多相臭氧催化氧化法处理水中邻苯二甲酸二丁酯的研究
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摘要
邻苯二甲酸二丁酯是邻苯二甲酸酯类污染物中十分常见的一种，是一种分布
广、难以自然降解、易富集的人工合成化合物。邻苯二甲酸二丁酯具有雌激素效
应，进入环境后会对动植物和人体健康造成危害。国内外采用生物法、光催化氧
化法等处理邻苯二甲酸酯类的研究均取得了一定成果，但使用多相臭氧催化氧化
技术处理邻苯二甲酸二丁酯的相关报道相对较少。针对这一现状，本论文对多相
臭氧催化氧化技术处理邻苯二甲酸二丁酯开展了较详细的研究。
本研究选用液液萃取以及气相色谱-质谱联用技术测定水中邻苯二甲酸二丁酯
的浓度。制备了多种催化剂，包括负载 Fe 的MCM-41(Fe/MCM-41)，负载 Fe 的
SBA-15(Fe/SBA-15)，负载 Fe 的活性炭(Fe/AC)，以及负载 Al，Mn，W等不同金
属的固相催化剂，并考察了各种催化剂催化臭氧降解邻苯二甲酸二丁酯的效果。
研究发现，投加 Fe/AC 后臭氧催化氧化去除邻苯二甲酸二丁酯的效果最优，并进
一步采用 X射线衍射，X射线光电子能谱，透射电子显微镜等材料表征手段对
Fe/AC 进行了结构、性能、表面形态等多方面的分析。
本论文选择了催化效果最好的 Fe/AC 为催化剂对多相臭氧催化氧化法去除水
中的邻苯二甲酸二丁酯进行了深入研究，重点研究了几种不同的影响因素(不同 Fe
负载量的改性活性炭、催化剂投加量、臭氧浓度、pH 及自由基清除剂叔丁醇)对臭
氧催化氧化去除邻苯二甲酸二丁酯催化效果的影响。此外还分析了几种不同实验
条件下臭氧催化氧化降解邻苯二甲酸二丁酯的反应动力学过程，并对其反应机理
和邻苯二甲酸二丁酯的降解途径进行了初步探讨。
结果表明，活性炭表面负载的 Fe 为羟基氧化铁 FeOOH，随着 Fe 负载量的增
加活性炭的比表面积、孔容、孔径均呈现下降的趋势。投加催化剂 Fe/AC 增加了
反应体系中羟基自由基的产生量，使邻苯二甲酸二丁酯的去除效果显著提高。当
Fe 负载量为 15%、水溶液初始 pH 值为 8时，催化剂的催化效果最好；臭氧浓度
越高，臭氧催化氧化去除邻苯二甲酸二丁酯的效率越高；由于自由基清除剂叔丁
醇抑制了羟基自由基的产生，添加叔丁醇后催化臭氧氧化去除邻苯二甲酸二丁酯
的效果明显降低，且中间产物的含量增加；臭氧单独氧化及不同臭氧浓度下臭氧
催化氧化去除邻苯二甲酸二丁酯的过程均遵循一级反应动力学模式。
关键词：环境内分泌干扰物 邻苯二甲酸二丁酯 多相臭氧催化氧化 活
性炭 羟基氧化铁
ABSTRACT
Dibutyl phthalate is a common organic pollutant that belongs to phthalate esters.
It’s a kind of synthetic compounds which is widespread, biodegraded slowly and
enriched easily. Dibutyl phthalate has estrogenic effects. While released into
environment, dibutyl phthalate will cause harm to animals, plants and human
healthy. The studies for phthalate esters removal with biological method and
photocatalytic oxidation technique have gained some achievements. However, the
relevant research in regard to heterogeneous catalytic ozonation of dibutyl phthalate
is seldom. Considering this situation, this article performs a detailed study on
heterogeneous catalytic ozonation of dibutyl phthalate in aqueous.
In this study, we used Liquid-Liquid Extraction and GC-MS to measure the
concentration of dibutyl phthalate.We had prepared different kinds of catalysts
including Fe/MCM-41, Fe/SBA-15, Fe/AC and other solid catalysts loaded with Al,
Mn, and W. We had investigated their efficiency of removing dibutyl phthalate in
catalytic ozonation reaction system. The removal efficiency of dibutyl phehalate
reached the highest in presence of iron-loaded activated carbon (Fe/AC). In addition,
we used some material characterization methods such as XRD, XPS, TEM to
analyse its structure, property and surface morphology, etc.
This study choosed Fe/AC as the catalyst and made some deeply exploration in
the research of heterogeneous catalytic ozonation of dibutyl phthalate. The effects of
iron-loading content, catalyst dosage, ozone concentration, the water pH, and
tert-butyl alcohol were mainly investigated. Moreover, we also did some reaction
kinetics studies in difficult experiment conditions and made some discussiones
about mechanism and degradation pathway in heterogeneous catalytic ozonation of
dibutyl phthalate.
Our results shows that the iron-loaded activated carbon was mainly in the form of
goethite which declined the catalyst surface area, pore volume and pore diameter.
After adding iron-loaded activated carbon, the generation of hydroxyl radical
increased which leading to the promotion of dibutyl phthalate removal. Iron loading
content of 15% and initial water pH of 8 achieved highest DBP removal among all
the tried conditions. With the ozone concentration increasing, the efficiency of
dibutyl phthalate removal was promoted. As tert-butyl alcohol is negative for the
generation of hydroxyl radical, the removal efficiency of dibutyl phthalate reduced,
and the quality of intermediate products increased obviously after adding it in the
reaction system. The ozonation and heterogeneous catalytic ozonation of dibutyl
phthalate are the first order reactions.
Key Words: environmental endocrine disrupting chemicals, dibutyl phthalate,
heterogeneous catalytic ozonation, activated carbon, FeOOH
目录
中文摘要
ABSTRACT
第一章绪论.......................................................................................................................1
1.1 环境内分泌干扰物................................................................................................1
1.1.1 环境内分泌干扰物的定义与分类 ................................................................1
1.1.2 环境内分泌干扰物的危害..............................................................................2
1.2 邻苯二甲酸酯类环境激素 PAEs..........................................................................2
1.2.1 PAEs 的来源与种类.........................................................................................2
1.2.2 我国水体中 PAEs 的分布...............................................................................3
1.2.3 邻苯二甲酸二丁酯 DBP.................................................................................4
1.3 水体中 PAEs 前处理与检测技术.........................................................................5
1.3.1 前处理技术......................................................................................................5
1.3.2 检测技术..........................................................................................................6
1.4 邻苯二甲酸酯类废水处理研究进展....................................................................7
1.4.1 生物法..............................................................................................................7
1.4.2 物理吸附法......................................................................................................8
1.4.3 高级氧化法......................................................................................................9
1.5 臭氧催化氧化研究现状......................................................................................10
1.5.1 臭氧的理化性质与制备................................................................................10
1.5.2 臭氧催化氧化技术........................................................................................11
1.6 研究意义与内容..................................................................................................13
1.6.1 研究意义........................................................................................................13
1.6.2 研究内容........................................................................................................14
第二章 实验材料与方法...............................................................................................15
2.1 实验仪器与试剂..................................................................................................15
2.2 材料表征方法及仪器..........................................................................................16
2.2.1 X 射线衍射(XRD)..........................................................................................16
2.2.2 X 射线光电子能谱(XPS)...............................................................................16
2.2.3 透射电子显微镜(TEM).................................................................................17
2.2.4 比表面积和孔结构........................................................................................17
2.2.5 表面零点核点 pHpzc....................................................................................17
2.2.6 Fe 负载量的测定............................................................................................17
2.3 检测及实验方法..................................................................................................17
2.3.1 DBP 检测方法................................................................................................17
2.3.2 气相臭氧浓度的测定....................................................................................18
2.3.3 液相臭氧浓度的测定....................................................................................19
2.4 臭氧催化氧化去除 DBP 实验方法.....................................................................20
第三章 催化材料的制备与表征分析...........................................................................22
3.1 材料的制备..........................................................................................................22
3.1.1 活性炭 AC 预处理……………....................................................................22
3.1.2 改性活性炭 AC 材料的制备........................................................................22
3.1.3 改性介孔分子筛材料 MCM-41 的制备......................................................22
3.1.4 改性介孔分子筛材料 SBA-15 的制备........................................................23
3.2 Fe/AC 材料分析....................................................................................................24
3.2.1 比表面积与孔结构分析................................................................................24
3.2.2 XRD 分析.......................................................................................................27
3.2.3 XPS 分析........................................................................................................28
3.2.4 TEM 分析.......................................................................................................30
3.2.5 金属 Fe 离子的溶出率.................................................................................30
3.2.6 表面零电荷点 pHpzc.....................................................................................31
3.3 本章小结…….....................................................................................................32
第四章 臭氧催化氧化去除 DBP 效果分析与讨论......................................................33
4.1 DBP 检测方法的确定…......................................................................................33
4.2 臭氧浓度..............................................................................................................34
4.2.1 气相中臭氧浓度............................................................................................34
4.2.2 水相中臭氧浓度............................................................................................34
4.3 不同催化材料臭氧催化氧化去除 DBP 效果的比较.........................................35
4.4 Fe/AC 臭氧催化氧化去除 DBP 的影响因素.......................................................36
4.4.1 Fe 负载量对臭氧催化氧化去除 DBP 的影响...............................................36
4.4.2 15%Fe/AC 投加量对臭氧催化氧化去除 DBP 的影响................................38
4.4.3 水中臭氧浓度对 15%Fe/AC 臭氧催化氧化去除 DBP 的影响..................40
4.4.4 叔丁醇(TBA)对15%Fe/AC 臭氧催化氧化去除 DBP 的影响...................41
4.4.5 pH 对15%Fe/AC 臭氧催化氧化去除 DBP 的影响.....................................45
4.5 臭氧催化氧化去除 DBP 的反应动力学研究.....................................................46
4.6 探讨臭氧催化氧化反应机理及 DBP 的降解途径.............................................48
4.6.1 Fe/AC 臭氧催化氧化反应机理.....................................................................48
4.6.2 DBP 降解途径分析........................................................................................48
4.7 本章小结……......................................................................................................49
第五章 结论与展望.......................................................................................................52
5.1 结论......................................................................................................................52
5.2 展望......................................................................................................................53
参考文献.........................................................................................................................54
在读期间公开发表论文和承担科研项目及取得成果.................................................61
致谢.................................................................................................................................62
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作者：侯斌
分类：高等教育资料
价格：15积分
属性：66 页
大小：2.88MB
格式：PDF
时间：2025-01-09
