褐铁矿纳米结构化相变零价铁及其除磷性能
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摘要
利用X射线粉末衍射仪、X射线荧光光谱仪、热分析仪、场发射扫描电镜表征手段研究了铜陵褐铁矿的矿物组成及其形貌形态特征,通过热处理方式获得褐铁矿纳米结构化相变零价铁作为动态柱填料并探究其除磷性能。结果表明,铜陵褐铁矿主要由针铁矿(>90%)和石英组成,针铁矿晶体呈针状和片状,具纳米尺寸,集合体呈笋状和球状;热处理促使针铁矿进一步纳米结构化相变形成零价铁,具多孔结构、高比表面积特征;零价铁作为动态柱填料净化模拟含磷(5mg/L)废水可运行1年以上,磷去除效率超过99%,出水磷浓度达到城镇污水一级A排放标准(0.5mg/L)。研究结果可促进褐铁矿资源在保护环境中的应用,也为深度处理含磷废水提供一种新材料。
XRD,XRF,TG/DTG and FESEM were utilized to study characteristics of the mineral phase and morphology of limonite from the Tongling area. Zero valent iron( ZVI) was prepared by thermally treating limonite in hydrogen and is then used to study the performance on removal of phosphate from aqueous solution in this paper. The result shows that the Tongling limonite was mainly composed of goethite( over 90%) and quartz. The goethite occurs as nano-sized acicular and flaky crystals in bamboo shoot and ball shaped aggregates. Thermal treatment of goethite resulted in its nano-structuring and the formation of zero valent iron with properties of porous structure and large specific surface area in the goethite. The zero valent iron was utilized as filter to remove phosphate from phosphate-bearing water( 5 mg/L) and is able to be run for over one year,with the removal efficiency of over 99%. The P concentration of treated waste water is lower than 0. 5 mg/L which can satisfy the national discharge standard of pollutants for municipal waste water treatment plant. This will favor the application of the limonite in field of environment protection,especially as a new material for treating P-containing sewage.
XRD,XRF,TG/DTG and FESEM were utilized to study characteristics of the mineral phase and morphology of limonite from the Tongling area. Zero valent iron( ZVI) was prepared by thermally treating limonite in hydrogen and is then used to study the performance on removal of phosphate from aqueous solution in this paper. The result shows that the Tongling limonite was mainly composed of goethite( over 90%) and quartz. The goethite occurs as nano-sized acicular and flaky crystals in bamboo shoot and ball shaped aggregates. Thermal treatment of goethite resulted in its nano-structuring and the formation of zero valent iron with properties of porous structure and large specific surface area in the goethite. The zero valent iron was utilized as filter to remove phosphate from phosphate-bearing water( 5 mg/L) and is able to be run for over one year,with the removal efficiency of over 99%. The P concentration of treated waste water is lower than 0. 5 mg/L which can satisfy the national discharge standard of pollutants for municipal waste water treatment plant. This will favor the application of the limonite in field of environment protection,especially as a new material for treating P-containing sewage.
引文
Chang D Y,Chen T H,Liu H B,Xi Y F,Qing C S,Xie Q Q,Frost RL.2014.A new approach to prepare ZVI and its application in removal of Cr(Ⅵ)from aqueous solution.Chemical Engineering Journal,244:264-272
Cornell R M,Schwertmann U.2003.The iron oxides:structure,properties,reactions,occurences and uses.2th edition.Weinheim:Wiley-VCH
Di Palma L,Gueye M T,Petrucci E.2015.Hexavalent chromium reduction in contaminated soil:A comparison between ferrous sulphate and nanoscale zero-valent iron.Journal of Hazardous Materials,281:70-76
Liu H B,Chen T H,Xie Q Q,Zou X H,Qing C S,Frost R L.2012Kinetic study of goethite dehydration and the effect of aluminium substitution on the dehydrate.Thermochimica Acta,545:20-25
Liu H B,Chen T H,Zou X H,Qing C S,Frost R L.2013a.Therma treatment of natural goethite:Thermal transformation and physica properties.Thermochimica Acta,568:115-121
Liu H B,Chen T H,Zou X H,Xie Q Q,Qing C S,Chen D,Frost R L2013b.Removal of phosphorus using NZVI derived from reducing natural goethite.Chemical Engineering Journal,234:80-87
Liu H B,Chen T H,Qing C S,Xie Q Q,Frost R L.2013c.Confirmation of the assignment of vibrations of goethite:An ATR and IESstudy of goethite structure.Spectrochimica Acta Part A:Molecular and Biomolecular Spectroscopy,116:154-159
Ruan H D,Frost R L,Kloprogge J T.2001.The behavior of hydroxyl units of synthetic goethite and its dehydroxylated product hematite Spectrochimica Acta Part A:Molecular and Biomolecular Spectroscopy,57(13):2575-2586
Shen C Y,Lu W L,Huang Y F,Wu J X,Zhang H Y.2015.Removal o bismerthiazol from water using zerovalent iron:Batch studies and mechanism interpretation.Chemical Engineering Journal,260:411-418
邓雁希,许虹,黄玲,钟佐燊.2005.矿物材料对城市生活污水中磷的去除.有色金属,57(2):136-138
黄丽,刘畅,胡红青,刘凡,李学垣.2007.不同p H下有机酸对针铁矿和膨润土吸附Cd2+、Pb2+的影响.土壤学报,44(4):643-649
李超,杨守业.2012.长江沉积物中赤铁矿和针铁矿的漫反射光谱分析.地球科学-中国地质大学学报,37(S1):11-19
刘瑞,秦善,鲁安怀,郑喜珅,王丽娟,赵东军.2003.锰氧化物和氢氧化物中的孔道结构矿物及其环境属性.矿物岩石,23(4):28-33
彭喜花,陆勇.2012.凹土/聚合氯化铁复合材料处理含磷废水的研究.硅酸盐通报,31(6):1457-1461
王菊,陈天虎,李平,谢晶晶,马炳德,曹光跃.2012.黄铁矿净化水中低浓度磷.矿物学报,32(2):238-243
王荣昌,司书鹏,杨殿海,励建全,赵建夫.2013.温度对生物强化除磷工艺反硝化除磷效果的影响.环境科学学报,33(6):1535-1544
许虹,张静,高一鸣.2008.利用矿物方解石进行水体除磷实验研究地学前缘,15(4):138-141
翟由涛.2010.吸附法除磷研究进展.安徽农业科学,38(15):8154-8158
周玮,季俊峰,William B,陈骏.2007.利用漫反射光谱鉴定红黏土中针铁矿和赤铁矿.高校地质学报,13(4):730-736
邹雪华,陈天虎,刘海波,陈冬,张萍,谢巧勤.2013.热处理针铁矿的结构与色度演化.硅酸盐学报,41(5):669-673
Cornell R M,Schwertmann U.2003.The iron oxides:structure,properties,reactions,occurences and uses.2th edition.Weinheim:Wiley-VCH
Di Palma L,Gueye M T,Petrucci E.2015.Hexavalent chromium reduction in contaminated soil:A comparison between ferrous sulphate and nanoscale zero-valent iron.Journal of Hazardous Materials,281:70-76
Liu H B,Chen T H,Xie Q Q,Zou X H,Qing C S,Frost R L.2012Kinetic study of goethite dehydration and the effect of aluminium substitution on the dehydrate.Thermochimica Acta,545:20-25
Liu H B,Chen T H,Zou X H,Qing C S,Frost R L.2013a.Therma treatment of natural goethite:Thermal transformation and physica properties.Thermochimica Acta,568:115-121
Liu H B,Chen T H,Zou X H,Xie Q Q,Qing C S,Chen D,Frost R L2013b.Removal of phosphorus using NZVI derived from reducing natural goethite.Chemical Engineering Journal,234:80-87
Liu H B,Chen T H,Qing C S,Xie Q Q,Frost R L.2013c.Confirmation of the assignment of vibrations of goethite:An ATR and IESstudy of goethite structure.Spectrochimica Acta Part A:Molecular and Biomolecular Spectroscopy,116:154-159
Ruan H D,Frost R L,Kloprogge J T.2001.The behavior of hydroxyl units of synthetic goethite and its dehydroxylated product hematite Spectrochimica Acta Part A:Molecular and Biomolecular Spectroscopy,57(13):2575-2586
Shen C Y,Lu W L,Huang Y F,Wu J X,Zhang H Y.2015.Removal o bismerthiazol from water using zerovalent iron:Batch studies and mechanism interpretation.Chemical Engineering Journal,260:411-418
邓雁希,许虹,黄玲,钟佐燊.2005.矿物材料对城市生活污水中磷的去除.有色金属,57(2):136-138
黄丽,刘畅,胡红青,刘凡,李学垣.2007.不同p H下有机酸对针铁矿和膨润土吸附Cd2+、Pb2+的影响.土壤学报,44(4):643-649
李超,杨守业.2012.长江沉积物中赤铁矿和针铁矿的漫反射光谱分析.地球科学-中国地质大学学报,37(S1):11-19
刘瑞,秦善,鲁安怀,郑喜珅,王丽娟,赵东军.2003.锰氧化物和氢氧化物中的孔道结构矿物及其环境属性.矿物岩石,23(4):28-33
彭喜花,陆勇.2012.凹土/聚合氯化铁复合材料处理含磷废水的研究.硅酸盐通报,31(6):1457-1461
王菊,陈天虎,李平,谢晶晶,马炳德,曹光跃.2012.黄铁矿净化水中低浓度磷.矿物学报,32(2):238-243
王荣昌,司书鹏,杨殿海,励建全,赵建夫.2013.温度对生物强化除磷工艺反硝化除磷效果的影响.环境科学学报,33(6):1535-1544
许虹,张静,高一鸣.2008.利用矿物方解石进行水体除磷实验研究地学前缘,15(4):138-141
翟由涛.2010.吸附法除磷研究进展.安徽农业科学,38(15):8154-8158
周玮,季俊峰,William B,陈骏.2007.利用漫反射光谱鉴定红黏土中针铁矿和赤铁矿.高校地质学报,13(4):730-736
邹雪华,陈天虎,刘海波,陈冬,张萍,谢巧勤.2013.热处理针铁矿的结构与色度演化.硅酸盐学报,41(5):669-673