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研究生:李佳欣
研究生(外文):Chia-Hsin Li
論文名稱:複合性二氧化鈦/活性碳觸媒之光催化系統處理染料廢水之研究
論文名稱(外文):Study on the Treatment of Dye Wastewater by Titanium Dioxide/Activated Carbon Composite Photocatalysts
指導教授:謝永旭謝永旭引用關係
學位類別:博士
校院名稱:國立中興大學
系所名稱:環境工程學系所
學門:工程學門
學類:環境工程學類
論文種類:學術論文
論文出版年:2008
畢業學年度:96
語文別:中文
論文頁數:85
中文關鍵詞:複合性觸媒二氧化鈦活性碳染料
外文關鍵詞:composite catalysttitanium dioxideactivated carbondye
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本研究目的在於製備複合式二氧化鈦/活性碳觸媒,探討此系統光催化處理染料水溶液之分解效率與反應動力行為以及光觸媒與吸附劑之相互關係。
實驗結果顯示,以溶膠凝膠法自行製備二氧化鈦粉體,當四異丙烷氧化鈦、異丙醇及乙酸的莫耳數比為1:2:8,經500℃鍛燒90分鐘後可得到具最佳光催化活性之觸媒。由精密儀器分析可知,二氧化鈦之顆粒大小約為20 nm,結晶構造為銳鈦礦,零電荷點約為6.90;複合式光觸媒之比表面積值與活性碳的複合比例呈現正相關。由光催化實驗及觸媒沈降實驗結果得知,二氧化鈦與粉末狀活性碳的複合確實可促進光催化反應之進行且有助於提升觸媒沈降性,又以在中性環境沈降效果最佳。
應用複合式光觸媒處理亞甲基藍於鹼性系統有最佳之光活性,但用於降解染料Acid Yellow 17則是在酸性系統比中性或鹼性系統有較佳之光活性;當系統中觸媒添加量相同時,複合比例以PT60 (60 wt% TiO2-40 wt% PAC)有最佳的光催化效果;複合式光觸媒之降解效率隨著初始濃度增加而降低,以初始濃度75 mg/L有最大的降解量,相當於每克的複合式觸媒PT60可分解81.24 mg的染料Acid Yellow 17。實驗結果顯示光催化反應過程中吸附於觸媒表面的染料濃度皆低於觸媒的吸附飽和量,利用反應終止後進行脫附程序以修正光催化反應行為,可成功地簡化真實光催化反應行為之推求,且光觸媒對染料之分解及脫色反應皆符合簡化之Langmuir-Hinshelwood擬ㄧ階動力模式。
This study investigated the preparation of titanium dioxide/activated carbon composite catalysts, the photocatalytic degradation of dye wastewater, and the relationship between photocatalysts and adsorbents. TiO2 powders were obtained using sol-gel process under the design of the Taguchi’s method. The best candidate for photodegradation is obtained under the condition of the molar ratio of titanium isopropoxide, isopropyl alcohol and acetic acid kept at 1:2:8, calcined at 500℃ for 90 min and then dried after mixing with an adequate amount of activated carbon in water solution for 30 min. X-ray powder diffraction patterns suggest that the grain size of TiO2 is about 20 nm and the crystal structure is mainly in anatase form. The pHZPC of titanium dioxide has been measured to be 6.90. The surface area of composite catalysts is proportional to the ratio of activated carbon synthesized. The synthesis of titanium dioxide and activated carbon is a great benefit to the degradation of dye wastewater and the settleability of catalysts. In the alkaline solution, better photodegradation efficiency of methylene blue is achieved than in the neutral or acidic solution. However, the best photodegradation of Acid Yellow 17 is taken place in the acid solution. As far as the component proportion of photocatalyst is concerned, PT60 (60 wt% TiO2-40 wt% PAC) has the best efficiency, and the photodegradation efficiency decreases with an increase in initial dye concentration. The results also clearly indicate the dye concentration adsorbed on the surface of the composite catalysts during the photocatalytic reaction is lower than the saturated adsorptive concentration in the dark. The kinetic behaviors have been successfully described in a simplified Langmuir-Hinshelwood model.
目錄
中文摘要………………………………………..…………………………… i
Abstract……………………………………………………………………… ii
目錄………………………..………………………………………………… iii
表目錄……………………………..………………………………………… v
圖目錄……………………………..………………………………………… vi
第一章 緒論…………………………..…………………………………… 1
1-1 研究緣起………………..……………………………………. 1
1-2 研究內容與目的………………..……………………………. 2
第二章 文獻回顧…………………………..……………………………... 3
2-1 染料概論……………………..………..……………………... 3
2-2 二氧化鈦光觸媒……………………...………………......….. 5
2-3 吸附技術與光催化的結合………………..…………………. 12
2-4 溶膠凝膠法………………….…………………….…………. 14
2-5 田口式實驗計畫法—直交表法.………….....……………..... 16
第三章 材料與方法…………………………….......…………………...... 22
3-1 實驗架構與內容………….......……………………................ 22
3-2 實驗藥品……………….......……..………………….............. 24
3-3 實驗設備………………….......………..…………….............. 25
3-4 實驗方法………………….......………..…………….............. 26
3-4-1 光觸媒之製備…......................………….…............ 26
3-4-2 紫外光/光觸媒氧化程序………................…….. 27
3-5 分析項目及方法…………………...…..…………….............. 28
3-5-1 光觸媒分析…………...............………..…….......... 28
3-5-2 樣品分析…………..................…………..…............ 29
第四章 結果與討論…………………………….......…………………...... 31
4-1 二氧化鈦之最佳製備條件實驗………….......…………….... 31
4-2 光觸媒之特性分析………………………………………....... 35
4-3 複合式光觸媒系統之光活性測試…………………............... 42
4-3-1 背景試驗……………................…………................ 42
4-3-2 pH效應………………….………………………... 47

4-3-3 觸媒複合比例效應…………………………..…… 55
4-3-4 染料初始濃度效應……….......……………........... 61
4-4 反應動力模式分析………….......……………………............ 64
4-4-1 真實光催化反應行為之模擬……………........... 64
4-4-2 光催化反應行為之修正.......…………………..... 66
第五章 結論與建議……………………………….………….................... 73
5-1 結論………….......…………………….................................... 73
5-2 建議………….......…………………….................................... 74
參考文獻………………………………………….…………………………. 75
附錄..………………………………...………………………………………. 79

表目錄
表2-1 Acid Yellow 17染料之結構式及合成原料……….....…………. 5
表2-2 可被二氧化鈦光催化或礦化的有機物質…………...…………. 6
表2-3 實驗計劃法-傳統式與田口式之比較……...…………..……... 18
表2-4 L9直交表………………………………………………………… 19
表3-1 L9直交表之各控制變因水準……………………..………………. 27
表3-2 高效率液相層析儀分析條件………………………...……….. 30
表4-1 二氧化鈦光觸媒之L9直交表實驗結果...……………………… 32
表4-2 二氧化鈦製備因子之變異數分析表…………………………… 33
表4-3 L9直交表中各變因之回應值……………………………...……. 33
表4-4 TiO2、PAC及不同複合比例光觸媒之比表面積值….....……... 38
表4-5 不同pH值之光催化染料AY 17效率分析……………………. 52
表4-6 活性碳的複合對光催化降解染料AY 17之影響……………… 54
表4-7 不同染料初始濃度之去除量…………………………………… 63
表4-8 各批次反應之擬一階反應動力常數表………………………… 72

圖目錄
圖2-1 半導體受光激發後之電子-電洞生成及界面反應示意圖….. 10
圖2-2 乙酸與Ti(OC3H7)4反應(a) chelating form,(b) bridging form. 16
圖3-1 實驗架構圖……………………………………………....…….. 23
圖3-2 實驗裝置圖………………………………………….…..….….. 28
圖4-1 不同二氧化鈦製備條件下,亞甲基藍脫色率隨時間變化圖.. 32
圖4-2 最佳製備條件下,二氧化鈦光活性測試之重複試驗.………. 34
圖4-3 PAC之SEM圖……………………………………..….………. 35
圖4-4 TiO2之SEM圖……..……………………………...…….…...... 35
圖4-5 PT90之SEM圖……..……………………………….….…..…. 36
圖4-6 PT80之SEM圖..………………………………….….……..…. 36
圖4-7 PT70之SEM圖...…………………………...…….….……..…. 36
圖4-8 PT60之SEM圖.…………..…………………..….…..……...… 36
圖4-9 PT50之SEM圖.……..………………………..……...……...… 36
圖4-10 TiO2之XRD圖...……………………………………….....…… 37
圖4-11 PT60之XRD圖……………………..……………….….…...… 37
圖4-12 TiO2與PT90之光激螢光圖譜..…………………….….……… 41
圖4-13 不同觸媒複合比例的複合式觸媒之光激螢光圖譜…..………. 41
圖4-14 直接光解試驗之亞甲基藍脫色率隨時間變化圖..…..……...… 42
圖4-15 直接光解試驗之染料AY 17脫色率隨時間變化圖..………..... 43
圖4-16 直接光解試驗之染料AY 17去除率隨時間變化圖..………..... 43
圖4-17 直接光解試驗之染料AY 17礦化率隨時間變化圖..………..... 44
圖4-18 吸附試驗之亞甲基藍脫色率隨時間變化圖………..…….…… 45
圖4-19 吸附試驗及脫附程序之染料Acid Yellow 17脫色率隨時間變化圖...………………..………………………………………….. 45
圖4-20 吸附試驗及脫附程序之染料Acid Yellow 17去除率隨時間變化圖...…………………..………………………….…..….…….. 46
圖4-21 吸附試驗及脫附程序之染料Acid Yellow 17礦化率隨時間變化圖...…………………..………………………….…..…….….. 46
圖4-22 不同pH值之亞甲基藍脫色率隨時間變化圖……..……...….. 47
圖4-23 不同pH值之亞甲基藍光催化效率與吸附效率分析……....... 48
圖4-24 活性碳的複合對亞甲基藍脫色率之影響……….……….……. 49
圖4-25 不同pH值之染料AY 17脫色率隨時間變化圖……………… 50
圖4-26 不同pH值之染料AY 17去除率隨時間變化圖……………… 50
圖4-27 不同pH值之染料AY 17礦化率隨時間變化圖…………..….. 51
圖4-28 活性碳的複合對染料AY 17脫色率之影響……………..….… 53
圖4-29 活性碳的複合對染料AY 17去除率之影響……………..….… 53
圖4-30 活性碳的複合對染料AY 17礦化率之影響……………..….… 54
圖4-31 不同觸媒複合比例之染料AY 17脫色率隨時間變化圖…...… 56
圖4-32 不同觸媒複合比例之染料AY 17脫色率分析.……...…..……. 56
圖4-33 不同觸媒複合比例之染料AY 17去除率隨時間變化圖……... 57
圖4-34 不同觸媒複合比例之染料AY 17去除率分析.………….……. 57
圖4-35 不同觸媒複合比例之染料AY 17礦化率隨時間變化圖…...… 58
圖4-36 不同觸媒複合比例之染料AY 17礦化率分析.………….……. 58
圖4-37 複合式與個別添加二氧化鈦/活性碳對染料AY 17脫色率之影響…………………………..………..…………………......…60
圖4-38 複合式與個別添加二氧化鈦/活性碳對染料AY 17礦化率之影響…………………………………………..……………….... 60
圖4-39 不同染料初始濃度之脫色率隨時間變化圖………………….. 61
圖4-40 不同染料初始濃度之去除率隨時間變化圖………………….. 62
圖4-41 不同染料初始濃度之礦化率隨時間變化圖………………...... 62
圖4-42 不同反應終止時間之染料AY 17脫色率分析….…….…...…. 65
圖4-43 不同反應終止時間之染料AY 17去除率分析….……………. 65
圖4-44 不同反應終止時間之染料AY 17礦化率分析….………….… 66
圖4-45 真實光催化反應之擬一階反應動力模擬…………….....……. 67
圖4-46 不同反應動力模擬方法之染料脫色率隨時間變化圖(原始數據)…………...……………………………………...……. 68
圖4-47 不同反應動力模擬方法之染料去除率隨時間變化圖(原始數據)……………..………………………………...…………. 68
圖4-48 不同反應動力模擬方法之染料脫色率隨時間變化圖(修正)…………………….………………………………………. 69
圖4-49 不同反應動力模擬方法之染料去除率隨時間變化圖(修正)…………………………………………………….…….… 70
圖4-50 染料AY 17脫色反應之擬一階反應動力模擬比較..…..………. 70
圖4-51 染料AY 17分解反應之擬一階反應動力模擬比較..…………... 71
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