臺灣博碩士論文加值系統

半導體、光電面板業、石化化工業等產業，製程大量使用含硫有機溶劑或二硫化碳，易生成還原性硫化物，嗅覺閾值低，易造成臭味問題。本研究探討化學及生物氧化法去除含硫異味物質。
研究第一部分主題為「以次氯酸鈉氧化水溶液中之二甲基硫(DMS, dimethyl sulfide)」。以不同初始反應pH、氧化劑量及ORP值，批次實驗DMS初始濃度約為100 mg/L，以GC-FID分析溶液中DMS、DMSO (dimethyl sulfone)、DMSO2 (dimethyl sulfur dioxide)濃度，並對水溶液pH值、ORP值及餘氯濃度進行監測。結果顯示，次氯酸鈉氧化DMS反應快速，反應時間小於0.75 min即可將DMS完全氧化；氧化劑量小於理論值，即可將DMS完全轉化成穩定產物DMSO2；最佳操作初始條件為微鹼性pH=8.2時，反應後的水溶液為中性，無產生Cl2(g)及HCl (g)酸氣問題；初始條件為酸性時，DMS與次氯酸反應使pH值更形降低，致HOCl轉化為氯氣逸散。
研究第二部分主題為「生物濾床氧化二硫化碳初探」。使用兩段式生物濾床，上層濾床頂部為進氣空間且連接灑水設備，下層濾床不灑水，水由上層濾床重力落下，兩層濾床濾料填充高度為0.33mH，總填料體積為0.1056 m3，濾料使用全新蛇木屑未植種，空塔停留時間(EBRT)為63 s，進氣含硫化氫(10-20 ppm)及二硫化碳(20-60 ppm)進行微生物馴養。蛇木屑生物濾床經兩個月微生物馴養後，具去除硫化氫及二硫化碳能力，硫化氫去除效率可達99%，二硫化碳最佳去除效率達86%，濾床於中性及酸性環境對二硫化碳皆有去除效果，濾料酸鹼值易調整，反應產物硫酸根可隨循環水更換去除，壓降小操作容易。

Sulfur-containing organic solvents or carbon disulfide have been used extensively in semiconductor, TFT-LCD, and synthetic fiber (viscous rayon) industries in the last decades. These compounds can easily be converted into reduced-sulfur ones which exhibit low odor threshold characteristics and arise public complaints once releasing into environments. This paper intended to oxide these compounds by both chemical and biological approaches for the purpose of odor reduction.
The first topic was investigations on the oxidation of aqueous DMS (dimethyl sulfide) by using sodium hypochlorite as an oxidant. Results indicated that with an initial DMS concentration of 100 mg/L, it required only 0.75 min or 45 s to convert the DMS completely into its final oxidation product, DMSO2 (dimethyl sulfur dioxide). The required dosage of the oxidant was a little less than the theoretical value. In addition, it was found that initial pH of the batch reaction liquid be kept at around 8.2 for achieving a neutral final solution which emitted only a trace of gaseous chlorine and hydrochloric acid odors.
The second one was a trail investigation on the biodegradation of gas-borne hydrogen sulfide and carbon disulfide by a trickling-bed biofilter packed solely with fern chips. Glucose and milk powder were used as main nutrients for microbial film development and enhancer for the biodegradation of sulfides. Results indicated that after an acclimation period of around two months, approximately 99 and 86% of the influent hydrogen sulfide (10-20 ppm) and carbon disulfide (20-60 ppm), respectively, could be removed with an empty bed retention time of around 63 s for the gas in the packed bed. Both neutral or acidic environments were suitable for the biodegradation reaction and the metabolites (mainly, sulfuric acid) could easily be removed from the chips by washing them with water. In the future, efforts should be done to increase the removal capacity of carbon disulfide.

目錄
謝誌 1
中文摘要 2
英文摘要 3
目錄 4
表目錄 7
圖目錄 8
第一章 前言 10
1-1 異味硫化物簡介 10
1-2 研究目的及內容 13
1-2-1 次氯酸鈉化學氧化二甲基硫(DMS) 13
1-2-2 生物濾床生物氧化含二硫化碳廢氣初探 13
第二章 文獻回顧 14
2-1 異味硫化物來源 14
2-1-1 二甲基硫(DMS)主要來源 14
2-1-2 二硫化碳(CS2)主要來源 14
2-2 異味硫化物特性 15
2-2-1 二甲基硫(DMS)特性 15
2-2-2 二硫化碳(CS2)特性 15
2-3 常見揮發性有機廢氣及臭氣控制技術 15
2-3-1 物理性處理方法介紹 18
2-3-2 化學性處理方法介紹 18
2-3-3 生物性處理方法介紹 30
2-4 異味硫化物相關文獻探討 33
2-4-1 次氯酸鈉化學氧化DMS相關文獻探討 33
2-4-2 生物濾床氧化二硫化碳相關文獻探討 39
第三章 實驗材料、設備及方法 42
3-1以次氯酸鈉化學氧化DMS研究實驗設備及藥品 42
3-1-1 實驗藥品 42
3-1-2 分析方法及儀器 42
3-1-3 實驗流程 42
3-1-4 實驗設計及目的 44
3-2 生物濾床生物氧化含CS2廢氣研究設備及藥品 45
3-2-1 實驗藥品 45
3-2-2 分析方法及儀器 46
3-2-3 分析項目 46
3-2-4 實驗設計及目的 46
3-2-5 實驗設備 49
第四章 結果與討論 54
4-1 次氯酸鈉氧化DMS研究結果 54
4-1-1 實際所需劑量比 54
4-1-2 初始pH值對反應影響 58
4-1-3 反應前後pH值變化 61
4-1-4 不同反應時間反應產物濃度變化 63
4-1-5 反應前後水溶液ORP值變化 64
4-1-6 實場應用經濟效益評估 65
4-2 生物濾床氧化含二硫化碳廢氣初探研究結果 69
4-2-1 微生物馴養 69
4-2-2 濾料營養鹽添加 72
4-2-3 濾料硫酸根 73
4-2-4 濾料環境變化 74
4-2-5 濾床操作溫度變化 77
4-2-6 生物濾床壓損討論 77
4-2-7 生物濾床填充高度與去除率關係 78
第五章 結論及建議 79
5-1-1 次氯酸鈉氧化二甲基硫研究結論 79
5-1-2 次氯酸鈉氧化二甲基硫研究建議 79
5-2-1 生物濾床氧化含二硫化碳廢氣研究結論 79
5-2-2 生物濾床氧化含二硫化碳廢氣研究建議 80
參考文獻 81
附錄
附錄一 檢量線資料 88
附錄二 儀器再現性試驗 90
附錄三 次氯酸鈉氧化DMS實驗數據 91
附錄四 生物濾床紀錄 97

1.周明顯，2007，”臭味及揮發性有機物控制”，初版，高雄市，國立中山大學出版社
2.Lei Zhu , J. Michael Nicovich and Paul H. Wine, 2003. “Temperature-dependent kinetics studies of aqueous phase reaction of hydroxyl radicals with dimethylsulfoxide, dimethylsulfone, and methanesulfonate.” Aquat. Sci. vol.65 pp. 425-435
3.Christian Griebler and Doris Slezak, 2000. “Microbial activity in aquatic environments measured by dimethyl sulfoxide reduction and intercomparison with commonly used methods.” Applied And Environmental Microbiology, vol.67, p100-109
4.Hiroyuki Fuse, Osamu Takimura, Kazuo Kamimura, Katsuji Murakami, and Yukiho Yamaoka, 1997. “Oxidation of dimethyl sulfide by plant pigments.” J Mar Biotechnol ,vol.5,pp158-161
5.楊宗逸，2006，以固相微萃取法結合可攜式氣相層析儀偵測二甲基硫和二甲基二硫之應用研究，國立台灣大學公共衛生學院環境衛生研究所，碩士論文
6.Wikipedia，2009，Dimethyl sulfide，<http://en.wikipedia.org/wiki/Dimethyl_sulfide>
7.Bates, T. S., R. J. Charlson and R. H. Gammon, 1987. “Evidence for the climatic role of marine biogenic sulphur.” Nature, vol.329, pp. 319-321
8.Kelly, D.P. and Smith, N.A.，1990.”Organic sulfur compounds in the environment.”Adv. Microbiol. Ecol.,vol.11, pp.345-385
9.National Institute for Occupational Safety and Health,1977,”Criteria for a recommended standard occupational exposure to carbon disulfide.”, Washington,DC, US Department of Health, Education, and Welfare.
10.Izmerov, N.F., ed.,1983,”Carbon disulfide.”, Moscow, Centre of International Projects.(GKNT)
11.Karnofski, M.A.,1975,”Odor generation in the Kraft process.” J. Chem. Educ.,vol. 52,pp.490-492
12.E. Smet, P. Lens, H. Van Langenhove,1998,”Treatment of waste gases contaminated with odorus sulfur compounds.”, England, Taylor & Francis
13.Sivela, S.,1980,”Dimethyl sulfide as g growth substrate for an obligately chemolithotrophic Thiobacillus.In Commentations Physico-Mathematicae, Dissert. No. 1,pp-1-69. (Simos, L.,Ed.) Helsinki, Societas Scientiarum Fennica.
14.台灣勞工衛生研究相關技術資料彙編，第三章，第七節，”二硫化碳”，< http://oldwww.iosh.gov.tw/netbook/te2-7.htm>
15.Miller, F.C. and Macauley, B.J., 1988, “Odours arising from mushroom composting: a review.” Austr. J. Exp. Agric. ,vol28, pp.553-560
16.Lovelock, J. E., Maggs, R.J.,and Rasmussen, R.A.,1972, “Atmospheric dimethyl sulphide and the natural sulfur cycle.”,Nature, vol.237, pp.452-453
17.De Zwart, J.M.M. and Kuenen, J.G.,1992,”C1-cycle of of sulfur compounds.”, Biodegradation, vol.3, pp.37-59
18.吳信賢、林樹崧、賴慶智，「應用於半導體業有機廢氣處理的氧化洗滌技術」 產業環保工程實務技術研討會　論文集，經濟部工業局編，民國90年11月1日。
19.周明顯，「排氣中揮發性有機物之生物洗滌處理法」，經濟部工業局九十一年度工業污染防治研習訓練講義，2002。
20.周家德，2005，飼料乾燥排氣化學洗滌除臭，國立中山大學環境工程研究所，碩士論文
21.USEPA: Handbook, “Control Technologies for Hazardous Air Pollutants”, EPA/625/6-91/014, June, 1991.(工研院化工所翻譯，1994)。
22.Reza Iranpour, Huub H.J. Cox, Marc A. Deshusses, and Edward D. Schroeder, 2005,”Literature review of air pollution control biofilters and biotrickling filters for odor and volatile organic compound removal.”Environmental progress, vol.24, pp. 254-267
23.Smet, E., Van Langenhove, H.,Verstraete,W.,1997,”Isobutyraldehyde as a competitor of the dimethyl sulfide degrading activity in biofilters.”Biodegradation, vol.8, pp.53-59
24.Giggey, M.D., Dwinal, C.A., Pinnette, J.R.& O’Brien, M.A., 1994,”performance testing of biofilters in a cold climate.”pp.4-29/4-39, Proceedings of odor and volatile organic compound emission control for municipal and industrial wastewater treatment facilities, Alexandria, VA: Water Environment Federation.
25.Singleton B. & Milligan, D.”Removal of H2S, methyl mercaptan, dimethyl sulfide, and dimethyl disulfide with biofiltration.”(source unknown)
26.Vaith,K., J. Heydoran,1997,”Comparision of biofilter performance for hydrogen sulfide ,methyl mercaptan, carbon disulfide, and dimethyl disulfide removal.”pp9-1/9-12, Proceedings of odor and volatile organic compound emission control for municipal and industrial wastewater treatment facilities, Alexandria, VA: Water Environment Federation
27.Deshusses, M.A.,Cox, H.H.J., Schroeder, E.D. &Converse, B.M., 2001,”Controlling odor and VOCs with bioreactors.”Final Report, WERF Project 98-CTS-4, Alexandria, VA: Water Environment Research Foundation.
28.Hugler, W., Acosta, C.M., Benavente, J.L.&Revah ,S.,1998,”Biological treatment of carbon disulfide laden air from sponge manufacturing facility.”Proceedings of Annual Meeting and Exhibition of the Air and Waste Managemant Association, Paper 98 WAA. 11P, Pittsburgh, PA: Air Waste Management Association.
29.Hugler, W.,Acosto, C.,&Revah, S.,1999,”Biological removal of carbon disulfide from waste air streams.”Environmental Progress, vol.18, pp.173-177
30.Tatsuya Koito, Masafumi Tekawa, and Arata Toyota, 1998. “A novel treatment technique for DMSO wastewater.” IEEE Transactions on semiconductor manufacturing, vol. 11, pp.3-8
31..Park, S.-J., Yoon, T.-I., Bae, J.-H., Seo, H.-J., Park, H.-J.,2001, “Biological Treatment of Wastewater Containing Dimethyl Sulphoxide from The Semi-Conductor Industry.” Process Biochemistry, vol. 36,pp.579–589
32.Glindemann, D., Novak, J. and Witherspoon, J., 2006,”Dimethyl Sulfoxide (DMSO) Waste Residues and Municipal Waste Water Odor by Dimethyl Sulfide (DMS): the North-East WPCP Plant of Philadelphia.” Environmental Science & Technology, vol-40, pp. 202-207.
33.Hiroshi Katoh, Isao Kuniyoshi, Mitsuyo Hirai, Makoto Shoda, 1995. “Studies of the oxidation mechanism of sulphur-contaioning gases on wet activated carbon fibre.” Applied Catalysis B: Environmental ,vol.6, pp.255-262
34.Endalkachew Sahle-Demessie & Venu Gopal Devulapelli, 2008,”Vapor phase oxidation of dimethyl sulfide with ozone over V2O5/TiO2 catalyst.”Applied Catalysis B: Environmental, vol. 84, pp.408-419
35.C. Cantau, S. Larribau, T. Pigot, M. Simon, M.T. Maurette and S. Lacombe, 2007. “Oxidation of nauseous sulfur compounds by pohotocatalysis or photosensitization.” Catalysis Today 122 (2007) pp. 27-38
36.K. Demeestere, J. Dewulf, B. D. Witte, and H. V. Langenhove, 2005. “Titanium dioxide mediated heterogeneous photocatalytic degradation of gaseous dimethyl sulfide: Parameter study and reaction pathways.” Applied Catalysis B: Environmental 60 (2005) 93–106
37.Eric Lichtfouse, Jan Schwarzbauer, Didier Robert,2005, “Environmental Chemistry: Chap. 56 Treatment of wastewater containing dimethyl sulfoxide (DMSO)” Germany: Springer Berlin Heidelberg New York
38.Albert T. Lebedev, Gulnara M. Shaydullina, Natalia A. Sinikova, and Nina V. Harchevnikova, 2004. “GC-MS comparison of behavior of chlorine and sodium hypochlorite towards organic compounds dissolved in water.” Water Research ,vol.38, pp. 3713-3718
39.T. Hartikainen, J. Ruuskanen, K. Raty, A. von Wright & P.J. Martikainen, 2000, “Physiology and taxonomy of Thiobacillus strain TJ330,which oxidizes carbon disulphide (CS2).”Applied Microbiology, vol.89, pp.580-586
40.Smith, N.A. & Kelly, D.P.,1988,”Oxidation of carbon disulphide as the sole source of energy for the autotrophic growth of Thiobacillus thioparus strain TK-m.”Journal of General Microbiology, vol. 134, pp.3041-3048
41.Sergio Alcantara, Isabel Estrada, Ma Soledad Vasquez & Sergio Revah,1999,”Carbon disulfide oxidation by microbial consortium from a trickling filter.”Biotechnology Letters, vol. 21, pp. 815-819
42.T. Hartikainen and J. Ruuskanen,2001,”Carbon disulfide and Hydrogen sulfide removal with a peat biofilter.”J. Air&Waste Manage. Assoc., vol. 51, pp. 387-392
43.Kenneth C. Schiffer and Howard E. Hesketh,1996,” Wet Scrubbers.” U.S.A.:CRC Press
44.Nist Chemistry WebBook，2009，NIST Standard Reference Database Number 69，<http://webbook.nist.gov/chemistry/>
45.Shuler M.L. & Kargi F.,1992,”Bioprocess engineering-basic concepts.”Prentice Hall, Englewood Cliffs.
46.Sergio Revah, Juan M.&Morgan-Sagastume, 2005,”Biotechnology for odor and air pollution control: 3 methods of odor and VOC control.”Shareefdeen/Singh(Eds),Springer-Verlag Berlin Heidelberg
47.Ongcharit C.,Sublette K.,Shah Y.,1991,”Oxidation of hydrogen sulfide by flocculated Thioballus denitrificans in a continuous culture.”Biotechnol. Bioeng., vol.37, pp,497-504
48.Arjan Pol. Chris van der Drift.&Huub J. M. Op den Camp, 2007,“Isolation of a carbon disulfide utilizing Thiomonas sp. and its application in a biotrickling filter.”Applied Microbial and Cell Physiology, vol. 74, pp.439-446