H-mordenite

For cumene production (from benzene and propene) a new process has been developed in which H-mordenite (with high Si/Al) serves as the catalyst. Here the... 

Selective synthesis of ethylenediamine from ethanolamine over modified H-mordenite catalyst... 

Experiments were carried out using isotopically labelled methanol (97% 0) and ethanol (98% purchased from MSD Isotopes. Anhydrous isobutanol was purchased from Aldrich Chemical Co., Inc. and contained the natural abimdances of orygen isotopes, i.e. 99.8% and 0.2% O. Nafion-H was obtained fi om C. G. Processing, Inc. and Amberlyst resins were provided by Rohm and Haas. The 2SM-5 zeolite was provided by Mobil Research Development Corp. H-Mordenite, montmorillonite K-10, and silica-alumina 980 were obtained firom Norton, Aldrich, and Davison, respectively. y-AIumina was prepared from Catapal-B fi om Vista. 

The probe reaction utilized a 1/1 molar mixture of methanol and isobutanol over H-mordenite, a strongly acidic zeolite comprised of linear one-dimensional channels made up of 12-ring 6.5 by 7.0 A windows [8]. There is a side-pocket system in H-... 

The results in Table 3 show that H-mordenite has a high selectivity and activity for dehydration of methanol to dimethylether. At 150°C, 1.66 mol/kg catal/hr or 95% of the methanol had been converted to dimethylether. This rate is consistent with that foimd by Bandiera and Naccache [10] for dehydration of methanol only over H-mordenite, 1.4 mol/kg catal/hr, when extrt lat to 150°C. At the same time, only 0.076 mol/kg catal/hr or 4% of the isobutanol present has been converted. In contrast, over the HZSM-5 zeolite, both methanol and isobutanol are converted. In fact, at 175 X, isobutanol conversion was higher than methanol conversion over HZSM-5. This presents a seemingly paradoxical case of shape selectivity. H-Mordenite, the zeolite with the larger channels, selectively dehydrates the smaller alcohol in the 1/1 methanol/ isobutanol mixture. HZSM-5, with smaller diameter pores, shows no such selectivity. In the absence of methanol, under the same conditions at 15(fC, isobutanol reacted over H-mordenite at the rate of 0.13 mol/kg catal/hr, higher than in the presence of methanol, but still far less than over H M-5 or other catalysts in this study. 

Space time yields of products formed over H-mordenite and HZSM-5 from a methanol/isobutanol = 1/1 reactant mixture (1.72 mol/kg catal/hr of each) at 0.1 MPa. 

The plausible cause of shape selectivity to DME in H-mordenite is the presence of the active protons wittun the side-pockets of mordenite that are accessible only to methanol. The protonated methanol molecule, a methyl oxonium ion, undergoes rear-attack by a second methanol molecule entering the side-pocket from the main channel... 

Conclusive evidence has been presented that surface-catalyzed coupling of alcohols to ethers proceeds predominantly the S 2 pathway, in which product composition, oxygen retention, and chiral inversion is controlled 1 "competitive double parkir of reactant alcohols or by transition state shape selectivity. These two features afforded by the use of solid add catalysts result in selectivities that are superior to solution reactions. High resolution XPS data demonstrate that Brpnsted add centers activate the alcohols for ether synthesis over sulfonic add resins, and the reaction conditions in zeolites indicate that Brpnsted adds are active centers therein, too. Two different shape-selectivity effects on the alcohol coupling pathway were observed herein transition-state constraint in HZSM-5 and reactant approach constraint in H-mordenite. None of these effects is a molecular sieving of the reactant molecules in the main zeolite channels, as both methanol and isobutanol have dimensions smaller than the main channel diameters in ZSM-S and mordenite. 

The concept of extractive reaction, which was conceived over 40 years ago, has connections with acid hydrolysis of pentosans in an aqueous medium to give furfural, which readily polymerizes in the presence of an acid. The use of a water-immiscible solvent, such as tetralin allows the labile furfural to be extracted and thus prevents polymerization, increases the yield, and improves the recovery procedures. In the recent past an interesting and useful method has been suggested by Rivalier et al. (1995) for acid-catalysed dehydration of hexoses to 5-hydroxy methyl furfural. Here, a new solid-liquid-liquid extractor reactor has been suggested with zeolites in protonic form like H-Y-faujasite, H-mordenite, H-beta, and H-ZSM-5, in suspension in the aqueous phase and with simultaneous extraction of the intermediate product with a solvent, like methyl Aobutyl ketone, circulating countercurrently. 

Sheldon and co-workers (Elings et al, 1995) have used H-Mordenite to rearrange allyl phenyl ether to 2-allyl phenol and subsequent cyclysation to 2-methyl dihydrobenzofuran. 

This chapter compares the reaction of gas-phase methylation of phenol with methanol in basic and in acid catalysis, with the aim of investigating how the transformations occurring on methanol affect the catalytic performance and the reaction mechanism. It is proposed that with the basic catalyst, Mg/Fe/0, the tme alkylating agent is formaldehyde, obtained by dehydrogenation of methanol. Formaldehyde reacts with phenol to yield salicyl alcohol, which rapidly dehydrogenates to salicyladehyde. The latter was isolated in tests made by feeding directly a formalin/phenol aqueous solution. Salicylaldehyde then transforms to o-cresol, the main product of the basic-catalyzed methylation of phenol, likely by means of an intramolecular H-transfer with formaldehyde. With an acid catalyst, H-mordenite, the main products were anisole and cresols moreover, methanol was transformed to alkylaromatics. 

Figures 44.1 and 44.2 report the performance in the gas-phase phenol methylation of the H-mordenite and of the Mg/Fe/O catalyst, respectively. The differences between the two catalysts concerned both the transformations occurring on methanol and the type of phenolic products obtained. The H-mordenite was very active at 350°C the conversion of phenol was 80%. A further increase of temperature led to a decrease of conversion. This can be attributed to a progressive deactivation of the catalyst, due to...

Figure 44.3. Conversion of methanol (O), yields of alkylaromaties (A) and yields to light componnds (CO + CO2 + CH4) (O) as functions of temperature. Feed composition (molar fractions) methanol 0.12, nitrogen 0.88. Catalyst H-mordenite.

Figure 44.5. Conversion of phenol ( ), molar selectivity to anisole (X), o-cresol (O), p-cresol (A), 2,6-xylenol (O), salicylaldehyde ( ) and polyalkylated phenols ( ) as functions of temperature. Catalyst H-mordenite. Feed composition N2 89.3%, formaldehyde 1.7%, phenol 0.46%, methanol 0.03% and water 8.5%.

Satsuma, A., Enjoji, T., Shimizu, K.I. et al. (1998) Reactivity of surface nitrate species in the selective reduction of NO with propene over Na-H-mordenite as investigated by dynamic FTIR spectroscopy,./. Chem. Soc., Faraday Trans., 94, 301. 

The three-function model introduced in the preceding section has been established on an H-mordenite (HMOR) supported cobalt—palladium catalyst [12], For the sake of demonstration, model catalysts with a unique function, i.e. FI, F2 or F3, (Figure 5.1), were prepared to separately give evidence of the major role of each active site (Figure 5.1). Let us note that three functions does not necessarily mean three different active sites, but in the case of CoPd/HMOR material, three different sites were identified. 

The results indicate that the zeolite can selectively extract specific compounds from the reaction medium, due to the different affinity towards each of them. This makes possible to develop reactant concentrations inside pores which are different from the bulk ones. This property is a function of the zeolite hydrophobic characteristics, which are affected by the Si/Al ratio. The best zeolite is that one which does not interact too strongly neither with more polar molecules, so to allow activation of formaldehyde to proceed faster, nor with the least polar ones. The intermediate Si/Al ratio in H-mordenites is able to develop the optimal concentration ratio between reactants inside the pores, and to reach the highest yield to vanillols. 

Figure 2 Conversion of guaiacol (X), selectivity to vanillols (o), to monoaryl by-products (v) and to diaryl by-products (ct) as functions of the Si/AI ratio of H-mordenites. Reaction time, 2 h other reaction conditions as in Figure 1. H-mordenites were supplied by Engelhard.

The NO spectrum has now been studied for the molecule adsorbed on ZnO, ZnS (18), 7-AI2O3, silica-alumina, silica-magnesia (20), an A-type zeolite (97), H-mordenite (98), and a variety of Y-type zeolites including NaY (19), MgY, CaY, BaY, SrY (81), decationated-Y (19), ScY, LaY, and A1HY (99). The nitric oxide molecule has mainly been used as a... 

DRIFT spectroscopy was used to determine Av0h shifts, induced by adsorption of N2 and hexane for zeolite H-ZSM-5 (ZSM-a and ZSM-b, Si/Al=15.5 and 26), H-mordenite (Mor-a and Mor-b, Si/AI— 6.8 and 10) and H-Y (Y-a and Y-b, Si/Al=2.5 and 10.4) samples. Catalysts were activated in 02 flow at 773 K in situ in the DRIFTS cell and contacted than with N2 at pressures up to 9 bar at 298 K or with 6.1% hexane/He mixture at 553 K, i.e., under reaction conditions. Catalytic activities of the solids were measured in a flow-through microreactor and kapp was obtained as slope of -ln(l-X0) vs. W/F plots. The concentration of Bronsted acid sites was determined by measuring the NH4+ ion-exchange capacity of the zeolite. The site specific apparent rate constant, TOFBapp, was obtained as the ratio of kapp and the concentration of Bronsted acid sites. 

An early report from Shukla et al.129 showed efficient hydrolysis and isomerization reactions of disaccharides, including cellobiose, maltose, and lactose, over zeolites type A, X, and Y. Abbadi et al.130 studied the hydrolysis of maltose, amylose, and starch over the zeolitic materials H-mordenite, H-beta, and mesoporous MCM-41. The effect of temperature and pressure, as well as that of the Si/Al ratio of H-mordenite and H-beta zeolites, on their catalytic activity was investigated for the... 

The presence o a large pore zeolite, H-mordenite, reduced the end point of only slightly. Moraromatics with substantial amount of C q aromatics, but it deactivated very rapidly. 

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