高温高压条件下非纯CO2−水体系的pH原位测量和预测模型

高启荣; 雷宏武; 蔡雨娜; 白冰; 李静

doi:10.19509/j.cnki.dzkq.tb20240421

高温高压条件下非纯CO₂−水体系的pH原位测量和预测模型

doi: 10.19509/j.cnki.dzkq.tb20240421

高启荣^{1, 2,},
雷宏武^2, ,,
蔡雨娜³,
白冰²,
李静¹

1 .
中国地质大学（武汉）环境学院，武汉 430078
2 .
中国科学院武汉岩土力学研究所，岩土力学与工程安全全国重点实验室，武汉 430071
3 .
武汉大学，武汉 430071

基金项目: 国家重点研发青年科学家项目（2023YFB4104100）；国家自然科学基金联合重点基金项目（U2344226）；国家自然科学基金项目（42472364）；中国石油科技创新基金项目（2021 D002–1102）

详细信息

作者简介:
高启荣：E-mail：2661638966@qq.com

通讯作者:
E-mail：hongwulei2008@aliyun.com

中图分类号: O655；X701
计量
- 文章访问数: 343
- PDF下载量: 22
- 被引次数: 0
出版历程
- 收稿日期: 2024-07-30
- 录用日期: 2024-09-19
- 修回日期: 2024-09-18
- 网络出版日期: 2024-11-27

In situ pH measurement and prediction modelling of the impure CO₂-water system under high-temperature and high-pressure conditions

GAO Qirong^{1, 2
,},
LEI Hongwu^{2
, ,},
CAI Yuna³,
BAI Bing²,
LI Jing¹

1 .
School of Environmental Studies, China University of Geosciences (Wuhan), Wuhan 430078, China
2 .
State Key Laboratory of Geomechanics and Geotechnical Engineering Safety, Institute of Rock and Soil Mechanics, Chinese Academy of Sciences, Wuhan 430071, China
3 .
Wuhan University, Wuhan 430071, China

More Information

Author Bio:
E-mail：2661638966@qq.com

Corresponding author: E-mail：hongwulei2008@aliyun.com

摘要

摘要:
含CO₂的气体注入到深部含水层中会溶解形成碳酸，导致含水层的pH值下降，进而造成矿物的溶解或沉淀，影响CO₂地质利用与封存的安全性和有效性。pH值作为能表征溶液化学性质的重要参数，因此通过实验测量纯/非纯CO₂饱和溶液体系的pH值，并结合模型预测可以评估CO₂地质封存条件下的化学变化。在原位条件下通过电势法和光谱法测量了温度范围35～93℃、压力范围0.38～18 MPa时，纯CO₂-H₂O体系和非纯CO₂-H₂O体系的pH值；并建立了基于溶解度校准的组分化学平衡模型，对纯/非纯CO₂-H₂O体系的pH值进行了计算和预测评价。结果表明：N₂和CH₄均会对CO₂饱和体系产生影响，使CO₂在水中的溶解度降低，pH值增大，且CH₄的影响大于N₂。模型能较好地进行纯CO₂-水体系的pH值预测，最大偏差不超过0.05个pH；在非纯CO₂-H₂O体系中有一定的偏差，主要为50℃以及CO₂和杂质气体比例为1∶9的条件下，偏差在0.15个pH值以内。电势法和光谱法能进行高温高压条件下的原位pH值测量，纯/非纯CO₂-H₂O体系的pH预测模型具有较好的准确性，本文的研究成果为非纯CO₂注入地层产生的化学变化提供了理论参考，对提高碳封存的安全性和有效性具有重要意义。
- 非纯CO₂ /
- CO₂饱和溶液体系 /
- 非纯CO₂−水体系 /
- 原位pH测量 /
- pH值预测
Abstract: The dissolution of CO2-containing gases into deep aquifers results in the formation of carbonic acid, which lowers the pH value of the aquifer and may cause the dissolution or precipitation of minerals, thereby affecting the safety and effectiveness of CO2 geological utilization and storage. </sec><sec><title>Objective
pH is a key parameter for characterizing the chemical properties of a solution. Experimental measurement and model prediction of the pH values of pure and impure CO₂-saturated systems can be used to evaluate the chemical changes under CO₂ geological storage conditions.
Methods
In this study, the pH values of pure and impure CO₂-water systems were measured in situ using potentiometric and spectroscopic methods, under temperatures conditions ranging from 35 to 93℃ and pressure condictions raging from 0.38 to 18 MPa. A component chemical equilibrium model calibrated using solubility data, was developed to calculate and predict the pH values of pure and impure CO₂-water systems.
Results
The results show that that N₂ and CH₄ influence the CO₂-saturated systems by reducing CO₂ solubility in water and increasing the pH value, with CH₄ having a greater effect than N₂. The model can accurately predict the pH values of pure CO₂-water systems, with a maximum deviation within 0.05 pH units. In impure CO₂-water systems, deviations are mainly observed under the condition of 50℃ and a CO₂-to-impurity gas ratio of 1∶9, with deviations within 0.15 pH units.
Conclusion
The potentiometric and spectroscopic methods are applicable for in situ pH measurements under high-temperature and high-pressure conditions, and the pH prediction model for pure and impure CO₂-water systems shows good accuracy. The findings provide theoretical support for understanding the chemical changes induced by the injection of impure CO₂ into geological formations, which is of great significance for enhancing the safety and effectiveness of carbon storage.
- impure CO₂ /
- CO₂-saturated system /
- impure CO₂-water system /
- in situ pH measurement /
- pH prediction

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图 1 电势法(a)和光谱法(b)原位测量pH实验装置示意图

Figure 1. Schematic diagram of the experimental setup for in situ measurement of pH by potentiometric method (a) and spectroscopic method (b)

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图 2 50℃下磷酸氢二钠−磷酸二氢钠缓冲液中溴酚蓝指示剂的紫外−可见光光谱

Figure 2. UV-vis spectra of bromophenol blue in disodium hydrogen phosphate-sodium dihydrogen phosphate buffer at 50℃

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图 3 50℃时纯和非纯CO₂-水体系的2种测量方法pH实测值

Figure 3. Measured pH by two methods for pure and impure CO₂-water system at 50℃

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图 4 原位条件下纯和非纯CO₂-水体系的pH实测值

Figure 4. Measured pH for pure and impure CO₂-water system under in situ conditions

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图 5 原位条件下不同气体比例的非纯CO₂-水体系的光谱法pH实测值

Figure 5. Measured pH by spectroscopic method for impure CO₂-water systems with different gas ratios under in situ conditions

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图 6 CO₂气-液平衡常数（取log10）随温度和压力的变化

Figure 6. Variation of CO₂ gas-liquid equilibrium constant (log10) with temperature and pressure

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图 7 不同温度下的各模型CO₂溶解度计算值随压力的变化

Figure 7. Calculated values of CO₂ solubility as a function of pressure for each model at different temperatures

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图 8 纯CO₂-H₂O体系的pH实测值与计算值随压力的变化

Figure 8. Measured and calculated pH for the pure CO₂-water system as a function of pressure

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图 9 不同气体摩尔比的CO₂-N₂-H₂O体系的pH实测值与计算值随压力的变化

Figure 9. Measured and calculated pH for CO₂-N₂-water system with different gas ratios as a function of pressure

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图 10 不同气体摩尔比的CO₂-CH₄-H₂O体系的pH实测值与计算值随压力的变化

Figure 10. Measured and calculated pH for CO₂-CH₄-water system with different gas ratios as a function of pressure

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图 11 不同浓度下CO₂-H₂O-NaHCO₃体系的pH实测值

Figure 11. Measured pH of CO₂-H₂O-NaHCO₃ system at different salinities

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图 12 CO₂-H₂O-NaHCO₃体系的pH实测值与计算值在不同压力下随温度的变化

Figure 12. Measured and calculated pH of CO₂-H₂O-NaHCO₃ system as a function of temperature at different pressures

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表 1 不同温度下溴酚蓝指示剂的$ p{K}' $和$ {e}_{1} $、$ {e}_{2} $、$ {e}_{3} $

Table 1. Measured $ p{K}' $ and $ {e}_{1} $，$ {e}_{2} $，$ {e}_{3} $ of bromophenol blue at different temperatures

温度/℃	$ p{K}' $	$ {e}_{1} $	$ {e}_{2} $	$ {e}_{3} $
50	4.186	0.0161	2.984	0.0484
75^[31]	4.275	0.0053	3.126	0.0311
93^[31]	4.376	0.0051	3.331	0.0387
$pK'$.反应平衡常数与离子活度系数的函数；${e_1}$，${e_2}$，${e_3}$.各吸光系数的比值

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表 2 原位条件下纯/非纯CO₂−水饱和体系的pH测量结果

Table 2. Measured pH for pure/impure CO₂-water saturated systems under in situ conditions

方法	体系	总压力/MPa	CO₂分压/MPa	35℃ pH	总压力/MPa	CO₂分压/MPa	50℃ pH	总压力/MPa	CO₂分压/MPa	70℃pH
电势法	CO₂-H₂O	0.38	0.38	3.66	0.36	0.36	3.70	0.37	0.37	3.79
		0.60	0.60	3.59	0.61	0.61	3.62	0.60	0.60	3.73
		1.01	1.01	3.48	1.00	1.00	3.48	1.01	1.01	3.56
		2.43	2.43	3.35	2.42	2.42	3.34	2.42	2.42	3.40
		6.28	6.28	3.21	6.28	6.28	3.22	6.28	6.28	3.25
	CO₂-N₂-H₂O （1∶1）	0.79	0.40	3.62	0.77	0.39	3.68	0.78	0.39	3.88
		1.20	0.60	3.58	1.18	0.59	3.62	1.20	0.60	3.60
		2.00	1.00	3.47	2.01	1.01	3.50	2.01	1.01	3.53
		4.79	2.40	3.37	4.80	2.40	3.39	4.80	2.40	3.45
		12.01	6.01	3.24	12.00	6.00	3.27	12.00	6.00	3.36

方法	体系	总压力/MPa	CO₂分压/MPa	50℃ pH	总压力/MPa	CO₂分压/MPa	75℃ pH	总压力/MPa	CO₂分压/MPa	93℃ pH
光谱法	CO₂-H₂O	0.38	0.38	3.75	0.38	0.38	3.93	0.38	0.38	3.98
		0.60	0.60	3.61	0.60	0.60	3.71	0.60	0.60	3.86
		1.00	1.00	3.55	1.00	1.00	3.65	1.00	1.00	3.69
		2.42	2.42	3.36	2.42	2.42	3.41	2.42	2.42	3.47
		6.30	6.30	3.17	6.30	6.30	3.21	6.30	6.30	3.24
		9.00	9.00	3.13	9.00	9	3.17	9	9	3.23
		12.00	12.00	3.11	12	12	3.15	12	12	3.19
		15.00	15.00	3.10	15	15	3.12	15	15	3.14
		18.00	18.00	3.08	18	18	3.10	18	18	3.13
	CO₂-N₂-H₂O （1∶1）	0.76	0.38	3.76	0.76	0.38	3.80	0.76	0.38	3.89
		1.20	0.60	3.68	1.20	0.60	3.69	1.20	0.60	3.78
		2.00	1.00	3.59	2.00	1.0	3.59	2.00	1.00	3.69
		4.80	2.40	3.36	4.80	2.40	3.45	4.80	2.40	3.50
		12.00	6.00	3.25	12.00	6.00	3.28	12.00	6.00	3.37
	CO₂-CH₄-H₂O （1∶1）	0.76	0.38	3.78	0.76	0.38	3.83	0.76	0.38	3.87
		1.20	0.60	3.69	1.20	0.60	3.75	1.20	0.60	3.79
		2.00	1.00	3.59	2.00	1.00	3.62	2.00	1.00	3.69
		4.80	2.40	3.48	4.80	2.40	3.48	4.80	2.40	3.53
		12.00	6.00	3.32	12.00	6.00	3.35	12.00	6.00	3.39
	CO₂-N₂-H₂O （3∶7）	1.30	0.39	3.78	1.30	0.39	3.80	1.30	0.39	3.91
		2.00	0.60	3.66	2.00	0.60	3.71	2.00	0.60	3.80
		3.00	0.90	3.60	3	0.90	3.62	3	0.90	3.73
		6.00	1.80	3.50	6	1.80	3.53	6	1.80	3.60
		16.00	4.80	3.33	16	4.80	3.40	16	4.80	3.43
	CO₂-CH₄-H₂O （3∶7）	1.30	0.39	3.74	1.30	0.39	3.78	1.30	0.39	3.91
		2.00	0.60	3.69	2.00	0.60	3.70	2.00	0.60	3.79
		3.00	0.90	3.58	3	0.90	3.62	3	0.90	3.70
		6.00	1.80	3.47	6	1.80	3.54	6	1.80	3.60
		16.00	4.80	3.41	16	4.80	3.40	16	4.80	3.48
	CO₂-N₂-H₂O （1∶9）	3.90	0.39	3.76	3.90	0.39	3.88	3.90	0.39	3.91
		6.00	0.60	3.68	6	0.6	3.78	6.0	0.60	3.82
		9.00	0.90	3.60	9	0.9	3.69	9	0.90	3.74
		18.00	1.80	3.51	18	1.8	3.61	18	1.80	3.63
	CO₂-CH₄-H₂O （1∶9）	3.90	0.39	3.78	3.90	0.39	3.84	3.90	0.39	3.93
		6.00	0.60	3.71	6	0.6	3.76	6.00	0.60	3.86
		9.00	0.90	3.63	9	0.9	3.67	9	0.90	3.77
		18.00	1.80	3.56	18	1.8	3.59	18	1.80	3.66
注：反应系统中气体比例为摩尔比，下同

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表 3 纯/非纯CO₂-水体系的pH预测模型

Table 3. pH prediction models for pure/impure CO₂-water systems

化学反应式	数学表达式
气−液平衡：
$ {\mathrm{C}\mathrm{O}}_{2\left(\mathrm{g}\right)}+{\mathrm{H}}_{2}\mathrm{O}\leftrightarrow {\mathrm{H}\mathrm{C}\mathrm{O}}_{3}^{-}+{\mathrm{H}}^{+} $	$ {y}_{g}P{\varnothing }_{g}{K}_{g}=\prod\limits_{j=1}^{N_c}{c}_{j}^{{v}_{gj}}{\gamma }_{j}^{{v}_{gj}}，g=1,\cdots ,{N}_{g} $ 式中：$ {y}_{g} $气体组分在气相中的摩尔浓度；$ {\varnothing }_{g} $为气体逸度系数；$ P $为压力；$ {K}_{g} $为气−液平衡常数；$ {c}_{j} $为主要组分浓度；$ {\gamma }_{j} $为活度系数；$ {v}_{gj} $为气体组分与主要组分的反应系数；$ N_c $，$ {N}_{g} $分别为主要组分和气体组分数目
$ {\mathrm{N}}_{2\left(\mathrm{g}\right)}\leftrightarrow {\mathrm{N}}_{2\left(\mathrm{a}\mathrm{q}\right)} $
$ {\mathrm{C}\mathrm{H}}_{4\left(\mathrm{g}\right)}\leftrightarrow {\mathrm{C}\mathrm{H}}_{4\left(\mathrm{a}\mathrm{q}\right)} $
水溶液中化学组分平衡：
$ {\mathrm{C}\mathrm{O}}_{3}^{2-}+{\mathrm{H}}^{+}\leftrightarrow {\mathrm{H}\mathrm{C}\mathrm{O}}_{3}^{-} $	$ {c}_{k}={K}_{k}^{-1}{\gamma }_{k}^{-1}\prod\limits_{j=1}^{N_c}{c}_{j}^{{v}_{kj}}{\gamma }_{j}^{{v}_{kj}}，k=1,\cdots ,{N}_{a} $ 式中：$ {c}_{k} $为次要组分；$ {K}_{k} $为液相中化学反应平衡常数；$ {v}_{kj} $为次要组分与主要组分的反应系数；$ {N}_{a} $为液相中次要组分数目
$ {\mathrm{H}}_{2}\mathrm{O}+{\mathrm{C}\mathrm{O}}_{2\left(\mathrm{a}\mathrm{q}\right)}\leftrightarrow {\mathrm{H}\mathrm{C}\mathrm{O}}_{3}^{-}+{\mathrm{H}}^{+} $
$ {\mathrm{H}}^{+}+{\mathrm{O}\mathrm{H}}^{-}\leftrightarrow {\mathrm{H}}_{2}\mathrm{O} $

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