三元体系KBr-KCl-H_2O373 K相平衡研究
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摘要
针对川西盆地富硼钾溴地下卤水组成,采用等温溶解平衡法研究了三元体系KCl-KBr-H2O在373K时的相平衡关系,测定了373K条件下平衡溶液的溶解度和密度,依据湿渣法和X射线衍射相结合的方法对平衡固相组成做了分析和鉴定。根据实验数据绘制了相应的相图和密度图,发现该三元体系在373K条件下属于完全互溶的固体溶液型相图,在373K的溶解度等温图中有1个固溶体结晶区K(Cl,Br),1条单变量曲线。而后简单讨论了密度的变化规律,并回归了平衡液相与相对应的固相组成数据之间的三次方程。
According to the composition of the brine resources in the west of Sichuan basin,phase equilibria in the ternary system KCl-KBr-H2O at 373Khave been studied by isothermal solution saturation method.The solubilities and densities of the solutions in the ternary system were determined experimentally.The equilibrium solid phases were also determined by analyzing wet residues and X-ray spectroscopy.Using the experimental data,the phase diagram of the ternary system was obtained,which comprises one univariant curve and one stationary phase in the crystallization filed of K(Cl,Br).The ternary system is a solid solution type.The density transformation rules were then discussed briefly,and the solid phase composition data were fitted with a cubic equation of the equilibrium liquid composition.
According to the composition of the brine resources in the west of Sichuan basin,phase equilibria in the ternary system KCl-KBr-H2O at 373Khave been studied by isothermal solution saturation method.The solubilities and densities of the solutions in the ternary system were determined experimentally.The equilibrium solid phases were also determined by analyzing wet residues and X-ray spectroscopy.Using the experimental data,the phase diagram of the ternary system was obtained,which comprises one univariant curve and one stationary phase in the crystallization filed of K(Cl,Br).The ternary system is a solid solution type.The density transformation rules were then discussed briefly,and the solid phase composition data were fitted with a cubic equation of the equilibrium liquid composition.
引文
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[19]中科院青海盐湖所.卤水和盐的分析方法[M].北京:科学出版社,1984.Institute of Qinghai Salt-Lake in Chinese Academy of Sciences.Analytical Methods of Brines and Salts[M].Beijing:Science Press,1984.(in Chinese)
[2]林耀庭.四川盆地卤水钾硼碘溴资源开发利用可持续发展的对策思考[J].盐湖研究,2001,9(2):56-60.Lin Yaoting.Study on sustainable development of potassium boron iodine and bromine in brine of Sichuan basin[J].J Salt Lake Res,2001,9(2):56-60.(in Chinese)
[3]李丹,孟令宗,郭亚飞.含固溶体水盐体系的相平衡研究进展[J].化学世界,2011,9:56-59.Li Dan,Meng Lingzong,Guo Yafei.Progress on study of phase equilibria of solid solution-containing salt-water systems[J].Chem World,2011,9:56-59.(in Chinese)
[4]牛自得,程芳琴.水盐体系相图及其应用[M].天津:天津大学出版社,2002.Niu Zide,Cheng Fangqin.The Phase Diagram of SaltWater System and Its Application[M].Tianjin:Tianjin University Press,2002.(in Chinese)
[5]翁延博.五元体系Na+,K+,Mg2+//Cl-,Br--H2O313K相平衡研究[D].天津:天津大学,2008.Weng Yanbo.Study on Phase Equilibria of the Quinary System Na+,K+,Mg2+//Cl-,Br--H2O at 313 K[D].Tianjin:Tianjin University,2008.(in Chinese)
[6]任宝山,曹吉林.带固溶体的水盐体系相平衡热力学关联[J].高校化学工程学报,2003,17(2):119-122.Ren Baoshan,Cao Jilin.Thermodynamics correlation of the phase equilibrium for the brine-salt system containing solid solution[J].J Chem Eng Chin Univ,2003,17(2):119-122.(in Chinese)
[7]Peng Y,Zeng Y,Su S.Metastable phase equilibrium and solution properties of the quaternary system Li+,K+//Cl-,and SO2-4-H2O at 273.15K[J].J Chem Eng Data,2011,56:458-463.
[8]Zeng Y,Zheng Z Y.Phase equilibria for the aqueous system containing sodium,potassium,carbonate,and sulfate ions at 273.15K[J].J Chem Eng Data,2009,54:1244-1248.
[9]Christomir C.An isopiestic study of aqueous NaBr and KBr at 50℃: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].Geochim Cosmochim Acta,2007,71:3557-3569.
[10]Michael S,Jana K,Andreas N.An improved model incorporating Pitzer’s equations for calculation of thermodynamic properties of pore solutions implemented into an efficient program code[J].Construct Build Mater,2008,22:1841-1850.
[11]Speneer R J,Moller N,Weare H.The predietion of mineral solubilities in natural waters:aehemieal equilibrium model for the Na-K-Ca-Mg-Cl-H2O system at temperatures below 25℃[J].Geochim Cosmochim Acta,1990,54:575-590.
[12]翁延博,王彦飞,王静康,等.K+//Cl-,Br--H2O三元体系298K,313K,333K时的相平衡[J].高校化学工程学报,2007,21(4):695-699.Weng Yanbo,Wang Yanfei,Wang Jingkang,et al.Phase diagram for the ternary system of K+//Cl-,Br--H2O at 298K,313Kand 333K[J].J Chem Eng Chin Univ,2007,21(4):695-699.(in Chinese)
[13]张凯杰,桑世华,王丹,等.KCl-KBr-H2O三元体系323K时的相平衡研究[J].盐业与化工,2011,35(6):5-7.Zhang Kaijie,Sang Shihua,Wang Dan,et al.Study on the phase equilibria in the ternary system KCl-KBr-H2O at 323K[J].J Salt Chem Ind,2011,35(6):5-7.(in Chinese)
[14]翁延博,王静康,尹秋响,等.NaCl-NaBr-H2O三组分物系的固液平衡[J].石油化工,2007,36(4):358-361.Weng Yanbo,Wang Jingkang,Yin Qiuxiang,et al.Solid-liquid equilibrium of NaCl-NaBr-H2O ternary system[J].Petrochem Tech,2007,36(4):358-361.(in Chinese)
[15]王丹,桑世华,曾晓晓,等.KCl-KBr-K2SO4-H2O四组分物系323K相平衡[J].石油化工,2011,40(3):285-288.Wang Dan,Sang Shihua,Zeng Xiaoxiao,et al.Phase equilibrium of KCl-KBr-K2SO4-H2O quaternary system at 323K[J].Petrochem Tech,2011,40(3):285-288.(in Chinese)
[16]Zhang K J,Sang S H,Li T,et al.Liquid-solid equilibria in the quaternary system KCl-KBr-K2SO4-H2O at348K[J].J Chem Eng Data,2013,58(1):115-117.
[17]Cui R Z,Sang S H,Hu Y X.Solid-liquid equilibria in the quaternary systems KCl-KBr-K2B4O7-H2O and KCl-KBr-K2SO4-H2O at 373K[J].J Chem Eng Data,2013,58(2):477-481.
[18]张明玖,吕秉玲.100℃Na+,NH4/Cl-,SO2-4,H2O体系相图[J].化学学报,1994,52(7):634-638.Zhang Mingjiu,LüBingling.Study on phase diagram of the Na+,NH+4/Cl-,SO2-4,H2O system at 100℃[J].Acta Chim Sin,1994,52(7):634-638.(in Chinese)
[19]中科院青海盐湖所.卤水和盐的分析方法[M].北京:科学出版社,1984.Institute of Qinghai Salt-Lake in Chinese Academy of Sciences.Analytical Methods of Brines and Salts[M].Beijing:Science Press,1984.(in Chinese)
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