草酸助剂强化酸浸法提取硫酸烧渣中的铁
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摘要
硫酸烧渣中铁氧化物活性较差,难以高效回收利用,且目前所报道的助剂强化酸浸法存在着诸如助剂用量大、易产生H_2S等有害气体、铁的浸取率仍有待于进一步提高等不足。为了解决上述问题,本文依据所提出的助剂选择原则,筛选并确定草酸为较适宜的酸浸助剂,并对其作为酸浸助剂的作用机理进行了初步探讨。通过单因素条件实验和正交实验,考察并确定了较适宜的酸浸工艺条件:反应时间7.5h,草酸助剂加入量20%,硫酸浸液质量分数50%,反应温度98℃。此条件下,硫酸烧渣中铁的浸取率可达95.7%。样品的XRD、EDS分析结果显示:相比于未添加草酸助剂的酸浸残渣,添加草酸助剂后的酸浸残渣中铁含量明显降低,说明草酸助剂的添加明显促进了硫酸烧渣中铁的浸出。
Iron oxides in pyrite cinder are difficult to be recycled efficiently for its poor activity, and there are some disadvantages in the presently reported intensified acid leaching methods, such as high dosage of auxiliary agent, production of harmful H_2 S and low leaching rate of iron. On the basis of the asproposed selection principles of auxiliary agents, oxalic acid was selected as the more suitable auxiliary agent in the leaching process to overcome the above disadvantages and its action mechanism on the acid leaching was preliminarily discussed. Taking the leaching rate of iron in pyrite cinder as the main index,the leaching conditions were investigated through single-factor experiments and orthogonal experiments and the leaching condition was optimized as follows: reaction time 7.5 h, addition of oxalic acid 20%, the mass fraction of sulfuric acid 50%, reaction temperature 98℃, under which the leaching rate of iron could reach 95.7%. The XRD patterns and EDS spectrum of the sample showed that when adding oxalic acid,the content of iron in the leaching residue decreased significantly compared to that without addition of oxalic acid, which suggesting that the addition of oxalic acid obviously promoted the extraction of iron from pyrite cinder.
Iron oxides in pyrite cinder are difficult to be recycled efficiently for its poor activity, and there are some disadvantages in the presently reported intensified acid leaching methods, such as high dosage of auxiliary agent, production of harmful H_2 S and low leaching rate of iron. On the basis of the asproposed selection principles of auxiliary agents, oxalic acid was selected as the more suitable auxiliary agent in the leaching process to overcome the above disadvantages and its action mechanism on the acid leaching was preliminarily discussed. Taking the leaching rate of iron in pyrite cinder as the main index,the leaching conditions were investigated through single-factor experiments and orthogonal experiments and the leaching condition was optimized as follows: reaction time 7.5 h, addition of oxalic acid 20%, the mass fraction of sulfuric acid 50%, reaction temperature 98℃, under which the leaching rate of iron could reach 95.7%. The XRD patterns and EDS spectrum of the sample showed that when adding oxalic acid,the content of iron in the leaching residue decreased significantly compared to that without addition of oxalic acid, which suggesting that the addition of oxalic acid obviously promoted the extraction of iron from pyrite cinder.
引文
[1]张仲伟,陈吉春,李旭.硫铁矿烧渣制备铁系化工产品研究方法综述[J].化工矿产地质,2004,26(3):181-185.ZHANG Zhongwei,CHEN Jichun,LI Xu.Summary of studying methods on preparation of iron-based prodcts from greigite cinder[J].Geology of Chemical Minerals,2004,26(3):181-185.
[2]李崇.中国硫酸工业现状及“十三五”发展思路[J].硫酸工业,2016(1):1-6.LI Chong.Status of China sulphuric acid industry and development planning ideas in the thirteenth five-year plan period[J].Sulphuric Acid Industry,2016(1):1-6.
[3]李国旺.硫酸渣富铁降硫工艺研究[D].贵阳:贵州大学,2015.LI Guowang.Research on enrichment of iron and reduction of sulfur in pyrite cinder[D].Guiyang:Guizhou University,2015.
[4]VINALS J,BALART M J,ROCA A.Inertization of pyrite cinders and co-inertization with electric arc furnace flue dusts by pyroconsolidation at solid state[J].Waste Management,2002,22(7):773-782.
[5]JIAN L,WEN S M,YU C,et al.Process optimization and reaction mechanism of removing copper from an Fe-rich pyrite cinder using chlorination roasting[J].Journal of Iron and Steel Research International,2013,20(8):20-26.
[6]徐玉萍.硫铁矿烧渣制复合聚铁混凝剂及其性能研究[J].化学研究与应用,2017,29(9):1429-1432.XU Yuping.Study on preparation and properties of poly ferric coagulant from pyrite cinder[J].Chemical Research and Application,2017,29(9):1429-1432.
[7]傅开彬,焦宇,徐信,等.山东某硫铁矿烧渣硫酸浸取液制备铁红工艺研究[J].应用化工,2018,47(2):293-295.FU Kaibin,JIAO Yu,XU Xin,et al.Preparation of iron oxide red from sulfuric acid solution of a pyrite cinder from Shandong province[J].Applied Chemical Industry,2018,47(2):293-295.
[8]ZHENG Y J,GONG Z Q,CHEN B Z,et al.Preparation of solid polyferric sulfate from pyrite cinders and its structure feature[J].Trans.Nonferrous Met.Soc.China,2003,13(3):690-694.
[9]ZHENG Y J,GONG Z Q,LIU L H,et al.Comparisons of species and coagulation effects of PFS solution and solid PFS from pyrite cinders[J].Trans.Nonferrous Met.Soc.China,2002,12(5):983-986.
[10]ZOU Z,XUAN A G,YAN Z G,et al.Preparation of Fe3O4,particles from copper/iron ore cinder and their microwave absorption properties[J].Chemical Engineering Science,2010,65(1):160-164.
[11]徐杰,李书营,王瑞.硫铁矿烧渣的综合利用研究[J].环境科学与管理,2010,35(2):153-157.XU Jie,LI Shuying,WANG Rui.Utilization of pyrite cinder[J].Environmental Science and Management,2010,35(2):153-157.
[12]陈永亮,陈吉春.以硫铁矿烧渣制备聚合硫酸铁的新工艺[J].资源环境与工程,2006,20(4):467-481.CHEN Yongliang,CHEN Jichun.A new preparation process of polyferric sulfate from pyrite cinders[J].Resources Environment&Engineering,2006,20(4):467-481.
[13]ALP I,DEVECI H,YAZICI E Y,et al.Potential use of pyrite cinders as raw material in cement production:results of industrial scale trial operations[J].Journal of Hazardous Materials,2009,166(1):144-149.
[14]占寿祥,郑雅杰.硫铁矿烧渣酸溶反应动力学研究[J].化学工程,2006,34(11):36-39.ZHAN Shouxiang,ZHENG Yajie.Study on leaching kinetics of pyrite cinder[J].Chemical Engineering,2006,34(11):36-39.
[15]左豪恩,温建康,崔兴兰,等.硫酸渣脱硫制备高品质铁精矿研究进展[J].工程科学学报,2018,40(1):1-8.ZUO Haoen,WEN Jiankang,CUI Xinglan,et al.Review of research process on preparation of high-quality iron concentrate from pyrite cinder by desulphurization[J].Chinese Journal of Engineering,2018,40(1):1-8.
[16]董风芝.硫铁矿烧渣用作炼铁原料研究进展[J].化工矿物与加工,2012,41(8):41-44.DONG Fengzhi.Progress on research of utilizing pyrite cinder as raw materials for iron-making[J].Industrial Minerals&Processing,2012,41(8):41-44.
[17]郑晓虹,陈玉峰,黄升光,等.硫酸浸取法从硫铁矿烧渣中提取铁的研究[J].化工进展,2003,22(2):165-168.ZHENG Xiaohong,CHEN Yufeng,HUANG Shengguang,et al.Investigation on extracting iron from pyrite cinder by sulfuric acid leaching[J].Chemical Industry and Engineering Progress,2003,22(2):165-168.
[18]李威,华涛,周启星.盐酸酸溶硫铁矿烧渣的最佳工艺条件[J].应用基础与工程科学学报,2008,16(6):795-801.LI Wei,HUA Tao,ZHOU Qixing.Optimum technical conditions study of dissolving pyrite cinders by hydrochloric acid[J].Journal of Basic Science and Engineering,2008,16(6):795-801.
[19]金程,李登新.硫酸烧渣还原浸取铁[J].有色金属(冶炼部分),2012(1):9-12.JIN Cheng,LI Dengxin.Reductive leaching of iron from sulfate slag[J].Nonferrous Metals(Extractive Metallurgy),2012(1):9-12.
[20]方亮.药剂学[M].3版.北京:中国医药科技出版社,2016:84.FANG Liang.Pharmaceutics[M].3th ed.Beijing:China Medical Science Press,2016:84.
[21]李志金,李登新,张武学,等.酸浸渣制取硫酸亚铁的研究[J].再生资源研究,2006(6):32-35.LI Zhijin,LI Dengxin,ZHANG Wuxue,et al.The research on preparation ferrous sulfate from acid leaching tailings[J].Recyclable Resources and Circular Economy,2006(6):32-35.
[22]金程.强化酸浸法回收硫酸烧渣中铁的研究[D].上海:东华大学,2012.JIN Cheng.Study on reinforced acid leaching of ferric iron in pyrite cinder[D].Shanghai:Donghua University,2012.
[23]詹咏,张焕焕,疏醒,等.硫铁矿烧渣铁系氧化物的酸溶特性[J].上海理工大学学报,2017,39(1):90-96.ZHAN Yong,ZHANG Huanhuan,SHU Xing,et al.Acid dissolution properties of ferric oxide in pyrite cinder[J].Journal of University of Shanghai for Science and Technology,2017,39(1):90-96.
[24]刘培,江健,刘宗宽,等.双酸法提取硫铁矿烧渣中铁[J].化工学报,2013,64(7):2619-2624.LIU P,JIANG J,LIU Z K,et al.Iron extraction from pyrite cinder by mixed acid[J].Journal of Chemical Industry and Engineering,2013,64(7):2619-2624.
[25]陆俭洁.铁矿石中全铁含量测定方法的改进--重铬酸钾法测定铁矿石中铁含量实验的改进[J].中南民族学院学报(自然科学版),2000,19(3):81-83.LU Jianjie.Improvement of the determination of iron in ferrous ore by K2Cr2O7[J].Journal of South-Central University for Nationalities(Natural Science Edition),2000,19(3):81-83.
[26]刘自亮.粉煤灰制备铝硅合金过程中预处理除铁工艺研究[D].昆明:昆明理工大学,2016.LIU Ziliang.Study on the removal process of iron in the preparation of aluminum silicon alloy from fly ash[D].Kunming:Kunming University of Science and Technology,2016.
[27]钱红辉.氧化铁脱硫剂的制备、改性及回收利用研究[D].武汉:武汉科技大学,2010.QIAN Honghui.The research on preparation,modification and recycling of iron oxide desulfurizer[D].Wuhan:Wuhan University of Science and Technology,2010.
[28]石志霞,余章龙,彭程,等.低品位铝土矿草酸光催化除铁研究[J].材料导报,2015,29(s2):125-128.SHI Zhixia,YU Zhanglong,PENG Cheng,et al.Sunlight irondiationassisted removal of iron oxide from low grade bauxite using oxalic acid[J].Material Review,2015,29(s2):125-128.
[2]李崇.中国硫酸工业现状及“十三五”发展思路[J].硫酸工业,2016(1):1-6.LI Chong.Status of China sulphuric acid industry and development planning ideas in the thirteenth five-year plan period[J].Sulphuric Acid Industry,2016(1):1-6.
[3]李国旺.硫酸渣富铁降硫工艺研究[D].贵阳:贵州大学,2015.LI Guowang.Research on enrichment of iron and reduction of sulfur in pyrite cinder[D].Guiyang:Guizhou University,2015.
[4]VINALS J,BALART M J,ROCA A.Inertization of pyrite cinders and co-inertization with electric arc furnace flue dusts by pyroconsolidation at solid state[J].Waste Management,2002,22(7):773-782.
[5]JIAN L,WEN S M,YU C,et al.Process optimization and reaction mechanism of removing copper from an Fe-rich pyrite cinder using chlorination roasting[J].Journal of Iron and Steel Research International,2013,20(8):20-26.
[6]徐玉萍.硫铁矿烧渣制复合聚铁混凝剂及其性能研究[J].化学研究与应用,2017,29(9):1429-1432.XU Yuping.Study on preparation and properties of poly ferric coagulant from pyrite cinder[J].Chemical Research and Application,2017,29(9):1429-1432.
[7]傅开彬,焦宇,徐信,等.山东某硫铁矿烧渣硫酸浸取液制备铁红工艺研究[J].应用化工,2018,47(2):293-295.FU Kaibin,JIAO Yu,XU Xin,et al.Preparation of iron oxide red from sulfuric acid solution of a pyrite cinder from Shandong province[J].Applied Chemical Industry,2018,47(2):293-295.
[8]ZHENG Y J,GONG Z Q,CHEN B Z,et al.Preparation of solid polyferric sulfate from pyrite cinders and its structure feature[J].Trans.Nonferrous Met.Soc.China,2003,13(3):690-694.
[9]ZHENG Y J,GONG Z Q,LIU L H,et al.Comparisons of species and coagulation effects of PFS solution and solid PFS from pyrite cinders[J].Trans.Nonferrous Met.Soc.China,2002,12(5):983-986.
[10]ZOU Z,XUAN A G,YAN Z G,et al.Preparation of Fe3O4,particles from copper/iron ore cinder and their microwave absorption properties[J].Chemical Engineering Science,2010,65(1):160-164.
[11]徐杰,李书营,王瑞.硫铁矿烧渣的综合利用研究[J].环境科学与管理,2010,35(2):153-157.XU Jie,LI Shuying,WANG Rui.Utilization of pyrite cinder[J].Environmental Science and Management,2010,35(2):153-157.
[12]陈永亮,陈吉春.以硫铁矿烧渣制备聚合硫酸铁的新工艺[J].资源环境与工程,2006,20(4):467-481.CHEN Yongliang,CHEN Jichun.A new preparation process of polyferric sulfate from pyrite cinders[J].Resources Environment&Engineering,2006,20(4):467-481.
[13]ALP I,DEVECI H,YAZICI E Y,et al.Potential use of pyrite cinders as raw material in cement production:results of industrial scale trial operations[J].Journal of Hazardous Materials,2009,166(1):144-149.
[14]占寿祥,郑雅杰.硫铁矿烧渣酸溶反应动力学研究[J].化学工程,2006,34(11):36-39.ZHAN Shouxiang,ZHENG Yajie.Study on leaching kinetics of pyrite cinder[J].Chemical Engineering,2006,34(11):36-39.
[15]左豪恩,温建康,崔兴兰,等.硫酸渣脱硫制备高品质铁精矿研究进展[J].工程科学学报,2018,40(1):1-8.ZUO Haoen,WEN Jiankang,CUI Xinglan,et al.Review of research process on preparation of high-quality iron concentrate from pyrite cinder by desulphurization[J].Chinese Journal of Engineering,2018,40(1):1-8.
[16]董风芝.硫铁矿烧渣用作炼铁原料研究进展[J].化工矿物与加工,2012,41(8):41-44.DONG Fengzhi.Progress on research of utilizing pyrite cinder as raw materials for iron-making[J].Industrial Minerals&Processing,2012,41(8):41-44.
[17]郑晓虹,陈玉峰,黄升光,等.硫酸浸取法从硫铁矿烧渣中提取铁的研究[J].化工进展,2003,22(2):165-168.ZHENG Xiaohong,CHEN Yufeng,HUANG Shengguang,et al.Investigation on extracting iron from pyrite cinder by sulfuric acid leaching[J].Chemical Industry and Engineering Progress,2003,22(2):165-168.
[18]李威,华涛,周启星.盐酸酸溶硫铁矿烧渣的最佳工艺条件[J].应用基础与工程科学学报,2008,16(6):795-801.LI Wei,HUA Tao,ZHOU Qixing.Optimum technical conditions study of dissolving pyrite cinders by hydrochloric acid[J].Journal of Basic Science and Engineering,2008,16(6):795-801.
[19]金程,李登新.硫酸烧渣还原浸取铁[J].有色金属(冶炼部分),2012(1):9-12.JIN Cheng,LI Dengxin.Reductive leaching of iron from sulfate slag[J].Nonferrous Metals(Extractive Metallurgy),2012(1):9-12.
[20]方亮.药剂学[M].3版.北京:中国医药科技出版社,2016:84.FANG Liang.Pharmaceutics[M].3th ed.Beijing:China Medical Science Press,2016:84.
[21]李志金,李登新,张武学,等.酸浸渣制取硫酸亚铁的研究[J].再生资源研究,2006(6):32-35.LI Zhijin,LI Dengxin,ZHANG Wuxue,et al.The research on preparation ferrous sulfate from acid leaching tailings[J].Recyclable Resources and Circular Economy,2006(6):32-35.
[22]金程.强化酸浸法回收硫酸烧渣中铁的研究[D].上海:东华大学,2012.JIN Cheng.Study on reinforced acid leaching of ferric iron in pyrite cinder[D].Shanghai:Donghua University,2012.
[23]詹咏,张焕焕,疏醒,等.硫铁矿烧渣铁系氧化物的酸溶特性[J].上海理工大学学报,2017,39(1):90-96.ZHAN Yong,ZHANG Huanhuan,SHU Xing,et al.Acid dissolution properties of ferric oxide in pyrite cinder[J].Journal of University of Shanghai for Science and Technology,2017,39(1):90-96.
[24]刘培,江健,刘宗宽,等.双酸法提取硫铁矿烧渣中铁[J].化工学报,2013,64(7):2619-2624.LIU P,JIANG J,LIU Z K,et al.Iron extraction from pyrite cinder by mixed acid[J].Journal of Chemical Industry and Engineering,2013,64(7):2619-2624.
[25]陆俭洁.铁矿石中全铁含量测定方法的改进--重铬酸钾法测定铁矿石中铁含量实验的改进[J].中南民族学院学报(自然科学版),2000,19(3):81-83.LU Jianjie.Improvement of the determination of iron in ferrous ore by K2Cr2O7[J].Journal of South-Central University for Nationalities(Natural Science Edition),2000,19(3):81-83.
[26]刘自亮.粉煤灰制备铝硅合金过程中预处理除铁工艺研究[D].昆明:昆明理工大学,2016.LIU Ziliang.Study on the removal process of iron in the preparation of aluminum silicon alloy from fly ash[D].Kunming:Kunming University of Science and Technology,2016.
[27]钱红辉.氧化铁脱硫剂的制备、改性及回收利用研究[D].武汉:武汉科技大学,2010.QIAN Honghui.The research on preparation,modification and recycling of iron oxide desulfurizer[D].Wuhan:Wuhan University of Science and Technology,2010.
[28]石志霞,余章龙,彭程,等.低品位铝土矿草酸光催化除铁研究[J].材料导报,2015,29(s2):125-128.SHI Zhixia,YU Zhanglong,PENG Cheng,et al.Sunlight irondiationassisted removal of iron oxide from low grade bauxite using oxalic acid[J].Material Review,2015,29(s2):125-128.