钢渣、电石渣增强硫化砷渣稳定化/固化机制

doi:10.11949/0438-1157.20240267

化工学报 ›› 2024, Vol. 75 ›› Issue (7): 2656-2669.DOI: 10.11949/0438-1157.20240267

钢渣、电石渣增强硫化砷渣稳定化/固化机制

张亚斌¹^,²(), 苏杨¹^,², 张慧荣¹^,², 宋一朋³, 李健⁴, 郭彦霞¹^,²()

^1.山西大学环境与资源学院国家环境保护煤炭废弃物资源化高效利用技术重点实验室，山西太原 030006
^2.山西省黄河实验室，山西太原 030006
^3.山西省太原固体废物处置中心（有限公司），山西太原 030000
^4.山西大地生态环境技术研究院有限公司，山西太原 030012

收稿日期:2024-03-05 修回日期:2024-04-27 出版日期:2024-07-25 发布日期:2024-08-09
通讯作者: 郭彦霞
作者简介:张亚斌(1984—)，男，博士，副教授，zhangyabin@sxu.edu.cn
基金资助:
国家重点研发计划项目(2021YFC2902604);山西省黄河实验室科技攻关计划项目(YRL-202106);山西省基础研究计划项目(20210302123457)

Mechanism of enhanced arsenic sulfide stabilization/solidification by using steel slag and carbide slag

Yabin ZHANG¹^,²(), Yang SU¹^,², Huirong ZHANG¹^,², Yipeng SONG³, Jian LI⁴, Yanxia GUO¹^,²()

^1.State Environmental Protection Key Laboratory of Efficient Resource Utilization Techniques of Coal Waste, School of Environment and Resources, Shanxi University, Taiyuan 030006, Shanxi, China
^2.Shanxi Laboratory for Yellow River, Taiyuan 030006, Shanxi, China
^3.Shanxi Taiyuan Solid Waste Disposal Centre (Co. , Ltd. ), Taiyuan 030000, Shanxi, China
^4.Dadi Ecological Environment Technology Research Institute Co. , Ltd. , Taiyuan 030012, Shanxi, China

Received:2024-03-05 Revised:2024-04-27 Online:2024-07-25 Published:2024-08-09
Contact: Yanxia GUO

摘要/Abstract

摘要：

随着金属冶炼等工业的发展，难以处理的硫化砷渣大量堆存，对资源环境和人体健康造成严重危害。稳定化/固化技术是一种应用前景广阔的高效固砷技术，但是药剂消耗大、成本高、对复杂高浓度砷渣处理效果差等问题一直限制着该技术的发展。以低成本、高活性的钢渣和电石渣代替化学稳定剂，利用酸改性钢渣、铁离子和H₂O₂形成高级氧化/稳定化体系，随后在水泥作用下固化。通过XRD、FTIR、XPS等对上述过程进行表征，结果显示低价态砷、硫和有机物质被高效氧化成稳定的高价态钙铁盐，最终形成的固化体结构较为稳定。工艺优化后，1.0 g硫化砷渣在0.2 g钢渣、0.5 g H₂O₂、0.3 g电石渣和1.0 g水泥的分步协同稳定化/固化处理后，固化体抗压强度为5.7 MPa，砷浸出浓度仅为0.66 mg·L^-1，远低于1.2 mg·L^-1的安全填埋标准。

关键词: 硫化砷渣, 钢渣, 高级氧化, 稳定化, 固化

Abstract:

With the development of metal smelting and other industries, a large amount of arsenic sulfide slag that is difficult to handle is accumulated, causing serious harm to resources, the environment and human health. The stabilization/solidification technology represents a highly efficient method for fixing arsenic with promising applications. However, the high reagent consumption and cost, along with limited efficacy in treating complex and highly concentrated arsenic slag, have hindered the progress of this technology. In this study, low-cost and highly active steel slag and carbide slag were employed instead of chemical stabilizers to create an advanced oxidation/stabilization system through acid-activated steel slag, iron ions, and H₂O₂, then it was solidified with cement. The aforementioned processes were characterized by using XRD, FTIR, XPS techniques and so on. It is demonstrated that the low-valence arsenic compounds, sulfur compounds, and organic substances are effectively oxidized to form stable high-valence calcium iron salts while maintaining structural stability after solidification. Following process optimization steps involving 0.2 g steel slag, 0.5 g H₂O₂, 0.3 g carbide slag, and 1.0 g cement for stepwise synergistic stabilization/solidification treatment of 1.0 g arsenic sulfide slag, the compressive strength of the solidified body is 5.7 MPa, and the arsenic leaching concentration is only 0.66 mg·L^-1,^{which is far lower than the safe landfill standard of 1.2 mg·L^-1.}

Key words: arsenic sulfide slag, steel slag, advanced oxidation, stabilization, solidification

中图分类号:

X 705

张亚斌, 苏杨, 张慧荣, 宋一朋, 李健, 郭彦霞. 钢渣、电石渣增强硫化砷渣稳定化/固化机制[J]. 化工学报, 2024, 75(7): 2656-2669.

Yabin ZHANG, Yang SU, Huirong ZHANG, Yipeng SONG, Jian LI, Yanxia GUO. Mechanism of enhanced arsenic sulfide stabilization/solidification by using steel slag and carbide slag[J]. CIESC Journal, 2024, 75(7): 2656-2669.

图/表 11

图1 ASS稳定化工艺路线

Fig.1 Process route for ASS stabilization

图2 干燥ASS的形貌结构分析

Fig.2 Morphology and structural analysis of desiccated ASS

表1 酸处理前后SS主要成分的XRF分析

Table 1 XRF analysis of main components of SS before and after acid treatment

成分	活化前				活化后
成分	CaO	Fe₂O₃	SiO₂	Al₂O₃	CaO	Fe₂O₃	SiO₂	Al₂O₃
质量分数/%	58.4	13.5	10.1	7.3	37.7	21.2	16.2	11.2

图3 SS酸处理前后的形貌和结构分析

Fig.3 Morphology and structural analysis of SS before and after acid treatment

图4 不同SS用量酸处理后Fe、Ca离子浸出浓度变化曲线

Fig.4 Leaching concentration curves of Fe and Ca ions following acid treatment with varying SS dosage

表2 不同酸处理条件下铁、钙浸出分析

Table 2 Investigation of iron and calcium leaching under various acid treatment conditions

pH	Fe²⁺浓度/(mg·L^-1)		Fe³⁺浓度/(mg·L^-1)		Ca²⁺浓度/(mg·L^-1)
pH	25^oC	60^oC	25^oC	60^oC	25^oC		60^oC
1.0	165.9	185.0	89.0	131.0	4222.0	4300.0
2.0	132.0	139.7	37.0	99.1	4140.0	4250.0
3.0	82.7	96.3	20.3	42.5	3140.0	3600.0

图5 H0S1O0、H0S0O1、H0S1O1、H1S1O1 4种稳定化工艺不同条件下砷离子浓度变化曲线

Fig.5 Arsenic ion concentration variation curves under different conditions for four stabilization processes: H0S1O0, H0S0O1, H0S1O1, and H1S1O1

图6 不同稳定化工艺砷钙渣的微观形貌分析

Fig.6 Micro-morphology analysis of arsenic calcium slag with various stabilization processes

图7 不同稳定化工艺砷钙渣的FTIR、XRD分析

Fig.7 FTIR and XRD analysis of arsenic calcium slag with various stabilization processes

图8 不同稳定化工艺砷钙渣中As、S、C的XPS谱图

Fig.8 XPS spectra of As, S, and C in arsenic calcium slag with various stabilization processes

图9 不同工艺砷钙渣不同配比条件下固化体抗压强度、砷浸出浓度及微观形貌分析

Fig.9 Analysis of compressive strength, As leaching concentration, and microstructure of solidified bodies prepared with different processes and different proportions

参考文献 30

1	徐建兵, 沈强华, 陈雯, 等. 含砷废渣处理现状及对策[J]. 矿冶, 2017, 26(3): 82-86.
	Xu J B, Shen Q H, Chen W, et al. The present situation and the countermeasure of the processing of arsenic residues[J]. Mining and Metallurgy, 2017, 26(3): 82-86.
2	Mandal B K, Suzuki K T. Arsenic round the world: a review[J]. Talanta, 2002, 58(1): 201-235.
3	Su C, Jiang L Q, Zhang W J. A review on heavy metal contamination in the soil worldwide: situation, impact and remediation techniques[J]. Environmental Skeptics and Critics, 2014, 3(2): 24-38.
4	龙冬清, 贾军峰, 何田妹, 等. 硫化砷渣稳定化/固化处理及其效果评价[J]. 环保科技, 2014, 20(3): 7-11.
	Long D Q, Jia J F, He T M, et al. Stabilization/solidification of arsenic sulfide residue and effect evaluation[J]. Environmental Protection and Technology, 2014, 20(3): 7-11.
5	李艺. 有色多金属矿山砷污染对生态环境的影响及其治理分析[J]. 地球与环境, 2008, 36(3): 256-260.
	Li Y. Impacts of arsenic pollution from nonferrous multi-metal mines on ecological environment and its governance analysis[J]. Earth and Environment, 2008, 36(3): 256-260.
6	Zhao H R, Xia B C, Fan C, et al. Human health risk from soil heavy metal contamination under different land uses near Dabaoshan Mine, Southern China[J]. Science of the Total Environment, 2012, 417/418: 45-54.
7	Shibayama A, Takasaki Y, William T, et al. Treatment of smelting residue for arsenic removal and recovery of copper using pyro-hydrometallurgical process[J]. Journal of Hazardous Materials, 2010, 181(1/2/3): 1016-1023.
8	Song S, Lopez-Valdivieso A, Hernandez-Campos D J, et al. Arsenic removal from high-arsenic water by enhanced coagulation with ferric ions and coarse calcite[J]. Water Research, 2006, 40(2): 364-372.
9	De Klerk R J, Jia Y F, Daenzer R, et al. Continuous circuit coprecipitation of arsenic(‍Ⅴ) with ferric iron by lime neutralization: process parameter effects on arsenic removal and precipitate quality[J]. Hydrometallurgy, 2012, 111: 65-72.
10	卢琼, 杜颖, 杜冬云. 从硫化砷渣回收单质硫和砷[J]. 硫酸工业, 2016(1): 24-27.
	Lu Q, Du Y, Du D Y. Recovery of sulphur and arsenic from arsenic sulphide residue [J]. Sulphuric Acid Industry, 2016(1): 24-27.
11	王青, 廖亚龙, 周娟, 等. 含砷物料制备As₂O₃的研究进展[J]. 环境工程, 2015, 33(3): 97-101, 105.
	Wang Q, Liao Y L, Zhou J, et al. Reviewer on preparation of arsenic oxide from materials containing arsenic[J]. Environmental Engineering, 2015, 33(3): 97-101, 105.
12	Mollah M Y A, Kesmez M, Cocke D L. An X-ray diffraction (XRD) and Fourier transform infrared spectroscopic (FT-IR) investigation of the long-term effect on the solidification/stabilization (S/S) of arsenic(‍Ⅴ) in Portland cement type-V[J]. Science of the Total Environment, 2004, 325(1/2/3): 255-262.
13	王永良, 杨晓玲, 董永霞, 等. pH调整剂对含砷酸性废水中氧化Fe(Ⅱ)共沉淀固砷行为的影响[J]. 化工学报, 2019, 70(9): 3511-3516.
	Wang Y L, Yang X L, Dong Y X, et al. Effect of pH adjustment on immobilization of arsenic by coprecipitation through oxidizing Fe(‍Ⅱ) in acidic wastewater containing arsenic[J]. CIESC Journal, 2019, 70(9): 3511-3516.
14	于冰冰, 颜湘华, 王兴润, 等. 不同稳定化材料对废渣中As的固定效果[J]. 中国环境科学, 2019, 39(9): 3887-3896.
	Yu B B, Yan X H, Wang X R, et al. Stabilization effects of different materials on arsenic-containing slag[J]. China Environmental Science, 2019, 39(9): 3887-3896.
15	陶志超, 周新涛, 罗中秋, 等. 含砷废渣水泥固化/稳定化技术研究进展[J]. 材料导报, 2016, 30(9): 132-136, 143.
	Tao Z C, Zhou X T, Luo Z Q, et al. Progress on the solidification/immobilization of arsenic-bearing waste cement[J]. Materials Reports, 2016, 30(9): 132-136, 143.
16	Palfy P, Vircikova E, Molnar L. Processing of arsenic waste by precipitation and solidification[J]. Waste Management, 1999, 19(1): 55-59.
17	张微. 硫化砷渣预氧化转型-水泥固化技术处理研究[J]. 中国有色冶金, 2020, 49(5): 67-74.
	Zhang W. Study on the pre-oxidation transformation-cement fixation technology for arsenic sulfide residues[J]. China Nonferrous Metallurgy, 2020, 49(5): 67-74.
18	钟琦, 任雪娇, 李行德. 酸性高砷污泥稳定化固化的初步研究[J]. 云南化工, 2021, 48(10): 50-51, 58.
	Zhong Q, Ren X J, Li H D. Preliminary study on stabilization and solidification of acidic high arsenic sludge[J]. Yunnan Chemical Technology, 2021, 48(10): 50-51, 58.
19	柯平超, 刘志宏, 刘智勇, 等. 固砷矿物臭葱石组成与结构及其浸出稳定性研究现状[J]. 化工学报, 2016, 67(11): 4533-4540.
	Ke P C, Liu Z H, Liu Z Y, et al. Research status on composition, structure, and leaching stability of an arsenic solidification mineral scorodite[J]. CIESC Journal, 2016, 67(11): 4533-4540.
20	刘守庆, 罗中秋, 和森, 等. 高炉矿渣-粉煤灰地聚合物胶凝材料固化砷钙渣[J]. 化工进展, 2017, 36(7): 2660-2666.
	Liu S Q, Luo Z Q, He S, et al. Solidification/stabilization of calcium arsenate waste with blast furnace slag and fly ash geopolymer materials[J]. Chemical Industry and Engineering Progress, 2017, 36(7): 2660-2666.
21	Pan S Y, Adhikari R, Chen Y H, et al. Integrated and innovative steel slag utilization for iron reclamation, green material production and CO₂ fixation via accelerated carbonation[J]. Journal of Cleaner Production, 2016, 137: 617-631.
22	赵立文, 朱干宇, 李少鹏, 等. 电石渣特性及综合利用研究进展[J]. 洁净煤技术, 2021, 27(3):13-26.
	Zhao L W, Zhu G Y, Li S P, et al. Research progress on characteristics and comprehensive utilization of calcium carbide slag[J]. Clean Coal Technology, 2021, 27(3): 13-26.
23	郝峰焱. 钢渣基活性材料固砷机理及其应用[D]. 昆明: 昆明理工大学, 2020.
	Hao F Y. Arsenic fixation mechanism of steel slag-based active materials and its application [D]. Kunming: Kunming University of Science and Technology, 2020.
24	夏娜娜. 改性钢渣对海水中汞和砷的吸附性能研究[D]. 青岛: 中国海洋大学, 2013.
	Xia N N. Adsorption properties of modified steel slag for removal of mercury and arsenic from seawater[D]. Qingdao: Ocean University of China, 2013.
25	芦柏年. 电石渣对含砷污泥的稳定化处理及其机制研究[D]. 武汉: 华中科技大学, 2020.
	Lu B N. Stabilization of arsenic-bearing sludge by carbide slag[D]. Wuhan: Huazhong University of Science and Technology, 2020.
26	徐媛. 含砷石膏渣水泥固化及强化机制研究[D]. 昆明: 昆明理工大学, 2017.
	Xu Y. Study on solidification and strengthening mechanism of arsenic-containing gypsum slag cement[D]. Kunming: Kunming University of Science and Technology, 2017.
27	国家环境保护总局. 危险废物鉴别标准腐蚀性鉴别: [S]. 北京: 中国环境科学出版社, 2007.
	State Environmental Protection Administration of the People’‍s Republic of China. Identification for standards hazardous wastes- Identification for corrosivity: [S]. Beijing: China Environmental Science Press, 2007.
28	任云亮, 王晨晔, 张洪恩, 等. 有机-无机复合介质浸出对钢渣中含铁物相的影响[J]. 过程工程学报, 2015, 15(3): 430-434.
	Ren Y L, Wang C Y, Zhang H E, et al. Change of iron-containing phases in steelmaking slag in leaching process with organic-inorganic composite medium[J]. The Chinese Journal of Process Engineering, 2015, 15(3): 430-434.
29	Zhang A Y, Huang N H, Zhang C, et al. Heterogeneous Fenton decontamination of organoarsenicals and simultaneous adsorption of released arsenic with reduced secondary pollution[J]. Chemical Engineering Journal, 2018, 344: 1-11.
30	邹敏, 沈玉, 刘娟红. 钢渣粉在水泥基材料中应用研究综述[J]. 硅酸盐通报, 2021, 40(9): 2964-2977.
	Zou M, Shen Y, Liu J H. Review on application of steel slag powder in cement-based materials[J]. Bulletin of the Chinese Ceramic Society, 2021, 40(9): 2964-2977.

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钢渣、电石渣增强硫化砷渣稳定化/固化机制

Mechanism of enhanced arsenic sulfide stabilization/solidification by using steel slag and carbide slag

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