四川盆地地下卤水含溴锶五元体系多温相平衡实验研究及计算
发布时间：2019-06-19 06:49
【摘要】：本文针对四川盆地地下卤水富含钾硼溴锶的特点,采用等温溶解平衡法研究了尚未见文献报道的298 K条件下五元体系NaBr KBr Na_2SO_4 K_2SO_4 Na_2B_4O_7 K_2B_4O_7 H_2O,298 K及323 K条件下五元体系NaBr KBr MgBr_2 CaBr_2 H_2O,323 K条件下五元体系NaBr KBr MgBr_2 SrBr_2 H_2O和348 K条件下四元体系NaBr KBr Na_2SO_4 K_2SO_4 H_2O及其相关子体系的相平衡关系,测定了上述各体系平衡液相组成并绘制了相应的相图,运用Pitzer模型进行部分体系的溶解度计算。298 K、323 K和348 K条件下NaBr SrBr_2 H_2O和KBr SrBr_2 H_2O三元体系以及348 K条件下NaBr Na_2SO_4 H_2O和KBr K_2SO_4 H_2O三元体系的相图均为简单共饱和型,即无复盐及固溶体生成。四元体系NaBr KBr Na_2SO_4 K_2SO_4 H_2O在298 K和348 K条件下均有复盐钾芒硝(Na_2SO_4·3K_2SO_4),两个条件下的相图对比,348 K条件下无NaSO_4·10H_2O出现。298 K条件下NaBr Na_2SO_4 Na_2B_4O_7 H_2O、KBr K_2SO_4 K_2B_4O_7 H_2O和NaBr KBr Na_2B_4O_7 K_2B_4O_7 H_2O;298 K和323 K条件下NaBr KBr SrBr_2 H_2O,NaBr KBr CaBr_2 H_2O;323 K条件下NaBr MgBr_2 SrBr_2 H_2O体系的相图均为简单共饱和型。298 K和323 K条件下NaBr KBr MgBr_2 H_2O和KBr CaBr_2 MgBr_2 H_2O以及323 K条件下KBr MgBr_2 SrBr_2 H_2O均有复盐KBr·MgBr_2·6H_2O,其中KBr CaBr_2 MgBr_2 H_2O体系在323 K条件下还有复盐2MgBr_2·CaBr_2·12H_2O生成。交互五元体系NaBr KBr Na_2SO_4 K_2SO_4 Na_2B_4O_7 K_2B_4O_7 H_2O在298 K条件下有复盐钾芒硝(Na_2SO_4·3K_2SO_4),在以Na_2B_4O_7饱和条件下的干盐图中有五个共饱点、十一条单变量曲线和七个平衡固相结晶区,对应的平衡固相分别为Na_2SO_4、Na_2SO_4·10H_2O、NaBr·2H_2O、K_2SO_4、Na_2SO_4·3K_2SO_4、K_2B_4O_7·4H_2O和KBr。简单五元体系Na Br KBr MgBr_2 CaBr_2 H_2O(KBr饱和)的相图在298 K条件下含有两个共饱点,五条单变量曲线和四个结晶区分别为NaBr·2H_2O、NaBr、KBr、KBr·MgBr_2·6H_2O和CaBr_2·6H_2O。该体系的相图在323 K条件下有三个共饱点、七条单变量曲线和六个结晶区,分别为KBr·MgBr_2·6H_2O、2MgBr_2·CaBr_2·12H_2O、NaBr·2H_2O、NaBr、KBr和CaBr_2·4H_2O的结晶区。简单五元体系NaBr KBr MgBr_2 SrBr_2 H_2O在323 K条件下有复盐KBr·MgBr_2·6H_2O。在该体系的相图中有三个共饱点、十条单变量曲线和六个结晶区:NaBr·2H_2O,NaBr,MgBr_2·6H_2O,SrBr_2·6H_2O,KBr·MgBr_2·6H_2O和KBr。采用三元体系中的实验溶解度数据,拟合得出未见文献报道的混合离子参数:298 K条件下ΨNa,SO_4,B_4O5(OH)4、ΨK,SO_4,B_4O5(OH)4、θBr,B_4O5(OH)4、ΨNa,Br,B_4O5(OH)4、ΨK,Br,B_4O5(OH)4、θMg,Sr、ΨNa,Sr,Br、ΨK,Sr,Br、ΨMg,Sr,Br和ΨMg,Sr,Cl和348 K条件下ΨNa,Br,SO_4、ΨK,Br,SO_4,并进一步根据Pitzer电解质模型,采用粒子群算法,对部分体系进行了溶解度模拟。所计算体系如下:298 K下四个三元体系(NaBr SrBr_2 H_2O、KBr SrBr_2 H_2O、MgBr_2 SrBr_2 H_2O和MgCl2 SrCl2 H_2O);298 K下七个简单四元体系(NaBr KBr SrBr_2 H_2O、NaBr MgBr_2 SrBr_2 H_2O、KBr MgBr_2 SrBr_2 H_2O、NaCl MgCl2 SrCl2 H_2O、KCl MgCl2 SrCl2 H_2O、NaBr Na_2SO_4 Na_2B_4O_7 H_2O和KBr K_2SO_4 K_2B_4O_7 H_2O);298 K和323 K条件下三个简单四元体系(NaBr KBr MgBr_2 H_2O、NaBr KBr CaBr_2 H_2O和KBr MgBr_2 CaBr_2 H_2O);以及298 K和348 K条件下一个交互四元体系(NaBr KBr Na_2SO_4 K_2SO_4 H_2O)。计算与实验的结果相比较,发现计算相图与实验相图基本吻合。对误差的成因进行分析。
[Abstract]:In this paper, a five-element system NaBr KBr MgBr _ 2CaBr _ 2H _ 2O, which has not been reported under the conditions of 298K under the conditions of 298K, NaBr KBr Na _ 2SO _ 4K _ 2SO _ 4Na _ 2B _ 4O _ 7K _ 2B _ 4O _ 7H _ 2O, 298K and 323K under the condition of 298K, which has not been reported in the literature, is studied in this paper. The phase equilibrium of NaBr KBr Na _ 2SO _ 4K _ 2SO _ 4 H _ 2O and its related sub-system under the condition of 323K under the condition of NaBr KBr MgBr _ 2SrBr _ 2H _ 2O and 348K was determined. The equilibrium liquid phase composition of the above system was measured and the corresponding phase diagram was drawn. The solubility of the partial system was calculated by using the Pitzer model. The phase diagrams of NaBr SrBr _ 2H _ 2O and KBr SrBr _ 2H _ 2O ternary system under the conditions of 323K and 348K and the ternary system of NaBr Na _ 2SO _ 4 H _ 2O and KBr K _ 2SO _ 4 H _ 2O under the condition of 348K are of simple co-saturation type, that is, no complex salt and solid solution generation. The quaternary system NaBr KBr Na _ 2SO _ 4K _ 2SO _ 4 H _ 2O has the compound salt mirabilite (Na _ 2SO _ 4 路 3K _ 2SO _ 4) under the conditions of 298K and 348K, and the phase diagram under two conditions is compared with the phase diagram under the condition of 348 K. NaBr Na _ 2SO _ 4Na _ 2B _ 4O _ 7H _ 2O, KBr K _ 2SO _ 4K _ 2B _ 4O _ 7H _ 2O and NaBr KBr Na _ 2B _ 4O _ 7K _ 2B _ 4O _ 7H _ 2O; 298K and 323K under the condition of 298K, NaBr KBr SrBr _ 2H _ 2O, The phase diagrams of NaBr KBr _ 2SrBr _ 2H _ 2O system under the conditions of NaBr KBr _ 2SrBr _ 2H _ 2O and 323K are of simple co-saturation type. Under the conditions of 298K and 323K, the phase diagrams of NaBr _ 2SrBr _ 2H _ 2O and KBr _ 2MgBr _ 2H _ 2O and KBr _ 2SrBr _ 2H _ 2O have complex salt KBr. MgBr _ 2 路 6H _ 2O. The KBr _ 2MgBr _ 2H _ 2O system is formed by the complex salt of 2MgBr _ 2 路 CaBr _ 2 路 12H _ 2O under the condition of 323K. The five-element system NaBr KBr Na _ 2SO _ 4K _ 2SO _ 4Na _ 2B _ 4O _ 7K _ 2B _ 4O _ 7H _ 2O has five co-saturation points, eleven single-variable curves and seven equilibrium solid-phase crystal areas under the condition of 298K. The corresponding equilibrium solid phase is Na _ 2SO _ 4, Na _ 2SO _ 4 路 10H _ 2O and NaBr 路 2H _ 2O. K_2SO_4,Na_2SO_4路3K_2SO_4,K_2B_4O_7路4H_2O鍜孠Br. The phase diagram of the simple five-element system Na Br KBr MgBr _ 2CaBr _ 2H _ 2O (KBr saturation) contains two co-saturation points under the condition of 298K. The five single-variable curves and the four crystallization areas are NaBr 路 2H _ 2O, NaBr, KBr, KBr 路 MgBr _ 2 路 6H _ 2O and CaBr _ 2 路 6H _ 2O. The phase diagram of the system has three co-saturation points, seven single-variable curves and six crystallization zones under the condition of 323K. The phase diagram of the system is KBr. MgBr _ 2 路 6H _ 2O, 2MgBr _ 2 路 CaBr _ 2 路 12H _ 2O, NaBr 路 2H _ 2O, NaBr, KBr and CaBr _ 2 路 4H _ 2O. The simple five-element system NaBr KBr MgBr _ 2SrBr _ 2H _ 2O has the complex salt KBr 路 MgBr _ 2 路 6H _ 2O under the condition of 323K. In the phase diagram of the system, there are three co-saturation points, ten single-variable curves and six crystallization regions: NaBr 路 2H _ 2O, NaBr, MgBr _ 2 路 6H _ 2O, SrBr _ 2 路 6H _ 2O, KBr 路 MgBr _ 2 路 6H _ 2O and KBr. The experimental solubility data of ternary system was used to fit the mixed ion parameters: Na, SO _ 4, B _ 4O5 (OH)4, HCK, SO _ 4, B _ 4O5 (OH)4, HCK, SO _ 4, B _ 4O5 (OH)4, NaBr, B _ 4O5 (OH)4, NaNa, Br, B _ 4O5 (OH)4, HCK, Br, B _ 4O5 (OH)4, HCK, Sr, NaNa, Sr, Br, HCK, Sr, Br, Under the conditions of Mg, Sr, Br, and Mg, Sr, Cl, and 348 K, Na, Br, SO _ 4, HCK, Br, SO _ 4 were obtained, and the solubility of some systems was simulated by particle swarm optimization based on the Pitzer electrolyte model. The calculated system is as follows: four ternary systems (NaBr SrBr _ 2H _ 2O, KBr SrBr _ 2H _ 2O, MgBr _ 2SrBr _ 2H _ 2O and MgCl2 SrCl2 H _ 2O) at 298K; seven simple quaternary systems (NaBr KBr SrBr _ 2H _ 2O, NaBr MgBr _ 2SrBr _ 2H _ 2O, KBr MgBr _ 2SrBr _ 2H _ 2O, NaCl MgCl2 SrCl2 H _ 2O, KCl MgCl2 SrCl2 H _ 2O, NaBr Na _ 2SO _ 4Na _ 2B _ 4O _ 7H _ 2O and KBr _ 2SO _ 4K _ 2B _ 4O _ 7H _ 2O) under 298K; Three simple four systems (NaBr KBr MgBr _ 2H _ 2O, NaBr KBr, CaBr _ 2H _ 2O and KBr MgBr _ 2CaBr _ 2H _ 2O) under the conditions of 298K and 323K, and an interaction system under the conditions of 298K and 348K (NaBr KBr Na _ 2SO _ 4K _ 2SO _ 4H _ 2O). The results of the calculation and the experimental results are compared, and the calculated phase diagram is in agreement with the experimental phase diagram. The cause of the error is analyzed.
【学位授予单位】：成都理工大学
【学位级别】：博士
【学位授予年份】：2017
【分类号】：TS392;O642.42
本文编号：2502180
[Abstract]:In this paper, a five-element system NaBr KBr MgBr _ 2CaBr _ 2H _ 2O, which has not been reported under the conditions of 298K under the conditions of 298K, NaBr KBr Na _ 2SO _ 4K _ 2SO _ 4Na _ 2B _ 4O _ 7K _ 2B _ 4O _ 7H _ 2O, 298K and 323K under the condition of 298K, which has not been reported in the literature, is studied in this paper. The phase equilibrium of NaBr KBr Na _ 2SO _ 4K _ 2SO _ 4 H _ 2O and its related sub-system under the condition of 323K under the condition of NaBr KBr MgBr _ 2SrBr _ 2H _ 2O and 348K was determined. The equilibrium liquid phase composition of the above system was measured and the corresponding phase diagram was drawn. The solubility of the partial system was calculated by using the Pitzer model. The phase diagrams of NaBr SrBr _ 2H _ 2O and KBr SrBr _ 2H _ 2O ternary system under the conditions of 323K and 348K and the ternary system of NaBr Na _ 2SO _ 4 H _ 2O and KBr K _ 2SO _ 4 H _ 2O under the condition of 348K are of simple co-saturation type, that is, no complex salt and solid solution generation. The quaternary system NaBr KBr Na _ 2SO _ 4K _ 2SO _ 4 H _ 2O has the compound salt mirabilite (Na _ 2SO _ 4 路 3K _ 2SO _ 4) under the conditions of 298K and 348K, and the phase diagram under two conditions is compared with the phase diagram under the condition of 348 K. NaBr Na _ 2SO _ 4Na _ 2B _ 4O _ 7H _ 2O, KBr K _ 2SO _ 4K _ 2B _ 4O _ 7H _ 2O and NaBr KBr Na _ 2B _ 4O _ 7K _ 2B _ 4O _ 7H _ 2O; 298K and 323K under the condition of 298K, NaBr KBr SrBr _ 2H _ 2O, The phase diagrams of NaBr KBr _ 2SrBr _ 2H _ 2O system under the conditions of NaBr KBr _ 2SrBr _ 2H _ 2O and 323K are of simple co-saturation type. Under the conditions of 298K and 323K, the phase diagrams of NaBr _ 2SrBr _ 2H _ 2O and KBr _ 2MgBr _ 2H _ 2O and KBr _ 2SrBr _ 2H _ 2O have complex salt KBr. MgBr _ 2 路 6H _ 2O. The KBr _ 2MgBr _ 2H _ 2O system is formed by the complex salt of 2MgBr _ 2 路 CaBr _ 2 路 12H _ 2O under the condition of 323K. The five-element system NaBr KBr Na _ 2SO _ 4K _ 2SO _ 4Na _ 2B _ 4O _ 7K _ 2B _ 4O _ 7H _ 2O has five co-saturation points, eleven single-variable curves and seven equilibrium solid-phase crystal areas under the condition of 298K. The corresponding equilibrium solid phase is Na _ 2SO _ 4, Na _ 2SO _ 4 路 10H _ 2O and NaBr 路 2H _ 2O. K_2SO_4,Na_2SO_4路3K_2SO_4,K_2B_4O_7路4H_2O鍜孠Br. The phase diagram of the simple five-element system Na Br KBr MgBr _ 2CaBr _ 2H _ 2O (KBr saturation) contains two co-saturation points under the condition of 298K. The five single-variable curves and the four crystallization areas are NaBr 路 2H _ 2O, NaBr, KBr, KBr 路 MgBr _ 2 路 6H _ 2O and CaBr _ 2 路 6H _ 2O. The phase diagram of the system has three co-saturation points, seven single-variable curves and six crystallization zones under the condition of 323K. The phase diagram of the system is KBr. MgBr _ 2 路 6H _ 2O, 2MgBr _ 2 路 CaBr _ 2 路 12H _ 2O, NaBr 路 2H _ 2O, NaBr, KBr and CaBr _ 2 路 4H _ 2O. The simple five-element system NaBr KBr MgBr _ 2SrBr _ 2H _ 2O has the complex salt KBr 路 MgBr _ 2 路 6H _ 2O under the condition of 323K. In the phase diagram of the system, there are three co-saturation points, ten single-variable curves and six crystallization regions: NaBr 路 2H _ 2O, NaBr, MgBr _ 2 路 6H _ 2O, SrBr _ 2 路 6H _ 2O, KBr 路 MgBr _ 2 路 6H _ 2O and KBr. The experimental solubility data of ternary system was used to fit the mixed ion parameters: Na, SO _ 4, B _ 4O5 (OH)4, HCK, SO _ 4, B _ 4O5 (OH)4, HCK, SO _ 4, B _ 4O5 (OH)4, NaBr, B _ 4O5 (OH)4, NaNa, Br, B _ 4O5 (OH)4, HCK, Br, B _ 4O5 (OH)4, HCK, Sr, NaNa, Sr, Br, HCK, Sr, Br, Under the conditions of Mg, Sr, Br, and Mg, Sr, Cl, and 348 K, Na, Br, SO _ 4, HCK, Br, SO _ 4 were obtained, and the solubility of some systems was simulated by particle swarm optimization based on the Pitzer electrolyte model. The calculated system is as follows: four ternary systems (NaBr SrBr _ 2H _ 2O, KBr SrBr _ 2H _ 2O, MgBr _ 2SrBr _ 2H _ 2O and MgCl2 SrCl2 H _ 2O) at 298K; seven simple quaternary systems (NaBr KBr SrBr _ 2H _ 2O, NaBr MgBr _ 2SrBr _ 2H _ 2O, KBr MgBr _ 2SrBr _ 2H _ 2O, NaCl MgCl2 SrCl2 H _ 2O, KCl MgCl2 SrCl2 H _ 2O, NaBr Na _ 2SO _ 4Na _ 2B _ 4O _ 7H _ 2O and KBr _ 2SO _ 4K _ 2B _ 4O _ 7H _ 2O) under 298K; Three simple four systems (NaBr KBr MgBr _ 2H _ 2O, NaBr KBr, CaBr _ 2H _ 2O and KBr MgBr _ 2CaBr _ 2H _ 2O) under the conditions of 298K and 323K, and an interaction system under the conditions of 298K and 348K (NaBr KBr Na _ 2SO _ 4K _ 2SO _ 4H _ 2O). The results of the calculation and the experimental results are compared, and the calculated phase diagram is in agreement with the experimental phase diagram. The cause of the error is analyzed.
【学位授予单位】：成都理工大学
【学位级别】：博士
【学位授予年份】：2017
【分类号】：TS392;O642.42
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