• 关键词：MnO₂/Al₂O₃催化剂  喹啉  煤化工废水  臭氧催化氧化  臭氧微气泡

• 基金项目：黑龙江省自然科学基金（No.LH2020D010）；城市水资源与水环境国家重实验室基金项目（No.ESK202004）

• 王树涛
• 哈尔滨工业大学, 城市水资源与水环境国家重点实验室, 哈尔滨 150090

• 王莹
• 北京高能时代环境技术股份有限公司, 北京 100095

• 孟富臣
• 哈尔滨工业大学, 城市水资源与水环境国家重点实验室, 哈尔滨 150090

• 李宛伦
• 哈尔滨工业大学, 城市水资源与水环境国家重点实验室, 哈尔滨 150090

• 尤宏
• 哈尔滨工业大学, 城市水资源与水环境国家重点实验室, 哈尔滨 150090

• 摘要：制备了纳米MnO₂，并以Al₂O₃为载体制备了掺杂型MnO₂/Al₂O₃颗粒催化剂.催化剂焙烧温度和时间分别为500℃和4 h、MnO₂质量分数为8%时，催化剂具有最高的臭氧催化氧化活性.SEM分析表明，纳米MnO₂均匀分布于Al₂O₃载体表面.MnO₂/Al₂O₃催化剂的比表面积（BET）为183.22 m²·g^-1，平均孔容为0.27 cm³·g^-1，平均孔径为4.87 nm.建立了MnO₂/Al₂O₃催化剂-微气泡臭氧催化反应体系，研究了该体系对喹啉的降解去除效果及其机理.臭氧微气泡的平均粒径为61.7 μm.微气泡臭氧投量为30 mg·L^-1时，反应60 min后喹啉去除率能达到95%以上；反应20 min后，MnO₂/Al₂O₃催化剂-微气泡臭氧体系对实际煤化工废水二级出水的TOC去除率可达到55%以上.以叔丁醇作为分子探针，证明了羟基自由基（·OH）氧化作用在臭氧微气泡催化氧化体系中对喹啉的降解起到主导作用.

• Abstract：A doped catalyst MnO₂/Al₂O₃ was prepared by using Al₂O₃ as the support. The catalyst exhibit the highest activity when the calcination temperature and duration was 500 ℃ and 4 h, respectively, and the mass percent of MnO₂ was 8%. The nano-sized MnO₂ was distributed on the surface of the Al₂O₃ support according to the scanning electron scope (SEM) analysis. The specific surface area (BET), average pore volume and pore diameter of the catalyst reached 183.22 m²·g^-1, 0.27 cm³·g^-1 and 4.87 nm, respectively. A catalyst ozonation system was established with MnO₂/Al₂O₃ and microbubble ozone. The removal rate of quinoline reached >95% at the ozone dose of 30 mg·L^-1 and the reaction time of 60 min. The TOC removal rate for the secondary effluent of the real coal chemical wastewater achieved 55% after 20 min reaction at the ozone dose of 180 mg·L^-1·h^-1. In addition, it is proved that ·OH dominated the removal of quinoline in the catalytic ozonation reaction with MnO₂/Al₂O₃ catalyst by using tertiary butanol (TBA) as molecular probe.

• Key words：MnO₂/Al₂O₃ catalyst  quinoline  coal chemical wastewater  catalytic ozonation  microbubble ozone

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