KNO3介稳区宽度的研究及初级成核动力学计算

doi:10.19964/j.issn.1006-4990.2023-0530

Abstract

Abstract:

For investigating the cooling crystallization process of KNO₃ in a ternary KNO₃-NaNO₃-H₂O mixture system，the solubility of KNO₃ was measured by static equilibrium method in the temperature range from 293.15 K to 341.38 K.In order to present the relationship between solubility and temperature，the experimental data was fitted by the Apelblat equation and Van′t Hoff equation，and the dissolution enthalpy and dissolution entropy of KNO₃ were calculated.Then，the effects of NaNO₃ content，stirring rate，and cooling rate on the width of the metastable zone（MSZW） of KNO₃ in the temperature range from 298.03 K to 332.30 K were analyzed by using an ultrasonic velocity sensor.The results showed that the existence of NaNO₃would make the MSZW of KNO₃ narrow，but the effect was limited，and the MSZW became narrow with the increase of stirring rate and wide with the increase of cooling rate.Based on the measured solubility and dissolution enthalpy，the primary nucleation kinetics of KNO₃ were investigated.The nucleation order m obtained using the self-consistent Nývlt-like equation was less than 3.Instantaneous nucleation was the dominant nucleation mechanism of KNO₃，and the nucleation rate showed a tendency to increase firstly and then decrease with increasing saturation temperature.In the classical three-dimensional nucleation theory，nucleation was more likely to occur，and when the saturation temperature reached a certain level，the solid-liquid interface energy γ tended to be stable.Furthermore，the high-purity KNO₃ product was obtained by cooling crystallization with agricultural potassium nitrate as raw material.When the saturated KNO₃ solution was cooled from 343.15 K to 298.15 K，the stirring rate was 300 r/min，the cooling rate was 25 K/h，and the seed crystal was added，the Na⁺ content in the solution was only 0.001 1%.

Key words: potassium nitrate, sodium nitrate, metastable zone, nucleation kinetics, industrial crystallization

CLC Number:

TQ131.13

ZOU Yang, LU Zhiyan, HU Zhilin, SUN Ze. Study on metastable zone width and primary nucleation kinetics for cooling crystallization of KNO₃[J]. Inorganic Chemicals Industry, 2024, 56(9): 67-74.

Figures/Tables 19

Fig.1

Table 1

Fig.2

Fig.3

Table 2

Fig.4

Table 3

Fig.5

Table 4

Thermodynamic model parameters of KNO3-NaNO3-H2O system"

w（NaNO₃）/ %	方程类型	拟合方程	R²
0	Apelblat	$l n x = 166.311 3 - (10 146.469 6 / T s) - 23.698 2 l n T s$	0.999 9
0	Van′t Hoff	$l n x = 6.179 9 - 2 657.745 7 / T s$	0.995 1
2	Apelblat	$l n x = 148.493 3 - (9 279.482 7 / T s) - 21.080 4 l n T s$	0.999 5
2	Van′t Hoff	$l n x = 6.050 7 - 2 617.994 4 / T s$	0.995 0
3	Apelblat	$l n x = 153.864 6 - (9 539.454 8 / T s) - 21.871 3 l n T s$	0.999 3
3	Van′t Hoff	$l n x = 6.077 3 - 2 628.018 3 / T s$	0.995 3
4	Apelblat	$l n x = 174.617 3 - 10 589.815 5 / T s - 24.902 5 l n T s$	0.999 3
4	Van′t Hoff	$l n x = 6.348 3 - 2 720.526 9 / T s$	0.994 4
5	Apelblat	$l n x = 166.291 1 - (10 168.594 6 / T s) - 23.687 3 l n T s$	0.999 5
5	Van′t Hoff	$l n x = 6.233 0 - 2 683.297 1 / T s$	0.994 9
6	Apelblat	$l n x = 179.556 7 - (10 793.983 4 / T s) - 25.647 3 l n T s$	0.998 7
6	Van′t Hoff	$l n x = 6.254 5 - 2 689.313 8 / T s$	0.993 5

Table 4

Table 5

Dissolution enthalpy and entropy of KNO3"

硝酸钠含量/%	$Δ H d$ /（kJ·mol^-1）	$Δ S d$ /（J·mol^-1·K^-1）	R²
文献［22］	20.78	47.25	0.994 7
文献［23］	20.84	47.05	0.995 0
0	22.12	51.45	0.995 7
2	21.79	50.38	0.995 5
3	21.87	50.60	0.995 1
4	22.64	52.85	0.994 1
5	22.33	51.89	0.994 6
6	22.38	52.07	0.993 3

Table 5

Fig.6

Fig.7

Fig.8

Fig.9

Table 6

Fig.10

Table 7

Fig.11

Table 8

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筛网孔径/μm	晶种粒径/μm	筛网孔径/μm	晶种粒径/μm
380~500	436	230~250	216
325~380	362	160~230	183
250~325	287

温度/ K	文献［22］溶解度/g	文献［23］溶解度/g	实验溶解度/g	与文献［22］相对偏差/%	与文献［23］相对偏差/%
293.15		31.60	31.77		0.54
303.15	45.80	45.30	45.99	0.41	1.52
313.15	63.90	61.30	64.42	0.81	5.09
323.15	85.50		85.80	0.35
333.15	110.00	106.00	110.62	0.56	4.36
343.15	138.00		—
353.15		167.00	—

T₀/K	m	φ	f/K×10²	R²
298.03	1.74	-6.19	3.18	0.872 4
302.97	1.73	-6.38	2.36	0.870 9
307.88	1.61	-6.83	1.94	0.939 7
312.80	0.96	-8.45	8.72	0.869 2
317.72	0.84	-9.35	9.06	0.955 7
322.47	0.84	-9.80	6.12	0.946 9

T₀/K	F₁	F	F₁/F	A/f	BT_lim³×10^-5	R²
298.03	9 716.64	37 494.04	0.26	1.42	2.10	0.980 8
302.97	14 192.66	54 643.05	0.26	1.36	1.46	0.937 2
307.88	34 040.48	125 163.90	0.27	1.10	0.62	0.860 7
312.80	181 076.62	604 924.40	0.30	0.76	0.12	0.665 2
317.72	469 463.03	1 566 360.00	0.30	0.73	0.05	0.838 1
322.47	987 117.47	3 349 680.00	0.29	0.75	0.02	0.944 7

项目	标准要求/%	冷却结晶产品/%
硝酸钾（KNO₃）含量	≥99.9	99.9
水分（干燥失重）	≤0.10	0.001
水不溶物的含量	≤0.005	0.003
氯化物（以Cl计）含量	≤0.005	0.000 3
钠（以Na计）含量	≤0.01	0.001 1

National Inorganic Salts Information Center

Inorganic Acid-Base-Salt Committee of CIESC

Study on metastable zone width and primary nucleation kinetics for cooling crystallization of KNO₃

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Study on metastable zone width and primary nucleation kinetics for cooling crystallization of KNO3