Zeolite adsorbate aromatics

Plee, D. and Methivier, A. (2002) Agglomerated zeolite adsorbents, process for their preparation, and their use for adsorbing paraxylene from aromatic C8 fractions. U.S. Patent 5,410,815. 

Zeolites have an enormous impact on our daily lives, both directly and indirectly. For example, upstream hydrocarbons such as aromatics and olefins are produced using zeolite catalysts. The aromatics or olefins are then separated from the reaction mixtures using zeolite adsorbents. The purified components produced by these zeolite-based methods are then used in downstream processes to produce products that we use daily, such as clothes, furniture, foods, construchon materials and materials to build roads, automobile parts, fuels, gasoline, etc. In addihon to the indirect impacts mentioned above, zeolites also have a direct impact on our daily lives. For example, zeolites are used as builders in detergent formulations. 

Let us consider a zeolite adsorbent for selective separation in an important oil refinery stream that contains aromatic compounds. 

Thermogenesis of Specific Adsorption Sites of Zeolites and Their Effects on the Spectra of Adsorbed Aromatic Amines... 

Unique adsorption selectivities are employed in the separation of 0, aromatic isomers, a classical problem that cannot be easily solved by distillation, crystallization, or solvent extraction (10). Although xylene [106-42-3] can be separated by crystallization, its recovery is limited because of the formation of eutectic with / -xylene [108-58-3]. However, either jfr-xylene, -xylene, 0-xylene [95-47-6]y or ethylbenzene [100A1 -4] can be extracted selectively by suitable modification of Zeolitic adsorbents. 

The intracrystalline diffusivities of llZSM-5 zeolite were directly measured for several hydrocarbons at higher temperatures (373-773 K) by the constant volume method. High silicious HZSM-5 zeolite, which has no activity for reactions, was used as the adsorbent. Aromatics benzene, xylene-isomers ortho-, meta- and para-xylene) and toluene, and paraffins n-hexane, n-pentane, p-octane and iso-octane, were used as adsorbates. Intracrystalline diffusivities of aromatics markedly depended on the minimum size of the aromatics and that of paraffins depended on the carbon number (molecular weight of the paraffins). A method was developed for predicting diffusivity in terras of pore diameter and molecular properties of hydrocarbons. This method was found to well represent the experimental results. 

The teehnique of desorption by simulated countercurrent flow displacement is also applied to other separation operations the separation of ethylbenzene from a mixture of aromatics and that of olefins from a mixture of olefins and paraffins. The composition of the zeolite adsorbent is adjusted in each case to optimize the effectiveness of the separation Na-Y or KSr-X zeohtes for ethylbenzene and Ca-X or Sr-X for olefins. The nature of the liquid desorbent also depends on the molecule to be separated. 

The effective cross-section of an /z-alkane molecule is smaller than 5 A the effective cross-section of branched, cyclic, or aromatic hydrocarbon molecules is larger than 5 A. Therefore only n-alkanes are adsorbed by a 5-A zeolite all other types of hydrocarbons are excluded. The adsorbed n-alkanes can be recovered by different methods and are subsequently available in a pure form, for further processing. 

Ebex [Ethylbenzene extraction] A version of the Sorbex process, for extracting ethylbenzene from mixtures of aromatic C8 isomers. The adsorbent is a zeolite. It had not been commercialized as of 1984. 

Then, contrary to our previous hypothesis, the reaction proceeds via a Bai2 displacement of aniline on DMC. The product, mono-A -methyl aniline (PhNHMe), plausibly adsorbs into the zeohte in a different way with respect to anihne, because different H-bonds (N H — O-zeolite) take place with the solid. As recently reported by Su et al., A-methyl amines also may interact with NaY by H-bonding between the protons of the methyl group and the oxygen atoms of the zeolite this probably forces the molecule a bit far from the catalytic surface in a fashion less apt to meet DMC and react with it. This behavior can account for the mono-A-methyl selectivity observed, which is specific to the use of DMC in the presence of alkali metal exchanged faujasites in fact, the bis-A-methylation of primary aromatic amines occurs easily with conventional methylating agents (i.e., dimethyl sulfate). ... 

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. 

Utilization of zeolite acidic strength in Cg-aromatics (xylens) systems is illustrated next. In the presence of strong acids, xylene isomers have varying basicity (Table 6.5), with m-xylene being the most basic and p-xylene the least basic among the Cg-aromatics [27]. Based on the basicity of the xylenes, the acidity of each zeolite can be properly adjusted to selectively adsorb m-xylene or p-xylene. As demonstrated in Figure 6.4, a more acidic zeolite such as NaY will selectively adsorb m-xylene from other Cg-aromatics [28, 29], In contrast. Figure 6.5 shows that a weaker acidic zeolite such as KY will selectively adsorb p-xylene from other Cg-aromatics [30, 31]. In both systems, toluene was used as the desorbent. 

Examples of rate-selective adsorption are demonstrated using silicalite adsorbent for separation of Ciq-Cm n-paraffins from non- -paraffins [40, 41] and Ciq-Ch mono-methyl-paraffins from non-n-paraffins [42-45]. Silicalite is a ten-ringed zeolite with a pore opening of 5.4A x 5.7 A [22]. In the case of -paraffins/non-n-paraffins separation [40, 41], n-paraffins enter the pores of silicalite freely, but non-n-paraffins such as aromatics, naphthenes and iso-paraffins diffuse into the pores more slowly. However, the diffusion rates of both normal -paraffins and non-n-paraffins increase with temperature. So, one would expect to see minimal separation of n-paraffins from non-n-paraffins at high temperatures but high separation at lower temperature. 

The faujasite zeolite in the UOP Parex process has some finite affinity for aU the aromatic species in the mixed xylene feed, indicated by the fact that selectivities between the components are typically less than five. Because the adsorbent has the tendency to adsorb all aromatic species in the feed to some extent, the fundamental variable dictating the adsorption zone operation is the ratio of zeolitic selective pore volume circulated past the feedpoint by the stepping action of the rotary valve per the volume of aromatics conveyed to the adsorption chambers. Typically this ratio is set to obtain a certain target recovery of p-xylene. 

Guo, G.-Q., Chen, H., and Ying-Cai, L. (2000) Separation of p-xylene from C8 aromatics on binder-free hydrophobic adsorbent of MFI zeolite. I. Studies on static equilibrium. Micropor. Mesopor. Mater., 39, 149-161. 

The object of this work was to study the influence of pretreated, decationized NH4-zeolites on adsorbed A,iV-dimethylaniline molecules. Such influence is caused by, proton-donating and electron-deficient active sites in decationized zeolites. Interaction of an aromatic amine molecule (M) with the proton-donating site leads to the formation of the MH+ molecule ion interaction with the electron-deficient site results in the M+ cation radical. Stabilization of these states by adsorption leads to the... 

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