臺灣博碩士論文加值系統

在目前市面上各式的儲存媒體中，因光碟片具有記錄容量大、體積小、保存壽命長、攜帶方便與成本低廉等特性，因此光碟片儲存媒體的重要性與需求量與日俱增。然而，在生產光碟片的過程中也會伴隨產生大量的有機廢氣及廢液，這些有機污染物質如不妥善作處理，勢必將會對環境造成莫大的傷害。
光碟製程中的記錄層塗佈與洗邊等製程是大量使用及產生有機廢氣及廢溶劑的污染來源。光碟片製造業主要污染物為氟化醇(TFP)、丙酮、乙醇、乙二醇醚、2-丁酮等，其中以醇類為最大宗，醇類中又以氟化醇最難處理。
本論文所探討處理之光碟廠的污染物質主要分為兩類，即含氟化醇的洗滌廢水，及含氟化醇、乙醇、丙酮等有機廢溶劑。針對這兩類不同來源及特性之污染物質探討可行且有效的處理程序。
第一類為含低濃度之氟化醇洗滌廢水。因氟化醇具有高水溶性，在光碟製程中所產生含低濃度的氟化醇廢氣先以氧化洗滌方式作氣液間的反應處理，經過反應後的廢氣達排放標準予以排放，而殘餘的洗滌廢水可藉由高級氧化處理單元後再作重複循環利用。本文即針對濕式洗滌法所產生含氟化醇廢水，探討其配合Fenton氧化法作為氧化處理單元之可行性，其中的主要操作參數包括TFP初始濃度、pH值、反應時間、過氧化氫濃度、亞鐵離子濃度、加藥方式等等。研究中討論各種處理方法及操作參數對處理成效的影響，並以總和(Lumped)反應動力學與通式(Generalized)反應動力學等模式探討Fenton氧化法的機制。經實驗結果顯示可幾乎完全去除廢水中的氟化醇，而廢水COD值亦可符合放流水標準，因此為處理含氟化醇洗滌廢水之可行方法。
第二類為含有高濃度丙酮、乙醇、氟化醇等有機物質之廢溶劑。氟化醇乃屬於高單價的有機溶劑，一般光碟廠會利用互溶性高的有機溶劑，如乙醇、丙酮等將殘餘的氟化醇溶劑作收集，以利後續作分離回收再利用。本文分別採用批次與分段蒸餾的方式作分離氟化醇、回收丙酮、乙醇等溶劑的研究探討。當進行第一段蒸餾後，可收集之冷凝液中的輕沸物丙酮濃度約75%，而第二段的蒸餾則可收集丙酮濃度達93%。此時所回收的冷凝液中所含有的氟化醇濃度已相當稀少，因此有利於後續作更近一歨地分離及回收處理。

Among the memory storage media available, optical devise is the most popular one due primarily to that it has large capacity, long storage life and stability, good portability and relatively low cost. Hence this device has become more importance and gained increasing demand. However, production of the optical memory device is accompanied by significant amounts of waste organic gases and solution. Proper disposal of these waste gases and solution is essentially a must in order to reduce their negative environmental impact.
The coating step of the CD-R and DVD-R productions is mainly responsible for the generation of the organic waste gases and solvents. Among the various pollutants, tetra-fluoro-propanol (TFP), acetone, ethanol, etc are the major ones and TFP is the one which is most difficult to deal with. The present research focuses on two types of major pollutants. The first is the waste rinsing solution that contains small amount of TFP and the second is the waste solvent which contains, in addition to acetone and ethanol, significant amounts of TFT and other impurities.
The waste rinsing solution was obtained from the packed-bed washing tower in which the waste organic components were removed from the waste gaseous streams. The waste rinsing solution was treated in a batch mode by the Fenton oxidation process in an attempt to remove its TFP and COD simultaneously. Primary operating variables considered in the experimental tests included initial TFP concentration, pH, oxidation time, amounts of H2O2 and FeSO4 and the mode of the reagent addition. Optimal operating variables were empirically determined in the test runs. Test results indicated that over 99% TFT destruction and 80% COD removal could be achieved. Furthermore, lumped and generalized kinetic models were adopted in the work to model the mechanism of the oxidation process.
In the treatment of waste solvent, recovery of acetone and ethanol is the main focus. A simple batch distillation apparatus with a side condenser was designed for this purpose. The experimental tests showed that in a single stage distillation, over 75% of acetone and ethanol can be recovered and the recovered solvent mixture containing negligible amount of TFT can readily recycled for reuse.

摘要. …………………….Ⅰ
Abstract. ……………………………Ⅱ
致謝. ……………………………Ⅲ
目錄. ……………………………Ⅳ
表目錄. ……………………………………………...Ⅵ
圖目錄. ……………………………………………..Ⅶ
第一章 緒論. ……………………………………………..1
1.1 前言 1
1.2 光碟製程概述 3
1.2.1 光碟片製程 4
1.2.2 光碟片紀錄原理 10
1.2.3 色素層種類 12
1.3 污染物來源及特性 19
1.4 研究動機 22
1.5 研究內容 24
第二章 基本理論與文獻回顧 25
2.1 揮發性有機物之處理技術簡介 25
2.2 Fenton氧化法 28
2.3 Fenton氧化法去除有機物之影響因素 31
2.4 Fenton氧化動力學模式 32
2.4.1總和動力學模式 33
2.4.2通式動力學模式 35
2.5 廢溶劑回收處理 37
2.5.1 廢溶劑產生現況 37
2.5.2 廢溶劑回收處理技術 38
2.5.3 蒸餾分離回收處理技術 40
第三章 實驗裝置及分析方法 45
3.1 含氟化醇洗滌廢水之氧化處理 45
3.1.1 Fenton氧化法實驗設備 45
3.1.2實驗流程及步驟 47
3.2 廢溶劑之回收處理 49
3.2.1蒸餾實驗設備 49
3.2.2實驗流程及步驟 49
3.3 分析方法及設備 52
3.3.1主要有機溶劑之濃度分析 52
3.3.2 過氧化氫的氧化特性及濃度分析 53
3.3.3 水質分析 55
3.3.4 分析設備 56
3.4 實驗藥品 57
第四章 氧化處理含氟化醇洗滌廢水之實驗結果與討論 60
4.1 Fenton氧化法中各變數影響之實驗結果 60
4.1.1 反應時間 60
4.1.2 pH值 60
4.1.3 過氧化氫加藥量 61
4.1.4 亞鐵鹽加藥量 61
4.1.5 加藥方式 62
4.1.6 模擬廢水初始濃度 62
4.1.7 最佳經濟加藥量 79
4.2 Fenton氧化動力學討論 95
4.2.1 總合反應動力學 95
4.2.2 通式反應動力學 99
第五章 回收處理廢溶劑之實驗結果與討論 103
5.1 冷凝水溫度對蒸餾回收效果之影響 103
5.2 蒸餾過程中冷凝液之累積量與時間的變化 103
5.3 沸騰溫度隨時間的變化 103
5.4 蒸餾產物濃度對時間之關係 104
5.5 分段蒸餾對回收效果之比較 104
5.6 不同蒸餾管管長對回收效果之比較 104
第六章 結論與建議 115
6.1 結論 115
6.1.1含氟化醇洗滌廢水之氧化處理 115
6.1.2廢溶劑之回收處理 116
6.2 建議 117
參考文獻 118
附錄 123

1.Aldershof B. K., Dennis R. M. and Kunitsky C. J., Study of Decomposition of Four Commercially Available Hydrogen Peroxide Solutions by Fenton''s Reagent, Water Environment Research, 69, 1052-1059 (1997).
2.Anonymous, DVD-R 2.0, Optical Disc Systems, 7-8(2002).
Balanosky E., Herrera F., Lopez A. and Kiwi J. Oxidation Degradation of Textile Waste Water Modeling Reactor Performance, Water Research, 34, 582-596(2000).
3.Benefield L. D., Judkins J. F. Jr. and Weand B. L., Process Chemistry for Water and Wastewater Treatment, Prentice Hall(1982).
4.Bornside, D.E., Macosko, C.W., and Scriven, L.E., 0n the Modeling of Spin Coating, Journal of Imaging Techchnology, 13, 122-130(1987).
5.Chen,B.T., Investigation of the Solvent Evaporation Effect on Spin Coating of Thin Films, Polymer Engineering and Science, 23, 399-407(1983).
6.Chou S. and Huang C. Experimental Design for Treatment a Dyeing/ Finishing Wastewater by FBR-Fenton Method, 24th Conference on Wastewater Treatment Technology, Taiwan, 231-237 (1999).
7.Foussard, J. N., Debellfontaine, H. and Besombes-vailhe, j., Efficient Elimination of Organic Liquid Waste: Wet Air Oxidation, Journal of Environmental Engineering, ASCE, 115, 367-385 (1989).
8.Gonzalez-Velasco, J.R., Gutierrez-Ortiz, M.A.;Costresana-Pelayou, J.M., Gonzalez-Marcos, Industrial and Engineering Chemical Research, 26, 745(1987).
9.Gulays H., Process for the Removal of Recalcitrant Organics from Industrial Wastewater, Water Science and Technology, 36, 9-16 (1997).
10.Huang C. P., Dong C. D. and Tang Z. H. Advanced Chemical Oxidation : Its Present Role and Potential Future in Hazardous Waste Treatment, Waste Management, 13, 361-377(1993).
11.Kang Y. W. and Hwang K. Y. Effect of Reaction Conditions on the Oxidation Efficiency in the Fenton Process, Water Research, 34, 2786-2790(2000).
12.Khan F. I. and Ghoshal A. K., “Removal of Volatile Organic Compounds form Polluted Air,” Journal of Loss Prevention in the Industries, 13, 527-545 (2000).
13.Lawrence,C.J., The Mechanics of Spin Coating of Polymer Films, Physics of Fluids, 31, 2786-2795(1988).
14.Lawrence,C.J., Spin Coating with Slow Evaporation, Physics of Fluids, 2, 453-456(1990).
15.Levison, W.A., A.mold, and O. Dehodgins, Spin Coating Behavior of Polyimide Precursor Solutions, Polymer Engineering and Science, 33, 980-987(1993).
16.Li, L., Chen, P. and Gloyna, E. F., Generalized Kinetic Model for Wet Oxidation of Organic Compounds, AIChE Journal, 37, 1687-1697 (1991).
18.Lidia S., and Claudia J. and Santosh N. K. A Comparative Study on Oxidation of Disperse Dyes by Electrochemical Process, Ozone, Hypochlorite and Fenton reagent. Water Research, 35, 2129-2136 (2001).
19.Lin, Fred Hung-Jye, Simulation of Benzene/Toluene Distillation and Two- Point Control, Proceedings Symposium on Transport Phenomena and Applications, Taipei,128-136(1996).
20.Lin, Fred Hung-Jye and Chuei-Tin Chang, Revamping an Azeotropic Distillation for Energy Conservation and Entrainer Recovery, Proceedings Symposium on Transport Phenomena and Applications, Taipei, 105-115(2001).
21.Lin, Fred Hung-Jye, Azeotropic Distillation for Absolute Alcohol with n-Pentane as the Entrainer, Proceedings Symposium on Transport Phenomena and Applications, Taipei,151-163(2002).
22Lindsey M. E. and Tarr M. A. Quantitation of Hydroxyl Radical during Fenton Oxidation Following a Single Addition of Iron and Peroxide. Chemosphere ,41, 409-417(2000).
23.Lin, S. H. and Cheng, C. C., Treatment of Landfill Leachate by Combined Electro-Fenton Oxidation and Sequencing Batch Reactor Method, Water Research, 34, 4243-4249(2000).
24.Lunar L., Sicilia d. and Rubio S., Degradation of Photographic Developers by Fenton’s Reagent: Condition Optimization and Kinetics for Metol Oxidation, Water Research, 34, 1791-1802 (2000).
25.Luyben, M. L., Tyreus, B. D., Industrial Design/Control Study for the Vinyl Acetate Monomer Process, Computers & Chemical Engineering 22(7-8), 867(1998).
26.Luyben, W. L., Some Practical Aspects of Optimal Batch Distillation Design, Industrial and Engineering Chemical Process Design and Development, 10, 54-59(1971).
27.Luyben, W. L., Multicomponent Batch Distillation I Ternary System with Slop Recycle, Industrial and Engineering Chemical Research, 27, 642-647(1988).
28.Moreau, W. M., Semiconductor Lithography, Plenum Press, New York (1988).
29.Rehg,T.J.,and Higgins,B.G., The Effect of Inertia and Interfacial Shear on a Rotating Disk, Physics of Fluids, 31, 1360-1371(1988).
30.Ruska, W. S., Microelectronic Processing, McGraw Hill, New York (1988).
31.Solozhenko, E. G., Soboleva, N. M. and Goncharuk, V. V., Decolourization of Azodye Solutions by Fenton’s Oxidation, Water Research, 29, 2206-2210 (1995).
32.Talinli I. and Anderson G. K., Interference of Hydrogon Peroxide on the Standard COD Test, Water Research, 26, 107-110(1992).
33.Yen,S.C.and Wanng,J.S., Mass Transfer and Fluid Flow Due to a Rotating Disk with External Forced Convection, Chemical Engineering Science, 47, 2001-2008(1992).
34.Zhang, Q. and Chuang, K. T., Lumped Kinetic Model for Catalytic Wet Oxidation of Organic Compounds in Industrial Wastewater, AIChE Journal, 45, 145(1999).
35.Zhu W., Yang Z. and Wang L., Application of Ferrous-Hydrogen Peroxide for the Treatment of H-acid Manufacturing Process Wastewater, Water Research, 30, 2949-2959(1996).
36.盧滄海、賴龍山，"廢溶劑回收可行性調查"，廢棄物交換回收再利用研討會論文集，12(1988).
37.林冠宇，廢有機溶劑簡易回收裝置，塗料及塗裝技術雜誌創刊號，9(1991).
38.胡子陵，以活性碳床處理廢有機溶劑蒸氣，中正理工學院博士學位論文(1993).
39.王志達，旋轉塗佈之研究，國立台灣大學化學工程研究所博士學位論文(1995).
40.邱永亮，魏盛德編譯，染料化學，徐氏基金會出版，台北，10(1997).
41.黃耀輝、陳致君、黃國豪，印刷電路板業高濃度廢液高級處理技術比較，工研院化工所(1998).
42.陳維弘，異丙醇、環己烷與水三成分非均勻相共沸蒸餾系統之分析與控制，中原大學化學工程學系碩士論文(1999).
43.蔡永興、吳美惠、翁志聖，國內廢溶劑處理現況介紹，1999工程實務技術研討會論文集，122-129(1999).
44.汪仲甫，光碟燒錄技術徹底研究，旗標出版社，台北，5(1999).
45.陳建勳，高密度儲存媒體染料之研究，朝陽科技大學應用化學研究所碩士學位論文(2000).
46.曾淑華，CD-R光碟片仍是記錄型光碟片市場主流，工研院經資中心IT1S計畫，10(2000).
47.江昌達，高濃度半導體廢水之處理與回收，元智大學化學工程學系碩士論文(2001).
48.賴慶智，電子產業及特定行業改善輔導示範推廣及管制標準研訂專案計畫，行政院環保署，12(2001).
49.卓錦松，旋轉塗佈與光碟保護層製作，元智大學化學工程學系碩士論文(2001).
50.劉彥君、黃耀輝、楊慕震，共沸蒸餾方法與滲透蒸發方法回收IPA之比較與經濟評估，第二十三屆輸送現相與其應用專題研討會專輯(2001).
51.吳信賢、林樹榮，光碟製程揮發性有機廢氣去除-高級氧化技術之應用，化工資訊，5(2003).
52.施柏均，光碟片產業評析，產業報告，台証証卷(2003).
53.陳建仲，光碟片產業需求持續上揚，產業榮景在2004年仍看好，元大京華投顧(2003).
54.郭枝群，台灣光碟片製造業的產業分析，台灣大學財務金融學系碩士論文(2004).