臺灣博碩士論文加值系統

氯氣於工業中用途廣泛，工業級的氯氣除一般已知添加於自來水中用以消毒， 亦可用於作為鹽酸、漂白粉、聚氯乙烯塑膠PVC之製造原料。同時也運用在製造溶劑四氯化碳CCl4及氯仿CHCl3。另外與磷，三氯化磷等磷系化合物亦可合成亞磷酸二甲酯、亞磷酸二乙酯等作為塑膠添加劑、抗氧化劑、難燃劑及農藥等用途。電子級的氯氣，則因其具強氧化性且對矽、二氧化矽具良好選擇性，而使用於半導體之乾式蝕刻製程與熱氧化層之品質改善工作。
本製程為以工業級的氯氣作為原料，利用吸附，蒸餾等化工單元操作方式，使原料中雜質與氯氣分離，達到將工業級的氯氣純化為純度更高的電子級的氯氣之目的，作為下游半導體業者蝕刻等用途。製程中，蒸餾塔之操作條件對產品純度具有關鍵之作用。反應曲面法(Response Surface Methodology)為一實驗設計方法，此方法透過因子設計、篩選等步驟，配合所欲達成之結果或特性，利用曲面之不斷逼近方式找出試驗，製程之適合操作點。
本研究之內容即在於以反應曲面法針對氯氣純化製程中最關鍵之蒸餾單元，以實驗設計方式進行一有系統之試驗，先透過因子的篩選實驗，決定對於反應變數具顯著影響的因子。接著進行反應曲面實驗，利用數據解析與相關的統計技術，建立一可靠的迴歸模型，並依此找出最適化之操作變數，減少因頻繁改變因子所產生之系統擾動，達成製程改善之目標。

Chlorine has a wide application in different industry. Industrial grade chlorine can be applied in additive for sterilization in water, the raw material of hydrochloric acid, bleaching powder and polyvinyl chloride (PVC), also used in solvent manufacture of carbon tetrachloride(CCl4), chloroform(CHCl3). There are also applied for plastic additive, anti-oxidant, fire resistant and pesticides after it reacts with phosphorous and phosphorus trichloride to be phosphorous acid dimethyl ester, phosphorous acid diethyl ester and so on. Electronic grade chlorine can be commonly used dry etching process and quality improvement of thermal oxidation layer due to goodness in reaction selectivity to silicone and silicon dioxide.
The process we studied is chlorine purification from industrial grade to electronic grade via unit operation in chemical engineering as adsorption, distillation section, removing impurity by separation from pure chlorine, to be products which be applied in semiconductor. The key performance we focused is distillation system to get good quality. Response surface methodology (RSM) is method for DOE, By factorial design and screen significant factors, accompany the result characteristic, to approach the optimize operation point on curvature surface via a series experiment .
The study we did is major in distillation system, the key process, execute a series test. Screen factors via factor design to decide the significant ones. Then run RSM, analyze data by statistic technique to build a reliable model. Finally, the study will try to figure out a optimize point through RSM model to get more stability in process and reach initial improvement purpose.

中文摘要--------------------------------------------- i
英文摘要---------------------------------------------- ii
誌謝 ---------------------------------------------- iii
目錄 ---------------------------------------------- iv
表目錄 ---------------------------------------------- vi
圖目錄 ---------------------------------------------- viii
一、 緒論----------------------------------------------- 1
1.1 氯氣的性質---------------------------------------------- 1
1.2 氯氣的製造------------------------------------------------5
1.3 氯氣於工業上的應用-----------------------------------------9
1.4 高純度氯氣於半導體業的應用－以電漿蝕刻為例-----------------12
1.5 研究動機與目的--------------------------------------------16
1.6 各章節說明------------------------------------- ---- 17
二、 文獻回顧-------------------------------------- 19
2.1 實驗設計與反應曲面法的發展----------------------------------19
2.2 反應曲面法文獻整理---------------------------- 23
三、 實驗裝置------------------------------------- 25
3.1 氯氣純化製程介紹------------------------------------------ 25
3.1.1 進料----------------------------------- 25
3.1.2 吸附單元------------------------------------- 25
3.1.3 蒸餾單元--------------------------------------- 25
3.2 實驗裝置與變數說明---------------------------- 27
3.3 分析系統------------------------------ 28
3.3.1 分析儀器諸元------------------------ 28
3.3.2 儀器校驗------------------------------------------- 29
3.3.3 量測系統分析-------------------------------- 30
四、 實驗方法與步驟------------------------------ 33
4.1 因子設計實驗------------------------------- 33
4.2 反應曲面法-------------------------------------- 38
4.3 實驗相關的統計技術---------------------------- 47
4.3.1 迴歸理論－殘差分析----------------------------------- 47
4.3.2 ANOVA變異數分析---------------------------------- 49
4.3.3 串數理論與連檢定------------------------------- 52
4.3.4 T檢定------------------------------------------- 55
4.4 實驗流程------------------------------------ 56
4.4.1 實驗步驟------------------------------------- 56
4.4.2 實驗變數與範圍------------------------------- 68
4.5 實驗的解析度---------------------------------- 70
4.5.1 集區與交絡------------------------------------ 70
4.5.2 解析度的說明--------------------------------- 70
五、 實驗結果與討論-------------------------------- 73
5.1 因子設計實驗數據分析-------------------------- 73
5.1.1 ANOVA變異數分析----------------------------------- 74
5.1.2 殘差分析-------------------------------------------- 74
5.1.3 數據的串數分析---------------------------------78
5.2 因子與交互作用效果計算-----------------------78
5.3 找出顯著因子------------------------------------ 88
5.4 反應曲面實驗數據分析--------------------------------------- 91
5.4.1 曲率的計算--------------------------------------------- 92
5.4.2 評估不同因子二次方項參配於模型之效應--------------------- 93
5.4.3 三種模型的ANOVA比較------------------------------------------94
5.4.4 殘差分析-------------------------------------------------- 100
5.4.5 模型中個別因子之效應----------------------------------102
5.4.6 模型中2因子交互作用之效應------------------------------------102
5.5 等高線圖與曲面圖-------------------------------------106
5.6 製程變數的最適化-------------------------------------- 113
六、 結論------------------------------------------- 117
參考文獻 ----------------------------------------------- 120
附錄一 文獻整理表------------------------------- 127
附錄二 F分配表(α＝0.05)--------------------------- 154
附錄三 T分配的臨界值------------------------------ 155
自傳 ----------------------------------------- 156

參考文獻
1.Fauuvarque,Jacqueline,1996, “The Chlorine Industry”,Pure ＆Appl.
Chem.,vol. 68,no. 9,pp.1713-1720.
2.楊寶旺，雷敏宏，1987，專科化學，第三版，高立，臺北。
3.莊達人，1999，VLSI製造技術，第四版，高立，臺北。
4.Motupally,Sathya,Mah,Dennie T.,Freire,Francisco J. and Weidner,John
W. , 1998,“Recycling Chlorine from Hydrogen Chloride-A New and
Economical Electrolytic Process”,The Electrochemical Society
Interface,Fall,pp.32-36.
5.Keenan and William, Charles ,1976,General College Chemistry, 5th
edition, Harper & Row,USA.
6.Carrillo,Angel,Puente,M. Esther and Bashan,Yoav,1996, “Application
of Diluted Chlorine Dioxide to Radish and Lettuce Nurseries
Insignificantly Reduced Plant Development”,Ecotoxicology and
Environmental Safety,vol. 35,pp.57-66.
7.Ward,N. Robert,Wolfe,Roy l. and Olson,Betty H., “Effect of pH,
Application Technique, and Chlorine-to-Nitrogen Ratio on
Disinfectant Activity of Inorganic Chloramines with Pure Culture
Bacteria ”,Applied and Environmental
Microbiology,vol.48.no.3,pp.508-514 ,September.
8.Petrlik,Jindrich,2006, “The Spolchemie Chlor-Alkali and Chlorine
Based Chemical Production Plant in Usti Nad Labem(Czech Republic)-A
Case Study for Unintentional Production of
Hexachlorobenzene ”,International POPs Elimination Project,January.
9.Lee,Woo Hyoung,Wahman,David G.,Bishop,Paul L. and Pressman,Jonathan
G.,2011, “Free Chlorine and Monochloramine Application to
Nitrifying Biofilm:Comparison of Biofilm Penetration ,Activity,and
Viability”,Environ. Sci.Technol.,vol 45,pp.1412-1419.
10.陳清庭，張翼，2006，“氯氣氣瓶櫃洩漏危害分析與改善研究”，工業安全科技，
pp.46-53，June。
11.“微流道蒸餾技術發展”，工業技術研究院能源資訊網站。
12.何宗仁，“化工製程分離技術簡介”，2006，工業技術研究院材料與化工研究所。
13.Amago, Tatsuyuki,2001,“Sizing Optimization Using Response Surface
Method in FOA”, R＆D Review of Toyota CRDL, vol.1,no. 37.
14.Liu,J.-L.and Lee,T.-F.,2010, “A Modified Non-dominated Sorting
Genetic Algorithm with Fractional Factorial Design for Multi-
objective Optimization Problems”,Journal of Mechanics,vol.26,no.
2,pp.143-156,June.
15.Green,Stephanie,Liu,Ping-Yu and O’Sullivan,Janet,2002, “Factorial
Design Considerations”,Journal of Clinical
Oncology,vol.20,no.16,pp.3424-3430,August.
16.Chun,Chung,Heineken,Katy,Szeto,Dongmei,Ryll,Thomas,Chamow,Steve
and Chung,John D.,2003, “Application of Factorial Design to
Accelerate Identification of CHO Growth Factor
Requirements”,Biotechnol. Prog.,vol.19,no.1,pp.52-57.
17.Kovo,A.S.,2006, “Application of Full 42 Factorial Design for the
Development and Characterization of Insecticidal Soap from Neem
Oil”,Leonardo Electronic Journal of Practices and Technologies,no.
8,pp.29-40,January-June.
18.Griffith,Josefa M.,Burgess Clifford,Caroline E.,Rudnick,Leslie
R.,Schobert,Harold H. and Martin,Pedro D.,2004, “Coal Extraction
Using Light Cycle Oil:A Factorial Design Study of Process
Paramaters”,Prepr.Pap.-Am.Chem.Soc.,Div.Fuel
Chem.,vol.49,no.2,pp.627-629.
19.Beattie,Scott D. and Lin,K.J.,2004, “Rotated Factorial Designs for
Computer experiment”,中國統計學報,42卷,4期,pp.431-450,12月.
20.林宗佑，2009，應用實驗設計法於難溶藥物處方之研究，私立嘉南藥理科技大學，碩士
論文。
21.Foster,Aaron M.,Stafford Christopher M.,Karim,Alamgir and
Amis,Eric J.,2003, “Combinatorial Adhesion Measurements：Factorial
Design Concepts for Data Collection and Library
Evaluation ”,Polymeric Material：Science＆Engineering,vol.
88,pp.490-491.
22.Bose,Mausumi,2003, “The Mathematics of Symmetrical Factorial
Designs”,Resonance,pp.14-19,September.
23.Costa,Nuno and Pereira,Zulema Lopes,2007, “Objective Methods for
Analysing Unreplicated Factorial Designs”,Proceedings of the World
Congress on Engineering 2007 vol. 2,London,U.K.,July 2-4.
24.Adeleye,J.O.,Salam,K.K. and Adetunde,I.A,2009, “Analysis of
Rheological Properties of Treated Nitrogen Clay Using Factorial
Design”,European Journal of Scientific Research,vol. 37,no.
3,pp.426-438.
25.Roussel,Christian,Popescu,Christina and
Shibata,Tohru,1996, “Factorial Design Approach to Studying the
high-performance liquid chromatographic chiral separation of N-
arylthiazolin-2-(thi)one Atropisimers on CHIRALCEL OJ”,Journal of
Chromatography A,vol. 772,pp.177-188.
26.Abdel-Khalek,Nagui A.,2000, “Factorial Design for Column Flotation
of Phosphate Wastes”,Physicochemical Problems of Mineral
Processing,vol.34,pp.34-35.
27.Bingham,Derek,Sitter,Randy,Kelly,Elizabeth,Moore,Leslie and
Olivas,J. David,2008, “Factorial Designs with Multiple Levels of
Randomization”, Statistica Sinica,vol18,pp.493-513.
28.Lllias,Rosi Md,Fen,Tien Siew,Rahman,Roshanida A,Abdua Rashid,Noor
Aini,Wan Yusoff,Ean Mohtar,Hamid, Aidil Abd,Hassan Osman and
Kamaruddin,Kamarulzaman,2003 ,“Application of Factorial Design to
Study the Effect of Temperature,Initial pH and Agitation on the
Production of Cyclodextrin Glucanotrabsferase from Alkalophilic
Bacillus sp. G1 ”,Science Asia,vol 29,pp.135-140.
29.Fontes,Gizele Cardoso,Fonseca Amaral,Priscilla
Filomena,Nele,Marcio and Zarur Coelho,Maria Alice, 2010,“Factorial
Design to Optimize Biosurfactant Production by Yarrowia
Lipolytica”,Journal of Biomedicine and Biotechnology,vol 2010,pp.1-
8.
30.Ye,Kenny Q.,2004, “A Note on Regular Fractional Factorial Designs”,
Statistica Sinica,vol 14,pp.1069-1074.
31.Phoa,Frederick K. H. and Xu,Hongquan,2009, “Quarter-Fraction
Factorial Designs Constructed via Quaternary Codes”,The Annals of
Statistics,vol. 37,no.5A,pp.2561-2581.
32.白賜清，2002，工業實驗計劃法，第四版，中華民國品質學會，臺北。
33.Thomas, Pyzdek, 2000, The Six Sigma Handbook：A Complete Guide for
Greenbelts,Blackbelts, and Managers at All Levels, McGraw-Hill,
USA.
34.Vicente,G.,Coteron,A.,Martinez,M. and Aracil,J.,1998, “Application
of the Factorial Designs of Experiment and Response Surface
Methodology to Optimize Biodiesel Production ”,Industrial Crops
and Productions,vol 8,pp.29-35.
35.Dehghan,Solmaz,Aboofazeli,Reza,Avadi,Mohammadreza and
Khaksar,Ramin,2010, “Formation Optimization of Nifedipine
Containing Microspheres Using Factorial Design”,African Journal of
Pharmacy and Pharmacology ,vol 4,no. 6,pp.346-354,June.
36.Shaw,Robert,Festing,Michael F. W. ,Peers ,Ian and Furlong,Larry,
2002,“Use of Factorial Designs to Optimize Animal Experiments and
Reduce Animal Use”,ILAR Journal,vol.43,no.4,pp.223-232.
37.Nor Aishah, Saidina Amin and Yamani, Zakaria Zaki,
2003, “Optimization of Oxidative Coupling of Methane Using
Response Surface Methodology”, Journal Teknologi, vol.39, pp.35-52.
38.Goutam, Mukhopadhyay, Jasmina, Khanam and Arunabha, Nanda , 2010,
“Application of Using Response Surface Methodology in Enrichment
of Whey by Foam Fractionation Method”, International Journal of
Chemical Engineering Research, vol.1,no. 2, pp.57-72.
39.Arvind, Kumar, Prasad, B. and Mishra, I. M., 2009, “Optimization
of Acrylonitrile Removal by Activated Carbon-Granular Using
Response Surface Methodology”,Canadian Journal of Chemical
Engineering, vol.87, pp.637-643.
40.Wang ,Jun, Lu, Dingqiang, Zhao, Hui, Ling, Xiuquan, Jiang, Ben and
Ouyang,Pingkai, 2009, “Application of Response Surface Methodology
Optimization for The Production of Caffeic Acid from Tobacco
Waste”, African Journal of Biotechnology,vol.8,no. 8, pp.1416-1424.
41.劉銘純，彭錦樵，2002，“反應曲面法應用於滾筒式茶機最適操作之研究”，
中興大學農業機械學刊，vol.11，no. 2，pp.45-56。
42.Baladhandayutham, Suresh, Thangavelu, Viruthagiri and Ezhumalai,
Sasikumar, 2009,“Optimization of Process Variables Using Response
Surface Methodology (RSM) in the Solid－State Fermentative
Production of Pectinase by Aspergillus Awamori”,As. J. Food Ag-
Ind., vol.2,no. 3, pp.302-314.
43.Sin ,H.N., Yusof ,S., Abdul Hamid, N. Sheikh and Rahman, R. Abd. ,
2006, “Optimization of Hot Water Extraction for Sapodilla Juice
Using Response Surface Methodology”, Journal of Food Engineering,
vol.74,pp. 352-358.
44.Ligia, Rodrigues, Jose, Teixeira, Rosario, Oliveira and Henny C.
van der, Mei, 2006, “Response Surface Optimization of The Medium
Components for The Production of Biosurfactants by Probiotic
Bacteria”, Process Biochemistry, vol.41, pp.1-10.
45.Muthuvelayudham, R. and Viruthagiri ,T. , 2010, “Application of
Central Composite Design Based Response Surface Methodology in
Parameter Optimization and Cellulase Production Using Agricultural
Waste”, Internal Journal of Chemical and Biological Engineering,
vol.3,no. 2, pp.97-104.
46.Molnapat, Songpim, Pilanee, Vaithanomsat and Sawitri,
Chuntranuluck, 2010, “Optimization of Pectate Lyase Production
from Paenibacillus Polymyxa N10 Using Response Surface
Methodology”, The Open Biology Journal, vol.3, pp.1-7.
47.顏子殷，2005，積體電路產品封裝後溫度循環試驗結果改善探討－以光學讀取
頭元件(PDIC)的封裝作業實驗計劃法為例，朝陽科技大學，碩士論文。
48.Andjelija, Malenovic, Darko, Ivanovic, Mirjana, Medenica and
Biljana, Jancic , 2004, “Application of The Response Surface
Methodology for RP-HPLC Analysis of Lidocaine and Cetrimonium
Bromide”, Acta Chim. Slov., vol.51, pp.559-566.
49.Montgomery, Douglas C. , 2009, Design and Analysis of Experiment,
Seventh Edition,John Wiley＆Sons, USA.
50.蘇芳貴，2000，相關與迴歸分析，第一版，復漢，臺南。
51.葉怡成，2005，實驗計劃法－製程與產品最佳化，第一版，五南，臺北。
52.Yalcinkaya, S.Erdem, Yildiz, Nuray, Sacak, Mehmet and
Calimli ,Ayla, 2010, “Preparation of Polystyrene/Montmorillonite
Nanocomposite: Optimization by Response Surface Methodology
(RSM) ”, Turk J. Chem., vol.34,pp. 581-592.
53.Zhang ,Xiaoyong, Zhou, Jinyan, Fu, Wen, Li ,Zhidong, Zhong, Juan,
Yang, Jie, Xiao,Liang and Tan, Hong, 2010, “Response Surface
Methodology Used for Statistical Optimization of Jieanpeptide
Production by Bacillus Subtilis”, Electronic Journal of
Biotechnology, vol.4,no. 13.
54.白賜清，1991，品質管制之相關與迴歸分析，第五版，中華民國品質學會，臺
北。
55.Malcolmson, L.J., Matsuo, R.R. and Balshaw, R., “Textural
Optimization of Spaghetti Using Response Surface Methodology：
Effect of Drying Temperature and Durum Protein Level” ,Cereal
Chem. ,vol.70,no. 4,pp.417-423.
56.Abalos, A, Maximo, F, Manresa, MA and Bastida, J,
2002, “Utilization of Response Surface Methodology to Optimize The
Culture Media for The Production of Rhamnolipids by Pseudomonas
Aeruginosa AT10”, J Chem Technol Biotechnol ,vol.77,pp.777-784.
57.Muthukumar, M., Mohan, D. and Rajendran, M., 2003, “Optimization
of Mix Proportions of Mineral Aggregates Using Box Behnken Design
of Experiments”, Cement ＆Concrete Composites,vol.25,pp.751－758.
58.Theppayal, T. and Prasertsanl, S., 2004, “ Optimization of Rubber
Wood Drying by Response Surface Method and Multiple Contour
Plots”, Drying Technology,vol.22,no.7, pp. 1637-1660.
59.Sathyanaranan,J.,Kunthala,J. and Gurumurthy,K, 2011 , “
Methodology for Riboflavin Production by Lactobacillus Fermentum
Isolated from Yoghurt Sample”, Internal Food Research
Journal ,vol.18,pp.149-158.
60.Prakash, Om , Talat, Mahe, Hasan, S.H. and Pandey, Rajesh
K. ,2008, “ Factorial Design for Optimization of Enzymatic
Detection of Cadmium in Aqueous Solution Using Immobilized Urease
from Vegetable Waste”, Bioresource Technology,vol.99,pp.7565-7572.
61.Adinarayana, K and Ellaiah, P,2002 , “Response Surface
Optimization of The Critical Medium Components for The Production
of Alkaline Protease by A Newly Isolated Bacillus sp”, J Pharm
Pharmaceut Sci ,vol.5,no.3,pp.272-278.
62.Mane, P., Mossi, K.,and Green, C.,2009, “Optimization Energy
Harvesting Parameters Using Response Surface Methodology”, IEEE
Trans Ultrason Ferroelectr Freq Control,vol.56,no. 3,pp.429-436 .
63.Palaniyappan, M., Vijayagopal, V., Viswanathan, Renuka and
Viruthagirl, T.,2009, “Statistical Optimization of
Substrate,Carbon and Nitrogen Source by Response Surface
Methodology for Pectinase Production Using Aspergillus Fumigates
MTCC 870 in Submerged Fermentation” , African Journal of
Biotechnilogy, vol. 8,no.22,pp.6355-6363.
64.Pansuriya, Ruchir C. and Singhal, Rekha S., 2010, “Response
Surface Methodology for Optimization of Production of Lovastatin
by Solid State Fermentation”, Brazilian Journal of
Microbiology ,vol.41,pp.164-172.
65.Deyhimi, Farzad, Arabieh, Massoud and Parvin, Lida,
2006, “Optimization of The Emerson-Trinder Enzymatic Reaction by
Response Surface Methodology”, Biocatalysis and
Biotransformation,vol 24,no. 4,pp.263-271, July-August .
66.Alizadeh, Mohammad, Hamedi, Manouchehr and Khosroshahi,
Asghar ,2005 , “Optimization Sensorial Quality of Iranian White
Brine Cheese Using Response Surface Methodology”, JOURNAL OF FOOD
SCIENCE ,vol.70,pp.299-303.