跳到主要內容

臺灣博碩士論文加值系統

(3.231.230.177) 您好!臺灣時間:2021/07/28 22:19
字體大小: 字級放大   字級縮小   預設字形  
回查詢結果 :::

詳目顯示

我願授權國圖
: 
twitterline
研究生:邵琬淳
研究生(外文):Wan-Chun Shao
論文名稱:添加N-甲基甲醯胺和4-甲基嗎啉對於甲烷水合物分解狀態與生成動力學影響之實驗量測
論文名稱(外文):Measurements for the Dissociation Conditions and Formation Kinetics of Methane Hydrate in the Presence of 4- Methlymorpholine and N-Methylformamide
指導教授:陳延平陳延平引用關係
口試委員:陳立仁林祥泰
口試日期:2015-06-23
學位類別:碩士
校院名稱:國立臺灣大學
系所名稱:化學工程學研究所
學門:工程學門
學類:化學工程學類
論文種類:學術論文
論文出版年:2015
畢業學年度:103
語文別:中文
論文頁數:123
中文關鍵詞:甲烷水合物熱力學相平衡等容溫度循環法水合物生成動力學4-甲基嗎啉N-甲基甲醯胺四氫呋喃
外文關鍵詞:methane hydrateisochoric methoddissociation conditionformation kineticstetrahydrofuranN-methylformamide4-methylmorpholine
相關次數:
  • 被引用被引用:1
  • 點閱點閱:108
  • 評分評分:
  • 下載下載:0
  • 收藏至我的研究室書目清單書目收藏:0
本研究延續採用先前已建立之高壓設備裝置,並利用等容溫度循環法量測甲烷水合物分解之熱力學三相相平衡曲線 (H-Lw-V),探討不同添加劑以及濃度對於甲烷水合物系統熱力學相平衡數據的影響。在水合物動力學部份,以等容先降溫後升壓之方法量測甲烷水合物,探討在不同變因下對於水合物的生成行為有何影響。
本研究選用添加劑為N-甲基甲醯胺 (N-Methylformamide) 及4-甲基嗎啉 (4-Methylmorpholine),實驗結果顯示當N-甲基甲醯胺及4-甲基嗎啉存在時,使甲烷水合物相平衡曲線往低溫高壓移動,縮小水合物穩定形成的溫壓區域,達到熱力學抑制的效果,且此抑制效果亦隨著添加劑濃度增加而提升,添加30 wt% N-甲基甲醯胺時,約可抑制9 K;添加30 wt% 4-甲基嗎啉,約可抑制6 K。在水合物生成動力學部分,以壓力為變因,固定系統溫度的方式進行動力學實驗,並以過飽和梯度視為實驗趨動力。本研究以四氫呋喃(Tetrahydrofuran) 來進行實驗。實驗結果顯示,當趨動力越大時,水合物生成之誘導時間有越短的趨勢,水合物前半段的生成速率有較快的趨勢,平衡時甲烷所消耗的總量也有增加的趨勢,可以提升水合物的生成量。另外,動力學實驗以4-甲基嗎啉之水合物系統進行實驗量測,探討驅動力對甲烷水合物生成行為的影響。實驗結果顯示,系統初始驅動力較高,可縮短誘導時間,亦可提升水合物的生成量,對於水合物初始生成速率則無明顯的影響。


In this study, an apparatus which can be operated at low temperature and high pressure conditions was set up to measure the hydrate-liquid water-vapor (H-Lw-V) three-phase dissociation conditions of methane hydrate in the presence of additives by employing the isochoric method. The certain additives to system of methane + water were investigated for their effects on the phase boundary of methane hydrate. Also, the kinetic behavior of methane hydrate was investigated in an isochoric system to see how factors (e.g. sub-cooling temperature, experimental pressure) would affect the formation kinetics of methane hydrate.

In this work, N-methylformamide and 4-methylmorpholine were chosen as additives. The addition of N-methylformamide and 4-methylmorpholine in methane hydrate system shifted hydrate phase boundaries to higher pressure and lower temperatureand thus the hydrate stability region was reduce. Furthermore, the inhibition effect increased when the concentration of N-methylformamide and 4-methylmorpholine in hydrate system increased. With 30 wt% N-methylformamide, the equilibrium temperature decreases about 9.05 K at given pressure in comparison to that of pure water system. With 30 wt% 4-methylmorpholine, the equilibrium temperature decreases about 6.85 K at given pressure in comparison to that of pure water system.

In the formation kinetics of methane hydrate, tetrahydrofuran was chosen as additive. With increasing degree of supersaturation, the results showed that tetrahydrofuran could shorten the induction time needed for hydrate formation. In addition, the kinetic experiment also chose 4-methylmorpholine as additive.


摘要 I
Abstract II
目錄 IV
表目錄 VI
圖目錄 VIII
第一章緒論 1
1-1天然氣水合物簡介 2
1-2天然氣水合物的發展 4
1-3天然氣水合物相關應用 6
1-4研究動機與方向 9
第二章文獻回顧 11
2-1相關理論 11
2-1.1自由度計算與水合物相圖 11
2-1.2水合物生成機制 14
2-1.3記憶效應 15
2-2水合物結構之鑑定 17
第三章實驗裝置與方法 20
3-1實驗藥品與設備 20
3-2實驗方法 21
3-3 實驗步驟 22
3-3.1熱力學 22
3-3.2動力學 25
3-4實驗數據分析 27
第四章結果與討論 30
4-1溫度循環流程之探討 30
4-2純水系統對比實驗 32
4-3添加劑的選用 33
4-4甲烷水合物於添加劑系統的相平衡實驗量測 35
4-4.1快速溫度循環 35
4-4.2甲烷+純水+N-甲基甲醯胺之水合物系統相平衡數據 37
4-4.3甲烷+純水+4-甲基嗎啉之水合物系統相平衡數據 39
4-5甲烷水合物於添加劑系統的生成動力學實驗量測 41
4-5.1甲烷+純水+四氫呋喃之水合物系統 41
4-5.2甲烷+純水+4-甲基嗎啉之水合物系統 43
第五章結論 46
參考文獻 116

Afzal, W., Mohammadi, A. H. and Richon, D., ''Experimental measurements and predictions of dissociation conditions for methane, ethane, propane, and carbon dioxide simple hydrates in the presence of diethylene glycol aqueous solutions,'' Journal of Chemical and Engineering Data, 53, 663-666 (2008)
Chatti, I., Delahaye, A., Fournaison, L., Petitet, J. P., ''Benefits and drawbacks of clathrate hydrates: a review of their areas of interest,'' Energy Conversion and Management, 46(9-10) 1333-1343 (2005)
CRC, Handbook of Chemistry and Physics 96th
De Deugd, R. M., Jager, M. D.,Arons, J. D., ''Mixed hydrates of methane and water-soluble hydrocarbons modeling of empirical results,'' AIChE Journal., 47(3), 693-704 (2001)
Deroo, J. L., Peters, C. J., Lichtenthaler, R. N. and Diepen, G. A. M., ''Occurrence of methane hydrate in saturated and unsaturated solutions of sodium chloride and water in dependence of temperature and pressure, '' AIChE Journal, 29, 651-657 (1983)
Englezos, P. and Ngan, Y. T., ''Effect of polyethylene oxide on gas hydrate phase-equilibria, '' Fluid Phase Equilibria, 92, 271-288 (1994)
Golombok, M., Ineke, E., Luzardo, J.C.R., He, Y.Y. and Zitha, P.,'' Resolving CO2 and methane hydrate formation kinetics,'' Environmental Chemistry Letters, 7, 325-330 (2009)
Grozdanic, D. K., ''Acentric factor estimation from the corresponding statesprinciple,'' Journal of the Serbian Chemical Society., 71, 213-221 (2006)
Hara, T., Hashimoto, S., Sugahara, T. and Ohgaki, K., ''Large pressure depression of methane hydrate by adding 1,1-dimethylcyclohexane,'' Chemical Engineering Science, 60, 3117-3119 (2005)
He, Y., Rudolph, E. S. J., Zitha, P. L. J.,Golombok, M., ''Kinetics of CO2 and methane hydrate formation: An experimental analysis in the bulk phase,'' Fuel 90, 272-279.(2011)
Jager, M.D., de Deugd, R.M., Peters, C.J., de Swaan Arons, J. and Sloan, E.D., ''Experimental determination and modeling of structure II hydrates in mixtures of methane+water+1,4-dioxane,'' Fluid Phase Equilibria, 165, 209-223 (1999)
Jeffrey, G.A., ''Hydrate inclusion compounds,'' Journal of Inclusion Phenomena, 1, 211-222 (1984)
Kang, S. P. and Lee, H., ''Recovery of CO2 from flue gas using gas hydrate., Thermodynamic verification through phase equilibrium measurements,'' Environmental Science and Technology, 34, 4397-4400 (2000)
Khokhar, A. A., Gudmundsson, J. S. and Sloan, E. D., ''Gas storage in structure H hydrates,'' Fluid Phase Equilibria, 150-151, 383-392 (1998)
Kozaki, T., Takeya, S. and Ohmura, R., ''Phase Equilibrium and Crystallographic Structures of Clathrate Hydrates Formed in Methane+2,2-Dimethylpentane plus Water System,'' Journal of Chemical and Engineering Data, 53, 2820-2823 (2008)
Kvenvolden, K. A., ''Potential effects of gas hydrate on human welfare,'' Proceedings of the National Academy of Sciences of the United States of America, 96(7), 3420-3426 (1999)
Kvenvolden, K.A. and Rogers, B.W. ''Gaia’s breath—global methane exhalations,'' Marine and Petroleum Geology, 22, 579-590 (2005)
Lederhos, J. P., Long, J. P., Sum, A., Christiansen, R. L. and Sloan, E. D., ''Effective kinetic inhibitors for natural gas hydrates,'' Chemical Engineering Science, 51, 1221-1229 (1996)
Lee, H. J., Lee, J. D.,Linga, P., Englezos, P., Kim, Y. S., Lee, M. S., Kim, Y. D.,''Gas hydrate formation process for pre-combustion capture of carbon dioxide,'' Energy, 35, 2729-2733 (2010)
Lee, J., Shin, C. and Lee, Y., ''Experimental investigation to improve the storage potentials of gas hydrate under the unstirring condition,'' Energy and Fuels, 24, 1129-1134 (2010)
Lee, J. D., Susilo, R. and Englezos, P., ''Kinetics of structure H gas hydrate,'' Energy and Fuels, 19, 1008-1015 (2005)
Lee, Y., Lee, S., Park, S., Kim, Y., Lee, J. W. and Seo, Y., ''2-Propanol As a Co-Guest of Structure II Hydrates in the Presence of Help Gases,'' Journal of Physical Chemistry B, 117, 2449−2455 (2013)
Linga, P., Kumar, R., Englezos, P., ''Gas hydrate formation from hydrogen/carbon dioxide and nitrogen/carbon dioxide gas mixtures,'' Chemical Engineering Science, 62, 4268-4276 (2007)
Luzi, M., Schicks, J. M., Naumann, R. and Erzinger, J., ''Systematic kinetic studies on mixed gas hydrates by Raman spectroscopy and powder X-ray diffraction,'' Journal of Chemical Thermodynamics, 48, 28-35 (2012)
Makogon Y. F., ''Natural gas hydrates – A promising source of energy,'' Journal of Natural Gas Science and Engineering, 2, 49–59 (2010)
Mehta, A. P. and Sloan, E. D., ''Structure-H hydrate phase-equilibria of methane plus liquid-hydrocarbon mixtures,'' Journal of Chemical and Engineering Data, 38, 580-582 (1993)
Mimachi, H., Ito, M., Takahashi, M. & Sano, K., ''Examination of Self-Preservation Mechanism for Hydrate Pellet by Internal Texture Analysis,'' Mitsui Zosen Technical Review, 205, 20-24 (2012)
Mohammadi, A. H., Aftal, W. and Richon, D., ''Experimental data and predictions of dissociation conditions for ethane and propane simple hydrates in the presence of distilled water and methane, ethane, propane, and carbon dioxide simple hydrates in the presence of ethanol aqueous solutions, '' Journal of Chemical and Engineering Data, 53, 73-76 (2008a)
Mohammadi, A. H., Afzal, W. and Richon, D., ''Experimental data and predictions of dissociation conditions for ethane and propane simple hydrates in the presence of methanol, ethylene glycol, and triethylene glycol aqueous solutions, '' Journal of Chemical and Engineering Data, 53, 683-686 (2008b)
Mohammadi, A. H., Afzal, W. and Richon, D., ''Gas hydrates of methane, ethane, propane, and carbon dioxide in the presence of single NaCl, KCl, and CaCl2 aqueous solutions: Experimental measurements and predictions of dissociation conditions, '' Journal of Chemical Thermodynamics, 40, 1693-1697 (2008c)
Mohammadi, A. H., Kraouti, I. and Richon, D. ''Experimental Data and Predictions of Dissociation Conditions for Methane, Ethane, Propane, and Carbon Dioxide Simple Hydrates in the Presence of Glycerol Aqueous Solutions,'' Industrial and Engineering Chemistry Research, 47, 8492-8495 (2008d)
Mooijer-van den Heuvel, M. M., Peters, C. J. and Arons, J. D. ''Influence of water-insoluble organic components on the gas hydrate equilibrium conditions of methane,'' Fluid Phase Equilibria, 172, 73-91 (2000)
Mooijer-van den Heuvel, M. M., ''Phase behaviour and structural aspects of ternary clathrate hydrate systems - The role of additives,'' Proefschrift, 1-260 (2004)
Mooijer-van den Heuvel, M. M., Sawirjo, N. M. and Peters, C. J., ''Influence of fluoroalkanes on the phase behaviour of methane gas hydrate systems,'' Fluid Phase Equilibria, 241, 124-137 (2006)
Nakamura, T., Makino, T., Sugahara, T. and Ohgaki, K., ''Stability boundaries of gas hydrates helped by methane-structure-H hydrates of methylcyclohexane and cis-1,2-dimethylcyclohexane, ''Chemical Engineering Science, 58, 269-273 (2003)
Ng, H. J. and Robinson, D. B., ''Hydrate formation in systems containing methane, ethane, propane, carbon-dioxide or hydrogen-sulfide in the presence of methanol, '' Fluid Phase Equilibria, 21, 145-155 (1985)
North, W. J., Blackwell, V. R. and Morgan, J. J., ''Studies of CO2 hydrate formationand dissolution, Environmental,'' Science and Technology, 32, 676-681 (1998)
Ohmura, R., Uchida, T., Takeya, S., Nagao, J., Minagawa, H., Ebinuma, T. and Narita, H., '' Phase equilibrium for structure - H hydrates formed with methane and either pinacolone (3,3-dimethyl-2-butanone) or pinacolylalcohol (3,3-dimethyl-2-butanol),'' Journal of Chemical and Engineering Data, 48, 1337-1340 (2003)
Ohmura, R., Matsuda, S., Takeya, S., Ebinuma, T. and Narita, H., ''Phase equilibrium for structure-H hydrates formed with methane and methyl-substituted cyclic ether,'' International Journal of Thermophysics, 26, 1515-1523 (2005)
Ostergaard, K. K., Tohidi, B., Anderson, R., Todd, A. C. and Danesh, A., ''Can 2-propanol form clathrate hydrates?, '' Industrial and Engineering Chemistry Research, 41, 2064-2068 (2002)
Ota, M., Abe, Y., Watanabe, M., Smith, R. L., Inomata, H., ''Methane recovery from methane hydrate using pressurized CO2,'' Fluid Phase Equilibria, 228, 553-559 (2005)
Park, S., Ro, H., Lee, J.W., Kang H., Lee, H., ''Morpholine-Induced Thermodynamic and Kinetic Inhibitions on Gas, '' Energy & Fuels, 23, 6581-6586 (2013)
Rauh, F. and Mizaikoff, B., ''Spectroscopic methods in gas hydrate research,'' Analytical and Bioanalytical Chemistry, 402, 163-173 (2012)
Sabil, K. M., Duarte, A. R. C., Zevenbergen, J., Ahmad, M. M., Yusup, S., Omar, A. A. and Peters, C. J., ''Kinetic of formation for single carbon dioxide and mixed carbon dioxide and tetrahydrofuran hydrates in water and sodium chloride aqueous solution,'' International Journal of Greenhouse Gas Control, 4, 798-805 (2010)
Seo, Y. T., Kang, S. P. and Lee, H., ''Experimental determination and thermodynamic modeling of methane and nitrogen hydrates in the presence of THF, propyleneoxide, 1,4-dioxane and acetone,'' Fluid Phase Equilibria, 189, 99-110 (2001)
Sloan, E. D., ''Fundamental principles and applications of natural gas hydrates,'' Nature, 426, 353-359 (2003)
Sloan, E. D. and Fleyfel, F., ''Hydrate dissociation enthalpy and guest size,'' Fluid Phase Equilibria, 76, 123-140 (1992)
Sloan, E. D. and Koh, C. A., ''Clathrate hydrates of natural gases,'' Third Edition, 1-699 (2008)
Stern, L.A., Circone, S., Kirby, S.H. & Durham,W.B., ''Anomalous Preservation of Methane Hydrate at 1 atm, '' Journal of Physical Chemistry B, 105, 1756-1762 (2001)
Szycher''s Handbook of Polyurethanes, 2nd Edition
Thomas, S. and Dawe, R. A., ''Review of ways to transport natural gas energy fromcountries which do not need the gas for domestic use,'' Energy, 28, 1461-1477 (2003)
Tohidi, B., Danesh, A., Burgassm, R.W., Todd, A.C., '' Equilibrium data and thermodynamic modelling of cyclohexane gas hydrates,'' Chemical Engineering Science, 51, 159-163 (1996)
Tohidi, B., Danesh, A., Tabatabaei A.R., Todd, A.C., ''Vapor−Hydrate Equilibrium Ratio Charts for Heavy Hydrocarbon Compounds: 1. Structure-II Hydrates:  Benzene, Cyclopentane, Cyclohexane, and Neopentane,'' Industrial & Engineering Chemistry Research, 36, 2871-2874 (1997)
Tohidi, B., Danesh, A., Todd, A. C., Burgass, R. W. and Ostergaard, K. K., ''Equilibrium data and thermodynamic modelling of cyclopentane and neopentane hydrates, '' Fluid Phase Equilibria, 138, 241-250 (1997)
李立婷 添加乙醯胺、環戊醇及1,3-二氧六環對於甲烷水合物分解狀態與動力學數據之實驗量測,國立臺灣大學化學工程學研究所碩士論文 (2014)
阮郁雯 添加環戊酮與二丙酮醇對於甲烷水合物分解狀態與動力學數據之實驗量測,國立臺灣大學化學工程學研究所碩士論文 (2013)
吳宗澤 添加2-呋喃甲胺對於甲烷水合物分解狀態與動力學數據之實驗量測,國立臺灣大學化學工程學研究所碩士論文 (2012)
鄭智恬 添加2,5-二氫呋喃、3,4-二氫-2H-

QRCODE
 
 
 
 
 
                                                                                                                                                                                                                                                                                                                                                                                                               
第一頁 上一頁 下一頁 最後一頁 top