Clay catalyst, activated manufacture

Kaolin had little or no cracking activity, and catalyst activity as tested in the laboratory was directly related to silica-alumina gel content. However, the catalyst performed much better in commercial tests than anticipated from laboratory testing. Undoubtedly, this open structure encountered much less severe conditions at the outer surface of the microsphere during regenerations and made internal catalytic surfaces more readily available. This first of the so-called "semisynthetics" was called Nalco 783, and the matrix is still used in many forms some 28 years later.(7,13) Today it is estimated that some 200,000 tons/yr. of kaolin clay is used for cracking catalyst manufacture as reported by Georgia Kaolin Corporation.(24) Figure 10 shows the pore volume distribution for Nalco 783 and two other commercial semisynthetics from that period. 

In 1940, Houdry Process Corporation initiated commercial manufacture of a synthetic silica-alumina catalyst at Paulsboro, New Jersey (133). The synthetic catalyst is produced in pellet form (51,265) and contains 12 to 13% alumina (221,276). It has the advantages of controlled chemical composition, higher purity, and greater heat stability, but is more expensive than the activated-clay catalyst. 

Preferred bentonite clays are those whose chief constituent is mont-morillonite, a mineral of the composition corresponding to the empirical formula, 4Si02-Al203 H20. The principal sources of raw clay for the manufacture of the presently most widely used natural catalyst (Filtrol Corporation) are deposits in Arizona and Mississippi. The clay from these deposits contains appreciable amounts of impurities, principally CaO, MgO, and Fe203, which replace part of the A1203 in the ideal montmorillonite structure. The catalyst is prepared by leaching the raw clay with dilute sulfuric acid until about half of the alumina and associated impurities is removed. The resulting product is then washed, partially dried, and extruded into pellets, after which it is activated by calcination. A typical analysis of the finished catalyst is as follows (Mills, 12). 

The high-specific-surface-area supports (10 to 100 m /g or more) are natural or manufactured materials that normally are handled as fine powders. When processed into the finished catalyst pellet, these materials often give rise to pore size distributions of the macro-micro type mentioned previously. The micropores exist within the powder itself, and the macropores are created between the fine particles when they are compressed together in a pellet press. Diatomaceous earth and pumice (or cellular lava) are naturally occurring low-cost materials that are representative of this class of catalyst support. Among the synthetic carriers that can be created by modem technology are those derived from clays, bauxite, activated carbon, and xerogels of silica gel and alumina gel. 

Remarkably, seventy years after Houdry s utilization of the catalytic properties of activated clay and the subsequent development of ci ystalline aluminosilicate catalysts that arc a magnitude more catalytically active, the same fundamental principles remain the basis for the modern manufacture of gasoline, heating oils, and petrochemicals. 

The filler is a clay incorporated into the catalyst to dilute its activity. Kaoline [A. 2(OH)2, Si205] is the most common clay used in the FCC catalyst. One FCC catalyst manufacturer uses kaoline clay as a skeleton to grow the zeolite in situ. 

In the manufacturing of USY catalyst, the zeolite, clay, and binder are slurried together. If the binder is not active, an alumina component having catalytic properties may also be added. The well-mixed slurry solution is then fed to a spray dryer. The function of a spray dryer is to form microspheres by evaporating the slurry solution, through the use of atomizers, in the presence of hot air. The type of spray dr er and the drying conditions determine the size and distribution of catalyst particles. 

Catalyst-manufacturing methods can be classified into two broad categories. In one, a naturally occurring solid material is treated to alter its physical or chemical properties. The treated solids are sometimes referred to as natural catalysts. These include the Filtrol activated clays and the bauxite Cycloversion catalyst. In the other category of methods, the solid catalyst is produced synthetically by interaction of aqueous solutions of the raw materials. 

Acylation of 2-methoxynaphthalene with acetic anhydride was carried out using different solid acid catalysts such as zeolites, acid activated clays, ion exchange resins and sulphated zirconia. The products of the reaction are precursors of many organic and pharmaceutical intermediates. For example, the para isomer of the reaction product, 6-methoxy-2-naphthalene-a-methyl ketone is useful as a raw material for the manufacture of well-known anti-inflammatory dru called naproxen. The reaction products were isolated and confirmed by their melting points, H-NMR, gas chromatography, etc. 

Methyl terf-butyl ether (MTBE) is an important industrial product used as oxygenate additive in reformulated gasoline. Environmental concern makes its future uncertain, however. Although mainly manufactured by reaction of isobutylene with methanol, it is also produced commercially from methanol and fcrr-butyl alcohol, a by-product of propylene oxide manufacture. Numerous observations from the use of heteropoly acids have been reported. These compounds were used either as neat acids [74], or supported on oxides [75], silica or K-10 montmorillonite [76]. They were also used in silica-included form [77] and as acidic cesium salts [74,77]. Other catalysts studied were sulfated ZrOj [76], Amberlyst 15 ion-exchange resin [76], HZSM-5 [76], HF-treated montmorillonite, and commercial mineral acid-activated clays [75]. Hydrogen fluoride-treatment of montmorillonite has been shown to furnish particularly active and stable acid sites thereby ensuring high MTBE selectivity (up to 94% at 413 K) [75]. 

Union Carbide discovered X Y zeolites but it remained to Plank and Rosinski (1964, Mobil Oil) to apply these zeolites to clay or silica alumina-based FCC catalysts and thereby achieve a considerable boost to activity and selectivity. It is pleasing to note that Plank and Rosinski were introduced to the US patent office inventors Hall of Fame for this discovery (Figures 22-24) Table VI documents of history of FCC catalyst manufacture. 

A viable process for manufacturing polyolefin-clay nanocomposifes by in situ polymerization requires adequate catalytic activity, desirable polymer microstructure, and physical properties including processibility, a high level of clay exfoliation fhaf remains stable under processing conditions and, preferably, inexpensive catalysf components. The work described in the previous two sections focused on achieving in situ polymerization with clay-supported transition metal complexes, and there was less emphasis on optimization of polymer properties and/or clay dispersion. Since 2000, many more comprehensive studies have been undertaken that attempt to characterize and optimize the entire system, from the supported catalyst to the nanocomposite material. The remainder of this chapter covers work published in the past decade on clay-polyolefin nanocomposites of ethylene and propylene homopolymers, as well as their copolymers, made by in situ polymerization. The emphasis is on the catalyst compositions and catalyst-clay interactions that determine the success of one-step methods to synthesize polyolefins with enhanced physical properties. 

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