Chemical storage B.Brazier 2010. BACKGROUND Fire and explosion are only two of the many hazards....

Chemical storageChemical storage

B.Brazier 2010B.Brazier 2010

BACKGROUNDBACKGROUND

• Fire and explosion are only two of Fire and explosion are only two of the many hazards. the many hazards.

• Over 500 chemical-storage incidents Over 500 chemical-storage incidents were over the past 5 years. were over the past 5 years.

• These incidents occurred due to These incidents occurred due to unsafe chemical storage practices. unsafe chemical storage practices.


Storage-related incidentsStorage-related incidents

• Principal causes:Principal causes:• 1. Improper or non-existent labeling of 1. Improper or non-existent labeling of

chemicals in storage.chemicals in storage.• 2. Storage of chemicals beyond the 2. Storage of chemicals beyond the

recommended shelf-life. recommended shelf-life. • 3. Degradation of chemical storage 3. Degradation of chemical storage

containers. ("Polyethylene Bottles containers. ("Polyethylene Bottles Containing Corrosive Chemicals May Containing Corrosive Chemicals May Deteriorate With Prolonged Use,"Deteriorate With Prolonged Use,"


IMPROPER LABELING IMPROPER LABELING

• Small amounts of "left-over" chemicals had Small amounts of "left-over" chemicals had accumulated over several years. accumulated over several years.

• The chemicals were prepared for recycling or disposal The chemicals were prepared for recycling or disposal by removing the chemicals from their individual by removing the chemicals from their individual containers and putting them into a plastic bucket.containers and putting them into a plastic bucket.

• Powder that was thought to be a base material was Powder that was thought to be a base material was poured from an unlabeled jar into the bucket, poured from an unlabeled jar into the bucket, resulting in spontaneous ignition. resulting in spontaneous ignition.

• The building then had to be evacuated, and the fire The building then had to be evacuated, and the fire department was summoned to put out the fire.department was summoned to put out the fire.

• Analysis performed by the laboratory later revealed Analysis performed by the laboratory later revealed that the powder was maleic anhydride, that the powder was maleic anhydride,


EXTENDED TIME IN STORAGEEXTENDED TIME IN STORAGE• Unrefrigerated ether cannot be stored safely for Unrefrigerated ether cannot be stored safely for

over 6 months because peroxides, which are over 6 months because peroxides, which are shock-sensitive, can form and cause an shock-sensitive, can form and cause an explosion.explosion.

• The building that housed the 18 ether containers The building that housed the 18 ether containers had to be evacuated, and barricades had to be had to be evacuated, and barricades had to be assembled to protect flammable inventory. assembled to protect flammable inventory.

• The peroxides were then neutralized with ferrous The peroxides were then neutralized with ferrous sulphate, and all 21 containers were removed.sulphate, and all 21 containers were removed.

• Periodic inspection and removal of outdated Periodic inspection and removal of outdated chemicals in storage would have prevented the chemicals in storage would have prevented the incident. incident.


Storage rulesStorage rules

1.1. Label all chemicals. The name and address of Label all chemicals. The name and address of the manufacturer or other responsible party the manufacturer or other responsible party must be listed on the label. Chemicals with a must be listed on the label. Chemicals with a shelf life should be labeled with the date shelf life should be labeled with the date received. received.

2.2. Store chemicals in the locations Store chemicals in the locations recommended (i.e., where the temperature recommended (i.e., where the temperature range, vibration, or the amount of light does range, vibration, or the amount of light does not exceed the manufacturer's not exceed the manufacturer's recommendations). Make sure that chemicals recommendations). Make sure that chemicals that are stored together are compatible. that are stored together are compatible.


Storage rulesStorage rules

3. Inspect annually all chemicals in 3. Inspect annually all chemicals in stock and storage.stock and storage.

4. Hazardous chemicals should be 4. Hazardous chemicals should be inspected every 6 months. inspected every 6 months.

5. Some hazardous chemicals may 5. Some hazardous chemicals may require more frequent inspections. require more frequent inspections.

6. Any outdated materials should be 6. Any outdated materials should be properly disposed of or replaced if properly disposed of or replaced if necessary necessary


RulesRules

7. Keep only enough inventory necessary 7. Keep only enough inventory necessary for uninterrupted operation. for uninterrupted operation.

8. Chemical inventory should be 8. Chemical inventory should be maintained at a minimum to reduce maintained at a minimum to reduce fire, exposure, and disposal hazards fire, exposure, and disposal hazards

9. Rotate new shipments of chemicals 9. Rotate new shipments of chemicals with existing stock so that the oldest with existing stock so that the oldest stock is available first. stock is available first.


Storing Storing AcidsAcids

• Store large bottles of acids on low shelf or in Store large bottles of acids on low shelf or in acid cabinets.acid cabinets.

• Segregate oxidizing acids from organic acids, Segregate oxidizing acids from organic acids, flammables and combustible materials.flammables and combustible materials.

• Segregate acids from bases and active metals Segregate acids from bases and active metals such as sodium, potassium, etc.such as sodium, potassium, etc.

• Use bottle carrier for transporting acid bottles.Use bottle carrier for transporting acid bottles.

• Have spill control pillows or acid neutralizers Have spill control pillows or acid neutralizers available in case of spill.available in case of spill.


Strong Oxidizing AcidsStrong Oxidizing Acids

• Chromic AcidChromic Acid

• Nitric AcidNitric Acid

• Hydrobromic AcidHydrobromic Acid

• Perchloric AcidPerchloric Acid

• Iodic AcidIodic Acid

• Sulfuric AcidSulfuric Acid


Organic AcidsOrganic Acids

• Acetic AcidAcetic Acid

• PhenolPhenol

• Benzoic AcidBenzoic Acid

• Trichloracetic AcidTrichloracetic Acid


Storing BasesStoring Bases

• Segregate bases from acidsSegregate bases from acids

• Store solutions of inorganic Store solutions of inorganic hydroxides in polyethylene hydroxides in polyethylene containers.containers.

• Have spill control pillows or caustic Have spill control pillows or caustic neutralizers available for spills.neutralizers available for spills.


BasesBases

• Ammonium HydroxideAmmonium Hydroxide

• Calcium HydroxideCalcium Hydroxide

• BicarbonatesBicarbonates

• Potassium HydroxidePotassium Hydroxide

• CarbonatesCarbonates

• Sodium HydroxideSodium Hydroxide


FlammableFlammable

• Store in approved safety cans or cabinetsStore in approved safety cans or cabinets

• Segregate from oxidizing acids and oxidizers.Segregate from oxidizing acids and oxidizers.

• Keep away from any source of ignition: Keep away from any source of ignition: flames, heat or sparks.flames, heat or sparks.

• Know where fire fighting equipment is stored Know where fire fighting equipment is stored and how to use.and how to use.

• If volatile flammable liquids are stored in a If volatile flammable liquids are stored in a refrigerator it must be in an explosion-proof refrigerator it must be in an explosion-proof (lab-safe) refrigerator.(lab-safe) refrigerator.


Flammable SolidsFlammable Solids

• Benzoyl peroxideBenzoyl peroxide

• Phosphorous, yellowPhosphorous, yellow

• Calcium CarbideCalcium Carbide

• Picric AcidsPicric Acids


Flammable GasesFlammable Gases

• AcetyleneAcetylene

• Ethylene OxideEthylene Oxide

• AmmoniaAmmonia

• FormaldehydeFormaldehyde

• ButaneButane

• HydrogenHydrogen

• Carbon Carbon MonoxideMonoxide

•Hydrogen Sulfide•Ethane•Methane•Ethyl Chloride•Propane•Ethylene•Propylene


Storage of OxidizersStorage of Oxidizers

• Store in a cool, dry place.Store in a cool, dry place.

• Keep away from flammable and Keep away from flammable and combustible materials, such as paper combustible materials, such as paper or wood.or wood.

• Keep away from reducing agents Keep away from reducing agents such as zinc, alkaline metals, formic such as zinc, alkaline metals, formic acid.acid.


Oxidizers - SolidsOxidizers - Solids

• Ammonium DichromateAmmonium Dichromate

• NitratesNitrates

• Ammonium PerchlorateAmmonium Perchlorate

• Ammonium PersulfateAmmonium Persulfate

• Benzoyl PeroxideBenzoyl Peroxide• BromatesBromates• Calcium HypochloriteCalcium Hypochlorite• ChloratesChlorates• Chromium TrioxideChromium Trioxide• Ferric TrioxideFerric Trioxide• Ferric ChlorideFerric Chloride• HypochloriteHypochlorite• IodineIodine

•Permanganic Acid•Periodic Acid•Potassium Dichromate•Potassium Ferricyanide•Potassium Permanganate•Potassium Persulfate•Peroxides, Salts of•Sodium Chlorite, •Sodium DichromateIodates•Sodium Nitrate•Sodium Perborate


Pyrophoric Substances:Pyrophoric Substances: • These ignite spontaneously on contact with air. Store in a These ignite spontaneously on contact with air. Store in a

cool, dry placecool, dry place. .

BoronCadmiumCalciumChromium*Cobalt*DiboraneTitanium*Dichloroborane2-Furaldehyde

Iron*Lead*Manganese*Nickel*Cobalt*Phosphorous, SodiumYellow*Zinc*


Light Sensitive Light Sensitive ChemicalsChemicals• Avoid exposure to light & Store in amber bottles in a Avoid exposure to light & Store in amber bottles in a

cool, dry place.cool, dry place.

BromineBromine Oleic AcidOleic Acid

Ethyl EtherEthyl Ether Potassium FerricyanidePotassium Ferricyanide

Ferric Ammonium CitrateFerric Ammonium Citrate Silver saltsSilver salts

Hydrobromic AcidHydrobromic Acid Sodium IodideSodium Iodide

Mercuric SaltsMercuric Salts Mercurous NitrateMercurous NitrateB.Brazier 2010B.Brazier 2010

CarcinogensCarcinogens

• Label all containers as Cancer Label all containers as Cancer Suspect Agents.Suspect Agents.

• Store according to hazardous nature Store according to hazardous nature of chemicals, e.g., flammable, of chemicals, e.g., flammable, corrosive.corrosive.

• When necessary, store securely.When necessary, store securely.


CarcinogensCarcinogens

• Antimony compoundsAntimony compounds• AcrylonitrileAcrylonitrile• Arsenic compoundsArsenic compounds• BenzeneBenzene• BenzidineBenzidine• ChloroformChloroform• BerylliumBeryllium• Dimethyl SulfateDimethyl Sulfate

•Cadmium compounds•Dioxane•Chromates,Salts of•Ethylene Dibromide•Beta-Naphthylamine•Hydrazine•Vinyl Chloride•Nickel Carbonyl


Chemical Segregation and Chemical Segregation and Storage Groups Storage Groups

• Stanford Storage Group Stanford Storage Group Classification SystemClassification System

• used to segregate chemicals stored used to segregate chemicals stored in the laboratory. in the laboratory.

• It is based on physical and chemical It is based on physical and chemical reactivity information found in the reactivity information found in the MSDS or other references. MSDS or other references.


Storage GroupsStorage Groups

• Storage Groups are groups of chemicals Storage Groups are groups of chemicals that will not react violently if mixed that will not react violently if mixed together. together.

• Stanford has about 10,000 unique Stanford has about 10,000 unique chemicals classified according this chemicals classified according this system in the SCIMS Database. system in the SCIMS Database.

• The Stanford Storage Group system was The Stanford Storage Group system was developed for laboratory scale storage developed for laboratory scale storage


STANFORD COMPATIBLE STANFORD COMPATIBLE STORAGE GROUP CODESSTORAGE GROUP CODES• A letter designation is given to each compatible A letter designation is given to each compatible

group of materials. group of materials. • For example, "A" represents "compatible organic For example, "A" represents "compatible organic

bases, flammables and poisons". bases, flammables and poisons". • "G" is "not intrinsically reactive, flammable or "G" is "not intrinsically reactive, flammable or

combustible". combustible". • A chemical that is incompatible with other chemicals A chemical that is incompatible with other chemicals

in all of the other Storage Groups must be placed in in all of the other Storage Groups must be placed in Storage Group "X". Storage Group "X" chemicals Storage Group "X". Storage Group "X" chemicals must be segregated from all other chemicals.must be segregated from all other chemicals.

• If the information is not available, then Storage If the information is not available, then Storage Group "U" will be assigned. Group "U" will be assigned.




SEGREGATE CHEMICALS BY SEGREGATE CHEMICALS BY COMPATIBLE STORAGE GROUPSCOMPATIBLE STORAGE GROUPS

• Segregate chemicals in a compatible Segregate chemicals in a compatible fashion according to the compatible fashion according to the compatible Storage Groups. Storage Groups.

• If a particular item does not yet have a If a particular item does not yet have a storage group designated, the storage group designated, the researcher must use his best judgement researcher must use his best judgement on how best to store the material.on how best to store the material.

• Keep the different storage groups in Keep the different storage groups in separate cabinets, if possible. separate cabinets, if possible.



• In areas that contain items from In areas that contain items from more than one storage group, there more than one storage group, there is no need to store them is no need to store them alphabetically by storage group (i.e. alphabetically by storage group (i.e. A then B then C). The letters are just A then B then C). The letters are just an arbitrary convention. an arbitrary convention.



• If you must store items from more than one If you must store items from more than one storage group on the same shelf, they must storage group on the same shelf, they must have separate secondary containment for each have separate secondary containment for each group. group.

• For example:For example:– Acetic acid (Storage group "D", organic acid) Acetic acid (Storage group "D", organic acid) – Hydrochloric acid (Storage group "F", inorganic acid) Hydrochloric acid (Storage group "F", inorganic acid) – Nitric acid (Storage group "E", oxidizing) Nitric acid (Storage group "E", oxidizing)

• These all acids but they are incompatible and These all acids but they are incompatible and must be stored in separate secondary must be stored in separate secondary containment and on separate shelves within containment and on separate shelves within the same cabinet. the same cabinet.






Store in same cabinet Store in same cabinet

• If you must store items from many If you must store items from many storage groups in the same cabinet storage groups in the same cabinet with more than one shelf,with more than one shelf,

• put storage group "B" and "X" on the put storage group "B" and "X" on the top shelf. top shelf.

• This will prevent other chemicals This will prevent other chemicals from dripping on them. from dripping on them.



Flammable liquid storageFlammable liquid storage

• If the total quantity of flammable If the total quantity of flammable liquids exceeds 5 Lt, they must be liquids exceeds 5 Lt, they must be stored in a flammable liquid storage stored in a flammable liquid storage cabinet except when in active use. cabinet except when in active use.


OTHER STORAGE OTHER STORAGE CONSIDERATIONS:CONSIDERATIONS:

• Long-term storage on bench tops or in fume Long-term storage on bench tops or in fume hoods is discouraged. hoods is discouraged.

• All containers MUST remain closed except All containers MUST remain closed except when actively adding or removing materials. when actively adding or removing materials. Do not store funnels in open containers. Do not store funnels in open containers.

• Never store hazardous materials next to or Never store hazardous materials next to or above sinks. This includes dark rooms with above sinks. This includes dark rooms with waste fixer stored adjacent to open floor waste fixer stored adjacent to open floor drains. drains.


OTHER STORAGE OTHER STORAGE CONSIDERATIONS:CONSIDERATIONS:

• Store solids above liquids. Store solids above liquids.

• Avoid exposing stored chemicals to Avoid exposing stored chemicals to building heat or to direct sunlight. building heat or to direct sunlight.

• All chemical storage shelving must All chemical storage shelving must have lips and seismic restraints. have lips and seismic restraints.

• Use explosion-proof refrigerators Use explosion-proof refrigerators when storing flammables in a when storing flammables in a refrigerator. refrigerator.



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Chemical storage B.Brazier 2010. BACKGROUND Fire and explosion are only two of the many hazards....

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