盐酸体系中辉锑矿的臭氧协同氧化浸出动力学
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摘要
采用动力学研究的方法对盐酸体系中辉锑矿的臭氧协同氧化浸出过程进行了研究,分别探索了温度、盐酸浓度、气体流量和搅拌速度等因素对该过程中锑浸出率的影响;在此基础上,对该浸出过程进行动力学计算。结果表明:在温度75℃、盐酸浓度4.50 mol/L、气体流量2.0 L/min和搅拌速度500 r/min的条件下浸出50 min后,锑浸出率可以达到59.13%。辉锑矿的臭氧协同氧化浸出符合收缩核模型,过程反应速率受混合过程控制,计算得到表观活化能为15.98 k J/mol,并最终建立了该浸出过程的动力学总方程式。
A kinetic study method was used to study the synergistic oxidation and leaching of lanthanide with ozone in the hydrochloric acid system. The factors affecting the leaching rate such as temperature, concentration of hydrochloric acid, gas flow rate and stirring speed were investigated. On this basis, the kinetics of the leaching process was calculated. The results show that the antimony extraction is 59.13% after leaching for 50 min at the conditions of temperature 75 ℃, hydrochloric acid concentration 4.50 mol/L, gas flow rate 2.0 L/min, and stirring speed 500 r/min. The process is consistent with the shrinkage model, the process reaction rate is controlled by the mixing process, the apparent activation energy calculated is 15.98 k J/mol, and the general equation of dynamics of the leaching process is finally established.
A kinetic study method was used to study the synergistic oxidation and leaching of lanthanide with ozone in the hydrochloric acid system. The factors affecting the leaching rate such as temperature, concentration of hydrochloric acid, gas flow rate and stirring speed were investigated. On this basis, the kinetics of the leaching process was calculated. The results show that the antimony extraction is 59.13% after leaching for 50 min at the conditions of temperature 75 ℃, hydrochloric acid concentration 4.50 mol/L, gas flow rate 2.0 L/min, and stirring speed 500 r/min. The process is consistent with the shrinkage model, the process reaction rate is controlled by the mixing process, the apparent activation energy calculated is 15.98 k J/mol, and the general equation of dynamics of the leaching process is finally established.
引文
[1]TIAN Qing-hua,WANG Heng-li,XIN Yu-tao,GUO Xue-yi.Effect of selected parameters on stibnite concentrates leaching by ozone[J].Hydrometallurgy,2016,165:295-299.
[2]陈永明,黄潮,唐谟堂,姚维义,唐朝波,皮关华.硫化锑精矿还原造锍熔炼一步炼锑[J].中国有色金属学报,2005,15(8):1311-1316.CHEN Yong-ming,HUANG Chao,TANG Mo-tang,YAO Wei-yi,TAO Chao-bo,PI Guan-hua.Production of antimony by directly reducing-matting smelting of stibnite concentrate[J].The Chinese Journal of Nonferrous Metals,2005,15(8):1311-1316.
[3]叶龙刚,唐朝波,唐谟堂,杨建广,陈永明,杨声海,何静.硫化锑精矿低温熔炼新工艺[J].中南大学学报(自然科学版),2012,43(9):3338-3343.YE Long-gang,TANG Chao-bo,TANG Mo-tang,YANG Jian-guang,CHEN Yong-ming,YANG Sheng-hai,HE Jing.Separation antimony from stibnite concentrate through a low temperature smelting[J].Journal of Central South University(Science and Technology),2012,43(9):3338-3343.
[4]ANDERSON C G.The metallurgy of antimony[J].Chemie der Erde-Geochemistry,2012,72:3-8.
[5]RASCHMAN P,SMINCAKOVA E.Kinetics of leaching of stibnite by mixed Na2S and Na OH solutions[J].Hydrometallurgy,2012,113:60-66.
[6]UBALDINI S,VEGLIO F,FORNARI P,ABBRUZZESE C.Process flow-sheet for gold and antimony recovery from stibnite[J].Hydrometallurgy,2000,57(3):187-199.
[7]刘小文,杨建广,伍永田,李静,唐朝波,陈永明,唐谟堂.由辉锑矿低温固硫熔炼制取粗锑[J].中国有色金属学报,2012,22(10):2896-2901.LIU Xiao-wen,YANG Jian-guang,WU Yong-tian,LI Jing,TANG Chao-bo,CHEN Yong-ming,TANG Mo-tang.Separation of needle antimony from stibnite through low-temperature sulfur-fixing smelting process[J].The Chinese Journal of Nonferrous Metals,2012,22(10):2896-2901.
[8]LOUTFY H M,IBRAHIM A S.Electrolytic recovery of antimony from nature stibnite ore[J].Hydrometallurgy,1996,43(1/3):265-275.
[9]GUDYANGA F P,MAHLANGU T,CHIFAMBA J,SIMBI D J.Reductive-oxidative pretreatment of a stibnite flotation concentrate:Thermodynamic and kinetic considerations[J].Minerals Engineering,1998,11(6):563-580.
[10]唐谟堂,赵天从,鲁君乐.新氯化-水解法的原理和应用[J].中南大学学报(自然科学版),1992,23(4):405-411.TANG Mo-tang,ZHAO Tian-cong,LU Jun-le.Principle and application of the new chlorination-hydrolization process[J].Journal of Central South University(Science and Technology),1992,23(4):405-411.
[11]YANG Jian-guang,WU Yong-tian.A hydrometallurgical process for the separation and recovery of antimony[J].Hydrometallurgy,2014,143:68-74.
[12]UKASIK M,HAVLIK T.Effect of selected parameters on tetrahedrite leaching by ozone[J].Hydrometallurgy,2005,77(1):139-145.
[13]LI Qing-cui,LI Deng-xin,QIAN Fang-jun.Pre-oxidation of high-sulfur and high-arsenic refractory gold concentrate by ozone and ferric ions in acidic media[J].Hydrometallurgy,2009,97:61-66.
[14]湛雪辉,李朝辉,湛含辉,李飞,曹芬,李侠.臭氧-过氧化氢联合浸出方铅矿[J].中南大学学报(自然科学版),2012,43(5):1651-1655.ZHAN Xue-hui,LI Zhao-hui,ZHAN Han-hui,LI Fei,CAO Fen,LI Xia.Combined leaching of galena by ozone-hydrogen peroxide solution[J].Journal of Central South University(Science and Technology),2012,43(5):1651-1655.
[15]TIAN Qing-hua,XIN Yun-tao,JIAO Cui-yan,GUO Xue-yi.Recovery of cobalt from cobalt chloride solution under the action of ozone[J].Advanced Materials Research,2012,460:317-320.
[16]TIAN Qing-hua,GUO Xue-yi,YI Yu,LI Zhi-hai.Kinetics of oxidation-precipitation of cobalt(Ⅱ)from solution by ozone[J].Transactions of Nonferrous Metals Society of China,2010,20(1):42-45.
[17]薛娟琴,毛维博,卢曦,李京仙,王玉洁,吴明.超声波辅助硫化镍矿氧化浸出动力学[J].中国有色金属学报,2010,20(5):1013-1020.XUE Juan-qin,MAO Wei-bo,LU Xi,LI Jing-xian,WANG Yu-jie,WU Ming.Dynamics of ultrasound-assisted oxidation leaching of nickel sulfide concentrate[J].The Chinese Journal of Nonferrous Metals,2010,20(5):1013-1020.
[18]徐志峰,朱辉,王成彦.富氧硫酸体系中硫化锌精矿的常压直接浸出动力学[J].中国有色金属学报,2013,23(12):3340-3347.XU Zhi-feng,ZHU Hui,WANG Cheng-yan.Atmospheric direct leaching kinetics of zinc sulfide concentrate in oxygen-rich sulfuric acid system[J].The Chinese Journal of Nonferrous Metals,2013,23(12):3340-3347.
[19]李宏煦,苍大强,陈景河,邱冠周.生物因素对次生硫化铜矿堆浸过程动力学的影响[J].中国有色金属学报,2007,17(2):331-335.LI Hong-xu,CANG Da-qiang,CHEN Jing-he,QIU Guan-zhou.Effect of biological factors on heap bioleaching kinetics of secondary copper sulfide[J].The Chinese Journal of Nonferrous Metals,2007,17(2):331-335.
[20]QIU Ting-sheng,NIE Guang-hua,WANG Jun-feng,CUI Li-feng.Kinetic process of oxidative leaching of chalcopyrite under low oxygen pressure and low temperature[J].Transactions of Nonferrous Metals Society of China,2007,17(2):418-422.
[21]HAVLIK T,DVORSCIKOVA J,LVANOVA Z,KAMMEL R.Sulphuric acid chalcopyrite leaching using ozone as oxidant[J].Metall,1999,53(1):57-60.
[22]周宗侯,廖星.溶液中锑铁物相分析的研究[J].冶金分析,1990,10(1):29-32.ZHOU Zong-hou,LIAO Xing.Investigation on chemical phase analysis of antimony and iron in the solution[J].Metallurgical Analysis,1990,10(1):29-32.
[23]郑雅杰,陈昆昆.采用Na2SO3溶液从硒渣中选择性浸出Se及其动力学[J].中国有色金属学报,2012,22(2):585-591.ZHENG Ya-jie,CHEN Kun-kun.Selective leaching Se from selenium residue by Na2SO3 solutions and leaching kinetics[J].The Chinese Journal of Nonferrous Metals,2012,22(2):585-591.
[24]AWE S A,SAMUELSSON C,SANDSTROM A.Dissolution kinetics of tetrahedrite mineral in alkaline sulphide media[J].Hydrometallurgy,2010,103:167-172.
[25]TIAN Qing-hua,WANG Heng-li,XIN Yun-tao,LI Dong,GUO Xue-yi.Ozonation leaching of a complex sulfidic antimony ore in hydrochloric acid solution[J].Hydrometallurgy,2016,159:126-131.
[26]ZHENG Ya-jie,CHEN Kun-kun.Leaching kinetics of selenium from selenium-tellurium-rich materials in sodium sulfite solutions[J].Transactions of Nonferrous Metals Society of China,2014,24(2):536-543.
[2]陈永明,黄潮,唐谟堂,姚维义,唐朝波,皮关华.硫化锑精矿还原造锍熔炼一步炼锑[J].中国有色金属学报,2005,15(8):1311-1316.CHEN Yong-ming,HUANG Chao,TANG Mo-tang,YAO Wei-yi,TAO Chao-bo,PI Guan-hua.Production of antimony by directly reducing-matting smelting of stibnite concentrate[J].The Chinese Journal of Nonferrous Metals,2005,15(8):1311-1316.
[3]叶龙刚,唐朝波,唐谟堂,杨建广,陈永明,杨声海,何静.硫化锑精矿低温熔炼新工艺[J].中南大学学报(自然科学版),2012,43(9):3338-3343.YE Long-gang,TANG Chao-bo,TANG Mo-tang,YANG Jian-guang,CHEN Yong-ming,YANG Sheng-hai,HE Jing.Separation antimony from stibnite concentrate through a low temperature smelting[J].Journal of Central South University(Science and Technology),2012,43(9):3338-3343.
[4]ANDERSON C G.The metallurgy of antimony[J].Chemie der Erde-Geochemistry,2012,72:3-8.
[5]RASCHMAN P,SMINCAKOVA E.Kinetics of leaching of stibnite by mixed Na2S and Na OH solutions[J].Hydrometallurgy,2012,113:60-66.
[6]UBALDINI S,VEGLIO F,FORNARI P,ABBRUZZESE C.Process flow-sheet for gold and antimony recovery from stibnite[J].Hydrometallurgy,2000,57(3):187-199.
[7]刘小文,杨建广,伍永田,李静,唐朝波,陈永明,唐谟堂.由辉锑矿低温固硫熔炼制取粗锑[J].中国有色金属学报,2012,22(10):2896-2901.LIU Xiao-wen,YANG Jian-guang,WU Yong-tian,LI Jing,TANG Chao-bo,CHEN Yong-ming,TANG Mo-tang.Separation of needle antimony from stibnite through low-temperature sulfur-fixing smelting process[J].The Chinese Journal of Nonferrous Metals,2012,22(10):2896-2901.
[8]LOUTFY H M,IBRAHIM A S.Electrolytic recovery of antimony from nature stibnite ore[J].Hydrometallurgy,1996,43(1/3):265-275.
[9]GUDYANGA F P,MAHLANGU T,CHIFAMBA J,SIMBI D J.Reductive-oxidative pretreatment of a stibnite flotation concentrate:Thermodynamic and kinetic considerations[J].Minerals Engineering,1998,11(6):563-580.
[10]唐谟堂,赵天从,鲁君乐.新氯化-水解法的原理和应用[J].中南大学学报(自然科学版),1992,23(4):405-411.TANG Mo-tang,ZHAO Tian-cong,LU Jun-le.Principle and application of the new chlorination-hydrolization process[J].Journal of Central South University(Science and Technology),1992,23(4):405-411.
[11]YANG Jian-guang,WU Yong-tian.A hydrometallurgical process for the separation and recovery of antimony[J].Hydrometallurgy,2014,143:68-74.
[12]UKASIK M,HAVLIK T.Effect of selected parameters on tetrahedrite leaching by ozone[J].Hydrometallurgy,2005,77(1):139-145.
[13]LI Qing-cui,LI Deng-xin,QIAN Fang-jun.Pre-oxidation of high-sulfur and high-arsenic refractory gold concentrate by ozone and ferric ions in acidic media[J].Hydrometallurgy,2009,97:61-66.
[14]湛雪辉,李朝辉,湛含辉,李飞,曹芬,李侠.臭氧-过氧化氢联合浸出方铅矿[J].中南大学学报(自然科学版),2012,43(5):1651-1655.ZHAN Xue-hui,LI Zhao-hui,ZHAN Han-hui,LI Fei,CAO Fen,LI Xia.Combined leaching of galena by ozone-hydrogen peroxide solution[J].Journal of Central South University(Science and Technology),2012,43(5):1651-1655.
[15]TIAN Qing-hua,XIN Yun-tao,JIAO Cui-yan,GUO Xue-yi.Recovery of cobalt from cobalt chloride solution under the action of ozone[J].Advanced Materials Research,2012,460:317-320.
[16]TIAN Qing-hua,GUO Xue-yi,YI Yu,LI Zhi-hai.Kinetics of oxidation-precipitation of cobalt(Ⅱ)from solution by ozone[J].Transactions of Nonferrous Metals Society of China,2010,20(1):42-45.
[17]薛娟琴,毛维博,卢曦,李京仙,王玉洁,吴明.超声波辅助硫化镍矿氧化浸出动力学[J].中国有色金属学报,2010,20(5):1013-1020.XUE Juan-qin,MAO Wei-bo,LU Xi,LI Jing-xian,WANG Yu-jie,WU Ming.Dynamics of ultrasound-assisted oxidation leaching of nickel sulfide concentrate[J].The Chinese Journal of Nonferrous Metals,2010,20(5):1013-1020.
[18]徐志峰,朱辉,王成彦.富氧硫酸体系中硫化锌精矿的常压直接浸出动力学[J].中国有色金属学报,2013,23(12):3340-3347.XU Zhi-feng,ZHU Hui,WANG Cheng-yan.Atmospheric direct leaching kinetics of zinc sulfide concentrate in oxygen-rich sulfuric acid system[J].The Chinese Journal of Nonferrous Metals,2013,23(12):3340-3347.
[19]李宏煦,苍大强,陈景河,邱冠周.生物因素对次生硫化铜矿堆浸过程动力学的影响[J].中国有色金属学报,2007,17(2):331-335.LI Hong-xu,CANG Da-qiang,CHEN Jing-he,QIU Guan-zhou.Effect of biological factors on heap bioleaching kinetics of secondary copper sulfide[J].The Chinese Journal of Nonferrous Metals,2007,17(2):331-335.
[20]QIU Ting-sheng,NIE Guang-hua,WANG Jun-feng,CUI Li-feng.Kinetic process of oxidative leaching of chalcopyrite under low oxygen pressure and low temperature[J].Transactions of Nonferrous Metals Society of China,2007,17(2):418-422.
[21]HAVLIK T,DVORSCIKOVA J,LVANOVA Z,KAMMEL R.Sulphuric acid chalcopyrite leaching using ozone as oxidant[J].Metall,1999,53(1):57-60.
[22]周宗侯,廖星.溶液中锑铁物相分析的研究[J].冶金分析,1990,10(1):29-32.ZHOU Zong-hou,LIAO Xing.Investigation on chemical phase analysis of antimony and iron in the solution[J].Metallurgical Analysis,1990,10(1):29-32.
[23]郑雅杰,陈昆昆.采用Na2SO3溶液从硒渣中选择性浸出Se及其动力学[J].中国有色金属学报,2012,22(2):585-591.ZHENG Ya-jie,CHEN Kun-kun.Selective leaching Se from selenium residue by Na2SO3 solutions and leaching kinetics[J].The Chinese Journal of Nonferrous Metals,2012,22(2):585-591.
[24]AWE S A,SAMUELSSON C,SANDSTROM A.Dissolution kinetics of tetrahedrite mineral in alkaline sulphide media[J].Hydrometallurgy,2010,103:167-172.
[25]TIAN Qing-hua,WANG Heng-li,XIN Yun-tao,LI Dong,GUO Xue-yi.Ozonation leaching of a complex sulfidic antimony ore in hydrochloric acid solution[J].Hydrometallurgy,2016,159:126-131.
[26]ZHENG Ya-jie,CHEN Kun-kun.Leaching kinetics of selenium from selenium-tellurium-rich materials in sodium sulfite solutions[J].Transactions of Nonferrous Metals Society of China,2014,24(2):536-543.