紫金铜尾矿中明矾石直接加压酸浸
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摘要
为解决传统明矾石提钾、铝研究一直存在的大规模产业化过程复杂、高成本等难题,以紫金矿业选铜尾矿浮选得到的明矾石为原料,首次提出采用硫酸直接加压酸浸新工艺,在明矾石未经过煅烧情况下铝、钾的浸出率可以分别达到98.54%、95.73%,远高于常压浸出效果,而且工艺过程简单,提取成本低,反应过程较佳的工艺参数为:温度220℃、酸矿比(g/g)为3:1、酸含量为25%(质量分数)、反应时间120 min、搅拌速率为600 r/min。通过X射线衍射和扫描电镜的分析表明:明矾石结构被充分破坏,浸出渣的主要成分为SiO_2。
In order to solve the difficulty of high cost and wide industrialization in the traditional techniques of extracting potassium and aluminum from alunite, the alunite floated from the tailings of Zijin copper ore was processed by non-roasting pressure acid-leaching. Compared with normal pressure leaching process, it can not only improve the leaching ratio of K and Al to 95.73% and 98.54%, respectively, but also have simpler technological route and low cost. Based on experimental research, the optimal leaching parameters are leaching temperature of 220 ℃, acid to ore ratio(g/g) of 3:1, initial acid concentration of 25%, leaching time of 120 min and stirring rate of 600 r/min. Analysis of the high pressure acid leaching residue by X-Ray powder diffraction and scanning electron microscope analysis indicates that crystal structure of alunite is completely destroyed, and the main chemical composition of leaching residue is SiO_2.
In order to solve the difficulty of high cost and wide industrialization in the traditional techniques of extracting potassium and aluminum from alunite, the alunite floated from the tailings of Zijin copper ore was processed by non-roasting pressure acid-leaching. Compared with normal pressure leaching process, it can not only improve the leaching ratio of K and Al to 95.73% and 98.54%, respectively, but also have simpler technological route and low cost. Based on experimental research, the optimal leaching parameters are leaching temperature of 220 ℃, acid to ore ratio(g/g) of 3:1, initial acid concentration of 25%, leaching time of 120 min and stirring rate of 600 r/min. Analysis of the high pressure acid leaching residue by X-Ray powder diffraction and scanning electron microscope analysis indicates that crystal structure of alunite is completely destroyed, and the main chemical composition of leaching residue is SiO_2.
引文
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[14]沈青峰,衷水平,王瑞永.紫金山选铜尾矿综合利用明矾石工艺研究[J].矿产保护与利用,2011(5):88-91.SHEN Qing-feng,ZHONG Shui-ping,WANG Rui-yong.Study on the preparation of silica white from copper tailings[J].Conservation and Utilization of Mineral Resources,2011(5):88-91.
[15]肖军辉,冯启明,樊珊萍,徐龙华,王振.玻利维亚铜钨、锡多金属尾矿的综合利用[J].中国有色金属学报,2013,23(10):2949-2960.XIAO Jun-hui,FENG Qi-ming,FAN Shan-ping,XU Long-hua,WANG Zhen.Comprehensive utilization of copper,tungsten and tin polymetallic tailings in Bolivia[J].The Chinese Journal of Nonferrous Metals,2013,23(10):2949-2960.
[16]李达,蒋开喜,蒋训雄,汪胜东,范艳青.明矾石精矿焙烧脱水机理研究[J].中国资源综合利用,2014(11):20-23.LI Da,JIANG Kai-xi,JIANG Xun-xiong,WANG Sheng-dong,FAN Yan-qing.A study on the mechanism of dehydration of alunite ore by roasting[J].China Resources Comprehensive Utilization,2014(11):20-23.
[17]傅培鑫,徐元植.明矾石脱水和热解过程的化学热力学研究[J].科学通报,1980(10):452-456.FU Pei-xin,XU Yuan-zhi.Chemical thermodynamics research of alunite during dehydration and pyrolysis process[J].Chinese Science Bulletin,1980(10):452-456.
[18]李旻廷,李存兄,邓志敢,吴惠玲,梁艳辉,魏昶.加压酸浸法回收黑色页岩中的钒[J].中国有色金属学报,2008,18(1):74-78.LI Min-ting,LI Cun-xiong,DENG Zhi-gan,WU Hui-ling,LIANG Yan-hui,WEI Chang.Recovery of vanadium from black shale by means of pressure acid leaching[J].The Chinese Journal of Nonferrous Metals,2008,18(1):74-78.
[19]旷戈,胡松,蔡洋洋,李欢,杨惊喜,裴文涛,蔡相毅,刘瑜.一种明矾石直接加压酸浸提取钾铝的方法:中国,CN105217658A[P].2016-01-06.KUANG Ge,HU Song,CAI Yang-yang,LI Huan,YANG Jing-xi,PEI Wen-tao,CAI Xiang-yi,LIU Yu.A process of extracting K and Al fromalunite by directly pressure acidleaching:China,CN105217658A[P].2016-01-06.
[20]傅培鑫,潘同汉.一种利用钾明矾生产硫酸钾和氯化铝的方法:中国,CN104743583A[P].2015-07-01.FU Pei-xin,PAN Tong-han.A method of manufacture K2SO4 and Al Cl3 with potassium alum:China,CN104743583A[P].2015-07-01.
[21]旷戈,尚亚伟,陈光炉,孙加兴,胡松,金冉.一种从含钾、铝矿石中提取氢氧化铝的方法:中国,CN104445325A[P].2015-03-25.KUANG Ge,SHANG Ya-wei,CHEN Guang-lu,SUN Jia-xing,HU Song,JIN Ran.A process of extracting Al(OH)3 from ore contained potassium and aluminum:China,CN104445325A[P].2015-03-25.
[22]KUANG Ge,LI Huan,HU Song,JIN Ran,LIU Shan-jun,GUO Hui.Recovery of aluminium and lithium from gypsum residue obtained in the process of lithium extraction from lepidolite[J].Hydrometallurgy,2015(157):214-218.
[23]金冉,旷戈,胡松.钾长石氟化学酸碱联合法提钾铝技术研究[J].化工矿物与加工,2015(4):25-28.JIN Ran,KUANG Ge,HU Song.Research on acid-alkali combined extraction of potassium from K-feldspar by fluorine chemical process[J].Industrial Minerals&Processing,2015(4):25-28.
[24]刘玉民,齐涛,王丽娜,初景龙,张懿.KOH亚熔盐法分解钛铁矿[J].过程工程学报,2009,9(2):319-323.LIU Yu-min,QI Tao,WANG Li-na,CHU Jing-long,ZHANG Yi.Decomposition of ilmenite in KOH sub-molten salt[J].The Chinese Journal of Process Engineering,2009,9(2):319-323.
[25]牟望重,张廷安,吕国志,古岩,豆志河.硫化锌氧压浸出过程的φ-p H图[J].中国有色金属学报,2010,20(8):1641-1643.MU Wang-zhong,ZHANG Ting-an,LüGuo-zhi,GU Yan,DOU Zhi-he.φ-p H figure during oxidative pressure leaching of zinc sulfide[J].The Chinese Journal of Nonferrous Metals,2008,20(8):1641-1643.
[26]马荣骏.湿法冶金原理[M].北京:冶金工业出版社,2007:325-332.MA Rong-jun.Principle on hydrometallurgy[M].Beijing:Metallurgical Industry Press,2007:325-332.
[27]刘诚,傅建国.高压酸浸技术开发及工程化应用[J].世界有色金属,2014(10):20-22.LIIU Cheng,FU Jian-guo.Development and engineering application of high pressure acid leaching technology[J].World Nonferrous Metals,2014(10):20-22.
[2]商照聪,刘刚,包剑.我国钾资源开发技术进展与展望[J].化肥工业,2012,39(4):5-8.SHANG Zhao-cong,LIU Gang,BAO Jian.Progress and prospect of technology for development of potassium resources in China[J].Journal of the Chemical Fertilizer Industry,2012,39(4):5-8.
[3]宋婧,曾令可,税安泽,刘艳春,王慧.钾明矾蓄热性能的研究与改善[J].人工晶体学报,2007,36(2):358-362.SONG Jing,ZENG Ling-ke,SHUI An-ze,LIU Yan-chun,WANG Hui.Study on heat storage property and improvement of aluminum potassium sulfate[J].Journal of Synthetic Crystals,2007,36(2):358-362.
[4]叶钊,赵景总,廖骥,张汉辉.明矾制硫酸钾和氧化铝的研究[J].福州大学学报(自然科学版),1996(1):105-107.YE Zhao,ZHAO Jing-zong,LIAO Ji,ZHANG Han-hui.A study of the separation of aluminum oxide and potassium sulfate from k-alum[J].Journal of Fuzhou University(Natural Science),1996(1):105-107.
[5]KUCUK F,YILDIZ K.The decomposition kinetics of mechanically activated alunite ore in air atmosphere by thermogravimetry[J].Thermochim Acta,2006,448(2):107-110.
[6]王瑞永.明矾石精矿水浸-结晶法制备硫酸钾试验研究[J].有色冶金设计与研究,2014(3):14-16.WANG Rui-yong.Experimental research on water leaching-crystallization process to produce potassium sulfate from alunite concentrate[J].Nonferrous Metals Engineering&Research,2014(3):14-16.
[7]韩效钊,徐超,张兴法,王雄,许民才.热分解法综合利用明矾石工艺研究[J].矿冶工程,2002(1):72-74.HAN Xiao-zhao,XU Chao,ZHANG Xing-fa,WANG Xiong,XU Min-cai.A process of utilizing alumstone comprehensively by thermal decomposition[J].Mining and Metallurgical Engineering,2002(1):72-74.
[8]阮仁满,谭希发,衷水平,伍赠玲,刘晓英.利用热压浸出工艺从明矾石提取氧化铝与硫酸钾:中国,CN101913633A[P].2015-12-15.RUAN Ren-man,TAN Xi-fa,ZHONG Shui-ping,WU Zeng-ling,LIU Xiao-ying.A new technology to produce potassium sulfate and alumina from aluniteby hot-pressing leaching:China,CN101913633A[P].2015-12-15.
[9]OZDEMIR M,CETISLI H.Extraction kinetics of alunite in sulfuric acid and hydrochloric acid[J].Hydrometallurgy,2005,76(3/4):217-224.
[10]ZHAO Wei,YAO Xi,ZHONG Shui-pin,ZHU Yuan-yuan,YANG Xuan,YI Lin-yun,LI Gang,SONG Jing,YU Hong-dong,RUAN Ren-man,QI Tao.Extraction of Al and K salts from associated alunite tailings by an acidcalcination-water leaching method[J].Journal of Cleaner Production,2015(107):786-792.
[11]丁幸,洪玉平,童东绅,周春晖,俞卫华.明矾石的下游产品及其应用[J].中国非金属矿工业导刊,2012,95(2):24-27.DING-Xing,HONG Yu-ping,TONG Dong-shen,ZHOU Chun-hui,YU Wei-hua.Downstream products of alunite and their application[J].China Non-metallic Mining Industry Herald,2012,95(2):24-27.
[12]王晓琳,姬长生,任海兵.我国明矾石资源综合利用现状与发展前景研究[J].中国矿业,2010,19(4):15-17.WANG Xiao-lin,JI Chang-sheng,REN Hai-bing.A study of present situation of comprehensive utilization and development prospect of alunite in China[J].China Mining Magazine,2010,19(4):15-17.
[13]陈波,涂剑锋,邹来昌.紫金山尾矿回收明矾石与地开石的浮选试验研究[J].有色金属(选矿部分),2014(6):62-65.CHEN Bo,TU Jian-feng,ZOU Lai-chang.Experimental study on flotation of alunite and dickitefrom copper tailings in Zijinshan[J].Nonferrous Metals(Mieral Processing Section),2014(6):62-65.
[14]沈青峰,衷水平,王瑞永.紫金山选铜尾矿综合利用明矾石工艺研究[J].矿产保护与利用,2011(5):88-91.SHEN Qing-feng,ZHONG Shui-ping,WANG Rui-yong.Study on the preparation of silica white from copper tailings[J].Conservation and Utilization of Mineral Resources,2011(5):88-91.
[15]肖军辉,冯启明,樊珊萍,徐龙华,王振.玻利维亚铜钨、锡多金属尾矿的综合利用[J].中国有色金属学报,2013,23(10):2949-2960.XIAO Jun-hui,FENG Qi-ming,FAN Shan-ping,XU Long-hua,WANG Zhen.Comprehensive utilization of copper,tungsten and tin polymetallic tailings in Bolivia[J].The Chinese Journal of Nonferrous Metals,2013,23(10):2949-2960.
[16]李达,蒋开喜,蒋训雄,汪胜东,范艳青.明矾石精矿焙烧脱水机理研究[J].中国资源综合利用,2014(11):20-23.LI Da,JIANG Kai-xi,JIANG Xun-xiong,WANG Sheng-dong,FAN Yan-qing.A study on the mechanism of dehydration of alunite ore by roasting[J].China Resources Comprehensive Utilization,2014(11):20-23.
[17]傅培鑫,徐元植.明矾石脱水和热解过程的化学热力学研究[J].科学通报,1980(10):452-456.FU Pei-xin,XU Yuan-zhi.Chemical thermodynamics research of alunite during dehydration and pyrolysis process[J].Chinese Science Bulletin,1980(10):452-456.
[18]李旻廷,李存兄,邓志敢,吴惠玲,梁艳辉,魏昶.加压酸浸法回收黑色页岩中的钒[J].中国有色金属学报,2008,18(1):74-78.LI Min-ting,LI Cun-xiong,DENG Zhi-gan,WU Hui-ling,LIANG Yan-hui,WEI Chang.Recovery of vanadium from black shale by means of pressure acid leaching[J].The Chinese Journal of Nonferrous Metals,2008,18(1):74-78.
[19]旷戈,胡松,蔡洋洋,李欢,杨惊喜,裴文涛,蔡相毅,刘瑜.一种明矾石直接加压酸浸提取钾铝的方法:中国,CN105217658A[P].2016-01-06.KUANG Ge,HU Song,CAI Yang-yang,LI Huan,YANG Jing-xi,PEI Wen-tao,CAI Xiang-yi,LIU Yu.A process of extracting K and Al fromalunite by directly pressure acidleaching:China,CN105217658A[P].2016-01-06.
[20]傅培鑫,潘同汉.一种利用钾明矾生产硫酸钾和氯化铝的方法:中国,CN104743583A[P].2015-07-01.FU Pei-xin,PAN Tong-han.A method of manufacture K2SO4 and Al Cl3 with potassium alum:China,CN104743583A[P].2015-07-01.
[21]旷戈,尚亚伟,陈光炉,孙加兴,胡松,金冉.一种从含钾、铝矿石中提取氢氧化铝的方法:中国,CN104445325A[P].2015-03-25.KUANG Ge,SHANG Ya-wei,CHEN Guang-lu,SUN Jia-xing,HU Song,JIN Ran.A process of extracting Al(OH)3 from ore contained potassium and aluminum:China,CN104445325A[P].2015-03-25.
[22]KUANG Ge,LI Huan,HU Song,JIN Ran,LIU Shan-jun,GUO Hui.Recovery of aluminium and lithium from gypsum residue obtained in the process of lithium extraction from lepidolite[J].Hydrometallurgy,2015(157):214-218.
[23]金冉,旷戈,胡松.钾长石氟化学酸碱联合法提钾铝技术研究[J].化工矿物与加工,2015(4):25-28.JIN Ran,KUANG Ge,HU Song.Research on acid-alkali combined extraction of potassium from K-feldspar by fluorine chemical process[J].Industrial Minerals&Processing,2015(4):25-28.
[24]刘玉民,齐涛,王丽娜,初景龙,张懿.KOH亚熔盐法分解钛铁矿[J].过程工程学报,2009,9(2):319-323.LIU Yu-min,QI Tao,WANG Li-na,CHU Jing-long,ZHANG Yi.Decomposition of ilmenite in KOH sub-molten salt[J].The Chinese Journal of Process Engineering,2009,9(2):319-323.
[25]牟望重,张廷安,吕国志,古岩,豆志河.硫化锌氧压浸出过程的φ-p H图[J].中国有色金属学报,2010,20(8):1641-1643.MU Wang-zhong,ZHANG Ting-an,LüGuo-zhi,GU Yan,DOU Zhi-he.φ-p H figure during oxidative pressure leaching of zinc sulfide[J].The Chinese Journal of Nonferrous Metals,2008,20(8):1641-1643.
[26]马荣骏.湿法冶金原理[M].北京:冶金工业出版社,2007:325-332.MA Rong-jun.Principle on hydrometallurgy[M].Beijing:Metallurgical Industry Press,2007:325-332.
[27]刘诚,傅建国.高压酸浸技术开发及工程化应用[J].世界有色金属,2014(10):20-22.LIIU Cheng,FU Jian-guo.Development and engineering application of high pressure acid leaching technology[J].World Nonferrous Metals,2014(10):20-22.