高岭石与氧化铁在还原焙烧过程中的反应行为（英文）
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摘要
铝硅酸盐矿物中氧化硅和氧化铝的预先分离对从高硅含铝物料中提取氧化铝具有重要意义。本文作者研究高岭石与氧化铁在还原焙烧过程中的反应行为。热力学计算以及还原焙烧实验结果表明,由氧化铁还原得到的氧化亚铁优先与高岭石中的氧化铝反应而生成铝酸亚铁;与此同时,高岭石中的氧化硅转变为石英固溶体或者方石英固溶体。在有足量碳粉存在的条件下,过量的氧化亚铁和氧化硅反应生成的硅酸亚铁随着焙烧温度的升高进一步还原成氧化硅和金属铁。然而,升高焙烧温度及降低Fe_2O_3/Al_2O_3的摩尔比均能促进莫来石的形成。控制高岭土、赤铁矿和煤灰中Fe_2O_3/Al_2O_3/C摩尔比为1.2:2.0:1.2,在1373 K下还原焙烧60 min即可实现高岭石完全转变为独立的氧化硅和铝酸亚铁。研究结果有望为铝硅酸盐矿物中氧化铝和氧化硅的综合利用提供新技术。
The pre-separation of silica and alumina in aluminosilicates is of great significance for efficiently treating alumina-/silica-bearing minerals for alumina production. In this work, the reaction behavior of kaolinite with ferric oxide during reduction roasting was investigated. The results of thermodynamic analyses and reduction roasting experiments show that ferrous oxide obtained from ferric oxide reduction preferentially reacts with alumina in kaolinite to form hercynite, meanwhile the silica in kaolinite is transformed into quartz solid solution and/or cristobalite solid solution. With increasing roasting temperature, fayalite formed by reaction of surplus ferrous oxide with silica at low temperature is reduced to silica and metallic iron in the presence of sufficient carbon dosage. However, increasing roasting temperature and decreasing Fe_2O_3/Al_2O_3 molar ratio favor mullite formation. The complete conversion of kaolinte into free silica and hercynite can be obtained by roasting raw meal of kaolin, ferric oxide and coal powder with Fe_2O_3/Al_2O_3/C molar ratio of 1.2:2.0:1.2 at 1373 K for 60 min. This work may facilitate the development of a technique for comprehensively utilizing silica and alumina in aluminosilicates.
The pre-separation of silica and alumina in aluminosilicates is of great significance for efficiently treating alumina-/silica-bearing minerals for alumina production. In this work, the reaction behavior of kaolinite with ferric oxide during reduction roasting was investigated. The results of thermodynamic analyses and reduction roasting experiments show that ferrous oxide obtained from ferric oxide reduction preferentially reacts with alumina in kaolinite to form hercynite, meanwhile the silica in kaolinite is transformed into quartz solid solution and/or cristobalite solid solution. With increasing roasting temperature, fayalite formed by reaction of surplus ferrous oxide with silica at low temperature is reduced to silica and metallic iron in the presence of sufficient carbon dosage. However, increasing roasting temperature and decreasing Fe_2O_3/Al_2O_3 molar ratio favor mullite formation. The complete conversion of kaolinte into free silica and hercynite can be obtained by roasting raw meal of kaolin, ferric oxide and coal powder with Fe_2O_3/Al_2O_3/C molar ratio of 1.2:2.0:1.2 at 1373 K for 60 min. This work may facilitate the development of a technique for comprehensively utilizing silica and alumina in aluminosilicates.
引文
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[16]LEE S,KIM Y J,MOON H S.Phase transformation sequence from kaolinite to mullite investigated by an energy-filtering transmission electron microscope[J].Journal of the American Ceramic Society,1999,82(11):2841-2848.
[17]OKADA K,ōTSUKA N,OSSAKA J.Characterization of spinel phase formed in the kaolinite-mullite thermal sequence[J].Journal of the American Ceramic Society,1986,69(10):C251-C253.
[18]SANZ J,MADANI A,SERRATOSA J M.Aluminum-27 and silicon-29 magic-angle spinning nuclear magnetic resonance study of the kaolinite-mullite transformation[J].Journal of the American Ceramic Society,1988,71(10):C418-C421.
[19]SONUPARLAK B,SARIKAYA M,AKSAY I A.Spinel phase formation during the 980°C exothermic reaction in the kaolinite-tomullite reaction series[J].Journal of the American Ceramic Society,1987,70(11):837-842.
[20]SEGNIT E R,GELB T.Metastable quartz-type structures formed from kaolinite by solid state reaction[J].American Mineralogist,1972,57:1505-1514.
[21]TAKEUCHI N,TAKAHASHI H,ISHIDA S,HORIIE F,WAKAMATSU M.Mechanistic study of solid-state reaction between kaolinite and ferrous oxide at high temperatures[J].Journal of the Ceramic Society of Japan,2000,108(10):876-881.
[22]ZHOU Qiu-sheng,LI Chuang,LI Xiao-bin,PENG Zhi-hong,LIUGui-hua,QI Tian-gui.Reaction behavior of ferric oxide in system Fe2O3-SiO2-Al2O3 during reductive sintering process[J].Transactions of Nonferrous Metals Society of China,2016,26:842-848.
[23]BARIN I.Thermochemical data of pure substances[M].Weinheim:VCH Verlagsgesellschaft mbH,1995.
[2]XIA Liu-yin,ZHONG Hong,LIU Guang-yi,HUANG Zhi-qiang,CHANG Qing-wei.Flotation separation of the aluminosilicates from diaspore by a Gemini cationic collector[J].International Journal of Mineral Processing,2009,92:74-83.
[3]USGS(United States Geological Survey).Mineral commodity summaries:Bauxite and alumina[EB/OL].https://minerals.usgs.gov/minerals/pubs/commodity/bauxite/mcs-2017-bauxi.pdf
[4]LIU Hai-bin,LIU Zhen-ling.Recycling utilization patterns of coal mining waste in China[J].Resources,Conservation and Recycling,2010,54:1331-1340.
[5]GUO Yan-xia,LV Hui-bin,YANG Xi,CHENG Fang-qin.Al Cl3·6H2O recovery from the acid leaching liquor of coal gangue by using concentrated hydrochloric inpouring[J].Separation and Purification Technology,2015,151:177-183.
[6]XIAO Jin,LI Fa-chuang,ZHONG Qi-fan,BAO Hong-guang,WANG Bing-jie,HUANG Jin-di,ZHANG Yan-bing.Separation of aluminum and silica from coal gangue by elevated temperature acid leaching for the preparation of alumina and SiC[J].Hydrometallurgy,2015,155:118-124.
[7]LI Guang-hui,ZENG Jing-hua,LUO Jun,LIU Ming-xia,JIANG Tao,QIU Guan-zhou.Thermal transformation of pyrophyllite and alkali dissolution behavior of silicon[J].Applied Clay Science,2014,99:282-288.
[8]YAN Ke-zhou,GUO Yan-xia,FANG Li,CUI Li,CHENG Fang-qin,LI Tong-yang.Decomposition and phase transformation mechanism of kaolinite calcined with sodium carbonate[J].Applied Clay Science,2017,147:90-96.
[9]GENG Xue-wen,MA Hong-wen,SU Shuang-qing,MA Shi-lin.The preparation of aluminum hydroxide from high-alumina gangue desilication residues based on soda lime sintering method[J].Bulletin of Mineralogy,Petrology and Geochemistry,2012,31(6):635-639.(in Chinese)
[10]QIU Guan-zhou,JIANG Tao,LI Guang-hui,FAN Xiao-hui,HUANG Zhu-cheng.Activation and removal of silicon in kaolinite by thermochemical process[J].Scandinavian Journal of Metallurgy,2004,33:121-128.
[11]BONN H S,GINSBERG H.Method for reducing the silica content of alumina-containing materials of the clay type:US patent,2939764[P].1960-06-07.
[12]RAYZMAN V L,PEVZNER I Z,SIZYAKOV V M,NI L P,FILIPOVICH I K,ATURIN A V.Extracting silica and alumina from low-grade bauxite[J].Journal of the Minerals,Metals&Materials Society,2003,55:47-50.
[13]SMITH P.The processing of high silica bauxites-Review of existing and potential processes[J].Hydrometallurgy,2009,98:162-176.
[14]CHAKRABORTY A K,GHOSH D K.Reexamination of the kaolinite-to-mullite reaction series[J].Journal of the American Ceramic Society,1978,61(3-4):170-173.
[15]CHAKRABORTY A K.Formation of silicon-aluminum spinel[J].Journal of the American Ceramic Society,1979,62(3-4):120-124.
[16]LEE S,KIM Y J,MOON H S.Phase transformation sequence from kaolinite to mullite investigated by an energy-filtering transmission electron microscope[J].Journal of the American Ceramic Society,1999,82(11):2841-2848.
[17]OKADA K,ōTSUKA N,OSSAKA J.Characterization of spinel phase formed in the kaolinite-mullite thermal sequence[J].Journal of the American Ceramic Society,1986,69(10):C251-C253.
[18]SANZ J,MADANI A,SERRATOSA J M.Aluminum-27 and silicon-29 magic-angle spinning nuclear magnetic resonance study of the kaolinite-mullite transformation[J].Journal of the American Ceramic Society,1988,71(10):C418-C421.
[19]SONUPARLAK B,SARIKAYA M,AKSAY I A.Spinel phase formation during the 980°C exothermic reaction in the kaolinite-tomullite reaction series[J].Journal of the American Ceramic Society,1987,70(11):837-842.
[20]SEGNIT E R,GELB T.Metastable quartz-type structures formed from kaolinite by solid state reaction[J].American Mineralogist,1972,57:1505-1514.
[21]TAKEUCHI N,TAKAHASHI H,ISHIDA S,HORIIE F,WAKAMATSU M.Mechanistic study of solid-state reaction between kaolinite and ferrous oxide at high temperatures[J].Journal of the Ceramic Society of Japan,2000,108(10):876-881.
[22]ZHOU Qiu-sheng,LI Chuang,LI Xiao-bin,PENG Zhi-hong,LIUGui-hua,QI Tian-gui.Reaction behavior of ferric oxide in system Fe2O3-SiO2-Al2O3 during reductive sintering process[J].Transactions of Nonferrous Metals Society of China,2016,26:842-848.
[23]BARIN I.Thermochemical data of pure substances[M].Weinheim:VCH Verlagsgesellschaft mbH,1995.
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