Pillared zeolite

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). 

Two categories of mesoporous solids are of special interest M41S type materials and pillared or delaminated derivatives of layered zeolite precursors (pillared zeolites in short). The M41S family, first reported in early 1990 s [1], has been extensively studied [2,3]. These materials exhibit broad structural and compositional diversity coupled with relative ease of preparation, which provides new opportunities for applications as catalysts, sorption and support media. The second class owes its existence to the discovery that some zeolite crystallizations can produce a lamellar intermediate phase, structurally resembling zeolites but lacking complete 3-dimensional connectivity in the as-synthesized form [4]. The complete zeolite framework is obtained from such layered zeolite precursor as the layers become fused, e.g. upon calcination. The layers posses zeolitic characteristics such as strong acidity and microporosity. Consequently, mesoporous solids derived from layered zeolite precursors have potentially attractive characteristics different from M41S and the zeolite species... 

This paper addresses two issues concerning practical aspects of synthesis and utility of pillared zeolites. First it shows how to demonstrate that the observed mesoporous attributes of a particular preparation are not due to undesired M41S contamination. This possibility arises because of the similarity of synthesis regime in both cases aluminosilicate substrates treated with cationic surfactant at high pH and temperature. Second issue concerns the benefits of pillaring zeolite precursor as manifested via improved catalytic performance. Herein we compare the properties of MCM-41 and the pillared zeolite MCM-36 obtained with cetyltrimethylammonium cation as the swelling/templating surfactant. 

Figure 1. Preparation of the pillared zeolite MCM-36. The pillars are shown schematically as ellipsoids, which do not represent the real props.

A great deal of research effort aimed at enlargement of the zeolite and zeotype structures resulted in numerous papers on the synthesis, properties, and characterization of delaminated and pillared zeolitic materials and mesoporous molecular sieves with amor-... 

Zhang XY, Liu DX, Xu DD, Asahina S, Cychosz KA, Agrawal KV, Wahedi YA, Bhan A, Hashimi SA, Terasaki O, Thommes M, Tsapatsis M (2012) Synthesis of Self-Pillared Zeolite Nanosheets by Repetitive Branching. Science 336 1684-1687... 

Preparation of Pillared Clay Catalysts. PAG products are used for the preparation of zeolite-like catalysts by intercalation, the insertion of Al polycations molecules between the alurninosiHcate sheets of clay (3,33). Aqueous clay suspensions are slowly added to vigorously stirred PAG solutions, and the reaction mixture is aged for several hours. The clay is separated from the PAG solution and washed free of chloride ion. The treated clay is first dried at low temperature and then calcined in air at 450—500°G, producing a high surface area material having a regular-sized pore opening of about 0.6 to... 

Pillared clays (MELS) are aLso covered in this review. MELS have three-dimensional network structure like zeolites, and, unlike clays, which have two-dimensional layered structures, pillared cationic and anionic clays have been studied. Phthalocyanins intercalated in anionic clays have given interesting results for wastewater purification (Vaccari, 1998). 

The hydroamination of alkenes has been performed in the presence of heterogeneous acidic catalysts such as zeolites, amorphous aluminosilicates, phosphates, mesoporous oxides, pillared interlayered clays (PILCs), amorphous oxides, acid-treated sheet silicates or NafioN-H resins. They can be used either under batch conditions or in continuous operation at high temperature (above 200°C) under high pressure (above 100 bar). 

Other metal oxide catalysts studied for the SCR-NH3 reaction include iron, copper, chromium and manganese oxides supported on various oxides, introduced into zeolite cavities or added to pillared-type clays. Copper catalysts and copper-nickel catalysts, in particular, show some advantages when NO—N02 mixtures are present in the feed and S02 is absent [31b], such as in the case of nitric acid plant tail emissions. The mechanism of NO reduction over copper- and manganese-based catalysts is different from that over vanadia—titania based catalysts. Scheme 1.1 reports the proposed mechanism of SCR-NH3 over Cu-alumina catalysts [31b],... 

The alkylation of phenol investigated over H-MCM-22, H-ITQ-2 and H-MCM-36 showed that the delamelation and pillaring did not improve the catalytic activity and this was explained on the secondary processes taking place during the preparation of the corresponding materials, and which strongly affect the total acidity and the acidity on the external surface. Also, the composition of the reaction products is not influenced to a considerable extent by product shape selectivity effects. This seems to show that the tert-butylation reaction preferentially proceed at (or close to) the external surface of the zeolite layers. 

The XRD patterns demonstrated that the MCM-22 zeolites were well crystallized and pillars have been created in the MCM-36 sample, respectively. Thus, the last material exhibited a typical intense peak at 29 2°, corresponding to a Aspacing of 4 nm. The textural properties of solids (Table 1) indicated that the pillaring in MCM-36 resulted in increases in BET specific surface area and external surface area compared with the MCM-22 zeolite. 

Patents assigned to Mobil (217) describe the use of boron trifluoride supported on several porous carriers. BF3 supported on silica was found to exhibit a slightly higher performance with added water in the alkylation of a mixed alkene feed at 273 K. It was also shown that self-alkylation activity was considerably lower than that with HF as catalyst. Another patent (218) describes the use of a pillared layered silicate, MCM-25, promoted with BF3 to give a high-quality alkylate at temperatures of about 273 K. BF3 was also supported on zeolite BEA, with adsorbed water still present (219). This composite catalyst exhibited low butene isomerization activity, which was evident from the inferior results obtained with 1-butene. At low reaction temperatures, the product quality was superior to that of HF alkylate. 

Auroux, A. (2002) Microcalorimetry methods to study the acidity and reactivity of zeolites. Pillared clays and mesoporous materials. Top. Catal., 19, 205-213. 

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... 

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