Handling of Organic Peroxides

German Regulations - UK Regulations - French Regulations - Dutch Regulations

Organic peroxides must always be handled by skilled personnel, wearing appropriate equipment.  Goggles, gloves, a face mask and a helmet should be worn whenever handling peroxides. Peroxides are formulated to reduce risks. However, these safer formulations remain sensitive and must be handled with care.

Classification and labeling depend on product properties and are described in the material safety data sheet according to the Directive 67/548/EEC and its amendments. The relevant symbols and Risk and Safety phrases are on the label.

In addition to this labeling (according to the European Directive), each package is also identified by the yellow N°5.2 "Organic Peroxide" warning symbol.

Handling procedures should be set up to ensure that peroxides are protected from sources of heat such as hot ambient air, radiators, pipes, direct sunlight, sparks and flames. The recommended storage temperature should be observed at all times. Smoking must be strictly forbidden.

At the work place, only the minimum quantity of peroxide required for one operation should be stored. Return of unused organic peroxide to the original container is not allowed due to risk of contamination. The material must be disposed of.

Dispensing and weighing should be done in a specially designated area and should not be permitted in the storage area.

Spilled materials should be soaked up immediately on an inert absorbent such as Vermiculite or Perlite. The contaminated absorbent should be taken up by non-sparking equipment and disposed of according to local regulations. The area where the spillage occurred should then be cleaned with water containing a surfactant to guarantee that no traces of peroxide are left in the area.

Packaging is chosen in accordance with the characteristics of the organic peroxide. For transportation, only approved packaging material may be used; moreover, the maximum quantity of peroxide per packaging unit is given by transportation regulations.

When peroxides are transported or when they are stored during a long period, pressure can build up within the container due to a small amount of decomposition or volatility of a component in the peroxide formulation. Polyethylene is therefore the preferred packing material since it is relatively inert and is flexible enough to withstand normal pressure build-up.

Peroxides should not be kept in glass or metal vessels where a build up of pressure by decomposition cannot be observed.

Organic peroxides must be kept in their original containers, as contact with rust, ashes, dirt, accelerators, promotors and many chemicals can lead to a violent decomposition.

Storage
Storage regulations vary from one country to another and it is essential to check with local authorities and insurance companies on specific regulations.

In most cases, the regulation (if a regulation exists) defines:

-- A classification group depending on the hazard involved (flammability, decomposition, burning, or explosive properties)
-- The requirements for the storage construction. These specific classifications are available on request (our peroxides are classified according to all existing regulations).

However, the following requirements must be applied in all cases. More specific information is given in your local regulation.

Basic Requirements

A peroxide storage facility must be:

• Located away from the manufacturing area: the hazards linked to the storage of peroxides involve effects outside of the storage building and required safety distances. The minimum safety distances required by local regulations vary according to the country.
• Used exclusively for organic peroxides to avoid contamination. 
• Built with construction material according to local regulations. 
• Equipped with specific electrical installations (explosion proof), heating and cooling systems. 
• Kept under controlled temperature conditions: the maximum storage temperature must not be exceeded and temperature alarms must be installed. 
• Provided with vent relief system and fire protection equipment (water sprays, sprinklers, deluges). 
• Equipped with retaining basins to prevent accidental discharge to the environment. 
• Clearly identified as "peroxide storage" and marked outside "No smoking".

Recommendations to avoid accidents

What to do before delivery of a peroxide:

• Check if the material safety data sheet is available.
• Read MSDS carefully.
• Check the required storage temperature.
• Read the storage requirements.

What to do on arrival:

• Check if the storage building is at the required temperature.
• Mark each container with itsdelivery date.
  Check if the delivered product is at a temperature below the required temperature. If not, the transportation was incorrect. If temperature of the product is above SADT, don't put in storage with other products.
• Check the packages carefully for leakage and spillage.

How to store the product safely:

• Ensure an air cooling circulation of ~ 5 cm between each package and ~ 30 cms with the walls.
• Always verify that the door of the storage area is closed.
• Avoid leaving the door open during long periods. 
• Follow the maximum amount recommended for the storage area.

If the refrigeration system fails:

• The failure is easy to detect in a well built storage area (temperature alarm, etc.), and the time before an accident is long enough to implement preventive measures: refrigeration back-up, transfer to another storage.

How to dispose of the product:

• Disposal must be accomplished in accordance with local regulations.
• Small quantities of organic peroxides that are spilled or became contaminated, or any samples no longer needed should be destroyed.
• Spilled solid peroxides should be carefully swept together, collected into suitable labeled container, and destroyed. Large quantities of organic peroxides must be handled and disposed of differently.
• Peroxide formulation should be diluted in mineral oil or fuel oil to an active oxygen content of less than 1% and then be burnt in an incinerator. This must be done in accordance with local regulations.

What to do with the empty containers:

• They have to be emptied completely and must also be transported as dangerous goods. Follow local regulations.  Some answers may be provided by your supplier.

Safe use and handling of organic peroxide initiator:

1. Know the storage temperature and do not exceed it.
2. Know the SADT "Danger Temperature" and respect it.
3. Equip storage area properly.
4. Have fire extinguishers available.
5. Rotate inventory: "First In, First Out".
6. Take only the amount that will be used.
7. Do NOT return unused initiator to storage buildings.
8. Rinse and slash containers prior to disposal.
9. Immediately clean up spills and dispose of them properly.
10. Protect your eyes and skin.
11. Use appropriate Personal Protective Equipment (PPE).
12. Initiator in large vessels should be diluted.
13. Know your plant's emergency procedures.