates extremely toxic products of combustion, such as hydrogen chloride and phosgene.
COST REPORT
The cost of Dichloromethane is very low, but this cost is only apparent. This compound is a very strong solvent, but also a very high rate of evapouration.
It can be compared to ether, which leads to repeated use to clean and dissolve pollution, often on resins and elastomers used in moulding, laminating or coating.
A simple observation is required:
DREAL inspectors can also make a report on this basis.
The purchasing departments of companies will also have to take into account the economic status of dichloromethane and compare it to any alternative solvent.
Source INRS ED 6058 (in collaboration with CNAMTS, CRAM and CGSS services)
"evaluation of the rate of evapouration and the concentration of a VOC in a workplace atmosphere"
NEWS
New licencing fee on chlorinated solvents
Users of organo-halogenated solvents (dichloromethane) must declare:
- the complete reference of the solvent they purchase
- the name of the manufacturer
- the annual tonnage purchased, expressed in chlorine equivalence (a calculation example is provided in Annex 2 of CERFA 51313.03)
- the type of treatment carried out and the amount of waste declared
- the authorised treatment center
The forms are to be completed and sent to the Water Agencies.
Regular monitoring of releases (including atmospheric) will be carried out.
form on www.lesagencesdeleau.fr
Section on "Use of organo-halogenated solvents"
declaration of activity and its instructions
