臺灣博碩士論文加值系統

本研究利用水熱法於120 oC下成功製備以鈣基為主並具有混合金屬鎂、鋁成份的有機金屬骨架Ca-Mg/Al-MOF，並利用其結構的多孔性與元素的均一分布，在經過高溫(600 oC)鍛燒後，生成具多孔性之氧化鈣基奈米材料捕獲劑。研究內容探討不同成份及不同反應條件所合成而得的Ca-Mg-MOF及Ca-Mg/Al-MOF在高溫(700 oC)二氧化碳捕獲之效能提升結果及原因。其中以XRD及FTIR鑑定其特徵結構及鍵結、透過SEM與EDS觀察形貌與元素分布，並搭配XPS進一步的驗證結構，而粉體之熱性質捕獲效能則藉由TGA測試。第一部分以雙金屬成份Ca-Mg-MOF為主，改變不同金屬比例、不同合成時間、溫度，觀察其生成機制並調控最可終成份及顆粒大小。由MOF為前驅物得到的純鈣成份捕獲劑之捕獲量高達74 wt%，相當接近理論值(78 wt%)，然而經多次吸脫附過程其效能於第十個迴圈降至45 wt%，整體維持率僅61%。透過惰性材料的添加，此現象可顯著改善，在最佳化條件下，總金屬鈣含量85 mole%之85-Ca-Mg-MOF具有適中的鎂量可改變整體形貌之顆粒大小，有利於提高後續之有效反應面積，在鍛燒後生成的抗劣化相成份MgO可防止由CaO聚集而造成的劣化，進而提升整體捕獲效能，於第十個迴圈後仍有61 wt%的捕獲量，整體維持率為95%。第二部分以鋁部份取代鎂合成Ca-Mg/Al-MOF。經過十個二氧化碳吸脫附捕獲迴圈之維持率可達97%，並可提升吸附過程的反應動力；然而，過高含量的鋁將造成有效鈣量的下降而使捕獲量降低。故再經由合成不同鎂、鋁含量之前驅物，本研究發現當將其含量降至總金屬之3 mole%，可得到具有最佳效能之捕獲劑C97-2.5M/0.5A-MOF-O，推測是由於此含量可使結構中之鈣、鎂、鋁三成分之作用最佳化，於100個二氧化碳吸脫附迴圈可達到相當優異之捕獲量71 wt%，並具有良好的整體維持率77%。

In this study, Ca-based mixed-metal metal organic framework (Ca-Mg/Al-MOF) has been designed as precursor material for carbon dioxide (CO2) capture in order to enhance the CO2 capture capacity and stability during multiple carbonation-calcination cycles. The Ca-Mg/Al-MOFs were constructed from self-assembly of metal ions and organic ligands to make metal ions uniformly distributed through the whole structure. The mixed-metal Ca-Mg/Al-MOF nanoparticles were successfully synthesized through hydrothermal method. Upon heat treatment at 600 oC, the Ca-based mixed-metal Ca-Mg/Al-MOF would gradually transform to CaO and MgO nanoparticles along with the amorphous aluminum oxide distributed in the CaO matrix to prevent the sorbents from degradation. PXRD, FTIR and SEM were used to identify the structure and characterize the morphology. The CO2 capture capacity and multiple carbonation-calcination cyclic tests were performed by TGA.
In the first part of the study, we investigated the structure properties of binary x-Ca-Mg-MOFs with different Ca2+/Mg2+ ratios at various reaction temperature and time. The 85-Ca-Mg-MOF synthesized at 120 oC for 18 hr have displayed the most optimal CO2 adsorption behavior. The single metal component Ca-MOF sorbent have the highest CO2 capture capacity up to 72 wt%, but a lower stability of 61% due to severe particle aggregation. In contrast, the capture capacity of 85-Ca-Mg-MOF sorbent was slightly decreased to 61 wt%, but the stability was dramatically promoted to 95%.
In the second part, ternary mixed-metal 85-Ca-Mgx/Al15-x MOFs were synthesized and it was found that the CO2 capture stability can be further improved to 98%. Moreover, through tailoring the Mg/Al ratios and total contents, C97-2.5M/0.5A-MOF-O showed the best performance, not only having the high stability of ~97% but also maintaining the highest capacity of 71 wt%. The above results revealed that by choosing MOF material as sorbent precursor and altering its compositions deliberately, successful promotion in efficient multiple carbonation-calcination CO2 uptake cycles can be achieved. The concept of using Ca-based MOF materials combined with mixed-metal ions for CO2 capture showed potential route for breaking the limitation of conventional CO2 capture sorbents.

摘要 I
Abstract III
誌謝 V
Table of Contents VI
List of Figures VIII
List of Tables XIII
Chapter 1 Introduction 1
Chapter 2 Literatures Review 4
2-1 Greenhouse Gas Emission and Global Warming 4
2-2 Carbon Capture and Sequestration 6
2-3 Capture Methods and Porous Sorbent Materials 8
2-3.1 Low-temperature CO2 Capture Sorbents 8
2-3.2 Intermediate-temperature CO2 Capture Sorbents 12
2-3.3 High-temperature CO2 Capture Sorbents 13
2-4 Metal-Organic Framework 17
2-4.1 General Structure Properties and Composition 17
2-4.2 Synthesis Routes 21
2-4.3 Applications 22
Chapter 3 Materials and Experiment Method 25
3-1 Materials 25
3-2 Method 25
3-3 Characterization 26
Chapter 4 Binary Ca-Mg Metal-Organic Framework as Precursor Material for CaO-based Sorbent in CO2 Capture 29
4-1 Characterizations of Ca-Mg Mixed-Metal MOF Structures and Properties 29
4-1.1 Different Metal Ratios of the Mixed-Metal x-Ca-Mg-MOFs 29
4-1.2 Different Reaction Times of the Mixed-Metal 85-Ca-Mg-MOFs 34
4-1.3 Different Reaction Temperatures of the Mixed-Metal 85-Ca-Mg-MOFs 38
4-2 Formation Mechanism of Mixed-Metal x-Ca-Mg MOFs 42
4-3 High-Temperature CO2 Capture and Carbonation-Calcination Cyclic Performance 46
4-3.1 Effect of Different Ca/Mg Ratios 46
4-3.2 Effect of Different Reaction Times and Temperatures 53
Chapter 5 Multi-Metals Ca-Mg/Al Metal-Organic Framework as Precursor Material for CaO-based Sorbent in CO2 Capture Efficiency Enhancement 57
5-1 Different Mg, Al ratios of Mixed-Metal 85-Ca-Mg/Al-MOFs 57
5-2 High-Temperature CO2 Capture and Carbonation-Calcination Cyclic Performance63
5-2.1 The Effect of Mg/Al ratios 63
5-2.2 The Effect of Mg/Al contents 69
5-2.3 Long-term CO2 Carbonation-Calcination Cyclic Performances 75
Chapter 6 Conclusion 78
Chapter 7 Reference 80

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