臺灣博碩士論文加值系統

國軍的彈藥在使用的過程中，火炸藥成分均可能因處理不當殘留於營區或訓場中，造成環境水體或土壤污染，進而影響人體健康。面對營區可能潛在火炸藥污染問題，如何經濟有效的處理受火炸藥污染水體及土壤，成為現今研究之重要課題。
本研究即以零價鐵進行模擬現地處理受火炸藥污染水體，進而探討各操作條件下的處理成效。
經由一系列火炸藥RDX在不同濃度、pH值、反應溫度及零價鐵粒徑等因素反應的實驗結果得知：酸性、較高溫度、零價鐵濃度較高或粒徑較小條件下有助於RDX降解反應進行。
總結本研究所獲結果可知以零價鐵對火炸藥RDX進行降解可行性高；實驗結果可供未來在實場上進行火炸藥污染整治參考。

The fire explosive compositions may be left in camps or in the training field due to improper handling of military munitions. This may result the pollution in water or soil to affect human health. Facing the potentially explosive pollution problems in the camp, how effective processing explosives-contaminated water and soil, become a important research topic

This study includes the simulation of using zero-valent iron for ground water which was contaminated by explosives, and treatment effectiveness under various operating conditions.

A series of treatment of explosive RDX by different concentrations , acid concntrations, temperature and zero-Valent iron particle sizes were resulted acidic concontreation, higher temperature, high concentration Zero-Valent iron or small grain size helping RDX degradation reaction.
Summarize the results in this research, we know that zero-valent iron can treat fire explosives RDX efficiently. Degradation of this experimental results can be used in real game explosives and pollution control reference in the future.

以奈米零價鐵處理硝基火炸藥污染之研究
目錄
第一章、緒論……………………………………………………………………1
1.1 研究動機…………………………………………………………………1
1.2 研究目的…………………………………………………………………1
1.3 研究架構…………………………………………………………………2
第二章、文獻回顧………………………………………………………………4
2.1 火炸藥的特性……………………………………………………………4
2.1.1 火炸藥的歷史演進……………………………………………………4
2.1.2 火炸藥的分類…………………………………………………………4
2.2 火炸藥的環境流佈及宿命………………………………………………6
2.2.1 火炸藥的毒性測試……………………………………………………6
2.2.2 火炸藥的環境污染……………………………………………………10
2.2.3 土壤中的火炸藥處理方式……………………………………………16
2.3 硝基火炸藥反應機構研究………………………………………………33
2.3.1 火炸藥化學結構反應特性……………………………………………33
2.3.2硝基火炸藥分解機構…………………………………………………34
2.4 以零價鐵處理火炸藥之相關研究………………………………………39
第三章、研究設備及方法……………………………………………………41
3.1 實驗分析設備……………………………………………………………41
3.1.1 氣相層析質譜儀(GC/MS) ……………………………………………41
3.1.2 掃描式電子顯微鏡(SEM) ……………………………………………43
3.1.3分光光度計(UV/Vis) …………………………………………………44
3.2 研究方法及步驟…………………………………………………………45
3.2.1 奈米零價鐵之製備……………………………………………………45
3.2.2 以零價鐵處理水溶液中的火炸藥……………………………………47
3.2.3 生物毒性測試…………………………………………………………48
第四章、結果與討論…………………………………………………………50
4.1 零價鐵對含RDX之水溶液的反應情形…………………………………50
4.1.1 pH值小有助於RDX降解反應進行……………………………………50
4.1.2 較高溫度有助於RDX降解反應進行…………………………………52
4.1.3 零價鐵濃度較高有助於RDX降解反應進行…………………………53
4.1.4 零價鐵粒徑小有助於RDX降解反應進行……………………………53
4.2 零價鐵對含RDX之水溶液的反應毒性…………………………………55
第五章、結論…………………………………………………………………56
5.1 結論………………………………………………………………………56
5.2 未來展望…………………………………………………………………57
第六章、參考文獻……………………………………………………………59
表目錄
表1有毒物的毒性分類………………………………………………………12
表2火炸藥生產中排放污染物的毒性數據…………………………………12
表3軍事用相關火炸藥的水質標準…………………………………………14
表4在地下水中火炸藥的分解率及濃度……………………………………15
表5美國Joliet兵工廠的受污染土壤之成分………………………………19
表6生物降解法之現地處理方式實驗條件…………………………………22
表7生物降解法之現地處理方式實驗結果…………………………………22
表8苯環進行親電子性取代反應的官能基影響效應………………………34

圖目錄
圖1 本研究之架構流程圖……………………………………………………3
圖2 生物降解法之土壤泥漿反應器實驗結果………………………………21
圖3 土壤過氧化鈣氧化整治法………………………………………………25
圖4 土壤過氧化鈣氧化整治法之實驗結果…………………………………25
圖5 過氧化鈣處理法的實例…………………………………………………26
圖 6零價鐵還原法處理TNT水溶液之實驗結果……………………………28
圖 7 鐵粉還原法處理含TNT與 RDX土壤之實驗結果………………………28
圖 8 燃燒法與堆肥法之費用比較…………………………………………30
圖 9 電動力原理示意圖……………………………………………………31
圖10 去羰基反應的反應機構圖……………………………………………35
圖11 苯環上硝基的水解反應機構圖………………………………………35
圖12 硝胺基的氫化反應機構圖……………………………………………36
圖13 TNT於堆肥時的轉化反應機構………………………………………37
圖14 RDX的厭氧轉化途徑…………………………………………………38
圖15 奈米零價鐵降解TNT可能反應路徑…………………………………39
圖16 奈米零價鐵降解RDX可能反應路徑…………………………………40
圖17 氣相層析質譜儀分析流程……………………………………………42
圖18 RDX質譜儀分析圖……………………………………………………42
圖19分光光度計作用原理…………………………………………………44
圖20 SEM下之奈米零價鐵…………………………………………………46
圖21 SEM下之奈米零價鐵…………………………………………………46
圖22 尋找最佳控制因子及分析條件之流程………………………………47
圖23 空白生菌培養基照片…………………………………………………49
圖24 廢水原液菌落培養結果照片…………………………………………49
圖 25 pH值為變因的條件下，對水溶液中RDX降解之影響…………………51
圖26 反應最終的pH值趨勢………………………………………………51
圖 27 溫度為變因的條件下，對水溶液中RDX降解之影響…………………52
圖 28 反應最終的pH值趨勢…………………………………………………52
圖 29 零價鐵濃度為變因的條件下，對水溶液中RDX降解之影……………53
圖 30 500nm的零價鐵，對水溶液中RDX降解之影響………………………54
圖 31 100nm的零價鐵，對水溶液中RDX降解之影響………………………54
圖32 毒性反應趨勢圖………………………………………………………55
圖 33 RDX降解產物變化圖……………………………………………………55

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[75]-謝明君-奈米零價鐵降解受TNT、RDX 及HMX高能火炸藥污染水體之研究-中華民國九十六年七月-元智大學碩士論文
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