光卤石中氯化钾溶解度、介穏区、诱导期测定

doi:10.11962/1006-4990.2019-0406

摘要/Abstract

摘要：

采用变温溶解动态法测定了光卤石中氯化钾的溶解度,并用简化固液平衡方程对溶解度数据做了拟合。研究了搅拌速度、降温速率对介穏区宽度以及不同过饱和度对诱导期的影响。结果表明：简化固液平衡方程能够对氯化钾溶解度拟合良好;介穏区宽度随降温速率的升高而变宽,随搅拌速度增大而变窄;诱导期随过饱和度的增大而变短,且在不同温度下,相同过饱和度下的诱导期相近。应用经典Nyvlt理论方程和3D成核原理,结合实验介穏区及诱导期数据,计算了光卤石中氯化钾的成核级数为2.46~2.51,在283.15、293.15、303.15 K条件下,氯化钾在该体系中表面张力γ为0.019 8~0.556 0,表面能因子f<3,结晶连续生长。

关键词: 溶解度, 介稳区, 诱导期, 氯化钾

Abstract:

The solubility of potassium chloride in carnallite was determined by variable temperature dissolution dynamic method.Solubility data were calculated by simplified solid-liquid equilibrium equation.The effects of stirring speed and cool-ing rate on the width of the medial zone and the different supersaturation on the induction period were studied.The results showed that the simplified solid-liquid equilibrium equation can fit well to the solubility of potassium chloride;the width of the medial zone widens with the increase of the temperature drop rate,and becomes narrower with the increase of the stirring speed,the induction period is shorter withthe increase of the supersaturation,and the induction period at the same supersatu-ration is similar at different temperatures.Using the classical Nyvlt theoretical equation and 3D nucleation principle,com-bined with the data of experimental mediation and induction period,the nucleation series of potassium chloride in carnallite was calculated to be 2.46~2.51,and the surface tension γ of potassium chloride in the system is 0.019 8~0.556 0 at 283.15,293.15,303.15 K,the surface energy factor f<3,and the crystal grows continuously.

Key words: solubility, metastable zone, induction period, potassium chloride

中图分类号:

TQ131.13

齐美玲,王刚,张莉媛,解玉龙. 光卤石中氯化钾溶解度、介穏区、诱导期测定[J]. 无机盐工业, 2020, 52(5): 45-49.

Qi Meiling,Wang Gang,Zhang Liyuan,Xie Yulong. Determination of KCl solubility,interfacial region and induction period in carnallite[J]. Inorganic Chemicals Industry, 2020, 52(5): 45-49.

图/表 9

表1

图1

表2

图2

图3

图4

表3

表4

图5

参考文献 15

[1]	王兴富, 王石军, 田红斌 , 等. 青海盐湖提钾技术进展与我国钾肥工业的发展[J]. 化工矿物与加工, 2017(11):48-52.
[2]	Yong M A, Zhu Jiawen, Chen Kui , et al. Study on the properties of metastable zone of phosphoric acid crystal[J]. Journal of Chemical Engineering of Chinese Universities, 2010,24(2):331-335.
[3]	Lu Y H, Ching C B . Study on the metastable zone width of ketoprofen[J]. Chirality, 2010,18(4):239-244.
[4]	Kashchiev D, Borissova A, Hammond R B , et al. Effect of cooling rate on the critical undercooling for crystallization[J]. Journal of Crystal Growth, 2010,312(5):698-704.
[5]	Sangwal K, Mielniczek Brzoska E . Effect of impurities on metastable zone width for the growth of ammonium oxalate monohydrate cryst-als from aqueous solutions[J]. Journal of Crystal Growth, 2004,267(3/4):662-675.
[6]	Kadam S S, Kulkarni S A, Ribera R C , et al. A new view on the metastable zone width during cooling crystallization[J]. Chemical Engineering Science, 2012,72:10-19.
[7]	Peng B, Zi J, Yan W . Measurement and correlation of solubilities of luteolin in organic solvents at different temperatures[J]. Journal of Chemical & Engineering Data, 2006,51(6):2038-2040.
[8]	李小娜 . 对苯二酚冷却结晶过程研究[D]. 天津:天津大学, 2006.
[9]	刘欣玉, 孙杰, 罗义芬 , 等. ADN的溶解度、结晶介稳区及诱导期的测定[J]. 含能材料, 2019(9).Doi: 10.11943/CJEM2018267.
[10]	Kubota Noriaki . A new interpretation of metastable zone widths me-asured for unseeded solutions[J]. Journal of Crystal Growth, 2008,310(3):629-634.
[11]	Nyvlt J . Kinetics of nucleation in solutions[J]. Journal of Crystal Growth, 1968,3/4:377-383.
[12]	Sangwal K . A novel self consistent Nyvlt like equation for metastable zone width determined by the polythermal method[J]. Crystal Research & Technology, 2009,44(4):231-247.
[13]	Mullin, J W . Crystallization[M]. 4th ed Oxford:Butterworth-Heine-mann, 2001: 206.
[14]	Ushasree P M, Muralidharan R, Jayavel R , et al. Metastable zone width,induction period and interfacial energy of zinc tris(thiourea) sulfate[J]. Journal of Crystal Growth, 2000,210(4):741-745.
[15]	Jing D, Wang J, Zhang M , et al. Nucleation kinetics and growth model of penicillin sulfoxide in butyl acetate[J]. Chemical Engi-neering & Technology, 2013,36(10):1773-1778.

项目	质量分数/%	含量/g	项目	质量分数/%	含量/g
KCl	21.72	32.66	CaCl₂	0.52	0.01
MgCl₂	23.39	35.17	H₂O	33.50	50.38
NaCl	20.87	31.38	总干盐	66.50	100.00

温度/K	x₁	x₂	x₃	x
273.15	0.024 68	0.024 48	0.024 56	0.024 56
283.15	0.026 33	0.026 34	0.026 31	0.026 33
293.15	0.027 89	0.027 83	0.027 82	0.028 07
303.15	0.029 3 3	0.029 44	0.029 37	0.029 68
313.15	0.031 42	0.031 44	0.031 43	0.031 43

温度/K	成核拟合公式	m	R²
283.15	ln ΔT_max=1.170 8+0.339 1 ln b	2.51	0.963 08
293.15	ln ΔT_max=1.110 8+0.403 3 ln b	2.48	0.969 96
303.15	ln ΔT_max=0.991 8+0.403 3 ln b	2.48	0.975 81
313.15	ln ΔT_max=0.973 3+0.402 1 ln b	2.49	0.987 54
323.15	ln ΔT_max=0.908 4+0.406 4 ln b	2.46	0.983 55

温度/ K	低过饱和度			高过饱和度
温度/ K	α	γ/ （MJ・m^-2）	f	α	γ/ （MJ・m^-2）	f
283.15	0.011 88	2.217 3	0.356 7	0.217 52	5.844 2	0.940 1
293.15	0.011 87	2.295 0	0.356 6	0.228 65	6.152 1	0.955 9
303.15	0.012 59	2.420 3	0.363 7	0.213 16	6.214 9	0.933 8

首页

全国无机盐信息中心

中国化工学会

无机酸碱盐专业委员会