化学学报 ›› 2008, Vol. 66 ›› Issue (12): 1483-1489. 上一篇    下一篇

研究论文

MgSO4-Na2SO4-H2O三元体系100 ℃沸腾蒸发非平衡态成盐特征

周 桓* 崔世广 沙作良 袁建军   

  1. (天津科技大学天津海洋资源与化学重点实验室 天津 300457)
  • 投稿日期:2007-10-24 修回日期:2007-12-07 发布日期:2008-06-28
  • 通讯作者: 周桓

Non-equilibrium Behavior of Salt-forming in Boiling Evaporation Process for the System of MgSO4-Na2SO4-H2O at 100 ℃

ZHOU, Huan* CUI, Shi-Guang SHA, Zuo-Liang YUAN, Jian-Jun   

  1. (Tianjin Key Laboratory of Marine Resources and Chemistry, Tianjin University of Science and Technology, Tianjin 300457)
  • Received:2007-10-24 Revised:2007-12-07 Published:2008-06-28
  • Contact: ZHOU, Huan

采用140 ℃恒温热源, 对MgSO4-Na2SO4-H2O体系溶液进行100 ℃恒温沸腾蒸发, 蒸发强度为140~160 g/(h•L), 监测初始析盐点和固相析出后固液相组成随蒸发进程的变化, 总结成盐特征, 提出反映非平衡态成盐特征的初级成盐区、扩展成盐区等概念. 研究发现(1)平衡相图上的同成分复盐3Na2SO4• MgSO4和Na2SO4• MgSO4•2.5H2O变为异成分复盐; (2)对Na2SO4和3Na2SO4•MgSO4的平衡共饱和液蒸发, 首先析出的是Na2SO4, 其单固相析出率为60.86%, 3Na2SO4•MgSO4和Na2SO4•MgSO4•2.5H2O的共饱和液也具有相同特征; (3)蒸发过程的初级成盐区与溶解平衡相区有显著区别. 用硫酸钠的耶涅克指数表示相区宽度, Na2SO4初级成盐区宽度从平衡态的21.02扩大到32.76; 而Na2SO4•MgSO4•2.5H2O则从41.40缩减为25.71; (4)在晶种存在的条件下, 各种盐的成盐区比初级成盐区有不同程度的扩展, 如Na2SO4, 3Na2SO4•MgSO4等盐的成盐区分别扩展了7.72和8.81. 扩展成盐区与初级成盐区的交叠形成了非平衡条件下特有的条件成盐区, 析盐种类取决于晶种的种类.

关键词: 相图, 沸腾蒸发, 非平衡态, MgSO4-Na2SO4-H2O相图, 沸腾蒸发, 非平衡态, MgSO4-Na2SO4-H2O

The non-equilibrium behavior of salt forming was experimentally determined for the system of MgSO4-Na2SO4-H2O during evaporation. The experiments of evaporation were carried out at a constant boiling temperature of 100 ℃ by a heating agent of fixed temperature of 140 ℃. The used evaporation intensity was about 140~160 g/(h•L). The compositions of liquid and solid phases were analyzed at the occurring point of the primary nucleation and the following points of further evaporation. Based on the results, the concept of primary and extended salt forming region was given. The experimental results show that: (1) Both 3Na2SO4•MgSO4 and Na2SO4•MgSO4•2.5H2O belong to the same-composition complex-salt in an equilibrium state, but change to different-composition complex-salt in a non-equilibrium state. (2) When evaporating solution which was co-saturated for Na2SO4 and 3Na2SO4•MgSO4 in equilibrium diagram, the Na2SO4 was only crystallized out. The Na2SO4 can be only crystallized up to 60.86% of the total Na2SO4 in the original solution. The same behavior was found for the co-saturated solution of 3Na2SO4•MgSO4 and Na2SO4•MgSO4•2.5H2O. (3) The primary salt-forming region is largely different from the equilibrium region. Based on the Jänecke index, the width of the primary forming region of Na2SO4 was extended from 21.02 to 32.76, the width of the primary forming region of Na2SO4•MgSO4•2.5H2O was reduced from 41.40 to 25.71. (4) Under the condition of having crystal seeds, the width of salt-forming region is larger than that of the primary salt-forming region in different degrees for different salts, for example the region width of Na2SO4 and 3Na2SO4•MgSO4 increased by 7.72 and 8.81 respectively. The overlay region of the primary and extended salt-forming region was found in the non-equilibrium state. The kinds of salt forming depend on those of crystal seeds.

Key words: phase diagram, boiling evaporation, non-equilibrium state, MgSO4-Na2SO4-H2O