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题名: 染料均相氧化降解和羟自由基测定方法的研究
作者: 徐向荣
学位类别: 硕士
答辩日期: 1998
授予单位: 中国科学院研究生院
授予地点: 北京
导师: 王文华
关键词: 染料溶液 ; dye solution ; Fenton 试剂 ; Fenton's reagent ; 高锰酸钾 ; potassium permanganate ; 脱色 ; decolorization ; 羟自由基 ; hydroxyl radical ; 化学发光法 ; chemiluminescence ; 分光光度法 ; spectrophotometry ; 荧光法 ; fluorimetry
中文摘要:       本论文综述了均相氧化法和自由基测定方法进展;研究了Fenton试剂法、类Fenton试剂法和高锰酸钾法处理六大类十八种染料溶液,并将Fenton试剂法初步用于实际染料废水的处理;建立了化学发光法、分光光度法和荧光法等三种测定Fenton反应中产生的羟自由基的方法。分别用Fenton试剂法和高猛酸钾法对酸性、活性、直接、分散、还原和阳离子六大类十八种染料进行均相氧化降解规律的研究。Fenton试剂法对染料的处理具有一定的选择性,对水溶性染料中的酸性、活性、直接和阳离子染料的处理效果较好。高锰酸钾法对分散染料的脱色效果优于Fenton试剂法;对酸性、活性、直接和阳离子染料,其脱色率与Fenton试剂法接近;与Fenton试剂法一样,该法对还原染料的脱色效果不好。总有机碳和离子色谱的测定结果表明,高锰酸钾法虽能较好地去除染料废水的色度,但对有机物的降解不彻底。将Fenton试剂法初步用于处理酸性媒介漂蓝B实际染料废水,获得了较好的处理效果。研究了不同金属离子和UV光催化下,过氧化氢对染料罗丹明B溶液的氧化处理效果。结果为Fe~(2+)/UV >Cu~(2+)/UV >Fe~(2+) >Cu~(2+) >Mn~(2+)/UV >Ag~+/UV >Mn~(2+) > Ag~+。通过对还原蓝RSN溶液的处理,得知Fenton/UV 体系的处理效果大于Fenton与H_2O_2/UV两种体系处理效果的加和,即紫外光与亚铁离子对过氧化氢的催化作用存在协同效应。建立了三种测定Fenton反应中产生的羟自由基的方法。化学发光法以酵母为发光底物。该方法已用于染料溶液中羟自由基的测定,并同TOC法作了比较。Fenton反应产生的羟自由基与二甲亚砜反应,生成甲基亚磺酸,再与坚牢蓝BB盐反应生成偶氮砜,分光光度法测定其含量可间接测定OH·的生成量。通过对测定条件的研究,得到最佳实验方案。该法已用于食品中羟自由基清除剂的筛选 。荧光法为一种新的测定Fenton反应产生羟自由基OH·的方法。Ce~(3+)在稀硫酸中能产生特征荧光,其最大激发波长和发射波长分别为280 nm和360 nm。Fenton反应产生的OH·能将Ce~(3+)氧化成Ce~(4+),用荧光法测定Ce~(3+)的荧光强度变化即可间接测定羟自由基的产生量。通过对测定条件的研究,得到最佳实验条件。该方法灵敏度高、稳定性好、操作简便、测定快速,可作为一种简便的筛选羟自由基清除剂的方法。
英文摘要:        This thesis reviewed the advances in homogeneous-phase oxidation technology and methods for the determination of hydroxyl radicals. Six types, including eighteen kinds of dye solutions, were oxidized by Fenton's reagent, Fenton-like reagents and potassium permanganate. Fenton's reagent was used in dye wastewater treatment. Three methods for the determination of hydroxyl radicals produced in Fenton reaction were established, including chemiluminescent method, spectrophotometry and fluorimetry. Eighteen kinds dye solutions, including acidic, reactive, direct, disperse, vat and cationic dye, were treated by Fenton's reagent and Fenton-like reagent respectively. The results showed the selectivity of oxidation based on the types of dye solution and high decolorization and TOC removal were obtained for the acidic, reactive, direct and cationic dye. The decolorization of disperse solution with potassium permanganate was superior to Fenton's reagent. Similar to Fenton's reagent, potassium permanganate functioned well for the decolorization of reactive, acidic, direct and cationic dyes but for vat dye. The results of total organic carbon and ion chromatography showed that potassium permanganate couldn't degrade dye solution completely. The decomposition of Rodamine B were studied by the Fenton-like reagents. The decomposition sequence was Fe~(2+)/UV >Cu~(2+)/UV >Fe~(2+) >Cu~(2+) >Mn~(2+)/UV >Ag~+/UV >Mn~(2+) > Ag~+. Fenton's reagent, Fenton/UV and H_2O_2/UV system were used in degradation of Vat Blue RSN dye solution. The results showed that the effect of Fenton/UV system was the synergistic function of Fenton and H_2O_2/UV system. Three methods for the determination of hydroxyl radicals produced in Fenton reaction were established. Yeast was chosen as chemiluminescent matrix in the chemiluminescent method. The method was applied to the determination of hydroxyl radicals in the dye solution. The spectrophotometry was established as follows: hydroxyl radicals react with dimethyl sulfoxide to produce methane sulfinic acid, which can further react with Fast Blue BB salt to form light yellow diazosulfone. The method was applied to sieve the hydroxyl radical scavenger. The fluorimetry was based on that characteristic fluorescence of Ce~(3+) was quenched by hydroxyl radical in diluted sulfuric acid at λex/λem 280nm/360nm. As a sensitive, stable, simple and rapid, it can be used for the selection of antioxidants.
内容类型: 学位论文
URI标识: http://ir.rcees.ac.cn/handle/311016/34932
Appears in Collections:环境水质学国家重点实验室_学位论文

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Recommended Citation:
徐向荣. 染料均相氧化降解和羟自由基测定方法的研究[D]. 北京. 中国科学院研究生院. 1998.
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