臭氧/过氧化氢在循环水反应器中催化氧化处理有机废水的研究

doi:10.19965/j.cnki.iwt.2025-0216

摘要/Abstract

摘要：

针对工业难降解有机废水的高效深度处理需求，开展了非均相臭氧催化氧化技术的系统研究。以γ-Al₂O₃作为催化剂，过氧化氢作为增强剂，使用循环水反应器对实际工业生产中产生的有机废水进行深度处理，以COD的去除效果作为指标对反应体系的臭氧催化效率进行评价。系统考察了进出水方向及废水流量、催化剂投加量、初始pH、臭氧浓度等关键参数对处理效果的影响。通过X射线衍射、扫描电子显微镜、三维荧光光谱和紫外-可见吸收光谱等表征手段分析了催化剂特性及废水中有机物的降解行为。结果表明，臭氧催化氧化技术可有效降解有机废水中的多种复杂有机物（如溶解性微生物产物、类腐殖酸等），从而使废水COD显著下降。在反应体系中投加微量过氧化氢后COD的去除效率得到进一步提高，对照实验证实臭氧与过氧化氢之间存在协同作用，可显著增强对有机物的氧化降解效果。催化剂在经过5次循环使用后，未出现明显的性能下降。对催化系统进行经济性评估，在规模化应用的前提下，吨水处理成本约为24.22元，在相关废水深度处理技术中具有一定优势。

关键词: 非均相臭氧催化氧化, 臭氧, 过氧化氢, 废水深度处理

Abstract:

A systematic study on heterogeneous ozone catalytic oxidation technology has been conducted to meet the demand for efficient deep treatment of industrial recalcitrant organic wastewater. Using γ-Al₂O₃ as the catalyst and hydrogen peroxide as the enhancer, a circulating water reactor was used to deeply treat organic wastewater generated in actual industrial production. The removal efficiency of COD was used as an indicator to evaluate the ozone catalytic efficiency of the reaction system. The influences of inlet and outlet direction, and the key parameters such as wastewater flow rate, catalyst dosage, initial pH, and ozone concentration on the treatment effect were systematically investigated. The characteristics of the catalyst and the degradation behavior of organic matter in wastewater were analyzed by characterization methods such as X-ray diffraction, scanning electron microscopy, three-dimensional fluorescence spectroscopy, and ultraviolet-visible absorption spectroscopy. The results indicated that ozone catalytic oxidation technology could effectively degrade various complex organic compounds (such as soluble microbial products, humic acids, etc.) in organic wastewater, thereby significantly reducing the COD of the wastewater. After adding trace amount of hydrogen peroxide to the reaction system, the COD removal efficiency was further improved. Comparative experiments confirmed the synergistic effect between ozone and hydrogen peroxide, which could significantly enhance the oxidative degradation of organic matter. After 5 cycles of usage, the performance of catalyst did not show significant degradation. The economic evaluation of the catalytic system showed that under the premise of large-scale application, the treatment cost for one ton of water was about 24.22 yuan, which had certain advantages in related wastewater deep treatment technologies.

Key words: heterogeneous ozone catalytic oxidation, ozone, hydrogen peroxide, wastewater advanced treatment

中图分类号:

X703.1

付志强, 佟欣慧, 贾见果, 李亮, 安希忠, 杨晓红. 臭氧/过氧化氢在循环水反应器中催化氧化处理有机废水的研究[J]. 工业水处理, 2026, 46(2): 102-110.

Zhiqiang FU, Xinhui TONG, Jianguo JIA, Liang LI, Xizhong AN, Xiaohong YANG. Catalytic oxidation treatment of organic wastewater by ozone/ hydrogen peroxide in a recirculating water reactor[J]. Industrial Water Treatment, 2026, 46(2): 102-110.

https://www.iwt.cn/CN/Y2026/V46/I2/102

图/表 16

图1 臭氧催化氧化连续流实验装置示意

Fig.1 Schematic diagram of continuous flow experimental device for catalytic ozone oxidation

图2 进出水方向对COD去除效果的影响

Fig.2 Effect of influent and effluent directions on COD removal

图3 进水流量对COD去除效果的影响

Fig.3 Effect of inflow rate on COD removal

图4 进气流量对COD去除效果的影响

Fig.4 Effect of inlet airflow on COD removal

图5 单个反应器催化剂投加量对COD去除效果的影响

Fig.5 Effect of catalyst dosage in a single reactor on COD removal

图6 初始pH对COD去除效果的影响

Fig.6 Effect of initial pH on COD removal

图7 进气中臭氧质量浓度对COD去除效果的影响

Fig.7 Effect of ozone concentration in the intake air on COD removal

图8 过氧化氢对COD去除效果的影响及反应前后水样的紫外-可见吸收光谱

Fig.8 Effect of hydrogen peroxide on COD removal effect and UV-vis spectra of water sample before and after reaction

表1 过氧化氢存在下反应前后水样pH变化

Table 1 Change of pH of water samples before and after reaction in the presence of hydrogen peroxide

反应前pH	反应后pH
3	5
5	6
6	6
9	6
11	9

图9 臭氧/过氧化氢催化氧化稳定性测试

Fig.9 Stability test for catalytic oxidation of ozone/hydrogen peroxide

图10 γ-Al₂O₃催化剂在使用前后的XRD（a）、使用前的SEM（b）和使用后的SEM（c）

Fig.10 XRD image before and after use （a），SEM image before use （b），and SEM image after use of γ-Al₂O₃ catalyst（c）

图11 反应前（a）、不加过氧化氢反应后（b）及加入过氧化氢反应后（c）水样的三维荧光光谱

Fig.11 Three dimensional fluorescence spectra of water samples before reaction （a），after reaction without hydrogen peroxide （b），and after reaction with hydrogen peroxide （c）

表2 荧光区域划分

Table 2 Fluorescence region delineation

区域	有机物类型	激发波长/nm	发射波长/nm
Ⅰ	类酪氨酸	220~250	280~330
Ⅱ	类色氨酸	220~250	330~380
Ⅲ	类富里酸	220~250	380~550
Ⅳ	溶解性微生物产物	250~450	280~380
Ⅴ	类腐殖酸	250~450	380~550

表3 实验室规模5次运行的成本分析

Table 3 Cost analysis of five laboratory scale operations

项目	单价	消耗量	费用/ （元·L^-1）
小计			0.589 54
Al₂O₃催化剂	6.2元/kg	0.04 kg/L	0.248 00
电费	0.6元/（kW·h）	0.325 kW·h/L	0.195 00
冷凝水费	0.1元/t	0.000 4 t/L	0.000 04
氨水	34元/L	0.001 25 L/L	0.042 50
过氧化氢	52元/L	0.002 L/L	0.104 00

表4 臭氧/过氧化氢催化氧化系统预计运行成本汇总

Table 4 Summary of the estimated operating costs of the ozone/hydrogen peroxide catalytic oxidation system

项目	单价	消耗量	年费用/万元
小计			353.63
循环冷却水费	0.1元/t	240 t/d	0.88
电费	0.6元/（kW·h）	730 kW·h/d	15.99
氢氧化钠	1.1元/kg	302.78 kg/d	12.16
过氧化氢	100元/t	0.89 t/d	32.49
氧气	0.4元/Nm³	14 000 Nm³	204.4
催化剂	6 200元/t	141.47 t/a	87.71

表5 臭氧相关水处理技术运行成本

Table 5 Operating costs of ozone-related water treatment technologies

处理工艺	废水类型	运行成本/ （元·m^-3）	参考文献
臭氧/电凝絮技术	钢铁工业废水	41.22	〔19〕
臭氧/过氧化氢催化	垃圾渗滤液	51.40	〔20〕
臭氧/紫外光催化技术	合成废水	23.51	〔21〕
臭氧/声波诱导技术	乳品工业污泥	29.83	〔22〕
光催化/臭氧催化技术	合成废水	38.95	〔23〕
本研究工艺	有机废水	24.22

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