-
摘要: 青海柴达木盆地深部地下卤水中富含大量钾、钙、锶、溴等元素, 是极具综合利用价值的液态矿产资源, 可作为钾盐潜在开发资源。本文根据该地下卤水的组成特点, 采用等温溶解平衡法对四元体系KBr-CaBr2-SrBr2-H2O 在298.15 K 时溶解度和相平衡规律进行详细的研究。测定该体系各盐在溶液中的溶解度和平衡固相组成, 根据实验结果绘制相应的稳定平衡相图和水含量图。该四元体系在298.15 K 下没有复盐和固溶体生成, 其平衡相图中有一个共饱点, 三条单变量曲线, 和三个固相结晶区(KBr、CaBr2∙6H2O、SrBr2∙6H2O)。基于Pitzer 模型, 对该四元体系在298.15 K 下的溶解度进行模拟计算, 绘制出计算相图, 计算相图与实验相图基本吻合。Abstract: The deep underground brine of Qaidam Basin in Qinghai is rich in potassium, calcium, strontium, bromine and other elements, making it a liquid mineral resource with great comprehensive utilization value.Notably, its brine can be developed as a potential potassium salt resource.In this study, the solubility and phase equilibrium of the quaternary KBr-CaBr2-SrBr2-H2O system at 298.15 K were studied in detail using the isothermal dissolution equilibrium method, based on the compositional characteristics of the deep underground brine.The solubility and equilibrium solid-phase compositions of the relevant salts of this system were determined.Based on the experimental data, a diagram of the stable phase equilibrium and water content of the system at specific temperature conditions has been plotted.This phase diagram has no complex salt and solid solution generation at 298.15 K, has one invariant point, three univariant dissolution curves, and three solid-phase crystalline zones (KBr, CaBr2∙6H2O, SrBr2∙6H2O).Based on the Pitzer model, the solubility of this quaternary system at 298.15 K was predicted, and its calculated phase diagram agrees well with the experimental phase diagram.
-
Key words:
- potassium salts /
- phase diagram /
- bromides /
- brine mineral systems /
- deep brines
-
-
符阳晓, 桑世华, 崔瑞芝, 2022.KBr-K2SO4-H2O 体系在318.15 K下的热力学性质和相平衡预测研究[J].盐湖研究, 30(4):72-82.
韩佳欢, 郑绵平, 乜贞, 等, 2024.我国深层地下卤水钾、锂资源及其开发前景[J].盐湖研究, 32(2): 90-100.
侯献华, 樊馥, 郑绵平, 等, 2017.青海盐湖钾盐资源开发利用及产业发展[J].科技导报, 35(12): 67-71.
刘兴起, 蔡克勤, 于升松, 2002.柴达木盆地盐湖形成演化与水体来源关系的地球化学初步模拟: Pitzer 模型的应用[J].地球化学, 31(5): 501-507.
聂国亮, 桑世华, 崔瑞芝, 2019.298 K 和323 K 条件下五元体系NaBr-KBr-MgBr2-CaBr2-H2O 相平衡研究[J].化工学报, 70(9): 3267-3274.
彭昌炜, 桑世华, 崔瑞芝, 等, 2022.五元体系NaBr-KBr-MgBr2-CaBr2-H2O 在298.15 K 下的空间立体相图研究[J].化工学报, 73(11): 4850-4858.
桑世华, 刘佳, 杨晓军, 等, 2023.三元体系KCl-K2B4O7-H2O在318.15 K 下热力学活度系数及相平衡实验和预测[J].化工学报, 74(10): 4051-4062.
宋彭生, 董亚萍, 李武, 2017.Li+, Na+, K+/Cl–, S
-H2O 五元体系25 ℃相图及其应用[J].盐湖研究, 25(3): 9-17.
王雪莹, 黄雪莉, 黄河, 等, 2020.–15℃下Na+, K+, Mg2+//Cl-, NO3-, S
-H2O 体系相平衡研究[J].化工学报, 71(11):5059-5066.
王莹, 2023.中国钾资源供需现状与资源保障程度[J].矿产勘查, 14(10): 1805-1813.
伍倩, 乜贞, 卜令忠, 等, 2018.盐湖卤水Li+, Na+/C
–H2O 三元体系 298.15 K 稳定相平衡研究[J].化工矿物与加工, 47(2): 15-18, 45.
郑绵平, 侯献华, 2017.青海盐湖资源综合利用与可持续发展战略[J].科技导报, 35(12): 11-13.
郑绵平, 张永生, 刘喜方, 等, 2016.中国盐湖科学技术研究的若干进展与展望[J].地质学报, 90(9): 2123-2166.
郑绵平, 张震, 侯献华, 等, 2015.中国钾资源远景与矿业发展战略[J].国土资源情报, (10): 3-9.
中国地质调查局, 2023.中国矿产资源报告[EB/OL].[2023-10-27].https://www.mnr.gov.cn/dt/ywbb/202310/t2023 1027_2804635.htm.
CHRISTOV C, 2007.An isopiestic study of aqueous NaBr and KBr at 50 °C: Chemical equilibrium model of solution behavior and solubility in the NaBr-H2O, KBr-H2O and Na-K-Br-H2O systems to high concentration and temperature[J].Geochimica et Cosmochimica Acta, 71(14): 3557-3569.
CHRISTOV C, 2011.Isopiestic investigation of the osmotic coefficients of aqueous CaBr2 and study of bromide salt solubility in the NaBr-CaBr2-H2O system at 50 °C:Thermodynamic model of solution behavior and solid-liquid equilibria in the CaBr2-H2O, and NaBr-CaBr2-H2O systems to high concentration and temperature[J].Calphad-Computer Coupling of Phase Diagrams and Thermochemistry, 35(1):42-53.
CHRISTOV C, 2012.Study of bromide salts solubility in the(m1KBr+m2CaBr2)(aq) system at T=323.15 K.Thermodynamic model of solution behaviour and(solid+liquid) equilibria in the ternaries(m1KBr+m2CaBr2)(aq), and (m1MgBr2+m2CaBr2)(aq), and in the quinary (Na+K+Mg+Ca+Br+H2O) systems to high concentration and temperature[J].The Journal of Chemical Thermodynamics, 55: 7-22.
CUI Ruizhi, LI Wu, DONG Yaping, et al., 2020.Measured and Predicted Solubility Phase Diagrams of Quaternary Systems LiBr-NaBr-MgBr2-H2O and LiBr-KBr-MgBr2-H2O at 298.15 K[J].Chemical Research in Chinese Universities, 36(6): 1234-1240.
FU Yangxiao, SANG Shihua, CUI Ruizhi, 2022.Thermodynamic Properties and Phase Equilibrium Prediction of KBr–K2SO4–H2O System at 318.15 K[J].Journal of Salt Lake Research, 30(4): 72-82(in Chinese with English abstract).
Geological Survey of China, 2023.China Mineral Resources Report[EB/OL].[2023-10-27].https://www.mnr.gov.cn/dt/ywbb/202310/t20231027_2804635.htm(in Chinese).
GREENBERG J P, MØLLER N, 1989.The prediction of mineral solubilities in natural waters: A chemical equilibrium model for the Na-K-Ca-Cl-SO4-H2O system to high concentration from 0 to 250 ℃[J].Geochimica et Cosmochimica Acta, 53(10): 2503-2518.
HAN Jiahuan, ZHENG Mianping, NIE Zhen, et al., 2024.Lithium and potassium resources of oilfield brine and development prospects in China[J].Journal of Salt Lake Research, 32(2):90-100(in Chinese with English abstract).
HARVIE C E, MØLLER N, WEARE J H, 1984.The Prediction of Mineral Solubilities in Natural-Waters: The Na-K-Mg-Ca-HCl-SO4-OH-HCO3-CO3-CO2-H2O System to High Ionic Strengths at 25 ℃[J].Geochimica et Cosmochimica Acta, 48(4): 723-751.
HOU Xianhua, FAN Fu, ZHENG Mianping, et al., 2017.Development and utilization of potash resources of saline lakes in Qinghai Province[J].Science & Technology Review, 35(12):67-71(in Chinese with English abstract).
KELLER A, BURGER J, HASSE H, et al., 2021.Application of the Pitzer model for describing the evaporation of seawater[J].Desalination, 503(1): 114866.
KIM H T, FREDERICK W J, 1988.Evaluation of pitzer ion interaction parameters of aqueous electrolytes at 25 ℃.1.Single salt parameters[J].Journal of Chemical and Engineering Data, 33(2): 177-184.
LIU Xingqi, CAI Keqing, YU Shengsong, 2002.Geochemical simulation of formation and evolution of salt lakes and their water sources in Qardam Basin: Application of Pitzer’s model[J].Geochimica, 31(5): 501-507(in Chinese with English abstract).
NIE Guoliang, CUI Ruizhi, SANG Shihua, et al., 2020.Experimental study and theoretical simulation of fluid phase equilibrium in the subsystems of quinary system NaBr–KBr–MgBr2–SrBr2–H2O at 298 K[J].Journal of Molecular Liquids, 306(15): 112635.
NIE Guoliang, SANG Shihua, CUI Ruizhi, 2019.Phase equilibria in quinary system NaBr–KBr–MgBr2–CaBr2–H2O at 298 K and 323 K[J].CIESC Journal, 70(9): 3267-3274(in Chinese with English abstract).
PENG Changwei, SANG Shihua, CUI Ruizhi, et al., 2022.Studies on three-dimensional phase diagram of the quinary system NaBr–KBr–MgBr2–CaBr2–H2O at 298.15 K[J].CIESC Journal, 73(11): 4850-4858(in Chinese with English abstract).
REDDY D C, ANANTHASWAMY J, 1990.Thermodynamic properties of aqueous electrolyte solutions: an e.m.f.study of{KCl(mA)+SrCl2(mB)}(aq) at the temperatures 298.15 K, 308.15 K, and 318.15 K[J].The Journal of Chemical Thermodynamics, 22(10): 1015-1023.
SANG Shihua, LIU Jia, YANG Xiaojun, et al., 2023.Measurements and predictions of thermodynamic activity coefficients and phase equilibria in ternary system KCl-K2B4O7-H2O[J].CIESC Journal, 74(10): 4051-4062(in Chinese with English abstract).
SONG Pengsheng, DONG Yaping, LI Wu, 2017.Phase Diagram of the quinary system Li+, Na+, K+/Cl-, S
-H2O at 25 °C System and Its Application[J].Journal of Salt Lake Research, 25(3): 9-17(in Chinese with English abstract).
WANG Xueying, HUANG Xueli, HUANG He, et al., 2020.Study on Phase equilibrium of system Na+, K+, Mg2+//Cl-, N
, S
-H2O at–15 ℃[J].CIESC Journal, 71(11): 5059-5066(in Chinese with English abstract).
WANG Ying, 2023.The supply and demand status and resource guarantee degree of potash in China[J].Mineral Exploration, 14(10): 1805-1813(in Chinese with English abstract).
WU Qian, NIE Zhen, BU Lingzhong, et al., 2018.Research on stable phase equilibrium in ternary system Li+, Na+/C
-H2O[J].Industrial Minerals & Processing, 47(2): 15-18, 45(in Chinese with English abstract).
ZHANG Xueping, WANG Wei, ZHANG Hanzhong, et al., 2021.Solid-Liquid Phase Equilibria in the Ternary System CaBr2-SrBr2-H2O at 273, 298, and 323 K[J].Journal of Chemical and Engineering Data, 66(1): 138-145.
ZHENG Mianping, HOU Xianhua, 2017.Comprehensive utilization and sustainable development strategy of salt lake resources in Qinghai[J].Science & Technology Review, 35(12):11-13(in Chinese with English abstract).
ZHENG Mianping, ZHANG Zheng, HOU Xianhua, et al., 2015.The prospects and the mining development strategy of potassium resources in China[J].Land and Resources Information, (10): 3-9(in Chinese with English abstract).
ZHNEG Mianping, ZHANG Yongsheng, LIU Fangxi, et al., 2016.Some Progress and Prospects of Scientific and Technological Research on Salt Lakes in China[J].Acta Geologica Sinica, 90(9): 2123-2166(in Chinese with English abstract).
-
计量
- 文章访问数: 41
- PDF下载数: 13
- 施引文献: 0