液相臭氧化反应机理研究及在化学耗氧量测定中的应用
摘要
臭氧化因强大的氧化能力且不会产生二次污染，是处理水中有机污染物的理想方法。采用紫外光辐射臭氧化(O_3／UV)，或利用半导体紫外光催化臭氧化(O_3／UV／光催化剂)的臭氧高级氧化技术被证明比单独臭氧化反应具有更为有效的氧化能力。随着对臭氧高级氧化技术研究的不断深入，各种技术联用方法和氧化过程理论被提出，其应用领域也不断扩大。本文系统的研究了酚类化合物O_3／UV氧化过程的动力学及其反应机理并在此基础上设计出快速监测水体中化学耗氧量(COD)的新方法，成功应用于淡水和海水实际水样的COD测定。
全文分为六章：1．文献综述：臭氧、高级氧化技术及化学耗氧量的应用和发展；2．利用基于紫外光辅助臭氧化反应的流动注射化学发光法测定水相中溶解臭氧的方法研究；3．紫外光催化臭氧氧化的流动注射化学发光法测定酚类化合物溶液的COD方法研究；4．几种酚类化合物紫外光辅助臭氧化动力学过程研究及其反应机理探讨；5．流动注射化学发光法测定实际淡水水样和海水水样COD方法研究；6．O_3／UV／TiO_2氧化手段的研究及其在COD监测领域应用探讨。
第一章通过文献综述，讨论了臭氧的性质、制备和水相中臭氧的应用，并归纳了水相中臭氧的检测方法：介绍了臭氧高级氧化技术的原理和应用；回顾了COD监测方法的现状及发展，并展望了未来COD监测方法研究的发展方向。
第二章研究了一种基于臭氧氧化鲁米诺产生化学发光的现象测定水中臭氧浓度的方法。采用鲁米诺作为发光剂，对不同浓度的臭氧水溶液分析表明，其浓度与发光信号强度呈线性关系，由此可以测定浓度低至15.066μg／L的臭氧溶液。通过向反应体系中加入Co~(+2)，有效的抑制了水中痕量
摘要
金属离子对鲁米诺发光的催化干扰。
第三章介绍了一种基于臭氧氧化鲁米诺发光测定臭氧浓度而监测
COD的新方法。选择六种酚类化合物为分析样本，利用仇/UV氧化手段
对样本溶液消解并监测反应前后体系中氏浓度的变化，由03在反应过程
中消耗的量来衡量样本溶液COD值。对样本化合物测定表明，与传统COD
检测方法相比，新方法利用流动注射系统加快分析速度，完成一个样品的
测定只需5一1伽min，且操作简单。
第四章研究了酚类化合物臭氧化反应的动力学过程和反应机理。结果
表明在紫外光催化条件下，酚类化合物与臭氧反应以直接臭氧氧化和间
接·OH氧化两种方式进行，且均有较高的反应速率常数。快速的反应显
示，O抓W氧化手段能够在较短的反应时间内将分析样品溶液彻底氧化，
满足快速COD分析中的样品氧化消解需要。通过HPLC一MS手段得到酚类
化合物不同反应时间的氧化产物信息，并推测出该化合物臭氧化反应机理。
由即LC谱图表明，酚类化合物能够在较短时间被氧化完全，但彻底消解
生成的二级反应产物则需要较长的反应时间。
第五章利用液相臭氧氧化化学发光的COD监测方法测定采集自不同
地区的实际水样。该监测方法的COD检测范围在0.6mg/]卜24m岁L之间，
适合地表天然水体的COD分析，尤其对于海水分析与传统法相比具有明显
优势。水样分析显示其COD监测结果的相对标准偏差小于10%。
第六章初步探讨了仇几即/五仇联用技术用于氧化消解有机物。研究结
果证明，与03川V手段相比，03/L时/Ti仇表现出更强的氧化能力，而且能
够在更短的时间将有机物完全氧化，能够满足短时间内充分消解有机物的
要求，在COD连续快速监测中具有研究价值和应用前景。
本论文的贡献在于:
1.利用臭氧氧化鲁米诺产生化学发光现象，建立了一种测定水中溶解
摘要
臭氧浓度的新方法。检测灵敏，快速，适于共存干扰较小的水体中臭氧浓
度测定。
2.系统研究了酚类化合物臭氧化反应，揭示了其紫外光催化臭氧化反
应动力学速率常数，推测了酚类化合物臭氧化反应机理，充实了臭氧化反
应理论。
3.提出了一种应用紫外光催化臭氧氧化鲁米诺产生化学发光来测定
水体COD含量的新方法，并成功应用于淡水和海水实际水样的COD测定.
与传统方法相比，具有简便、快速、无二次污染、对样品消解充分的优点，
具有应用前景。
Because of the powerful oxidation capability, no producing more toxic compounds than removed ones and neither introducing foreign matter to the medium, ozonation is an ideal technique to deal with the organic pollutants in aqueous and has been applied in COD determining. Advance oxidation processes (AOPs) referring to ozonation are the cooperation of ozonation and other oxidative means, which have been proved that it has a more powerful oxidation capability than that of ozonation alone. For example, a certain organic compound can hardly be degraded by ozonation alone, but a combination of both ozone and UV irradiation (UV/O3) or ozonation combining with semiconductor photocatalysis can improve the oxidation efficiency. It indicates that AOPs referring to ozonation should be a more prospective oxidant applied in COD determining than ozonation alone. This work studied in detailed the ozonation kinetics of phenolic compounds and their ozonation reaction mechanisms under the UV irradiation, developed a new metho
d to determine chemical oxygen demand (COD) utilizing the oxidation technique of UV/O3 and applied this method successfully in determining of natural water samples. The dissertation consists of 6 parts: (1) A review of the application and development of the ozone technique, AOPs and the methods for determining COD. (2) Developing a new method for determining ozone in aqueous (D03) based on the ozone oxidative flow injection chemiluminescence (FI-CL) reaction. (3) the study for determining COD of the phenolic compounds utilizing flow injection chemiluminescence (FI-CL) analysis method based on the UV/O3 process. (4) Investigating of the ozonation kinetics processes and
ozonation reaction mechanism of the phenolic compounds. (5) Determining COD of natural water samples collected from different area using the FI-CL method. (6) the investigation for the oxidation capability of Os/UV combining with TiO2 photocatalysis (Oa/UV/TiO2) and the discussion of the application of O3/UV/TiO2 in COD determining.
In the first chapter of the thesis, more than 100 references were reviewed and the background of the research was given. The properties, generation methods, applications and monitoring for ozone in aqueous were introduced in detailed. The oxidative principle and application points referring to AOPs were reviewed. The status quo and development of the COD determination were discussed. The intending foreground for COD determining was prospected. In the end of this chapter, the new method for COD determining based on the oxidation technique of Oa/UV was put forward.
In chapter 2, A new method for determining DO3 was built based on the phenomena that luminol can be oxidized by DO3 to produce luminescence. The experimental results show that the concentrations of DO3 have a linear relationship with the integral of the CL intensity within 100s. By this linear relationship, the unknown concentrations of DO3 of a certain water sample could be gained by measuring its CL intensity. The DO3 concentration of a drinking water sample is 0.818mg/L measured by FI-CL method and RSD is 8.54%. Compared with the result of 0.843mg/L measured by the indigo method, there is a recovery of 97.03%. By adding Co2+, the interference of CL catalyzed by trace metal existing in aqueous was sheltered effectively. NaHCO3, as the OH free radical scavenger, was introduced into the FI system to eliminate the CL that was produced by the oxidation of ?OH.
IT
In the third chapter, A new method for determining COD was developed based on the measurement of DO3 depicted in chapter 2. The oxidation means of UV/O3 was applied and the changes of the DO3 concentration in solutions were inspected by CL detector. The working curve for the COD determination was gamed by measuring the CL signals of the different concentrations of potassium biphthalate solutions. Several phenolic compounds were oxidized by UV/O3 and the results of their COD can be gained by calculating the consumption of DO3.
In chapter 4, the ozonation kinetics processes and ozonation mechanism
全文分为六章：1．文献综述：臭氧、高级氧化技术及化学耗氧量的应用和发展；2．利用基于紫外光辅助臭氧化反应的流动注射化学发光法测定水相中溶解臭氧的方法研究；3．紫外光催化臭氧氧化的流动注射化学发光法测定酚类化合物溶液的COD方法研究；4．几种酚类化合物紫外光辅助臭氧化动力学过程研究及其反应机理探讨；5．流动注射化学发光法测定实际淡水水样和海水水样COD方法研究；6．O_3／UV／TiO_2氧化手段的研究及其在COD监测领域应用探讨。
第一章通过文献综述，讨论了臭氧的性质、制备和水相中臭氧的应用，并归纳了水相中臭氧的检测方法：介绍了臭氧高级氧化技术的原理和应用；回顾了COD监测方法的现状及发展，并展望了未来COD监测方法研究的发展方向。
第二章研究了一种基于臭氧氧化鲁米诺产生化学发光的现象测定水中臭氧浓度的方法。采用鲁米诺作为发光剂，对不同浓度的臭氧水溶液分析表明，其浓度与发光信号强度呈线性关系，由此可以测定浓度低至15.066μg／L的臭氧溶液。通过向反应体系中加入Co~(+2)，有效的抑制了水中痕量
摘要
金属离子对鲁米诺发光的催化干扰。
第三章介绍了一种基于臭氧氧化鲁米诺发光测定臭氧浓度而监测
COD的新方法。选择六种酚类化合物为分析样本，利用仇/UV氧化手段
对样本溶液消解并监测反应前后体系中氏浓度的变化，由03在反应过程
中消耗的量来衡量样本溶液COD值。对样本化合物测定表明，与传统COD
检测方法相比，新方法利用流动注射系统加快分析速度，完成一个样品的
测定只需5一1伽min，且操作简单。
第四章研究了酚类化合物臭氧化反应的动力学过程和反应机理。结果
表明在紫外光催化条件下，酚类化合物与臭氧反应以直接臭氧氧化和间
接·OH氧化两种方式进行，且均有较高的反应速率常数。快速的反应显
示，O抓W氧化手段能够在较短的反应时间内将分析样品溶液彻底氧化，
满足快速COD分析中的样品氧化消解需要。通过HPLC一MS手段得到酚类
化合物不同反应时间的氧化产物信息，并推测出该化合物臭氧化反应机理。
由即LC谱图表明，酚类化合物能够在较短时间被氧化完全，但彻底消解
生成的二级反应产物则需要较长的反应时间。
第五章利用液相臭氧氧化化学发光的COD监测方法测定采集自不同
地区的实际水样。该监测方法的COD检测范围在0.6mg/]卜24m岁L之间，
适合地表天然水体的COD分析，尤其对于海水分析与传统法相比具有明显
优势。水样分析显示其COD监测结果的相对标准偏差小于10%。
第六章初步探讨了仇几即/五仇联用技术用于氧化消解有机物。研究结
果证明，与03川V手段相比，03/L时/Ti仇表现出更强的氧化能力，而且能
够在更短的时间将有机物完全氧化，能够满足短时间内充分消解有机物的
要求，在COD连续快速监测中具有研究价值和应用前景。
本论文的贡献在于:
1.利用臭氧氧化鲁米诺产生化学发光现象，建立了一种测定水中溶解
摘要
臭氧浓度的新方法。检测灵敏，快速，适于共存干扰较小的水体中臭氧浓
度测定。
2.系统研究了酚类化合物臭氧化反应，揭示了其紫外光催化臭氧化反
应动力学速率常数，推测了酚类化合物臭氧化反应机理，充实了臭氧化反
应理论。
3.提出了一种应用紫外光催化臭氧氧化鲁米诺产生化学发光来测定
水体COD含量的新方法，并成功应用于淡水和海水实际水样的COD测定.
与传统方法相比，具有简便、快速、无二次污染、对样品消解充分的优点，
具有应用前景。
Because of the powerful oxidation capability, no producing more toxic compounds than removed ones and neither introducing foreign matter to the medium, ozonation is an ideal technique to deal with the organic pollutants in aqueous and has been applied in COD determining. Advance oxidation processes (AOPs) referring to ozonation are the cooperation of ozonation and other oxidative means, which have been proved that it has a more powerful oxidation capability than that of ozonation alone. For example, a certain organic compound can hardly be degraded by ozonation alone, but a combination of both ozone and UV irradiation (UV/O3) or ozonation combining with semiconductor photocatalysis can improve the oxidation efficiency. It indicates that AOPs referring to ozonation should be a more prospective oxidant applied in COD determining than ozonation alone. This work studied in detailed the ozonation kinetics of phenolic compounds and their ozonation reaction mechanisms under the UV irradiation, developed a new metho
d to determine chemical oxygen demand (COD) utilizing the oxidation technique of UV/O3 and applied this method successfully in determining of natural water samples. The dissertation consists of 6 parts: (1) A review of the application and development of the ozone technique, AOPs and the methods for determining COD. (2) Developing a new method for determining ozone in aqueous (D03) based on the ozone oxidative flow injection chemiluminescence (FI-CL) reaction. (3) the study for determining COD of the phenolic compounds utilizing flow injection chemiluminescence (FI-CL) analysis method based on the UV/O3 process. (4) Investigating of the ozonation kinetics processes and
ozonation reaction mechanism of the phenolic compounds. (5) Determining COD of natural water samples collected from different area using the FI-CL method. (6) the investigation for the oxidation capability of Os/UV combining with TiO2 photocatalysis (Oa/UV/TiO2) and the discussion of the application of O3/UV/TiO2 in COD determining.
In the first chapter of the thesis, more than 100 references were reviewed and the background of the research was given. The properties, generation methods, applications and monitoring for ozone in aqueous were introduced in detailed. The oxidative principle and application points referring to AOPs were reviewed. The status quo and development of the COD determination were discussed. The intending foreground for COD determining was prospected. In the end of this chapter, the new method for COD determining based on the oxidation technique of Oa/UV was put forward.
In chapter 2, A new method for determining DO3 was built based on the phenomena that luminol can be oxidized by DO3 to produce luminescence. The experimental results show that the concentrations of DO3 have a linear relationship with the integral of the CL intensity within 100s. By this linear relationship, the unknown concentrations of DO3 of a certain water sample could be gained by measuring its CL intensity. The DO3 concentration of a drinking water sample is 0.818mg/L measured by FI-CL method and RSD is 8.54%. Compared with the result of 0.843mg/L measured by the indigo method, there is a recovery of 97.03%. By adding Co2+, the interference of CL catalyzed by trace metal existing in aqueous was sheltered effectively. NaHCO3, as the OH free radical scavenger, was introduced into the FI system to eliminate the CL that was produced by the oxidation of ?OH.
IT
In the third chapter, A new method for determining COD was developed based on the measurement of DO3 depicted in chapter 2. The oxidation means of UV/O3 was applied and the changes of the DO3 concentration in solutions were inspected by CL detector. The working curve for the COD determination was gamed by measuring the CL signals of the different concentrations of potassium biphthalate solutions. Several phenolic compounds were oxidized by UV/O3 and the results of their COD can be gained by calculating the consumption of DO3.
In chapter 4, the ozonation kinetics processes and ozonation mechanism
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