改性二氧化钛负载贵金属Ru催化剂催化降解苯胺溶液

doi:10.1016/S1872-2067(17)62848-1

催化学报 ›› 2017, Vol. 38 ›› Issue (7): 1155-1165.DOI: 10.1016/S1872-2067(17)62848-1

改性二氧化钛负载贵金属Ru催化剂催化降解苯胺溶液

宋明光, 王筠松, 郭耘, 王丽, 詹望成, 郭杨龙, 卢冠忠

华东理工大学化学与分子工程学院, 工业催化教育部重点实验室, 上海 200237

出版日期:2017-07-18 发布日期:2017-06-27
通讯作者: 郭耘, 王筠松
基金资助:
国家自然科学基金（21333003，21577034）；国家重点基础研究发展计划（2013CB933200）；国家高技术研究发展计划（2015AA034603）；中央高校基础科研专项资金（WJ1514020）.

Catalytic wet oxidation of aniline over Ru catalysts supported on a modified TiO₂

Mingguang Song, Yunsong Wang, Yun Guo, Li Wang, Wangcheng Zhan, Yanglong Guo, Guanzhong Lu

Key Laboratory for Advanced Materials and Research Institute of Industrial Catalysis, School of Chemistry and Molecular Engineering, East China University of Science and Technology, Shanghai 200237, China

Online:2017-07-18 Published:2017-06-27
Contact: 10.1016/S1872-2067(17)62848-1
Supported by:
This work was financially supported by the National Natural Science Foundation of China (21333003, 21577034), National Basic Research Program of China (2013CB933200), National High Technology Research and Development Program of China (2015AA034603), and the Fundamental Research Funds for the Central Universities (WJ1514020).

摘要/Abstract

摘要：

苯胺类废水污染物具有结构复杂、浓度高、不易生物降解、生物毒性大等特点，传统的苯胺降解措施存在着许多弊端，很难达到排放标准.催化湿法氧化技术（CWAO）主要针对降解高浓度难降解的有机废水，表现出降解效率高、反应时间短、对生物毒性物质的废水降解效果良好等优点，越来越受到人们的重视.但催化剂在使用过程中，需要在高温高压下进行，且有机物降解产生了有机酸，使得催化剂的活性组分流失和载体的物理化学性质发生变化，导致其催化活性下降.因此，需要开发出一种降解活性高，性能稳定的催化剂成为此技术在工业中广泛应用的关键.
本文采用溶胶凝胶法对二氧化钛进行改性，制备了Ti_0.9Zr_0.1O₂和Ti_0.9Ce_0.1O₂载体，采用过量浸渍法将三氯化钌负载到载体表面制备了2% Ru/Ti_0.9Zr_0.1O₂和2% Ru/Ti_0.9Ce_0.1O₂催化剂.在高温高压反应条件下，以苯胺为催化湿法氧化污染物，对不同催化剂湿法降解苯胺进行比较研究，系统地探究了催化降解的反应温度和反应压力对苯胺降解的影响.此外，利用HPLC-MS鉴定出催化降解产生的中间产物，确定了催化降解的反应路径图.在改性的催化剂中，2% Ru/Ti_0.9Zr_0.1O₂催化剂表现出最高的催化降解活性和稳定性.在初始苯胺浓度4 g/L，催化剂浓度4 g/L，反应温度180℃，O₂压力1.5 MPa下，反应时间5 h后，苯胺完全转化，COD转化率达88.3%.并且催化剂进行三次循环试验后，苯胺转化率仍接近100%.
X射线衍射和N₂物理吸附结果表明，Ce，Zr掺杂到TiO₂晶格中形成了共溶体，其晶格尺寸更小，比表面积和孔体积更大.负载贵金属后，并未出现其他晶相，说明贵金属均匀分散在载体表面.透射电镜结果表明，贵金属负载在改性TiO₂上表现出较好的分散性和较小的颗粒尺寸，为催化降解苯胺提供更多的催化活性位点，而Ru/TiO₂催化剂表面，贵金属发生团聚现象且颗粒尺寸大.X射线光电子能谱结果表明，Ce，Zr的掺杂使得TiO₂表面活性氧和四价Ru的含量增加，更多的表面活性氧成为催化降解苯胺的直接原因.H₂程序升温还原结果表明，在300-400 ℃处还原峰对应于催化剂载体晶格氧的还原，改性后，其还原峰增至2倍，即使在贫氧环境下，改性催化剂可以及时从载体中释放晶格氧，为催化降解苯胺提供更多的活性氧.

关键词: 催化湿法氧化, 物理化学, 苯胺转化率, 碳沉积

Abstract:

The catalytic wet air oxidation of aniline over Ru catalysts supported on modified TiO₂ (TiO₂, Ti_0.9Ce_0.1O₂, Ti_0.9Zr_0.1O₂) is investigated. A series of characterization techniques are conducted to determine the relationship between the physico-chemical properties and the catalytic performance. As a result of the good metal dispersion and large number of surface oxygen species, the Ru/Ti_0.9Zr_0.1O₂ catalyst presents the best catalytic activity among the tested samples. The effects of the operating conditions on the reaction are investigated and the optimal reaction conditions are determined. Based on the relationship between the by-products concentration and the reaction time, the reaction path for the catalytic oxidation of aniline is established. Carbonaceous deposits on the surface of the support are known to be the main reason for catalyst deactivation. The catalysts maintain a constant activity even after three consecutive cycles.

Key words: Catalystic wet air oxidation, Physico-chemical, Aniline removal, Carbon deposites

宋明光, 王筠松, 郭耘, 王丽, 詹望成, 郭杨龙, 卢冠忠. 改性二氧化钛负载贵金属Ru催化剂催化降解苯胺溶液[J]. 催化学报, 2017, 38(7): 1155-1165.

Mingguang Song, Yunsong Wang, Yun Guo, Li Wang, Wangcheng Zhan, Yanglong Guo, Guanzhong Lu. Catalytic wet oxidation of aniline over Ru catalysts supported on a modified TiO₂[J]. Chinese Journal of Catalysis, 2017, 38(7): 1155-1165.

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改性二氧化钛负载贵金属Ru催化剂催化降解苯胺溶液

Catalytic wet oxidation of aniline over Ru catalysts supported on a modified TiO₂

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改性二氧化钛负载贵金属Ru催化剂催化降解苯胺溶液

Catalytic wet oxidation of aniline over Ru catalysts supported on a modified TiO2

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Catalytic wet oxidation of aniline over Ru catalysts supported on a modified TiO₂