Phase Equilibrium of Methane Hydrates in the Presence of AlCl<sub>3</sub>

ZHENG Yan-hong; LEI Huai-yan; WANG Feng; WU Bao-xiang

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Article Navigation > Acta Sedimentologica Sinica > 2002 > 20(3): 519-523

ZHENG Yan-hong, LEI Huai-yan, WANG Feng, WU Bao-xiang. Phase Equilibrium of Methane Hydrates in the Presence of AlCl3[J]. Acta Sedimentologica Sinica, 2002, 20(3): 519-523.

Citation:

ZHENG Yan-hong, LEI Huai-yan, WANG Feng, WU Bao-xiang. Phase Equilibrium of Methane Hydrates in the Presence of AlCl₃[J]. Acta Sedimentologica Sinica, 2002, 20(3): 519-523.

Phase Equilibrium of Methane Hydrates in the Presence of AlCl₃

1 State Key Laboratory of Gas Geochemistry, Lanzhou Institute of Geology, Chinese Academy Sciences, Lanzhou,730000;
2 University of Petroleum, Beijing,102249

Received Date: 2001-09-06

Abstract

Methane hydrates are nonstoichiometric crystalline compounds. They are formed by Water molecules that are linked together With hydrogen bonds and f or ma three -dimensional structure With cavities. The cavities can be occupied by certain molecules of methane gases. One cavity can accommodate only one molecule. These molecules should not interfere With the hydrogen bonds among the Water molecules，and they should have molecular diameters that are smaller than the diameter of the cavity. Methane hydrates play an important role in the exploitation，transportation,and processing of natural gas. There is a risk of hydrate formation at all the stages of natural gas handling due to the operating conditions of pressure and temperature that favor hydrate formation. We mainly discussed the equilibrium conditions of methane hydrates in this paper. The three- phase(H- LW- V）equilibrium of the methane hydrate experiment system in aqueous solutions containing AlCl ₃ Was experimentally measured at pressures ranging from 4. 040 to 8. 382 MPa and at temperatures between 272. 15 and 278. 15K using the isothermal pressure search method. The addition of AlCl ₃ exhibited a stronger inhibition effect as that observed f or other electrolytes(KCl)With the same concentration and discussed the reason. An empirical exponential equation is proposed to Well correlate the measured data for aqueous solution. The computed values matched the experimental data obtained in this Work very Well. At last,the aqueous solutions containing AlCl₃ is a better inhibitor for oil gas pipeline in the oil-gas industry.
- methane hydrates,
- AlCl₃solutions,
- phase equilibrium

References

[1]	Frost E M,Deaton W M.Gas hydrate composition and equilibrium data [J]. Oil and Gas J, 1946, 45: 170～178
[2]	Guang-Jin Chen, Tian-Min Guo. Thermodynamic modeling of hydrate formation based on new concepts [J]. Fluid Phase Equilibrium, 1996, 122 : 43～65
[3]	Tatsuo Maekawa,Noboru Iami. Equilibrium conditions of methane and ethane hydrates in aqueous electrolyte solutions [J]. Geological Survey of Japan, 1995
[4]	Englezos P,Bishnoi P R. Prediction of gas hydrate formation conditions in aqueous electrolyte solutions [J]. AIChE J, 1988, 34: 1 718～1 721
[5]	Adisasmito S, et al. Hydrates of carbon dioxide and methane mixtures [J]. J Chem Eng Data, 1991, 36:68～71
[6]	AslejΦssang, Ellen Stange. Calculation of gas hydrate equilibrium in presence of aqueous salt solutions using a new predictive activity model [C]. Annuals New York Academy of Sciences
[7]	Dholabhai P D, et al. Equilibrium conditions for methane hydrate formation in aqueous mixed electrolyte solutions [J]. Can J Chen Eng, 1991, 69:800～805
[8]	Englezos P,Bishnoi P R.Experimental study on the equilibrium ethane hydrate formation conditions in aqueous electrolyte solutions[J]. I.& EC Research, 1991,30:1 655～1 659
[9]	Dholhai P D, Bishnoi P R.Hydrate equilibrium conditions in aqueous electrolyte solutions: mixtures of methane and carbon dioxide[J]. J Chem Eng Data, 1994, 39:191～194
[10]	Robinson D B,Ng H-J. Research report RR-66; Gas Processors Association.Tulsa, OK; 1983
[11]	Ng H-J,Robinson D B. Research Report RR-74; Gas Processors Association: Tulsa, OK, 1984
[12]	Ng H-J, Robinson D B. Fluid phase equilib. 1985, 21:145
[13]	Song K Y,Kobayashi R. Final hydrate stability conditions of a methane and propane mixture in the presence of pure water and aqueous solutions of methanol and ethylene glycol[J]. Fluid Phase Equilib, 1989, 47:295～308
[14]	Knox W G, Hess M, Jones G E,Smith H B.The hyorsate process[J]. Chem. Eng. Prog.,1961, 57:66
[15]	Kubota H, Shimizu K, Tanaka Y, Makita T J.Dissociation heat transfer characteristics of methane hydrateds[J]. Chem. Eng. Jpn., 1984, 17:423
[16]	Berecz E, Balla Achs M. Research report No. 37 (185-XI-1-1974 OGIL), NME, Technical university of heavy industry, Miskoic, Hungary, as summarized in: Gas Hydrates; Studies in Inorganic Chemistry. Vol 4; New York: Elsevier, 1983. 343
[17]	Sloan E D.Clathrate Hydrates of Natural Gases[M].New York: Marcell Dekker, Inc.,1990
[18]	Bishnoi P R, Dholabhai P D. Experimental study on propane hydrate equilibrium conditions in aqueous electrolyte solutions[J]. Fluid Phase Equilibria, 1993, 83: 455～462
[19]	Englezos P, Bishnoi P R. Formation condition in aqueous in electrolyte solution Ind[J]. Eng. Chem. Res., 1991, 30:1 655～1 659
[20]	Mei Donghai, Liao Jian, Yang Jitao, Guo Tianmin. Hydrate formation of a synthetic natural gas mixture in aqueous solutions containing electrolyte, Methanol, and (Electrolte+Methanol)[J]. J. Chem. Eng Data, 1998,43:178～182
[21]	Majumadar A, Mahmoodaghdam E, Boshinoi P R. Equilibrium hydrate formation conditions for hydrogen, sulfide, carbon dioxide, and ethane in aqueous solutions of ethylene glycol and sodium chloride[J]. J. Chem. Eng. Data, 2000, 45:20～22
[22]	马昌锋.水合物分离技术[D].2001[Ma Changfeng.The dissertation of the hydrates.[D].2001]
[23]	雷怀彦,王先彬等.天然气水合物研究现状与未来挑战[J]. 沉积学报,1999, 17(3):493～498[Lei Huaiyan,Wang Xianbin,et al.The research situation and future challenge on natural gas hydrates [J].Acta Sedimentologica Sinica,1999,17(3):493～498]
[24]	雷怀彦,王先彬,郑艳红等.天然气水合物地质前景[J]. 沉积学报, 1999, 17:846～853[Lei Huaiyan,Wang Xianbin,Zheng Yanhong,et al.The geological perspective of natural gas hydrates [J].Acta Sedimentologica Sinica,1999,17(Suppl):846～853]

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Phase Equilibrium of Methane Hydrates in the Presence of AlCl₃

1 State Key Laboratory of Gas Geochemistry, Lanzhou Institute of Geology, Chinese Academy Sciences, Lanzhou,730000;

2 University of Petroleum, Beijing,102249

Received Date: 2001-09-06

Key words:

Abstract: Methane hydrates are nonstoichiometric crystalline compounds. They are formed by Water molecules that are linked together With hydrogen bonds and f or ma three -dimensional structure With cavities. The cavities can be occupied by certain molecules of methane gases. One cavity can accommodate only one molecule. These molecules should not interfere With the hydrogen bonds among the Water molecules，and they should have molecular diameters that are smaller than the diameter of the cavity. Methane hydrates play an important role in the exploitation，transportation,and processing of natural gas. There is a risk of hydrate formation at all the stages of natural gas handling due to the operating conditions of pressure and temperature that favor hydrate formation. We mainly discussed the equilibrium conditions of methane hydrates in this paper. The three- phase(H- LW- V）equilibrium of the methane hydrate experiment system in aqueous solutions containing AlCl ₃ Was experimentally measured at pressures ranging from 4. 040 to 8. 382 MPa and at temperatures between 272. 15 and 278. 15K using the isothermal pressure search method. The addition of AlCl ₃ exhibited a stronger inhibition effect as that observed f or other electrolytes(KCl)With the same concentration and discussed the reason. An empirical exponential equation is proposed to Well correlate the measured data for aqueous solution. The computed values matched the experimental data obtained in this Work very Well. At last,the aqueous solutions containing AlCl₃ is a better inhibitor for oil gas pipeline in the oil-gas industry.

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Reference (24)

[1]	Frost E M,Deaton W M.Gas hydrate composition and equilibrium data [J]. Oil and Gas J, 1946, 45: 170～178
[2]	Guang-Jin Chen, Tian-Min Guo. Thermodynamic modeling of hydrate formation based on new concepts [J]. Fluid Phase Equilibrium, 1996, 122 : 43～65
[3]	Tatsuo Maekawa,Noboru Iami. Equilibrium conditions of methane and ethane hydrates in aqueous electrolyte solutions [J]. Geological Survey of Japan, 1995
[4]	Englezos P,Bishnoi P R. Prediction of gas hydrate formation conditions in aqueous electrolyte solutions [J]. AIChE J, 1988, 34: 1 718～1 721
[5]	Adisasmito S, et al. Hydrates of carbon dioxide and methane mixtures [J]. J Chem Eng Data, 1991, 36:68～71
[6]	AslejΦssang, Ellen Stange. Calculation of gas hydrate equilibrium in presence of aqueous salt solutions using a new predictive activity model [C]. Annuals New York Academy of Sciences
[7]	Dholabhai P D, et al. Equilibrium conditions for methane hydrate formation in aqueous mixed electrolyte solutions [J]. Can J Chen Eng, 1991, 69:800～805
[8]	Englezos P,Bishnoi P R.Experimental study on the equilibrium ethane hydrate formation conditions in aqueous electrolyte solutions[J]. I.& EC Research, 1991,30:1 655～1 659
[9]	Dholhai P D, Bishnoi P R.Hydrate equilibrium conditions in aqueous electrolyte solutions: mixtures of methane and carbon dioxide[J]. J Chem Eng Data, 1994, 39:191～194
[10]	Robinson D B,Ng H-J. Research report RR-66; Gas Processors Association.Tulsa, OK; 1983
[11]	Ng H-J,Robinson D B. Research Report RR-74; Gas Processors Association: Tulsa, OK, 1984
[12]	Ng H-J, Robinson D B. Fluid phase equilib. 1985, 21:145
[13]	Song K Y,Kobayashi R. Final hydrate stability conditions of a methane and propane mixture in the presence of pure water and aqueous solutions of methanol and ethylene glycol[J]. Fluid Phase Equilib, 1989, 47:295～308
[14]	Knox W G, Hess M, Jones G E,Smith H B.The hyorsate process[J]. Chem. Eng. Prog.,1961, 57:66
[15]	Kubota H, Shimizu K, Tanaka Y, Makita T J.Dissociation heat transfer characteristics of methane hydrateds[J]. Chem. Eng. Jpn., 1984, 17:423
[16]	Berecz E, Balla Achs M. Research report No. 37 (185-XI-1-1974 OGIL), NME, Technical university of heavy industry, Miskoic, Hungary, as summarized in: Gas Hydrates; Studies in Inorganic Chemistry. Vol 4; New York: Elsevier, 1983. 343
[17]	Sloan E D.Clathrate Hydrates of Natural Gases[M].New York: Marcell Dekker, Inc.,1990
[18]	Bishnoi P R, Dholabhai P D. Experimental study on propane hydrate equilibrium conditions in aqueous electrolyte solutions[J]. Fluid Phase Equilibria, 1993, 83: 455～462
[19]	Englezos P, Bishnoi P R. Formation condition in aqueous in electrolyte solution Ind[J]. Eng. Chem. Res., 1991, 30:1 655～1 659
[20]	Mei Donghai, Liao Jian, Yang Jitao, Guo Tianmin. Hydrate formation of a synthetic natural gas mixture in aqueous solutions containing electrolyte, Methanol, and (Electrolte+Methanol)[J]. J. Chem. Eng Data, 1998,43:178～182
[21]	Majumadar A, Mahmoodaghdam E, Boshinoi P R. Equilibrium hydrate formation conditions for hydrogen, sulfide, carbon dioxide, and ethane in aqueous solutions of ethylene glycol and sodium chloride[J]. J. Chem. Eng. Data, 2000, 45:20～22
[22]	马昌锋.水合物分离技术[D].2001[Ma Changfeng.The dissertation of the hydrates.[D].2001]
[23]	雷怀彦,王先彬等.天然气水合物研究现状与未来挑战[J]. 沉积学报,1999, 17(3):493～498[Lei Huaiyan,Wang Xianbin,et al.The research situation and future challenge on natural gas hydrates [J].Acta Sedimentologica Sinica,1999,17(3):493～498]
[24]	雷怀彦,王先彬,郑艳红等.天然气水合物地质前景[J]. 沉积学报, 1999, 17:846～853[Lei Huaiyan,Wang Xianbin,Zheng Yanhong,et al.The geological perspective of natural gas hydrates [J].Acta Sedimentologica Sinica,1999,17(Suppl):846～853]

Phase Equilibrium of Methane Hydrates in the Presence of AlCl₃

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Phase Equilibrium of Methane Hydrates in the Presence of AlCl₃

1 State Key Laboratory of Gas Geochemistry, Lanzhou Institute of Geology, Chinese Academy Sciences, Lanzhou,730000;

2 University of Petroleum, Beijing,102249

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Phase Equilibrium of Methane Hydrates in the Presence of AlCl3

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Phase Equilibrium of Methane Hydrates in the Presence of AlCl3

1 State Key Laboratory of Gas Geochemistry, Lanzhou Institute of Geology, Chinese Academy Sciences, Lanzhou,730000; 2 University of Petroleum, Beijing,102249

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Phase Equilibrium of Methane Hydrates in the Presence of AlCl₃

Phase Equilibrium of Methane Hydrates in the Presence of AlCl₃

1 State Key Laboratory of Gas Geochemistry, Lanzhou Institute of Geology, Chinese Academy Sciences, Lanzhou,730000;

2 University of Petroleum, Beijing,102249