天青石锶废渣氯化钡浸出及其动力学研究

doi:10.11949/0438-1157.20200993

摘要/Abstract

摘要：

天青石生产碳酸锶后剩下的锶废渣，因含有大量的锶资源，属于一种二次资源。目前天青石锶废渣主要通过碳酸盐转化-盐酸浸出两步法来制备SrCl₂，制备过程复杂。实验以BaCl₂为浸出剂，浸出酸预处理后的天青石锶废渣中的SrSO₄，通过一步浸出得到SrCl₂。分别考察了浸出时间、浸出温度、BaCl₂/SrSO₄摩尔比、液固比对锶浸出率的影响。结果表明：浸出时间120 min，浸出温度90℃，BaCl₂/SrSO₄摩尔比2.0，初始液固比10 ml/g时的锶浸出率达到了68.79%。该浸出过程符合未反应核缩模型，且主要受BaSO₄产物层扩散控制，其表观活化能为38.75 kJ/mol。Ba²⁺部分或全部取代SrSO₄中的锶，使得锶废渣中的锶以SrCl₂的形式被浸出。

关键词: 锶废渣, 氯化钡, 浸出, 动力学, 取代

Abstract:

The strontium waste residue left after the production of strontium carbonate from celestite is a secondary resource because it contains a large amount of strontium resources. At present, strontium celestite waste residue is mainly used to prepare SrCl₂ through a two-step method of carbonate conversion and hydrochloric acid leaching, and the preparation process is complicated. In the experiment, BaCl₂ was used as the leaching agent to extract SrSO₄ from the strontium lapis lazuli waste residue after acid pretreatment, and SrCl₂ was obtained by one-step leaching. The effects of leaching time, leaching temperature, BaCl₂/SrSO₄ molar ratio, and liquid-solid ratio on the leaching rate of strontium were investigated respectively. The results showed that when the leaching time was 120 min, the leaching temperature was 90℃, the molar ratio of BaCl₂/SrSO₄ was 2.0, and the initial liquid-to-solid ratio was 10 ml/g, the strontium leaching rate reached 68.79%. The leaching process conforms to the unreacted nuclear shrinkage model and is mainly controlled by the diffusion of the BaSO₄ product layer, and its apparent activation energy is 38.75 kJ/mol. Ba²⁺ partially or completely replaces the strontium in SrSO₄, so that the strontium in the strontium waste residue is leached in the form of SrCl₂.

Key words: strontium waste residue, barium chloride, leaching, dynamics, replace

中图分类号:

TF 803.21

何宇, 刘作华, 栾进华, 崔志伟, 张雄, 毛玲玲, 陶长元. 天青石锶废渣氯化钡浸出及其动力学研究[J]. 化工学报, 2021, 72(4): 2086-2093.

HE Yu, LIU Zuohua, LUAN Jinhua, CUI Zhiwei, ZHANG Xiong, MAO Lingling, TAO Changyuan. Study on the leaching and kinetics of strontium celestite residue with barium chloride[J]. CIESC Journal, 2021, 72(4): 2086-2093.

图/表 11

图1 锶废渣酸处理前后的XRD谱图

Fig.1 XRD patterns of strontium waste residue before and after acid treatment

表1 酸处理前后锶废渣组成

Table 1 Composition of strontium waste residue before and after acid treatment

样品	组成/%(质量)
样品	Sr	Ca	Si	S	Mg	Ba	Other
酸处理前锶废渣	19.04	13.56	9.38	6.61	4.29	0.49	46.63
酸处理后锶废渣	17.88	2.80	17.30	6.12	1.43	0.56	53.91

图2 酸处理前后锶废渣的SEM图

Fig.2 SEM images of strontium waste residue before and after acid treatment

图3 酸处理后锶废渣的EDS表征

Fig.3 EDS characterization of strontium waste residue after acid treatment

图4 浸出时间、浸出温度对锶浸出率的影响

Fig.4 Effects of leaching time and leaching temperature on strontium leaching ratio

图5 BaCl2/SrSO4摩尔比对锶浸出率的影响

Fig.5 Effect of BaCl2/SrSO4 molar ratio on strontium leaching rate

图6 初始液固比对锶浸出率的影响

Fig.6 Effect of initial liquid-solid ratio on strontium leaching rate

图7 浸出过程动力学模型

Fig.7 Kinetic model of leaching process

图8 BaCl2浸出过程中的Arrhenius拟合曲线

Fig.8 Arrhenius fitting curve during BaCl2 leaching process

图9 浸出渣XRD谱图

Fig.9 XRD pattern of leaching residue

表2 浸出后锶废渣组成

Table 2 Composition of strontium waste residue after leaching

样品	组成/%(质量)
样品	Sr	Ca	Si	S	Mg	Ba	Other
酸处理后锶废渣	17.88	2.80	17.30	6.12	1.43	0.56	53.91
浸出后锶废渣	6.44	3.06	16.49	6.13	2.05	11.63	54.20

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