Zeolite conversion

Figure 3.1 Acetylation at 373 K with acetic anhydride of a series of aromatic compounds over HBEA-15 zeolite. Conversion (XSUB) of anisole ( ), 2-methoxynaphthalene (x), m-xylene ( ), toluene ( ), 2-methylnaphthalene (o) and fluorobenzene (a) versus time. Reprinted from Journal of Catalysis, Vol. 230, Guidotti et al. Acetylation of aromatic compounds with H-BEA zeolite the influence of the substituents on the reactivity and on the catalyst stability, pp. 375-383, Copyright (2005), with permission from Elsevier...

Figure 6. The inhibition of Cubic P zeolite conversion to SSZ-13 when the Cubic P has been pretreated with Diquat 4. Br has no inhibitory effect.

Zeolite Conversion rKlc%l Selectivity [glc %] 2-Methyl-propanal Selectivity [glc %] 2-Methyl-butanal... 

Alkali metal-exchanged zeolites have been used to prepare activated alkenes of interest as prepolymers by Knoevenagel condensation of malononitrile with ketones having different positive charge density on the carbon of the carbonyl group benzophenone, cyclohexanone, and p-aminoacetophenone [85]. The reactivity depends both on ketone structure (the order of reactivity was benzophenone > cyclohexanone > p-aminoacetophenone) and on the catalyst used. For instance, when malononitrile is condensed with cyclohexanone in the presence of a CsY zeolite conversion was very low. CsX zeolite, however, which has a substantial number of basic sites with pX in the range 9 < P a < 10.7 and some with 10.7 < < 13.3 could be used to perform... 

In a second processing step, the depropanized effluent of the zeolitic conversion is etherified with methanol on a cationic resin. 

Previous Work in Zeolite Conversion of Biomass Vapors. Applications of zeolites for the conversion of oxygenates in general and biomass pyrolysis products in particular has been previously reviewed (1,2). Over the last decade, Mobil researchers (e.g., 3-5) and others (6-17) have examined a variety of oxygenated compounds over HZSM-5 catalysts of various origins. Several investigators have converted wood pyrolysis products (10-14). 

MFI Zeolite Conversion, % Ethylene, wt% Ethy lene/Propy lene... 

In order to augment the quantity and quality of final synthesis yield as obtained from conventional hydrothermal activation, another modified method has been introduced which utihzes two different steps, an initial high temperature fusion of fly ash-alkah mixture, prior to employing the final stage of hydrothermal activation of the fused product. The main variables have been fusion temperature and time, alkali type and its concentration and crystallization time in hydrothermal synthesis process, which can affect the quahty and yield of final product. As such, it has been confirmed that the final yield can be quantified to exhibit zeolitic conversion up to 62 % together with by production of alkaline waste solution which can become a threat to the environment after disposal. A flowchart of the synthesis process is depicted in Fig. 3.3 [1, 2, 9, 10, 12, 43, 44]. 

As a general rule, conversion of a zeolite from one ionic form to another in one single batch equiUbration is difficult, even when the zeolite is selective for the incoming cation. Considering also the common selectivity reversal exhibited by most zeolites, conversion by a single equilibration becomes a practical impossibility in most cases. 

The ortho- and meto-isomers are bulkier than the para-iaomer and diffuse less readily in the zeolite pores. The transport restriction favours their conversion into the /lara-isomer, which is fonned in excess of the equilibrium concentration. Because the selectivity is transport influenced, it is dependent on the path length for transport, which is the length of the zeolite crystallites. 

Zeolites are tire product of a hydrotliennal conversion process [28]. As such tliey can be found in sedimentary deposits especially in areas tliat show signs of fonner volcanic activity. There are about 40 naturally occurring zeolite types. Types such as chabazite, clinoptilolite, mordenite and phillipsite occur witli up to 80% phase purity in quite large... 

Methanol conversion to hydrocarbons over various zeolites (370X, 1 atm, 1 LHSV)... 

The vapor-phase Badger process (Eigure 10-2), which has been commercialized since 1980, can accept dilute ethylene streams such as those produced from ECC off gas. A zeolite type heterogeneous catalyst is used in a fixed bed process. The reaction conditions are 420°C and 200-300 psi. Over 98% yield is obtained at 90% conversion." Polyethylbenzene (polyalkylated) and unreacted benzene are recycled and join the fresh feed to the reactor. The reactor effluent is fed to the benzene fractionation system to recover unreacted benzene. The bottoms... 

The process which was developed hy DOW involves cyclodimerization of hutadiene over a proprietary copper-loaded zeolite catalyst at moderate temperature and pressure (100°C and 250 psig). To increase the yield, the cyclodimerization step takes place in a liquid phase process over the catalyst. Selectivity for vinylcyclohexene (VCH) was over 99%. In the second step VCH is oxidized with oxygen over a proprietary oxide catalyst in presence of steam. Conversion over 90% and selectivity to styrene of 92% could he achieved. ... 

There are several theories about the chemistry of vanadium poisoning. The most prominent involves conversion of VjOj to vanadic acid (H-iVO ) under regenerator conditions. Vanadic acid, through hydrolysis, extracts the tetrahedral alumina in the zeolite crystal structure, causing it to collapse. 

These metals, when deposited on the E-cat catalyst, increase coke and gas-making tendencies of the catalyst. They cause dehydrogenation reactions, which increase hydrogen production and decrease gasoline yields. Vanadium can also destroy the zeolite activity and thus lead to lower conversion. The deleterious effects of these metals also depend on the regenerator temperature the rate of deactivation of a metal-laden catalyst increases as the regenerator temperature increases. 

Silica gel [11] or alumina [11a, 12] alone, or silica and alumina together modified by Lewis-acid treatment [13] and zeolites [14], have been widely used as catalysts in Diels-Alder reactions, and these solids have also been tested as catalysts in asymmetric Diels-Alder reactions [12,13b,14]. Activated silica gel and alumina at 140 °C were used [15] to catalyze the asymmetric cycloaddition of (-)-menthyl-N-acetyl-a, S-dehydroalaninate (3) (R = NHCOMe) with cyclopentadiene in the key step for synthesizing optically active cycloaliphatic a-amino acids. When the reactions were carried out in the absence of solvent, a higher conversion was obtained. Some results are reported in Table 4.5 and compared with those obtained by using silica and alumina modified by treatment with Lewis acids. Silica gel gives a reasonable percentage of conversion after 24 h with complete diastereofacial selectivity in exo addition. 

The use of zeolites is particularly advantageous for self-Diels-Alder reactions of gaseous dienes because it reduces the polymerization of the reactant. An example is the cyclodimerization of 1,3-butadiene to 4-vinylcyclohexene [20a] carried out at 250 °C with satisfactory conversion when non-acidic zeolites, such as large-pore zeolites Na-ZSM-20, Na- S and Na-Y, are used. 

BROMIDES IN ZEOLITE SYNTHESIS / ZEOLITES IN BROMIDE SYNTHESIS AND CONVERSION... 

Quaternary ammonium compounds (quats) are prepared - by moderate heating of the amine and the alkyl halide in a suitable solvent - as the chlorides or the bromides. Subsequently conversion to the hydroxides may be carried out. Major applications of the quat chlorides are as fabric softeners and as starch cationizing agent. Several bio-active compounds (agrochemicals, pharmaceuticals) possess the quat-structure. Important applications of quat bromides are in phase transfer catalysis and in zeolite synthesis. 

Zeolites as catalysts and promoters in organic bromide synthesis and conversion In the second part of this contribution the use of zeolites in the synthesis and conversion of organic bromides will be discussed (ref. 16). 

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