O3/H2O2微纳米气泡催化氧化体系处理高盐化工废水工艺优化研究

Optimization for the catalytic oxidation system of O3/H2O2 micro-nano bubbles for the treatment of highly saline chemical wastewater

  • 摘要: 化工废水通过反渗透(RO)处理后产生高盐、高有机物浓度的RO浓水,传统臭氧氧化处理对其中有机物去除效率低。臭氧/双氧水(O3/H2O2)微纳米气泡催化氧化能提高RO浓水中难降解有机物的去除效果,但存在H2O2投加方式不合理导致的废水氧化效率低、矿化不彻底等问题。以某化工园区生化处理尾水和循环冷却水的RO处理浓水(简称尾水和循环水)为处理对象,应用O3/H2O2微纳米气泡催化氧化技术并优化H2O2投加策略,分析初始pH、H2O2投加方式对有机物去除效果的影响,并探讨在线监测氧化还原电位(ORP)响应H2O2投加方式对实际高盐化工废水处理工程中臭氧段的氧化处理效果。结果表明:在pH=7.4的弱碱性条件下,尾水和循环水单独臭氧微纳米气泡体系对有机物去除效果最优;根据ORP变化在过程中投加H2O2较初始投加能提升有机物去除效果,尾水和循环水的TOC去除率分别提升了48.0%和2.3%;过程投加中,当每次投加H2O2 1 mL(尾水共投3次、循环水共投4次),设定ORP阈值达900 mV时投加H2O2效果最佳,尾水和循环水的TOC去除率较300 mV分别提升17.0%和4.6%;根据ORP变化高频率多段投加H2O2更有利于有机物去除,但工程设计中分三段投加更合理可行〔d(ORP)/dT=200~300 mV/min时投加1次H2O2,共投加3次〕。研究表明,O3/H2O2微纳米气泡处理工艺中,根据在线ORP监测分三段投加H2O2的策略能保证处理效能且具备工程可行性。

     

    Abstract: Chemical wastewater treated via reverse osmosis (RO) generates concentrate with high salt and organic matter concentrations. Traditional ozone oxidation treatment has low efficiency in removing organic matter from such wastewater. Ozone/hydrogen peroxide (O3/H2O2) micro-nano bubble catalytic oxidation can enhance the removal efficiency of recalcitrant organic matter in RO concentrate, but it faces challenges such as low oxidation efficiency and incomplete mineralization. This study treated RO concentrate from two sources in a chemical industrial park: biological treatment effluent and circulating cooling water (referred to as effluent and circulating water). It applied O3/H2O2 micro-nano bubble catalytic oxidation technology and optimized the H2O2 dosing strategy. The effects of initial pH, H2O2 dosing schemes on organic matter removal efficiency were analyzed. The study also explored the use of online monitoring of ORP to guide H2O2 dosing schemes and its impact on the oxidation treatment effectiveness of the ozone stage in actual high-salinity chemical wastewater treatment projects. The results indicated that under weakly alkaline conditions with pH=7.4, the ozone micro-nano bubble system alone achieved the best organic matter removal efficiency for effluent and circulating water. H2O2 dosing based on ORP changes during the process improved organic matter removal efficiency compared to a single initial dosing, with TOC removal rates for effluent and circulating water increasing by 48.0% and 2.3%, respectively. During the process dosing, when H2O2 was dosed at 1 mL per dosage (three doses for effluent and four doses for circulating water), setting the ORP threshold to 900 mV resulted in the best H2O2 dosing effect, with TOC removal rates for effluent and circulating water increasing by 17.0% and 4.6%, respectively, compared to 300 mV. While high-frequency, multi-stage H2O2 dosing based on ORP changes was more beneficial for organic matter removal, a three-stage dosing strategy was more reasonable and feasible in engineering design (H2O2 was dosed once when d(ORP)/dT=200-300 mV/min, with a total of three doses). The research indicates that in the O3/H2O2 micro-nano bubble treatment process, the strategy of dosing H2O2 in three stages based on online ORP monitoring ensures treatment efficiency and has engineering feasibility.

     

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