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| DC 欄位 | 值 | 語言 |
|---|---|---|
| dc.contributor.advisor | 游文岳 | zh_TW |
| dc.contributor.advisor | Wen-Yueh Yu | en |
| dc.contributor.author | 李冠輝 | zh_TW |
| dc.contributor.author | Kuan-Hui Lee | en |
| dc.date.accessioned | 2021-07-10T21:52:17Z | - |
| dc.date.available | 2024-08-15 | - |
| dc.date.copyright | 2019-08-22 | - |
| dc.date.issued | 2019 | - |
| dc.date.submitted | 2002-01-01 | - |
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Journal of Alloys and Compounds 720, 360–368 (2017). 86. Álvarez, M. G., Plíšková, M., Segarra, A. M., Medina, F. &Figueras, F. Synthesis of glycerol carbonates by transesterification of glycerol in a continuous system using supported hydrotalcites as catalysts. Applied Catalysis B: Environmental 113–114, 212–220 (2012). | - |
| dc.identifier.uri | http://tdr.lib.ntu.edu.tw/jspui/handle/123456789/77239 | - |
| dc.description.abstract | 將生質柴油製程中過剩的副產物甘油轉換為高經濟價值的化學品，已成為異相觸媒領域中一項蓬勃發展的議題。本研究中，吾人使用溶膠凝膠法中的檸檬酸聚合錯和物法（polymeric citrate complex method，即Pechini method）製備鹼金與鹼土族鈦酸鹽類觸媒，以應用於甘油與碳酸二甲酯（dimethyl carbonate）轉酯化合成碳酸甘油酯（glycerol carbonate）。文中探討之鹼金與鹼土族包含鋰、鈉、鉀、鎂、鈣、鍶，製備所得觸媒材料使用X光粉末繞射儀（powder XRD）、拉曼光譜儀（Raman）、氮氣吸脫附儀 (BET method)、原子吸收光譜儀（AAS）、程溫脫附儀（CO2-TPD）、熱重分析儀（TGA）與場發式掃描電子顯微鏡（FE-SEM）等儀器鑑定，以觀察材料結構、組成與其表面形貌。
經批次的活性篩選測試結果顯示，使用鈦酸鈉與鈦酸鉀之碳酸甘油酯產率可高於50%，但其結構在反應後易衰退；鹼土族鈦酸鹽活性較差（產率普遍低於30%），但其反應後之結構相較前者穩定，而在鹼土族金屬鈦酸鹽類中摻入鹼金族金屬能保有其結構，並大幅度地改善甘油轉化率與碳酸甘油酯產率；以煅燒溫度攝氏700度、鈉：鈣莫爾比0.4：1.0之鈦酸鈣（命名為0.4Na-Ca-Ti-C700）作為觸媒，對甘油轉酯化反應之促進作用最大，推測其活性位置可能來自於煅燒過程中形成的鈉物質。吾人更進一步由催化反應參數－時間、溫度、反應物比例及觸媒添加量尋求最適化之反應條件。取用0.200克之0.4Na-Ca-Ti-C700投入至含有碳酸二甲酯/甘油莫爾比為 4.0之批次反應器，於攝氏75度下反應 2 小時，可獲得產率高達91% 之碳酸甘油酯與93%之甘油轉化率，對碳酸甘油酯之選擇率為98%。 | zh_TW |
| dc.description.abstract | The valorization of surplus glycerol produced from biodiesel industry has become a prosperous issue in the application of heterogeneous catalysts. Herein, we designed a series of novel titanate catalysts for the synthesis of glycerol carbonate from glycerol. The titanates catalysts were prepared via the sol-gel method using polymeric citrate complex route (i.e. Pechini method), and they were evaluated for the transesterification of glycerol with dimethyl carbonate in a batch system. These titanate catalysts were characterized by powder XRD, Raman, AAS, N2 physical adsorption (BET method), temperature-programmed desorption of CO2 (CO2-TPD), TGA, and FE-SEM. The findings in the screening test indicate that applying sodium titanate and potassium titanates obtained YGLC of more than 50%; however, the structures of them were relatively unstable. Moreover, it was revealed that the activity of alkaline metal (Mg, Ca, Sr) titanates with additions of alkali metal (Li, Na, K) were highly improved on the conversion of glycerol (XGLY) and the yield of GLC (YGLC). The sodium promoted calcium titanate with a molar ratio of Na/Ca = 0.4 designated 0.4Na-Ca-Ti-C700 demonstrates the best promotion effect. The active sites might be attributed to the sodium species formed during calcination. The influence of the reaction time, temperature, the molar ratio of reactants (DMC/GLY), and calcination temperature on the catalytic activity of 0.4Na-Ca-Ti-C700 were investigated. The optimized result shows that under the condition of time = 2h, temperature = 75 °C, the molar ratio of DMC/GLY = 4, and amount of catalyst = 0.200 g, the YGLC of ca. 91%, XGLY of 93%, and selectivity of 98% toward GLC were achieved over 0.4Na-Ca-Ti-C700. | en |
| dc.description.provenance | Made available in DSpace on 2021-07-10T21:52:17Z (GMT). No. of bitstreams: 1 ntu-108-R06524086-1.pdf: 9427762 bytes, checksum: eacb2f498f824984f578557d8749ee6f (MD5) Previous issue date: 2019 | en |
| dc.description.tableofcontents | 口試委員會審定書 I
致謝 II 中文摘要 III Abstract IV Table of Contents V List of Figures IX List of Tables XVI Chapter 1 Introduction 1 1.1 Research background 1 1.2 Glycerol: the platform molecule 3 1.2.1 Glycerol Carbonate: a versatile chemical 4 1.2.2 Synthetic strategy of glycerol carbonate 5 1.3 Catalytic mechanism 10 1.3.1 Base-catalysed reaction of glycerol 10 1.3.2 The side reaction: decomposition of glycerol carbonate 11 1.4 Catalyst Development of glycerol transesterification 13 1.4.1 Homogeneous catalyst 13 1.4.2 Heterogeneous catalyst 13 1.4.3 Titanate catalysts 17 1.5 Sol-Gel method 20 Chapter 2 Experimental section 28 2.1 Chemicals 28 2.2 Instruments 29 2.3 Preparation of catalysts: polymeric complex method 30 2.4 Characterization of catalysts 34 2.4.1 Powder X-ray diffraction (powder XRD) 34 2.4.2 Raman spectroscopy 36 2.4.3 Atomic absorption spectroscopy (AAS) 40 2.4.4 Scanning Electron Microscopy (SEM) 40 2.4.5 BET specific surface area 41 2.4.6 Temperature-programmed desorption of CO2 (CO2-TPD) 42 2.4.7 Thermogravimetric Analysis (TGA) 44 2.5 Catalytic testing 46 2.5.1 Screening test (condition: temperature = 75 °C, time = 2 h, amount of catalyst = 0.200 g, molar ratio of DMC/GLY = 4) 46 2.5.2 Optimized study (catalyst: 0.4Na-Ca-Ti-C600, 700, 800) 47 2.6 Product analysis: gas chromatography 49 Chapter 3 Results and discussion 56 3.1 Alkali titanates 56 3.1.1 Activity & reusability of catalyst 56 3.1.2 AAS 57 3.1.3 Powder XRD 58 3.1.4 Raman spectroscopy 62 3.1.5 FE-SEM 67 3.2 Alkaline titanates 70 3.2.1 Activity test 70 3.2.2 Powder XRD 70 3.2.3 Raman spectroscopy 74 3.3 Influence of alkali addition onto Magnesium titanate 77 3.3.1 Activity test 77 3.3.2 Powder XRD 77 3.3.3 Raman spectroscopy 80 3.4 Influence of alkali addition onto Calcium titanate 82 3.4.1 Activity test 82 3.4.2 Powder XRD 83 3.4.3 CO2–TPD of 0.8Na-Ca-Ti-C800 86 3.4.4 TGA-DTA of 0.8Na-Ca-Ti-C800 87 3.5 Influence of alkali addition onto Strontium titanate 88 3.5.1 Activity test & reusability of catalyst 88 3.5.2 AAS 89 3.5.3 Powder XRD 90 3.5.4 Raman spectroscopy 93 3.6 Effect of calcination temperature on the precursor of 0.4Na-Ca-Ti-CX00 95 3.6.1 Activity & reusability of catalyst 95 3.6.2 AAS 96 3.6.3 Powder XRD 97 3.6.4 Raman spectroscopy 99 3.6.5 FE-SEM 100 3.7 Optimization: effect of reaction temperature 102 3.8 Optimization: effect of reaction time 104 3.9 Optimization: effect of DMC-to-GLY molar ratio 106 3.10 Optimization: effect of catalyst amount 108 Chapter 4 Concluding remark 110 4.1 Conclusion 110 4.2 Future work 111 Supplements 112 References 115 | - |
| dc.language.iso | en | - |
| dc.title | 以溶膠－凝膠法製備鈦酸鹽類及其在碳酸甘油酯合成之應用 | zh_TW |
| dc.title | Preparation of Titanates via Sol-Gel Method and Its Application to the Synthesis of Glycerol Carbonate | en |
| dc.type | Thesis | - |
| dc.date.schoolyear | 107-2 | - |
| dc.description.degree | 碩士 | - |
| dc.contributor.oralexamcommittee | 林進榮;龔仲偉 | zh_TW |
| dc.contributor.oralexamcommittee | Chin-Jung Lin;Chung-Wei Kung | en |
| dc.subject.keyword | 甘油轉酯化,碳酸甘油酯,溶膠-凝膠法,異相觸媒,鈦酸鹽類, | zh_TW |
| dc.subject.keyword | transesterification of glycerol,glycerol carbonate,sol-gel method,Pechini method,heterogeneous catalyst,titanates, | en |
| dc.relation.page | 124 | - |
| dc.identifier.doi | 10.6342/NTU201902515 | - |
| dc.rights.note | 未授權 | - |
| dc.date.accepted | 2019-08-14 | - |
| dc.contributor.author-college | 工學院 | - |
| dc.contributor.author-dept | 化學工程學系 | - |
| 顯示於系所單位： | 化學工程學系 | |
文件中的檔案：
| 檔案 | 大小 | 格式 | |
|---|---|---|---|
| ntu-107-2.pdf 目前未授權公開取用 | 9.21 MB | Adobe PDF |
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