钒页岩氧压酸浸过程中V与Fe的分离工艺研究
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摘要
为了确定湖北某钒页岩氧压酸浸条件,以K_2SO_4为添加剂,对在氧压酸浸提V过程中K_2SO_4用量、硫酸的体积浓度、氧分压、浸出温度、浸出时间对V、Fe浸出率的影响进行了研究。结果表明,在K_2SO_4用量为7%、硫酸浓度为15%、浸出时间为5 h、氧分压为2.0 MPa、浸出温度为190℃条件下,V的浸出率为89.90%、Fe的浸出率仅为5.73%,较无K_2SO_4条件下V的浸出率提高,Fe的浸出率大幅降低。XRD、FTIR分析表明,K_2SO_4的介入能强化云母晶体结构的破坏,促进V的释放,提高了V浸出率;K+、SO2-4和Fe3+反应生成斜钾铁矾((KFe(SO4)2)沉淀,降低了Fe的浸出率,这是V与Fe有效分离的主要原因。因此,钒页岩氧压酸浸过程中适量添加K_2SO_4,不仅能提高V浸出率,而且能有效分离V与Fe,减少Fe对后续萃取工艺的不利影响。
In order to explore the conditions of oxygen pressure acid leaching for a vanadium shale in Hubei,with K_2SO_4 as additive,the influence of K_2SO_4 dosage,concentration of sulfuric acid,oxygen partial pressure,leaching temperature,and leaching time on leaching rate of vanadium and iron are investigated respectively during the extraction of Vanadium from black shale by oxygen pressure acid leaching.The results showed that under the conditions of K_2SO_4 dosage 7%,the concentration of H2 SO415%,leaching temperature 190 ℃ for 5 h at 2.0 MPa,the leaching rate of vanadium was 89.90% while the leaching rate of iron was only 5.73%.Obviously,the leaching rate of vanadium is increased,and the leaching rate of iron is greatly reduced compared with the tests without K_2SO_4.XRD phase and FTIR analysis showed that the addition of K_2SO_4 intensified the crystal structure destruction of mica which can promote the release of vanadium and increase its leaching rate. Yavapaiite sediment(KFe(SO4)2) formed by the reaction of K+,SO2+4 and Fe3+reduces the leaching rate of iron,that is the main reason for separating vanadium and iron.Therefore,in the oxygen pressure acid leaching process of vanadium shale,the proper addition of K_2SO_4 can increase the leaching rate of vanadium,and also effectively separate Vanadium and Iron,and reduce the negatively effects of Fe on the subsequent extraction process.
In order to explore the conditions of oxygen pressure acid leaching for a vanadium shale in Hubei,with K_2SO_4 as additive,the influence of K_2SO_4 dosage,concentration of sulfuric acid,oxygen partial pressure,leaching temperature,and leaching time on leaching rate of vanadium and iron are investigated respectively during the extraction of Vanadium from black shale by oxygen pressure acid leaching.The results showed that under the conditions of K_2SO_4 dosage 7%,the concentration of H2 SO415%,leaching temperature 190 ℃ for 5 h at 2.0 MPa,the leaching rate of vanadium was 89.90% while the leaching rate of iron was only 5.73%.Obviously,the leaching rate of vanadium is increased,and the leaching rate of iron is greatly reduced compared with the tests without K_2SO_4.XRD phase and FTIR analysis showed that the addition of K_2SO_4 intensified the crystal structure destruction of mica which can promote the release of vanadium and increase its leaching rate. Yavapaiite sediment(KFe(SO4)2) formed by the reaction of K+,SO2+4 and Fe3+reduces the leaching rate of iron,that is the main reason for separating vanadium and iron.Therefore,in the oxygen pressure acid leaching process of vanadium shale,the proper addition of K_2SO_4 can increase the leaching rate of vanadium,and also effectively separate Vanadium and Iron,and reduce the negatively effects of Fe on the subsequent extraction process.
引文
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[13]张成松,赵婷.赤铁矿除铁法在湿法炼锌工艺中的应用[J].湖南有色金属,2014(2):39-41.Zhang Chengsong,Zhao Ting.Applacationof the hematite process for removing iron in the zinc hydrometallurgical production[J].Hunan Nonferrous Metals,2014(2):39-41.
[14]Chen Xiangyang.Lan Xinzhe.Zhang Qiuli,et al.Leaching vanadium by high concentration sulfuric acid from stone coal[J].Transactions of Nonferrous Metals Society of China,2010(z1):123-126.
[15]赵杰,张一敏,黄晶,等.石煤空白焙烧—加助浸剂酸浸提钒工艺研究[J].稀有金属,2013(3):446-452.Zhao Jie,Zhang Yimin,Huang Jing,et al.Process of blank roastingsulphuric acid leaching of vanadium with leaching agent from stone coal[J].Chinese Journal of Rare Metals,2013(3):446-452.
[16]张廷安,牟望重,豆志河,等.转炉钒渣氧压酸浸过程V-FeH2O系的电位-p H图[J].中国有色金属学报,2011(11):2936-2945.Zhang Ting'an,Mu Wangzhong,Dou Zhihe,et al.Potential—p H diagrams for V-Fe-H2O system during oxygen pressure acid leaching of vanadium-bearing converter slags[J].The Chinese Journal of Nonferrous Metals,2011(11):2936-2945.
[2]李存兄,魏昶,李旻廷,等.石煤氧压酸浸提钒工艺优化[J].中国有色金属学报,2008(1):84-87.Li Cunxiong,Wei Chang,Li Minting,et al.Process optimization of vanadium extraction from black shale by acidic oxidizing pressure leaching[J].The Chinese Journal of Nonferrous Metals,2008(1):84-87.
[3]胡凯龙,刘旭恒.含钒石煤焙烧工艺综述[J].稀有金属与硬质合金,2015(1):1-6.Hu Kailong,Liu Xuheng.Review of roasting of vanadium-bearing carbonaceous shale[J].Rare Metals and Cemented Carbids,2015(1):1-6.
[4]戴子林,张恩普.从石煤钒矿中浸钒技术的研究现状[J].矿冶工程,2015(6):85-88.Dai Zilin,Zhang Enpu.Technicalstatus of leaching vanadium from stone coal vanadium ore[J].Mining and Metallurgical Engineering,2015(6):85-88.
[5]王继民,曹洪杨,吴斌秀,等.氧压酸浸法从脱锌氧化硬锌渣中选择性浸出锗和铟[J].有色金属:冶炼部分,2013(3):47-50.Wang Jimin,Cao Hongyang,Wu Binxiu,et al.Selective leaching of germanium and indium from dezincification oxidized hard zinc slag with oxygen pressure leaching process[J].Nonferrous Metals:Extractive Metallurgy,2013(3):47-50.
[6]薛楠楠,张一敏,刘涛,等.某云母型含钒石煤氧压与常压酸浸提钒比较[J].金属矿山,2014(9):64-68.Xue Nannan,Zhang Yimin,Liu Tao,et al.Comparison of atmosphere pressure acid leaching and oxygen pressure acid leaching for vanadium extracting from mica-type stone coal[J].Metal Mine,2014(9):64-68.
[7]Li Minting,Wei Chang,Fan Gang,et al.Extraction of vanadium from black shale using pressure acid leaching[J].Hydrometallurgy,2009,98:308-323.
[8]李道,刘涛,张一敏,等.石煤酸浸提钒过程中V、Fe、Al的浸出行为研究[J].有色金属,2016(6):50-53.Li Dao,Liu Tao,Zhang Yimin,et al.Leaching Behaviour of V,Fe,Al during vanadium extraction from stone coal by sufuric acid leaching[J].Nonferrous Metals:Extractive Metallurgy,2016(6):50-53.
[9]Huang Jun,Zhang Yimin,Huang Jing,et al.Selective leaching of vanadium from roasted stone coal by dilute sulfuric acid dephosphorization-two-stage pressure acid leaching[J].Minerals,2016(3):75.
[10]Xue Nannan,Zhang Yimin,Liu Tao,et al.Effects of hydration and hardening of calcium sulfate on muscovite dissolution during pressure acid leaching of black shale[J].Journal of Cleaner Production,2017,149:989-998.
[11]Crundwell F K.The mechanism of dissolution of minerals in acidic and alkaline solutions:PartⅡApplication of a new theory to silicates,aluminosilicates and quartz[J].Hydrometallurgy,2014,149:265-275.
[12]谢晓峰,李磊,王华,等.铜电解液净化除铁的研究进展[J].材料导报,2014(15):108-112.Xie Xiaofeng,Li Lei,Wang Hua,et al.Research progress for removal of iron in copper electrolyte[J].Materials Review,2014(15):108-112.
[13]张成松,赵婷.赤铁矿除铁法在湿法炼锌工艺中的应用[J].湖南有色金属,2014(2):39-41.Zhang Chengsong,Zhao Ting.Applacationof the hematite process for removing iron in the zinc hydrometallurgical production[J].Hunan Nonferrous Metals,2014(2):39-41.
[14]Chen Xiangyang.Lan Xinzhe.Zhang Qiuli,et al.Leaching vanadium by high concentration sulfuric acid from stone coal[J].Transactions of Nonferrous Metals Society of China,2010(z1):123-126.
[15]赵杰,张一敏,黄晶,等.石煤空白焙烧—加助浸剂酸浸提钒工艺研究[J].稀有金属,2013(3):446-452.Zhao Jie,Zhang Yimin,Huang Jing,et al.Process of blank roastingsulphuric acid leaching of vanadium with leaching agent from stone coal[J].Chinese Journal of Rare Metals,2013(3):446-452.
[16]张廷安,牟望重,豆志河,等.转炉钒渣氧压酸浸过程V-FeH2O系的电位-p H图[J].中国有色金属学报,2011(11):2936-2945.Zhang Ting'an,Mu Wangzhong,Dou Zhihe,et al.Potential—p H diagrams for V-Fe-H2O system during oxygen pressure acid leaching of vanadium-bearing converter slags[J].The Chinese Journal of Nonferrous Metals,2011(11):2936-2945.