黄国强,何泰锋
AuthorsHTML:黄国强，何泰锋
AuthorsListE:Huang Guoqiang,He Taifeng
AuthorsHTMLE:Huang Guoqiang，He Taifeng
Unit:天津大学化工学院，天津 300350
Unit_EngLish:School of Chemical Engineering and Technology，Tianjin University，Tianjin 300350，China
Abstract_Chinese:为去除改良西门子法循环氢气中的微量磷化氢杂质，使用浸渍法对 5A 分子筛分别负载了氯化铜和醋酸铜 制成了改性吸附剂．分别对空白/5A、氯化铜/5A 和醋酸铜/5A 3 种吸附剂进行了磷化氢吸附穿透实验，吸附实验结 果证明铜盐的负载能显著增加 5A 分子筛对磷化氢的吸附能力，其中醋酸铜/5A 的吸附性能最好，在实验室固定床 中穿透吸附容量达空白/5A 的 7 倍以上．分别考察了浸渍液浓度、吸附温度、磷化氢浓度和进气流速对醋酸铜/5A 吸附性能的影响：醋酸铜/5A 对磷化氢的吸附性能随醋酸铜浸渍液浓度(0.1～0.3 mol/L)的增加而增强；在-15 ～ 50 ℃内醋酸铜/5A 对磷化氢吸附性能随温度升高而增强；磷化氢浓度在 50×10-6～500×10-6 范围内，进气流速在 100～200 mL/min 范围内时醋酸铜/5A 吸附性能保持稳定．对吸附磷化氢饱和后的醋酸铜/5A 分别采用了热氮气吹扫 和热空气煅烧两种方式进行再生，然后分别对其进行了磷化氢吸附穿透实验，实验结果证明醋酸铜/5A 具有优秀的 再生能力，可以通过热空气煅烧的方式恢复 90%的磷化氢吸附性能，是一种理想的磷化氢吸附材料．采用了 BET、 XRD、XPS 对醋酸铜/5A 物化性质进行了表征：BET 表征结果证明醋酸铜/5A 有更多的微孔结构，这有利于磷化氢 的吸附；XRD 和 XPS 表征结果证明醋酸铜/5A 的吸附磷化氢的活性组分以氧化铜为主，吸附磷化氢后的产物为氧 化亚铜和正磷酸．
Abstract_English:To remove trace phosphine impurities in the circulating hydrogen of the improved Siemens method， modified 5A molecular sieve adsorbents were prepared by impregnation with copper chloride and copper acetate. Phosphine adsorption experiments were performed on blank/5A，CuCl2/5A，and Cu(CH3COO)2/5A. The adsorption experiment results showed that the copper salts could significantly increase the phosphine adsorption capacity of 5A. Among the salts，Cu(CH3COO)2/5A had the best adsorption performance，and its penetration adsorption capacity in a laboratory fixed bed was over seven times that of blank/5A. The effects of the impregnant concentration，adsorption temperature，phosphine concentration，and inlet flow rate on the adsorption performance of Cu(CH3COO)2/5A were investigated. The adsorption performance increased with the increase in Cu(CH3 COO)2 concentration(0.1— 0.3 mol/L)and with the increase in temperature in the range of -15—50 ℃；moreover，the adsorption performance of Cu(CH3COO)2/5A could remain stable when the phosphine concentration was in the range of 50×10-6—500×10-6 and the inlet flow rate was in the range of 100—200 mL/min. The used Cu(CH3COO)2/5A was regenerated by hot nitrogen purging and hot air calcination. The phosphine adsorption experimental results showed that Cu(CH3COO)2/5A had an excellent regeneration ability and could restore 90% of the phosphine adsorption capacityby hot air calcination，indicating that it is an ideal phosphine adsorption material. The physical and chemical properties of Cu(CH3COO)2/5A were characterized by Brunauer-Emmett-Teller(BET)characterization，X-ray diffraction(XRD) ， and X-ray photoelectron spectroscopy(XPS). The BET characterization results showed that Cu(CH3COO)2/5A had a more microporous structure，which is beneficial to the phosphine adsorption. The XRD and XPS characterization results showed that the active component of Cu(CH3COO)2/5A was mainly CuO，and the produce after phosphine adsorption were Cu2O and H3PO4.
Keyword_Chinese:改良西门子法；循环氢；磷化氢；醋酸铜/5A；氧化铜
Keywords_English:improved Siemens method；circulating hydrogen；phosphine；Cu(CH3COO)2/5A；CuO

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