CO2埋存中的状态方程研究进展与展望

doi:10.13809/j.cnki.cn32-1825/te.2023.03.005

摘要/Abstract

摘要：

在废弃油气藏中进行CO₂埋存，能够减少温室气体在大气中的直接排放量，是减缓温室效应的有效途径之一。改进常规的气液相平衡理论，应用热力学状态方程研究CO₂-烃-地层水体系，对揭示CO₂地下埋存的溶解机理具有十分重要的意义。总结了热力学状态方程对CO₂-烃-地层水体系相平衡计算方面的国内外研究进展，指出其实际应用中的不足，分析了其发展趋势，包括：应进一步研究适用于非理想体系的状态方程和混合规则，准确预测该体系热力学性质变化规律；拓展研究体系的地层水离子差异，使之与真实CO₂埋存条件相符合；将CO₂中相态变化的物理过程与地层水中矿物溶解析出的化学过程耦合。

关键词: CO₂埋存, CO₂-烃-地层水体系, 状态方程, 热力学性质, 相平衡

Abstract:

CO₂ storage in abandoned oil and gas reservoirs can reduce the direct emissions of greenhouse gases in the atmosphere, which is one of the effective ways to mitigate the greenhouse effect. Improving the conventional gas-liquid phase equilibrium theory and applying the thermodynamic equation of state to study the CO₂-hydrocarbon-groundwater system are of great significance to reveal the dissolution mechanism of CO₂ buried in the subsurface. The research progress of thermodynamic equation of state in the phase equilibrium calculation of CO₂-hydrocarbon-formation water system at home and abroad is summarized.The shortcomings in its practical application are pointed out, and its development trend is analyzed, including: the equation of state and mixing rules suitable for non-ideal systems should be further studied to accurately predict the change law of thermodynamic properties of the system; the expansion of the difference of formation water ions in the research system to make it consistent with the real CO₂ storage conditions; the physical process of phase change in CO₂ is coupled with the chemical process of mineral dissolution and precipitation in formation water.

Key words: CO₂ storage, CO₂-hydrocarbon-formation water system, state equation, thermodynamic property, phase equilibrium

中图分类号:

TE37

王建猛,陈杰,吉礼东,刘荣和,张骞,黄东杰,颜平. CO₂埋存中的状态方程研究进展与展望[J]. 油气藏评价与开发, 2023, 13(3): 305-312.

WANG Jianmeng,CHEN Jie,JI Lidong,LIU Ronghe,ZHANG Qian,HUANG Dongjie,YAN Ping. Research progress and prospect of state equation in CO₂ storage[J]. Petroleum Reservoir Evaluation and Development, 2023, 13(3): 305-312.

图/表 4

表1

不同立方型状态方程的引力项"

状态方程	$ψ$ 项
van der Waals	$a v 2$
Soave-Redlich-Kwong	$a T v v + b$
Peng-Robinson	$a T v v + b + v v - b$

表1

图1

表2

表3

参考文献 46

[1]	范秦楚, 阮玉蛟, 周军. 碳达峰碳中和目标下国内天然气净化厂运行现状与展望[J]. 石油与天然气化工, 2023, 52(1): 25-31.
	FAN Qinchu, RUAN Yujiao, ZHOU Jun. Current status and prospect of domestic natural gas purification plants under the target of carbon peaking and carbon neutralization[J]. Chemical Engineering of Oil & Gas, 2023, 52(1): 25-31.
[2]	周微, 纪文, 李佳忆, 等. 天然气净化厂余压发电项目温室气体减排潜力研究[J]. 石油与天然气化工, 2023, 52(1): 50-53.
	ZHOU Wei, JI Wen, LI Jiayi, et al. Study on the potential of greenhouse gas emission reduction of natural gas purification plant residual pressure power generation project[J]. Chemical Engineering of Oil & Gas, 2023, 52(1): 50-53.
[3]	张路. 基于缔合理论的CO₂-烃-地层水体系热力学研究[D]. 成都: 西南石油大学, 2018.
	ZHANG Lu. Study on the thermodynamics of CO₂-hydrocarbon-formation water system by using the association theory[D]. Chengdu: Southwest Petroleum University, 2018.
[4]	刘树阳, 张毅, 宋永臣, 等. CO₂-CH₄体系热力学性质(PVTx)研究进展[J]. 中国科学: 技术科学, 2019, 49(12): 1429-1441.
	LIU Shuyang, ZHANG Yi, SONG Yongchen, et al. Research progress on the thermodynamic properties(PVTx)of a CO₂-CH₄ mixture system[J]. Scientia Sinica(Technologica), 2019, 49(12): 1429-1441.
[5]	CHAPMAN W G, GUBBINS K E, JACKSON G, et al. New reference equation of state for associating liquids[J]. Industrial & Engineering Chemistry Research, 1990, 29(8): 1709-1721. doi: 10.1021/ie00104a021
[6]	MÜLLER E A, GUBBINS K E. Molecular-based equations of state for associating fluids: A review of SAFT and related approaches[J]. Industrial & Engineering Chemistry Research, 2001, 40(10): 2193-2211. doi: 10.1021/ie000773w
[7]	ISLAM A W, CARLSON E S. Application of SAFT equation for CO₂+H₂O phase equilibrium calculations over a wide temperature and pressure range[J]. Fluid Phase Equilibria, 2012, 321: 17-24. doi: 10.1016/j.fluid.2012.02.016
[8]	向晶. 高含CO₂天然气与水体系相平衡预测模型研究[D]. 成都: 西南石油大学, 2018.
	XIANG Jing. Study on the phase equilibrium prediction model of high CO₂ natural gas and water system[D]. Chengdu: Southwest Petroleum University, 2018.
[9]	MIRI R, AAGAARD P, HELLEVANG H. Examination of CO₂-SO₂ solubility in water by SAFT1. Implications for CO₂ transport and storage[J]. Journal of Physical Chemistry B, 2014, 118(34): 10214-10223. doi: 10.1021/jp505562j
[10]	SUN R, LAI S C, DUBESSY J. Calculation of vapor-liquid equilibrium and PVTx properties of geological fluid system with SAFT-LJ EOS including multi-polar contribution. Part Ⅲ. Extension to water-light hydrocarbons systems[J]. Geochimica et Cosmochimica Acta, 2014, 125: 504-518. doi: 10.1016/j.gca.2013.10.027
[11]	李雅婧. CO₂(CH₄-H₂O)体系在近临界区的气液相平衡和PVTx性质的精确计算及应用[D]. 西安: 西北大学, 2020.
	LI Yajing. Thermodynamic models for accurate calculations and applications of vapor-liquid equilibrium and PVTx properties of CO₂(CH₄-H₂O) system inside the critical region[D]. Xi'an: Northwest University, 2020.
[12]	SANCHEZ-VICENTE Y, TAY W J, AL GHAFRI S Z, et al. Thermodynamics of carbon dioxide-hydrocarbon systems[J]. Applied Energy, 2018, 220: 629-642. doi: 10.1016/j.apenergy.2018.03.136
[13]	GIMENO B, MARTÍNEZ-CASASNOVAS S, VELASCO I, et al. Thermodynamic properties of CO₂+SO₂+CH₄ mixtures over wide ranges of temperature and pressure. Evaluation of CO₂/SO₂ co-capture in presence of CH₄ for CCS[J]. Fuel, 2019, 255: 115800. doi: 10.1016/j.fuel.2019.115800
[14]	JI X Y, TAN S P, ADIDHARMA H, et al. SAFT1-RPM approximation extended to phase equilibria and densities of CO₂-H₂O and CO₂-H₂O-NaCl systems[J]. Industrial & Engineering Chemistry Research, 2005, 44(22): 8419-8427. doi: 10.1021/ie050725h
[15]	SUN R, DUBESSY J. Prediction of vapor-liquid equilibrium and PVTx properties of geological fluid system with SAFT-LJ EOS including multi-polar contribution. Part Ⅱ: Application to H₂O-NaCl and CO₂-H₂O-NaCl system[J]. Geochimica et Cosmochimica Acta, 2012, 88: 130-145. doi: 10.1016/j.gca.2012.04.025
[16]	HASSANPOURYOUZBAND A, FARAHANI M V, YANG J H, et al. Solubility of flue gas or carbon dioxide-nitrogen gas mixtures in water and aqueous solutions of salts: Experimental measurement and thermodynamic modeling[J]. Industrial & Engineering Chemistry Research, 2019, 58(8): 3377-3394. doi: 10.1021/acs.iecr.8b04352
[17]	JOHANNES D, WALLS V D. Reprint of: The equation of state for gases and liquids[J]. The Journal of Supercritical Fluids, 2010, 55(2): 403-414. doi: 10.1016/j.supflu.2010.11.001
[18]	SOAVE G. Equilibrium constants from a modified Redlich-Kwong equation of state[J]. Chemical Engineering Science, 1972, 27(6): 1197-1203. doi: 10.1016/0009-2509(72)80096-4
[19]	PENG D Y, ROBINSON D B. A new two-constant equation of state[J]. Industrial & Engineering Chemistry Fundamentals, 1976, 15(1): 59-64.
[20]	SØRENSEN H, PEDERSEN K S, CHRISTENSEN P L. Modeling of gas solubility in brine[J]. Organic Geochemistry, 2002, 33(6): 635-642. doi: 10.1016/S0146-6380(02)00022-0
[21]	侯大力, 罗平亚, 王长权, 等. 高温高压下CO₂在水中溶解度实验及理论模型[J]. 吉林大学学报(地球科学版), 2015, 45(2): 564-572.
	HOU Dali, LUO Pingya, WANG Changquan, et al. Experimental research and theoretical model for CO₂ solubility in water under high temperature and high pressure[J]. Journal of Jilin University(Earth Science Edition), 2015, 45(2): 564-572.
[22]	李靖. 高温高压高含CO₂天然气在地层水中溶解度理论研究[D]. 成都: 西南石油大学, 2017.
	LI Jing. Theoretical study on solubility of high CO₂ content natural gas in formation water at high temperature and high pressure[D]. Chengdu: Southwest Petroleum University, 2017.
[23]	SUN Z T, LI H Z. Phase behavior modeling for carbon dioxide/brine mixtures using PR EOS and Huron-Vidal mixing rule[C]// Paper presented at the ASME 2022 41st International Conference on Ocean, Offshore and Arctic Engineering, Hamburg, Germany, June 2022.
[24]	ZHAO H N, LVOV S N. Phase behavior of the CO₂-H₂O system at temperatures of 273-623 K and pressures of 0.1-200 MPa using Peng-Robinson-Stryjek-Vera equation of state with a modified Wong-Sandler mixing rule: An extension to the CO₂-CH₄-H₂O system[J]. Fluid Phase Equilibria, 2016, 417: 96-108. doi: 10.1016/j.fluid.2016.02.027
[25]	YANG F F, LIU Q, DUAN Y Y, et al. On the temperature dependence of the α function in the cubic equation of state[J]. Chemical Engineering Science, 2018, 192: 565-575. doi: 10.1016/j.ces.2018.08.014
[26]	张雪丽. 中国北方主要盆地地下咸水中CO₂溶解度研究[D]. 北京: 中国地质大学(北京), 2016.
	ZHANG Xueli. Measurment and Modeling of CO₂ solubility in formation brine in major basins in north China[D]. Beijing: China University of Geosciences(Beijing), 2016.
[27]	LASALA S, CHIESA P, PRIVAT R, et al. Modeling the thermodynamics of fluids treated by CO₂ capture processes with Peng-Robinson + residual Helmholtz energy-based mixing rules[J]. Industrial & Engineering Chemistry Research, 2017, 56(8): 2259-2276. doi: 10.1021/acs.iecr.6b04190
[28]	ISABELA T B, GUIRARDELLO R. Thermodynamic calculation for the formation of methane and carbon dioxide hydrates[J]. Chemical Engineering Transactions, 2022, 92: 379-384.
[29]	LI Z D, WANAT E, LUN L, et al. Fluid property model for carbon capture and storage by volume-translated Peng-Robinson equation of state and Lohrenz-Bray-Clark viscosity correlation[C]// Paper SPE-212584-MS presented at the SPE Reservoir Characterisation and Simulation Conference and Exhibition, Abu Dhabi, UAE, January 2023.
[30]	韩晓红, 陈光明, 王勤, 等. 状态方程研究进展[J]. 天然气化工(C1 化学与化工), 2005, 30(5): 52-61.
	HAN Xiaohong, CHEN Guangming, WANG Qing, et al. Research progress of equation of state[J]. Natural Gas Chemical Industry, 2005, 30(5): 52-61.
[31]	DUAN Z H, MØLLER N, WEARE J H. An equation of state for the CH₄-CO₂-H₂O system: I. Pure systems from 0 to 1 000 ℃ and 0 to 8 000 bar[J]. Geochimica et Cosmochimica Acta, 1992, 56(7): 2605-2617. doi: 10.1016/0016-7037(92)90347-L
[32]	DUAN Z H, MØLLER N, WEARE J H. An equation of state for the CH₄-CO₂-H₂O system: Ⅱ. Mixtures from 50 to 1 000 ℃ and 0 to 1 000 bar[J]. Geochimica et Cosmochimica Acta, 1992, 56(7): 2619-2631. doi: 10.1016/0016-7037(92)90348-M
[33]	DUAN Z H, SUN R. 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. doi: 10.1016/S0009-2541(02)00263-2
[34]	DUAN Z H, SUN R, ZHU C, et al. An improved model for the calculation of CO₂ solubility in aqueous solutions containing Na⁺, K⁺, Ca²⁺, Mg²⁺, Cl^-, and SO₄^2-[J]. Marine Chemistry, 2006, 98(2): 131-139. doi: 10.1016/j.marchem.2005.09.001
[35]	DUAN Z H, LI D. Coupled phase and aqueous species equilibrium of the H₂O-CO₂-NaCl-CaCO₃ system from 0 to 250 ℃, 1 to 1 000 bar with NaCl concentrations up to saturation of halite[J]. Geochimica et Cosmochimica Acta, 2008, 72(20): 5128-5145. doi: 10.1016/j.gca.2008.07.025
[36]	LIU G F, HE L Y, FAN Z Q, et al. Investigation of gas solubility and its effects on natural gas reserve and production in tight formations[J]. Fuel, 2021, 295(6): 120507. doi: 10.1016/j.fuel.2021.120507
[37]	CHABAB S, THÉVENEAU P, CORVISIER J, et al. Thermodynamic study of the CO₂-H₂O-NaCl system: Measurements of CO₂ solubility and modeling of phase equilibria using Soreide and Whitson, electrolyte CPA and SIT models[J]. International Journal of Greenhouse Gas Control, 2019, 91: 102825. doi: 10.1016/j.ijggc.2019.102825
[38]	LI Y T, QIAO Z H, SUN S Y, et al. Thermodynamic modeling of CO₂ solubility in saline water using NVT flash with the cubic-Plus-association equation of state[J]. Fluid Phase Equilibria, 2020, 520(1): 112657. doi: 10.1016/j.fluid.2020.112657
[39]	涂汉敏, 郭平, 贾钠, 等. CPA方程对CO₂-水体系相态研究[J]. 岩性油气藏, 2018, 30(4): 113-119.
	TU Hanmin, GUO Ping, JIA Na, et al. Calculation of phase behavior for CO₂-water mixtures using CPA EoS[J]. Lithologic Reservoirs, 2018, 30(4): 113-119.
[40]	BJØRNER M G, KONTOGEORGIS G M. Modeling derivative properties and binary mixtures with CO₂ using the CPA and the quadrupolar CPA equations of state[J]. Fluid Phase Equilibria, 2016, 408: 151-169. doi: 10.1016/j.fluid.2015.08.011
[41]	王珺瑶, 张月, 邓帅, 等. CO₂混合物热物性在 CCS 研究中的作用: 实验数据, 理论模型和典型应用[J]. 化工进展, 2019, 38(3): 1244-1258.
	WANG Junyao, ZHANG Yue, DENG Shuai, et al. Role of thermodynamic properties of CO₂ mixtures in CCS: Data, models and typical applications[J]. Chemical Industry and Engineering Progress, 2019, 38(3): 1244-1258.
[42]	税蕾蕾, 郭来源, 徐新德, 等. 莺歌海盆地乐东10区CO₂包裹体特征及其流体充注史[J]. 石油实验地质, 2021, 43(5): 835-843.
	SHUI Leilei, GUO Laiyuan, XU Xinde, et al. Fluid charging history in Ledong 10 area, Yinggehai Basin, revealed by CO₂ inclusion characteristics[J]. Petroleum Geology & Experiment, 2021, 43(5): 835-843.
[43]	李超, 陈祖华, 胡世莱, 等. 新疆油田JL区块特低渗透油藏CO₂-化学剂复合吞吐技术应用研究[J]. 油气地质与采收率, 2021, 28(3): 134-141.
	LI Chao, CHEN Zuhua, HU Shilai, et al. Application of CO₂-chemical agent composite huff and puff in extra-low permeability reservoir of Block JL in Xinjiang Oilfield[J]. Petroleum Geology and Recovery Efficiency, 2021, 28(3): 134-141.
[44]	郭永伟, 闫方平, 王晶, 等. 致密砂岩油藏CO₂驱固相沉积规律及其储层伤害特征[J]. 岩性油气藏, 2021, 33(3): 153-161.
	GUO Yongwei, YAN Fangping, WANG Jing, et al. Characteristics of solid deposition and reservoir damage of CO₂ flooding in tight sandstone reservoirs[J]. Lithologic Reservoirs, 2021, 33(3): 153-161.
[45]	AASEN A, HAMMER M, SKAUGEN G, et al. Thermodynamic models to accurately describe the PVTxy-behavior of water/carbon dioxide mixtures[J]. Fluid Phase Equilibria, 2017, 442: 125-139. doi: 10.1016/j.fluid.2017.02.006
[46]	PEREZ A G, COQUELET C, PARICAUD P, et al. Comparative study of vapour-liquid equilibrium and density modelling of mixtures related to carbon capture and storage with the SRK, PR, PC-SAFT and SAFT-VR Mie equations of state for industrial uses[J]. Fluid Phase Equilibria, 2017, 440: 19-35. doi: 10.1016/j.fluid.2017.02.018

状态方程		温度/K	压力/MPa	研究体系	平均相对偏差/ %
状态方程		温度/K	压力/MPa	研究体系	气液相平衡	气相密度	液相密度
统计缔合流体理论状态方程	SAFT^[7]	283~573	0.1~60.0	CO₂, H₂O
	SAFT^[8]	414~421	0.1~60.0	CO₂, H₂O
	SAFT1^[9]	303~373	6.0~30.0	CO₂, SO₂, H₂O	2.70		0.29
	SAFT-LJ^[10]	273~627	0.1~154.2	H₂O, CH₄, C₂H₆, C₃H₈, nC₄H₁₀	2.80
	SAFT-LJ+RG^[11]	270~301	5.7~8.5	CO₂, CH₄, H₂O	7.47、13.70、16.60
	SAFT-γ Mie^[12]	283~473	0.1~68.0	CO₂, nC₇H₁₆		2.0	4.00
	PC-SAFT^[13]	263~373	0.1~30.0	CO₂, H₂O, SO₂	<3.10	0.8	0.80
	SAFT1-RPM^[14]	285~473	0~20.0	CO₂, H₂O, NaCl	<0.50		0.28
	SAFT-LJ^[15]	273~573	0~100.0	CO₂, H₂O, NaCl	3.30		0.60
	PC-SAFT^[16]	273.25~303.05	0.1~22.0	CO₂, N₂, H₂O, NaCl
立方型状态方程	SRK-HV^[20]	245~383	0.1~350.0	CO₂, CH₄, H₂O	3.00~9.30
	PR-HV^[21]	308~408	0.1~50.0	CO₂, H₂O, NaCl	2.69
	PR-HV^[22]	303~523	0.1~50.0	CO₂, CH₄, H₂O, NaCl	5.11
	PR-HV^[23]	273~550	0~80.0	CO₂, H₂O, NaCl, KCl, CaCl₂, MgCl₂	0.15
	PRSV-SW^[24]	273~623	0.1~200.0	CO₂, CH₄, H₂O	6.80~7.40
	SRK-Prausnitz^[26]	313~393	5~20.0	CO₂, H₂O	3.29
	PR-Wilson^[27]	223~598	0.6~100.0	CO₂, H₂O
	PR-VT^[29]	310.95~449.85	4.82~18.17	CO₂, CH₄, H₂S, H₂O, NaCl
维里型状态方程	Duan（1992）^[31,32]	323~1 273	0.1~100.0	CO₂, CH₄, H₂O	15.00~20.00
	Duan（2003）^[33]	273~533	0.1~200.0	CO₂, H₂O, NaCl	约7.00
	Duan（2006）^[34]	273~533	0.1~200.0	CO₂, H₂O, Na⁺, K⁺, Ca²⁺, Mg²⁺, Cl^-	约3.00
	Duan（2008）^[35]	273~523	0.1~100.0	CO₂, H₂O, NaCl, CaCO₃	<5.00
多类型结合状态方程	PR-Henry模型^[36]	283~363	0~50.0	CO₂, N₂, 碳氢化合物, 盐水	2.24
	e-PR-CPA模型^[37]	322.97~373.38	3~22.9	CO₂, H₂O, NaCl	4.00
	PR-CPA模型^[38]	297~323.15	0~40.0	CO₂,H₂O,NaCl,KCl,CaCl₂,MgCl₂,Na₂SO₄
	SRK-CPA模型^[39]	308~473	0.1~480.0	CO₂, H₂O
	qCPA模型^[40]	213~582	0.3~20.0	CO₂, 碳氢化合物

类型	特点	不足
统计缔合流体理论状态方程	①将热力学性质和分子间的物理作用力相结合，更准确地描述复杂流体； ②可用于简单离子溶液相平衡计算； ③在CO₂-烃-地层水体系相平衡计算方面有很大发展空间	①多应用于CO₂、H₂O、烃等二元混合物的相平衡计算，对于多元混合物的相平衡计算研究较少； ②考虑的盐溶液多为NaCl，没有拓展到实际地层中其他盐成分； ③模型较为复杂，计算量大，不易与地层水中矿物溶解沉淀的化学反应过程耦合
立方型状态方程	①通过改进混合规则和相互作用参数，使其能够定量描述高度非理想混合体系的气液相平衡； ②计算相对简单，广泛应用于工程实际中	①存在适用温度压力范围，对适用范围外的预测精度较差； ②状态方程和混合规则参数受温度变化影响，需要精准的实验数据进行拟合； ③对离子溶液体系相平衡研究不充分，研究离子种类不丰富
维里型状态方程	①维里状态方程计算精度较高； ②多应用于烃类等单组分	①不适用于含CO₂、烃类分子和地层水多元体系的相平衡计算； ②形式复杂，参数较多，难以推广到实际应用
多类型结合状态方程	①将不同理论及模型的优点相结合，提高了研究体系的相平衡预测精度； ②近些年研究充分，有较大发展潜力	模型较为复杂，计算量较大

CO₂埋存中的状态方程研究进展与展望

Research progress and prospect of state equation in CO₂ storage

RichHTML

PDF (PC)

赞

可视化

摘要/Abstract

引用本文

使用本文

图/表 4

参考文献 46

相关文章 2

Metrics

本文评价

推荐阅读 10

[1]	杨宇,徐启林,刘荣和,黄东杰,颜平,王建猛. 枯竭气藏CO₂封存中的相平衡规律研究 [J]. 油气藏评价与开发, 2023, 13(3): 280-287.
[2]	姜颜波. 多孔介质对注CO₂原油相态影响实验及表征 [J]. 油气藏评价与开发, 2020, 10(3): 23-27.