臺灣博碩士論文加值系統

由於自然界中，積累於儲氣層中的天然氣氣體成份，和直接由源岩 (Source Rock) 產生的氣體成份，存在著相當大的差異，故可推測一般而言，天然氣的移棲 (Migration) 路徑越長時，其氣體成份受到二次分異 (Secondary Fractionation) 作用的可能性就越高。本研究便著重於探討天然氣在移棲過程中，流經黏土礦物（高嶺石及蒙脫石）和有機物（煤和湖相頁岩）等物質時，吸附 (Adsorption) 及擴散 (Diffusion) 作用對天然氣氣體成份變化的影響。研究的結果顯示，就選擇性吸附而言，黏土礦物和有機物，對分子量大之天然氣成份 (Wet hydrocarbon gases) 的吸附效果，較輕烴類如甲烷來的大許多；而就不同吸附劑而言，黏土礦物的吸附程度和選擇性吸附效果，遠低於有機物和活性碳。另一方面，就擴散作用而言，天然氣中輕烴類成份的擴散速率，較分子量大之氣體成份擴散速率快；且可利用擴散模擬之實驗數據，配合費克定律 (Fick’s Law) 求得天然氣中各氣體成份的擴散係數 (Diffusion Coefficient)。此實驗結果意味，天然氣移棲過程中，黏土礦物吸附作用造成成份分異的程度較差，然而，當天然氣流經富集大量有機物的路徑時，將會造成天然氣成份產生明顯的分異，故可映射到天然氣的初次移棲 (Primary Migration) 過程上，當天然氣由源岩生成，或流經含有大量有機物的生油層時，由於吸附效應，便可使其成份富集甲烷。另一方面，在天然氣的移棲過程中，由於擴散作用的影響，便可使其氣體成份產生相當大的改變，由於輕烴類的擴散速率較快，故可推測，當天然氣移棲路徑越長時，輕烴類成份由源岩移動到儲氣層中的機率也越高。

There is a conspicuous difference in compositions of natural gases between that accumulated in reservoir and that generated from source rocks. In general, the longer the migration pathway of natural gas, the more likely that any type of secondary fractionation of its composition can be significant. This study focuses on examining the influence of adsorption and diffusion on natural gas composition for clays and organic matter during migration. Our preliminary results show that clays (kaolinite and montmorillonite), organic matter (coal and lacustrine shale), and an activated carbon can preferentially adsorb wet hydrocarbon gases over methane but the adsorption level and selectivity are much lower for clays than for organic matter and activated carbon. This implies that the adsorption of natural gas in organic-rich pathway may result in a significant fractionation during migration whereas the extents of the fractionation due to adsorption on clays may be less. The diffusion experiments, on the other hand, show that methane has a higher diffusion rate than wet hydrocarbon gases, implying that dry hydrocarbon gas may migrate more efficiently from source rock to accumulation than wet hydrocarbon gases.

中文摘要i
英文摘要ii
目錄iii
表目錄vii
圖目錄ix
第一章 緒論 1
1-1 前言 1
1-2 研究動機及目的 2
1-3 前人研究 4
1-3-1 天然氣氣體組成 4
1-3-2 天然氣的生成 7
1-3-3 天然氣的移棲 9
1-3-4 天然氣的積累 10
1-3-5 吸附作用 10
1-3-6 擴散作用 12
第二章 實驗方法與材料 15
2-1 實驗模擬材料 15
2-1-1 天然氣氣樣 15
2-1-2 使用於吸附及擴散之材料 16
2-2 實驗器材 26
2-2-1 吸附作用 26
2-2-2 擴散作用 26
2-3 實驗方法 28
2-3-1 吸附作用 28
2-3-2 擴散作用 30
第三章 儀器設備 34
3-1 HP 6890 氣相層析儀 34
3-1-1 注射口 (Inlet) 36
3-1-2 層析管柱 (Column) 38
3-1-3 偵檢器 (Detector) 40
3-1-4 加熱爐 (Oven) 43
3-1-5 搭配氣體 45
3-2 檢量線 46
3-3 HP化學工作站 48
第四章 實驗資料與處理 49
4-1 吸附作用 49
4-1-1 吸附量的計算 49
4-1-2 活性碳吸附量 52
4-1-3 各吸附劑吸附量 58
4-2 擴散作用 59
4-2-1 費克定律 59
4-2-2 擴散係數 61
第五章 實驗結果與討論 66
5-1 吸附作用 66
5-1-1 各氣體分子選擇性吸附 66
5-1-2 各吸附劑吸附效果比較 68
5-1-3 各吸附劑對氣體分子選擇性吸附的比較69
5-1-4 溫度、吸附劑量及吸附質壓力對吸附量的影響72
5-1-5 吸附質壓力對吸附量的影響 74
5-1-6 吸附質飽和蒸汽壓影響 76
5-1-7 吸附量與吸附劑比表面積的比較 80
5-1-8 吸附劑表面積利用率比較 83
5-1-9 吸附質動力學模式比較 83
5-2 擴散作用 88
5-2-1 甲烷擴散量的變化 88
5-2-2 各氣體分子的選擇性擴散 89
5-2-3 各氣體分子間擴散量的比較 89
5-2-4 高嶺石及蒙脫石擴散量比較 91
5-2-5 費克定律與擴散係數 93
5-3 綜合討論 95
5-3-1 選擇性吸附 95
5-3-2 吸附量差異 95
5-3-3 影響吸附的變因 96
5-3-4 各氣體分子的選擇性擴散 97
5-3-5 岩樣孔隙率對擴散的影響 97
第六章 結論 99
6-1 實驗結果之結論 99
6-1-1 吸附作用 99
6-1-2 擴散作用 100
6-2 地質意義上的影響 101
第七章 未來研究方向 103
7-1 吸附質壓力實驗 103
7-2 水分對吸附的影響 103
7-3 擴散模擬實驗 104
7-4 同位素值的量測 104
參考文獻 105
附錄A 吸附模擬各吸附劑實驗數據 109
附錄B 費克定律的推導 119
附錄C 擴散模擬蒙脫石實驗數據 122
附錄D 動力學一級反應模式 124
附錄E 動力學二級反應模式 126
附錄F 動力學Elovich反應模式 128

中文部份：
江右君 (1999) 活性碳物化特性對揮發性有機物吸附之影響，國立台灣大學環境工程學研究所博士論文
胡見義 (1985) 世界天然氣勘探開採動向及發展我國天然氣的建議，天然氣工業，5 (1) : 1 — 4
徐永昌 (1994) 天然氣成因理論及應用，科學出版社，共414頁。
郝石生，黃志龍和高耀斌 (1991) 輕烴擴散係數的研究及天然氣運聚動平衡原理，石油學報 (ACTA PETROLEI SINICA)，第12卷，第3期，pp. 17-24
黃鼎松 (1993) 我們的家鄉苗栗─地質篇，苗栗市：苗栗縣政府，共158頁。
戴金星 等 (1986) 天然氣地質學，石油工業出版社
英文部份：
Agilent Technologies, (1998) HP 6890 GC and ChemStation Operation. Hewlett-Packard Company, US, Student Manual, Volume 1 and 2.
Chiang, P. C. and You, J. H., (1988) Adsorption and Desorption of Phenolic, Benzyl and Naphthyl Compounds by Activated Carbon. Proceedings of the 1988 NSC/CSIR Binational Symposium on Environmental Technology, Taipei, Taiwan ROC, Oct. 1988.
Chien, S. H. and Clayton, W. R., (1980) Application of Elovich equation to the kinetics of phosphate release and sorption in soils. Soil Science Society of America Journal, 44, pp. 265-268.
Clayton, C., (1991) Carbon isotope fractionation during natural gas generation from kerogen. Marine and Petroleum Geology, 8, pp. 232-240.
Faure, G., (1998) Principles and Applications of Geochemistry / A Comprehensive Textbook for Geology Students / Second Edition. Prentice Hall, Upper Saddle River, New Jersey 07458. 600 p.
Gregg, S. J., and Sing, K. S. W., (1967) Adsorption, Surface Area and Porosity, Academic Press, New York.
Hunt, J. M., (1995) Petroleum Geochemistry and Geology / Second Edition. W. H. Freeman and Company, New York. 743 p.
Krooss, B., (1988) Experimental investigation of the molecular migration of C (super 1) -C (super 6) hydrocarbons: kinetics of hydrocarbon release from source rocks. Organic Geochemistry, 13, pp. 513-523.
Leythaeuser, D., Schaefer, R. G., Yukler, A., (1982) Role of diffusion in primary migration of hydrocarbons. AAPG Bulletin, 66, No. 4.
Low, P. F., (1960) Clays and clay minerals, V. 8. Natl. Conf. Clays and Clay Minerals, (Issued as Internat. Earth Science Ser. Mon. 9 of Pergamon Press, New York.) pp.170-182.
Marchetti, S., (1979) Design parameters in geotechnical engineering--Parametres deconception dans la geotechnique. European Regional Conference of the International Society for Soil Mechanics and Foundation Engineering, 2, No. 7, pp. 239-244.
Olphen, H. Van., and Fripiat J. J., (1979) Data handbook for clay materials and other non-metallic minerals. Pergamon Press. Data prepared under the auspices of the OECD and the Clay Minerals Society.
Peters, K. E., (1986) Guidelines for evaluating petroleum source rock using programmed pyrolysis. AAPG Bulletin, 70, pp. 318-329.
Price, L. C. and Schoell, M., (1995) Constraints on the origins of hydrocarbon gas from compositions of gases at their site of origin. Nature, 378, pp. 368-371.
Prinzhofer A. and Pernaton E., (1997) Isotopically light methane in natural gas: bacterial imprint or diffusive fractionation? Chemical Geology, 142, pp. 193-200.
Rice, D. D., (1993) Composition and origins of coalbed gas. In: Law, B.E., Rice, D. D., (Eds.), Hydrocarbons from Coal. AAPG Studies in Geology no. 38, Tulsa, pp. 159-184.
Ruthven, D. M., (1984) Principles of Adsorption and Adsorption Process. John Wiley and Sons, New York.
Sing, K. S. W., Everett, D. H., Haul, R. A. W., Moscou, L., Pierotti, R. A., Rouquerol, J. and Siemieniewska, T., (1985) Reporting Physisorption Data for Gas/Solid Systems — with Special Reference to the Determination of Surface Area and Porosity. Pure and Appl. Chem., 57(4), pp. 603-619.
Sircar, S., (1987) New Adsorption-Condensation Theory for Adsorption of Vapors on Porous Activated Carbons. Carbon, 25, pp. 39-48.
Sokolov, B. S., (1956) Sravnitelnaya kharakteristika doeifelskikh otlozhenii tsentralnykh i vostochnykh raionov Russkoi platformy. Trudy - Vsesouznyy Naucno-Issledovatelskiy Geologorazvedocnyy Neftanoy Institut, Geohimiceskiy Sbornik., 95, pp.36-88.
Sparks, D. L., (1989) Kinetics and mechanisms of molybdate absorption/desorption at the goethite/water interface using pressure-jump relaxation. Soil Science Society of America Journal, 53, pp. 1028-1034.
Tissot, B. P. and Welte, D. H., (1978) Petroleum Formation and Occurrence — A New Approach to Oil and Gas Exploration. Springer — Verlag Berlin Heidelberg, New York, 538 p.
Waples, D. W., (1985) Geochemistry in Petroleum Exploration. International Human Resources Development Corporation, (IHRDC) Boston. 232 p.
Whiticar, M. J., (1996) Stable isotope geochemistry of coals, humic kerogens and related natural gases. International Journal of Coal Geology, 32, pp. 191-215.
其他參考資料：
李明誠 (1987) 石油與天然氣運移，石油工業出版社，共165頁。
李明誠 (1994) 石油與天然氣運移（第二版），石油工業出版社，共250頁。
黃怡禎 譯 (2000) 礦物學，地球科學文教基金會。原書名：Manual of Mineralogy 21ST Ed，C. Klein and C. S. Hurlbut, Jr. 原著，John Wiley and Sons 授權獨家翻譯，共689頁。
戴金星，戚厚發和郝石生 (1989) 天然氣地質學概論（石油地質探勘技術培訓教材），石油工業出版社，共203頁。
Aylmore, L. A. G., (1974) Gas sorption in clay mineral systems. Clays and Clay Minerals, 22, pp. 175-183.
Balard, H., Saada, A., Siffert, B., and Papirer E., (1997) Influence of water on the retention of organic probes on clays studied by IGC. Clays and Clay Minerals, 45, No. 4, pp. 489-495.
Bradley, R. H., and Rand, B., (1995) On the physical adsorption of vapors by microporous carbons. Journal of Colloid and Interface Science, 169, pp. 168-176.
Inan, S., (2000) Gaseous hydrocarbons generated during pyrolysis of petroleum source rocks using unconventional grain-size: implications for natural gas composition. Organic Geochemistry, 31, pp. 1409-1418.
Jagiello, J., Bandosz, T. J., and Schwarz, J. A., (1992) Inverse Gas Chromatographic Study of Activated Carbons: The Effect of Controlled Oxidation on Microstructure and Surface Chemical Functionality. Journal of Colloid and Interface Science, 151, No. 2, pp. 433-445.
James, A. T., (1990) Correlation of reservoired gases using the carbon isotopic compositions of wet gas components. AAPG Bulletin, 74, No.9, pp. 1441-1458.
Kloprogge, J. T., Korbijn, L., and Koster, T. P. M., (1997) Head-space gaschromatography, a quick and simple method to screen adsorption capabilities of porous materials: adsorption of chlorobenzene on modified montmorillonite. Applied Clay Science, 12, pp. 85-91.
Krooss, B. M., Leythaeuser, D., and Schaefer, R. G., (1992) The quantification of diffusive hydrocarbon losses through cap rocks of natural gas reservoirs; a reevaluation. AAPG Bulletin, 76, No.3, pp. 403-406.
Lu, X. C., Li, F. C., and Watson, A. T., (1995) Adsorption studies of natural gas storage in Devonian shales. SPE Formation Evaluation, 10, pp. 109-113.
Mango, F. D., (1997) The light hydrocarbons in petroleum: a critical review. Organic Geochemistry, 26, pp. 417-440.
Morrissey, Fergus A., and Grismer, Mark E., (1999) Kinetics of volatile organic compound sorption/desorption on clay minerals. Journal of Contaminant Hydrology, 36, pp. 291-312.
Nelson, J. S., and Simmons, E. C., (1992) The quantification of diffusive hydrocarbon losses through cap rocks of natural gas reservoirs; a reevaluation; discussion and reply. AAPG Bulletin, 76, No.11, pp. 1839-1841.
Nelson, J. S., and Simmons, E. C., (1995) Diffusion of methane and ethane through the reservoir cap rock: implications for the timing and duration of catagenesis. AAPG Bulletin, 79, No. 7, pp. 1064-1074.
Prinzhofer, A., and Huc, A. Y., (1995) Genetic and post-genetic molecular and isotopic fractionations in natural gases. Chemical Geology, 126, pp. 281-290.
Rosario, H. H., Lourdes, D., and Gelacio, A. A., (1999) Adsorption equilibria and kinetics of CO2, CH4 and N2 in natural zeolites. Separation and Purification Technology, 15, pp. 163-173.
Sommer, S. E., (1981) Geological and environmental factors involved in natural gas accidents. Environmental Geology and Water Sciences, 3, pp. 213-220.
Stoessell, R. K., and Byrne, P. A., (1982) Methane solubilities in clay slurries. Clays and Clay Minerals, 30, No. 1, pp. 67-72.
Syngayevskiy, Y. D., Lebedev, V. S., Safronova, T. P., and Sushilin, A. V., (1980) Study of fractionation of carbon isotopes during migration of hydrocarbons in the gas phase through rocks. Petroleum Geology, 16, pp. 36-39.
Valenzuela, D. P., and Myers, A. L., (1989) Adsorption equilibrium data handbook. Englewood Cliffs, N.J. : Prentice Hall, 366 p.
Volzone, Cristina, Thompson, John G., Melnitchenko, Alexandra, Ortiga, Jose, Palethorpe, and Stephen R., (1999) Selective gas adsorption by amorphous clay-mineral derivatives. Clays and Clay minerals, 47, No. 5, pp. 647-657.
Welte, D. H., Schaefer, R. G., and Yalcin, M. N., (1988) Gas generation from source rocks; aspects of a quantitative treatment. Chemical Geology, 71, pp. 105-116.
Wood, G. O., (1992) Activated carbon adsorption capacities for vapors. Carbon, 30, No. 4, pp. 593-599.