PRODUCTION FROM ETHYLENE

Ethylene is now the most important starting material for the production of
acetaldehyde. Most of the present capacity works by the direct oxidation of ethylene.
Direct Oxidation of Ethylene
This process was developed between 1957 and 1959 by Wacker-Chemie and
Hoechst [42]. Formally, the reaction proceeds as follows:
1
C2 H 4 + O2 CH 3 CHO244 kj/mol
2

An aqueous solution of

PdCI 2

and

CuCI 2

is used as catalyst. Acetaldehyde

formation had already been observed in the reaction between ethylene and aqueous
palladium chloride. This reaction is almost quantitative:
C2 H 4 + PdCI 2 + H 2 O CH 3 CHO+ Pd+2 HCI

In the Wacker-Hoechst process, metallic palladium is reoxidized by

CuCI 2

which is then regenerated with oxygen:

Pd+2 CuCI 2 2 PdCI 2 +2 CuCI
1
2CuCI + O2 +2 HCI 2CuCI 2 + H 2 O
2

Therefore only a very small amount of

PdCI 2

is required for the conversion of

ethylene. The reaction of ethylene with palladium chloride is the rate-determining step.
One- and two-stage versions of the process are on stream.
One-Stage Method: In the one-stage method, an ethylene oxygen mixture reacts with
the catalyst solution. During the reaction a stationary state is established in which
CuCI 2
reaction (formation of acetaldehyde and reduction of
) and oxidation
(reoxidation of
C and 400 kPa.

CuCI ) proceed at the same rate. Reaction conditions are about 130

Two-Stage Method: In the two stage process ethylene and oxygen (air) react in the
liquid phase in two stages. In the first stage ethylene is almost completely converted to
acetaldehyde in one pass in a tubular plug-flow reactor made of titanium. The reaction
is conducted at 125-130 oC and 1.13 MPa palladium and cupric chloride catalysts.
Acetaldehyde produced in the first reactor is removed from the reaction loop by
adiabatic flashing in a tower. The flash step also removes the heat of reaction. The
catalyst solution is recycled from the flash tower base to the second stage (or oxidation)
reactor where the cuprous salt is oxidized to the cupric state with air. A schematic
diagram is given as follows. ( PDF STE)

(wiki)

Acetaldehyde

Chlorinated aldehydes

Unconverted ethylene

Carbon dioxide

Acetic acid

Chloromethane

Ethyl chloride

Minor side products

The yield in both type of process is

nearly the same. The balance of the two stage process is as follows:
Ethylene gives:
%95 acetaldehyde
%1.9 chlorinated aldehydes
%1.1 unconverted ethylene
%0.8 carbon dioxide
%0.7 acetic acid
%0.1 chloromethane
%0.1 ethyl chloride
%0.3 ethane, methane, crotonaldehyde and
other minor side products
In both one and two-stage processes the acetaldehyde yield is about 95% and
the production costs are virtually the same. The advantage of using dilute gases in the
two-stage method is balanced by higher investment costs.