铵盐体系电解锰渣中石膏的转变规律

doi:10.16085/j.issn.1000-6613.2021-2397

化工进展 ›› 2022, Vol. 41 ›› Issue (9): 5115-5121.DOI: 10.16085/j.issn.1000-6613.2021-2397

铵盐体系电解锰渣中石膏的转变规律

曾一凡¹(), 舒建成¹(), 杨慧敏¹, 赵志胜¹, 陈梦君¹, 杨勇²^,³, 刘仁龙²

^1.西南科技大学固体废物处理与资源化教育部重点实验室，四川绵阳 621000
^2.重庆大学化学化工学院，重庆 401331
^3.南方锰业集团有限责任公司大新锰矿分公司，广西南宁 532315

收稿日期:2021-11-23 修回日期:2022-03-28 出版日期:2022-09-25 发布日期:2022-09-27
通讯作者: 舒建成
作者简介:曾一凡（1999—），男，硕士研究生，研究方向为固废处置。E-mail：zyfswust@163.com。
基金资助:
国家重点研发计划(2018YFC1903500);国家自然科学基金(52174386)

Transformation law of gypsum from electrolytic manganese residue in ammonium salt system

ZENG Yifan¹(), SHU Jiancheng¹(), YANG Huimin¹, ZHAO Zhisheng¹, CHEN Mengjun¹, YANG Yong²^,³, LIU Renlong²

^1.Key Laboratory of Solid Waste Treatment and Resource Recycle (SWUST), Ministry of Education, Southwest University of Science and Technology, Mianyang 621010, Sichuan, China
^2.College of Chemistry and Chemical Engineering, Chongqing University, Chongqing 401331, China
^3.Daxin Manganese Mine Branch, Nanfang Manganese Industry Group Co. , Ltd. , Nanning 532315, Guangxi, China

Received:2021-11-23 Revised:2022-03-28 Online:2022-09-25 Published:2022-09-27
Contact: SHU Jiancheng

摘要/Abstract

摘要：

电解锰渣已成为阻碍电解锰行业发展的瓶颈，其中锰渣含有的大量石膏是限制其资源化利用的关键。针对锰渣中石膏浸出问题，本文研究了NH₄HCO₃和NH₄Cl用量、浸出初始pH、浸出时间、浸出温度对锰渣中石膏转变规律的影响。研究结果表明，当锰渣与NH₄HCO₃和NH₄Cl之间的质量比为20∶8∶1.5、固液比为1∶5、浸出初始pH为7.5、浸出温度为70℃、浸出时间为120min时，石膏的浸出率达到90.0%；浸出锰渣主要物相含有CaCO₃、SiO₂、Ca₂Mn₂(OH)₄Si₄O₁₁·2H₂O、Mg_5.0Al₆Fe₄Si_2.5Al_1.5O₁₀(OH)₈以及KAl₃Si₃O₁₀(OH)₂等，其中浸出锰渣中MnO含量由未浸出前的7.45%提高到14.71%。转变规律表明，NH₄HCO₃与锰渣中的石膏反应转变成(NH₄)₂SO₄和CaCO₃，而NH₄Cl作为盐试剂可进一步促进石膏的溶解，从而提高石膏的浸出率。

关键词: 电解锰渣, 石膏, 转变规律, 工业固废, 铵盐体系

Abstract:

Electrolytic manganese residue (EMR) has become a bottleneck hindering the development of electrolytic manganese industry, and the large amount of gypsum in EMR is the key to limit its resource utilization. Aiming at the problem of gypsum leaching from EMR, the effects of NH₄HCO₃ and NH₄Cl dosage, initial pH of leaching, leaching time and leaching temperature on the transformation law of gypsum in manganese residue were studied. The results showed that the leaching efficiency of gypsum in EMR was 90.0% when the mass ratio of manganese residue to NH₄HCO₃ and NH₄Cl was 20∶8∶1.5, the solid-liquid ratio was 1∶5, the initial pH of leaching was 7.5, the leaching temperature was 70℃ and the leaching time was 120min. The main phases of the leaching EMR included CaCO₃, SiO₂, Ca₂Mn₂(OH)₄Si₄O₁₁·2H₂O, Mg_5.0Al₆Fe₄Si_2.5Al_1.5O₁₀(OH)₈ and KAl₃Si₃O₁₀(OH)₂, and the content of MnO in EMR increased from 7.45% to 14.71% after leaching. The transformation law of gypsum in EMR indicated that NH₄HCO₃ reacted with gypsum in EMR to convert into (NH₄)₂SO₄ and CaCO₃, and NH₄Cl as a salt reagent can further promote the dissolution of gypsum, and thus improving the leaching efficiency of gypsum.

Key words: electrolytic manganese residue, gypsum, transformation rule, industrial solid waste, ammonium salt system

中图分类号:

X753

曾一凡, 舒建成, 杨慧敏, 赵志胜, 陈梦君, 杨勇, 刘仁龙. 铵盐体系电解锰渣中石膏的转变规律[J]. 化工进展, 2022, 41(9): 5115-5121.

ZENG Yifan, SHU Jiancheng, YANG Huimin, ZHAO Zhisheng, CHEN Mengjun, YANG Yong, LIU Renlong. Transformation law of gypsum from electrolytic manganese residue in ammonium salt system[J]. Chemical Industry and Engineering Progress, 2022, 41(9): 5115-5121.

图/表 7

图1 NH4HCO3用量和浸出初始pH对石膏浸出率的影响

图2 NH4Cl用量与固液比对石膏浸出率的影响

图3 浸出温度和浸出时间对石膏浸出率的影响（电解锰渣∶NH4HCO3∶NH4Cl质量比为20∶8∶1.5，电解锰渣∶水固液比为1∶5，浸出初始pH为7.5）

表1 不同条件下电解锰渣的化学成分单位：%（质量分数）

名称	SO₃	SiO₂	CaO	Fe₂O₃	MnO	Al₂O₃	MgO	Cl	Na₂O	其他
空白	30.3	23.61	21.71	10.55	7.45	2.56	1.84	0.03	0.10	1.85
浸出锰渣1^#	4.92	32.03	24.75	14.29	12.87	3.29	3.66	0.58	0.18	3.43
浸出锰渣2^#	3.19	32.42	24.04	13.86	14.71	3.36	4.12	0.23	0.20	3.87
浸出锰渣3^#	4.03	33.00	24.30	14.55	12.97	3.36	4.09	0.18	0.16	3.36
浸出锰渣4^#	6.08	32.07	23.21	14.21	12.68	3.36	4.08	0.58	0.17	3.56

图4 不同温度下浸出电解锰渣XRD和FTIR分析（浸出渣1#，浸出温度60℃；浸出渣2#，浸出温度70℃；浸出渣3#，浸出温度80℃；浸出渣4#，浸出温度90℃，反应条件：电解锰渣∶NH4HCO3∶NH4Cl质量比为20∶8∶1.5，浸出初始pH为7.5，电解锰渣∶水固液比为1∶5，浸出时间120min）

表2 不同反应条件下浸出液中重金属元素浓度单位：mg/L

名称	Mg²⁺	Mn²⁺	Pb²⁺	Cr³⁺	Cu²⁺	Zn²⁺
空白	275	222.9	0.323	0.78	0	0
浸出液1^#	187.2	3.57	0.249	0	0.057	0.166
浸出液2^#	209.1	5.4	0.519	0	0.408	0.118
浸出液3^#	148.2	21.69	0.088	0	1.042	0.299
浸出液4^#	144.5	26.89	0.188	0	1.527	0.394

图5 浸出锰渣SEM、EDS、Mapping图谱（电解锰渣∶NH4HCO3∶NH4Cl质量比为20∶8∶1.5，浸出初始pH为7.5，浸出温度70℃，电解锰渣与水固液比为1∶5，浸出时间120min）

参考文献 27

1	徐金荣. 电解锰渣无害化处理技术及资源化利用研究进展[J]. 中国锰业, 2020, 38(6): 1-6.
	XU Jinrong. A research progress on harmless treatment technology and resource utilization of electrolytic manganese residue[J]. China’s Manganese Industry, 2020, 38(6): 1-6.
2	LI Jia, Ying LYU, JIAO Xiangke, et al. Electrolytic manganese residue based autoclaved bricks with Ca(OH)₂ and thermal-mechanical activated K-feldspar additions[J]. Construction and Building Materials, 2020, 230: 116848.
3	王瑞祥, 赵鑫, 李棉, 等. 铜冶炼炉渣浮选尾矿的硫酸浸出及动力学研究[J]. 金属矿山, 2017(12): 189-193.
	WANG Ruixiang, ZHAO Xin, LI Mian, et al. Sulfuric acid leaching and kinetics of flotation tailings from copper smelting slag[J]. Metal Mine, 2017(12): 189-193.
4	谭立群, 杨娟. 2021年1—2月电解金属锰创新联盟运行简报[J]. 中国锰业, 2021, 39(1): 68-69.
	TAN Liqun, YANG Juan. January to February 2021 operation briefing of electrolytic manganese metal innovation alliance, 2021[J]. China Manganese Industry, 2021, 39(1): 68-69.
5	全国锰业技术委员会. 大变局下的电解金属锰企业救赎之路[J]. 中国锰业, 2021, 39(1): 1-2.
	China National Mn Industry Technology Committee. The road to redemption of electrolytic metal manganese enterprises under the great change[J]. China Manganese Industry, 2021, 39(1): 1-2.
6	何德军, 舒建成, 陈梦君, 等. 电解锰渣建材资源化研究现状与展望[J]. 化工进展, 2020, 39(10): 4227-4237.
	HE Dejun, SHU Jiancheng, CHEN Mengjun, et al. Current status and future prospects of electrolytic manganese residue reused as building materials[J]. Chemical Industry and Engineering Progress, 2020, 39(10): 4227-4237.
7	WANG Dengquan, WANG Qiang, XUE Junfeng. Reuse of hazardous electrolytic manganese residue: detailed leaching characterization and novel application as a cementitious material[J]. Resources, Conservation and Recycling, 2020, 154: 104645.
8	SHU Jiancheng, CHEN Mengjun, WU Haiping, et al. An innovative method for synergistic stabilization/solidification of Mn²⁺, NH₄ ⁺-N, PO₄ ^3- and F^- in electrolytic manganese residue and phosphogypsum[J]. Journal of Hazardous Materials, 2019, 376: 212-222.
9	王智, 孙军, 钱觉时, 等. 电解锰渣中硫酸盐性质的研究[J]. 材料导报, 2010, 24(10): 61-64.
	WANG Zhi, SUN Jun, QIAN Jueshi, et al. Study on sulfate of electrolytic manganese residue[J]. Materials Review, 2010, 24(10): 61-64.
10	国家质量监督检验检疫总局, 中国国家标准化管理委员会. 通用硅酸盐水泥: [S]. 北京: 中国标准出版社, 2008.
	General Administration of Quality Supervision, Inspection and Quarantine of the People’s Republic of China, Standardization Administration of the People’s Republic of China. Common Portland cement: [S]. Beijing: Standards Press of China, 2008.
11	龙谨, 杨凤龙, 吴钦雪, 等. 磷石膏对土壤的性能影响研究综述[J]. 广州化工, 2021, 49(19): 35-37.
	LONG Jin, YANG Fenglong, WU Qinxue, et al. Study on effects of phosphogypsum on soil properties[J]. Guangzhou Chemical Industry, 2021, 49(19): 35-37.
12	陈波, 宋兴福, 许妍霞, 等. 响应面法优化氨碳化-钙转化连续法制备碳酸钙工艺[J]. 无机盐工业, 2016, 48(9): 18-22.
	CHEN Bo, SONG Xingfu, XU Yanxia, et al. Optimization of preparation of calcium carbonate from continuous crystallization process of ammonium carbonate and conversion of calcium sulfate by response surface methodology[J]. Inorganic Chemicals Industry, 2016, 48(9): 18-22.
13	陈红亮, 龙黔, 舒建成, 等. 碳酸盐对电解锰渣中可溶性锰固定和硫酸钙转化的研究[J]. 工业安全与环保, 2017, 43(5): 81-84, 89.
	CHEN Hongliang, LONG Qian, SHU Jiancheng, et al. Study of soluble manganese immobilization and calcium sulfate conversion from electrolytic manganese residue by using carbonate[J]. Industrial Safety and Environmental Protection, 2017, 43(5): 81-84, 89.
14	梁亚琴, 孙红娟, 彭同江. 氯化铵溶液浸取磷石膏中硫酸钙的实验研究[J]. 非金属矿, 2014, 37(4): 69-72.
	LIANG Yaqin, SUN Hongjuan, PENG Tongjiang. Study of the leaching calcium sulfate from phosphogypsum with ammonium chloride solution[J]. Non-Metallic Mines, 2014, 37(4): 69-72.
15	杨晓红, 薛希仕, 张露露, 等. 电解锰渣盐酸浸取钙的动力学研究[J]. 无机盐工业, 2021, 53(1): 82-86.
	YANG Xiaohong, XUE Xishi, ZHANG Lulu, et al. Kinetics study of calcium leaching from electrolytic manganese residue by hydrochloric acid[J]. Inorganic Chemicals Industry, 2021, 53(1): 82-86.
16	冯雅丽, 马玉文, 李浩然. 盐湖副产硫酸钙转化法制备高纯氧化钙[J]. 中南大学学报(自然科学版), 2012, 43(8): 3308-3313.
	FENG Yali, MA Yuwen, LI Haoran. Preparation of high-purity calcium oxide from salt lake by-product calcium sulfate by conversion method[J]. Journal of Central South University (Science and Technology), 2012, 43(8): 3308-3313.
17	刘佳. 磷石膏制备硫酸铵的工艺研究[D]. 贵阳：贵州大学, 2009.
	LIU Jia. Study on preparation of ammonium sulfate from phosphogypsum[D]. Guiyang: Guizhou University, 2009.
18	吴建锋, 宋谋胜, 徐晓虹, 等. 电解锰渣的综合利用进展与研究展望[J]. 环境工程学报, 2014, 8(7): 2645-2652.
	WU Jianfeng, SONG Musheng, XU Xiaohong, et al. Prospects and advances of comprehensive utilization of electrolytic manganese residue[J]. Chinese Journal of Environmental Engineering, 2014, 8(7): 2645-2652.
19	仵亚妮, 化全县, 汤建伟, 等. 磷石膏制备碳酸钙晶须的工艺研究[J]. 化工矿物与加工, 2011, 40(12): 18-22.
	WU Yani, HUA Quanxian, TANG Jianwei, et al. Studies on preparation technology of calcium carbonate whiskers from phosphogypsum[J]. Industrial Minerals & Processing, 2011, 40(12): 18-22.
20	HU Ruizhu, HUANG Tinglin, WEN Gang, et al. Pilot study on the softening rules and regulation of water at various hardness levels within a chemical crystallization circulating pellet fluidized bed system[J]. Journal of Water Process Engineering, 2021, 41: 102000.
21	CHEN Qiuju, DING Wenjin, SUN Hongjuan, et al. Indirect mineral carbonation of phosphogypsum for CO₂ sequestration[J]. Energy, 2020, 206: 118148.
22	BOYD Victoria, YOON Hongkyu, ZHANG Changyong, et al. Influence of Mg²⁺ on CaCO₃ precipitation during subsurface reactive transport in a homogeneous silicon-etched pore network[J]. Geochimica et Cosmochimica Acta, 2014, 135: 321-335.
23	DAVIS K J, DOVE P M, DE YOREO J J. The role of Mg²⁺ as an impurity in calcite growth[J]. Science, 2000, 290(5494): 1134-1137.
24	田萍, 宁朋歌, 曹宏斌, 等. 二水硫酸钙在铵盐溶液中溶解度测定及热力学计算[J]. 过程工程学报, 2012, 12(4): 625-630.
	TIAN Ping, NING Pengge, CAO Hongbin, et al. Solubility measurement of calcium sulfate dihydrate in NH₄Cl-(NH₄)₂SO₄ solutions and thermodynamic calculation[J]. The Chinese Journal of Process Engineering, 2012, 12(4): 625-630.
25	熊双贵, 高之清. 无机化学[M]. 武汉: 华中科技大学出版社, 2011: 86-91.
	XIONG Shuanggui, GAO Zhiqing. Inorganic chemistry[M]. Wuhan: Huazhong University of Science and Technology Press, 2011: 86-91.
26	蓝际荣, 孙燕, 潘滢, 等. 球磨与助剂强化选择性回收电解锰渣中的锰[J]. 中国有色金属学报, 2019, 29(8): 1749-1755.
	LAN Jirong, SUN Yan, PAN Ying, et al. Ball milling and auxiliary enhancement for selective recovery of manganese in EMRs[J]. The Chinese Journal of Nonferrous Metals, 2019, 29(8): 1749-1755.
27	胡瑞柱, 黄廷林, 刘泽男. 碳酸钙诱导结晶动力学影响因素研究[J]. 中国环境科学, 2021, 41(8): 3584-3589.
	HU Ruizhu, HUANG Tinglin, LIU Zenan. Influencing factors of induced crystallization kinetics of calcium carbonate[J]. China Environmental Science, 2021, 41(8): 3584-3589.

[1]	丁文金, 刘卓齐, 卢海臣, 孙红娟, 彭同江. CH₃COONa-NH₄OH-H₂O体系下磷石膏矿化CO₂-联产高纯CaCO₃[J]. 化工进展, 2023, 42(7): 3824-3833.
[2]	李文秀, 杨宇航, 黄艳, 王涛, 王镭, 方梦祥. 二氧化碳矿化高钙基固废制备微细碳酸钙研究进展[J]. 化工进展, 2023, 42(4): 2047-2057.
[3]	毕强, 梅毅, 夏举佩. 磷Ⅱ型无水石膏制备及活性联合激发基础研究[J]. 化工进展, 2023, 42(10): 5427-5435.
[4]	范旭阳, 陈延信, 赵博, 张蕾蕾. 气体硫黄还原磷石膏制酸新工艺预还原数值模拟[J]. 化工进展, 2023, 42(10): 5414-5426.
[5]	汪潇, 金彪, 张小婷, 张建武, 王宇斌, 苑冬冬, 杨留栓. 氯盐体系下阳离子对脱硫石膏晶须水热结晶的影响及其机理[J]. 化工进展, 2022, 41(7): 3957-3965.
[6]	赵亮, 王岩, 王刚, 方向晨, 段晓光, 王少彬. 石蜡@糊化面粉相变微胶囊及其在建材中的应用[J]. 化工进展, 2022, 41(5): 2566-2573.
[7]	邓亚玲, 舒建成, 陈梦君, 雷天涯, 曾祥菲, 杨勇, 刘作华. 不同堆存时间电解锰渣的理化特性分析[J]. 化工进展, 2022, 41(4): 2161-2170.
[8]	何民宇, 刘维燥, 刘清才, 秦治峰. CO₂矿物封存技术研究进展[J]. 化工进展, 2022, 41(4): 1825-1833.
[9]	聂紫萌, 杨点, 熊玉路, 李英杰, 田森林, 宁平. 电解锰渣浆液烟气脱硫性能及机制[J]. 化工进展, 2022, 41(2): 1063-1072.
[10]	张宇, 杨家豪, 刘瑜, 宋子玉, 何涵潇, 赵风清. Ⅱ型无水磷石膏凝结硬化过程调控技术[J]. 化工进展, 2022, 41(10): 5637-5644.
[11]	熊玉路, 徐子豪, 李英杰, 田森林, 宁平. 惰性气氛下电解锰渣高温还原焙烧脱硫[J]. 化工进展, 2021, 40(S1): 319-325.
[12]	田晓华, 张宇, 赵风清. 钢渣-磷酸体系对磷建筑石膏凝结性能的调节作用机制[J]. 化工进展, 2021, 40(8): 4438-4444.
[13]	何德军, 舒建成, 陈梦君, 王建义, 高遇事, 王宁, 顾汉念. 电解锰渣建材资源化研究现状与展望[J]. 化工进展, 2020, 39(10): 4227-4237.
[14]	黄浩,王涛,方梦祥. 二氧化碳矿化养护混凝土技术及新型材料研究进展[J]. 化工进展, 2019, 38(10): 4363-4373.
[15]	蒋美雪, 孙红娟, 彭同江. 钛石膏硫酸浸取法提取铁质氧化物及石膏的物相变化[J]. 化工进展, 2019, 38(04): 2030-2036.

铵盐体系电解锰渣中石膏的转变规律

Transformation law of gypsum from electrolytic manganese residue in ammonium salt system

RichHTML

PDF (PC)

可视化

摘要/Abstract

引用本文

使用本文

图/表 7

参考文献 27

相关文章 15

编辑推荐

Metrics

本文评价