电解锰渣中锰的柠檬酸浸出工艺及机理研究

硅酸盐通报 ›› 2023, Vol. 42 ›› Issue (6): 2071-2080.

所属专题：资源综合利用

电解锰渣中锰的柠檬酸浸出工艺及机理研究

张欢欢^1,2, 方双明^1,2, 付娟^1,2, 程金科^1,2

1.贵州大学化学与化工学院,贵阳 550025;
2.贵州省高性能砼材料及成型工程技术研究中心,龙里 561200

收稿日期:2023-04-12 修订日期:2023-04-12 出版日期:2023-06-15 发布日期:2023-06-25
通信作者: 程金科,博士,副教授。E-mail:36273332@qq.com
作者简介:张欢欢(1996—),女,硕士研究生。主要从事固体废弃物资源化利用的研究。E-mail:2252467842@qq.com
基金资助:
国家重点研发计划(2018YFC1903503);贵州省科技厅工程技术研究中心项目(黔科合平台-JXCX[2021]002);贵州省科技支撑计划(黔科合支撑[2021]一般331)

Leaching Process and Mechanism of Manganese from Electrolytic Manganese Slag by Citric Acid

ZHANG Huanhuan^1,2, FANG Shuangming^1,2, FU Juan^1,2, CHENG Jinke^1,2

1. College of Chemical Engineering, Guizhou University, Guiyang 550025, China;
2. High Performance Concrete Materials and Forming Engineering Technology Research Center of Guizhou, Longli 561200, China

Received:2023-04-12 Revised:2023-04-12 Online:2023-06-15 Published:2023-06-25

摘要/Abstract

摘要： 电解锰渣中锰浓度较高,不仅浪费锰资源,还会制约锰渣综合利用。以柠檬酸为助剂高效浸出锰渣中的锰可促进锰渣资源化利用和电解锰行业绿色低碳发展。本文研究浸出工艺参数对锰渣中锰浸出浓度的影响,通过物相、结构、价态、形貌和动力学分析建立锰浸出模型,探讨浸出机理。结果表明:当柠檬酸掺量25%(质量分数)、液固比5∶1、浸出时间30 min时,锰浸出效果较好,浸出率为93.6%。锰浸出动力学符合收缩核模型,受化学反应和固体膜层混合控制。柠檬酸将高价态锰还原为二价锰,二价锰与柠檬酸以1∶2配位形成螯合物,螯合方式为柠檬酸分子的羧基和羟基共同参与成键。

关键词: 电解锰渣, 柠檬酸, 锰浸出, 工艺参数, 浸出机理

Abstract: The concentration of manganese in electrolytic manganese slag is higher, which not only wastes manganese resources, but also will restrict the comprehensive utilization of manganese residue. The high efficiency leaching of manganese from manganese residue with citric acid as additive can promote the resource utilization of manganese residue and the green and low-carbon development of electrolytic manganese industry. The influence of leaching parameters on the manganese leaching concentration in manganese slag was studied. A manganese leaching model was established by analyzing the phase, structure, valence, morphology and kinetics, and the leaching mechanism was discussed. The results show that when the citric acid content is 25% (mass fraction), the liquid-solid ratio is 5∶1, and the leaching time is 30 min, the manganese leaching effect is better, and the leaching rate is 93.6%. The kinetics of manganese leaching is in accordance with the shrinking core model, which is controlled by the mixture of chemical reaction and solid film. The high valence manganese is reduced to the divalent manganese by citric acid, and then the divalent manganese and citric acid coordinate to form a chelate in the form of 1∶2, in which the carboxyl and hydroxyl groups of citric acid molecules jointly participate in bonding.

Key words: electrolytic manganese residue, citric acid, manganese leaching, process parameter, leaching mechanism

中图分类号:

X781.1

张欢欢, 方双明, 付娟, 程金科. 电解锰渣中锰的柠檬酸浸出工艺及机理研究[J]. 硅酸盐通报, 2023, 42(6): 2071-2080.

ZHANG Huanhuan, FANG Shuangming, FU Juan, CHENG Jinke. Leaching Process and Mechanism of Manganese from Electrolytic Manganese Slag by Citric Acid[J]. BULLETIN OF THE CHINESE CERAMIC SOCIETY, 2023, 42(6): 2071-2080.

参考文献

[1] HE S C, WILSON B P, LUNDSTRÖM M, et al. Hazard-free treatment of electrolytic manganese residue and recovery of manganese using low temperature roasting-water washing process[J]. Journal of Hazardous Materials, 2021, 402: 123561.
[2] HE D J, LUO Z G, ZENG X F, et al. Electrolytic manganese residue disposal based on basic burning raw material: heavy metals solidification/stabilization and long-term stability[J]. Science of the Total Environment, 2022, 825: 153774.
[3] CHEN H L, LONG Q, ZHOU F, et al. Elec-accumulating behaviors of manganese in the electrokinetics-processed electrolytic manganese residue with carbon dioxide and oxalic acid[J]. Journal of Electroanalytical Chemistry, 2020, 865: 114162.
[4] CHOUSIDIS N, IOANNOU I, BATIS G. Utilization of electrolytic manganese dioxide waste in concrete exposed to salt crystallization[J]. Construction and Building Materials, 2018, 158: 708-718.
[5] LI C X, ZHONG H, WANG S, et al. Removal of basic dye (methylene blue) from aqueous solution using zeolite synthesized from electrolytic manganese residue[J]. Journal of Industrial and Engineering Chemistry, 2015, 23: 344-352.
[6] ZHOU C B, DU B, WANG N F, et al. Preparation and strength property of autoclaved bricks fromelectrolytic manganese residue[J]. Journal of Cleaner Production, 2014, 84: 707-714.
[7] WU F F, LI X P, ZHONG H, et al. Utilization of electrolytic manganese residues in production of porous ceramics[J]. International Journal of Applied Ceramic Technology, 2016, 13(3): 511-521.
[8] LI J, SUN P, LI J X, et al. Synthesis of electrolytic manganese residue-fly ash based geopolymers with high compressive strength[J]. Construction and Building Materials, 2020, 248: 118489.
[9] 孟小燕, 蒋彬, 李云飞, 等. 电解锰渣二次提取锰和氨氮的研究[J]. 环境工程学报, 2011, 5(4): 903-908.
MENG X Y, JIANG B, LI Y F, et al. Research on second extraction of manganese and ammonia nitrogen from eletrolytic manganese residue[J]. Chinese Journal of Environmental Engineering, 2011, 5(4): 903-908 (in Chinese).
[10] WANG N F, FANG Z J, PENG S, et al. Recovery of soluble manganese from electrolyte manganese residue using a combination of ammonia and CO₂[J]. Hydrometallurgy, 2016, 164: 288-294.
[11] LAN J R, SUN Y, CHEN X H, et al. Bio-leaching of manganese from electrolytic manganese slag by Microbacterium trichothecenolyticum Y1: Mechanism and characteristics of microbial metabolites[J]. Bioresource Technology, 2021, 319: 124056.
[12] TIAN Y, SHU J C, CHEN M J, et al. Manganese and ammonia nitrogen recovery from electrolytic manganese residue by electric field enhanced leaching[J]. Journal of Cleaner Production, 2019, 236: 117708.
[13] HE S C, JIANG D Y, HONG M H, et al. Hazard-free treatment and resource utilisation of electrolytic manganese residue: a review[J]. Journal of Cleaner Production, 2021, 306: 127224.
[14] LAN J R, DONG Y Q, XIANG Y W, et al. Selective recovery of manganese from electrolytic manganese residue by using water as extractant under mechanochemical ball grinding: mechanism and kinetics[J]. Journal of Hazardous Materials, 2021, 415: 125556.
[15] AI C M, SUN P P, WU A X, et al. Accelerating leaching of copper ore with surfactant and the analysis of reaction kinetics[J]. International Journal of Minerals, Metallurgy, and Materials, 2019, 26(3): 274-281.
[16] SAHA A, LEE J, PANCERA S M, et al. New insights into the transformation of calcium sulfate hemihydrate to gypsum using time-resolved cryogenic transmission electron microscopy[J]. Langmuir: the ACS Journal of Surfaces and Colloids, 2012, 28(30): 11182-11187.
[17] 彭家惠, 陈明凤, 瞿金东, 等. 柠檬酸对建筑石膏水化的影响及其机理研究[J]. 建筑材料学报, 2005, 8(1): 94-99.
PENG J H, CHEN M F, QU J D, et al. Effect of citric acid on the process of hydration of building gypsum and its retarding mechanism[J]. Journal of Building Materials, 2005, 8(1): 94-99 (in Chinese).
[18] LAN J R, ZHANG S S, MEI T, et al. Mechanochemical modification of electrolytic manganese residue: ammonium nitrogen recycling, heavy metal solidification, and baking-free brick preparation[J]. Journal of Cleaner Production, 2021, 329: 129727.
[19] ZHOU Y H, WU S S, LIU R L, et al. Efficient recovery of manganese and ammonia nitrogen from filter-pressing electrolytic manganese residue by organic complexation[J]. Journal of Water Process Engineering, 2022, 45: 102532.
[20] MAJID A, AHMAD N, RIZWAN M, et al. Effects of Mn ion implantation on XPS spectroscopy[J]. Journal of Electronic Materials, 2018, 47(2): 1555-1559.
[21] GAO A L, SUN Z H, LI S P, et al. The mechanism of manganese dissolution on Li_1.6Mn_1.6O₄ ion sieves with HCl[J]. Dalton Transactions (Cambridge, England: 2003), 2018, 47(11): 3864-3871.
[22] 邓亚玲, 舒建成, 陈梦君, 等. 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.
DENG Y L, SHU J C, CHEN M J, et al. Physical and chemical properties analysis of electrolytic manganese residue in different storage times[J]. Chemical Industry and Engineering Progress, 2022, 41(4): 2161-2170 (in Chinese).
[23] 王政. 硫酸法回收磷尾矿中磷和镁及其动力学研究[D]. 贵阳: 贵州大学, 2009.
WANG Z. Study on recovery of phosphorus and magnesium from phosphorus tailings by sulfuric acid method and its kinetics[D]. Guiyang: Guizhou University, 2009 (in Chinese).
[24] 舒建成. 电解锰渣中锰和氨氮的强化转化方法研究[D]. 重庆: 重庆大学, 2017.
SHU J C. Study on enhanced transformation method of manganese and ammonia nitrogen in electrolytic manganese slag[D]. Chongqing: Chongqing University, 2017 (in Chinese).
[25] 程德平. 若干锰配位聚集体的结构化学研究[D]. 杭州: 浙江大学, 1999.
CHENG D P. Study on structural chemistry of some manganese coordination aggregates[D]. Hangzhou: Zhejiang University, 1999 (in Chinese).
[26] SALUNKHE G, SENGUPTA A, BODA A, et al. Application of hybrid MOF composite in extraction of f-block elements: experimental and computational investigation[J]. Chemosphere, 2022, 287: 132232.

电解锰渣中锰的柠檬酸浸出工艺及机理研究

Leaching Process and Mechanism of Manganese from Electrolytic Manganese Slag by Citric Acid

PDF (PC)

可视化

摘要/Abstract

引用本文

使用本文

参考文献

相关文章 15

编辑推荐

Metrics

本文评价

[1]	张先伟, 高永红, 王平, 李江山, 刘世宇, 郎雷, 雷学文. 电解锰渣-生活垃圾焚烧底渣协同制备路面基层材料试验研究[J]. 硅酸盐通报, 2023, 42(4): 1363-1373.
[2]	卓耀彬, 吕碧飞, 宋小文, 杨辰龙, 叶晓平, 陈旭绍. 玻璃管水平拉制成型过程的数值模拟[J]. 硅酸盐通报, 2023, 42(3): 1096-1105.
[3]	张梦宇, 李太, 杜汕霖, 黄振玲, 赵亮, 吕国强, 马文会. 直拉法单晶硅制备过程控氧技术研究进展[J]. 硅酸盐通报, 2022, 41(9): 3259-3271.
[4]	陈冠宇, 吴南, 杨康, 王元帅, 孙旭东, 李晓东. 金属离子和柠檬酸的配比对Y₂O₃-MgO纳米粉体及其纳米复相陶瓷性能的影响[J]. 硅酸盐通报, 2022, 41(5): 1788-1796.
[5]	陈迎雪, 廖宜顺, 万方琪, 陈明洋, 余竞硕. 缓凝剂对氯氧镁水泥水化历程的影响[J]. 硅酸盐通报, 2022, 41(4): 1222-1228.
[6]	刘士朋, 张欢欢, 程金科. 电解锰渣中氨氮的草酸浸取工艺及机理研究[J]. 硅酸盐通报, 2022, 41(2): 715-724.
[7]	冯圣霞, 杨敏, 张煜, 段江飞, 贺维龙, 李瑞. 电解锰渣中Mn²⁺的固化及动力学研究[J]. 硅酸盐通报, 2021, 40(7): 2313-2319.
[8]	张歆, 刘方, 朱健, 陈祖拥. 基于电解锰渣-磷石膏复合胶凝材料的制备与表征[J]. 硅酸盐通报, 2021, 40(5): 1610-1619.
[9]	韩康, 管学茂, 王燕峰, 刘松辉, 李一凡. 加压水溶液法制备工艺对α型高强石膏性能的影响[J]. 硅酸盐通报, 2021, 40(5): 1620-1630.
[10]	李佳欣;欧哲顺;文建鑫;文蓝萱;孙朋;李佳. 碱热活化EMR基地聚合物对Cd2+和Pb2+的固化[J]. 硅酸盐通报, 2020, 39(5): 1566-1572.
[11]	尤晓宇;王家伟;王海峰;赵平源. 混料含水率对电解锰渣免烧砖性能的影响[J]. 硅酸盐通报, 2020, 39(10): 3311-3315.
[12]	谈翔;李月明;王竹梅;高轶群;沈宗洋;乐少文;濮秦衡. 以CA为络合剂水热法合成硅酸锆粉体的研究[J]. 硅酸盐通报, 2019, 38(6): 1694-169.
[13]	胡明玉;樊财进;叶晓春;刘章君. 工艺参数对煤矿废弃物泡沫隔热陶瓷孔结构和力学性能的影响[J]. 硅酸盐通报, 2019, 38(3): 627-633.
[14]	孙朋;李佳欣;吕莹;乌日拉格;马梦雨;文建鑫;李佳. 碱热预处理电解锰渣对制备地质聚合物的影响[J]. 硅酸盐通报, 2019, 38(12): 3746-375.
[15]	彭秋菊;李佳;杜冬云;叶恒朋. 响应面法优化电解锰渣的微波活化有效硅工艺条件[J]. 硅酸盐通报, 2018, 37(8): 2548-2554.