在工业生产过程中，纺织、造纸、制药等行业会产生大量难降解有机物废水，对生态环境和人类健康均构成严重威胁，亟需有效的处理技术。在高级氧化技术中，非均相催化臭氧氧化技术和Fenton技术操作简便，有机物处理效率高，被广泛用于有机废水的处理，但目前对于不同反应体系降解典型有机物的性能缺少系统比较性研究，通过非均相催化臭氧氧化技术和Fenton技术去除不同化学结构的有机物的矿化性能不明晰。本文选取海绵铁、粉末铁、MnO₂/Al₂O₃三种常见铁基及锰基催化剂分别构建非均相催化臭氧氧化系统，先探究不同实验条件下非均相催化臭氧氧化体系及Fenton体系降解对硝基苯酚性能差异及实验条件影响；再选取具有不同化学结构和碳链长度的典型有机物作为探针污染物，探究非均相催化臭氧氧化体系和Fenton体系矿化去除水中不同化学结构有机物的结构选择性和差异性，并探讨导致这种结构差异性和选择性的可能的分子机制。

选取对硝基苯酚作为典型难降解有机污染物，分别以海绵铁、粉末铁、MnO₂/Al₂O₃作为非均相催化臭氧氧化反应的催化剂，分别构建固定床和流化床反应体系、铁基和锰基催化剂反应体系，探究各自降解有机物的最佳反应条件。确定当pH₀=7.0时，海绵铁、MnO₂/Al₂O₃均可有效催化去除PNP，当污染物初始浓度为300mg/L、反应40min时即可实现对PNP的完全去除，反应120min后PNP矿化率均可达90%以上。在以粉末铁为催化剂的流化床反应体系中，随反应进行pH不断降低。对比不同实验条件下Fenton体系去除对硝基苯酚的差异，发现pH=2.5～4.0时PNP均有较好的降解效果，H₂O₂与COD的最佳质量比为2.125:1；H₂O₂与Fe²⁺的摩尔比为5:1。固定床体系的催化性能和反应动力学常数要优于流化床。反应平衡后Fenton体系与非均相催化臭氧氧化体系中PNP去除率和矿化率无显著差别，但Fenton反应的反应动力学更为快速，其反应速率常数远大于非均相催化臭氧氧化体系。

以海绵铁、粉末铁、MnO₂/Al₂O₃作为催化剂分别降解具有不同化学结构的有机物，污染物的降解均符合一级反应动力学方程。在非均相催化臭氧氧化反应体系内有机物的去除差异主要与有机物中是否含有碳碳不饱和键有关，尤其是是否存在大π键至关重要，而有机物的碳链长度、环状结构及所带官能团的类别对其去除率影响不大。含有苯环的芳香类有机物包括苯酚、苯甲醇、苯甲醛、苯甲酸钠、卞胺、对硝基苯酚，在以海绵铁、MnO₂/Al₂O₃为催化剂的固定床催化臭氧氧化系统中，反应120min后矿化率高达61.2~93.1%；芳香类化合物上的官能团差异对其可矿化性的影响不显著。所有不同碳链长度的饱和碳链与饱和环状有机物，不管是醇类、醛类、羧酸类，它们在催化臭氧氧化系统中都表现出很低的可矿化性，仅维持在5.1~42.1%之间。在分别以海绵铁、MnO₂/Al₂O₃为催化剂的固定床催化臭氧氧化系统中，起始阶段催化剂可吸附去除部分有机物，而在以粉末铁为催化剂的流化床催化臭氧氧化系统中吸附机制不明显。但通过对比固定床、流化床反应体系中降解效果差异，发现反应体系内传质效率并不是导致反应平衡后有机物降解效果产生差异的主要因素。通过对比以海绵铁、MnO₂/Al₂O₃为催化剂的反应体系中降解效果差异，发现催化剂种类也不是导致非均相催化臭氧氧化系统中有机物最终降解效果差异的主要因素。

通过Fenton体系降解具有不同化学结构的有机物，发现在Fenton体系内有机物的去除差异与非均相催化臭氧氧化体系中所得到的结果一致，即其主要与有机物中是否含有碳碳不饱和键有关，有机物的碳链长度及其所带官能团对其降解效率影响不大。分别计算并统计了两体系中的反应速率常数和最终去除效果，认为在以羟基自由基为主要活性物质的高级氧化技术氧化降解有机物时，可能遵循同样的规律，即含有碳碳不饱和键，尤其是大π键的有机物更易被去除和矿化，其Fenton可矿化率高达77.2~89.1%。而不含碳碳不饱和键的饱和碳链与饱和环状有机物，不管是醇类、醛类、羧酸类，它们在Fenton氧化系统中都表现出较低的矿化效率，仅维持在8.6~36.6%之间。

可生化性高、易被生物降解的饱和直链醇类、醛类和羧酸类有机物在非均相催化臭氧氧化和芬顿氧化体系中并没有体现出良好的可矿化性，其矿化率最高仅42.1%；而一些通常难以被生物降解的有机污染物其结构中常常带有大π键，在上述高级氧化系统中却可以得到有效的矿化去除，如苯酚、苯甲醛、苯甲酸钠、对硝基苯酚等，其矿化率均可达90.0%以上。上述高级氧化与生物降解在化学结构选择性上几近互补的规律，为污水处理过程中高级氧化技术与生物降解技术协同处理成分复杂、单一技术难以达标的综合废水，提供了理论佐证与支持。

In the industrial production process, industries such as textiles, papermaking, and pharmaceuticals generate a large amount of refractory organic wastewater, posing a serious threat to the ecological environment and human health. Effective treatment technologies are urgently needed. Among Advanced oxidation process, heterogeneous catalysis ozonation technology and Fenton technology are easy to operate and have high organic matter treatment efficiency, which are widely used in the treatment of organic wastewater. However, there is a lack of systematic comparative research on the performance of different reaction systems to degrade typical organic matters. The mineralization performance of heterogeneous catalysis ozonation technology and Fenton technology to remove organic matters with different chemical structures is not clear. In this paper, sponge iron, powdered iron, and MnO₂/Al₂O₃, three common iron-based and manganese-based catalysts, were selected to construct heterogeneous catalysis ozonation systems. First, the heterogeneous catalysis ozonation system and Fenton system degradation under different experimental conditions were investigated to investigate the performance differences of nitrophenol and the effects of experimental conditions; Then typical organics with different chemical structures and carbon chain lengths were selected as probe pollutants to explore the structural selectivity and difference of heterogeneous catalysis ozonation system and Fenton system for mineralizing and removing organics with different chemical structures in water, and explore the possible molecular mechanism leading to this structural difference and selectivity.

P-nitrophenol was selected as a typical refractory organic pollutant, sponge iron, powdered iron, and MnO₂/Al₂O₃were used as catalysts for heterogeneous catalysis ozonation, respectively, to build fixed bed and fluidized bed reaction systems, iron based and manganese-based catalyst reaction systems, and explore the best reaction conditions for each self-degrading organic compound. When pH₀=7.0, sponge iron and MnO₂/Al₂O₃ can effectively catalyze the removal of PNP. When the initial concentration of pollutants is 300mg/L and the reaction is 40 minutes, complete removal of PNP can be achieved. After 120 minutes of reaction, the mineralization rate of PNP can reach over 90%. In a fluidized bed reaction system using powdered iron as catalyst, the pH continuously decreases as the reaction progresses. Comparing the difference of removal of p-nitrophenol by Fenton system under different experimental conditions, it was found that PNP had a better degradation effect when pH=2.5~4.0, and the optimal mass ratio of H₂O₂ to COD was 2.125:1; The molar ratio of H₂O₂ to Fe²⁺is 5:1. The catalytic performance and reaction kinetic constants of the fixed bed system are superior to those of the fluidized bed system. After reaction equilibrium, there is no significant difference in PNP removal rate and mineralization rate between Fenton system and heterogeneous catalysis ozonation system, but the reaction kinetics of Fenton reaction is faster, and its reaction rate constant is far greater than that of heterogeneous catalysis ozonation system.

Sponge iron, powdered iron, and MnO₂/Al₂O₃ were used as catalysts to degrade organic compounds with different chemical structures, and the degradation of pollutants followed the first-order reaction kinetics equation. The difference in the removal of organics in the heterogeneous catalysis ozonation reaction system is mainly related to whether there are carbon carbon unsaturated bonds in the organics, especially whether there are large π bonds, while the carbon chain length, ring structure and the type of functional groups of organics have little influence on the removal rate. Aromatic organic compounds containing benzene ring include phenol, benzyl alcohol, benzaldehyde, sodium benzoate, benzamine and p-nitrophenol. In the fixed bed catalytic ozonation system with sponge iron and MnO₂/Al₂O₃ as catalysts, the mineralization rate after 120 min reaction is as high as 61.2~93.1%; The difference in functional groups on aromatic compounds has no significant impact on their mineralization. All saturated carbon chains and saturated cyclic organic compounds with different carbon chain lengths, whether alcohols, aldehydes, or carboxylic acids, exhibit low mineralization in catalytic ozonation systems, maintaining only between 5.1% and 42.1%. In fixed bed catalytic ozonation systems using sponge iron and MnO₂/Al₂O₃ as catalysts, the initial stage catalyst can adsorb and remove some organic matter, while the adsorption mechanism is not obvious in fluidized bed catalytic ozonation systems using powdered iron as catalyst. However, by comparing the differences in degradation effects between fixed bed and fluidized bed reaction systems, it was found that the mass transfer efficiency within the reaction system is not the main factor leading to differences in the degradation effects of organic matter after reaction equilibrium. By comparing the degradation effects of sponge iron and MnO₂/Al₂O₃ as catalysts in the reaction system, it was found that the type of catalyst was not the main factor leading to the difference in the final degradation effect of organic matter in the heterogeneous catalysis ozonation system.

The Fenton system was used to degrade organics with different chemical structures. It was found that the difference in the removal of organics in the Fenton system was consistent with the results obtained in the heterogeneous catalysis ozonation system, that is, it was mainly related to whether there were carbon carbon unsaturated bonds in the organics, and the carbon chain length of the organics and their functional groups had little effect on the degradation efficiency. The reaction rate constant and the final removal effect in the two systems were calculated and counted respectively. It was considered that the same rule might be followed when Advanced oxidation process with hydroxyl radical as the main active substance oxidized and degraded organics, that is, organics containing carbon carbon unsaturated bonds, especially those with large π bonds, were easier to be removed and mineralized, and the Fenton mineralization rate was as high as 77.2~89.1%. However, saturated carbon chains and saturated cyclic organic compounds without carbon carbon unsaturated bonds, whether alcohols, aldehydes, or carboxylic acids, exhibit low mineralization efficiency in the Fenton oxidation system, maintaining only between 8.6% and 36.6%.

Saturated straight chain alcohols, aldehydes and carboxylic acids with high biodegradability and easy biodegradation did not show good mineralizability in heterogeneous catalysis ozonation and Fenton oxidation systems, with the highest mineralization rate of only 42.1%; While some organic pollutants that are usually difficult to be biodegraded often have large π bonds in their structures, they can be effectively mineralized and removed in the above advanced oxidation systems, such as phenol, benzaldehyde, sodium benzoate, p-nitrophenol, etc., and their mineralization rates can all reach more than 90.0%. The above law that advanced oxidation and biodegradation are nearly complementary in chemical structure selectivity provides theoretical evidence and support for Advanced oxidation process and biodegradation technology to jointly treat comprehensive wastewater with complex components and difficult to reach the standard with a single technology in the sewage treatment process.