Chromium silicalite

Table 4.4 Chromium silicalite cleavage of styrene with aqueous hydrogen...

The following catalyst preparations are described phosphotungstic acid on y-aiumina, ammonium molybdate on a cross-linked polystyrene anionic exchange resin, metal(IV) phosphates, and chromium silicalite. 

We thank the Organic Chemistry Group at Widnes R D. We also wish to thank our university collaborators, particularly Professor Bob Johnstone, and Dr. Preciosa Pires (Liverpool University, metal(IV) phosphates), Professor Bill Griffith, and Dr. Melanie Gresley (Imperial College, immobilized polyoxometalates). Professor Roger Sheldon, and Dr. Jihad Dakka (Delft University, chromium silicalite). 

Similarly, the CrAPO-5- and chromium silicalite-1 (CrS-l)-catalyzed oxidation of aromatic side-chains with TBHP or O2 as the primary oxidant [27-31] almost certainly arises as a result of soluble chromium(VI) leached from the catalyst. The same probably applies to benzylic oxidations with TBHP catalyzed by chromium-pillared montmorillonite [32]. More recently, a chromium Schiff s base complex tethered to the mesoporous silica, MCM-41, was claimed [33] to be an active and stable catalyst for the autoxidation of alkylaromatic side-chains. It would seem unlikely, however, that Schiff s base ligands can survive autoxidation conditions. Indeed, on the basis of our experience with chromium-substituted molecular sieves we consider it unlikely that a heterogeneous chromium catalyst can be developed that is both active and stable to leaching under normal oxidizing conditions with O2 or RO2H in the liquid phase. Similarly, vanadium-substituted molecular sieves are also unstable towards leaching under oxidizing conditions in the liquid phase [6,34]. 

Singh, A. and Selvam, T. (1996). Liquid Phase Oxidation Reactions over Chromium Silicalite-1 (CrS-1) Molecular Sieves, J. Mol Catal A Chem., 113, pp. 489 97. 

Zhao, X. and Wang, X. (2010). Characterizations and Catalytic properties of chromium silicalite-2 prepared by direct hydrothermal synthesis and impregnation, Catal. Lett., 135, pp. 233-240. 

The presence of methylenic bands shifted at higher frequency in the very early stages of the polymerization reaction has also been reported by Nishimura and Thomas [114]. A few years later, Spoto et al. [30,77] reported an ethylene polymerization study on a Cr/silicalite, the aluminum-free ZSM-5 molecular sieve. This system is characterized by localized nests of hydroxyls [26,27,115], which can act as grafting centers for chromium ions, thus showing a definite propensity for the formation of mononuclear chromium species. In these samples two types of chromium are present those located in the internal nests and those located on the external surface. Besides the doublet at 2920-2850 cm two additional broad bands at 2931 and 2860 cm are observed. Even in this favorable case no evidence of CH3 groups was obtained [30,77]. The first doublet is assigned to the CH2 stretching mode of the chains formed on the external surface of the zeolite. The bands at 2931 and... 

Chromium-containing silicalite-2, CrS-2, has been synthesized and shown to catalyze similar reactions using TBHP as an oxidant [109]. Notably, TBHP has been reported to be an ineffective oxidant in TS-1 catalyzed oxidations [26]. However, it has been claimed that aTS-1-TBHP combination exhibits activity in the oxidative cleavage of the C=C double bond of silyl enol ethers to produce dicarboxylic acids [110]. 

The discovery in the early 80 s of titanium silicalites [62-64] opened the new application perspective of zeolitic materials as oxidation catalysts. Several reactions of partial oxidation of organic reactants using dilute solutions of hydrogen peroxide could for the first time be performed selectively in very mild conditions. Other elements inserted in the lattice of silicalites have since been shown to have similarly interesting catalytic properties including, vanadium, zirconium, chromium and more recently tin and arsenic [65]. Titanium silicalites with both MFI (TS-1) and MEL (TS-2) structures have however been the object of more attention and they still seem to display unmatched properties. Indeed some of these reactions like the oxyfunctionalization of alkanes [66-69] by H2O2 are not activated by other Ti containing catalysts (with the exception of Ti-Al-Beta [70]). The same situation... 

The demonstration by Enichem workers [1] that titanium silicalite (TS-1) catalyzes a variety of synthetically useful oxidations with 30% aqueous hydrogen was a major breakthrough in the field of zeolite catalysis [2], The success of TS-1 prompted a flourish of activity in the synthesis of other titanium-substituted molecular sieves, such as titanium silicalite-2 (TS-2) [3], Ti-ZSM-48 [4] Ti-Al-mordenite [5], Ti-Al-beta [6]and Ti-MCM-41 [7]. Moreover, this interest has also been extended to the synthesis of redox molecular sieves involving framework substitution by other metals, e.g. chromium, cobalt, vanadium, etc. [8]. 

The synthesis of cyclohexanone, which is an intermediate in the manufacture of nylon 6 and nylon 6,6 is an important industrial process [1], One of the major current routes for the synthesis of cyclohexanone is the liquid-phase autoxidation of cyclohexane at 125-160 °C and 10 bar followed by the selective decomposition of the intermediate cyclohexyl hydroperoxide, using a soluble cobalt catalyst, to a mixture of cyclohexanol and cyclohexanone [2]. These severe conditions are necessary due to the low reactivity of cyclohexane towards autoxidation. Due to the high reactivity of the products in the autoxidation step conversions must be kept low (<10%) [3,4]. Heterogeneous catalysts potentially offer several advantages over their homogeneous counterparts, for example, ease of recovery and recycling and enhanced stability. Recently we found that chromium substituted aluminophosphate-5 and chromium substituted silicalite-1 (CrS-1) are active, selective and recyclable catalysts for the decomposition of cyclohexyl hydroperoxide to cyclohexanone [5j. 

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. 

Powder X-ray profiles of silicalite-1 prepared by various research workers, during their preparation of molecular sieves by isomorphously substituting the T element by titanium, tin, zirconium, vanadium, chromium, molybdenum, differ in their crystallinity (80-95%) and their unit cell volume values (Table 1). It is obvious from the Table that whenever a metal ion is being substituted, a metal free all silica polymorph should also be prepared for deciphering the unit cell expansion. The variation in the unit cell volume obtained by various workers is an indication of the inherent problems in synthesising zeolites and molecular sieves with repeatable metal substitution in the framework. 

Successful application of DRS together with complementary methods like ESR, XRD, XAS, IR, SEM, NMR etc. for characterization of the synthesized micro-porous materials with respect to incorporation into the framework has been further reported for MFI-type vanadium silicalites [74, 75], for VAPO-5, MgAPO-5 and MgVAPO-5 [76], for MFI-type ferrisilicalite [77] and for insertion of chromium in a number of molecular sieves [78]. In the case of the latter, essentially nonframework species could be identified and even in Cr-silicalite and CrAPO-5 Cr + showed no tendency to change from octahedral to tetrahedral coordination. 

In this paper preliminary results of the synthesis and characterization of model composites, consisting of Si wafers covered with thin layers of chromium, manganese and iron oxide and a silicalite-1 coating are presented. 

Recently, Cr incorporation was claimed in silicalite-2 (CrS-2) prepared by heating at 170 °C an alkali-free gel containing TEOS, chromium nitrate and TBA-... 

As an example, the joint analysis of IR and Raman spectra provided evidence of the partial ordering of cations in a Fe-Cr corundum-type mixed sesquioxides, which are used industrially as high temperature water-gas shift catalysts, but are also active in olefin oxidative dehydrogenation. X-ray diffraction (XRD) patterns of these solids indicate the conmdum-type structure without any superstructure. This implies that iron and chromium ions are randomly distributed. IR and Raman spectra instead definitely show that cations are at least partially ordered in layers such as in the ilmenite-type superstructure. Similarly, XRD analysis shows a cubic (non-ferroelectric) structure of nanometric BaTi03, while vibrational spectroscopies reveal microscopic asymmetry of this structure. Similarly, IR spectroscopy allowed the determination of the state of vanadium in solid solution in Ti02 anatase catalysts, and the presence of Ti" + in the silicalite framework of TSl catalysts, " used for the selective oxidation of phenol and the ammoximation of cyclohexanone with hydrogen peroxide. 

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