以紫外線/臭氧程序處理染料廢水之光反應器設計研究 林奇璋、申永順
E-mail: 9123232@mail.dyu.edu.tw
摘 要
本研究旨在發展與建立以高級氧化程序處理染料廢水之連續環狀雙套管式光反應器設計方程式, 探討模式係藉由結合光氧 化系統中之反應機制、各反應成份之質量平衡方程式,以及紫外線光強 度分佈模式,並經由不同反應條件(如水力停留時 間、光反應器幾何尺寸、水溶液PH值、紫外線光 強度等)及染料物種(如反應性染料 REACTIVE RED 141、酸性染料ACID BLUE 62、直接染料DIRECT YELLOW 86等)之實驗驗證,以評估光反應器設計方程式之合理性與可行性。研究重點係 以UV/O3及 UV/H2O2/O3程序處理染料廢水為主題,架構整體反應系統,經由染料污染物及氧化劑質量平衡之計算 , 評估氧化劑及紫外線之使用效率,以做為高級氧化程序效能及操作條件之取決依據,並比較不同 類型之染料污染物在各光 氧化系統中反應特性的差異,從而建立光氧化程序處理染料廢水之光反應 器設計方程式,以做為以光為主體之高級氧化程 序未來實際商業應用研究之基礎及參考。 在UV/O3及UV/H2O2/O3程序中,染料去除效率主要受到染料本身之初始濃度 之降低、染料溶液 PH值之降低、紫外線光強度之提高、氧化劑添加劑量之增加及光反應器內外半徑比之降低而升高。 在 該兩種程序下,三種染料之去除率順序為,UV/O3程序下BLUE 62>RED 141>YELLOW 86; UV/H2O2/O3程序 下RED 141>BLUE 62>YELLOW 86。各種AOPS程序處理染料分別去除率順序為 UV/H2O2/O3>UV/O3>H2O2/O3
>O3。 結合各反應成分之質量平衡方程式與無限線光源分佈模式,所推導與建立之光反應器設計方程式, 可合理描述 以UV/O3及UV/H2O2/O3程序處理染料在各操作條件下之反應行為。
關鍵詞 : 高級氧化程序、染料廢水、環狀光反應器、設計方程式 目錄
第一章 前言--P1 第二章 理論背景及文獻回顧--P4 2.1染整廢水特性簡介 4 2.1.1染料之化學結構及發色原--P4 2.1.2染料之分 類--P5 2.1.3染整廢水之來源及特性--P7 2.1.4一般染整廢水處理方法--P8 2.2光分解反應程序之理論--P11 2.2.1紫外線之特性 及應用--P11 2.2.2光學基本名詞之定義--P13 2.2.3光化學之反應理論--P18 2.3 UV/O3光解程序之反應機制與應用--P23 2.3.1 O3之一般性質--P23 2.3.2 UV/O3程序之反應機制--P25 2.4 UV/H2O2/O3光解程序之反應機制與應用--P33 2.4.1 H2O2之一 般性質--P33 2.4.2UV/H2O2程序之反應機制--P33 2.4.3UV/O3/H2O2程序之反應機制--P34 2.5光化學反應器之模擬設 計--P39 2.5.1光源模式之基本概念--P40 2.5.2光化學反應器設計與模擬--P44 第三章 研究目的--P53 第四章 實驗程序與設 備--P55 4.1實驗設備與儀器--P55 4.2實驗藥品--P56 4.3實驗裝置--P58 4.4實驗步驟--P61 4.4.1背景實驗--P61 4.4.2以UV/O3程 序處理染料水溶液--P66 4.4.3以UV/O3/H2O2程序處理染料水溶液--P67 4.5分析測定方法--P67 第五章 結果與討論--P71 5.1 背景實驗--P71 5.1.1染料於液相中之穩定性實驗--P71 5.1.2以紫外線直接光解染料實驗--P73 5.1.3以O3直接分解染料水溶液 實驗--P73 5.1.4以H2O2直接分解染料水溶液實驗--P78 5.2以UV/O3程序處理染料溶液之反應行為--P78 5.2.1以UV/O3程序 處理含RED 141染料溶液之反應行為--P82 5.2.2以紫外線/臭氧程序處理不同染料水溶液之比較--P101 5.2.3以紫外線/臭氧程 序處理含染料溶液之光反應器設計與模擬 104 5.3以UV/ H2O2/O3程序處理染料溶液之反應行為--P118 5.3.1
以UV/H2O2/O3程序處理含RED 141染料溶液之反應行為--P118 5.3.2不同染料之反應行為比較--P134 5.3.3
以UV/H2O2/O3程序處理含染料溶液之光反應器設計與模擬--P137 5.4比較各種高級氧化程序處理染料溶液之反應行 為--P148 5.4.1紫外線光強度效應--P148 5.4.2染料初始濃度效應--P152 5.4.3臭氧/染料進流比效應--P154 5.4.4臭氧劑量效 應--P156 5.4.5溶液PH值效應--P157 5.4.6光反應器尺寸效應--P161 第六章 結論與建議--P163 參考文獻--P165 附錄--P173 參考文獻
1.王文,"以臭氧相關程序處理含亞速靈農藥水溶液之研究",碩士論文,國立台灣科技大學化工所, 民國八十五年。 2.王登楷,"以高 級氧化程序處理揮染整廢水之光反應器設計研究",碩士論文,大葉大學環工所, 民國九十年。 3.方長福,"染整廢水以新型反應器進行 臭氧脫色研究",碩士論文,國立台灣工業技術學院化工所, 民國八十六年。 4.申永順,"以高級氧化程序處理揮發性有機污染物反應行 為及光反應器設計之研究",博士論文,國 立台灣科技大學化工所,民國八十七年。 5.申永順,"以紫外線/過氧化氫程序處理含氯酚類 有機溶液反應行為之研究",碩士論文,國立台灣 科技大學化工所,民國八十一年。 6.行政院環境保護署,"水污染防治法-放流水標準"
,民國九十年二月七日修正。 7.和田洋六,水處理技術(應用篇),地人書館,民國八十一年。 8.林億芳,"利用UV/H2O2光化學氧化 處理含酸性染料廢水之研究",碩士論文,國立台灣大學環工所, 民國八十三年。 9.祝德杭,"UV/H2O2系統分解水中氯苯類污染物與 減毒效果之研究",碩士論文,中央大學環工所, 民國八十八年。 10.涂善勇,"化學混凝法探討染整廢水脫色之研究",碩士論文,私立
淡江大學水資源暨環境工程研究所, 民國八十年。 11.徐永錢、方長福,"新氣捲式設備中以臭氧處理數種染料水溶液",第二十一屆廢 水處理技術研討會論集,第 148-154頁,民國八十五年。 12.陳姍玗、簡良榮、張嘉修、陳博彥,"以混合菌相進行廢水褪色之生態工程 研究", 第二十五屆廢水處 理技術研討會論文集,第6-11頁,民國八十九年。 13.黃全億,"臭氧在捲器攪拌槽中對染料水溶液之脫色及 臭氧利用率之研究",碩士論文,國立台灣工業 技術學院化工所,民國八十三年。 14.經濟部環保署工業減廢聯合輔導小組,「工業減廢 技術手冊1-染整工業」,第20-43頁,民國八十二年。 15.經濟部環保署工業減廢聯合輔導小組,「工業減廢技術手冊4-染整工業」,
第21-23頁,民國八十四年。 16.經濟部工業污染防治技術手冊,「高級氧化程序在廢水處理上的應用」,民國八十二年。 17.魏漣邦、
張敏超、楊耿豪、許楹昇,"化學混凝脫色最佳組合劑量之研究",第二十五屆廢水處理技術研 討會論文集,第 674-678頁,民國八十九 年。 18.顧洋,"紫外線/臭氧氧化程序在廢水處理上之應用",工業污染防治第十四卷,第四期,第248-261頁, 民國八十四年。 19.劉博 文、周明顯、高志明、黃伯仁,"利用臭氧及紫外線照射去除染整廢水色度之最佳操作參數探討", 第二十五屆廢水處理技術研討會論文 集,第 551-555頁,民國八十九年。 20.ABE, K. AND TANAKA, K. (1999) "EFFECT OF FE2+ ON UV-ILLUMINATED OZONATION OF NITROPHENOLIC COMPOUNDS", CHEMOSPHERE , 38, 12, 2747-2752. 21.AKEHATA, T., SHIRAL, T., ISHIZOKI, N., AND ITO, K., (1973) "AVERAGE LIGHT INTENSITY IN AN ANNULAR PHOTOCHEMICAL REACTOR", KAG. KOG., 37, 1026-1031.
22.ALFANO, O. M., ROMERO, R. L. AND CASSANO, A. E., (1984) "RADIATION FIELD INSIDE A CYLINDRI -CAL PHOTOREACTOR IRRADIATION FROM THE BOTTOM", CHEM. ENG. REA., 1, 506-522. 23.BELLAMY, W. D. (1998)
"TREATMENT OF VOC-CONTAMINATED GROUNDWATER BY HYDROGEN PEROXIDE AND OZONE OXIDATION" RES. J.
WPCF. 26, 9-17. 24.BOLTON, J. R., (1999) "CALCULATION OF ULTRAVIOLET FLUENCE RATE DISTRIBUTIONS IN AN ANNULAR REACTOR: SIGNIFICANCE OF REFRACTION AND PEFLECTION", WAT. RES., 34, 13, 3315-3324. 25.BORUP, M. B.
AND MIDDLEBROOKS E. J., (1987) "PHOTOCATALYED OXADATION OF TOXIC ORGANICS", WAT. SCI. TECH, 19, 4, 381-390.
26.CHU, W. AND MA C.W., (2000) "QUANTITATIVE PREDICTION OF DIRECT AND INDIRCET DYE OZONATION KINETICS", WAT. RES., 34, 12, 3153-3160. 27.DUGUET, J. P. AND BRODARA, E. (1986) "IMPROVEMENT IN THE EFFECTIVNESS OF
OZONATION OF DRINKING WATER THROUGH THE USE OF HYDROGEN PEROXIDE" OZONE SCI. ENG. 2, 241-257.
28.DUSSERT, B. W. (1997) "ADVENCED OXIDATION:ULTRAVIOLET LIGHT HELPS ADVENCED OXIDATION TECHNOLOGIES OUTSHINE OTHER TREATMENT SYSTEMS FOR ORGANICS IN WASTEWATER AND GROUNDWATER", INDUSTRIAL WASTEWATER, 29-35. 29.ESPLUGAS, S. G., J. CONTRERAS, PASCUAL, S. E. RODRIGUEZ, M. (2002) "COMPARISON OF DIFFERE -NT ADVANCED OXIDATION PROCESSES FOR PHENOL DEGRADATION", WAT. RES, 36, 1034-1042. 30.FUJIHIRE, M., SATOH, Y. AND OSA, T., (1982) "HETEROGENEOUS PHOTOCATALYTIC REACTION ON SEMICONDUCTOR MATERIALS. II EFFECT OF PH AND CU2+ IONS ON THE PHOTO-FENTON TYPE REACTION", BULL. CHEM. SOC., JPN, 55, 666. 31.GEBHARD, T. J., (1978) PH.D. THESIS, NORTHWESTERN UNIVERSITY, EVANSTON, ILLINOIS. GERALD R. AND RUPERT B., (1994) "UV/O3
、UV/H2O2、UV/TIO2 AND THE PHOTO-FENTON REACTION 32.COMPARISON OF ADVANCED OXIDATION PROCESSES FOR WASTEWATER TREATMENT", CHEMOSPHERE. 28, 8, 1447-1454. 33.GLAZE, W. H. AND KANG, J. W., (1987) "THE
CHEMISTRY OF WATER TREATMENT PROCESSES INVLOVIN -G OZONE, HYDROGEN PEROXIDE AND ULREAVIOLET RADIATION" OZONE SCI. ENG. 9, 335-352. 34.GRAU, P., (1991) "TEXTILE INDUSTRY WASTEWATERS TREATMENT", JOURNAL WATER SCI. TECHNOL., 24, 1, 97-103. 35.HARRIS, P. R. AND DRANOFF. J. S., (1965) "A STUDY OF PERFECTLY MIXED PHOTOCHEMICAL REACTOR -S", AICHE. JOURNAL, 11, 497-502. 36.HORNING, R. H., (1997) "CHARACTERIZATION AND TREATMENT OF TEXTILE DYEING WASTEWATER", TEXTILE CHEMIST AND COLORIST, 9, 4, 24-27. 37.HORNING, J.
BADER H., (1982) "DETERMINATION OF OZONE IN WATER BY THE INDIGO METHOD", OZONE -SCI. ENGR. 38.HORNING, J., BADER H., HAAG, W. R., STAEHELIN, J. (1985) "RATE CONSTANTS OF REACTIONS OF OZONE WITH ORGANIC AND
INORGANIC COMPOUNDS IN WATER- Ⅲ. INORGANIC COMPOUNDS AND RADICALS" 39.WATER RES., 19, 993-1005. JAIN, R., GRAESSLEY, W. W., AND DRANOFF, J. S., (1971) "DESIGN AND ANALYSIS OF A PHOTOREA -CTOR FOR STYRENE
POLYMERIZATION", IND. ENG. CHEM. PROD. RES., 10, 293-298. 40.JACOB, S. M. AND DRANOFF, J. S., (1970) "LIGHT
INTENSITY PROFILES IN AN ELLIPTICAL PHOTOR -EACTOR", AICHE. JOURNAL, 16, 359-363. 41.JACOB, S. M. AND DRANOFF, J. S., (1968) "DESIGN AND ANALYSIS OF PERFECTLY MIXED PHOTOCHEM -ICAL REACTORS", CHEM. ENG. PROG. SYM.
SER., 64, 54-63. 42.JACOB, S. M., AND DRANOFF, J. S., (1966) "RADIAL SCALE-UP OF PERFECTLY MIXED PHOTOCHEMICAL REACTORS", CHEM. ENG. PROG. SYMP. SER., 62. 43.JONES, B. M., LANGLOIS, G. W., AND SAKAJI, R. H., (1985) "EFFECT OF OZONATION AND UV IRRAD -IATION ON BIOREFRACTORY ORGANIC SOLUTES IN OIL SHALE RETORT WATER", ENVIRON. PROG., 4, 252. 44.ITO, K , W., NISHIJIMA, J., ALOYSIUS, W., BAES, U., EIJI, S., AND MITSUMASA, O ., (1998)
"COMPARISON OF OZONATION AND AOPS COMBINED WITH BIODEGRADATION FOR REMOVAL OF THM PRECUR -SORS IN TREATED SEWAGE EFFLUENTS" , WAT. SCI. TECH. 38, 7, 179-186. 45.KIN, K. T., DEGENOVA, J., SHADMAN, F., (1998)
"OXIDATION OF ORGANIC IMPURITIES IN THE REC -YCLE AND RECLAIM LOOPS OF ULTRA-PURE WATER PLANT", CLEAN PROCESSES 1, 31-38. KUO, W. S., (1999) "EFFECT OF PHOTOLYTIC OZONATION ON BIODEGRADABILITY AND TOXICITY OF 46.INDUSTRIAL WASTEWATER", J. OF ENVIRON. SCI. AND HEALTH, PART A: ENVIRON. SCI. AND ENGR. &
TOXIC AND HAZAR. SUBSTANCES CONTROL, 34, 4, 919-933. 47.KUO, C. H AND HONG, L., (1994) "THE ROLE OF HYDROGEN RADICAL IN THE OXIDATION OF HAZARDO -US POLLUTANTS BY HYDROGEN PEROXIDE-OZONE MIXTURE" 12TH
WORLD CONGRESS OF THE INTERNATIO -NAL OZONE ASSOCIATION, 291-302. 48.LEGRINI O, OLIVEROS E, AND BRAUN A . M., (1983) "PHOTOCHEMICAL PROCESSES FOR WATER TREATM -ENT" CHEM REV , 93, 671-98. 49.LIAKOU, S., PAVLOU, S., AND LYBERATOS, G., (1997) "OZONATION OF AZO DYES," WAT. SCI. AND TECHNOL., 35, 4, 279-286. 50.LI, X. Z. AND ZHAO, Y.
G. (1999) " ADVANCED TREATMENT OF DYEING WASTEWATER FOR REUSE" WAT. SCT. TECH. 39, 10-11, 249-255. 51.MARCO, A., ESPLUGAS, S. AND SAUM, G. (1997) "HOW AND WHY COMBINE CHEMICAL AND BIOLOGICAL PROCESSESFOE
WASTEWATER TREATMENT",WAT.SCI TECH, 35, 4, 321-327. 52.MARECHAL, A. M. AND SLOKAR, Y. M., (1997)
"DECOLORATION OF CHLOROTRIAZINE REACTIVE AZO DYES WITH H2O2/UV", DYES AND PIGMENTS, 33, 4, 281-298.
53.MAGELLI, F. AND SANTARELLI, F., (1978) "THE MODELLING OF BATCH PHOTOREACTORS", CHEM. ENG. SCI., 33, 611-614.
54.MA C.W. AND CHU, W. (2001) "PHOTODEGRADATION MECHANISM AND RATE IMPROVEMENT OF CHLORINATED AROMATIC DYE IN NON-IONIC SURFACTANT SOLUTIONS", WAT. RES. 35, 10, 2456-2459. 55.MILANO, J. C., ESCALLON, B., AND VERNET, J. L., (1990) "PHOTOLYSIS OF 1,2-DIBROMO 3-CHLORO PROPANE IN WATER", WAT. RES., 24, 5, 557. 56.OLLIS, D. F., (1991) "COMPARATIVE ASPECTS OF ADVANCE OXIDATION PROCESS", PAPER PRESENTED AT ACS , I & EC DIVISION SPECIAL SYM., ATLANTA GEORGIA,OCT. 1-3. 57.OGATA, Y., TOMIZAWA, K., AND TAKAGI, K., (1981) "PHOTO-OXIDATION OF FORMIC, AECTIC AND PROPIONIC ACIDS WITH AQUEOUS HYDROGEN PEROXIDE", CAN. J. CHEM., 59, 14.
58.PERKOWSKI, J. K. LEDAKOWICZ, S (2000) "ADVANCED OXIDATION OF TEXTILE WASTEWATERS", OZONE SCIENCE &
ENGINEERING , 22, 535-550. 59.PERKINS, W. S., WALSH, K., REED., I. E., AND NAMBOODRI, C. G., (1996) "DEMOSTRATION OF REUSE OF SPENT DYEBATH WATER FOLLOWING COLOR REMOVAL WITH OZONE," TEXTILE CHEMIST AND COLORIST, 28, 1, 31-37. 60.PRENGLE, H. W. JR., MAUK, C. E. (1978) "NEW TECHNOLOGY:OZONE/UV CHEMICAL OXIDATION
WASTEWATER PROCESS FOR METEAL COMPLEXES", ORGANIC SPECIES AND DISINFECTION. AICHE SYM. 24, 228-249.
61.ROGER, M. AND VILLERMAUX, J., (1983) "MODELLING OF LIGHT ABSORPTION IN PHOTOREACTORS, DENSITY
PROFILE AND EFFICIENCY OF LIGHT ABSORPTION IN A CYLINDRICAL REACTOR AND EXPERIMENTAL COMPARISON OF FIVE MODELS", CHEM. ENG. JOURNAL, 26, 85-93. 62.ROMERO, R. L., ALFANO, O. M., MARCHETTI, J. L., AND CASSANO, A. E., (1983) "MODELLING AND PARAMETRIC SENSITUVITY OF AN ANNULAR PHOTOREACTOR WITH COMPLEX KINETIC", CHEM. ENG. JOURNAL, 26, 85-93. 63.SHU, H. Y. AND HUANG, C. R., (1995) "DEGRADATION OF COMMERCIAL AZO DYES IN WATER USING OZONATION AND UV ENHANCED OZONATION PROCESS", CHEMOSPHERE, 31, 8, 3813-3825.
64.SUNDSTROM, D. W. AND WEIR, B. A. (1990)"DESTRUCTION OF MIXTURES OF POLLUTANTS BY UV-CATALYZED OXIDATION WITH HYDROGEN PEROXIDE", ACS SYMP. SERIES, 422, 67-76. 65.SUIDAN, M. T. AND SEVERIN, B. F., (1986)
"LIGHT INTENSITY MODELS FOR ANNULAR UV DISINFECTION REACTORS", AICHE. JOURNAL, 32, 11, 1902-1909.
66.VERHOEVEN, J. W., (1996) "GLOSSARY OF TERMS USED IN PHOTOCHEMISTRY", PURE APPL. CHEM., 68, 2223-2286.
67.WEIR, B. A., SUNDSTROM, D. W., AND KLEI, H. E., (1987) "DESTURCTION OF BENZENE BY ULTRAVIOLET
LIGHT-CATALYZED OXIDATION WITH HYDROGEN PEROXIDE", HAZARDOUS WASTE AND HAZARDOUS MATERIALS, 4, 2, 165.