Carbon molecular sieve material selection

New Adsorbent Materials. SihcaUte and other hydrophobic molecular sieves, the new family of AlPO molecular sieves, and steadily increasing families of other new molecular sieves (including stmctures with much larger pores than those now commercially available), as well as new carbon molecular sieves and pillared interlayer clays (PILCS), will become more available for commercial appHcations, including adsorption. Adsorbents with enhanced performance, both highly selective physical adsorbents and easily regenerated, weak chemisorbents will be developed, as will new rate-selective adsorbents. 

Carbon molecular sieves are produced by controlled pyrolysis and subsequent oxidation of coal, anthracite, or organic polymer materials. They differ from zeolites in that the micropores are not determined by the crystal structure and there is therefore always some distribution of micropore size. However, by careful control of the manufacturing process the micropore size distribution can be kept surprisingly narrow, so that efficient size-selective adsorption separations are possible with such adsorbents. Carbon molecular sieves also have a well-defined bi-modal (macropore-micropore) size distribution, so there are many similarities between the adsorption kinetic behavior of zeolitic and carbon molecular sieve systems. 

The above examples of shape selective reactions show the complexity of such systems and that several factors need to be considered before shape selective control can be realized. The use of other porous supports besides zeolites such as carbon molecular sieves, clays, pillared clays and related materials to catalyze shape selective reactions appears to be growing. Molecular modeling of the spatial constraints of various pores is also an area of increased research effort. 

Carbon molecular sieve membranes. Molecular sieve carbons can be produced by controlled pyrolysis of selected polymers as mentioned in 3.2.7 Pyrolysis. Carbon molecular sieves with a mean pore diameter from 025 to 1 nm are known to have high separation selectivities for molecules differing by as little as 0.02 nm in critical dimensions. Besides the separation properties, these amorphous materials with more or less regular pore structures may also provide catalytic properties. Carbon molecular sieve membranes in sheet and hollow fiber (with a fiber outer diameter of 5 pm to 1 mm) forms can be derived from cellulose and its derivatives, certain acrylics, peach-tar mesophase or certain thermosetting polymers such as phenolic resins and oxidized polyacrylonitrile by pyrolysis in an inert atmosphere [Koresh and Soffer, 1983 Soffer et al., 1987 Murphy, 1988]. 

Successful separation of alkanes and alkenes has been documented when microporous membranes have been used [79,138]. The physiochemical properties, size, and shape of the molecules will play an important role for the separation, hence critical temperatures and gas molecule configurations should be carefully evaluated for the gases in mixture. On the basis of gas properties and process conditions, the separation may be performed according to selective surface flow or molecular sieving (refer to Section 4.2 on transport). The transport may also be enhanced by having a Ag compound in the membrane. The Ag ion will form a reversible complex with the alkene, and facilitated transport results. Selectivities in the range of 200-300 have been reported for separation of ethene-ethane and propene-propane [138]. Successful separation of alkanes and alkenes will be important for the petrochemical industry. Today the surplus hydrocarbons in the purge gas are usually flared. Membranes which should be suitable for this application are the carbon molecular sieves (see Section 4.3.2) and nanostructured materials (Section 4.3.3). 

Carbon molecular sieves, or carbogoric sieves are amorphous materials made by pyrolyz-ing coal, coconut shells, pitch, phenol-formaldehyde resin, or other polymers. EKslocations of aromatic microdomains in a glassy matrix give their porosity. Pores are slit-shaped. Pore structure is controlled by the temperature of the pyrolysis. Pore widths range from 3 A to 10 A. Acarbogenic sieve made from polyfurfuryl alcohol and combined with silica-alumina was selective for monomethylamine production from methanol and ammonia [54]. 

Recently, carbon molecular sieves have been fabricated in the form of planar membranes and hollow tubes by the pyrolysis of polyacrylonitrile in suitable forms (12-16). Very high separation selectivities have been reported with these materials. Their pore sizes are in the range from 3 to 5.2A. Selectivities of greater than 100 1 are observed between molecules which differ by as little as 0.2A in their critical dimensions. Kinetics of adsorption on these materials have been determined (2.,ii,l ) -... 

Activated carbon adsorbents generally show very little selectivity in the adsorption of molecules of different size. However, by special activation procedures it is possible to prepare carbon adsorbents with a very narrow distribution of micropore size and which therefore behave as molecular sieves. The earliest examples of carbon molecular sieves appear to have been prepared by decomposition of polyvinylidene dichloride (Saran) but more recently a wide variety of starting materials have been used. Most commercial carbon sieves are prepared from anthracite or hard coal by controlled oxidation and subsequent thermal treatment. The pore structure may be modified to some extent by subsequent treatment including controlled cracking of hydrocarbons within the micropore system and partial gasification under carefully regulated conditions. ... 

Another kind of membrane material is represented by a group of nanoporous, hydrogen-selective carbon molecular sieve membranes, which exhibit excellent permeation characteristics and hydrogen permeabilities competitive with metallic membranes (Harale et al., 2007). Furthermore, they are unaffected by CO or hydrogen sulfide (H2S) contamination. Nevertheless, their hydrothermal stability is not guaranteed at r > 623 K. 

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