Zeolite offretite

Monodirectional 12 membered ring zeolites (offretite, L, mordenite and 0) are very inefficient as catalysts for formaldehyde benzene condensation to give diphenylmethane, esterification of phenylacetio acid with equimolar amounts of ethanol, Friedel-Crafts acylation of 3-phenylpropanoyl chloride with anisole and Claisen-Schmidt condensation of acetophenone with benzaldehyde. This fact has been attributed to diffusional constraints of organic compounds inside the channels. By contrast, the behaviour of the tridireotional f zeolite is very similar to that of dealuminated HY zeolites, inoreasing the turnover of the acid sites with the framework Si-to-Al ratio. 

The frameworks of zeolites offretite and erionite consist of layers of linked cancrinite and gmelinite cages arranged so that in the case of erionite the orientation of alternate layers blocks the 12MR chaimels whereas in offretite the channel is elear (7, 8). 

Experiments which have been carried out indicate that the results discussed above which have all been obtained on H-ZSM-5 zeolites are actually valid for all protonated zeolites. Experiments have so far been carried out on protonated ZSM-11, erionite, mordenite, faujasite (Y-zeolite), offretite, ferrierite and L-zeolite (ref. 4). Till now, all the the investigated zeolites have given fully concordant results. While they all exhibit the same behaviour as regards activation, their resistance to deactivation and their product spectrum are in many cases dramatically different. Offretite for instance deactivates almost completely after a couple of hours with high activity, and the dominant hydrocarbon, by far, is methane (ref. 4). 

This process carries out the vapor phase oxychlorination of ethane, in the presence of oxygen or air enriched with oxygen, between 350 and 450°C, and between Oil and 10.10 Pa absolute. It employs a catalyst system based on silver doped by derivatives of manganese, cobalt or nickel, and possibly of rare earths (such as lanthanum), and which is employed in mass form or supported on a Y-type zeolite (offretite). 

In situ NMR experiments of various types have been applied by several groups in an attempt to better understand MTG chemistry on HZSM-5 and other materials. Figure 11 shows results from a study by Anderson et al. on the reactions of methanol on the zeolite Offretite [24]. The catalyst was activated and loaded with 30 wt % methanol- C and sealed in a Pyrex capsule. The in situ experiment was performed by alternating between off-line heating steps and spectral acquisition at room temperature. Methanol was converted to dimethyl ether and then, after heating at 573 K for 10 minutes, to a mixture of hydrocarbons. 

Campana, L., Selloni, A., Weber, J., Goursot, A. (1997). Cation siting and dynamical properties of zeolite offretite from first-principles molecular dynamics. Journal of Physical Chemistry, 101, 9932. 

Figure C2.12.4. Typical polyhedra found in zeolites (a) sodalite cage found in sodalite, zeolite A or faujasite (b) cancrinite or a-cage found in cancrinite, erionite, offretite or gmelinite (c) the 5-ring polyhedron found in ZSM-5 and ZSM-11 (d) the large cavity of the faujasite stmcture and (e) the a-cage fonning the large cavity in zeolite A.

One of the earliest direct bonuses of imaging zeolitic catalysts by HRTEM was the discovery (10) that the nominally phase-pure ZSM-5 (structure code MFI) contained sub-unit-cell coherent intergrowths of ZSM-11 (MEL). It soon became apparent (46) that, depending on the mode of synthesis of these and other pentasil (zeolitic) catalysts, some specimens of ZSM-5 contained recurrent (regular) intergrowths of ZSM-11. It also emerged that intergrowths of offretite and erionite are features of both nominally phase-pure erionite and of pure offretite and of many members of the so-called ABC-6 family of zeolites (47). 

Zeolites are crystalline aluminosilicates with a regular pore structure. These materials have been used in major catalytic processes for a number of years. The application using the largest quantities of zeolites is FCC [102]. The zeolites with significant cracking activity are dealuminated Y zeolites that exhibit greatly increased hydrothermal stability, and are accordingly called ultrastable Y zeolites (USY), ZSM-5 (alternatively known as MFI), mordenite, offretite, and erionite [103]. 

The adsorption microcalorimetry has been also used to measure the heats of adsorption of ammonia and pyridine at 150°C on zeolites with variable offretite-erionite character [241]. The offretite sample (Si/Al = 3.9) exhibited only one population of sites with adsorption heats of NH3 near 155 kJ/mol. The presence of erionite domains in the crystals provoked the appearance of different acid site strengths and densities, as well as the presence of very strong acid sites attributed to the presence of extra-framework Al. In contrast, when the same adsorption experiments were repeated using pyridine, only crystals free from stacking faults, such as H-offretite, adsorbed this probe molecule. The presence of erionite domains in offretite drastically reduced pyridine adsorption. In crystals with erionite character, pyridine uptake could not be measured. Thus, it appears that chemisorption experiments with pyridine could serve as a diagnostic tool to quickly prove the existence of stacking faults in offretite-type crystals [241]. 

The isomorphous replacement of aluminum by gallium in the framework structure of zeolites (beta, MFI, offretite, faujasite) offers new opportunities for modified acidity and subsequently modified catalytic activity such as enhanced selectivity toward aromatic hydrocarbons [249,250]. The Ga + ions in zeolites can occupy tetrahedral framework sites (T) and nonframework cationic positions. 

Microcalorimetric experiments of NH3 adsorption have shown that the isomor-phous substitution of A1 with Ga in various zeolite frameworks (offretite, faujasite, beta) leads to reduced acid site strength, density, and distribution [250,252,253], To a lesser extent, a similar behavior has also been observed in the case of a MFI framework [51,254]. A drastic reduction in the acid site density of H,Ga-offretites has been reported, while the initial acid site strength remained high [248,250]. 

Matsuda and his co-workers examined the isopropylation of biphenyl over H-offretite and SAPO-ll.52 H-Offretite has pore size of 0.67x0.68 nm, but its pores have cages in the channels.30 SAPO-ll has pores of 0.63x0.39 nm.30 H-Offretite was less selective for the formation of 4,4 -DIPB than HM although their catalytic activities were comparable. SAPO-ll exhibited a comparable selectivity for 4,4 -DIPB to HM although catalytic activity was low. The formation of 4,4 -DIPB over these two zeolites was shape-selective compared to the thermodynamically attainable level. 

Among the early investigations of methanol adsorption and conversion on acidic zeolites, most of the H and C MAS NMR experiments were performed under batch reaction conditions with glass inserts in which the catalyst samples were fused. Zeolites HZSM-5 76a,204,206,264-272), HY 71,72), H-EMT 273), HZSM-12 274), HZSM-23 275), H-erionite 275), H-mordenite 271,272), and H-offretite 275,276), silicoaluminophosphates H-SAPO-5 271,274), H-SAPO-11 274), and H-SAPO-34 76,277,278), as well as montemorillonite 279) and saponite 279) were investigated as catalysts. 

Table VII (51). The relevant free dimensions are often similar for zeolite and nonzeolite. Urea (free diameter 5.2 A) is like Sieve A (free diameter of windows 4.3 A) in accommodating n- but not isoparaffins. Thiourea (6.1 A) and offretite (6.3 A) have channels with similar free diameters as do 0-cyclodextrin (7-8 A) and zeolite L (7.1 X 7.8 A). In thiourea the loose fit of n-paraffins in the tunnel appears to destabilize the adducts (85, 36). The same is true of disc-shaped molecules comprising only benzenoid rings. However, if suitably bulky saturated side chains are attached (cyclohexyl-benzene or fertf-butylbenzene), then adduction readily occurs. Heterocy-clics, like unsubstituted aromatics, do not readily form adducts. Thus flat molecules also exert a destabilizing effect upon the tunnels of a circular cross section. Such stability problems do not arise with the robust, permanent zeolite structures, and this constitutes an interesting distinction. Offretite, for example, readily sorbs benzene or heterocyclics with or without alkyl side chains, provided only that they are not too large to permeate the structure.

Because of the high surface free energy at the liquid-solid interface, it is suggested that the stages of nucleation, transport of species by surface diffusion, and crystallization occur at the interface in the boundary layer. Culfaz and Sand in this volume (48) propose a mechanism with nucleation at the solid-liquid interface. This mechanism should be most evident in more concentrated gel systems where interparticle contact is maximized for aggregation, coalescence, or ripening processes. The epitaxy observed by Kerr et al. (84) in cocrystallization of zeolites L, offretite, and erionite further supports a surface nucleation mechanism. 

N2 02, neopentane) in the zeolites A, X, L, mordenite, omega, and a synthetic offretite type have been determined from isotherms. These have been compared with the void volumes calculated from the known crystal structures. For most adsorbates the measured and calculated void volumes are in good agreement. However, helium and nitrogen exhibit anomalous behavior. A void volume-framework density relation for zeolites is given. 

Unlike the usual amorphous, microporous adsorbents, it is possible to calculate the theoretical micropore volume of a dehydrated zeolite from the known crystal structure. We have performed these calculations here for several of the better known zeolites including zeolite A, zeolite X, zeolite L, mordenite (Zeolon), (8) zeolite omega, (4) and the zeolite 0 (offretite... 

Table VI. Void Volume in Zeolite O (Offretite Type)a...

Offretite Type. The synthetic offretite-type zeolite, TMA-O, consists of a framework structure formed by linked cancrinite-type units in columns and enclosing a large C-axis channel (18). These columns are further joined by gmelinite-type units. The calculated total void space including the cancrinite units is 0.244 cm3/gram. The measured adsorption pore volumes shown in Table VI show that even a hydrocarbon such as n-butane... 

Figure 1. Relationship between the measured adsorption volumes, Fp (measd) and calculated void volume Vp of several zeolites. The dashed line corresponds to Vp (measd) = Vp (calcd). The symbols represent the zeolites as described in Tables I-VI A, X, L, Z (mordenite Zeolon), omega (to), and offretite-type 0. Vertical shaded areas containing plotted values of Vp (measd) correspond to calculated values of Vp for the main pore systems. The narrow area, 0, corresponds to the main c-axis void of zeolite 0. The value of Vp for Zt = Vp for zeolite 0. Symbols with the subscript t (At Xt) etc.) represent values of Vp for the total void volume shown by narrow shaded areas. The neopentane (NP) volumes lie consistently below the dashed line thus showing a paeking effect. In all of these zeolites of varying structure, the H20 and N2 volumes correspond with complete filling of the total voids even though this is not possible in the case of N2 in zeolites A, X, and L.

Ion-Exchanged Forms of Zeolite L, Erionite, and Offretite and Sorption of Inert Gases... 

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