Decationization and dealumination of clinoptilolite tuff and ammonium exchange on acid-modified tuff

The paper presents results of investigation of exchange of the clinoptilolite tuff cations with hydrogen ions from HCl solution of concentration 0.1 mmol cm−3 and ammonium ions solutions of concentrations 0.0071 to 2.6 mmol cm−3. Molal concentrations, x (mmol g−1) of cations exchanged in acid solution and in ammonium ions solutions were compared with molal concentrations of cations obtained by determination of the cation-exchange capacity of clinoptilolite tuff. The obtained results show that at ammonium ion concentrations lower than 0.1 mmol cm−3, with regard to exchange capacity for particular ions, best exchanged are Na+ ions, followed by Mg2+ and Ca2+ ions, while exchange of K+ ions is the poorest (Na+ > Mg2+ > Ca2+ > K+). At ammonium concentrations from 0.2 to 1 mmol cm−3 the order is Na+ > Ca2+ > Mg2+> K+. At concentrations higher than 1 mmol cm−3 the order is Na+ > Ca2+ > K+ > Mg2+. The results are a consequence of the uptake of hydrogen ions by zeolite samples in ammonium ions solutions at concentrations lower than 1 mmol cm−3 and indicate the importance of Mg2+ (besides Na+ ions) for the exchange between clinoptilolite cations and H+ ions, in contrast to K+ ions, whose participation in the reaction with H+ ions is the lowest. During decationization of the clinoptilolite in acid solution, best exchanged are Na+, Mg2+, and Ca2+ ions, while exchange of K+ ions is the poorest. Due to poor exchange of K+ and H+ ions and good exchange of Na+, Mg2+, and Ca2+ ions, it is to be assumed that preservation of stability of the clinoptilolite structure is caused by K+ ions present in the channel C. Clinoptilolite is dissolved in the clinoptilolite A and B channels where Na+, Mg2+, and Ca2+ ions are present. On the acid-modified clinoptilolite samples, exchange of ammonium ions is poorer than on natural zeolite. The longer the contact time of the zeolite and acid solution, the worse ammonium ions exchange. It can be assumed that H+ ions exchanged with zeolite cations are consumed for solution of aluminum in the clinoptilolite structure; therefore the concentration of H+ ions as exchangeable cations decreases. In the ammonium ion solution at a concentration of 0.0065 mmol cm−3, from the acid-modified zeolite samples, Al3+ ions are exchanged best, followed by Na+, Mg2+, Ca2+, and K+ ions. Further to the results, it is to be assumed that exchangeable Al3+ ions available from clinoptilolite dissolution are best exchanged with H+ ions in acid solution.