四川盆地地下鹵水含溴鍶五元體系多溫相平衡實驗研究及計算
發(fā)布時間：2019-06-19 06:49
【摘要】：本文針對四川盆地地下鹵水富含鉀硼溴鍶的特點,采用等溫溶解平衡法研究了尚未見文獻(xiàn)報道的298 K條件下五元體系NaBr KBr Na_2SO_4 K_2SO_4 Na_2B_4O_7 K_2B_4O_7 H_2O,298 K及323 K條件下五元體系NaBr KBr MgBr_2 CaBr_2 H_2O,323 K條件下五元體系NaBr KBr MgBr_2 SrBr_2 H_2O和348 K條件下四元體系NaBr KBr Na_2SO_4 K_2SO_4 H_2O及其相關(guān)子體系的相平衡關(guān)系,測定了上述各體系平衡液相組成并繪制了相應(yīng)的相圖,運用Pitzer模型進行部分體系的溶解度計算。298 K、323 K和348 K條件下NaBr SrBr_2 H_2O和KBr SrBr_2 H_2O三元體系以及348 K條件下NaBr Na_2SO_4 H_2O和KBr K_2SO_4 H_2O三元體系的相圖均為簡單共飽和型,即無復(fù)鹽及固溶體生成。四元體系NaBr KBr Na_2SO_4 K_2SO_4 H_2O在298 K和348 K條件下均有復(fù)鹽鉀芒硝(Na_2SO_4·3K_2SO_4),兩個條件下的相圖對比,348 K條件下無NaSO_4·10H_2O出現(xiàn)。298 K條件下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條件下NaBr KBr SrBr_2 H_2O,NaBr KBr CaBr_2 H_2O;323 K條件下NaBr MgBr_2 SrBr_2 H_2O體系的相圖均為簡單共飽和型。298 K和323 K條件下NaBr KBr MgBr_2 H_2O和KBr CaBr_2 MgBr_2 H_2O以及323 K條件下KBr MgBr_2 SrBr_2 H_2O均有復(fù)鹽KBr·MgBr_2·6H_2O,其中KBr CaBr_2 MgBr_2 H_2O體系在323 K條件下還有復(fù)鹽2MgBr_2·CaBr_2·12H_2O生成。交互五元體系NaBr KBr Na_2SO_4 K_2SO_4 Na_2B_4O_7 K_2B_4O_7 H_2O在298 K條件下有復(fù)鹽鉀芒硝(Na_2SO_4·3K_2SO_4),在以Na_2B_4O_7飽和條件下的干鹽圖中有五個共飽點、十一條單變量曲線和七個平衡固相結(jié)晶區(qū),對應(yīng)的平衡固相分別為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。簡單五元體系Na Br KBr MgBr_2 CaBr_2 H_2O(KBr飽和)的相圖在298 K條件下含有兩個共飽點,五條單變量曲線和四個結(jié)晶區(qū)分別為NaBr·2H_2O、NaBr、KBr、KBr·MgBr_2·6H_2O和CaBr_2·6H_2O。該體系的相圖在323 K條件下有三個共飽點、七條單變量曲線和六個結(jié)晶區(qū),分別為KBr·MgBr_2·6H_2O、2MgBr_2·CaBr_2·12H_2O、NaBr·2H_2O、NaBr、KBr和CaBr_2·4H_2O的結(jié)晶區(qū)。簡單五元體系NaBr KBr MgBr_2 SrBr_2 H_2O在323 K條件下有復(fù)鹽KBr·MgBr_2·6H_2O。在該體系的相圖中有三個共飽點、十條單變量曲線和六個結(jié)晶區(qū):NaBr·2H_2O,NaBr,MgBr_2·6H_2O,SrBr_2·6H_2O,KBr·MgBr_2·6H_2O和KBr。采用三元體系中的實驗溶解度數(shù)據(jù),擬合得出未見文獻(xiàn)報道的混合離子參數(shù):298 K條件下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條件下ΨNa,Br,SO_4、ΨK,Br,SO_4,并進一步根據(jù)Pitzer電解質(zhì)模型,采用粒子群算法,對部分體系進行了溶解度模擬。所計算體系如下:298 K下四個三元體系(NaBr SrBr_2 H_2O、KBr SrBr_2 H_2O、MgBr_2 SrBr_2 H_2O和MgCl2 SrCl2 H_2O);298 K下七個簡單四元體系(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條件下三個簡單四元體系(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條件下一個交互四元體系(NaBr KBr Na_2SO_4 K_2SO_4 H_2O)。計算與實驗的結(jié)果相比較,發(fā)現(xiàn)計算相圖與實驗相圖基本吻合。對誤差的成因進行分析。
[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.
【學(xué)位授予單位】：成都理工大學(xué)
【學(xué)位級別】：博士
【學(xué)位授予年份】：2017
【分類號】：TS392;O642.42
本文編號：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.
【學(xué)位授予單位】：成都理工大學(xué)
【學(xué)位級別】：博士
【學(xué)位授予年份】：2017
【分類號】：TS392;O642.42
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