粗四氯化钛有机物精制除钒尾渣提钒技术
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摘要
从四氯化钛有机物精制除钒尾渣中提钒并制备V_2O_5产品,研究了精制除钒尾渣焙烧温度、浸出剂加入量、液固比、浸出温度、浸出时间对尾渣中钒转化和溶出率的影响。结果表明,焙烧温度大于600℃时,可高效脱除精制除钒尾渣中的碳和氯((27)0.1%),且低价钒被氧化为高价,钒主要以V_2O_5形式存在。对焙烧后的尾渣以Na_2CO_3水溶液为浸出剂,液固比6 mL/g及80℃下浸出60 min,钒浸出率为85.5%,浸出液仅含少量Si, Al, Ti杂质,以NH_4~+:V=2.5:1(摩尔比)直接加铵盐沉钒,得到NH_4VO_3,经干燥、煅烧制得V_2O_5产品,可满足99级粉钒指标要求,全流程钒收率为75%。
In the process of preparing titanium tetrachloride by chlorination technology, vanadium oxychloride and titanium tetrachloride will be extracted and condensed at the same time. Because of the close boiling point, aluminum powder or organic substance is used to remove vanadium oxychloride from titanium tetrachloride in order to prepare titanium products such as sponge titanium, titanium dioxide and so on. The tailing produced崾 ?rganic refining was a kind of high-quality raw material for vanadium extraction due to the high content of(20 wt%), and the impurity element is relatively few. In view of the extraction of vanadium from the tailing obtained by organic refining of titanium tetrachloride and the preparation of vanadium pentoxide product, the roasting temperature, the amount of leaching agent, the ratio of liquid to solid and the leaching temperature were studied. Furthermore, the effect of leaching time on the conversion rate and dissolution rate of vanadium in the tailing were studied respectively. The results showed that when calcination temperature was higher than 600℃, carbon and chlorine could be removed efficiently(<0.1%). Vanadium mainly existed in the form of vanadium pentoxide in the slag after roasting. The roasted slag was leached with sodium carbonate aqueous solution, the ratio of liquid to solid was 6 mL/g, the leaching rate of vanadium was 85.5% at 80 ℃ for 60 min. The leaching solution contained only a small amount of Si, Al, Ti, P impurities, which was suitable to precipitate vanadium product directly. Ammonium metavanadate was prepared by addition of ammonium salt with NH_4~+:V=2.5:1(molar ratio), and stirring at room temperature for 120 min, after filtering, washing, drying and calcining to obtain vanadium pentoxide. The chemical composition of vanadium pentoxide can fully meet the requirement of grade 99 powder vanadium. The vanadium yield of the whole process was 75%.
In the process of preparing titanium tetrachloride by chlorination technology, vanadium oxychloride and titanium tetrachloride will be extracted and condensed at the same time. Because of the close boiling point, aluminum powder or organic substance is used to remove vanadium oxychloride from titanium tetrachloride in order to prepare titanium products such as sponge titanium, titanium dioxide and so on. The tailing produced崾 ?rganic refining was a kind of high-quality raw material for vanadium extraction due to the high content of(20 wt%), and the impurity element is relatively few. In view of the extraction of vanadium from the tailing obtained by organic refining of titanium tetrachloride and the preparation of vanadium pentoxide product, the roasting temperature, the amount of leaching agent, the ratio of liquid to solid and the leaching temperature were studied. Furthermore, the effect of leaching time on the conversion rate and dissolution rate of vanadium in the tailing were studied respectively. The results showed that when calcination temperature was higher than 600℃, carbon and chlorine could be removed efficiently(<0.1%). Vanadium mainly existed in the form of vanadium pentoxide in the slag after roasting. The roasted slag was leached with sodium carbonate aqueous solution, the ratio of liquid to solid was 6 mL/g, the leaching rate of vanadium was 85.5% at 80 ℃ for 60 min. The leaching solution contained only a small amount of Si, Al, Ti, P impurities, which was suitable to precipitate vanadium product directly. Ammonium metavanadate was prepared by addition of ammonium salt with NH_4~+:V=2.5:1(molar ratio), and stirring at room temperature for 120 min, after filtering, washing, drying and calcining to obtain vanadium pentoxide. The chemical composition of vanadium pentoxide can fully meet the requirement of grade 99 powder vanadium. The vanadium yield of the whole process was 75%.
引文
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[2]孙朝晖.钒新技术及钒产业发展前景分析[J].钢铁钒钛,2012,33(1):1-7.Sun Z H.Analysis on new vanadium technologies and prospects of vanadium industry[J].Iron Steel Vanadium Titanium,2012,33(1):1-7.
[3]孙朝晖.钒产业发展之我见[J].矿产综合利用,2008,(6):40-44.Sun Z H.Review on the development of vanadium industry[J].Multipurpose Utilization of Mineral Resource,2008,(6):40-44.
[4]Li H Y,Fang H X,Wang K,et al.Asynchronous extraction of vanadium and chromium from vanadium slag by stepwise sodium roasting-water leaching[J].Hydrometallurgy,2015,156:124-135.
[5]Mahdavian A,Shafyei A,Alamdari K A,et al.Recovery of vanadium from Esfahan Steel Company steel slag:optimizing of roasting and leaching parameters[J].International Journal of ISSI,2006,3(2):17-21.
[6]周丽.高含钒粗四氯化钛有机物预处理除钒工艺研究[J].钢铁钒钛,2017,38(4):24-28.Zhou L.Study on the organics pretreatment of crude titanium tetrachloride with high content of vanadium for vanadium removal[J].Iron Steel Vanadium Titanium,2017,38(4):24-28
[7]李良,周丽,李冬勤,等.TiCl4精制尾渣的回收利用研究[J].钢铁钒钛,2016,37(5):76-79.Li L,Zhou L,Li D Q,et al.Study on the recycle technology of the slag from refinin process of TiCl4[J].Iron Steel Vanadium Titanium,2016,37(5):16-21.
[8]于静,章平,陈天祥,等.粗四氯化钛有机物除钒工艺研究[J].贵州工业大学学报(自然科学版),2008,37(2):29-32.Yu J,Zhang P,Chen T X,et al.Technical study of removing vanadium from raw titanium tetrachloride by organics[J].Journal of Guizhou University of Technology(Edition of Natural Science),2008,37(2):29-32.
[9]王学文,张力萍,肖连生,等.粗TiCl4铜丝塔除钒废水沉淀泥浆综合回收工艺[J].中国有色金属学报,2008,18(1):422-427.Wang X W,Zhang L P,Xiao L S,et al.Comprehensive recovery of precipitate of wastewater in removing vanadium from raw TiCl4with copper-wire[J].The Chinese Journal of Nonferrous Metals,2008,18(1):422-427.
[10]孙莹,王宁,袁继维,等.海绵钛生产中铜丝除钒废弃物的回收实验与分析[J].矿物学报,2009,29(1):124-128.Sun Y,Wang N,Yuan J W,et al.Recycle experiment and analysis of the waste brought in the process of removing vanadium by copper wires in titianium sponge?s production[J].Acta Mineralogica Sinica,2009,29(1):124-128.
[11]刘邦煜,王宁,袁继维,等.四氯化钛精制除钒废弃物的综合利用[J].化工环保,2009,29(1):58-61.Liu B Y,Wang N,Yuan J W,et al.Comprehensive utilization of waste in titanium tetrachloride refining[J].Environmental Protection of Chemical Industry,2009,29(1):58-61.
[12]柳云龙,桂劲松.四氯化钛精制车间氯化物泥浆提钒新工艺[J].钛工业进展,2013,30(3):36-39.Liu Y L,Gui J S.A new technology of vanadium extraction from chloride mud in the TiCl4 refining workshop[J].Titanium Industry Progress,2013,30(3):36-39.
[13]Aarabi-Karasgani M,Rashchi F,Mostoufi N,et al.Leaching of vanadium from LD converter slag using sulfuric acid[J].Hydrometallurgy,2010,102(1/4):14-21.
[14]He D S,Feng Q M,Zhang G F,et al.An environmentally-friendly technology of vanadium extraction from stone coal[J].Minerals Engineering,2007,20(12):1184-1186.
[15]刘新运,戴子林,郝文彬,等.红钒碱溶法制备高纯V2O5的研究[J].中国质量与标准导报,2014,4(8):65-67.Liu X Y,Dai Z L,Hao W B,et al.Preparation of high purity V2O5by alkali dissolution of red cake[J].China Quality and Standards Review,2014,4(8):65-67.