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,吉礼东等. 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.

Jianmeng WANG,Jie CHEN,Lidong JI, et al. 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

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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

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