酸性天然气与水体系内超临界-气-液-水合物多相平衡模型

doi:10.7623/syxb202109008

石油学报 ›› 2021, Vol. 42 ›› Issue (9): 1212-1223.DOI: 10.7623/syxb202109008

酸性天然气与水体系内超临界-气-液-水合物多相平衡模型

孙小辉¹, 孙宝江¹, 王志远¹, 李航宇¹, Pan Lehua², 高永海¹, 廖友强¹

1. 中国石油大学(华东)石油工程学院山东青岛 266580;
2. 美国加利福尼亚大学伯克利分校劳伦斯伯克利国家实验室美国加利福尼亚 94720

收稿日期:2020-12-25 修回日期:2021-05-26 出版日期:2021-09-25 发布日期:2021-10-12
通讯作者: 孙宝江,男,1963年11月生,1985年获华东石油学院学士学位,1999年获北京大学博士学位,现为中国石油大学(华东)教授、博士生导师,主要从事深水钻完井和井筒多相流基础理论研究工作。Email:sunbj1128@126.com
作者简介:孙小辉,男,1991年3月生,2013年获中国石油大学(华东)学士学位,2020年获中国石油大学(华东)博士学位,现为中国石油大学(华东)师资博士后,主要从事多组分流体多相平衡与多相流理论研究工作。Email:sxh049306@163.com
基金资助:
博士后创新人才支持计划项目（BX2021374）和山东省博士后创新人才支持计划项目（SDBX2020005）资助。

Supercritical-gas-liquid-hydrate multiphase equilibrium model in the sour natural gas and water system

Sun Xiaohui¹, Sun Baojiang¹, Wang Zhiyuan¹, Li Hangyu¹, Pan Lehua², Gao Yonghai¹, Liao Youqiang¹

1. School of Petroleum Engineering, China University of Petroleum, Shandong Qingdao 266580, China;
2. Lawrence Berkeley National Laboratory, University of California, CA 94720, USA

Received:2020-12-25 Revised:2021-05-26 Online:2021-09-25 Published:2021-10-12

摘要/Abstract

摘要： 针对酸性天然气与水体系内超临界-气-液-水合物多相平衡，构建了基于Gibbs自由能最小化原理的多组分流体多相平衡模型。为了提高其鲁棒性和计算精度，提出了相态稳定性判别的热力学判据和相组成分析的约束优化模型；考虑分子间非对称相互作用，建立了改进的Peng-Robinson状态方程，提出了统一的气体多参数平衡常数关系式，构建了不同相态中的逸度模型；建立了CH₄+CO₂+H₂S+H₂O体系的相平衡实验数据库，提出了对相平衡模型参数进行同步确定的多参数非线性拟合算法。与传统模型对比结果表明，新模型的收敛性更好、计算误差更小。

关键词: 酸性气体, 相平衡, 水合物, Gibbs自由能, 最小化

Abstract: As for the supercritical-gas-liquid-hydrate multiphase equilibrium in the sour natural gas and water system, a multi-component fluid multiphase equilibrium model is established based on the minimization principle of Gibbs free energy. To improve the robustness and calculation accuracy of the above model, this paper proposes a thermodynamic criterion for phase stability judgment and a constrained optimization model for phase composition analysis. Considering the asymmetric interaction between molecules, the paper establishes an improved Peng-Robinson equation of state, puts forward a unified multi-parameter equilibrium constant relation of gas, and sets up a fugacity model under different phase states. Moreover, the paper establishes an experiment database of phase equilibrium of the CH₄+CO₂+H₂S+H₂O system, and proposes a multi-parameter nonlinear fitting algorithm for the simultaneous determination of parameters of the phase equilibrium model. Compared with the traditional model, the proposed model has better convergence and smaller calculation errors.

Key words: acid gas, phase equilibrium, hydrate, Gibbs free energy, minimization

中图分类号:

O642.42

孙小辉, 孙宝江, 王志远, 李航宇, Pan Lehua, 高永海, 廖友强. 酸性天然气与水体系内超临界-气-液-水合物多相平衡模型[J]. 石油学报, 2021, 42(9): 1212-1223.

Sun Xiaohui, Sun Baojiang, Wang Zhiyuan, Li Hangyu, Pan Lehua, Gao Yonghai, Liao Youqiang. Supercritical-gas-liquid-hydrate multiphase equilibrium model in the sour natural gas and water system[J]. Acta Petrolei Sinica, 2021, 42(9): 1212-1223.

参考文献

[1] 徐宝昌, 周家立, 刘伟, 等. 基于数据驱动的钻井过程气侵工况预测方法[J]. 石油学报, 2019, 40(10):1263-1269.
XU Baochang, ZHOU Jiali, LIU Wei, et al.Data driven prediction method for gas cut in drilling process[J]. Acta Petrolei Sinica, 2019, 40(10):1263-1269.
[2] 胡伟, 吕成远, 王锐, 等.水驱转CO₂混相驱渗流机理及传质特征[J]. 石油学报, 2018, 39(2):201-207.
HU Wei, LÜ Chengyuan, WANG Rui, et al.Porous flow mechanisms and mass transfer characteristics of CO₂ miscible flooding after water flooding[J]. Acta Petrolei Sinica, 2018, 39(2):201-207.
[3] 赵省民, 邓坚, 饶竹, 等.漠河盆地浅部气体特征及对天然气水合物形成的意义[J]. 石油学报, 2018, 39(3):266-277.
ZHAO Xingmin, DENG Jian, RAO Zhu, et al.Shallow gas characteristics in Mohe Basin, Northeast China and its significance to gas hydrate formation[J]. Acta Petrolei Sinica, 2018, 39(3):266-277.
[4] 韩海水, 李实, 姚小琪, 等.基于摩尔密度的原油-CO₂体系膨胀能力预测方法[J]. 石油学报, 2018, 39(4):456-462.
HAN Haishui, LI Shi, YAO Xiaoqi, et al.Swelling ability prediction method of crude oil-CO₂ system based on molar density[J]. Acta Petrolei Sinica, 2018, 39(4):456-462.
[5] DANESH A.PVT and phase behaviour of petroleum reservoir fluids[M]. Amsterdam:Elsevier, 1998.
[6] BALLARD A L.A non-ideal hydrate solid solution model for a multi-phase equilibria program[D].Golden:Colorado School of Mines, 2001.
[7] KHAN M N, WARRIER P, PETERS C J, et al.Advancements in hydrate phase equilibria and modeling of gas hydrates systems[J]. Fluid Phase Equilibria, 2018, 463:48-61.
[8] MICHELSEN M L.The isothermal flash problem.part I.stability[J]. Fluid Phase Equilibria, 1982, 9(1):1-19.
[9] MICHELSEN M L.The isothermal flash problem.part II.phase-split calculation[J]. Fluid Phase Equilibria, 1982, 9(1):21-40.
[10] REAGAN M T, MORIDIS G J, SEIM K S.Fast parametric relationships for the large-scale reservoir simulation of mixed CH₄-CO₂ gas hydrate systems[J]. Computers & Geosciences, 2017, 103:191-203.
[11] 陈光进.化工热力学[M]. 北京:石油工业出版社, 2006.
CHEN Guangjin.Chemical engineering thermodynamics[M]. Beijing:Petroleum Industry Press, 2006.
[12] AL-SAHHAF T A, KIDNAY A J, SLOAN E D.Liquid+vapor equilibriums in the nitrogen+carbon dioxide+methane system[J]. Industrial & Engineering Chemistry Fundamentals, 1983, 22(4):372-380.
[13] PENG Dingyu, ROBINSON D B.A new two-constant equation of state[J]. Industrial & Engineering Chemistry Fundamentals, 1976, 15(1):59-64.
[14] 孙小辉.考虑流体相变的深水井筒多相流动规律研究[D].青岛:中国石油大学(华东), 2020.
SUN Xiaohui.Research on the multiphase flow rules in deepwater wellbore considering the phase transitions of fluids[D].Qingdao:China University of Petroleum, 2020.
[15] THÉVENEAU P, COQUELET C, RICHON D.Vapour-liquid equilibrium data for the hydrogen sulphide+n-heptane system at temperatures from 293.25 to 373.22 K and pressures up to about 6.9 MPa[J]. Fluid Phase Equilibria, 2006, 249(1/2):179-186.
[16] GMEHLING J.Dortmund data bank[EB/OL].[2019-06-08].http://www.ddbst.com/free-data.html.
[17] ANDERSON F E, PRAUSNITZ J M.Inhibition of gas hydrates by methanol[J]. AIChE Journal, 1986, 32(8):1321-1333.
[18] PARRISH W R, PRAUSNITZ J M.Dissociation pressures of gas hydrates formed by gas mixtures[J]. Industrial & Engineering Chemistry Process Design and Development, 1972, 11(1):26-35.
[19] LE QUANG D, LE QUANG D, BOUILLOT B, et al.Experimental procedure and results to measure the composition of gas hydrate, during crystallization and at equilibrium, from N₂-CO₂-CH₄-C₂H₆-C₃H₈-C₄H₁₀ gas mixtures[J]. Fluid Phase Equilibria, 2016, 413:10-21.
[20] ZIRRAHI M, AZIN R, HASSANZADEH H, et al.Mutual solubility of CH₄, CO₂, H₂S, and their mixtures in brine under subsurface disposal conditions[J]. Fluid Phase Equilibria, 2012, 324:80-93.
[21] COQUELET C, CHAPOY A, RICHON D.Development of a new alpha function for the Peng-Robinson equation of state:comparative study of alpha function models for pure gases (natural gas components)and water-gas systems[J]. International Journal of Thermophysics, 2004, 25(1):133-158.
[22] DUAN Zhenhao, MAO Shide.A thermodynamic model for calculating methane solubility, density and gas phase composition of methane-bearing aqueous fluids from 273 to 523 K and from 1 to 2000 bar[J]. Geochimica et Cosmochimica Acta, 2006, 70(13):3369-3386.
[23] KLAUDA J B, SANDLER S I.A fugacity model for gas hydrate phase equilibria[J]. Industrial & Engineering Chemistry Research, 2000, 39(9):3377-3386.
[24] CARROLL J J, MATHER A E.A model for the solubility of light hydrocarbons in water and aqueous solutions of alkanolamines[J]. Chemical Engineering Science, 1997, 52(4):545-552.
[25] FERNÁNDEZ-PRINI R, ALVAREZ J L, HARVEY A H.Henry's constants and vapor-liquid distribution constants for gaseous solutes in H₂O and D₂O at high temperatures[J]. Journal of Physical and Chemical Reference Data, 2003, 32(2):903-916.
[26] YAWS C L, HOPPER J R, WANG Xiaomei, et al.Calculating solubility & Henry's law constants for gases in water[J]. Chemical Engineering, 1999, 106(6):102-105.
[27] SPYCHER N, PRUESS K, ENNIS-KING J.CO₂-H₂O mixtures in the geological sequestration of CO₂.I.assessment and calculation of mutual solubilities from 12 to 100℃ and up to 600 bar[J]. Geochimica et Cosmochimica Acta, 2003, 67(16):3015-3031.
[28] HOU Shuxin, MAITLAND G C, TRUSLER J P M.Measurement and modeling of the phase behavior of the (carbon dioxide+water)mixture at temperatures from 298.15 K to 448.15 K[J]. The Journal of Supercritical Fluids, 2013, 73:87-96.
[29] DUAN Zhenhao, SUN Rui.An improved model calculating CO₂ solubility in pure water and aqueous NaCl solutions from 273 to 533 K and from 0 to 2 000 bar[J]. Chemical Geology, 2003, 193(3/4):257-271.
[30] CARROLL J J, MATHER A E.The solubility of hydrogen sulphide in water from 0 to 90℃ and pressures to 1 MPa[J]. Geochimica et Cosmochimica Acta, 1989, 53(6):1163-1170.
[31] DUAN Zhenhao, SUN Rui, LIU Rong, et al.Accurate thermodynamic model for the calculation of H₂S solubility in pure water and brines[J]. Energy & Fuels, 2007, 21(4):2056-2065.
[32] LEE J L, MATHER A E.Solubility of hydrogen sulfide in water[J]. Berichte Der Bunsengesellschaft für Physikalische Chemie, 1977, 81(10):1020-1023.
[33] BELANDRIA V, ESLAMIMANESH A, MOHAMMADI A H, et al.Compositional analysis and hydrate dissociation conditions measurements for carbon dioxide+methane+water system[J]. Industrial & Engineering Chemistry Research, 2011, 50(9):5783-5794.
[34] ROBINSON D B, LORENZO A P, MACRYGEORGOS C A.The carbon dioxide-hydrogen sulphide-methane system:part II.phase behavior at 40°f.and 160°f[J]. The Canadian Journal of Chemical Engineering, 1959, 37(6):212-217.
[35] NG H J, ROBINSON D B, LEU A D.Critical phenomena in a mixture of methane, carbon dioxide and hydrogen sulfide[J]. Fluid Phase Equilibria, 1985, 19(3):273-286.
[36] DOUABUL A A, RILEY J P.The solubility of gases in distilled water and seawater-V.hydrogen sulphide[J]. Deep Sea Research Part A.Oceanographic Research Papers, 1979, 26(3):259-268.
[37] AL GHAFRI S Z S, FORTE E, MAITLAND G C, et al.Experimental and modeling study of the phase behavior of (methane+CO₂+water)mixtures[J]. The Journal of Physical Chemistry B, 2014, 118(49):14461-14478.
[38] SAVARY V, BERGER G, DUBOIS M, et al.The solubility of CO₂+H₂S mixtures in water and 2 M NaCl at 120℃ and pressures up to 35 MPa[J]. International Journal of Greenhouse Gas Control, 2012, 10:123-133.
[39] HUANG S S S, LEU A D, NG H J, et al.The phase behavior of two mixtures of methane, carbon dioxide, hydrogen sulfide, and water[J]. Fluid Phase Equilibria, 1985, 19(1/2):21-32.
[40] KASTANIDIS P, ROMANOS G E, STUBOS A K, et al.Two- and three-phase equilibrium experimental measurements for the ternary CH₄+CO₂+H₂O mixture[J]. Fluid Phase Equilibria, 2017, 451:96-105.
[41] OHGAKI K, TAKANO K, SANGAWA H, et al.Methane exploitation by carbon dioxide from gas hydrates-phase equilibria for CO₂-CH₄ mixed hydrate system[J]. Journal of Chemical Engineering of Japan, 1996, 29(3):478-483.
[42] UNRUH C H, KATZ D L.Gas hydrates of carbon dioxide-methane mixtures[J]. Journal of Petroleum Technology, 1949, 1(4):83-86.
[43] ADISASMITO S, FRANK III R J, SLOAN JR E D.Hydrates of carbon dioxide and methane mixtures[J]. Journal of Chemical and Engineering Data, 1991, 36(1):68-71.
[44] WARD Z T.Phase equilibria of gas hydrates containing hydrogen sulfide and carbon dioxide[D].Golden:Colorado School of Mines, 2015.
[45] ROBINSON D B, HUTTON J B.Hydrate formation in systems containing methane, hydrogen sulphide and carbon dioxide[J]. Journal of Canadian Petroleum Technology, 1967, 6(1):6-9.
[46] SUN C Y, CHEN G J, LIN W, et al.Hydrate formation conditions of sour natural gases[J]. Journal of Chemical & Engineering Data, 2003, 48(3):600-602.
[47] MOHAMMADI A H, RICHON D.Hydrate phase equilibria of gaseous mixtures of methane+carbon dioxide+hydrogen sulfide[J]. Chemical Engineering Communications, 2015, 202(5):629-633.

酸性天然气与水体系内超临界-气-液-水合物多相平衡模型

Supercritical-gas-liquid-hydrate multiphase equilibrium model in the sour natural gas and water system

PDF

可视化

摘要/Abstract

引用本文

使用本文

参考文献

相关文章 15

编辑推荐

Metrics

本文评价

[1]	张智, 赵苑瑾, 张喆, 蔡楠, 刘和兴, 马传华, 梁继文. 深水井开采制度对天然气水合物分解的影响[J]. 石油学报, 2022, 43(2): 281-292.
[2]	周世琛, 周博, 薛世峰, 公彬. 基于离散元法的天然气水合物沉积物剪切带演化机理[J]. 石油学报, 2022, 43(1): 101-111.
[3]	王志远, 张剑波, 孟文波, 孙宝江, 孙金声, 王金堂, 刘大辉, 王金波. 深水气井天然气水合物生成、沉积特性与防治方法[J]. 石油学报, 2021, 42(6): 776-790.
[4]	雷裕红, 宋颖睿, 张立宽, 苗来成, 程明, 刘乃贵. 海洋天然气水合物成藏系统研究进展及发展方向[J]. 石油学报, 2021, 42(6): 801-820.
[5]	徐立涛, 何玉林, 石万忠, 梁金强, 王任, 杜浩, 张伟, 李冠华. 琼东南盆地深水区天然气水合物成藏主控因素及模式[J]. 石油学报, 2021, 42(5): 598-610.
[6]	孙嘉鑫, 张凌, 宁伏龙, 刘天乐, 方彬, 李彦龙, 刘昌岭, 蒋国盛. 天然气水合物藏增产研究现状与展望[J]. 石油学报, 2021, 42(4): 523-540.
[7]	宋传真, 赵海宁, 张慧. 氮气对塔河油田原油轻质组分抽提作用实验与评价[J]. 石油学报, 2021, 42(3): 341-349.
[8]	卢海龙, 尚世龙, 陈雪君, 秦绪文, 古利娟, 邱海峻. 天然气水合物开发数值模拟器研究进展及发展趋势[J]. 石油学报, 2021, 42(11): 1516-1530.
[9]	周世琛, 郇筱林, 陈宇琪, 周博, 薛世峰, 公彬. 天然气水合物沉积物不排水剪切特性的离散元模拟[J]. 石油学报, 2021, 42(1): 73-83.
[10]	王辉, 周子钰, 周博, 薛世峰, 林英松. 颗粒抗滚动作用对水合物沉积物宏观及微观力学特性的影响[J]. 石油学报, 2020, 41(7): 885-894.
[11]	窦晓峰, 宁伏龙, 李彦龙, 刘昌岭, 孙嘉鑫, 李杨, 李晓东, 赵颖杰, 张凌, 刘乐乐. 基于连续-离散介质耦合的水合物储层出砂数值模拟[J]. 石油学报, 2020, 41(5): 629-642.
[12]	董长银, 宋洋, 周玉刚, 徐鸿志, 王剑, 刘亚宾, 王力智. 天然气水合物储层泥质细粉砂挡砂介质堵塞规律与微观挡砂机制[J]. 石油学报, 2020, 41(10): 1248-1258.
[13]	李占东, 刘建辉, 李中, 李阳, 张海翔, 王殿举, 庞鸿. 天然气水合物降压开采出砂定量预测新模型[J]. 石油学报, 2019, 40(S2): 160-167.
[14]	祝效华, 孙汉文, 赵金洲, 张烈辉, 张爽. 天然气水合物沉积物等效变弹性模量损伤本构模型[J]. 石油学报, 2019, 40(9): 1085-1094.
[15]	高永海, 孟文波, 崔燕春, 张崇, 陈野, 董钊, 孙金声, 孙宝江. 深水气井水合物沉积预测新模型[J]. 石油学报, 2019, 40(8): 975-982.