铜基改性吸附剂对磷化氢的吸附去除研究  

Adsorption and Removal of Phosphine by Copper-Based Modified Adsorbent

作　　者：黄国强[1] 张宇[1] Huang Guoqiang;Zhang Yu(School of Chemical Engineering and Technology,Tianjin University,Tianjin 300350,China)

机构地区：[1]天津大学化工学院,天津300350

出　　处：《天津大学学报（自然科学与工程技术版）》2022年第11期1166-1173,共8页Journal of Tianjin University：Science and Technology

基　　金：国家自然科学基金资助项目(21676197).

摘　　要：针对多晶硅生产过程中循环氢气中存在较多磷化氢杂质影响多晶硅产品质量的问题,采用浸渍法制备氯化铜改性分子筛吸附剂,以含100×10^(-6)磷化氢的氢气作为实验气体,在30℃下进行动态吸附实验,研究了载体种类、铜盐负载量、吸附剂煅烧温度和吸附空速对磷化氢吸附去除效果的影响.实验结果表明:采用浸渍法制得的CuCl_(2)改性分子筛吸附剂对磷化氢吸附性能较好,在300℃下煅烧制得的负载10%CuCl_(2)/5A的吸附效果最好,最大穿透吸附容量达到12.65 mg/g,吸附突破时间为540 min.载体种类、铜盐负载量以及空速均对磷化氢去除产生重要影响,实验所用的4种载体中,5A分子筛具有较好的吸附效果.增加载铜量可显著提高吸附剂性能,但当负载量增加至10%后,进一步增加载铜量吸附效果无显著提升.动态吸附实验最佳吸附空速为1500h^(-1),空速过低磷化氢在吸附剂表面扩散过慢,不利于活性物质与磷化氢反应;空速过高则反应停留时间短,也会降低磷化氢去除效率.煅烧温度对于活性物质CuO的生成以及吸附剂结构产生重要影响,较为合适的煅烧温度为300℃.XRD、TGDSC及H_(2)-TPR表征表明:样品制备过程中发生氯化铜的水解生成碱式氯化铜,在50~250℃范围内煅烧,碱式氯化铜的分解反应产生氧化铜.但煅烧温度过高易导致吸附剂烧结,影响吸附剂的强度和吸附性能.The presence of many phosphine impurities in the circulating hydrogen during the production of polysilicon affects the quality of polysilicon.To solve this problem,a copper chloride modified molecular sieve adsorbent was prepared by the impregnation method and the hydrogen containing 100×10^(-6) phosphine was used as the experimental gas.The dynamic adsorption experiment was carried out at 30℃.Effects of the molecular sieve carrier type,copper salt loading,calcination temperature,and adsorption space velocity on the adsorption removal of phosphine were investigated.Experimental results showed that the CuCl_(2) modified molecular sieve adsorbent prepared by the impregnation method had a good adsorption performance for phosphine.Moreover,10%CuCl_(2)/5A calcined at 300℃ exhibited the best adsorption effect with a maximum adsorption capacity of 12.65 mg/g and an adsorption breakthrough time of 540 min.The type of carrier,copper salt loading,and space velocity have an important influence on the removal of phosphine.Among the four carriers used in the experiment,the 5A molecular sieve as the carrier has the best ad-sorption.The effect is an ideal carrier material for an adsorbent.Increasing the copper loading of the carrier up to 10%can significantly improve the performance of the adsorbent.However,when the loading is further increased,the copper loading of the carrier does not significantly improve the adsorption effect.The optimal adsorption space velocity for dynamic adsorption experiments is 1500h^(-1).If the space velocity is too low,the diffusion of phosphine on the surface of the adsorbent will be too slow,which is not conducive to the reaction;if the space velocity is too high,the reaction residence time will be short,which will also reduce the effective removal of phosphine.The calcination temperature has an important effect on the formation of the active material CuO and the structure of the adsorbent.The suitable calcination temperature is found to be 300℃.XRD,TG-DSC,and H_(2)-TPR characterizations sh

关 键 词：循环氢气 磷化氢 CuCl2/5A 吸附 煅烧温度 空速 

分 类 号：TQ126.3[化学工程—无机化工]