铜渣复合硅锰水淬渣后的改质提铁研究

doi:10.19964/j.issn.1006-4990.2022-0230

摘要/Abstract

摘要：

铜材等金属材料在生产过程中产生的大量水渣、干渣等冶金渣，其综合利用水平较低，成为冶金业高质量绿色发展亟须解决的难点。为有效回收铜渣中的铁元素，将工业铜渣与硅锰水淬渣混合后按一定比例添加氧化钙及氧化锰进行成分改质，利用FactSage对混合渣料中矿物相随温度的变化趋势进行了预测，借助XRD对改质前后渣料中的矿物相变化进行了对比，通过SEM和EDS对改质后混合渣料中主要矿物相的形态、分布和特征进行了表征。实验结果表明：改质后混合渣料中的矿物相以尖晶石相和硅酸盐相为主；碱度提高后，改质样品中的硅酸盐相增多但尖晶石相减少；混合渣料的碱度为1.5时改质效果最好，其铁品位为44%（质量分数）、铁回收率为95%。

关键词: 铜渣, 硅锰水淬渣, 改质, 尖晶石, 硅酸盐

Abstract:

A large amount of metallurgical slag such as water slag and dry slag has been produced in the production process of copper and other metal materials，its comprehensive utilization level is low，which is becoming the focus and difficulty to be solved urgently for high-quality green development of metallurgical industry.In order to effectively recover Fe from copper slag，industrial copper slag was mixed with silicon-manganese water quenched slag and modified by adding CaO and MnO in a certain proportion.The trend of mineral phases in the mixed slag with temperature was predicted by FactSage，and the changes of mineral phases in the slag before and after modification were compared by XRD，and the morphology，distribution and characteristics of the main mineral phases in the modified mixed slag were characterized by SEM and EDS.The experimental results showed that the mineral phase in the modified mixed slag was dominated by spinel phase and silicate phase.With the increase of alkalinity，the silicate phase in the modified sample was increased but the spinel phase was decreased.The best modification effect was achieved when the alkalinity of the mixed slag was 1.5，and the mass fraction of its iron grade was 44% and the recovery rate was 95%.

Key words: copper slag, silicon manganese water quenching slag, reformation, spinel, silicate

中图分类号:

TQ138.11

郑彬,蒋亮,韩凤兰,马鸿儒,祁志宏,苏辉. 铜渣复合硅锰水淬渣后的改质提铁研究[J]. 无机盐工业, 2023, 55(1): 136-143.

ZHENG Bin,JIANG Liang,HAN Fenglan,MA Hongru,QI Zhihong,SU Hui. Study on reformation and extracting iron of copper slag and silicon-manganese water quenched slag composites[J]. Inorganic Chemicals Industry, 2023, 55(1): 136-143.

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参考文献 39

1	National Bureau of Statistics of China. Monthly data[EB/OL].（2021-11-30）[2021-12-30].
2	SHI Caijun, MEYER C, BEHNOOD A. Utilization of copper slag in cement and concrete[J].Resources，Conservation and Recycling, 2008, 52（10）：1115-1120.
3	苗希望, 白智韬, 卢光华, 等. 典型铁合金渣的资源化综合利用研究现状与发展趋势[J].工程科学学报, 2020, 42（6）：663-679.
	MIAO Xiwang, BAI Zhitao, LU Guanghua, et al. Review of comprehensive utilization of typical ferroalloy slags[J].Chinese Journal of Engineering, 2020, 42（6）：663-679.
4	李宇, 刘月明. 我国冶金固废大宗利用技术的研究进展及趋势[J].工程科学学报, 2021, 43（12）：1713-1724.
	LI Yu, LIU Yueming. Progress and trend of bulk utilization technology of metallurgical solid wastes in China[J].Chinese Journal of Engineering, 2021, 43（12）：1713-1724.
5	吴龙, 郝以党. 铜渣资源化利用现况及高效化利用探讨[J].中国有色冶金, 2015, 44（2）：61-64.
	WU Long, HAO Yidang. The investigation of utilization status of copper slag resources and efficient utilization[J].China Nonferrous Metallurgy, 2015, 44（2）：61-64.
6	杨涛, 胡建杭, 王华, 等. 铜电炉冶炼贫化渣焙烧富集Fe₃O₄ [J].过程工程学报, 2011, 11（4）：613-619.
	YANG Tao, HU Jianhang, WANG Hua, et al. Concentration of Fe₃O₄ in roasted slag from copper impoverishment smelting[J].The Chinese Journal of Process Engineering, 2011, 11（4）：613- 619.
7	许冬, 春铁军, 陈锦安. 铜渣高温快速还原焙烧-磁选回收铁的研究[J].矿冶工程, 2017, 37（1）：89-91, 95.
	XU Dong, CHUN Tiejun, CHEN Jinan. Iron recovery from copper slag by a combined technique of high-temperature reduction roasting and magnetic separation[J].Mining and Metallurgical Engineering, 2017, 37（1）：89-91, 95.
8	CHOI S, KIM J，OH S，et al. Hydro-thermal reaction according to the CaO/SiO₂ mole-ratio in silico-manganese slag[J].Journal of Material Cycles and Waste Management, 2017, 19（1）：374-381.
9	PAN De'an, LI Lili, WU Yufeng, et al. Characteristics and properties of glass-ceramics using lead fuming slag[J].Journal of Cleaner Production, 2018, 175：251-256.
10	SEMYKINA A, SHATOKHA V, IWASE M, et al. Kinetics of oxidation of divalent iron to trivalent state in liquid FeO-CaO-SiO₂ slags[J].Metallurgical and Materials Transactions B, 2010, 41（6）：1230-1239.
11	FILCENCO OLTEANU A, DOBRE T, PANTURU E, et al. Experimental process analysis and mathematical modeling for selective gold leaching from slag through wet chlorination[J].Hydrometallurgy, 2014, 144-145：170-185.
12	薛超龙, 李慧, 梁精龙, 等. 铜渣资源回收的研究现状及展望[J].中国冶金, 2022, 32（2）：108-114.
	XUE Chaolong, LI Hui, LIANG Jinglong, et al. Research status and prospects of copper slag resource recovery[J].China Metallurgy, 2022, 32（2）：108-114.
13	WANG Dengquan, WANG Qiang, HUANG Zongxian. Reuse of copper slag as a supplementary cementitious material：Reactivity and safety[J].Resources，Conservation and Recycling, 2020, 162.Doi：10.1016/j.resconrec.2020.105037. doi: 10.1016/j.resconrec.2020.105037
14	SHARIFI Y, AFSHOON I, ASAD-ABADI S, et al. Environmental protection by using waste copper slag as a coarse aggregate in self-compacting concrete[J].Journal of Environmental Management, 2020, 271.Doi：10.1016/j.jenvman.2020.111013. doi: 10.1016/j.jenvman.2020.111013
15	包焕均, 张晓雪, 王洪阳, 等. 铜渣中铁硅分离的研究进展[J].有色金属科学与工程, 2021, 12（5）：30-38.
	BAO Huanjun, ZHANG Xiaoxue, WANG Hongyang, et al. Research progress on the separation of iron and silicon from copper slag[J].Nonferrous Metals Science and Engineering, 2021, 12（5）：30-38.
16	SHU Q F, LIU Y. Effects of basicity，MgO and MnO on mineralogical phases of CaO-FeO _x -SiO₂-P₂O₅ slag[J].Ironmaking & Steelmaking, 2018, 45（4）：363-370.
17	LI Siwei, PAN Jian, ZHU Deqing, et al. A novel process to upgrade the copper slag by direct reduction-magnetic separation with the addition of Na₂CO₃ and CaO[J].Powder Technology, 2019, 347：159-169.
18	刘金生, 姜平国, 肖义钰, 等. 从铜渣中回收铁的研究现状及其新方法的提出[J].有色金属科学与工程, 2019, 10（2）：19-24.
	LIU Jinsheng, JIANG Pingguo, XIAO Yiyu, et al. Research status and new method of recovering iron from copper slag[J].Nonferrous Metals Science and Engineering, 2019, 10（2）：19-24.
19	蒋亮, 吴婷, 马良富, 等. 改质转炉钢渣的易磨性研究[J].硅酸盐通报, 2018, 37（12）：4034-4039.
	JIANG Liang, WU Ting, MA Liangfu, et al. Research on grindability of modified BOF slag[J].Bulletin of the Chinese Ceramic Society, 2018, 37（12）：4034-4039.
20	牛丽萍, 刘捷元, 宋锦波, 等. 熔融铜渣天然气还原过程的研究[J].材料与冶金学报, 2016, 15（3）：200-204, 208.
	NIU Liping, LIU Jieyuan, SONG Jinbo, et al. Study on reduction process of melting copper slag with natural gas[J].Journal of Materials and Metallurgy, 2016, 15（3）：200-204, 208.
21	ZHANG Xufang, NI Wen, WU Junyu, et al. Hydration mechanism of a cementitious material prepared with Si-Mn slag[J].International Journal of Minerals，Metallurgy，and Materials, 2011, 18（2）：234-239.
22	LI Jianli, MOU Qiqiang, ZENG Qiang, et al. Experimental study on precipitation behavior of spinels in stainless steel-making slag under heating treatment[J].Processes, 2019, 7（8）.Doi：10.3390/pr7080487. doi: 10.3390/pr7080487
23	BALE C W. FactSage thermochemical software and databases：Recent developments[J].Calphad, 2009, 33（2）：295-311.
24	JIANG Pingguo, LIU Jinsheng, XIAO Yiyu, et al. Recovery of iron from copper slag via modified roasting in CO-CO₂ mixed gas and magnetic separation[J].Journal of Iron and Steel Research International, 2020, 27（7）：796-806.
25	高颖, 王伟赫, 陈萌, 等. 钢渣体积膨胀行为及改性方法研究进展[J].科学技术与工程, 2021, 21（33）：14040-14048.
	GAO Ying, WANG Weihe, CHEN Meng, et al. Research progress on bulk expansion behavior and modification methods of steel slag[J].Science Technology and Engineering, 2021, 21（33）：14040-14048.
26	占寿罡, 许冬. 从铜渣选铜尾矿中回收铁的试验研究[J].中国有色冶金, 2015, 44（5）：49-52.
	ZHAN Shougang, XU Dong. Experimental study on recovery of Fe from flotation tailings of copper slag[J].China Nonferrous Metallurgy, 2015, 44（5）：49-52.
27	CHEN Min, AVARMAA K, TASKINEN P, et al. An experimental study on the phase equilibria of FeO _x -saturated iron silicate slags and metallic copper alloys at 1 200-1 300 ℃[J].Calphad, 2022, 77.Doi：10.1016/j.calphad.2022.102418. doi: 10.1016/j.calphad.2022.102418
28	张琳, 刘先阳, 库建刚. 氧化钙在铜渣还原过程中的作用[J].中国冶金, 2019, 29（9）：9-14, 28.
	ZHANG Lin, LIU Xianyang, KU Jiangang. Effect of calcium oxide on reduction of copper slag[J].China Metallurgy, 2019, 29（9）：9-14, 28.
29	KU Jiangang, ZHANG Lin, FU Weng, et al. Mechanistic study on calcium ion diffusion into fayalite：A step toward sustainable management of copper slag[J].Journal of Hazardous Materials, 2021, 410.Doi：10.1016/j.jhazmat.2020.124630. doi: 10.1016/j.jhazmat.2020.124630
30	李磊, 胡建杭, 王华. 铜渣熔融还原炼铁过程研究[J].过程工程学报, 2011, 11（1）：65-71.
	LI Lei, HU Jianhang, WANG Hua. Study on smelting reduction ironmaking of copper slag[J].The Chinese Journal of Process Engineering, 2011, 11（1）：65-71.
31	张淑会, 王宝勇, 兰臣臣, 等. 铜渣中有价金属元素回收技术的研究现状及展望[J].中国有色冶金, 2022, 51（3）：84-93.
	ZHANG Shuhui, WANG Baoyong, LAN Chenchen, et al. Current status and prospect of recovery technology of valuable metal elements in copper slag[J].China Nonferrous Metallurgy, 2022, 51（3）：84-93.
32	LI Qiuju, YANG Fanxi, WANG Ziyang, et al. Study on mechanism of oxidation modification of copper slag[J].Transactions of the Indian Institute of Metals, 2019, 72（12）：3223-3231.
33	ISCHENKO V， Y-S JANG, KORMANN M, et al. The effect of SiC substrate microstructure and impurities on the phase formation in carbide-derived carbon[J].Carbon, 2011, 49（4）：1189-1198.
34	GUO Zhengqi, ZHU Deqing, PAN Jian, et al. Improving beneficiation of copper and iron from copper slag by modifying the molten copper slag[J].Metals, 2016, 6（4）.Doi：10.3390/met6040086. doi: 10.3390/met6040086
35	ZUO Zongliang, YU Qingbo, LIU Junxiang, et al. Effects of CaO on reduction of copper slag by biomass based on ion and molecule coexistence theory and thermogravimetric experiments[J].ISIJ International, 2017, 57（2）：220-227.
36	LI Jianli, XU Anjun, HE Dongfeng, et al. Effect of FeO on the formation of spinel phases and chromium distribution in the CaO-SiO₂-MgO-Al₂O₃-Cr₂O₃ system[J].International Journal of Minerals，Metallurgy，and Materials, 2013, 20（3）：253-258.
37	TURHDOGAN E T. 高温工艺物理化学[M].魏季，傅杰，译.北京：冶金工业出版社, 1988.
38	DOS REIS SILVA D, VILELA A C F, HECK N C, et al. Solidification behavior of CaO-SiO₂-Al₂O₃ mold fluxes containing MgO and low TiO₂ content using single hot thermocouple technique（SHTT）：Continuous-cooling-transformation（CCT） and viscosity analysis[J].Steel Research International, 2018, 89（2）.Doi：10.1002/srin.201700246. doi: 10.1002/srin.201700246
39	GASKELL T. Self-diffusion in liquid metals：A generalized stokes-einstein equation[J].Journal of Non-Crystalline Solids, 1984, 61-62：913-918.

渣料	主要化学成分质量分数
渣料	SiO₂	Al₂O₃	CaO	MnO	MgO	Fe₂O₃	ZnO	CuO	其他
铜渣	14.4	0.00	8.74	0.00	0.00	64.01	2.13	3.77	6.95
硅锰水淬渣	41.33	21.64	16.49	7.32	5.21	0.79	0.00	0.00	7.22

编号	w（铜渣）∶w（硅锰水淬渣）∶ w（CaO）∶w（MnO）	主要化学成分						碱度
编号	w（铜渣）∶w（硅锰水淬渣）∶ w（CaO）∶w（MnO）	w（SiO₂）/%	w（Fe₂O₃）/%	w（Al₂O₃）/%	w（MnO）/%	w（MgO）/%	w（CaO）/%	碱度
S1	48%∶25%∶19%∶8%	19.0	35.0	6.0	10	1.4	28.6	1.5
S2	46%∶24%∶22%∶8%	18.0	34.0	5.8	9.8	1.4	31	1.7
S3	44%∶23%∶25%∶8%	17.7	32.5	5.5	9.4	1.3	33.6	1.9

编号	可能存在的物相	a（O）	a（Si）	a（Al）	a（Ca）	a（Mn）	a（Mg）	a（Fe）
a1	Spinel	54.42	0.00	1.65	1.26	8.33	5.36	28.98
a2	Ca₂Al₂SiO₇	59.82	9.42	8.94	14.99	0.00	0.75	6.07
a3	Ca₂SiO₄	52.04	16.8	0.00	31.05	0.00	0.00	0.00
a4	CaFeSi₂O₆	61.11	6.13	2.26	11.65	1.87	0.00	16.97
b1	Spinel	55.56	0.00	3.16	1.33	7.9	6.35	25.7
b2	Ca₂Al₂SiO₇	60.59	8.86	9.63	15.09	0.00	0.00	5.82
b3	Ca₂SiO₄	62.64	13.17	0.00	23.87	0.00	0.00	0.32
b4	CaFeSi₂O₆	60.12	6.80	1.89	10.58	1.80	1.32	17.42
c1	Spinel	57.92	0.00	2.89	0.98	7.93	8.15	22.14
c2	Ca₂Al₂SiO₇	61.29	8.14	11.07	14.4	0.00	0.23	4.86
c3	Ca₂SiO₄	66.57	11.54	0.00	21.5	0.13	0.00	0.26
c4	CaFeSi₂O₆	61.31	7.85	4.76	13.01	1.34	0.42	11.31
c5	Ca₂Fe₂O₅	57.69	0.00	0.73	11.83	4.46	0.00	25.28

编号	碱度	黏度/（Pa·s）
编号	碱度	1 000 ℃	1 100 ℃	1 200 ℃	1 300 ℃	1 400 ℃
S1	1.5	0.851	0.398	0.207	0.118	0.071
S2	1.7	0.859	0.400	0.207	0.117	0.071
S3	1.9	0.867	0.402	0.208	0.117	0.07

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