钒化工冶金固废资源化清洁利用
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摘要
采用整体化增值利用、多组元高效提取、末端无害化处置的策略,通过关键核心技术创新和集成,开发了具有产业化价值的低成本、高效钒化工冶金固废资源化清洁利用技术集成体系。提钒尾渣通过亚熔盐技术高效提钒后,渣中的钒含量(以V_2O_5计)降低至0.2wt%以下,铁含量(以Fe_2O_3计)富集至60wt%以上;再经钙化脱钠后终渣中钠含量(以Na_2O计)低于2wt%,可大比例替代低钒高品位铁精矿用于配矿烧结,配矿量由原来的20 kg/t提高至60 kg/t。将块状、粉状铬泥通过添加有机粘结剂和65碳化硅做成球骨架,加工成粒径5~30 mm的球状物并烘烤,加入炼钢工序,所制钢筋的屈服和抗拉强度均比常规工艺高,对钢筋性能提高有一定作用。采用钒酸铁部分替代V_2O_5冶炼钒铁技术上可行,1 t钒酸铁可代替209 kg V_2O_5,钒铁消耗0.2 t,钒回收率在90%以上,并生产出A级50钒铁产品。50钒铁炉渣作为粘结配料可提高钒钛烧结矿强度,在回收利用渣中钒、镁、钙元素的同时,使钒钛烧结矿转鼓指数提高2%~4%。
In view of the fact that the solid waste resources such as vanadium tailings, chromium mud, vanadium mud, iron vanadate mud and slag of Fe V50 produced in the vanadium chemical and metallurgical industry were difficult to be utilized on a large scale, a low-cost and high-efficiency vanadium chemical smelting industry with industrialized value was developed by adopting the strategy of integrated value-added utilization, multicomponent high-efficient extraction and end harmless disposal, and through the innovation and integration of key core technologies, a low-cost and high-efficiency integrated technology for clean utilization of solid waste of vanadium chemical metallurgy with industrial value has been developed. After vanadium tailings were extracted by sub-molten salt technology, V_2O_5 content in the final slag was reduced to below 0.2 wt%, and Fe_2O_3 content in the final slag was enriched to over 60 wt%. The Na_2O content in the final slag was less than 2 wt% after calcification and desalination, which could replace the low-vanadium and highgrade iron concentrate in a large proportion for ore blending and sintering, from the original 20 kg/t to 60 kg/t. The bulk and powder chromium mud was made into spherical skeleton by adding organic binder and 65 silicon carbide, processed into spherical material of 5~30 mm diameter and baked, and then added into steel-making process. Compared with conventional process, the yield strength and tensile strength were improved, which had a certain effect on improving the performance of reinforcing bars. It was feasible to use iron vanadate to partly replace vanadium pentoxide in ferrovanadium smelting. 1 t iron vanadate can replace 209 kg of vanadium pentoxide. The consumption of iron vanadium per ton was 0.2 t. The recovery rate of vanadium was over 90%. Slag of FeV50 as a "bonding" ingredient to improve the strength of V-Ti sinter, while recovering and utilizing V, Mg and Ca elements in the slag, the drum index of V-Ti sinter increased by 2%~4%.
In view of the fact that the solid waste resources such as vanadium tailings, chromium mud, vanadium mud, iron vanadate mud and slag of Fe V50 produced in the vanadium chemical and metallurgical industry were difficult to be utilized on a large scale, a low-cost and high-efficiency vanadium chemical smelting industry with industrialized value was developed by adopting the strategy of integrated value-added utilization, multicomponent high-efficient extraction and end harmless disposal, and through the innovation and integration of key core technologies, a low-cost and high-efficiency integrated technology for clean utilization of solid waste of vanadium chemical metallurgy with industrial value has been developed. After vanadium tailings were extracted by sub-molten salt technology, V_2O_5 content in the final slag was reduced to below 0.2 wt%, and Fe_2O_3 content in the final slag was enriched to over 60 wt%. The Na_2O content in the final slag was less than 2 wt% after calcification and desalination, which could replace the low-vanadium and highgrade iron concentrate in a large proportion for ore blending and sintering, from the original 20 kg/t to 60 kg/t. The bulk and powder chromium mud was made into spherical skeleton by adding organic binder and 65 silicon carbide, processed into spherical material of 5~30 mm diameter and baked, and then added into steel-making process. Compared with conventional process, the yield strength and tensile strength were improved, which had a certain effect on improving the performance of reinforcing bars. It was feasible to use iron vanadate to partly replace vanadium pentoxide in ferrovanadium smelting. 1 t iron vanadate can replace 209 kg of vanadium pentoxide. The consumption of iron vanadium per ton was 0.2 t. The recovery rate of vanadium was over 90%. Slag of FeV50 as a "bonding" ingredient to improve the strength of V-Ti sinter, while recovering and utilizing V, Mg and Ca elements in the slag, the drum index of V-Ti sinter increased by 2%~4%.
引文
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[19]高明磊,陈东辉,石立新,等.碳酸钠焙烧铝系钒铁炉渣共提取钒与铝[J].过程工程学报,2012,12(4):576-582.Gao M L,Chen D H,Shi L X,et al.Recovery of vanadium and aluminum in ferrovanadium slag from thermite method by sodium carbonate-roasting[J].The Chinese Journal of Process Engineering,2012,12(4):576-582.
[20]陈亮.从钒浸出液中沉淀结晶型钒酸铁试验研究[J].湿法冶金,2010,29(3):171-175.Cheng L.Study on precipitation of crystal-forming fervanite from vanadium leaching solution[J].Hydrometallurgy of China,2010,29(3):171-175.
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[22]周冰晶,王海旭,白丽,等.一次尾渣与钒泥提钒尾渣混合焙烧提钒研究[J].云南化工,2018,45(7):48-49.Zhou B J,Wang H X,Bai L,et al.Study on vanadium extraction from vanadium sludge by mixed roasting with vanadium sludge from vanadium sludge[J].Yunnan Chemical Technology,2018,45(7):48-49.
[23]李东明,卢永杰,孟旭光,等.炉渣碱度对钒铁冶炼的影响[J].河北冶金,2015,(10):12-13,20.Li D M,Lu Y J,Meng X G,et al.Influence of slag basicity on ferrovanadium smelting[J].Hebei Metallurgy,2015,(10):12-13,20.
[24]刘彦丽,冯少武.石钢烧结原料配比变化对烧结矿RDI影响的研究[J].河北冶金,2006,(1):13-15.Liu Y L,Feng S W.Influence of change in sintering burden ratio to change on sinter RDI[J].Hebei Metallurgy,2006,(1):13-15.
[25]张玉柱,客海滨,王丽丽,等.降低石钢烧结矿低温还原粉化率的研究[J].烧结球团,2007,(2):27-32.Zhang Y Z,Ke H B,Wang L L,et al.Investigation on reducing RDIof Shigang sinter[J].Sintering and Pelletizing,2007,(2):27-32.
[26]杨军.烧结厂265 m2烧结机配加蛇纹石工业试验的研究与实践[J].莱钢科技,2009,(1):44-46.Yang J.Research and practice on industrial test of adding serpentine to 265 m2 sintering machine in sintering plant[J].Laigang Science&Technology,2009,(1):44-46.
[2]邹建新,李亮.钒钛产品生产工艺与设备[M].北京:化学工业出版社,2014:186-210.Zhou J X,Li L.Production technology and equipment of vanadium and titanium products[M].Beijing:Chemical Industry Press,2014:186-210.
[3]杨绍利.钒钛材料[M].北京:冶金工业出版社,2007:19-20.Yang S L.Vanadium titanium materials[M].Beijing:Metallurgical Industry Press,2007:19-20.
[4]高明磊,李兰杰,白丽,等.钒化工固废循环利用与设计[C]//重庆大学,钒钛资源综合利用产业技术创新战略联盟-攀钢集团研究院有限公司.第三届钒钛微合金化高强钢开发应用技术暨第四届钒产业先进技术交流会论文集.2017:202-206.Gao M L,Li L J,Bai L,et al.Based on the vanadium chemical industry chain of circular economy planning and design[C]//Chongqing University,Vanadium and Titanium Resources Comprehensive Utilization Industry Technology Innovation Strategic Alliance-Pangang Group Research Institute Co.,Ltd.Papers Collection of the Third Development and Application Technology of Vanadium and Titanium Microalloyed High Strength Steel and the Fourth Advanced Technology Exchange Conference of Vanadium and Titanium Industry.2017:202-206.
[5]高明磊,李兰杰,白丽,等.钒化工固废循环利用新模式[J].北方钒钛,2018,(1):1-4.Gao M L,Li L J,Bai L,et al.New model of solid waste recycling in vanadium chemical industry[J].Northern Vanadium and Titanium,2018,(1):1-4.
[6]侯静,吴恩辉,李军.提钒尾渣的综合利用研究现状及进展[J].矿产保护与利用,2017,(6):103-108.Hou J,Wu E H,Li J.Current situation and progress of comprehensive utilization of vanadium extraction tailings[J].Conservation and Utilization of Mineral Resources,2017,(6):103-108.
[7]曾冠武,郝建璋.提钒尾渣脱钠技术研究[J].钢铁钒钛,2019,40(1):78-82,104.Zeng G W,Hao J Z.Study on desodium technology of vanadium extraction tailings[J].Iron Steel Vanadium Titanium,2019,40(1):78-82,104.
[8]张海平,丁跃华,郝建璋,等.钠化提钒尾渣脱钠实验[J].昆明理工大学学报(自然科学版),2015,40(6):8-12.Zhang H P,Ding Y H,Hao J Z,et al.Technology of eliminating sodium from extracted vanadium tailings[J].Journal of Kunming University of Science and Technology(Natural Science Edition),2015,40(6):8-12.
[9]孟利鹏,赵楚,王少娜,等.国内提钒尾渣再提钒技术研究进展[J].钢铁钒钛,2015,36(3):49-56.Meng L P,Zhao C,Wang S N,et al.Improvement of vanadium extraction from extracted vanadium residue in China[J].Iron Steel Vanadium Titanium,2015,36(3):49-56.
[10]Yang H F,Jing L L,Zhang B G.Recovery of iron from vanadium tailings with coal-based direct reduction followed by magnetic separation[J].Journal of Hazardous Materials,2011,185:1405-1411.
[11]张国杰,关淑平.絮凝助凝剂在钒液净化系统的应用研究[J].当代化工研究,2018,(6):52-53.Zhang G J,Guan S P.Study on application of flocculation coagulant aid in vanadium liquid purification system[J].Modern Chemical Research,2018,(6):52-53.
[12]王震宇,王少伟,周雅平.钒冶金废水污泥资源化利用[J].冶金与材料,2018,38(4):164-165,167.Wang Z Y,Wang S W,Zhou Y P.Utilization of sludge from vanadium metallurgical wastewater[J].Metallurgy and Materials,2018,38(4):164-165,167.
[13]马闯,高峻峰,黄振宇,等.从含钒铬泥中提取V、Cr的工艺研究[J].稀有金属与硬质合金,2016,44(3):17-20.Ma C,Gao J F,Huang Z Y,et al.Technological study on extraction of vanadium and chromium from vanadium-bearing chromium residue[J].Rare Metals and Cemented Carbides,2016,44(3):17-20.
[14]白瑞国.承钢钒钛矿资源高效清洁利用技术及发展[J].河北冶金,2015,(12):1-5.Bai R G.Technology and development of high-efficiency clean utilization of vanadium-titanium ore resource in Cheng steel[J].Hebei Metallurgy,2015,(12):1-5.
[15]李兰杰,陈东辉,白瑞国,等.含钒尾渣亚熔盐浸出提钒[J].过程工程学报,2011,11(5):747-754.Li L J,Chen D H,Bai R G,et al.Leaching of vanadium from vanadium-containing residue by NaOH sub-molten salt[J].The Chinese Journal of Process Engineering,2011,11(5):747-754.
[16]李兰杰,陈东辉,白瑞国,等.钒渣中钒铬提取技术研究进展[J].矿产综合利用,2013,(2):7-11.Li L J,Chen D H,Bai R G,et al.Research progress of extraction technology for vanadium&chromium from vanadium slags[J].Multipurpose Utilization of Mineral Resources,2013,(2):7-11.
[17]李兰杰.提钒尾渣资源化利用应用基础研究[D].沈阳:东北大学,2013:27-30.Li L J.Fundamental applied research on resource utilization of vanadium tailings[D].Shenyang:Northeastern University,2013:27-30.
[18]李兰杰,赵备备,王海旭,等.提钒尾渣高效脱碱及配矿炼铁工艺[J].过程工程学报,2017,17(1):138-143.Li L J,Zhao B B,Wang H X,et al.Research on resource utilization and high value utilization technology of the extracted vanadium residue[J].The Chinese Journal of Process Engineering,2017,17(1):138-143.
[19]高明磊,陈东辉,石立新,等.碳酸钠焙烧铝系钒铁炉渣共提取钒与铝[J].过程工程学报,2012,12(4):576-582.Gao M L,Chen D H,Shi L X,et al.Recovery of vanadium and aluminum in ferrovanadium slag from thermite method by sodium carbonate-roasting[J].The Chinese Journal of Process Engineering,2012,12(4):576-582.
[20]陈亮.从钒浸出液中沉淀结晶型钒酸铁试验研究[J].湿法冶金,2010,29(3):171-175.Cheng L.Study on precipitation of crystal-forming fervanite from vanadium leaching solution[J].Hydrometallurgy of China,2010,29(3):171-175.
[21]耿立唐,李兰杰,赵备备,等.钒化工流程高效提取钒元素[J].过程工程学报,2017,17(4):744-750.Geng L T,Li L J,Zhao B B,et al.High efficiency leaching of vanadium in vanadium chemical process[J].The Chinese Journal of Process Engineering,2017,17(4):744-750.
[22]周冰晶,王海旭,白丽,等.一次尾渣与钒泥提钒尾渣混合焙烧提钒研究[J].云南化工,2018,45(7):48-49.Zhou B J,Wang H X,Bai L,et al.Study on vanadium extraction from vanadium sludge by mixed roasting with vanadium sludge from vanadium sludge[J].Yunnan Chemical Technology,2018,45(7):48-49.
[23]李东明,卢永杰,孟旭光,等.炉渣碱度对钒铁冶炼的影响[J].河北冶金,2015,(10):12-13,20.Li D M,Lu Y J,Meng X G,et al.Influence of slag basicity on ferrovanadium smelting[J].Hebei Metallurgy,2015,(10):12-13,20.
[24]刘彦丽,冯少武.石钢烧结原料配比变化对烧结矿RDI影响的研究[J].河北冶金,2006,(1):13-15.Liu Y L,Feng S W.Influence of change in sintering burden ratio to change on sinter RDI[J].Hebei Metallurgy,2006,(1):13-15.
[25]张玉柱,客海滨,王丽丽,等.降低石钢烧结矿低温还原粉化率的研究[J].烧结球团,2007,(2):27-32.Zhang Y Z,Ke H B,Wang L L,et al.Investigation on reducing RDIof Shigang sinter[J].Sintering and Pelletizing,2007,(2):27-32.
[26]杨军.烧结厂265 m2烧结机配加蛇纹石工业试验的研究与实践[J].莱钢科技,2009,(1):44-46.Yang J.Research and practice on industrial test of adding serpentine to 265 m2 sintering machine in sintering plant[J].Laigang Science&Technology,2009,(1):44-46.
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