【作者】 刘杰；

【导师】 张卫东；

【作者基本信息】 北京化工大学 ， 化学工程与技术， 2012， 硕士

【摘要】 有机硅化合物兼具有机和无机材料的优良性质，应用广泛。甲基氯硅烷是制备有机硅产品最重要的单体，是有机硅工业的基础和支柱，其中二甲基二氯硅烷单体的需求量最大。直接合成法目前是该单体最经济的合成途径。实际生产中，催化剂对直接合成法的反应性能影响很大；目前，有机硅领域应用最广泛的催化剂为Cu-Cu₂O-CuO三元催化剂。本研究系统考察了液相合成法中实验条件对目的产物的影响。研究发现，液相合成过程中，实验温度、老化时间、溶剂类型等条件对Cu及其氧化物材料的粒径、形貌及Cu-Cu₂O两相组成有显著影响。本研究将所得Cu及其氧化物材料进行了相关表征，并用作模型主催化剂催化直接合成反应生产二甲基二氯硅烷，考察了催化剂粒径、形貌及Cu-Cu₂O两相组成对直接合成反应的影响。研究发现：（1）所制样品粒径范围内，催化剂粒径对硅粉转化率影响不大，约为12%；目的产物选择性则随催化剂粒径增大而逐渐降低，3种Cu₂O催化剂上的二甲基二氯硅烷选择性分别为86.48%，80.65%和74.31%。硅粉表面以催化剂颗粒为中心发生了辐射状刻蚀消耗，且随催化剂粒径增大，反应积碳生成量增加；（2）3种形貌催化剂上的二甲基二氯硅烷选择性分别为73.94%，78.09%和83.89%，目的产物选择性升高；硅粉转化率升高，分别为14.5%，16.0%和23.6%。当催化剂形貌为片状时，反应中形成的Cu3Si活性相更加均一，缓解了局部热点情况，使反应积碳量下降，M2选择性升高；（3）纯Cu相和纯Cu₂O相催化直接合成反应时，目的产物选择性差异较大，分别为51.5%和69.6%；硅粉转化率约为24%，相差不大。当催化剂为Cu-Cu₂O混合组分时，M2选择性随Cu₂O含量的增多不断升高，当Cu含量为15.7%时，硅粉转化率最高可达35%。Cu和Cu₂O两相间存在协同催化作用，且两相均一度越高，协同作用越明显。更多还原

【Abstract】 Organic silane compound shows advantages both of organic andinorganic materials. Methylchlorosilane is the most important monomerfor the production of Organic silane material, among whichdimethyldichlorosilane （M₂） is in the largest demand. The direct synthesisis the most popular way of M2production, which is strongly influencedby the catalyst. The most popular commercial catalyst is Cu-Cu₂O-CuOsysterm presently.The effect of conditions of solusion phase method to the material wasstudied. It was found that the temperature, aging time, type of solvent etchave a substantial effect on the particle size, morphology and Cu-Cu₂Oratio of Cu and its oxide.The as-synthesized Cu and its oxide were then characterized and used asmodel catalyst in direct synthesis. The effect of particle size, morphologyand Cu-Cu₂O ratio of catalyst to the direct synthesis was studied. It wasfound that:（1）The particle size of the Cu₂O microparticles has asubstantial effect on the M2selectivity, but has no obvious effect on the Si conversion （about12%）. The M₂selectivity over Cu₂O microparticleswith three size ranges of100¹50nm,0.5¹μm, and1²μm were86.48%，80.65%and74.31%, respectively. Surface morphology of Si andcontact mass at different stages shows that the carbon deposition isrelated to the catalyst size.（2）The morphology of the Cu₂O-CuOmicroparticles has a substantial effect on the M2selectivity and the Siconversion. The M2selectivity over microparticles of3kinds ofmorphology were73.94%,78.09%and83.89%, and the corresponding Siconversion were14.5%,16.0%and23.6%. The sliced catalyst causedmore dispersed Cu3Si and the less carbon deposition, which led to higherM2selectivity.（3） While pure Cu and Cu₂O was used to catalyze thedirect synthesis, Si conversions were both²4%and the M2selectivitywere51.5%and69.6%respectively. While Cu and Cu₂O mixedmicroparticls was used to catalyze the direct synthesis, M2selectivityincreased with the increasing Cu₂O content, and the maximum Siconversions was35%when Cu content was15.7%in catalyst. There wasan evident synergetic effect between Cu and Cu₂O, which increased withthe better homogenicity of Cu and Cu₂O.更多还原