6/22/2008

Wacker process

Acetaldehyde production

• Important intermediate (2 million t/a) for production of acetic acid

(40%) and ethyl acetate (60 %)
• Until the 1960: production from acetylene and water in diluted sulfuric
acid (yield around 98 %)
• Since the 1970ies: Wacker-Hoechst-process
• Single or two-step process with oxygen or air as oxidant and Pd/Cu
catalyst
• Two-step process: higher investment and energy costs; more
chlorinated hydrocarbons in waste stream, yet still preferred (costs for
air separation plant, as required for single step process, are even
higher)

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Acetaldehyde from ethene

ƒ 85% of world acetaldehyde production by Wacker process

ƒ Exothermic catalytic direct oxidation with two component catalyst
PdCl2 and CuCl2

Reactions in the Wacker process

• Catalytic oxidation of ethene with H2O

• Pd regeneration with CuCl2

• Cu+ re-oxidation with oxygen and hcl

• Regeneration is rate determining

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Catalytic cycle

Catalytic cycle

2−
[ PdCl4 ] ⋅ [C2 H 4 ]
rCH 3CHO = k ⋅
[Cl − ][ H + ]

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Single stage process

• Reaction of highly pure ethene and oxygen in a bubble column
• 120 – 130 °C, 3 bar, conversion per pass: 35 - 45%
• Effluent gas is cooled, separated from catalyst and scrubbed with water for
acetaldehyde recovery
• Excess
E ethene
th is
i recycled
l d tto th
the reactor.
t A smallll partt iis purged
d tto preventt
inert gas accumulation

Two stage process

ƒ Ethene reaction and Cu+ re-oxidation take place in different bubble columns.
ƒ 105 – 110 °C, 10 bar, almost complete conversion of ethene
ƒ No loop gas required
ƒ Acetaldehyde recovery by extractive distillation like in single stage process

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Comparison of the processes

• Acetaldehyde yield almost equal (about 95%)
• Expensive construction materials required
• Lower investment costs in the single stage process, because of the
need of only one reactor
• In two stage process air (less expensive) can be used for the re-
oxidation instead of pure oxygen
• No explosive ethene/O2 mixtures in two stage process