Montmorillonite clays dehydration

Dehydration of 1-pentanol or 2-pentanol to the corresponding olefins has been accompHshed, in high purity and yields, by vapor-phase heterogeneous catalyzed processes using a variety of catalysts including neutral gamma —Al Og catalyst doped with an alkah metal (23), zinc aluminate (24,25), hthiated clays (26), Ca2(P0 2 montmorillonite clays (28). Dehydration of 2-methyl-1-butanol occurs over zinc aluminate catalyst at... 

Succinic acid. Succinic add is also available via fermentation of glucose, and has the potential to become a large-scale industrial chemical in the future. However, there are only a few reports on dehydration reactions involving succinic acids in the literature, and most of these are concerned with esterification to produce dialkyl esters. The synthesis of various dialkyl esters was reported using metal exchanged montmorillonite clays (Na, Mn ", ... 

There has been an enormous technological interest in tertfa/j-butanol (tBA) dehydration during the past thirty years, first as a primary route to methyl te/f-butyl ether (MTBE) (1) and more recently for the production of isooctane and polyisobutylene (2). A number of commercializable processes have been developed for isobutylene manufacture (eq 1) in both the USA and Japan (3,4). These processes typically involve either vapor-phase tBA dehydration over a silica-alumina catalyst at 260-370°C, or liquid-phase processing utilizing either homogenous (sulfonic acid), or solid acid catalysis (e.g. acidic cationic resins). More recently, tBA dehydration has been examined using silica-supported heteropoly acids (5), montmorillonite clays (6), titanosilicates (7), as well as the use of compressed liquid water (8). 

Interpretation of the mechanisms of the hydrocarbon desorption reactions mentioned above was considered (31,291) with due regard for the possible role of clay dehydration. While this water evolution process is not regarded as a heterogeneous catalytic reaction, it is at least possible that water loss occurs at an interface (293) so that estimations of preexponential factors per unit area can be made. On this assumption, Arrhenius parameters (in the units used throughout the present review) were calculated from the available observations in the literature and it was found (Fig. 9, Table V, S) that compensation trends were present in the kinetic data for the dehydration reactions of illite (+) (294), kaolinite ( ) (293,295 298), montmorillonite (x) (294) and muscovite (O) (299). If these surface reactions are at least partially reversible,... 

In order to further validate our in-situ approach, we have realised a dehydration/re-hydration cycle for Ca-Montmorillonite in the same conditions as for Tobermorite. As presented in Figure 6 , the clay dehydration occurs at constant atmospheric pressure with increasing temperature the interlayer distance shifts from 16 A to 11 A. The inverse process, rehydration, is easily obtained at 300 K by increasing the water vapour pressure the interlamellar distance first shifts from 11.5 A to 14 A for P/Po<0.2 at larger pressure the swelling is more progressive and easily detected as shown in Figure 6 . 

Etherification catalysts include mineral acids such as sulfuric and perchloric acid, but these tend to provide double the amounts of dehydration products compared with other catalysts. Lewis acids such as boron trifluoride and iron (Ill)-exchanged montmorillonite clays are also effective at catalyzing these reactions. Boron trifluoride provides the most consistent yields increases in catalyst concentration generally increase ether yields and/or reduce reaction times. Iron (III) clays provided high... 

MW-expedited dehydration reactions using montmorillonite K 10 clay [70] (Schs. 6.20 and 6.21) or Envirocat reagent, EPZG [71] (Schs. 6.20 and 6.21) have been demonstrated in a facile preparation of imines and enamines via the reactions of primary and secondary amines with aldehydes and ketones, respectively. The generation of polar transition state intermediates in such reactions and their enhanced... 

A simple montmorillonite K 10 clay surface is one among numerous acidic supports that have been explored for the Beckmann rearrangement of oximes (Scheme 6.27) [54]. However, the conditions are not adaptable for the aldoximes that are readily dehydrated to the corresponding nitriles under solventless conditions. Zinc chloride has been used in the above rearrangement for benzaldehyde and 2-hydroxyacetophe-none, the later being adapted for the synthesis of benzoxazoles. 

The role of structural Fe(III) In reactions with benzidine was also demonstrated by Mossbauer spectroscopy at very high adsorption levels (i.e., intercalation conditions) on montmorillonite (40). Upon dehydration of the clay, a yellow color and regeneration of Fe2+ to Fe3+ was observed. This was explained by the equilibria... 

The zeolite crystals are in the form of fine powders, which would cause a very high pressure drop in a packed bed. They have to be formed into granules of approximately 3 mm in diameter, by using clay binders, such as kaolinite and montmorillonite. The methods consist of pelletization with binders under pressure into short cylinders, wet extrusion with a fluid into continuous cylinders, and granulation by rolling with binders into spheres. They also need to be dehydrated and calcined to remove volatile components before use. 

The peculiar layer structure of these clays gives them cation exchange and intercalation properties that can be very useful. Molecules, such as water, and polar organic molecules, such as glycol, can easily intercalate between the layers and cause the clay to swell. Water enters the interlayer region as integral numbers of complete layers. Calcium montmorillonite usually has two layers of water molecules but the sodium form can have one, two, or three water layers this causes the interlayer spacing to increase stepwise from about 960 pm in the dehydrated clay to 1250, 1550, and 1900 pm as each successive layer of water forms. 

Clays are aluminosilicates with a two-dimensional or layered structure including the common sheet 2 1 alumino- and magnesium- silicates (montmorillonite, hectorite, micas, vermiculites) (figure 7.4) and 1 1 minerals (kaolinites, chlorites). These materials swell in water and polar solvents, up to the point where there remains no mutual interaction between the clay sheets. After dehydration below 393 K, the clay can be restored in its original state, however dehydration at higher temperatures causes irreversible collapse of the structure in the sense that the clay platelets are electrostatically bonded by dehydrated cations and exhibit no adsorption. 

Tennakoon et al. (1983) IR Clays, montmorillonite Dehydration, intercalation, phase stability + + + Alcohol intercalation at elevated pressures... 

There are more complicated structures nuermediate between pyrophyllite and talc with variable substitution of Al and Mg. ElectroneulraKty is maintained by hydrated cations between layers. Thus the montmorillonites arc unusual clays lorming thixotropic aqueous suspensions that arc used as well-drilling muds and in nondrip paints. They are derived from the formulation AUCOHliSi Oin-xH, with variable amounts of water, Mg " " (in place of some Al ). and compensating cations. M" (M = Ca in fuller s earth, which is converted to bentonite. M = Na). Vermiculile likewise has variable amounts of water and cations. It dehydrates (O a talc-like structure with much expansion when heated (see page 750). 

With fresh activated-clay catalyst, endothermic peaks are observed at temperatures of about 300, 1200, and 1600°F. These three peaks are attributed to loss of physically adsorbed water, loss of chemically bound (hydroxyl) water, and collapse of the montmorillonite structure, respectively. The hydroxyl water originally present amounts to 3 or 4%. The magnitude of the peak at 1200°F. decreases if the sample is heated above 800°F. prior to thermal analysis, and disappears completely if the sample is calcined at 1100°F. The thermal-analysis curve for the dehydrated catalyst is flat up to the point at which the montmorillonite structure begins to disappear. If the catalyst has not been heated above 1450°F., it becomes rehydrated upon exposure to moisture and a new endothermic peak appears in the curve between 800 and 1000°F. The size of the new peak increases as that of the original hydroxyl-water peak decreases it corresponds to 1.5 to 2.0% sorbed water with catalyst that has been rehydrated after calcination at 1100°F. The rehydration capacity of the catalyst decreases as the catalyst becomes partially deactivated with use. 

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