蛇纹石酸浸淋洗液中硫酸镁的溶析结晶优化

彭祥玉; 刘文宝; 刘文刚; 王振; 于茜

doi:10.3969/j.issn.1000-6532.2023.02.007

蛇纹石酸浸淋洗液中硫酸镁的溶析结晶优化

doi: 10.3969/j.issn.1000-6532.2023.02.007

彭祥玉^1,,
刘文宝^1, ,,
刘文刚¹,
王振²,
于茜¹

1.
东北大学资源与土木工程学院，辽宁　沈阳　110819
2.
96854部队工程项目管理室，辽宁　沈阳　110819

基金项目: 中央高校基本科研业务费研究生科研创新项目(N2001018).

详细信息

作者简介:
彭祥玉（1992-），女，博士，研究方向为含镁非金属矿综合回收利用

通讯作者:
刘文宝（1988-），男，博士，副教授，从事含镁非金属矿综合回收利用研究

中图分类号: TD985;TQ132.2
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出版历程
- 收稿日期: 2020-03-08

Study on Optimization of Extracting Magnesium Sulfate from Acid-leaching Eluent of Serpentine by Solventing-out Crystallization

1.
School of Resources & Civil Engineering, Northeastern University, Shenyang, Liaoning, China
2.
Engineering Project Management Office of 96854 Unit, Shenyang, Liaoning, China

摘要

摘要: 为了充分的利用我国含镁非金属矿资源，提高蛇纹石中所含镁资源的综合回收率，本研究提出了一种在常温常压下从蛇纹石矿淋洗液中富集镁元素的新工艺。该工艺采用了溶析结晶法对蛇纹石酸浸淋洗液中的镁进行回收，通过响应曲面法优化实验条件，明确较佳的结晶工艺条件。研究过程中考查了结晶温度、结晶时间以及溶析剂无水乙醇用量对硫酸镁结晶析出的影响及主要因素之间的交互作用，由研究结果可得较佳的优化条件为：结晶时间为97 min，结晶温度为18 °C，无水乙醇用量为68 mL，该条件下硫酸镁的析出率可达93.52%，与回归方程模型的预测值相吻合。同时通过响应曲面图和等高线图分析，更加直观反映了各个因素对硫酸镁析出率的影响及交互作用的强弱，结果表明，无水乙醇用量显著影响硫酸镁的析出，结晶温度影响较小，无水乙醇用量与结晶温度及时间的交互作用都比较显著。研究过程中获得的结晶产物为棒条状的六水硫酸镁，符合国内Ⅳ类MgSO₄·nH₂O产品的生产要求。
- 溶析结晶 /
- 蛇纹石 /
- 淋洗液 /
- 硫酸镁 /
- 响应曲面法
Abstract: In order to make full use of China's non-metallic mineral resources containing magnesium, and improve the comprehensive recovery rate of magnesium in serpentine, a new process of enriching magnesium from serpentine leaching solution at normal temperature and pressure was proposed. In this process, the solution crystallization method was used to recover the magnesium from the acid leaching solution of serpentine. The test conditions were optimized by response surface methodology to determine the optimal crystallization process conditions. In this study, response surface method was employed to optimize test conditions and select the best crystallization process conditions. In addition, the effect and interaction of crystallization time, temperature, and absolute ethanol consumption on magnesium sulfate crystallization efficiency were study. The results showed that the magnesium sulfate crystallization efficiency reached 93.52% under the optimum condition (crystallization time: 97 min, crystallization temperature: 18°C and absolute ethanol consumption: 68 mL). Moreover, the absolute ethanol consumption exhibited significant influence on magnesium sulfate crystallization, while temperature had the least effect, and the interaction between absolute ethanol consumption and crystallization temperature or time was significant. The crystalline product was rod-shaped magnesium sulfate hexahydrate, which met the production requirements of domestic class IV MgSO₄·nH₂O products.
- Solventing-out crystallization /
- Serpentine /
- Eluent /
- Magnesium sulfate /
- Response surface methodology

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图 1 无水乙醇加入量对硫酸镁析出率的影响

Figure 1. Effect of quantity of adding ethanol on crystallization rate of magnesium sulfate

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图 2 温度对硫酸镁析出率的影响

Figure 2. Effect of temperature on crystallization rate of magnesium sulfate

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图 3 时间对硫酸镁析出率的影响

Figure 3. Effect of time on crystallization rate of magnesium sulfate

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图 4 硫酸镁析出模型预期值和实际值的对比

Figure 4. Comparison of Magnesium sulfate precipitates model prediction with experimental data

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图 5 硫酸镁析出率的响应曲面和等高线

Figure 5. Response surface and contour plots for magnesium sulfate crystallization efficiency

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图 6 结晶产品的XRD

Figure 6. XRD pattern of crystalline products

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图 7 结晶产品的SEM-EDS分析

Figure 7. SEM-EDS pattern of crystalline product

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表 1 蛇纹石样品的荧光分析结果/%

Table 1. XRF results of serpentine samples

MgO	SiO₂	Fe₂O₃	Al₂O₃	CaO	P₂O₅	Cr₂O₃	K₂O	SO₃
43.72	54.28	0.458	0.124	1.25	0.125	0.0277	0.0125	0.003

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表 2 Box-Behnken设计实验结果

Table 2. Box-Behnken experimental design matrix and results

序号	A/min	B/°C	C/mL	硫酸镁析出率/%
1	60	25	60	91.83
2	100	25	30	61.52
3	60	25	60	90.26
4	60	15	90	76.98
5	60	25	60	90.44
6	20	35	60	86.23
7	60	25	60	88.23
8	100	15	60	93.71
9	60	35	30	54.6
10	100	25	90	88.74
11	100	35	60	83.23
12	60	25	60	89.21
13	20	25	30	58.08
14	60	15	30	68.59
15	60	35	90	89.59
16	20	15	60	85.21
17	20	25	90	81.16

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表 3 响应曲面方差分析

Table 3. Response surface analysis of variance

方差来源	平方和	自由度	均方	F值	P值	显著性
模型	2503.72	9	278.19	76.90	< 0.0001	***
A	34.11	1	34.11	9.43	0.0180	*
B	14.69	1	14.69	4.06	0.0837	—
C	1096.99	1	1096.99	303.25	< 0.0001	***
AB	4.28	1	4.28	1.18	0.3125	—
AC	33.06	1	33.06	9.14	0.0193	*
BC	176.89	1	176.89	48.90	0.0002	*
A2	9.25	1	9.25	2.56	0.1539	—
B2	8.45	1	8.45	2.34	0.1702	—
C2	1096.43	1	1096.43	303.09	< 0.0001	***
残差	25.32	7	3.62	—	—	—
失拟误差	17.96	3	5.99	3.25	0.1424	—
纯误差	7.37	4	1.84	—	—	—
总和	2529.05	16	—	—	—	—
注：P值小于0.0500表示模型项显著，大于0.1000的值表示模型项不显著；*代表显著性。

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