Abstract: Phosphorus impurities in the chlorosilane mixture was difficult to be separated due to their similar boiling points. The adsorbents of 13X zeolite (13X) and 13X zeolite modified with CuCl₂ (Cu-13X)compared with adsorbents of metal oxide were prepared to adsorb trace PCl₃ in this study. The Ultraviolet-visible spectroscopy (UV-vis)was used to determine the content of trace phosphorus in the chlorosilanes. The effects of the composition of the hydrolysate and the phase state of the raw materials on the determination of phosphorus impurity content with UV-vis were investigated based on the analysis of the contents of phosphorus in water and in the chlorosilanes. Besides, the breakthrough curves at 20℃ were investigated to determine the performance of the adsorbents of 13X and Cu-13X. The results showed that the pre-treatment phase state of chlorosilanes samples with the high purity nitrogen used as carrier gas is gas phase when they were passed into the high-purity water and the determined mass fraction of phosphorus in chlorosilanes varied between 0.0003 and 0.03. The adsorption performance of Cu-13X was enhanced after modified with CuCl₂. When the volume of the mixture solution increased to 120mL in the breakthrough experiment process, the removal efficiency of the complexation adsorbents for PCl₃ was still greater than about 80%, whereas the adsorption capacity of the 13X zeolite disappeared due to complete breakthrough when the volume of the mixture solution was 20mL.

Key words: chlorosilanes, phosphorus trichloride, hydrolysis, azeotrope, adsorption, zeolite

摘要： 针对混合氯硅烷原料中沸点接近、分离困难的含磷杂质物系，对比金属氧化物吸附剂，以13X分子筛（13X）及负载CuCl₂的13X分子筛（Cu-13X）作为络合吸附剂进行气相吸附实验，并采用紫外分光光度计检测氯硅烷中磷杂质含量，结合水中和氯硅烷原料中磷含量分析实验考察了氯硅烷原料预处理过程中水解液组成、氯硅烷原料的相态对用紫外分光光度计检测磷杂质含量范围的影响规律及机理，探究了13X及Cu-13X在20℃时作为络合吸附剂的突破曲线。结果表明，氯硅烷原料的预处理相态为气相并以高纯氮气作载气通入高纯水中，氯硅烷中磷杂质质量含量的检测范围为0.0003～0.03，13X经过CuCl₂浸渍改性后性能得到大幅度提升，当穿透实验进行到混合液体积为120mL时，络合吸附剂对PCl₃的脱除效率仍大于80%，而在混合液体积20mL，左右13X-分子筛则被完全穿透失去吸附能力。

关键词: 氯硅烷, 三氯化磷, 水解, 共沸(混合)物, 吸附, 沸石