臺灣博碩士論文加值系統

溫室效應為近年來氣候變遷的主因，溫室氣體中以二氧化碳的影響為最大宗，在國際能源局(International Energy Agency，IEA)對二氧化碳的減排技術當中，以「碳捕獲與封存技術(Carbon dioxide capture and storage，CCS)」最可降低目前大氣中之二氧化碳濃度，然而將捕獲之二氧化碳除了進行地底封存以外，更能轉變成為綠色化學品，其中以二氧化碳與環氧化物之環加成反應研究最為多元，因其產物可作為多項高分子材料之中間體，但由於其為一催化反應，所以觸媒的選用相當重要，為了能夠簡化反應後之分離程序，本研究將以開發異相觸媒為首要考量。於過去研究中，若觸媒與環氧化物間有氫鍵的產生，將有助於觸媒之效能，因此本實驗以旋轉盤反應器製備氫氧化鎂，希望其可與環氧化物間產生氫鍵，有助於環加成反應。超重力系統在製備奈米材料的研究上已發展多年，其設備特性為體積小、反應時間短，在高重力場下增加了質傳效率且能運用於連續操作程序，與水熱法、溶膠凝膠法等高耗能、耗時的批次實驗方法相比，較易於工業上發展。
本研究以旋轉盤反應器，利用氯化鎂與氫氧化鈉水溶液製備氫氧化鎂粒子，將實驗參數固定為：氯化鎂與氫氧化鈉莫耳比1：2、旋轉盤轉速2500rpm、液體流率0.28L/min，探討氯化鎂水溶液濃度改變對氫氧化鎂粒子的影響，並將氫氧化鎂粒子作為二氧化碳與環氧丙烷之環加成反應觸媒，研究反應溫度、反應壓力、反應時間對環加成反應之影響。其實驗結果顯示，以0.5M之氯化鎂水溶液所製備而成的氫氧化鎂粒子有著293.1m2/g的高比表面積，且其粒子之凝聚情況較其他二者少。在環加成反應的部分，反應溫度為180℃、反應壓力10kg/cm2、反應時間15小時，為最佳之操作條件，將所製備之氫氧化鎂在該條件下，且不添加共催化劑或溶劑的狀況，進行二氧化碳與環氧丙烷之環加成反應，可到達91.5%之產率，由此可證明氫氧化鎂粒子有著良好的催化效果。
最後將本實驗之氫氧化鎂經鍛燒程序後生成之氧化鎂，在反應溫度為180℃、反應壓力10kg/cm2、反應時間15小時下，進行環加成反應，其結果顯示，氫氧化鎂的催化效果優於氧化鎂，推測主要原因為氫氧化鎂可與環氧化物產生氫鍵，有利於開環反應，造成氫氧化鎂之優異效能表現。

CO2 is the primary greenhouse gas which causes global warming in recent decade. According to the International Energy Agency’s report, carbon capture and storage is the key method for reduction of the global CO2 emissions. The captured CO2 can not only be stored which knows as carbon sequestration but also be applied for many other economic utilization.
Cyclic carbonate synthesis from CO2 and epoxide can be used as intermediates in the production of polymer. Catalyst plays an important role in cycloaddition reaction. Current research has found that hydrogen bond donors can activate the epoxides and enhance the reaction. Using the heterogeneous catalysts can decrease the difficulty of separation of the catalyst and product, making the process suitable for industrial operation.
High-gravity system has been developed for many years. In the field of crystal engineering, high-gravity technique can be used to produce nanoparticles. The characteristics of high–gravity system are small equipment size, short reaction time, high mass–transfer rate and capable for continuous operation. High-gravity system has higher commercial potential than hydrothermal method and sol-gel method, which are time-consuming, expensive and difficult to scale up.
The purpose of this research is to synthesize magnesium hydroxide in spinning disk reactor and investigate the efficiency of magnesium hydroxide as a catalyst in cycloaddition reaction. Magnesium hydroxide is prepared by mixing MgCl2 solution and Na(OH)2 solution in spinning disk reactor. The molar ratio of MgCl2 to Na(OH)2 is 1:2 and the rotational speed is 2500rpm. The liquid flow of two reactants are 0.28L/min. The effect of MgCl2 concentration on the particle size and catalytic property of Mg(OH)2 is investigated.
In the cycloaddition reaction of CO2 and propylene oxide, the effect of temperature, pressure and reaction time on the cycloaddition efficiency is investigated. According to the results, Mg(OH)2 particles having a high surface area of 293.1 m2/g, are produced from 0.5M MgCl2 solution. Using the Mg(OH)2 particles in the cycloaddition reaction, a propylene carbonate yield of 91.5% is obtained at P = 10kg/cm2, T = 180℃ and time = 15hr, while no co-catalysts or solvents are required.
Furthermore, the cycloaddition reaction using MgO, which is produced by calcination of Mg(OH)2 is performed. Accordion to the results, the catalytic efficiency of Mg(OH)2 is better than that of MgO. The reason is that Mg(OH)2 has hydrogen bond donors that can activate the epoxides and make the cycloaddition reaction more easier.

目錄
摘要 I
Abstract III
目錄 V
圖目錄 VIII
表目錄 XII
第一章 緒論 1
第二章 文獻回顧 4
2-1 二氧化碳減排技術簡介 4
2-1-1 再生能源 6
2-1-2 二氧化碳捕獲及封存技術 8
2-2 二氧化碳再利用 12
2-2-1 物理性直接應用 12
2-2-2 化學性轉化應用 14
2-3 環加成反應中常見觸媒種類 19
2-3-1 離子液體 21
2-3-2 鹼金屬鹽類 24
2-3-3 金屬氧化物 27
2-4 製備氫氧化鎂與氧化鎂之方法 32
2-4-1 水熱法 32
2-4-2 微乳液法 33
2-4-3 溶膠凝膠法 35
2-4-4 沉澱法 38
2-5 超重力技術 42
2-5-1 超重力技術簡介 42
2-5-2 超重力系統製備奈米粉體之研究 46
第三章 研究構想 54
第四章 實驗材料與步驟 56
4-1 實驗藥品 56
4-2 實驗裝置 57
4-3 實驗步驟 58
4-3-1 氫氧化鎂/氧化鎂粒子製備 58
4-3-2 二氧化碳環加成反應 59
4-3-3二氧化碳環加成反應轉化率、選擇比和產率計算 60
4-4　儀器分析與鑑定 61
第五章 結果與討論 64
5-1 氫氧化鎂之合成 64
5-2 氫氧化鎂於二氧化碳環加成反應之結果 72
5-2-1 反應溫度對環加成反應之影響 72
5-2-2 二氧化碳壓力對環加成反應之影響 74
5-2-3 時間對環加成反應之影響 76
5-2-4 不同濃度所製備之氫氧化鎂粒子對環加成反應之影響 77
5-2-5 氫氧化鎂粒子之環加成反應機制圖 79
5-3 氧化鎂於二氧化碳環加成反應之結果 81
5-3-1 氧化鎂粒子與氫氧化鎂粒子之二氧化碳環加成反應 83
5-3-2 氧化鎂之反應機制圖 84
5-4 氫氧化鎂粒子之效能與其他文獻之比較 86
第六章 結論 91
參考文獻 93
附錄 104
摘要 I
Abstract III
目錄 V
圖目錄 VIII
表目錄 XII
第一章 緒論 1
第二章 文獻回顧 4
2-1 二氧化碳減排技術簡介 4
2-1-1 再生能源 6
2-1-2 二氧化碳捕獲及封存技術 8
2-2 二氧化碳再利用 12
2-2-1 物理性直接應用 12
2-2-2 化學性轉化應用 14
2-3 環加成反應中常見觸媒種類 19
2-3-1 離子液體 21
2-3-2 鹼金屬鹽類 24
2-3-3 金屬氧化物 27
2-4 製備氫氧化鎂與氧化鎂之方法 32
2-4-1 水熱法 32
2-4-2 微乳液法 33
2-4-3 溶膠凝膠法 35
2-4-4 沉澱法 38
2-5 超重力技術 42
2-5-1 超重力技術簡介 42
2-5-2 超重力系統製備奈米粉體之研究 46
第三章 研究構想 54
第四章 實驗材料與步驟 56
4-1 實驗藥品 56
4-2 實驗裝置 57
4-3 實驗步驟 58
4-3-1 氫氧化鎂/氧化鎂粒子製備 58
4-3-2 二氧化碳環加成反應 59
4-3-3二氧化碳環加成反應轉化率、選擇比和產率計算 60
4-4　儀器分析與鑑定 61
第五章 結果與討論 64
5-1 氫氧化鎂之合成 64
5-2 氫氧化鎂於二氧化碳環加成反應之結果 72
5-2-1 反應溫度對環加成反應之影響 72
5-2-2 二氧化碳壓力對環加成反應之影響 74
5-2-3 時間對環加成反應之影響 76
5-2-4 不同濃度所製備之氫氧化鎂粒子對環加成反應之影響 77
5-2-5 氫氧化鎂粒子之環加成反應機制圖 79
5-3 氧化鎂於二氧化碳環加成反應之結果 81
5-3-1 氧化鎂粒子與氫氧化鎂粒子之二氧化碳環加成反應 83
5-3-2 氧化鎂之反應機制圖 84
5-4 氫氧化鎂粒子之效能與其他文獻之比較 86
第六章 結論 91
參考文獻 93
附錄 104
附錄1- 1 反應條件100℃、10kg/cm2、15hr之NMR圖譜 104
附錄1- 2 反應條件120℃、10kg/cm2、15hr之NMR圖譜 104
附錄1- 3 反應條件150℃、10kg/cm2、15hr之NMR圖譜 105
附錄1- 4 反應條件180℃、10kg/cm2、15hr之NMR圖譜 105
附錄1- 5 反應條件210℃、10kg/cm2、15hr之NMR圖譜 106

附錄2- 1 反應條件180℃、1kg/cm2、15hr之NMR圖譜 107
附錄2- 2 反應條件180℃、5kg/cm2、15hr之NMR圖譜 107
附錄2- 3 反應條件180℃、8kg/cm2、15hr之NMR圖譜 108
附錄2- 4 反應條件180℃、10kg/cm2、15hr之NMR圖譜 108
附錄2- 5 反應條件180℃、12kg/cm2、15hr之NMR圖譜 109

附錄3- 1 反應條件180℃、10kg/cm2、6hr之NMR圖譜 110
附錄3- 2 反應條件180℃、10kg/cm2、9hr之NMR圖譜 110
附錄3- 3 反應條件180℃、10kg/cm2、15hr之NMR圖譜 111
附錄3- 4 反應條件180℃、10kg/cm2、18hr之NMR圖譜 111
附錄3- 5 反應條件180℃、10kg/cm2、24hr之NMR圖譜 112

 
圖目錄
圖1-1二氧化碳於大氣中濃度年增圖(Zhang, 2012) 1
圖1-2二氧化碳於化學性轉化應用分類(Madea,2014) 2

圖2- 1減少二氧化碳排放量關鍵技術之藍圖(IEA, 2016) 4
圖2- 2 2013年之國際能量消耗來源比例圖(REN21, 2015) 5
圖2-3地熱發電示意圖(科技生活網-地熱能,2013) 7
圖2- 4 二氧化碳再利用遠景示意圖(IEA, 2016) 8
圖2- 5二氧化碳捕獲技術示意圖(Leung et al., 2014) 9
圖2- 6 礦化封存於工廠上之應用示意圖(IPPC, 2005) 11
圖2- 7台灣二氧化碳地質封存模式及安全檢測(林殿順, 2010) 11
圖2- 8 二氧化碳於商業上之應用比例(Global CCS Institute, 2011) 12
圖2- 9 二氧化碳石油增產技術示意圖(Kuuskraa et al.,2014) 14
圖2- 10二氧化碳的化學性轉化(Arakawa et al., 2001) 15
圖2- 11 Kolbe-Schmitt reaction示意圖(Lisdsey ,A. S. and H.Jeskey,1957) 17
圖2- 12二氧化碳與環氧化物之環加成反應示意圖(Sun et al., 2005) 17
圖2- 13環狀碳酸酯之應用(Sun et al., 2005) 18
圖2- 14環加成反應中有無使用觸媒於速率決定步驟中所需相對能量比較圖(Wang et al., 2012) 20
圖2- 15密度泛含理論模擬環加成反應之所需相對能量及反應機制圖(Wang et al ., 2012) 20
圖2- 16離子液體種類(Kawanami et al,2003) 23
圖2- 17 反應之(a)壓力(b)溫度(c)時間對環加成反應之影響(環氧丙烷: 29克; NaI∙2H2O : 1mol% ;(a)120℃,1h (b)1.0MPa,1h(c)120℃,1MPa ; (1)碳酸丙烯酯產率(2)碳酸丙烯酯選擇比) (Zhou et al,2010) 26
圖2- 18鎂-氧-鋁金屬氧化物觸媒於環加成反應之反應機制(Yamaguchi et al., 1999) 28
圖2- 19氧化鎂觸媒之反應機制示意圖(Yano et al., 1997) 29
圖2- 20不同水熱時間(a) 2.5小時(b) 5小時(c) 8小時(d) 16小時製備出的氫氧化鎂經過燒結後之氧化鎂TEM圖(Yan et al., 2002)。 33
圖2- 21 微乳液法之反應示意圖(Li et al., 2016) 34
圖2- 22 氫氧化碳酸鎂/石蠟複合奈米粒子之SEM圖(Li et al., 2016) 35
圖2- 23不同鍛燒溫度之氧化鎂SEM/TEM圖，鍛燒溫度：(a)/(d) 550℃；(b)/(e)：700℃；(c)/(f)：850℃；(g)為圖(a)之EDS位置(Li et al., 2016) 35
圖2- 24溶膠凝膠法步驟(徐悅, 2011) 36
圖2- 25 鍛燒溫度對晶體影響之XRD圖(Wang et al., 1998) 37
圖2- 26溶膠凝膠法之製備過程所產生之網狀結構於鍛燒過程中會產生之晶體缺陷示意圖(Wang et al., 1998) 37
圖2- 27鍛燒溫度的提升將針狀氫氧化鎂脫水成為顆粒狀氧化鎂 (a) 150℃ (b) 400℃ (c) 600 ℃ (Wang et al., 1998) 38
圖2- 28 SEM圖(a) sample1 (b) sample 2 (c) sample 3 (d) sample 4 40
圖2- 29 TEM圖(a)未使用分散劑(b)初始濃度5% (c)初始濃度25% (Lv et al., 2004) 41
圖2- 30旋轉填充床之結構示意圖( Ng et al., 2012 ) 43
圖2- 31 (a)加裝擋板之葉片式旋轉填充床示意圖 44
圖2- 32旋轉盤反應器之結構示意圖(Chin et al. , 2008) 45
圖2- 33 旋轉盤反應器之液膜流動過程示意圖(Chin et al. , 2008) 45
圖2- 34垂直式旋轉盤反應器示意圖(Chang et al., 2007) 46
圖2- 35 超重力系統中之分離率探討 47
圖2- 36 不同進料流率下提高旋轉盤轉速對分離率之影響(Tai et al., 2006) 48
圖2- 37 氯化鎂水溶液濃度:0.83M ;[Mg2+]/[NaOH] = 1/2 ;液體流率:0.28 L/min ;旋轉盤反應器轉速:2000 rpm (Tai et al., 2007) 49
圖2- 38 液體流率改變對粒徑影響:(●)液體流率:0.28 L/min(▓)液體流率:0.75 L/min (Tai et al., 2007) 50
圖2- 39 濃度改變對粒徑大小影響(Tai et al,2007) 51
圖2- 40 (a)濃度改變對粒徑分布的改變：(b)濃度改變對粒徑大小的改變：(x) 0.01M ; (▲) 0.2 M ; (o) 0.4M (Tai et al., 2007) 51
圖2- 41 (a)旋轉填充床與傳統攪拌反應器之粒徑分布(Sun et al.,2015) 53

圖3- 1本研究之研究構想示意圖 55

圖4- 1旋轉盤反應應示意圖 57
圖4- 2高壓反應釜裝置 58

圖5- 1氫氧化鎂之XRD圖 65
圖5- 2商用氫氧化鎂之XRD圖 65
圖5- 3氫氧化鎂之熱重分析(DTA/TGA) 66
圖5- 4 (a)0.2M(b)0.5M(c)0.83M之氯化鎂水溶液所製備之氫氧化鎂 68
圖5- 5 不同濃度下所製備之氫氧化鎂SEM圖(a)0.2 M(b)0.5 M(c)0.83M 69
圖5- 6 於旋轉盤反應器製備但未經過超音波震盪處理之氫氧化鎂粒子之 SEM圖 70
圖5- 7 傳統攪拌所製備之氫氧化鎂SEM圖 71
圖5- 8市售之氫氧化鎂SEM圖 72
圖5- 9反應溫度對環加成反應之影響 73
圖5- 10二氧化碳壓力對環加成反應之影響 75
圖5- 11 反應時間對環加成反應之影響 77
圖5- 12 不同濃度所製備之氫氧化鎂粒子對環加成反應之影響 78
圖5- 13環氧丙烷與二氧化碳於氫氧化鎂粒子催化下之反應機制圖 80
圖5- 14 氧化鎂之XRD圖 81
圖5- 15 氧化鎂之熱重分析 82
圖5- 16氧化鎂之SEM圖 83
圖5- 17添加氧化鎂、氫氧化鎂之效能差異 84
圖5- 18環氧丙烷與二氧化碳於氧化鎂粒子催化下之反應機制圖 85

表目錄
表2- 1各離子液體組合對環加成反應之影響(Peng et al., 2001) 22
表2- 2二氧化碳添加量與溫度改變對環加成反應之影響 (Peng et al., 2001) 22
表2- 3BMImBF4重複使用之結果(Peng et al., 2001) 22
表2- 4 不同離子液體組合與反應條件之效能結果(Kawanami et al., 2003) 23
表2- 5 鹽類及其帶結晶水鹽類對於環加成反應之影響(Zhou et al., 2010) 25
表2- 6 各類環氧化物於環加成反應之結果(Zhou et al,2010) 26
表2- 7鎂-氧-鋁金屬氧化物觸媒於不同環氧化物之效能表 (Yamaguchi et al., 1999) 28
表2- 8氧化鎂於環加成反應之結果(Yano et al., 1997) 29
表2- 9 各類金屬氧化物於環加成反應之研究(Dai et al., 2009) 30
表2- 10能與環氧化物產生氫鍵之觸媒效能(Wang et al., 2012) 31
表2- 11氧化石墨烯與石墨烯之效能差異(Lan et al., 2014) 31
表2- 12各類鎂鹽與沉澱劑及反應溫度表(Henrist et al,2003) 39
表2- 13表面活性劑及高分子分散劑對氫氧化鎂粒子粒徑之影響 (Lv et al., 2004) 41

表5- 1 氯化鎂水溶液之濃度改變對比表面積的影響 67
表5- 2傳統攪拌與旋轉盤反應器之產率比較 71
表5- 3反應溫度對環加成反應之轉化率、選擇比、產率之影響 74
表5- 4二氧化碳壓力對環加成反應之轉化率、選擇比、產率之影響 75
表5- 5 反應時間對環加成反應之轉化率、選擇比、產率之影響 77
表5- 6不同濃度所製備之氫氧化鎂粒子對環加成反應中轉化率、選擇比與產率之影響 79
表5- 7 氧化鎂、氫氧化鎂觸媒對轉化率、選擇比與產率之影響 84
表5- 8氫氧化鎂與其他文獻於二氧化碳與環氧丙烷之環加成反應比較 87
表5- 9 ZIF、MOF與本實驗Mg(OH)2之合成原料與價格及效能表現 88

Aresta, M., A. Dibenedetto, L. Gianfrate, C. Pastore, "Nb(V) compounds as epoxides carboxylation catalysts: the role of the solvent, "Journal of Molecular Catalysis A: Chemical, vol. 204–205, pp. 245–252, 2003

Arakawa, H., M. Aresta, J. N. Armor, M. A. Barteau, E. J. Beckman, A. T. Bell, J. E. Bercaw, C. Creutz, E. Dinjus, D. A. Dixon, K. Domen, D. L. DuBois, J. Eckert, E. Fujita, D. H. Gibson, W. A. Goddard, D. W. Goodman, J. Keller, G. J. Kubas, H. H. Kung, J. E. Lyons, L. E. Manzer, T. J. Marks, K. Morokuma, K. M. Nicholas, R. Periana, L. Que, J. Rostrup-Nielson, W. M.H. Sachtler, L. D. Schmidt, A. Sen, G. A. Somorjai, P. C.Stair, R. Stults, W. Tumas, "Catalysis Research of Relevance to Carbon Managemet: Progress, Challenges, and Opportunities, "Chemical Review , vol.101, pp.953-996., 2001

Baiker A., "Supercritical fluids in heterogeneous catalysis,"Chemical Reviews, vol. 99, pp. 453-474., 1999

Bhalchandra M. B. , S. Fujita, Y. Ikushima, M. Arai, "Synthesis of dimethyl carbonate and glycols from carbon dioxide, epoxides, and methanol using heterogeneous basic metal oxide catalysts with high activity and selectivity" Applied Catalysis A: General ,vol.219, pp.259–266, 2001

Chang, M.H., H. S. Liu, C.Y. Tai, "Preparation of copper oxide nanoparticles and its application in nanofluid",Powder Technology,vol.207, pp.378-386.,
2007

Chen, Y.S., Y. D. Tai, M. H. Chang, H. S. Liu, "Characteristics of micromixing in a rotating packed bed, "Journal of the Chinese Institute of Chemical Engineering,vol.37, pp.63-69.,2006

Chen ,K.J., Y.S. Chen,"Intensified production of biodiesel using a spinning disk reactor" Chemical Engineering and Processing ,vol.78, pp.67–72 ,2014

Chen ,J. F., Y. L. Li, Y.H. Wang, J. Yun, D. Cao, " Preparation and characterization of zinc sulfide nanoparticles under high-gravity environment, " Materials Research Bulletin, vol.39,pp.185–194 ,2004

Chen ,J. F. ,Y. H. Wang, F. Guo, X.M. Wang, and C. Zheng; " Synthesis of Nanoparticles with Novel Technology: High-Gravity Reactive Precipitation" Industrial Engineering & Chemistry Research..,vol.39, pp.948-954.,2000

Chin, S. F. , K. S. Iyer, C. L. Raston,and M. Saunders , "Size Selective Synthesis of Superparamagnetic Nanoparticles in Thin Fluids under Continuous Flow Conditions" Advanced Functional Materials., vol. 18,pp. 922–927.(2008)

Dabir ,H., M. Davarpanah, A. Ahmadpour, "Effects of different operating parameters on the particle size of silver chloride nanoparticles prepared in a spinning disk reactor," Applied Physics A ,vol. 120,pp.105–113,2015

Dai ,W. L., S. L. Luo, S. F. Yin, C. T. Au; " The direct transformation of carbon dioxide to organic carbonates over heterogeneous catalysts" Applied Catalysis A: General ,vol.366, pp.2–12, 2009

Dehkordi, A., M. and A. Vafaeimanesh, " Synthesis of Barium Sulfate Nanoparticles Using a Spinning Disk Reactor: Effects of
Supersaturation, Disk Rotation Speed, Free Ion Ratio, and Disk Diameter" Industrial Engineerig Chemistry Research, vol.48, pp.7574–7580,2009

Henrist ,C., J. P. Mathieu, C. Vogels, A. Rulmont, R. Cloot "Morphological study of magnesium hydroxide nanoparticles precipitated in dilute aqueous solution" Journal of Crystal Growth ,vol.249, pp.321–330 ,2003

Howell ,B. A. and M. Alomari, "Thermal degradation Of poly (propyleneoxide)" ,2009

Hwang, G. Y., R. Roshan, H. S. Ryu, H. M. Jeong, S. Ravi, M. Kim, D. W. Park "A highly efficient zeolitic imidazolate framework catalyst for the co-catalyst and solvent free synthesis of cyclic carbonates from CO2,"Journal of CO2 Utilization , vol.15,pp.123–130,2016

Ilgen, O., A. N. Akin "Transesterification of Canola Oil to Biodiesel Using MgO Loaded with KOH as a Heterogeneous Catalyst," Energy & Fuels,vol.23,pp.1786–1789 ,2009

Johnston ,K. P. and P. S. Shah, "Materials science. Making nanoscale materials with supercritical fluids," Science, vol. 303, pp. 482-3, 2004

Jung ,J. and M. Perrut, "Particle design using supercritical fluids: Literature and patent survey," The Journal of Supercritical Fluids, vol.20,pp.179-219, 2001.

Kamelia V. K. B., W. A. E. Dunk, M. Vicevic, R. J. Jachuck, V. Sage, D. J. Macquarrie, J. H. Clark, "Classical Cationic Polymerization of Styrene in a Spinning Disc Reactor Using Silica-Supported BF3 Catalyst" Journal of Applied Polymer Science, vol. 101, pp.8 –19 ,2006

Kawanami, H.,A. Sasaki, K. Matsuia and Y. Ikushima " A rapid and effective synthesis of propylene carbonate using a supercritical CO2–ionic liquid system" Chemical Communications.pp.896–897,2003

Kelleher, T. and J. R. Fair, "Distillation Studies in a High-Gravity Contactor" Industrial Engineering Chemistry Research,vol.35,pp.4646-4655, 1996

King, J. W. and L. L. Williams, "Utilization of critical fluids in processing semiconductors and their related materials," Current Opinion in Solid State and Materials Science, vol. 7, pp. 413-424, 2003

Kongpanna, P., V. Pavarajarn, R.Gani, S. Assabumrungrat," Techno-economic evaluation of different CO2-based processes for dimethyl carbonate production" Chemical Engineering Research and Design ,vol.93,pp.496-
510 ,2015

Kuruppathparambil R. R., T. Jose, R. Babu, G. Y. Hwanga, A. C. Kathalikkattil, D. W. Kim, D. W. Park ," A room temperature synthesizable and environmental friendly heterogeneous ZIF-67 catalyst for the solvent less and co-catalyst free synthesis of cyclic carbonates " Applied Catalysis B: Environmental ,vol.18,pp.2562–569 ,2016

Kuuskraa ,V. , P. DiPietro, "CO2 Enhanced Oil Recovery: The Enabling Technology for CO2 Capture and Storage",2014

Lan ,D. H. , F. M. Yang, S. L. Luo, C. T. Au, S. F. Yin " Water-tolerant graphene oxide as a high-efficiency catalyst for the synthesis of propylene carbonate from propylene oxide and carbon dioxide" CARBON,vol.73, pp.351–360 ,2014

Leung, Y.C., G. Caramanna, M. M. Maroto-Valer; " An overview of current status of carbon dioxide capture and storage technologies" Renewable and Sustainable Energy Reviews,vol39,pp.426–443, 2014

Li, S. B., B. J. Zhou, B. Ren, L. Xing, L. X. Tan, L. C. Dong, J. Li "Preparation of MgO nanomaterials by microemulsion-based oil/water interface precipitation," Materials Letters ,vol.171,pp.204–207, 2016

Lin, C. C. and W. T. Liu "Removal of an Undesired Component from a Valuable Product Using a Rotating Packed Bed" Journal of Industrial and Engineering Chemistry, vol 12, No.3,pp. 455-459,200

Lisdsey, A. S. and H. Jeskey, "The Kolbe-Schmitt Reaction," Chemical Reviews, vol. 57, pp. 583–620, 1957.

Lv, J. , L. Qiu, B. Qu, "Controlled growth of three morphological structures of magnesium hydroxide nanoparticles by wet precipitation method" Journal of Crystal Growth ,vol.267, pp.676–684 ,2004

Ma, H. J., Y. S. Chen, "Evaluation of effectiveness of highly concentrated alkanolamine solutions for capturing CO2 in a rotating packed bed" International Journal of Greenhouse Gas Control, vol.55 pp.55–59,2016

Maeda, C., Y. Miyazaki and T. Ema " Recent Progress in Catalytic Conversions of Carbon Dioxide " Catalyst Science Technology, vol.14, pp.1482-1497, 2014

Mousavi, B., S. Chaemchuen, B. Moosavi, Z. Luo, N. Gholampour, F. Verpoort " Zeolitic Imidazole Framework-67 as an Efficient Heterogeneous Catalyst in the Conversion of CO2 to Cyclic Carbonate" New Journal Chemistry, vol. 40, pp.5170-5176, 2016

Ng, C. M.,P. C. Chen and S. Manickam, "Green High-Gravitational Synthesis of Silver Nanoparticles Using a Rotating Packed Bed Reactor (RPBR), " Industrial & Engineering Chemistry Research ,vol.51,pp.5375−5381,2012

O''Neil, A. and J. J. Watkins, "Green chemistry in the microelectronics industry," Green Chemistry, vol. 6, pp. 363, 2004

Peng, J. and Y. Deng "Cycloaddition of carbon dioxide to propylene oxide by ionic liquid" New Journal of Chemistry, vol.25, pp.639-641,2001

Pütün, Ersan "Catalytic pyrolysis of biomass: Effects of pyrolysis temperature, sweeping gas flow rate and MgO catalyst " Energy , vol.35, pp.2761-
2766, 2010

Ramin, M., N. Vegten, J. D. Grunwaldt, A. Baiker " Simple preparation routes towards novel Zn-based catalysts for the solventless synthesis of propylene carbonate using dense carbon dioxide" Journal of Molecular Catalysis A: Chemical, vol.258, pp.165–171, 2006

Savage, P. E., S. Gopalan, T. I. Mizan, C. J. Martino, and E. E. Brock, "Reactions at supercritical conditions: Applications and fundamentals,"
American Institute of Chemical Engineers, vol. 41, pp. 1723-1778, 1995

Song, G. , Y. D. Ding, X. Zhu ,Q. Liao "Carbon dioxide adsorption characteristics of synthesized MgO with various porous structures achieved by varying calcination temperature. " Colloids and Surfaces A: Physicochem. Engineering Aspects, vol.470, pp.39–45 , 2015

Song, J. , Z. Zhang, S. Hu, T. Wu, T. Jiang and B. Han " MOF-5/n-Bu4NBr an efficient catalyst system for the synthesis of cyclic carbonates from epoxides and CO2 under mild conditions" Green Chemistry,vol.11, pp.1031–1036 ,2009

Sun, J., S. Fujita, and M. Arai, "Development in the green synthesis of cyclic carbonate from carbon dioxide using ionic liquids," Journal of Organometallic Chemistry, vol.690,pp.3490-3497, 2005

Sun, Q. , B. Chen, X. W., M. Wang, C. Zhang, X. F. Zeng, J. X., Wang,J. F. Chen " Preparation of Transparent Suspension of Lamellar Magnesium Hydroxide Nanocrystals Using a High-Gravity Reactive Precipitation Combined with Surface Modification" Industrial Engineering Chemistry Research,vol.54, pp.666−671,2015

Sung,W. D. , Y. S. Chen "Characteristics of a rotating packed bed equipped with blade packings and baffles" Separation and Purification Technology ,vol.93 , pp. 52–58,2012

Tai, Y. D., Y. H. Wang, C. T. Tai and H.S. Liu "Preparation of Silver Nanoparticles Using a Spinning Disk Reactor in a Continuous Mode" Industrial Engineering Chemistry Research.,vol.48,pp.10104–10109., 2009
Tai,Y. D. , C. T. Tai, M. H. Chang, H. S. Liu, "Synthesis of Magnesium Hydroxide and Oxide Nanoparticles Using a Spinning Disk Reactor" Industrial Engineering Chemistry Research.,vol.46,pp.5536-5541.,2007

Tai ,Y. D., C. T. Tai, H. S. Liu "Synthesis of submicron barium carbonate using a high-gravity technique" Chemical Engineering Science ,vol. 61, pp.7479 – 7486.,2006

Tharun, J., G. Mathai, A. C. Kathalikkattil, R. Roshan, Y. S. Won, S. J. Cho, J. S.Chang and Dae-Won Park"Exploring the Catalytic Potential of ZIF-90: Solventless and Co-Catalyst-Free Synthesis of Propylene Carbonate from Propylene Oxide and CO2"; Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim ,2014

Wang, J.A., O. Novaro, X. Bokhimi, T. Lopez, R. Gomez, J. Navarrete, M. E. Llanosc, E. Lopez-Salinas ; " Characterizations of the thermal decomposition of brucite prepared by sol–gel technique for synthesis of nanocrystalline MgO"; Materials Letters ,vol.35, pp.317–323 ,1998

Wang, J. Q., J. Sun, W. G. Cheng, K. Dong, X. P. Zhang and S. J. Zhang "Experimental and theoretical studies on hydrogen bond-promoted fixation of carbon dioxide and epoxides in cyclic carbonates" Physical Chemistry Chemical Physics, vol.14, pp.11021–11026 ,2012

Wang, M., H. K. Zou, L. Shao, J. F. Chen " Controlling factors and mechanism of preparing needlelike CaCO3under high-gravity environment" Powder Technology ,vol.142,pp.166–174,2004

Yan, L., J. Zhuang, X. Sun, Z. Deng, Y. Li " Formation of rod-like Mg(OH)2 nanocrystallites under hydrothermal conditions and the conversion to MgO nanorods by thermal dehydration. " Materials Chemistry and Physics , vol.76, pp.119–122 , 2002

Yano, T. , H. Matsui, T. Koike, H. Ishiguro, H. Fujihara, M. Yoshihara ,T. Maeshima " Magnesium oxide-catalysed reaction of carbon dioxide with an epoxide with retention of stereochemistry" Chemical Communication,
pp.1129-1130, 1997

Yasuda, H., L. N. He, T. Takahashi, T. Sakakura " Non-halogen catalysts for propylene carbonate synthesis from CO2 under supercritical conditions" Applied Catalysis A: General ,vol.298, pp.177-180 , 2006

Yuan, G. Q. , Y. J. Shan, H. F. , Jiang, C. R. QI "Mg(OH)Cl/KI as a Highly Active Heterogeneous Catalyst for the Synthesis of Cyclic Carbonates from CO2and Epoxides under Solvent-Free Conditions" Chinese Journal of Chemistry, vol.26, 947-951, 2008

Zhang, N. , J. Li, D, Liu, Q. Wang, X. Zhou, Y. Yi; " Researchof CO2 Emission Reduction Technology" 2012 年兩岸環境與能源研討會暨第一屆全球華人環境與能源研討會支援二氧化減排的上下游技術,2012
Zhou , X., Y. Zhang , X. Yang, J. Yao, G. Wang, " Hydrated Alkali Metal Halides as Efficient Catalysts for the Synthesis of Cyclic Carbonates from CO2 and Epoxides"Chinese Journal of Catalysis, vol.31, pp.765–768.2010

Global CCS Institute "Accelerating the Uptake of CCS: Industrial use of Capture Carbon dioxide " , 2011

International Energy Agency- 20 years of carbon capture and storage –
Accelerating future deployment , 2016

IPCC, 2005: IPCC special report on Carbon Dioxide Capture & Storage, 2005

REN 21 : RENEWABLES 2015 GLOBAL STATUS REPORT , 2015

科技生活網：地熱能示意圖
朱榮、仇永全、薛立秋、張貴、梁立新、高峰，中國專利:CN1664118，
,2005
林殿順;“台灣二氧化碳地質封存潛能及安全性”中華經濟研究院-經濟
前瞻之環保專欄11月,2010
徐悅 ;’’凝膠的研究進展’’ , 2011
張敏超;’’ 離子液體特性及其在化學上的應用’’ 工業材料雜誌325期, 2014
鄭業揚, "二氧化碳與環氧丙烷在批次與連續式反應的動力學研究," 義 守
大 學生物技術與化學工程研究所碩士論文, 2012