研究生: |
楊盛强 Sheng-Chiang Yang |
---|---|
論文名稱: |
奈米級FeZSM-5觸媒及其酚合成活性研究 Nanosized FeZSM-5 Catalyst and It’s Activity in Phenol Synthesis |
指導教授: |
劉端祺
Tuan-Chi Liu |
口試委員: |
蕭敬業
Ching-Yeh Hsio 陳郁文 Yu-Wen Chen |
學位類別: |
碩士 Master |
系所名稱: |
工程學院 - 化學工程系 Department of Chemical Engineering |
論文出版年: | 2007 |
畢業學年度: | 95 |
語文別: | 中文 |
論文頁數: | 108 |
中文關鍵詞: | 奈米級 、FeZSM-5 、水熱法 、骨架 |
外文關鍵詞: | Nanosized, FeZSM-5, hydrothermal method, framework |
相關次數: | 點閱:189 下載:2 |
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本研究以水熱法合成出奈米級的ZSM-5與FeZSM-5,比較其於氧化亞氮直接氧化苯製酚的活性,同時研究FeZSM-5觸媒中之鐵含量對反應活性的影響,以找出最佳鐵含量之FeZSM-5觸媒。
本實驗中所合成的觸媒以各種儀器鑑定其性質,包括以XRD鑑定觸媒的結晶;以XANES鑑定Fe於FeZSM-5骨架中的鍵結情形;以FESEM、BET及XRD半高寬,分析觸媒粒徑;以EDX及ICP-MS測量觸媒組成;以NH3-TPD及FTIR來了解觸媒的酸性。
觸媒之苯直接氧化製酚活性是在常壓下測試,使用直通微型管狀反應器,反應物為苯及氧化亞氮,反應物以連續流動方式流經觸媒床,使用觸媒的重量為0.4克,反應後的產物以氣象層析儀分析。
研究的結果發現,鐵可存在於ZSM-5的骨架中,但有一最大的鋁取代量,在本研究所用的合成條件下,合成母液中的Al,進入沸石骨架的比例低於Si,所合成的ZSM-5之粒徑小於FeZSM-5,在ZSM-5上的酸以Lewis酸為主,在FeZSM-5以Brønsted酸為主。
觸媒活性測試的結果發現,在適量的鐵下,FeZSM-5較ZSM-5的活性高,於 (Fe+Al) / Si = 1 / 60 的各FeZSM-5觸媒中Fe/Al的最佳比值介於0.2至0.7之間, ZSM-5的鐵含量過多時,氧化活性過強,不利於酚的生成。
Nanosized ZSM-5and FeZSM-5 were synthesized and their activities in the production of phenol by direct benzene oxidation were examined. The effect of ion content in FeZSM-5 for the direct oxidation was investigated to explore the optimum amount of ion in FeZSM-5.
The catalysts synthesized in this research were characterized using varied instruments and methods: Using XRD to know the crystalline structures of the catalysts, XANES to understand the bonding structure of the Fe in FeZSM-5 framework, FESEM, BET and half width of XRD peak to measure the catalyst size, EDX and ICP-MS to explore the catalyst composition and finally utilizing NH3-TPD and FTIR to understand the acid condition of the catalysts.
The activity of the catalysts in the direct oxidation of benzene for phenol was studied under atmospheric pressure using a micro-reactor. The reactants, included benzene and nitrous oxide, flew continuously through the catalyst bed. The bed, in a typical run, contained 0.4 gram of catalyst. The products from the reaction were analyzed by gas chromatograph.
The results of this research show that the FeZSM-5 in this study contains Fe in its framework, but there exists a maximum amount of the ion. In synthesizing ZSM-5, large fraction of the silicon ion in the mother liquid enters the framework than that of aluminum ion. The crystalline size of ZSM-5 is, in genera, smaller than that of FeZSM-5 synthesized under the same condition. In addition, the acid on ZSM-5 is mostly Lewis acid while that in FeZSM-5 is mainly Brønsted acid.
FeZSM-5 catalyst with proper amount of ion is more active than ZSM-5. Among the FeZSM-5 of (Fe+Al) / Si = 1 / 60, the one with a Fe/Al ratio between 0.2 and 0.7 exhibits the highest activity. Excess amount of ion in FeZSM-5 results in too high a oxidation ability and is not favored for the production of phenol.
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