Acetate Technology

Using Reactive
Distillation
CLAUDIA VON SCALA
LARS GTZE
PETER MORITZ
SULZER CHEMTECH

Acetates are products frequently used in

the chemical industry. They have a wide
range of applications, especially as a
solvent in the cellulose, paint, coating
and rubber industry. Together with
various partners, Sulzer Chemtech has
developed processes for the synthesis of
ethyl and butyl acetate, as well as for the
hydrolysis of methyl acetate, and now
offers this acetate technology for licensing. The key feature of the processes, for
which patent protection has been
applied, is a reactive distillation column.

Reactive distillation, i.e. the

combination of chemical
reaction and distillative product
separation, offers several advantages in comparison with conventional processes, in which the reaction and product separation are
done in series. Since the products
are separated simultaneously from
the reaction mixture, no chemical
equilibrium can be established,
and therefore the reaction velocity
is maintained at a high rate. Consequently, reactive distillation is
especially advantageous for equilibrium-limited reactions. This also
applies to processes for the production and hydrolysis of acetates.
Furthermore, reactive distillation
may facilitate the suppression of
side reactions. In addition, the

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SULZER TECHNICAL REVIEW 3/2001

heat of reaction can be utilized for

the mass transfer operation in a
reactive distillation column. The
capital investment and operating
costs are therefore lower compared
with the conventional processes.
Sulzer Chemtech uses the structured catalytic packings KatapakS or Katapak-SP for the reaction
zone of the reactive distillation
columns (see box).
The standard scope of supply
for the acetate technology, i.e. for
the production and hydrolysis of
acetates, provided by Sulzer
Chemtech includes the process
design, basic engineering, the supply of key equipment especially
Katapak-S/-SP and distillation column internals as well as pilot
tests and test runs (Fig. 1).

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0682 2026-1

1 Sulzer Chemtech offers different processes in acetate

technology. The scope of supply also includes pilot tests.
(Photo: Sulzer Chemtech pilot plant in Winterthur)

Sulzer Chemtech licenses processes for the production of ethyl and

butyl acetate, as well as for the
hydrolysis of methyl acetate,
which have been developed together with partner companies from
the very beginning. The design of
these plants includes modern
methods for the process synthesis
(Fig. 2). The developed processes
are not only suitable for new, but
also for existing plants. The latter
can be revamped without major
modifications. Thanks to the energy savings in comparison with conventional processes, the costs for
the revamp can be amortized very
quickly.

2 Sulzer Chemtech employs modern methods

for the design of plants using acetate
technology. (Photo: Residue curve
analysis using program package
of DDBST GmbH)

HYDROLYSIS OF
METHYL ACETATE
Sulzer Chemtech has developed
together with Wacker-Chemie
GmbH a new process for the
hydrolysis of methyl acetate. It is
characterized by the combination
of a pre-reactor with a reactive distillation column. The first plant
with this process is operating at
Wackers site in Burghausen, Germany (Fig. 3). Large quantities of
methyl acetate are formed as a side
product during the production of
polyvinyl alcohol (PVA). The
hydrolysis of the methyl acetate
enables methanol and acetic acid
to be recovered and recycled to the

PVA production. In the new developed process, excess methyl

acetate and water are fed to a prereactor, in which the hydrolysis
reaction takes place close to the
chemical equilibrium. The reactor
outlet is connected with the reactive distillation column, where the
reaction conversion is increased
exceeding the equilibrium conversion, so that an almost complete
conversion can be achieved. The
bottom product stream of the reactive distillation column, containing acetic acid, methanol, water

SULZER TECHNICAL REVIEW 3/2001

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and only small amounts of methyl

acetate, is fed to a distillation column, in which technically pure
methanol is recovered as a top
product (Fig. 4). The remaining
components of the bottom product
stream are separated in a further
distillation column. Depending on
the mode of operation, it is also
possible to recover pure acetic acid
in the bottom of the second distillation column.
The advantages of this process
result from the combination of a
pre-reactor and a reactive distillation column, which allows a methyl
acetate conversion of up to 99%

3 The first plant constructed according to the process developed by Sulzer Chemtech and Wacker for the hydrolysis of
methyl acetate is located at Wackers site in Burghausen, Germany. The plant has been operating since November 2000.
(In the figure: on the left the pre-reactor,
on the right the reactive distillation column.)

and enables the methanol to be

recovered with only one column.
No expensive extractive distillation is necessary. Thanks to the
high methyl acetate conversion, it
is also possible to avoid the recycling of azeotropic mixtures, which
are otherwise formed in large
quantities. In general, the reactive
distillation is a very energy-efficient process variant. In comparison with the conventional process,
it is possible to achieve energy savings of up to 50% with the SulzerWacker process. The costs for the
revamp to this process are therefore amortized within a period of
about two years.
The pre-reactor also offers a further advantage. Its filling, an
acidic ion exchange resin, not only
serves as a catalyst for the reaction, but also as a guard bed for
metallic ions, which could other-

wise gain access to the feed and

thus deactivate the catalyst in the
reactive distillation column. In
other words, the pre-reactor prolongs the lifetime of the catalyst in
the column. The replacement of
the catalyst material in the prereactor is not very time-consuming
and is less expensive than the
replacement within the column.

ETHYL ACETATE TECHNOLOGY

Sulzer Chemtech has developed
together with Chemopetrol a
process for the production of ethyl
acetate. In a first step, excess
ethanol and acetic acid are fed to a
pre-reactor (Fig. 5). The reaction
mixture leaving the reactor is then
fed to the upper part of the reaction
zone of the reactive distillation column. Additional ethanol is admitted below the reaction zone, so that
acetic acid and ethanol are flowing

4 Thanks to the combination of pre-reactor and reactive distillation,

the methyl acetate is hydrolyzed up to 99%. Technically pure methanol
is recovered as top product in a downstream distillation column from
the bottom stream of the reactive distillation.
Methyl acetate

Lights

Methanol

Water

Water

Pre-reactor

Acetic acid
Reactive
distillation

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SULZER TECHNICAL REVIEW 3/2001

Methanol
separation

Acetic acid
concentration

Reactive
distillation

Ethyl acetate
purification

Water
purification

5 As in the case of the hydrolysis of methyl acetate, the pre-reactor

also plays a decisive role in the synthesis of ethyl acetate.

Purge

Pre-reactor
Ethanol
Ethyl acetate
grade A

Acetic
acid
Ethanol

Ethyl acetate
grade B

Reaction water

through the reaction zone countercurrently to each other. At the top

of the reactive distillation column,
an azeotropic mixture of ethyl
acetate, ethanol and water is
obtained, which is separated with
a decanter into a water and an
organic phase. The major part of
the organic phase is purified in a
further distillation column, where
ethyl acetate is obtained in various
degrees of purity as bottom product and as side stream.

BUTYL ACETATE TECHNOLOGY

Sulzer Chemtech has also developed a process with Chemopetrol
for the production of butyl acetate,
which is formed from butanol and
acetic acid. The pre-reactor plays a
decisive role, enabling the major
part of the esterification reaction
to be effected under moderate conditions. The reaction zone in the
reactive distillation column can
thus be kept much shorter, so that
the residence time on the catalyst
at higher temperatures is reduced
appreciably and side reactions are
prevented.

FOR MORE DETAILS

Purge

Water

Sulzer Chemtech AG
Peter Moritz
Postfach 65
CH-8404 Winterthur
Switzerland
Telephone +41 (0)52-262 61 71
Fax
+41 (0)52-262 00 76
E-mail
peter.moritz@sulzer.com

REACTIVE DISTILLATION WITH KATAPAK-S

Katapak-S is a structured packing in which the catalyst granules are embedded. The
packing is used primarily for reactive distillation, but it is also suitable as a catalyst
support in continuous fixed-bed reactors. Since nearly every heterogeneous, i.e. solid,
catalyst can be embedded in its structure, Katapak-S can be used for different reaction
types, such as esterification, etherification, alkylation or hydrogenation. In Katapak-S,
the catalyst particles are immobilized in sandwiches between two sheets of metal wire
gauze. The packing type Katapak-SP is used if higher mass transfer efficiency is
required. Layers of distillation packing Mellapak are integrated, either alternatively
with Katapak-S or directly in
the Katapak structure (see also
0699 2714-3
STR 4/1999, p. 29).

In the structured packing

Katapak-S, the catalyst is
embedded in sandwiches and
thus fixed in position. The key
feature of the acetate technology
offered by Sulzer Chemtech is a
reactive distillation column with
Katapak-S/-SP.

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