Adsorbents pillared clays

ESR has also been used in the characterization of species adsorbed on pillared clays, i.e. smectites with hydroxy-aluminium interlayers. Adsorption of Cu(II) on hydroxy-aluminium hectorite produced mobile hexaaquacopper(II) and Cu(II) chemisorbed to... 

The number of acid sites on pillared clays was determined by means of temperature programmed desorption (TPD) of ammonia. In each TPD experiment, a sample weighing about 0.5 g was treated in vacuo for 1 h at a given temperature in the range 400 - 600°C. Ammonia was adsorbed at a desired temperature (100-300°C) for 30 min and evacuated for 30 min. This sample was heated to 700°C at a rate of 10°C/min and desorbed ammonia was monitored by thermal conductivity detector. As water was desorbed simultaneously with ammonia, the ammonia TPD spectrum was obtained by point-by-point subtraction of the water desorption spectrum obtained with the sample which had not adsorbed ammonia. 

This chapter discusses the fundamental principles for designing nanoporous adsorbents and recent progress in new sorbent materials. For sorbent design, detail discussion is given on both fundamental interaction forces and the effects of pore size and geometry on adsorption. A summary discussion is made on recent progress on the following types of materials as sorbents activated carbon, activated alumina, silica gel, MCM-41, zeolites, n -complexation sorbents, carbon nano tubes, heteropoly compounds, and pillared clays. 2001 Academic Press. 

Nanoporous materials like zeolites and related materials, mesoporous molecular sieves, clays, pillared clays, the majority of silica, alumina, active carbons, titanium dioxides, magnesium oxides, carbon nanotubes and metal-organic frameworks are the most widely studied and applied adsorbents. In the case of crystalline and ordered nanoporous materials such as zeolites and related materials, and mesoporous molecular sieves, their categorization as nanoporous materials are not debated. However, in the case of amorphous porous materials, they possess bigger pores together with pores sized less than 100 nm. Nevertheless, in the majority of cases, the nanoporous component is the most important part of the porosity. 

It is a mass transfer between a mobile, solid, or liquid phase, and the adsorption bed packed in a reactor. To carry out adsorption, a reactor, where a dynamic adsorption process will occur, is packed with an adsorbent [2], The adsorbents normally used for these applications are active carbons, zeolites and related materials, silica, mesoporous molecular sieves, alumina, titanium dioxide, magnesium oxide, clays, and pillared clays. 

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. 

According to Cool and Vansant (1996), pores between 0.7 and 1.1 nm are probably present in all pillared clays, whereas the narrow and wider pores are particular features of the Zr-laponite and Zr-hectorite. A relatively high adsorption affinity (i.e. the low pressure capacity) of Zr-laponite for cyclohexane was attributed to the presence of a large number of narrow pores, giving rise to enhanced adsorbate-adsorbent interactions. 

Many applications of AFM to pillared clays or zeolites have not specifically addressed the porosity characteristics, but rather the occurrence of adsorbed surface Al species in, e.g., pillared montmorillonite [41], or the crystal growth processes, adsorption on porous surfaces and the surface structure of natural zeolites [42]. Sugiyama et al. [43] succeeded to reveal the ordered pore structure of the (001) surface of mordenite after removal of impurities that clogged the pores. The authors indicated that resolution in AFM imaging of zeolites is significantly affected by the magnitude of the periodical corrugation on the crystal surface, so that if the surface contains deep pores only the pore structure, but not the atomic structure, can be resolved. 

These clays have been hybridized with diverse structural types of components such as nanoparticles, clusters, complex compounds, polymers, molecules, and ions. Their potential apphcations are found in many fields as inorganic catalysts, adsorbents, ceramics, coatings, and even drug delivery carriers. Various preparation methods have been developed such as pillaring, intercalation, and delamination techniques. The representative examples include organic-clay hybrids," metal oxide-pillared clays, " and bioclay hybrids. ... 

In order to improve the textural properties of particle-clay nanohybrids, bulky organic cations are intercalated as a kind of template into particle-intercalated clays before stabilization procedures. Intercalation of the organic cations results in the removal of some of the intercalated nanoparticles and/or in their rearrangement. Subsequent calcination leads to formation of additional pore space that is highly correlated to the geometry and size of the templates. This technique allows fine tuning of textural properties in the preparation of particle-clay nanohybrids. The clay nanohybrids intercalated with metals, oxides, and complexes have a broad range of applications. In particular, metal oxide particle-pillared clays have excellent potentials as catalysts, catalyst supports, selective adsorbents, etc. " ... 

Fig. 2 Scheme for recycling surfactant-modified pillared clay mineral adsorbents during thermal treatment of toxicant. From Michot and Pinnavaia (1991), with kind permission from the Clay Minerals Society. 

A combination of sc carbon dioxide and light has been used in flow reactors to make some metal complexes not possible by other methods, for example, cyclopentadi-enylMn(CO)2(H2) and Cr(CO)s(ethylene).179 A man ganese hydride has been added to olefins in carbon dioxide.180 A zeolite in sc carbon dioxide selectively adsorbs 2,7-dimethylnaphthalene so that it can be separated from the desired 2,6-dimethylnaphthalene.181 The latter is oxidized to the dicarboxylic acid for conversion to a highermelting analogue of poly(ethylene terephthalate). A pillared clay made in supercritical carbon dioxide had a higher... 

Amount of surfactant (mmol/meq), aluminium adsorbed (mg/g of clay), pillar density number (PDN), 001 spacings (pillared clay catalyst samples. 

The so-called pillared montmorillonities are prepared by intercalating oligomeric metal hydroxide ions into interlayers [31], Pillared clays have high surface areas and the structural parameters of their mlcropores vary as function of the pillaring material and preparation conditions. These materials show promise for use as high-performance adsorbents and active catalysts. Yamazaki et al. [99] performed N2 adsorption experiments to investigate the structure of pores and sizes of pillars of montmorillonites pillared with Al and Cr. 

Ferreira et al. produced a high-activity metallocene catalyst (1457 kg PE/(mol Zr h atm)) by supporting Cp2ZrCl2 (II) on a pillared clay. Calcium montmorillonite was pillared with Keggin ions, [Ali304(0H)24 12H20] +, to increase its Lewis acidity. The clay was pretreated at 200°C to remove adsorbed water, then exposed to a toluene solution of MAO at 50°C to attenuate its Bronsted acidity. High activity was maintained over a period of 1 h at 50°C. The apparent absence of the usual rapid metallocenium deactivation processes was attributed to the suppression of bimolecular interactions in the supported catalyst. 

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