2.

4 Manufacturing Process
The two principal processes for the industrial production of methyl chloride are
reaction of hydrogen chloride and methanol, and chlorination of methane. Several
variants of both processes are used.
Chlorination of methane yields other chlorinated hydrocarbons in substantial amounts;
indeed, under certain condition, methyl chloride may not be the principal product.
Because the co products like methylene chloride, chloroform, and carbon
tetrachloride, is as commercially important as methyl chloride. Methane chlorination
can be regarded as a multiple product process rather than one with several byproducts.
The methanol-hydrogen chloride reaction yields methyl chloride as the main product
with small amounts of dimethyl ether as the only byproduct. It is commercially
carried out in both liquid phase and gas phase processes. Hydrogen chloride is often
the determining factor in choosing the best route to produce methyl chloride.

1) Chlorination of methane
Methane can be chlorinated thermally, photochemically, or catalytically. Thermal
chlorination, the most difficult method, may be carried out in the absence of light or
catalysts. It is a free radical chain reaction limited by the presence of oxygen and
other free radical inhibitors.
In a typical thermal chlorination process, the chlorine methane mixture, with an
excess of methane, is fed to a reactor where it mixes with gas previously subjected to
reaction. By regulating the chlorine gas flow rate and, consequently, the heat produced
by the chlorination reaction, the temperature is maintained at 400-500C.the gas from
the reactor is cooled and the hydrogen chloride removed by water washing in a
packed tower. Hydrochloric acid thus obtained is generally commercially salable and
is, therefore, advantageous to the economics of the process.finally; the product gas is
scrubbed with caustic liquor, dried by refrigeration, and further cooled to effect its
liquefaction. Uncondensed methane is returned to the reactor. The liquefied gas is
then fractionally distilled. On fractionation, a typical reaction product yields 35%
methyl chloride, 45 wt% methylene chloride, and 20 wt% chloroform plus a small

amount of carbon tetrachloride. The relative amount of these components can be

changed by varying the reaction conditions.
Chloromethane namely methyl chloride (CH3Cl), methylene chloride (CH3Cl2),
Chloroform (CHCl3) and Carbon Tetrachloride (CCl4) are produced by direct
chlorination of CH4 in a gas phase reaction without any catalyst.
Reaction

Heat of Reaction (kcal/gmol)

CH4 +Cl2 CH3Cl+HCl

-24.3

CH3Cl+Cl2 CH2Cl2 +HCl

-24.0

CH2Cl2 +Cl2 CHCl3 +HCl

-24.0

CHCl3 + H2 CCl4 + HCl

-24.1

The reactions are very exothermic. The feed molar ratio affects the product
distribution. When CH4/Cl2 is about 1.8, then more CH3Cl is produced. On the other
hand, when CH4 is chosen as a limiting reactant, more of CCl 4 is produced. Therefore,
depending upon the product demand, the feed ratio is adjusted.
2) Hydro chlorination of Methanol
Liquid phase:
Silicon producers use methyl chloride in its manufacture and produce an aqueous
hydrochloric acid stream as a byproduct. This byproduct HCl is converted back to
methyl chloride by hydrochlorination.in fact, it is possible to produce methyl chloride
directly from the chloromethylsilane hydrolysis step in the silicone process.
Liquid mixtures of methanol and hydrochloric acid slowly yield methyl chloride even
at 0C.the typical process is carried out by contacting the alcohol with hydrochloric
acid at 70 to 160C and 0.1-1 MPa in the presence of a catalyst such as zinc chloride,
quatemary amines or with no catalyst at all. Typically 0.5 to 3% of the methanol is
converted to dimethyl ether. Product methyl chloride is taken out of the reactor as a

vapor and is cooled to condense as much of the water vapor and HCl as
possible.dimethyl ether and the residual water is then removed and the finished
methyl chloride is condensed.
Gas phase:
The vaporized methanol and hydrogen chloride, mixed and are heated to 180200C.reaction occurs on passage through a convertor packed with 1.68-2.38 mm
alumina gel at 350C.the product gas is cooled,water-scrubbed,and liquefied.
Conversion of over 95% of the methanol is commonly obtained. Gamma-alumina has
been used as a catalyst, silica, or pumice; silica-aluminas; zeolites; attapulgus clay; or
carbon.
CH3OH (g) + HCl (g) CH3Cl (g) + H2O (g) + 7.25 kcal/mol
The hydroxyl group of methanol is replaced by chlorine from the hydrogen chloride
molecule, and the result is methyl chloride and water.
An advantage of the process is that high yields are possible, and the single product
methyl chloride can be produced with relatively little coproducts.Care must be taken
that the reacting conditions do not favor the competing reaction whereby two
molecules of methanol combine to produce dimethyl ether.
2CH3OH (g) CH3OCH3 (g) + H2O (g) + 5.9 kcal/mol
This is the only significant side reaction which takes place in the hydro chlorination
reaction.
2.5 Selected Manufacturing Process
The two main routes for the production of methyl chloride are methane chlorination
and methanol hydro chlorination. The best prominent route is methanol hydro
chlorination because of the following reasons:

At first look one might reach the conclusion that the use of methanol than methane
as a source of carbon for the production of methyl chloride would result in a more
expensive operation.however, where only methyl chloride is desired and the plant

capacity is relatively small, the hydro chlorination route offers some advantage
over chlorination of methane.

Methane chlorination requires very high purity methane for feed. This generally
must be prepared by cryogenic distillation of natural gas. This is relatively high
investment unit.

The large volume of gases handled and recycled results in the need for large
equipment for methane chlorination unit.

Another consideration in favor of a hydro chlorination route to methyl chloride is

the fact that there is no byproduct hydrogen chloride. Unless a good value can be
realized for the HCl, this alone can more than offset the difference between the
costs of methane and methanol.

Hydrogen chloride is often the determining factor in choosing the best route to
produce methyl chloride. The chlorination route produces HCl whose disposal
generally has become increasingly difficult for chlorinated hydrocarbon producers.
While the hydro chlorination route consumes HCl.

As a result of the ready and low cost availability of methanol (via the low pressure
methanol synthesis technique) and its facile transport and storage, the method also
offers the advantage of avoiding the need for placing production facilities in the
vicinity of a methane supply.

Uses
Chloromethane is a hydrocarbon used as an industrial solvent. It has been used as an
aerosol propellant, as a refrigerant and as a local anesthetic.
Methyl chloride is used mainly in the production of silicones where it is used to make
methylate silicon. It is also used in the production of agricultural chemicals, methyl
cellulose, quaternary amines, and butyl rubber and for miscellaneous uses including
tetra methyl lead.

Methyl chloride was used widely in refrigerators in the past, but generally this use has
been taken over by newer chemicals such as Freon.

Approximately thirteen percent of methyl chloride is used as a raw material for

cellulose ethers such as methyl cellulose, hydroxyproply methylcellulose, and
hydroxybutyl methylcellulose. All of these are used as thickeners and binders in
pharmaceuticals, toiletries, and food products. It is also used in the manufacture of
building products such as drywall joint cement formulations, cement formulations,
stucco, mortars, etc.
Another eleven percent of the methyl chloride produced goes into the production of
water treatment chemicals such as flocculants. Flocculants are used to coagulate and
separate solids from water.
Methyl chloride is also consumed in the production of certain quaternary ammonium
compounds such as dimethyl ammonium chloride, which is an ingredient found in
fabric softeners. These markets consume approximately 5 percent of the methyl
chloride produced.
Methyl chloride is a raw material used in the production of agricultural chemicals
known as herbicides. They include paraquat, monosodium methanearson, and
disodium methanearsonate. This makes up approximately 3% of the methyl chloride
market.

Another two percent of the methyl chloride production is used in the production of
heat stabilizers for PVC known as methyltin. The remaining nine percent goes into
various uses such butyl elastomers and organomodified clays. Butyl elastomers are
used in such things as inner tubes and inner liners for tires as well as caulks, sealants,
and pharmaceuticals. Organomodified clays are used primarily in drilling mud in the
oil and gas industry to impart lubricity and viscosity to the system.