水泥窑烧成带用MgO-ZrO_2质耐火材料的研究
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摘要
二十世纪七十年代以来，随着世界范围内环保意识的加强和发展绿色工业的要求，国外水泥窑用碱性耐火材料已发生了近乎根本性的转变。引发这种转变的主要原因是消除“铬公害”来保护人类的生存环境。作为水泥窑用关键材料—镁铬砖，使用过程中在碱和硫的作用下，生成水溶性的且能毒害人畜并致癌的六价铬盐化合物R_2Cr(Ⅵ)O_4和R_2[SCr(Ⅵ)]O_4等有害化合物，通过水泥窑的废气和粉尘排放，尤其是用后残砖在存放过程中受水淋溶出而外渗污染环境，特别是污染水源，导致适合水泥窑用的镁铬砖开始在发达国家逐步逐出历史舞台。
镁铬砖最早出现的替代品是镁白云石砖。镁白云石砖对水泥熟料具有亲和性且化学稳定性好，从而具有良好的挂窑皮性，但其存在着易水化和抗热震性差的缺点。取代镁铬砖的尖晶石砖具有优良的抗热震稳定性，但其在使用时不能形成稳定的窑皮，而且热导率高，导致这两种砖都不能够完全替代镁铬材料在水泥回转窑上的使用。
本研究课题采用95烧结镁砂，96电熔镁砂，单斜氧化锆，锆英砂(ZrO_2·SiO_2)，Zr(OH)_4凝胶等作为原料，进行了水泥窑用镁锆质耐火材料的研究。实验结果表明：以96电熔镁砂为细粉配以95电熔镁砂作为颗粒制作的试样性能优于以95烧结镁砂细粉配以95电熔镁砂作为颗粒的试样。而在ZrO_2的三种引入方式中，引入单斜氧化锆的试样抗水泥熟料侵蚀性最好，而挂窑皮性最差；引入锆英砂的试样虽然其挂窑皮性很好，但抗侵蚀性是最差的。综合考虑：引入Zr(OH)_4凝胶的试样性能最好，其抗压和抗折强度也是最高的。此研究成果对我国水泥窑用耐火材料无铬化具有一定的理论指导作用和生产使用价值。
From the end of 1970s, because of the improvement of environmental protection and the need of development green industry, there are great changes have happened to the basic bricks used in cement rotary kiln. The cause of the change is elimination of chrome — pollution and protection of human living environment. As the key refractory in the burning zone of the cement rotary kiln, the Magnesia — chrome bricks form the water — soluble compound R_2Cr(VI)O_4 or R_2[SCr(VI)]O_4 which are harmful for human being and animals under the action of alkali and sulfur . The poisoned compound could be compelled through the wasteful gas and dust. The bricks that had been used suffer the rain and the poisoned compound could pollute environment, specially the water. The Magnesia — chrome bricks are gradually limited in developed countries, and would be instead.
The first material instead of the magnesia — chrome bricks is Magnesia — dolomite bricks. The Magnesia — dolomite brick has the appetency and good stability of chemistry, which result in the superior coating adherence and corrosion resistance to cement raw materials. It also has the disadvantages of hydration and bad thermal — shock resistance. Spinal brick has the good thermal — shock resistance, however it has the disadvantages such as the bad coating adherence and high heat — conducting rate. All these disadvantages cause they could not completely instead of the Magnesia — chrome bricks which is used in the sinter-zone of the cement rotary kiln.
We use 95 sintered magnesia, 96 fused magnesia, c-ZrO_2, Zircon (ZrO_2·SiO_2), Zr(OH)_4gel as the raw material for the research of MgO-ZrO_2 series refractoriness in sinter zone of cement kiln. The experimental result is: the specimens that is made up of 96 fused magnesia fine power and 95 fused magnesia grain is better than the specimens which is made up of 95 sintered magnesia fine power and 95 fused magnesia grain. In the three additive ways of ZrO_2 the cement corrosion resistance of the specimen which is addicted with C-ZrO_2 is the best, and the cement adherence is the worst;however the specimen which has the best cement adherence, its cement corrosion resistance ability is the worst. Thus according to the experimental phenomenon, we can gain the conclusion: the performance of the specimen that is addicted with Zr(OH)_4 gel is better, its compressive strength and the fold strength are high. What we had researched makes a useful attempt in the procession of free chrome for cement refractoriness in china. And it also have guideing function for theory and value in use for production in the procession of free chrome for cement refractory in china.
镁铬砖最早出现的替代品是镁白云石砖。镁白云石砖对水泥熟料具有亲和性且化学稳定性好，从而具有良好的挂窑皮性，但其存在着易水化和抗热震性差的缺点。取代镁铬砖的尖晶石砖具有优良的抗热震稳定性，但其在使用时不能形成稳定的窑皮，而且热导率高，导致这两种砖都不能够完全替代镁铬材料在水泥回转窑上的使用。
本研究课题采用95烧结镁砂，96电熔镁砂，单斜氧化锆，锆英砂(ZrO_2·SiO_2)，Zr(OH)_4凝胶等作为原料，进行了水泥窑用镁锆质耐火材料的研究。实验结果表明：以96电熔镁砂为细粉配以95电熔镁砂作为颗粒制作的试样性能优于以95烧结镁砂细粉配以95电熔镁砂作为颗粒的试样。而在ZrO_2的三种引入方式中，引入单斜氧化锆的试样抗水泥熟料侵蚀性最好，而挂窑皮性最差；引入锆英砂的试样虽然其挂窑皮性很好，但抗侵蚀性是最差的。综合考虑：引入Zr(OH)_4凝胶的试样性能最好，其抗压和抗折强度也是最高的。此研究成果对我国水泥窑用耐火材料无铬化具有一定的理论指导作用和生产使用价值。
From the end of 1970s, because of the improvement of environmental protection and the need of development green industry, there are great changes have happened to the basic bricks used in cement rotary kiln. The cause of the change is elimination of chrome — pollution and protection of human living environment. As the key refractory in the burning zone of the cement rotary kiln, the Magnesia — chrome bricks form the water — soluble compound R_2Cr(VI)O_4 or R_2[SCr(VI)]O_4 which are harmful for human being and animals under the action of alkali and sulfur . The poisoned compound could be compelled through the wasteful gas and dust. The bricks that had been used suffer the rain and the poisoned compound could pollute environment, specially the water. The Magnesia — chrome bricks are gradually limited in developed countries, and would be instead.
The first material instead of the magnesia — chrome bricks is Magnesia — dolomite bricks. The Magnesia — dolomite brick has the appetency and good stability of chemistry, which result in the superior coating adherence and corrosion resistance to cement raw materials. It also has the disadvantages of hydration and bad thermal — shock resistance. Spinal brick has the good thermal — shock resistance, however it has the disadvantages such as the bad coating adherence and high heat — conducting rate. All these disadvantages cause they could not completely instead of the Magnesia — chrome bricks which is used in the sinter-zone of the cement rotary kiln.
We use 95 sintered magnesia, 96 fused magnesia, c-ZrO_2, Zircon (ZrO_2·SiO_2), Zr(OH)_4gel as the raw material for the research of MgO-ZrO_2 series refractoriness in sinter zone of cement kiln. The experimental result is: the specimens that is made up of 96 fused magnesia fine power and 95 fused magnesia grain is better than the specimens which is made up of 95 sintered magnesia fine power and 95 fused magnesia grain. In the three additive ways of ZrO_2 the cement corrosion resistance of the specimen which is addicted with C-ZrO_2 is the best, and the cement adherence is the worst;however the specimen which has the best cement adherence, its cement corrosion resistance ability is the worst. Thus according to the experimental phenomenon, we can gain the conclusion: the performance of the specimen that is addicted with Zr(OH)_4 gel is better, its compressive strength and the fold strength are high. What we had researched makes a useful attempt in the procession of free chrome for cement refractoriness in china. And it also have guideing function for theory and value in use for production in the procession of free chrome for cement refractory in china.
引文
[1] 徐秀芳译．波特兰水泥与混合水泥工艺．中国建筑工业出版社，1986．P110
[2] 卢一国译．水泥窑用耐火材料的化学损毁．国外耐火材料，1993，No，2：P44
[3] 沈威，黄文熙，闵盘荣．水泥工艺学．武汉工业大学出版社，1991．P130～140
[4] 廖建国译．水泥窑用耐火材料无铬砖的演变．国外耐火材料，2003，(5)：P6～10
[5] 周季楠．水泥窑用碱性耐火材料及水泥工业用耐火材料的发展动向．内部资料《水泥窑用耐火材料》，2000，P10～15
[6] 廖建国译．水泥窑用耐火材料无铬砖的演变．国外耐火材料，2003，(5)：P6～10
[7] 刘秉金．水泥窑用碱性砖趋向无铬化．《第六届水泥窑用耐火材料技术交流会论文集》，2003年4月，P142～143
[8] G. Weibel, Go ttingen. Chrome-ore-free refractory brickwork for the transion and sintering zone of rotary cement kilns.ZKG, 1990(9):P256～258
[9] 李宝生．耐火材料在大型水泥回转窑内的使用与展望．全国新型干法水泥窑用耐火材料技术研讨及窑衬配套经济交流会，2000年6月，P68～69
[10] 陆纯煊，曾大凡，丁抗生．新一代干法水泥窑用新一代窑衬材料．江苏《水泥工程》杂志社《水泥窑用耐火材料新技术论文集》2000年3月，P83～86
[11] 傅正义，魏诗榴．CaO的机械力化学活化．硅酸盐学报，1989，17(4)：P308～314
[12] 顾华志，汪厚植，洪彦若等．机械化学对Ca(OH)_2包覆CaCO_3复合粉体的抗水化性能影响．2004年全国耐火材料综合学术年会论文集，鞍山：P347～355
[13] 陈开献，陈肇友．混合稀土氧化物与Fe_2O_3对白云石烧结性能和抗水化性能的影响．耐火材料，1992，26(4)：P187～190
[14] 徐延庆，陈肇友．稀土氧化物对白云石烧结与抗水化性的影响．耐火材料，1992，26(5)：P282～286
[15] Vonp Barth,H.J. Kistna, Gottingen.Deutsch land Classification Von. Magnesia—Steiner nach Specification and Gebrauchswent in sement drehrofen. ZKG, 1994,(8):P474～478
[16] Bernard Moore, Martin Firth and David Evans. Development in refractoriness for cement kilns. World Cement, 1991,(12):P5～12
[17] 金利萍，夏辉译．水泥回转窑用碱性炉材的技术进步．国外耐火材料，2005，(4)：P2～3
[18] 张银亮，姚全灵译．水泥窑过渡带高蚀损部位用的耐火材料．国外耐火材料，1998，(9)：P38～41
[19] Hiroshima Kino, Masato Mori, Toyotas Obana, et al. Properties of MgO-TiO_2-Al_2O_3 aggregates. Proceedings of UN ITECR 2003 Congress, Osaka, Japan: P165～167
[20] AraiMasashi, Shigeru Ukwa. The development of chrome-free bricks for burning zone of cement rotary kiln. Proceedings of UN ITECR'2003 Congress, Osaka, Japan: P43～46
[21] Makoto Ohio, Kozo Tokunaga, Yoshihito Tsuchiya, et al. Applications of chrome-free basic bricks to cement rotary kilns in Japan. Proceedings of UN ITECR 2003 Congress, Osaka, Japan: P27～30
[22] 小田康义．Preventive methods for hydration of calcia and dolomite clinkers．耐火物，1989，41(1)：P21～26
[23] 王诚训．ZrO_2复合耐火材料．冶金工业出版社，1997
[24] 李君，杨彬，王金相等．MgO-ZrO_2材料的烧结、显微结构和性能．耐火材料，1996，No．2：P69～71
[25] 胡延恕，李振，崔淑贤等．氧化锆对碱性耐火材料使用性能的影响．耐火材料，1995，No．3：P149～153
[26] 涂军波，张文杰，汪厚植等．烧结合成镁锆熟料的研究．耐火材料，1999，33(3)：P144～146
[27] 朱伯铨，李楠，甘菲芳等．电熔镁锆合成料的组成对显微结构和性能的影响．耐火材料，1999，No．6：P310～312
[28] 朱伯铨，李楠，甘菲芳等．电熔镁锆合成料抗渣性研究．耐火材料，2000，No．3：P130～132
[29] 朱伯铨，李楠，甘菲芳等．SiO_2对镁锆合成料抗渣性的影响．武汉科技大学学报，2000，Vol．23，No．2：P26～28
[30] 朱伯铨，李楠，甘菲芳等．电熔镁锆合成料中SiO_2的赋存状态及分布特征．武汉科技大学学报，2000，Vol．23，No．1：P139～141
[31] 李君．MgO-ZrO_2复合材料组成、结构及性能关系的研究．洛阳耐火材料研究院硕士论文，1994
[32] 大坪正和等．MgO-ZrO_2质原料的特征．耐火物，1992，44(7)：P427～428
[33] 笠井清人等．Slag penetration mechanism of magnesia zirconia castable refractories．耐火物，1993，45(8)：P491～492．
[34] 八百井英雄等Development of magnesia ziron castable for steel ladle slag line．耐 火物，1993，45(9)：P521～522
[35] 花桐诚思．耐火物．1991，(6)：P284～292
[36] 许珂敬，许煜汾．表面活性剂在制备ZrO_2微粉的作用．材料研究学报，1999，Vol．13，No．4：P434～436
[37] 杨广慧，张彦．纳米氧化锆的制备及应用[J]．化工新材料，1999，27(5)：P21
[38] 陈宗淇，戴闽光．胶体化学[M]．北京：高等教育出版社，1985：P180～183
[39] 郭玉香，栾舰，田风仁．锆英石对镁砂烧结性及其制品性能的影响．耐火材料，2001，35(5)：P281～282
[40] Zhou Ningsheng, Li Zaigeng, Zhang Sanhua, et al. Bonding modes and development in bonding system of monolithic refractoriness. Proc. of the 3rd International Workshop on Technology and Development of Refractories,Luoyang,China,2000:P21～42
[41] 徐延庆，叶国田．水泥窑含ZrO_2耐火材料．耐火材料，2003，37(2)：P105～107
[42] 程本军，杨彬，王金相等．MgO-ZrO_2材料的抗侵蚀性能研究．耐火材料，2004，38(1)：P15～17
[2] 卢一国译．水泥窑用耐火材料的化学损毁．国外耐火材料，1993，No，2：P44
[3] 沈威，黄文熙，闵盘荣．水泥工艺学．武汉工业大学出版社，1991．P130～140
[4] 廖建国译．水泥窑用耐火材料无铬砖的演变．国外耐火材料，2003，(5)：P6～10
[5] 周季楠．水泥窑用碱性耐火材料及水泥工业用耐火材料的发展动向．内部资料《水泥窑用耐火材料》，2000，P10～15
[6] 廖建国译．水泥窑用耐火材料无铬砖的演变．国外耐火材料，2003，(5)：P6～10
[7] 刘秉金．水泥窑用碱性砖趋向无铬化．《第六届水泥窑用耐火材料技术交流会论文集》，2003年4月，P142～143
[8] G. Weibel, Go ttingen. Chrome-ore-free refractory brickwork for the transion and sintering zone of rotary cement kilns.ZKG, 1990(9):P256～258
[9] 李宝生．耐火材料在大型水泥回转窑内的使用与展望．全国新型干法水泥窑用耐火材料技术研讨及窑衬配套经济交流会，2000年6月，P68～69
[10] 陆纯煊，曾大凡，丁抗生．新一代干法水泥窑用新一代窑衬材料．江苏《水泥工程》杂志社《水泥窑用耐火材料新技术论文集》2000年3月，P83～86
[11] 傅正义，魏诗榴．CaO的机械力化学活化．硅酸盐学报，1989，17(4)：P308～314
[12] 顾华志，汪厚植，洪彦若等．机械化学对Ca(OH)_2包覆CaCO_3复合粉体的抗水化性能影响．2004年全国耐火材料综合学术年会论文集，鞍山：P347～355
[13] 陈开献，陈肇友．混合稀土氧化物与Fe_2O_3对白云石烧结性能和抗水化性能的影响．耐火材料，1992，26(4)：P187～190
[14] 徐延庆，陈肇友．稀土氧化物对白云石烧结与抗水化性的影响．耐火材料，1992，26(5)：P282～286
[15] Vonp Barth,H.J. Kistna, Gottingen.Deutsch land Classification Von. Magnesia—Steiner nach Specification and Gebrauchswent in sement drehrofen. ZKG, 1994,(8):P474～478
[16] Bernard Moore, Martin Firth and David Evans. Development in refractoriness for cement kilns. World Cement, 1991,(12):P5～12
[17] 金利萍，夏辉译．水泥回转窑用碱性炉材的技术进步．国外耐火材料，2005，(4)：P2～3
[18] 张银亮，姚全灵译．水泥窑过渡带高蚀损部位用的耐火材料．国外耐火材料，1998，(9)：P38～41
[19] Hiroshima Kino, Masato Mori, Toyotas Obana, et al. Properties of MgO-TiO_2-Al_2O_3 aggregates. Proceedings of UN ITECR 2003 Congress, Osaka, Japan: P165～167
[20] AraiMasashi, Shigeru Ukwa. The development of chrome-free bricks for burning zone of cement rotary kiln. Proceedings of UN ITECR'2003 Congress, Osaka, Japan: P43～46
[21] Makoto Ohio, Kozo Tokunaga, Yoshihito Tsuchiya, et al. Applications of chrome-free basic bricks to cement rotary kilns in Japan. Proceedings of UN ITECR 2003 Congress, Osaka, Japan: P27～30
[22] 小田康义．Preventive methods for hydration of calcia and dolomite clinkers．耐火物，1989，41(1)：P21～26
[23] 王诚训．ZrO_2复合耐火材料．冶金工业出版社，1997
[24] 李君，杨彬，王金相等．MgO-ZrO_2材料的烧结、显微结构和性能．耐火材料，1996，No．2：P69～71
[25] 胡延恕，李振，崔淑贤等．氧化锆对碱性耐火材料使用性能的影响．耐火材料，1995，No．3：P149～153
[26] 涂军波，张文杰，汪厚植等．烧结合成镁锆熟料的研究．耐火材料，1999，33(3)：P144～146
[27] 朱伯铨，李楠，甘菲芳等．电熔镁锆合成料的组成对显微结构和性能的影响．耐火材料，1999，No．6：P310～312
[28] 朱伯铨，李楠，甘菲芳等．电熔镁锆合成料抗渣性研究．耐火材料，2000，No．3：P130～132
[29] 朱伯铨，李楠，甘菲芳等．SiO_2对镁锆合成料抗渣性的影响．武汉科技大学学报，2000，Vol．23，No．2：P26～28
[30] 朱伯铨，李楠，甘菲芳等．电熔镁锆合成料中SiO_2的赋存状态及分布特征．武汉科技大学学报，2000，Vol．23，No．1：P139～141
[31] 李君．MgO-ZrO_2复合材料组成、结构及性能关系的研究．洛阳耐火材料研究院硕士论文，1994
[32] 大坪正和等．MgO-ZrO_2质原料的特征．耐火物，1992，44(7)：P427～428
[33] 笠井清人等．Slag penetration mechanism of magnesia zirconia castable refractories．耐火物，1993，45(8)：P491～492．
[34] 八百井英雄等Development of magnesia ziron castable for steel ladle slag line．耐 火物，1993，45(9)：P521～522
[35] 花桐诚思．耐火物．1991，(6)：P284～292
[36] 许珂敬，许煜汾．表面活性剂在制备ZrO_2微粉的作用．材料研究学报，1999，Vol．13，No．4：P434～436
[37] 杨广慧，张彦．纳米氧化锆的制备及应用[J]．化工新材料，1999，27(5)：P21
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