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研究生(外文):Ru-Yi Lin
論文名稱(外文):The Degradation of 2,4-Dichlorophenol by CuO-activated Peroxydisulfate Process: Kinetics and Mechanism.
指導教授(外文):Yi-Pin Lin
外文關鍵詞:peroxydisulfate (PDS)24-dichlorophenol (24-DCP)copper oxide (CuO)groundwater remediationnon-radical process
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Peroxydisulfate (PDS) has been considered as a promising oxidant for in-situ chemical oxidation for groundwater remediation. PDS is stable in aqueous phase allowing it to travel a great distance to reach contaminants far from the injection well and can be activated to generate sulfate radical that is capable of degrading a variety of organic pollutants. In the presence of halide ions, however, sulfate radical can oxidize these ions to form halogen radicals that can react with ubiquitous organic matter to form toxic halogenated organic compounds. CuO has been recently used to activate PDS and superior efficiency was found for the removal of chlorophenols. Unlike other systems, no sulfate radical seems to be produced by this process. However, the kinetic for the PDS/CuO process is still unclear. In this research, the mechanisms and kinetics for the degradation of 2,4-dichlorophenol (2,4-DCP) by the PDS/CuO process were investigated. It was found that only the adsorbed PDS on the CuO surface instead of the PDS in the bulk solution was activated. Radical scavenging studies also demonstrated that the degradation of 2,4-DCP by the PDS/CuO process is a non-radical process. The effects of water chemistry on this process were also investigated. It was found that the rate of 2,4-DCP degradation was proportional to the CuO dosage employed and the surface area normalized initial rate constants converged to a single value. However, the normalized rate constants increased with the increasing PDS dosage and decreasing 2,4-DCP concentrations, which could possibly result from the use of bulk PDS concentration instead of adsorbed PDS concentration in the calculations. In terms of the influence of pH, the highest rate of degradation was found at the neutral condition. Overall, 2,4-DCP could be well-degraded by the PDS/CuO process. CuO acts like an electron shuttle transferring the electron from 2,4-DCP to adsorbed PDS.
致謝 i
摘要 ii
Abstract iv
1.1 Research background 1
1.2 Objectives 3
2.1 Peroxydisulfate-based advanced oxidation processes 4
2.2 Homogeneous and heterogeneous activation for PDS 6
2.3 CuO-activated PDS process 8
2.4 Effects of solid morphology on the performance of heterogeneous activation 10
2.5 2,4-DCP 12
3.1 Chemicals and reagents 13
3.2 Preparation of copper oxide 13
3.2.1 Preparation of cotton copper oxide 13
3.2.2 Preparation of hollow copper oxide 14
3.2.3 Preparation of flower and coral copper oxide 14
3.3 Characterization of CuO 15
3.4 Batch reaction 16
3.5 Analysis methods 16
3.5.1 Analysis method for PDS 16
3.5.2 Analysis method for 2,4-DCP 17
3.5.3 Analysis method for the leaching of CuO 18
4.1 Characterization of CuO particles prepared by four different methods 19
4.2 Control experiments: reaction/adsorption in the dual-compound systems of PDS, CuO and 2,4-DCP 24
4.3 Effects of CuO dose, PDS dose, 2-4-DCP concentration and pH on the degradation of 2,4-DCP by the PDS/CuO process 29
4.3.1 Effect of CuO dosage 29
4.3.2 Effect of PDS dosage 33
4.3.3 Effect of 2,4-DCP dosage 35
4.3.4 Effect of pH 35
4.4 The correlation between the loss of PDS and 2,4-DCP degradation 40
4.5 Effect of morphology of CuO 42
4.6 Radical scavenger study 46
5.1 Conclusions 49
5.2 Recommendations 50
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