Adsorbents, clay-type

Bentonite is a rock rich in montmorillonite that has usually resulted from the alteration of volcanic dust (ash) of the intermediate (latitic) siliceous types. In general, reUcts of partially unaltered feldspar, quartz, or volcanic glass shards offer evidence of the parent rock. Most adsorbent clays, bleaching clays, and many clay catalysts are smectites, although some are palygorskite [1337-76 ]. 

The specific area is measured in m2/gramme. Its value can vary from 1-5 m2/g in the case of, for example, coarse kaolin to about 100 m2/ g for certain plastic clay types. The measurement for example takes place by adsorption of gases like nitrogen. The adsorbed amount is measured as a function of the pressure. At a certain N2 pressure nitrogen molecules at the surface of the solid particles are adsorbed and pressed into the pores. Consequently, this method is also suitable for measuring porosity and pore size distribution. 

This picture is useful but does not match all adsorbents. Gel-type ion-exchange resins have no permanent pores. Instead they consist of a tangled network of interconnected polymer chains into which the solvent dissolves. In effect, Cp = 0. Macroporous ion-exchange resins have permanent pores and Cp > 0, but often < 1.0 for large molecules. Many activated carbons have both macropores and micropores thus, there are two internal porosities. Molecular sieve zeolite adsorbents are used as pellets that are a omerates of zeolite crystals and a binder such as clay. In this case, there is an interpellet porosity (typically, 0.32), an intercrystal porosity ( pi 0.23) and an intracrystal porosity ( p2 0.19), which has < 1.0... 

Dry angular grain clay-type sorbents are useful for traction in slippery areas and as an adsorbent. 

Soils properties are very sensitive to the type of exchangeable ions. Calcium imparts favorable physical properties to the soil, while adsorbed sodium causes clay dispersion and swelling. It is generally recognized that an exchangeable sodium percentage of 10 is sufficient to cause soil dispersion, reduction of soil permeability and impaired growth of some crop plants. On the other hand, excess salt concentration prevents the dispersive effect of adsorbed sodium. 

Two types of swelling may occur. Surface hydration is one type of swelling in which water molecules are adsorbed on crystal surfaces. Hydrogen bonding holds a layer of water molecules to the oxygen atoms exposed on the crystal surfaces. Subsequent layers of water molecules align to form a quasi-crystalline structure between unit layers which results in an increased c-spacing. All types of clays swell in this manner. 

If such fillers are to be used, they should have a neutral or slightly alkaline pH, otherwise additives such as ethylene glycol and triethanolamine, which are preferentially adsorbed on the surface of the filler, should be used, preventing any undesirable interference reactions between the filler and the crosslinking peroxide. These additives must, however, always be added to the mix before the peroxide. With some mineral fillers, such as some types of clay, the polymer may be bound to the filler by means of silane treatment, and the surface of the filler becomes completely non-polar. Consequently, the interaction with the polymer matrix increases, while the adsorption of the crosslinking peroxide by the filler is severely suppressed. 

The preparation of this type of catalyst is quite simple. HPAs such as phos-photungstic acid were adsorbed onto inorganic supports such as clays, alumina, and active carbon. Subsequently, the metal complex was added to form the immobilized catalyst. If necessary, the catalyst can be pre-reduced. These types of catalysts were developed mainly for enantioselective hydrogenations. For instance, a supported chiral catalyst that was based on a cationic Rh(DIPAMP) complex, phosphotungstic acid and alumina showed an ee-value of 93% with a TOF of about 100 IT1 in the hydrogenation of 2-acetamidoacrylic acid methyl ester (Fig. 42.4 Table 42.2). 

At moderate to high salt concentrations (>0.01 M) the adsorbability of Cd was lower from chloride than from nitrate solutions as was the increase in distibution coefficent with increasing pH, possibly as a result of the formation in solution of complexes of the type CdCl n, which have a lower affinity for the clay than the free solvated ion. Adsorbability of Cd and Co increased with increasing pH, particularly at high salt... 

Isaacson and Sawhney (60) studied the reactions of a number of phenols and smectite with transition metal (Cu, FeJ+) and nontransition metal exchangeable cations. IR spectra of the clay-phenol complexes showed that all the clays studied transformed the sorbed phenols. The transformation occurred to a much greater extent in clays with transition metal cations than in those with the non-transition metal cations. In a subsequent study, Sawhney et al. (61) studied the polymerization of 2,6-dimethylphenol on air-dried homoionic Na-, Ca-, A1-, and Fe-smectite at 50°C. A portion of the adsorbed 2,6-dimethylphenol was transformed into dimers, trimers, tetramers, and quinone-type compounds. The nature of the exchange cations had an effect on both sorption and transformation and decreased in the order Fe Al > Ca > Na. 

The linear equilibrium isotherm adsorption relationship (Eq. 11) requires a constant rate of adsorption, and is most often not physically valid because the ability of clay solid particles to absorb pollutants decreases as the adsorbed amount of pollutant increases, contrary to expectations from the liner model. If the rate of adsorption decreases rapidly as the concentration in the pore fluid increases, the simple Freundlich type model (Eqs. 8 and 9) must be extended to properly portray the adsorption relationship. Few models can faithfully portray the adsorption relationship for multicomponent COM-pollutant systems where some of the components are adsorbed and others are desorbed. It is therefore necessary to perform initial tests with the natural system to choose the adsorption model specific to the problem at hand. From leaching-column experimental data, using field materials (soil solids and COMs solutions), and model calibration, the following general function can be successfully applied [155] ... 

Clay minerals with their own surface properties affect the near surface water in different ways. The adsorbed water in the case of kaolinite consists only of water molecules ( pure water), whereas water adsorbed on a smectite-type mineral is an aqueous solution, due to the presence of exchangeable cations on the 2 1 layer sihcate. Sposito (1989) noted the generally accepted description that the spatial extent of adsorbed water on a phyUosilicate surface is about 1.0 nm (two to three layers of water molecules) from the basal plane of the clay mineral. 

Transformation of organic contaminants adsorbed on clay materials is a surface-mediated process controlled by the molecular structure, the type of clay, and the clay-saturating cation, with the rate of contaminant conversion affected by the... 

The Indians of the Peruvian Altiplano eat potatoes with a dip of clay and a mustard-like herb. They say the clay removes the bitter taste and prevents stomach pains or vomiting after eating large amounts of potatoes. The people who eat clay intend detoxication. This may explain how Indians started to utilize and domesticate wild potatoes. Indeed, experiments have shown that four different types of edible clay adsorb the glycoalkaloid tomatine under simulated... 

---