氯硅烷中痕量磷杂质的检测方法及应用

doi:10.16085/j.issn.1000-6613.2017-0782

化工进展 ›› 2018, Vol. 37 ›› Issue (01): 406-413.DOI: 10.16085/j.issn.1000-6613.2017-0782

氯硅烷中痕量磷杂质的检测方法及应用

刘帅峰, 黄国强

天津大学化工学院, 天津 300350

收稿日期:2017-04-28 修回日期:2017-07-27 出版日期:2018-01-05 发布日期:2018-01-05
通讯作者: 黄国强,博士,副教授,主要从事多晶硅精馏领域的研究、开发与工程设计。
作者简介:刘帅峰(1993-),男,硕士研究生,从事基于络合吸附-精馏协同法除四氯化硅中极微量硼、磷杂质的研究工作。
基金资助:
国家自然科学基金项目（21676197）。

Determination method and application of trace amounts of phosphorus in chlorosilanes

LIU Shuaifeng, HUANG Guoqiang

School of Chemical Engineering and Technology, Tianjin University, Tianjin 300350, China

Received:2017-04-28 Revised:2017-07-27 Online:2018-01-05 Published:2018-01-05

摘要/Abstract

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

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

中图分类号:

TQ127.2

刘帅峰, 黄国强. 氯硅烷中痕量磷杂质的检测方法及应用[J]. 化工进展, 2018, 37(01): 406-413.

LIU Shuaifeng, HUANG Guoqiang. Determination method and application of trace amounts of phosphorus in chlorosilanes[J]. Chemical Industry and Engineering Progress, 2018, 37(01): 406-413.

参考文献

[1] 徐远志. 改良西门子法制备工艺及其生产技术现状[J]. 云南冶金,2011,40(1):52-55. XU Yuanzhi. The preparation technology and current situation of industrial practice of improved siemens process[J]. Yunnan Metallurgy,2011,40(1):52-55.
[2] KRAY W D. Purification of chlorosilanes:US4481178[P]. 1984-06-11.
[3] BRADLEY H B. Purification of silicon compounds:US3188168[P]. 1965-08-06.
[4] DARNELL R D,INGLE W M. Purification of silicon source materials:US4409195[P]. 1982-08-19.
[5] CASWELL E G. Method for purifying silance:US2971607[P]. 1961-02-14.
[6] BRINK R G,DEITERING N H,GREENE M H,et al. Phosphorous removal from tetrachlorosilane:US5232602[P]. 1993-08-03.
[7] XU X,HUANG G. Effect of 13X zeolite modified with CuCl₂ and ZnCl₂ for removing phosphine from circular hydrogen of a polysilicon chemical vapor deposition stove[J]. Industrial & Engineering Chemistry Research,2016,55:1380-1386.
[8] XU X,HUANG G,QI S. Properties of AC and 13X zeolite modified with CuCl₂ and Cu(NO₃)₂ in phosphine removal and the adsorptive mechanisms[J]. Chemical Engineering Journal,2017,316:563-572.
[9] MOTOMIZU S,WAKIMOTO T,TOEI K,et al. Spectrophotometric determination of phosphate in river waters with molybdate and malachite green[J]. Automatica,1983,108(1284):3227.
[10] AFKHAMI A,NOROOZ-ASL R. Cloud point extraction for the spectrophotometric determination of phosphorus (Ⅴ) in water samples[J]. J. Hazard Mater.,2009,167(1/2/3):752-755.
[11] LANCASTER W A,EVERINGHAM M R. Spectrophotometric determination of traces of phosphorus in silicon tetrachloride utilizing an extractive separation[J]. Analytical Chemistry,1964,36(1):283-292.
[12] SCHULTE B K,SHIVE L W. Determination of phosphoryl chloride and detection of phosphorus trichloride in electronic grade trichlorosilane by gas chromatography with thermionic detection[J]. Analytical Chemistry,1982,54(13):2392-2393.
[13] BERCHMANS S,LSSA T B,SINGH P. Determination of inorganic phosphate by electroanalytical methods:a review[J]. Analytica Chimica Acta,2012,729(11):7.
[14] WARWICK C,GUERREIRO A,SOARES A. Sensing and analysis of soluble phosphates in environmental samples:a review[J]. Biosensors & Bioelectronics,2013,41(1):1-11.
[15] DIAS C C,JANI K P,MURUGAIYAN P,et al. Determination of trace amounts of phosphorus in trichloro-and tetrachlorosilane[J]. Analyst,1975,100(1189):259-262.
[16] 龚艳,闻胜,李书谦,等. 钼酸铵分光光度法测定水质中总磷时砷的干扰消除研究[J]. 分析测试技术与仪器,2011,17(1):36-41. GONG Yan,WEN Sheng,LI Shuqian,et al. Study on cancellation of arsenic interference in determination of total phosphorus in water by ammonium molybdate spectrophotometry[J]. Analysis and Testing Technology and Instruments,2011,17(1):36-41.
[17] 贾润中,李敏,杨静怡. 钼酸铵分光光度法测定水中总磷方法的改进[J]. 山东化工,2015,44(20):69-70. JIA Runzhong,LI Min,YANG Jingyi. Improved method for determination of total phosphorus in water by ammonium molybdate spectrophotometric method[J]. Shandong Chemical Industry,2015,44(20):69-70.
[18] MOTOMIZU S,LI Z H. Trace and ultratrace analysis methods for the determination of phosphorus by flow-injection techniques[J]. Talanta,2005,66(2):332-340.
[19] 张云晖,杨晓静,亢若谷,等. 电感耦合等离子体原子发射光谱法测定工业硅中8种杂质元素[J]. 冶金分析,2013,33(2):55-59. ZHANG Yunhui,YANG Xiaojing,KANG Ruogu,et al. Determination of eight impurity elements in industrial silicon by inductively coupled plasma atomic emission spectrometry[J]. Metallurgical Analysis,2013,33(2):55-59.
[20] 赵丽,余家国,程蓓,等. 单分散二氧化硅球形颗粒的制备与形成机理[J]. 化学学报,2003,61(4):562-566. ZHAO Li,YU Jiaguo,CHENG Bei,et al. Preparation and formation mechanisms of monodispersed silicon dioxide spherical particles[J]. Acta Chimica Sinica,2003,61(4):562-566.
[21] JIAN L. The effect of catalysts on TEOS hydrolysis-condensation mechanism[J]. Journal of Inorganic Materials,1997,12(3):363-369.

氯硅烷中痕量磷杂质的检测方法及应用

Determination method and application of trace amounts of phosphorus in chlorosilanes

PDF (PC)

可视化

摘要/Abstract

引用本文

使用本文

参考文献

相关文章 15

编辑推荐

Metrics

本文评价

[1]	崔守成, 徐洪波, 彭楠. 两种MOFs材料用于O₂/He吸附分离的模拟分析[J]. 化工进展, 2023, 42(S1): 382-390.
[2]	陈崇明, 陈秋, 宫云茜, 车凯, 郁金星, 孙楠楠. 分子筛基CO₂吸附剂研究进展[J]. 化工进展, 2023, 42(S1): 411-419.
[3]	许春树, 姚庆达, 梁永贤, 周华龙. 共价有机框架材料功能化策略及其对Hg(Ⅱ)和Cr(Ⅵ)的吸附性能研究进展[J]. 化工进展, 2023, 42(S1): 461-478.
[4]	顾永正, 张永生. HBr改性飞灰对Hg⁰的动态吸附及动力学模型[J]. 化工进展, 2023, 42(S1): 498-509.
[5]	郭强, 赵文凯, 肖永厚. 增强流体扰动强化变压吸附甲硫醚/氮气分离的数值模拟[J]. 化工进展, 2023, 42(S1): 64-72.
[6]	王胜岩, 邓帅, 赵睿恺. 变电吸附二氧化碳捕集技术研究进展[J]. 化工进展, 2023, 42(S1): 233-245.
[7]	葛亚粉, 孙宇, 肖鹏, 刘琦, 刘波, 孙成蓥, 巩雁军. 分子筛去除VOCs的研究进展[J]. 化工进展, 2023, 42(9): 4716-4730.
[8]	李由, 吴越, 钟禹, 林琦璇, 任俊莉. 酸性熔盐水合物预处理麦秆高效制备木糖及其对酶解效率的影响[J]. 化工进展, 2023, 42(9): 4974-4983.
[9]	杨莹, 侯豪杰, 黄瑞, 崔煜, 王兵, 刘健, 鲍卫仁, 常丽萍, 王建成, 韩丽娜. 利用煤焦油中酚类物质Stöber法制备碳纳米球用于CO₂吸附[J]. 化工进展, 2023, 42(9): 5011-5018.
[10]	潘宜昌, 周荣飞, 邢卫红. 高效分离同碳数烃的先进微孔膜：现状与挑战[J]. 化工进展, 2023, 42(8): 3926-3942.
[11]	张振, 李丹, 陈辰, 吴菁岚, 应汉杰, 乔浩. 吸附树脂对唾液酸的分离纯化[J]. 化工进展, 2023, 42(8): 4153-4158.
[12]	王兰江, 梁瑜, 汤琼, 唐明兴, 李学宽, 刘雷, 董晋湘. 快速热解铂前体合成高分散的Pt/HY催化剂及其萘深度加氢性能[J]. 化工进展, 2023, 42(8): 4159-4166.
[13]	姜晶, 陈霄宇, 张瑞妍, 盛光遥. 载锰生物炭制备及其在环境修复中应用研究进展[J]. 化工进展, 2023, 42(8): 4385-4397.
[14]	于静文, 宋璐娜, 刘砚超, 吕瑞东, 武蒙蒙, 冯宇, 李忠, 米杰. 一种吲哚基超交联聚合物In-HCP对水中碘的吸附作用[J]. 化工进展, 2023, 42(7): 3674-3683.
[15]	李艳玲, 卓振, 池亮, 陈曦, 孙堂磊, 刘鹏, 雷廷宙. 氮掺杂生物炭的制备与应用研究进展[J]. 化工进展, 2023, 42(7): 3720-3735.