Kinetics of Reactive Species in Water Produced by Ultraviolet Light Oxidation Processes

紫外光氧化过程产生的水中活性物质的动力学

• 批准号: 10450290
• 负责人: SUGAWARA Takuo
• 金额: $ 4.54万
• 依托单位: AKITA UNIVERSITY
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for Scientific Research (B)
• 财政年份: 1998
• 资助国家: 日本
• 起止时间: 1998 至 1999
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-10450290/
• 关键词: ultra-violet light oxidation; reactive species; total organic carbon; advanced oxidation process; ethanol; acetic acid; hydroxyl radical; hydroperoxy radical; ヒドロキシルラジカル; 紫外線酸化; エキシマーランプ; 超純水; 低級アルコール

Advanced oxidation processes (AOPs), which utilize reactive species produced by ultraviolet-light oxidation, have attracted much attention as innovative technology for environmental conservation. The purpose of this study was to kinetically elucidate behavior of the reactive species in water for fundamental information on photochemical reactor design.Model chemicals: ethanol (concentrations of 10ppm order) and its decomposition intermediates, acetic acid and oxalic acid in water, were decomposed in a batch-recycle photochemical-reaction system with (a) VUV(172nm) irradiation, (b) VUV+UVC(185+254nm) irradiation, and (c) UVC(254nm) irradiation accompanied by HィイD22ィエD2OィイD22ィエD2. Concentrations of reaction intermediates (acetaldehyde, formaldehyde, acetic acid, oxalic acid, formic acid) and TOC were sequentially determined; HィイD22ィエD2OィイD22ィエD2, COィイD22ィエD2 and pH changes were also traced. Experimental results were evaluated first by a conventional kinetic expression, then by a new reaction model which took consideration of elementary processes incorporated in radiation chemistry.Regeneration rate of HィイD22ィエD2OィイD22ィエD2 was lower than those observed in the previous decomposition experiments of methanol, formaldehyde, and formic acid, the extent of regeneration solely depending on each reactant. Effect of organic concentration on TOC decomposition rate was also low irrespective of organic species. Successful simulation of the overall decomposition process was achieved by an analysis considering an extraordinarily long life-time of hydroperoxy radicals, compared with those of hydroxyl and organics-derived radicals including ion radicals. Part of the research work was presented at an international conference, APCRE99, in June 1999.

利用紫外光氧化产生的活性物质的高级氧化工艺（AOP）作为环境保护的创新技术而备受关注。本研究的目的是从动力学角度阐明水中活性物质的行为，以获得光化学反应器设计的基本信息。模型化学品：乙醇（浓度为 10ppm 量级）及其分解中间体、水中的乙酸和草酸，在分批循环光化学反应系统中通过 (a) VUV (172nm) 照射、(b) VUV+UVC(185+254nm)照射，以及(c)伴随HィイD22ィエD2OィイD22エD2的UVC(254nm)照射。依次测定反应中间体（乙醛、甲醛、乙酸、草酸、甲酸）和TOC的浓度；还追踪了 HィイD22ィエD2OィイD22ィエD2、COィイD22ィエD2 和 pH 变化。实验结果首先通过传统的动力学表达式进行评估，然后通过考虑辐射化学中的基本过程的新反应模型进行评估。HiiD22ィエD2OィイD22ィD2的再生率低于之前在甲醇、甲醛和甲酸分解实验中观察到的再生率，再生程度仅取决于每种反应物。无论有机物种类如何，有机浓度对 TOC 分解速率的影响也很低。通过分析，考虑到与羟基和有机物衍生的自由基（包括离子自由基）相比，氢过氧自由基的寿命非常长，成功模拟了整个分解过程。部分研究工作于 1999 年 6 月在国际会议 APCRE99 上发表。

项目成果

菅原拓男: "過酸化水素併用254nm光照射による水中ギ酸の酸化分解特性"化学工学論文集. 25巻・6号. 842-848 (1999)

Takuo Sukawara：“254 nm 光照射与过氧化氢结合对水中甲酸的氧化分解特性”，化学工程杂志，第 25 卷，第 6 期，842-848（1999 年）。

Sugawara, T., et al.: "Oxidative Decomposition Characteristics of Formic Acid in Water by Irradiation of 254-nm Light Accompanied by Hydrogen Peroxide Addition"KAGAKU KOGAKU RONBUNSHU. 25, No.6. 842-848 (1999)

Sukawara, T., et al.：“通过 254 nm 光照射并添加过氧化氢对水中甲酸的氧化分解特性”KAGAKU KOGAKU RONBUNSHU。