电解锰渣为主多源固废制备多孔陶粒及固定重金属锰的机理研究

doi:10.19964/j.issn.1006-4990.2024-0491

Abstract

Abstract:

A lightweight porous ceramsite was successfully synthesized using electrolytic manganese residue（EMR） as the primary raw material，supplemented by municipal sludge，graphite tailings，and bentonite.The pore structure evolution mechanism of the ceramsite was investigated through advanced analytical techniques，including X-ray diffraction（XRD），stereomicroscopy，and Fourier-transform infrared spectroscopy（FT-IR）.Additionally，the curing mechanism of Mn²⁺ was elucidated.The experimental results indicated that optimal conditions，determined via single-factor optimization，including a formulation comprising of 35% EMR and 35% sludge，25% of graphite tailings，a sintering temperature of 1 130 ℃，and a sintering duration of 15 minutes.Under these conditions，the resulting EMR-based ceramsite exhibited favorable physical properties：A bulk density of 651 kg/m³，an apparent density of 1 406 kg/m³，a compressive strength of 3.78 MPa，and a one-hour water absorption rate of 5.36%.During high-temperature sintering，the formation of liquid phase on the ceramsite surface effectively reduced water absorption.Internally，this liquid phase encapsulated gas bubbles，forming a closed-pore structure.The leaching behavior of Mn²⁺ was primarily attributed to MnSO₄ present in the EMR.The thermal decomposition of MnSO₄ was found to be reversible.CO and SO₂ gases trapped within the closed pores inhibited its decomposition，thereby influencing Mn²⁺ fixation.Furthermore，the presence of Fe₂O₃ from the sludge lowered the sintering temperature and promoted the formation of high-temperature liquid phases，which contributed to the retention of undecomposed MnSO₄.Consequently，increasing the EMR and sludge content from 35% to 45% led to an increase in Mn²⁺ leaching concentration from 0.33 mg/L to 0.84 mg/L.The immobilization mechanism of manganese involved both physical and chemical processes.Physically，the dense structure formed by the high-temperature liquid phase encapsulated Mn species.Chemically，Mn²⁺ participated in the formation of manganese-wollastonite and spinel-type ferrites under elevated temperatures，achieving effective chemical stabilization.This study not only significantly enhanced the utilization rate of EMR but also demonstrated a viable approach for the co-processing of multiple solid wastes into functional materials，offering practical insights and technical support for the resource recovery of large-volume solid waste.

Key words: electrolytic manganese residue, sludge, porous, ceramite, heavy metal solidification

CLC Number:

X757

LIANG Qingyang, XUE Fei, HUANG Xuquan, ZHAO Xiaorong, WANG Haojie, HAN Zilong, WANG Jun. Study on mechanism of preparation of porous ceramsite and fixation of heavy metal manganese from electrolytic manganese slag and multi-source solid waste[J]. Inorganic Chemicals Industry, 2025, 57(8): 102-109.

Figures/Tables 10

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References 24

[1]	HE Shichao， JIANG Daoyan， HONG Minghao，et al.Hazard-free treatment and resource utilisation of electrolytic manganese residue：A review［J］.Journal of Cleaner Production，2021，306：127224.
[2]	WEN Quan， LIU Bo， ZHANG Junjie，et al.Efficient leaching of manganese from electrolytic manganese residue and recovery of the leaching solution：Reuse and purification［J］.Separation and Purification Technology，2024，332：125648.
[3]	HE Weilong， LI Rui， ZHANG Yu，et al.Synergistic use of electrolytic manganese residue and barium slag to prepare belite-sulphoaluminate cement study［J］.Construction and Building Materials，2022，326：126672.
[4]	HE Dejun， CHEN Mengjun， LIU Hui.Electrolytic manganese residue pretreated by filter press-water washing and carbide slag：Manganese recycling，depth harmless and dispersion［J］.Process Safety and Environmental Protection，2024，186：1297-1306.
[5]	黄川，王飞，谭文发，等.电解锰渣烧制陶粒的试验研究［J］.非金属矿，2013，36（5）：11-13.
	HUANG Chuan， WANG Fei， TAN Wenfa，et al.Experimental study of sintered electrolytic manganese residue ceramic granules［J］.Non-Metallic Mines，2013，36（5）：11-13.
[6]	胡超超，王里奥，詹欣源，等.城市生活垃圾焚烧飞灰与电解锰渣烧制陶粒［J］.环境工程学报，2019，13（1）：177-185.
	HU Chaochao， WANG Li′ao， ZHAN Xinyuan，et al.Preparation of ceramsite with MSWI fly ash and electrolytic manganese residues［J］.Chinese Journal of Environmental Engineering，2019，13（1）：177-185.
[7]	叶东东，徐子芳，赵怡梵，等.电解锰渣陶粒共烧结温度影响机理研究［J］.材料导报，2022，36（11）：89-94.
	YE Dongdong， XU Zifang， ZHAO Yifan，et al.Influence mechanism of EMR ceramsite co-sintering temperature［J］.Materials Reports，2022，36（11）：89-94.
[8]	KE Xuan， CHEN Xiaohong， WANG Ting，et al.Immobilization mechanism of Mn²⁺ in electrolytic manganese residue using sintered ceramsites prepared by alkali-mechanical-roasting method［J］.Journal of Environmental Chemical Engineering，2024，12（2）：112419.
[9]	张云昊，柴轶凡，安胜利，等.选冶固废制备陶粒技术研究现状及展望［J］.金属矿山，2022（7）：259-266.
	ZHANG Yunhao， CHAI Yifan， AN Shengli，et al.Research status and prospects of ceramsite preparation technology using selecting and smelting solid waste［J］.Metal Mine，2022（7）：259-266.
[10]	LONG Yuyang， PU Kai， YANG Yuqiang，et al.Preparation of High-strength ceramsite from municipal solid waste incineration fly ash and clay based on CaO-SiO₂-Al₂O₃ system［J］.Construction and Building Materials，2023，368：130492.
[11]	PEI Jiannan， PAN Xiaolin， QI Yafei，et al.Preparation and characterization of ultra-lightweight ceramsite using non-expanded clay and waste sawdust［J］.Construction and Building Materials，2022，346：128410.
[12]	高育欣，李坤杰，马建峰，等.城市污泥掺量对煤气化渣陶粒性能影响［J］.硅酸盐通报，2021，40（2）：579-586.
	GAO Yuxin， LI Kunjie， MA Jianfeng，et al.Influence of municipal sludge dosage on performance of coal gasification slag ceramsite［J］.Bulletin of the Chinese Ceramic Society，2021，40（2）：579-586.
[13]	罗晖，钱觉时，陈伟，等.污水污泥页岩陶粒烧胀特性［J］.硅酸盐学报，2010，38（7）：1247-1252.
	LUO Hui， QIAN Jueshi， CHEN Wei，et al.Calcining expansion behavior of sewage sludge with shale［J］.Journal of the Chinese Ceramic Society，2010，38（7）：1247-1252.
[14]	王燕琳，贾冠华，杨凤玲.固硫灰-污泥陶粒的制备及其性能影响研究［J］.非金属矿，2022，45（3）：98-102，106.
	WANG Yanlin， JIA Guanhua， YANG Fengling.Study on preparation and properties of CFBC fly ash-sludge ceramsite［J］.Non-Metallic Mines，2022，45（3）：98-102，106.
[15]	李煜，赵伟，张兴华，等.高强萤石尾矿陶粒的制备及其性能研究［J］.无机盐工业，2023，55（5）：100-108，136.
	LI Yu， ZHAO Wei， ZHANG Xinghua，et al.Syudy on preparation of high-strength ceramsite from fluorite tailings and its properti-
	es［J］.Inorganic Chemicals Industry，2023，55（5）：100-108，136.
[16]	JIANG Jun， CHEN Song， JIN Chao，et al.Preparation and properties of high-strength lightweight aggregate ceramsite from nepheline tailings［J］.Construction and Building Materials，2023，368：130458.
[17]	刘明伟，许国仁，李圭白.Fe₂O₃对污泥与底泥制备轻质陶粒性能的影响［J］.哈尔滨工业大学学报，2012，44（10）：18- 21.
	LIU Mingwei， XU Guoren， LI Guibai.Effect of Fe₂O₃ on the characteristics of lightweight aggregate made from sewage sludge and river sediment［J］.Journal of Harbin Institute of Technology，2012，44（10）：18-21.
[18]	罗树琼，江壮壮，张海波，等.微波技术烧成拜耳法赤泥-渣土陶粒［J］.非金属矿，2022，45（4）：97-101，106.
	LUO Shuqiong， JIANG Zhuangzhuang， ZHANG Haibo，et al.Microwave technology sintering bayer red mud-muck ceramsites［J］.Non-Metallic Mines，2022，45（4）：97-101，106.
[19]	王志明，孙玉宁，王永龙，等.XRD和FTIR的掺硅酸钠富水材料强度演化机制［J］.光谱学与光谱分析，2019，39（10）： 3199.
	WANG Zhiming， SUN Yuning， WANG Yonglong，et al.Strength evolution mechanism of water-rich material blending with sodium silicate by XRD and FTIR［J］.Spectroscopy and Spectral Analysis，2019，39（10）：3199.
[20]	WANG Chaoqiang， DUAN Dingyi， HUANG Deming，et al.Lightweight ceramsite made of recycled waste coal gangue & municipal sludge：Particular heavy metals，physical performance and human health［J］.Journal of Cleaner Production，2022，376：134309.
[21]	XU Wei， ZHANG Yuyue， YAN Jun，et al.Microstructure and properties of high-strength lightweight ceramsites customised with ultra-fine copper tailings［J］.Construction and Building Materials，2024，429：136433.
[22]	PEI Jiannan， PAN Xiaolin， LV Zhongyang，et al.Synergistic mechanism to prepare ultra-lightweight ceramsite using multiple industrial solid wastes［J］.Construction and Building Materials，2024，425：136139.
[23]	罗忠涛，肖宇领，杨久俊，等.垃圾焚烧飞灰有毒重金属固化稳定技术研究综述［J］.环境污染与防治，2012，34（8）：58-62，68.
	LUO Zhongtao， XIAO Yuling， YANG Jiujun，et al.Progress on the solidification of toxic heavy metals in municipal solid waste incineration fly ash［J］.Environmental Pollution & Control，2012，34（8）：58-62，68.
[24]	柯国鹏，徐浩，杨如柱，等.典型固废基烧结陶粒工艺、重金属转化行为及其应用现状分析［J］.硅酸盐通报，2024，43（8）：2912-2923.
	KE Guopeng， XU Hao， YANG Ruzhu，et al.Process，heavy metal transformation behavior of typical solid waste-based sintering ceramsite and its application status analysis［J］.Bulletin of the Chinese Ceramic Society，2024，43（8）：2912-2923.

物质	w （SiO₂）	w （Al₂O₃）	w （Fe₂O₃）	w （SO₃）	w （CaO）	w （MgO）	w （P₂O₅）	w （K₂O）	w （MnO）
EMR	29.04	19.49	4.02	19.49	5.92	1.89	—	2.17	1.82
城市污泥	27.02	14.22	26.26	5.45	8.25	1.91	11.91	2.71	—
石墨尾矿	55.38	26.47	7.61	0.63	1.31	2.60	0.12	4.67	—
膨润土	70.08	16.53	2.08	—	1.26	2.71	—	1.85	—

编号	w（EMR）/ %	w（城市污泥）/%	w（石墨尾矿）/%	w（膨润土）/%	液固比
E1	45	45	5	5	0.50
E2	35	35	25	5	0.50
E3	25	25	45	5	0.50
E4	15	15	65	5	0.50

配方	烧结温度/℃	烧结时间/min	形态的影响
E1、E2	1 100	15	陶粒强度小，表面粗糙
E1、E2	1 120	15	表面略光滑，内部粘连性不强
E1、E2	1 130	15	表面光滑，强度适中
E1、E2	1 150	15	过度膨胀，粘连坩埚底部
E1、E2	1 200	15	完全液化在坩埚底部
E1、E2	1 130	10	外观不够光滑
E1、E2	1 130	20	轻微粘连坩埚底部
E1、E2	1 130	30	粘连坩埚底部

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Study on mechanism of preparation of porous ceramsite and fixation of heavy metal manganese from electrolytic manganese slag and multi-source solid waste

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