Cross-linked Smectites. IV. Preparation and Properties of Hydroxyaluminum-Pillared Ce- and La-Montmorillonites and Fluorinated NH4+-Montmorillonites

M. Tokarz1 and J. Shabtai
Department of Fuels Engineering, University of Utah Salt Lake City, Utah 84112
1 On leave of absence from the University of Mining and Metallurgy, Krakow, Poland.

Abstract: Reaction of hydroxy-Al oligocations with Ce3+- and La3+-exchanged montmorillonites, using 1.25, 1.60, or 2.0 mmole Al/g smectite, yielded partially pillared hydroxy-Al montmorillonite products containing a significant concentration of residual Ce3+ or La3+. After heat treatment at 250°C these products showed high surface areas (∼340–500 m2/g) and high basal X-ray powder diffraction spacings (18.0Å18.6 Å). Calcination at 400°–700°C resulted in lower surface areas of ∼200–450 m2/g and basal spacings of 16.3–18.3 Å, the values showing a gradual decrease with a decrease in the Al/smectite weight ratio and/or increase in the heat-treatment temperature. A major modification and improvement in the cross-linking procedure was achieved by fast aging (6–48 hr) of the hydroxy-Al oligomeric solution at 95°–100°C, instead of conventional aging for 2–3 weeks at 25°C.

Fluorinated NH4+-montmorillonites, containing 0.4 to 2.1 wt. % F, were prepared by reaction of NH4+-montmorillonite at 60°C with 1.0 to 3.0 N aqueous solutions of NH4F. Interaction of the fluorinated montmorillonites with hydroxy-Al oligocations, using a ratio of 2.0 mmole Al/g smectite, yielded a series of cross-linked fluorinated montmorillonites with basal spacings of 17.9–18.0 Å and surface areas of 180–325 m2/g after heat treatment at 250°C. Calcination at 400°–500°C resulted in lower d(001) (16.6–17.7 Å) and surface-area values (140–300 m2/g). Increase in the fluorine content caused gradual decrease in both values. Transmission electron microscopy of pillared Ce-montmorillonite showed a highly oriented network of well-separated, parallel unit layers with an interlayer distance, Δd(001), of 9–10 Å. Calculated lateral (interpillar) distances were in good agreement with the pore-size distributions determined in independent adsorption studies.

Key Words: Cross-linked smectite • Hydroxy-Al • Montmorillonite • Pillared interlayered clays • Pore-size distribution • Rare earth elements

Clays and Clay Minerals; April 1985 v. 33; no. 2; p. 89-98; DOI: 10.1346/CCMN.1985.0330202
© 1985, The Clay Minerals Society
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