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http://tdr.lib.ntu.edu.tw/jspui/handle/123456789/88212完整後設資料紀錄
| DC 欄位 | 值 | 語言 |
|---|---|---|
| dc.contributor.advisor | 吳紀聖 | zh_TW |
| dc.contributor.advisor | Chi-Sheng Wu | en |
| dc.contributor.author | 胡芮齊 | zh_TW |
| dc.contributor.author | Jui-Chi Hu | en |
| dc.date.accessioned | 2023-08-08T16:48:16Z | - |
| dc.date.available | 2023-11-09 | - |
| dc.date.copyright | 2023-08-08 | - |
| dc.date.issued | 2023 | - |
| dc.date.submitted | 2023-07-20 | - |
| dc.identifier.citation | IEA (2022), Global Energy Review: CO2 Emissions in 2021, IEA, Paris 2021.
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| dc.identifier.uri | http://tdr.lib.ntu.edu.tw/jspui/handle/123456789/88212 | - |
| dc.description.abstract | 甲醇(CH3OH)是工業上廣泛使用的化學原料之一。由於它擁有高的氫碳比，並且在常溫下是以液態存在，因此在文獻中常被討論作為氫能載體。二氧化碳氫化產甲醇不僅可以將氫氣儲存為甲醇，又可以達到二氧化碳再利用的目的，是近年來備受矚目的研究之一。工業上生產甲醇是以合成氣作為原料，並使用Cu/ZnO/Al2O3觸媒，但是由於熱力學限制，此反應傾向在高壓(5-10 MPa)的環境下操作。再者，反應過程中水是不可避免的副產物，然而水的產生不僅會抑制甲醇的選擇率，還會加速Cu的氧化和ZnO的聚集而使觸媒失活。
本研究旨在探討以疏水性材料六方氮化硼(h-BN)作為銅鋅觸媒的載體，進行二氧化碳氫化反應產甲醇。h-BN會先利用超音波處理或modified Hummers’ method進行前處理以增加金屬的附著度，再將銅、鋅等金屬以沉積-沉澱法擔載於h-BN上。我們設計了不同的方法和合成參數，討論不同的 h-BN 前處理方法、觸媒合成方法、金屬擔載量和促進劑種類對觸媒活性的影響。催化反應在 230 oC 和 1.0 MPa下進行。結果顯示，相較於商用觸媒，所有以h-BN為載體的觸媒均表現出較高的甲醇選擇性，並且在本研究中40 wt% Cu/ZnO/La2O3加上 0.3 mol% Mg 擔載在經modified Hummers’ method修飾的 h-BN 上表現出最高的觸媒活性。在200 oC、1.0 MPa下，甲醇時空產率達到105 mgMeOH/gcat/hr。本研究應用XRD、SEM、EDS、H2-TPR、CO2-TPD、XPS和接觸角等儀器對觸媒物性進行量測，討論對活性測試結果的影響。並根據不同反應條件下的結果進行了反應動力學擬合分析。此外，我們還在工研院進行高壓反應測試，已確認了觸媒在高壓環境下有更佳的表現，以利於後續對於h-BN觸媒的開發。 | zh_TW |
| dc.description.abstract | Methanol (CH3OH) is widely used for industrial purposes as a common chemical feedstock. Because of its high hydrogen-to-carbon ratio and being liquid under ambient conditions, methanol is widely recommended as hydrogen energy carrier in literature. CO2 hydrogenation to methanol not only stores hydrogen as methanol but also achieves the purpose of CO2 recycling. Industrially, Cu/ZnO/Al2O3 catalyst is used in CO2 hydrogenation to methanol, which needs to be operated under very high pressure (5-10 MPa) from the thermodynamic point of view. In addition, water, an inevitable by-product during the reaction, not only decreases the methanol selectivity but also promotes the oxidation of Cu and the aggregation of ZnO, resulting in the deactivation of the catalyst.
In this study, we used hydrophobic material, hexagonal boron nitride (h-BN), as the support of Cu/ZnO catalyst for CO2 hydrogenation to methanol. h-BN was pretreated by sonication or modified Hummers method to increase the adhesion of metal oxide. Cu/Zn metals were loaded on h-BN by the deposition-precipitation method. We designed different procedures and loading parameters to synthesize catalysts, including h-BN pretreatment method, catalyst synthesis method, metal loading, and promoter. The reaction was carried out at 230 oC and 1 MPa. The result indicated that all catalysts using h-BN as support showed higher methanol selectivity compared with those by Al2O3 support. We found that the catalyst using 40 wt% Cu/ZnO/La2O3 with 0.3 mol% Mg loaded on h-BN pretreated with modified Hummers’ method showed the highest activity in this study. The space-time yield of methanol reached 105 mgMeOH/gcat/hr at 1.0 MPa and 200 oC. The instruments XRD, SEM, EDS, H2-TPR, CO2-TPD, XPS, and contact angle were applied to evaluate the characteristics of catalysts and explain the activity test results. Chemical kinetic analysis was conducted based on the results obtained under different reaction conditions. Furthermore, a high-pressure reaction was carried out at the Industrial Technology Research Institute (ITRI) to confirm the excellent catalyst performance under industrial high-pressure operation, thus worth the further development of h-BN supported catalysts. | en |
| dc.description.provenance | Submitted by admin ntu (admin@lib.ntu.edu.tw) on 2023-08-08T16:48:16Z No. of bitstreams: 0 | en |
| dc.description.provenance | Made available in DSpace on 2023-08-08T16:48:16Z (GMT). No. of bitstreams: 0 | en |
| dc.description.tableofcontents | 致謝 i
中文摘要 ii ABSTRACT iii CONTENTS v LIST OF FIGURES ix LIST OF TABLES xiii 第 1 章 緒論 1 1.1 前言 1 1.2 研究動機與目標 4 1.3 論文總覽 5 第 2 章 文獻回顧 6 2.1 二氧化碳氫化產甲醇 6 2.1.1 反應途徑 6 2.1.2 動力學模型 9 2.1.3 觸媒的失活 10 2.2 二氧化碳氫化產甲醇觸媒 11 2.2.1 銅基觸媒 11 2.2.2 混摻金屬 12 2.3 2D材料 13 2.3.1 六方氮化硼 (hexagonal boron nitrie, h-BN) 13 2.3.2 Hummers’ method 15 第 3 章 實驗方法 17 3.1 實驗方法實驗藥品與儀器設備介紹 17 3.1.1 實驗藥品 17 3.1.2 實驗氣體 19 3.1.3 儀器設備 20 3.2 觸媒製備 22 3.2.1 h-BN 前處理 22 3.2.2 沉積-沉澱法 (Deposition-precipitation method) 23 3.3 動力學分析 25 3.4 氣相層析儀 32 3.4.1 熱傳導式偵測器 (TCD) 32 3.4.2 火焰離子化檢測儀 (FID) 32 3.5 觸媒分析原理介紹 34 3.5.1 X光繞射儀 (X-ray Diffraction, XRD) 34 3.5.2 傅立葉轉換紅外線光譜儀(Fourier-transform infrared spectroscopy, FT-IR) 35 3.5.3 拉曼光譜儀 (Raman) 36 3.5.4 熱重分析儀 (Thermogravimetric analysis，TGA) 37 3.5.5 水接觸角 (Contact angle)量測儀 37 3.5.6 掃描式電子顯微鏡 (Scanning Electron Microscope, SEM) 38 3.5.7 比表面積與孔洞分布測量儀 (N2 adsorption) 40 3.5.8 化學吸附儀 (Chemisorption Analyzers) 41 3.5.9 X射線光電子能譜儀 (X-ray photoelectron spectroscopy, XPS) 44 3.6 檢量線製作 46 3.6.1 二氧化碳檢量線 (GC-TCD) 46 3.6.2 一氧化碳檢量線 (GC-TCD) 47 3.6.3 氫氣檢量線 (GC-TCD) 48 3.6.4 甲醇檢量線 (GC-FID) 49 3.7 實驗儀器架設 50 3.7.1 壓力反應系統 50 3.8 工研院高壓測試 52 3.8.1 工研院反應系統 52 第 4 章 觸媒製備與鑑定 53 4.1 六方氮化硼之結構分析 53 4.1.1 h-BN之XRD分析 53 4.1.2 h-BN之FTIR & Raman分析 54 4.1.3 h-BN之XPS 分析 55 4.1.4 h-BN之SEM 分析 57 4.1.5 h-BN之H2-TPR & CO2-TPD 分析 58 4.2 XRD結晶繞射分析 59 4.3 熱重分析儀分析 63 4.4 水接觸角分析 64 4.5 掃描式電子顯微分析 65 4.6 BET 比表面積分析 71 4.7 H2-TPR & CO2-TPD分析 73 4.8 N2O-oxidation分析 80 4.9 X射線光電子能譜分析 81 第 5 章 結果與討論 96 5.1 不含觸媒之空白測試 96 5.2 促進劑之影響 96 5.3 金屬擔載比例之影響 99 5.4 h-BN對二氧化碳氫化反應影響 101 5.5 壓力、流速、進料比及溫度對氫化反應之影響 104 5.5.1 壓力 104 5.5.2 總流速(GHSV) 106 5.5.3 進料比(H2/CO2) 107 5.5.4 溫度 109 5.6 動力學擬合分析結果 112 5.7 工研院高壓測試結果 114 5.7.1 溫度、壓力的影響(ITRI) 114 5.7.2 GHSV的影響(ITRI) 116 5.7.3 與實驗室測試結果比較 118 5.8 文獻比較 121 第 6 章 結論與未來展望 123 參考文獻 125 Supporting Information 135 個人小傳 137 LIST OF FIGURES Figure 1.1 1 CO2 emissions from energy combustion and industrial processes[1] 1 Figure 1.1 2 Conversion of methanol into ethylene (or propylene) [2] 3 Figure 2.1 1 Possible reaction pathways of CO2 hydrogenation to CO, CH3OH, and CH4. *(X) indicates adsorbed species [16] 7 Figure 2.1 2 Mechanism of methanol synthesis and the formate route.[19] 8 Figure 2.1 3 Overview of the experimental temperature and pressure ranges used for fitting the kinetic models[22] of Graaf et al.[20], Vanden Bussche and Froment[21], Ma et al.[23], Seidel et al.[24] and Villa et al.[25]. 10 Figure 2.3 1 Structure of h-BN 14 Figure 2.3 2 Summary of chemical functionalization strategies of h-BN[44] 15 Figure 2.3 3 Modified Hummers' Method Mechanism 16 Figure 3.2 1 Procedure of probe sonication 22 Figure 3.2 2 Procedure of modified Hummers’ method 23 Figure 3.2 3 Procedure of deposition-precipitation method 24 Figure 3.2 4 Procedure of Cu/ZnO catalyst synthesis 25 Figure 3.5 1 Illustration of diffraction of X-rays by a crystal. [53] 34 Figure 3.5 2 Schematic of a sessile-drop contact angle system.[54] 38 Figure 3.5 3 Signals generated when a high-energy beam of electrons 39 Figure 3.5 4 Schematic of the different states in the gas adsorption[56] 41 Figure 3.5 5 Schematic of the interaction of an X-ray photon 45 Figure 3.6 1 Calibration line of CO2 46 Figure 3.6 2 Calibration line of CO 47 Figure 3.6 3 Calibration line of H2 48 Figure 3.6 4 Calibration line of CH3OH 49 Figure 3.7 1 Experiment setup 50 Figure 4.1 1 XRD pattern of pristine hBN and h-BN_H 53 Figure 4.1 2 (a) Raman spectra of h-BN and h-BN_H 54 Figure 4.1 3 FTIR spectra of h-BN and h-BN_H 55 Figure 4.1 4 XPS survey scan pattern of h-BN & h-BN_H 56 Figure 4.1 5 XPS survey scan pattern of B 1s of h-BN_H 56 Figure 4.1 6 SEM images of the hBN structure 57 Figure 4.1 7 SEM images of the hBN(Hummers’) structure 57 Figure 4.1 8 H2-TPR profile of h-BN 58 Figure 4.1 9 CO2-TPD profile of h-BN 58 Figure 4.2 1 XRD pattern of different wt% 3MgCZLa loading on h-BN 59 Figure 4.2 2 XRD pattern of fresh 30wt% 3MgCZM-hBN (M = La, Ga, Zr, Al) 60 Figure 4.2 3 XRD pattern of fresh 40wt% 3MgCZLa-hBN (Hummers’, soni., Non.) 61 Figure 4.2 4 XRD pattern of H2 reduced different wt% 3MgCZLa loading on h-BN 61 Figure 4.2 5 XRD pattern of H2 reduced 62 Figure 4.2 6 XRD pattern of H2 reduced 62 Figure 4.3 1 TGA result of h-BN catalyst with different pretreatment 63 Figure 4.4 1 Contact angle of commercial catalyst 64 Figure 4.4 2 Contact angle of (a) 3MgCZLa, 64 Figure 4.5 1 SEM images of 40 wt% 3MgCZLa-hBN(Non.) 66 Figure 4.5 2 SEM images of 40 wt% 3MgCZLa-hBN(soni.) 66 Figure 4.5 3 SEM images of 40 wt% 3MgCZLa-hBN(Hummers’) 67 Figure 4.5 4 SEM image of 40 wt% 3MgCZLa-hBN(Hummers’) 67 Figure 4.5 5 SEM-EDS of 40 wt% 3MgCZLa-hBN(Non.) 69 Figure 4.5 6 SEM-EDS of 40 wt% 3MgCZLa-hBN(soni.) 70 Figure 4.5 7 SEM-EDS of 40 wt% 3MgCZLa-hBN(Hummers’) 70 Figure 4.7 1 H2-TPR profiles of 30wt% CZM-hBN (M = La, Ga, Zr, Al) 74 Figure 4.7 2 Sketch of the reduced catalysts 76 Figure 4.7 3 CO2-TPD profiles of 30wt% 3MgCZM-hBN 76 Figure 4.7 4 H2-TPR profiles of 40wt% 3MgCZLa-hBN 78 Figure 4.7 5 CO2-TPD profiles of 40wt% 3MgCZLa-hBN 79 Figure 4.9 1 XPS survey scan pattern of 82 Figure 4.9 2 XPS Cu 2p pattern of 30wt% 3MgCZM-hBN (M = La, Ga, Zr, Al) 83 Figure 4.9 3 XPS Zn 2p pattern of 30wt% 3MgCZM-hBN (M = La, Ga, Zr, Al) 84 Figure 4.9 4 XPS O 1s pattern of 30wt% 3MgCZM-hBN (M = La, Ga, Zr, Al) 85 Figure 4.9 5 XPS analysis of 30wt% 3MgCZM-hBN (M = La, Ga, Zr, Al) 86 Figure 4.9 6 XPS survey scan pattern of 40wt% 3MgCZLa-hBN 89 Figure 4.9 7 XPS Cu 2p pattern of 40wt% 3MgCZLa-hBN 90 Figure 4.9 8 XPS Cu LMM pattern of 40wt% 3MgCZLa-hBN 90 Figure 4.9 9 XPS Zn 2p pattern of 40wt% 3MgCZLa-hBN 91 Figure 4.9 10 XPS Zn LMM pattern of 40wt% 3MgCZLa-hBN 92 Figure 4.9 11 XPS O 1s pattern of 40wt% 3MgCZLa-hBN 93 Figure 4.9 12 XPS La 3d pattern of 40wt% 3MgCZLa-hBN 94 Figure 5.2 1 Time on stream of 3MgCZM loading on h-BN (M = Al、La、Ga、Zr) 97 Figure 5.2 2 3MgCZM loading on h-BN (M = Al、La、Ga、Zr) 97 Figure 5.2 3 The relationship between the CO2 conversion and 98 Figure 5.2 4 The relationship between the MeOH selectivity and the CO2-TPD proportion of basic sites γ 99 Figure 5.3 1 Time on stream of different wt% of 3MgCZLa 100 Figure 5.3 2 Different wt% of 3MgCZLa loading on sonicated h-BN 101 Figure 5.4 1 Time on stream of 30 wt% 3MgCZLa-hBN 103 Figure 5.4 2 Time on stream of 40 wt% 3MgCZLa-hBN 103 Figure 5.4 3 Performance of 30-40 wt% 3MgCZLa-hBN 104 Figure 5.5 1 Pressure effect on methanol STY of 40% 3MgCZLa(CP)-hBN(Hummers') 106 Figure 5.5 2 GHSV effect of 40% 3MgCZLa(CP)-hBN(Hummers') 107 Figure 5.5 3 Influence of inlet flow H2/CO2 ratio on 40% 3MgCZLa-hBN(Hummers') 108 Figure 5.5 4 Temperature effect on 40% 3MgCZLa-hBN(Hummers') 109 Figure 5.5 5 Arrhenius plot for CO2 hydrogenation to methanol and the RWGS reaction over 40% 3MgCZLa-hBN(Hummers') 112 Figure 5.6 1 Parity plot representing the accuracy of the parameter estimation for four outlet molar fraction. 113 Figure 5.7 1 Temperature and pressure effect on CO2 conversion in ITRI 115 Figure 5.7 2 Temperature and pressure effect on MeOH selectivity in ITRI 115 Figure 5.7 3 Temperature and pressure effect on space time yield in ITRI 116 Figure 5.7 4 GHSV effect on CO2 conversion in ITRI 117 Figure 5.7 5 GHSV effect on MeOH selectivity in ITRI 117 Figure 5.7 6 GHSV effect on space time yield in ITRI 118 Figure 5.7 7 Arrhenius plot for CO2 hydrogenation to methanol and the RWGS reaction in ITRI test 119 LIST OF TABLES Table 1 1 Main chemicals products industrially produced from CO2 [4] 2 Table 3 1 Equilibrium constant of all the reactions[20] 28 Table 3 2 Adsorption constant from Graaf et al.[20] 29 Table 3 3 Kinetic constant of all the reactions[20] 30 Table 3 4 Thermal conductivity of different gases[57] 42 Table 4 1 BET surface area of different metal loading on h-BN 71 Table 4 2 BET surface area of different promoter 72 Table 4 3 BET surface area of h-BN and 72 Table 4 4 BET surface area of h-BN catalyst 73 Table 4 5 The H2-TPR results of 30wt% CZM-hBN (M = La, Ga, Zr, Al) 74 Table 4 6 The CO2-TPD results of 30wt% CZM-hBN (M = La, Ga, Zr, Al) 77 Table 4 7 The H2-TPR results of 40wt% 3MgCZLa-hBN (a) Non., (b) soni., (c) Hummers’ 78 Table 4 8 The CO2-TPD results of 40wt% 3MgCZLa-hBN (a) Non., (b) soni., (c) Hummers’ 80 Table 4 9 Textural properties of h-BN catalys with different pretreatment 81 Table 4 10 Oxygen vacancy ratio of the catalysts estimated by XPS. 85 Table 4 11 XPS parameters of 30wt% 3MgCZM-hBN (M = La, Ga, Zr, Al) 87 Table 4 12 Element composition of of 30wt% 3MgCZM-hBN (M = La, Ga, Zr, Al) calculated by XPS 88 Table 4 13 Surface atomic ratio of the catalysts estimated by XPS. 93 Table 4 14 XPS parameters of 40wt% 3MgCZLa-hBN catalyst 94 Table 4 15 Element composition of 40wt% 3MgCZLa-hBN calculated by XPS 95 Table 5 1 Catalyst performance under 1.0 MPa and atmosphere 105 Table 5 2 Activation energies of Cu-based catalysts in different reaction conditions.[3] 110 Table 5 3 Activation energies of methanol synthesis and RWGS reactions. 111 Table 5 4 Pre-exponential factor estimated by fitting 114 Table 5 5 Data of 40% 3MgCZLa-hBN(Hummers') in different system. 118 Table 5 6 Activation energies of 40% 3MgCZLa-hBN(Hummers') in different reaction conditions. 120 Table 5 7 Summary of catalytic performances in this study and literatures 121 | - |
| dc.language.iso | zh_TW | - |
| dc.subject | 疏水性 | zh_TW |
| dc.subject | 二氧化碳氫化 | zh_TW |
| dc.subject | 甲醇 | zh_TW |
| dc.subject | 氮化硼 | zh_TW |
| dc.subject | 銅鋅觸媒 | zh_TW |
| dc.subject | Methanol | en |
| dc.subject | CO2 hydrogenation | en |
| dc.subject | Cu/ZnO catalyst | en |
| dc.subject | Hydrophobic | en |
| dc.subject | Boron Nitride | en |
| dc.title | 疏水性材料六方氮化硼擔載Cu/ZnO應用於二氧化碳氫化產甲醇 | zh_TW |
| dc.title | Hydrophobic h-BN Supported Cu/ZnO for CO2 Hydrogenation to Methanol | en |
| dc.type | Thesis | - |
| dc.date.schoolyear | 111-2 | - |
| dc.description.degree | 碩士 | - |
| dc.contributor.oralexamcommittee | 雷敏宏;游文岳 | zh_TW |
| dc.contributor.oralexamcommittee | Min-Hon Rei;Wen-Yueh Yu | en |
| dc.subject.keyword | 二氧化碳氫化,甲醇,氮化硼,疏水性,銅鋅觸媒, | zh_TW |
| dc.subject.keyword | CO2 hydrogenation,Methanol,Boron Nitride,Hydrophobic,Cu/ZnO catalyst, | en |
| dc.relation.page | 137 | - |
| dc.identifier.doi | 10.6342/NTU202301646 | - |
| dc.rights.note | 同意授權(限校園內公開) | - |
| dc.date.accepted | 2023-07-21 | - |
| dc.contributor.author-college | 工學院 | - |
| dc.contributor.author-dept | 化學工程學系 | - |
| dc.date.embargo-lift | 2028-07-17 | - |
| 顯示於系所單位： | 化學工程學系 | |
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