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MethanolMethanolSafe HandlingSafe Handling

www.methanol.orgwww.methanol.org

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Recent IncidentsRecent Incidents

Methanol Storage TankExplosion Kills Two Workers at

Wastewater Treatment Plant

Daytona Beach, Florida

January 11

2006

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Recent IncidentsRecent Incidents

Biodiesel Plant Explosion

Decaturville, Tennessee

August 15

2008

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Recent IncidentsRecent Incidents

August 22

2008

Train Derailment and Explosionof Rail Cars

Carrying Methanol and Crude Oil

Luther, Oklahoma

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Recent IncidentsRecent Incidents

July 7

2009

Methanol tainted “Bootleg”Alcohol Kills 10

Injures Over 159

Ha Noi, Vietnam

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Methanol InstituteMethanol Institute

• MI Established in 1989

• Serves as the global tradeassociation for the worldMethanol Industry

• Directs Product StewardshipActivities

• Initiates Market DevelopmentEfforts

• The Voice of the GlobalMethanol Industry

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Product Stewardship Job #1Product Stewardship Job #1

• As the global trade association for themethanol industry, product stewardship isour primary concern.

• The Methanol Institute's ProductStewardship Committee is responsible formethanol health and safety initiatives,including product risk evaluation,exposure risks throughout the supplychain, education, and training on propermethanol handling. The productstewardship tools developed by thecommittee and its individual members willbenefit the global methanol industry.

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What is Methanol?What is Methanol?

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Properties of MethanolProperties of Methanol

• Simple molecule rich inhydrogen, with only asingle carbon bond.

• Clear and colorless liquidat room temperature andambient pressure.

• Also known as “woodalcohol,” methanol can beproduced from a widerange of feedstocks.

CHCH33OHOH

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Physical PropertiesPhysical Properties

• Name: Methanol

• Chemical Family:Aliphatic Alcohol

• Synonyms: Carbinol;Methyl Alcohol; WoodAlcohol; Wood Spirits

• Formula: CH3OH

• CAS #: 67-56-1

• Form: Colorless Liquid

• Odor: Faintly sweet alcohol

• Boiling Point: 148o

• Freezing Point: -144o

• pH: 7.2

• Solubility: 100%

• Vapor Density: 1.11 (@60o)

• Vapor Pressure: 1.86 psia(@68o)

• Density: 6.63 lb per gallon

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Methanol: EssentialMethanol: EssentialChemical Building BlockChemical Building Block

Source: Methanex

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World Methanol Demand

0

5000

10000

15000

20000

25000

30000

35000

40000

45000

50000

55000

2003 2004 2005 2006 2007 2008 2009 2010

(000

)T

on

nes

per

Yea

r

Formaldehyde MTBE Acetic Acid MMA/DMT Fuels Other

JJ & A

Op Rate

83 %

CAPACITY

100 %

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PolygenerationPolygeneration

Natural Gas

Coal

Synthesis Gas

Methanol

Methanol

Gasoline

Fuels DME

Chemicals

Formaldehyde

Acetic Acid

Olefins

Chemicals

MTBE

Fuels

CO2

Biomass

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UNDERSTANDING THEUNDERSTANDING THERISKSRISKS

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Must Knows of MethanolMust Knows of Methanol

Flammable

Burns with a clear, low heat flame

Difficult to see during daylight

Impact confined to size of spill

Biodegrades quickly

Soluble in water

Toxic

Readily absorbed into the body

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MethanolMethanol Safety Risks

• Methanol – 2 Key Safety Risks

Health

Fire

• These risks can be managed to keep yousafe

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Managing the Health Risk

• Four routes into the body• Breathing (inhalation) is the most common

• Skin contact

• Eye contact

• Swallowing (ingestion)

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Ceiling = 800ppm

Detect odour = 2000ppm

Time Weighted Average

TWA = 200ppm

Short Term Exposure Limit

STEL = 250ppm

Immediately dangerous tolife and health

IDLH = 6000ppm

CH3OH

Methanol InhalationMethanol InhalationToxicity DataToxicity Data

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Methanol IngestionMethanol Ingestion

● Symptoms of methanol poisoning:

• Weakness, dizziness, nausea, vomiting,dimness of vision and unconsciousness.

• Swallowing as little as 50 mL of methanol or lessthan ¼ cup can be fatal.

• Prognosis: Outcomes are excellent whenasymptomatic methanol-poisoned patients aretreated promptly.

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Treatment for exposureTreatment for exposure

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Managing the Health RiskManaging the Health Risk

• Treatment for Inhalation

Inhalation:

• Remove the person to fresh air – IF IT IS SAFETO DO SO

• May require artificial respiration

• Obtain medical attention – possibility of delayedonset of symptoms

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Managing the Health RiskManaging the Health Risk

• Treatment for Skin Contact

Contact with Skin:

• Remove clothing that is soaked with methanol;treat clothing as hazardous (flammable)

• Wash affected area with soap and water for 15minutes

• If irritation occurs, seek medical attention

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Managing the Health RiskManaging the Health Risk

• Treatment for Eye Contact

Contact with Eyes:

• Immediately flush with gently running water

• Continue for at least 15 minutes

• Ensure all surfaces and crevices are flushed bylifting upper and lower eyelids

• Obtain medical attention

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Managing the Health RiskManaging the Health Risk

• Treatment for Ingestion Ingestion:

• Swallowing even small amounts of methanol canbe life threatening

• Onset of symptoms may be delayed for 18 – 24hours

• Do NOT induce vomiting

• Obtain medical attention immediately

• Drinking ethanol blocks methanol metabolism

• Hospital injection of Antizol

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Personal ProtectionPersonal Protection

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Managing the Health RiskManaging the Health Risk

• Personal Protection

Protect the 4 routes of entry

• Skin contact

• Eyes

• Breathing

• Swallowing

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Low risk of vapour & Low volume splash

Fire retardant clothing

Gloves

• Silvershield or• Disposable 0.9mm Nitrile

Eye protection

• safety glasses with side shields• possibly full face shield

Boots

• full foot cover

Personal ProtectionPersonal Protection

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High risk of vapour & Low volume splash

Personal ProtectionPersonal Protection

Full chemical suit

Gloves

• chemical resistant rubber

Canister with full face mask

• Class 1 Organic Vapour• e.g., AX-P3

Boots

• chemical resistant rubber

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High risk of vapour & High volume splash

Personal ProtectionPersonal Protection

Full chemical suit

Gloves

• chemical resistant rubber

CABA / SCBA

• compressed air breathing apparatus• self-contained breathing apparatus

Boots

• chemical resistant rubber

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Large volume emergency response clean up

Personal ProtectionPersonal Protection

Full chemical suit

• Fully encapsulating suit

Gloves

• chemical resistant rubber

CABA / SCBA

• compressed air breathing apparatus• self-contained breathing apparatus

Boots

• chemical resistant rubber

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Detection of MethanolDetection of Methanol

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To avoid adverse health affects,monitor your atmosphere usingeither...

• Detector tubes

• Electronic Instruments

• Absorbent tubes

• Biological Monitoring (pre/postexposure)

Detection of MethanolDetection of Methanol

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One off reading

Require a pump

Sample air through tube

http://www.draeger.com/ST/internet/US/en/Products/Detection/Drager-Tubes/draeger_tubes.jsp

Detector TubesDetector Tubes

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Continued readout

Can set alarm

e.g., Draeger Toximeter PAC III

Sensor for CO2

Cross sensitive for Methanol

Electronic InstrumentsElectronic Instruments

http://www.draeger.com/ST/internet/US/en/Products/Detection/PortableInstruments/SingleGasMonitors/single_gas_monitors.jsp

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Tube with silica gel

Connected to pump

Analysis in laboratory by GasChromatography

Absorbent TubesAbsorbent Tubes

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Analysis of urine

• Baseline aprox. 2-5 mg/L

• >15mg/L considered exposed

Examination by Ophthalmologist

Analysis of blood

• liver functions

Biological MonitoringBiological Monitoring

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Managing Fire RiskManaging Fire Risk

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Methanol FlamesMethanol Flames

• Methanol burns with a clear blue flame and canbe very difficult to see in bright light / sunlight.

• Methanol can be on fire and you may not beable to tell.

• It is possible, though highly unlikely, thatspectators or firefighters might fail to notice theheat and unknowingly walk into a methanol fire.– Only indication may be a shimmering “heat

haze”– OR something burning nearby

• In the great majority of fires, however, burningmaterials (such as building materials, engine oil,upholstery, paint, etc.) would produce bothsmoke and visible flames.

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Flash point 11°C

LEL 6% UEL 36%

Autoignition point 470°C

@ 20°C a 40% solution will notignite (air/vapour mixture approx. 4%)

@ 20°C a 26% solution will self extinguish

Managing the Fire RiskManaging the Fire Risk

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Fire PreventionFire Prevention

• Methanol – Water mixtures aslow as 25% methanol will stillburn.

• One way to prevent a fire ifthere is a methanol spill is todilute with at least 4 partswater.– The mixture should be

contained; this creates a largervolume of liquid to clean up.

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Managing the Fire RiskManaging the Fire Risk

• Methanol Fire Risk

Methanol is flammable within a specific temperaturerange:

• Between 50°F and 106°F

• ( 10°C to 41°C )

This means that methanol will not burn attemperatures below 50°F / 10°C

Compared with gasoline:

methanol is harder to ignite

burns 75% slower

methanol fires release heat at only one-eight the rate ofgasoline

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Managing the Fire RiskManaging the Fire Risk

• Fire Tetrahedron has replacedthe fire triangle to understand theingredients necessary for mostfires.

• In order to ignite and burn, firesneed heat, fuel and oxygen.

• The fourth element is chemicalreaction that can feed more heaton a fire.

• Goal is to these elements toprevent fires from occurring.

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Managing the Fire RiskManaging the Fire Risk

• Fire Fighting

Fixed systems vs. portable systems

Materials – depending on size of fire &location

• CO2 extinguisher

• Dry chemical extinguisher

• Water; fine spray; mist; fog

• Foam – alcohol resistant type, e.g.,AFFF(R)

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ManagingManagingEnvironmental RiskEnvironmental Risk

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Environmental FateEnvironmental Fate

• Methanol is ubiquitous in theenvironment, and is readilybiodegradable.

• Methanol is injected into hundredsof U.S. wastewater treatment plantsto accelerate the biodegradation ofwastewater.

• Each year, 400 million gallons ofmethanol used in windshieldwasher fluid in the U.S.

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HalfHalf--Lives of Methanol andLives of Methanol andBenzene in the EnvironmentBenzene in the Environment

5-16

10-730

1-7

1-7

Surface Water

Groundwater

2-203-30Air

5-161-7Soil

Benzene

Half-Life (days)

Methanol

Half-Life (days)

EnvironmentalMedium

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Fate and TransportFate and Transport

• “The fate and transport of methanol in theenvironment is well understood. Methanolspills to the soil, groundwater, and surfacewater will quickly biodegrade under bothaerobic and anaerobic conditions and,consequently, methanol is not expected topersist. Methanol exhibits a lower toxicity tohumans and indigenous microbes thenconventional gasoline. Therefore, based onthis analysis, methanol appears to be a moreenvironmentally benign fuel compared toconventional gasoline.”– Malcolm Pirnie, Inc., January 1999

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• Treat situation as HAZARDOUS

• Eliminate all ignition sources, including vehicles

• Secure an area up to 500m radius around the spill/leak

• Restrict access to spill area, move people upwind

• Personnel entry - full chemical suit, CABA, rubber boots & gloves

• Fire fighters - full bunker gear, CABA, rubber boots and gloves

• Decontaminate all personnel and equipment

Spill ResponseSpill Response

For large spills:

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Spill ResponseSpill Response

• For Small Spills:

• Cat litter can be used as anabsorbent for small spills.

• SafetyVac® sells a line of machineswith capacities ranging from 16 to500 US gallons that safely vacuumspills.

• Safety Formula Two™ can alsorender methanol spills inert with asingle spray application

• Info at: www.safetyvac.com

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Safety ToolsSafety Tools

• The Methanol Institute’s ProductStewardship Committeerecognized the need forinformation to prevent futureincidents and developed thefollowing safety tools:

– Methanol Safe Handling Manual

– Crisis Communications Guidebook

– Methanol Safe Handling Video

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Methanol Safe HandlingMethanol Safe HandlingManualManual

• Prepared by Alliance ConsultingInternational, an environmental andhealth and safety professionalservices firm based in San Diego,California

• Purpose: “To promote the safehandling of methanol in order toprotect your health and that of yourco-workers, your workplace, theenvironment and your community”

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TopicsTopics

• Methanol General Industry Information

• Transportation and Storage

• Health and Safety

• Managing Methanol Safely: ProcessSafety

• Fire Safety

• Emergency Response

• Environmental Protection

• Product Stewardship

• Risk Communication

• Glossary; References; PhysicalProperties

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Content OrganizationContent Organization

• The Manual’s chapter organization andcontent are intended to provide convenientaccess to practical information.

• Key facts and useful references arehighlighted in the text.

• Additional technical data, such asmethanol’s chemical, physical, andthermodynamic properties can be found inthe appendices.

• Reference section presents lists ofscientific and technical resources for morein-depth research.

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Crisis CommunicationsCrisis CommunicationsGuidebookGuidebook

• Developed by Environ, aninternational environmentalconsulting firm.

• The Guidebook is intended to assistin preventing, preparing for, andresponding to a crisis situation.

• Effective communication involvescooperation with other stakeholders– employees, public authorities at alllevels, news media, members of thecommunity.

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TopicsTopics

• Emergency Management

• Prevention

• Preparedness/Mitigation

• Establishing the Emergency Response Team

• Identifying Key Audiences and DeliveringInformation

• Fixed Installations and Transport

• Terrorism

• Incident Investigations

• Product Stewardship

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Content OrganizationContent Organization

• The Guidebook uses fictional scenarios todescribe incident response procedures.

• Exhibits describe key global responseauthorities and include sample pressreleases.

• Contact information is provided for globalemergency response authorities, alongwith sample contact data tools.

• Example drills and exercises arepresented.

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Three Primary StepsThree Primary Steps

• Identifying the roles that make up theEmergency Response Team anddetermining who will fill those roles.

• Gathering contact information foremergency responders, governmentalagencies, and the media, makingpersonal introductions whereappropriate.

• Planning and conducting regularemergency drills and exercises,including the participation of localemergency responders.

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Global ReachGlobal Reach

• The Methanol Safe HandlingManual and Crisis CommunicationsGuidebook are posted on MI website’s “Health, Safety andEnvironment” page.

• These documents have beentranslated into Chinese/Mandarin;Spanish; Japanese; and Arabic.

• MI member companies distributingthroughout global distribution chain.

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Safe Handling VideoSafe Handling Video

• A Methanol Safe HandlingVideo has also beenproduced to complement theManual.

• Provide practical, hands-onguidance.

• Will be translated intomultiple languages.

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Methanol Source RequestMethanol Source Request

• Methanol Source Request fromMI’s web site homepage.

• Let us know how muchmethanol you need, where itwill be delivered, and howoften.

• We share your information withall of our member companiesand encourage them to contactyou directly to discuss priceand supply.

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ResourcesResources

• Resources from Methanol Institute atwww.methanol.org– Methanol Safe Handling Manual

– Crisis Communications Guidebook

– Methanol Health Effects and Safe Handling FactSheets

– Tables on methanol physical properties

• MI Member companies also offer valuableproduct stewardship resources.