PHYSICAL PROPERTIES OF METHANOL- Cetiner Engineering

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PHYSICAL PROPERTIES OF METHANOL: CH₃OH

Also called METHYL ALCOHOL, it is the simplest of a long series of organic compounds called alcohols; its molecular formula is CH₃OH.
The modern method of preparing methanol is based on the direct combination of carbon monoxide gas and hydrogen in the presence of a catalyst at
elevated temperatures and pressures. Most methanol is produced from the methane component of natural gas.

Pure methanol is an important material in chemical synthesis. Its derivatives are used in great quantities for building up a vast number of compounds,
among them many important synthetic dyestuffs, resins, drugs, and perfumes. Large quantities are converted to dimethylaniline for dyestuffs
and to formaldehyde for synthetic resins. It is also used in automotive antifreezes, in rocket fuels, and as a general solvent.
Methanol is also a high-octane, clean-burning fuel that is a potentially important substitute for gasoline in automotive vehicles.

Methanol is a colorless liquid, completely miscible with water and organic solvents and is very hygroscopic. It boils at 64.96° C (148.93° F) and
solidifies at -93.9° C (-137° F). It forms explosive mixtures with air and burns with a nonluminous flame. It is a violent poison; drinking mixtures
containing methanol has caused many cases of blindness or death. Methanol has a settled odor.
Methanol is a potent nerve poison. Key physical properties are:

Melting Point : -97.7 ⁰C

Boiling Point : 65 ⁰C

Relative Density : 0.79

Formula: CH₃OH

Molecular weight: 32.042 kg/kmol

Heat of Formation -201.3 MJ/kmol

Gibbs Free Energy -162.62 MJ/kmol

Freezing point: -97.7 °C

Boiling point: 64.6 °C (at atmospheric pressure)

Critical properties:

Critical temperature 512.6 K

Critical pressure 81 bar abs

Critical volume 0.118 m³/kmol

Liquid Properties:

Density 791 kg/m³ at 20 °C

Heat of Vaporization 35278 kJ/kmol

Viscosity:

a = 555.3 b = 260.6

where log(viscosity) = a * ( 1/T - 1/b )

viscosity: mNs/m² T: °K

Vapor Properties:

Heat capacity:

a = 21.152 b = 0.07092 c = 2.59E-05 d = -2.85E-08

where Cp = a + b*T + c*T² + d*T³

Cp: kJ/kmol.K T: °K

Vapour pressure:

a = 18.5875 b = 3626.55 c = -34.29

where ln(P) = a - b/(T+c) P: mmHg; T: °K

within range -16 to 91°C

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MANUFACTURE OF METHANOL: CH₃OH

Most of world methanol is manufactured from natural gas by a steam reforming process. Methane of natural gas is first mixed with steam at 3/1 ratio.
It is then reformed to carbon oxides and hydrogen under nickel catalyst at 1000°C and 20 Atm. Carbon oxides and hydrogen reacts exothermically at about
70 Atm pressure in the gas phase to form mainly methanol and water mixture. These reactions take place in the presence of Cu, Al and
Zn based catalyst.Crude methanol is cooled and condensed and fed through a distillation process to achieve 99.9 Mole% product purity.
The process is highly integrated. It uses the state-of-the art technologies to achieve low capital cost and higher conversion efficiency.

As an alternative, partial oxidation or oxygen aided processes are also used.

Methanol production economics are highly depended on the feedstock selection and feedstock prices. Methanol can be manufactured from any
hydrocarbon source; naphtha, oil, coal, wood, bio-mass, LPG, etc. The naphtha, fraction of crude oil distillation, is used as a raw material
in many older facilities for the manufacture of methanol. When naphtha is reacted with a high steam ratio, under pressure and at
high temperature, synthesis gas of low methane content is obtained. Most of the carbon from the naphtha is converted to carbon monoxide
and carbon dioxide:

			  1000 °C       
	CH4    +    H2O           ===>             CO      +       3H2      
				      Carbon          Hydrogen        
				      Monoxide   

	CO    +     H2O           ===>             CO2      +       H2      
				        Carbon          Hydrogen        
				        Dioxide

The mixture of hydrogen and carbon oxides is compressed and is passed over a catalyst under high pressure and at high temperature, methanol is formed.

				 400 °C        
	CO      +       2H2             ===>             CH3OH   
					    Methanol 

	CO2     +       3H2             ===>             CH3OH  + H2O 
					    Methanol

The mixture of methanol, water, other impurities is distilled to produce 99.95 Mole% methanol product purity.

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CHEMICAL PROPERTIES OF METHANOL: CH₃OH
Combustion of Methanol:

Methanol burns with a pale-blue, non-luminous flame to form carbon dioxide and steam.
2CH3OH + 302 ===> 2CO2 + 4H2O

Oxidation of Methanol:

Methanol is oxidized with acidified Potassium Dichromate, K2Cr2O7, or with acidified Sodium Dichromate, Na2Cr2O7, or with acidified
Potassium Permanganate, KMnO4, to form formaldehyde.

[O]
CH3OH ===> HCHO + H2

Methanol Formaldehyde

2H2 + O2 ===> 2H2O

If the oxidizing agent is in excess, the formaldehyde is further oxidized to formic acid and then to carbon dioxide and water.

[O] [O] HCHO ===> HCOOH ===> CO2 + H2O Formaldehyde Formic Acid

Catalytic Oxidation of Methanol:

The catalytic oxidation of methanol using platinum wire is of interest as it is used in model aircraft engines to replace the sparking plug arrangement
of the conventional petrol engine. The heat of reaction is sufficient to spark the engine.

Dehydrogenation of Methanol:

Methanol can also be oxidized to formaldehyde by passing its vapor over copper heated to 300 °C. Two atoms of hydrogen are eliminated from each
molecule to form hydrogen gas and hence this process is termed dehydrogenation.

Cu 300°C CH3OH ===> HCHO + H2 Methanol Formaldehyde

Dehydration of Methanol:

Methanol does not undergo dehydration reactions. Instead, in reaction with sulphuric acid the ester, dimethyl sulphate is formed.

concentrated H2SO4 2 CH3OH ===> (CH3)2SO4 + H2O Methanol Dimethyl Water Sulphate

Esterification of Methanol

Methanol reacts with organic acids to form esters.

H(+) CH3OH + HCOOH ===> HCOOCH3 + H2O Methanol Formic Methyl Water Acid Formate

Substitution of Methanol with Sodium

Methanol reacts with sodium at room temperature to liberate hydrogen. This reaction is similar to the reaction of sodium with ethanol.

2 CH3OH + 2 Na ===> 2CH3ONa + H2 Methanol Sodium Sodium Hydrogen Methoxide

Substitution of Methanol with Phosphorus Pentachloride

Methanol reacts with phosphorus pentachloride at room temperature to form hydrogen chloride, methyl chloride, (i.e. chloroethane) and phosphoryl
chloride.

CH3OH + PCl5 ===> HCl + CH3Cl + POCl3 Methanol Phosphorus Hydrogen Methyl Phosphoryl Pentachloride Chloride Chloride Chloride

Substitution of Methanol with Hydrogen Chloride

Methanol reacts with hydrogen chloride to form methyl chloride (i.e. chloromethane) and water. A dehydrating agent (e.g. zinc chloride) is used.

ZnCl2 CH3OH + HCl ===> CH3Cl + H2O Methanol Methyl Chloride
INDUSTRIAL USES OF METHANOL: CH₃OH

Methanol is an important merchant commodity chemical with 60 million MTPA demand capacity and it is used in the
manufacture of formaldehyde, as a solvent in the paint and varnish industry, and as anti-freeze, etc. Refer to attached figure for detailed
industrial uses of methanol.

Also refer to Material Safety Data Sheet: MSDS for Methanol - MSDS Number: M2015

GENERAL SAFETY INFORMATION FOR METHANOL: CH₃OH

Hazard Identification: DANGER! POISON! EXTREMELY FLAMMABLE LIQUID AND VAPOR! HIGH TOXICITY! FATAL IF SWALLOWED!
CANNOT BE MADE NONPOISONOUS!
Hazard Label:
Classification:
Category 1, Acute Toxicity Category 1, Flammable Liquid, Reproductive Toxicity 1B, Specific Target Organ Toxicity (Repeated Exposure)
In Liquid Form:
Flammable
If swallowed: May be fatal or cause blindness
If inhaled: Harmful
Absorbed through skin: Harmful.

In Vapor Form:
Flammable
Causes irritation to eyes, skin, lungs and respiratory tract
Affects central nervous system and liver.

High vapor concentration in air or liquid contact with eyes causes irritation, tearing and burning. Concentrations in air exceeding
1000 ppm may cause irritation of the mucous membranes. May cause central nervous system depression.

FIRST AID BRIEF FOR METHANOL: CH₃OH

Keep away from heat and ignition sources. Harmful if swallowed. Avoid inhaling vapors. Use with adequate ventilation.
Avoid contact with eyes, skin, and clothes. Wash thoroughly after handling. Keep container closed.

FIRST AID: CALL A PHYSICIAN.

SKIN: Remove contaminated clothing. Immediately flush skin with plenty of water for at least 15 minutes.

EYES: Wash eyes with plenty of water for at least 15 minutes, lifting lids occasionally. Seek Medical Aid.

INHALATION: Remove to fresh air. If not breathing, give artificial respiration. If breathing is difficult, give oxygen

INGESTION: If swallowed, induce vomiting immediately after giving two glasses of water. Never give anything by mouth to an
unconscious person.

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