几种有机难降解污染物的光催化氧化技术研究
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摘要
光催化氧化技术作为一种高级氧化技术，近年来在有机污染物处理中得到广泛的关注。本文就高浓度染料废水，难降解2，4—二氯苯酚模拟废水以及实际印钞废水为处理对象，采用TiO_2悬浮法进行处理，就催化剂投加量、催化剂晶型、电子受体、起始pH值、反应时间等因素对光催化氧化降解的影响进行探讨。
实验采用自制的光催化反应器进行实验。研究表明，TiO_2悬浮体系光催化氧化脱色效率与反应体系中TiO_2的投加量、印染废水浓度、光照、电子受体等诸多因素有关；在处理高浓度酸性蓝染料水溶液中，H_2O_2／UV／TiO_2、UV／TiO_2、UV／H_2O_2三种体系，H_2O_2／UV／TiO_2处理AB有较高的处理效率。而单纯提高TiO_2的投加量，由于羟基自由基的产生量很少，并没有显著地提高催化效果。投加H_2O_2少许便可以提高脱色率70％以上。随着起始浓度的降低，脱色率随之增加。并做了简单的机理探讨，研究表明，染色助剂对催化剂分散性，羟基自由基形成等影响是体系脱色率不高的主要因素。
在处理实际印钞废水中，催化剂的活性特征、用量、以及H_2O_2、Fe~(2+)、Fenton试剂、酸碱性等都对降解有一定的影响，在处理实际印钞废水中，研究了UV／H_2O_2、H_2O_2／Fe~(2+)、UV／H_2O_2／Fe~(2+)／H~+、UV／H_2O_2／Fe~(2+)／Fe~(3+)四种体系。结果表明，UV／H_2O_2／Fe~(2+)／H~+处理印钞废水有更高的处理效率。单纯的光催化氧化，或Fenton试剂法均不及两者结合处理效果好。光催化—Fenton试剂法处理印钞废水CODcr去除率达到50％以上，色度处理效果达到75％以上。
在处理2，4—二氯苯酚的实验中，首先建立起用紫外分光光度法测定2，4—二氯苯酚的方法。并确定了其可操作性和准确性，确定其可用来对2，4—二氯苯酚进行定量分析；其次UV／TiO_2系统降解2，4—二氯苯酚中，分析了降解速率与H_2O_2加入量，2，4—二氯苯酚的初始浓度、溶液pH值等的影响因素的关系。实验表明：2，4—二氯苯酚初始浓度对光催化氧化的影响可又Langmuir-Hinshelwood方程表示，其光催化反应可用零级动力学来描述。增加H_2O_2加入量可以提高2，4—二氯苯酚降解
速率，但当HZO:浓度达到一定程度时2，4一二氯苯酚降解速率的变化已
经不是很明显。2，4一二氯苯酚初始浓度越高，UV/HZO:降解越慢。酸
性条件下，苯酚降解效果最好。碱性条件下，不利于2，4一二氯苯酚的
降解。
光催化反应器的研究将是光催化氧化的一个热点，本文就现阶段的
光催化反应器研究做了一定的分析。并自己研制出一个实验用的光催化
反应器。
The technique of photocatalysis oxidation is a new kind of water treatment process with great potential application especially in the organic substances degradation for its outstanding effect . This paper mainly investigated the photocatalytic degradation of high concentration dyeing wastewater, 2,4-dicholorophenal simulated wastewater and printingbill wastewater, respectively. The functional mechanism, catalytic activity and the main problems including TiO2 crystalloid, pH value of solution, H2O2, initial organic concentration, electron receptor, metal ion, amount of catalyst and the dispersion situation in the liquid are discussed in details.
The photocatalytic reactor which is designed by author and manufactured by shanghai organic chemistry research institute is used in this experience. To examine the decoloring efficiency of suspension system, photocatalytic decolorization of a acid dye(Acid Blue 62) was studied as an example . the effect of TiO2 quantity, electron receptor, pH etc and the mechanism were studied in the condition of high concentration dye solution . Among the systems of TiO2/UV/ H2O2, TiO2/UV, UV/ H2O2, TiO2/UV/H2O2 presents the best one to degrade the AB dyeing wastewater. It is found that the decolourization effect only with TiO2 within short time have not been improved while improved up to 70% with the H2O2 input. The lower of the initial AB concentration, the higher the decoloring rate removal efficiency. The dyeing assistants has negative influence on the dispersity of TiO2 particles and the formation of HO, resulting in low decoloring efficiency.
In the process of the photocatalytic degradation of printingbill , the dosage and characteristic of TiO2, H2O2, Fe2+, Fenton reagent and pH are argued, the photodegradation can be improved in the condition of acid
in suspension system. The degradation efficiency of pritingbill wastewater by photocatalytic or Fenton reagent is no better than the combination of Fenton reagent and UV illumination.
Among the systems of UV/H2O2, H2O2/Fe2+ UV/H2O2/Fe2+/H+and UV/ H2O2/ Fe2+/Fe3+, UV/ H2O2/ Fe2+/H+ presents the best one to degrade the pritingbill wastewater . The decoloring rate and CODcr removal efficiency were 75% and 50% respectively.
The process of the photocatalytic degradation of 2,4-dicholorophenal by TiO2 was studied under high pressure mercury lamp. In order to study the photodegradation dynamics of 2,4-dicholorophenal in water, firstly, to establish the analysis methods of determination of 2,4-dicholorophenal , this part investigates the determination of 2,4-dicholorophenal by ultraviolet spectrophotometry and establishes the analysis methods of determination of 2,4-dicholorophenal by ultraviolet spectrophotometry and ascertain this method to determine the 2,4-dicholorophenal, secondly, to determine the mechanism of 2,4-dicholorophenal simulated water under different conditions, the relationship between the degradation rate and the initial organic concentration was found to follow Langmuir-Hinshelwood model and the result suggested that photocatalytic of 2,4-dicholorophenal was zero-order kinetics. The influences of various parameters were studied.
Finally , the recent development of photocatalytic reactor is presented and the trend is also predicted.
Mu Feng (Environmental Science and Engineering ) Supervised by: Prof. ZhuangHuisheng
实验采用自制的光催化反应器进行实验。研究表明，TiO_2悬浮体系光催化氧化脱色效率与反应体系中TiO_2的投加量、印染废水浓度、光照、电子受体等诸多因素有关；在处理高浓度酸性蓝染料水溶液中，H_2O_2／UV／TiO_2、UV／TiO_2、UV／H_2O_2三种体系，H_2O_2／UV／TiO_2处理AB有较高的处理效率。而单纯提高TiO_2的投加量，由于羟基自由基的产生量很少，并没有显著地提高催化效果。投加H_2O_2少许便可以提高脱色率70％以上。随着起始浓度的降低，脱色率随之增加。并做了简单的机理探讨，研究表明，染色助剂对催化剂分散性，羟基自由基形成等影响是体系脱色率不高的主要因素。
在处理实际印钞废水中，催化剂的活性特征、用量、以及H_2O_2、Fe~(2+)、Fenton试剂、酸碱性等都对降解有一定的影响，在处理实际印钞废水中，研究了UV／H_2O_2、H_2O_2／Fe~(2+)、UV／H_2O_2／Fe~(2+)／H~+、UV／H_2O_2／Fe~(2+)／Fe~(3+)四种体系。结果表明，UV／H_2O_2／Fe~(2+)／H~+处理印钞废水有更高的处理效率。单纯的光催化氧化，或Fenton试剂法均不及两者结合处理效果好。光催化—Fenton试剂法处理印钞废水CODcr去除率达到50％以上，色度处理效果达到75％以上。
在处理2，4—二氯苯酚的实验中，首先建立起用紫外分光光度法测定2，4—二氯苯酚的方法。并确定了其可操作性和准确性，确定其可用来对2，4—二氯苯酚进行定量分析；其次UV／TiO_2系统降解2，4—二氯苯酚中，分析了降解速率与H_2O_2加入量，2，4—二氯苯酚的初始浓度、溶液pH值等的影响因素的关系。实验表明：2，4—二氯苯酚初始浓度对光催化氧化的影响可又Langmuir-Hinshelwood方程表示，其光催化反应可用零级动力学来描述。增加H_2O_2加入量可以提高2，4—二氯苯酚降解
速率，但当HZO:浓度达到一定程度时2，4一二氯苯酚降解速率的变化已
经不是很明显。2，4一二氯苯酚初始浓度越高，UV/HZO:降解越慢。酸
性条件下，苯酚降解效果最好。碱性条件下，不利于2，4一二氯苯酚的
降解。
光催化反应器的研究将是光催化氧化的一个热点，本文就现阶段的
光催化反应器研究做了一定的分析。并自己研制出一个实验用的光催化
反应器。
The technique of photocatalysis oxidation is a new kind of water treatment process with great potential application especially in the organic substances degradation for its outstanding effect . This paper mainly investigated the photocatalytic degradation of high concentration dyeing wastewater, 2,4-dicholorophenal simulated wastewater and printingbill wastewater, respectively. The functional mechanism, catalytic activity and the main problems including TiO2 crystalloid, pH value of solution, H2O2, initial organic concentration, electron receptor, metal ion, amount of catalyst and the dispersion situation in the liquid are discussed in details.
The photocatalytic reactor which is designed by author and manufactured by shanghai organic chemistry research institute is used in this experience. To examine the decoloring efficiency of suspension system, photocatalytic decolorization of a acid dye(Acid Blue 62) was studied as an example . the effect of TiO2 quantity, electron receptor, pH etc and the mechanism were studied in the condition of high concentration dye solution . Among the systems of TiO2/UV/ H2O2, TiO2/UV, UV/ H2O2, TiO2/UV/H2O2 presents the best one to degrade the AB dyeing wastewater. It is found that the decolourization effect only with TiO2 within short time have not been improved while improved up to 70% with the H2O2 input. The lower of the initial AB concentration, the higher the decoloring rate removal efficiency. The dyeing assistants has negative influence on the dispersity of TiO2 particles and the formation of HO, resulting in low decoloring efficiency.
In the process of the photocatalytic degradation of printingbill , the dosage and characteristic of TiO2, H2O2, Fe2+, Fenton reagent and pH are argued, the photodegradation can be improved in the condition of acid
in suspension system. The degradation efficiency of pritingbill wastewater by photocatalytic or Fenton reagent is no better than the combination of Fenton reagent and UV illumination.
Among the systems of UV/H2O2, H2O2/Fe2+ UV/H2O2/Fe2+/H+and UV/ H2O2/ Fe2+/Fe3+, UV/ H2O2/ Fe2+/H+ presents the best one to degrade the pritingbill wastewater . The decoloring rate and CODcr removal efficiency were 75% and 50% respectively.
The process of the photocatalytic degradation of 2,4-dicholorophenal by TiO2 was studied under high pressure mercury lamp. In order to study the photodegradation dynamics of 2,4-dicholorophenal in water, firstly, to establish the analysis methods of determination of 2,4-dicholorophenal , this part investigates the determination of 2,4-dicholorophenal by ultraviolet spectrophotometry and establishes the analysis methods of determination of 2,4-dicholorophenal by ultraviolet spectrophotometry and ascertain this method to determine the 2,4-dicholorophenal, secondly, to determine the mechanism of 2,4-dicholorophenal simulated water under different conditions, the relationship between the degradation rate and the initial organic concentration was found to follow Langmuir-Hinshelwood model and the result suggested that photocatalytic of 2,4-dicholorophenal was zero-order kinetics. The influences of various parameters were studied.
Finally , the recent development of photocatalytic reactor is presented and the trend is also predicted.
Mu Feng (Environmental Science and Engineering ) Supervised by: Prof. ZhuangHuisheng
引文
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