Carbon molecular sieves adsorption

EPA. 1988f Method T02. Method for the determination of volatile organic compounds in ambient air by carbon molecular sieve adsorption and GC/MS. Compendium of methods for the determination of toxic organic compounds in ambient air. Atmospheric Research and Exposure Assessment Laboratory, Office of Research and Development, U.S. Environmental Protection Agency, RTP, NC. EPA/600/4-89/017. 

Carbon molecular sieve adsorption desorption at 350°C into a cryogenically cooled troop flash evaporated onto a capillary column GC/MS system recommended sample volume 10 L flow rate 100 mL/min. 

TO-2 Carbon molecular sieve adsorption, GC/MS analysis Highly volatile, nonpolar organics in the b.p. range -15° to +120°C... 

Active carbons Carbon molecular sieves Adsorption polymers Silica gels Narrow Wide Porous glasses Micro-/meso-/ macropores Zeolites Bleaching earth Activated alumina... 

Many simple systems that could be expected to form ideal Hquid mixtures are reasonably predicted by extending pure-species adsorption equiUbrium data to a multicomponent equation. The potential theory has been extended to binary mixtures of several hydrocarbons on activated carbon by assuming an ideal mixture (99) and to hydrocarbons on activated carbon and carbon molecular sieves, and to O2 and N2 on 5A and lOX zeoHtes (100). Mixture isotherms predicted by lAST agree with experimental data for methane + ethane and for ethylene + CO2 on activated carbon, and for CO + O2 and for propane + propylene on siUca gel (36). A statistical thermodynamic model has been successfully appHed to equiUbrium isotherms of several nonpolar species on 5A zeoHte, to predict multicomponent sorption equiUbria from the Henry constants for the pure components (26). A set of equations that incorporate surface heterogeneity into the lAST model provides a means for predicting multicomponent equiUbria, but the agreement is only good up to 50% surface saturation (9). 

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. 

Fig. 3. Pressure swing adsorption nitrogen generation system. CMS = carbon molecular sieve.

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. 

Air Adsorption onto carbon molecular sieve thermal desorption GC/MS (EPA Method T02) No data 91 (15% RSD) at 89 ng/L EPA 1988f... 

Selectivity. Selectivity in a physical adsorption system may depend on differences in either equilibrium or kinetics, but the great majority of adsorption separation processes depend on equilibrium-based selectivity. Significant kinetic selectivity is. in general, restricted to molecular sieve adsorbents—carbon molecular sieves, zeolites, or zeolite analogues. 

To achieve a significant adsorptive capacity an adsorbent must have a high specific area, which implies a highly porous structure with very small micropores. Such microporous solids can be produced in several different ways. Adsorbents such as silica gel and activated alumina are made by precipitation of colloidal particles, followed by dehydration. Carbon adsorbents are prepared by controlled burn-out of carbonaceous materials such as coal, lignite, and coconut shells. The crystalline adsorbents (zeolite and zeolite analogues are different in that the dimensions of the micropores are determined by the crystal structure and there is therefore virtually no distribution of micropore size. Although structurally very different from the crystalline adsorbents, carbon molecular sieves also have a very narrow distribution of pore size. The adsorptive properties depend on the pore size and the pore size distribution as well as on the nature of the solid surface. 

Gawrys, M., Fastyn, P., Gawlowski, J., Gierczak, T. and Niedzielski, J. (2001) Prevention of water vapour adsorption by carbon molecular sieves in sampling humid gases. Journal of Chromatography A, 933, 107-16. 

The primary requirement for an economic adsorption separation process is an adsorbent with sufficient selectivity, capacity, and life. Adsorption selectivity may depend either on a difference in adsorption equilibrium or, less commonly, on a difference in kinetics. Kinetic selectivity is generally possible only with microporous adsorbents such as zeolites or carbon molecular sieves. One can consider processes such as the separation of linear from branched hydrocarbons on a 5A zeolite sieve to be an extreme example of a kinetic separation. The critical molecular diameter of a branched or cyclic hydrocarbon is too large to allow penetration of the 5A zeolite crystal, whereas the linear species are just small enough to enter. The ratio of intracrystalline diffusivities is therefore effectively infinite, and a very clean separation is possible. 

In molecular sieve adsorbents, such as zeolites and carbon molecular sieves, the micropore size distribution is extremely narrow, thus allowing the possibility of kinetic separations based on differences in molecular size. However, this feature is utilized in only a few commercial adsorption separation processes, and in the majority of such processes the separation depends on differences in the adsorption equilibrium rather than on the kinetics, even though a molecular sieve adsorbent may be used. 

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. 

Physical adsorption at a surface is extremely rapid, and the kinetics of physical adsorption are invariably controlled by mass or heat transfer rather than by the intrinsic rate of the surface process. Biporous adsorbents such as pelleted zeolites or carbon molecular sieves offer three distinct resistances to mass transfer the external resistance of the... 

FIGURE 11 Sequence of steps in a two-bed pressure swing adsorption system, (a) Skarstrom cycle, (b) modified cycle for production of nitrogen using a carbon molecular sieve adsorbent. 

Cazorla-Amoros D, Alcaniz-Monge J, Casa-Lillo MA, and Linares-Solano A. C02 as an adsorptive to characterize carbon molecular sieves and activated carbons. Langmuir, 1998 14(16) 4589-4596. 

Lozano-Castello D, Cazorla-Amoros D, Linares-Solano A, and Quinn DF. Micropore size distributions of activated carbons and carbon molecular sieves assessed by high-pressure methane and carbon dioxide adsorption isotherms. J. Phys. Chem. B, 2002 106(36) 9372-9379. 

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. 

There are only four types of sorbents that have dominated the commercial use of adsorption activated carbon, molecular-sieve zeolites, sihca gel, and activated alumina. Estimates of worldwide annual sales of these sorbents are as follows (Humphry and Keller, 1997) ... 

DYNAMIC ADSORPTION OF TERT-BUTYLBENZENE, CYCLOHEXANE AND WATER VAPOURS ON FIXED ACTIVATED CARBON/MOLECULAR SIEVE BEDS... 

Abstract. Activated carbon Norit R 08 Extra, and molecular sieve type 4A, were investigated using dynamic (tert-butylbenzene (TBB), cyclohexane (CHX) and water vapour) adsorption methods. The TBB, CHX and water breakthrough plots for fixed activated carbon - molecular sieve beds were analyzed. It was found that the type of bed composition with mechanically mixed activated carbon with molecular sieve, or separated activated carbon and molecular sieve layers, affects the dynamic adsorption characteristics. 

Keywords activated carbons molecular sieve breakthrough dynamics tert-butylbenzene adsorption cyclohexane water breakthrough time... 

Table 1. Dynamic adsorption of TBB on carbon/molecular sieve beds. Table 2. Dynamic adsorption of cyclohexane. ...

Purification with PSA and Polymeric Membranes. The PSA process is based on the selective adsorption of gaseous compounds on a fixed bed of solid adsorbent in a series of identical adsorption beds. The adsorbent is an active carbon or a carbon-molecular sieve. Each bed undergoes a... 

Many new adsorbents have been developed over the past 20 years including carbon molecular sieves, new zeolites and aluminophosphates, pillared clays and model mesoporous solids. In addition, various spectroscopic, microscopic and scattering techniques can now be employed for studying the state of the adsorbate and microstructure of the adsorbent. Major advances have been made in the experimental measurement of isotherms and heats of adsorption and in the computer simulation of physisorption. 

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