摘要
本研究旨在探討利用近紫外光催化(Near Ultraviolet Light Photocatalytic)二氧化鈦(Titania Dioxide；TiO2)分解苯蒸氣之可行性，並進一步探討不同操作參數對苯轉化率之影響，此外，根據反應動力原理推導光催化分解苯蒸氣之反應動力模式及進行模擬研究。本研究所探討之操作參數包括：苯蒸氣進流濃度(239~478 mg/m3)、相對濕度(0 ~1.58×104 mg/m3)、反應溫度(100~260℃)及停留時間(3.1~10.3 sec)。

本研究採用環型填充床反應器進行苯蒸氣之光催化分解，光催化反應器中央置放一支15W近紫外光燈管之光源，以填充披覆在3 mm Pyrex玻璃珠之Degussa P-25 TiO2為光觸媒，於21 %含氧量下進行光催化分解實驗。研究結果顯示，苯蒸氣直接被近紫外光所分解之可能性極小，而必須經由異相光催化反應才能被快速分解。於相對濕度4.69×103~1.58×104 mg/m3時，苯之轉化率會隨反應溫度增加而增加，且最高可達100 %，但當反應溫度超過180℃以上，轉化率則有平緩下降之趨勢，即表示過高之反應溫度並無助於光催化分解苯蒸氣之進行，甚至略有抑制作用，而無水氣之狀態下，苯的光催化轉化率則非常低，在水分子濃度較低之情形下，反應溫度介於140~240℃時，苯之轉化率隨濕度增加而增加，但在水分子濃度超過1.16×104 mg/m3以上時，苯之轉化率並無明顯增加而呈現平衡關係，此外，當反應溫度為260℃時，無論在低或高水分子濃度情況下，均無法提昇苯之轉化率；研究結果顯示，當停留時間由3.1 sec增加至10.3 sec時，苯之轉化率由57 %提昇至100 %，因此，苯蒸氣光催化分解效率與停留時間呈相關性，而隨著進流濃度增加而降低，本轉化率則由100 %降低至65 %。

本研究係根據Langmuir-Hinshelwood(L-H)反應動力模式原理，推導結果顯示反應溫度介於160~260℃之實驗值與模擬值相當契合，因此，苯蒸氣在TiO2表面的光催化反應速率可使用L-H反應動力模式來描述之；然在反應溫度介於100~140℃之反應速率並不遵循L-H反應動力模式。L-H反應動力模式中反應速率常數(KLH)和吸附平衡常數(Kc和Kw)皆為反應溫度之函數，且均可用亞忍尼辛(Arrihenius Law)加以描述。由KLH、Kc、Kw隨反應溫度變化之趨勢得知，苯蒸氣在光催化反應之速率控制步驟為表面反應或產物脫附速率。

ABSTRACT
This study investigated the influence of temperature and humidity on the decomposition efficiency of benzene vapor in a packed-bed UV/TiO2 photocatalytical reactor. The packed-bed annular photocatalytical reactor illuminated by a 15-watt ultraviolet lamp was originally designed for this particular study. Pyrex glass beads coated with Degussa P-25 TiO2 (80 % anatase) were packed in the photocatalytical reactor. The operating parameters investigated in this study included reaction temperature (100-260℃), water vapor concentration (0-1.58×104 mg/m3), retention time (3.1-10.3 sec), and inlet benzene concentration (239-478 mg/m3).

Experimental results indicated that the decomposition efficiency of benzene increased with reaction temperature whish was lower than 180℃, for oxygen content of 21 %, water vapor concentration of 4.69×103- 1.58×104 mg/m3, and reaction temperature lower then 180℃. However, the decomposition efficiency of benzene could not be further increased for reaction temperature higher than 180℃. In addition, the decomposition efficiency of benzene increased with water vapor concentration which was lower than 1.16×104 mg/m3. For water vapor concentration higher than 1.16×104 mg/m3, the decomposition of benzene could not be further enhanced significantly. In this study, up to 100% of benzene decomposition could be achieved at water vapor concentration of 1.58×104 mg/m3 and reaction temperature of 180℃. Moreover, the decomposition efficiency of benzene increased from 57 to 100% as retention time increased from 3.1 to 10.3 seconds, while decreased from 100 to 65% as benzene concentration increased from 239 to 478 mg/m3.


Modified Langmiur-Hinshewood kinetic model was applied to simulate the photocatalytic decomposition of benzene in the annular packed-bed photocatalytic reactor. The simulation of experimental results was successfully developed to describe the reaction rate of benzene for various reaction temperatures (160-260℃) during the UV/TiO2 photocatalytical reaction process. Furthermore, reaction rate constant (KLH) and adsorption equilibrium constant (Kc and Kw) were functions of reaction temperature, where can the described by the Arrihenius Law. The rate controlling steps were either photocatalytic reaction on the surface adsorption of reaction products from the surface photocatalysts.

目 錄
摘要………………………………………………………………….. I
英文摘要…………………………………………………………….. Ⅲ
目錄……………………………………………………………….…. V
表目錄…………………………………………………………….…. IX
圖目錄……………………………………………………………….. XI
第一章 緒論………………………………………………………… 1-1
1-1 研究緣起…………………………………………………... 1-1
1-2 研究目的…………………………………………………... 1-8
第二章 文獻回顧…………………………………………………… 2-1
2-1 苯之特性及影響…………………………………………... 2-1
2-2 光催化反應之物理過程…………………………………... 2-2
2-2-1異相光催化反應之基本原理………………………... 2-8
2-2-2半導體電子之激發過程……………………………. 2-15
2-2-3光觸媒表面電子之轉移過程………………………... 2-21
2-3 半導體之基本特性……………………………………….. 2-21
2-3-1 n-型和p-型半導體……..……………..……………... 2-23
2-3-2二氧化鈦觸媒種類…………………………………... 2-25
2-4 光觸媒之製備……………..………………………………. 2-29
2-5 光催化反應器種類………………………………………... 2-31
2-5-1泥漿反應器…………………………………………... 2-32
2-5-2固定床反應器………………………………………... 2-32
2-5-3填充床反應器………………………………………... 2-32
2-5-4流體化床反應器……………………………………... 2-33
2-5-5光纖反應器…………………………………………... 2-33
2-6 影響UV/TiO2光催化反應之操作參數………………..…. 2-34
2-6-1光強度的影響………………………………………... 2-34
2-6-2光波長的影響………………………………………... 2-35
2-6-3溫度的影響………………………………………….. 2-35
2-6-4濕度的影響………………………………………….. 2-36
2-6-5氧濃度的影響……………………………………….. 2-39
2-7 光催化反應產物分析……………………………………... 2-40
2-8 光催化反應動力分析……………………………………... 2-43
第三章 研究方法…………………………………………………… 3-1
3-1 實驗設備………………………………………………….. 3-1
3-1-1 VOCS產生系統……………………………………… 3-1
3-1-2光催化反應系統…………………………………….. 3-1
3-1-3產物分析系統……………………………………….. 3-3
3-2 實驗材料及製備方法…………………………………….. 3-3
3-2-1實驗材料……………………………………………... 3-3
3-2-2 TiO2觸媒製備方法………………………………….. 3-6
3-3 實驗方法………………………………………….………. 3-6
3-3-1操作參數及範圍……………………………………… 3-6
3-3-2載體吸附和均相光催化反應測試…………………… 3-8
3-3-3不照光實驗…………………………………………… 3-8
3-3-4異相光催化反應測試………………………………… 3-8
3-3-5光活性持續性測試…………………………………… 3-8
3-3-6光觸媒再生實驗……………………………………… 3-9
3-3-7產物分析……………………………………………… 3-9
第四章 結果與討論………………………………………………… 4-1
4-1 光解反應測試…………………………………………..… 4-1
4-2 反應溫度對光催化分解苯之影響……………………….. 4-3
4-3 相對濕度對光催化分解苯之影響……………………….. 4-5
4-4 反應溫度協同相對濕度對光催化分解苯之影響……….. 4-5
4-5 停留時間對光催化分解苯之影響……………………….. 4-9
4-6 苯進流濃度對光催化分解反應之影響………………….. 4-13
4-7 反應動力分析結果……………………………………….. 4-17
第五章 結論與建議…….………………………...………………… 5-1
5-1 結論……………………………………………………….. 5-1
5-2 建議……………………………………………………….. 5-3
參考文獻…………………………………………………………….. 6-1
附錄A TiO2之基本物化特性……………………………………… A-1
附錄B不同觸媒製備方法及反應器種類之優缺點比較…………. B-1
附錄C C6H6檢量線…………………………………………………. C-1
附錄D求Kc值之線性迴歸圖.………………………………..……. D-1
附錄E求Kw及KLH值之線性迴歸圖.…………………………….. E-1
附錄F KLH、Kc及Kw與反應溫度之關係迴歸圖.………………… F-1

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