摘要
In this paper, the thermodynamics and kinetics of nature rutile carbochlorination in a fluidized-bed were investigated. The thermodynamic calculations of TiO2-C- C12 system show that when C is excess in the solid phase, titanium tetrachloride and carbon monoxide can exist sta- bly. At high temperature, the reaction with CO as the product is the dominant reaction. The appropriate reaction conditions are as follows： reaction temperature of 950 ℃, reaction time of 40 min, carbon ratio of 30 wt% of rutile, natural rutile particle size of -96 μm, petroleum coke size of -150 μm, and chlorine flow of 0.036 m3.h-1. Under the above conditions, the reaction conversion rate of TiO2 can reach about 95 %. This paper proposed a reaction rate model, and got a rutile chlorination rate formula, which is generally consistent with the experimental data. For the TiO2-C-C12 system, the reaction rate is dependent on the initial radius of rutile particle, density, and the partial pressures of C12. From 900 to 1,000 ℃, the apparent activation energy is 10.569 kJ.mo1-1, and the mass diffu- sion is found to be the main reaction-controlling step. The expression for the chlorine reaction rate in the C-C12 sys- tem is obtained, and it depends on the degree of reaction, the partial pressure of C12, and the size of rutile particle.
In this paper, the thermodynamics and kinetics of nature rutile carbochlorination in a fluidized-bed were investigated. The thermodynamic calculations of TiO2-C- C12 system show that when C is excess in the solid phase, titanium tetrachloride and carbon monoxide can exist sta- bly. At high temperature, the reaction with CO as the product is the dominant reaction. The appropriate reaction conditions are as follows： reaction temperature of 950 ℃, reaction time of 40 min, carbon ratio of 30 wt% of rutile, natural rutile particle size of -96 μm, petroleum coke size of -150 μm, and chlorine flow of 0.036 m3.h-1. Under the above conditions, the reaction conversion rate of TiO2 can reach about 95 %. This paper proposed a reaction rate model, and got a rutile chlorination rate formula, which is generally consistent with the experimental data. For the TiO2-C-C12 system, the reaction rate is dependent on the initial radius of rutile particle, density, and the partial pressures of C12. From 900 to 1,000 ℃, the apparent activation energy is 10.569 kJ.mo1-1, and the mass diffu- sion is found to be the main reaction-controlling step. The expression for the chlorine reaction rate in the C-C12 sys- tem is obtained, and it depends on the degree of reaction, the partial pressure of C12, and the size of rutile particle.
基金
financially supported by the National Natural Science Foundation of China(Nos.51374064,51004033,and 51074044)
the National High-Tech Research and Development Program of China(No.2012AA062303)
the National Key Technology Support Program during the 12th Five-Year Plan Period(No.2012BAE01B02)
the Fundamental Research Funds for the Central Universities(Nos.N130402012 and N130702001)
