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

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. 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,

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: 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

+ CH2=C\cH3 +/CH3 -~ CH3OH + C H 3 - C \ , CH3 to form the tertiary carbocation. 597

were also i n v e s t i g a t e d .3. The reactions were monitored by diluting 50-ul aliquots with 0. Here also. 1980. McCabe. thought to be [AlI304(OH)24(HzO)1217+.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. 1983).6 ~. 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. material calcined at 200~ was employed. Known weights of catalyst. 1983a. and Murray Clays and Clay Minerals 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 + . Montmorillonite from Upton. sedimentation was carried out to separate the <2-urn fraction.~ For all catalysis experiments. Two fractions were produced by sedimentation.85 g/cm3). 0. T h e yield i m p r o v e d i f a n excess o f t . 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 . The <2-um clay fraction was prepared by sedimentation. and Mg 2+. montmorillonite exchanged with the polycation [ A l t 3 0 4 ( O H ) z 4 ( H z O ) l z ] 7+. Wyoming. Martin. the basal spacing of this clay was 18. the clay. methanol and. followed by washing to remove excess exchanging salt in a manner similar to that employed for the Tonsil 13 clay.78% interlayer A1. In most experiments using isobutene as the reagent. 1. T h i s excess w a s necessary.8 ~ and the aluminum content was 0. the majority of experiments were performed in sealed. The solubility limit at room temperature and pressure was found to be ~ 1 mmole isobutene/ cm 3 of dioxan.04% K20. respectively. (1979). RESULTS AND DISCUSSION Catalyst preparation To aid later cation-exchange processes.m o n t m o r i l l o n i t e . The suspension was stirred for 30 min. Comparable experiments carried out using the Wyoming montmorillonite Volclay-200 showed no such collapse.4-dioxan solvent were added to the vessel.after the manner of OcceUi and Tindwa (1983) using Chlorhydrol (ACH) solutions (Reheis Chemicals Company). packed with 2% polyethylene glycol (PEG 20 M) plus 10% silver nitrate on Chromasorb P. and 2 meq/100 g of Na +. V a u g h a n et aL. brass vessels that were fitted with sampling ports and contained a magnetic stirrer. The finer fraction was subjected to ultrasonic treatment for 10 min.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. were used for each reaction. For reactions between methanol and t-butanol.4-dioxan and storing them in polytetrafluorethylene sealed vials prior to analysis by gas-liquid chromatography (GLC). only 0.4-dioxan was used as the reagent. AP+-montmorillonite was prepared by exposing some of this <2-~m fraction to an 0.25-inch i. The cation-exchange capacity totaled 103 meq/100 g of air-dry material and consisted of 68. Normally 0.. m e t h a n o l a n d t . The clay was isolated by centrifugation. The amount of isobutene was calculated from the volume and density (0. Reaction conditions and analysis In some experiments reactions were carried out under reflux. At this point the pH of the super'natant liquid was 4.5 g of catalyst was used.d. The clay was then centrifuged and resuspended in deionized water repeatedly until a test for excess salt proved negative. to which was added 5 cm 3 of 30% TIC13 solution (BDH).2% calculated if all interlayer exchange sites were filled with AI~3 polycations having 7 + charge. Federal Republic of Germany (Tonsil 13. and centrifuged again. 1979. Calcining the material at 200~ for 15 rain reduced the spacing slightly to i7. 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.b u t a n o l was e m p l o y e d (Figure 1). resuspended i n 250 cm 3 of hot deionized water. b e c a u s e .20% Na20. 33. K 1 0 a n d K306 (Sfid-Chemie AG). if necessary. but calcining at 400"C resulted in a broad peak extending from 5 ~ to 6~ (CoKa radiation).7-m glass column of 0. The clay was added to an 0. EXPERIMENTAL Catalyst characterization The bentonite used for most of this study came from Moosburg. The basal spacing of this clay was 14.1 g was employed. which suggested a significant collapse of the pillars between the clay layers. A pillared clay was produced by following example 1 in Vaughan et al. 0. Some of the <2-/zm Na+-montmorillonite was exchanged with a cationic oxyhydroxyaluminum species. reactions with Ti3+-montmorillonite. Cation exchange of the Wyoming montmorillonite was carried out using 0. 1. Reactions under reflux ( M e O H + t-BuOH) In preliminary reactions the ratios of the two liquid reagents. The isobutene was then liquefied and transferred to the reaction vessel using a syringe.3 M A1C13 solution (pH = 2.0% SiO2.598 Adams. a large quantity of the Tonsil 13 clay was exchanged initially with Na +.5% CaO. Loss on ignition was 7. a saturated solution ofisobutene in 1. pre-equilibrated at 12% relative humidity (RH). 20. a material having very high acidity for s u c h catalysts ( M o r i k a w a et aL. 1983b) a n d i n c l u d e A P + . An X-ray fluorescence (XRF) analysis gave 64.1%.t r e a t e d clays. after which it was heated to 70"C and stirred for an additional 30 rain before centrifugation. which was then sealed. so as to minimize exposure of the clay to atmospheric moisture. Siid-Chemie AG). however. a n d t w o c o m m e r c i a l a c i d . Ca 2+. and 1. This catalyst contained 3.8/~. Teflon-lined. All o f t h e s e c l a y .7) for 24 hr. 1. To prepare Ti3+-montmoriUonite.5 cm 3 of 1. the alcohols were added to the reaction vessel only a few seconds after the clay catalyst was added. 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 .6/~. dried at 40~ and mechanically ground. The surface area was 229 m2/g. An X-ray powder diffraction (XRD) examination showed that this fraction was ~ 98% montmorillonite with ~ 2% quartz impurity.07% TiO2. but for reactions involving the effect of variation in isobutene/metbanol ratios. the X-ray powder diffraction spacing decreased slightly to 16. . A vacuum desiccator containing silica gel was used to dry and store the pale blue clay.7/~. was used to study the dependence of reaction rate on concentration ofisobutene and methanol. and the <2-urn fraction was collected by sedimentation. 3.86% Fe203.5 g of the Na+-mont morillonite was suspended in 100 cm 3 of deionized water. This value is in reasonable agreement with the measured CEC (103 meq/100 g). In addition.8% A1203.42% MgO. The basal spacing of this clay was 18. In some experiments in which low concentrations of isohutene were employed. GLC measurements were made with a 2. 2. After the cation-exchange steps using ACH solutions the clay was dried in an oven overnight at 86~ After cooling. 1981).b u t a n o l .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.1 M solution of NaCI and heated to 70~ with vigorous stirring for 1 hr.7 M AIC13 solution for 24 hr. compared with the 5.

Comparison of catalytic efficiency of some derivatives of the montmorillonite from Moosburg. The a m o u n t of catalyst used in each reaction. MeOH : tBuOH ratios: O = 100: 200 mmole. no size-fractionation was performed on the original bentonite material. 9 = Pillared clay. Yield of methyl t-butyl ether from different ratios of methanol and t-butanol over AP+-montmorillonite. (1982) who used a montmorillonite from Wyoming. compared with 85 _ 13 kJ/mole. The commercial catalyst K10 had an activity which was c o m parable to. acid treatment until almost no f montmorillonite structure remains (Hojabri. The K10 catalyst is a clay which has been acid treated to some degree (Siid-Chemie. 9 = A13+-montmorillonite. but less than that of the AP+-clay. Total volume was constant. This lack of activity of pillared clays in low temperature..B u O H ) Reactions were carred out using differing ratios of methanol : t-butanol and either stoichiometric amounts or an excess of methanol. confirming the previous work of Adams et al.Vol. Reactions were carried out under reflux. 34.4-dioxan./x = ACH-montmorillonite.0 O O O O 1. Reactions were under reflux (60~ with a mole ratio ofMeOH : t-BuOH of 1:2. and the total volume were kept constant. All catalysts were pre-equilibrated at 12% R H to ensure reproducibility.5 0 30 time{rnin) 60 90 0 30 60 90 tirnelrnin) Figure 2. Repeat reactions showed virtually no increase in catalytic activity. 1982).0 2. the inherent acidity of the materials might simply be less. a procedure recommended by Vaughan et al.4dioxan was used as solvent. Comparable reactions were then performed using AP +clay and Amberlyst 15 catalysts. The activation energy was also lower for the resin-catalyzed reaction: 23 _ 5 kJ/mole. 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 methanol to t-butanol ratio. (1981)-. thereby blocking access for reactant molecules.5 0. .treatment with a m m o n i u m hydroxide-. and ethers was also noted by Diddams et al. 1971). The K306 catalyst is derived from the Moosburg bentonite by extensive. Figure 2 also shows that the ACH-clays and pillared clays had low activity. Its lack of activity is therefore not surprising (Adams et al.5 O 1. 1. i. 1985). x7 = 200:100 mmole. Figure 1. 1985) leaving exsolved AP + species in the interlayer region. Reactions in sealed vessels ( M e O H + t . I = Catalyst K10.4-dioxan was used as solvent./x = 150:150 mmole. acid-catalyzed reactions producing amines. esters. X = Catalyst K306. Alternatively.e. The ACH-clays were probably relatively inactive because the globular polycations left little free space in the interlayer region. as was total number of moles of the reactions. Its slightly lower activity is probably due to the fact that the catalyst contains material other than montmorillonite (Stid-Chemie..5 yield (rnmole) yie{d (mrnote) o I 0. after which the isobutene would be lost from the reflux apparatus. Federal Republic of Germany (Tonsil 13). 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. To improve the activity of the pillared clays. The solvent was 1. The AP+-montmorillonite was by far the best catalyst for the reaction (Figure 2).was followed to increase the cation-exchange capacity of the samples. t-butanol may undergo acid-catalyzed dehydration to isobutene (and water). 5. The rate of production of MTBE was found to be directly proportional to the concentration of t-butanol. 1 9 8 6 Methyl-t-butyl ether production using a montmorillonite catalyst O 599 2. No. (1984). 1.

4-dioxan were used (total volume = constant). (B) Effect on the rate of reaction of variation in concentration of methanol at 70"C. W i t h excess m e t h a n o l . A t a fixed c o n c e n t r a t i o n o f isobutene.. Martin. reactions were p e r f o r m e d with A P + . after this c o n c e n t r a t i o n reached that o f the isobutene. 0. In both parts of figure the rates are in arbitrary units. it was 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.. Reactions were carried out in sealed vessels using comparable quantifies of catalyst. ~ 3 cm 3 of 1. 0. 1978. 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. 1983). and Murray Clays and Clay Minerals A % 0 yield ~ A A A A-- g / A o _ o rut e (mmo[~i 3[. 1.. . Temperatures: I = 62". 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. 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. Both catalysts were pre-equilibrated at 12% RH. 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. O = 81 ~ zx = 90~ Figure 4.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 . 1978). 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. d i o x a n was used as solvent. 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) ~. G i c q u e l and Torck. 1978.4 cm 3 methanol (= 10 mmole) and ~ 3 cm 3 1. with an excess o f m e t h a nol. G i c q u e l a n d Torck. 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.1 g of AP§ catalyst was used with 2.4-dioxan was used as solvent. x7 = 70". and t-butanol. . 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. 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. A t higher m e t h a n o l concentrations. 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) Effect on the rate of reaction of variation in concentration of isobutene at 70"C with excess methanol. 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. the rate b e c a m e constant (Figure 4b).5-10 mmole methanol Total volume was kept constant.1 g of AP+-clay catalyst. In the present work. the rate decreased rapidly until. 1973). 1983). l .5 mmole isobutene and 0. 0. as it is in industrial processes.4-dioxan was used as solvent. 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.MTBE(i) + H + K6 M T B E ( i ) ~ MTBE(1). 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.600 Adams. methanol.~ 0 . 0 B 30 tirne(min) B O O O 90 2 3 isob utene (mmo[e) o 10 yield 6 Fete (tamale) 3 o 51 0 ~t 2 r I I G 6 MeOH(remote) B lO 0 30 time(rain) 60 90 Figure 3. McCabe.

. (1982) found no correlation between the basal spacing of a particular M "+-montmorillonite/solvent system and its catalytic ability.. Reactions were also carried out under the same conditions using Ti3+-montmorillonite.4-dioxan was used as solvent. the Amberlyst 15 was more efficient than the clay catalyst. 1984). The rate of the reaction was reduced (rather than increased) to about two thirds of that produced by AP+-clays alone. 1968). the range of solvents was extended to include carbon tetrachloride and toluene. Some of the freeze-dried clay was used directly (rather than after equilibration to 12% RH). it gave a 29% yield after 20 rain at 62~ compared with 14% for the clay (Figure 5). however. and 1 and i indicate the external liquid phase or an intercalated species respectively. No. Temperatures: + = 52~ I = 63". porous macrostructure (Weiss et al. In previous MTBE formations over clay catalysts. Second. i. 2% of the weight of the reactants. equilibrated (12% RH) clay was the same as for the oven-dried equilibrated clay. 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). As can be where A represents the alkene. the A13+-clay was freeze dried rather than dried in an oven before equilibration at 12% RH. Comparisonof the activity of (A) A13+-mont morilloniteand (B) Amberlyst 15 for reaction of methanol and isobutene. To make the comparison between clay catalysts and ion-exchange resin as close as possible. Based on the results obtained using different ratios of isobutene and methanol (Figure 4). produce increased reaction rates? No improvement in efficiency was noted. regardless of the type of catalyst. First. In the present investigation. 34. Reactions were carried out using A13+-clay catalysts and Amberlyst 15 resin over the temperature range of interest. 1. Adams et al. if the clay layers were held apart by solvent molecules..' torr) had a 20% greater activity due to greater acidity displayed by montmorillonites of low water content (Mortland and Raman. 1. however. but the 2 The basal spacing of this freeze-dried. methanol. 1977.e. e. and isobutene. Norrish and Raussell-Colom. 5. step (4) in this scheme is rate limiting.e...g. The activation energy of the clay-catalyzed reaction was again higher than that found for the resin. The beneficial effects are thought to be due to promotion of miscibility of reagents (Adams et aL.4-dioxan. . which had been produced using a low v a c u u m ( 1 0 . access of alcohol and alkene to the active site was not rate determining. in order to produce a material with a much more open. isobutene. 1 9 8 6 Methyl-t-butyl ether production using a montmorillonite catalyst 601 15 10 yield (mmote~ U ~ 15IB yield 10 2O 40 time(rain) (mm~ t r time(rain) Figure 5. Compared with previous experiments using the alcohols. 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.. even though no solvent is used in industrial processes. x7 = 72~ O = 82~ zx = 93~ 0 2'0 &O 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. 1978. Solvent effects All the reactions studied above were carried out in 1. 1983). 1952. This material. The activation energy reported here for Amberlyst-catalyzed reactions is considerably lower than that reported when no solvent was employed. These findings contrast with other higher temperature reactions where macroporosity leads to enhanced diffusion characteristics (Pinnavaia et al.. which confirms that in this reaction. a solvent that has been found to be efficacious in m a n y clay catalyzed reactions involving tertiary carbocation intermediates. MTBE production is apparently highly solvent dependent. Reactions were carried out in sealed vessels using comparable quantities of catalyst. 1962) which might.4-dioxan was also used in Amberlyst-catalyzed reactions. the relative efficiency of the clay was slightly greater.Vol.e. i. 25 kJ/mole compared with 70-80 kJ/mole (Ancillotti et al. Here also. 1983a). therefore. 44 _+ 3 kJ/mole compared with 25 + 13 kJ/mole. Gicquel and Torck. i.

however.. J. D. Bylina. seen from the data in Table 1.. (1984) Synthesis. D.018 0.H. Soc. Reactions reported in this paper t Solvent Rate (% yield/rain) Reactions reported by Adams et aL (1982) 2 Solvent Rate (% yield/rain) None Carbon tetrachloride Toluene 0. M. Quantities of reagents were 1 cm3 methanol. i. 528... the use of 1.. V. Chem. Chem. (1978) Mechanisms in the reacti~ between ~ fins and alcohols catalyzed by ion-exchange resins: J.4-dioxan significantly lowers the activation energy from that observed when other (or no) solvents are employed.. .09 g/cm 3. S. (1977) Ion exchange resin catalyzed addition of alcohols to olefins: J. 49-57. M. Csikos. This is. $254-255. CONCLUSIONS The catalytic activity of a range of montmorillonitebased catalysts for low-temperature MTBE production is broadly in line with their expected acidities.7 cm 3 isobutene.002 0.08 1.06 and 0. at room temperature and pressure.25 cm 3 of isobutene were used. methanol.... 46. i.. Masi Mauri.252 Reactions were carried out at 62~ and used 0. Jones. Clement. respectively. quantities of reagents used were 2 cm3 methanol. and 6. the solubility of isobutene in dioxan is greater than that in methanol. REFERENCES Adams. the most significant factor affecting the reaction rate was the concentration ofisobutene in the interlayer of the clay. F. As reported above. A. P. J.4-dioxan was the most efficient solvent studied. (1981) Low temperature reaction of alcohols to form t-butyl ethers using clay catalysts: J.002 0. H. I. 411-421. This concentration in turn depended on the isobutene concentration in the solvent or in methanol if no solvent was employed. Ancillotti. 4.. not the whole story inasmuch as they also found evidence of specific cation/solvent pairing. Where solvents were employed. Often. Munich. A.. Comm. Laky. DE 2. 129136.280 0. Massi Mauri. Adams. Catal. Clement. M. Moreover. Diddams. M. E. 1... A13+-clay > acid treated-clay (K10) >> ACH-treated clay ~ pillared clay. ECLP also analyzed the sedimented clays by X-ray fluorescence and X-ray powder diffraction. S. J. increasing the macroporosity in the clay had no effect on reaction rate. H. This decrease is probably due to the fact that 1. kindly donated the samples of Tonsil 13 and K-catalysts. at least if 1. and Purnell. Pescarollo. McCabe. 444. E. and Clement. W. and Murray Clays and Clay Minerals Table 1. L.013 0. (1975) Ether additives for gasoline: Ger. J.. Clapp.4-dioxan is used as the solvent.003 0. Adams. For both clay and resin catalysts. (1980) Chemical conversions using sheet silicates: simple method for producing methyl t-butyl ether: J. 4 pp. F. (1983b) Reactions of alcohols with alkenes over an aluminum-exchanged montmorillonite: Clays & Clay Minerals 31.. R. Clement. 1340-1342. 18. Ltd. 3 cm 3 solvent. The reaction in the clay does not appear to be diffusion controlled.. Pallay.062 0. D. however. Stid-Chemie AG... Addition of dioxan to the reactive mixture should reduce the concentration of methanol somewhat in the interlayer space of the clay. i. Ballantine. A. M.4-dioxan 0. 5 cm 3 methanol and 4. The activity of A13+-montmorilloniteat 60~ is ~ 50% of that exhibited by an acidic ion-exchange resin similar to that used industrially.3 cm 3 solvent.e.. It is not immediately obvious why dioxan should be so useful a solvent.4-dioxan is mutually miscible with all reactants and products in the concentration range studied. characterization.. 1003-1004.007 0. Soc.e. Res. M. Martin. J. The solubility of isobutene in methanol and dioxan was found to be 0. E. respectively. and Graham. Ancillotti.4-dioxan is used as the solvent. E. and Thomas. (ECLP) and the British Technology Group for support. Anonymous (1967) Amberlyst 15 Synthetic Resin Catalyst: Rhom and Haas Co. (1983a) Catalysis by montmorillonites: Clay Miner.. and Romagnoni. J. if 1.2-3.602 Adams. 2 Reactions below were carried out at 60~ and used 1 g of A13+-montmorillonite (Wyoming) (12% RH). S.. Pennsylvania. and Pescarollo. and catalytic activity of beidellite-montmorillonitelayered silicates and their pillared analogues: aT. Chem. Comm. 37-48.55 1.2-dimethoxyethane Diethylene glycol diethyl ether n-pentane Tetrahydropyran N-methylmorpholine Tetrahydrofuran 1. The activation energy using such a catalyst is higher than when using the resin.4-dioxan 1. M. M. 44 and 25 kJ/mole. 4 pp. Adams et al. Chem. Thomas. Catal.5 g of AP+-montmorillonite(12% RH). and isobutene are m u tually soluble in the concentration ranges employed here. D. (1982) suggested that miscibility of reagents and solvent is important and that dioxan. Graham. E. E.... Adams. 1. water.. M. J. J. (1982) Synthesis of methyl-t-butyl ether from methanol and isobutene using a clay catalyst: Clays & Clay Minerals 30. When no solvent was employed. Adams. H. T.8 cm 3. L. and Graham. 129-134... and 18-58 mmole isobutene. Effectof solvent upon the rate of production of MTBE from methanol and isobutene.. 1. Philadelphia. J. and Graham. S. ACKNOWLEDGMENTS We thank English Clays Lovering Pochin and Co. if methanol was in excess. Mol. Chem.e. and Vajta. J. H.

176. Catal. (1982) Method of promoting the activity of cation-exchangeable layered clay and zeolite catalysts in proton-catalyzed reactions: European Patent Application 0045618A2. 5. 965-968. W.803. 4 pp. M.. R. and Tindwa. 26. J. Mol. L. (1983) Use of stabilized pillared inteflayered clays as catalysts in reactions capable of catalysis by protons: European Patent Application 0083970A1. J. J. and Ikawa. J. A.059. T. Bull. Eng. (1973) Modifying agents raising octane number of gasoline: Japan Kokai 73. MTBE from butane: Hydrocarbon Processing Int. and Floris. Y. J. 306. 98-102. Catal. Gregory. 91-95. 8789.23. S.. Y. J. E. (1981) Pillared interlayered clay products: U. and structure: Clays & Clay Minerals 16. 1980. Landau. and Rodriguez.. (1983) Synthesis ofmethyl tertiary butyl ether catalyzed by ion-exchange resin. Vaughan. S. and Raythatha. and Nishizawa. (1971) Dimerization of propylene and its uses for isoprene manufacture: J. Heyden. Morikawa. D..S. and Maggee. Lussier. A. F. Y. D. Nishizawa. (1980) MTBE technology: Chem. J. ed. Conf. (1974) Gasoline composition with high octane number: Japan Kokai 74. 22-28. 23 pp. AppL Chem. 27. and Watanabe. Catal. Mol. (1983) Physiochemical properties of montmorillonite interlayered with cationic oxyaluminum pillars: Clays & Clay Minerals 31. 351-352. M. (Received 31 May 1985. (1980) Preparation of molecular sieves based on pillared interlayered clays (PILC): inProe. andTorck. Mortland. 44 pp. G. Watanabe. K. and Pettman. World. Kobayashi. Gregory.. and Prakash. 83. Y. 59. (1984) On the pillaring and determination ofsmectite clay catalysts by polyoxocations of aluminium: J. 15. 17 pp. J. (1973) General and specific acid catalysis in sulphonic acid resin: J. Ed. exchangeable cation. Influence of methanol concentration and temperature: J. 1986 Methyl-t-butyl ether production using a montmorillonite catalyst 603 Gates. 34. S. (1952) Skeletal structure in thixotropic gels: Naturwissenschaften 89. J. K. Naples. 5 pp. D. F. Letters. Patent Application GB 2. and Westlake. p. Catal. 27-31. (1980) Now. and Maggee. T.. 56. R.K. C.A. T. No. H. Federal Republic of Germany. D.. Kamiyama. Rees. W.. accepted 19 February 1986. 195-212. 393-398. R. T. 169178. J. Purnell. Gupta. S. Norrish. U. M. R . Muddaris. 5. and Lussier.408A. Hojabri. Tokumaru.. Fahn. H .. Moro-oka. Gicquel.. E. Pinnavaia. 1491) . Zeolites. and Hofmann. B. R. C. 9 pp. R. E. Patent 4. C. (1979) Pillared interlayered clay materials useful as catalysts and sorbents: U. R.. and Wesflake. L. J .. Lussier. T. 31. D. (1968) Surface acidity of smectites in relation to hydration. Weiss. (1962) Effect of freezing on the swelling of clay minerals: Clay Min. 916.090. Wang. Ed. R. T. 27. G. Pecci.. 2. M. (1977) Ether ups anti-knock of gasoline: Hydrocarbon Processing Int. Occelli. J. and Raussell-Colom. 94-101. V. and Raman. 5th Int. Tzou. V. M. Y. M. 27-31.. 918. D. W.. A. Vaughan. London. J. Ms. J..Vol.. 21. R . Biotech. B. and Ballantine. J. (1984) Competitive intercalation and intercalary kinetics: J. (1983) Conversion of methanol to low molecular weight hydrocarbons over Ti ion-exchanged form of layered silicate minerals: Chem. Munich. W. Siid-Chemie AG (1985) K-Catalysts: Sfid-Chemie AG. Vaughan.

Sign up to vote on this title
UsefulNot useful