橡胶籽油还原作用下铜渣的贫化
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摘要
针对铜渣贫化过程碳排放问题,以橡胶籽油取代柴油作为铜渣贫化的还原剂,研究铜渣贫化过程中的热力学,分析橡胶籽油贫化铜渣机理。在不同温度和时间条件下进行喷吹橡胶籽油贫化实验,分析铜渣磁性铁含量和粘度的变化,用XRD和SEM对贫化后炉渣进行分析。结果表明,喷吹还原过程中主要还原剂是裂解产生的碳单质、H2和CO。贫化过程中磁性铁被橡胶籽油在高温下的裂解产物(H2, CO, C)还原成FeO,与渣中的Si O2结合生成铁橄榄石(Fe2Si O4);随贫化温度升高,相同喷吹时间内铜渣的磁性铁含量和粘度逐渐降低,使渣中的Cu相互碰撞聚集,最终沉降到坩埚底部。随贫化进行铜渣中的铁橄榄石相增多,磁性铁相减少。在坩埚底部聚集的铜颗粒粒度由1 cm增至3 cm,铜回收率达86%。
For the sake of solve the problem of large amounts of carbon dioxide emissions and the environmental pollution caused during the process of copper slag dilution, a new method was proposed that using rubber seed oil replaced the diesel oil as a reducing agent for copper slag dilution. For proving the conception, the thermodynamic theory in the process of copper slag dilution was studied. The reaction mechanism of copper slag from rubber seed oil was analyzed. A large number reduction experiments were done that the rubber seed oil was also injected at different temperatures and time. Meanwhile the changes of magnetic iron content and viscosity of copper slag alsowere analyzed. The slag after dilution reduction was analyzed by XRD and SEM. The results showed that in the process of injection reduction the main reductant were carbon simple substance, hydrogen and carbon monoxide produced by rubber seed oil pyrolysis. Firstly, the magnetic iron was reduced to iron monoxide by the pyrolysis products(hydrogen, carbon monoxide, carbon simple substance), which could be produced by the rubber seed oil at high temperature. Meanwhile the iron monoxide combined with silicon dioxide in copper slag to form fayalite(ferric metasilicate). Secondly, the magnetic iron content in copper slag and the viscosity of copper slag can be reduced by increasing the temperature of dilution reduction. Copper in copper slag was collided and aggregated. Finally, the sediment accumulated at the bottom of the crucible. The ferrite phase increased and the magnet phase decreased during the dilution process. Copper particles first accumulated at the bottom of the crucible, then it increased from 1 cm to 3 cm slowly. The recovery rate of copper reached 86%.
For the sake of solve the problem of large amounts of carbon dioxide emissions and the environmental pollution caused during the process of copper slag dilution, a new method was proposed that using rubber seed oil replaced the diesel oil as a reducing agent for copper slag dilution. For proving the conception, the thermodynamic theory in the process of copper slag dilution was studied. The reaction mechanism of copper slag from rubber seed oil was analyzed. A large number reduction experiments were done that the rubber seed oil was also injected at different temperatures and time. Meanwhile the changes of magnetic iron content and viscosity of copper slag alsowere analyzed. The slag after dilution reduction was analyzed by XRD and SEM. The results showed that in the process of injection reduction the main reductant were carbon simple substance, hydrogen and carbon monoxide produced by rubber seed oil pyrolysis. Firstly, the magnetic iron was reduced to iron monoxide by the pyrolysis products(hydrogen, carbon monoxide, carbon simple substance), which could be produced by the rubber seed oil at high temperature. Meanwhile the iron monoxide combined with silicon dioxide in copper slag to form fayalite(ferric metasilicate). Secondly, the magnetic iron content in copper slag and the viscosity of copper slag can be reduced by increasing the temperature of dilution reduction. Copper in copper slag was collided and aggregated. Finally, the sediment accumulated at the bottom of the crucible. The ferrite phase increased and the magnet phase decreased during the dilution process. Copper particles first accumulated at the bottom of the crucible, then it increased from 1 cm to 3 cm slowly. The recovery rate of copper reached 86%.
引文
[1]Li L,Hu J H,Wang H.Smelting oxidation desulfurization of copper slags[J].Journal of Iron and Steel Research(International),2012,19(12):14-20.
[2]Guo Z,Zhu D,Pan J,et al.Improving beneficiation of copper and iron from copper slag by modifying the molten copper slag[J].Metals-Open Access Metallurgy Journal,2016,6(4):86-87.
[3]Long T V,Palacios J,Sanches M,et al.Recovery of molybdenum from copper slag[J].ISIJ International,2012,98(2):48-54.
[4]Coruh S,Ergun O N,Cheng T W.Treatment of copper industry waste and production of sintered glass-ceramic[J].Waste Management&Research:the Journal of the International Solid Wastes&Public Cleansing Association,ISWA,2006,24(3):234-241.
[5]Murari K,Siddique R,Jain K K.Use of waste copper slag,a sustainable material[J].Journal of Material Cycles&Waste Management,2015,17(1):13-26.
[6]Khanzadi M,Behnood A.Mechanical properties of high-strength concrete incorporating copper slag as coarse aggregate[J].Construction&Building Materials,2009,23(6):2183-2188.
[7]Wu W,Zhang W,Ma G.Optimum content of copper slag as a fine aggregate in high strength concrete[J].Materials&Design,2010,31(6):2878-2883.
[8]Shi C,Meyer C,Behnood A.Utilization of copper slag in cement and concrete[J].Resources Conservation&Recycling,2008,52(10):1115-1120.
[9]李磊,胡建杭,王华.铜渣熔融还原炼铁过程研究[J].过程工程学报,2011,11(1):65-71Li L,Hu J H,Wang H.Study on smelting reduction ironmaking of copper slag[J].The Chinese Journal of Process Engineering,2011,11(1):65-71
[10]Banda W,Morgan N,Eksteen J J.The role of slag modifiers on the selective recovery of cobalt and copper from waste smelter slag[J].Minerals Engineering,2002,15(11):899-907.
[11]Moskalyk R R,Alfantazi A M.Review of copper pyrometallurgical practice:today and tomorrow[J].Minerals Engineering,2003,16(10):893-919.
[12]Bruckard W J,Somerville M,Hao F.The recovery of copper,by flotation,from calcium-ferrite-based slags made in continuous pilot plant smelting trials[J].Minerals Engineering,2004,17(4):495-504.
[13]杨涛,胡建杭,王华,等.铜电炉冶炼贫化渣焙烧富集Fe3O4[J].过程工程学报,2011,11(4):613-619.Yang T,Hu J H,Wang H,et al.Enrichment of Fe3O4 in smelting lean slag by copper electric furnace[J].The Chinese Journal of Process Engineering,2011,11(4):613-619.
[14]张怀伟.基于直流电场和碳-氢复合还原改性的铜渣贫化过程的试验研究[D].上海:上海大学,2014:35-60.Zhang H W.Experimental study on the dilution process of copper slag modified by direct current field and carbon-hydrogen composite reduction[D].Shanghai:Shanghai University,2014:35-60.
[15]Vaisburd S,Berner A,Brandon D G,et al.Slags and mattes in vanyukov's process for the extraction of copper[J].Metallurgical&Materials Transactions B,2002,33(4):551-559.
[16]Li K Q,Ping S,Wang H Y,et al.Recovery of iron from copper slag by deep reduction and magnetic beneficiation[J].Journal of Mineral Metallurgy and Materials,2013,20(11):1035-1041.
[17]Fan Y,Shibata E,Iizuka A,et al.Crystallization behavior of copper smelter slag during molten oxidation[J].Metallurgical&Materials Transactions B,2015,46(5):2158-2164.
[18]张林楠,张力,王明玉,等.铜渣贫化的选择性还原过程[J].有色金属工程,2005,57(3):44-47.Zhang L N,Zhang L,Wang M Y,et al.Selective reduction process of copper slag dilution[J].Nonferrous Metal Engineering,2005,57(3):44-47.
[19]傅崇说.有色冶金原理,第2版[M].北京:冶金工业出版社,2007:75-79.Fu C S.Principles of nonferrous metallurgy,2nd Ed.[M].Beijing:Metallurgical Industry Press,2007:75-79.
[20]黄希祜.钢铁冶金原理,第3版[M].北京:冶金工业出版社,1981:4-18.Huang X H.Principles of iron and steel metallurgy,3rd Ed.[M].Beijing:Metallurgical Industry Press,1981:4-18.
[21]孙财.地沟油生物柴油喷吹还原转炉渣中磁性铁的实验研究[D].昆明:昆明理工大学,2016:39-51.Sun C.Experimental study on reduction of magnetic iron in converter slag by injection of gutter oil biodiesel[D].Kunming:Kunming University of Technology,2016:39-51.
[22]Matousek J.Thermodynamics of iron oxidation in metallurgical slags[J].JOM,2012,64(11):1314-1320.
[23]Nagasaka T,Hino M,Shiro B Y.Interfacial kinetics of hydrogen with liquid slag containing iron oxide[J].Metallurgical&Materials Transactions B,2000,31(5):945-955.
[24]Zhang H W,Sun F,Shi X Y,et al.The viscous and conductivity behavior of melts containing iron oxide in the FeOtSiO2-CaO-Cu2O system for copper smelting slags[J].Metallurgical&Materials Transactions B,2012,43(5):1046-1053.
[25]盛力,李江涛,张建坤,等.含固相铜冶炼渣的黏度计算及其应用[J].工程科学学报,2017,39(1):48-53.Sheng L,Li J T,Zhang J K,et al.Viscosity calculation and its application of the copper smelting slag containing solid phase[J].Chinese Journal of Engineering,2017,39(1):48-53.
[2]Guo Z,Zhu D,Pan J,et al.Improving beneficiation of copper and iron from copper slag by modifying the molten copper slag[J].Metals-Open Access Metallurgy Journal,2016,6(4):86-87.
[3]Long T V,Palacios J,Sanches M,et al.Recovery of molybdenum from copper slag[J].ISIJ International,2012,98(2):48-54.
[4]Coruh S,Ergun O N,Cheng T W.Treatment of copper industry waste and production of sintered glass-ceramic[J].Waste Management&Research:the Journal of the International Solid Wastes&Public Cleansing Association,ISWA,2006,24(3):234-241.
[5]Murari K,Siddique R,Jain K K.Use of waste copper slag,a sustainable material[J].Journal of Material Cycles&Waste Management,2015,17(1):13-26.
[6]Khanzadi M,Behnood A.Mechanical properties of high-strength concrete incorporating copper slag as coarse aggregate[J].Construction&Building Materials,2009,23(6):2183-2188.
[7]Wu W,Zhang W,Ma G.Optimum content of copper slag as a fine aggregate in high strength concrete[J].Materials&Design,2010,31(6):2878-2883.
[8]Shi C,Meyer C,Behnood A.Utilization of copper slag in cement and concrete[J].Resources Conservation&Recycling,2008,52(10):1115-1120.
[9]李磊,胡建杭,王华.铜渣熔融还原炼铁过程研究[J].过程工程学报,2011,11(1):65-71Li L,Hu J H,Wang H.Study on smelting reduction ironmaking of copper slag[J].The Chinese Journal of Process Engineering,2011,11(1):65-71
[10]Banda W,Morgan N,Eksteen J J.The role of slag modifiers on the selective recovery of cobalt and copper from waste smelter slag[J].Minerals Engineering,2002,15(11):899-907.
[11]Moskalyk R R,Alfantazi A M.Review of copper pyrometallurgical practice:today and tomorrow[J].Minerals Engineering,2003,16(10):893-919.
[12]Bruckard W J,Somerville M,Hao F.The recovery of copper,by flotation,from calcium-ferrite-based slags made in continuous pilot plant smelting trials[J].Minerals Engineering,2004,17(4):495-504.
[13]杨涛,胡建杭,王华,等.铜电炉冶炼贫化渣焙烧富集Fe3O4[J].过程工程学报,2011,11(4):613-619.Yang T,Hu J H,Wang H,et al.Enrichment of Fe3O4 in smelting lean slag by copper electric furnace[J].The Chinese Journal of Process Engineering,2011,11(4):613-619.
[14]张怀伟.基于直流电场和碳-氢复合还原改性的铜渣贫化过程的试验研究[D].上海:上海大学,2014:35-60.Zhang H W.Experimental study on the dilution process of copper slag modified by direct current field and carbon-hydrogen composite reduction[D].Shanghai:Shanghai University,2014:35-60.
[15]Vaisburd S,Berner A,Brandon D G,et al.Slags and mattes in vanyukov's process for the extraction of copper[J].Metallurgical&Materials Transactions B,2002,33(4):551-559.
[16]Li K Q,Ping S,Wang H Y,et al.Recovery of iron from copper slag by deep reduction and magnetic beneficiation[J].Journal of Mineral Metallurgy and Materials,2013,20(11):1035-1041.
[17]Fan Y,Shibata E,Iizuka A,et al.Crystallization behavior of copper smelter slag during molten oxidation[J].Metallurgical&Materials Transactions B,2015,46(5):2158-2164.
[18]张林楠,张力,王明玉,等.铜渣贫化的选择性还原过程[J].有色金属工程,2005,57(3):44-47.Zhang L N,Zhang L,Wang M Y,et al.Selective reduction process of copper slag dilution[J].Nonferrous Metal Engineering,2005,57(3):44-47.
[19]傅崇说.有色冶金原理,第2版[M].北京:冶金工业出版社,2007:75-79.Fu C S.Principles of nonferrous metallurgy,2nd Ed.[M].Beijing:Metallurgical Industry Press,2007:75-79.
[20]黄希祜.钢铁冶金原理,第3版[M].北京:冶金工业出版社,1981:4-18.Huang X H.Principles of iron and steel metallurgy,3rd Ed.[M].Beijing:Metallurgical Industry Press,1981:4-18.
[21]孙财.地沟油生物柴油喷吹还原转炉渣中磁性铁的实验研究[D].昆明:昆明理工大学,2016:39-51.Sun C.Experimental study on reduction of magnetic iron in converter slag by injection of gutter oil biodiesel[D].Kunming:Kunming University of Technology,2016:39-51.
[22]Matousek J.Thermodynamics of iron oxidation in metallurgical slags[J].JOM,2012,64(11):1314-1320.
[23]Nagasaka T,Hino M,Shiro B Y.Interfacial kinetics of hydrogen with liquid slag containing iron oxide[J].Metallurgical&Materials Transactions B,2000,31(5):945-955.
[24]Zhang H W,Sun F,Shi X Y,et al.The viscous and conductivity behavior of melts containing iron oxide in the FeOtSiO2-CaO-Cu2O system for copper smelting slags[J].Metallurgical&Materials Transactions B,2012,43(5):1046-1053.
[25]盛力,李江涛,张建坤,等.含固相铜冶炼渣的黏度计算及其应用[J].工程科学学报,2017,39(1):48-53.Sheng L,Li J T,Zhang J K,et al.Viscosity calculation and its application of the copper smelting slag containing solid phase[J].Chinese Journal of Engineering,2017,39(1):48-53.