Study on Precipitation Kinetics of Calcium Pyro-Vanadate and Thermodynamics of Vanadium Water System

Abstract

Selective catalytic reduction (SCR) is a technology widely used in large coal-fired units to remove nitrogen oxides from flue gas, but it also generates a large number of waste catalysts every year. At present, the recovery of V from discarded SCR catalysts has good application prospects and environmental significance. In this paper, the kinetics and thermodynamics of vanadium precipitation process are described with the vanadium-containing liquid of waste denitration catalyst recovered by alkali leaching as raw material and CaCl2 as precipitant in order to further explore the mechanism of vanadium precipitation. The kinetics study showed that the crystallization process of calcium pyrovanadate can be well-described by Avrami kinetic model when the precipitation time is 95–130 min, and the vanadium precipitation temperature is 60–80 °C. After that, the Arrhenius equation was used to analyze the fitted kinetic data, and the apparent activation energy Ea of vanadium precipitation reaction was calculated to be 98.196 kJ/mol, and the pre exponential factor A = 8.59 × 1039 min−1. Thermodynamic study showed that when the pH of the vanadium water system is low, the +5 valence vanadium in the solution mainly exists in the form of VO2+ cation. When the pH is between 0–1, the solubility of vanadium reaches the minimum and then increases the solution pH again, and various polymerized anions are formed in the vanadium water system. When the temperature is 25 °C, the activity of vanadium in vanadium-containing solution is 10−1, the pH of solution is 8–12, and the existence form of +5 valence vanadium in solution is mainly HV2O73−. By analyzing the existing forms of V with different activities in a vanadium water system at 25 °C, it can be seen that with the decrease of V activity in liquid, the dominant region of polymerized vanadium-containing species in the potential pH diagram will disappear, indicating that vanadium mainly exists in the form of mononuclear ions in low-concentration vanadium-containing solutions, which is not conducive to precipitation. Therefore, in the process of precipitation of vanadium in solution, the concentration of V should be increased as much as possible.