Thermal properties and pyrolysis kinetics of phosphate-rock acid-insoluble residues

Abstract

In the phosphorous–sulphur two-step process for the clean production of phosphoric acid, a phosphate-rock acid-insoluble residue (PAIR) is a solid filter residue obtained via the phosphoric acid acidolysis of phosphate rock (PR). PAIR combined with other raw materials can be used to prepare cement, ceramics and glasses, opening a potential avenue for large-scale PAIR utilisation. However, the preparation of such materials requires high-temperatures calcination. Understanding the high-temperature thermal properties of PAIR can enable its more targeted comprehensive utilisation or disposal. In this study, the thermal properties and pyrolysis kinetics of PAIR were systematically studied using a multiple heating rate method based on thermogravimetric analysis and a kinetic model. Results showed that from room temperature to 1200 °C, the main changes in the PAIR were the complete removal of fluorine and sulphur, partial removal of phosphorus and conversion of quartz to cristobalite. Moreover, during these processes, H2O(g), NH3, N2, CO2, SO2, P2O5(g), CO, CF3+ and organic gases were volatilised. Herein, the pyrolysis kinetics of PAIR is divided into five stages. Stage 1 (conversion rate ɑ: 0.05–0.2) conforms to the random nucleation and growth as well as the Avrami–Erofeev (n = 2/3) mechanism; the corresponding mechanism function is F(ɑ) = [−Ln(1 − ɑ)]2/3. Stage 2 (ɑ: 0.2–0.4) conforms to the first-order chemical reaction mechanism; the corresponding mechanism function is F(ɑ) = −Ln(1 − ɑ). Stage 3 (ɑ: 0.4–0.6) conforms to the phase boundary–controlled reaction and one-dimensional movement mechanism; the corresponding mechanism function is F(ɑ) = ɑ. Stage 4 (ɑ: 0.6–0.8) conforms to the three-dimensional diffusion process (Jander model); the corresponding mechanism function is F(ɑ) = [1 − (1 − ɑ)1/3]2. Stage 5 (ɑ: 0.6–0.95) conforms to the one-dimensional diffusion process; the corresponding mechanism function is F(ɑ) = ɑ2.