臺灣博碩士論文加值系統

在考量光電產業廢水處理之成本居高不下以及污染防治設備之設置與維護保養負擔，本研究擬利用高重力式之旋轉填充床，配合進行臭氧對有機廢水之強制性質傳與氧化程序，開發適用於光電製程現場之廢水處理設備單元。擬開發之設備乃藉由臭氧之高氧化能力，將製程廢水中之有機物氧化分解，同時透過旋轉填充床之高質傳特性，克服以往臭氧程序因溶解度不足而無法有效處理大量廢水之窘境，且因臭氧利用率提升，能於製程現場及時將廢水分解並減少尾氣臭氧濃度，進而降低操作成本且免於臭氧廢氣之後處理。
旋轉填充床是以離心的方式產生高重力場，藉此產生極大的剪切力使液膜變薄或液滴變小，以增加氣液接觸面積進而提升質傳效率。實驗結果也顯示液相體積質傳係數隨液體流量增加而增加，且與轉速的0.51次方成正比。在旋轉填充床中以過氧化氫/臭氧程序處理含異丙醇水溶液可有效提升異丙醇之去除率，由實驗結果顯示，隨著轉速提高，異丙醇去除率會提高，但增加趨勢逐漸減緩，此時反應速率決定步驟應由質傳控制轉變為反應控制；液體流量增加和異丙醇去除率呈線性關係，此外也縮短反應時間大幅提升對污染物的處理效率；水溶液pH值提高會促進液相臭氧自解，而鹼催化的現象也會使得氫氧自由基更易生成，有利於污染物的去除。然而，對不同污染物而言，隨著不同的溶液pH值會有不同的競爭反應，因此最適化的pH值會隨著污染物的種類而有所不同。適量的過氧化氫可促進臭氧生成氫氧自由基提升氧化速率而過量的過氧化氫會捕捉氫氧自由基抑制反應，其最適過氧化氫/臭氧添加莫耳劑量比為0.5；在低轉速下添加過氧化氫可大幅提升甲酚之去除率，以降低動力消耗；在高pH值時，過氧化氫添加效應是較明顯的。

Organic wastewater could be treated at various levels in this project to evaluate the potentiality of rotating packed bed in wastewater treatment, especially in TFT-LCD and semiconductor manufacturing. In this study, the degree of isopropyl alcohol (IPA) and acetone removal was defined from the observed data and employed to quantify the treating efficiency of ozonation process in rotating packed bed reactor.
This work deals with the hydrogen peroxide / ozone system. The decomposition of isopropyl alcohol (IPA) in aqueous solutions using a rotating packed bed reactor by H2O2/O3 process were studied under various operation conditions such as rotor speed, gas/liquid flow rate ratio, [H2O2](aq)/[O3](g) molar ratio and solution pH. The centrifugal acceleration generates powerful shear force to render thinner liquid film and smaller droplets on the packing of reactor. Experimental results indicated that the values of kLa for ozone transfer in the rotating packed bed reactor increased with the decreasing gas/liquid flow rate ratio. In this case, a theoretical correlation for predicting kLa in a rotating packed bed was developed which showed that kLa should increase with the liquid flow rate (L0.76) and was proportional to 0.51 order of the rotor speed. It may be concluded that factors affecting H2O2/O3 oxidation efficiency from strong to weak can be ranked as gas/liquid flow rate ratio to rotor speed.
Experimental results indicated that the reaction rate constant of isopropyl alcohol (IPA) increased with an increase in the rotor speed and decreasing gas/liquid flow rate ratio. However, the removal rate constant of total organic carbon (TOC) were not notably affected by the variation of the rotor speed and the gas/liquid flow rate ratio. In the H2O2/O3 system, low concentration of hydrogen peroxide increases oxidation rates of isopropyl alcohol (IPA) while higher concentration of hydrogen peroxide inhibits the oxidation. Initially, the optimal conditions for applying the H2O2/O3 system were sought using isopropyl alcohol (IPA). In a closed reactor with isopropyl alcohol (IPA) the oxidation velocity is faster with a solution pH of 9 and a consumption of 0.5 mol H2O2 mol-1 of ozone introduced in alkaline solution was observed.

Acknowledgments…………………………………………………………………………………Ι
English abstract………………………………………………………………………………ΙΙ
Chinese abstract………………………………………………………………………………ΙV
Table of Contents………………………………………………………………………………V
List of Figures………………………………………………………………………………VΙΙΙ
List of Tables…………………………………………………………………………………ХΙΙ
Chapter 1 Introduction…………………………………………………………………………1
1.1 Background……………………………………………………………………………1
1.2 Objectives and Scope………………………………………………………………3
Chapter 2 Literature Review…………………………………………………………………4
2.1 Ozonation Process…………………………………………………………………………5
2.1.1 Physical and chemical properties of ozone………………………………………5
2.1.2 Mass transfer behavior of ozone……………………………………………………7
2.1.3 Ozonation pathway………………………………………………………………………12
2.2 Hydrogen Peroxide / Ozone Oxidation Process………………………………………16
2.2.1 Properties of hydrogen peroxide and H2O2 / O3 oxidation process…………16
2.2.2 Effect of solution pH…………………………………………………………………20
2.2.3 Effect on [H2O2](aq)/[O3](g) molar ratio………………………………………22
2.3 Rotating Packed bed………………………………………………………………………25
2.3.1 Principle and conformation…………………………………………………………25
2.3.2 Characteristic of rotating packed bed……………………………………………30
2.3.3 Operation factors………………………………………………………………………35
Chapter 3 Experimental………………………………………………………………………40
3.1 Measurements………………………………………………………………………………40
3.2 Chemicals……………………………………………………………………………………41
3.3 Apparatus and Reactor Design…………………………………………………………42
3.4 Experimental Procedures…………………………………………………………………47
3.5 Experimental Framework...…………………………………….………………………52
3.6 Methods………………………………………………………………………………………55
Chapter 4 Results and Discussion…………………………………………………………60
4.1 Mass Transfer Behavior of Ozone in a Rotating Packed Bed Reactor…………60
4.1.1 Effect of rotor speed…………………………………………………………………61
4.1.2 Effect of gas/liquid flow rate ratio……………………………………………66
4.1.3 Effect of ozone dosage………………………………………………………………72
4.1.4 Effect of solution pH…………………………………………………………………77
4.1.5 Mass transfer behavior of ozone with continuous H2O2 solution addition.81
4.2 Decomposition of Isopropyl Alcohol in Aqueous Solution by the H2O2/O3 Process in a Rotating Packed Bed Reactor………………………………………………86
4.2.1 Property of isopropyl alcohol and background experiments…………………86
4.2.2 Effect of rotor speed…………………………………………………………………92
4.2.3 Effect of gas/liquid flow rate ratio……………………………………………100
4.2.4 Effect of solution pH………………………………………………………………106
4.2.5 Effect of [H2O2](aq)/[O3](g) molar ratio………………………………………112
4.3 Decomposition of Acetone in Aqueous Solution by the H2O2/O3 Process in a Rotating Packed Bed Reactor………………………………………………………………119
4.3.1 Property of acetone and background experiments………………………………119
4.3.2 Effect of rotor speed………………………………………………………………123
4.3.3 Effect of gas/liquid flow rate ratio……………………………………………128
4.3.4 Effect of solution pH………………………………………………………………134
4.3.5 Effect of [H2O2](aq)/[O3](g) molar ratio………………………………………139
4.4 Comparison between H2O2/O3 Oxidation of Isopropyl Alcohol and Acetone...146
4.4.1 Series reaction………………………………………………………………………148
4.4.2 Influence of physical parameter…………………………………………………149
4.4.3 Influence of chemical parameter………………………...………………………154
Chapter 5 Conclusions and Recommendations……………………………………………155
5.1 Conclusions………………………………………………………………………………155
5.2 Recommendations…………………………………………………………………………157
Nomenclature……………………………………………………………………………………158
Reference………………………………………………………………………………………160
Vita………………………………………………………………………………………………168

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