methanol booklet final low

Safe Handling Guidelines for Methanol

GPIC IS aReSPonSIbleCaRe ComPanyResponsible Care is the cultural foundation of GPIC’s commitment to health, safety, security, communities and the environment.Although there are hazards associated with methanol, they can be managed to minimise potential risks to people and the environment during the life cycle of methanol.

PReSIdent’S meSSaGe

Dr. Abdulrahman Jawahery

GPIC President

In GPIC, we are committed to upholding our mission and endeavour to use only the best practices in all our manufacturing processes, systems and procedures. As a socially responsible company, we continuously strive to maintain the GPIC facility in a safe, healthy and environmentally friendly manner. Our commitment towards a responsible business management process across the lifecycle of our product’s, has resulted in our achievement of the highest quality products to the complete satisfaction of our worldwide customers and end users.

Our product handling and export facility is the main link between our process and export activities. This facility is part of critical operations that require vigilance and strict adherence to safety, health and environmental regulations and best practices. Such compliance will reduce the risk of injuries and prevent environmental pollution and ensures the delivery of best product quality throughout the supply chain cycle down to the end user, in the safest and most efficient manner.

This booklet endorses our proactive product stewardship management, reflecting our

commitments, as an accredited Responsible Care (RC 14001) organisation, as well as an active member of the industrial community on an international level; toward Protect and Sustain initiatives. The booklet outlines the objective of increasing awareness of all personnel involved in the field of handling and transporting methanol including customers. It also highlights the importance of safety, security and hygiene and other key characteristics and aspects related to this product, namely, storage, transfer and export operations.

ContentS1- Brief About GPIC

2- What is Methanol?

3- MSDS

4- GPIC’s Products Handling & Export Facility

5- GPIC Rules & Requirements

6- Safety & Emergency Response

7- Glossary

Page 1

Page 2

Page 3

Page 8

Page 9

Page 10

Page 13

DISCLAIMER MESSAGEThe guidelines illustrated in this book are a summary of practices that are proven to be appropriate and suitable for the handling, transport and storage of ammonia and GPIC shall not be liable for errors, omissions or incorrect use of these guidelines. The mentioned data are based on the current state of knowledge and insights, and cannot be considered as guaranteed.

Gulf Petrochemical Industries Company (GPIC) was formed in December 1979, as an equal partnership between the governments of Bahrain, Saudi Arabia and Kuwait. A site of 600,000 square metres was successfully reclaimed from the sea to house GPIC’s first petrochemical plant, namely ammonia and methanol, with production capacities of 1,000 tonnes per day of each product.

The production of ammonia was commenced on 19 June 1985 and methanol production on 2 July 1985, with the first product being exported in August 1985. In December 1989, both Ammonia and Methanol plants were expanded (debottlenecked) to capacities of 1,200 tonnes per day for each product.

In September 1995, GPIC signed a contract with Mitsubishi Heavy Industries Ltd. (MHI) Japan for the design and construction of a Granular Urea Plant with a capacity of 1,700 tonnes per day. This project was successfully completed in record time and the Urea plant was commissioned successfully and production was achieved on 7 January 1998.

The challenges of climate change have always been taken seriously at GPIC, and in order to manage our greenhouse gas emissions we commissioned the Middle East’s first Carbon Dioxide Recovery plant in 2009. The unit designed by MHI has a design capacity to capture 450 MT of carbon dioxide per day from the Methanol plant reformer stack flue gases and recycle back.

GPIC export facilities for ammonia and methanol are situated at the Bahrain Petroleum Company (BAPCO) wharf in Sitra. Two ammonia and two methanol hydraulic loading arms are utilised to load the liquid product into tanker ships. The export lines stretch over a length of around 4 km from the GPIC complex.

1- bRIef about GPICMethanol is a hydrocarbon that is derived from natural gas, comprised of carbon, hydrogen and oxygen. Its chemical formula is CH3OH. Methanol is a colourless alcohol and a neutral and flammable liquid. It is miscible with water, alcohols, esters and most other organic solvents.

GPIC produces Methanol using a catalytic process with natural gas and steam as the feedstock. The natural gas is catalytically reformed to carbon oxides and hydrogen. The resulting synthesis gas mixture is circulated under pressure and moderate temperature in the presence of a metallic catalyst and converted to crude methanol. The crude methanol is distilled to yield commercial chemical grade methanol.

Methanol is the main element for many chemicals and products. Other uses include windshield washer,

antifreeze, fuels, waste water treatment and biodiesel production. Other common names for methanol include methyl alcohol, methyl hydrate, wood spirit, wood alcohol and methyl hydroxide.

The awareness of personnel involved in exporting, transporting and storing of methanol is a prime factor with a view to ensuring that the product is handled, transported and stored, incorporating the measures for preserving its quality. This book highlights important guidelines, characteristics and precautions necessary to ensure proper care is taken to protect the product and the personnel. Terminal safety, security and environmental guidelines are also addressed in the book for the benefit of all personnel involved.

2- WHat IS metHanol?

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3- mSdSThe material safety data sheet (MSDS) provides the first insight and quick reference for personnel dealing directly with the product.

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metHanol mateRIal Safety data SHeet

Section 1. Chemical Product and Company Identification

Section 4. First Aid Measures

Section 5. Fire Fighting Measures

Section 2. Composition and Information on Ingredients

Section 3. Hazards Identification

Section 1. Chemical Product and Company Identification Product Name: Methanol GHS Product Identifier: Methanol Synonym: Carbinol; Methyl alcohol; Methyl hydroxide; Wood alcohol; Monohydroxymethane; Wood naptha; Wood spirits; Columbian spirits; Methanol. Chemical Name: Methanol Chemical Formula: CH3OH

Contact Information: Gulf Petrochemical Industries Company 51, Road 1401 Um Al-Baydh 614 Sitra, Kingdom of Bahrain P.O. Box : 26730 Email: [email protected] In Case of Emergency: +973 17 731777

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Section 2. Composition and Information on Ingredients Composition Name: CAS # % by Weight Methanol 67-56-1 >99% !

Section 3. Hazards Identification Emergency Overview:

Classification: Flammable Liquid Category 1 Hazard Communication:

DANGER! Extremely flammable liquid and vapour. Fatal if swallowed. May damage fertility for the unborn child (fetotoxic and teratogenic effects). May cause damage to eyes and central nervous system if ingested or inhaled.

Hazards: Colourless liquid, with a mild characteristic alcohol odour when pure. Hygroscopic.

Flammability Liquid and vapour methanol burns with a clean, clear flame which is almost invisible in daylight or a light blue flame. Can decompose at high temperatures forming carbon monoxide and formaldehyde. Vapours are heavier than air and may travel to a source of ignition and flash back. Vapours can spread along the ground and collect in low or confined areas.

NFPA Ratings Health = 1; Fire = 3; Reactivity = 0 Potential Acute Health Effects:

May be fatal or cause blindness if swallowed. Vapour harmful. Flammable liquid and vapour. Harmful if swallowed, inhaled, or absorbed through the skin. Causes eye, skin, and respiratory tract irritation. May cause central nervous system depression. Cannot be made non-poisonous.

Label

Potential Chronic Health Effects:

1- Carcinogenic Effects:

Not available.

2- Mutagenic Effects:

Not available.

3- Teratogenic Effects:

Not available.

4- Developmental Toxicity:

Not available.

Health Hazards: Avoid contact with eyes, skin and clothing, Wash thoroughly after handling.

Physical Hazards: Not available. Physical Form: Liquid. Appearance: Colourless liquid, Flash Point: 12!, 53.6". Odour: Alcohol-Like, weak odour. Potential Health Effects:








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Section 4. First Aid Measures Eye Contact: In case of contact, immediately flush eyes with plenty of water

for at least 15 minutes. Get medical aid. Skin Contact: In case of contact, immediately flush skin with plenty of water

for at least 15 minutes while removing contaminated clothing and shoes. Get medical aid immediately. Wash clothing before reuse.

Inhalation: If inhaled remove to fresh air. If not breathing, give artificial respiration. If breathing is difficult, give oxygen. Get medical aid.

Notes to Physician:

Acute exposure to methanol, either through ingestion or breathing high airborne concentrations can result in symptoms appearing between 40 minutes and 72 hours after exposure. Symptoms and signs are usually limited to the Central Nervous System (CNS), eyes and gastrointestinal tract. Because of the initial CNS’s effects of headache, vertigo, lethargy and confusion, there may be an impression of ethanol intoxication. Blurred vision, decreased acuity and photophobia are common complaints. Treatment with ipecac or lavage is indicated in any patient presenting within two hours of ingestion. A profound metabolic acidosis occurs in severe poisoning and serum bicarbonate levels are more accurate measure of severity than serum methanol levels. Treatment protocols are available from most major hospitals and early collaboration with appropriate hospitals is recommended. Effects may be delayed.

Antidote: Ethanol significantly decreases the toxicity of methanol because it competes for the same metabolic enzymes, and has been used to treat methanol poisoning.

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Notes to Physician:



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Notes to Physician:



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Section 5. Fire Fighting Measures General Information:

• As in any fire, wear a self-contained breathing apparatus in pressure-demand. MSHA/NIOSH (approved or equivalent), and full protective gear during a fire, irritating and highly toxic gases may be generated by thermal decomposition or combustion.

• Use water spray to keep fire-exposed containers cool. Water may be ineffective. Material is lighter than water and fire may be spread by the use of water.

• Vapours are heavier than air and may travel to a source of ignition and flash back. Vapours can spread along the ground and collect in low or confined areas.

Flammable Properties Flammability of the Product:

Flammable

Auto-Ignition Temperature:

455 oC (851.00 oF)

Flash Points: 12 oC (53.60 oF) Flammable Limits:

Lower 6.0 vol %, upper 31.00 vol%

Products of Combustion:

These products are carbon oxides (CO, CO2), and water (H2O).

Fire Fighting Media and Instructions:

• For small fires, use dry chemical, carbon dioxide, water spray or alcohol-resistant foam.

• General purpose synthetic foams or protein foams may work, but much less effectively.


Special Remarks on Fire Hazards:

• Methanol vapours may burn with an invisible flame. • During a fire, carbon monoxide, carbon dioxide and

irritating and toxic gases such as formaldehyde may be generated.

• Vapours can accumulate in confined spaces resulting in a toxicity and flammability hazard.

Special Remarks on Explosion Hazards:

• Close containers may rupture violently and suddenly, releasing large quantities of methanol when exposed to fire or excessive heat for a sufficient period of time

• Vapours are slightly heavier than air and may travel long distances toward source of ignition. Not available.

Unusual Fire and Explosion Hazards:

Not available.

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Section 7. Handling and Storage

Section 8. Exposure Controls/Personal Protection

Section 6. Accidental Release MeasuresSection 6. Accidental Release Measures General information:

Use proper personal protective equipment as indicated in Section 8.

Spill/ leaks: 1- Use water spray to disperse the gas/vapour. Methanol is a water pollutant. Minimize the use of water to prevent environment pollution.

2- Remove all sources of ignition. 3- Absorb spill using an absorbent, non-combustible

material such as earth, sand, or vermiculite. Do not use combustible materials such as sawdust.

4- Use spark-proof tools. Provide ventilation. A vapour suppressing foam may be used to reduce vapours. Water spray may reduce vapour but may not prevent ignition in closed spaces.

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Section 7. Handling and Storage Precautions for Handling:

1- No smoking or open flame in storage, use or handling areas.

2- Use explosion proof electrical equipment. Ensure proper electrical grounding procedures are in place.

3- Wash thoroughly after handling. Remove contaminated clothing and wash before reuse.

4- Ground and bond containers when transferring material. 5- Use spark-proof tools and explosion proof equipment. 6- Avoid contact with eyes, skin, and clothing. 7- Empty containers retain product residue, (liquid and/or

vapour), and can be dangerous. Keep container tightly closed. So as not to ingest or inhale.

8- Do not pressurize, cut, weld, braze, solder, drill, grind, or expose empty containers to heat, sparks or open flames. Use only with adequate ventilation.

9- Keep away from heat, sparks and flame. Avoid use in confined spaces.

Storage: 1- Keep away from heat, sparks, and flame. Keep away from sources of ignition.

2- Store in a cool, dry, well-ventilated area away from incompatible substances. Flammables-area. Keep containers tightly closed.

3- Tanks must be grounded, vented, and should have vapour emission controls.

4- Tanks must be diked as per NFPA or API Standards. 5- A flammable mixture of methanol vapour and air is

possible inside a storage tank or transportation tank, and handlers should take appropriate precautions to reduce the risk of ignition. Handlers must eliminate ignition sources or purge the tank with an inert gas such as nitrogen.

6- All equipment must be grounded / bonded when transferring product in order to avoid static discharge from the equipment, and subsequent possible fire.

7- Avoid storage with incompatible materials. Anhydrous methanol is not corrosive to most metals at ambient temperatures except lead, nickel, monel, cast iron and high silicon iron. Coatings of copper (or Copper alloys), zinc (including galvanized steel), or aluminium are unsuitable for storage. These materials may be attacked slowly by the methanol.

8- Storage tanks of welded construction are normally satisfactory.

9- Plastics are suitable only for short term storage of methanol.

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Section 8. Exposure Controls/Personal Protection Engineering Controls:

Use explosion- proof ventilation equipment in confined areas. Facilities storing or utilising this material should be equipped with an eyewash facility and a safety shower. Use adequate general or local exhaust ventilation to keep airborne concentrations below the permissible exposure limits.

Respiratory Protection

Follow the OSHA respirator regulations found in 29 CFR 1910.134 or European Standard EN 149. Use a NIOSH/MSHA or European Standard EN 149 approved respirator if exposure limits are exceeded or if irritation or other symptoms are experienced. NIOSH/OSHA recommendations for methanol concentrations in air:

1- Up to 2000 ppm: supplied air respirator. 2- Up to 5000 ppm: supplied air respirator operated in a

continuous flow mode. 3- Up to 6000 ppm: supplied air respirator with a tight-fitting

face piece operated in a continuous flow mode; or Full face piece self-contained breathing apparatus or Full face piece supplied air respirator.

4- Cartridge type respirators are NOT recommended. Emergency or Planned entry into unknown concentrations or IDLH conditions: Respirator: Respirator selection must be done by a qualified person and be

based upon a risk assessment of the work activities. Respirators must be fit tested and users must be clean shaven where the respirator seals to the face. Exposure must be kept at or below the applicable exposure limits and the maximum use concentration of the respirator must not be exceeded.

Skin Protection: Wear butyl rubber gloves, apron, and/or clothing. Eye and Face Protection

Face shield and chemical splash goggles when transferring is taking place. Contact lenses should not be worn when working with methanol.

Footwear Chemical resistant and as specified by the workplace Other Eyewash and showers should be located near work areas. !

Section 7. Handling and Storage Precautions for Handling:

1- No smoking or open flame in storage, use or handling areas.

2- Use explosion proof electrical equipment. Ensure proper electrical grounding procedures are in place.

3- Wash thoroughly after handling. Remove contaminated clothing and wash before reuse.

4- Ground and bond containers when transferring material. 5- Use spark-proof tools and explosion proof equipment. 6- Avoid contact with eyes, skin, and clothing. 7- Empty containers retain product residue, (liquid and/or

vapour), and can be dangerous. Keep container tightly closed. So as not to ingest or inhale.

8- Do not pressurize, cut, weld, braze, solder, drill, grind, or expose empty containers to heat, sparks or open flames. Use only with adequate ventilation.

9- Keep away from heat, sparks and flame. Avoid use in confined spaces.

Storage: 1- Keep away from heat, sparks, and flame. Keep away from sources of ignition.

2- Store in a cool, dry, well-ventilated area away from incompatible substances. Flammables-area. Keep containers tightly closed.

3- Tanks must be grounded, vented, and should have vapour emission controls.

4- Tanks must be diked as per NFPA or API Standards. 5- A flammable mixture of methanol vapour and air is

possible inside a storage tank or transportation tank, and handlers should take appropriate precautions to reduce the risk of ignition. Handlers must eliminate ignition sources or purge the tank with an inert gas such as nitrogen.

6- All equipment must be grounded / bonded when transferring product in order to avoid static discharge from the equipment, and subsequent possible fire.

7- Avoid storage with incompatible materials. Anhydrous methanol is not corrosive to most metals at ambient temperatures except lead, nickel, monel, cast iron and high silicon iron. Coatings of copper (or Copper alloys), zinc (including galvanized steel), or aluminium are unsuitable for storage. These materials may be attacked slowly by the methanol.

8- Storage tanks of welded construction are normally satisfactory.

9- Plastics are suitable only for short term storage of methanol.

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Flammable


455 oC (851.00 oF)

















Not available.

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Flammable


455 oC (851.00 oF)

















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Flammable


455 oC (851.00 oF)

















Not available.

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Section 6. Accidental Release Measures General information:

Use proper personal protective equipment as indicated in Section 8.

Spill/ leaks: 1- Use water spray to disperse the gas/vapour. Methanol is a water pollutant. Minimize the use of water to prevent environment pollution.

2- Remove all sources of ignition. 3- Absorb spill using an absorbent, non-combustible

material such as earth, sand, or vermiculite. Do not use combustible materials such as sawdust.

4- Use spark-proof tools. Provide ventilation. A vapour suppressing foam may be used to reduce vapours. Water spray may reduce vapour but may not prevent ignition in closed spaces.

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6

US DOT CANADA TDG Shipping Name: Methanol Methanol Hazard Class: 3 3 UN Number: UN1230 UN1230 Packing Group: II II Additional Information:

Reportable Quantity (RQ) 5000 lbs (2270 kg) Limited Quantity ! 1 litre

Flash Point 12" ERG Guide Number: 131

IATA IMO Shipping Name: Methanol Methanol Hazard Cl#ss: 3 3 UN Number: UN1230 UN1230 Packing G#oup: II II Additional Information:

1. Packaging Instruction (passenger aircraft) 305

2. 1 litre maximum package

1. Flash point = 11 °C 2. EmS No F-E, S-D 3. Stowage Category “,B” 4. Clear of living quarters

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GPIC IS CommItted

to PRoteCt & SuStaIn PRoduCt

SteWaRdSHIP

Section 13. Disposal Considerations

Section 14. Transport Information

Aquatic Fate: Methanol is not expected to adsorb to suspended solids and sediment. Volatilization from water surfaces is expected based upon a Henry’s Law constant 4.55 X 10-6 atm m3/mol. Volatilization half-lives for a model river and model lake are three and 35 day, respectively. According to a classification scheme, a BCF of less than 10 measured in fish, suggests bioconcentration in aquatic organisms is low. Hydrolysis and photolysis in sunlit surface waters is not expected to be an important environmental fate process for methanol since this compound lacks functional groups that hydrolyze or absorb light under environmentally relevant conditions. Methanol has been shown to undergo rapid biodegradation in a variety of screening studies using sewage seed and activated sludge inoculum, which suggests that biodegradation will occur in aquatic environments.

Atmospheric Fate:

Methanol is expected to exist solely as a vapour in the ambient atmosphere. Vapour–phase methanol is degraded in the atmosphere, by reaction with photo chemically-produced hydroxyl radicals; the half-life for this reaction in air is estimated to be 17 days, calculated from its rate constant of 9.4 X 10-13cu-cm/molecule-sec at 25 oC.

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Ecotoxicity: Fish: Fathead Minnow: 29.4 g/L; 96 Hr; LC50 (unspecified); Rainbow trout: LC50 = 13-68 mg/L; 96 Hr.; 12 degrees C; LC50 = 8000 mg/L; 48 Hr.; Unspecified Goldfish: 250 ppm; 11 Hr; resulted in death Fish: 8000 mg/L; 48 Hr; LC50 (unspecified) Bacteria: Phytobacterium phosphoreum: EC50 = 51,000-320,000 mg/L; 30 minutes; EC50Daphnea Pulex water flea, <24 hr old; immobilization

1. 19,500 mg/ltr/18 hr; static 22 DegC, 2. 23,500 mg/ltr/24 hr 3. 22,200 mg/ltr/48 hr

Log Kow: -0.82 to -0.66 Half Life(hr) air: 427 Half Life(hr) H2O: Surface water:

5.3 - 64

Henry’s Law Constant (atm m3/mol)

4.55 X 10-6

BOD5 0.76-1.12 COD 1.0-1.5. 99% ThOD 1.05 Biological Concentration Factor (BCF)

0.2-1.0

TLm (48 hr) 8000 mg/ltr (trout) Toxicity Anthropoda

NOEL 10 g/L/48 hr (Daphnia)

HSNO Classification:

9.3 Harmful to Terrestrial vertebrates

Methanol in Fresh Water or salt water may have serious effects on aquatic life. A study on methanol’s toxic effects on sewage sludge bacteria reported little effect on digestion at 0.1% while 0.5% methanol retarded digestion. Methanol will be broken down into carbon dioxide and water.

Environmental Fate:

Dangerous to aquatic life in high concentrations. Aquatic toxicity rating: TLm 96>1000 ppm. May be dangerous if it enters water intakes. Methyl alcohol is expected to biodegrade in soil and water very rapidly. This product will show high soil mobility and will be degraded from the ambient atmosphere by the reaction with photochemically produced hyroxyl radicals with an estimated half-life of 17.8 days. Bioconcentration factor for fish (golden ide) < 10. Based on a log Kow of -0.77, the BCF value for methanol can be estimated to be 0.2.

Biodegradability: Biodegrades easily in water and soil. Bioaccumulation: Terrestrial fate: Based on a classification scheme, an estimated Koc value of 1

determined from a structure estimation method indicates that methanol is expected to have very high mobility in soil. Volatilization of methanol from moist soil surfaces is expected to be an important fate process given a Henry’s Law constant of 4.55 X 10-6 atm m3/mol. The potential of volatilization of methanol from dry soil surfaces may exist based upon a vapour pressure of 127 mmHg. Biodegratation is expected to be an important fate process for methanol.

Aquatic Fate: Methanol is not expected to adsorb to suspended solids and sediment. Volatilization from water surfaces is expected based upon a Henry’s Law constant 4.55 X 10-6 atm m3/mol. Volatilization half-lives for a model river and model lake are three and 35 day, respectively. According to a classification scheme, a BCF of less than 10 measured in fish, suggests bioconcentration in aquatic organisms is low. Hydrolysis and photolysis in sunlit surface waters is not expected to be an important environmental fate process for methanol since this compound lacks functional groups that hydrolyze or absorb light under environmentally relevant conditions. Methanol has been shown to undergo rapid biodegradation in a variety of screening studies using sewage seed and activated sludge inoculum, which suggests that biodegradation will occur in aquatic environments.

Waste Disposal: • Disposal shall comply to the federal, provincial and local government’s statutory requirement.

• Empty containers may contain hazardous residue. Return to supplier for reuse if possible. Never weld, cut or grind empty containers.

• While disposing containers make sure that they are well rinsed with water and then disposed of at an authorised landfill. After cleaning all the labels to be removed.

Resource Conservation and Recovery Act (RCRA) U-Series:

Waste number U154 (Ignitable waste).

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Section 9. Physical and Chemical Properties

Section 10. Stability and Reactivity Data

Section 11. Toxicological Information Section 12. Ecological Information

Section 11. Toxicological Information RTECS#: PC1400000 Primary Routes of Entry

1- Skin Contact; Skin Absorption; Eye Contact; Ingestion; Inhalation;

Acute Exposure: Inhalation 2- Inhalation of high airborne concentrations can also

irritate mucous membranes, cause headaches, sleepiness, nausea, confusion, loss of consciousness, digestive and visual disturbances and even death. NOTE: Odour threshold of methanol is several times higher than the TLC-TWA. Depending upon the severity of poisoning and the promptness of treatment, survivors may recover completely or may have permanent blindness, vision disturbances and/or nervous system effects. Concentrations in air exceeding 1000 ppm may cause irritation of the mucous membranes.

a. Inhalation, rabbit: LC50 = 81000 mg/m3/14H; b. Inhalation, rat: LC50 = 64000 ppm/4H;

Eye Contact: 3- Methanol is a mild to moderate eye irritant. High vapour concentration or liquid eye contact causes irritation, tearing and burning. Draize test on Rabbit eye

a. 40 mg Moderate b. 100 mg/24H Moderate

Skin Contact: 4- Methanol is moderately irritating to the skin. Methanol can be absorbed through the skin and harmful effects have been reported by this route of entry. Effects are similar to those described in Inhalation.

a. Draize test, rabbit, skin: 20 mg/24H Moderate b. Skin, rabbit : LD50 = 15800 mg/kg;

Section 11. Toxicological Information RTECS#: PC1400000 Primary Routes of Entry

1- Skin Contact; Skin Absorption; Eye Contact; Ingestion; Inhalation;

Acute Exposure: Inhalation 2- Inhalation of high airborne concentrations can also

irritate mucous membranes, cause headaches, sleepiness, nausea, confusion, loss of consciousness, digestive and visual disturbances and even death. NOTE: Odour threshold of methanol is several times higher than the TLC-TWA. Depending upon the severity of poisoning and the promptness of treatment, survivors may recover completely or may have permanent blindness, vision disturbances and/or nervous system effects. Concentrations in air exceeding 1000 ppm may cause irritation of the mucous membranes.

a. Inhalation, rabbit: LC50 = 81000 mg/m3/14H; b. Inhalation, rat: LC50 = 64000 ppm/4H;

Eye Contact: 3- Methanol is a mild to moderate eye irritant. High vapour concentration or liquid eye contact causes irritation, tearing and burning. Draize test on Rabbit eye

a. 40 mg Moderate b. 100 mg/24H Moderate

Skin Contact: 4- Methanol is moderately irritating to the skin. Methanol can be absorbed through the skin and harmful effects have been reported by this route of entry. Effects are similar to those described in Inhalation.

a. Draize test, rabbit, skin: 20 mg/24H Moderate b. Skin, rabbit : LD50 = 15800 mg/kg;

Ingestion: 1- Swallowing even small amounts of methanol could potentially cause blindness or death. Effects of sub lethal doses may be nausea, headache, abdominal pain, vomiting and visual disturbances ranging from blurred vision to light sensitivity.

a. Oral, mouse: LD50 = 7300 mg/kg; b. Oral, rabbit: LD50 = 14200 mg/kg; c. Oral, rat: LD50 = 5600 mg/kg; d. Human LDLo Oral: 143 mg/kg; Human LDLo Oral:

428 mg/kg; Human TCLo Inhalation; 300 ppm caused

e. Monkey LDLo Skin: 393 mg/kg. Methanol is significantly less toxic to most experimental animals than humans, because most animal species metabolize methanol differently.

f. Non-primate species do not ordinarily show symptoms of metabolic acidosis or the visual effects which have been observed in primates and humans.

Chronic Exposure

Irritancy Prolonged contact with skin may defat tissue causing dermatitis or aggravate existing skin problems.

Sensitisation: None reported. Carcinogenicity: Not listed by ACGIH, IARC, NTP as a carcinogen. Teratogenicity: There is no human information available. Methanol is

considered to be a potential developmental hazard based on animal data. In animal experiments, methanol has caused fetotoxicity or teratogenic effects without maternal toxicity.

Reproductive Toxicity:

Information available does not suggest that methanol is a reproductive toxin.

Mutagenicity: See actual entry in RTECS for complete information. Neurotoxicity: ACGIH cites neuropathy, vision and CNS under TLV basis. Section 12. Ecological Information

Ecotoxicity: Fish:

Fathead Minnow: 29.4 g/L; 96 Hr; LC50 (unspecified); Rainbow trout: LC50 = 13-68 mg/L; 96 Hr.; 12 degrees C; LC50 = 8000 mg/L; 48 Hr.; Unspecified Goldfish: 250 ppm; 11 Hr; resulted in death Fish: 8000 mg/L; 48 Hr; LC50 (unspecified) Bacteria: Phytobacterium phosphoreum: EC50 = 51,000-320,000 mg/L; 30 minutes; EC50Daphnea Pulex water flea, <24 hr old; immobilization

1- 19,500 mg/ltr/18 hr; static 22 DegC, 2- 23,500 mg/ltr/24 hr 3- 22,200 mg/ltr/48 hr

Log Kow: -0.82 to -0.66 Half Life(hr) air: 427 Half Life(hr) H2O: Surface water:

5.3 - 64

Henry’s Law Constant (atm m3/mol)

4.55 X 10-6

BOD5 0.76-1.12 COD 1.0-1.5. 99% ThOD 1.05 Biological Concentration Factor (BCF)

0.2-1.0

TLm (48 hr) 8000 mg/ltr (trout) Toxicity Anthropoda

NOEL 10 g/L/48 hr (Daphnia)

HSNO Classification:

9.3 Harmful to Terrestrial vertebrates

Methanol in Fresh Water or salt water may have serious effects on aquatic life. A study on methanol’s toxic effects on sewage sludge bacteria reported little effect on digestion at 0.1% while 0.5% methanol retarded digestion. Methanol will be broken down into carbon dioxide and water.

Stability: Stable under normal temperatures and pressures.

Incompatibility with various substances:

Oxidizing agents, reducing agents, acids, alkali metals, potassium, sodium, metals as powders (e.g. hafnium, raney nickel), acid anhydrides, acid chlorides, powdered aluminium, powdered magnesium.

Instability Temperature:

Not available.

Conditions to avoid:

Avoid high temperatures, ignition sources, sparks, confined spaces.

Hazardous Decomposition Products:

Carbon monoxide, irritating and toxic fumes and gases, carbon dioxide, formaldehyde.

Polymerization:

Will not occur.

Possibility of Hazardous Reactions:

Avoid contact with strong oxidizers, strong mineral or organic acids and strong bases. Contact with these materials may cause a violent or explosive reaction.

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Ingestion: 1- Swallowing even small amounts of methanol could potentially cause blindness or death. Effects of sub lethal doses may be nausea, headache, abdominal pain, vomiting and visual disturbances ranging from blurred vision to light sensitivity.

a. Oral, mouse: LD50 = 7300 mg/kg; b. Oral, rabbit: LD50 = 14200 mg/kg; c. Oral, rat: LD50 = 5600 mg/kg; d. Human LDLo Oral: 143 mg/kg; Human LDLo Oral:

428 mg/kg; Human TCLo Inhalation; 300 ppm caused

e. Monkey LDLo Skin: 393 mg/kg. Methanol is significantly less toxic to most experimental animals than humans, because most animal species metabolize methanol differently.

f. Non-primate species do not ordinarily show symptoms of metabolic acidosis or the visual effects which have been observed in primates and humans.

Chronic Exposure

Irritancy Prolonged contact with skin may defat tissue causing dermatitis or aggravate existing skin problems.

Sensitisation: None reported. Carcinogenicity: Not listed by ACGIH, IARC, NTP as a carcinogen. Teratogenicity: There is no human information available. Methanol is

considered to be a potential developmental hazard based on animal data. In animal experiments, methanol has caused fetotoxicity or teratogenic effects without maternal toxicity.

Reproductive Toxicity:

Information available does not suggest that methanol is a reproductive toxin.

Mutagenicity: See actual entry in RTECS for complete information. Neurotoxicity: ACGIH cites neuropathy, vision and CNS under TLV basis.

Physical state and appearance:

Clear liquid, clear, colourless - APHA: 10 max

Odour: Alcohol-like - weak odour Molecular Weight:

32.04 g/mol

pH (1% soln/water):

Not available.

Boiling Point: 64.7 deg C @ 760 mmHg Melting Point: -98 oC Flash Point: 11.0 oC Auto Ignition Temperature:

464 oC

Critical Temperature:

239.4 oC.

Specific Gravity/ Density:

7910 g/cm3 @ 20°C

Vapour Pressure:

12.8 KPa @ 20 oC

Vapour Density: 1.105 @ 15 oC (Air=1) Dispersion Properties:

See solubility in water.

Solubility in Water:

Completely miscible.

Solvent Solubility:

Soluble in all proportions in ethanol, benzene, other alcohols, chloroform, diethyl ether, other ethers, esters, ketones and most organic solvents.

Viscosity: 0.55 cP 20 oC Evaporation Rate:

5.2 (Ether=1)

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5

5

4- GPIC’S PRoduCtS HandlInG & exPoRt faCIlIty

GPIC’s storage facilities comprise two storage tanks which serve to contain / hold the methanol that will be supplied from the intermediate storage. Each tank has a storage capacity of 20,000 tonnes. Methanol is transferred from the tanks to the ship by means of loading pumps. Generally, two pumps are required for ship loading while the third pump serves as a standby at a maximum loading rate of 1200 MT/HR through a dedicated export line of 16” diameter and approximately 4 km long.

GPIC utilises the Sitra wharf owned by BAPCO to

load methanol into ships. Two methanol loading arms are provided, one at Berth No.1 and one at Berth No.2, which are operated hydraulically to move the arm to the appropriate position for connection to the ship manifold. Provision is also available for loading methanol into road tankers for local sale upon special request.

Section 15. Other Regulatory Information Section 16. Other Information Disclaimer: This Material Safety Data Sheet has been prepared in accordance with ANSI Z400.1 and contains information believed to be accurate and complete at the date of preparation. The statements contained herein are offered for informational purposes only and are based upon technical data. GPIC believes them to be accurate but does not purport to be all-inclusive. The information above is believed to be accurate and represents the best information currently available to us. However, we make no warranty of merchantability or any other warranty, express or implied, with respect to such information, and we assume no liability resulting from its use. Users should make their own investigations to determine the suitability of the information for their particular purposes. In no event shall GPIC be liable for any claims, losses, or damages of any third party or for lost profits or any special, indirect, incidental, consequential or exemplary damages, whatsoever arising, even if GPIC has been advised of the possibility of such damages. Revised: All sections have been revised on 16th August, 2012.

1- GPIC’s Products Handling & Export Facility:

Disclaimer: This Material Safety Data Sheet has been prepared in accordance with ANSI Z400.1 and contains information believed to be accurate and complete at the date of preparation. The statements contained herein are offered for informational purposes only and are based upon technical data. GPIC believes them to be accurate but does not purport to be all-inclusive. The information above is believed to be accurate and represents the best information currently available to us. However, we make no warranty of merchantability or any other warranty, express or implied, with respect to such information, and we assume no liability resulting from its use. Users should make their own investigations to determine the suitability of the information for their particular purposes. In no event shall GPIC be liable for any claims, losses, or damages of any third party or for lost profits or any special, indirect, incidental, consequential or exemplary damages, whatsoever arising, even if GPIC has been advised of the possibility of such damages. Revised: All sections have been revised on 16th August, 2012.

1- GPIC’s Products Handling & Export Facility:

Toxic Substances Control Act (TSCA):

Listed on the TSCA inventory.

Health & Safety Reporting List:

Not listed in the Health & Safety Reporting List.

Chemical Test Rules None of the chemicals in this product are under a Chemical Test Rule.

Section 12b: None of the chemicals are listed under TSCA Section 12b.

CERCLA Hazardous Substances and corresponding RQs

Reportable Quantity (RQ) 5000 lb (2270 kg)

Superfund Amendment and Reauthorization Act (SARA) SARA Codes Section 302 Extremely Hazardous Substances

None of the chemicals in this product have a Threshold Planning Quantity (TPQ)

SARA Codes Immediate, fire. Section 313 This material contains methanol which is subject to

the reporting requirements of Section 313 of SARA Title III and 40 CFR Part 373.

Clean Air Act(CAA): Listed as a hazardous air pollutant (HAP). This material does not contain any Class 1 Ozone depletors. This material does not contain any Class 2 Ozone depletors.

Clean Water Act (CWA): • None of the chemicals in this product are listed as Hazardous Substances under the CWA.

• None of the chemicals in this product are listed as Priority Pollutants under the CWA.

• None of the chemicals in this product are listed as Toxic Pollutants under the CWA.

OSHA: None of the chemicals in this product are considered highly hazardous by OSHA.

European/International Regulations European Labelling in Accordance with EC Directives Hazard Symbols: • T F Risk Phrases: • R 11 Highly flammable.

• R 23/24/25 Toxic by inhalation, in contact with skin and if swallowed.

• R 39/23/24/25 Toxic: danger of very serious irreversible effects through inhalation, in contact with skin and if swallowed.

Safety Phrases: • S 16 Keep away from sources of ignition - No smoking.

• S 36/37 Wear suitable protective clothing and gloves.

• S 45 In case of accident or if you feel unwell,

Safety Phrases: • S 16 Keep away from sources of ignition - No smoking.

• S 36/37 Wear suitable protective clothing and gloves.

• S 45 In case of accident or if you feel unwell, seek medical advice immediately (show the label where possible).

• S 7 Keep container tightly closed. WGK (Water Danger/Protection)

Low Danger to Water – (1)

Canada - DSL/NDSL Listed on Canada's DSL List. Canada – WHMIS: This product has a WHMIS classification of B2, D1B,

D2B. This product has been classified in accordance with the hazard criteria of the Controlled Products Regulations and the MSDS contains all of the information required by the regulations.

Canadian Ingredient Disclosure List:

Listed on the Canadian Ingredient Disclosure List.

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7 8

5-PoRt RuleS & RequIRementS5.1 loCatIon:

GPIC’s loading facilities are situated at Sitra wharf, which is owned by Bahrain Petroleum Company (BAPCO). The wharf also houses Bahrain Gas Company’s (BANAGAS) loading facility which includes 7 berths, two of which are each equipped with both an ammonia and a methanol loading arm (Berth No.1 and Berth No.2). The two loading arms at each berth allows GPIC to load either methanol or ammonia from any vacant berth of the two, based on their availability.

Rules and regulations which are applicable to other ports within the Kingdom of Bahrain, are also applied to this port. As such, the port is subject to Customs and complies with the International Ship and Port Facility Security code (ISPS). All personnel using this port are subject to Immigration and Customs Controls pertaining to such a facility.

5.2 SeCuRIty RequIRementS:

Ships calling at Sitra Marine Port to load methanol must declare their security level according to the ISPS code.

• Ships’ crews are not allowed to enter or exit the Sitra wharf without authorisation from the Immigration Office.

• Visitors to ships must obtain clearance from the Immigration Office through the ship’s agent before allowed access.

• Goods to and from ships must be cleared by the Customs Officer and inspected by Sitra port Security.

• A ship’s crew members are not allowed to proceed from ship to shore without being accompanied by the ship’s agent representatives.

• A ship’s crew members must be subjected to a Sitra port Security search prior to exit from or entry to the port.

• Shore personnel and contractors are strictly prohibited from receiving or delivering goods/items to ship’s crew members.

• Unauthorised personnel not involved in the loading operation are restricted from boarding the ships.

5.3 SHIP-SHoRe PRe-loadInG meetInGIn order to achieve a smooth, efficient and safe operation and so that all security requirements are fully understood, acknowledged and implemented by the ship’s personnel; a meeting is conducted between shore and ship representatives prior to commencement of loading operations.

To facilitate this, shore representatives and the ship’s Master/Chief Officer will jointly complete a number of forms/letters as listed below:

• Smoking location onboard vessel.

• Loading arm safe working area.

• Safety requirements for vessel loading at Sitra.

• Ship/Shore log sheet.

• Ship/Shore Safety check list.

• Receipt of Material Safety Data Sheet.

• ISPS form (counter signed by terminal security officer).

All the above aspects will be discussed and mutually agreed between the ship and shore representatives, any controversial point must be authorised and countersigned by both parties. Also, a radio hand set is handed over to the ship for communication during loading operations.

6.1 Safety:

To ensure maximum safety at Sitra Wharf, several precautions have been set.

• A total of 15 remote operated high firefighting monitors have been distributed at the wharf.

• Two foam tanks with pumps and operating panels are situated at each side of the jetty.

• Five fire water pumps are located at the trestle entrance. (3 main pumps and 2 jockey pumps).

• GPIC provides additional mobile fire water monitors at each side of the jetty, equipped with foam tanks for quick intervention during any emergency.

• Break glass fire alarms have been provided at each side of the jetty.

• 12 escape masks have been placed at each side of the jetty.

• Fire blankets and eye wash stations/showers are located at both sides of the jetty.

• 7 breathing apparatuses (7 Ltrs each) are located at the South side office.

• 4 spare oxygen cylinders have been provided at the South office.

• One gas suit, two fire suits and two chemical suits have been provided at the South office as well.

• CO2 and dry powder extinguishers have been made available at the South office.

• When a Methanol ship is planned for berthing, all maintenance activities will be suspended, and entry to Sitra wharf will be under control.

6.2 uSeful faCtS about metHanol

• Methanol burns with a clear flame and without smoke, so it is difficult to see in daylight. Methanol will still burn at four parts of water to one part of methanol. The fire may be detected by the heat generated, a heat haze, or burning of materials in the affected area.

• When transferring or storing methanol, dedicated systems are preferable. Non-dedicated systems should be cleaned, flushed and sampled before being used, in order to ensure product integrity. Equipment should be clearly labelled to indicate that it is for methanol service only. When not in use, the equipment must be protected from contamination.

• Whenever possible, contain land spills by forming mechanical or chemical barriers. Remove spilled product with explosion proof pumps or vacuum equipment. Treat the surface with sorbent materials, such as vermiculite or activated carbon, to remove the remaining methanol. Remove the sorbents after use. Soil contaminated with methanol should be removed and remediated.

• Spills into large natural bodies of water, such as rivers and oceans, cannot be recovered. Whenever possible, contain spills to small surface waters using natural or mechanical barriers. Then remove the contained material with explosion proof pumps or vacuum equipment.

6.3 emeRGenCy ReSPonSe: In case of emergency, the following actions are to be taken:

• Call the emergency response telephone number as indicated.

• If no access to a telephone, use a VHF radio to announce

6- Safety & emeRGenCy ReSPonSe

10

Ships must ensure maximum safety precautions are followed when loading at Sitra wharf and all crew members or visitors must wear appropriate personal protective equipment (PPE) at all times when the ship is alongside.

9

“EMERGENCY” three times.

• Suspend loading operation immediately.

• As an immediate precautionary measure, isolate spill or leak area for at least 50 metres (150 feet) in all directions.

• Keep unauthorised personnel away.

• Stay upwind.

• Keep out of low areas.

• Ventilate closed spaces before entering.

• Personal Protective clothing:

• Personal protective equipment for the responders should at a minimum include:

- Wear positive pressure self-contained breathing apparatus (SCBA).- Wear chemical protective clothing that is specifically recommended by the manufacturer. It may provide little or no thermal protection.- Structural firefighters’ protective clothing provides limited protection in fire situations ONLY, it is not effective in spills situations where direct contact with the substance is possible.

• Fire:

• If Methanol ignition occurs in daylight hours, it is unlikely that the fire will be detected visually until it spreads to adjacent materials that emit a luminous flame or a visible plume of smoke.

• If a Methanol source is emitting large quantities of vapour, it is only a matter of time before ignition and flashback occurs.

• Small fire: Use dry chemical, CO2, water spray or alcohol-resistant foam.

• Large fire:

- Water spray, fog or alcohol-resistant foam.- Move containers from fire area if you can do it without risk.- Dike fire-control water for later disposal. Do not scatter the material.- Use water spray or fog. Do not use straight streams.

• Fire involving tanks:

• Fight fire from maximum distance or use unmanned hose holders or monitor nozzles.

• Cool containers with flooding quantities of water until well after fire is out.

• Withdraw immediately in case of rising sound from venting safety devices or discolouration of tank.

• Always stay away from tanks engulfed in fire.

• For massive fires, use unmanned hose holders or monitor nozzles, if this is impossible, withdraw from area and let fire burn.

• Spill or Leak:

• Fully encapsulating vapour protective clothing should be worn for spills and leaks with no fire.

• Stop or reduce methanol release rate at the point of release if can be done safely.

• If there are noxious vapours, evacuate, sound alarm and notify supervisor.

• Eliminate all ignition sources to a safe standoff distance from the point of release and nearby methanol pooling.

• All equipment used when handling the product must be grounded.

• Do not touch or walk through spilled material.

• Stop leak if you can do it without risk.

• Prevent entry into waterways, sewers, basements or confined areas.

• A vapour suppressing foam may be used to reduce vapours.

• Small spill: Absorb with earth, sand or other non-combustible material and transfer to containers for later disposal. And use clean non-sparking tools to collect absorbed material.

• Large spill: Dike far ahead of liquid spill for later disposal. Water spray may reduce vapour, but may not prevent ignition in closed spaces.

• First aid:

• Move victim to fresh air.

• Call emergency medical service.

• Give artificial respiration if victim is not breathing.

• Do not use mouth-to-mouth method if victim

• Methanol is biodegrades in low concentrations.

• Methanol is soluble in water.

• Do not dispose of methanol in the environment.

• Impact is confined to the immediate area of the release.

There is an adverse effect on water life - if the release is large enough.

• Contain the release, dispose of methanol safety.

• Stay upwind of the release or fire.

• Evacuate the area where the atmosphere is above acceptable limits,i.e.,200 ppm methanol in air, or if you can smell a faint odour of alcohol.

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6.4 envIRonmental faCtoRS:

12

ingested or inhaled the substance; give artificial respiration with the aid of a pocket mask equipped with a one-way valve or other proper respiratory medical device.

• Administer oxygen if breathing is difficult.

• Remove and isolate contaminated clothing and shoes.

• In case of contact with substance, immediately flush skin or eyes with running water for at least 20 minutes.

• Wash skin with soap and water.

• In case of burns, immediately cool affected skin for as long as possible with cold water. Do not remove clothing if adhering to skin.

• Keep victim warm and quiet.

• Effects of exposure (inhalation, ingestion or skin contact) to substance may be delayed.

• Ensure that the medical personnel are aware of the materials involved and take precautions to protect themselves.

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CAS No. : Each chemical has a discrete Chemical Abstracts

Service (CAS) registry number. This number will accurately

indicate the chemical being described.

UN No. : United Nations Number. This is the number

allocated by the United Nations and is used internationally

by emergency services to quickly identify a hazardous

chemical in the event of an accident.

Class 1: Explosives

Class 2: Gases: Compressed, Liquefied of Dissolved under pressure

Class 3: Flammable Liquids

Class 4: Flammable Solids, Substances liable to spontaneous combustion, Flammable substances if wetted

Class 5: Oxidizing agents and Organic Peroxides.

Class 6: Poisonous (toxic) and infectious substances

Class 7: Radioactive substances.

Class 8: Corrosive Substances

Class 9: Miscellaneous dangerous goods.

UEL (Upper Explosive limit): The lowest concentration limits

(normally measured in % volume to air) of a gas or vapour

that will be able to support ignition and burn or explode.

LEL (Lower Explosive Limit): The lowest concentration limits

(normally measured in % volume to air) of a gas or vapour

that will be able to support ignition and burn or explode.

OSHA PEL : Permissible Exposure Limit. American equivalent

of TLV (Threshold Limit Value) and WES (Workplace Exposure

Standards), as determined by the Occupational Safety

and Health Administration. (OSHA-USA)

TLV-TWA : Threshold Value Time Weighted Average: is

defined as concentration of the substance in air that can

be breathed for five consecutive eight hour working days

(40 hour work week) by most people without adverse

effect.

ORL - RAT LD 50 : Values given are the concentrations or

quantities of a chemical that will cause the death of 50% of

a population of the rat model for inhalation and ingestion.

Hazchem Code : The Hazchem Code is a code used

to identify the emergency response action in chemical

related emergencies.

Bio accumulation : Biological accumulation

Eco Toxicity : Ecological Toxicity

IDLH : The Immediately Dangerous to Life and Health

value - This concentration represents a maximum level

from which one could escape within 30 minutes without

any escape - impairing symptoms or any irreversible health

effects. The concentrations are reported in either parts per

million (PPM) or milligrams per cubic metre (mg/m3).

TLV-STEL : Short Term Exposure Limit - The concentration

to which it is believed that workers can be exposed

continuously for a short period of time without suffering

from 1) Irritation 2) Chronic or irreversible tissue damage or

3) Narcosis of a sufficient degree to increase the likelihood

of accidental injury, impair self-rescue or materially reduce

7-GloSSaRywork efficiency, provided that the daily TLV-TWA is not

exceeded. It is not a separate independent exposure

limit, rather it supplements the time - weighted average

(TWA) limit where there are recognised acute effects from

a substance where toxic effects are primarily of a chronic

nature.

STEL is defined as a 15-minute TWA exposure which should

not be exceeded at any time during a working day even if

the 8-hour TWA is within the TLV-TWA. Exposure above TLV-

TWA up to STEL should not be longer than 15 minutes and

should not occur more than four times per day.

TLV-C : Threshold Limit Value-Ceiling - the concentration

that should not be exceeded during any part of the

working exposure.

13 14

noteS

15

P.O.Box 26730, Manama, Kingdom of Bahrain Tel: +973 1773 1777 - Fax: +973 1773 1047 Email: [email protected] Website: www.gpic.com

Issue 1 - January 2014

Gulf Petrochemical Industries Company, (BSC)

methanol booklet final low

Documents

product handling

methanol production

gpic facility

production of ammonia

safe handling guidelines

export operations

field of handling

best practices