Clay Minerals (1983) 18, 431-435.

THE PRODUCTION OF ETHYL ACETATE FROM

ETHYLENE AND ACETIC ACID USING CLAY
CATALYSTS

R. GREGORY, D. J. H . SMITH AND D. J. W E S T L A K E

BP Research Centre, Chertsey Road, Sunbury-on-Thames, Middlesex TW16 7LN

(Received 17 June 1983)

A B S T R A C T: Wyoming bentonite, exchanged with cations of high charge density, is an

efficient and selectivecatalyst for the production of ethyl acetate, in a single step, from ethylene
and acetic acid. The reaction occurs in the interlamellar space of the clay where it is proposed
that strong Br6nsted acid sites on the clay coupled with highly polarized intercalated reactants
produce a reaction which is otherwise difficultto carry out.

Montmorillonites have both Br6nsted and Lewis acid sites and when exchanged with
cations having a high charge density produce highly-active catalysts for proton-catalysed
reactions. Intercalated organic molecules are mobile and can be highly polarized when
situated in the space between the charged clay layers. These exchanged montmorillonites
have been successfully used as catalysts, e.g. for the dehydration of alcohols to di-alkyl
ethers (Ballantine et al., 198 l a), the condensation of primary amines to secondary amines
(Ballantine et al., 1981b) and the esterification of organic acids by alkenes (Ballantine et
al., 198 lc); all these are thought to be interlamellar reactions.
The present study is also concerned with esterification, and examines the catalytic
activity of different ion-exchanged Wyoming bentonites in the reaction of ethylene and
acetic acid to yield ethyl acetate. This difficult reaction (equation l) requires catalysts with
strong Br6nsted activity:

C H 2 = C H 2 + CH3COOH ~ CH3COOC2H 5 (1)

EXPERIMENTAL
Hydrogen-bentonite was made by ion-exchanging Wyoming bentonite with cold 5 M
sulphurie acid, washing to remove all extraneous ions, and then drying at 80~ in air. AI-,
Cu(II)-, Fe(III)- and Cr(III)-bentonites were made in a similar manner by exchange with
0.5 M solutions of aluminium sulphate, copper(II) sulphate, iron(III) nitrate and
chromium (III) nitrate, respectively.
Several preparations of H-bentonite were shown by X-ray diffraction to have a basal
d001 spacing of between 12.0 and 12.9/k, by thermogravimetric analysis to contain about
8% wt/wt water (probably present as a monolayer), and by adsorption to have a BET
surface area of 40-60 m2/g. Preparations of Al-bentonite had a basal d0o1 spacing of
14.0-14.5 /k, about 8% wt/wt water, and a BET surface area of 50-60 mZ/g. Similar
values were obtained with other ion-exchanged bentonites used in this work.
9 1983 The Mineralogical Society
432 R. Gregory et al.
Batch reactions were carried out in a stainless steel autoclave (100 ml) charged with
acetic acid (80 g), catalyst (10 g) and sufficient ethylene gas to give a 55 bar pressure at a
reaction temperature of 200~ The reactions were carried out for 2.5 h, and the ethylene
to acetic acid molar ratio was approximately 2:1. Gas was vented from the cooled
autoclave, and the liquid products weighed and analysed by gas c h r o m a t o g r a p h y using a
88 • 5' P o r a p a k Q column with a flame ionization detector.

RESULTS AND DISCUSSION

In order to compare relative activities of ion-exchanged clays in batch reactions of acetic

acid and ethylene to give ethyl acetate, it is necessary to establish standard conditions as a
basis for parameter variations. The conditions shown in Table 1 were selected. Although
these conditions are not optimum for this reaction, since the reaction proceeds faster at
higher temperatures and pressures, they are in a region where catalyst activity can be
easily compared.

Effect of different cations on the activity of the bentonite catalyst

Several ion-exchanged W y o m i n g bentonites were examined as catalysts in this reaction
under s t a n d a r d conditions and the results of these experiments are shown in Table 2. The
yield o f ethyl acetate obtained in these experiments was directly proportional to the activity
of the catalyst, since t h e r m o d y n a m i c equilibrium was not reached under these conditions.
Therefore, it appears that the activity o f the catalysts increases from untreated W y o m i n g
bentonite (exchangeable Na) through to the most active, H-bentonite.

TABLE 1. Standard reaction conditions.

Catalyst: dried at 80~

Acetic acid: catalyst weight ratio 8 :1
Ethylene: acetic acid mole ratio 2:1
Reaction temperature 200~
Reaction pressure 55 bar
Reaction time 2.5 h

TABLE 2. Variations in ethyl acetate yield for Wyoming

bentonite ion-exchanged with different cations examined
under the conditions in Table 1.
Cation % molar yield
Ion-exchanged charge density of ethyl acetate
cation (charge/A3) based on acetic acid

H+ -- 31
AP+ 5.8 13
Fe 3+ 2.7 11
Cr 3+ 4-3 13
Cu 2+ 1-4 7
Na + 0.4 1
 Clay catalysts for ethyl acetate 433
Increases in catalyst activity generally correspond to increased charge density of the
exchanged cation. The higher the charge density of the exchanged cation, the greater will
be the polarizing power of these cations in the interlamellar space inducing ionization of
acetic acid and any remaining solvent water molecules. The strong Br6nsted acidity of
these ion-exchanged clays has been suggested to derive, at least in part, from the enhanced
polarization of the solvent water molecules (Thomas, 1982).

AI(H20) 3+ = AI(OH) (H20) 2+ + H + (2)

Thus the best catalyst might be expected to be H-bentonite by a large margin because this
catalyst would not only provide a more polarizable interlamellar environment but also
H3 O+ cations to increase Br6nsted acidity,

Effect of pre-reaction heat treatment on the activity orAl-bentonite

When Al-bentonite catalyst was dried above the usual temperature (80~ in air for 4 h)
prior to reaction, the yield of ethyl acetate increased. Fig. 2 shows that the maximum
catalyst activity of 21% ethyl acetate was achieved by drying at 200~ XRD examination
showed that the d00, spacing of this catalyst was the same as that of the catalyst dried at
80~ Thermogravimetric analysis indicated that the catalyst dried at 200~ still
contained ~ 3 % wt/wt water which corresponds to less than half the maximum water
content of the mono-layer spacing.
It is not clear what causes this increased catalyst activity. A clay becomes more acidic as
it is dehydrated (Mortland et al., 1968; Frenkel, 1974), and the increased activity of the
Al-bentonite dried at 200~ can be attributed to increased Brfnsted acidity produced by
the same ionizing effects of the highly charged cations operating on less solvent water
molecules (equation 2). However, acetic acid and ethylene molecules are thought to fill
interlamellar space during reaction and replace most, if not all, of the water molecules; the
interlamellar environment of the differently heated clays under reaction conditions should
thus be similar, assuming the interlamellar spacing is the same, and similar results might be
expected.

50

40

30-
\

~ 20-

10-

i i / i
100 200 300 40O
Catalyst drying temperature (~

FIG. 1. Variation in molar yield of ethyl acetate from acetic acid with differentpre-reactionheat
treatments. --Al-bentonite, -H+-bentonite.
434 R. Gregory et al.
With drying temperature above 200 ~C, further decreases in intercalated water molecules
cause the edges of the lamellar structures to collapse irreversibly, and access to the
interlamellar sites is therefore lost. At even higher temperatures (300~ total lamellar
collapse occurs, leaving only exposed surface activity. This suggests that the bulk of the
reaction is occurring in interlamellar space, since when this is denied to the reactants
catalyst activity is drastically reduced.
H-bentonite behaved in a similar manner to the Al-bentonite catalyst but the maximum
catalytic activity was displaced to lower drying temperatures (Fig. 1). Drying at 200~
was sufficient to produce a collapsed catalyst which gave a 5% yield of ethyl acetate.

Selectivity to ethyl acetate

All cation-exchanged bentonites examined in this work showed greater than 99%
selectivity for conversion to ethyl acetate. The ethylene gas remaining in the autoclave after
reaction was not examined but there was no evidence of any other ethylene-derived
products in the liquid products in which some ethylene was dissolved.

Mechanism for formation of ethyl acetate

The bulk of the reaction between ethylene and acetic acid occurs in the interlamellar
spaces between the clay layers. This has been shown to be the case because collapsed
catalysts with no interlamellar spaces have drastically reduced activity. In the conditions
used in this work, the catalyst is stirred in liquid acetic acid containing dissolved ethylene
which is in equilibrium with the gas and vapour phase. The acetic acid is believed to largely
replace the bulk of intercalated water present in the fresh catalyst before the reaction
commences. The ethylene molecules are then free to enter and leave the highly polarized
interlamellar regions where reaction occurs.
The reaction is catalysed by Br6nsted acidity. A hydrogen ion from a Br6nsted acid site
on the clay (see equation 2) adds to ethylene to give an ethyl carbocation (equation 3). In
the highly polarized acetic acid environment this carbocation reacts to give ethyl acetate
(equation 4). The Lewis acid sites on the clay will aid polarization of the acetic acid, which
could allow direct reaction with ethylene leading to an ion-pair intermediate as shown in
equation 5.
+

CHz=CH z + H + ~ CH3CH 2 (3)

CHa~H2 + CH3COOH = CH3COOC2H 5 + H + (4)
+ o

CH 2 H CH 3 ~ CH2CH 3 + O ~ C H s (5)

The proposed mechanism is consistent with increased catalytic activity observed with
increased charge density of the exchanged cations, giving greater polarization of acetic acid
and increased Br6nsted acidity. Also, with hydrogen bentonite an additional source of
protons is provided.
Hydrogen- and Al-bentonites recovered from several reactions were shown by Raman
spectroscopy to have very small amounts of low-molecular-weight polyethylene deposited
on the catalyst. It is likely that polyethylene is formed on both the external and
interlamellar surfaces; in a continuous reaction this could build up and block reactant
 Clay catalysts f o r ethyl acetate 435
access to reactive interlamellar sites and lead to catalyst deactivation. The mechanism
leading to polyethylene formation involves ethyl carbocation addition to ethylene followed
by further ethylene addition (equation 6).
CH3~H2 C.~=CH2 + C.2=CH~ +
CH3 (CH2)2CH 2 , CH3(CH2)4CH 2 (6)

This reaction might also be expected to produce butyl and hexyl acetates by reaction of
intermediate carbocations with the more a b u n d a n t acetic acid (equation 4) but, even if
present, the amounts produced were too small to be observed by gas chromatographic
analysis of the liquid reaction products. Thus it is believed that ethylene oligomerization is
only a very minor side reaction.

CONCLUSION
This work has shown that W y o m i n g bentonites exchanged with cations of high charge
density are efficient and selective catalysts for the production o f ethyl acetate from ethylene
and acetic acid. The reaction occurs in the interlamellar space where it is p r o p o s e d that
strong Br6nsted acid sites on the clay coupled with highly polarized reactants lead to the
formation of ethyl acetate.

ACKNOWLEDGMENTS
The authors wish to thank the British Petroleum Company plc for permission to publish this paper.

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