不同堆存时间电解锰渣的理化特性分析

doi:10.16085/j.issn.1000-6613.2021-0823

摘要/Abstract

摘要：

渣场堆存的电解锰渣中含有大量易迁移的锰和氨氮，极易污染周边环境。本文系统研究了不同堆存时间（3个月~10年）电解锰渣的pH、含水率、电导率、金属总量、浸出毒性和化学形态等理化特性，采用X射线衍射（XRD）、扫描电子显微镜（SEM）、能谱仪（EDS）以及X射线光电子能谱（XPS）等分析手段，探察电解锰渣在不同堆存时间下的物相组成、微观形貌、表面电子价态等变化规律。研究结果表明，随着堆存时间增加，锰渣的pH、含水率和电导率下降，可溶性Mn²⁺、Ca²⁺、Mg²⁺、Se⁴⁺和NH $4 +$ -N浓度降低，其中可交换态和碳酸盐结合态的Mn是Mn元素流失的主要形态。同时，堆存10年的电解锰渣仍存在较大的环境污染风险，其中电解锰渣中的Cu、Cr、Cd、Pb、Zn等金属总量远超广西土壤背景值，Se⁴⁺的浸出浓度是《危险废物鉴别标准浸出毒性鉴别》（GB 5085.3—2007）中浓度限值的11倍，Mn²⁺和NH $4 +$ -N的浸出浓度是《污水综合排放标准》（GB/T 8978—1996）一级标准限值的102倍和45倍。不同堆存时间的电解锰渣中锰和氨氮主要以(NH₄)(Mn,Ca,Mg)PO₄·H₂O、(NH₄)₂SO₄、MnSO₄·H₂O、MnCO₃、Mn₂O₃、MnO₂等物相存在，含铁物相主要包括FeS₂、FeOOH、Fe₃O₄和Fe₂O₃等，且电解锰渣中还含有Al₄(OH)₈(Si₄O₁₀)、Al₂Mg₄(OH)₁₂(CO₃)·3H₂O和KAl(SO₄)₂·12H₂O等黏土矿物。此外，随着堆存时间的增加，电解锰渣的平均孔径减小，块状、柱状和绒球形的电解锰渣颗粒交错包裹现象增加，同时Fe(OH)₃胶体颗粒也逐渐转变成FeOOH、Fe₂O₃等含铁物相。本研究成果为电解锰渣无害化处理与资源化利用提供了基础理论支持。

关键词: 电解锰渣, 理化特性, 堆存时间, 锰, 氨氮

Abstract:

Electrolytic manganese residue (EMR) stored in the residue yard contains a large amount of manganese (Mn²⁺) and ammonia nitrogen (NH $4 +$ -N), which can easily migrate and pollute the surrounding environment. Therefore, the physical and chemical properties of EMR with different storage time (3 months to 10 years), such as pH, water content, conductivity, total metal content, leaching toxicity, chemical morphology and phase structure, were systematically studied. The phase composition, micro morphology and surface electronic valence of EMR with different storage time were analyzed by XRD, SEM and XPS. The results showed that with the storage time increased, pH, the water content, electrical conductivity and the contents of soluble Mn²⁺, Ca²⁺, Mg²⁺, Se⁴⁺ and NH $4 +$ -N decreased. Exchangeable and carbonates bound Mn were the main forms of Mn loss. EMR stored for 10 years still had a great risk of environmental pollution. The total amount of Cu, Cr, Cd, Pb, and Zn far exceeded the background value of Guangxi soil. The leaching concentration of Se⁴⁺ was 11 times of the concentration limit in 《Identification standards for hazardous wastes—Identification for extraction toxicity》 (GB 5085.3—2007). The leaching concentration of Mn²⁺ and NH $4 +$ -N were 102 times and 45 times of the first class standard limit of 《Integrated wastewater discharge standard》 (GB/T 8978—1996). The main forms of Mn²⁺ and NH $4 +$ -N in EMR with different storage time were (NH₄)(Mn,Ca,Mg)PO₄·H₂O, (NH₄)₂SO₄, MnSO₄·H₂O, MnCO₃, Mn₂O₃ and MnO₂. Iron-containing phases mainly included FeS₂, FeOOH, Fe₃O₄ and Fe₂O₃. And it also contained clay minerals, including Al₄(OH)₈(Si₄O₁₀), Al₂Mg₄(OH)₁₂(CO₃)·3H₂O and KAl(SO₄)₂·12H₂O. In addition, with increasing storage time, the average pore size of EMR decreased, and the phenomenon of crisscross inclusion of massive, columnar and ball like particles increased. The Fe(OH)₃ colloid particles gradually transformed into FeOOH, Fe₂O₃ and other iron-containing phases. The research results provided basic theoretical support for the harmless treatment and resource utilization of EMR.

Key words: electrolytic manganese residue, physical and chemical properties, storage times, manganese, ammonia nitrogen

中图分类号:

X753

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.

DENG Yaling, SHU Jiancheng, CHEN Mengjun, LEI Tianya, ZENG Xiangfei, YANG Yong, LIU Zuohua. Physical and chemical properties analysis of electrolytic manganese residue in different storage times[J]. Chemical Industry and Engineering Progress, 2022, 41(4): 2161-2170.

图/表 14

图1 不同堆存时间电解锰渣pH、含水率和电导率变化

表1 不同堆存时间电解锰渣的元素总量变化单位：mg·kg-1

堆存时间编号	Mn	Ca	Mg	Se	Cu	Cr	Cd	Pb	Zn	Fe	Al
a	71700	102500	18105	480	550	274	250	350	895	56400	13010
b	58150	90600	14955	340	535	295	150	345	1020	56600	14905
c	51200	74100	9960	305	521	240	120	380	695	59100	19790
d	37505	83250	8615	290	512	225	135	362	562	56650	16275
e	34960	96600	8165	260	523	230	110	350	600	68550	18145
f	29865	81350	8205	190	518	200	115	341	553	73850	22255

表2 土壤重金属污染评价标准 (mg·kg-1)

评价标准			Cu	Cr	Cd	Pb	Zn	Mn
土壤质量标准	Ⅰ	自然背景	35	90	0.2	35	100	—
		<6.5	50	150	0.3	250	200	—
	Ⅱ	6.5~7.5	100	200	0.3	300	250	—
		>7.5	100	250	0.6	350	300	—
	Ⅲ	＞6.5	400	300	1	500	500	—
广西土壤背景值			23.1	65.3	0.073	19.5	51.8	176

表3 不同堆存时间电解锰渣中各元素浸出浓度变化单位：mg·L-1

堆存时间编号	Mn²⁺	NH $4 +$ -N	Se⁴⁺	Pb²⁺	Cd²⁺	总Cr	Cu²⁺	Zn²⁺	Ni²⁺
a	1533	6675	8.7	0.73	0.12	0.32	45.3	38.1	3.5
b	859.3	6425	6.4	0.62	0.15	0.45	36.5	30.3	3.8
c	777.4	5675	15.2	0.63	0.26	0.41	37.2	27.2	4.2
d	772.5	2175	11.9	0.74	0.21	0.32	38.6	26.9	4.3
e	509.6	925	10.9	0.82	0.39	0.30	39.3	30.8	3.8
f	204.4	675	11.4	0.76	0.35	0.25	37.5	29.8	3.1
GB 8978—1996 一级	2.0	15.0	—	1.0	0.1	1.5	0.5	2.0	1.0

表3 不同堆存时间电解锰渣中各元素浸出浓度变化单位：mg·L-1

堆存时间编号	Mn²⁺	NH $4 +$ -N	Se⁴⁺	Pb²⁺	Cd²⁺	总Cr	Cu²⁺	Zn²⁺	Ni²⁺
a	1533	6675	8.7	0.73	0.12	0.32	45.3	38.1	3.5
b	859.3	6425	6.4	0.62	0.15	0.45	36.5	30.3	3.8
c	777.4	5675	15.2	0.63	0.26	0.41	37.2	27.2	4.2
d	772.5	2175	11.9	0.74	0.21	0.32	38.6	26.9	4.3
e	509.6	925	10.9	0.82	0.39	0.30	39.3	30.8	3.8
f	204.4	675	11.4	0.76	0.35	0.25	37.5	29.8	3.1
GB 8978—1996 一级	2.0	15.0	—	1.0	0.1	1.5	0.5	2.0	1.0

表4 不同堆存时间电解锰渣中总量锰、可溶性锰浓度、锰溶出率变化

堆存时间编号	总量锰/mg·kg^-1	可溶性锰/mg·L^-1	锰溶出率/%
a	71700	1533	19.2
b	58150	859.3	13.3
c	51200	777.4	13.7
d	37505	772.5	18.5
e	34960	509.6	13.1
f	29865	204.4	6.2

表5 不同堆存时间电解锰渣中总量锰和可溶性锰变化的相关性

项目	总量锰	可溶性锰
总量锰	1
可溶性锰	0.009**	1

图2 不同堆存时间电解锰渣中Mn、Fe、Se、Zn、As、Pb和Cr元素形态变化

图3 不同堆存时间电解锰渣XRD谱图

表6 不同堆存时间电解锰渣XRF分析 (%)

堆存时间编号	SO₃	SiO₂	CaO	Fe₂O₃	MnO	Al₂O₃	MgO	K₂O	P₂O₅	TiO₂	BaO	其他
a	32.43	26.6	16.23	9.78	7.97	2.82	2.48	0.74	0.33	0.17	0.18	0.27
b	31.72	25.24	17.31	10.40	8.76	2.69	2.03	0.78	0.35	0.19	0.21	0.32
c	30.18	25.76	16.38	13.29	7.79	3.31	1.43	0.85	0.39	0.22	0.21	0.19
d	31.29	28.07	17.52	10.37	5.95	3.32	1.65	0.89	0.35	0.17	0.22	0.20
e	31.43	27.27	19.32	10.20	5.19	3.60	1.35	0.73	0.34	0.21	0.17	0.19
f	28.29	33.12	16.98	9.80	4.02	4.50	1.32	1.03	0.30	0.26	0.21	0.17

图4 堆存3个月电解锰渣SEM-EDS-Mapping

图5 不同堆存时间电解锰渣SEM

图6 不同堆存时间电解锰渣BET分析

表7 不同堆存时间电解锰渣中Fe元素结合能变化以及对应形态

XPS扫描区域	堆存时间编号	参数	FeOOH	Fe₃O₄	γ-Fe₂O₃	卫星峰
Fe 2p_3/2	a	结合能/eV	711.56	714.61	717.68	720.27
		含量/%	57.51	14.31	14.31
	b	结合能/eV	711.47	714.35	717.21	721.14
		含量/%	56.68	14.54	15.82
	c	结合能/eV	711.23	713.87	716.56	720.22
		含量/%	56.41	15.52	16.26
	d	结合能/eV	711.48	714.1	716.81	720.92
		含量/%	55.56	14.33	16.24
	e	结合能/eV	711.39	714.21	717.21	721.96
		含量/%	55.04	16.23	15.72
	f	结合能/eV	711.64	714.33	718.26	721.23
		含量/%	49.18	24.96	14.10

表8 不同堆存时间电解锰渣中Mn元素结合能变化以及对应形态

XPS扫描区域	堆存时间编号	参数	Mn₂O₃	MnO₂	KMnO₄
Mn 2p_3/2	a	结合能/eV	641.44	642.67	646.7
		含量/%	19.53	64.16	16.31
	b	结合能/eV	641.57	643.23	646.85
		含量/%	42.6	42.61	14.79
	c	结合能/eV	641.73	643.43	646.77
		含量/%	50.29	34.92	14.79
	d	结合能/eV	641.5	643.28	646.82
		含量/%	50.42	36.39	13.19
	e	结合能/eV	641.85	644.08	647.49
		含量/%	54.09	29.28	16.63
	f	结合能/eV	641.88	643.87	647.2
		含量/%	59.84	25.88	14.28

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