菱锰矿浸出前后理化特性及界面水化行为变化规律

doi:10.16085/j.issn.1000-6613.2023-1429

摘要/Abstract

摘要：

高含水率电解锰渣已成为制约我国电解锰行业发展的瓶颈。本研究分析了菱锰矿浸出前后矿物组成、微观形貌等理化特性，同时考察了菱锰矿浸出前后亲水系数、润湿热、含水率以及过滤性能。研究结果表明：菱锰矿浸出后得到的电解锰渣中出现了高岭石、水钙沸石等亲水性黏土矿物，同时得到的电解锰渣中出现了结构水和结晶水的红外特征峰，含水率由菱锰矿浸出前的17.68%增加至32.67%，润湿热由0.743J/g增加至3.879J/g，亲水系数由1.117增加至2.233；此外，菱锰矿浸出后得到的电解锰渣渣浆过滤性能受黏土矿物影响，过滤速率由菱锰矿浸出前的10.318mL/min下降到5.296mL/min。本研究为电解锰渣含水率控制技术研发提供了理论支持。

关键词: 菱锰矿, 酸浸, 电解锰渣, 理化特性, 界面水化行为

Abstract:

Electrolytic manganese residue (EMR) with high water content has become a bottleneck restricting the development of China's EMR industry. In this study, the physicochemical properties such as mineral composition and microscopic morphology were analyzed before and after the leaching of rhodochrosite, and the hydrophilic coefficient, wetting heat, water content and filtration performance before and after the leaching of rhodochrosite were investigated. The results showed that the hydrophilic clay minerals such as kaolinite and hydrotalcite zeolite appeared in the EMR after leaching. At the same time, the new infrared characteristic peaks of structural and crystal water appeared in the electrolytic manganese residue after leaching. The water content after leaching increased from 17.68% to 32.67%, the wettability heat increased from 0.743J/g to 3.879J/g and the hydrophilic coefficient increased from 1.117 to 2.233. In addition, the filtration performance of the leached EMR was affected by clay minerals and the filtration rate after leaching decreased from 10.318mL/min to 5.296mL/min. This study provided theoretical support for the research and development of water content control technology in the electrolytic manganese residue.

Key words: rhodochrosite, acid leaching, electrolytic manganese residue, physicochemical properties, interface hydration behavior

中图分类号:

X753

李子寒, 舒建成, 曹文星, 杨慧敏, 陈梦君. 菱锰矿浸出前后理化特性及界面水化行为变化规律[J]. 化工进展, 2024, 43(9): 5320-5328.

LI Zihan, SHU Jiancheng, CAO Wenxing, YANG Huimin, CHEN Mengjun. Physicochemical properties of rhodochrosite before and after leaching and the changing law of interface hydration behavior[J]. Chemical Industry and Engineering Progress, 2024, 43(9): 5320-5328.

图/表 10

表1 菱锰矿浸出前后XRF分析

样品	成分质量分数/%
样品	SiO₂	MnO	CaO	Fe₂O₃	Al₂O₃	MgO	SO₃	其他
菱锰矿	33.46	30.53	15.68	10.77	3.44	2.85	0.94	2.33
电解锰渣	23.32	8.14	20.90	11.87	2.42	1.43	30.57	1.35

图1 菱锰矿和电解锰渣X射线衍射谱图

图2 菱锰矿和电解锰渣SEM-EDS-Mapping图

图3 菱锰矿[(a)~(f)]和电解锰渣[(g)~(l)]显微镜图片透射单偏光[(a)、(b)、(g)、(h)]；透射正交光[(c)、(d)、(i)、(j)]；反射单偏光图[(e)、(f)、(k)、(l)]

图4 菱锰矿和电解锰渣的低温氮气吸附脱附曲线（a）和BJH曲线（b）

表2 菱锰矿和电解锰渣平均孔径、比表面积以及孔容

参数	浸出前	浸出后
平均孔径/nm	10.165	14.328
比表面积/m²∙g^-1	8.20	17.06
孔容/cm²·g^-1	1.88	3.92

图5 菱锰矿和电解锰渣光电子能谱

图6 菱锰矿浸出前后FTIR谱图

表3 菱锰矿和电解锰渣水化参数

参数	浸出前	浸出后
亲水系数	1.117	2.233
含水率/%	17.68	32.67
润湿热/J·g^-1	0.743	3.879
恒压过滤常数K	1.72×10^-5	1.34×10^-5
过滤速率/mL·min^-1	10.318	5.296
滤饼比阻/m·kg^-1	2.00×10⁷	4.86×10⁷

图7 菱锰矿和电解锰渣恒压过滤常数K拟合图

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