Organoclays from alkaline-treated acid-activated clays

The cetyltrimethylammonium hydroxide (C16TMAOH) solution was proposed for the preparation of organoclays. Montmorillonite clay was acid activated at different acid/clay (a/c) (in mass) ratios, then treated with alkaline (sodium hydroxide) solution before being reacted with C16TMAOH solution. The acid activation caused a reduction in the number of cation exchange sites, and hence improved the exfoliation of the silicate sheets at higher pH values. The basal spacing increased significantly from 2.20 to 4.01 nm, and depended on the a/c ratios. The acid-activated clays with a/c ratios greater than 0.3 adsorbed significant amounts of C16TMA cations with a basal spacing of 4.01 nm compared with the non-acid-activated montmorillonite (2.51 nm). Meanwhile, the treatment of NaOH solution yielded clays with similar properties to that of the raw used clay. The XRF data, FT-IR, and 29Si MAS-NMR techniques confirmed that the resulting amorphous silica during the acid activation was dissolved, and accompanied by a dramatical reduction in the surface areas. Similar amounts of C16TMA cations were adsorbed, i.e., close to 1 mmol g-1, with a single basal spacing of 2.52 nm, independently of the treated acid-activated clays. The in-situ powder XRD studies revealed that an increase of the basal spacing to 4.20 nm was observed at intermediate temperatures ranging from 50 to 150 degree C for organo-acid-activated clays with basal spacing of 4.01 nm, while a continuous decrease of the basal spacing was observed for organoclays with a basal spacing of 2.52 nm. At higher temperatures greater than 250 degree C, the decomposition of the surfactant occurs, and the basal spacing decreases to a value of about 1.4 nm.