臺灣博碩士論文加值系統

中文摘要

臭氧程序在水溶液系統之污染物處理的應用中，臭氧質傳與自解對有機物的去除反應有相當大的影響。為瞭解催化式臭氧程序反應系統中觸媒對於臭氧之質傳係數、自解速率常數和反應速率常數的影響，本實驗使用Al2O3、MnO2、SiO2和PAC四種觸媒，在不同反應條件下，分別進行單純臭氧自解與質傳，以及在含有機物(Red 4染料)之氧化反應實驗，於催化式臭氧系統中探討不同觸媒在不同操作條件下，對染料去除行為之影響。
實驗結果顯示各類觸媒之添加對於臭氧之質傳係數略有增加，臭氧自解速率常數以添加PAC時有最佳促進效果。在本研究範圍內，觸媒劑量對於臭氧質傳係數之促進影響不大，但對臭氧自解常數而言，Al2O3與PAC之劑量效應對於臭氧質傳係數之促進情形較為明顯。在低pH條件下，MnO2觸媒對臭氧之促進質傳較為明顯，添加MnO2時，臭氧之質傳係數KLa值約為0.5488min-1，其質傳效果隨pH之升高而降低。PAC觸媒對臭氧之自解反應速率之影響較其他觸媒更為明顯，臭氧自解之速率隨pH值增高而增加，在pH9添加PAC時，臭氧的自解速率常數kd值約為2.3141 min-1。
實驗發現，以PAC觸媒對增進Red 4脫色反應速率之效率最佳，其餘各類觸媒劑量之增加對於Red 4反應速率之促進並不明顯，在高pH值下觸媒之添加可增加Red 4染料之反應速率，顯示臭氧可藉由觸媒之添加，提升OH‧與Red 4之間接氧化作用。本研究提出三種反應模式，可合理說明臭氧結合不同觸媒時，對於水中有機物臭氧化反應機制與反應行為之影響。

ABSTRACT

Mass transfer and self-decomposition behaviors of ozone molecular are the most important factors on the treatment efficiency of ozonation process for decomposing pollutants in aqueous solutions. The purpose of this study is to investigate the effects of catalytic types and amount on the mass transfer and self-decomposition behaviors of ozone molecular under various operational conditions. The catalysis used in this work were Al2O3, MnO2, SiO2, and PAC. The decoloration of Red 4 dye wastewater by ozonation with or without different catalysis was explored to examine the influence of various catalysis on the removal rate of Red 4.
Experimental results showed that mass transfer rate of ozone can be slightly raised by the addition of catalysis, and the most significant one to lift the mass transfer rate was found to be PAC. The promoting effect of catalytic amount of each catalysis on the mass transfer rate of ozone was found to be negligible. However, the promoting effect of catalytic amount of Al2O3 and PAC on the self-decomposition rate of ozone was found to be relatively obvious. At lower pH levels, the promoting effect of adding MnO2 on the mass transfer rate of ozone is noteworthy compared to other catalysis while its value of KLa was determined to be 0.5488min-1. The self-decomposition rate constant (kd) of ozone increased with increasing pH and the value was determined to be 2.3141 min-1 at pH 9.
In the system of the decomposition of Red 4 by ozonation, the promoting effect of adding PAC on the decoloration rate of Red 4 was found to be the largest one compared to other catalysis that those promoting effect was relatively trivial. The reaction rate of Red 4 by ozonation can be raised by adding catalysis at higher pH levels indicating that the indirect oxidation reaction of Red 4 by OH. which is generated by the reaction of ozone and hydroxide ions can be effectively elevated. Three possible reaction models were proposed to reasonably describe the reaction mechanisms of ozone and Red 4 on or off the surface of catalysis in aqueous solutions.

目錄

封面內頁
簽名頁
授權書……………………………………………………………....iii
中文摘要…………………………………………………………....iv
英文摘要…………………………………………………………. ...v
誌謝………………………………………………………………….vi
目錄………………..………………………………..……………...vii
圖目錄………………..……………………………..…………….…x
表目錄………………………………………………..…………....xix
符號說明………………………………………………………..xxiiiv

第一章　前言………………………………………..…………...…1
1.1研究緣起……………………………………..………..1
1.2研究目的…………………………………..…………..2
第二章　理論背景及文獻回顧…………………………………….4
2.1臭氧的自解行為……………………..……………….4
2.2 臭氧的質傳行為…………………………….……….5
2.3 臭氧的反應行為……………………………………..7
2.3.1 金屬氧化物…………………………………..….11
2.3.2 活性碳…………………………………………...15
2.4 催化性臭氧化程序之文獻………………………...20
2.4.1 異相催化性臭氧化系統之相關文獻…………..21
2.4.1.1 Al2O3觸媒………………………………..….21
2.4.1.2 MnO2觸媒…………………………………..25
2.4.1.3 SiO2 觸媒……………………………………26
2.4.1.4 AC 觸媒…………………………………….28
2.4.2 同相催化性臭氧化系統之相關文獻…………30
第三章　研究目的…………………………….…….……….........34
第四章　實驗程序與設備…………………….…….….…...…….36
4.1實驗設備………………………….…….….………..36
4.2實驗藥品………………………………..….………..37
4.3實驗裝置………………………….……….………...38
4.4實驗步驟………………………….…....….………...39
4.5分析測定方法……………………….…………..…..41
第五章 結果與討論……………………………….………….…..46
5.1單純O3自解…………………………….……….…46
5.1.1 無觸媒條件下臭氧之質傳及自解行為…........47
5.1.2 有觸媒條件下臭氧之質傳及自解行為.……...50
5.1.2.1 添加Al2O3觸媒…………….………………50
1.pH效應……………………..….………………..50
2.劑量效應...........................................................52
5.1.2.2 添加MnO2觸媒……….…………….……..57
1.pH效應…………………….……………………57
2.劑量效應…………………….…………….........59
5.1.2.3 添加SiO2觸媒………………………………64
1.pH效應………………………………………….64
2.劑量效應……………………………………......66
5.1.2.4 添加PAC觸媒……………………….………70
1.pH效應………………………………………….70
2.劑量效應………………………………………...72
5.1.2.5 綜合比較……………………………………..76
5.2 以催化臭氧程序處理含Red 4 水溶液
之反應行為…………………………………….……...86
5.2.1 無觸媒條件下有機物之臭氧化反應……........86
5.2.2 有觸媒條件下有機物之臭氧化反應….………87
5.2.2.1添加Al2O3觸媒…………………….…….…88
1.pH效應………………………………….………88
2.劑量效應…………………………….………….93
5.2.2.2添加MnO2觸媒………………………………99
1.pH效應……………………………….…………99
2.劑量效應…………………………………........103
5.2.2.3添加SiO2觸媒……………………..……….109
1.pH效應………………………………………...109
2.劑量效應………………………….……………113
5.2.2.4添加PAC觸媒………………….………..…119
1.pH效應………………………………………...119
2.劑量效應…………………………………........123
5.2.2.5 綜合比較-pH效應……………………..….129
第六章　結果與建議…………………………………………….152
參考文獻………………………………………………………….154

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