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Methanol

Overview Purification and removal of water Introduction to Toxicology Clinical manifestations Poisoning treatment Methanol gasoline Standards for Use of Food Additives Uses Production method Chemical properties Toxicity Hazards & Safety Information

CAS No.67-56-1
Chemical Name:Methanol
Synonyms:CH3OH;metanol;ACID RED;S NO 250;Metanolo;Methylol;Carbinol;Methanol;ai3-00409;coat-b1400
CBNumber:CB7854099
Molecular Formula:CH4O
Formula Weight:32.04
MOL File:67-56-1.mol
Methanol Property
Melting point : -98 °C(lit.)
Boiling point : 65.4 °C(lit.)
density : 0.791 g/mL at 25 °C
vapor density : 1.11 (vs air)
vapor pressure : 410 mm Hg ( 50 °C)
refractive index : n20/D 1.329(lit.)
Fp : 52 °F
storage temp. : Store at RT.
color : <10(APHA)
Water Solubility : miscible
Merck : 14,5957
BRN : 1098229
CAS DataBase Reference: 67-56-1(CAS DataBase Reference)
NIST Chemistry Reference: Methyl alcohol(67-56-1)
EPA Substance Registry System: Methanol(67-56-1)
Safety
Hazard Codes : Xn,T,F
Risk Statements : 10-20/21/22-68/20/21/22-39/23/24/25-23/24/25-11-40-36-36/38-23/25
Safety Statements : 36/37-7-45-16-24/25-23-24-26
RIDADR : UN 1170 3/PG 2
WGK Germany : 1
RTECS : PC1400000
F : 3-10
HazardClass : 3
PackingGroup : II
Hazardous Substances Data: 67-56-1(Hazardous Substances Data)

Methanol Chemical Properties,Usage,Production

Overview
Methanol, molecular formula CH3OH, also known as "wood alcohol" or "methyl hydroxide", is an organic compound and is also the simplest saturated monohydric alcohol. It appears as colorless, transparent, flammable and volatile liquid. Mistakenly drinking of 5 to 10 ml methanol can lead to blindness while drinking a lot can lead to death. Methanol, at room temperature, is non-corrosive to metals (lead, aluminum excluded) with a slight alcohol odor. Its relative density is 0.792 (20/4°C); the boiling point is 64.5 ° C; the flash point is 12.22 ° C; the spontaneous combustion point is 463.89 °C and the vapor density is 1.11; the vapor pressure is 13.33 KPa (100mmHg 21.2 ° C); the vapor and air mixture explosion limit is 6 (6/10 ° C) ~ 36.5% (volume ratio); it is miscible with water, ethanol, ether, benzene, ketones, halogenated hydrocarbons and many other organic solvents. It is typically used as a solvent, antifreeze, fuel, or neutralizing agent. Methanol can be completely burned in the air and  release carbon dioxide and water: 2 CH3OH +3 O2 → 2 CO2 +4 H2O; The methanol flame is almost colorless, so we should be careful for ignition of it. Many bacteria, upon hypoxia metabolism, will produce methanol. Therefore, there is a small amount of methanol in the air vapor, but is subject to oxidation by the oxygen in the air within a few days in the sunlight to become carbon dioxide.
Purification and removal of water
Ordinary unrefined methanol contains 0.02% acetone and 0.1% water while the content of these impurities in industrial methanol is 0.5% to 1%. In order to obtain methanol having a purity of 99.9% or more, methanol may be fractionated by a fractional distillation column. Fractions at 64 °C were collected and then dehydrated with magnesium (same as for the preparation of absolute ethanol). Methanol is toxic. During treatment, we should avoid the inhalation of its vapor.
Introduction to Toxicology
(Male) oral LDLo: 6422 mg / kg; TDLo: 3429 mg / kg. Female oral TDLo: 4mg / kg. Another report, the human oral LDLo: 428mg / kg, 143mg / kg range; inhalation TCLo: 86000mg / m3, at the range of 300ppm. Rat oral LD50: 5628mg / kg; inhalation LC50: 64000ppm / 4H. The mice were orally LD50: 7300 mg / kg; inhaled LCLo: 50 gm / m3 / 2H. Rabbit percutaneous LD50: 15800 mg / kg. Methanol, after being absorbed into the body, can be quickly distributed in the body tissues, of which the cerebrospinal fluid, blood, bile and urine contains the highest content while the content of aqueous humor and vitreous humor is also high and the lowest content is found in bone marrow and adipose tissue. Methanol is subject to liver metabolism. Under the action of alcohol dehydrogenase, it can be subject to oxidation into formaldehyde and then oxidized to formic acid. This product has slow oxidation in vivo, only accounting for 1/7 of the ethanol with the excretion rate being also slow and having significant accumulation effect. Methanol not oxidized can be excreted by the respiratory tract and kidney with part of it subjecting to slow discharge through the gastrointestinal tract. Presumably inhalation of methanol at a concentration 39.3 ~ 65.5g / m ^ 3 in the air for 30 to 60 minutes can cause poisoning. Oral administration of 5 ~ 10ml, can cause severe poisoning; an oral 15ml, or separate oral administration to 124 ~ 164ml in total in two days can cause blindness. There are reports regarding administration of 30ml once can be fatal. The major effect of methanol is on in the nervous system with significant anesthetic effect and being able to cause brain edema. The anesthetic concentration of methanol is relatively close to LC and thus having greater risk.
It has a special selective effect on the optic nerve and retina, being able to easily lead to optic atrophy, further resulting in blindness. The methanol vapor has a strong stimulating effect on the respiratory mucosa. The toxicity of methanol is related to the accumulation of its metabolites formaldehyde and formic acid. It was previously thought that the main toxic effects is caused by formaldehyde, formaldehyde can inhibit the retina oxidative phosphorylation process so that the membrane can’t synthesize ATP and the cell undergoes degeneration, finally leading to optic atrophy. Recent studies have shown that formaldehyde can be quickly metabolized to formic acid. The metabolic acidosis and eye damage caused by acute poisoning is mainly related to formic acid content. Methanol can cause in vivo inhibition of certain oxidase system, further inhibiting the aerobic decomposition of sugar, further resulting in the accumulation of lactic acid and other organic acids and formic acid accumulation, and causing acidosis. It is generally believed that the toxicity of methanol is caused by its own and its metabolites. DLH: +6000 ppm [R28]
Clinical manifestations
The major damaged target organ after acute methanol poisoning is the central nervous system, optic nerve and retina. The incubation period of inhalation poisoning is generally 1 to 72 hours, sometimes as long as 96 hours; the value for oral poisoning is generally 8 to 36 hours; if administrating ethanol at the same time, the incubation period can be a bit longer. Clinical features
Stimulation symptoms: Inhalation of methanol vapor can cause eye and respiratory mucosa irritation. Central nervous symptoms: patients often have dizziness, headache, dizziness, fatigue, gait staggering, insomnia, indifferent expression, confusion and so on. In severe cases, there are haziness, coma and epileptic convulsions. Patients of severe oral poisoning may have extrapyramidal symptoms of damage or Parkinson's syndrome. Head CT examination revealed lentiform nucleus and subcortical central white matter symmetry infarction necrosis, hallucinations, depression and other symptoms.
Eye symptoms: the initial performance: immediately shadow, flash, blurred vision, eye pain, photophobia, diplopia and so on. In severe cases, there is dramatic visual decline, being able to cause persistent blindness. Examination shows pupil dilation or shrinkage, having slower or disappearance of sense of light, getting optic disc edema, peripheral retinal hyperemia, hemorrhage, edema with optic atrophy in later phase. Acidosis: reduced carbon dioxide binding capability with cyanosis, deepened and fast Kussmaul breathing in severe cases. Digestive system and other symptoms: patients can have nausea, vomiting, abdominal pain, etc., can be complicated by liver damage. Oral poisoning may be complicated by acute pancreatitis. In a small number of cases, it is associated with tachycardia, myocarditis, S-T and T wave changes, and acute renal failure and so on. Patients of severe acute methanol poisoning can get severe headache, nausea, vomiting and sharp decline in vision, or even blindness, confusion, delirium, convulsions and coma. They may finally die due to respiratory failure. According to the history of methanol exposure, there is short-term clinical manifestations including central nervous system damage, eye damage and metabolic acidosis, refer to on-site hygiene survey, except for other similar performance of the disease, comprehensive analysis of the diagnosis is not difficult. If necessary, we can perform blood and urine methanol determination. In early phase, the poisoning should be distinguished from cold, neurasthenia and acute gastroenteritis. In addition, it should be also distinguished from methyl chloride, ethylene glycol acute poisoning and encephalopathy, optic nerve damage caused by other reasons. It must be asked in detail about occupational history, conducted of on-site health survey and closely observed of disease progression, together with laboratory tests so that we can come to the correct diagnosis.
Poisoning treatment
The patient should be immediately removed from the scene, removed of contaminated clothing. Patients of oral administration can apply 1% sodium bicarbonate for gastric lavage with magnesium sulfate catharsis. Clear the absorbed methanol in the body. Dialysis therapy: severe poisoning patients should be subject to early hemodialysis or peritoneal dialysis, in order to reduce the symptoms of poisoning, save the patient's life and reduce the sequelae. Hemodialysis therapy indications are:
① blood methanol> 15.6mmol / L; or formic acid> 4.34mmol / L;
② severe metabolic acidosis;
③ severe visual impairment or optic disc retinal edema. Antidote: ethanol is the poisoning antidote of the methanol.
The application of ethanol can prevent methanol oxidation, and promote methanol discharge. Use 10% glucose solution to formulate 5% ethanol solution for slowly intravenous infusion. There is not much domestic clinical experience. Correct acidosis: According to blood gas analysis or carbon dioxide binding force determination and clinical manifestations, perform early administration of sodium bicarbonate solution or sodium lactate solution. Support and symptomatic treatment: according to the condition, actively prevent and treat cerebral edema, reduce intracranial pressure, improve blood circulation, prevent optic neuropathy. Maintain respiratory and circulatory function, maintain electrolyte balance. Given a large number of B vitamins. It has been suggested of the application of formic acid salts and 4-methylpyrazole (4MP) for treatment of methanol poisoning. The experimental study in monkey has confirmed the efficacy. However, so far it has been not yet used in clinical.
Methanol gasoline
Methanol gasoline refers to the M series mixture fuel made of addition of methanol to the gasoline and formulated using methanol fuel solvent. Among them, M15 (add 15% methanol in gasoline) clean methanol gasoline is used as vehicle fuel, respectively, used in a variety of gasoline engines. It can be applied to substitute the finished gasoline without changing the existing engine structure, and can also be mixed with refined oil. The methanol mixed fuel has excellent thermal efficiency, power, start-up and being economical. It is also characterized by lowering the emissions, saving oil and being safe and convenient. Methanol gasoline types of M35, M15, M20, M50, N85 and M100 with different blend ratios have been developed around the world according to the conditions of different countries. At present, the commercial methanol is mainly M85 (85% methanol + 15% gasoline) and M100 with M100 performance being better than M85 and having greater environmental advantages.
Standards for Use of Food Additives
Name Food allowed to use it as additives Function of the additive Maximal allowable amount(g/kg) Maximal allowable residue(g/kg)
Methanol Food Processing aid for food industry / It should be generally removed before the final product except in cases where residue amount has been documented.
Uses
1. Methanol is widely used, being basic organic chemical raw materials and high-quality fuel. It is mainly used in fine chemicals, plastics and other fields to manufacture formaldehyde, acetic acid, methyl chloride, methylamine, dimethyl sulfate and other organic products, being the raw materials of pesticides and pharmaceuticals. Methanol, after the deep processing, can be used as a new type of clean fuel and can also be added to the gasoline for blending.
2. Methanol oxidation of formaldehyde
3. Methanol, at high temperature, the presence of pumice silver, catalyst or other solid catalyst, can be subject to direct oxidation into formaldehyde. At present, more than 40% of methanol at home and abroad is used for the production of formaldehyde, further for production of synthetic resins, plastics and other chemical raw materials. POM is an excellent-performance engineering plastics with very extensive applications. Formaldehyde is also used to make butanediol, urotropine, nearly 100 kinds of downstream products.
4. Manufacturing of methylamine from methanol amination
5. Methanol is mixed with ammonia in a certain proportion. Under the pressure of 370-420 DEG C and 5.0-20.0MPa, use activated alumina as a catalyst to obtain a mixture of monomethylamine, dimethylamine and trimethylamine, followed by distillation to obtain mono, di or trimethylamine products. Mono-, di-, and tri- methylamine can be applied to the fields of pesticides, pharmaceuticals and dyes or used as organic raw materials intermediates.
6. Methanol, under the presence of metal silicoaluminium catalyst or ZSM-5 type molecular sieve, can be used to make dimethyl ether through dehydration.
7. Dehydrogenation of Methanol can lead to Methyl Formate.
8. Methyl formate is a raw material of organic synthesis and can be used for making formamide, dimethyl formamide. Formamide is the raw material of medicine, spices and dyes and can also be used as paper processing agent, the softener of the fiber industry and the polar solvents of organic synthesis. Dimethylformamide is an important organic chemical raw material and excellent solvent, can be used as gas absorbers and applied to fields of pesticides, synthetic leather, polyacrylonitrile spinning and butadiene extraction.
9.    Extraction solvent; the maximum allowable residue of the finished product: spice oil resin 50mg / kg; hops extract 2.2mg / kg.
10. GB 2760-96 lists it as a food processing aids.
11. It is used as analysis reagent and chromatography reagent as well as for organic synthesis
12. It is mainly used in the preparation of formaldehyde and as a methylating agent and solvent in organic synthesis, being the raw material of methyl tert-butyl ether. It can also be used as automotive fuel
13. It can be used for the separation of calcium sulfate and magnesium sulfate, separation of strontium bromide and barium bromide and determination of boron reagent.
14. It is one of the basic organic raw materials. Mainly used in the manufacture of formaldehyde, acetic acid, methyl chloride, methylamine and dimethyl sulfate and other organic products. It is also one of the raw materials of pesticides (pesticides, acaricide), medicine (sulfonamides, heminomycin, etc.), Synthesis of dimethyl terephthalate, methyl methacrylate and methyl acrylate. It is also an important solvent and can also be mixed with gasoline as an alternative fuel for application. Since the 1980s, methanol has been used to produce gasoline octane value additives methyl tert-butyl ether, methanol gasoline, methanol fuel, and methanol protein products, greatly promoting the development of methanol production and market demands.
15. It can be used as basic organic raw materials, solvents and antifreeze agent. Mainly used for formaldehyde, flavor, dyes, medicine, gunpowder, antifreeze and so on.
16. It can be used for the preparation of Karl Fischer reagent to determine the trace amount of water contained in the alcohol, saturated hydrocarbons, benzene, chloroform and pyridine.
Production method
Industrial synthesis of methanol almost all applies pressurized catalytic hydrogenation process of carbon monoxide with the technology process including gas making, synthetic purification, methanol synthesis and crude methanol distillation and other processes. The purification of crude methanol involves rectification and chemical treatment. Chemical treatment is mainly used to destroy alkali impurities that is difficult to be removed in the distillation process, and adjust the pH value; distillation is mainly to remove volatile components such as dimethyl ether, and the hardly volatile components, ethanol, high-carbon alcohol and water. The purity after crude distillation can generally reach more than 98%.
It is obtained through catalytic reaction between carbon monoxide and hydrogen under high pressure.
It can be obtained through the partial oxidation of natural-gas hydrocarbons.
Chemical properties
It appears as colorless, transparent, flammable and volatile polar liquid. Pure product has slight alcohol smell while crude product has unpleasant pungent. It is miscible with water, ethanol, ether, benzene, ketones and most other organic solvents.
Toxicity
ADI is limited to GMP (FAO / WHO, 2001).
Toxic, can cause blindness.
LD50: 5628 mg / kg (rat, oral).
Hazards & Safety Information
Category Flammable liquids
Toxicity grading Low toxicity
Acute Toxicity Oral - Rat LD50: 5628 mg / kg; Oral - mouse LD50: 7300 mg / kg
Stimulation Data Eye - Rabbit 100 mg / 24h Medium; Skin - Rabbit 20 mg / 24h Medium Moderate
EXPLOSIVES HAZARDOUS CHARACTERISTICS being explosive when mixed with air
Flammability and hazard characteristics being flammable in the case of fire, high temperature and oxidant with combustion release irritant smoke; mistakenly administration can lead to blindness
Storage and transportation characteristics Treasury: ventilated, low-temperature and dry; store it separately from oxidants and acids
Extinguishing agent dry powder, dry sand, carbon dioxide, foam, 1211 extinguishing agent
Occupational Standard TWA 260 mg / m3; STEL 310 mg / m3
Chemical Properties
Colorless liquid
Usage
Meets ACS specifications
Usage
Suitable for HPLC, spectrophotometry, and some LC-MS applications
Usage
high purity grade for ICP-MS detection
Usage
Suitable for volatile organics analysis by GC-MS
General Description
A colorless fairly volatile liquid with a faintly sweet pungent odor like that of ethyl alcohol. Completely mixes with water. The vapors are slightly heavier than air and may travel some distance to a source of ignition and flash back. Any accumulation of vapors in confined spaces, such as buildings or sewers, may explode if ignited. Used to make chemicals, to remove water from automotive and aviation fuels, as a solvent for paints and plastics, and as an ingredient in a wide variety of products.
Air & Water Reactions
Highly flammable. Soluble in water in all proportions.
Reactivity Profile
Methanol reacts violently with acetyl bromide [Merck 11th ed. 1989]. Mixtures with concentrated sulfuric acid and concentrated hydrogen peroxide can cause explosions. Reacts with hypochlorous acid either in water solution or mixed water/carbon tetrachloride solution to give methyl hypochlorite, which decomposes in the cold and may explode on exposure to sunlight or heat. Gives the same product with chlorine. Can react explosively with isocyanates under basic conditions. The presence of an inert solvent mitigates this reaction [Wischmeyer 1969]. A violent exothermic reaction occurred between methyl alcohol and bromine in a mixing cylinder [MCA Case History 1863. 1972]. A flask of anhydrous lead perchlorate dissolved in Methanol exploded when Methanol was disturbed [J. Am. Chem. Soc. 52:2391. 1930]. P4O6 reacts violently with Methanol. (Thorpe, T. E. et al., J. Chem. Soc., 1890, 57, 569-573). Ethanol or Methanol can ignite on contact with a platinum-black catalyst. (Urben 1794).
Health Hazard
Exposure to excessive vapor causes eye irritation, head- ache, fatigue and drowsiness. High concentrations can produce central nervous system depression and optic nerve damage. 50,000 ppm will probably cause death in 1 to 2 hrs. Can be absorbed through skin. Swallowing may cause death or eye damage.
Fire Hazard
Behavior in Fire: Containers may explode.
Methanol Preparation Products And Raw materials
Raw materials
HEAVY CUT RESIDUE OIL Residuum L(+)-Lactic acid CARBON MONOXIDE tert-Butyl methyl ether Oxygen CARBON DIOXIDE METALLURGICAL COKE Hydrogen Sodium hydroxide Lactic acid 2 DIESEL FUEL METHANE
Preparation Products
1-Chloropinacolone 3'-DIMETHYLAMINOACETOPHENONE Potassium methoxide TRIETHYLENE GLYCOL MONOMETHYL ETHER Vinyltrimethoxysilane METHYL TRICOSANOATE Ethyl 3-(benzylamino)propanoate Diphenyldimethoxysilane 3-Glycidoxypropyltrimethoxysilane 4-Bromobenzyl alcohol 2-Amino-4-methoxypyridine 1,5-NAPHTHALENEDISULFONIC ACID DISODIUM SALT, DIHYDRATE, 98 4-MORPHOLINECARBOXAMIDINE FEMA 2062 2-Thiophenecarboxylic acid hydrazide 2-Methoxy-3-isobutyl pyrazine H-DL-PRO-OME HCL 3,5-Dimethoxybenzyl alcohol 4-(METHOXYCARBONYL)NICOTINIC ACID METHYL HYDROGEN GLUTARATE METHYL 3-AMINOBENZOATE Methyl 3,4-dimethylbenzoate 1-(1,3-DIHYDRO-1-OXOISOBENZOFURAN-3-YL)UREA (1H-IMIDAZOL-2-YL)-METHANOL 2-OXO-6-PHENYL-4-(TRIFLUOROMETHYL)-1,2-DIHYDRO-3-PYRIDINECARBONITRILE 5-Bromo-4,6-dihydroxypyrimidine NICOTINIC ACID HYDRAZIDE 3-Methacryloxypropyltrimethoxysilane METHYL STEARATE TETRAHYDRO-3-FUROIC ACID 2-Quinolinemethanamine Dipropylene glycol monomethyl ether 5-BROMO-2-CHLORO-4-METHOXYPYRIMIDINE 4-Hydroxy-5-fluorpyrimidine 5-METHYL-2-HEXANOL N,N'-BISBENZYLIDENEBENZIDINE Methyl 4-aminobutyrate hydrochloride 3-Chloropropyltrimethoxysilane methylated albumin 3-(METHOXYCARBONYL)PYRIDINE-2-CARBOXYLIC ACID
Methanol Suppliers      Global( 370)Suppliers     
SupplierTelFaxEmailCountryProdListAdvantage
J & K SCIENTIFIC LTD. 400-666-7788 +86-10-82848833+86-10-82849933jkinfo@jkchemical.com;market6@jkchemical.comCHINA 96839 76
Spectrum Chemical Manufacturing Corp. 021-67601398-808021-57711696gduan@spectrumchina.netCHINA 9351 60
Shanghai Aladdin Bio-Chem Technology Co.,LTD 021-20337333/400-620-6333021-50323701sale@aladdin-e.comCHINA 24323 65
Shanghai Macklin Biochemical Co.,Ltd. 021-51821711021-51821727sales@macklin.cnCHINA 13259 55
Meryer (Shanghai) Chemical Technology Co., Ltd. +86-(0)21-61259100(Shanghai) +86-(0)755-86170099(ShenZhen) +86-(0)10-59487313(Beijing)+86-(0)21-61259102(Shanghai) +86-(0)755-86170066(ShenZhen) +86-(0)10-88580358(Beijing)sh@meryer.comCHINA 40406 62
Sinopharm Chemical Reagent Co,Ltd. 86-21-6321012386-21-63290778 86-21-63218885sj_scrc@sinopharm.comCHINA 10002 79
Energy Chemical 021-58432009 / 400-005-6266021-58436166-800info@energy-chemical.comCHINA 44200 61
Alfa Aesar 400-610-6006; 021-67582000021-67582001/03/05saleschina@alfa-asia.comCHINA 30330 84
TCI (Shanghai) Development Co., Ltd. 800-988-0390021-67121385sales@tcishanghai.com.cnCHINA 22834 81
Beijing dtftchem Technology Co., Ltd. 13651141086; 86(10)60275028、6027582086 (10) 60270825dtftchem@sina.comCHINA 3442 62
 
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