MgCl2-xNa2O·yB2O3-H2O体系三方硼镁石结晶工艺及动力学研究

doi:10.19964/j.issn.1006-4990.2024-0683

Abstract

Abstract:

Magnesium borate is an important boron-containing raw material in the production of alkali-free glass fiber and ceramics.To address issues such as slow reaction rates，low yields，and high costs in the laboratory synthesis of the hydrated magnesium borate（e.g，macallisterite） for glass applications，a study was conducted on the crystallization process and kinetics of macallisterite in the concentrated salt solutions of MgCl₂-xNa₂O·yB₂O₃-H₂O.Firstly，based on MgCl₂·6H₂O，NaOH and H₃BO₃ as raw materials，the response surface methodology（RSM） was used to design and optimize the crystallization process conditions of macallisterite，and a crystallization yield prediction model was established.Secondly，based on the theory of crystal growth diffusion，the crystallization mechanism and kinetics of macallisterite were studied，and the crystallization rate equation was obtained.Finally，based on the comprehensive utilization strategy of boron and magnesium resources in salt lakes，the old brine saturated with magnesium chloride was used as raw matrerials to synthesize the macallisterite.The results showed that the predicted boron crystallization yield was 80.56% in B₂O₃ according to the RSM model，and the experimental value was 81.58% with a relative error of 1.25%.It indicated that the model was reliable and the crystallization yield was improved.The growth mechanism of the macallisterite was the multi-nucleus controlled crystal surface growth model of MA-2，and the crystallization rate was significantly increased.The crystallization yield of the macallisterite synthesized from the old brine was more than 74%，which was lower than that of the optimization experiment.The main reason was due to the decrease in boron concentration and the different mechanisms by which coexisting SO₄^2- ions affect the multi boron species in the solution.The above research not only provided technical support for the industrial production of hydrated magnesium borate for glass，but also provided new ideas for the comprehensive utilization of boron and magnesium resources in salt lake brine.

Key words: macallisterite, response surface methodology, crystallization process, kinetics, salt lake brine

CLC Number:

TQ132.2

HU Zhenrong, ZHANG Manman, SHI Chenglong, PENG Jiaoyu, ZHOU Yannan, DONG Yaping, LI Wu. Study on crystallization process and kinetic of macallisterite in concentrated MgCl₂-xNa₂O·yB₂O₃-H₂O solution[J]. Inorganic Chemicals Industry, 2025, 57(10): 64-74.

Figures/Tables 19

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References 25

[1]	贺茂勇，张宁，文雪琴，等.硼同位素高精度测定进展、应用及挑战［J］.东华理工大学学报（自然科学版），2023，46（6）：597- 607.
	HE Maoyong， ZHANG Ning， WEN Xueqin，et al.Progress，applications，and challenges in high precision measurement of boron isotopes［J］.Journal of East China University of Technology（Natural Science），2023，46（6）：597-607.
[2]	INKRATAITE G， SKRUODIENE M， SKAUDZIUS R.Synthesis and investigation of novel boron- and magnesium-doped YAG：Ce and LuAG：Ce phosphor ceramics［J］.Luminescence，2024，39（1）：e4673.
[3]	LIU Jingfei， LI Yuanbing， YIN Bo，et al.Novel magnesium borate ceramic matrix composites with glass fiber reinforcement［J］.Ceramics International，2023，49（7）：11197-11203.
[4]	ALEXEY S， VITA V.Investigation of BaSO₄-KPO₃-Na₂B₄O₇ low-melting glass system as a basis for synthesis of a glass-solder material［J］.Key Engineering Materials，2021，6152：60-64.
[5]	赵鋆，周桓.盐湖卤水体系硼的存在形态及其分布规律的研究进展［J］.盐科学与化工，2024，53（1）：1-7.
	ZHAO Yun， ZHOU Huan.Research progress on the existing forms and distribution patterns of boron in salt lake brine systems［J］.Journal of Salt Science and Chemical Industry，2024，53（1）：1-7.
[6]	CHI Mengjiao， LIU Yahan， ZHOU Tao，et al.Ni doping improving magnesium borate microwave dielectric ceramic for LTCC via cold sintering and post-annealing process［J］.Journal of Materials Science：Materials in Electronics，2023，34（3）：235.
[7]	YANG Rui， JIA Qingchao， ZHANG Liangzhu，et al.Unveiling the effect of phase separation on crystallization of calcium borosilicate glass-ceramics［J］.Ceramics International，2024，50（7）：11003-11011.
[8]	孟令宗，邓天龙，段超文，等.三方硼镁石合成方法研究［J］.世界科技研究与发展，2010，32（6）：825-826.
	MENG Lingzong， DENG Tianlong， DUAN Chaowen，et al.A synthetic method for mcallisterite［J］.World Sci-Tech R&D，2010，32（6）：825-826.
[9]	HABERMANN F， BURKMANN K， KRAUS J，et al.Thermodynamic and kinetic study of the thermal dehydrogenation of Sr（AlH₄）₂ taking into account the by-products NaCl and LiCl［J］.Journal of Alloys and Compounds，2024，980：173476.
[10]	刘志宏，胡满成，高世扬.2MgO·2B₂O₃·MgCl₂·14H₂O-7.8%H3BO3-H2O体系多温相关系研究［J］.高等学校化学学报，2003，24（2）：189-194.
	LIU Zhihong， HU Mancheng， GAO Shiyang.Phase relation of 2MgO·2B₂O₃·MgCl₂·14H₂O-7.8%H₃BO₃-H₂O system at various temperatures［J］.Chemical Research in Chinese Universities，2003，24（2）：189-194.
[11]	KIPCAK A S， YILDIRIM M， AYDIN YUKSEL S，et al.The synthesis and physical properties of magnesium borate mineral of admontite synthesized from sodium borates［J］.Advances in Materials Science and Engineering，2014，2014：819745.
[12]	YILDIRIM M， KIPCAK A S， DERUN E M.Sonochemical-assisted magnesium borate synthesis from different boron sources［J］.Polish Journal of Chemical Technology，2017，19（1）：81-88.
[13]	彭姣玉，谈钰琴，杨克利，等.盐湖水氯镁石合成三方硼镁石的结晶机理及动力学研究［J］.无机盐工业，2023，55（10）：56-62.
	PENG Jiaoyu， TAN Yuqin， YANG Keli，et al.Study on crystallization mechanism and kinetics of macallisterite synthesized with bischofite from salt lake［J］.Inorganic Chemicals Industry，2023，55（10）：56-62.
[14]	LIN Yong， GYAKWAA F， KOKKONEN T，et al.Investigation on crystallization of CaO-Al₂O₃-B₂O₃-BaO slag using differential scanning calorimeter and in situ high-temperature Raman spectroscopy［J］.Steel Research International，2024，24（4）：2400697.
[15]	JESSEN C， KORNATH A J.Synthesis and structure of protonated sulfur dioxide［J］.Angewandte Chemie International Edition，2024，63（20）：e202401953.
[16]	KOROLEVA O N， NEVOLINA L A， KRIVENKO A P.Crystallization of Na- and Cs-bearing borosilicate melts：Results of Raman spectroscopy［J］.Geochemistry International，2024，62（10）：1057-1064.
[17]	彭姣玉，多杰卓么，黄保坤，等.拉曼积分球光谱仪对盐水溶液中B（OH）₃的定量分析［J］.盐湖研究，2024，32（2）：30-37.
	PENG Jiaoyu， DUOJIE Zhuome， HUANG Baokun，et al.Quantitative analysis of boric acid（B（OH）₃）in aqueous salt solution by simplified Raman integrating sphere［J］.Journal of Salt Lake Research，2024，32（2）：30-37.
[18]	贾艳萍，马艳菊，管文昕，等.响应面法优化Fe⁰/H₂O₂体系降解染料废水的工艺条件及机理［J］.化工学报，2025，76（1）：348-362.
	JIA Yanping， MA Yanju， GUAN Wenxin，et al.Process conditions optimization and degradation mechanism of dye wastewater by Fe⁰/H₂O₂ system using response surface methodology［J］.CIESC Journal，2025，76（1）：348-362.
[19]	FERREIRA N， VIANA T， HENRIQUES B，et al.Application of response surface methodology and box-behnken design for the optimization of mercury removal by Ulva sp［J］.Journal of Hazardous Materials，2023，445：130405.
[20]	郭元亨，皮冬伟，陶进，等.响应曲面法优化赤藓糖醇结晶工艺［J］.食品与发酵工业，2024，50（9）：56-63.
	GUO Yuanheng， PI Dongwei， TAO Jin，et al.Crystallization process optimization of erythritol by response surface methodology［J］.Food and Fermentation Industries，2024，50（9）：56-63.
[21]	POLAT S， SAYAN P.Box-behnken experimental design for zinc borate Zn₂B₆O₁₁·7H₂O［J］.Journal of Boron，2020：5（3）：152- 161.
[22]	KALASHGRANI M， BABAPOOR A， MOUSAVI S，et al.Synthesis of isoreticular metal organic framework-3 （IRMOF-3） porous nanostructure and its effect on naphthalene adsorption：Optimized by response surface methodology［J］.Separations，2023，10（4）：261.
[23]	彭姣玉，张波，陈婧，等.大柴旦富硼浓缩盐卤中硼酸镁盐稀释结晶动力学［J］.无机化学学报，2019，35（10）：1821-1833.
	PENG Jiaoyu， ZHANG Bo， CHEN Jing，et al.Crystallization kinetics of Mg-borates precipitating from diluted boron-containing brine of da Qaidam saline lake［J］.Chinese Journal of Inorganic Chemistry，2019，35（10）：1821-1833.
[24]	ZHANG Ye， YAN Xiao， WANG Li，et al.Forsterite refractory preparation using magnesium resources from salt lake brines［J］.Minerals Engineering，2023，203：108333.
[25]	FUKUDA H， TSUCHIYA K， TOBA Y，et al.Rapid boron removal from wastewater using low-crystalline magnesium oxide［J］.Journal of Environmental Chemical Engineering，2020，8（5）：104171.

实验号	温度（X₁）/℃	w（B₂O₃）（X₂）/%	n（NaOH）: n（H₃BO₃）（X₃）	晶种加入量（X₄）/g	结晶产率/%
实验号	温度（X₁）/℃	w（B₂O₃）（X₂）/%	n（NaOH）: n（H₃BO₃）（X₃）	晶种加入量（X₄）/g	实际值	预测值
1	15	3.88	1.8:5	0.30	62.08	63.21
2	20	3.88	2.0:5	0.30	61.82	59.28
3	25	4.08	1.8:5	0.30	65.73	65.05
4	20	3.88	1.8:5	0.50	61.21	62.22
5	20	3.98	1.6:5	0.10	64.18	65.29
6	20	3.98	1.6:5	0.50	62.11	61.42
7	20	3.98	1.8:5	0.30	72.24	71.68
8	20	4.08	1.8:5	0.50	67.54	69.61
9	20	3.98	1.8:5	0.30	72.24	71.68
10	20	3.88	1.8:5	0.10	67.75	66.92
11	25	3.88	1.8:5	0.30	64.63	65.11
12	20	3.88	1.6:5	0.30	61.65	62.40
13	15	3.98	2.0:5	0.30	63.92	66.30
14	20	4.08	2.0:5	0.30	73.94	71.50
15	15	3.98	1.8:5	0.50	66.91	65.59
16	20	3.98	2.0:5	0.50	61.19	60.53
17	25	3.98	2.0:5	0.30	59.15	61.26
18	15	4.08	1.8:5	0.30	79.87	79.84
19	20	4.08	1.6:5	0.30	65.89	66.74
20	25	3.98	1.8:5	0.10	65.09	64.72
21	20	3.98	1.8:5	0.30	68.81	71.68
22	15	3.98	1.8:5	0.10	76.33	75.05
23	20	4.08	1.8:5	0.10	75.85	76.08
24	20	3.98	1.8:5	0.30	72.86	71.68
25	15	3.98	1.6:5	0.30	67.75	66.88
26	25	3.98	1.6:5	0.30	60.16	59.02
27	20	3.98	1.8:5	0.30	72.23	71.68
28	25	3.98	1.8:5	0.50	63.43	63.02
29	20	3.98	2.0:5	0.10	66.68	67.83

变异来源	平方和	自由度	均方	F值	P值	显著性
模型	770.56	14	55.04	14.94	<0.000 1	极显著
X₁	124.61	1	124.61	33.83	<0.000 1	极显著
X₂	205.68	1	205.68	55.83	<0.000 1	极显著
X₃	2.05	1	2.05	0.56	0.468 0	不显著
X₄	93.47	1	93.47	25.37	0.000 2	极显著
X₁X₂	69.64	1	69.64	18.90	0.000 7	极显著
X₁X₃	1.99	1	1.99	0.54	0.474 7	不显著
X₁X₄	15.05	1	15.05	4.09	0.062 8	不显著
X₂X₃	15.52	1	15.52	4.21	0.059 3	不显著
X₂X₄	0.78	1	0.78	0.21	0.651 8	不显著
X₃X₄	2.92	1	2.92	0.79	0.388 0	不显著
X₁²	40.30	1	40.30	10.94	0.005 2	极显著
X₂²	5.01	1	5.01	1.36	0.263 0	不显著
X₃²	219.62	1	219.62	59.61	<0.000 1	极显著
X₄²	28.34	1	28.34	7.69	0.014 9	显著
残差	51.58	14	3.68
失拟项	41.02	10	4.10	1.55	0.356 2	不显著
纯误差	10.56	4	2.64
总和	822.14	28

平行实验	温度/ ℃	w（B₂O₃）/ %	n（NaOH）: n（H₃BO₃）	晶种加入量/g	结晶产率/%			相对误差/%
平行实验	温度/ ℃	w（B₂O₃）/ %	n（NaOH）: n（H₃BO₃）	晶种加入量/g	实际值	实际平均值	预测值	相对误差/%
实验1	15	4.08	1.86:5	0.10	81.54	81.58	80.56	1.25
实验2	15	4.08	1.86:5	0.10	80.23
实验3	15	4.08	1.86:5	0.10	82.96

动力学模型	残差平方和S	速率常数k	拟合优度R²
MA-1	35.165 4	5.761 0	0.279 3
MA-2	0.305 4	0.110 7	0.984 8
MA-3	2.398 6	0.049 3	0.850 8
MA-4	5.698 8	0.022 3	0.621 7
MB-1	129.653 8	0.001 0	0.454 7
MB-2	129.653 8	0.001 0	0.454 7
MB-3	129.653 8	0.001 0	0.454 7
MB-4	129.653 8	0.001 0	0.454 7
MC-1	1.064 6	0.149 7	0.936 2
MC-2	3.437 2	0.078 4	0.731 1
MC-3	6.663 6	0.044 0	0.462 9
MC-4	9.610 3	0.027 1	0.281 3

名称	w（Li⁺）	w（Na⁺）	w（K⁺）	w（Mg²⁺）	w（Cl^-）	w（SO₄^2-）	w（B₂O₃）
老卤原料	0.12	0.31	0.20	8.84	23.87	1.09	0.46
老卤溶液	0.05	0.92	0.04	3.90	10.78	0.51	3.70
MgCl₂溶液	—	1.02	—	4.30	12.47	0.12	4.08
MgSO₄溶液	—	1.03	—	4.31	0.15	17.65	4.08

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Inorganic Acid-Base-Salt Committee of CIESC

Study on crystallization process and kinetic of macallisterite in concentrated MgCl₂-xNa₂O·yB₂O₃-H₂O solution

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Study on crystallization process and kinetic of macallisterite in concentrated MgCl2-xNa2O·yB2O3-H2O solution