Synthetic mordenite

Synthetic H+ L.P. Mordenitec Synthetic Na+ L.P. Mordenited Synthetic Na+ Mordenite6... 

Mordenite (Synthetic Zeoeite) erom Huber NaAISi-O 2 3H2O Properties BET specific surface area 340 m /g [851], 149 m-/g [877,858],... 

Fig. 3. Model of the crystal structure of the mineral mordenite showing the main channel formed by 12-membered ring and small channels which contain some of the sodium cations. Synthetic types of mordenite exhibit the adsorption behavior of a 12-membered ring, whereas the mineral does not, probably...

The zeoHtes used for catalysis are principally modified forms of zeoHte Y, acid forms of synthetic mordenite, and ZSM-5. 

Adsorbents Table 16-3 classifies common adsorbents by structure type and water adsorption characteristics. Structured adsorbents take advantage of their crystalline structure (zeolites and sllicalite) and/or their molecular sieving properties. The hydrophobic (nonpolar surface) or hydrophihc (polar surface) character may vary depending on the competing adsorbate. A large number of zeolites have been identified, and these include both synthetic and naturally occurring (e.g., mordenite and chabazite) varieties. 

Natural zeolites may bear the name of the mineral (mordenite, faujasite, ferrier-ite, silicalite), or sometimes that of the discoverer, e.g. Barrerite after Professor Barrer, or the place where they were found, e.g. Bikitaite from Bikita, Zimbabwe. Synthetic zeolites are usually named after the industry or university where they were developed, e.g. VPI comes from Virginia Polytechnic Institute, and ZSM stands for Zeolite Socony Mobil. 

These microporous crystalline materials possess a framework consisting of AIO4 and SiC>4 tetrahedra linked to each other by the oxygen atoms at the comer points of each tetrahedron. The tetrahedral connections lead to the formation of a three-dimensional structure having pores, channels, and cavities of uniform size and dimensions that are similar to those of small molecules. Depending on the arrangement of the tetrahedral connections, which is influenced by the method used for their preparation, several predictable structures may be obtained. The most commonly used zeolites for synthetic transformations include large-pore zeolites, such as zeolites X, Y, Beta, or mordenite, medium-pore zeolites, such as ZSM-5, and small-pore zeolites such as zeolite A (Table I). The latter, whose pore diameters are between 0.3... 

Catalytic Dewaxing Also called CDW. A hydiocracking process for removing waxes (linear aliphatic hydrocarbons) from petroleum streams by converting them to lower molecular weight hydrocarbons. The catalyst is a synthetic mordenite. Developed by BP two units were operating in 1988. 

ZENITE LCP resins, 20 80 Zenz plot, 77 797, 798 Zeolite(s), 76 811, 812-814, 77 161. See also Molecular sieve entries Synthetic zeolite entries, Mordenite acidic, 76 825... 

Structural characteristics. Both natural and synthetic mordenite have an orthorhombic structure that consists of parallel, 12-membered ring channels in the c-direction, having an eliptical cross-section with dimensions of 6,7 x 7.0 A (Figure 9). Smaller 8-membered ring channels with dimensions of 2.9 x 5.7 A, which are perpendicular to the main channels, are too small to allow the movement of molecules from one main channel to another. Mordenite has been synthesized in a "large -port" and "small-port" form that have different sorption properties. A typical unit cell content is Na0[(A10o)o(Si0o)/rJ. 24 HO. 8 28 2 40... 

We have examined the rate constants for disproportionation and isomerization for a variety of zeolites, using a commercial-type feed containing 70% m-xylene and 30% o-xylene in a fixed-bed flow reactor. The results, listed in Table I, show the exceptionally low disproportionation/isomerization selectivity of ZSM-5 relative to synthetic faujasite. Synthetic mordenite and ZSM-4 have intermediate selectivities. 

The correlation between selectivity and intracrystalline free space can be readily accounted for in terms of the mechanisms of the reactions involved. The acid-catalyzed xylene isomerization occurs via 1,2-methyl shifts in protonated xylenes (Figure 3). A mechanism via two transalkylation steps as proposed for synthetic faujasite (8) can be ruled out in view of the strictly consecutive nature of the isomerization sequence o m p and the low activity for disproportionation. Disproportionation involves a large diphenylmethane-type intermediate (Figure 4). It is suggested that this intermediate can form readily in the large intracrystalline cavity (diameter. 1.3 nm) of faujasite, but is sterically inhibited in the smaller pores of mordenite and ZSM-4 (d -0.8 nm) and especially of ZSM-5 (d -0.6 nm). Thus, transition state selectivity rather than shape selective diffusion are responsible for the high xylene isomerization selectivity of ZSM-5. 

The effect of different zeolite structures and pore systems is also reflected in the data of Table II. With the intermediate pore ZSM-5, xylene is apparently much less reactive than ethylbenzene, both as an alkyl donor and acceptor, than it is with the large pore zeolites, ZSM-4 and synthetic mordenite. 

This may be partly the result of increased steric crowding in the transition state of transalkylation. Another contributory factor to the increased selectivity in ZSM-5 is the higher diffusion rate of ethylbenzene vs m-/o-xylene in ZSM-5 and hence a higher steady state concentration ratio [EB]/[xyl] in the zeolite interior than in the outside phase. Diffusional restriction for xylenes vs ethylbenzene may also be indicated by the better selectivity of synthetic mordenite vs ZSM-4, since the former had a larger crystal size. 

There is no systematic nomenclature developed for molecular sieve materials. The discoverer of a synthehc species based on a characteristic X-ray powder diffraction pattern and chemical composihon typicaUy assigns trivial symbols. The early syn-thehc materials discovered by Milton, Breck and coworkers at Uruon Carbide used the modem Lahn alphabet, for example, zeoHtes A, B, X, Y, L. The use of the Greek alphabet was inihated by Mobil and Union Carbide with the zeoHtes alpha, beta, omega. Many of the synthetic zeoHtes which have the structural topology of mineral zeoHte species were assigned the name of the mineral, for example, syn-thehc mordenite, chabazite, erionite and offretite.The molecular sieve Hterature is replete with acronyms ZSM-5, -11, ZK-4 (Mobil), EU-1, FU-1, NU-1 (ICI), LZ-210, AlPO, SAPO, MeAPO, etc. (Union Carbide, UOP) and ECR-1 (Exxon). The one pubHcaHon on nomenclature by lUPAC in 1979 is Hmited to the then-known zeoHte-type materials [3]. 

The low silica zeolites represented by zeolites A and X are aluminum-saturated, have the highest cation concentration and give optimum adsorption properties in terms of capacity, pore size and three-dimensional channel systems. They represent highly heterogeneous surfaces with a strongly hydrophilic surface selectivity. The intermediate Si/Al zeolites (Si/Al of 2-5) consist of the natural zeohtes eri-onite, chabazite, clinoptilolite and mordenite, and the synthetic zeolites Y, mordenite, omega and L. These materials are still hydrophilic in this Si/Al range. 

B. Synthetic zeolites Y, L, large pore mordenite, omega... 

Commercially significant zeolites include the synthetic zeolites type A (LTA), X (FAU), Y (FAU), L (LTL), mordenite (MOR), ZSM-5 (MFI), beta ( BEA/BEC), MCM-22 (MTW), zeolites E (EDI) andW (MER) and the natural zeolites mordenite (MOR), chabazite (CHA), erionite (ERl) and clinoptiloUte (HEU). Details of the structures of some of these are given in this section. Tables in each section lists the type material (the common name for the material for which the three letter code was established), the chemical formula representative of the unit cell contents for the type material, the space group and lattice parameters, the pore structure and known mineral and synthetic forms. 

Synthetic mordenite (a zeolite having 7-A-diameter, one-dimensional channels Se Se particle domains were incorporated into zeolite channels 558... 

A-, X-, Y-, and AIPO-5-molecular sieves and synthetic mordenite Se Predominantly trigonal helical chains of selenium were incorporated into the zeolite channels 559... 

Five zeolite minerals have been considered identical with mordenite with space group Cmcm. The possibility of a family of structures is considered four related ordered structures including Cmcm are proposed. Two of these (Cmcm and Imcm) have a one-dimensional system of large pores. The remaining pair (Cmmm and Immm) have a two-dimensional pore system with a second set of smaller channels. X-ray diffraction results show that synthetic and most mineral specimens have the Cmcm structure but also reveal mixtures of Cmmm, Immm, and Imcm with the Cmcm structure in three mineral specimens. Electron diffraction examination of a ptilolite sample reveals the Cmcm structure with an inter growth of the idealized structure Cmmm. Further tentative evidence for the existence of more than one ((mordenitef) framework structure, based on physical property characteristics, is discussed. 

Two sets of patterns were calculated for each structure with and without sodium cations (Table II). These results indicated that the effect of the cations could be ignored. This is confirmed by actual patterns for the Na and H forms of a synthetic mordenite. Because mordenite has a low cation content, cation effects on peak intensities should be minimal. 

X-ray powder patterns determined in the present studies and from the literature are summarized in Table III. The observed patterns for Zeolon 100 Na and Zeolon 100 H (synthetic sodium and hydrogen large port mordenites) arc in excellent agreement with the calculated patterns for the Cmcm structure. 

A previous examination of a synthetic calcium mordenite 15) revealed an orthorhombic cell. A synthetic strontium mordenite 16) had a C-centered orthorhombic cell although Kerr 12) reported that a few crystals giving electron diffraction patterns corresponding approximately to the body-centered structure Immm) have been synthesized hydro-thermally from aluminosilicate gels containing strontium similar to those gels which yielded a strontium-mordenite. ... 

Many mineral and synthetic samples examined by Bennett and Gard 17,18) gave typical C-centered orthorhombic diffraction patterns and with few exceptions had streaks in the hOl section, indicating an incomplete c-glide plane. A few crystals gave electron diffraction patterns having diffuse maxima in the hOl streaks, which could be interpreted as representing an I-centered mordenite structure. 

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