化工进展 ›› 2022, Vol. 41 ›› Issue (1): 493-502.DOI: 10.16085/j.issn.1000-6613.2021-1703

• 资源与环境化工 • 上一篇    下一篇

臭氧催化氧化降解煤化工高盐废水有机物的机理

王吉坤1,2(), 李阳1,2(), 陈贵锋1,2, 刘敏1,2, 寇丽红1,2, 王琦1,2, 何毅聪1,2   

  1. 1.煤炭科学技术研究院有限公司,北京 100013
    2.煤炭资源高效开采与洁净利用国家重点实验室,北京 100013
  • 收稿日期:2021-08-10 修回日期:2021-09-25 出版日期:2022-01-05 发布日期:2022-01-24
  • 通讯作者: 李阳
  • 作者简介:王吉坤(1989—),男,硕士,助理研究员,研究方向为煤化工废水处理。E-mail:304336935@qq.com
  • 基金资助:
    政府间国际科技创新合作重点专项(2019YFE0103300)

Catalytic oxidation mechanism of organics degradation by ozone in high-salt wastewater of coal chemical industry

WANG Jikun1,2(), LI Yang1,2(), CHEN Guifeng1,2, LIU Min1,2, KOU Lihong1,2, WANG Qi1,2, HE Yicong1,2   

  1. 1.Coal Science and Technology Co. , Ltd. , Beijing 100013, China
    2.State Key Laboratory of Coal Mining and Clean Utilization, Beijing 100013, China
  • Received:2021-08-10 Revised:2021-09-25 Online:2022-01-05 Published:2022-01-24
  • Contact: LI Yang

摘要:

研究了臭氧催化氧化降解煤化工高盐废水有机物的机理。实验采集了国内典型煤化工企业高盐废水,明确了水中盐离子的组成及含量;制备高盐性臭氧催化剂,研究了不同活性组分对臭氧催化氧化效率的影响,确定了最佳的臭氧催化剂;对臭氧催化剂开展表征分析,明确催化剂表观形貌、元素组成及负载情况;最后采用甲酸模拟水样,研究臭氧催化氧化作用方式、臭氧衰减率变化、羟基自由基(·OH)变化、H2O2变化及超氧自由基(·O2-)变化,明确臭氧催化氧化作用机理及反应历程。结果表明:煤化工高盐废水阳离子主要为钠离子,其次是钾离子、钙离子、镁离子;阴离子主要为氯离子、硫酸根,其次是硝酸根离子;通过研究不同活性组分对臭氧催化氧化效率确定最佳催化剂为SiO2/Al2O3-Fe2O3。对催化剂开展表征分析发现:催化剂载体为硅铝复合氧化物,铁作为活性组分均匀负载于载体上。臭氧催化氧化降解机理研究发现:臭氧催化氧化过程遵从羟基自由基作用机理,O3通过衰减产生羟基自由基,而催化剂的加入促进了·OH生成;反应过程中产生的H2O2量与·?OH有关,·?OH越多,H2O2产生量越多,但·O2-的产生与·OH没关系。

关键词: 煤化工高盐废水, 臭氧催化氧化, 催化剂, 表征分析, 降解机理

Abstract:

The mechanism of catalytic oxidation degradation of organics in high salt wastewater of coal chemical industry by ozone was studied. Firstly, the high-salt wastewater of a typical coal chemical enterprises in China was collected, and the composition and content of various salt ions in the water were determined. Secondly, the effects of different active components on the efficiency of ozone catalytic oxidation were studied to screen the best ozone catalyst. Characterization analysis was carried out on the ozone catalyst to determine the apparent morphology, element composition and active component loading of the catalyst. Finally, the simulated water sample with formic acid was used to study the action mode of ozone catalytic oxidation, the change of ozone attenuation rate, the change of hydroxyl radical(·OH), H2O2 and superoxide radical (·O2-) to reveal the action mechanism and reaction process of ozone catalytic oxidation. The results showed that the cations of the high-salt wastewater from coal chemical industry were mainly sodium ions, followed by potassium ion, calcium ion, and magnesium ion. The anions were mainly chloride ions and sulfate ions, followed by nitrate ions. By studying the effect of different active components on the ozone catalytic oxidation efficiency, we found the best catalyst was SiO2/Al2O3-Fe2O3. The characterization analysis of the catalyst showed that the catalyst's support was SiO2/Al2O3, and iron was loaded on the support as the active component. Through the degradation mechanism study, it was found that the process of ozone catalytic oxidation followed the action mechanism of hydroxyl radical. i.e. O3 produced hydroxyl radical through attenuation, and the addition of the catalyst promoted the formation of ·OH. The amount of H2O2 produced during the reaction was related to·OH. The more·OH, the more H2O2 was produced, but the production of·O2- was not related to·OH.

Key words: high salt wastewater of coal chemical industry, ozone catalytic oxidation, catalyst, characterization analysis, degradation mechanism

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