1,4 Butanediol (HOCH2-CH2-CH2-CH2OH)

With
increasing the demand of tetrahydrofuran and
polybutylene terephthalate; 1,4 Butanediol has received
considerable interest during recent years.
It is exclusively used as an intermediate for the
manufacture of a large number of chemicals and polymers.
1,4 Butanediol is also used in the manufacture of
butyrolactone which is used in manufacture of n-Methyl-2-
pyrollidone (NMP); an important solvent used in petroleum
and petrochemical industries.
It is also finding applications in textile, leather, food and
pharmaceutical industries.
Global consumption of 1,4-Butanediol is about
Tetrahydrofuran (38.5%), butyrolactone (13.2%),
Polyurethane (11.5%), Polybutylene terephthalate( 28.6%),
copolymer ethers( 4.5%)and miscellaneous (3.7%).
Various processes used for the manufacture
of 1,4 Butanediol are:
Acetone and formaldehyde route
Butadiene Route via Acetoxylation
Butadiene Route via chlorination route
Maleic anhydride route
Propylene route
Acetylene and formaldehyde route:
This is involves catalytic reaction of
formaldehyde with acetylene in the presence
of copper based catalyst at 1000C and 5 bar
to yield 1,4 Butynediol which is hydrogenated
in two stages.
In the first stage hydrogen is carried out in
the presence of Ni catalyst at 50-600C to yield
1,4 Butanediol.
Catalytic Acetoxylation of Butadiene:
This process involves catalytic acetoxylation
of butadiene to yield 1,4 Diacetoxy-2-
butenes which on subsequent hydrogenation
followed by Hydrolysis yield 1,4 Butanediol.
Catalytic acetoxylation of Butadiene for production of 1,4 Butanediol
Butadiene via Chlorination:
This involves chlorination of butadiene and
hydrogenation of mixture of 1,4 dichloro-2-
butene and 3,4-dichloro-1-butene.
1,4-Butanediol through Maleic anhydride Route
In another process maleic anhydride is first
converted to ethyl maleate which is
subjected to hydrogenation followed by
hydrogenolysis.

Propylene Route:
In this propylene is first converted to allyl
alcohol .
Hydroformylation of allyl alcohol gives an
aldehyde which on hydrogenation gives 1,4-
Butanediol.
 Chloroprene(CH2=CHCl=CH2)
Which is mainly used in oil, solvent and cracking process.
Process technology:
Acetylene route:
This is two stage process.
In the first stage, acetylene is dimerized to mono vinyl
acetate at a temperature of about 50-100 0C & 0.1-0.4
Mpa pressure in the presence of cuprous chloride.
In the second stage gaseous vinyl acetate is reacted
with HCl in the presence of cuprous chloride at 50 0 C &
0.2Mpa pressure to yield chloroprene.
Byproducts are: Dichlorobutenes, methylvinylketones,
etc.,
Butadiene Route:
The process involves chlorination of
butadiene in the gas phase at 2500C-3000C
which produces a mixture of 3,4-dichloro-1-
butene & 1,4-dichloro-2-butene.
The latter isomerized to 3,4-dichloro-1-
butene in the presence of cuprous chloride
at a temperature of 102-1250C.
Dehydrochlorination of 3,4-dichloro-1-
butene in the presence NaOH yields
Chloroprene.
 Isoprene
Isoprene is one of the most important C5
hydrocarbons and finds application in manufacture
of polyisoprene elastomers which are available in
various forms.
Goodyear process is one of the worlds largest
producers of Isoprene rubber.
Process technology:
Recovery from C5 stream of cracker plant
Propylene dimer route (GOODYEAR PROCESS)
Isobutylene & formaldehyde route (Bayer process)
Isobutylene & methylal route
Acetylene route
Goodyear process:
In three stage process.
In this propylene dimerized in the presence of
tripropylaluminium in combination with nickel
or platinum to yield 2-methyl-1-pentene.
In the second stage 2-methyl-1-pentene is
isomerized to 2-methyl 2-pentene in the
presence of acid catalyst which is subsequently
cracked to produce isoprene and methane.
Isoprene from Propylene Dimer Route
Isobutylene and methylal route:
In this process methanol is first reacted with
formaldehyde in the presence of acid
catalyst to yield methylal which is reacted
with isobutylene in the vapour phase to
produce isoprene.
Acetylene route:
In the first stage acetylene is reacted with
acetone in the presence of potash solution to
produce methyl butynol which on selective
hydrogenation in the presence of palladium
gives methyl butenol.
On dehydration at atmospheric and a
temperature of 3000C on alumina methyl
butenol to yields Isoprene.