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研究生:李彥儒
研究生(外文):Yen-Ru Lee
論文名稱:以鈀/高密度聚乙烯觸媒及氫氣在超臨界二氧化碳中降解2﹐4-二溴聯苯
論文名稱(外文):Reduction of 2,4- Dibromobiphenyl by Palladium/High-density polyethylene with Hydrogen Gas in Supercritical Carbon Dioxide
指導教授:葉華光葉華光引用關係
指導教授(外文):Hwa-Kwang Yak
學位類別:碩士
校院名稱:中原大學
系所名稱:化學研究所
學門:自然科學學門
學類:化學學類
論文種類:學術論文
論文出版年:2014
畢業學年度:102
語文別:中文
論文頁數:125
中文關鍵詞:2﹐4-二溴聯苯降解超臨界二氧化碳
外文關鍵詞:supercritical carbon dioxidedegradation2﹐4 - dibromobiphenyl.
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多溴聯苯(PBBs,Polybrominated biphenyls)在自然界的存在對人體健康有害,當物質由工廠或桶裝、瓶裝等容器釋放出來時,就會排放到環境中,將多溴聯苯暴露到空氣裡,還有當你接觸到它或是經由呼吸、攝取含有多溴聯苯的食物或飲料,甚至是皮膚接觸等等都有可能讓多溴聯苯進入體內,對人體健康造成傷害。
本研究利用將高密度聚乙烯置於高壓槽中,溫度130℃,超臨界二氧化碳壓力為200atm,反應3小時後,讓壓力於幾秒內降至常壓下,再將微孔洞HDPE及palladium hexafluoroacetylacetonate置於高壓槽中, 使用90℃的溫度,於超臨界二氧化碳100atm下,再反應3小時,最後快速洩壓於常壓,之後將氫氣導入高壓槽中,並在溫度 90℃下維持約10分鐘,製作成我們本次研究所需要的觸媒。
透過Pd/HDPE(Palladium hexafluoroacetylacetonate High-density polyethylene)為觸媒降解多溴聯苯當中的2,4- dibromobiphenyl,使其在高溫下可以降解成毒性較低的bicyclohexane(雙環己烷)、biphenyl(聯苯)、cyclohexylbenzene(環己苯),並且透過加入內標法定量在各個溫度、壓力、流速下或是回收體積等等各種變因中的降解後殘留百分比。開發出一種可以有效降解多溴聯苯的方法,而且我們發現,研究中的反應時間相比其他研究優化許多,甚至對於相同降解時間的光降解研究而言,本研究(99.4%)降解率也比該研究(91.3%)高。在溫度上本研究只需要90゚C的溫度就可以對二溴聯苯進行降解,相較於雜多酸鋅鹽催化反應的320゚C高溫而言,本研究較為節能。
透過本研究可以使二溴聯苯降解的更完全,使用節能又對環境無害的超臨界二氧化碳萃取法透過這樣的方法,讓連生物都難分解的二溴聯苯有機汙染物能更有效的降解成對環境較無害的產物。







Under this study, we use the high-pressure tank into the HDPE the temperature is greater than 130 ℃ under pressure 200atm, the reaction for 3 hours, after which the pressure was decreased to atmospheric conditions in a matter of seconds, the microporous HDPE hole into the high pressure vessel and palladium hexafluoroacetylacetonate, with greater than 90 ℃ in temperature, pressure 100atm, and then reacted for 3 hours, and finally at atmospheric pressure rapidly, then the high pressure hydrogen gas is introduced into said groove, and at 90 ℃ maintaining about 10 minutes, the experiment produced a catalyst we need.
Before making use of the catalyst Pd / HDPE will be placed in a supercritical system, the use of 90 degrees and the pressure 200atm the reaction for 8 hours and then extraction with a flow rate of 0.3 to 0.5 of the supercritical carbon dioxide charged 300ml six hours, then using gas chromatography Gas chromatography-mass spectrometry (GC-MS) coupled with previously by the standard Bicyclohexane, Cyclohexylbenzene, Biphenyl, 2,4-Dibiromobiphenyl and 4 - chlorobiphenyl make the calibration curve, to match the standard method quantitatively obtain optimum catalyst degradation rate of 99.4%.







摘要...........................................I
Abstract......................................III
謝誌...........................................V
目錄...........................................VI
圖目錄.........................................X
表目錄.........................................XIV

第一章、緒論...............................................1
第二章 文獻回顧............................................3
2-1多溴聯苯...............................................3
2-1-1 、多溴聯苯(PBBs, Polybrominated biphenyls)簡介.......3
2-1-2 、多溴聯苯在環境中的變化...............................4
2-1-3 、多溴聯苯進出人體的案例...............................6
2-1-4 、多溴聯苯對人體的危害.................................9
2-2 鈀/高密度聚乙烯的觸媒介紹................................12
2-2-1、高密度聚乙烯的簡介...................................12
2-2-3、鈀的介紹...........................................18
2-3 超臨界流體............................................22
2-3-1、超臨界流體技術的歷史回顧..............................22
2-3-2、超臨界流體特性......................................23
2-4 現有的多溴聯苯降解方法..................................35
2-4-1、多溴聯苯的脫鹵還原反應...............................35
2-4-2、二溴聯苯與雜多鋅鹽在近臨界水氧化降解....................36
2-4-3、二溴聯苯在有機溶劑中通過UV/ O3降解.....................37
2-4-4、利用超聲波降解二溴聯苯................................38
2-4-5、二氧化鈦水溶液和摻雜二氧化鈦的納米管陣列光電催化降解二溴聯苯.39
第三章 實驗方法與設備.......................................41
3-1、實驗藥品介紹..........................................41
3-2、實驗設備介紹..........................................43
3-3、 實驗流程..........................................46
3-4、觸媒製造流程..........................................55
3-5、檢量線的製作..........................................56
第四章 結果與討論..........................................59
4-1、觸媒:...............................................60
4-1-1、觸媒的作用的圖解.....................................60
4-1-2、觸媒的作用方式......................................62
4-1-3 、觸媒SEM圖.........................................63
4-2、內標的選擇..........................................65
4-3、探討壓力對降解效果的影響...............................68
4-3-1、二氧化碳的壓力探討..................................68
4-3-2、氫氣壓力的探討.....................................74
4-3、討探溫度對降解的影響..................................75
4-4、探討反應時間對降解的影響...............................82
4-5最佳條件與還原結果......................................87
4-6本研究與其他降解方法的比較...............................90
第五章 結論..............................................92
第六章 參考文獻...........................................95
圖 1、多溴聯苯的結構圖..............................4
圖 2、固體、氣體、液體和超臨界流體之溫度壓力分界圖......26
圖 3、超臨界流體儀器實體圖..........................43
圖 4 、氣相層析質譜儀實體圖.........................44
圖 5 、場發射掃描式電子顯微鏡的實體圖.................45
圖 6、不鏽鋼槽細部構造簡圖(載自Valco公司網頁)........ 45
圖 7、反應槽組合圖簡圖.............................46
圖 8 、烘箱的內部構造簡圖...........................47
圖 9、超臨界流體儀器簡圖............................48
圖 10、超臨界流體幫浦控制器(Pump Controller)簡圖....51
圖 11、超臨界流體控溫裝置控制的面板簡圖...............52
圖 12、降解2,4- dibromobiphenyl反應中觸媒的作用方式圖解 ...............................................60
圖 13、觸媒的實體圖...............................61
圖 14、觸媒SEM圖反應前X 1800 、5.0kv..............64
圖 15、觸媒SEM圖反應前X 1500 、4.0kv..............64
圖 16、觸媒SEM圖反應前X 2000 、4.0kv..............64
圖 17、觸媒SEM圖反應前X 600 、4.0kv ...............64
圖18、觸媒SEM圖反應前X 2200 、4.0kv ...............64
圖19、觸媒SEM圖反應前X 3300 、4.0kv ...............64
圖20、本研究的檢量線層析圖.........................65
圖 21、2,4- dibromobiphenyl的降解途徑圖...........66
圖 22用Hexane:Acetone = 9:1沖堤管柱中觸媒的層析圖..68
圖 23、2,4- dibromobiphenyl 在100 atm 、90゚C 下反應30分鐘的層析圖...................................71
圖 24、2,4- dibromobiphenyl 在150 atm 、90゚C 下反應30分鐘的層析圖...................................72
圖 25、2,4- dibromobiphenyl 在200 atm 、90゚C 下反應30分鐘的層析圖...................................72
圖 26、2,4- dibromobiphenyl 在200 atm 、90゚C 下反應2小時的層析圖.....................................76
圖 27、2,4- dibromobiphenyl 在200 atm 、100゚C 下反應2小時的層析圖....................................77
圖 28、2,4- dibromobiphenyl 在200 atm 、105゚C 下反應2小時的層析圖....................................77
圖 29、2,4- dibromobiphenyl 在200 atm 、90゚C 下反應9小時的層析圖.....................................79
圖 30、2,4- dibromobiphenyl 在200 atm 、100゚C 下反應9小時的層析圖....................................80
圖 31、2,4- dibromobiphenyl 在200 atm 、105゚C 下反應9小時的層析圖....................................80
圖 32、2,4- dibromobiphenyl 在200 atm 、90゚C 下反應30分鐘的層析圖...................................84
圖 33、2,4- dibromobiphenyl 在200 atm 、90゚C 下反應2小時的層析圖.....................................84
圖 34、2,4- dibromobiphenyl 在200 atm 、90゚C 下反應6小時層析圖.......................................85
圖 35、2,4- dibromobiphenyl 在200 atm 、90゚C 下反應8小時層析圖.......................................85
圖36、2,4- dibromobiphenyl 在200 atm 、90゚C 下反應9小時層析圖.........................................86
圖 37、降解2,4- dibromobiphenyl 在200 atm 90゚C下的各種反應時間對應含量百分比長條圖.......................87

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