新型酞菁催化剂的制备及降解染料性能

doi:10.11949/j.issn.0438-1157.20180407

化工学报 ›› 2018, Vol. 69 ›› Issue (12): 5090-5099.DOI: 10.11949/j.issn.0438-1157.20180407

• 催化、动力学与反应器 • 上一篇下一篇

新型酞菁催化剂的制备及降解染料性能

游东辉¹, 程治良¹, 李敢³, 张峰³, 吕芳蕾³, 姜广彬³, 全学军¹, 韦建卫², 杨鲁⁴, 李硕¹

1. 重庆理工大学化学化工学院, 重庆 400054;
2. 重庆理工大学理学院, 重庆 400054;
3. 胜利油田石油工程技术研究院, 山东东营 257000;
4. 重庆市生活垃圾资源化处理协同创新中心, 重庆 401331

收稿日期:2018-04-18 修回日期:2018-08-26 出版日期:2018-12-05 发布日期:2018-12-05
通讯作者: 李硕
基金资助:
国家自然科学基金项目（21176273）；重庆市基础与前沿研究计划项目（cstc2015jcyjA20005，cstc2016jcyjA0508）；重庆市教委科学技术研究项目（KJ1600927，KJ1400915）；重庆市生活垃圾资源化处理协同创新中心资助项目（Shljzyh2017-003）。

Preparation and catalytic degradation property research of novel phthalocyanine

YOU Donghui¹, CHENG Zhiliang¹, LI Gan³, ZHANG Feng³, LYU Fanglei³, JIANG Guangbin³, QUAN Xuejun¹, WEI Jianwei², YANG Lu⁴, LI Shuo¹

1. College of Chemistry and Chemical Engineering, Chongqing University of Technology, Chongqing 400054, China;
2. College of Technology, Chongqing University of Technology, Chongqing 400054, China;
3. Shengli Oil Field Petroleum Engineering Technology Research Institute, Dongying 257000, Shandong, China;
4. Chongqing Municipal Solid Waste Resource Utilization & Treatment Collaborative Innovation Center, Chongqing 401331, China

Received:2018-04-18 Revised:2018-08-26 Online:2018-12-05 Published:2018-12-05
Supported by:
supported by the National Natural Science Foundation of China (21176273), the Chongqing Research Program of Basic Research and Frontier Technology (cstc2016jcyjA0508, cstc2015jcyjA20005), the Scientific and Technological Research Program of Chongqing Municipal Education Commission (KJ1600927,KJ1400915) and the Foundation of Chongqing Municipal Solid Waste Resource Utilization & Treatment Collaborative Innovation Center(Shljzyh2017-003).

摘要/Abstract

摘要：

大规模降解中性条件下的染料废水是染料废水处理的难点之一。设计、制备了新型羟基取代酞菁钴（CoTHPc）催化剂，对结构进行了表征。使用Siesta软件模拟了CoTHPc与酸性红G（AR1）结合的能量变化，并以氨基酞菁钴（CoTAPc）为参照。结果表明：中性条件下CoTHPc对AR1的吸附能力优于CoTAPc，CoTAPc与AR1的结合能力在氢氧根离子协助下大幅提升。研究了不同pH、温度、氧化剂浓度、自由基抑制剂等条件对CoTHPc/H₂O₂体系性能的影响。实验结果显示：CoTHPc最佳催化条件为pH=7.0、T=343 K、20 mmol/（L H₂O₂），CoTAPc最佳催化条件为pH=10、T=354 K、50 mmol/（L H₂O₂），与计算结果相符。CoTHPc/H₂O₂为非羟基自由基催化机理。综上所述：CoTHPc/H₂O₂催化体系能够在中性条件下发挥催化功能，对降解成分复杂的印染废水具有较好的应用前景。

关键词: 羟基钴酞菁, 分子模拟, 催化剂, 非羟基自由基, 降解

Abstract:

Large scale degradation of dye wastewater under neutral conditions is one of key difficulties in dye wastewater disposal. A novel hydroxyl-substituted cobalt phthalocyanine (CoTHPc) catalyst was synthesized and characterized by NMR and high resolution mass spectrometry. The binding energies of CoTHPc and amino phthalocyanine cobalt compund (CoTAPc) with acid red G (AR1) were simulated by Siesta software. The results showed that the adsorption capacity of CoTHPc with AR1 was better than that of CoTAPc under neutral conditions. The binding ability of CoTAPc to AR1 is greatly enhanced within the existence of hydroxide radical. The effects on the performances of the CoTHPc/H₂O₂ and CoTAPc/H₂O₂ systems by different pH, temperature, oxidant concentration and isopropanol were investigated as well as the degradation mechanism. The results showed that the optimal catalytic conditions for CoTHPc were pH=7.0, T=343 K, and 20 mmol/(L H₂O₂), and the optimal catalytic conditions for CoTAPc were pH=10, T=354 K, and 50 mmol/(L H₂O₂). The results also released that isopropanol as a free radical inhibitor does not stop or inhibit the catalytic oxidation reaction, so both CoThPc/H₂O₂ and CoTAPc/H₂O₂ systems are non-hydroxyl radical mechanisms. In summary, the CoTHPc/H₂O₂ catalytic system is one of feasible solutions for the degradation of complex dye wastewater under neutral conditions and has a great application prospect for complex printing and dyeing wastewater.

Key words: hydroxycobalt phthalocyanine, molecular simulation, catalyst, non-hydroxyl free radicals, degradation

中图分类号:

TQ201

游东辉, 程治良, 李敢, 张峰, 吕芳蕾, 姜广彬, 全学军, 韦建卫, 杨鲁, 李硕. 新型酞菁催化剂的制备及降解染料性能[J]. 化工学报, 2018, 69(12): 5090-5099.

YOU Donghui, CHENG Zhiliang, LI Gan, ZHANG Feng, LYU Fanglei, JIANG Guangbin, QUAN Xuejun, WEI Jianwei, YANG Lu, LI Shuo. Preparation and catalytic degradation property research of novel phthalocyanine[J]. CIESC Journal, 2018, 69(12): 5090-5099.

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新型酞菁催化剂的制备及降解染料性能

Preparation and catalytic degradation property research of novel phthalocyanine

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