低品位钼精矿氧化焙烧过程的反应行为
|
摘要
研究品位为39.27%的低品位钼精矿的氧化焙烧热力学、物相演变规律及焙烧特征。热力学分析表明:MoS2氧化的趋势仅次于Fe S2氧化趋势,能生成多种价态的氧化物,且生成的Mo O3可与多种金属氧化物反应生成钼酸盐,其中生成钼酸钙的趋势最大。焙烧过程包括MoS2氧化不充分、Mo O3稳定存在和钼酸盐生成3个阶段,温度过高或时间过长易生成不利于后续钼溶出的钼酸盐和低价氧化钼,适宜的焙烧温度为650~675℃、焙烧时间为2 h左右。氧化焙烧后,氨浸的钼溶出率仅为84.02%,浸出渣中钼含量高达13.93%,XRD分析表明浸出渣的组成以钼酸钙为主。采用Na2CO3为浸出剂对氨浸渣进行二次浸出,可将氨浸渣中的钼酸钙溶出,最终钼的总回收率可达90.82%。
Thermodynamics of oxidation roasting, phase evolution rules and roasting characteristics of low grade molybdenum concentrate with grade of 39.27% were studied. Thermodynamics analyses show that the oxidation tendency of MoS2 is second to that of Fe S2, so it is easily oxidized and generates several oxide products. Furthermore,Mo O3 could react with various metal oxides to generate molybdate in which calcium molybdate generates most easily.Roasting process contains three stages of incomplete oxidization of MoS2, stable existence of Mo O3 and generation of molybdate. Molybdate and low valence molybdenum oxide, which go against subsequent leaching, will easily generate at over high temperature or for long time. The suitable temperature is 650-675 ℃ and the roasting time is 2 h. After roasting, ammonia leaching rate of molybdenum is only about 84.02%, residue of Mo in leaching residue reaches 13.93%.XRD analysis shows that calcium molybdate is the main component in leaching residue. When Na2CO3 is used as the leaching reagent, calcium molybdate can be extracted during leaching residue, and the ultimate recovery rate of Mo can reach 90.82%.
Thermodynamics of oxidation roasting, phase evolution rules and roasting characteristics of low grade molybdenum concentrate with grade of 39.27% were studied. Thermodynamics analyses show that the oxidation tendency of MoS2 is second to that of Fe S2, so it is easily oxidized and generates several oxide products. Furthermore,Mo O3 could react with various metal oxides to generate molybdate in which calcium molybdate generates most easily.Roasting process contains three stages of incomplete oxidization of MoS2, stable existence of Mo O3 and generation of molybdate. Molybdate and low valence molybdenum oxide, which go against subsequent leaching, will easily generate at over high temperature or for long time. The suitable temperature is 650-675 ℃ and the roasting time is 2 h. After roasting, ammonia leaching rate of molybdenum is only about 84.02%, residue of Mo in leaching residue reaches 13.93%.XRD analysis shows that calcium molybdate is the main component in leaching residue. When Na2CO3 is used as the leaching reagent, calcium molybdate can be extracted during leaching residue, and the ultimate recovery rate of Mo can reach 90.82%.
引文
[1]罗振中.钼的应用及其发展[J].中国钼业,1998,27(2):7-10.LUO Zheng-zhong.Application and development of molybdenum[J].China Molybdenum Industry,1998,27(2):7-10.
[2]ZHANG Jiu-xing.The mechanism of strengthening and toughening of rare earth molybdenum alloy[C]//Proceeding of the l3th International Plansee Seminar.Bildstein:Metallwerk,1993.
[3]LINDSTROM R E,SCHEINER B J.Extraetion of molybdenum from ores by electro-oxidation[J].Bureau of Mines Metals Reeovery Program USBM Tech Progress Rep,1972,10(5):4-7.
[4]张文朴.我国钼资源中稀贵金属的综合利用与再生回收研发进展[J].稀有金属与硬质合金,2007,35(2):35-40.ZHANG Wen-pu.Progress of research and development of utilization and reproduction reclamation of china rare and noble metals in molybdenum resources[J].Rare Metals and Cemented Carbides,2007,35(2):35-40.
[5]向铁根.钼冶金[M].长沙:中南大学出版社,2002:1-20.XIANG Tie-gen.Molybdenum metallurgy[M].Changsha:Central South University Press,2002:1-20.
[6]吴爱祥.我国钼资源的分布与特征[J].中国钼业,1994,53(4):5-6.WU Ai-xiang.Distribution and characteristic of china molybdenum resources[J].China Molybdenum Industry,1994,53(4):5-6.
[7]张启修,赵秦生.钨钼冶金[M].北京:冶金工业出版社,2005.ZHANG Qi-xiu,ZHAO Qin-sheng.Tungsten-molybdenum metallurgy[M].Beijing:Metallurgical Industry Press,2005.
[8]WARREN I H,MOUNSEY D M.Factors influencing the selective leaching of molybdenum with sodium hypochlorite from copper/molybdenum sulphide minerals[J].Hydrometallurgy,1983,10(3):343-357.
[9]BHAPPU R R,REYNOLDS E H,STAHMENNW S.Studies on hypochlorite leaching of molybdenum[J].Unit Processes in Hydrometallurgy,1963:95-113.
[10]彭建蓉,杨大锦,陈加希,阎江峰.原生钼矿加压碱浸试验研究[J].稀有金属,2007,31:110-113.PENG Jian-rong,YANG Da-jin,CHEN Jia-xi,YAN Jiang-feng.Study on pressure alkaline leaching original molybdenum[J].Chinese Journal of Rare Metals,2007,31:110-113.
[11]CAO Zhan-fang,ZHONG Hong,LIU Guang-yi.Electricoxidation kinetics of molybdenite concentrate in acidic Na Cl solution[J].The Canadian Journal of Chemical Engineering,2009,87(6):93-94.
[12]符剑刚,钟宏,彭斌.超声强化电氧化法湿法分解辉相矿[J].过程工程学报,2005,5(4):389-392.FU Jian-gang,ZHONG Hong,PENG Bin.Study on ultrasonic strengthening wet digestion of molybdnite by electro oxidation method[J].The Chinese Journal of Process Engineering,2005,5(4):389-392.
[13]SHARMA T.Physico-chemical processing of low grade manganese ore[J].International Journal of Mineral Processing,1992,35(3/4):191-203.
[14]任宝江.回转窑焙烧钼精矿的生产实践[J].有色金属:冶炼部分,1999(2):18-20.REN Bao-jiang.Production practice of molybdenum concentrate roasting by rotary kiln[J].Nonferrous Metals:Extractive Metallurgy,1999(2):18-20.
[15]MEHUGH L F,BARCHERS D E.Roasting of molybdenite on centrates containing flotation oils.US,4523948[P].1985-06-18.
[16]MEHUGH L F,GODSSEHALK J,KUZIOR M.Climax conversionⅢ[C]//Vancouver:The XⅥCanadian Institute of Mining and Metallurgy Annu Meeting,1977:8.
[17]MAHESHC J,MAY W A.Fluidized-bed roasting of molybdenites concentrates.US,6190625[P].2001-02-20.
[18]杨洪英,俞娟,佟琳琳,罗文杰.低品位复杂钼精矿的提纯工艺[J].中国有色金属学报,2013,23(7):2016-2018.YANG Hong-ying,YU Juan,TONG Lin-lin,LUO Wen-jie.Purification process of low grade complex molybdenum concentrates[J].The Chinese Journal of Nonferrous Metals,2013,23(7):2016-2018.
[19]WANG Si-fu,WEI Chang,DENG Zhi-gan,LI Cun-xiong,LI Xin-bing,WU Jun,WANG Ming-shuang,ZHANG Fan.Extracion of molybdenum and nickel from Ni-Mo ore by pressure acid leaching[J].Transactions of Nonferrous Metals Society of China,2013,23(10):3083-3088.
[2]ZHANG Jiu-xing.The mechanism of strengthening and toughening of rare earth molybdenum alloy[C]//Proceeding of the l3th International Plansee Seminar.Bildstein:Metallwerk,1993.
[3]LINDSTROM R E,SCHEINER B J.Extraetion of molybdenum from ores by electro-oxidation[J].Bureau of Mines Metals Reeovery Program USBM Tech Progress Rep,1972,10(5):4-7.
[4]张文朴.我国钼资源中稀贵金属的综合利用与再生回收研发进展[J].稀有金属与硬质合金,2007,35(2):35-40.ZHANG Wen-pu.Progress of research and development of utilization and reproduction reclamation of china rare and noble metals in molybdenum resources[J].Rare Metals and Cemented Carbides,2007,35(2):35-40.
[5]向铁根.钼冶金[M].长沙:中南大学出版社,2002:1-20.XIANG Tie-gen.Molybdenum metallurgy[M].Changsha:Central South University Press,2002:1-20.
[6]吴爱祥.我国钼资源的分布与特征[J].中国钼业,1994,53(4):5-6.WU Ai-xiang.Distribution and characteristic of china molybdenum resources[J].China Molybdenum Industry,1994,53(4):5-6.
[7]张启修,赵秦生.钨钼冶金[M].北京:冶金工业出版社,2005.ZHANG Qi-xiu,ZHAO Qin-sheng.Tungsten-molybdenum metallurgy[M].Beijing:Metallurgical Industry Press,2005.
[8]WARREN I H,MOUNSEY D M.Factors influencing the selective leaching of molybdenum with sodium hypochlorite from copper/molybdenum sulphide minerals[J].Hydrometallurgy,1983,10(3):343-357.
[9]BHAPPU R R,REYNOLDS E H,STAHMENNW S.Studies on hypochlorite leaching of molybdenum[J].Unit Processes in Hydrometallurgy,1963:95-113.
[10]彭建蓉,杨大锦,陈加希,阎江峰.原生钼矿加压碱浸试验研究[J].稀有金属,2007,31:110-113.PENG Jian-rong,YANG Da-jin,CHEN Jia-xi,YAN Jiang-feng.Study on pressure alkaline leaching original molybdenum[J].Chinese Journal of Rare Metals,2007,31:110-113.
[11]CAO Zhan-fang,ZHONG Hong,LIU Guang-yi.Electricoxidation kinetics of molybdenite concentrate in acidic Na Cl solution[J].The Canadian Journal of Chemical Engineering,2009,87(6):93-94.
[12]符剑刚,钟宏,彭斌.超声强化电氧化法湿法分解辉相矿[J].过程工程学报,2005,5(4):389-392.FU Jian-gang,ZHONG Hong,PENG Bin.Study on ultrasonic strengthening wet digestion of molybdnite by electro oxidation method[J].The Chinese Journal of Process Engineering,2005,5(4):389-392.
[13]SHARMA T.Physico-chemical processing of low grade manganese ore[J].International Journal of Mineral Processing,1992,35(3/4):191-203.
[14]任宝江.回转窑焙烧钼精矿的生产实践[J].有色金属:冶炼部分,1999(2):18-20.REN Bao-jiang.Production practice of molybdenum concentrate roasting by rotary kiln[J].Nonferrous Metals:Extractive Metallurgy,1999(2):18-20.
[15]MEHUGH L F,BARCHERS D E.Roasting of molybdenite on centrates containing flotation oils.US,4523948[P].1985-06-18.
[16]MEHUGH L F,GODSSEHALK J,KUZIOR M.Climax conversionⅢ[C]//Vancouver:The XⅥCanadian Institute of Mining and Metallurgy Annu Meeting,1977:8.
[17]MAHESHC J,MAY W A.Fluidized-bed roasting of molybdenites concentrates.US,6190625[P].2001-02-20.
[18]杨洪英,俞娟,佟琳琳,罗文杰.低品位复杂钼精矿的提纯工艺[J].中国有色金属学报,2013,23(7):2016-2018.YANG Hong-ying,YU Juan,TONG Lin-lin,LUO Wen-jie.Purification process of low grade complex molybdenum concentrates[J].The Chinese Journal of Nonferrous Metals,2013,23(7):2016-2018.
[19]WANG Si-fu,WEI Chang,DENG Zhi-gan,LI Cun-xiong,LI Xin-bing,WU Jun,WANG Ming-shuang,ZHANG Fan.Extracion of molybdenum and nickel from Ni-Mo ore by pressure acid leaching[J].Transactions of Nonferrous Metals Society of China,2013,23(10):3083-3088.