电解锰渣基复合材料制备及对Cd2+的去除研究

doi:10.19964/j.issn.1006-4990.2025-0113

Abstract

Abstract:

In this study，Ca-Fe-Mn composite materials（CFM） were prepared by acid leaching-co-precipitation method for the resource utilisation of electrolytic manganese residue（EMR） and the treatment of cadmium-containing wastewater to systematically investigate the removal efficacy and mechanism of Cd²⁺.The effects of CFM dosage（0.2~1.5 g/L），initial pH（2.0~7.0） and reaction temperature（303~323 K） were investigated to elucidate the Cd²⁺ removal mechanism by combining with the adsorption kinetics，isothermal model fitting，and characterisation by X-ray diffractometer（XRD） and scanning electron microscope（SEM）.The results showed that the Cd²⁺ concentration in the effluent was reduced to below 0.1 mg/L when the dosage of CFM was 1.0 g/L，which met the limit value of “Comprehensive Wastewater Discharge Standard”（GB 8978—1996）.The maximum theoretical adsorption capacity of 129.96 mg/g was achieved at 323 K in a wide range of pH 3.0~7.0，and the Cd²⁺ removal rate was >99%.The adsorption process was conformed to the quasi-secondary kinetic model（R²>0.99） and Langmuir model （R²>0.98），which indicated that the removal of Cd²⁺ by CFM was a monolayer adsorption with chemisorption as the main method，and the rate of the whole adsorption process was mainly controlled by surface diffusion.The characterisation results demonstrated that the Cd²⁺ removal mechanism was a synergistic effect of surface precipitation，electrostatic attraction，interlayer intercalation and homogeneous substitution.The material combined high adsorption efficiency，wide pH adaptability and stability，and the process was simple and low cost，which provided a new way for EMR resourcefulness and heavy metal pollution control.

Key words: electrolytic manganese residue, removal Cd²⁺, acid leaching-co-precipitation, Ca-Fe-Mn composite materials

CLC Number:

TQ137.1

HAN Qingwen, YUAN Jiaxin, ZHAN Wei, HUANG Ping, NAN Fangming, CHEN Donghui, TAN Jie. Study on preparation of electrolytic manganese slag-based composites and their Cd²⁺ removal[J]. Inorganic Chemicals Industry, 2026, 58(3): 85-95.

Figures/Tables 18

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References 39

[1]	BHATTACHARYYA K，SEN D， BANIK A K，et al.Adsorptive removal of cadmium from aqueous medium-a critical review［J］.Phy-sics and Chemistry of the Earth， A/B/C Parts，2024，134：103538.
[2]	兰馨，郭帅庭，李彬.吸附法处理水中重金属的解吸附研究进展［J］.山东化工，2020，49（10）：81-82，84.
	LAN Xin， GUO Shuaiting， LI Bin.Reviews on desorption of heavy metal in water by adsorption method［J］.Shandong Chemical Industry，2020，49（10）：81-82，84.
[3]	董馨予，王海峰，贺跃，等.电解锰渣的浸出毒性分析及无害化处理［J］.无机盐工业，2023，55（5）：85-90.
	DONG Xinyu， WANG Haifeng， HE Yue，et al.Exleaching toxicity analysis and harmless treatment of electrolytic manganese resi-due［J］.Inorganic Chemicals Industry，2023，55（5）：85-90.
[4]	HE Dejun， SHU Jiancheng， WANG Rong，et al.A critical review on approaches for electrolytic manganese residue treatment and disposal technology：Reduction，pretreatment，and reuse［J］.Journal of Hazardous Materials，2021，418：126235.
[5]	李家乐，万廷勇，柯平超，等.电解锰渣无害化与资源化处理技术研究进展［J］.无机盐工业，2025，57（12）：Doi：10.19964/j.issn.1006-4990.2025-0126.
	LI Jiale， WAN Tingyong， KE Pingchao，et al.Research progress on harmless and resource treatment technology of electrolytic manganese residue［J］.Inorganic Chemicals Industry，2025，57（12）：Doi：10.19964/j.issn.1006-4990.2025-0126.
[6]	熊鑫，谢更新，晏铭，等.黏土矿物复合材料固化电解锰渣中Mn的研究［J］.环境科学与技术，2022，45（9）：57-63.
	XIONG Xin， XIE Gengxin， YAN Ming，et al.Study on solidification efficiency of Mn in electrolytic manganese residue by clay mi-neral composites［J］.Environmental Science & Technology，2022，45（9）：57-63.
[7]	王鹏星，祝楚微，汪玉碧，等.电解锰渣有价元素回收及有害物质处理技术研究进展［J］.化工矿物与加工，2022，51（7）：1- 9.
	WANG Pengxing， ZHU Chuwei， WANG Yubi，et al.Research progress of the technology for recovery of the valuable elements from electrolytic manganese slag and processing hazardous substances［J］.Industrial Minerals & Processing，2022，51（7）：1-9.
[8]	FU Yong， QIAO Hongxia， FENG Qiong，et al.Review of new methods for resource utilisation of electrolytic manganese residue and its application in building materials［J］.Construction and Building Materials，2023，401：132901.
[9]	SU Huili， ZHOU Wentao， Xianjun LYU，et al.Remediation treatment and resource utilization trends of electrolytic manganese residue［J］.Minerals Engineering，2023，202：108264.
[10]	孙煜琳，李杰瑞，苏向东，等.电解锰渣性质的研究进展及资源化利用展望［J］.山东化工，2022，51（1）：102-105.
	SUN Yulin， LI Jierui， SU Xiangdong，et al.Research progress on properties on electrolytic manganese slag and prospect of resource utilization［J］.Shandong Chemical Industry，2022，51（1）：102-105.
[11]	唐雪莲，李会泉，胡应燕，等.电解锰渣资源化回收利用技术研究进展及“双碳”影响评估［J］.有色金属（冶炼部分），2024（11）：177-186.
	TANG Xuelian， LI Huiquan， HU Yingyan，et al.Research progress on resource recovery and utilization of electrolytic manganese slag and impact assessment of carbon peak and carbon neutrality［J］.Nonferrous Metals（Extractive Metallurgy），2024（11）：177-186.
[12]	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.
[13]	孙燕，蓝际荣，郭莉，等.利用电解锰渣制备As（Ⅲ）吸附材料及其性能研究［J］.化工学报，2019，70（6）：2377-2385.
	SUN Yan， LAN Jirong， GUO Li，et al.Preparation of As（Ⅲ） adsorbent material by electrolytic manganese slag and its properti-es［J］.CIESC Journal，2019，70（6）：2377-2385.
[14]	马梦雨，魏华，宋小龙，等.电解锰渣-方解石复合吸附剂对水中镉的吸附［J］.非金属矿，2020，43（3）：89-92.
	MA Mengyu， WEI Hua， SONG Xiaolong，et al.Adsorption behaviors of Cd（Ⅱ） by electrolytic manganese residues-calcite composite adsorbent［J］.Non-Metallic Mines，2020，43（3）：89-92.
[15]	马时成.利用锰渣制备吸附剂及对Cu（Ⅱ）的吸附研究［D］.贵阳：贵州师范大学，2020.
	MA Shicheng.Preparation of absorbent based on manganese residue and adsorption of Cu（Ⅱ）［D］.Guiyang：Guizhou normal University，2020.
[16]	魏华，宋小龙，杨秀端，等.电解锰渣-壳聚糖复合吸附剂对Cr（Ⅵ）的吸附［J］.非金属矿，2021，44（6）：101-104.
	WEI Hua， SONG Xiaolong， YANG Xiuduan，et al.Adsorption behaviors of Cr（Ⅵ） by electrolytic manganese residues-chitosan adsorbent［J］.Non-Metallic Mines，2021，44（6）：101-104.
[17]	TOPARE N S， WADGAONKAR V S.A review on application of low-cost adsorbents for heavy metals removal from wastewater［J］.Materials Today：Proceedings，2023，77：8-18.
[18]	GAO Ming， WANG Wei， YANG Hongbing，et al.Efficient removal of fluoride from aqueous solutions using 3D flower-like hierarchical zinc-magnesium-aluminum ternary oxide microsphe-res［J］.Chemical Engineering Journal，2020，380：122459.
[19]	MA Mengyu， DU Yaguang， BAO Shenxu，et al.Removal of cadmium and lead from aqueous solutions by thermal activated electrolytic manganese residues［J］.Science of the Total Environment，2020，748：141490.
[20]	YIN Guangcai， CHEN Xingling， SARKAR B，et al.Co-adsorpt-ion mechanisms of Cd（Ⅱ） and As（Ⅲ） by an Fe-Mn binary oxide biochar in aqueous solution［J］.Chemical Engineering Journal，2023，466：143199.
[21]	MA Mengyu， WANG Ting， KE Xuan，et al.A novel slag composite for the adsorption of heavy metals：Preparation，characterization and mechanisms［J］.Environmental Research，2023，216：114442.
[22]	LAN Jirong， SUN Yan， GUO Li，et al.Highly efficient removal of As（Ⅴ） with modified electrolytic manganese residues（M-EMRs） as a novel adsorbent［J］.Journal of Alloys and Compounds，2019，811：151973.
[23]	ZONG Yiming， WANG Xinxiang， ZHANG Hao，et al.Preparation of a ternary composite based on water caltrop shell derived biochar and gelatin/alginate for cadmium removal from contamina-ted water：Performances assessment and mechanism insight［J］.International Journal of Biological Macromolecules，2023，234：123637.
[24]	JI Xianguo， LIU Yucan， GAO Zhonglu，et al.Efficiency and mechanism of adsorption for imidacloprid removal from water by Fe-Mg co-modified water hyacinth-based biochar：Batch adsorption，fixed-bed adsorption，and DFT calculation［J］.Separation and Purification Technology，2024，330：125235.
[25]	BEHBAHANI E S， DASHTIAN K， GHAEDI M.Fe₃O₄-FeMoS₄：Promise magnetite LDH-based adsorbent for simultaneous removal of Pb（Ⅱ），Cd（Ⅱ），and Cu（Ⅱ） heavy metal ions［J］.Jo-urnal of Hazardous Materials，2021，410：124560.
[26]	SONG Wen， ZHANG Xue， ZHANG Lu，et al.Removal of various aqueous heavy metals by polyethylene glycol modified MgAl-LDH：Adsorption mechanisms and vital role of precipitation［J］.Journal of Molecular Liquids，2023，375：121386.
[27]	HOSSAIN M T， KHANDAKER S， BASHAR M M，et al.Simultaneous toxic Cd（Ⅱ） and Pb（Ⅱ） encapsulation from contaminated water using Mg/Al-LDH composite materials［J］.Journal of Molecular Liquids，2022，368：120810.
[28]	WANG Yifan， LI Jianen， XU Liang，et al.EDTA functionalized Mg/Al hydroxides modified biochar for Pb（Ⅱ） and Cd（Ⅱ） removal：Adsorption performance and mechanism［J］.Separation and Purification Technology，2024，335：126199.
[29]	YIN Guangcai， SONG Xiaowang， TAO Lin，et al.Novel Fe-Mn binary oxide-biochar as an adsorbent for removing Cd（Ⅱ） from aqueous solutions［J］.Chemical Engineering Journal，2020，389：124465.
[30]	AL-GHOUTI M A， DA’ANA D A.Guidelines for the use and interpretation of adsorption isotherm models：A review［J］.Journal of Hazardous Materials，2020，393：122383.
[31]	XIAO Wei， LIAO Yumei， DENG Ling，et al.Simultaneous removal of arsenic and cadmium in aqueous solution by a novel hydrotalcite-like absorbent FeMnCa-LDHs［J］.Inorganic Chemistry Communications，2024，163：112312.
[32]	NGUYEN H K D， VAN NGUYEN H， NGUYEN V A.Effect of synthetic conditions on the structure of mesoporous Mg-Al-Co hydrotalcite［J］.Journal of Molecular Structure，2018，1171：25- 32.
[33]	XU Shaodong， LI Dong， GUO Xueyi，et al.Selenium（Ⅵ） removal from caustic solution by synthetic Ca-Al-Cl layered double hydroxides［J］.Transactions of Nonferrous Metals Society of China，2019，29（8）：1763-1775.
[34]	BIAN Liang， NIE Jianan， JIANG Xiaoqiang，et al.Selective adsorption of uranyl and potentially toxic metal ions at the core-shell MFe₂O₄-TiO₂（M=Mn，Fe，Zn，Co，or Ni） nanoparticles［J］.Journal of Hazardous Materials，2019，365：835-845.
[35]	LIU Bo， YUE Bo， HE Lili，et al.Synergistic solidification and mechanism research of electrolytic manganese residue and coal fly ash based on C-A-S-H gel material［J］.Journal of Environmental Management，2024，365：121600.
[36]	ZHU Jin， BAIG S ALI， SHENG Tiantian，et al.Fe₃O₄ and MnO₂ assembled on honeycomb briquette cinders（HBC） for arsenic removal from aqueous solutions［J］.Journal of Hazardous Materials，2015，286：220-228.
[37]	LAN Jirong， SUN Yan， HUANG Ping，et al.Using Electrolytic Manganese Residue to prepare novel nanocomposite catalysts for efficient degradation of Azo Dyes in Fenton-like processes［J］.Chemosphere，2020，252：126487.
[38]	DENG Jiahui， CHENG Yalin， LIU Min，et al.Fe-Mn co-embed carbon spheres for aqueous divalent Cd removal［J］.Colloids and Surfaces A：Physicochemical and Engineering Aspects，2021，612：126013.
[39]	LI Mengke， HE Zhiguo， ZHONG Hui，et al.Highly efficient persulfate catalyst prepared from modified electrolytic manganese residues coupled with biochar for the roxarsone removal［J］.Journal of Environmental Management，2023，328：116945.

质量浓度/ （mg·L^-1）	准一级动力学模型			准二级动力学模型			Elovich模型
质量浓度/ （mg·L^-1）	q_e/ （mg·g^-1）	k₁/ h^-1	R²	q_e/ （mg·g^-1）	k₂/ （g·mg^-1·h^-1）	R²	β/ （mg·g^-1）	α/ （mg·g^-1·min^-1）	R²
25	2.28	1.42	0.684 9	25.48	6.40	1.000 0	0.39	3.07	0.811 4
50	16.56	1.21	0.829 1	55.04	0.47	0.999 9	0.14	10.31	0.935 4
75	50.48	1.24	0.945 5	68.12	0.12	0.999 8	0.10	22.74	0.966 0

质量浓度/ （mg·L^-1）	表面扩散阶段			孔扩散阶段			平衡阶段
质量浓度/ （mg·L^-1）	q_t / （mg·g^-1）	k_p，1/ （mg·g^-1·min^-1/2）	R²	q_t / （mg·g^-1）	k_p，2/ （mg·g^-1·min^-1/2）	R²	C/ （mg·g^-1）	k_p，3/ （mg·g^-1·min^-1/2）	R²
25	60.56	0.34	0.843 6	20.55	4.83	0.977 9	3.45	8.65	0.991 0
50	53.41	0.07	0.890 9	30.87	2.88	0.976 4	8.97	7.57	0.997 6
75	25.34	0.01	0.929 8	24.67	0.10	0.636 0	5.07	5.98	0.968 6

温度/ K	Langmuir			Freundlich			DRK			Temkin
温度/ K	q_e/ （mg·g^-1）	K_L/ （L·mg^-1）	R²	1/n	K_F/［（mg·g^-1）· （L·mg^-1）^1/ⁿ ］	R²	E	q_m/ （mg·g^-1）	R²	B₁	K_t / （L·mol^-1）	R²
303	109.20	0.96	0.852 5	0.22	48.32	0.959 9	2 761.67	77.03	0.973 6	54.36	1.31	0.952 1
313	113.05	5.99	0.939 6	0.14	69.44	0.885 3	4 506.94	111.85	0.999 6	73.60	1.18	0.931 1
323	129.96	9.77	0.989 1	0.12	87.10	0.745 2	5 918.22	123.98	0.971 9	92.57	1.20	0.936 6

不同材料	最大吸附量/ （mg·g^-1）	实验条件
Fe₃O₄-FeMoS₄^［25］	140.50	pH=5
Mg-Al LDHs^［26］	69.11	pH=5~6
Mg/Al-LDHs^［27］	24.34	pH=3~7
E-Mg/Al-LDH BC^［28］	125.23	pH=5，298 K
FMBC^［29］	95.23	pH=5，298 K
CFM	129.96	pH=3.0~7.0，323 K

温度/ K	ΔG/ （kJ·mol^-1）	ΔH/ （kJ·mol^-1）	ΔS/ （kJ·mol^-1·K^-1）	R²
293	-8.57	85.42	0.32	0.95
303	-11.78
313	-14.98
323	-18.19

National Inorganic Salts Information Center

Inorganic Acid-Base-Salt Committee of CIESC

Study on preparation of electrolytic manganese slag-based composites and their Cd²⁺ removal

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Study on preparation of electrolytic manganese slag-based composites and their Cd2+ removal