Introduction

Vinyl acetate (VA) is an important chemical intermediate utilized in paints, adhesives and surface
coatings. It is a colorless, flammable liquid that also has a characteristic smell that can quickly become
irritating. This monomer is used principally in the production of polyvinyl acetate (PVAc) and other vinyl
acetate co-polymers. Polyvinyl acetate is a precursor of polyvinilyc alcohol and polyvinyl acetate resins
(PVA). Vinyl acetate is also copolymerized as a minor raw material for vinyl chloride and ethylene to form
commercial polymers and acrylic fibers.
Vinyl acetate is completely soluble in organic liquids but not in water. At 20 C a saturated solution
of the monomer in water can contain between 2-2.4% of vinyl acetate, while a saturated water solution in
vinyl acetate contains 1% of water. At 50C the solubility of the monomer in water increases in 0.1% in
regards to 20C, while the solubility of water in vinyl acetate doubles at 50C.
The worldwide production of vinyl acetate was about 5 million tonnes per year in 2005, with rapid
growth in the emerging markets. Higher efficiency can be achieved by upstream integration with the
production of low - cost acetic acid, as well as by downstream integration with the manufacturing of
polyvinyl acetate and polyvinyl alcohol.
Process 1: Production of Vinyl Acetate from Acetylene
The basic scheme of an industrial plant first comprises the passage of make- up and recycle
acetylene through a vaporizer operating at 0.13 X10 6 Pa abs, around 70 to 80 C, into which a
countercurrent stream of fresh and recirculation acetic acid is also introduced. This feed, pre- heated
between 170 and 190 C by heat exchange with the gaseous stream leaving the reaction zone and with
steam, is then sent to the reactor, which operates with a fixed or fluidized catalyst bed. The catalyst
consists of activated charcoal, impregnated to 20 to 30 per cent weight of zinc acetate. In the fixed bed
system, it is placed in tubes 5 cm in diameter and 3.5 to 4 m high, around which the circulation of a fluid
coolant serves to remove the heat generated by the reaction and to maintain temperature at about 200C. In
a fluidized bed, this control is achieved by means of coils sunk in the catalyst mass. Certain plants include
a continuous loop for catalyst regeneration by steam, involving the withdrawal of the solid impregnated with
the reactants. The acetylene recovered during this operation is recycled after boosting.
The gas stream leaving the reactor is cooled by heat exchange with the feed, and then partly
condensed by scrubbing with cold liquids. This is achieved by using the condensation products themselves,
acetic acid, or both in succession. Most of the residual gases, consisting mainly of acetylene, are recycled.
A small portion is purged to prevent the buildup of inert elements in the synthesis loop.
The condensates are purified by distillation in a sequence of columns. The light components are
first separated (=~ 35 trays) including gaseous acetylene, which is recycled, and acetaldehyde, acetone,
propionaldehyde, acrolein, etc. in the liquid state. An additional column may be used to purify the
acetaldehyde contained in this mixture and to return the stripped vinyl acetate and acetic acid to the
previous distillation stage. The sequence of operations includes the recovery of divinylacetylene and croton

aldehyde (packed column), and the purification of unconverted acetic acid by heavy ends separation of the
heavier components (30=~ trays).
To prevent the vinyl acetate from polymerizing during these distillations, it is necessary to operate
in the presence of an inhibitor (hydroquinone, diphenylamine, etc.).

Process 2: Production of Vinyl Acetate from Ethylene

Industrial transformation takes place in tubular reactors, usually two reactors in parallel. The fresh
and recycle acetic acid feed, to which are added make-up ethylene and recirculation ethylene previously
heated by heat exchange with the reactor output,, is first vaporized at about 140C and 1X106 Pa absolute,
and then raised to 160C by passage through a heat exchanger. The oxygen (and any alkaline acetate)
required is then added in proportions and dispersion conditions such that the composition of the mixture
lies outside the flammability range. A coolant fluid flow on the shell side of the reactor removes the heat
generated and produces low-pressure steam.
The gaseous stream leaving the reaction zone around 160C, at 0.7 X 10 6 Pa absolute, is cooled
to 130C by heat exchange with the ethylene recycle, and partly condensed by supplementary cooling,
absorption by acetic acid and scrubbing with water. This operation serves to recover the vinyl acetate
formed and any unconverted acid. The residual gases, chiefly consisting of ethylene and carbon dioxide,
are partly purged to prevent the accumulation of inerts in the synthesis loop, and mostly recompressed, and
then rid of CO2 by chemical absorption by potassium carbonate. This reagent is regenerated by stripping,
and the purified ethylene is recycled.
The aqueous solution of vinyl acetate and acetic acid is fractionated and purified by distillation. A
first column ( =60 trays) separates a 97 to 98 per cent weight acetic acid recycle stream at the bottom The
overhead units, condenser and settler, are common to two other columns (= 25 trays each), one for
stripping, and the second for dehydration of vinyl acetate. They are fed partly with the distillate from the first
separation, rich in vinyl acetate and incondensables (ethylene and oxygen) which, after recompression, are
sent to the reaction section, and partly with a vinyl acetate/water heteroazeotrope ( bp 1.013 = 66C, water
content 7.3 per cent weight) derived from the two other columns. Phase separation takes place in the
settler: two-thirds of the organic phase is used as reflux for the first distillation and the remaining third as
reflux for the third distillation, and the aqueous phase is sent to the stripper. The withdrawal contains few
organic compounds (1000 to 2000 ppm). The dehydration bottom stream is first subjected to light ends
separation (.25 trays) followed by heavy ends separation (= 100 to 120 trays), to yield vinyl acetate to
commercial specifications. This final separation is designed to remove ethyl acetate among the heavy
products, and the previous separation to remove methyl acetate and acetaldehyde among the light
components.
Vinyl acetate recovery and purification require operation in the presence of an inhibitor, which may
be gaseous (such as a mixture of 02 and CO2). The various units must be built of high-alloy steels (Cr/Ni
=18/8).

Process 3: Carbonylation of Methyl Acetate (developed in particular by Halcon)

This method is based on the use of synthesis gas to produce successively methanol, methyl
acetate, and acetic anhydride jointly with ethylidene diacetate, which then decomposes to vinyl acetate and
acetic acid, which is recycled to methyl acetate synthesis.

Carbonylation of methyl acetate is the essential step (molar yield = 85 per cent):

It takes place in the liquid phase around 130 to 160C and between 4 and 7X 106 Pa absolute, in
the presence of a catalyst complex based on palladium or rhodium, methyl iodide, and an amine or
phosphine as initiator. Acetic anhydride is formed as an intermediate. The conversion is directed toward the
production of ethylidene diacetate by increasing the proportion of CO in the synthesis gas.