非均相Fenton系统氧化降解高浓度聚乙烯醇废水的影响因素研究

Ye He, Dongsheng Zhou, Feng Liu, Xuefei Li, Xingdong Su, Jiawen Li, Jie Zhan
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摘要

聚乙烯醇(PVA)是一种高分子聚合物,具有良好的阻隔性、耐酸碱性和可降解性,可作为核工业中的个人辐射防护用品和污染控制用品,使用后产生可降解的放射性技术废料。PVA可降解技术废物的降解处理工艺可实现放射性核素的有效分离,减少放射性固体废物的产量。本研究采用浸渍-煅烧法制备了MnxOy/γ-Al2O3、CuxOy/γ-Al2O3、FexOy/γ-Al2O3和FexCuyMnzOw/γ-Al2O3纳米颗粒,作为氧化降解高浓度PVA有机废液的催化剂,并分析了聚乙烯醇(PVA)溶液初始pH、过氧化氢(H2O2)投加量、催化剂投加量和PVA溶液初始浓度对PVA降解的影响。结果表明,在PVA初始浓度为1%、溶液初始pH为3、反应温度为60℃、催化剂投加量为0.5 g/L、H2O2投加量为60 mL/L的条件下,feexcuymnzow /γ-Al2O3纳米颗粒作为催化剂的整体降解性最佳。此时,PVA的浓度下降率可达95%以上,降解产物的粘度平均分子量达到1395,分子量下降率达到99%,降解产物主要包括丁酮、苯甲醛、己醛、乙酸等不饱和小分子。此外,还探讨了纳米粒子催化过氧化氢生成羟基自由基的机理,提出了羟基自由基氧化降解PVA大分子的反应途径,为核工业中PVA可降解废弃物的减容处理提供了参考。
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Study on the Influencing Factors of Oxidation Degradation for High Concentration Polyvinyl Alcohol Wastewater in Heterogeneous Fenton System
Polyvinyl alcohol (PVA), a high molecular polymer, has good barrier property, acid or alkali resistance and degradability, which could be used as personal radiation protective equipment and pollution control articles in the nuclear industry, resulting in degradable radioactive technical wastes after use. The degradation treatment process of PVA degradable technology waste can realize validity separation of radionuclides and reduce the output of radioactive solid waste. In this study, MnxOy/γ-Al2O3, CuxOy/γ-Al2O3, FexOy/γ-Al2O3 and FexCuyMnzOw/γ-Al2O3 nanoparticles were prepared by the impregnation-calcination method, which were used as catalysts for the oxidative degradation of ultra-high concentration PVA organic waste solution, and the effects of initial pH of polyvinyl alcohol (PVA) solution, hydrogen peroxide (H2O2) dosing, catalyst dosing and initial concentration of PVA solution on the degradation of PVA were analyzed. The results showed that the best overall degradability was achieved by using FexCuyMnzOw/γ-Al2O3 nanoparticles as catalysts with the initial reaction concentration of PVA at 1%, the initial pH of the solution at 3, the reaction temperature at 60 °C, the catalyst dosage at 0.5 g/L and the H2O2 dosage at 60 mL/L. At this time, the concentration decrease rate of PVA could reach more than 95 %, the viscosity average molecular weight of degradation products reached 1395, the molecular weight decrease rate reached 99 %, and the degradation products mainly included butanone, benzaldehyde, hexanal, acetic acid and other unsaturated small molecules. In addition, the mechanism of hydroxyl radical generation by nanoparticles catalyzing hydrogen peroxide was discussed, and the reaction pathway of oxidative degradation of PVA macromolecules by hydroxyl radicals was proposed, which provided a reference for volume reduction treatment of PVA degradable waste in nuclear industry.
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