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http://tdr.lib.ntu.edu.tw/jspui/handle/123456789/102175完整後設資料紀錄
| DC 欄位 | 值 | 語言 |
|---|---|---|
| dc.contributor.advisor | 吳嘉文 | zh_TW |
| dc.contributor.advisor | Kevin C.-W. Wu | en |
| dc.contributor.author | 裴越方 | zh_TW |
| dc.contributor.author | Viet Phuong Bui | en |
| dc.date.accessioned | 2026-03-18T16:08:28Z | - |
| dc.date.available | 2026-03-19 | - |
| dc.date.copyright | 2026-03-18 | - |
| dc.date.issued | 2026 | - |
| dc.date.submitted | 2026-01-06 | - |
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| dc.identifier.uri | http://tdr.lib.ntu.edu.tw/jspui/handle/123456789/102175 | - |
| dc.description.abstract | 本研究提出了一種整合性策略，利用深共晶溶劑 (Deep Eutectic Solvents, DESs) 實現稻殼 (Rice Husk) 的高值化利用，以高效且環境友善的方式提取二氧化矽 (SiO2) 與木質素。本研究透過調控溫度與時間參數，對提取製程進行了系統性的最佳化。分離所得之木質素與 SiO2 經由 XRD、FT-IR、TGA 及 SEM 等技術進行了詳盡的材料特性分析。回收之非晶質 SiO2 隨後作為載體，利用起始濕潤含浸法 (incipient wetness impregnation method) 合成 NiZn/SiO2 雙金屬合金觸媒。綜合鑑定分析 (XRD、XPS、HR-TEM、XAS, ICP-OES) 證實了 NiZn 合金的成功形成及其優異的物理化學性質。隨後，本研究在溫和反應條件 (220 °C, 6 小時) 下，以甲酸作為原位 (in-situ) 氫源，評估 NiZn/SiO2 觸媒對商業木質素及稻殼衍生木質素之催化液化效能。經 GC-MS 分析證實，該催化系統展現卓越效能，THF 可溶性木質素油產率達 80.2 wt%，並對香草醛 (47.5%) 及其衍生物 (32.4%) 具有極佳的選擇性。藉由 2D-HSQC NMR 光譜輔助之反應機制探討顯示了顯著的結構變化，包括位於 δH/δC = 9.7/191.3 ppm 處明顯的香草醛醛基 (-CHO) 訊號峰。實驗結果顯示 Ni 與 Zn 之間存在協同效應：Zn 透過氧原子的孤對電子增強了木質素的吸附並促進 Cα-Cβ 鍵的弱化，而 Ni 則促進醚鍵的催化斷裂。此外，甲酸在反應中同時扮演水解助觸媒與氫氣來源的角色。本研究為稻殼的綜合利用提供了一種永續途徑，成功將其主要成分轉化為高附加價值產品。 | zh_TW |
| dc.description.abstract | This study presents an integrated strategy for the valorization of rice husk by employing Deep Eutectic Solvents (DESs) for the efficient and environmentally benign extraction of silica (SiO2) and lignin. The extraction process was systematically optimized by varying temperature and time. The isolated lignin and SiO2 were thoroughly characterized using XRD, FT-IR, TGA, and SEM. The recovered amorphous SiO2 was then utilized as a support for the synthesis of NiZn/SiO2 bimetallic alloy catalyst via the incipient wetness impregnation method. Comprehensive characterization (XRD, XPS, HR-TEM, XAS, and ICP-OES) confirmed the successful formation of the NiZn alloy and its favorable physicochemical properties. The NiZn/SiO2 catalyst was subsequently evaluated for the catalytic liquefaction of both commercial and rice husk-derived lignin, using formic acid as an in-situ hydrogen source under mild conditions (220 °C, 6 h). The catalytic system exhibited high performance, achieving an 80.2 wt% yield of THF-soluble lignin-oil with remarkable selectivity towards vanillin (47.5%) and its derivatives (32.4%), as confirmed by GC-MS analysis. Mechanistic investigations, supported by 2D-HSQC NMR spectroscopy, revealed significant structural changes, including a prominent vanillin-CHO peak at δH/δC = 9.7/191.3 ppm. The results suggest a synergistic effect between Ni and Zn; Zn enhances lignin adsorption via oxygen lone pairs and promotes Cα-Cβ bond weakening, while Ni facilitates catalytic ether bond cleavage. Additionally, formic acid acts as a hydrolytic co-catalyst and H2 source. This work provides a sustainable approach for the comprehensive utilization of rice husk, converting its major components into high-value products. | en |
| dc.description.provenance | Submitted by admin ntu (admin@lib.ntu.edu.tw) on 2026-03-18T16:08:28Z No. of bitstreams: 0 | en |
| dc.description.provenance | Made available in DSpace on 2026-03-18T16:08:28Z (GMT). No. of bitstreams: 0 | en |
| dc.description.tableofcontents | ACKNOWLEDGEMENTS I
摘要 III ABSTRACT IV TABLE OF CONTENTS VI LIST OF FIGURES XI LIST OF TABLES XV CHAPTER 1. INTRODUCTION 1 1. Lignocellulosic biomass and biorefinery concept 1 1.1.1 The shift from a fossil-based to a bio-based economy 1 1.1.2 Lignocellulosic biomass as a sustainable feedstock 2 1.2 Rice husk: a unique agro-waste resource 3 1.2.1 Rice production and rice husk waste 3 1.2.2 Compositional uniqueness: the lignocellulosic-silica matrix 6 1.2.3 Integrated biorefinery concept for rice husk 7 1.3 Advanced pretreatment and extraction strategies 8 1.3.1 Limitations of conventional fractionation methods 8 1.3.2 Evolution of green solvents: from Ionic Liquids to Deep Eutectic Solvents 9 1.3.3 DES-mediated extraction of lignin and silica 10 1.4 Lignin valorization to high-value aromatics 11 1.4.1 Vanillin: Market potential and biosynthetic heritage 11 1.4.2 Challenges in selective lignin depolymerization 12 1.5 Heterogeneous catalysis for biomass conversion 13 1.5.1 Transition metal catalysts (Ni-based system) 14 1.5.2 Alloy catalyst 14 1.5.3 Formic acid as in-situ hydrogen source 15 CHAPTER 2. LITERATURE REVIEW 17 2.1 Deep eutectic solvent (DES) in biomass fractionation 17 2.1.1 Physicochemical properties and tunability 17 2.1.2 Mechanism of lignin dissolution and cleavage 18 2.1.3 Factors affecting fractionation efficiency 19 2.2 Catalytic liquefaction strategies for lignin 20 2.2.1 Oxidative vs reductive depolymerization 20 2.2.2 Reductive depolymerization of lignin via transfer hydrogen 21 2.3 Design of heterogeneous catalysts 23 2.3.1 Ni-based catalysts in lignin valorization 23 2.3.2 Bimetallic synergy and electronic modulation 24 2.3.3 Support effect: the role of silica 24 2.4 Hydrogen donor systems (catalytic transfer hydrogenation – CTH) 25 2.4.1 Mechanism of formic acid decomposition 25 2.4.2 Advantages of CTH over molecular hydrogen 26 CHAPTER 3. OBJECTIVES 27 CHAPTER 4. EXPERIMENTAL 29 4.1 Chemicals and materials 29 4.2 DES synthesis and rice husk fractionation 30 4.2.1 Preparation of DES 30 4.2.2 Rice husk fractionation process 30 4.2.3 Separation and purification 31 4.3 Catalysts preparation 32 4.4 Liquefaction of lignin 33 4.4.1 Experimental setup and reaction procedure 33 4.4.2 Product recovery 34 4.5 Characterization techniques 35 4.5.1 X-ray Diffractometer (XRD) 35 4.5.2 Fourier-transform infrared spectroscopy (FTIR) 36 4.5.3 Differential scanning calorimetry/thermogravimetry (DSC/TGA) 37 4.5.4 Nuclear magnetic resonance (NMR) 37 4.5.5 Field emission scanning electron microscope (FE-SEM) 38 4.5.6 Field emission transmission electron microscopy (FE-TEM) 38 4.5.7 X-ray Photoelectron Spectroscopy (XPS) 39 4.5.8 X-ray Absorption Spectroscopy (XAS) 40 4.5.9 Inductively Coupled Plasma - Optical Emission Spectroscopy (ICP-OES) 41 4.5.10 Gas Chromatography-Mass Spectrometer (GC-MS) 41 CHAPTER 5. RESULTS AND DISCUSSION 43 5.1 Optimization of extraction conditions 43 5.1.1 Effect of DES molar ratio 43 5.1.2 Effect of extraction temperature 44 5.1.3 Effect of extraction time 45 5.1.4 Effect of ratio between rice husk and DES 47 5.2 Characterization of the extracted silica and lignin 48 5.2.1 Structure of extracted lignin 48 5.2.2 Properties of recovered silica 50 5.3 Synthesis and characterization of NiZn/SiO2 catalysts 51 5.3.1 Crystalline Structure (XRD) 51 5.3.2 Surface chemistry and electronic state (XPS) 53 5.3.3 Morphology and distribution (TEM/EDS) 56 5.3.4 X-ray absorption spectroscopy (XAS) 57 5.4 Catalytic liquefaction of lignin 60 5.4.1 Catalyst screening 60 5.4.2 Optimization of reaction parameters 63 5.5 Comparison between different types of lignin 66 5.6 Bio-oils analysis 69 5.6.1 Product analysis by 2D HSQC NMR 69 5.6.2 Product analysis by FT-IR 72 5.7 Reusability of catalysts and role of formic acid 74 5.8 Proposed mechanism 77 CHAPTER 6. CONCLUSIONS 80 CHAPTER 7. FUTURE PROSPECT 82 REFERENCES 84 APPENDIX 107 | - |
| dc.language.iso | en | - |
| dc.subject | 稻殼 | - |
| dc.subject | 深共晶溶劑 | - |
| dc.subject | 生質油 | - |
| dc.subject | 香草醛 | - |
| dc.subject | 合金觸媒 | - |
| dc.subject | Rice husk | - |
| dc.subject | deep eutectic solvent | - |
| dc.subject | bio-oils | - |
| dc.subject | vanillin | - |
| dc.subject | alloy catalyst | - |
| dc.title | 稻殼之整合高值化利用：深共晶溶劑萃取木質素/二氧化矽及其經 NiZn/SiO2 催化液化製備具高香草醛選擇性之生物油 | zh_TW |
| dc.title | Integrated Valorization of Rice Husk: Deep Eutectic Solvent Extraction of Lignin/SiO2 and its NiZn/SiO2 Catalyzed Liquefaction to Bio-oil with High Vanillin Selectivity | en |
| dc.type | Thesis | - |
| dc.date.schoolyear | 114-1 | - |
| dc.description.degree | 碩士 | - |
| dc.contributor.oralexamcommittee | 神谷裕一;中島清隆 | zh_TW |
| dc.contributor.oralexamcommittee | Yuichi Kamiya;Kiyotaka Nakajima | en |
| dc.subject.keyword | 稻殼,深共晶溶劑生質油香草醛合金觸媒 | zh_TW |
| dc.subject.keyword | Rice husk,deep eutectic solventbio-oilsvanillinalloy catalyst | en |
| dc.relation.page | 109 | - |
| dc.identifier.doi | 10.6342/NTU202600029 | - |
| dc.rights.note | 同意授權(限校園內公開) | - |
| dc.date.accepted | 2026-01-06 | - |
| dc.contributor.author-college | 工學院 | - |
| dc.contributor.author-dept | 化學工程學系 | - |
| dc.date.embargo-lift | 2031-01-05 | - |
| 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-114-1.pdf 未授權公開取用 | 15.75 MB | Adobe PDF | 檢視/開啟 |
系統中的文件，除了特別指名其著作權條款之外，均受到著作權保護，並且保留所有的權利。