化工学报 ›› 2020, Vol. 71 ›› Issue (12): 5561-5567.DOI: 10.11949/0438-1157.20200407

• 催化、动力学与反应器 • 上一篇    下一篇

稳定高效Ru/TiO2-ZrO2催化剂处理苯酚磺酸废水

杨霁豪(),耿莉莉,叶松寿,谢建榕,张诺伟,陈秉辉()   

  1. 厦门大学化学化工学院,福建 厦门 361005
  • 收稿日期:2020-04-11 修回日期:2020-07-06 出版日期:2020-12-05 发布日期:2020-12-05
  • 通讯作者: 陈秉辉
  • 作者简介:杨霁豪(1996—),男,硕士研究生,20620171151213@stu.xmu.edu.cn
  • 基金资助:
    国家自然科学基金项目(21673187);中央高校基本科研业务费专项资金(20720180021)

Stable and efficient Ru/TiO2-ZrO2 catalysts for catalytic wet air oxidation of phenolsulfonic acid wastewater treatment

YANG Jihao(),GENG Lili,YE Songshou,XIE Jianrong,ZHANG Nuowei,CHEN Binghui()   

  1. College of Chemistry and Chemical Engineering, Xiamen University, Xiamen 361005, Fujian, China
  • Received:2020-04-11 Revised:2020-07-06 Online:2020-12-05 Published:2020-12-05
  • Contact: CHEN Binghui

摘要:

催化湿式氧化(CWAO)技术可高效处理有机废水,但现有催化剂的性能,尤其是其稳定性距工业应用还有很大差距。利用ZrO2对TiO2载体进行掺杂调变,研制出了具有良好稳定性的Ru/TiO2-ZrO2催化湿式氧化催化剂。结果表明, Ru/TiO2催化剂在进行连续5次催化湿式氧化降解苯酚磺酸(phenolsulfonic acid,PSA)废水的反应后,总有机碳(total organic carbon,TOC)转化率由99.1%降低至65.3%;而Ru/TiO2-ZrO2催化剂在Ti/Zr质量比为9∶1~7∶3范围内,能表现出优良的反应性能,在连续5次反应后, TOC转化率稳定保持在90%以上。X射线仪衍射(XRD)、N2吸脱附(BET)、X射线扫描微探针电子能谱仪(XPS)、氢气程序升温还原(H2-TPR)和电感耦合等离子体发射光谱(ICP-OES)表征结果表明:ZrO2能够进入TiO2的晶格,TiO2-ZrO2固溶体的生成阻止了TiO2由锐钛矿相向金红石相的转变。另外,ZrO2的调变加强了Ru与载体的相互作用,有效抑制了活性金属Ru的流失。稳定的载体结构和良好的抗流失性能是Ru/TiO2-ZrO2催化剂具有优良反应性能的主要原因。

关键词: 催化湿式氧化, 复合氧化物载体, 苯酚磺酸废水, 稳定性, 无害化处理

Abstract:

Catalytic wet air oxidation (CWAO) technology can efficiently treat organic wastewater, but the performance of existing catalysts, especially its stability, is far from industrial applications. In this study, ZrO2 was used to modify TiO2 support to form the stable Ru/TiO2-ZrO2 catalysts. It was found that the Ru/TiO2-ZrO2 catalysts showed excellent performance for catalytic wet air oxidation of phenolsulfonic acid wastewater. They gave high total organic carbon (TOC) conversions (>90%) and remained stable in 5 consecutive running in the Ti/Zr ratio range from 9∶1 to 7∶3. On the other hand, TOC conversion decreased from 99.1% to 65.3% in 5 consecutive cycles for the conventional Ru/TiO2 catalyst. The characterization results of XRD, BET, XPS, H2-TPR and ICP-OES indicated that ZrO2 can enter the lattice of TiO2 to form TiO2-ZrO2 solid solution, which prevented the transformation of TiO2 from anatase to rutile. In addition, the modification of ZrO2 strengthened the interaction between Ru and the support, which effectively inhibited the leaching of Ru metal. The stable support structure and good anti-loss performance are the main reasons for the excellent reaction performance of Ru/TiO2-ZrO2 catalyst.

Key words: catalytic wet air oxidation, composite oxide support, phenolsulfonic acid wastewater, stability, harmless treatment

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