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PROCESS 1: PRODUCTION OF ACETALDEHYDE FROM ETHANOL VIA
OXIDATION PROCESS
PROCESS FLOW DIAGRAM
Source: Ullman’s Encyclopedia of Industrial Chemistry
PROCESS DESCRIPTION
Acetaldehyde is produced commercially by the catalytic oxidation of ethanol. Alcohol
vapors are passed and preheated air over a silver catalyst at 4800 ◦C carries out the oxidation.
CH3CH2OH + ½ O2 → CH3CHO + H2O, ∆H = 242 kJ/mol (57.84 kcal / mol)
In this process ethanol is mixed with air and passed over a silver catalyst at 500 – 650 ◦C in
the reactor. The high temperature gas (acetaldehyde and unconverted alcohol) from the outlet
of oxidizer is cooled and condensed, then sent to scrubber to absorb acetaldehyde and
unconverted ethanol. Nitrogen, Hydrogen, Methane, Carbon monoxide and carbon dioxide gas
and other inert gases are discharged from the top of the tower. The diluted acetaldehyde
solution at the bottom of the scrubber, which contains acetaldehyde, alcohol, acetic acid, and
water, is sent to the distillation tower after heating, the gas phase fraction from the tower top,
after condensation, is partly collected, which is 99% acetaldehyde and the most portion is
refluxed back. The ethanol and water solution discharged from the bottom of the distillation
tower is pressed into ethanol recovery tower, where ethanol is separated from butanol, ethyl
acetate, and most of the water. These impurities exit in bottom Stream and are sent to waste
treatment. The distillate consists of an 85-wt.% solution of ethanol, which is then recycled back
in the feed.
PROCESS 2: PRODUCTION OF ACETALDEHYDE FROM ETHYLENE VIA
OXIDATION PROCESS
PROCESS DESCRIPTION
Ethylene and oxygen are charged into the lower part of the reaction tower. The
catalyst is circulated via the separating vessel by the airlift principle and thoroughly
mixed with the gas. Reaction conditions are about 130 ◦C and 400 kPa. An
acetaldehyde – water vapor mixture, together with unconverted gas, is withdrawn from
the separating vessel; from this mixture the reaction products are separated by cooling
and washing with water and unconverted gas is returned to the reactor. A small portion
is discharged from the cycle gas as exhaust gas to prevent accumulation of inert gases
in the cycle gas; these inert gases are either introduced as contamination of the feed
gas (nitrogen, inert hydrocarbons) or formed as byproducts (carbon dioxide). A partial

stream of catalyst is heated to 160 ◦C to decompose byproducts that have accumulated
in the catalyst. Crude acetaldehyde obtained during washing of the reaction products is
distilled in two stages. The first stage is an extractive distillation with water in which
lights ends having lower boiling points than acetaldehyde (chloromethane,
chloroethane, and carbon dioxide) are separated at the top, while water and higher-
boiling byproducts, such as acetic acid, crotonaldehyde, or chlorinated acetaldehydes,
are withdrawn together with acetaldehyde at the bottom. In the second column
acetaldehyde is purified by fractional distillation Below is the involved reaction of
ethylene with an aqueous palladium chloride solution to form acetaldehyde.
C2H4+PdCl2 + H2O → CH3CHO +Pd +2HCl
The metallic palladium is reoxidized to PdCl2 with CuCl2 and the cuprous
chloride formed is reoxidized with oxygen or air.
Pd + 2CuCl2→ PdCl2 +2CuCl
2CuCl+1/2 O2 + 2HCl → 2CuCl2 + H2O
The net result is a process in which ethylene is oxidized continuously through a
series of oxidation – reduction reactions.
C2H4 + ½ O2→ CH3CHO ∆H = -244 kJ(102.1 kcal)

PROCESS 3: PRODUCTION OF ACETALDEHYDE FROM ACETYLENE VIA LIQUID
PHASE REACTION
PROCESS DESCRIPTION
A special designed hydrator converts acetylene to acetaldehyde by managing
following chemical reactions.
C2H2 + H2O → CH3CHO ∆H = + 151 Kcal
The hydrator is operated at 1.5 to 2.5 atm pressure and 80-100 oC temperature.
Acetylene is fed continuously through the liquid catalyst. The temperature is maintained
by steam, it is injected at the bottom of the column. The hydrator is made of stainless
steel or with ferrosilicon. The top stream of the hydrator is sent to a cooler. All the water
vapour is condensed and recycled. The second cooler takes the outlet from the first
one. Acetaldehyde is condensed along with trace of water. Unreacted acetylene and
non-condensable vapour is feed to a water scrubber. The water scrubber is operated at
temperature of 10 oC. Traces of acetaldehyde and water-soluble compounds are
scrubbed down. Remaining gases are used as fuel or recycled to the dehydrator. The
liquid catalyst is a solution made of mercury (II) sulphate dispersed in sulphuric acid. As
acetaldehyde is good reducing agent it reduces Hg(II) to Hg(I) and finally reducing Hg(I)
to Hg. Fluidized bed type equipment is used as hydrator. Even zinc oxide, magnesium
oxide and iron oxide are used in place of mercury. In general, calculations 680 kg of
acetylene, 0.1 kg of mercury are consumed to produce one ton of acetaldehyde. The
conversion of this process is about 50-60% per pass. Catalyst is regenerated through
the process.

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PROCESS 1: PRODUCTION OF ACETALDEHYDE FROM ETHANOL VIA

PROCESS FLOW DIAGRAM

Source: Ullman’s Encyclopedia of Industrial Chemistry

Acetaldehyde is produced commercially by the catalytic oxidation of ethanol. Alcohol

CH3CH2OH + ½ O2 → CH3CHO + H2O, ∆H = 242 kJ/mol (57.84 kcal / mol)

PROCESS FLOW DIAGRAM

Source: Ullman’s Encyclopedia of Industrial Chemistry

gas (nitrogen, inert hydrocarbons) or formed as byproducts (carbon dioxide). A partial

lights ends having lower boiling points than acetaldehyde (chloromethane,

boiling byproducts, such as acetic acid, crotonaldehyde, or chlorinated acetaldehydes,

acetaldehyde is purified by fractional distillation Below is the involved reaction of

ethylene with an aqueous palladium chloride solution to form acetaldehyde.

C2H4+PdCl2 + H2O → CH3CHO +Pd +2HCl

chloride formed is reoxidized with oxygen or air.

Pd + 2CuCl2→ PdCl2 +2CuCl

2CuCl+1/2 O2 + 2HCl → 2CuCl2 + H2O

The net result is a process in which ethylene is oxidized continuously through a

series of oxidation – reduction reactions.

C2H4 + ½ O2→ CH3CHO ∆H = -244 kJ(102.1 kcal)

PROCESS FLOW DIAGRAM

Source: Ullman’s Encyclopedia of Industrial Chemistry

A special designed hydrator converts acetylene to acetaldehyde by managing

following chemical reactions.

C2H2 + H2O → CH3CHO ∆H = + 151 Kcal

temperature of 10 oC. Traces of acetaldehyde and water-soluble compounds are

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