Type Zeolite Catalysts

Since 1981, three-way catalytic systems have been standard in new cars sold in North America.6,280 These systems consist of platinum, palladium, and rhodium catalysts dispersed on an activated alumina layer ( wash-coat ) on a ceramic honeycomb monolith the Pt and Pd serve primarily to catalyze oxidation of the CO and hydrocarbons, and the Rh to catalyze reduction of the NO. These converters operate with a near-stoichiometric air-fuel mix at 400-600 °C higher temperatures may cause the Rh to react with the washcoat. In some designs, the catalyst bed is electrically heated at start-up to avoid the problem of temporarily excessive CO emissions from a cold catalyst. Zeolite-type catalysts containing bound metal atoms or ions (e.g., Cu/ZSM-5) have been proposed as alternatives to systems based on precious metals. 

Standard vanadium type SCR catalysts have an upper temperature limit of about 450°C. Above this temperatme conversion drops rapidly as a result of ammonia oxidation and at even higher temperatures deactivation follows. For developing new catalysts zeolite type catalysts were chosen new developments showed a very high SCR activity for a combination of CuH-MOR H-MOR in a temperature window of 200 - 600°C [6]. 

Black Staining a) Manganese greensand or manganese zeolite-type catalyst-filter to limit of 6 ppm or 15 ppm, respectively (combined Fe and Mn), with pH not lower than 6.7 value... 

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... 

When supported complexes are the catalysts, two types of ionic solid were used zeolites and clays. The structures of these solids (microporous and lamellar respectively) help to improve the stability of the complex catalyst under the reaction conditions by preventing the catalytic species from undergoing dimerization or aggregation, both phenomena which are known to be deactivating. In some cases, the pore walls can tune the selectivity of the reaction by steric effects. The strong similarities of zeolites with the protein portion of natural enzymes was emphasized by Herron.20 The protein protects the active site from side reactions, sieves the substrate molecules, and provides a stereochemically demanding void. Metal complexes have been encapsulated in zeolites, successfully mimicking metalloenzymes for oxidation reactions. Two methods of synthesis of such encapsulated/intercalated complexes have been tested, as follows. 

Catalytic dewaxing, in which straight-chain paraffin hydrocarbons are selectively cracked on zeolite-type catalysts, and the lower-boiling reaction products are separated from the dewaxed lubricating oil by fractionation. 

Cao, Y., Kessas, R., Naccache, C., and Taarit, Y.B. (1999) Alkylation of benzene with dodecene. The activity and selectivity of zeolite type catalysts as a function of the porous structure. Appl. Catal, 184, 231-238. 

The low H/C-ratio of FCC feed derived from liquefied biomass led to low conversion and poor gasoline selectivity. Addition of alumina to the matrix resulted in a catalyst more active for heavy oil cracking but with a poor selectivity. Alumina-montmorillonite catalysts showed activities for heavy oil cracking comparable to that of a conventional, zeolite based, cracking catalyst. Effects of matrix composition and zeolite type on the heavy oil cracking performance are discussed. 

The cyclocondensation of l,3-amino alcohols with carboxylic acid derivatives is a method often applied for the synthesis of 5,6-dihydro-4/7-l,3-oxazines <1996CHEC-II(6)301 >. Ebsorb-4, a weakly acidic zeolite-type adsorbent with 4 A pore size, proved an efficient catalyst of the cyclization of benzoic acid and 3-aminopropanol <2002TL3985>. In the presence of zinc chloride as a catalyst, the expulsion of ammonia drove the reactions of 3-aminopropanol with nitriles to completion, affording 2-substituted 5,6-dihydro-47f-l,3-oxazines in good yields... 

Ether production from the reaction of monohydric alcohols with linear olefins has also been demonstrated under more severe conditions using a zeolite-type catalyst system (15). However, it has not been commercialized as yet. 

The enhanced diffusivity of polynuclear compounds in sc C02 has been utilized to enhance catalyst lifetimes in both 1-butene/isoparaffin alkylations (Clark and Subramaniam, 1998 Gao et al., 1996). The former may be catalyzed using a number of solid acid catalysts (zeolites, sulfated zeolites, etc.), and the use of sc C02 as a solvent/diluent permits the alkylations to be carried out at relatively mild temperatures, leading to the increased production of valuable trimethylpentanes (which are used as high-octane gasoline blending components). The enhancement of product selectivity in the latter process is believed to result from rapid diffusion of ethylbenzene product away from the Y-type zeolite catalysts, thus preventing product isomerization to xylenes. 

Although the theory includes the impact of matrix contribution, we will restrict our discussions primarily to low matrix activity catalysts, and highlight the differences in zeolite type. 

There are two values of surface area and volume of nitrogen adsorbed (BJH method), obtained with the parent H-Y zeolite and the H-Y/TFA sample (Table 1) the first corresponds to the zeolite-type micropores and the other, to the mesopores. Figure 1 shows the pore size distribution of the H-Y/TFA catalyst there is a sharp peak (not shown here) in the micropore region and another peak at 4nm in the mesopore region. Such a bimodal pore size distribution was also observed with the parent zeolite. 

Metal silicalite catalysts based on ZSM-5 zeolite type materials have been used for the hydroxylation of olefins. The silicalites need to contain a certain amount of A102 units to be active.136... 

Each zeolite type can be easily obtained over a wide range of compositions directly by synthesis and/or after various post synthesis treatments. Moreover, various compounds can be introduced or even synthesized within the zeolite pores (ship in a bottle synthesis). This explains why zeolites can be used as acid, base, acid-base, redox and bifunctional catalysts, most of the applications being however in acid and in bifunctional catalysis. 

In the isomerization of styrene oxides in a fixed bed reactor under gas phase conditions, the catalytic performance of various catalysts on the activity, selectivity and service time was screened at 300°C and WHSV = 2-3h" . As shown in Fig. 15.1, zeolites with MFI-structure are superior to other zeolite types and non zeolitic molecular sieves, as well as greatly superior to amorphous metal oxides. 

Ce-, V-containing zeolite, and other zeolitic type catalysts... 

According to this concept, Masuda et al. [75] studied the catalytic cracking of the oil coming from a previous thermal pyrolysis step of polyethylene at 450°C in the bench-scale fixed-bed reactor shown in Figure 3.11. The catalysts employed were different zeolite types REY (rare earth exchanged zeolite Y), Ni-REY (nickel and rare earth... 

A major shortcoming of zeolite-type catalysts is their sensitivity to hydrogen chloride and HCl acid, which canses destrnction of a catalyst in concentrations above 200 ppm HCl. Considering the fact, plastic wastes often contains PVC the application of expensive zeolite-type catalysts is disadvantageons. 

The catalyst is not consumed or poisoned, unlike zeolite type catalysts. The metal plates do however get fouled with a tar-like residue and terephthalic acid and therefore the reaction tower needs to be stripped down periodically and the plates polished back to their pristine form. 

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