臺灣博碩士論文加值系統

高級氧化程序應用於廢水中難分解有機物之氧化為一具有前景的技術。隨著國內高科技產業蓬勃發展，異丙醇溶劑被業界大量使用，廢水含生物難分解之異丙醇亦大幅增加，增加了廢水處理之困難度與環境問題之複雜性。因此，本研究乃設計實驗系統來測試各種高級氧化程序（包括(O3, O3/UV, H2O2/UV, H2O2/O3, H2O2/O3/UV)對於異丙醇氧化降解之影響，並調整不同實驗參數與因子以瞭解其影響程度。另外，本研究亦針對臭氧高級氧化程序建立其質量傳輸與化學氧化之模式，以用於預測異丙醇之分解與中間產物之形成。實驗結果得知，高級氧化程序降解異丙醇的反應會受到不同溶液pH值的影響，當pH值為3及7時，以H2O2/O3/UV為最佳降解之程序，可完全去除水中1 g/L異丙醇，且完全礦化率分別為58 %、80 %。然而，當pH提升至10，H2O2/O3 和H2O2/O3/UV兩者對異丙醇之降解能力皆趨於相當，亦能完全去除水中1 g/L異丙醇，且完全礦化率皆降為40 %。若選擇H2O2/O3/UV程序且放大其操作參數以適用於半導體實際廢水中之異丙醇達完全去除，整體處理成本之評估較目前委外燃燒的方式每年可節省40 %以上。
本研究以臭氧作為主要高級氧化機制對於異丙醇之降解效率較其它高級氧化程序為佳，而且發現異丙醇降解過程之主要副產物為丙酮，次要副產物則如甲酸、乙酸以及草酸等。此外，結合質量傳輸和反應動力之模式可以預測異丙醇降解與主要副產物丙酮之生成情形。臭氧自解反應於純水中pH 值為3及7時皆為一階反應，而且在臭氧質量傳輸結果發現：由於水中的氫氧根離子會加速臭氧發生自解的化學反應，因此pH值愈高會加速臭氧的質傳速率。
如果結合化學反應動力，將臭氧分子和氫氧自由基對異丙醇與其它副產物的反應速率常數納入考量，模式建立之聯立非線性方程式可藉由Mathematica來預測臭氧與主要反應物的濃度變化，預測結果顯示：當pH值為3及7時，在臭氧及臭氧結合UV的反應係數分別為0.008、0.0236、1.4931、1.4909，發現臭氧結合UV此程序會產生較多的氫氧自由基而形成複雜的競爭機制使得反應係數大於臭氧程序。

Advanced oxidation processes (AOPs) is a promising technology for the treatment of wastewaters containing non-easily removable organic compounds. 2-propanol (IPA) was a group of special interest due to its high toxicity and low biodegradability. This thesis evaluates IPA degradation by several of AOP processes (O3, O3/UV, H2O2/UV, H2O2/O3, H2O2/O3/UV). The degradation has been carried out at various physic-chemical conditions. The results at different pH demonstrate that H2O2/O3/UV process is most efficient either at pH 3 and 7. Under such circumstance, 1 g/L of IPA can be decomposed completely and the TOC mineralization is achieved by 58 % and 80 %. However, at pH 10 the IPA removal efficiency by H2O2/O3 and UV/H2O2/O3 processes was almost identical, but the decomposition becomes lower comparing to acidic or neutral pHs. If applying UV/H2O2/O3 process to a pilot-scale plant, economic evaluation has demonstrated that using AOPs would save approximately 40% cost comparing with incineration treatment.
It is concluded that ozone based AOP processes are more efficient at IPA removal in wastewater than other AOPs. Acetone is identified as a primary degradation intermediate and subsequently acetic acid, formic acid, oxalic acid are identified as secondary degradation intermediates. In addition, an oxidation model incorporating mass transfer and kinetics approach based upon the rate constants for the reactions with ozone and OH radicals was developed to predict the degradation of IPA and its main byproduct of acetone formation. The self decomposition of ozone in buffered DDI water at pH 3 and 7 both occurred via a first order reaction. The ozone mass transfer coefficients are considerably higher at pH 7 than pH 3 due to the participation in the chemical reaction towards hydroxyl ion.
The oxidation model considering side reactions between ozone and OH radicals towards with other byproducts or impurities has been established using non-linear simultaneous differential equations. The reaction coefficients for IPA degradation are 0.008, 0.0236, 1.4931, 1.4909 1/sec at pH 3 and 7 in O3 and O3/UV processes, respectively. The larger reaction coefficient found in ozone/UV system indicates more competition mechanisms for hydroxyl radicals in such complicated reaction system.

TABLE OF CONTENTS
中文摘要 Ⅰ
ABSTRACT Ⅱ
LIST OF TABLES Ⅵ
LIST OF FIGURES Ⅶ
CHAPTER 1 INTRODUCTION 1
1.1 Research Background 1
1.2 Research Motivation 1
1.3 Research Goals 3
CHAPTER 2 LITERATURE REVIEW 4
2.1 Semiconductor Industry 4
2.1.1 Manufacturing Processes in Semiconductor Industry 5
2.1.2 Pollution Produced from Semiconductor Processes 6
2.2 Characteristic of Isopropyl Alcohol 7
2.3 Ozonation 8
2.3.1 Generation of Ozone 8
2.3.2 Physical and Chemical Properties 9
2.3.3 Mass Transfer of Ozone 11
2.3.3.1 Physical Absorption 11
2.3.3.2 Absorption with chemical reaction 13
2.3.4 Reaction of Ozone towards with Organic Matters 16
2.3.4.1 Direct-O3 Reaction 17
2.3.4.2 Free-radical Reactions 20
2.4 Advanced Oxidation Processes 22
2.4.1 Hydroxyl Radicals 24
2.4.2 UV/hydrogen peroxide 25
2.4.3 UV/Ozone 26
2.4.4 Peroxone (H2O2/O3) 27
2.4.5 (H2O2/O3/UV) 28
2.5 Review of Oxidation Mechanisms of IPA and Acetone 29
2.6 Review of IPA Oxidation Treatment 33
Chapter 3 MATERIALS AND METHODS 35
3.1 Phase I 37
3.2 Phase II 40
3.3 Materials 44
3.4 Experimental procedures 45
3.4.1 Phase I 45
3.4.2 Phase II 45
3.4.2.1 Ozone Mass-Transfer Model 45
3.4.2.2 OH Radical Kinetic Study 46
3.4.2.3 Integrated Model Development 47
3.5. Analytical procedures 51
Chapter 4 RESULTS AND DISCUSSION 52
4.1 Phase I 52
4.1.1 Background Experiments (O2 Stripping, H2O2 Dosage, UV) 52
4.1.2 O3 and O3/UV Processes 53
4.1.3 H2O2/UV Process 57
4.1.4 H2O2/O3 Process 58
4.1.5 H2O2/O3/UV Process 63
4.1.6 Comparison of AOPs on IPA Degradation 65
4.1.7 Economic Analysis for IPA Degradation Using AOPs 66
4.1.8 Product Formation and Identification during IPA Oxidation 68
4.1.9 Intermediates Formation Pathway during IPA Oxidation 70
4.2 Phase II 72
4.2.1 Self-Decomposition of Ozone in Water 72
4.2.2 Ozone Mass-Transfer Coefficient KLa 73
4.2.3 O3/UV Mass-Transfer 77
4.2.4 Kinetic study 78
4.2.5 Model Establishment 81
4.2.6 Comparison between experimental result and model prediction 82
Chapter 5 CONCLUSION ＆ SUGGESTION 88
5.1 Conclusion 89
5.2 Suggestion 90
REFERENCES 91
APPENDIX 97

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