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Using Methanol Safely

G.C. Wellon, P.Eng.Manager, Responsible Care

04 February 2008

Overview

• Methanex – who we are

• Responsible Care – why we care

• Methanol and its properties

• Health affects & first aid

• Protection & Detection

• Fire Prevention

• Spill Response

• Resources Available

Methanex Corporation

• Methanex Corporation

8 Methanex is the world’s largest methanol producer and marketer

8 Head office in Vancouver, Canada

8 Production facilities in Chile, New Zealand and Trinidad

8 Marketing offices located in Asia Pacific, Europe, North America and South America

Methanex Global Supply Chain

OfficeOffice

Production HubProduction Hub

Flexible AssetFlexible Asset

Responsible Care®

• Responsible Care®

8 Responsible Care®, originated by the Canadian Chemical Producers’ Association, is a guiding principle that Methanex applies globally as its commitment to:

• Health and safety – employees, suppliers, customersand all methanol users

• Environmental protection

• Safe operation in communities where Methanex operates

Responsible Care®

• Responsible Care®

8 Incorporated into all Methanex business units

8 Encompasses the life cycle of our products –

• inception Þ manufacture Þ use Þ ultimate disposal

8 Recognise & respond to community concerns

8 Increase knowledge by providing information to customers, end users, community, and others


• Traditional Methanex customers – large chemical manufacturers

8 Other applications becoming more common and growing rapidly

• DME, biodiesel manufacture, Waste water treatment

8 As the largest MeOH producer, Methanex has a responsibility to communicate about Methanol safety

8 Why do we think this is necessary?

Recent Incidents

Firefighters arrive at the scene of a methanol storage tank that exploded, claiming the lives of two municipal workers. Photo: WESH-TV, Orlando, FL.

January 11, 2006

Recent Incidents

Biodiesel fire in Canby, ORPhoto courtesy: Canby Fire

June 23, 2006

Methanol

• Methanol

8 Clear, colorless liquid

8 Made up of carbon, hydrogen and oxygen

methanol CH3OH

Methanol

• Methanol

8 Used as a building block for other chemicals:

• formaldehyde, acetic acid, methyl amine, methyl methacrylate …

• which in turn are used to make adhesives, paints, plastics, resins, textiles …

8 Many other uses:

• windshield wiper fluid

• biodiesel

• waste water treatment

• fuel – race cars, model aircraft, fuel cells, cooking

Flammable

Burns with a clear, low heat flame

Difficult to see during daylight

Impact confined to size of spill

Biodegrades quickly

Soluble in water

Readily absorbed into the body

Important Properties of Methanol

Methanol Safety Risks

• Methanol – 2 Key Safety Risks

8 Fire

8 Health

• These risks can be managed to keep you safe

Managing the Health Risk

• Methanol Health Risk

8 As a liquid or vapour, methanol is poisonous

• Cannot be made to be non-poisonous

Ceiling = 800ppm

Detect odour = 2000ppm

Time Weighted Average

TWA = 200ppm

Short Term Exposure Limit

STEL = 250ppm

Immediately dangerous to life and health

IDLH = 6000ppm

CH3OH

Methanol Inhalation Toxicity Data

A 0.1 % solution @ 20°C gives an air/vapour mixture above the solution of 200ppm (TWA)

A 100% solution @ 20°C gives an air/vapour mixture above the solution of 105,000ppm (IDLH @ 6000)

CH3OH

Methanol Inhalation Toxicity Data



8 Symptoms of methanol poisoning:

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

• Swallowing as little as 50 mL or less than¼ cup can be fatal



8 4 routes into the body

• Skin contact

• Eyes

• Breathing

• Swallowing

• Health Effects

8 Skin Contact

• May cause dermatitis

8 Eye Contact

• May cause irritation, tearing and burning

8 Inhalation

• Methanol will absorb into the body very quickly as a vapour with weakness and dizziness coming on fast

8 Ingestion

• 50 ml can be fatal, as little as a mouth full



• Personal Treatment if Exposed

8 Contact with Skin:

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

• Wash affected area with soap and water for 15 minutes

• If irritation occurs, seek medical attention



8 Contact with Eyes:

• Immediately flush with gently running water

• Continue for at least 15 minutes

• Ensure all surfaces and crevices are flushed by lifting upper and lower eyelids

• Obtain medical attention



8 Inhalation:

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

• May require artificial respiration

• Obtain medical attention – possibility of delayed onset of symptoms



8 Ingestion:

• Swallowing even small amounts of methanol can belife threatening

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

• Do NOT induce vomiting

• Obtain medical attention immediately


• Personal Protection

8 Protect the 4 routes of entry

• Skin contact

• Eyes

• Breathing

• Swallowing

Low risk of vapour & Low volume splash

8 Fire retardant clothing

8 Gloves

• Silvershield or • Disposable 0.9mm Nitrile

8 Eye protection

• safety glasses with side shields• possibly full face shield

8 Boots

• full foot cover

Personal Protection

High risk of vapour & Low volume splash

Personal Protection

8 Full chemical suit

8 Gloves

• chemical resistant rubber

8 Canister with full face mask

• Class 1 Organic Vapour• e.g., AX-P3

8 Boots


High risk of vapour & High volume splash

Personal Protection


8 Gloves


8 CABA / SCBA

• compressed air breathing apparatus• self-contained breathing apparatus

8 Boots


Large volume emergency response clean up

Personal Protection


• Fully encapsulating suit

8 Gloves


8 CABA / SCBA

• compressed air breathing apparatus• self-contained breatheing apparatus

8 Boots


8 Methanex uses SCBA / CABA Respiratory Protection

Personal Protection

8 Can use canisters with Full Face Mask

• Class 1 organic vapour or AX-P3

• Monitor atmosphere if using canisters

• Can use @ 500ppm for aprox. 20 min

To avoid adverse health affects, monitor your atmosphere using either...

• Detector tubes

• Electronic Instruments

• Absorbent tubes

• Biological Monitoring

Detection of Methanol

8 One off reading

8 Require a pump

8 Sample air through tube

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

Detector Tubes

8 Continued readout

8 Can set alarm

8 e.g., Draeger Toximeter PAC III

8 Sensor for CO2

8 Cross sensitive for Methanol

Electronic Instruments

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

8 Tube with silica gel

8 Connected to pump

8 Analysis in laboratory by Gas Chromatography

Absorbent Tubes

8 Analysis of urine

• Baseline aprox. 2-5 mg/L

• >15mg/L considered exposed

8 Examination by Opthamologist

8 Analysis of blood

• liver functions

Biological Monitoring

Flash point 11°C

LEL 6% UEL 36%

Autoignition point 470°C

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

Managing the Fire Risk

When is methanol flammable?


• Methanol Fire Risk

8 Methanol is flammable within a specific temperature range:

• Between 50°F and 106°F

• ( 10°C to 41°C )

8 This means that methanol will not burn at temperatures below 50°F / 10°C


• Methanol Fire Risk

8 Methanol burns with a clear blue flame

8 Very difficult to see in bright light / sunlight

8 Methanol can be on fire and you may not be able to tell

• Only indication may be a shimmering “heat haze”

• OR something burning nearby


• Fire Prevention

8 Methanol – Water mixtures as low as 25% methanol are still classified as flammable (NFPA)

8 One way to prevent a fire if there is a methanol spill is to dilute with at least 4 parts water

• Note that mixtures below 25% can still burn, but it’s more difficult to do so

• The mixture should be contained; this creates a larger volume of liquid to clean up


• Fire Prevention

8 Fire Triangle

• Requires all three elements present to have a fire

FUEL

OXYGENIGNITIONSOURCE

( methanol is a fuel )


• Fire Prevention

8 Fire Triangle

• Aim is to break the triangle

FUEL

OXYGEN

General, best precaution is

ELIMINATION of IGNITION SOURCES


• Fire Prevention

8 Fire Triangle

• Aim is to break the triangle

• Some companies, some applications require removal of O2

• More complicated and expensive to achieve

FUEL

IGNITIONSOURCE


• Fire Detection

8 High tech solutions:

• Heat sensors• Infrared cameras• Alarms

8 Low tech solutions:

• Operator on watch• Pressurized tubing near potential leak locations


• Fire Fighting

8 Fixed systems vs. portable systems

8 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)

• 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 Response

Procedure for a large spill:

Resources

• Resources from Methanex

8 More information about methanol or its safety

• Material Safety Data Sheet

o 15 languages

• Technical Information & Safe Handling Guide for Methanol

o 9 languages

• Land-based safety training video

o 10 languages

• Ship-based safety training video

o 12 languages

• Biodiesel-focused methanol safety video

Resources

• Resources from Methanex

8 More information about methanol or its safety

• Internet: www.methanex.com

• E-mail: [email protected] [email protected]

• Phone: Vancouver, Canada +1-604-661-2600

Dallas, Texas +1-972-702-0909

(for other locations, please see Methanex web site above)


Q&A