电解锰渣中Mn2+的固化及动力学研究

摘要/Abstract

摘要： 电解锰渣(EMR)中大量可溶性锰会带来严重的环境问题,需要对其进行固化处理。本文利用CaO固化电解锰渣中Mn²⁺及其动力学机制,系统考察了CaO添加量、液固比、温度和反应时间对Mn²⁺固化率的影响。通过XRD、SEM-EDS对原EMR和预处理EMR的物相组成、表面形貌检测分析,探讨固化反应机理。结果表明,在CaO与EMR质量比6:100、液固比4:1、温度55 ℃、反应时间150 min条件下,Mn²⁺固化率为99.72%。机理研究表明,电解锰渣中Mn²⁺以MnO₂和MnOOH的形式固化。动力学分析结果表明,氧化钙固化Mn²⁺过程受化学反应和残留固体膜层扩散混合控制,反应表观活化能为11.713 5 kJ/mol。本研究提供了一种简单有效的改性锰渣方法,可用于指导锰渣可持续利用。

关键词: 电解锰渣, 氧化钙, 固化, 动力学, 活化能, 收缩未反应核模型

Abstract: The soluble manganese in electrolytic manganese residue (EMR) leads to serious environmental problems, and it’s important to solidify the soluble manganese. In this article, the immobilization of Mn²⁺ in EMR curing by CaO and its kinetic mechanism were studied. The effects of the content of CaO, liquid-solid ratio, temperature and reaction time on the Mn²⁺precipitation efficiency were investigated systematically. The structure and morphology of raw EMR and treated EMR were characterized by XRD and SEM-EDS. The results show that with the CaO:EMR mass ratio of 6:100, liquid:solid ratio of 4:1, temperature of 55 ℃, and reacting time of 150 min, the Mn²⁺ precipitation efficiency is 99.72%. The mechanism demonstrated that Mn²⁺ is immobilized in the form of groutite (MnOOH) and ramsdellite (MnO₂). The results of kinetics show that it is controlled by the chemical reaction and diffusion mixing of the residual solid film, and the apparent activation energy of the reaction is 11.713 5 kJ/mol. This study provides a simple and effective method to modify manganese residue, which can be applied to guide the sustainable utilization of manganese residue.

Key words: electrolytic manganese residue, calcium oxide, immobilization, kinetics, activation energy, shrinkage unreacted nucleus model

中图分类号:

X753

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.

FENG Shengxia, YANG Min, ZHANG Yu, DUAN Jiangfei, HE Weilong, LI Rui. Immobilization and Kinetics of Mn²⁺ in Electrolytic Manganese Residue[J]. BULLETIN OF THE CHINESE CERAMIC SOCIETY, 2021, 40(7): 2313-2319.

参考文献

[1] 杨晓红,向欣,薛希仕.电解锰渣酸浸实验条件探究[J].硅酸盐通报,2018,37(7):2326-2330.
YANG X H, XIANG X, XUE X S. Study on acid leaching experimental conditions of electrolytic manganese residue[J]. Bulletin of the Chinese Ceramic Society, 2018, 37(7): 2326-2330 (in Chinese).
[2] 张超,王帅,钟宏,等.电解锰渣无害化处理与资源化利用技术研究进展[J].矿产保护与利用,2019,39(3):111-118.
ZHANG C, WANG S, ZHONG H, et al. Review on decontamination and resource utilization of electrolytic manganese residue technology[J]. Conservation and Utilization of Mineral Resources, 2019, 39(3): 111-118 (in Chinese).
[3] 高武斌,王志增,赵伟洁,等.电解锰渣复合Fe-Mn-Cu-Co系红外辐射材料的制备及性能研究[J].功能材料,2015,46(6):6076-6080.
GAO W B, WANG Z Z, ZHAO W J, et al. Preparation and properties of electrolytic manganese slag composite Fe-Mn-Cu-Co based infrared radiation material[J]. Journal of Functional Materials, 2015, 46(6): 6076-6080 (in Chinese).
[4] 王积伟,周长波,杜兵,等.电解锰渣无害化处理技术[J].环境工程学报,2014,8(1):329-333.
WANG J W, ZHOU C B, DU B, et al. Harmless treatment technology of manganese slag[J]. Chinese Journal of Environmental Engineering, 2014, 8(1): 329-333 (in Chinese).
[5] 叶芬,成昊,徐丽,等.利用电解锰渣制备轻质多孔陶瓷块状材料的研究[J].无机盐工业,2018,50(10):62-65.
YE F, CHENG H, XU L, et al. Study on preparation of porous lightweight ceramic mass material with electrolytic manganese residue[J]. Inorganic Chemicals Industry, 2018, 50(10): 62-65 (in Chinese).
[6] 吴霜,王家伟,刘利,等.电解锰渣综合利用评述[J].无机盐工业,2016,48(4):22-25.
WU S, WANG J W, LIU L, et al. Review on comprehensive utilization of electrolytic manganese slag[J]. Inorganic Chemicals Industry, 2016, 48(4): 22-25 (in Chinese).
[7] ZHAN X Y, WANG L A, HU C C, et al. Co-disposal of MSWI fly ash and electrolytic manganese residue based on geopolymeric system[J]. Waste Management, 2018, 82: 62-70.
[8] LI J, LV Y, JIAO X K, 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.
[9] ZHANG Y L, LIU X M, XU Y T, et al. Synergic effects of electrolytic manganese residue-red mud-carbide slag on the road base strength and durability properties[J]. Construction and Building Materials, 2019, 220: 364-374.
[10] 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.
[11] WANG J, PENG B, CHAI L Y, et al. Preparation of electrolytic manganese residue-ground granulated blastfurnace slag cement[J]. Powder Technology, 2013, 241: 12-18.
[12] 胡春燕,于宏兵.电解锰渣制备陶瓷砖[J].硅酸盐通报,2010,29(1):112-115.
HU C Y, YU H B. Preparation of ceramic tiles using electrolytic manganese residue[J]. Bulletin of the Chinese Ceramic Society, 2010, 29(1): 112-115 (in Chinese).
[13] 尤晓宇,王家伟,王海峰,等.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.
YOU X Y, WANG J W, WANG H F, et al. Influence of water content of mixture on properties of unburned brick with electrolytic manganese slag[J]. Bulletin of the Chinese Ceramic Society, 2020, 39(10): 3311-3315 (in Chinese).
[14] 秦吉涛,王家伟,王海峰,等.水泥添加量对电解锰渣免烧砖性能的影响[J].硅酸盐通报,2017,36(10):3511-3515.
QIN J T, WANG J W, WANG H F, et al. Effect of cement addition on the properties of unburned brick of electrolytic manganese slag[J]. Bulletin of the Chinese Ceramic Society, 2017, 36(10): 3511-3515 (in Chinese).
[15] 徐风广.含锰废渣用于公路路基回填土的试验研究[J].中国锰业,2001,19(4):1-3
XU F G. Experimental research on application of Mn-slag to roadbed backfill[J]. China’s Manganese Industry, 2001, 19(4): 1-3 (in Chinese)
[16] ZHOU C B, WANG J W, WANG N F. Treating electrolytic manganese residue with alkaline additives for stabilizing manganese and removing ammonia[J]. Korean Journal of Chemical Engineering, 2013, 30(11): 2037-2042.
[17] CHEN H L, LONG Q, ZHANG Y T, et al. A novel method for the stabilization of soluble contaminants in electrolytic manganese residue: using low-cost phosphogypsum leachate and magnesia/calcium oxide[J]. Ecotoxicology and Environmental Safety, 2020, 194: 110384.
[18] SHU J C, LI B, CHEN M J, et al. An innovative method for manganese (Mn²⁺) and ammonia nitrogen ($NH_{4}^{+}$—N) stabilization/solidification in electrolytic manganese residue by basic burning raw material[J]. Chemosphere, 2020, 253: 126896.
[19] CHEN H L, LIU R L, LIU Z H, et al. Immobilization of Mn and $NH_{4}^{+}$—N from electrolytic manganese residue waste[J]. Environmental Science and Pollution Research, 2016, 23(12): 12352-12361.
[20] 邹琴,刘海燕,谢华磊.电解锰渣碱浸提硅工艺及动力学研究[J].矿冶工程,2018,38(2):83-87.
ZOU Q, LIU H Y, XIE H L. Leaching process of electrolytic manganese slag by alkali solution and its kinetics[J]. Mining and Metallurgical Engineering, 2018, 38(2): 83-87 (in Chinese).
[21] 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. Researches on strengthen transformation method of manganese and ammonia nitrogen from electrolytic manganese residue[D]. Chongqing: Chongqing University, 2017 (in Chinese).
[22] 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.
[23] 陈红亮,张玉涛,张秋云,等.酸法还原浸出电解锰渣中锰和铁的工艺条件和动力学分析[J].硅酸盐通报,2017,36(8):2844-2849.
CHEN H L, ZHANG Y T, ZHANG Q Y, et al. Technology conditions and kinetics analysis of manganese and iron ions leaching from electrolytic manganese residue by acid reduction[J]. Bulletin of the Chinese Ceramic Society, 2017, 36(8): 2844-2849 (in Chinese).

电解锰渣中Mn²⁺的固化及动力学研究

Immobilization and Kinetics of Mn²⁺ in Electrolytic Manganese Residue

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]	阮永芬, 杨冰, 吴龙, 刘克文, 朱强. 化学改良湖相泥炭质土的配合比设计及其应用[J]. 硅酸盐通报, 2021, 40(7): 2240-2247.
[2]	王伟齐, 孙红, 葛修润. 碱激发作用下海相软土固化研究[J]. 硅酸盐通报, 2021, 40(7): 2248-2255.
[3]	乔京生, 王旭影, 王冠泓, 赵建业. 粒化高炉矿渣微粉固化淤泥质土的动力特性及微观机理[J]. 硅酸盐通报, 2021, 40(7): 2306-2312.
[4]	崔聪聪, 李珊, 李伟, 包建勋, 张舸, 王功. 立体光固化3D打印成型碳化硅陶瓷的烧结特性[J]. 硅酸盐通报, 2021, 40(6): 1937-1942.
[5]	陈汝菲, 段文艳, 王功, 刘兵山, 刘晓冬, 李鑫. Si₃N₄粉体的表面改性及其对立体光刻成型的影响[J]. 硅酸盐通报, 2021, 40(6): 1957-1964.
[6]	韩卓群, 李伶, 刘时浩, 邱坤, 王守兴, 刘福田. 光固化ZrO₂陶瓷料浆的流变性能研究[J]. 硅酸盐通报, 2021, 40(6): 1965-1971.
[7]	李人骏, 张玲, 张晓序, 王志刚, 胡於江. TiO₂的添加对铝铬固溶体烧结动力学的影响[J]. 硅酸盐通报, 2021, 40(6): 2104-2109.
[8]	冯庆革, 梁思亮, 杨义, 柏秀奎, 王东波, 赵政术, 黄丽霖. FeS与TiO₂共存对水泥熟料中Ti的固化与迁移及矿物组成的影响[J]. 硅酸盐通报, 2021, 40(5): 1453-1461.
[9]	刘柳, 胡佩伟, 高润琴, 程港莉, 姚瑶. 纳米零价铁强化高岭石去除水中Cr(VI)及机制研究[J]. 硅酸盐通报, 2021, 40(5): 1529-1535.
[10]	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.
[11]	高金瑞, 饶美娟, 张克昌, 邓青山. 铁相组分对铁相和高铁低钙水泥熟料水化性能及抗侵蚀性能影响[J]. 硅酸盐通报, 2021, 40(4): 1097-1102.
[12]	刘广英, 郭向宇, 戴仕炳, 戴仕宝, 满晓磊. 煅烧温度对天然水硬石灰物理力学特性影响研究[J]. 硅酸盐通报, 2021, 40(3): 883-888.
[13]	许颖, 陈锐, 韦其颖, 徐婷婷. 活化牡蛎壳固化余泥渣土及其机理分析[J]. 硅酸盐通报, 2021, 40(3): 900-906.
[14]	胡盛, 张明浩, 胡卫兵. 反应时间对镁铝水滑石制备及其吸附性能的影响[J]. 硅酸盐通报, 2021, 40(3): 1022-1028.
[15]	王浩, 邓航, 刘数华. 锑尾矿粉基复合胶凝材料的制备及水化特性[J]. 硅酸盐通报, 2021, 40(2): 534-541.