Kinetics and thermodynamic parameters for the manufacturing of anhydrous zirconium tetrafluoride with ammonium acid fluoride as fluorinating agent

Abstract

More than 30 percent of the global demand for zircon (ZrSiO4) is supplied by South Africa. A significant amount of the zircon is exported, and beneficiated products are then imported for industrial applications locally. Beneficiating the zircon locally could have a positive impact on the local market, since zircon is only one of many such cases. Ammonium acid fluoride serves as an alternative anhydrous fluorinating agent for zircon in the synthesis of several metal fluorides1,2. It provides an effective dry fluorinating method and is easier to handle than hydrogen fluoride or fluorine gas. Zircon exposed to extreme plasma temperatures dissociates and becomes more reactive. The reaction of the plasma-dissociated zircon (ZrO2·SiO2) with the ammonium acid fluoride (NH4F·xHF, where x = 1 to 5) forms two main intermediate compounds (NH4)3ZrF7(s) and (NH4)2SiF6(s), the latter decomposing to form volatile products at relatively low temperatures, providing easy separation of the silicon and zirconium compounds. The ammonium zirconate compound decomposes to form zirconium tetrafluoride (ZrF4), which can be further manufactured into zirconium metal, to name but one product. Data on the kinetics of the reaction of ammonium acid fluoride with zircon and plasma-dissociated zircon, combined with the thermodynamic parameters of the reaction, is essential for the development of an industrial process for the production of a precursor for the manufacturing of zirconium metal, namely anhydrous ZrF4. Both the reaction kinetics and reaction parameters will be included in this study, as well as some proof that the reaction proceeds to ZrF4 on a small batch scale. If the exact reaction parameters can be pinned down, a wide spectrum of anhydrous metal fluorides can be synthesized through this fluorination route.