A Mechanism Study Of The Formation Of Sodium Vanadate Compounds Under The Conditions Of The Salt-Roast Process

A study has been made of the reaction mechanisms occurring during the salt-roast process to form water-soluble sodium vanadate compounds from the vanadium oxide compounds present in vanadium-bearing ores and concentrates. Two reactions have been identified, either of which lead to water-soluble compounds--oxidation of sodium chloride by water vapor and. oxidation of sodium chloride by oxygen. The former reaction has been found to be predominant in the salt-roast process. A kinetic treatment of the data has shown that for the formation of sodium metavanadate the rate-controlling step in the reaction, in which sodium chloride is oxidized by water vapor is the decomposition of a species containing water and sodiumm chloride, on the surface at the gas-solid interface. For the formation of sodium pyrovanadate, the rate-controlling step is the decomposition of a species containing water and sodium metavaradate on the surface. The transportation of water through the system, perhaps as a sodium chloride-water complex or a sodium metavanadate-water complex, and the actual chemical reaction are relatively fast compared to the initial surface decomposition step. A similar treatment on the data for the oxidation, of sodium chloride by oxygen has shown that the rate-controlling step, is the actual transportation of oxygen from the gas-solid interface to the reactive site. This transportation is by a sequence of two diffusion processes. Transportation during the early stages of the reaction is by the diffusion of oxygen through a continuous layer of reaction product. After, the first few minutes of reaction time a second diffusion process begins and is continuous for the remainder of the reaction. This second diffusion process involves the diffusion of oxygen, through a layer of reaction product that has developed voids around which the oxygen must diffuse. The hindering, nature of this latter process causes the rate of transportation of oxygen to the reaction site to be considerably slower than by the simple diffusion mechanism initially followed. A thermodynamic treatment of the data has shown that the energy of activation for the decomposition of the water-sodium chloride species on the surface is -12.1 Kcal. per mole. For the decomposition of the water-sodium metavanadate species on the surface' the energy of activation is -15.1 Kcal. per mole. The results of this study indicate the limiting mechanisms of the basic reactions occurring during the salt-roast process. These results suggest what variables should be examined in applying this information to actual plant operations.