Rehydration Driven Acid Impregnation of Thermally Pretreated Ca-Bentonite-Evolution of the Clay Structure

A new approach to acid activation of raw Ca-bentonite was explored. The method consisted in dehydration of clay by thermal pretreatment at 200 °C, followed by immediate impregnation with H₂SO₄ solution. The acid concentration was 1.5 × or 2.0 × cation exchange capacity (CEC) of clay. The volume of the liquid was adjusted so as to leave the material in the apparently dry state. Structural evolution of the activated solids after 1, 2, 3, and 4 weeks of storage was monitored with X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FTIR), ²⁷Al magic angle spinning nuclear magnetic resonance (MAS NMR), and chemical analysis. In the macroscopically dry solids, the rehydrated interlayer Ca²⁺ underwent rapid exchange with H₃O⁺ and formed extra-framework gypsum. Acid attack on montmorillonite structure resulted in continuous removal of layer forming Mg, Al, and Fe cations, with Mg²⁺ being eliminated most efficiently. No significant damage to the montmorillonite lattice was observed. Al was extracted both from the tetrahedral and the octahedral sheets. Under less acidic conditions, the monohydrated H-montmorillonite changed upon storage to bi-hydrated form, as a result of clay auto-transformation. Higher concentrations of acid in the pore network of clay stabilized the H-form of montmorillonite. The data indicate that compositional transformation of acid impregnated bentonite extended beyond the one month of aging investigated in the present work.