臺灣博碩士論文加值系統

二氧化碳地質封存為二氧化碳減量的有效方法之一，地質封存是指將二氧化碳注入到油氣田、深部鹽水層或煤層。本實驗目的在於探討在台灣地區將二氧化碳封存於煤層之可行性，20個來自台灣中北部中新世煤層之樣本，分別為木山層、石底層和南莊層，採用壓力體積測量法將二氧化碳注入煤樣，模擬地下煤層壓力條件，實驗數據由Langmuir Isotherm model 進行 Langmuir Pressure 及Langmuir Volume 參數擬合。實驗首先將樣本粉碎至60 mesh，在烘箱加熱至100℃脫水後，放置到儲煤罐中抽真空並逐步增加壓力至800 psi，接著逐步減壓以觀測壓力變化對吸脫附的影響，並檢視吸脫附作用所造成的遲滯現象。再將煤樣工業分析及煤岩分析之結果和吸附量對比後，發現固定碳，煤級及鏡煤素含量與吸附量成正相關，而固定碳及鏡煤素含量與孔隙大小亦有相關性，所以推測孔隙大小會影響吸附量。本實驗吸脫附結果顯示，台灣煤樣氣體吸附量約250 scf/ton ~500 scf/ton。根據Langmuir Isotherm model 分析結果，以大東山煤礦煤樣對二氧化碳等溫吸脫附量為最高，可能原因為在烘乾前內含水份填充於孔隙中，而烘乾後產生較多孔隙造成吸附量增加。掃描式電子顯微鏡影像顯示以黏土礦物為主之礦物質填充孔隙，為導致氣體吸附量下降之主因。

Geological sequestration of CO2 into depleted oil reservoir, saline aquifer or unmineable coal seam is now being actively investigated for the purpose of reducing greenhouse gas in the atmosphere. Understanding the physical, chemical, and thermodynamic phenomena occurred with CO2 injection is very important in making a reliable prediction of sequestration. This study examined the feasibility of carbon dioxide sequestration into unmineable coal seams in Taiwan. A total of 20 Miocene-aged coal samples from Western Foothill Belt, NW Taiwan, were collected. The stratigraphy include Mushan, Shihti, and Nanchuang Formation from bottom up. Proximate and petrographic analyses include maceral composition and vitrinite reflectance were also measured. Carbon dioxide adsorption isotherms were analyzed at 35℃ and up to 800 psi, by using a gravimetric ad/desorption apparatus. Isotherms were then fitted with a modified Langmuir Isotherm model by using Langmuir Pressure and Langmuir Volume so the model can be applied to supercritical conditions. According to the result of adsorption experiment, the pressure and temperature were quite significant. The gas storage capacity of CO2 was about 250~500 scf/ton at pressure up to 800 psi. Comparing the results of adsorption capacity with Proximate and Petrographic analyses, the Langmuir Volume shows a strong positive correlation with fixed carbon and vitrinite content. Furthermore, Adsorption capacity is closely related to micropores which were also rank and maceral dependent. It is noticed that the observed coal pore structures were affected by rank, and thus exhibit different diffusion rate. Finally, images under SEM were evaluated to understand the pathways of gas sorption.The filling mineral matter (mostly clay) will lead to the decrease of gas sorption.

摘要...i
Abstract...ii
誌謝...iii
目錄...iv
圖目錄...vi
表目錄...viii
符號說明...ix
第一章 緒論...1
1.1 研究動機與目的...1
1.2 研究區域地層背景概述...3
1.3 內文概述...8
第二章 文獻回顧...10
2.1 煤的基本性質...10
2.2 成煤作用...12
2.3 煤岩類型與結構...15
2.4 氣體吸脫附原理...16
2.5 影響氣體吸附與脫附之因素...18
2.5.1 煤素質...18
2.5.2 煤級...20
2.5.3 煤岩結構...22
2.5.4 遲滯效應...23
2.6 吸脫附計算...24
2.6.1 Langmuir Isotherm...24
2.6.2 偏差因子(Z factor)...25
2.6.3 氣體吸附量(Mavor's Gas storage capacity)...25
第三章 研究方法...29
3.1 研究流程...29
3.2 研究樣本...30
3.3 物理特性分析...31
3.3.1 工業分析...31
3.3.2 煤樣比表面積分析...33
3.3.3 掃描式電子顯微鏡...35
3.4 有機地球化學分析...36
3.4.1 元素分析...36
3.4.2 煤餅製作與拋光...38
3.4.3 煤素質成份分析...38
3.4.4 鏡煤素反射率量測...39
3.5 吸附實驗...40
第四章 結果與討論...45
4.1 二氧化碳等溫吸脫附結果分析...45
4.1.1 Langmuir Isotherm model 參數擬合...54
4.1.2 二氧化碳吸附最佳擬合曲線結果...55
4.2 煤樣材料特性與Langmuir Isotherm model 參數之關聯性...58
4.2.1 工業分析...58
4.2.2 煤樣比表面積分析...61
4.2.3 元素分析...63
4.2.4 煤素質成分分析...66
4.2.5 鏡煤素反射率量測...68
4.2.6 煤樣顯微觀察...69
第五章 結論...73
參考文獻...75
附錄...82

［1］台灣因應氣候變化綱要公約資訊網，京都議定書。
http://www.tri.org.tw/unfccc/Unfccc/UNFCCC02.htm.
［2］Metz, B.,O. Davidson, H. C. de Coninck, M. Loos, and L. A. Meyer, IPCC Special Report on Carbon Dioxide Capture and Storage. Cambridge University Press, 2005.
［3］Faiz, M.M., Saghafi, A., Barclay, S.A., Stalker, L., Sherwood, N.R. and Whitford, D.J., “Evaluating geological sequestration of CO2 in bituminous coals: The southern Sydney Basin, Australia as a natural analogue”, International Journal of Greenhouse Gas Control, 1, 223-235, 2007.
［4］Wildenborg, A.F.B and van der Meer, L.G.H, “The Use of oil, gas and coal fields as CO2 sinks, proceedings of workshop on carbon dioxide capture and storage, Canada, 1-179, 2002.
［5］Busch, A., Gensterblum, Y., Krooss, B.M. and Siemons, N., “Investigation of high-pressure selective adsorption/desorption behaviour of CO2 and CH4 on coals: an experimental study”, International Journal of Coal Geology, 66, 53-68, 2006.
［6］Busch, A. and Gensterblum, Y., “CBM and CO2-ECBM related sorption processes in coal: A review”, International Journal of Coal Geology, 87, 49-71, 2011.
［7］Robertson, E.P., “Economic analysis of carbon dioxide sequestration in Powder River Basin coal”, International Journal of Coal Geology, 77, 234-241, 2009.
［8］鄧屬予，“臺灣的沉積岩”，經濟部中央地質調查所，共235頁，1997。
［9］魏稽生，“台灣能源礦產及地下水資源”，台灣經濟礦物，第3卷，68-121，2000。
［10］何春蓀，“台灣基隆沿海區至桃園大溪間煤田地質及構造”，經濟部中央地質調查所，第2號，17-70，1975。
［11］Ting, F.T.C., “Petrographic techniques in coal analysis. In: Karr, C., Jr.(Eds.), Analytical Methods for Coal and Coal Products”, Academic Press, Inc., New York, 3-26,1978.
［12］Stopes, M. C., “On the petrology of banded bituminous coals”, Fuel, 14, 4-13, 1935.
［13］Stach, E., Mackowsky, M. T.., Teichmüller, Taylor, G. H., Chandra, D. and Teichmüller, R., “Stach’s Textbook of coal petrology”, Berlin Stuttgar, Gebruder Borntraeger, 1982.
［14］Ting, F. T. C., “Coal macerals. In: R.A. Meyers, Editor, Coal Structure”, Academic Press, New York, 7-49, 1982.
［15］林孟嬿，“不同成熟度之有機成分探討”，國立中央大學應用地質研究所，碩士論文，2008。
［16］ASTM, Classification of coals by rank, D388-77, 1977.
［17］Magoon, L.B., Dow, W.G., “The petroleum system-from source to trap”, The American Association of Petroleum Geologists, 95-97, 1994.
［18］Peters, K.E., Cassa, M.R., “The petroleum system-from source to trap, applied source-rock geochemistry. In: Magoon L. B., Dow W. G.（Eds.）”, American Association of Petroleum Geologists Memoir , 60, 93-120, 1994.
［19］劉保淇，“煤層孔隙率與滲透率特性評估”，國立中央大學應用地質研究所，碩士論文，2010。
［20］Tissot, B.P., Welte, D.H., “Petroleum formation and occurrence；a New approach to oil gas exploration”, 699, Berlin, Heidelberg, New York, 1984.
［21］Sitler, J.A., “Effects of source material on vitrinite reflectance”, Master thesis, West Virginia University, 103 pp., 1979.
［22］謝慧禎，“石油系統之有機材料與熱成熟度特性探討”，國立中央大學應用地質研究所，碩士論文，2004。
［23］Baskin, D.K., “Atomic H/C ration of Kerogen as an estimate of thermal maturity and organic matter conversion”, The American Association of Petroleum Geologists Bulletin, 81, 1431-1450, 1997.
［24］孫立中，“抑制鏡煤素反射率之量測成因－以分離台灣裕峰煤為例”，國立中央大學地球物理研究所，博士論文，2000。
［25］Gamson, P.D. and Beamish, B.B., “Coal type, microstructure and gas flow behaviour of Bowen Basin coals”, Symposium on coalbed methane research and development in Australia, 43-67, 1992.
［26］International Union of Pure and Applied Chemistry, “Reporting physisorption data for gas/solid systems with special reference to the determination of surface area and porosity”, 54, 2201-22l8, 1982.
［27］Rodrigues, C. F., and Lemos de Sousa, M. L., “The measurement of coal porosity with different gases”, International Journal of Coal Geology , 48, 245-251, 2002.
［28］Ruthven, D. M., “Principles of Adsorption and Adsorption Processes”, John Wiley & Sons Inc, 1984.
［29］Faiz, M., Saghafi, A., Sherwood, N. and Wang, I., “The influence of petrological properties and burial history on coal seam methane reservoir characterisation, Sydney Basin, Australia”, International Journal of Coal Geology, 70, 193-208, 2007.
［30］Bromhal, G.S., Sams, W.N., Jikich, S., Ertekin, T. and Smith, D.H., “Simulation of CO2 sequestration in coal beds: The effects of sorption isotherms”, Chemical Geology, 217, 201-211, 2005.
［31］Keller, J.U. and Staudt, R., Gas Adsorption Equilibria, 1-421, 2005.
［32］Gregg,S.J. and Sing,K.S.W, “Adsorption surface area and porosity”,2nd ed., Academic Press,New York,1982.
［33］Harpalani, S., Prusty, B. K. and Dutta, P., “Methane/CO2 Sorption Modeling for Coalbed Methane Production and CO2 Sequestration”, Energy & Fuels, 20, 1591-1599, 2006.
［34］Faiz, M.M., “ Gaseous hydrocarbons in the southern Sydney Basin”, 13th Newcastle Symp. Adv. Study Sydney Basin, 175–182, 1995.
［35］Gurdal, G. and Yalcin M.N., “Pore volume and surface area of the Carboniferous coalsfrom the Zonguldak basin (NW Turkey) and their variationswith rank and maceral composition”, International Journal of Coal Geology, 48, 133-144, 2001.
［36］Day, S., Duffy, G., Sakurovs, R. and Weir, S., “Effect of coal properties on CO2 sorption capacity under supercritical conditions”, International Journal of Greenhouse Gas control, 2, 342-352, 2008.
［37］Faiz, M.M., Aziz, N.I., Hutton, A.C. and Jones, B.G., “Porosity and gas sorption capacity of some eastern Australian coals in relation to coal rank and composition”, Symposium on coalbed methane research and development in Australia, 9-13, 1992.
［38］Mukhopadhyay, P.K., MacDonald, D.J., Calder, J.H., “Evaluation of coalbed methane potential of the Stellarton Basin”, Nova Scotia, Canada, based on geological physical and chemical properties. Proceedings of the 1995 International Unconventional Gas Symposium. Tuscaloosa, AL, USA, 311 – 320, 1995.
［39］Garnier, Ch., Finqueneisel, G., Zimny, T., Pokryszka, Z., Lafortune, S., Defossez, P.D.C. and Gaucher, E.C., “Selection of coals of different maturities for CO2 Storage by modelling of CH4 and CO2 adsorption isotherms”, International Journal of Coal Geology, 87, 80-86, 2011.
［40］Gan, H., Nandi, S.P., Walker, P.L., “Nature of the porosity in American coals”, Fuel ,51, 272–277, 1972.
［41］Crosdale, P. J., Beamish, B.B., Valix, M., “Coalbed methane sorption related to coal composition”, International Journal of Coal Geology ,35,147–158,1998.
［42］Beamish, B.B., Gamson, P.D., “Laboratory studies: sorption behaviour and microstructure of Bowen Basin coals”, In: Oldroyd, G.C. (Ed.), Final Report ERDC Project 1464-Prediction of Natural Gas Production from Coal Seams, Energy Research Development, Canberra, 2, 128 , 1993
［43］Ozdemir, E., Morsi, B.I., Schroeder, K., “CO2 adsorption capacity of Argonne premium coals”, Fuels, 83, 1085-1094, 2004.
［44］Harpalani,s., and Chen,G., “Estimation of changes in fracture porosity of coal with gas emission”,Fuel,74,1491-1498,1995.
［45］洪旭文，“定量結構活性關係法預測活性碳吸附低濃度揮發性有機物之研究”，國立成功大學環境工程研究所碩士論文，2000。
［46］Langmuir, I., “The adsorption of gases on plane surfaces of glass, mica and platinum”, J. Am. Chem. Soc., 40(8), 1361-1403, 1918.
［47］Atkins, P.W., Elements of physical chemistry, 5th ed, 2009.
［48］Gas Research Institute (GRI), “A guide to determining coalbed gas content”,1995.
［49］Hall, K.R. and Yarborough, L., “A new equation of state for Z-Factor calculations”, Oil and Gas Journal, 71(25), 82-93, 1973.
［50］Mavor, M.J., Owen, L.B., Pratt, T.J., “Measurement and evaluation of coal sorption isotherm data”, Society of Petroleum Engineers Annual Technical Conference and Exhibition SPE20728, 157-170,1990.
［51］Brunauer, S., Emmett, P.H. and Teller, E., “Adsorption of Gases in Multimolecular Layers”, J. Am. Chem. Soc., 60, 309-319, 1938.
［52］ASTM, Standard D-279, ASTM Standard Manual, 26, 350-354, 1977.
［53］ASTM, Standard D-2799, Microscopical determination of volume percent of physical components in a polished specimen of coal, ASTM, Philadephia, PA, 1-4, 1980.
［54］Romanov, V., Soong, Y., Schroeder, K., “Volumetric effects in coal sorption capacity measurements”, Eng.Technol, 29,368-374,2006.
［55］吳萬全，“台煤岩相特性之探討及應用”，臺灣礦業，第四十二卷，78-98，1990。