六價鐵降解ＴＮＴ與Tetryl之研究｜國立清華大學博碩士論文庫

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研究生：	尤美文 You, Mei-Wen
論文名稱：	六價鐵降解ＴＮＴ與Tetryl之研究 The investigation on degradation of TNT and Tetryl by Ferrate
指導教授：	王竹方 Wang, Chu-Fang
口試委員:
學位類別：	碩士 Master
系所名稱：	原子科學院 - 生醫工程與環境科學系 Department of Biomedical Engineering and Environmental Sciences
論文出版年：	2009
畢業學年度：	97
語文別：	英文
論文頁數：	94
中文關鍵詞：	三硝基甲苯、四硝基炸藥、降解、超高效液相層析質譜儀
外文關鍵詞：	TNT, Degradation, Ferrrate, Tetryl, UPLC-MS/MS
相關次數：	點閱：2 下載：0
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高鐵酸鉀（六價鐵）為一種新型淨水氧化劑，能有效地除去水中的懸浮物、重金屬及多種有機污染物，高鐵酸鉀與污染物反應後不會產生任何有害物質，且對水生生物的呼吸作用沒有不良影響，是一種集氧化、吸附、混凝、助凝、殺菌、除臭為一體的多功能綠色水處理劑。其製作方法可由濕式氧化法來合成，其原理乃利用次氯酸在強鹼下，把三價鐵氧化成六價鐵離子，並在高濃度之KOH溶液下使高鐵酸鉀固體沉澱出來，之後可以紫外/可見光譜儀分析(505nm)高鐵酸鉀之純度。本研究主要是進行六價鐵的製備研究及其降解火炸藥的可行性探討，研究結果指出當硝酸鐵濃度為150mM，次氯酸鈉為170mM,而氫氧化鈉鉀控制在2.5M的條件下，可生成產量較大且品質較佳的六價鐵。六價鐵會隨濃度或pH值的變化而對火炸藥有不同的去除效果，故研究中控制不同pH值、加藥量及火炸藥濃度來探討不同實驗參數對去除率之影響。動力學研究則以六價鐵降解三種不同濃度高能火炸藥，實驗結果代入簡化的Langmuir-Hinshelwood動力學模式計算，研究結果顯示降解反應為一階反應，本研究亦建立UPLC/MS/MS的分析方法用以鑑定火炸藥經由六價鐵降解所產生的中間產物。

Potassium ferrate is a kind of noval oxidant for water purification; it can remove organic pollutants in water effectively. After reacting with pollutants, potassium ferrate will not produce any harmful substance, and it does not have toxic effects to aquatic biological breathing. Potassium ferrate is the integrative multi-functional green water treatment agent that is a kind of collection for oxidization, absorbability, coagulation, disinfection and deodorization. Potassium ferrate can be synthesized by wet oxidation method; its principle is that in strong base condition, ClO- can oxidize Fe3+ to Fe6+, and then add saturated KOH solution to precipitate solid potassium ferrate. The optimum conditions for the preparation of ferrate processes were observed with an initial Fe(NO3)3．9H2O concentration of 150mM, initial NaOCl concentration of 150mM and initial NaOH concentration of 2.5M. During the experiment, the influence of pH, dosage and the concentration of explosives on the ferrate oxidation process were examined for understanding of the explosives remoal by ferrate. The rate constants were determined by a Langmuir–Hinshelwood kinetic model incorporating the various species equilibriums for the explosive compounds. The results can be used for practical explosives wastewater process design and support the process information required. The degradation by-products were investigated using UPLC/MS/MS, in order to build a profile for the characterization of byproducts from the degradation of explosives. The characterization of explosives by the intermediates profile was demonstrated on a variety of explosives samples.

中文摘要................................................I
Abstract................................................II
Content Index.......................................... III
Figure Index............................................IV
Table Index...................................................VII
Table Index...................................................X
Chapter 1 Introduction..................................1
1 Motivation..........................................1
2 Objectives..........................................3
3 Flowchart of Thesis.................................4
Chapter 2 Literature review ............................6
1 Classification of Explosives........................6
2 Toxicity and Physical-chemical Property of Explosives.8
2.1 2,4,6-trinitropheny-N-methylnitramine(Tetry)........8
2.2 Trinitrotoluene(TNT)................................8
2.3Pollution of Explosives to the Emvironment..........10
3 Method for the removal of Explosive from the wastewater................................................12
3.1Biological Treatment Process.........................12
3.2Electrochemical Treatment Process....................15
3.3Advanced Oxidation Process(AOP)......................16
4 Properties of Ferrate(VI) ............................19
4.1 Compared with electric potential of Ferrate and other
oxidant...................................................22
4.2 Species Distribution of Fe(VI) in Aqueous Solution..................................................23
4.3 Method of Prepare...................................24
4.3.1 Wet Oxidation.....................................25
4.3.2 Dry Oxidation....................................26
4.3.3 Electrolysis....................................26
4.4 Applications of Ferrate.............................27
5 Analytcal methods for determing explosives................................................29
5.1 Gas Chromatography............................................29
5.2 HPLC......................................................32
5.3 UPLC-MS/MS..........................................33
Chapter 3 Experimental and method.........................40
1 Reagents and methods...................................................40
2 Experimental procedures...............................41
2.1 Flowchart of experimental procedure.................41
2.2 Preparation of sodium ferrate.......................42
2.3 Degradation of explosives by ferrate................45
3 Apparatus and conditions..............................46
3.1 UV/VIS spctrometer..... ............................46
2.2 High performance liquid chromatograph...............47
2.2 Ultra performance liqui chromatograph – electrospray – tandem mass spectrometryl.................48
Chapter 4 Results and discussion................................................50
1 Optimization of ferrate ion generation................50
2 Explosives degradation by K2FeO4....................................................54
2.1 pH effect on explosives degradation with Fe(VI).....54
1.2 Effect of K2FeO4 concentration......................56
2.3 Effect of initial explosives concentration..........58
3 Explosives degradation pathway........................64
3.1 Tetryl degradation pathway..........................64
3.2 TNT degradation pathway.............................77
Chapter 5 Conclusion and direction........................88
1 Conclusions...........................................88
2 Future directions.....................................89
Reference ................................................90

                                

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