Aluminum smectite

Transmission electron micrographs show hectorite and nontronite as elongated, lath-shaped units, whereas the other smectite clays appear more nearly equidimensional. A broken surface of smectite clays typically shows a "com flakes" or "oak leaf surface texture (54). High temperature minerals formed upon heating smectites vary considerably with the compositions of the clays. Spinels commonly appear at 800—1000°C, and dissolve at higher temperatures. Quartz, especially cristobalite, appears and mullite forms if the content of aluminum is adequate (38). 

The original pillared clays were made by (/) mixing smectite with a polymeric cationic hydroxy metal complex such as aluminum chlorhydrol (2) allowing a minimal amount of time for the cationic hydroxy metal complex to exchange with the interlayer cations and (7) calcining the resulting material to decompose the hydroxy metal complex (110). A number of newer methods have been developed to make pillared clays (111—117). 

Allophane and Imogolite. AUophane is an amorphous clay that is essentially an amorphous soHd solution of sUica, alumina, and water (82). In allophane less than one-half of the aluminum is held in tetrahedral coordinations and the Si02 to AI2O2 ratio typically varies between 1.3 and 2.0, but values as low as 0.83 have been reported. The typical morphology of allophane is cylindrical (37). AUophane may be associated with haUoysite, smectite minerals, or it may occur as a homogeneous mixture with evansite, an amorphous soHd solution of phosphoms, alumina, and water. Its composition, hydration, and properties vary. Chemical analyses of two allophane samples are given in Table 5. 

Smectite is the first secondary mineral to form upon rock weathering in the semi-arid to sub-humid tropics. Smectite clay retains most of the ions, notably Ca2+ and Mg2+, released from weathering primary silicates. Iron, present as Fe2+ in primary minerals, is preserved in the smectite crystal lattice as Fe3+. The smectites become unstable as weathering proceeds and basic cations and silica are removed by leaching. Fe3+-compounds however remain in the soil, lending it a reddish color aluminum is retained in kaolinite and A1-oxides. Leached soil components accumulate at poorly drained, lower terrain positions where they precipitate and form new smectitic clays that remain stable as long as the pH is above neutral. Additional circumstances for the dominance of clays are ... 

Fig. 23.6. Calculated saturation indices (log Q/K) of aluminum-bearing minerals plotted versus temperature for a hot spring water from Gjogur, Hveravik, Iceland. Lines for most of the minerals are not labeled, due to space limitations. Sampling temperature is 72 °C and predicted equilibrium temperature (arrow) is about 80 °C. Clinoptilolite (zeolite) minerals are the most supersaturated minerals below this temperature and saponite (smectite clay) minerals are the most supersaturated above it.

Clays composed of layers are called layered silicates. The most common sheets are tetrahedral silicon and octahedral aluminum (see Figure 3.2, Figure 3.3, and Figure 3.4). Three common representative clays in soil are 1 1 kalo-inite, 2 1 fine-grained micas, and 2 1 smectites that is, kaolinites have one sheet of silicon tetrahedra and one sheet of aluminum octahedra. The finegrained mica and smectites have two sheets of silicon tetrahedra and one sheet... 

The Smectite Clays. The smectite-type clays are distinctive in that they expand and cause significant destruction to synthetic (human-made) structures. In this type of 2 1 clay, isomorphous substitution occurs in the aluminum sheet. If there is substitution of lower-oxidation-state metal such as magnesium, there will be an unsatisfied pair of bonding electrons in the interior of the crystal and there will be no noticeable change in the surface. Because the charge is in the interior of the crystal, its attraction for cations is diminished by distance. Thus, smectite crystals are not held together strongly by cations and are able to incorporate more water and ions between sheets when the environment is wet and less when it is dry. 

Kaolin Minerals. The 1 1 structures include a group of aluminosilicate minerals which are termed collectively the kaolin minerals specifically these are kaolinite, dickite, nacrite, and halloysite. The basic 1 1 layer for all of these minerals has the composition AlgSigOj-fOHJj, there is a small amount of substitution of iron for aluminum, ana fluoride for hydroxyl ion. All, except halloysite, are normally anhydrous and do not expand (as do the smectites) upon exposure to water and most organic molecules. As a result, they generally have a rather small surface area, on the order of 10 nr... 

Iron impurities in clays have been thought responsible for these type of catalysts low carbon selectivity (4,5). The purpose of this paper is to investigate and report the influence that the location, chemical state and environment of iron impurities have on the cracking properties of pillared clays prepared by reacting several smectites with aluminum chlorhydroxide solutions. 

Fig. 1. Hydroxyl absorption bands for several smectites pillared with aluminum chlorhydroxide (ACH) soluctions A) Wyoming ACH-bentonite B) Texas ACH-bentonite C) Fe-bentonite D) ACH- Fe bentonite) E) (ACH, Fe)-bentonite and F) ACH-nontronite. Samples a) have been dried at 200 C and then loaded with pyridine and degassed at b) 200 C, c) 300 C, d) 400 C and e) 500 C in vacuo for 2 hours at each temperature.

Here we report the synthesis and catalytic application of a new porous clay heterostructure material derived from synthetic saponite as the layered host. Saponite is a tetrahedrally charged smectite clay wherein the aluminum substitutes for silicon in the tetrahedral sheet of the 2 1 layer lattice structure. In alumina - pillared form saponite is an effective solid acid catalyst [8-10], but its catalytic utility is limited in part by a pore structure in the micropore domain. The PCH form of saponite should be much more accessible for large molecule catalysis. Accordingly, Friedel-Crafts alkylation of bulky 2, 4-di-tert-butylphenol (DBP) (molecular size (A) 9.5x6.1x4.4) with cinnamyl alcohol to produce 6,8-di-tert-butyl-2, 3-dihydro[4H] benzopyran (molecular size (A) 13.5x7.9x 4.9) was used as a probe reaction for SAP-PCH. This large substrate reaction also was selected in part because only mesoporous molecular sieves are known to provide the accessible acid sites for catalysis [11]. Conventional zeolites and pillared clays are poor catalysts for this reaction because the reagents cannot readily access the small micropores. 

Intact soil cores (6.7 cm i.d.) were taken with spilt spoon at depths of 1 to 2 meters from a field test site located approximately 50 km east of Cincinnati, Ohio. The soil in this interval consists mainly of quartz (60%) and clay minerals (35%) with minor amounts of plagioclase and potassium feldspar. The majority of clay is illite and smectite, with minor amount of kaolinite. Soil chemical properties were analyzed prior to, and after, electroosmosis, in order to evaluate the effects of electroosmosis on the distribution of elements within the soil column. Sampled cores were wrapped in aluminum foil and stored at 12°C until the EO cell was assembled. 

Moinereau, J. (1977). Absorption of humic compounds by a hydrogen(-i-), aluminum(3+) montmorillonite. Presence of smectite in the interlayer space of organomineral complexes of the andosols. Clay Min. 12,75-82. 

The three-sheet or 2 1 layer lattice silicates consist of two silica tetrahedral sheets between which is an octahedral sheet. These three sheets form a layer approximately 10 A thick. The oxygens at the tips of the tetrahedra point towards the center octahedral sheet and substitute for two-thirds of the octahedrally coordinated hydroxyls. The 2 1 clay minerals include the mica and smectite groups which are by far the most abundant of the clay minerals. The pure end members of this type are talc, a hydrous magnesium silicate pyrophyllite, a hydrous aluminum silicate and minnesotaite, a hydrous iron silicate. 

Figure 2. Structure of a typical chlorite-like hydroxy-interlayered clay in which the galleries of a 2 1 smectite structure are filled, or nearly so, with brucite-like sheets of mainly edge-shared Mg(OH) octahedra. Aluminum occasionally substitutes for magnesium in the brucite sheet to provide the charge balance necessary for electrical neutrality.

Clay minerals are hydrous aluminum phyllosilicates made of sheets or layers composed of tetrahedra and octahedra. This mineral type includes the following groups kaolinite, smectite, illite, and chlorite. In the case of smectite, each layer comprises two sublayers of tetrahedra with an inserted octahedral layer, where, between layers, an interlayer space where the exchangeable cations are located is formed [131-133], In Figure 2.24... 

Bentonite occurs commercially as powders ranging in colors and tints from off white to pale brown to gray depending on the cations present in natural deposits. It comprises natural smectite clays consisting primarily of colloidal hydrated aluminum silicates of the montmorillonite or hectorite type of minerals with varying quantities of alkalies, alkaline earths, and iron. It is insoluble in water, in alcohol, in dilute acids, and in alkalies. 

Clays and particles of soil organic matter have negative charges and high CECs, as confirmed by the following values 150-500 meq/100 g for organic matter and 3-150 meq/100 g for clay minerals (as kaolinite and smectite). On the other hand, aluminum and iron hydroxide colloids tend to be hydrophobic, with surface positive charges, and, consequently, they are predominantly anion adsorbers. 

Finally, clays such as the smectites almost invariably have a net negative structural charge because of isomorphous substitution of cations of lower charge than would be present in a balanced structure. In kaolinite, the amphoteric nature of the hydrated aluminum and silica surface contributes more to surface charge than does substitution. As a result of either substitution or surface dissociation, a region of counter ions (exchangeable and... 

---