基于Pitzer模型预测Na-K-Ca-Mg-Cl-H2O溶液的密度

doi:10.13745/j.esf.sf.2021.1.55

地学前缘 ›› 2021, Vol. 28 ›› Issue (6): 179-186.DOI: 10.13745/j.esf.sf.2021.1.55

基于Pitzer模型预测Na-K-Ca-Mg-Cl-H₂O溶液的密度

路淼^1,2, 李东东¹, 李武¹, 董亚萍¹, 胡斌^1,*

1.中国科学院青海盐湖研究所中国科学院盐湖资源综合高效利用重点实验室/青海省盐湖资源化学重点实验室, 青海西宁 810008;
2.中国科学院大学, 北京 100049

收稿日期:2021-01-08 修回日期:2021-02-16 出版日期:2021-11-25 发布日期:2021-11-25
通讯作者: ^*胡斌(1980—),男,副研究员,硕士生导师,主要从事溶液热力学模型研究。 E-mail:hubin@isl.ac.cn
作者简介:路淼(1996—),女,硕士研究生,物理化学专业。E-mail:lumiao@isl.ac.cn
基金资助:
国家重点研发计划项目(2017YFC0602805); 中国科学院国际伙伴计划项目(122363KYSB20190033)

Density prediction for the Na-K-Ca-Mg-Cl-H₂O system using the Pitzer model

LU Miao^1,2, LI Dongdong¹, LI Wu¹, DONG Yaping¹, HU Bin^1,*

1. CAS Key Laboratory of Comprehensive and Highly Efficient Utilization of Salt Lake Resources/Qinghai Provincial Key Laboratory of Resources and Chemistry of Salt Lake, Qinghai Institute of Salt Lakes, Chinese Academy of Sciences, Xining 810008, China;
2. University of Chinese Academy of Sciences, Beijing 100049, China

Received:2021-01-08 Revised:2021-02-16 Online:2021-11-25 Published:2021-11-25

摘要/Abstract

摘要： 天然水体系的体积性质与压力、温度、组成的相关性(PVTx性质)研究在地球化学、盐湖化工等领域有广泛的应用。密度是卤水最基本的体积性质,不仅可以通过实验测定,还可以用理论模型进行预测。建立富钾卤水密度与组成、温度的关联模型有助于认识钾在复杂卤水中的富集、迁移规律。为了构建基于Pitzer离子相互作用模型的卤水密度预测方法,本文用高精度振荡管密度计测定了常压下KCl、CaCl₂纯盐溶液以及最高离子强度为11.8 mol·kg^-1的混合溶液在283~323 K下的密度,用所测得的密度通过Pitzer离子相互作用模型拟合得到多温下Pitzer单电解质参数和Pitzer混合参数。用Pitzer模型参数计算了Na-K-Ca-Mg-Cl-H₂O体系293~313 K的密度,计算密度值与实验值的相对偏差在±0.25%以内,计算的结果整体上要优于文献值,文献在计算中均未考虑Pitzer混合参数项。结果表明,K、Ca、Cl离子间的相互作用对于Na-K-Ca-Mg-Cl-H₂O溶液的密度有显著的影响,本文获得的Pitzer参数反映了这些离子间的相互作用,可用于计算含有K、Ca、Cl离子的复杂卤水密度的预测。

关键词: 密度, 天然水, KCl, CaCl₂, Pitzer离子相互作用模型

Abstract: PVTx properties of natural water are widely used in geochemistry and salt lake industry. By establishing the correlation between density, composition, temperature and pressure of potassium-rich brine, one can better understand the enrichment and migration of potassium in complex brine systems. In order to construct a prediction model for brine density based on the Pitzer model, densities of KCl and CaCl₂ aqueous solutions and their mixtures were measured by vibrating-tube densitometry. The concentrations of single solute solutions were near saturation, and ionic strengths of aqueous mixtures were from 1.8 to 11.8 mol·kg^-1. The Pitzer single electrolyte parameters and Pitzer mixing parameters at various temperatures between 283-323 K were obtained by Pitzer ion interaction model fitting using the measured densities, and the Pitzer volumetric parameters were obtained by fitting the volumetric Pitzer model to the experimental data. Densities of the Na-K-Ca-Mg-Cl-H₂O hexary system over the temperature range of 293-313 K were calculated. The calculated density was in good agreement with the experimental results, with the relative error within 0.25%. The results show that ionic interactions had a significant effect on the density of the hexary system. The Pitzer parameters obtained in this paper reflect the interactions between these ions and can be used to make density predictions for complex brines containing K, Ca and Cl ions.

Key words: density, natural water, KCl, CaCl₂, Pitzer ion interaction model

中图分类号:

路淼, 李东东, 李武, 董亚萍, 胡斌. 基于Pitzer模型预测Na-K-Ca-Mg-Cl-H₂O溶液的密度[J]. 地学前缘, 2021, 28(6): 179-186.

LU Miao, LI Dongdong, LI Wu, DONG Yaping, HU Bin. Density prediction for the Na-K-Ca-Mg-Cl-H₂O system using the Pitzer model[J]. Earth Science Frontiers, 2021, 28(6): 179-186.

参考文献

[1] MAO S, HU J, ZHANG Y, et al.A predictive model for the PVTx properties of CO₂-H₂O-NaCl fluid mixture up to high temperature and high pressure[J]. Applied Geochemistry, 2015, 54(3): 54-64.
[2] HOSHINO K, ITAMI T, SHIOKAWA R, et al.A possible role of boiling in ore deposition: a numerical approach[J]. Resource Geology, 2005, 56(1): 49-54.
[3] 王石军. 盐湖卤水密度的计算及应用[J]. 盐湖研究, 2000, 41(4): 44-49.
[4] LEWIS G N, RANDALL M.Thermodynamics[M]. New York: McGraw-Hill, 1961: 723.
[5] HARNED H S, OWEN B B.The physical chemistry of electrolyte solutions[M]. New York: Reinhold, 1958: 803.
[6] 周迅, 姜长龙, 韩桂君, 等. 沉积盆地深层地下卤水资源量评价之若干探讨[J]. 地球学报, 2013, 34(5): 610-616.
[7] YOUNG T F, SMITH M B.Thermodynamic properties of mixtures of electrolytes in aqueous solutions[J]. Journal of Physical Chemistry, 1954, 58(9): 716-724.
[8] LALIBERTE M, COOPER W E.Model for calculating the density of aqueous electrolyte solutions[J]. Journal of Chemical and Engineering Data, 2004, 49(5): 1141-1151.
[9] HU Y F.An empirical approach for estimating the density of multicomponent aqueous solutions obeying the linear isopiestic relation[J]. Journal of Solution Chemistry, 2000, 29(12): 1229-1236.
[10] PITZER K S.Thermodynamics of electrolytes. I. Theoretical basis and general equations[J]. Journal of Physical Chemistry, 1972, 77(2): 268-277.
[11] PITZER K S.Activity coefficients in electrolyte solutions[M]. 2nd ed. Boca Raton: CRC Press, 1991: 1-552.
[12] KRUMGALZ B S, POGORELSKII R, SOKOLOV A, et al.Volumetric ion interaction parameters for single-solute aqueous electrolyte solutions at various temperatures[J]. Journal of Physical and Chemical Reference Data, 2000, 29(5): 1123-1140.
[13] KRUMGALZ B S, STARINSKY A, PITZER K S.Ion-interaction approach: pressure effect on the solubility of some mineral in submarine brines and seawater[J]. Journal of Solution Chemistry, 1999, 28(6): 667-692.
[14] MONNIN C.An ion interaction model for the volumetric properties of natural waters density of the solution and partial molal volumes of electrolytes to high-concentrations at 25 ℃[J]. Geochimica et Cosmochimica Acta, 1989, 53(6): 1177-1188.
[15] KUMAR A.Densities and apparent molal volumes of aqueous KCl-CaCl₂ mixtures at 298.15 K[J]. Journal of Chemical and Engineering Data, 1986, 31(1): 21-23.
[16] ZHANG H L, CHEN G H, HAN S J.Viscosity and density of H₂O+NaCl+CaCl₂ and H₂O+KCl+CaCl₂[J]. Journal of Chemical and Engineering Data, 1997, 42(3): 526-530.
[17] DENG T L, LI D C, WANG S Q.Metastable phase equilibrium in the aqueous ternary system (KCl-CaCl₂-H₂O) at (288.15 and 308.15) K[J]. Journal of Chemical and Engineering Data, 2008, 53(4): 1007-1011.
[18] ARCHER D G.Thermodynamic properties of NaCl+H₂O system. II thermodynamic properties of NaCl(aq), NaCl·2H₂O(cr), and phase equilibria[J]. Journal of Physical and Chemical Reference Data, 1992, 21(4): 793-829.
[19] HU B, HNĚDKOVSKÝL, HEFTER G, et al. Densities and molar volumes of aqueous solutions of LiClO₄ at temperatures from 293 to 343 K[J]. Journal of Chemical and Engineering Data, 2016, 61(4): 1388-1394.
[20] WAGNER W, PRUSS A.The IAPWS formulation 1995 for the thermodynamic properties of ordinary water substance for general and scientific use[J]. Journal of Physical and Chemical Reference Data, 2002, 31(2): 387-535.
[21] MAO S D, PENG Q B, Wang M, et al.The PVTx properties of aqueous electrolyte solutions containing Li+, Na+, K+, Mg²+, Ca²+, Cl- and $SO_{4}^{2-}$ under conditions of CO₂ capture and sequestration[J]. Applied Geochemistry, 2017, 86(11): 105-120.
[22] LACH A, BALLERAT-BUSSEROLLES K, ANDRE L, et al.Experimental data and modeling of solution density and heat capacity in the Na-K-Ca-Mg-Cl-H₂O system up to 353.15 K and 5 mol·kg^-1 ionic strength[J]. Journal of Chemical and Engineering Data, 2017, 62(10): 3561-3576.

基于Pitzer模型预测Na-K-Ca-Mg-Cl-H₂O溶液的密度

Density prediction for the Na-K-Ca-Mg-Cl-H₂O system using the Pitzer model

RichHTML

PDF (PC)

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]	周尚, 徐继尚, 刘勇, 李广雪, 李安龙, 曹立华, 翟科, 徐继正, 权永峥. 西太暖池区生物组分对海底表层沉积物物理力学性质的影响[J]. 地学前缘, 2022, 29(5): 119-132.
[2]	宋鹰, 张俊霞, Andrei Stepashko, 袁万明, 丛旭日. 基于核密度估计的碎屑颗粒年龄分析及应用:松辽盆地构造事件定年[J]. 地学前缘, 2016, 23(4): 265-276.
[3]	王茜茜, 万天丰, 袁玉松, 邱登峰. 鄂西地区燕山期古构造应力场初步定量研究[J]. 地学前缘, 2016, 23(2): 269-279.
[4]	郭晶晶,夏学齐,杨忠芳. 长江流域典型区域土壤碳库变化及其影响因素[J]. 地学前缘, 2015, 22(6): 241-250.
[5]	刘德汉,肖贤明,田辉,王一刚,汪泽成,闵育顺. 论川东北地区发现的高密度甲烷包裹体类型与油裂解气和页岩气勘探评价[J]. 地学前缘, 2013, 20(1): 64-71.
[6]	奚小环, 李敏*, 张秀芝, 张燕平, 张德存, 张建新, 窦磊, 杨奕. 中国中东部平原及周边地区土壤有机碳分布与变化趋势研究[J]. 地学前缘, 2013, 20(1): 154-165.
[7]	魏然, 杨忠芳, 侯青叶, 尹国胜, 衷存堤, 邓国辉, 马逸麟. 江西省鄱阳湖流域农田生态系统土壤Se元素含量变化研究[J]. 地学前缘, 2012, 19(1): 277-289.
[8]	刘飞, 杨柯, 李括, 彭敏, 聂海峰. 我国四种典型土类有机碳剖面分布特征[J]. 地学前缘, 2011, 18(6): 20-26.
[9]	赵传冬, 刘国栋, 杨柯, 聂海峰, 彭敏, 李括, 刘飞, 李延生. 黑龙江省扎龙湿地及其周边地区土壤碳储量估算与1986年以来的变化趋势研究[J]. 地学前缘, 2011, 18(6): 27-33.
[10]	张秀芝, 赵相雷, 李宏亮, 王志军, 劳晓光, 谢伟明. 河北平原土壤有机碳储量及固碳机制研究[J]. 地学前缘, 2011, 18(6): 41-55.
[11]	夏学齐, 杨忠芳, 余涛, 侯青叶, 白荣杰, 崔玉军. 中国东北地区20世纪末土地利用变化的土壤碳源汇效应[J]. 地学前缘, 2011, 18(6): 56-63.
[12]	鞠玮，侯贵廷，潘文庆，韩剑发，琚岩. 塔中Ⅰ号断裂带北段构造裂缝面密度与分形统计[J]. 地学前缘, 2011, 18(3): 317-323.
[13]	王诗东，庹先国，李怀良，葛宝. 氡气测量法-高密度电法在断层定位中的应用[J]. 地学前缘, 2011, 18(2): 315-320.
[14]	奚小环, 杨忠芳, 崔玉军, 孙淑梅, 于成广, 李敏. 东北平原土壤有机碳分布与变化趋势研究[J]. 地学前缘, 2010, 17(3): 213-221.
[15]	成秋明张生元左仁广陈志军谢淑云夏庆霖徐德义姚凌青. 多重分形滤波方法和地球化学信息提取技术研究与进展[J]. 地学前缘, 2009, 16(2): 185-198.