三氯氢硅歧化反应动力学及反应精馏制备硅烷研究

Kinetics for disproportionation reaction of trichlorosilane and preparation of silane by reactive distillation

在固定床反应器中,探讨了PA100、Amberlyst 21、D301R、D66对三氯氢硅歧化反应催化效果,筛选出最佳催化剂PA100。以PA100为催化剂,反应温度在330~400 K,研究三氯氢硅歧化反应动力学,探究了反应温度、催化剂填充量及催化剂颗粒大小对三氯氢硅歧化反应的影响。实验结果表明,在一定范围内,反应温度越高,反应速率越快,平衡时三氯氢硅转化率越高;催化剂填充量和颗粒大小对平衡时三氯氢硅转化率几乎没有影响。根据三氯氢硅歧化反应机理和实验研究,建立三氯氢硅歧化反应动力学模型,计算化学平衡常数,通过Arrhenius公式得出三氯氢硅歧化反应正反应活化能129. 60 kJ/mol,逆反应活化能61. 74 kJ/mol,对催化剂PA100进行SEM、TEM表征。

Catalytic efficiencies of PA100,Amberlyst21,D301 R and D66 on the disproportionation reaction of trichlorosilane are investigated in a fixed-bed reactor and PA100 is found to be the optimum catalyst.The kinetics for the disproportionation reaction of trichlorosilane is studied by using PA100 as catalyst at reaction temperature between 330 K and 400 K. Effects of the reaction temperature,loading amount of catalyst and particle size of the catalyst on the disproportionation reaction of trichlorosilane are investigated. The test results indicate that within a certain temperature range,the higher the reaction temperature,the faster the reaction rate and the higher the trichlorosilane conversion rate at equilibrium.Moreover,neither catalyst dosage nor particle size affect the conversion rate of trichlorosilane at equilibrium.According to the disproportionation mechanism of trichlorosilane and experiments,a kinetic model for the disproportionation of trichlorosilane is established and chemical equilibrium constant is calculated.Based on the Arrhenius equation,the activation energies for the forward and reverse reactions of trichlorosilane disproportionation are 129. 60 k J·mol-1 and 61. 74 k J·mol-1,respectively.PA100 is characterized by SEM and TEM.