Research status and prospect of recycling technology of converter slag containing phosphorus
ZHOU Chao-gang1,2, YANG Hui-ze1, AI Li-qun1,2, WANG Shu-huan1,2, HU Jin-zhen1, CHEN Hu3
1. College of Metallurgy and Energy, North China University of Science and Technology, Tangshan 063210, Hebei, China; 2. Tangshan Special Metallurgy and Material Preparation Laboratory, Tangshan 063210, Hebei, China; 3. Steelmaking Department, Shougang Jingtang United Iron and Steel Co., Ltd., Tangshan 063200, Hebei, China
Abstract:In order to realize the efficient recycling of converter phosphorus containing steel slag, the production status,composition,source,and migration and enrichment mechanism of phosphorus,mineralogical structure,and research status of dephosphorization technology of converter slag are systematically analyzed. On this basis,through the discussion and summary the recycling technology of converter phosphorus-containing steel slag,it shows that the current steel slag recycling technology has the disadvantages of low phosphorus resource utilization efficiency and large energy consumption of steel slag. Therefore,it is an inevitable trend to determine the utilization mode according to the phosphorus content of steel slag and reduce the energy loss of steel slag as much as possible in the recycling process. Based on the previous research,the prospect of efficient recycling of low phosphorus slag and high phosphorus slag is further prospected,so as to provide theoretical basis and technical reference for iron and steel enterprises to improve the recycling rate of converter phosphorus-containing steel slag and reduce the production cost of raw materials.
周朝刚, 杨会泽, 艾立群, 王书桓, 胡锦榛, 陈虎. 转炉含磷钢渣循环利用技术的研究现状及展望[J]. 钢铁, 2021, 56(2): 22-39.
ZHOU Chao-gang, YANG Hui-ze, AI Li-qun, WANG Shu-huan, HU Jin-zhen, CHEN Hu. Research status and prospect of recycling technology of converter slag containing phosphorus[J]. Iron and Steel, 2021, 56(2): 22-39.
[1] 何环宇,倪红卫,甘万贵,等. 炼钢渣的冶金资源化利用及评价[J]. 武汉工程大学学报,2009,31(1):41.(HE Huan-yu,NI Hong-wei,GAN Wan-gui,et al. Resource utilization and evaluation of the steelmaking waste slag reuse in metallurgic flied[J]. Journal of Wuhan Institute of Technology,2009,31(1):41.) [2] 常苏娟,朱杰勇,刘益,等. 世界磷矿资源形势分析[J]. 化工矿物与加工,2010,39(9):1.(CHANG Su-juan,ZHU Jie-yong,LIU Yi,et al. Situation of the world's phosphate resources[J]. Minerals and Processing,2010,39(9):1.) [3] GUO J L,BAO Y P,WANG M. Steel slag in China: Treatment,recycling,and management[J]. Waste Management,2018,78:318. [4] 李嵩. BSSF滚筒法钢渣处理技术发展现况研究[J]. 环境工程,2013,31(3):113.(LI Song. A review on development of BSSF technology[J]. Environmental Engineering,2013,31(3):113.) [5] 郭家林,赵俊学,黄敏. 钢渣综合利用技术综述及建议[J]. 中国冶金,2009,19(2):35.(GUO Jia-lin,ZHAO Jun-xue,HUANG Min. Technical summary and suggestions of comprehensive utilization of steel slag[J]. China Metallurgy,2009,19(2):35.) [6] 刘浏. 转炉炼钢的技术进步[J]. 炼钢,2000(5):1.(LIU Liu. Technological progress in converter steelmaking[J]. Steelmaking,2000(5):1.) [7] 梁强,曾加庆,齐渊洪. 含磷炉渣处理技术的回顾与展望[J]. 钢铁,2015,50(1):69.(LIANG Qiang,ZENG Jia-qing,QI Yuan-hong. Retrospect and prospect of the technology of phosphatic slag treatment[J]. Iron and Steel,2015,50(1):69.) [8] ZHANG X,CHEN J,JIANG J,et al. The potential utilization of slag generated from iron and steelmaking industries:A review[J]. Environ Geochem Health,2020,42:1321. [9] ZHAO J H,YAN P Y,WANG D M. Research on mineral characteristics of converter steel slag and its comprehensive utilization of internal and external recycle[J]. Journal of Cleaner Production,2017,156:50. [10] 黄勇刚,狄焕芬,祝春水. 钢渣综合利用的途径[J]. 工业安全与环保,2005(1):44.(HUANG Yong-gang,DI Huan-fen,ZHU Chun-shui. Approaches to comprehensive utilizing of steel slag[J]. Industrial Safety and Environmental Protection,2005(1):44.) [11] Jung S,Do Y,Choi J. Reduction behavior of BOF type slags by solid carbon[J]. Steel Research International,2006,77(5):305. [12] Ryu J Y. Kinetics of phosphorus vaporization from slag[J]. Transaction,1999(1):59. [13] 高本恒,郝以党,张淑苓,等. 钢渣综合利用现状及发展趋势[J]. 环境工程,2016,34(s1):776.(GAO Ben-heng,HAO Yi-dang,ZHANG Shu-ling,et al. Development trend and comprehensive utilization of steel slag[J]. Environmental Engineering,2016,34(s1):776.) [14] 吕心刚. 钢渣的处理方式及利用途径探讨[J]. 河南冶金,2013,21(3):27.(LÜ Xin-gang. Discussion on treatment methods and utilization approaches of steel slag[J]. Henan Metallurgy,2013,21(3):27.) [15] 沈建中. 钢渣综合利用和处理方法的述评与探索[J]. 中国冶金,2008,18(5):12.(SHEN Jian-zhong. Comprehensive utilization and treatment process of steel slag[J]. China Metallurgy,2008,18(5):12.) [16] 吉立鹏. 钢铁厂磷素流的路径分析及探讨[J]. 中国冶金,2018,28(6):19.(JI Li-peng. Analysis and discussion on path of phosphorus flow in iron and steel plant[J]. China Metallurgy,2018,28(6):19.) [17] Dippenaar R. Industrial uses of slag(the use and re-use of iron and steelmaking slags)[J]. Ironmaking and Steelmaking,2005,32(1):35. [18] Ito G J. Distribution equilibrium of phosphorus between 2CaO·SiO2 and CaO-SiO2-Fe2O3 liquid phase slag[J]. ISIJ International,1981,67(4):126. [19] Suito H,Inoue R. Behavior of phosphorous transfer from CaO-FetO-P2O5-SiO2 slag to CaO particles[J]. ISIJ International,2006,46(2):180. [20] Inoue R,Suito H. Phosphorous partition between 2CaO·SiO2 particles and 2CaO-SiO2-FetO slags[J]. ISIJ International,2006,46(2):174. [21] Yang X,Matsuura H,Tsukihashi F. Condensation of P2O5 at the interface between 2CaO·SiO2 and 2CaO-SiO2-FeOx- P2O5 slag[J]. ISIJ International,2009,49(9):1298. [22] WANG N,LIANG Z G,CHEN M,et al. Phosphorous enrichment in molten adjusted converter slag:Part II Enrichment behavior of phosphorus in CaO-SiO2-FeOx-P2O5 molten slag[J]. Journal of Iron and Steel Research,International,2011,18(12):22. [23] Shimauchi K I,Shin K Y,Shibata H. Distribution of P2O5 between solid dicalcium silicate and liquid phases in CaO-SiO2-Fe2O3 system[J]. Tetsu-to-Hagane,2009,49(49):505. [24] XI S L,WANG W L. Isothermal crystallization study of (2CaO·SiO2-3CaO·P2O5) solid solution in the 45 mass% CaO-30 mass% SiO2-20 mass% FeOt-5 mass% P2O5 system at 1 623 K[J]. Steel Research International,2015,86(6):1622. [25] Kitamura S,Shibata H,Shimauchi K,et al. The importance of dicalcium-silicate on hot metal dephosphorization reaction[J]. Metallurgical Research and Technology,2008,105(5):263. [26] ZHOU C G,LI J,SHI C B,et al. Dependence of temperature and slag composition on dephosphorization at the first deslagging in BOF steelmaking process[J]. High Temperature Materials and Processes,2015,35(4):433. [27] ZHOU H M,BAO Y P,LIN L. Distribution of P2O5 between phosphorus-enrichment phase and matrix phase in phosphorus-containing slag[J]. Steel Research International,2013,84(9):863. [28] 申莹莹. CaO-SiO2-FetO-P2O5渣系中磷富集动力学的研究[D]. 沈阳:东北大学,2010.(SHEN Ying-ying. Study on Kinetics of Phosphorous Enrichment in CaO-SiO2-FetO-P2O5 Slag[D]. Shenyang:Northeastern University,2010.) [29] 林路,包燕平,王敏,等. 二氧化钛改质对含磷转炉渣中磷富集行为的影响[J]. 北京科技大学学报,2014,36(8):1013.(LIN Lu,BAO Yan-ping,WANG Min,et al. Influence of titania modification on phosphorus enrichment in P-bearing steelmaking slag[J]. Chinese Journal of Engineering,2014,36(8):1013.) [30] JIANG L,DIAO J,YAN X M,et al. Effect of Al2O3 on enrichment of phosphorus in hot metal dephosphorization slag[J]. ISIJ International,2015,55(3):564. [31] 尾野均,韩光烈. 利用2CaO·SiO2颗粒上浮分离现象的转炉渣脱磷法[J]. 湖南冶金,1987(s1):32.(Ono H,Han Guang-lie. Dephosphorization of converter slag using 2CaO·SiO2 particles floating upward[J]. Hunan Metallurgy,1987(s1):32.) [32] Hitoshi O,Inagaki A,Masui T,et al. Removal of phosphorus from LD converter slag by floating of dicalcium silicate during solidification[J]. Tetsu-to-Hagané,1980,66(9):1317. [33] Kazuyo M Y,Hironari K,Tetsuya G. Recycling effects of residual slag after magnetic separation for phosphorus recovery from hot metal dephosphorization slag[J]. ISIJ International,2010,50(1):65. [34] Fujita T,Iwasaki I. Phosphorus removal from steelmaking slags slow cooled in a non-oxidizing atmosphere by magnetic separation/flotation[J]. Transaction of the ISS,1989(1):47. [35] Hironari K,Kazuyo M Y,Tetsuya N. Magnetic separation of phosphorus enriched phase from multiphase dephosphorization slag[J]. ISIJ International,2010,50(1):59. [36] Hideki O,Kobata K,Usui T. Carbon reduction rate of phosphorus in oxide melt[J]. Journal of JSEM,2012,12:209. [37] Masahito T. A reproducing method of refinement slag:Japan,08325622[P/OL]. 1996-12-10[2020-06-28]. https://www.j-platpat.inpit.go.jp/h0000. [38] Morita K,Guo M,Oka N,et al. Resurrection of the iron and phosphorus resource in steel-making slag[J]. Journal of Material Cycle and Waste Management, 2002,4(2):93. [39] 吕岩,张猛,艾立群,等. 微波处理碳热还原转炉钢渣的脱磷实验研究[J]. 炼钢,2010,26(4):70.(LÜ Yan,ZHANG Meng,AI Li-qun,et al. Experimental research on dephosphorization of converter slag by microwave heating and carbon thermal reduction[J]. Steelmaking,2010,26(4):70.) [40] 王艺慈,李海洋,李双威,等. 转炉钢渣气化脱磷反应的热力学分析及试验[J]. 钢铁研究学报,2016,28(6):31.(WANG Yi-ci,LI Hai-yang,LI Shuang-wei,et al. Thermodynamic analysis and experiment on gasification dephosphorization reaction of converter slag[J]. Journal of Iron and Steel Research,2016,28(6):31.) [41] 李光强,张峰,张力,等. 高温碳热还原进行转炉渣资源化的研究[J]. 材料与冶金学报,2003(3):167.(LI Guang-qiang,ZHANG Feng,ZHANG Li,et al. Recycle of converter slag by high temperature carbon thermal reduction[J]. Journal of Materials and Metallurgy,2003(3):167.) [42] 王书桓,吴艳青,徐志荣,等. 硅还原转炉熔渣气化脱磷热力学分析[J]. 炼钢,2008,24(1):31.(WANG Shu-huan,WU Yan-qing,XU Zhi-rong,et al. Thermodynamic analysis on gasificating dephosphorization of converter slag by silicon reduction[J]. Steelmaking,2008,24(1):31.) [43] 吴艳青. 硅还原转炉渣气化脱磷热力学和动力学基础研究[D]. 唐山:河北理工大学,2007.(WU Yan-qing. Thermodynamics and Kinetics of Gasificating Dephosphorization from Slag by Silicon Reduction[J]. Tangshan: North China University of Science and Technology,2007.) [44] Makhija D,Rath R K,Mukherjee A K. Application of enhanced gravity technique for separation of iron phase from LD slag[J]. Metallurgical Research and Technology,2019,116(3):303. [45] LI C,GAO J T,WANG Z,et al. Separation of Fe-bearing and P-bearing phase from the steelmaking slag by super gravity[J]. ISIJ International,2017,57(4):767. [46] LI C,GAO J,GUO Z C. Separation of phosphorus- and iron-enriched phase from CaO-SiO2-FeO-MgO-P2O5melt with super gravity[J]. Metallurgical and Materials Transactions B,2016,47:1516. [47] 朱桂林,杨景玲,郝以党,等. 我国钢铁渣综合利用“十一五”现状和“十二五”展望[J]. 中国钢铁业,2011(7):12.(ZHU Gui-lin,YANG Jing-ling,HAO Yi-dang,et al. The current situation of comprehensive utilization of iron and steel slag in the 11th Five Year Plan and the prospect of the 12th Five Year Plan[J]. China Steel,2011(7):12.) [48] 张朝晖,廖杰龙,巨建涛,等. 钢渣处理工艺与国内外钢渣利用技术[J]. 钢铁研究学报,2013,25(7):1.(ZHANG Chao-hui,LIAO Jie-long,JU Jian-tao,et al. Treatment process and utilization technology of steel slag in China and abroad[J]. Journal of Iron and Steel Research,2013,25(7):1.) [49] JIANG M F,YU Y,WANG D Y,et al. Effect of modification treatment for reduction of dephosphorization slag in hot metal bath[J]. Journal of Iron and Steel Research, International,2013,20(1):1. [50] DIAO J,XIE B,WANG Y H,et al. Recovery of phosphorus from dephosphorization slag produced by duplex high phosphorus hot metal refining[J]. ISIJ International,2012,52(6):955. [51] 陆天龙,刘栋,杨光照,等. 钢渣综合利用及尾渣中铁的回收研究进展[J]. 热加工工艺,2017,46(17):14.(LU Tian-long,LIU Dong,YANG Guang-zhao,et al. Research progress on comprehensive utilization of steel slag and iron recovery from tailings[J]. Hot Working Technology,2017,46(17):14.) [52] 王莉,曹盛,闫占辉,等. 炼钢厂含铁固体废弃物资源化回收利用[J]. 中国冶金,2018,28(3):73.(WANG Li,CAO Sheng,YAN Zhan-hui,et al. Recycling and utilization of iron containing solid waste resource in steelmaking plant[J]. China Metallurgy,2018,28(3):73.) [53] 吴贺,龙跃. 钢渣用作烧结熔剂的应用现状及分析[J]. 安徽冶金,2013(3):14.(WU He,LONG Yue. Application of steelmaking slag as sintering flux[J]. Anhui Metallurgy,2013(3):14.) [54] 章耿. 宝钢钢渣综合利用现状[J]. 宝钢技术,2006(1):20.(ZHANG Geng. Status of comprehensive utilization of steel slag at baosteel[J]. Baosteel Technology,2006(1):20.) [55] 韩凤光,邱海雨,聂慧远,等. 梅山烧结配加转炉钢渣的试验研究[J]. 烧结球团,2006(5):15.(HAN Feng-guang,QIU Hai-yu,NIE Hui-yuan,et al. Experiment of proportioning BOS in sintering production in MeiShan I&S Co[J]. Sintering and Pelletizing,2006(5):15.) [56] Motz H,Geiseler J. Products of steel slags an opportunity to save natural resources[J]. Waste Manage,2001,21:285. [57] Svyazhin A G,Shakhpazov E K,Romanovich D A. Recycling of slags in ferrous metallurgy[J]. Metallurgist,1998,42(4):129. [58] Suguna S V,Venu R M,Rao B V,et al. Recycling ladle furnace slag as flux in steelmaking:A review[J]. Journal of Sustainable Metallurgy,2019(5):449. [59] 刘浏. 中国氧气转炉炼钢技术的进步[J]. 中国冶金,2005,15(2):4.(LIU Liu. Technical progress of oxygen converter steelmaking in China[J]. China Metallurgy,2005,15(2):4.) [60] 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.) [61] 么洪勇. 转炉溅渣护炉冶炼因素对气化脱磷的影响[J]. 钢铁钒钛,2017,38(6):108.(ME Hong-yong. Effect of slag splashing on gasification dephosphorization in converter[J]. Iron Steel Vanadium Titanium,2017,38(6):108.) [62] 薛月凯,李晨晓,王书桓,等. 转炉终渣气化脱磷优化试验研究[J]. 钢铁钒钛,2018,39(5):93.(XUE Yue-kai,LI Chen-xiao,WANG Shu-huan,et al. Optimization of dephosphorization rate of converter final slag by gasification dephosphorization[J]. Iron Steel Vanadium Titanium,2018,39(5):93.) [63] 周朝刚,艾立群,王书桓,等. 气化脱磷机理及对下炉次冶炼过程的影响研究[J]. 钢铁钒钛,2018,39(6):129.(ZHOU Chao-gang,AI Li-qun,WANG Shu-huan,et al. Study on mechanism of gasification dephosphorization and influence of next heat smelting process[J]. Iron Steel Vanadium Titanium,2018,39(6):129.) [64] 李晨晓,王书桓,薛月凯,等. 焦粉还原转炉熔渣气化脱磷试验[J]. 钢铁,2018,53(9):20.(LI Chen-xiao,WANG Shu-huan,XUE Yue-kai,et al. Experiment on gasification dephosphorization with coke powder reducing converter molten slag[J]. Iron and Steel,2018,53(9):20.) [65] 雷加鹏. 国内钢渣处理技术的特点[J]. 钢铁研究,2010,38(5):46.(LEI Jia-peng. Characteristics of steel slag treatment processes in China[J]. Research on Iron and Steel,2010,38(5):46.) [66] Masanori N,Nobuhiro M,Sun-Joong K,et al. Fundamental experiment to extract phosphorous selectively from steelmaking slag by leaching[J]. ISIJ International,2014,54(8):1983. [67] Shigeru S,Ioka D,Hayashi T,et al. Recovery of phosphate from unused resources[J]. Phosphorus Research Bulletin,2011,25:18. [68] Shigeru S,Shinomiya I, Kitora R. Recovery and enrichment of phosphorus from the nitric acid extract of dephosphorization slag[J]. Journal of Chemical Engineering of Japan,2014,47(6):483. [69] DIAO J,JIANG L,WANG Y,et al. P2O5 solubility of dephosphorization slag in citric acid[J]. Phosphorus and Sulfur and the Related Elements,2015,190(3):387. [70] LÜ N N,SU C,KONG H,et al. Dissolution mechanism of various elements from steelmaking slag into citric acid solution[J]. Metallurgical Research and Technology,2019,116:321. [71] LI L,BAO Y P,WANG M. P2O5 solubility behavior and resource utilization of P-Bearing slag[J]. ISIJ International,2014,54(12):2746. [72] 王占军. 含磷转炉钢渣磷选择性富集过程中的物理化学性质研究[D]. 北京:北京科技大学,2017.(WANG Zhan-jun. Investigation on Physical and Chemical Properties of P-Bearing Steelmaking Slags during the Selective Enrichment Process of Phosphorus[D]. Beijing:University of Science and Technology Beijing,2017.) [73] DIAO J,KE Z,JIANG L,et al. Influence of Al2O3 modification on phosphorus enrichment in high phosphorus slag[J]. Mineral Processing and Extractive Metallurgy,2016,125(2):103. [74] 相会强,王林,刘彦君,等. 钢渣在建筑领域的综合利用及展望[J]. 中国冶金,2005,15(9):49.(XIANG Hui-qiang,WANG Lin,LIU Yan-jun,et al. Comprehensive utilization of steel-making slag on construction field and its prospect[J]. China Metallurgy,2005,15(9):49.) [75] HUANG Y,LIU Z S. Investigation on phosphogypsum-steel slag-granulated blast-furnace slag-limestone cement[J]. Construction Building Materials,2010,24(7):1296. [76] 石洪志,王如意,陈荣欢,等. 不锈钢钢渣用作水泥混合材及其安全性分析[J]. 建筑材料学报,2010,13(6):802.(SHI Hong-zhi,WANG Ru-yi,CHEN Rong-huan,et al. Safety analysis of stainless steel slag used as composite cement admixture[J]. Journal of Building Materials,2010,13(6):802.) [77] CHEN D Y,TAN K F. Study on mineral admixture of concrete prepared with electric furnace slag[J]. Bull Chinese Ceram Soc,2006,25(6):73. [78] 何亮,詹程阳,吕松涛,等. 钢渣沥青混合料应用现状[J]. 交通运输工程学报,2020,20(2):15.(HE Liang,ZHAN Cheng-yang,LÜ Song-tao,et al. Application status of steel slag asphalt mixture[J]. Journal of Traffic and Transportation Engineering,2020,20(2):15.) [79] 李超,陈宗武,谢君,等. 钢渣沥青混凝土技术及其应用研究进展[J]. 材料导报,2017,31(3):86.(LI Chao,CHEN Zong-wu,XIE Jun,et al. A technological and applicational review on steel slag asphalt mixture[J]. Materials Reports,2017,31(3):86.) [80] Ahmedzadea P,Sengoz B. Evaluation of steel slag coarse aggregate in hot mix asphalt concrete[J]. Journal of Hazardous Materials,2009,165:300. [81] 张大旺,王栋民,朴春爱,等. 钢渣掺量对3D打印地质聚合物材料新拌浆体流变性的影响[J]. 应用基础与工程科学学报,2018,26(3):596.(ZHANG Da-wang,WANG Dong-min,PIAO Chun-ai,et al. Effect of steel slag content on the rheology of 3D printing geopolymer pastes[J]. Journal of Basic Science and Engineering,2018,26(3):596.) [82] SUN Y,YAO M S,ZHANG J P,et al. Indirect CO2 mineral sequestration by steelmaking slag with NH4Cl as leaching solution[J]. Chemical Engineering Journal,2011,173:437. [83] CHANG E E,PAN S Y,CHEN Y H,et al. CO2 sequestration by carbonation of steelmaking slags in an autoclave reactor[J]. Journal of Hazardous Materials,2011,195:107. [84] Eloneva S,Tei S,Salminen J,et al. Fixation of CO2 by carbonating calcium derived from blast furnace slag[J]. Energy,2008,33:1461. [85] Lekakh S,Robertson D,Rawlins C,et al. Investigation of a two-stage aqueous reactor design for carbon dioxide sequestration using steelmaking slag[J]. Metallurgical and Materials Transactions: B,2008,39(3):484. [86] Toshiaki K,Takashi K,Chika K,et al. Environmental impact evaluation of steelmaking slag applied to coastal area development[J]. Tetsu-to-Hagané,2020,106(1):50. [87] Harunor R K,Mukaddas A B,Syed M K,et al. Effects of selected treatments on the production of rice in acid sulfate soils in a simulation study[J]. Journal of Agriculture and Rural Development in the Tropics and Subtropics,2006,50(3):109.