Pillared cracking

Pillared clays are smectite minerals or iUite-smectite minerals that have been stmcturaHy modified to contain pillars of stable inorganic oxide. The pillars prop open the smectite stmcture so they have a basal space of approximately 3.0 nm. Typical metals in the pillars include Al, Zr, Ti, Ce, and Fe, and these materials are used in catalytic processes to crack heavy cmde oils (110—112). 

MCM-22, with a larger pore volume than ZSM-5, revealed behavior intermediate between what was observed for large- and medium-pore zeolites (126). Unverricht et al. (141) also examined MCM-22 at 353 and 393 K, it was found to produce mainly cracked products and dimethylhexanes and to deactivate rapidly. MCM-36 gained considerable interest that is evidenced by the patent literature (171-174). MCM-36 is a pillared zeolite based on the structure of MCM-22. Ideally, it should contain mesopores between layers of MCM-22 crystallites. This structure was found to be much more active and stable than MCM-22 (175). Alkane cracking experiments with zeolites having various pore dimensions evidenced the preference of monomolecular over sterically more demanding bimolecular pathways, such as hydride transfer, in small- and medium-pore zeolites (146). 

Ti(3,10). Interest in pillared clays was increased by the report (11) that they were more active than Y zeolites for the catalytic conversion of bulky molecules. Indeed, Lussier et al (3 ) observed a good activity for cracking of a heavy gas oil, and Occelli (13) reported a gasoline yield comparable to that of zeolites using a... 

Table 4 Catalytic properties of pillared clays in the cracking of an heavy gas oil. Select vities are expressed in wt%.

In conclusion, pillared clays catalysts are not as good as initially predicted for the cracking of heavy gas oils, mainly because of the iron contamination of natural clays. There is a probability that they could be applied for the conversion of hydrotreated gas oils, giving a slightly lower gasoline yield, but higher octane number than REY zeolites. 

Effect of Aging of Pillaring Reagent on the Microstnicture and Cracking Activi of Pillared Clay... 

Aging of hydroxyalumlnum polycation solutions used to prepare pillared clays affects the properties. Including surface area and cracking activity, of these pillared clays. The effects were correlated with the state of hydrolysis of the aged solutions. Dilution of the pillaring reagent, Chlorhydrol, causes depolymerlzatlon of polycations present In this reagent and the formation of new polycations which react to form the pillared clay. 

Lower dilution levels did not allow sufficient depolymerlzatlon and higher dilution caused excessive depolymerlzatlon In the aged solutions. Pillared clays prepared from aged dilute solutions had an enhanced microstructure which showed an Increased activity for selectively cracking large molecules to the light cycle oil range. This microstructure Is lost In the presence of steam which also reduces the formation of catalytic coke. Addition of rare earth zeolite to pillared clay can partially overcome the effects of this loss of microstructure. 

In this section we first describe the results of measurements made on fresh and aged solutions. Potentlometric, pH, measurements, which Indicate the extent of hydrolysis of the aluminum Ions, were made on all solutions during the aging process. Next, we report surface areas of pillared clays made from the aged solutions. Finally, we will discuss the cracking activities of some selected pillared clay samples. 

Cracking Activity. In the previous section, we demonstrated that aging conditions affect the surface area of pillared clays. Here, we discuss the cracking activities of some selected aged PILCs. 

The acidic properties of alumina pillared clays have been extensively studied from the interest in using the pillared clays as cracking catalysts [21-24]. Sakurai et al. [25] studied the acidic properties of the alumina pillared clays with different kinds of silicate layers and concluded that the alumina pillars between the silicate layers did not have any acidity and that the role played by the pillars was only to make the original acidity of the silicate interlayers more easily accessible through opening the interlayer spaces. 

The Effects of Iron Impurities on the Cracking Properties of Pillared Clays... 

Iron impurities in clays have been thought responsible for these type of catalysts low carbon selectivity (4,5). The purpose of this paper is to investigate and report the influence that the location, chemical state and environment of iron impurities have on the cracking properties of pillared clays prepared by reacting several smectites with aluminum chlorhydroxide solutions. 

Table 2. Microactivity test results for several pillared clay catalysts after calcination in air at 400 C for lOh. The zeolitic cracking catalyst has been aoed for 5 hours at 760 C with 100% steam at 1 atm. ...

At MAT conditions, montmorilIonites pillared with alumina clusters, and having similar surface area, generate (at a given conversion level) similar amounts of coke (when used to crack gas oil) irrespective of the iron content of the parent bentonite. Thus, the presence of iron cannot be used to explain the high tendency for coke (and light gas) make of pillared clay catalysts. 

The activity advantage of zeolite catalysts over amorphous silica-alumina has well been documented, Weisz and his associates [1] reported that faujasite Y zeolite showed 10 to 10 times greater activity for the cracking of n-hexane than silica-alumina. Wang and Lunsford et al. [2] also noted that acidic Y zeolites were active for the disproportionation of toluene while silica-alumina was inactive. The activity difference between zeolite and silica-alumina has been attributed to their acidic properties. It is, however, difficult to explain the superactivity of zeolite relative to silica-alumina on the basis of acidity, since the number of acid sites of Y-type zeolite is only about 10 times larger than that of silica-alumina. To account for it, Wang et al. [2] proposed that the microporous structure of zeolite enhanced the concentration of reactant molecules at the acid sites. The purpose of the present work is to show that such a microporous effect is valid for pillared clay catalysts. 

More recently, various attempts have been made to develop cracking catalysts from pillared smectite clays, in which the layers are separated and held apart by the intercalation of large cations. Pillared clays (PILCs) have large surface areas within fairly well-ordered micropore structures (pore widths in die approximate range 0.6-1.2 nm). It is not surprising that these materials have attracted considerable interest with the prospect of an alternative type of catalytic shape selectivity (Thomas, 1994 Thomas etal., 1997 Fripiat, 1997). 

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