一水硫酸锰在H2SO4-H2O二元体系中的结晶动力学研究

doi:10.19964/j.issn.1006-4990.2023-0531

Abstract

Abstract:

In order to improve the quality of monohydrate manganese sulfate crystal products and guide the design of monohydrate manganese sulfate crystallization process，the solubility data of monohydrate manganese sulfate in the H₂SO₄-H₂O binary system was measured by dynamic method.The solubility data was fitted using the Apelblat equation，and the relationship between the parameters of the Apelblat equation and pH value was obtained.The solubility data showed that in the H₂SO₄-H₂O binary system，the saturation solubility of manganese sulfate monohydrate was rapidly decreased with the decrease of system pH.The nucleation and growth rates of monohydrate manganese sulfate crystals were measured at different pH values in the MSMPR crystallization system.The results showed that a decrease in pH had a significant promoting effect on the growth of monohydrate manganese sulfate crystals and an inhibitory effect on crystal nucleation.Based on the particle balance equation，the nucleation and growth rates of monohydrate manganese sulfate crystals were calculated，and the nucleation and growth rate equations under different pH conditions were obtained.Finally，the POLY2D equation was used to fit the nucleation and growth rates of manganese sulfate monohydrate crystals.The relevant research results could provide reference for the design of industrial crystallization process of manganese sulfate monohydrate.

Key words: solubility, manganese sulfate monohydrate, crystal nucleation, crystal growth

CLC Number:

O742

SU Hang, SONG Jitian, HUANG Zhiqiang, DONG Qing, ZHANG Yaxiong. Study on crystallization kinetics of manganese sulfate monohydrate in H₂SO₄-H₂O binary system[J]. Inorganic Chemicals Industry, 2024, 56(8): 40-46.

Figures/Tables 9

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Table 1

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References 25

1	王崇国，刘广龙，金小容，等.锂离子电池正极材料的研究进展［J］.当代化工研究，2023（9）：12-14.
	WANG Chongguo， LIU Guanglong， JIN Xiaorong，et al.Research progress of lithium⁃ion battery cathode material［J］.Modern Che⁃Research mical，2023（9）：12-14.
2	韩啸，张成锟，吴华龙，等.锂离子电池的工作原理与关键材料［J］.金属功能材料，2021，28（2）：37-58.
	HAN Xiao， ZHANG Chengkun， WU Hualong，et al.Working mechanism and key materials of the lithium ion batteries［J］.Metallic Functional Materials，2021，28（2）：37-58.
3	刘德新，马腾跃，安金玲，等.锰基钠离子电池正极材料设计及电化学性能研究［J］.无机盐工业，2024，56（3）：51-55.
	LIU Dexin， MA Tengyue， AN Jinling，et al.Study on cathode material design and electrochemical properties of manganese⁃based sodium ion battery［J］.Inorganic Chemicals Industry，2024，56（3）：51-55.
4	中华人民共和国工业和信息化部. 电池用硫酸锰：［S］.北京：化工出版社，2016.
5	MOHAGHEGHI M， ASKARI M.Kinetics of the antisolvent crystallization of manganese sulfate monohydrate from a pregnant leach solution［J］.Chemical Papers，2024，78（3）：1529-1535.
6	张曼曼，张德友，周进，等.离心萃取制备电池级硫酸锰［J］.电池，2023，53（4）：424-427.
	ZHANG Manman， ZHANG Deyou， ZHOU Jin，et al.Preparation of battery grade manganese sulfate by centrifugal extraction［J］.Battery Bimonthly，2023，53（4）：424-427.
7	邹兴.高纯硫酸锰生产技术现状［J］.中国锰业，2018，36（6）：4-6.
	ZOU Xing.Present situation of production technology of high purity manganese sulfate［J］.China′s Manganese Industry，2018， 36（6）：4-6.
8	王天雄，刘京，范玉英.菱锰矿浸出液制备电池级硫酸锰的技术研究［J］.中国锰业，2015，33（2）：22-25.
	WANG Tianxiong， LIU Jing， FAN Yuying.A study on preparation of battery grade manganese sulfate with rhodochrosite leachate［J］.China′s Manganese Industry，2015，33（2）：22-25.
9	杨攀，王家伟，王松，等.蒸发结晶法深度净化硫酸锰工艺研究［J］.矿冶工程，2022，42（3）：88-91.
	YANG Pan， WANG Jiawei， WANG Song，et al.Deep purification of manganese sulfate by evaporation and crystallization［J］.Mining and Metallurgical Engineering，2022，42（3）：88-91.
10	刘中华.高温结晶法制备硫酸锰的工艺及自动连续装置：中国，107055622［P］.2017-06-12.
11	何雨林，李富杰，罗志虹，等.工业硫酸锰高温结晶纯化制备电池级硫酸锰的研究［J］.矿冶工程，2019，39（3）：85-88.
	HE Yulin， LI Fujie， LUO Zhihong，et al.Preparation of battery⁃grade manganese sulfate by purification of industrial⁃grade manganese sulfate with high⁃temperature crystallization method［J］.Mining and Metallurgical Engineering，2019，39（3）：85-88.
12	SAFAEEFAR P， ANG H M， TADE M O，et al.Growth kinetics of manganese sulphate from heating and salting⁃out batch crystallisation［J］.Developments in Chemical Engineering and Mineral Processing，2006，14（1/2）：303-312.
13	ZHANG Xueping， LIU Youquan， ZHOU Lang，et al.Experiment and calculation of phase equilibrium in quaternary system NaBr-KBr-CaBr₂-H₂O at 273.15 K containing in gas field brine of Sichuan Basin［J］.Russian Journal of Physical Chemistry A，2023，97（7）：1368-1375.
14	CAO Yun， DU Shichao， KE Xiao，et al.Interplay between thermodynamics and kinetics on polymorphic behavior of vortioxetine hydrobromide in reactive crystallization［J］.Organic Process Research & Development，2020，24（7）：1233-1243.
15	LUO Yanghui， WU Guogan， SUN Baiwang.Antisolvent crystallization of biapenem：Estimation of growth and nucleation kineti⁃cs［J］.Journal of Chemical & Engineering Data，2013，58（3）：588-597.
16	张得江.磷酸钠间歇及连续结晶过程的研究［D］.天津：天津大学，2018.
	ZHANG Dejiang.Research on batch and continuous crystallization processes of sodium phosphate［D］.Tianjin：Tianjin University，2018.
17	周桓，张闯，白晓琴，等.KCl-MgCl₂-H₂O体系25 ℃盐析光卤石的等温热力学与结晶规律［J］.天津科技大学学报，2014， 29（6）：46-51.
	ZHOU Huan， ZHANG Chuang， BAI Xiaoqin，et al.Isothermal thermodynamics and crystallization behavior of carnallite salt⁃out in KCl-MgCl₂-H₂O system at 25 ℃［J］.Journal of Tianjin University of Science & Technology，2014，29（6）：46-51.
18	APELBLAT A， MANZUROLA E.Solubilities of o-acetylsalicylic，4-aminosalicylic，3，5-dinitrosalicylic，and p-toluic acid，and magnesium-DL-aspartate in water from T=（278 to 348） K［J］.The Journal of Chemical Thermodynamics，1999，31（1）：85-91.
19	刘光启，马连湘，项曙光.化学化工物性数据手册-无机卷［M］.2版.北京：化学工业出版社，2013.
20	RANDOLPH A D， LARSON M A.Theory of particulate proces⁃ses⁃chapter 1［J］.Theory of Particulate Processes，1971，47（9）：1-11.
21	OREHEK J， TESLIĆ D， LIKOZAR B.Continuous crystallization processes in pharmaceutical manufacturing：A review［J］.Organic Process Research & Development，2021，25（1）：16-42.
22	KOUGOULOS E， JONES A G， WOOD-KACZMAR M W.Estimation of crystallization kinetics for an organic fine chemical using a modified continuous cooling mixed suspension mixed product removal（MSMPR） crystallizer［J］.Journal of Crystal Growth，2005，273（3/4）：520-528.
23	叶铁林.化工结晶过程原理及应用［M］.北京：北京工业大学出版社，2006.
24	丁绪淮，谈遒.工业结晶［M］.北京：化学工业出版社，1985.
25	汪镇安.化工工艺设计手册.上册［M］.北京：化学工业出版社，2003. （上接第39页）

T/K	X_cal/ （10^-2 mol·mol^-1）	X_ref^［19］/ （10^-2 mol·mol^-1）	RD/%	X_cal/ （10^-2 mol·mol^-1）	X_exp/ （10^-2 mol·mol^-1）	RD/%	X_cal/ （10^-2 mol·mol^-1）	X_exp/ （10^-2 mol·mol^-1）	RD/%	X_cal/ （10^-2 mol·mol^-1）	X_exp/ （10^-2 mol·mol^-1）	RD/%
T/K	pH=4.7			pH=3.5			pH=2.5			pH=1.6
373.15	3.46	3.43	-0.87	3.49	3.27	-6.73	3.20	2.97	-7.74	2.60	2.58	-0.78
363.15	4.26	4.34	1.84	4.28	4.19	-2.15	3.85	3.97	3.02	3.06	3.07	0.33
353.15	5.11	5.44	6.07	5.13	5.12	1.54	4.54	4.56	0.44	3.54	3.59	1.39
343.15	5.95			5.94	5.81	-2.24	5.19	5.29	1.89	3.98	4.10	2.93
333.15	6.63	6.39	-3.76	6.60	6.15	-6.45	5.72	5.47	-4.57	4.36	4.19	-4.06
323.15	7.00			6.95	6.47	-5.78	6.01	5.74	-4.70	4.59	4.54	-1.10
313.15	6.93	7.15	3.08	6.86	6.86	-0.59	5.97	6.12	2.45	4.64	4.71	1.49

pH	停留时间/ h	相对过饱和度	粒数密度/ m^-4	生长速率/ （m·s^-1）	成核速率/ （m³·s）^-1	生长速率方程G=K_Gσ^g			成核速率方程B=K_Nσⁿ
pH	停留时间/ h	相对过饱和度	粒数密度/ m^-4	生长速率/ （m·s^-1）	成核速率/ （m³·s）^-1	K_G	g		K_N		n
1.6	0.10	0.041	4.02×10²¹	1.40×10^-7	5.63×10¹⁴	6.520×10^-6	1.208	1.539×10²⁰		3.919
	0.25	0.022	8.64×10²⁰	5.59×10^-8	4.82×10¹³
	0.50	0.008	5.83×10²⁰	3.06×10^-8	1.78×10¹³
2.5	0.10	0.039	1.22×10²²	1.25×10^-7	1.53×10¹⁵	7.823×10^-6	1.279	3.102×10¹⁹		3.057
	0.25	0.020	4.14×10²¹	4.66×10^-8	1.93×10¹⁴
	0.50	0.009	1.69×10²¹	2.66×10^-8	4.49×10¹³
3.5	0.10	0.048	1.35×10²³	6.48×10^-8	8.78×10¹⁵	1.330×10^-6	0.995	1.077×10¹⁸		1.583
	0.25	0.020	9.27×10²²	2.74×10^-8	2.54×10¹⁵
	0.50	0.013	3.83×10²²	1.74×10^-8	6.66×10¹⁴
4.7	0.10	0.042	4.41×10²³	3.05×10^-8	1.34×10¹⁶	8.006×10^-7	1.034	1.323×10²⁰		2.900
	0.25	0.023	1.61×10²³	1.47×10^-8	2.36×10¹⁵
	0.50	0.013	3.88×10²²	1.03×10^-8	3.99×10¹⁴

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Study on crystallization kinetics of manganese sulfate monohydrate in H₂SO₄-H₂O binary system

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Study on crystallization kinetics of manganese sulfate monohydrate in H2SO4-H2O binary system