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| DC 欄位 | 值 | 語言 |
|---|---|---|
| dc.contributor.advisor | 吳嘉文(Chia-Wen Wu) | |
| dc.contributor.author | Yu-Ting Chiu | en |
| dc.contributor.author | 邱瑜婷 | zh_TW |
| dc.date.accessioned | 2021-06-07T23:44:08Z | - |
| dc.date.copyright | 2014-07-29 | |
| dc.date.issued | 2014 | |
| dc.date.submitted | 2014-07-14 | |
| dc.identifier.citation | [1] www.ren21.net, REN21 2013.
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| dc.identifier.uri | http://tdr.lib.ntu.edu.tw/jspui/handle/123456789/16708 | - |
| dc.description.abstract | 近年來由於石油短缺的問題，使得人們對於替代能源的需求日漸益增，因此本研究致力果糖、5-羥甲基糠醛(5-Hydroxymethyl furfural, HMF)至生質燃料─2,5-二甲基呋喃(2,5-dimethylfuran, DMF)的製備。在許多生質燃料中，2,5-二甲基呋喃(DMF)因其所具有的優異性質，例如高能量密度、高效配送、易儲存、高安全係數等特點，使2,5-二甲基呋喃(DMF)成為最具有吸引力及發展潛力的生質燃料。
本研究首先合成出三種不同酸官能化的中孔洞二氧化矽奈米粒子(mesoporous silica nanoparticles, MSNs)，由於中孔洞二氧化矽奈米粒子(MSNs)具有高比表面積及易表面改質等特點，因此本研究以此材料作為反應的異相固態觸媒。本研究共將三種酸官能基成功嫁接於中孔洞二氧化矽奈米粒子(MSNs)上，同時利用X光繞射儀(X-ray diffraction, XRD)、掃描式電子顯微鏡(scanning electron microscopy, SEM)、穿透式電子顯微鏡(transmission electron microscopy, TEM)、氮氣吸/脫附孔隙儀(nitrogen adsorption/desorption isotherms)等儀器進行材料鑑定，並將這些帶有磺酸根、羧酸根和亞磷酸根的中孔洞二氧化矽奈米粒子(MSNs)分別以S-MSN、C-MSN、P-MSN表示。實驗結果顯示在四氫呋喃(tetrahydrofuran, THF)系統、反應溫度75°C及反應時間15小時的條件下，S-MSN和C-MSN分別有助於果糖至5-羥甲基糠醛(HMF)、5-羥甲基糠醛(HMF)至2,5-二甲基呋喃(DMF)的轉化反應。因此，本研究利用這兩種固態催化劑(S-MSN和C-MSN)有效地進行果糖-5-羥甲基糠醛-2,5-二甲基呋喃的序列式反應，其最佳2,5-二甲基呋喃產率可達69 mol %。 此外，本研究也以系統性的方式進行5-羥甲基糠醛(HMF)至2,5-二甲基呋喃(DMF)反應路徑的探討。由上述結果可知本研究所合成的酸官能化中孔洞二氧化矽奈米粒子可作為有效的反應催化劑，同時並顯示出酸官能化中孔洞二氧化矽奈米粒子在生質轉換的應用潛力。 | zh_TW |
| dc.description.abstract | Due to strong demand for green and economical alternatives to traditional fossil fuels, this study is focused on the production of 2,5-dimethylfuran (DMF) converted from fructose or 5-hydroxymethylfurfural (HMF). In many biomass-derived liquid fuels, 2,5-dimethylfuran (DMF) is the most attractive one because of its excellent properties such as high energy density, efficient distribution, easier storage, and higher safety coefficient.
In this study, we synthesized several acid-functionalized mesoporous silica nanoparticles (MSNs) as solid heterogeneous catalysts because of several advantages of MSNs including high surface area and easy surface functionalization. Three acid-functionalized MSNs (i.e. sulfonic acid, carboxylic acid and phosphoric acid for S-MSN, C-MSN and P-MSN, respectively) were synthesized and characterized with X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), nitrogen adsorption/desorption isotherms and so on. It was found that S-MSN and C-MSN exhibited the highest efficiency for fructose-to-HMF and HMF-to-DMF, respectively, conversion in tetrahydrofuran (THF) system under mild conditions (75 °C, 15 hr). Therefore, we utilized these two catalysts to achieve efficient and subsequent fructose-to-HMF-to-DMF conversion with highest DMF yield of 69 mol%. The pathway of the HMF-to-DMF conversion was systematically studies. The acid-functionalized MSN materials synthesized in this study have shown potential applications as efficient catalysts for biomass conversion. | en |
| dc.description.provenance | Made available in DSpace on 2021-06-07T23:44:08Z (GMT). No. of bitstreams: 1 ntu-103-R01524048-1.pdf: 8312844 bytes, checksum: f5bb2d38158cd8b07683d895840588d2 (MD5) Previous issue date: 2014 | en |
| dc.description.tableofcontents | 致謝 I
ABSTRACT II 摘要 IV 目錄 V 圖目錄 IX 表目錄 XVI 第1章 緒論 1 第2章 文獻回顧 6 2.1 生質能轉換 6 2.1.1 常見的生質轉換 6 2.1.2 果糖轉化至5-羥甲基糠醛(HMF)之反應機制 11 2.1.3 2,5-二甲基呋喃(DMF)之製備方法 13 2.1.3.1 雙相系統合成法 13 2.1.3.2 N,N-dimethylacetamide系統合成法 17 2.1.3.3 離子液體合成法 20 2.1.3.4 甲酸系統合成法 28 2.2 奈米孔洞材料 31 2.2.1 奈米孔洞材料之合成 31 2.2.2 奈米孔洞材料之表面改質 34 2.2.2.1 嫁接法(Grafting) 34 2.2.2.2 共縮合法(Co-condensation method) 35 2.2.2.3 有機中孔洞二氧化矽合成法 36 2.2.3 用於生質能源轉換的固態觸媒 37 2.2.3.1 用於果糖脫水至HMF的固態觸媒 37 2.2.3.2 用於HMF氫化至DMF的固態觸媒 41 2.2.4 中孔洞材料與上述固態觸媒的優缺點 43 第3章 研究目的與動機 45 第4章 實驗步驟 47 4.1 材料 47 4.1.1 化學藥品清單 47 4.1.2 分析儀器設備 48 4.2 檢量線及滯留時間 49 4.2.1 高性能液相層析儀分析(HPLC) 49 4.2.2 氣相層析儀-質譜儀(GC-MS) 50 4.3 計算方法及定義 54 4.4 固體催化劑合成 55 4.4.1 中孔洞二氧化矽奈米粒子(Mesoporous Silica Nanocatalyst, MSN)合成 55 4.4.2 中孔洞二氧化矽奈米粒子之表面官能化─嫁接磺酸官能基(S-MSN) 55 4.4.3 中孔洞二氧化矽奈米粒子之表面官能化─嫁接羧酸官能基(C-MSN) 56 4.4.4 中孔洞二氧化矽奈米粒子之表面官能化─嫁接亞磷酸官能基(P-MSN) 58 4.4.5 中孔洞二氧化矽奈米粒子之表面官能化─嫁接雙官能基(Bif.-MSN) 59 4.5 反應操作 60 4.5.1 果糖至5-羥甲基糠醛之轉換 60 4.5.2 5-羥甲基糠醛至2,5-二甲基呋喃之轉換 60 4.5.3 中間產物之轉換 61 4.5.4 果糖至2,5-二甲基呋喃(DMF)之序列式轉換 62 4.6 材料之回收性及穩定性測試 63 4.7 材料之酸強度及酸量測試 63 第5章 結果與討論 64 5.1 材料鑑定 64 5.1.1 中孔洞二氧化矽奈米粒子之形貌 64 5.1.2 中孔洞二氧化矽奈米粒子之孔洞特性 66 5.1.3 中孔洞二氧化矽奈米粒子之官能基鍵結定性及定量 67 5.1.4 中孔洞二氧化矽奈米粒子之酸強度及酸量 72 5.2 反應 74 5.2.1 5-羥甲基糠醛(HMF)之轉換至2,5-二甲基呋喃(DMF)之轉換 74 5.2.2 果糖至5-羥甲基糠醛(HMF) 78 5.2.3 果糖至2,5-二甲基呋喃(DMF)之序列式轉換 83 5.3 反應路徑探討──中間產物之轉換 85 5.3.1 不同反應時間下之DMF (2,5-dimethylfuran)轉化反應 87 5.3.2 不同反應時間下之MFM (5-methylfurfuryl alcohol)轉化反應 88 5.3.3 不同反應時間下之BHMF (2,5-bis(hydroxymethyl)furan)轉化反應 89 5.3.4 不同反應時間下之MFAD (5-methyl-2-furancarboxaldehyde)轉化反應 91 5.3.5 不同反應時間下之DFF (2,5-furandicarboxaldehyde)轉化反應 92 5.3.6 不同反應時間下之AMF (5-acetoxymethyl-2-furaldehyde)轉化反應 93 5.3.7 HMF (5-hydroxymethyl furfural)之反應路徑 94 第6章 結論 96 第7章 未來展望 97 第8章 參考文獻 98 附錄 103 附錄一、酸強度測試之指示劑 103 附錄二、化合物縮寫對照表 103 附錄三、化合物之HPLC檢量線 104 附錄四、化合物之GC-MS圖譜 105 附錄五、化合物之GC-MS檢量線 109 附錄六、官能化中孔洞二氧化矽奈米粒子之SAXS圖 112 附錄七、中孔洞二氧化矽奈米粒子之31P固態核磁共振光譜 112 附錄八、反應路徑探討之反應結果數據 113 附錄九、雙官能化中孔洞二氧化矽奈米粒子之果糖轉換─ ONE-POT REACTION 114 附錄十、果糖至2,5-二甲基呋喃(DMF)之一步驟轉換(ONE-POT) 119 | |
| dc.language.iso | zh-TW | |
| dc.title | "合成酸官能化中孔洞二氧化矽奈米粒子做為可回收式固體催化劑應用於果糖-5-羥甲基糠醛(HMF)-2,5-二甲基呋喃(DMF)的序列式生質轉換" | zh_TW |
| dc.title | Efficient and Subsequent Production of 2,5-dimethylfuran (DMF) from Fructose and 5-Hydroxymethyl furfural (HMF) Using Acid-Functionalized Mesoporous Silica Nanocatalysts | en |
| dc.type | Thesis | |
| dc.date.schoolyear | 102-2 | |
| dc.description.degree | 碩士 | |
| dc.contributor.oralexamcommittee | 鄭淑芬(Shu-Fen Chen),蔡振章(Chen-Chang Tsai),張根源(Ken-Yuan Chang),陳文華(Wen-Hua Chen) | |
| dc.subject.keyword | 中孔洞二氧化矽奈米粒子,2,5-二甲基?喃,5-羥甲基糠醛,果糖,官能化,生質燃料, | zh_TW |
| dc.subject.keyword | Mesoporous silica nanoparticles,2,5-dimethylfuran (DMF),5-hydroxymethylfurfural (5-HMF),fructose,functionalization,biofuel, | en |
| dc.relation.page | 120 | |
| dc.rights.note | 未授權 | |
| dc.date.accepted | 2014-07-14 | |
| dc.contributor.author-college | 工學院 | zh_TW |
| dc.contributor.author-dept | 化學工程學研究所 | zh_TW |
| 顯示於系所單位： | 化學工程學系 | |
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