Molecular sieves containing transition

Perego G, Millini R and Bellussi G 1998 Synthesis and characterization of molecular sieves containing transition metals in the framework Moiecuiar Sieves Science and Technoiogy vol 1, ed FI G Karge and J Weitkamp (Berlin ... 

Physico-chemical and catalytic properties of MCM-41 mesoporous molecular sieves containing transition metals (Cu, Ni, and Nb)... 

Perego, G., Millini, R. and Bellussi, G. (1998) Synthesis and Characterization of Molecular Sieves Containing Transition Metals in the Framework (eds H.G. 

Synthesis and Characterization of Molecular Sieves Containing Transition Metals in the Framework... 

The synthesis of molecular sieves containing transition metals in the framework represents a reliable route for preparing materials with novel catalytic properties. In spite of the large number of papers and patents claiming the incorporation of several transition metal ions in different microporous silica frameworks, unambiguous evidence in favor of the isomorphous substitution of silicon has been achieved only for Ti and Fe, for the former limited to few framework types. Some evidence exists also for V and Cr, but the data available do not allow definite conclusions to be drawn in this regard. 

Copper hydroxyphosphate also allows the direct hydroxylation of 2,3,6-TMP, leading to selectivities for TMHQ (1) of >80%. The main by-product is TMQ (5). Heterogeneous catalysts which have been used for the oxidation of 3 include zeolites, mesoporous materials and molecular sieves contaiiung transition metals. Molecular sieves containing transition metals such as vanadium or copper in the framework can simply be mixed with 2,3,6-TMP and H2O2 in acetoiutrile for the oxidation. ... 

Nickel aluminate, a spinel, has long been known to trap nickel. Metals like arsenic(19), antimony(20-21) and bismuth(20) are known to passivate transition elements and can be used to decrease and coke make. Sulfur is also a known inhibitor for nickel therefore, higher sulfur-containing crudes may be a little less sensitive to nickel poisoning. In our work we also found that nickel at low concentrations is actually a slight promoter of the cracking reaction when incorporated into a molecular sieve (Figure 17). 

Synthesis of transition metal containing molecular sieves (microporous as well as mesoporous) is one of the fastest developing areas in molecular sieve science, as evidenced by recent published reviews [1,2] Several transition metals have been substituted into crystalline silica or aluminophosphate frameworks to yield the corresponding metallosilicate or metalloaluminophosphate molecular sieves, However, the location of the metal species and their state always remain uncertain, despite the employment of numerous different characterization methods comprising IR, NMR and ESR spectroscopy. 

One coordination of bare Mn2+ ions was reported by Kevan et al. in (A1)MCM-41 [4], Because Co2+ spectra of type a and (3 are very different from the spectrum of tetrahedral Co2+ ion, none Co2+ ions were incorporated into framework position. Thus, the discrepancy in the number of reported cationic sites in Ref. [4] and in this work should reflect different metal loading in molecular sieve or differences in its chemical composition (Si/Al ratio). As it was already mentioned, population of transition metals in individa) cationic sites depends on the metal loading. The effect of the Si/Al ratio was not studied for MCM-41 matrix, but is well known for pentasil containing zeolites [1]. 

The oxidation of aniline was carried out in the liquid phase over a series of transition metal - substituted molecular sieves. For low oxidant/aniline ratios, azoxybenzene (AZY) was the major product formed over Ti-containing catalysts, the reaction was limited by diffusion for medium pore zeolites like TS-l and mesoporous silicas were preferred as they permitted the use of both H2O2 and tert-butyl hydroperoxide as oxidants. Higher oxidant/aniline ratios (>2) led to the formation of nitrobenzene (NB), whose selectivity was proportional to the catalyst concentration. In contrast, vanadium containing molecular sieves were only active with TBHP and aniline was converted very selectively into nitrobenzene for all oxidant concentrations. 

In the present paper, we report some aspects of the oxidation of aniline with various peroxides over a series of transition metal - containing molecular sieves having different structures. The influence of the catalyst structure, of the nature and concentration of the peroxide and of the incorporated metal are discussed. 

The as-synthesized and calcined CrAPO-5 and CrS-1 were characterized by XRD which showed that the samples were pure and had an API and MFI structure respectively. ICP analysis showed that both catalysts contained about 1 % chromium. The results observed in the decomposition of cyclohexenyl hydroperoxide over several redox active moleular sieves are presented in Table 1. CrAPO-5 and CrS-1 displayed rougly equal activity and selectivity in the decomposition of cyclohexenyl hydroperoxide. Blank reactions carried out with Silicalite-1 (S-1) and silicon incorporated Aluminophosphate-5 (SAPO-5) show low conversions confirming that the chromium was responsible for the catalysis. Other transition- metal subsituted molecular sieves showed low conversions. 

Since the incorporation of transition metals into the frameworks of zeolites or micro-porous ahiminophosphates to form heteroatom-containing molecular sieves with important application values, the synthesis, structure, and characterization of microporous transition metal phosphates have been extensively studied in the last decade. In particular, because transition metal cations possess redox and coordination features, they are a kind of catalytic material with useful applications, and promise potential... 

Most crystalline aluminosilicates have little intrinsic catalytic activity for hydrogenation reactions. However, a considerable amount of data has recently accumulated on the use of zero-valent metal-containing zeolites in many hydrocarbon transformations. Thus noble and transition metal molecular sieve catalysts active in hydrogenation (7,256-760), hydroisomerization (161-165), hydrodealkylation (157, 158,165-167), hydrocracking (168,169), and related processes have been prepared. Since a detailed discussion of this class of reactions is beyond the scope of this review, only a few comments on preparation and molecular-shape selectivity will be made. 

In the present study, silicon and transition metal substituted aluminophosphate molecular sieves have also been evaluated for activity and selectivity for para-xylene production via Cg aromatic isomerization. In commercial practice, Cg aromatic cuts are obtained from reformate gasoline and from pyrolysis naphtha streams. Both feeds contain a significant fraction of ethylbenzene which is difficult to separate from xylenes by physical techniques,... 

The catalytic properties of the aluminophosphate molecular sieves are also influenced by chemical composition. The introduction of transition metals into framework positions enhances the activity and selectivity for olefin isomerization relative to the silicoaluminophosphates. The transition metal containing aluminophosphates are also surprisingly more selective for Cs aromatic rearrangements than the corresponding SAPO molecular sieves, an effect which can not be attributed solely to improved shape selectivity. 

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