Oxygen adsorption molecular sieves

Isotherms for H2O and / -hexane adsorption at room temperature and for O2 adsorption at Hquid oxygen temperature on 13X (NaX) zeoHte and on the crystalline Si02 molecular sieve siHcaHte are are shown in Figure 8 (43). SiHcaHte adsorbs water very weaMy. Further modification of siHcaHte by fluoride incorporation provides an extremely hydrophobic adsorbent, shown in Figure 9 (44). These examples illustrate the broad range of properties of crystalline molecular sieves. 

Activated carbons contain chemisorbed oxygen in varying amounts unless special cate is taken to eliminate it. Desired adsorption properties often depend upon the amount and type of chemisorbed oxygen species on the surface. Therefore, the adsorption properties of an activated carbon adsorbent depend on its prior temperature and oxygen-exposure history. In contrast, molecular sieve 2eohtes and other oxide adsorbents are not affected by oxidi2ing or reducing conditions. 

Highly pure / -hexane can be produced by adsorption on molecular sieves (qv) (see Adsorption, liquid separation) (43). The pores admit normal paraffins but exclude isoparaffins, cycloparaffins, and aromatics. The normal paraffins are recovered by changing the temperature and/or pressure of the system or by elution with a Hquid that can be easily separated from / -hexane by distillation. Other than ben2ene, commercial hexanes also may contain small concentrations of olefins (qv) and compounds of sulfur, oxygen, and chlorine. These compounds caimot be tolerated in some chemical and solvent appHcations. In such cases, the commercial hexanes must be purified by hydrogenation. 

Experience in air separation plant operations and other ciyogenic processing plants has shown that local freeze-out of impurities such as carbon dioxide can occur at concentrations well below the solubihty limit. For this reason, the carbon dioxide content of the feed gas sub-jec t to the minimum operating temperature is usually kept below 50 ppm. The amine process and the molecular sieve adsorption process are the most widely used methods for carbon dioxide removal. The amine process involves adsorption of the impurity by a lean aqueous organic amine solution. With sufficient amine recirculation rate, the carbon dioxide in the treated gas can be reduced to less than 25 ppm. Oxygen is removed by a catalytic reaction with hydrogen to form water. 

The Sumitomo-BF PSA process uses carbon molecular sieves (CMS) as the selective adsorbent, CMS has a higher capacity of adsorption than zeolites for methane and oxygen, and it is considered to be advantageous for hydrogen purification. If dirty raw gases are fed to this process, minor amounts of heavy hydrocarbon components such as aromatics are likely to cause deterioration of the adsorbents. To remove the heavy hydrocarbons, prefilter columns that contain activated carbon are placed upstream of the main CMS adsorbent beds4. 

Adsorption Measurement. The capacities of the molecular sieves to adsorb vapor phase 1,3,5-triisopropylbenzene (97 %, Aldrich) and 1,2,4-triisopropylbenzene (99%, Camegie-Mellon University) were measured at 373 K using a McBain-Bakr balance. The adsorption temperature was chosen such that no chemical reactions of the adsorbates were observed. Prior to the adsorption experiment, the NH4+-forms of the solids (except SAPO-37) were dehydrated at 573 K under a vacuum of 10" 2 Torr. The as-made SAPO-37 was calcined at 793 K in an oxygen flow of 6 L/h in-situ in the adsorption system for removal of organic species and dehydration. The vapor pressure at 296 K of 1,3,5- and 1,2,4-triisopropylbenzene is approximately 0.45 Torr. The adsorption experiments were conducted at this pressure. 

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 remaining gas mixture now has the composition nitrogen 3.7 mol%, oxygen 1.0 mol%, methane 47.9 mol%, C02 47.4 mol%. The third heuristic in Table 3.1 applies try to match the products. The appropriate selector is sharp split . Table 3.8 present lists of characteristic properties. Potential methods are absorption, cryogenic distillation, molecular sieving, membranes and equilibrium adsorption. 

The second technique for C02/methane separation is membrane permeation, now standard in industry. Cryogenic distillation may be applied for methane-enrichment purposes with some technical precautions because of C02 freezing. Equilibrium adsorption on activated carbon would give poor separation. Molecular sieving would permit only the removal of oxygen and nitrogen. 

Adsorption. The adsorption properties for selected AlP0,-based molecular sieves are summarized in Table VIII. The adsorption data are arranged for each structure-type in order of increasing adsorbate size. The large pore structure-types (5, 36, 46) with pores defined by 12-rings of oxygen readily adsorb neopentane (kinetic dia. 0.62 nm>. The 5 and 46 structure-types have been... 

As noted earlier, the term adsorption is universally understood to mean the enrichment of one or more of the components in the region between between two bulk phases (i.e. the interfacial layer). In the present context, one of these phases is necessarily a solid and the other a fluid (i.e. gas or liquid). With certain systems (e.g. some metals exposed to hydrogen, oxygen or water), the adsorption process is accompanied by absorption, i.e. the penetration of the fluid into the solid phase. As already indicated, one may then use the term sorption (and the related terms sorbent, sorptive and sorbate). This is the convention that we shall adopt in the present book. The term sorption is used by some authors to denote the uptake of gas or liquid by a molecular sieve, but we do not favour this practice. 

The latter authors found that a reversible water isothenn was obtained after the low-temperature (i.e. 40°C) evacuation of a carbon cloth, which had been activated by oxidative HNO, treatment. The molecular sieve character of this material was reduced by evacuation at 400°C and this also led to the appearance of hysteresis in the water vapour isothenn. Barton and Koresh (1983) conclude that such hysteresis is mainly due to the concentration of surface oxides which dictate the adsorption value at which the change from cluster adsorption to a continuous adsorbed phase takes place . The relationship between the adsorption of water and the surface concentration of chemisorbed oxygen was first established by Walker and Janov (1968). Bansal et al. (1978a,b) also investigated the influence of the surface oxygen on the adsorption of water they concluded that at p/p° < 0.5 the level of water uptake is determined by the concentration of surface oxygen-containing structures. 

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