Studies on the chlorination of zircon: Part I. Static bed investigations

Abstract

Carbochlorination is an important unit operation in the processing of zirconium resources. In the article, the use of different reducing agents in zircon chlorination, to produce zirconium tetrachloride, has been examined on thermodynamic and other considerations. While numerous workers have investigated zircon chlorination, a literature survey shows that there is a wide variation in the reported effect of various process parameters on the chlorination rate and a wide scatter in the values for kinetic parameters such as order of reaction, activation energy, rate constant as also the rate law expression. This work is an extensive study on zircon chlorination and the article discusses the effect of process parameters such as charge particle size, gas and solid composition, gas flow rate, temperature, reaction duration, etc. on the chlorination rate, over a much wider range of the parameter values. During investigations in the static bed chlorinator, it was noticed that the initial rate and the total extent of chlorination are proportional to the exposed surface of the solid zircon-coke charge but independent of the depth or amount of the charge. Further, the stalled chlorination could be reactivated by remixing the solid charge. Also, while the reaction rate in general increased as the charge became finer, the effect of zircon particle size was much more predominant. The activation energy value for the chlorination showed a wide variation with other operating conditions. Likewise, the order of reaction with respect to chlorine decreased from two to zero as the chlorine concentration in the gaseous atmosphere increased. Interestingly, the chlorination rate initially increased with gas flow rate, then decreased, before finally becoming independent of the gas flow rate. Results also indicated that there is an optimum charge composition that yields the maximum chlorination rate and the article discusses the effect of the zircon to coke particle number ratio in the initial charge on the chlorination kinetics. With the help of these observations, it is possible to explain the wide variation in the reported effect of the various process parameters on zircon chlorination.