Vinyl acetate

Reaction of Acetic Acid with Ethylene and Oxygen:

Gas-Phase Reaction. The process was developed to an industrial scale only slightly later than the ethylene
liquid-phase process, and has been used in industry since 1968. Currently, 80% of world vinyl acetate capacity
uses the ethylene gas-phase process. There are two variants: one developed by National Distillers Products
(United States) and the other independently by Bayer in cooperation with Knapsack and Hoechst (Germany).
Most plants employ the Bayer – Hoechst variant, of which there are several versions. The original process has
been further developed by various operators. In the ethylene gas-phase process, ethylene reacts
exothermically with acetic acid and oxygen on solid bed catalysts, giving vinyl acetate and water:

All catalysts used in industry contain palladium and alkali metal salts on carrier materials, e.g., silicic acid,
aluminum oxide, lithium spinel, or activated charcoal. Additional activators can include gold, rhodium,
platinum, and cadmium. The reaction mechanism is assumed to involve either pure metal catalysis or a
reaction sequence according to the following equations:

In the process, which operates above 140°C and at overpressure 0.5 – 1.2MPa, practically no acetaldehyde is
formed, even if the acetic acid used as starting material contains water. Byproducts are water, CO2 and small
quantities of ethyl acetate, ethylidene diacetate, and glycol acetates.

Process Description

a) Acetic acid evaporator; b) Reactor; c) Steam drum; d) Countercurrent heat exchanger; e) Water
cooler; f) Recycle gas washing column; g) Recycle gas compressor; h) Water wash; i) Potash wash; j)
 Potash regeneration; k) Crude vinyl acetate collector; l) Predehydration column; m) Phase
separator

The recycle gas stream, which consists mainly of ethylene, is saturated with acetic acid in the evaporator (a)
and is then heated to the reaction temperature. The gas stream is then mixed with oxygen in a special unit.
The allowed oxygen concentration is determined by the flammability limits of the ethylene – oxygen mixture.
The flammability limit depends on temperature, pressure, and composition. It is shifted by additional
components, such as acetic acid, nitrogen, and argon, which are brought in with the oxygen, or by CO2. In
general, the oxygen concentration at the entry to the reactor is ≤ 8 vol %, based on the acetic-acidfree
mixture. It is essential to avoid gas mixtures capable of igniting; great care is taken in mixing in oxygen and
measuring the oxygen concentration. If the oxygen stream is switched off, the inlet line must be flushed with
nitrogen immediately to avoid back-diffusion of the circulating gas. The mixing chamber is usually installed
behind concrete walls. The heat of reaction is removed in the form of steam via (c) from the tube reactor (b)
by evaporative cooling in the shell side of the reactor. The reaction temperature is adjusted by the pressure of
the boiling water. The steam formed can be used within the plant itself in the workup section. The heat of
reaction is ca. 250 kJ/mol based on vinyl acetate, because of the simultaneous formation of CO2. Pressurized
water in a circulation loop is used for cooling in some plants. Ethylene conversion is 8 – 10%, and that of acetic
acid 15 – 35%. Oxygen conversion can be up to 90 %. As small quantities of alkali metal salt on the catalyst
migrate under the reaction conditions, traces of alkali metal salt are mixed with the gas at the entry to the
reactor. The gas mixture leaving the reactor is first cooled in (d) in countercurrent with the cold recycle
gas, which is thus warmed. There is virtually no condensation of the acetic acid, vinyl acetate, or water. The
dew point is generally not reached. The gas mixture is then led into the predehydration column (l) and then
cooled to about room temperature in (e). The liquid product consists of an acetic-acid-free mixture of vinyl
acetate and water. The mixture is separated in a phase separator (m) into an aqueous phase, which is
removed, and an organic vinyl acetate phase, which is recycled to the head of the predehydration column.
Between 40 and 50% of the water formed in the reaction is removed in this way without the need to supply
extra energy; this quantity of water does not need to be removed in the subsequent distillation of the crude
vinyl acetate. Most of the energy consumed in the distillation is used for water removal. Crude vinyl acetate,
which is low in water, collects in the sump of the predehydration column. The noncondensed vinyl acetate
fraction is washed out of the circulating gas with acetic acid in column (f). The remaining gas is recycled via
compressor (g), after addition of fresh ethylene. To remove the CO2 formed in the reaction, a partial stream of
recycle gas is first washed with water in column (h) to remove the remaining acetic acid. The CO2 is then
absorbed with potash solution in column (i). The potash solution is regenerated by depressurizing to normal
pressure and boiling (j).