基于逆溶解度性质的硫酸钠-水体系成核动力学的研究

doi:10.19964/j.issn.1006-4990.2021-0037

摘要/Abstract

摘要：

以逆溶解度性质的硫酸钠-水体系为研究对象,通过聚焦光速反射测量技术对硫酸钠-水体系升温结晶成核行为进行了研究,考察了升温速率、饱和温度对介稳区宽度的影响,通过经典成核理论模型确定了成核动力学参数,探讨了化学势和成核温度对成核速率的影响。结果表明：较小的升温速率、较高的饱和温度都会使介稳区宽度变窄;溶质在固液两相中的化学势差是结晶过程的驱动力,但它并不总是有利于成核过程。以上研究不仅为硫酸钠升温结晶工艺过程开发提供了基础物性数据,还有助于深入理解此类逆溶解度类型升温结晶的成核行为。

关键词: 硫酸钠, 成核, 介温区宽度, 结晶

Abstract:

Based on the inverse solubility of sodium sulfate-water system,the nucleation behavior of sodium sulfate-water system was studied by focused light velocity reflection measurement.The effect of heating rate and saturation temperature on the width of metastable zone was investigated.The nucleation kinetic parameters were determined by classical nucleation theory model,and the effect of chemical potential and nucleation temperature on the nucleation rate was discussed.The results showed that smaller heating rate and higher saturation temperature will narrow the width of metastable zone.The chemical potential difference of solute in solid-liquid two-phase was the driving force of crystallization process,but it was not always conducive to nucleation process.The above research not only provides basic physical property data for the development of sodium sulfate heating crystallization process,but also helps to deeply understand the nucleation behavior of this system with inverse solubility in the heating crystallization process.

Key words: sodium sulfate, nucleation, metastable zone width, crystallization

中图分类号:

TQ125.14

王彦飞,焦健,蒋淑婉,许史杰. 基于逆溶解度性质的硫酸钠-水体系成核动力学的研究[J]. 无机盐工业, 2021, 53(10): 41-46.

Wang Yanfei,Jiao Jian,Jiang Shuwan,Xu Shijie. Study on nucleation kinetics of sodium sulfate-water system based on inverse solubility[J]. Inorganic Chemicals Industry, 2021, 53(10): 41-46.

图/表 16

图1

图2

表1

图3

表2

表3

表4

图4

图5

图6

图7

图8

图9

图10

图11

表5

参考文献 15

[1]	陶道敏. 美国亚硫酸钠生产现状[J]. 无机盐工业, 2005, 37(6):61.
[2]	周永学, 王倩, 张筱军. 芒硝的临床运用与药理研究[J]. 陕西中医学院学报, 2007, 30(1):54-55.
[3]	Brabants G, Hubin M, Reichel E K, et al. Revisiting silicalite-1 nu-cleation in clear solution by electrochemical impedance spectrosco-py[J]. Langmuir:The ACS Journal of Surfaces and Colloids, 2017, 33(10):2581-2589.
[4]	Davey R J. Can the study of self-assembly in solution lead to a good model for the nucleation pathway:The case of tolfenamic acid[J]. Chemical Science, 2015, 6(6):3515-3524.
[5]	Chiarella R A, Gillon A L, Burton R C, et al. The nucleation of ino-sine:the impact of solution chemistry on the appearance of polymo-rphic and hydrated crystal forms[J]. Faraday Discussions, 2007, 136:179-193.
[6]	Xiong Lixuan, Ling Zhou, Zhang Xia, et al. Determination of metasta-ble zone widths and nucleation behavior of aspirin in acetic acid and acetic anhydride binary solvent mixture[J]. Journal of Molecu-lar Liquids, 2018, 269:805-815.
[7]	Somchai M, Flood A E. Validation of models predicting nucleation rates from induction times and metastable zone widths[J]. Chemical Engineering & Technology, 2018, 41(10):2066-2076.
[8]	Quan Y, Yang Y, Xu S, et al. Insight into the role of piperazine in the thermodynamics and nucleation kinetics of the triethylenediamine-methyl tertiary butyl ether system[J]. Crystengcomm, 2019, 21:948-956.
[9]	Ma S, Li C, Gao J, et al. Artificial neural network prediction of me-tastable zone widths in reactive crystallization of lithium carbona-te[J]. Industrial & Engineering Chemistry Research, 2020.Doi: 10.1021/acs.iecr.9b06074.
[10]	Xu S J, Bu Y Q, Jiang S W, et al. Insights into the role of solvents in nucleation kinetics of glutaric acid from metastable zone widths[J]. Industrial & Engineering Chemistry Research, 2021.Doi: 10.1021/acs.iecr.0c04368.
[11]	Yang H, Florence A J. Relating induction time and metastable zone width[J]. CrystEngComm, 2017, 19(28):3966-3978.
[12]	Noor S Z M, Camacho D M, Ma C Y, et al. The effect of crystallization conditions on the metastable zone width and nucleation kinetics of para-aminobenzoic acid in ethanol[J]. Chemical Engineering & Technology, 2020, 43(6).Doi: 10.1002/ceat.201900679.
[13]	Sangwal K. Recent developments in understanding of the metasta-ble zone width of different solutesolvent systems[J]. Journal of Cry-stal Growth, 2011, 318(1):103-109.
[14]	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.
[15]	Yang J, Xu S, Wang J, et al. Nucleation behavior of ethyl vanillin:Balance between chemical potential difference and saturation temperature[J]. Journal of Molecular Liquids, 2020, 303.Doi: 10.1016/j.molliq.2020.112609.

R/（K·h^-1）		R/（K·h^-1）		R/（K·h^-1）		R/（K·h^-1）
T₀=308.15 K		T₀=318.15 K		T₀=323.15 K		T₀=336.15 K
8.4	7.0	5.8	5.0	2.5	3.0	12.0	2.0
16.7	10.0	9.7	6.0	7.7	4.0	16.7	2.5
24.6	13.0	21.8	8.0	16.4	6.0	26.7	4.0
32.9	17.0	32.7	12.0	24.0	8.0	30.0	5.0

T/K	斜率（1/m）	成核级数（m）	R²
308.15	0.636	1.573	0.98
318.15	0.475	2.105	0.96
323.15	0.423	2.362	0.96
336.15	0.979	1.021	0.98

T₀/K	γ/ （mJ·m^-2）	f/A	f/10²⁷	A/10²² （个数·m^-3·s^-1）
308.15	0.89	24 485.29	2.08	8.48
318.15	0.78	21 502.85	1.99	9.27
323.15	0.58	31 854.51	1.95	6.12
336.15	0.33	31 888.91	1.87	5.85

R/ （K·h^-1）	γ/ （mJ·m^-2）	f/A	f/10²⁷	A/10²⁴ （个数·m^-3·s^-1）
7	0.18	265.21	2.08	7.83
13	0.20	268.07	2.08	7.75
23	0.28	268.05	2.08	7.75
30	0.31	273.27	2.08	7.60

ΔT/ K		ΔT/ K		ΔT/ K		ΔT/ K
T₀=308.15K		T₀=318.15K		T₀=323.15K		T₀=336.15K
7	1.55	5	0.80	3	0.47	2.0	0.30
10	1.65	6	0.96	4	0.63	2.5	0.38
13	2.14	8	1.28	6	0.94	4.0	0.60
17	2.80	12	1.92	8	1.26	5.0	0.75

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