Methanol Overview

Methanol is a liquid chemical with the formula CH3OH (often abbreviated MeOH). It is colorless, volatile, flammable, and poisonous. Methonal is made from the destructive distillation of wood and is chiefly synthesized from carbon monoxide and hydrogen. Its principal uses are in organic synthesis, as a fuel, solvent, and antifreeze.

Methanol is toxic. Drinking 10 ml of the substance will cause blindness; consuming as little as 100 ml will result in death. It is the simplest form of alcohol and has a distinctive odor that is similar to ethanol (drinking alcohol), but slightly sweeter.

Methanol is a polar liquid at room temperature. It is used as antifreeze, solvent, fuel, and as a denaturant for ethanol. The chemical is also used to produce biodiesel via transesterification reaction.

Because Methanol has toxic properties, it is frequently used as a denaturant additive for ethanol manufactured for industrial purposes. Methanol is frequently called wood alcohol because it was once produced primarily as a byproduct of the destructive distillation of wood.

Today, three methods are commonly used to produce synthesis gas from the methane component in natural gas. The methods are steam-methane or SMR, which is endothermic, partial oxidation with molecular oxygen, which is exothermic, and the combination of the two, which is referred to as autothermal reforming.

About Methanol

History
Ancient Egyptians used a mixture of substances that included Methanol in their embalming process. They obtained the Methanol from pyrolysis of wood. Pyrolysis is the chemical decomposition of condensed organic substances by heating.

However, pure Methanol wasn't isolated until 1661 by Robert Boyle, who produced the chemical through the distillation of boxwood. The chemical later became known as pyroxylic spirit. The French chemists Jean-Baptiste Dumas and Eugene Peligot determined its elemental composition in 1834.

The term "methyl" was derived from the word "methylene," which was coined by Dumas and Peligot in 1840. It was then applied to describe "methyl alcohol." The International Conference on Chemical Nomenclature shortened this to "Methanol" in 1892. When German chemists Alwin Mittasch and Mathias Pier developed a means to convert sythesis gas into Methanol, a patent was filed on Jan. 12, 1926.

In 2006 astronomers at Jodrell Bank Observatory using the Merlin array of radio telescopes, discovered a large clod of Methanol in space, 300 billion miles across.

Production
Catalysts that are capable of operating at lower temperatures such as copper are used to efficiently produce modern Methanol. Low pressure Methanol (LPM) was developed by ICI in the late 1960s with the technology owned by Johnson Matthey, the leading licensor of Methanol technology.
Natural gas is the most economical and widely used feedstock for Methanol production. However, other feedstocks can be used. Coal is increasing in popularity as a feedstock for Methanol production, particularly in China. Additionally, mature technologies available for biomass gasification are being implemented for Methanol production.

Toxicity
In humans, Methanol has a high toxicity. As little as 10 mL can cause permanent blindness if ingested by destruction of the optic nerve. Only 30 ml can be fatal, although the typical fatal dose is 100-125 ml (4 fl oz). However, toxic effects take hours before they are evident and effective antidotes can often prevent permanent damage.

Methanol is toxic by two mechanisms. First, Methanol, whether ingested, inhaled, or absorbed through the skin can be fatal due to its CNS depressant properties in the same manner as ethanol poisoning. Second, in a process of toxication, where it is metabolized to formic acid via formaldehyde in a process initiated by the enzyme alcohol dehydrogenase in the liver. The reaction to formate proceeds completely, with no detectable formaldehyde remaining. Formate is toxic because it inhibits mitochondrial cyochrome c oxidase, causing the symptoms of hypoxia at the cellular level, and also causing metabolic acidosis among a variety of other metabolic disturbances. Fetal tissue will not tolerate Methanol.

Methanol poisoning can be treated with the antidotes ethanol or fomepizole. Both of these drugs act to reduce the action of alcohol dehydrogenase on Methanol by means of competitive inhibition so it is excreted by the kidneys rather than being transformed into toxic metabolites.

The initial symptoms of Methanol intoxication include central nervous system depression, headache, dizziness, nausea, lack of coordination, confusion, and with sufficiently large doses, unconsciousness and death. The initial symptoms of Methanol exposure are usually less severe than the symptoms resulting from the ingestion of a similar quantity of ethanol.

Once the initial symptoms have passed, a second set of symptoms come into play, 10 to as many as 30 hours after the initial exposure to Methanol, including blurring or complete loss of vision and acidosis. These symptoms are the result of the accumulation of toxic levels of formate in the bloodstream, and may progress to death by respiratory failure. The Methanol ester derivatives do not share this toxicity.

Applications using Methanol

Methanol is a common laboratory solvent. It is especially useful for HPLC and UV/VIS spectroscopy due to its low UV cutoff.

Feedstock
By far, the largest use of Methanol is in manufacture of other chemicals. Approximately 40 percent of Methanol is converted to formaldehyde. It is then used to make other products as diverse as plastics, plywood, paints, explosives, and permanent press textiles.

In the early 1970s, Mobil developed a Methanol to gasoline process for producing vehicle ready gasoline. One of the facilities was built in New Zealand at Motunui in the 1980s. Then in the 1990s, the United States used large amounts of Methanol to produce the gasoline additive methyl tert-butyl ether (MTBE). MTBE was taken off the market in the US, it is still widely used in other parts of the world. In addition to direct use as a fuel, Methanol is a component in the transesterification of triglycerides to yield a form of biodeisel.

Other chemical derivatives of Methanol include dimethyl ether, which has replaced chlorofluorocarbons as an aerosol spray propellant, and acetic acid. Dimethyl ether or "DME" also can be blended with liquefied petroleum gas (LPG) for home heating and cooking, and can be used as a diesel replacement transportation fuel.

Fuel for vehicles
Methanol is used to fuel internal combustion engines on a limited basis, primarily because it is not nearly as flammable as gasoline. Methanol is more difficult to ignite than gasoline and produces just one-eighth of the heat. Many racing classes including drag racers and mud racers use Methanol as their primary fuel source. Methanol is required with a supercharged engine in a Top Alcohol Dragster and, until the end of 2006, all vehicles in the Indianapolis 500 had to run Methanol. Mud racers have mixed Methanol with gasoline and nitrous oxide to produce more power than gasoline and nitrous oxide alone.

One of the drawbacks of Methanol as a fuel is its corrosivity to some metals, including aluminium. Methanol, although a weak acid, attacks the oxide coating that normally protects the aluminium from corrosion:

          6 CH₃OH + Al₂O₃ → 2 Al(OCH₃)₃ + 3 H₂O

The resulting methoxide salts are soluble in Methanol, resulting in clean aluminium surface, which is readily oxidized by some dissolved oxygen. Also the Methanol can act as an oxidizer:

          6 CH₃OH + 2 Al → 2 Al(OCH₃)₃ + 3 H₂

This reciprocal process effectively fuels corrosion until either the metal is eaten away or the concentration of CH3OH is negligible. Concerns with Methanol's corrosivity have been addressed by using Methanol compatible materials, and fuel additives that serve as corrosion inhibitors.

When produced from wood or other organic materials, the resulting organic Methanol (bioalcohol) has been suggested as renewable alternative to petroleum-based hydrocarbons. Low levels of Methanol can be used in existing vehicles, with the use of proper cosolvents and corrosion inhibitors. The European Fuel Quality Directive allows up to 3 percent Methanol with an equal amount of cosolvent to be blended in gasoline sold in Europe. Today, China uses more than one billion gallons of Methanol per year as a transportation fuel in both low level blends in existing vehicles, and as high level blends in vehicles designed to accommodate the use of Methanol fuels.

Other applications
Methanol is a traditional denaturant for ethanol, thus giving the term "methylated spirit."

Methanol is also used as a solvent, and as an antifreeze in pipelines and windshield washer fluid.

In some wastewater treatment plants, a small amount of Methanol is added to wastewater to provide a food source of carbon for the denitrifying bacteria, which convert nitrates to nitrogen to reduce the denitrification of sensitive aquifers.

During World War II, Methanol was used as a fuel in several German military rocket designs, under the name M-Stoff, and in a mixture as C-Stoff.
In the early 1900s, Methanol was used as an automobile coolant antifreeze.

Methanol is also a denaturing agent in polyacrylamide gel electrophoresis.

Direct-Methanol fuel cells are unique in their low temperature, atmospheric pressure operation, allowing them to be miniaturized to an unprecedented degree. Combined with the relatively easy and safe storage and handling of Methanol, this may open the possibility of fuel cell-powered consumer electronics, such as laptop computers and mobile phones.

Methanol is also widely used as fuel in camping and boating stoves. Methanol burns well in unpressurized burners. Alcohol stoves often require little more than a cup to hold fuel. This lack of complexity makes them a favorite of hikers spending extended time in the wilderness.

Product Specification - Methanol

Material Safety Data Sheet

1. Product and Supplier Identification

2. Composition

3. Hazards Identification 
 
Routes of Entry: 
Skin Contact: Moderate Eye Contact: Moderate Ingestion: Major Inhalation: Major 
 
Effects of Short-Term (Acute) Exposure: 
 
Inhalation: Inhalation of high airborne concentrations can also irriate mucous membranes, cause headaches, sleepiness, nausea, confusion, loss of consciousness, digestive and visual disturbances and even death. NOTE: Odour threshhold of Methanol is several times higher than the TLV-TWA. Depending upon 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. 
 
Skin Contact: 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” 
 
Eye Contact: Methanol is a mild to moderate eye irritant. High vapour concentration or liquid contact with eyes causes irritation, tearing and burning. 
 
Ingestion: 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. 
 
Effects of Long-Term (Chronic) Exposure: Repeated exposure by inhalation or absorption may cause systemic poisoning, brain disorders, impaired vision and blindness. Inhalation may worsen conditions such as emphysema or bronchitis. Repeated skin contact may cause dermal irritation, dryness and cracking. 
 
Medical Conditions Aggravated By Exposure: Emphysema or bronchitis.
 
4. First Aid Measures 
 
Note: Emergency assistance may also be available from the local poison control centre. 
 
Eye Contact: Remove contact lenses if worn. In case of contact, immediately flush eyes with plenty of clean running water for at least 15 minutes, lifting the upper and lower eyelids occasionally. Obtain medical attention. 
 
Skin Contact: In case of contact, remove contaminated clothing. In a shower, wash affected areas with soap and water for at least 15 minutes. Seek medical attention if irritation occurs or persists. Wash clothing before reuse. 
 
Inhalation: Remove to fresh air, restore or assist breathing if necessary. Obtain medical attention. 
 
Ingestion: Swallowing Methanol is potentially life threatening. Onset of symptoms may be delayed for 18 to 24 hours after digestion. If conscious and medical aid is not immediately available, do not induce vomiting. In actual or suspected cases of ingestion, transport to medical facility immediately.
 
NOTE 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 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 a 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.
 
5. Fire Fighting Measures

Flash point: 11°C (TCC) 
Autoignition temperature: 385°C (NFPA 1978), 470°C (Kirk-Othmer 1981; Ullmann 1975) 
Lower Explosive Limit: 6% (NFPA, 1978) 
Upper Explosion Limit: 36% (NFPA, 1978), 36.5% (Ullmann, 1975) 
Sensitivity to Impact: Low 
Sensitivity to Static Discharge: Low 
Hazardous Combustion Products: Toxic gases and vapours; oxides of carbon and formaldehyde. 
 
Extinguishing Media: Small fires: Dry chemical, CO₂, water spray 
Large fires: Water spray, AFFF(R) (Aqueous Film Forming Foam (alcohol resistant)) type with either a 3% or 6% foam proportioning system. 
 
Fire Fighting Instructions: Methanol burns with a clean clear flame that is almost invisible in daylight. Stay upwind! Isolate and restrict area access. Concentrations of greater that 25% Methanol in water can be ignited. Use fine water spray or fog to control fire spread and cool adjacent structures or containers. Contain fire control water for later disposal. Fire fighters must wear full face, positive pressure, self-contained breathing apparatus or airline and appropriate protective clothing. Protective fire fighting structural clothing is not effective protection from Methanol. Do not walk through spilled product. 
 
NATIONAL FIRE PROTECTION ASSOCIATION (NFPA) HAZARD INDEX: 
          HEALTH: 1 
          FLAMMABILITY: 3 
          REACTIVITY: 0
 
 
6. Accidental Release Measures 
 
Overview: Flammable liquid which can burn without a visible flame. Release can cause an immediate risk of fire and explosion. Eliminate all ignition sources, stop leak and use absorbent materials. If necessary, contain spill by diking. Fluorocarbon alcohol resistant foams may be applied to spill to diminish vapour and fire hazard. Maximize Methanol recovery for recycling or re-use. Restrict access to area until completion of cleanup. Ensure cleanup is conducted by trained personnel only. Wear adequate personal protection and remove all sources of ignition. Notify all governmental agencies as required by law.
 
Personal Protection: Full face, positive pressure self-contained breathing apparatus or airline, and protective clothing must be worn. Protective fire fighting structural clothing is not effective protection from Methanol. 
Environmental Precautions: Biodegrades easily in water Methanol in fresh or salt water may have serious effects on aquatic life. A study on Methanol’s toxic efffects on sewage sludge bacteria reported little effect on digestion at 0.1% while 0.5% Methanol retarded digestion. Methanol will be broken down to carbon dioxide and water. 
Remedial Measures: Flammable liquid. Release can cause an immediate fire/explosion hazard. Eliminate all sources of ignition, stop leak and use absorbent materials. Collect liquid with explosion proof pumps. Do not walk through spill product as it may be on fire and not visible.  Large Spills: If necessary, contain spill by diking. Fluorocarbon alcohol resistant foams may be applied to spill to diminish vapour and fire hazard. Maximize Methanol recovery for recycling or reuse. Collect liquid with explosion proof pumps. 
Small Spills: Soak up spill with non-combustible absorbent material. Recover Methanol and dilute with water to reduce fire hazard. Prevent spilled Methanol from entering sewers, confined spaces, drains, or waterways. Restict access to unprotected personnel. Put material in suitable, covered, labeled containers. Flush area with water. 
 
7. Handling and Storage 
 
Handling Procedures: No smoking or open flame in storage, use or handling areas. Use explosion proof electrical equipment. Ensure proper electrical grouding procedures are in place. 
 
Storage: Store in totally enclosed equipment, designed to avoid ignition and human contact. Tanks must be grounded, vented, and should have vapour emission controls. Tanks must be diked. Avoid storage with incompatible materials. Anhydrous Methanol is non-corrosive to most metals at ambient temperatures except for lead, nickel, monel, cast iron and high silicon iron. Coatings of copper (or copper alloys), zinc (including galvanized steel), or aluminum are unsuitable for storage. These materials may be attacked slowly by the Methanol. Storage tanks of welded construction are normally satisfactory. They should be designed and built in conformance with good engineering practice for the material being stored. While plastics can be used for short term storage, they are generally not recommended for long-term storage due to deterioration effects and the subsequent risk of contamination.
 
Corrosion rates for several construction materials: 
 
<0.508 mm/year Cast iron, monel, lead, nickel 
<0.051 mm/year High silicon iron 
Some attack Polyethylene 
Satisfactory Neoprene, phenolic resins, polyesters, natural rubber, butyl rubber 
Resistant Polyvinyl chloride, unplasticized 
 
8. Exposure Controls, Personal Protection 

Engineering Controls: In confined areas, local and general ventilation should be provided to maintain
airborne concentrations below permissible exposure limits. Ventilation systems must be designed
according to approved engineering standards.
 
Respiratory Protection: NIOSH approved supplied air respirator when airborne concentrations exceed exposure limits. 
Skin protection: Butyl and nitrile rubbers are recommended for gloves. Check with manufacturer. Wear chemical resistant pants and jackets, preferably of butyl or nitrile rubber. Check with manufacturer. 
Eye and Face Protection: Face shield and chemical splash goggles when transferring is taking place. 
Footwear: Chemical resistant, and as specified by the workplace. 
Other: Eyewash and showers should be located near work areas. NOTE: PPE must not be considered a long-term solution to exposure control. PPE usage must be accompanied by employer programs to properly select, maintain, clean, fit and use. Consult a competent industrial hygiene resource to determine hazard potential and/or the PPE manufacturers to ensure adequate protection. 
 
9. Physical and Chemical Properties

Solubility in other Liquids: Soluble in all proportions in other alcohols, esters, ketones, ethers and most other organic solvents
 
10. Stability and Reactivity
 
Chemical Stability: Yes
 
Incompatibility: Yes. Avoid contact with strong oxidizers, strong mineral or organic acids, and strong bases. Contact with these materials may cause a violent or explosive reaction. May be corrosive to lead, aluminum, magnesium, and platinum.
 
Conditions of Reactivity: Presence of incompatible materials and ignition sources.
 
Hazardous Decomposition Products: Formaldehyde, carbon dioxide, and carbon monoxide.
 
Hazardous Polymerization: Will not occur.
 
11. Toxicological Information

12. Ecological Information
 
Environmental toxicity: Methanol in fresh 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.
 
Biodegradability: Biodegrades easily in water.
 
13. Disposal Considerations
 
Review federal, provincial or state, and local government requirements prior to disposal. Store material for disposal as indicated in Section #7, Handling and Storage. Disposal by controlled incineration or by secure land fill may be acceptable.
 
14. Transport Information

15. Regulatory Information

16. Other Information
 
Preparation Date: October 13, 2005

Shipping & Ordering Information

Methanol is available for shipping throughout the continental United States with one week lead time for delivery. Please call (401) 423-3100 for details. The product is delivered in bulk and semi-bulk by tanker trucks and railcar.

Contact
The Chemical Company
19 Narragansett Ave.
Post Office Box 436
Jamestown, RI 02835-0436

Telephone: (401) 423-3100
FAX: (401) 423-3102

Robert N. Roach III "Robb"
President
Cell: (401) 864-3111
Email: robb@thechemco.com