Molecular shape-selectivity, zeolite

At the low-molecular-weight end of the spectrum, a process newly commercialized by Mobil for converting methanol into gasoline has significantly expanded opportunities in C-1 chemistry— the upgrading of one-carbon molectrles to mrrlticarbon products. The process involves the use of ZSM-5, a shape-selective zeolite catalyst. (See "Zeolite and Shape-Selective Catalysts" in Chapter 9.)... 

Derouane, E.G., New aspects of molecular shape-selectivity catalysis by zeolite ZSM-5 Imelik, B. Naccache, C. ... 

Figure 4.20 MTG/MTO reaction path and aromatics distribution with different zeolites as catalysts. (Reprinted from C.D. Chang, W.H. Lang, W.K. Bell, Catalysis in Organic Reactions, Molecular Shape-Selective Catalysis in Zeolites, pp. 93-94. Copyright 1981. With permission from Marcel Dekker.)...

Gabelica, Z., and Vedrine, J.C. (1981) Molecular shape selectivity of ZSM-5, modified ZSM-5 and ZSM-11 type zeolites. Faraday Discuss. Chem. Soc,... 

In principle, all the kinetic concepts of intercalation introduced for layer-structured silicates hold for zeolites as well. Swelling, of course, is not found because of the rigidity of the three dimensional frame. The practical importance of zeolites as molecular sieves, cation exchangers, and catalysts (cracking and hydrocracking in petroleum industry) is enormous. Molecular shape-selective transport (large differences in diffusivities) and micro-environmental catalysis (in cages and channels)... 

The unique properties of zeolites and other micro- or mesoporous solids that may favour their application to fine chemical synthesis are (1) the compatibility between the size and shape of their channels or cavities with the size of the reactants and/or products (generally referred to as molecular shape selectivity) that may direct the reaction away from the thermodynamically favoured route (2) the occurrence of confinement effects increasing the concentration of reactants near the catalytic sites and (3) the ability to tune their catalytic properties (acidic, basic, or other) via various treatments as described in this Volume. 

Acetaldehyde decomposition, reaction pathway control, 14-15 Acetylene, continuous catalytic conversion over metal-modified shape-selective zeolite catalyst, 355-370 Acid-catalyzed shape selectivity in zeolites primary shape selectivity, 209-211 secondary shape selectivity, 211-213 Acid molecular sieves, reactions of m-diisopropylbenzene, 222-230 Activation of C-H, C-C, and C-0 bonds of oxygenates on Rh(l 11) bond-activation sequences, 350-353 divergence of alcohol and aldehyde decarbonylation pathways, 347-351 experimental procedure, 347 Additives, selectivity, 7,8r Adsorption of benzene on NaX and NaY zeolites, homogeneous, See Homogeneous adsorption of benzene on NaX and NaY zeolites... 

The catalytic properties associated with the molecular shape-selectivity exhibited by ZSM-5 are now well known. Recent work by Martens et al. (1995) has revealed that the external surfaces of zeolite crystals have also to be considered as potential shape-selective environments. Thus, strong evidence has been obtained for a lock-and-key model, which involves a form of pore mouth catalysis with bulky long-chain molecules that cannot penetrate into the intracrystalline micropores. The proposed lock-and-key model for n-alkane isomerization over ZSM-22 zeolite (with tubular pore openings of 0.55 x 0.45 nm) seems likely to be valid for other catalytic reactions. 

Zeolite ZSM-S has a three-dimensional pore structure with interconnected channels that have dimensions of 0.53 x 0.57 and 0.55 nm (162). Y zeolite and mordenite have wider openings of their principal channel networks, and these zeolites thus show less molecular shape selectivity than ZSM-5 zeolite. 

In addition to practical applications, metal cluster-derived catalysts, particularly intrazeolite metal cluster compounds, may aid in the identification of catalytically important bonding and structural patterns and thereby further our molecular understanding of surface science and heterogeneous catalysis. The ship-in-bottle technique for the synthesis of bulky metal-mixed metal cluster compounds inside zeolites and/or interlayered minerals has gained growing attention for the purpose of obtaining catalytic precursors surrounded by the interior constraint, imposing molecular shape selectivity. Such approaches may pave the way to offer the molecular architecture of hybrid (multifunctional) tailored catalysts to achieve the desired selectivity and stability for industrial processes. 

In the case of a soft large pore HY zeolite (with high Si/Al ratio), where the molecular shape selective effect does not take place, the a naphthalene derivatives can be synthesized (see Table 1) according to the molecular orbital theory indicated. 

P.B. Weisz and V.J. Frilette, Intracrystalline And Molecular-Shape-Selective Catalysis by Zeolite Salts. J. Phys. Chem., 1960, 64, 382-383. 

M. Niwa and Y. Murakami, CVD Zeolite Preparation, Characterization and Molecular Shape-selectivity. Mater. Chem. Phys., 1987, 17, 73-85. 

In 1960, Weisz, Frilette, and co-workers first reported molecular-shape selective cracking, alcohol dehydration, and hydration with small pore zeolites (6,7), and a comparison of sodium and calcium X zeolites in cracking of paraffins, olefins, and alkylaromatics (8). In 1961, Rabo and associates (9) presented data on the hydroisomerization of paraffins over various zeolites loaded with small amounts of noble metals. Since then, the field of zeolite catalysis has rapidly expanded,... 

Few detailed studies of olefinic dehydration products have been reported. Rapoport ei al. (105) found cis- and major products from n-pentanol dehydration over NaX only traces of 2-methyl-1-butene and 2-methyl-2-butene were reported. Thus, it is evident that double bond isomerization has accompanied or followed the dehydration reaction. Several authors (99,101,106) have suggested that diffusion processes may be rate controlling, or at least of some significance, in zeolite-catalyzed dehydration reactions. Molecular-shape selective alcohol dehydration (7) was discussed earlier. 

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. 

The concept of molecular shape-selective catalysis is based on the action of catalytically active sites internal to the zeolitic framework, to diffusivity resistance either to reactant molecules or to product molecules or to both and to void limitation to reaction intermediates.This implies an intimate interaction between the shape, size and configuration of the molecules and the dimension, geometry and tortuosity of the channels and cages of the zeolite. Several types of effects exist ... 

The relative distribution of para + meta aromatics in methanol conversion was increased over Mo exchanged ZSM-5 but not on the pyridine poisoned sample. The same increase trend was also observed in the disproportionation reaction over Mo exchanged zeolites (Fig. 3), thus a reasonable explanation is the presence of internal Mo. Both methanol and toluene conversions performed on zeolites are molecular shape selective processes. Internal Mo will create diffusional hindrances which will favour the formation of para aromatics (product selectivity). 

Chemical specificity will be achieved in the refinery of the future through the use of new catalysts. Catalysts are clearly a tool for creating and managing the desired chemical specificity. Shape-selective zeolite catalysts have been very effective in managing molecular composition based on size and shape. High-... 

A large amount of information has been published on catalytic cracking with molecular shape-selective catalysts, such as natural or synthetic crystalline aluminosilicates. Several excellent reviews have appeared on the chemistry of catalysis with zeolites (52, 53). Literature on hydrocracking of pure hydrocarbons and simple mixtures of hydrocarbons with zeolite-containing catalysts is limited. However, numerous patents on the use of zeolites in hydrocracking catalysts and published... 

E.G. Derouane, "Molecular Shape-Selective Catalysis in Zeolites - Selected Topics", Catalysis on the Energy Scene, Elsevier, p. 1-17 (1984). 

Some aspects of molecular shape-selective catalysis with hydrocarbons in zeolites J.A. Rabo... 

One of the first success of zeolites as catalysts, and the first commercial molecular shape selective catalytic process, was the use of erionite in a post-reforming process named selectoforming (39). Ihis 8 MR zeolite was able, based on the principle of size exclusion, to selectively crack the short chain n-parafiins to produce LPG. To avoid the deactivation by coke NiS was deposited on the zeolite. The erionite based catalyst is generally located at the bottom of the last reactor of the reformer unit and operates then at the reformer pressure, and at the temperature of the last reformer reactor. When more flexibility was to be achieved from the selectoforming, the catalyst is introduced... 

SOME ASPECTS OF MOLECULAR SHAPE-SELECTIVE CATALYSIS WITH HYDROCARBONS IN ZEOLITES... 

ABSTRACT. The amount of published work on molecular shape-selective catalysis with zeolites is vast. In this paper, a brief overview of the general principles involved in molecular shape-selectivity is provided. The recently proposed distinction between primary and secondary shape-selectivity is discussed. Whereas primary shape-selectivity is the result of the interaction of a reactant with a micropore system, secondary shape-selectivity is caused by mutual interactions of reactant molecules in micropores. The potential of diffusion/reaction kinetic analysis and molecular graphics for rationalizing molecular shape-selectivity is illustrated, and an alternative explanation for the cage and window effect in cracking and hydrocracking is proposed. Pore mouth catalysis is a speculative mechanism advanced for some systems (a combination of a specific zeolite and a reactant), which exhibit peculiar selectivities and for which the intracrystalline diffusion rates of reactants are very low. 

In early work on molecular shape-selectivity [1-3], three kinds of mechanisms were envisaged. Reactant selectivity occurs when some molecules of the feed are too bulky to diffuse through the zeolite pores and are prevented from reacting. Product selectivity occurs when among all the product molecules formed within the pores, only those with the proper dimensions can diffuse out and appear as products in the bulk. Restricted transition-state selectivity occurs when certain reactions are... 

The first examples of molecular shape-selective catalysis in zeolites were given by Weisz and Frilette in 1960 [1]. In those early days of zeolite catalysis, the applications were limited by the availability of 8-N and 12-MR zeolites only. An example of reactant selectivity on an 8-MR zeolite is the hydrocracking of a mixture of linear and branched alkanes on erionite [4]. n-Alkanes can diffuse through the 8-MR windows and are cracked inside the erionite cages, while isoalkanes have no access to the intracrystalline catalytic sites. A boom in molecular shape-selective catalysis occurred in the early eighties, with the application of medium-pore zeolites, especially of ZSM-5, in hydrocarbon conversion reactions involving alkylaromatics [5-7]. A typical example of product selectivity is found in the toluene all lation reaction with methanol on H-ZSM-5. Meta-, para- and ortho-xylene are made inside the ZSM-5 chaimels, but the product is enriched in para-xylene since this isomer has the smallest kinetic diameter and diffuses out most rapidly. Xylene isomerisation in H-ZSM-5 is an often cited example of tranSition-state shape selectivity. The diaryl type transition state complexes leading to trimethylbenzenes and coke cannot be accommodated in the pores of the ZSM-5 structure. 

For the acid catalysed conversion of hydrocarbons, the reaction mechanisms in absence of sterical hinderance are rather well understood, so that molecular shape-selective effects exerted by constrained environments can be isolated [8,9]. Shape-selective catalysis is also possible when other than acid functions are confined to the intracrystalline void volumes of zeolite crystals, e.g. metal [10,11], bifunctional [12] and basic functions [13]. Nowadays, catalysis on zeolites with organic substrates containing heteroatoms receives much attention. Molecular shape-selectivity seems to be superimposed on electronic factors determining the selectivities [14,15]. 

For the classic types of molecular shape-selectivity in zeolites, the reader is referred to the excellent review papers in literature [18-25]. In this paper we elaborate on the recently proposed distinction between primary and secondary shape-selectivity [26], and on the more or less abused concept of cage and window effects in cracl g and hydrocracking. In addition, some evidence available in literature for the speculative mechanism of pore mouth catalysis is presented. 

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