硫含量对KR脱硫渣中硫赋存状态的影响

doi:10.13228/j.boyuan.issn0449-749x.20210405

摘要
图/表
参考文献
相关文章 (15)

全文: PDF (3406 KB) HTML (1 KB)
输出: BibTeX | EndNote (RIS)

摘要 KR脱硫渣中的CaO是转炉冶炼工艺中重要的造渣原料,将其回用于钢铁冶炼工艺可降低冶金企业的CaO原料消耗,减少企业KR脱硫渣堆积量,节约企业冶炼的经济成本。KR脱硫渣中的2CaO·SiO₂(C2S)在转炉脱磷冶炼过程中可与炉渣中的磷形成稳定的2CaO·SiO₂-3CaO·P₂O₅固溶体,提高磷在渣中的稳定性。将KR脱硫渣代替活性石灰用作转炉造渣料,可促进转炉冶炼初期早化渣,提高转炉冶炼的脱磷效率。但由于KR脱硫渣中硫质量分数为1.0%～2.5%,将其直接用于转炉冶炼会导致钢水增硫。因此,采用FactSage8.0对炉渣中各物相凝固过程进行模拟,采用SEM-EDS、XRD对炉渣基本物相及微观形貌进行分析、检测,采用Image-ProPlus6.0对渣样中CaS平均晶粒面积进行分析,旨在明确硫含量对炉渣中硫赋存状态及析出行为的影响,为后续通过氧化性气氛脱除KR脱硫渣中的硫提供理论依据。热力学计算表明,硫质量分数为0.5%～2.5%时,炉渣中CaS析晶温度由1 240升高到1 390 ℃;当温度为1 600 ℃时,随着硫含量增加,炉渣中MeO#1相含量逐渐减少,炉渣黏度逐渐减小;硫质量分数为0.5%时,炉渣中硫以非晶态组织赋存;硫质量分数为1.0%～2.0%时,炉渣中硫主要以CaS形式赋存;硫质量分数为2.0%～2.5%时,炉渣中硫以CaS相和Ca₁₁(SiO₄)₄O₂S相赋存,Ca₁₁(SiO₄)₄O₂S主要赋存在硅酸盐相中。随着硫含量增加,炉渣中CaS晶粒长大速率逐渐增大,CaS平均晶粒面积逐渐增大,且炉渣中CaS晶粒逐渐由不规则结构演变为圆饼状结构。

	服务

	把本文推荐给朋友
	加入我的书架
	加入引用管理器
	E-mail Alert
	RSS
	作者相关文章
	朱仁林
	李建立
	余岳
	朱航宇

关键词 ： KR脱硫渣, 硫含量, 赋存状态, 析出行为, 微观结构, 凝固

Abstract：The CaO component in KR desulfurization slag is an important slagging raw material in converter smelting process. Its reuse in converter smelting can reduce the CaO raw material consumption as well as the accumulation of KR desulfurization slag for metallurgical enterprise, and save the economic cost of smelting. Moreover, 2CaO·SiO₂ (C2S) in the KR desulfurization slag can form stable C2S-C3P(2CaO·SiO₂-3CaO·P₂O₅) solid solution with phosphorus in the slag to improve the stability of phosphorus during converter dephosphorization smelting. Reusing KR desulfurization slag instead of activated lime as converter slag can promote early slagging in the initial stage of converter smelting and improve the dephosphorization efficiency. However, w((S)) in the KR desulfurization slag was 1.0%-2.5%, reusing it directly in converter smelting would lead to sulfur increase in molten steel. Therefore, in order to clarify the influence of sulfur content on occurrence state of sulfur in molten slag, and to provide a theoretical basis for subsequent effective removal of sulfur from KR desulfurization slag through oxidizing atmosphere,the solidification process of each phase in the molten slag was simulated by FactSage8.0, the basic phase and micro morphology of molten slag were analyzed and detected by SEM-EDS and XRD, and the average grain area of CaS in the slag sample was analyzed by Image-Proplus 6.0. Thermodynamic calculation showed that the crystallization temperature of CaS in molten slag increased from 1 240 to 1 390 ℃ when w((S)) was 0.5%-2.5% in the molten slag. In addition, the content of MeO#1 phase and the viscosity of slag gradually decreased in molten slag with the increase of sulfur content at 1 600 ℃. When w((S)) was 0.5%, the sulfur in the molten slag existed in amorphous structure, while w((S)) was 1.0%-2.0%, the sulfur mainly existed in the form of CaS. When w((S)) was 2.0%-2.5%, the sulfur existed in CaS phase and Ca₁₁ (SiO₄) ₄O₂S phase, and Ca₁₁ (SiO₄) ₄O₂S mainly existed in silicate phase. With the increase of sulfur content, the growth rate and average grain area of CaS in molten slag gradually increased, and the CaS grains gradually evolved from irregular structure to round structure.

Key words： KR desulfurization slag sulfur content occurrence state precipitation behavior microstructure solidification

收稿日期: 2021-07-16

引用本文:

朱仁林, 李建立, 余岳, 朱航宇. 硫含量对KR脱硫渣中硫赋存状态的影响[J]. 钢铁, 2022, 57(2): 54-62. ZHU Ren-lin, LI Jian-li, YU Yue, ZHU Hang-yu. Effect of sulfur content on occurrence state of sulfur in KR desulfurization slag[J]. Iron and Steel, 2022, 57(2): 54-62.

链接本文:

http://www.chinamet.cn/Jweb_gt/CN/10.13228/j.boyuan.issn0449-749x.20210405 或 http://www.chinamet.cn/Jweb_gt/CN/Y2022/V57/I2/54

[1] 石枚梅, 俞海明. 铁水预处理KR脱硫渣特点和资源化处理工艺的开发[J]. 特殊钢, 2013(6): 42.(SHI Mei-mei, YU Hai-ming. Characteristics of hot metal pretreatment KR desulphurized slag and development of recycling technology of resources[J]. Special Steel, 2013(6): 42.)
[2] 田鹏,武献民,薛月凯,等.钢铁渣综合利用现状及管控措施[J].冶金能源,2020,39(5):9.(TIAN Peng,WU Xian-min,XUE Yue-kai,et al. Comprehensive utilization and control measures of iron and steel slag[J].Energy for Metallurgical Industry,2020,39(5):9.)
[3] 张茂林, 徐安军. KR法与喷吹法在铁水脱硫中应用的比较[J]. 炼钢, 2009, 25(5):73. (ZHANG Mao-lin, XU An-jun. Comparison of application of KR method with that of injection method in hot metal desulphurization[J]. Steel Making, 2009, 25(5):73.)
[4] TONG Z B, MA G J, CAI X, et al. Characterization and valorization of kanbara reactor desulfurization waste slag of hot metal pretreatment[J]. Waste and Biomass Valorization, 2016, 7(1):1.
[5] 徐建飞, 王新华, 黄福祥, 等. KR脱硫渣矿相及硫在渣中分布[J]. 钢铁, 2015,50(1):15.(XU Jian-fei, WANG Xin-hua, HUANG Fu-xiang, et al. Analysis of phase and distribution of sulfur in KR desulfurization slag[J]. Iron and Steel, 2015,50(1):15.)
[6] Moreira A, Silva C A, Silva I A. Replacement of fluorspar in the desulfurization of hot metal[J]. Metallurgy and Materials, 2018, 71(2):261.
[7] Cho M K, Cheng J, Park J H, et al. Hot metal desulfurization by CaO-SiO₂-CaF₂-Na₂O slag saturated with MgO[J]. ISIJ International, 2010, 50(2):215.
[8] Hiraki T, Kobayashi J, Urushibata S, et al. Removal of Sulfur from CaF₂ containing desulfurization slag exhausted from secondary steelmaking process by oxidation[J]. Metallurgical and Materials Transactions B, 2012, 43(4):703.
[9] 吴启帆, 包燕平, 林路. KR脱硫渣矿物学特征及渣中硫行为[J]. 中国冶金, 2015, 25(8): 44.(WU Qi-fan, BAO Yan-ping, LIN Lu. Ineralogy characteristics and sulfur behavior of KR desulfurization slag[J]. China Metallurgy, 2015, 25(8): 44.)
[10] Kazuya F, Koichiro O, Taichi M, et al. Effective utilization of KR slag in iron ore sintering process[J]. Tetsu-to-Hagané,2017, 103(6): 357.
[11] 韩跃新, 王丽英, 李丽匣,等. 鞍钢脱硫扒渣的综合回收利用研究[J]. 矿冶工程, 2009(5): 29.(HAN Yue-xin, WANG Li-ying, LI Li-xia, et al. Comprehensive utilization of slag from desulphurization and slag skimming processes of Ansteel[J]. Mining and Metallurgical Engineering, 2009, 29(5): 29.)
[12] Kawatra S K, Ripke S J. Pelletizing steel mill desulfurization slag[J]. International Journal of Mineral Processing, 2002, 65(3):165.
[13] SHENG G H, HUANG P, WANG S S, et al. Potential reuse of slag from the kambara reactor desulfurization process of iron in an acidic mine drainage treatment[J]. Journal of Environmental Engineering, 2014, 140(7):04014023.
[14] 佟帅,李晨晓,王书桓,等.钢渣处理工艺及综合利用分析[J].冶金能源,2020,39(6):3.(TONG Shuai,LI Xiao-chen,WANG Shu-huan,et al.Steel slag treatment process and comprehensive utilization analysis[J]. Energy for Metallurgical Industry,2020,39(6):3.)
[15] Nakai Y, Kikuchi N, Iwasa M, et al. Development of slag recycling process in hot metal desulfurization with mechanical stirring[J]. Steel Research International, 2009, 80(10):727.
[16] LI J Y, ZHANG M, GUO M, et al. Enrichment mechanism of phosphate in CaO-SiO₂-FeO-Fe₂O₃-P₂O₅ steelmaking slags[J]. Metallurgical and Materials Transactions B, 2014, 45(5):1666.
[17] 郝华强,王书桓,张朝发,等. 转炉热态熔渣脱磷及循环利用生产实践[J]. 中国冶金, 2018, 28(6): 56.(HAO Hua-qiang,WANG Shu-huan,ZHANG Chao-fa,et al. Dephosphorization and recycle utilization practice of molten slag in converter[J]. China Metallurgy, 2018, 28(6): 56.)
[18] Hamano T, Horibe M, Ito K. The dissolution rate of solid lime into molten slag used for hot-metal dephosphorization [J]. ISIJ International, 2004, 44(2):263.
[19] Kitamura S, Saito S, Utagawa K, et al. Mass transfer of P₂O₅ between liquid slag and solid solution of 2CaO·SiO₂ and 3CaO·P₂O₅ [J]. ISIJ International, 2009, 49(12):1838.
[20] 江腾飞, 朱良, 刘风刚, 等. 铁水预处理脱硫渣铁回收再利用[J]. 钢铁, 2017, 52(2):24.(JIANG Teng-fei, ZHU Liang, LIU Feng-gang, et al. Recycling of desulfurization slag in pretreatment of hot metal[J]. Iron and Steel, 2017, 52(2):24.)
[21] Wright S, Zhang L, Sun S, et al. Viscosity of a CaO-MgO-Al₂O₃-SiO₂ melt containing spinel particles at 1 646 K[J]. Metallurgical and Materials Transactions B, 2000, 31(1):97.
[22] Wright S, Zhang L, Sun S Y, et al. Viscosities of calcium ferrite slags and calcium alumina-silicate slags containing spinel particles[J]. Journal of Non-Crystalline Solids, 2001, 282(1): 15.
[23] 毛红霞, 白晨光, 邱贵宝, 等. 非牛顿冶金熔渣流变特性的研究进展[J]. 重庆大学学报(自然科学版), 2005,28(6):52.(MAO Hong-xia, BAI Chen-guang, Qiu Gui-bao, et al. Development in research rheological characteristics of non-Newtonian metallurgical molten slags[J]. Journal of Chongqing University(Natural Science), 2005, 28(6): 24.)
[24] SHE A F, AN Z L, ZHANG Z, et al. Crystallization behavior of synthesized CaO-SiO₂-CaF₂-La₂O₃ rare earth-containing slag[J]. ISIJ International, 2020, 60(5): 832.
[25] 刘承军, 姜茂发, 王德永, 等. CaO-SiO₂-Na₂O-CaF₂-Al₂O₃-MgO渣系的结晶温度[J]. 特殊钢, 2003, 24(6):16.(LIU Cheng-jun, JIANG Mao-fa, WANG De-yong, et al. Crystallization temperature of CaO-SiO₂-Na₂O-CaF-Al₂O₃-MgO flux series[J]. Special Steel,2003,24(6):16.)
[26] 李继铮, 陈宝云. 保护渣熔渣结晶性能的研究[J]. 钢铁研究, 1998(1):11.(LI Ji-zheng, CHEN Bao-yun. Research on crystallization performance of powder and slag[J]. Research on Iron and Steel, 1998(1): 11.)
[27] 沈峰满. 冶金物理化学[M]. 北京:冶金工业出版社, 2017. (SHEN Feng-man. Physical Chemistry of Metallurgy[M].Beijing:Metallurgical Industry Press, 2017.)
[28] Esfahani S, Barati M. Effect of slag composition on the crystallization of synthetic CaO-SiO₂-Al₂O₃-MgO slags: Part I—Crystallization behavior[J]. Journal of Non-Crystalline Solids, 2016, 436:35.
[29] Esfahani S, Barati M. Effect of slag composition on the crystallization kinetics of synthetic CaO-SiO₂-Al₂O₃-MgO slags[J]. Metallurgical and Materials Transactions B, 2018, 49(5): 590.