【作者】 王丽丽；

【导师】 黄国强；

【作者基本信息】 天津大学 ， 化学工程， 2015， 硕士

【摘要】 近年来,以硅烷热解为基础的多晶硅生产方法以其具有投资小、能耗低、成本低、无污染等优势,受到了越来越多的关注。本文在充分调研国内外文献的基础上,对硅烷法中氯硅烷歧化反应的动力学及歧化反应中树脂催化剂的干燥特性进行了研究,为后续三氯氢硅歧化反应的工业化应用提供技术支持和理论指导。以大孔弱碱性阴离子交换树脂PA100和A-21为研究对象,对其干燥特性进行了研究。考察了干燥温度,物料层厚度对其干燥速率的影响,并建立了干燥曲线的半经验关联式。结果表明:树脂PA100和A-21的干燥规律基本类似,最优干燥条件下干燥温度及物料层厚度分别为70℃和3cm,湿分比降至5%时干燥时间分别为23.0h、23.7h。在最优干燥条件下,树脂PA100的胺基含量略高于A-21。根据国内外文献,选取了八种催化剂,在小型高压间歇釜式反应器中,考察它们对三氯氢硅歧化反应的影响。结果发现不同的树脂对三氯氢硅歧化反应的催化效果不同,大孔弱碱性阴离子交换树脂PA100的催化效果最好。并以PA100为研究对象,研究了不同催化剂用量、颗粒尺寸、温度和反应时间对三氯氢硅歧化反应的影响,测定了不同温度下三氯氢硅歧化反应的动力学数据,并用二级反应动力学模型对三氯氢硅歧化反应的动力学数据进行了拟合,从而得到氯硅烷歧化反应的动力学方程。结果表明,在催化剂用量为0.1334gcat·gTCS-1,温度为343.15K的条件下PA100的催化活性最好;内外扩散的影响可以忽略,温度的提高和催化剂浓度的提高,都能促进三氯氢硅歧化反应的发生;三氯氢硅歧化反应为二级反应,正反应的指前因子和活化能分别为5.292m3·kmol-1·s-1和9.199kcal/mol,逆反应的指前因子和活化能分别为4.779m3·kmol-1·s-1和5.544kcal/mol。在实验条件范围对获得以PA100为催化剂的三氯氢硅歧化反应动力学方程进行了验证,结果显示误差在5%范围内,表明模型具有较好的拟合精度,能准确反映三氯氢硅歧化反应过程及其动力学特征。更多还原

【Abstract】 In recent years,the process of producting polysilicon through silane has been paid more and more attention because of the advantages of small investment,low energy consumption,low cost and non-environment pollution.A research of the kinetics of the redistribution of trichlorosilane and the drying characteristics of resin catalysts were studied.The work can provide technical support and theoretical guidance for industrial.The drying characteristics of macroporous weak basic anion exchange resin PA100 and A-21 were analyzed,and the semi-empirical drying correlations of the two resins were also established.After a series of discussions,the results show that the drying characteristics of resin PA100 and A-21 are similar,and the best drying temperature and the best thickness of material are 70 ℃ and 3cm.The drying of resin PA100 needs about 23.0 h until the water content is reduced to 5% and A-21 is about 23.7 h. Under the best drying condition,the resin PA100 has a higher amine content than A-21.The redistribution reaction of trichlorosilane(SiHCl3,TCS) was studied by using eight different kinds of catalyst in a high pressure batch reactor.Effects of catalyst quantity,particle size,operating temperature and reaction time were examined.The reaction kinetic parameters were obtained by the the conversion of trichlorosilane change on reaction time.It has been found that the best condition for the conversion of trichlorosilane is at 343.15 K and mass ratio 0.1334gcat·gTCS-1 by using PA100 as the catalyst.The kinetic data analysis suggested that the reaction is second order for the forward and the backward reaction.The pre-exponential factor and activation energy are 5.292m3·kmol-1·s-1 and 9.199 kcal/mol for the forward reaction,the pre-exponential factor and activation energy are 4.779m3·kmol-1·s-1 and 5.544 kcal/mol for the backward reaction.Comparing the calculared values obtained by using the obtained kinetic equation with the experimental values of PA100 in 343.15 K,the margin of error is less than five percentage points.The results indicate that the model exhibits high fitting precision for simulation.更多还原