Zeolite recyclability

Zeolite Catalysts. Uaocal has iatroduced a fixed-bed fiquid-phase reactor system based oa a Y-type zeofite catalyst (62). The selectivity to cumene is geaeraHy betweea 70 and 90 wt %. The remaining components are primarily polyisopropylbenzenes, which are transalkylated to cumene ia a separate reactioa zoae to give an overall yield of cumene of about 99 wt %. The distillation requirements iavolve the separation of propane for LPG use, the recycle of excess benzene to the reaction zones, the separation of polyisopropylbenzene for transalkylation to cumene, and the production of a purified cumene product. 

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... 

Upon passing bromobenzene and hydrogen over zeolite Pt-H-beta dehydrobromination followed by hydrogenation and isomerization takes place. In this way undesired aromatic bromides can be recycled. 

Another major cause of waste is the use of mineral acids (H2SO4, H3PO4, etc.) and Lewis acids (AICI3, ZnCL), often in stoichiometric amounts, which cannot be recovered and recycled. A typical example is the HNO3/H2SO4 mixture used in aromatic nitrations. Consequently, there is a discernible trend towards the use of solid, recyclable Brpnsted and Lewis acids, e.g. zeolites, acidic clays, etc. (see later) as alternatives to conventional mineral and Lewis acids. 

Many standard reactions that are widely applied in the production of fine chemicals employ. strong mineral or Lewis acids, such as sulphuric acid and aluminium chloride, often in stoichiometric quantities. This generates waste streams containing large amounts of spent acid, which cannot easily be recovered and recycled. Replacement of these soluble mineral and Lewis acids by recyclable. solid acids, such as zeolites, acid clays, and related materials, would represent a major breakthrough, especially if they functioned in truly catalytic quantities. Consequently, the application of solid acids in fine chemicals synthesis is currently the focus of much attention (Downing et al., 1997). 

The liquid-phase hydration of cyclohexene is carried out by a Japanese company with a slurry of zeolite ZSM-5 as the catalyst. Here, the product separates into two layers and cyclohexano leaves in the organic cyclohexene phase and the catalyst stays in the aqueous phase, which is recycled. The two-phase strategy, therefore, has special significance in this case. A recent publication by Ogawa et al. (1998a) gives some details of this system. 

Smith et al. (1998) have reported selective para acetylation of anisole, phenetole, and diphenyl ether with carboxylic anhydrides at 100 °C, in the presence of catalytic quantities of zeolites H-beta. The zeolite can be recovered and recycled to give essentially the same yield as that given by fresh zeolite. 

On silica, the rate was lower than in the case of the free complex. The zeolite, however, shows a cooperative effect on the rate and on enantioselectivity of the reaction. The positive effect on the rate can be related to the strong capacity of the zeolite to adsorb H2. These zeolite-anchored complexes can also be recycled without loss of activity. 

Immobilization of chiral complexes in PDMS membranes offers a method for the generation of new chiral catalytic membranes. The heterogenization of the Jacobsen catalyst is difficult because the catalyst loses its enantioselectivity during immobilization on silica or carbon surfaces whereas the encapsulation in zeolites needs large cages. However, the occlusion of this complex in a PDMS matrix was successful.212 The complex is held sterically within the PDMS chains. The Jacobsen catalyst occluded in the membrane has activity and selectivity for the epoxidation of alkenes similar to that of the homogeneous one, but the immobilized catalyst is recyclable and stable. 

A number of zeolite syntheses result in incomplete conversion of all of the gel components to solid zeolite. In many cases the reactant Si/Al ratio is different than that of the product (usually higher), resulting in a silicate solution remaining behind. At the industrial scale this silicate solution is often recycled to minimize waste and raw material cost [34—36]. 

As documented in Chapter 5, zeolites are very powerful adsorbents used to separate many products from industrial process steams. In many cases, adsorption is the only separation tool when other conventional separation techniques such as distillation, extraction, membranes, crystallization and absorption are not applicable. For example, adsorption is the only process that can separate a mixture of C10-C14 olefins from a mixture of C10-C14 hydrocarbons. It has also been found that in certain processes, adsorption has many technological and economical advantages over conventional processes. This was seen, for example, when the separation of m-xylene from other Cg-aromatics by the HF-BF3 extraction process was replaced by adsorption using the UOP MX Sorbex process. Although zeolite separations have many advantages, there are some disadvantages such as complexity in the separation chemistry and the need to recover and recycle desorbents. 

Figure 16.n Hydrocracking catalyst performance in single stage recycle as a function of zeolite content and unit cell size. 

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