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酸鹼催化六員環化合物反應的探討 = Study on Acid-Base...

國立高雄大學應用化學系碩士班

酸鹼催化六員環化合物反應的探討 = Study on Acid-Base Catalysis of Six-Ring Compounds

紀錄類型:	書目-語言資料,印刷品 : 單行本
並列題名:	Study on Acid-Base Catalysis of Six-Ring Compounds
作者:	趙培宇,
其他團體作者:	國立高雄大學
出版地:	[高雄市]
出版者:	撰者;
出版年:	民100
面頁冊數:	125面圖，表格 : 30公分;
標題:	酸鹼共軛催化
標題:	acid-base catalysis
電子資源:	http://handle.ncl.edu.tw/11296/ndltd/55877576002931159387
附註:	參考書目：面123-125
摘要註:	本研究探討六員環化合物之酸鹼雙功能催化反應，以二甲基吡啶與甲苯側鏈烷化反應探討酸鹼共軛催化反應，另以酸－鹼雙功能觸媒催化醣類脫水反應，探討雙元觸媒系統設計。對於二甲基吡啶側鏈烷化反應，鹼預處理法修飾沸石會降低沸石樣品催化活性，隨著鹼處理溶液的強度提高，沸石觸媒活性隨之明顯下降，藉由吸附實驗與與感應耦合電漿分析結果推論，鹼預處理法產生氧化矽沉澱會殘留在孔道內，抑制了反應物與產物擴散速率，因而降低催化活性並且加速觸媒衰退速率。吾人發展了三段處理法技術，先以鹼預處理法後，續以中性鹽類清除殘留在孔道內的氧化矽，再進行鹼性離子交換。相較於一段式直接離子交換法，三段處理法之催化活性較高，單邊側鏈烷化產物methylvinylpyridine 選擇性高於85%，一段式直接離子交換法則以雙邊側鏈烷化產物di-vinylpyridine 為主。對於甲苯側鏈烷化催化反應，催化活性與擔體種類有關，在甲苯/甲醛之莫耳進料比為1，WHSV= 1 h-1，反應溫度400 C 的反應條件，高面積之SiO2 擔載型觸媒具有較高的催化活性(CT>10%)，同時產生苯乙烯與二甲苯。相對的，高表面積Al2O3 擔載型觸媒卻幾乎不具有催化活性。另以固體路易士酸擔載鹼性金屬氧化物，例如MgO/AlCl3 系統，在TOS=8 h，甲苯轉化率4%，苯乙烯選擇率50%，並無乙苯與二甲苯產物，似乎具有發展潛力。CeO2 擔載型觸媒主要產物則是二甲苯，若以低表面積的TiO2-ZrO2 作為擔體材料，催化活性偏低(CT<5%)。對於生質能脫水生成5-羥甲基糠醛(HMF)反應，果糖脫水生成HMF 屬於酸性催化反應，矽鋁比為10.5 的H 型絲光沸石之HMF 產率最高，MFI 型沸石則同時產生HMF 與levulinic acid。吾人發現，擔载磺酸根當量為5 之MCM-41 具有相當於絲光型沸石之催化活性。另外，含鋁之MCM-41 結晶化轉換生成微介孔複合孔洞材料hZ(50)，屬於MFI 結構，具有酸性，其催化性質優於傳統方法製備之ZSM-5，可以歸因於介孔結構的存在，較高的擴散係數有助於反應進行。相對的，葡萄糖脫水轉化成HMF 屬於酸鹼共軛催化反應，吾人首次發展雙功能沸石催化體系，發現擔载磺酸根當量為1/3 之鹼性LTL 沸石具有優良的催化活性，葡萄糖轉化率與HMF 選擇率分別是78%與83%。 The thesis studied the acid-base cxatalysis of six-ring compounds. Acid-baseproperties of metal oxide catalysts for side-chain alkylation of lutidine and toluene were explored. Acid-base bifunctional zeolite catalysts were developed for the dehydration of sugar compounds.Base treatment on MFI can generate mesopores by silica leaching but form silica debrids inside zeolitic micropores. In the side-chain alkylation of lutidine with methanol, declined activity and stability of base modified MFI was observed. As adsorption data suggested, the deteriorated performance of MFI is attributed to the reduced diffusivity. A three step protocol was developed. After the base treatment as the first step, neutral NH4NO3 treatment as the second step was added to be able to clean-up the silica debrids, followed by ion exchange with alkali metal salt as the last step. It was found that the product selectivity of lutidine alkylation with methanol varied dramatically with different ion exchange procedures. While alkaline exchanged MFI by the conventional one step procedure catalyzed in favor of di-alkylation product as di-vinylpyridine, MFI modified with the three step protocol catalyzed mainly mono-alkylation product as vinylpyridine at 85%.In side-chain alkylation of toluene, type of support significantly affects catalyst performances. At typical reaction conditions, toluene/MeOH molar ratio of 1, WHSV of 1 h-1 and 400C, high surface area SiO2 supported catalysts showed high activity (CT > 10%) with co-generation of styrene and xylene. On the other hand, most of Al2O3 supported catalysts showed no activity. Lewis acid solid supported catalyst, such as MgO/AlCl3, catalyzed toluene conversion of 4% producing styrene at 50% selectivity and no xylene and ethylbenzene. On the other hand, CeO2 supported catalysts produced mainly xylene. Very low activity of TiO2-ZrO2 catalyst systems was observed, which can be attributable to the low surface area.Fructose dehydration into 5-hydroxymethylfurfural (HMF) is an acid catalyzed reaction. Among zeolite catalysts, H-MOR showed the highest yield of HMF and MFI catalyzed co-generation of HMF and levulinic acid. We found that MCM-41 loaded with sulfonate group at 5 equivalent amounts showed comparable activity with H-MOR. Furthermroe, mesoporous MFI prepared from MCM-41 by dry gel method showed much higher HMF selectivity than the conventional MFI. The improved HMF selectivity is attributed to the enhanced diffusivity by introducing mesopores into zeolite structures. Dehydration of glucose into HMF is an acid-base catalyzed reaction. We found for the first time that basic LTL zeolite loaded with sulfonate at 1/3 equivalent amount showed glucose conversion of 78% and HMF selectivity of 83%.

酸鹼催化六員環化合物反應的探討 = Study on Acid-Base Catalysis of Six-Ring Compounds
趙, 培宇

酸鹼催化六員環化合物反應的探討 = Study on Acid-Base Catalysis of Six-Ring Compounds / 趙培宇撰 - [高雄市] : 撰者, 民100. - 125面 ; 圖，表格 ; 30公分.
參考書目：面123-125.
酸鹼共軛催化acid-base catalysis

酸鹼催化六員環化合物反應的探討 = Study on Acid-Base Catalysis of Six-Ring Compounds
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