镁热剂/铝热剂体系SHS法固化处理无钙焙烧铬渣
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摘要
采用Al-Fe_2O_3(铝热剂)和Mg-Fe_2O_3(镁热剂)2种自蔓延高温合成体系(SHS)对无钙焙烧铬渣(COPR)进行固化处理,并通过浸出毒性试验对自蔓延产物的无害化效果进行评估。研究结果表明:2种反应体系均可实现铬渣的高效无害化,其中铝热剂体系和镁热剂体系铬渣含量分别高达80%和85%,其自蔓延产物浸取浓度ρ(总铬)和ρ(六价铬)分别低于4.5、1.5 mg·L~(-1),符合生活垃圾填埋场污染控制标准GB 16889—2008,可进行填埋处置。在SHS反应过程中,六价铬还原率均高于90%,还原后的六价铬主要以非晶形式弥散分布于自蔓延产物中,且部分铬离子参与MgAlCrO_4尖晶石等矿物的形成,铬元素同时以物理和化学固定化的形式存在于自蔓延产物中。
Two self-propagation high-temperature synthesis systems(SHS),Al-Fe_2O_3(thermite) and Mg-Fe_2O_3(magnesium thermite),were utilized to immobilize the chromite ore processing residue(COPR) from lime-free roasting process.The solid waste-extraction procedure was adopted to evaluate the treatment efficiency of COPR.The results showed that the SHS was an effective remediation technology for COPR with maximum solidify rate of 80% and 85%,respectively.The leaching toxic concentrations of total Cr and Cr(Ⅵ) in solidified products were less than 4.5 and 1.5 mg·L-1 respectively,and the final products could be disposed in the landfill site according to GB 16889—2008.During the SHS process,the reduction rate of Cr(Ⅵ) was higher than 90% and the reducing substance was dispersed in the solidified products in the form of amorphous state.Meanwhile,parts of the chromium ions were participated in the formation of minerals such as Mg Al Cr O4 spinel.Eventually,the chromium element was incorporated into the wasteforms in the form of chemical immobilization and physical encapsulation.
Two self-propagation high-temperature synthesis systems(SHS),Al-Fe_2O_3(thermite) and Mg-Fe_2O_3(magnesium thermite),were utilized to immobilize the chromite ore processing residue(COPR) from lime-free roasting process.The solid waste-extraction procedure was adopted to evaluate the treatment efficiency of COPR.The results showed that the SHS was an effective remediation technology for COPR with maximum solidify rate of 80% and 85%,respectively.The leaching toxic concentrations of total Cr and Cr(Ⅵ) in solidified products were less than 4.5 and 1.5 mg·L-1 respectively,and the final products could be disposed in the landfill site according to GB 16889—2008.During the SHS process,the reduction rate of Cr(Ⅵ) was higher than 90% and the reducing substance was dispersed in the solidified products in the form of amorphous state.Meanwhile,parts of the chromium ions were participated in the formation of minerals such as Mg Al Cr O4 spinel.Eventually,the chromium element was incorporated into the wasteforms in the form of chemical immobilization and physical encapsulation.
引文
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[32]赵有文,苗杉杉,董志远,等.磷化铟中铁原子替位与填隙的热致转变及其对材料性质的影响[J].物理学报,2007,56(9):5536-5541.ZHAO Y W,MIAO S S,DONG Z Y,et al.Thermally induced Fe atom transition from substitutional to interstitial sites in In P and its influence on material property[J].Acta Physica Sinica,2007,56(9):5536-5541.
[33]李春虎,赵九生,王大祥,等.纳米Mg O和Mg Al2O4尖晶石的制备与表征[J].无机材料学报,1996,(3):557-560.LI C H,ZHAO J S,WANG D X,et al.Synthesis and characterization for the nanoparticles of Mg O and Mg Al2O4 Spinel[J].Journal of Inorganic Materials,1996,(3):557-560.
[34]CHENG T W,UENG T H,CHEN Y S,et al.Production of glass-ceramic from incinerator fly ash[J].Ceramics International,2002,28(7):779-783.
[2]QI T G,LIU N,LI X B,et al.Thermodynamics of chromite ore oxidative roasting process[J].Journal of Central South University,2011,18(1):83-88.
[3]CHEN G,WANG X H,DU H,et al.A clean and efficient leaching process for chromite ore[J].Minerals Engineering,2014,60(2):60-68.
[4]赵备备,王少娜,郑诗礼,等.铬盐无钙焙烧渣加压硫酸浸出[J].过程工程学报,2014,14(6):915-922.ZHAO B B,WANG S N,ZHENG S L,et al.Pressure leaching of chromium-containing slag from non-calcium roasting with sulfuric acid[J].The Chinese Journal of Process Engineering,2014,14(6):915-922.
[5]SUN Z,ZHENG S L,XU H B,et al.Oxidation decomposition of chromite ore in molten potassium hydroxide[J].International Journal of Mineral Processing,2007,83(1/2):60-67.
[6]ZHANG B,SHI P Y,JIANG M F.Advances towards a clean hydrometallurgical process for chromite[J].Minerals,2016,6(1):7.
[7]ALTUNDOGAN H S,OZER A,TUMEN F.A study on the reduction of hexavalent chromium in aqueous solutions by vinasse[J].Environmental Technology,2004,25(11):1257-1263.
[8]王天贵,余锡孟,俞力家.铬渣还原解毒工艺:101168085[P].2008-04-30.WANG T G,YU X M,YU L J.Chromium slag reduction detoxification technique:101168085[P].2008-04-30.
[9]WANG T G,HE M L,PAN Q.A new method for the treatment of chromite ore processing residues[J].Journal of Hazardous Materials,2007,149(2):440-444.
[10]MOON D H,WAZNE M,DERMATAS D,et al.Long-term treatment issues with chromite ore processing residue(COPR):Cr6+reduction and heave[J].Journal of Hazardous Materials,2007,143(3):629-635.
[11]MOON D H,WAZNE M,JAGUPILLA S C,et al.Particle size and p H effects on remediation of chromite ore processing residue using calcium polysulfide(Ca S5)[J].Science of the Total Environment,2008,399(1/2/3):2-10.
[12]QUAN X J,TAN H Q,ZHAO Y C,et al.Detoxification of chromium slag by chromate resistant bacteria[J].Journal of Hazardous Materials,2006,137(2):836-841.
[13]DHAL B,THATOI H N,DAS N N,et al.Chemical and microbial remediation of hexavalent chromium from contaminated soil and mining/metallurgical solid waste:a review[J].Journal of Hazardous Materials,2013,250/251:272-291.
[14]LAFOREST G,DUCHESNE J.Immobilization of chromium(Ⅵ)evaluated by binding isotherms for ground granulated blast furnace slag and ordinary Portland cement[J].Cement and Concrete Research,2005,35(12):2322-2332.
[15]SHI Y M,DU X H,MENG Q J,et al.Reaction process of chromium slag reduced by industrial waste in solid phase[J].Journal of Iron and Steel Research,International,2007,14(1):12-15.
[16]SUBRAHMANYAM J,VIJAYAKUMAR M.Self-propagating high-temperature synthesis[J].Journal of Materials Science,1992,27(23):6249-6273.
[17]LI B Y,RONG L J,LI Y Y,et al.Synthesis of porous Ni-Ti shape-memory alloys by self-propagating high-temperature synthesis:reaction mechanism and anisotropy in pore structure[J].Acta Materialia,2000,48(15):3895-3904.
[18]PORCU M,ORRU R,CAO G.On the use of industrial scraps for the treatment of zinc hydrometallurgical wastes by self-propagating reactions[J].Chemical Engineering Journal,2004,99(3):247-256.
[19]MAO X H,QIN Z G,YUAN X N,et al.Immobilization of simulated radioactive soil waste containing cerium by self-propagating high-temperature synthesis[J].Journal of Nuclear Materials,2013,443(1/2/3):428-431.
[20]胡文彬,刘威威,郑子樵,等.自蔓延高温反应过程中热化学的编程计算[J].中国有色金属学报,1994,(1):59-63.HU W B,LIU W W,ZHENG Z Q,et al.Programmed calculation of thermochemistry in self-propagating high temperature reaction[J].Transactions of Nonferrous Metals Society of China,1994,(1):59-63.
[21]WANG Y,ZHU J X.Preparation of lead oxide nanoparticles from cathode-ray tube funnel glass by self-propagating method[J].Journal of Hazardous Materials,2012,215/216:90-97.
[22]MOSSINO P.Some aspects in self-propagating high-temperature synthesis[J].Ceramics International,2004,30(3):311-332.
[23]路新,郭志猛,罗上庚,等.自蔓延高温合成固定放射性废物[J].硅酸盐学报,2003,31(2):205-208.LU X,GUO Z M,LUO S G,et al.Self-propagating high temperature synthesis of radioactive waste immobilization[J].Journal of the Chinese Ceramic Society,2003,31(2):205-208.
[24]HUANG X,HUANG T,LI S,et al.Immobilization of chromite ore processing residue with alkali-activated blast furnace slag-based geopolymer[J].Ceramics International,2016,42(8):9538-9549.
[25]CHEN M,ZHANG F S,ZHU J.Detoxification of cathode ray tube glass by self-propagating process[J].Journal of Hazardous Materials,2009,165(1/2/3):980-986.
[26]WANG L Y,PEHLKE R D.High temperature thermodynamics of the Cr-Cr2N-N2 system[J].Metallurgical and Materials Transactions B,1988,19(3):471-476.
[27]HIROTA K,TAKANO Y,YOSHINAKA M,et al.Hot isostatic pressing of chromium nitrides(Cr2N and Cr N)prepared by self-propagating high-temperature synthesis[J].Journal of the American Ceramic Society,2010,84(9):2120-2122.
[28]А.И.耶菲莫夫,等.无机化合物性质手册[M].高胜利,宋俊峰,过玮,译.西安:陕西科学技术出版社,1987.ЕФИMOBАИ,et al.Handbook of Inorganic Compounds Properties[M].GAO S L,SONG J F,GUO W,trans.Xi'an:Shaanxi Science and Technology Press,1987.
[29]GIANNINI C,GUDI A,MILLINI R.Quantitative phase analysis by combining the Rietveld and the whole-pattern decomposition methods[J].Journal of Applied Crystallography,2002,35(4):481-490.
[30]CHRYSOCHOOU M,DERMATAS D.Application of the Rietveld method to assess chromium(Ⅵ)speciation in chromite ore processing residue[J].Journal of Hazardous Materials,2007,141(2):370-377.
[31]TANI E,YOSHIMURA M,SOMIYA S.Revised phase diagram of the system Zr O2-Ce O2 below 1400℃[J].Journal of the American Ceramic Society,1983,66(7):506-510.
[32]赵有文,苗杉杉,董志远,等.磷化铟中铁原子替位与填隙的热致转变及其对材料性质的影响[J].物理学报,2007,56(9):5536-5541.ZHAO Y W,MIAO S S,DONG Z Y,et al.Thermally induced Fe atom transition from substitutional to interstitial sites in In P and its influence on material property[J].Acta Physica Sinica,2007,56(9):5536-5541.
[33]李春虎,赵九生,王大祥,等.纳米Mg O和Mg Al2O4尖晶石的制备与表征[J].无机材料学报,1996,(3):557-560.LI C H,ZHAO J S,WANG D X,et al.Synthesis and characterization for the nanoparticles of Mg O and Mg Al2O4 Spinel[J].Journal of Inorganic Materials,1996,(3):557-560.
[34]CHENG T W,UENG T H,CHEN Y S,et al.Production of glass-ceramic from incinerator fly ash[J].Ceramics International,2002,28(7):779-783.