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研究生:阮建能
研究生(外文):Chien-Neng Juan
論文名稱:TNT製程廢硫酸中有機物去除之研究
論文名稱(外文):A study on removal of organic compounds from spent sulfuric acid of TNT process
指導教授:陳文星陳文星引用關係
指導教授(外文):Wen-Shing Chen
學位類別:碩士
校院名稱:國立雲林科技大學
系所名稱:工業化學與災害防治研究所
學門:工程學門
學類:化學工程學類
論文種類:學術論文
論文出版年:2004
畢業學年度:92
語文別:中文
論文頁數:120
中文關鍵詞:廢硫酸混酸DNTTNTFenton氧化法UV/O3氧化法溶劑萃取法臭氧紫外光
外文關鍵詞:spent mixed acidDNTTNTFenton oxidationUV/O3oxidationsolvent extractionozone
相關次數:
  • 被引用被引用:6
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本研究應用Fenton氧化法、UV/Fenton氧化法、UV/O3氧化法及溶劑萃取法於去除三硝基甲苯(TNT)生產製程之廢硫酸/硝酸混酸所含之碳氫化合物。不僅可簡化後續之蒸餾程序,亦可作為其他產業之進料,達成資源回收之目的。
在前置處理程序中,稀釋法及冷凍結晶法可回收高純度之2,4-DNT晶體(>98%)。實驗結果顯示,Fenton氧化法在反應溫度70℃、亞鐵離子2000ppm及過氧化氫濃度7.6M時,有機物去除效率可達100%,証明此法適用於廢酸中有機物之去除,亦優於傳統之過氧化氫氧化法。
以Hexane或Heptane作為溶劑進行TNT廢硫酸中有機物之萃取(六次),實驗結果顯示反應溫度50℃、溶劑/廢酸=1/1下(V/V),有機物去除率可達73.38%以上,而增加溶劑/廢酸比值利於減少萃取次數。有機物所含成分於廢酸中之溶解度依次為:2,4,6-TNT >2,4-DNT >3,4-DNT >2,6-DNT > 2,3-DNT。
UV/O3系統應用於TNT廢硫酸之有機物去除,結果顯示臭氧未如預期地經由紫外光的照射產生H2O2,亦未進一步光解成氫氧自由基,而僅憑藉由臭氧的氧化力及UV光解作用進行反應。因此,UV/O3系統並不適於TNT廢硫酸中有機物之去除。
This study investigates the application of Fenton oxidation, UV/Fenton oxidation, UV/O3 oxidation, and solvent extraction methods for removing of organic compounds from spent mixed acid of TNT manufacturing process. The spent mixed acid obtained can be regenerated by vacuum distillation simply or become the feedstock of other industries to reach the goal of recycling.

Under the pretreatment, high purity 2,4-dinitrotoluene (>98 %) can be recovered by means of dilution manner and refrigeration method. According to the result of experiments, the removing efficiency of organic compounds reaches 100% under the condition of reaction temperature 70℃, Fe2+ 2000ppm and the concentration of hydrogen peroxide 7.6M (referred as Fenton reagent). That proves the feasible application of above method to remove the organic compounds of spent mixed acid, which is superior to the conventional one.

This research also explores the extracting efficiency (six stages) of hexane or heptane solvents on the organic compounds of spent mixed acid. It was found that the extracting efficiency reaches 73.38% under the conditions of rxn. temp. of 50℃ and solvent/acid volume ratio of 1/1. Nevertheless, it is beneficial to reduce extracting stages by the increase of solvent/acid volume ratio. Moreover, the solubility of organic compounds in spent acid was as following: 2,4,6-TNT> 2,4-DNT> 3,4-DNT> 2,6-DNT> 2,3-DNT.

The UV/O3 system has been used to remove organic compounds of spent mixed acid. It was found that hydrogen peroxide would not be produced expectedly from ozone illuminated by UV light. Further, hydroxyal radical could not be generated by decomposition of ozone. Therefore, UV/O3 system is suitable to remove organic compounds of spent mixed acid, which depends only on the oxidizing ability of ozone and photolysis of UV light.
中文摘要.................................................Ι
英文摘要.................................................Ⅲ
致謝.....................................................V
目錄.....................................................Ⅵ
表目錄....................................................X
圖目錄...................................................Ⅷ
第一章 前言
1-1 研究緣起............................................1
1-2 研究目的與內容......................................3
第二章 文獻回顧
2-1 TNT廢硫酸混酸之再生技術.............................5
2-2 Fenton程序之原理.....................................9
2-3 氫氧自由基生成之影響因素............................15
2-3-1 pH值之效應......................................15
2-3-2 亞鐵鹽劑量與種類之效應...........................16
2-3-3 H2O2 劑量之效應..................................17
2-4 Photo-Fenton程序之原理................................18
2-5 臭氧的性質...........................................21
2-5-2 臭氧的分子結構及性質............................21
2-6 臭氧的反應行為.....................................23
2-6-1 臭氧在水溶液中的自解............................23
2-6-2 臭氧在空氣中之分解..............................27
2-6-3-1 溶液pH 值對臭氧氧化反應的效應..............29
2-6-3-2 過氧化氫對臭氧氧化反應的效應................29
2-6-3-3 UV光對臭氧氧化反應的效應..................32
第三章 研究方法
3-1 實驗材料............................................35
3-1-1 TNT廢硫酸混酸..................................35
3-1-2 實驗藥品.........................................36
3-1-3 實驗設備........................................38
3-2 實驗分析方法........................................43
3-2-1 總有機碳分析(TOC)............................43
3-2-2 Karl-Fischer 水份測定.............................43
3-3-3 質譜儀(Mass spectrometer,MS)..................44
3-3-4 火燄離子化偵檢器(Flame Ionization Detector,FID)...45
3-3-5 熱解式氣相層析/質譜儀(Pyrolysis/GC-MS)..........46
3-3 實驗方法............................................47
3-3-1 前置實驗步驟.....................................48
3-3-2 Fenton法實驗步驟................................51
3-3-3 Photo-Fenton氧化法...............................53
3-3-4 溶劑萃取法......................................53
3-3-5 臭氧氧化法去除有機物............................57
3-3-5-1 純臭氧系統實驗...............................57
3-3-5-2 UV/O3系統實驗...............................58
第四章 結果與討論
4-1 廢硫酸混酸之基本性質................................59
4-2 前置實驗............................................60
4-3 Fenton 氧化法........................................68
4-3-1氫氧自由基的氧化作用.............................68
4-3-2溫度對Fenton氧化法之影響.........................69
4-3-3鐵鹽加藥量之影響..................................71
4-3-4 H2O2濃度之影響...................................73
4-4 Photo-Fenton氧化法....................................77
4-5 溶劑萃取法...........................................81
4-5-1 溫度對有機物萃取之影響............................81
4-5-2 溶劑萃取時之酸中水份分布..........................84
4-5-3 溶劑對廢酸之體積比例影響.........................85
4-5-4 廢酸中硫酸濃度對萃取之影響......................88
4-6以臭氧結合紫外光系統氧化有機物......................101
4-6-1 純臭氧系統之溫度影響............................101
4-6-2 紫外光照度與臭氧濃度之影響......................103
4-6-3 添加UV光對臭氧反應的影響......................106
第五章 結論..............................................111
參考文獻..................................................113
自述......................................................120
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