应用Bromley方程，结合草酸钠溶解热力学理论及其在水溶液、氢氧化钠溶液中的溶解度数据，得出草酸钠的Bromley参数为?0.045，并以此为基础建立铝酸钠溶液中草酸钠的溶解度计算模型。应用该模型计算纯铝酸钠溶液体系中草酸钠的溶解度，结果与文献数据吻合较好。在此基础上，模拟计算了拜耳法氧化铝生产过程中草酸钠平衡浓度的变化规律。结果表明：碱浓度越高、温度越低、苛性比越高，铝酸钠溶液中草酸钠平衡浓度越低；铝酸钠溶液体系中，碳酸钠、硫酸钠对草酸钠溶解度的影响很小。这些结果可以解释草酸钠在生产氧化铝过程中的积累和析出规律，有助于生产过程铝酸钠溶液中草酸钠含量的控制。
The calculation model of sodium oxalate’s solubility in sodium aluminate solution was established by Bromley equation with the solubility values of sodium oxalate in the aqueous and sodium hydroxide solution, and Bromley parameter of sodium oxalate calculated by this model is?0.045. Using this calculation model, the solubility values of sodium oxalate in sodium aluminate solution were calculated and a high degree of agreement can be reached compared with the data in literatures. On this basis, the equilibrium concentration values of sodium oxalate in Bayer liquors were calculated. The results show that, the higher the alkali concentration and caustic ratio are or the lower the temperature is, the lower the equilibrium concentration of sodium oxalate is. The concentration of sodium carbonate or sodium sulfate has little effect on the solubility of sodium oxalate. These results can explain the law of the accumulation and precipitation of sodium oxalate in alumina production process, and contribute to controlling the concentration of sodium oxalate in the process.
参考文献
| [1] | 李旺兴. 氧化铝生产理论与工艺[M]. 长沙:中南大学出版社, 2011:234-237. LI Wang-xing. Theory and process of alumina product[M]. Changsha:Central South University Press, 2011:234-237.,2011. |
| [2] | MYONG J K, SEONG O L. Overview of the behaviour of sodium oxalate in Bayer liquor and its effect of the process[J]. Light Metals, 2003(5):19-24.,2003. |
| [3] | 尹周澜,敬叶灵,陈启元,张艾民.聚合物对铝酸钠溶液种分过程的影响[J].中国有色金属学报,2007(06):1002-1007. |
| [4] | 陈文汨,付云枫.一种处理从工业铝酸钠溶液中结晶出来的草酸钠的方法:中国, 201110285220.X[P]. 2011-09-23. CHEN Wen-mi, FU Yun-feng. Method of sodium oxalate crystallization from sodium aluminate solution:China, 201110285220.X[P]. 2011-09-23.,2011. |
| [5] | 陈文汨,郭金权,陈学刚.结晶法去除工业铝酸钠溶液中草酸钠的研究[J].轻金属,2008(11):12-15. |
| [6] | GERVAIS S, JACQUES E, LAROCQUE G F. Organic control technologies in Bayer process[J]. Light Metals, 2004, 17(7):109-114.,2004. |
| [7] | TAYLOR M, HARRIS D J, CHEN H T. Methods and compositions for the removal of impurities and water from the Bayer process:United States, US 20090169447 A1[P]. 2009-07-02.,2009. |
| [8] | 皮溅清, 赵瑜, 刘桂华, 王永林. 一种铝酸钠溶液石灰苛化除草酸钠的方法:中国, 201310309531.4[P]. 2013-07-23. PI Jian-qing, ZHAO Yu, LIU Gui-hua, WANG Yong-lin. Method of sodium oxalate removal from sodium aluminate solution by causticization using lime:China, 201310309531.4[P]. 2013-07-23.,2013. |
| [9] | 张佰永, 齐东华. 一种铝酸钠溶液中草酸盐的去除系统及方法:中国, 200810011314.6[P]. 2008-05-08. ZHANG Bai-yong, QI Dong-hua. A systerm and method of removal of sodium oxalate from sodium aluminate solution:China, 200810011314.6[P]. 2008-05-08.,2008. |
| [10] | THE P J, BUSH J F. Solubility of sodium oxalate in Bayer liquor and a method of Control[J]. Light Metals, 1997, 35(4):5-10.,1997. |
| [11] | POWER G, LOH J. Organic compounds in the processing of lateritic bauxites to alumina. Part 1:Origins and chemistry of organics in the Bayer process[J]. Hydrometallurgy, 2010, 105(1/2):11-15.,2010. |
| [12] | GILBERT B, PHILIPPONNEAU. Physical chemistry models of oxalate and Gibbsite solubilities in Bayer solutions[J]. Light Metals, 1991, 15(8):97-102.,1991. |
| [13] | REYNOLDS J G. Application of mixture models to solubility calculations, using sodium oxalate as an example[J]. Separation Science and Technology, 2008, 43(9/10):2872-2886.,2008. |
| [14] | 覃东棉,刘桂华,李小斌,彭志宏,周秋生. Debye-Hückel理论的研究进展[J].材料导报:综述篇, 2010, 24(7):107-112. QIN Dong-mian, LIU Gui-hua, LI Xiao-bin, PENG Zhi-hong, ZHOU Qiu-sheng. Research progress of Debye-Hückel theory[J]. Material Herald:Review articles, 2010, 24(7):107-112.,2010. |
| [15] | BROMLEY L A. Thermodynamic properties of strong electrolytes in aqueous solutions[J]. American Institute of Chemical Engineers, 2004, 19(2):313-320.,2004. |
| [16] | BORGE G, CASTANO R, CARRIL M P. Development of a modified Bromley's methodology(MBM)for the estimation of ionic media effects on solution equilibria:Part 1. Calculation of the interaction parameters in the molar and molal scales at 25ºC[J]. Fluid Phase Equilibria, 1996, 121(1):85-98.,1996. |
| [17] | RAPOSO J C, SANZ J, BORGE G. Development of a modified Bromley's methodology for the estimation of ionic media effects on solution equilibria:Part 3. Application to the construction of thermodynamic models[J]. Fluid Phase Equilibria, 1999, 155(1):1-19.,1999. |
| [18] | RAPOSO J C, ZULOAGA O, OLAZABAL M A. Development of a modified Bromley methodology for the estimation of ionic media effects on solution equilibria:Part 5. The chemical model of boric acid in aqueous solution at 25 ºC and comparison with arsenious acid[J]. Fluid Phase Equilibria, 2003, 207(1):81-95.,2003. |
| [19] | BATELLA M, ALEXANDER A, ELI K. The molar enthalpies of solution and solubilities of ammonium, sodium and potassium oxalates in water[J]. Chem Thermodynamics, 2004(36):41-47.,2004. |
| [20] | DONALD J. Purification of Bayer process liquors:United States, US 4443416[P]. 1984-04-17.,1984. |
| [21] | 彭小奇,宋国辉,宋彦坡,张建智,刘振国.NaOH-NaAl（OH）4-Na2CO3-H2O体系活度因子的计算模型[J].中国有色金属学报,2009(07):1332-1337. |
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