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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 ex-
changed 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 bentonite-
based 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, Montmo-
rillonite.
2.0 2.0
O O O O
1.5 1.5
yield
yie{d
(mrnote) o I
(rnmole)
0.5 0.5
0 30 60 90 0 30 60 90
time{rnin) tirnelrnin)
Figure 1. Yield of methyl t-butyl ether from different ratios Figure 2. Comparison of catalytic efficiency of some deriv-
of methanol and t-butanol over AP+-montmorillonite. Re- atives of the montmorillonite from Moosburg, Federal Re-
actions were carried out under reflux. Total volume was con- public of Germany (Tonsil 13). Reactions were under reflux
stant, as was total number of moles of the reactions; 1,4- (60~ with a mole ratio ofMeOH : t-BuOH of 1:2; 1,4-dioxan
dioxan was used as solvent. MeOH : tBuOH ratios: O = 100: was used as solvent. 9 = A13+-montmorillonite; I = Catalyst
200 mmole;/x = 150:150 mmole; x7 = 200:100 mmole. K10; 9 = Pillared clay; X = Catalyst K306;/x = ACH-mont-
morillonite.
A
%0 ~ A A A A-- g
rut e
yield / _
(mmo[~i A o o
3[,~ , , ,
0 30 BO 90 0 l 2 3
tirne(min) isob utene (mmo[e)
B O O
o
10 6
yield
(tamale)
51
o
Fete
3
0
~t 2 G 6
r
MeOH(remote)
Figure 4. (A) Effect on the rate of reaction of variation in
I
B
I
lO
rates were only about one third of those found for A1~+-
clays at ~ 60~
15 Two further modifications were also made to the
basic A13+-montmorillonite-catalyzedreactions. First,
an attempt was made to improve the reactivity of the
10 clay by addition of concentrated HC1 at the rate given
yield by Gregory and Westlake (1982), i.e., 2% of the weight
(mmote~ of the reactants. The rate of the reaction was reduced
(rather than increased) to about two thirds of that pro-
duced by AP+-clays alone. Second, the A13+-clay was
U ~ freeze dried rather than dried in an oven before equil-
2O 40
15IB
ibration at 12% RH, in order to produce a material
time(rain) 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
yield10 alkene to the active site was not rate determining. These
findings contrast with other higher temperature reac-
tions where macroporosity leads to enhanced diffusion
(mm~ t characteristics (Pinnavaia et al., 1984).
Some of the freeze-dried clay was used directly (rath-
er than after equilibration to 12% RH). This material,
r
which had been produced using a low v a c u u m ( 1 0 - '
0 2'0 &O
time(rain) torr) had a 20% greater activity due to greater acidity
displayed by montmorillonites of low water content
Figure 5. Comparisonof the activity of (A) A13+-mont- (Mortland and Raman, 1968).
morilloniteand (B) Amberlyst 15 for reaction of methanol and
isobutene. Reactions were carried out in sealed vessels using
comparable quantities of catalyst, methanol, and isobutene; Solvent effects
1,4-dioxan was used as solvent. Temperatures: + = 52~ I =
63", x7 = 72~ O = 82~ zx = 93~ All the reactions studied above were carried out in
1,4-dioxan, a solvent that has been found to be effi-
cacious in m a n y clay catalyzed reactions involving ter-
where A represents the alkene, isobutene, and 1 and i tiary carbocation intermediates. The beneficial effects
indicate the external liquid phase or an intercalated are thought to be due to promotion of miscibility of
species respectively. Based on the results obtained us- reagents (Adams et aL, 1983a). To make the compar-
ing different ratios of isobutene and methanol (Figure ison between clay catalysts and ion-exchange resin as
4), step (4) in this scheme is rate limiting. The possi- close as possible, 1,4-dioxan was also used in Amber-
bility that dioxan could be the proton-carrying species lyst-catalyzed reactions, even though no solvent is used
involved in the protonation of the alkene in reactions in industrial processes. The activation energy reported
where it was used as solvent can be discounted at the here for Amberlyst-catalyzed reactions is considerably
concentration ratios used in this work in as much as lower than that reported when no solvent was em-
the PKA of dioxan is 2 units lower than the pKA of ployed, i.e., 25 kJ/mole compared with 70-80 kJ/mole
methanol. (Ancillotti et al., 1977, 1978; Gicquel and Torck, 1983).
Reactions were carried out using A13+-clay catalysts MTBE production is apparently highly solvent depen-
and Amberlyst 15 resin over the temperature range of dent, regardless of the type of catalyst.
interest. Here also, the Amberlyst 15 was more efficient In previous MTBE formations over clay catalysts,
than the clay catalyst, e.g., it gave a 29% yield after 20 Adams et al. (1982) found no correlation between the
rain at 62~ compared with 14% for the clay (Figure basal spacing of a particular M "+-montmorillonite/sol-
5). Compared with previous experiments using the al- vent system and its catalytic ability. In the present
cohols, however, the relative efficiency of the clay was investigation, the range of solvents was extended to
slightly greater. The activation energy of the clay-cat- include carbon tetrachloride and toluene. As can be
alyzed 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 2 The basal spacing of this freeze-dried, equilibrated (12%
same conditions using Ti3+-montmorillonite, but the RH) clay was the same as for the oven-dried equilibrated clay.
602 Adams, Martin, McCabe, and Murray Clays and Clay Minerals
Table 1. Effectof solvent upon the rate of production of MTBE from methanol and isobutene.
Reactions reported in this paper t Reactions reported by Adams et aL (1982) 2
Solvent Rate (% yield/rain) Solvent Rate (% yield/rain)
seen from the data in Table 1, 1,4-dioxan was the most mutually miscible with all reactants and products in
efficient solvent studied. the concentration range studied. Moreover, the solu-
It is not immediately obvious why dioxan should be bility of isobutene in dioxan is greater than that in
so useful a solvent. Adams et al. (1982) suggested that methanol.
miscibility of reagents and solvent is important and
ACKNOWLEDGMENTS
that dioxan, water, methanol, and isobutene are m u -
tually soluble in the concentration ranges employed We thank English Clays Lovering Pochin and Co.
here. This is, however, not the whole story inasmuch Ltd. (ECLP) and the British Technology Group for
as they also found evidence of specific cation/solvent support. Stid-Chemie AG, Munich, kindly donated the
pairing. Addition of dioxan to the reactive mixture samples of Tonsil 13 and K-catalysts. ECLP also ana-
should reduce the concentration of methanol some- lyzed the sedimented clays by X-ray fluorescence and
what in the interlayer space of the clay. As reported X-ray powder diffraction.
above, however, if methanol was in excess, the most REFERENCES
significant factor affecting the reaction rate was the
concentration ofisobutene in the interlayer of the clay. Adams, J. M., Clapp, T. V., and Clement, D. E. (1983a)
Catalysis by montmorillonites: Clay Miner. 18, 411-421.
This concentration in turn depended on the isobutene Adams, J, M., Clement, D. E., and Graham, S. H, (1981)
concentration in the solvent or in methanol if no sol- Low temperature reaction of alcohols to form t-butyl ethers
vent was employed. The solubility of isobutene in using clay catalysts: J. Chem. Res., $254-255.
methanol and dioxan was found to be 0.06 and 0.09 Adams, J. M., Clement, D. E., and Graham, S. H. (1982)
Synthesis of methyl-t-butyl ether from methanol and iso-
g/cm 3, respectively, at room temperature and pressure.
butene using a clay catalyst: Clays & Clay Minerals 30,
129-134.
CONCLUSIONS Adams, J. M., Clement, D. E., and Graham, S. H. (1983b)
Reactions of alcohols with alkenes over an aluminum-ex-
The catalytic activity of a range of montmorillonite- changed montmorillonite: Clays & Clay Minerals 31, 129-
based catalysts for low-temperature MTBE production 136.
Ancillotti, F., Masi Mauri, M., and Pescarollo, E. (1977) Ion
is broadly in line with their expected acidities, i.e., exchange resin catalyzed addition of alcohols to olefins: J.
A13+-clay > acid treated-clay (K10) >> ACH-treated Catal. 46, 49-57.
clay ~ pillared clay. Ancillotti, F., Massi Mauri, M., Pescarollo, E., and Roma-
The activity of A13+-montmorilloniteat 60~ is ~ 50% gnoni, L. (1978) Mechanisms in the reacti~ between ~
fins and alcohols catalyzed by ion-exchange resins: J. Mol.
of that exhibited by an acidic ion-exchange resin sim- Catal. 4, 37-48.
ilar to that used industrially. The reaction in the clay Anonymous (1967) Amberlyst 15 Synthetic Resin Catalyst:
does not appear to be diffusion controlled, at least if Rhom and Haas Co., Philadelphia, Pennsylvania, 4 pp.
1,4-dioxan is used as the solvent; increasing the mac- Bylina, A., Adams, J. M., Graham, S. H., and Thomas, J. M.
roporosity in the clay had no effect on reaction rate. (1980) Chemical conversions using sheet silicates: simple
method for producing methyl t-butyl ether: J. Chem. Soc.
The activation energy using such a catalyst is higher Chem. Comm., 1003-1004.
than when using the resin, i.e., 44 and 25 kJ/mole, Csikos, R., Laky, J., Pallay, I., and Vajta, L. (1975) Ether
respectively, if 1,4-dioxan is used as the solvent. For additives for gasoline: Ger. Often. DE 2, 444, 528, 4 pp.
both clay and resin catalysts, the use of 1,4-dioxan Diddams, P. A., Thomas, J. M., Jones, W., Ballantine, J. A.,
and Purnell, J.H. (1984) Synthesis, characterization, and
significantly lowers the activation energy from that ob- catalytic activity of beidellite-montmorillonitelayered sil-
served when other (or no) solvents are employed. This icates and their pillared analogues: aT. Chem. Soc. Chem.
decrease is probably due to the fact that 1,4-dioxan is Comm., 1340-1342,
Vol. 34, No. 5, 1986 Methyl-t-butyl ether production using a montmorillonite catalyst 603
Gates, B. C. and Rodriguez, W. (1973) General and specific Occelli, M. L. and Tindwa, R. M. (1983) Physiochemical
acid catalysis in sulphonic acid resin: J. Catal. 31, 27-31. properties of montmorillonite interlayered with cationic
Gicquel, A. andTorck, B. (1983) Synthesis ofmethyl tertiary oxyaluminum pillars: Clays & Clay Minerals 31, 22-28.
butyl ether catalyzed by ion-exchange resin. Influence of Pecci, G. and Floris, T. (1977) Ether ups anti-knock of
methanol concentration and temperature: J. Catal. 83, 9- gasoline: Hydrocarbon Processing Int. Ed. 56, 98-102.
18. Pinnavaia, T. J., Tzou, M. S., Landau, S. D., and Raythatha,
Gregory, R. and Westlake, D. J. (1982) Method of pro- R . H . (1984) On the pillaring and determination ofsmec-
moting the activity of cation-exchangeable layered clay and tite clay catalysts by polyoxocations of aluminium: J. Mol.
zeolite catalysts in proton-catalyzed reactions: European Catal. 27, 195-212.
Patent Application 0045618A2, 17 pp. Purnell, J. H. and Ballantine, J. A. (1984) Competitive in-
Gregory, R. and Wesflake, D. J. (1983) Use of stabilized tercalation and intercalary kinetics: J. Mol. Catal. 27, 169-
pillared inteflayered clays as catalysts in reactions capable 178.
of catalysis by protons: European Patent Application Siid-Chemie AG (1985) K-Catalysts: Sfid-Chemie AG,
0083970A1, 23 pp. Munich, Federal Republic of Germany, p. 2.
Gupta, J. C. and Prakash, J. (1980) MTBE technology: Chem. Vaughan, D. E. W. and Lussier, R . J . (1980) Preparation of
Eng. World, 15, 27-31. molecular sieves based on pillared interlayered clays (PILC):
Hojabri, F. (1971) Dimerization of propylene and its uses inProe. 5th Int. Conf. Zeolites, Naples, 1980, L. V. C. Rees,
for isoprene manufacture: J. AppL Chem. Biotech. 21, 87- ed., Heyden, London, 94-101.
89. Vaughan, D. E. W., Lussier, R. J., and Maggee, J. S. (1979)
Morikawa, Y., Wang, F., Moro-oka, Y., and Ikawa, T. (1983) Pillared interlayered clay materials useful as catalysts and
Conversion of methanol to low molecular weight hydro- sorbents: U.S. Patent 4,176,090, 9 pp.
carbons over Ti ion-exchanged form of layered silicate min- Vaughan, D. E. W., Lussier, R. J., and Maggee, J. S. (1981)
erals: Chem. Letters, 965-968. Pillared interlayered clay products: U.K. Patent Application
Mortland, M. M. and Raman, K. V. (1968) Surface acidity GB 2,059,408A, 5 pp.
of smectites in relation to hydration, exchangeable cation, Watanabe, Y., Kobayashi, J., and Nishizawa, T. (1973)
and structure: Clays & Clay Minerals 16, 393-398. Modifying agents raising octane number of gasoline: Japan
Muddaris, G. R. and Pettman, M. J. (1980) Now, MTBE Kokai 73,23,803, 4 pp.
from butane: Hydrocarbon Processing Int. Ed. 59, 91-95. Weiss, A., Fahn, R., and Hofmann, U. (1952) Skeletal struc-
Nishizawa, T., Tokumaru, T., Kamiyama, Y., and Watanabe, ture in thixotropic gels: Naturwissenschaften 89, 351-352.
Y. (1974) Gasoline composition with high octane number: (Received 31 May 1985; accepted 19 February 1986; Ms.
Japan Kokai 74, 26, 306, 44 pp. 1491)
Norrish, K. and Raussell-Colom, J.A. (1962) Effect of freez-
ing on the swelling of clay minerals: Clay Min. Bull. 5, 9-
16.