Clays and Clay Minerals, Vol. 34, No. 5,597-603, 1986.

METHYL t-BUTYL ETHER (MTBE) PRODUCTION:

A COMPARISON OF MONTMORILLONITE-DERIVED
CATALYSTS WITH A N ION-EXCHANGE RESIN
J. M. ADAMS, K. MARTIN, R. W. MCCABE, AND S. MURRAY
Edward Davies Chemical Laboratories, University College of Wales
Aberystwyth SY23 lINE, United Kingdom
Abstract--Montmorillonite-based catalysts were compared with an acidic ion-exchange resin of the type
used industrially for the production of methyl t-butyl ether (MTBE) from methanol and isobutene or
t-butanol. When 1,4-dioxan was used as solvent, Al3+-exchanged montmorillonites had about half the
efficiency of the resin Arnberlyst 15 at 60~ they were, however, about twice as efficient at this temperature
at Ti3+-montmorillonite or K10, a commercially available acid-treated bentonite. Montmorillonite exchanged with Chlorhydrol solutions to give interlayer [AI1304(OH)2(H20)12]7+ ions and pillared clays
derived from such materials were poor catalysts, as was K306, a more drastically acid-treated bentonitebased commercial catalyst. Freeze-drying of the AP+-day before reaction to produce a more open, porous
structure had no effect on its catalytic efficiency. The activation energy for the reaction of isobutene and
methanol in dioxan was 44 El/mole for an AP+-clay catalyst compared with 25 kJ/mole for reactions
catalyzed by Ambedyst 15. With no solvent (as in industrial processes), the rates of reaction were
considerably slower for both the clay- and resin-catalyzed reactions. As has been found previously for
resin-catalyzed reactions using stoichiometric amounts or an excess of methanol, the rate was proportional
to the isobutene concentration, and the rate-determining step appeared to be protonation of the alkene.
The performance of the AP+-clay catalyst was increased by reducing the water content of the clay. In
most reactions the clay catalysts were equilibrated at 12% relative humidity. Exposure of the clay to a
low vacuum (10-1 ton-) before use increased its catalytic activity from 50 to 60% of that of Amberlyst 15.
Key Words--Amberlyst 15, Catalysis, Chlorhydrol, Ion-exchange resin, Methyl t-butyl ether, Montmorillonite.

INTRODUCTION
Methyl t-butyl ether (MTBE) is an effective octane
booster for unleaded gasolines (Csikos et al., 1975;
Pecci and Floris, 1977; Nishizawa et al., 1974; Watanabe et al., 1973). It also acts as a v o l u m e extender,
by adding volume to the gasoline pool and by reducing
the severity of the naphtha reforming and related conversion operations (Muddaris and Pettman, 1980).
Industrial processes for the production o f M T B E are
based on liquid phase reaction o f methanol with isobutene over an acidic ion-exchange resin (Gupta and
Prakash, 1980). Most o f the processes are carried out
between 35 ~ and 90~ lower temperatures favor m o r e
complete conversion and longer catalyst lives but lower
reaction rates. The process is conducted at the lowest
pressures compatible with keeping the C4 feedstocks
in the liquid state (100-200 psi).
Ion-exchanged montmorillonites are acidic catalysts
(Mortland and Raman, 1968), and Bylina et al. (1980)
and Ad am s et al. (1982) reported that they can catalyze
the production o f M T B E from methanol and isobutene
or from methanol and t-butanol (Adams et al., 1981)
as follows:

Moreover, methods have been described for the acidtreatment o f montmorillonite-based catalysts and the
addition o f water to i m p r o v e their ability to catalyze
the production of M T B E (see e.g., Gregory and Westlake, 1982, 1983).
In the present work the activity of several catalysts
derived from a montmorillonite are compared with
that of the macroreticular sulphonic acid resin A m berlyst 15 (Anonymous, 1967) which is similar to the
acidic resin used industrially for the production o f
MTBE (Ancillotti et al., 1977). Ancillotti et al. (1977,
1978) and Gicquel and Torck (1983) showed that at
m e t h a n o l : i s o b u t e n e ratios reasonably close to unity
the pore spaces o f Ambeflyst 15 resin are filled with
methanol, which acts as the solvent at the reaction site
in the formation o f MTBE. The methanol molecules
pick up protons from the resin and become the catalytic
agents. The reaction shows first-order dependence on
isobutene concentration; thus the rate determining step
appears to be alkene protonation,

+ CH2=C\cH3
+/CH3
-~ CH3OH + C H 3 - C \
,
CH3
to form the tertiary carbocation.

M e O H + CH2=C(C[--I3)2 --* Me-O--(2(CH3)3

M e O H + HOC(CH3) 3 ~ Me-O-C(CH3)3 + HaP.
Copyright 9 1986, The Clay Minerals Society

597

598

Adams, Martin, McCabe; and Murray

T h e m a j o r i t y o f t h e catalysts s t u d i e d i n t h e p r e s e n t
i n v e s t i g a t i o n were r e l a t e d to A P + - m o n t m o r i l l o n i t e
w h i c h is k n o w n to b e h i g h l y acidic ( A d a m s et al.,
1983a, 1983b) a n d i n c l u d e A P + - m o n t m o r i l l o n i t e ,
montmorillonite
exchanged with the polycation
[ A l t 3 0 4 ( O H ) z 4 ( H z O ) l z ] 7+, a p i l l a r e d ( A 1 2 0 3 ) c l a y
( V a u g h a n a n d Lussier, 1980; V a u g h a n et aL, 1979,
1981), a n d t w o c o m m e r c i a l a c i d - t r e a t e d clays, K 1 0 a n d
K306 (Sfid-Chemie AG). In addition, reactions with
Ti3+-montmorillonite, a material having very high
acidity for s u c h catalysts ( M o r i k a w a et aL, 1983), were
also i n v e s t i g a t e d . All o f t h e s e c l a y - b a s e d c a t a l y s t s (inc l u d i n g K 1 0 a n d K 3 0 6 ) were d e r i v e d f r o m clay f r o m
t h e s a m e source.
EXPERIMENTAL

Catalyst characterization
The bentonite used for most of this study came from Moosburg, Federal Republic of Germany (Tonsil 13, Siid-Chemie
AG). The <2-um clay fraction was prepared by sedimentation. An X-ray powder diffraction (XRD) examination showed
that this fraction was ~ 98% montmorillonite with ~ 2% quartz
impurity. An X-ray fluorescence (XRF) analysis gave 64.0%
SiO2, 20.8% A1203, 3.86% Fe203, 0.07% TiO2, 1.5% CaO,
1.42% MgO, 0.04% K20, and 1.20% Na20. Loss on ignition
was 7.1%. The cation-exchange capacity totaled 103 meq/100
g of air-dry material and consisted of 68, 33, and 2 meq/100
g of Na +, Ca 2+, and Mg 2+, respectively.
Montmorillonite from Upton, Wyoming, was used to study
the dependence of reaction rate on concentration ofisobutene
and methanol. Here also, sedimentation was carried out to
separate the <2-urn fraction.

Catalyst preparation
To aid later cation-exchange processes, a large quantity of
the Tonsil 13 clay was exchanged initially with Na +, The clay
was added to an 0.1 M solution of NaCI and heated to 70~
with vigorous stirring for 1 hr. Two fractions were produced
by sedimentation. The finer fraction was subjected to ultrasonic treatment for 10 min, and the <2-urn fraction was
collected by sedimentation.
AP+-montmorillonite was prepared by exposing some of
this <2-~m fraction to an 0.3 M A1C13 solution (pH = 2.7)
for 24 hr. The clay was then centrifuged and resuspended in
deionized water repeatedly until a test for excess salt proved
negative. At this point the pH of the super'natant liquid was
4.3. The clay was isolated by centrifugation, dried at 40~
and mechanically ground. The basal spacing of this clay was
14.8 ~ and the aluminum content was 0.98% higher than
before aluminum exchange--a value correspondng to a cation-exchange capacity (CEC) of 109 meq/100 g if the aluminum is assumed to be present as A13+ monomers. This
value is in reasonable agreement with the measured CEC (103
meq/100 g). Some of the <2-/zm Na+-montmorillonite was
exchanged with a cationic oxyhydroxyaluminum species,
thought to be [AlI304(OH)24(HzO)1217+,after the manner of
OcceUi and Tindwa (1983) using Chlorhydrol (ACH) solutions (Reheis Chemicals Company). The basal spacing of this
clay was 18.6/~.
A pillared clay was produced by following example 1 in
Vaughan et al. (1979). After the cation-exchange steps using
ACH solutions the clay was dried in an oven overnight at
86~ After cooling, the basal spacing of this clay was 18.6
~. Calcining the material at 200~ for 15 rain reduced the
spacing slightly to i7.7/~, but calcining at 400"C resulted in
a broad peak extending from 5 ~ to 6~ (CoKa radiation),

Clays and Clay Minerals

which suggested a significant collapse of the pillars between

the clay layers.~ For all catalysis experiments, material calcined at 200~ was employed. This catalyst contained 3.78%
interlayer A1, compared with the 5.2% calculated if all interlayer exchange sites were filled with AI~3 polycations having
7 + charge. The surface area was 229 m2/g.
To prepare Ti3+-montmoriUonite, 2.5 g of the Na+-mont morillonite was suspended in 100 cm 3 of deionized water, to
which was added 5 cm 3 of 30% TIC13 solution (BDH). The
suspension was stirred for 30 min, after which it was heated
to 70"C and stirred for an additional 30 rain before centrifugation, resuspended i n 250 cm 3 of hot deionized water, and
centrifuged again. A vacuum desiccator containing silica gel
was used to dry and store the pale blue clay. Titration with
permanganate indicated that 90% of the cation-exchange sites
contained Ti 3+ and that the clay was stable over many weeks
when not exposed to the atmosphere.
Cation exchange of the Wyoming montmorillonite was carried out using 0.7 M AIC13 solution for 24 hr, followed by
washing to remove excess exchanging salt in a manner similar
to that employed for the Tonsil 13 clay.

Reaction conditions and analysis

In some experiments reactions were carried out under reflux; however, the majority of experiments were performed
in sealed, Teflon-lined, brass vessels that were fitted with
sampling ports and contained a magnetic stirrer. Known
weights of catalyst, pre-equilibrated at 12% relative humidity
(RH), were used for each reaction. Normally 0.5 g of catalyst
was used, but for reactions involving the effect of variation
in isobutene/metbanol ratios, only 0.1 g was employed.
For reactions between methanol and t-butanol, the alcohols
were added to the reaction vessel only a few seconds after the
clay catalyst was added, so as to minimize exposure of the
clay to atmospheric moisture. In most experiments using isobutene as the reagent, the clay, methanol and, if necessary,
1,4-dioxan solvent were added to the vessel, which was then
sealed. The isobutene was then liquefied and transferred to
the reaction vessel using a syringe. The amount of isobutene
was calculated from the volume and density (0.85 g/cm3). In
some experiments in which low concentrations of isohutene
were employed, a saturated solution ofisobutene in 1,4-dioxan was used as the reagent. The solubility limit at room temperature and pressure was found to be ~ 1 mmole isobutene/
cm 3 of dioxan.
The reactions were monitored by diluting 50-ul aliquots
with 0.5 cm 3 of 1,4-dioxan and storing them in polytetrafluorethylene sealed vials prior to analysis by gas-liquid chromatography (GLC). GLC measurements were made with a
2.7-m glass column of 0.25-inch i.d. packed with 2% polyethylene glycol (PEG 20 M) plus 10% silver nitrate on Chromasorb P.
RESULTS AND DISCUSSION

Reactions under reflux ( M e O H + t-BuOH)

In preliminary reactions the ratios of the two liquid
reagents, m e t h a n o l a n d t - b u t a n o l , were v a r i e d w h i l e
k e e p i n g t h e a m o u n t o f c a t a l y s t fixed a n d t h e t o t a l v o l u m e c o n s t a n t . T h e yield i m p r o v e d i f a n excess o f t - b u t a n o l was e m p l o y e d (Figure 1). T h i s excess w a s necessary, b e c a u s e , in a d d i t i o n to t h e f o r m a t i o n o f M T B E ,

Comparable experiments carried out using the Wyoming

montmorillonite Volclay-200 showed no such collapse; the
X-ray powder diffraction spacing decreased slightly to 16.8/~.

Vol. 34, No. 5, 1 9 8 6

Methyl-t-butyl ether production using a montmorillonite catalyst

599

2.0

2.0

1.5

1.5
O

yield
(rnmole)

yie{d
(mrnote)

0.5

0.5

30

60

90

time{rnin)
Figure 1. Yield of methyl t-butyl ether from different ratios
of methanol and t-butanol over AP+-montmorillonite. Reactions were carried out under reflux. Total volume was constant, as was total number of moles of the reactions; 1,4dioxan was used as solvent. MeOH : tBuOH ratios: O = 100:
200 mmole;/x = 150:150 mmole; x7 = 200:100 mmole.

t-butanol may undergo acid-catalyzed dehydration to

isobutene (and water), after which the isobutene would
be lost from the reflux apparatus.
A series of reactions were then carried out to c o m pare the efficiency of the montmorillonite catalysts for
the reaction of alcohols to give MTBE. The a m o u n t of
catalyst used in each reaction, the methanol to t-butanol ratio, and the total volume were kept constant.
All catalysts were pre-equilibrated at 12% R H to ensure
reproducibility. The AP+-montmorillonite was by far
the best catalyst for the reaction (Figure 2). The commercial catalyst K10 had an activity which was c o m parable to, but less than that of the AP+-clay, confirming the previous work of Adams et al. (1982) who used
a montmorillonite from Wyoming. The K10 catalyst
is a clay which has been acid treated to some degree
(Siid-Chemie, 1985) leaving exsolved AP + species in
the interlayer region. Its slightly lower activity is probably due to the fact that the catalyst contains material
other than montmorillonite (Stid-Chemie, 1985), i.e.,
no size-fractionation was performed on the original
bentonite material.
The K306 catalyst is derived from the Moosburg
bentonite by extensive, acid treatment until almost no
f
montmorillonite structure remains (Hojabri, 1971). Its
lack of activity is therefore not surprising (Adams et
al., 1982). Figure 2 also shows that the ACH-clays and
pillared clays had low activity. The ACH-clays were

30

60

90

tirnelrnin)
Figure 2. Comparison of catalytic efficiency of some derivatives of the montmorillonite from Moosburg, Federal Republic of Germany (Tonsil 13). Reactions were under reflux
(60~ with a mole ratio ofMeOH : t-BuOH of 1:2; 1,4-dioxan
was used as solvent. 9 = A13+-montmorillonite; I = Catalyst
K10; 9 = Pillared clay; X = Catalyst K306;/x = ACH-montmorillonite.

probably relatively inactive because the globular polycations left little free space in the interlayer region,
thereby blocking access for reactant molecules. Alternatively, the inherent acidity of the materials might
simply be less. To improve the activity of the pillared
clays, a procedure recommended by Vaughan et al.
(1981)-- treatment with a m m o n i u m hydroxide-- was
followed to increase the cation-exchange capacity of
the samples. Repeat reactions showed virtually no increase in catalytic activity. This lack of activity of pillared clays in low temperature, acid-catalyzed reactions
producing amines, esters, and ethers was also noted by
Diddams et al. (1984).
Reactions in sealed vessels ( M e O H + t - B u O H )

Reactions were carred out using differing ratios of

methanol : t-butanol and either stoichiometric amounts
or an excess of methanol. The solvent was 1,4-dioxan.
The rate of production of MTBE was found to be directly proportional to the concentration of t-butanol.
Comparable reactions were then performed using AP +clay and Amberlyst 15 catalysts. The Amberlyst 15
resin was somewhat more efficient (Figure 3) and gave
a yield of MTBE of 47% after 40 m i n at 80~ compared
with 18% for the clay catalyst. The activation energy
was also lower for the resin-catalyzed reaction: 23 _
5 kJ/mole, compared with 85 _ 13 kJ/mole.

600

Clays and Clay Minerals

Adams, Martin, McCabe, and Murray

%0

A A

yield

(mmo[~i

A A--

rut e

_
o

30

BO

90

3[,~

2
3
isob utene (mmo[e)

tirne(min)
B

o
6

10

Fete

yield

(tamale)

51

30
time(rain)

60

90

Figure 3. Comparison of activity of (A) AP+-montmorillonite and (B) Amberlyst 15 for reaction of methanol and
t-butanol to give methyl t-butyl ether and water. Both catalysts were pre-equilibrated at 12% RH. Reactions were carried
out in sealed vessels using comparable quantifies of catalyst,
methanol, and t-butanol; 1,4-dioxan was used as solvent.
Temperatures: I = 62", x7 = 70", O = 81 ~ zx = 90~

Reactions in sealed vessels ( M e O H + isobutene)

T o study the d e p e n d e n c e o f the rate o f f o r m a t i o n o f
M T B E on m e t h a n o l and isobutene concentrations, reactions were p e r f o r m e d with A P + - e x c h a n g e d m o n t morillonites at 70~ In each e x p e r i m e n t , d i o x a n was
used as solvent. W i t h excess m e t h a n o l , the rate was
directly p r o p o r t i o n a l to the isobutene c o n c e n t r a t i o n
(Figure 4a) as has been found for resin-catalyzed reactions (Ancillotti et al., 1978; G i c q u e l a n d Torck,
1983). A t a fixed c o n c e n t r a t i o n o f isobutene, the rate
o f M T B E p r o d u c t i o n rose with the m e t h a n o l concentration, but, after this c o n c e n t r a t i o n reached that o f the
isobutene, the rate b e c a m e constant (Figure 4b). T h i s
b e h a v i o r is distinctly different f r o m that o b s e r v e d for
A m b e r l y s t 15 resin (Ancillotti et al., 1978; G i c q u e l and
Torck, 1983), where the rate increased rapidly until the
m e t h a n o l c o n c e n t r a t i o n was a b o u t one tenth o f t h a t o f
the isobutene. A t higher m e t h a n o l concentrations, the
rate decreased rapidly until, with an excess o f m e t h a nol, it b e c a m e i n d e p e n d e n t o f m e t h a n o l c o n c e n t r a t i o n
(Ancillotti et al., 1978). In the present work, it was

~t
2

6
MeOH(remote)

lO

Figure 4. (A) Effect on the rate of reaction of variation in

concentration of isobutene at 70"C with excess methanol, 0.1
g of AP+-clay catalyst, 0.4 cm 3 methanol (= 10 mmole) and
~ 3 cm 3 1,4-dioxan were used (total volume = constant). (B)
Effect on the rate of reaction of variation in concentration of
methanol at 70"C. 0.1 g of AP
catalyst was used with
2.5 mmole isobutene and 0.5-10 mmole methanol Total volume was kept constant; ~ 3 cm 3 of 1,4-dioxan was used as
solvent. In both parts of figure the rates are in arbitrary units.

found that for b o t h types o f catalyst, w h e n m e t h a n o l

was in excess, as it is in industrial processes, the rate
was i n d e p e n d e n t o f m e t h a n o l concentration. A t l o w e r
concentrations o f m e t h a n o l the rate was e n h a n c e d w h e n
the A m b e r l y s t 15 catalyst was used. A n c i l l o t t i et aL
(1978) suggested that u n d e r these c o n d i t i o n s the alkene
is p r o t o n a t e d directly by the SO3H groups o f the resin,
which are m o r e acidic t h a n s o l v a t e d p r o t o n s (Gates
and Rodriguez, 1973).
F o l l o w i n g the type o f p r o c e d u r e a d o p t e d by Purnell
and Ballantine (1984) a reaction s c h e m e can be constructed, as s h o w n below:
KI

A(1) = A(i)
K2

MeOH(1) -~ M e O H ( i )
K3

M e O H ( i ) + H + = MeOH2(i)
+

K4

MeOH2(i) + A(i) ~ M e O H ( i ) + AH+(i)

K5

M e O H ( i ) + AH+(i) ~- MTBE(i) + H +
K6

M T B E ( i ) ~ MTBE(1),

Vol. 34, No. 5, 1 9 8 6

Methyl-t-butyl ether production using a montmorillonite catalyst

15
10
yield

(mmote~
U ~

2O
40
time(rain)

15IB
yield10

(mm~ t
r

2'0

&O

time(rain)
Figure 5. Comparisonof the activity of (A) A13+-montmorilloniteand (B) Amberlyst 15 for reaction of methanol and
isobutene. Reactions were carried out in sealed vessels using
comparable quantities of catalyst, methanol, and isobutene;
1,4-dioxan was used as solvent. Temperatures: + = 52~ I =
63", x7 = 72~ O = 82~ zx = 93~

where A represents the alkene, isobutene, and 1 and i

indicate the external liquid phase or an intercalated
species respectively. Based on the results obtained using different ratios of isobutene and methanol (Figure
4), step (4) in this scheme is rate limiting. The possibility that dioxan could be the proton-carrying species
involved in the protonation of the alkene in reactions
where it was used as solvent can be discounted at the
concentration ratios used in this work in as much as
the PKA of dioxan is 2 units lower than the pKA of
methanol.
Reactions were carried out using A13+-clay catalysts
and Amberlyst 15 resin over the temperature range of
interest. Here also, the Amberlyst 15 was more efficient
than the clay catalyst, e.g., it gave a 29% yield after 20
rain at 62~ compared with 14% for the clay (Figure
5). Compared with previous experiments using the alcohols, however, the relative efficiency of the clay was
slightly greater. The activation energy of the clay-catalyzed reaction was again higher than that found for
the resin; i.e., 44 _+ 3 kJ/mole compared with 25 + 13
kJ/mole. Reactions were also carried out under the
same conditions using Ti3+-montmorillonite, but the

601

rates were only about one third of those found for A1~+clays at ~ 60~
Two further modifications were also made to the
basic A13+-montmorillonite-catalyzedreactions. First,
an attempt was made to improve the reactivity of the
clay by addition of concentrated HC1 at the rate given
by Gregory and Westlake (1982), i.e., 2% of the weight
of the reactants. The rate of the reaction was reduced
(rather than increased) to about two thirds of that produced by AP+-clays alone. Second, the A13+-clay was
freeze dried rather than dried in an oven before equilibration at 12% RH, in order to produce a material
with a much more open, porous macrostructure (Weiss
et al., 1952; Norrish and Raussell-Colom, 1962) which
might, therefore, produce increased reaction rates? No
improvement in efficiency was noted, however, which
confirms that in this reaction, if the clay layers were
held apart by solvent molecules, access of alcohol and
alkene to the active site was not rate determining. These
findings contrast with other higher temperature reactions where macroporosity leads to enhanced diffusion
characteristics (Pinnavaia et al., 1984).
Some of the freeze-dried clay was used directly (rather than after equilibration to 12% RH). This material,
which had been produced using a low v a c u u m ( 1 0 - '
torr) had a 20% greater activity due to greater acidity
displayed by montmorillonites of low water content
(Mortland and Raman, 1968).

Solvent effects
All the reactions studied above were carried out in
1,4-dioxan, a solvent that has been found to be efficacious in m a n y clay catalyzed reactions involving tertiary carbocation intermediates. The beneficial effects
are thought to be due to promotion of miscibility of
reagents (Adams et aL, 1983a). To make the comparison between clay catalysts and ion-exchange resin as
close as possible, 1,4-dioxan was also used in Amberlyst-catalyzed reactions, even though no solvent is used
in industrial processes. The activation energy reported
here for Amberlyst-catalyzed reactions is considerably
lower than that reported when no solvent was employed, i.e., 25 kJ/mole compared with 70-80 kJ/mole
(Ancillotti et al., 1977, 1978; Gicquel and Torck, 1983).
MTBE production is apparently highly solvent dependent, regardless of the type of catalyst.
In previous MTBE formations over clay catalysts,
Adams et al. (1982) found no correlation between the
basal spacing of a particular M "+-montmorillonite/solvent system and its catalytic ability. In the present
investigation, the range of solvents was extended to
include carbon tetrachloride and toluene. As can be

2 The basal spacing of this freeze-dried, equilibrated (12%

RH) clay was the same as for the oven-dried equilibrated clay.

Adams, Martin, McCabe, and Murray

602

Clays and Clay Minerals

Table 1. Effectof solvent upon the rate of production of MTBE from methanol and isobutene.
Reactions reported by Adams et aL (1982) 2

Reactions reported in this paper t

Solvent

Rate (% yield/rain)

Solvent

Rate (% yield/rain)

None
Carbon tetrachloride
Toluene

0.280
0.062
0.08

1,4-dioxan

1.55

1,2-dimethoxyethane
Diethylene glycol diethyl ether
n-pentane
Tetrahydropyran
N-methylmorpholine
Tetrahydrofuran
1,4-dioxan

0.013
0.007
0.002
0.018
0.002
0.003
0.252

Reactions were carried out at 62~ and used 0.5 g of AP+-montmorillonite(12% RH). Where solvents were employed,
quantities of reagents used were 2 cm3 methanol, 1.7 cm 3 isobutene, and 6.3 cm 3 solvent. When no solvent was employed,
5 cm 3 methanol and 4.25 cm 3 of isobutene were used.
2 Reactions below were carried out at 60~ and used 1 g of A13+-montmorillonite (Wyoming) (12% RH). Quantities of
reagents were 1 cm3 methanol, 3 cm 3 solvent, and 18-58 mmole isobutene, i.e., 1.2-3.8 cm 3,
seen from the data in Table 1, 1,4-dioxan was the most
efficient solvent studied.
It is not immediately obvious why dioxan should be
so useful a solvent. Adams et al. (1982) suggested that
miscibility of reagents and solvent is important and
that dioxan, water, methanol, and isobutene are m u tually soluble in the concentration ranges employed
here. This is, however, not the whole story inasmuch
as they also found evidence of specific cation/solvent
pairing. Addition of dioxan to the reactive mixture
should reduce the concentration of methanol somewhat in the interlayer space of the clay. As reported
above, however, if methanol was in excess, the most
significant factor affecting the reaction rate was the
concentration ofisobutene in the interlayer of the clay.
This concentration in turn depended on the isobutene
concentration in the solvent or in methanol if no solvent was employed. The solubility of isobutene in
methanol and dioxan was found to be 0.06 and 0.09
g/cm 3, respectively, at room temperature and pressure.
CONCLUSIONS
The catalytic activity of a range of montmorillonitebased catalysts for low-temperature MTBE production
is broadly in line with their expected acidities, i.e.,
A13+-clay > acid treated-clay (K10) >> ACH-treated
clay ~ pillared clay.
The activity of A13+-montmorilloniteat 60~ is ~ 50%
of that exhibited by an acidic ion-exchange resin similar to that used industrially. The reaction in the clay
does not appear to be diffusion controlled, at least if
1,4-dioxan is used as the solvent; increasing the macroporosity in the clay had no effect on reaction rate.
The activation energy using such a catalyst is higher
than when using the resin, i.e., 44 and 25 kJ/mole,
respectively, if 1,4-dioxan is used as the solvent. For
both clay and resin catalysts, the use of 1,4-dioxan
significantly lowers the activation energy from that observed when other (or no) solvents are employed. This
decrease is probably due to the fact that 1,4-dioxan is

mutually miscible with all reactants and products in

the concentration range studied. Moreover, the solubility of isobutene in dioxan is greater than that in
methanol.
ACKNOWLEDGMENTS
We thank English Clays Lovering Pochin and Co.
Ltd. (ECLP) and the British Technology Group for
support. Stid-Chemie AG, Munich, kindly donated the
samples of Tonsil 13 and K-catalysts. ECLP also analyzed the sedimented clays by X-ray fluorescence and
X-ray powder diffraction.
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(Received 31 May 1985; accepted 19 February 1986; Ms.

1491)