天然气水合物生成影响因素及稳定性研究
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摘要
天然气水合物储存运输技术的开发有利于近海伴生气及零散气田的回收与利用,但是这种技术仍存在一系列问题需要解决。本论文对水合物的物理性质、生成影响因素和稳定性进行实验研究,为其工业应用打下基础。
论文开展了实验装置的设计、水合物物性测试、水合物生成实验、水合物储存实验、储运装置的设计、储运技术路线及其经济性分析等研究。
对水合物储气量、密度、比热和可燃性等进行了一系列实验测试,得到以下结论:实验测得的水合物的密度在0.8～0.95g/cm3之间;水合物的比热较小,零下20℃时水合物的比热为2.1J·g-1·℃-1;水合物燃烧受分解速度的影响不会发生爆炸。很多因素能影响水合物的生成,一定范围内,压力越高,温度越低,形成水合物的含气率越高;一定时间内,水合物含气率随着反应时间的增加逐渐增大;与纯水相比,加入十二烷基硫酸钠能大大提高了水合物的生成速度;水历史能缩短水合物形成的诱导时间,但其影响较小;搅拌能提高水合物的生成速度。研究了温度、压力、压实成型等对水合物稳定性的影响,水合物在不同温度(低温)常压储存,当水合物的自保性发挥作用后,水合物分解速度比较小;一定压力和压实处理都能提高了水合物的稳定性。对水合物陆上储存运输技术路线进行了初步研究,并与其它运输方式进行了技术、安全和经济方面的对比,水合物技术有一定优势,但是作为一种新技术,需要进一步开发和研究。
The development of natural gas hydrate storage and transportation technology is favorable for the recovery of offshore associated gas fields and the development of scattered gas field, but the technology still has a number of issues that need to be solved. This paper did experimental researches on the physical appearance, formation affection factors and stability of hydrates, and laid foundations for industrial application.
The major work of this paper includes: experimental device design, physical appearance test, formation and storage experiments of hydrate, storage device design, storage and transportation technology and its economical analysis, etc.
Experimental study was done on gas-bearing ratio, specific heat and flammability of hydrates. Density of hydrates measured in the experiment is during 0.8～0.95g/cm3. Specific heat of hydrates is small, which is 2.1J.g-1.℃-1 at the temperature of -20℃. Explosion will never happen during hydrates combustion due to the influence of decomposition rate. Many factors have impact on the formation of hydrates. In a certain range, the higher the pressure and the lower the temperature are, the higher the gas-bearing ratio of the formed hydrates will be. During a certain time, the gas-bearing ratio of hydrates increases with reaction time. Compared with pure water, the addition of sodium dodecyl sulfate can greatly increase the formation rate of hydrates. Water history can reduce the induction time of hydrates formation, but its influence is relatively small. Stirring can increase the formation rate of hydrates. Influences of temperature, pressure and compaction on the stability of hydrates and atmospheric storage at different temperature (low temperature) were studied. The decomposition rate of hydrates is relatively small after self-protection works. Pressure and compaction can improve the hydrates stability. Onshore storage and transportation technology is studied preliminarily, and is compared with other transportation methods at technological, safe and economical aspects. Hydrates technology has certain advantages, but as a new technology, it still needs further development and study.
论文开展了实验装置的设计、水合物物性测试、水合物生成实验、水合物储存实验、储运装置的设计、储运技术路线及其经济性分析等研究。
对水合物储气量、密度、比热和可燃性等进行了一系列实验测试,得到以下结论:实验测得的水合物的密度在0.8～0.95g/cm3之间;水合物的比热较小,零下20℃时水合物的比热为2.1J·g-1·℃-1;水合物燃烧受分解速度的影响不会发生爆炸。很多因素能影响水合物的生成,一定范围内,压力越高,温度越低,形成水合物的含气率越高;一定时间内,水合物含气率随着反应时间的增加逐渐增大;与纯水相比,加入十二烷基硫酸钠能大大提高了水合物的生成速度;水历史能缩短水合物形成的诱导时间,但其影响较小;搅拌能提高水合物的生成速度。研究了温度、压力、压实成型等对水合物稳定性的影响,水合物在不同温度(低温)常压储存,当水合物的自保性发挥作用后,水合物分解速度比较小;一定压力和压实处理都能提高了水合物的稳定性。对水合物陆上储存运输技术路线进行了初步研究,并与其它运输方式进行了技术、安全和经济方面的对比,水合物技术有一定优势,但是作为一种新技术,需要进一步开发和研究。
The development of natural gas hydrate storage and transportation technology is favorable for the recovery of offshore associated gas fields and the development of scattered gas field, but the technology still has a number of issues that need to be solved. This paper did experimental researches on the physical appearance, formation affection factors and stability of hydrates, and laid foundations for industrial application.
The major work of this paper includes: experimental device design, physical appearance test, formation and storage experiments of hydrate, storage device design, storage and transportation technology and its economical analysis, etc.
Experimental study was done on gas-bearing ratio, specific heat and flammability of hydrates. Density of hydrates measured in the experiment is during 0.8～0.95g/cm3. Specific heat of hydrates is small, which is 2.1J.g-1.℃-1 at the temperature of -20℃. Explosion will never happen during hydrates combustion due to the influence of decomposition rate. Many factors have impact on the formation of hydrates. In a certain range, the higher the pressure and the lower the temperature are, the higher the gas-bearing ratio of the formed hydrates will be. During a certain time, the gas-bearing ratio of hydrates increases with reaction time. Compared with pure water, the addition of sodium dodecyl sulfate can greatly increase the formation rate of hydrates. Water history can reduce the induction time of hydrates formation, but its influence is relatively small. Stirring can increase the formation rate of hydrates. Influences of temperature, pressure and compaction on the stability of hydrates and atmospheric storage at different temperature (low temperature) were studied. The decomposition rate of hydrates is relatively small after self-protection works. Pressure and compaction can improve the hydrates stability. Onshore storage and transportation technology is studied preliminarily, and is compared with other transportation methods at technological, safe and economical aspects. Hydrates technology has certain advantages, but as a new technology, it still needs further development and study.
引文
[1] Davy H . The Bakerian Lecture,On some of the combinations of oxymuriatic gas and oxygene and on the chemical relations of these principles to inflammable bodies [M] . Philos. Trans . R .Soc . London 101, (part 1), 1-35, 1811
[2] Miller B et a1.Hydrate storage of natural gas [M]. Am Gas Associ Mon,1946;28(2):63～67
[3] Gudmundsson J S Method for production of gas hydrate for transportation and storage[P].US Patent No.5536893,1996
[4] Handa Y P. Composition,enthalpy of dissociation,and heat capacities in the range 85 to 270K for clathrate hydrates of methane, ethane, and propane,and enthalpy of dissociation of isobutene hydrate,as determined by heat-flow calorimeter[J] . J Chem Thermodynamics, 1986,18:915 - 921.
[5] Yakushev V.S.,and Istomin V.A.,Gas hydrates Self-Preservation Effect[J] . Physics and Chemistry of Ice. Hokkaido University Press,Sapporo,1992:136-139
[6] Gudmundsson J S et a1.Natural gas hydrate an alternative to liquefied natural gas[J].Petroleum Review,1996,50(5):232-235
[7] Javanmardi J et a1.Economic evaluation of natural gas hydrate as an alternative for natural gas transportation[J] .Appl Herm Eng,2005
[8]韩小辉等.表面活性剂加速天然气水合物生成实验研究[J].天然气工业,2002;22(5):90～93
[9]郝文峰等.搅拌对甲烷水合物生成的影响[J].天然气化工.2005;30(3):5～7
[10] Carlo Giavarini,Filippo Maccioni.Self-Preservation at Low Pressures of Methane Hydrates with Various Gas Contents[J].Ind. Eng. Chem. Res,Vol 43,No 20,2004
[11]林微等.甲烷水合物热稳定性的研究[J].天然气工业,2005;25(2):169～171
[12]邓友生,徐学祖,张志新.甲烷水合物合成的初步研究[J] .冰川冻土,1993,15 (1):144 -148
[13] Paull C,Matsumoto R,Wallace P.Proc.ODP,Init.Reps.164,College Station,1996
[14] Circone S,Kirby S H,Pinkston J C and Stern L A.Measurement of gas yields and flow rates using a custom flowmeter[J].Review of Scientific Instruments,2001,72:2709-2716
[15]刘昌岭等.天然气水合物储气量直接测定的实验技术[J].天然气工业,2005,25 (3):44-47
[16]赵建忠等.煤层气水合物分解动力学实验研究[J].辽宁工程技术大学学报,2006,25:298-300
[17]许维秀等.甲烷水合物热稳定性的研究[J].石油天然气学报.2006,28(3):141-142
[18]田龙,樊栓狮,郝文峰.甲烷水合物常压分解[J].武汉理工大学学报.2006,28(7):23-26
[19] [原苏联]贝克CШ,马可岗ЮФ,福米纳BИ.气体水化物[M].北京:石油工业出版社,1987:93-95
[20] Walden A T.Making AVO sections more robust.Geophysical Prospecting,1991,39:915-942
[21]何晓霞等.一种精确计算天然气水合物密度的方法[J].天然气工业,2004,24 (10):30～31
[22] Toru Iwasaki,Yuuich Katoh,Shigeru Nagamori et al.CONTINUOUS NATURAL GAS HYDRATE PELLET PRODUCTION(NGHP) BY PROCESS DEVELOPMENT UNIT (PDU)[C].Proceedings of the Fifth International Conference on Gas Hydrates,June 12-16, 2005.Trondheim,Norway
[23] Handa Y P. Composition,enthalpy of dissociation,and heat capacities in the range 85 to 270K for clathrate hydrates of methane, ethane, and propane,and enthalpy of dissociation of isobutene hydrate,as determined by heat-flow calorimeter[J] . J Chem Thermodynamics, 1986,18:915 - 921.
[24] Rueff R M,Sloan E D,Yesavage V F. Heat capacity and heat of dissociation of methane hydrate[J] . AIChE Journal,1988,34(9):1468–1476.
[25] R M Reuff. The heat capacity and heat of dissociation of methane hydrates:a new approach[D] . Colorado:Colorado School of Mines,PhD Thesis,1985
[26] Lievois J S. Development of an automated,high pressure heat flux calorimeter and its application to measure the heat of dissociation of methane hydrate [D] . Houston,TX:Rice University,PhD Thesis,1987
[27] L A Stern,S H Kirby,WB Durham. Science,1996,273:1843～1848.
[28] Y Zhong,R E Rogers. Chem. Eng. Sci.,2000,55:4175～4187.
[29] Y Saito,T Kawasaki,T Okui et al. In:2nd Int. Conf. on Nature Gas Hydrate,Toulouse, 1996:459.
[30] Z G Sun,R Z Wang,R S Ma et al. Energy Conversion and Management,2003,44: 2733～2742.
[31] M akogon Y F. Hydrate of N ature Gas[M] . USA:Pennwell,1981.
[32] V ysniauskasA,Bishnoi P R. A Kinetic study ofmethane hydrate formation [J] . Chem ical Engineering Science,1983,38:1061-1072.
[33]赵永利.致冷剂气体水合物结晶生成过程及其形态学实验研究[D] .博士论文,中国科学技术大学,2001.
[34] Nerheim R M,ThorM S, Em il K S. Investigation of gas hydrate formation kinetics by laser light scattering [D] . Ph D Thesis,Norwegian Institute of Technology,Trondbeim,1993.
[2] Miller B et a1.Hydrate storage of natural gas [M]. Am Gas Associ Mon,1946;28(2):63～67
[3] Gudmundsson J S Method for production of gas hydrate for transportation and storage[P].US Patent No.5536893,1996
[4] Handa Y P. Composition,enthalpy of dissociation,and heat capacities in the range 85 to 270K for clathrate hydrates of methane, ethane, and propane,and enthalpy of dissociation of isobutene hydrate,as determined by heat-flow calorimeter[J] . J Chem Thermodynamics, 1986,18:915 - 921.
[5] Yakushev V.S.,and Istomin V.A.,Gas hydrates Self-Preservation Effect[J] . Physics and Chemistry of Ice. Hokkaido University Press,Sapporo,1992:136-139
[6] Gudmundsson J S et a1.Natural gas hydrate an alternative to liquefied natural gas[J].Petroleum Review,1996,50(5):232-235
[7] Javanmardi J et a1.Economic evaluation of natural gas hydrate as an alternative for natural gas transportation[J] .Appl Herm Eng,2005
[8]韩小辉等.表面活性剂加速天然气水合物生成实验研究[J].天然气工业,2002;22(5):90～93
[9]郝文峰等.搅拌对甲烷水合物生成的影响[J].天然气化工.2005;30(3):5～7
[10] Carlo Giavarini,Filippo Maccioni.Self-Preservation at Low Pressures of Methane Hydrates with Various Gas Contents[J].Ind. Eng. Chem. Res,Vol 43,No 20,2004
[11]林微等.甲烷水合物热稳定性的研究[J].天然气工业,2005;25(2):169～171
[12]邓友生,徐学祖,张志新.甲烷水合物合成的初步研究[J] .冰川冻土,1993,15 (1):144 -148
[13] Paull C,Matsumoto R,Wallace P.Proc.ODP,Init.Reps.164,College Station,1996
[14] Circone S,Kirby S H,Pinkston J C and Stern L A.Measurement of gas yields and flow rates using a custom flowmeter[J].Review of Scientific Instruments,2001,72:2709-2716
[15]刘昌岭等.天然气水合物储气量直接测定的实验技术[J].天然气工业,2005,25 (3):44-47
[16]赵建忠等.煤层气水合物分解动力学实验研究[J].辽宁工程技术大学学报,2006,25:298-300
[17]许维秀等.甲烷水合物热稳定性的研究[J].石油天然气学报.2006,28(3):141-142
[18]田龙,樊栓狮,郝文峰.甲烷水合物常压分解[J].武汉理工大学学报.2006,28(7):23-26
[19] [原苏联]贝克CШ,马可岗ЮФ,福米纳BИ.气体水化物[M].北京:石油工业出版社,1987:93-95
[20] Walden A T.Making AVO sections more robust.Geophysical Prospecting,1991,39:915-942
[21]何晓霞等.一种精确计算天然气水合物密度的方法[J].天然气工业,2004,24 (10):30～31
[22] Toru Iwasaki,Yuuich Katoh,Shigeru Nagamori et al.CONTINUOUS NATURAL GAS HYDRATE PELLET PRODUCTION(NGHP) BY PROCESS DEVELOPMENT UNIT (PDU)[C].Proceedings of the Fifth International Conference on Gas Hydrates,June 12-16, 2005.Trondheim,Norway
[23] Handa Y P. Composition,enthalpy of dissociation,and heat capacities in the range 85 to 270K for clathrate hydrates of methane, ethane, and propane,and enthalpy of dissociation of isobutene hydrate,as determined by heat-flow calorimeter[J] . J Chem Thermodynamics, 1986,18:915 - 921.
[24] Rueff R M,Sloan E D,Yesavage V F. Heat capacity and heat of dissociation of methane hydrate[J] . AIChE Journal,1988,34(9):1468–1476.
[25] R M Reuff. The heat capacity and heat of dissociation of methane hydrates:a new approach[D] . Colorado:Colorado School of Mines,PhD Thesis,1985
[26] Lievois J S. Development of an automated,high pressure heat flux calorimeter and its application to measure the heat of dissociation of methane hydrate [D] . Houston,TX:Rice University,PhD Thesis,1987
[27] L A Stern,S H Kirby,WB Durham. Science,1996,273:1843～1848.
[28] Y Zhong,R E Rogers. Chem. Eng. Sci.,2000,55:4175～4187.
[29] Y Saito,T Kawasaki,T Okui et al. In:2nd Int. Conf. on Nature Gas Hydrate,Toulouse, 1996:459.
[30] Z G Sun,R Z Wang,R S Ma et al. Energy Conversion and Management,2003,44: 2733～2742.
[31] M akogon Y F. Hydrate of N ature Gas[M] . USA:Pennwell,1981.
[32] V ysniauskasA,Bishnoi P R. A Kinetic study ofmethane hydrate formation [J] . Chem ical Engineering Science,1983,38:1061-1072.
[33]赵永利.致冷剂气体水合物结晶生成过程及其形态学实验研究[D] .博士论文,中国科学技术大学,2001.
[34] Nerheim R M,ThorM S, Em il K S. Investigation of gas hydrate formation kinetics by laser light scattering [D] . Ph D Thesis,Norwegian Institute of Technology,Trondbeim,1993.