本研究藉由建立新的處理技術提高某TFT-LCD (Thin Film Transistor-Liquid Crystal Displayer)廠現有排氣處理設備處理效率。研究可分為三部分，第一部分為化學洗滌添加硫化鈉還原處理蝕刻排氣中二氧化氮，第二部分以次氯酸鈉氧化二甲基硫排氣串聯活性碳還原吸附處理廢水廠異味排氣，第三部分為以生物濾床處理實廠沸石轉輪排氣試驗。
TFT-LCD製程蝕刻排氣主要成分為醋酸、硝酸、二氧化氮、磷酸及硫酸，現場鹼性洗滌塔對二氧化氮處理去除效果不佳，排氣有黃煙及酸味問題。研究添加硫化鈉及亞硫酸鈉進行模廠及實廠洗滌塔試驗結果顯示，硫化鈉可有效還原去除實廠排氣二氧化氮，二氧化氮主要還原產物為亞硝酸鹽。亨利常數顯示二氧化氮水溶性不佳，溶於液相濃度偏低，致硫化鈉會被水中溶氧消耗，造成硫化鈉消耗量較化學計量高。研究顯示二氧化氮去除效率為液相硫化鈉加藥控制，實廠與實驗室模擬試驗主要差異為實廠洗滌水含有高濃度硝酸根等鹽類，造成洗滌水之ORP值偏高影響還原反應進行，而實廠可經由ORP控制加藥節省操作成本，在NO2進氣濃度為20-40 ppm時，洗滌塔循環水建議操作條件為pH 12.5±0.1及ORP -400±10 mV。
另外，TFT-LCD製程製程使用含硫溶劑DMSO (dimethyl sulfoxide，二甲基亞碸)，造成廢水生物處理會產生含DMS (dimethyl sulfide，二甲基硫)惡臭氣體。實驗室以次氯酸鈉(NaOCl)溶液(有效氯71-182 mg/L)氧化DMS溶液(29.1-106 mg/L)試驗數據顯示，在初始pH值為7或8時，氧化劑量為化學計量時，次氯酸鈉可快速有效氧化DMS，形成穩定及低毒性之DMSO2(dimethyl sulfone，二甲基碸)；在初始條件pH為10時，僅有50%的DMS被氧化為DMSO2，顯示在鹼性條件下次氯酸鈉氧化力有限。以次氯酸鈉溶液氧化二甲基硫氣體試驗顯示，在提供足夠的有效氯濃度(92-102 mg/L)時反應為質傳控制，初始pH 7.8或10條件下，二甲基硫均可被完全氧化成DMSO2，因微量氣相DMS傳輸至液相即被次氯酸鈉氧化。實廠洗滌塔操作數據顯示，進氣DMS 250-930 ppm可被氧化去除至低於0.2 ppm，洗滌塔建議操作條件為pH 6.5-7.0及ORP 850-900 mV。
雖洗滌塔排氣DMS濃度低於0.2 ppm，但由於DMS嗅覺閥值為0.015 ppm，排氣仍有微異味，實驗室模擬以洗滌塔殘餘之氯氣氧化殘餘DMS氣體，另利用活性碳還原氯氣除去異味。試驗顯示，在氣相反應時間5秒、DMS進氣濃度<32.5 ppm、氯氣/DMS分子比大於1.5及氣體與活性碳空塔接觸約為0.5秒時，可將排氣處理至無味。
研究第三部分為以生物濾床處理經轉輪處理之VOCs排氣，以木屑做為填充料，長期試驗顯示，在循環水pH為6.5-8、氣體空塔停留時間(EBRT)小於2秒、牛奶添加量0.11 L/m3木屑.day、填料VOC負荷4.76±2.69 g/m3.hr時，生物濾床對VOC之平均去除率48.5±24.1 %，可將轉輪排氣殘餘之異味去除至無味。

This study aimed to develop new processes for reducing emissions of air pollutants from existing TFT-LCD (Thin Film Transistor-Liquid Crystal Displayer) manufacturing processes. The target pollutants were NO2, DMS (dimethyl sulfide), and VOCs (volatile organic compounds), and the study was thus divided into three parts.
The first part of the study was undertaken to explore a method for reducing acidic and yellowish NO2 exhausted from Al-etching process in several TFT-LCD plants. The efficiency of traditional caustic scrubbing for NO2 removal was poor and not suitable for treating etching vent gas with mixed acid gas and high-salinity scrubbing liquid. Field results indicated that Na2SO3 was a less effective agent than Na2S for reducing NO2 due to the fact that the former gave a lower oxidation reduction potential (ORP) value of the scrubbing liquid. When the scrubber with parameters of packing heights of 1.0-2.0 m, a liquid-to-gas ratio L/G of 0.48-2.64 L/m3 and superficial gas velocity U of 0.66-2.08 m/s was used to treat influent NO2 concentrations of several tenths of ppm, the NO2 removal depended on sulfide dose rather than the mass-transfer rate of NO2 to the liquid. A sodium sulfide dose of 1.530.22 kg/(kg NO2 removed) required for the influent NO2 of 30-50 ppm was obtained this sodium sulfide dose was higher than the stoichiometric value for aeration scrubbing. Sulfide addition using an ORP-controlled mode with an ORP of -400±10 mV and pH of 12.5±0.1 was suggested for reducing chemical costs and obtaining a desired NO2 concentration in the scrubbed gas.
The second part of the study was carried out to investigate the liquid-phase oxidation of DMS and oxidative scrubbing of DMS-containing gas using hypochlorite as an oxidant. Results showed that liquid phase reaction of aqueous DMS (initial DMS= 29.1 to 106 mg/L) by aqueous hypochlorite solution (initial available Cl2= 71.0 to 182 mg/L) rapidly converted all the DMS to stable dimethyl sulfone (DMSO2), using the stoichiometric available chlorine at a pH of 7 or 8. At pH 10, approximately 50% of DMS was oxidized to DMSO2, indicating the limited oxidative ability of hypochlorite in an alkaline solution. With sufficient available chlorine (initial available chlorine= 92 to 102 mg/L), the rate-limiting step for gas-borne DMS (31 to 177 ppm) scrubbing was the mass transfer of DMS to the solution, rather than the oxidation of DMS. Complete oxidation of absorbed DMS was observed in scrubbing liquids with pHs of 7, 8, and 10 because of higher concentrations of free available chlorine in the liquid compared with limited absorbed DMS. The tested field scrubber removed almost all DMS (approximately 250 to 930 ppm in the influent gas) with the scrubbing liquid maintained at an ORP of 850 to 900 mV and pH of 6.5 to 7.0.
However, even the DMS concentration of scrubber outlet gas was smaller than 0.2 ppm, it was still higher than the odor threshold (0.015 ppm) and so resulted in a little malodor. Laboratory experiments indicated that the use of residual chlorine gas left in the scrubbed gas as an oxidant can oxidize residual DMS and the remaining residual chlorine can be further reduced to HCl by granular activated carbon and adsorbed therein. Results also indicated that the tested GAC had only an equilibrium DMS adsorption capacity of 4.30 mg/g GAC with 15-30 ppm DMS. With a molar Cl2/DMS ratio (R) in the range of 1.5-2.0 and a gas-phase reaction time of 5 s, and an empty-bed-contact time (EBCT) of 0.58 s with the carbon bed, the influent DMS concentration of 32.5 ppm could be removed to below a detectable limit, and get a nearly-odor free gas. GAC acted as only a role of chlorine reduction for removing residual chlorine only.
In the third part, a biotrickling filter (BF) packed with 32 to 64 liters of wood chips with average sizes of 2.03 cm × 2.25 cm, wet packing density of 470 kg/m3, void fraction 0.57, and specific surface area of 300 m2/m3 was tested for the removal of < 10 ppm THC (total hydrocarbon, expressed as methane equivalent) in gases vented from a field zeolite rotary concentrator for waste gas treatment in a TFT-LCD manufacturing plant. With the operation parameters of EBRT (empty bed retention time) of 2.0 s, pH of 6.5-8.0, and daily nutrition milk of 0.11 L/m3 chips (10 g milk powder/m3 chips), the results indicated that 50% THC in the influent gas could be removed. It was estimated that approximately 0.016 USD is required for treating 1000 m3 of the vented gas from concentrators with a gas flow of 2,000 Nm3/min.

Content
謝誌 i
摘要 ii
Abstract iv
Content vi
Chapter 1 Introduction 1
1.1 Research background 1
1.2 Background of field tests 1
1.3 Literature review 2
1.4 Specific Objectives 3
1.5 Presentation of Dissertation 4
Chapter 2 Reduction of NO2 from Etching Vent Gases by Scrubbing with Caustic Sodium Sulfide Solution 6
2.1 Etching process 6
2.2 Previous studies related to gaseous NO2 treatments 6
2.3 Material and Methods of NO2 tests 10
2.4 Reduction mechanism of NO2 15
2.5 Field tests of NO2 16
2.6 Methodology of sulfide addition 25
Chapter 3 Elimination of DMS in Waste Gases by Chlorine Oxidation Followed by Activated Carbon Adsorption 29
3.1 DMS sources and treatments 29
3.2 Material and Methods of DMS treatment 33
3.3 Oxidation of DMS reaction by chlorine solution 37
3.4 Oxidation of DMS followed by GAC adsorption 47
Chapter 4 Biofiltration of VOCs in an Effluent Gas from Zeolite Rotor Concentrator 55
4.1 Previous study of biofiltration of VOCs 55
4.2 Material and Methods of Biofiltration 56
4.3 Biofiltration of VOCs from zeolite rotor concentrator 59
4.4 ESEM of wood-chips 63
Chapter 5 Summary 65
5.1 Conclusions 65
5.2 Suggestions 67
References 68

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