Preparation of MnO_2 and calcium silicate hydrate from electrolytic manganese residue and evaluation of adsorption properties
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摘要
Electrolytic manganese residue(EMR), a high volume byproduct resulting from the electrolytic manganese industry, was used as a cheap and abundant chemical source for preparing MnO2 and EMR-made calcium silicate hydrate(EMR-CSH). The MnO2 is successfully synthesized from the metal cations extracted from EMR, which can effectively recycle the manganese in the EMR. By the combination of XRD, SEM and EDX analysis, the as-prepared MnO2 is found to exhibit a single-phase with the purity of 90.3%. Furthermore, EMR-CSH is synthesized from EMR via hydrothermal method. Based on the detailed analyses using XRD, FT-IR, FE-SEM, EDX and BET surface area measurement, the product synthesized under the optimum conditions(p H 12.0 and 100 °C) is identified to be a calcium silicate hydrate with a specific surface area of 205 m2/g incorporating the slag-derived metals(Al and Mg) in its structure. The as-synthesized material shows good adsorption properties for removal of Mn2+ and phosphate ions diluted in water, making it a promising candidate for efficient bulk wastewater treatment. This conversion process, which enables us to fabricate two different kinds of valuable materials from EMR at low cost and through convenient preparation steps, is surely beneficial from the viewpoint of the chemical and economical use of EMR.
Electrolytic manganese residue(EMR), a high volume byproduct resulting from the electrolytic manganese industry, was used as a cheap and abundant chemical source for preparing MnO2 and EMR-made calcium silicate hydrate(EMR-CSH). The MnO2 is successfully synthesized from the metal cations extracted from EMR, which can effectively recycle the manganese in the EMR. By the combination of XRD, SEM and EDX analysis, the as-prepared MnO2 is found to exhibit a single-phase with the purity of 90.3%. Furthermore, EMR-CSH is synthesized from EMR via hydrothermal method. Based on the detailed analyses using XRD, FT-IR, FE-SEM, EDX and BET surface area measurement, the product synthesized under the optimum conditions(p H 12.0 and 100 °C) is identified to be a calcium silicate hydrate with a specific surface area of 205 m2/g incorporating the slag-derived metals(Al and Mg) in its structure. The as-synthesized material shows good adsorption properties for removal of Mn2+ and phosphate ions diluted in water, making it a promising candidate for efficient bulk wastewater treatment. This conversion process, which enables us to fabricate two different kinds of valuable materials from EMR at low cost and through convenient preparation steps, is surely beneficial from the viewpoint of the chemical and economical use of EMR.
Electrolytic manganese residue(EMR), a high volume byproduct resulting from the electrolytic manganese industry, was used as a cheap and abundant chemical source for preparing MnO2 and EMR-made calcium silicate hydrate(EMR-CSH). The MnO2 is successfully synthesized from the metal cations extracted from EMR, which can effectively recycle the manganese in the EMR. By the combination of XRD, SEM and EDX analysis, the as-prepared MnO2 is found to exhibit a single-phase with the purity of 90.3%. Furthermore, EMR-CSH is synthesized from EMR via hydrothermal method. Based on the detailed analyses using XRD, FT-IR, FE-SEM, EDX and BET surface area measurement, the product synthesized under the optimum conditions(p H 12.0 and 100 °C) is identified to be a calcium silicate hydrate with a specific surface area of 205 m2/g incorporating the slag-derived metals(Al and Mg) in its structure. The as-synthesized material shows good adsorption properties for removal of Mn2+ and phosphate ions diluted in water, making it a promising candidate for efficient bulk wastewater treatment. This conversion process, which enables us to fabricate two different kinds of valuable materials from EMR at low cost and through convenient preparation steps, is surely beneficial from the viewpoint of the chemical and economical use of EMR.
引文
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[6]LIU Jing-ling,CHEN Qiu-ying,LI Yong-li.Ecological risk assessment of water environment for Luanhe River Basin based on relative risk model[J].Ecotoxicology,2010,19(8):1400-1415.
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[10]ZHOU Zheng-guo,XU Long-jun,XIE Jin-lian,LIU Cheng-lun.Effect of manganese tailings on capsicum growth[J].Chinese Journal of Geochemistry,2009,28(4):427-431.
[11]WANG Jia,PENG Bing,CHAI Li-yuan,ZHANG Qiang,LIU Qin.Preparation of electrolytic manganese residue–ground granulated blast furnace slag cement[J].Powder Technology,2013,241:12-18.
[12]HOU Peng-kun,QIAN Jue-shi,WANG Zhi,DENG Cheng.Production of quasi-sulfoaluminate cementitious materials with electrolytic manganese residue[J].Cement and Concrete Composites,2012,34(2):248-254.
[13]LI Hui,ZHANG Zhao-hui,TANG Si-ping,LI Yan-an,ZHANG Yong-kang.Ultrasonically assisted acid extraction of manganese from slag[J].Ultrasonics Sonochemistry,2008,15(4):339-343.
[14]XIN Bao-ping,CHEN Bing,DUAN Ning,ZHOU Chang-bo.Extraction of manganese from electrolytic manganese residue by bioleaching[J].Bioresource Technology,2011,102(2):1683-1687.
[15]TAO Chang-yuan,SHA Ji-wen,LIU Zuo-hua,SUN Da-gui,DU Jun.Study on recovery of high valent maganese from KMn O4 slag[J].Chinese Journal of Environmental Engineering,2011,5(10):2342-2346.(in Chinese)
[16]TAN Shi-yu,LUO Ting,ZHU Bi-jue.Study on the recycling of manganese dioxide in process of hydroquinone production by aniline oxidation[J].Applied Chemical Industry,2009,38(10):1542-1544.(in Chinese)
[17]PENG Tie-feng,XU Long-jun,CHEN Hong-chong.Preparation and characterization of high specific surface area Mn3O4 from electrolytic manganese residue[J].Central European Journal of Chemistry,2010,8(5):1059-1068.
[18]YU P,KIRKPATRICK R J,POE B,MCMILLAN P F,CONG X D.Structure of calcium silicate hydrate(C-S-H):Near-,mid-,and far-infrared spectroscopy[J].Journal of the American Ceramic Society,1999,82(3):742-748.
[19]RICHARDSON I G.The calcium silicate hydrates[J].Cement and Concrete Research,2008,38(2):137-158.
[20]ZIEGLER F,GIERE R,JOHNSON C A.Sorption mechanisms of zinc to calcium silicate hydrate:Sorption and microscopic investigations[J].Environmental Science&Technology,2001,35(22):4556-4561.
[21]KUWAHARA Y,TAMAGAWA S,FUJITANI T,YAMASHITA H.A novel conversion process for waste slag:synthesis of calcium silicate hydrate from blast furnace slag and its application as a versatile adsorbent for water purification[J].Journal of Materials Chemistry A,2013,1:7199-7210.
[22]SOUTHAM D C,LEWIS T W,MCFARLANE A J,JOHNSTON J H.Amorphous calcium silicate as a chemisorbent for phosphate[J].Current Applied Physics,2004,4(2):355-358.
[23]LI Gui-cun,JIANG Li,PANG Hong-tao,PENG Hong-rui.Synthesis ofγ-Mn O2 single-crystalline nanobelts[J].Materials Letters,2007,61(16):3319-3322.
[24]WEI Ming-deng,KONISHI Y,ZHOU Hao-shen,SUGIHARA H,ARAKAWA H.Synthesis of single-crystal manganese dioxide nanowires by a soft chemical process[J].Nanotechnology,2005,16(2):245-249.
[25]SHEN Wei-guo,XIAO Li-qi,ZHAO Su-ling,ZHOU Ming-kai,MA Wei.Investigation on nano-scale microstructure of C-S-H with atomic force microscope[J].Journal of the Chinese Ceramic Society,2008,36(4):487-493.
[26]DONG Ya,LU Chun-hua,NI Ya-ru,XU Zhong-zi.Drug loading capacity and morphology controlling of hydration calcium silicate mesoporous spheres[J].Bulletin of the Chinese Ceramic Society,2012,31(3):511-515.(in Chinese)
[27]HE Yong-jia,ZHAO Xiao-gang,LU Lin-nu,STRUBLE L J,HU Shu-guang.Effect of C/S ratio on morphology and structure of hydrothermally synthesized calcium silicate hydrate[J].Journal of Wuhan University of Technology:Mater Sci Ed,2011,26(4):770-773.
[28]MEISZTERICS A,ROSTA L,PETERLIK H,ROHONCZY J,KUBUKI S,HENITS P,SINKO K.Structural characterization of gel-derived calcium silicate systems[J].The Journal of Physical Chemistry A,2010,114(38):10403-10411.
[29]YASUTAKA K,TAKATO Y,TAKASHI K,KOHSUKE M,HIROMI Y.Enhancement in adsorption and catalytic activity of enzymes immobilized on phosphorus-and calcium-modified MCM-41[J].The Journal of Physical Chemistry B,2011,115(34):10335-10345.
[30]JOHNSTON J H,SMALL A C.Photoactivity of nano-structured calcium silicate–titanium dioxide composite materials[J].Journal of Materials Chemistry,2011,21(4):1240-1245.
[2]DUAN Ning,DAN Zhi-gang,WANG Fan,PAN Cen-xuan,ZHOU Chang-bo,JIANG Lin-hua.Electrolytic manganese metal industry experience based China’s new model for cleaner production promotion[J].Journal of Cleaner Production,2011,19(17):2082-2087.
[3]LIU Tang-meng,ZHONG Hong,YIN Xin-rong.Research of resource utilization of electrolytic manganese slag[J].China’s Manganese Industry,2012,30:1-6.(in Chinese)
[4]SUNDARAY S K,NAYAK B B,LIN S,BHATTAC D.Geochemical speciation and risk assessment of heavy metals in the river estuarine sediments—A case study:Mahanadi basin,India[J].Journal of Hazardous Materials,2011,186(2):1837-1846.
[5]YAN Chang-zhou,LI Qing-zhao,ZHANG Xian,LI Guo-xin.Mobility and ecological risk assessment of heavy metals in surface sediments of Xiamen Bay and its adjacent areas,China[J].Environmental Earth Sciences,2010,60(7):1469-1479.
[6]LIU Jing-ling,CHEN Qiu-ying,LI Yong-li.Ecological risk assessment of water environment for Luanhe River Basin based on relative risk model[J].Ecotoxicology,2010,19(8):1400-1415.
[7]LI Chang-xin,ZHONG Hong,WANG Shuai,XUE Jian-rong.Leaching behavior and risk assessment of heavy metals in a landfill of electrolytic manganese residue in western Hunan,China[J].Human and Ecological Risk Assessment,2014,20(5):1249-1263.
[8]HU Nan,ZHENG Ji-fang,DING De-xin,LIU Jun,YANG Lu-qing,YIN Jie,LI Guang-yue,WANG Yong-dong,LIU Yu-long.Metal pollution in Huayuan River in Hunan Province in China by manganese sulphate waste residue[J].Bulletin of Environmental Contamination and Toxicology,2009,83(4):583-590.
[9]DUAN Ning,WANG Fan,ZHOU Chang-bo,ZHU Chun-lei,YU Hong-bing.Analysis of pollution materials generated from electrolytic manganese industries in China[J].Resources,Conservation and Recycling,2010,54(8):506-511.
[10]ZHOU Zheng-guo,XU Long-jun,XIE Jin-lian,LIU Cheng-lun.Effect of manganese tailings on capsicum growth[J].Chinese Journal of Geochemistry,2009,28(4):427-431.
[11]WANG Jia,PENG Bing,CHAI Li-yuan,ZHANG Qiang,LIU Qin.Preparation of electrolytic manganese residue–ground granulated blast furnace slag cement[J].Powder Technology,2013,241:12-18.
[12]HOU Peng-kun,QIAN Jue-shi,WANG Zhi,DENG Cheng.Production of quasi-sulfoaluminate cementitious materials with electrolytic manganese residue[J].Cement and Concrete Composites,2012,34(2):248-254.
[13]LI Hui,ZHANG Zhao-hui,TANG Si-ping,LI Yan-an,ZHANG Yong-kang.Ultrasonically assisted acid extraction of manganese from slag[J].Ultrasonics Sonochemistry,2008,15(4):339-343.
[14]XIN Bao-ping,CHEN Bing,DUAN Ning,ZHOU Chang-bo.Extraction of manganese from electrolytic manganese residue by bioleaching[J].Bioresource Technology,2011,102(2):1683-1687.
[15]TAO Chang-yuan,SHA Ji-wen,LIU Zuo-hua,SUN Da-gui,DU Jun.Study on recovery of high valent maganese from KMn O4 slag[J].Chinese Journal of Environmental Engineering,2011,5(10):2342-2346.(in Chinese)
[16]TAN Shi-yu,LUO Ting,ZHU Bi-jue.Study on the recycling of manganese dioxide in process of hydroquinone production by aniline oxidation[J].Applied Chemical Industry,2009,38(10):1542-1544.(in Chinese)
[17]PENG Tie-feng,XU Long-jun,CHEN Hong-chong.Preparation and characterization of high specific surface area Mn3O4 from electrolytic manganese residue[J].Central European Journal of Chemistry,2010,8(5):1059-1068.
[18]YU P,KIRKPATRICK R J,POE B,MCMILLAN P F,CONG X D.Structure of calcium silicate hydrate(C-S-H):Near-,mid-,and far-infrared spectroscopy[J].Journal of the American Ceramic Society,1999,82(3):742-748.
[19]RICHARDSON I G.The calcium silicate hydrates[J].Cement and Concrete Research,2008,38(2):137-158.
[20]ZIEGLER F,GIERE R,JOHNSON C A.Sorption mechanisms of zinc to calcium silicate hydrate:Sorption and microscopic investigations[J].Environmental Science&Technology,2001,35(22):4556-4561.
[21]KUWAHARA Y,TAMAGAWA S,FUJITANI T,YAMASHITA H.A novel conversion process for waste slag:synthesis of calcium silicate hydrate from blast furnace slag and its application as a versatile adsorbent for water purification[J].Journal of Materials Chemistry A,2013,1:7199-7210.
[22]SOUTHAM D C,LEWIS T W,MCFARLANE A J,JOHNSTON J H.Amorphous calcium silicate as a chemisorbent for phosphate[J].Current Applied Physics,2004,4(2):355-358.
[23]LI Gui-cun,JIANG Li,PANG Hong-tao,PENG Hong-rui.Synthesis ofγ-Mn O2 single-crystalline nanobelts[J].Materials Letters,2007,61(16):3319-3322.
[24]WEI Ming-deng,KONISHI Y,ZHOU Hao-shen,SUGIHARA H,ARAKAWA H.Synthesis of single-crystal manganese dioxide nanowires by a soft chemical process[J].Nanotechnology,2005,16(2):245-249.
[25]SHEN Wei-guo,XIAO Li-qi,ZHAO Su-ling,ZHOU Ming-kai,MA Wei.Investigation on nano-scale microstructure of C-S-H with atomic force microscope[J].Journal of the Chinese Ceramic Society,2008,36(4):487-493.
[26]DONG Ya,LU Chun-hua,NI Ya-ru,XU Zhong-zi.Drug loading capacity and morphology controlling of hydration calcium silicate mesoporous spheres[J].Bulletin of the Chinese Ceramic Society,2012,31(3):511-515.(in Chinese)
[27]HE Yong-jia,ZHAO Xiao-gang,LU Lin-nu,STRUBLE L J,HU Shu-guang.Effect of C/S ratio on morphology and structure of hydrothermally synthesized calcium silicate hydrate[J].Journal of Wuhan University of Technology:Mater Sci Ed,2011,26(4):770-773.
[28]MEISZTERICS A,ROSTA L,PETERLIK H,ROHONCZY J,KUBUKI S,HENITS P,SINKO K.Structural characterization of gel-derived calcium silicate systems[J].The Journal of Physical Chemistry A,2010,114(38):10403-10411.
[29]YASUTAKA K,TAKATO Y,TAKASHI K,KOHSUKE M,HIROMI Y.Enhancement in adsorption and catalytic activity of enzymes immobilized on phosphorus-and calcium-modified MCM-41[J].The Journal of Physical Chemistry B,2011,115(34):10335-10345.
[30]JOHNSTON J H,SMALL A C.Photoactivity of nano-structured calcium silicate–titanium dioxide composite materials[J].Journal of Materials Chemistry,2011,21(4):1240-1245.