粉煤灰质磷酸盐泡沫陶瓷制备工艺研究
摘要
粉煤灰是火力发电厂排放的工业固体废弃物。目前，世界上每年排灰约15亿吨。如果得不到及时有效地处理和利用，将会占用大量土地与良田，严重污染环境，影响气候，破坏生态。所以粉煤灰的综合利用已经成为世界各国共同关注的问题。
本文综合考虑了诸如粉煤灰烧结砖、粉煤灰加气混凝土、粉煤灰泡沫玻璃这些传统的粉煤灰利用技术，取其所长，弃其所短，开发了一种粉煤灰综合利用的新技术——粉煤灰质磷酸盐泡沫陶瓷。
粉煤灰质磷酸盐泡沫陶瓷的研究经历了两个过程：第一步，研究了粉煤灰质磷酸盐陶瓷的制备技术。考察了磷酸用量、助熔剂用量、烧结工艺(包括烧结温度、保温时间、升温速度及降温速度)等因素对材料性能的影响，并系统地考察了这些因素的相互关联性，获得了制各本体材料的优化方案。第二步，在本体材料的基础上通过添加适当种类和数量的发泡剂，对材料进行泡沫化处理，通过多因素的关联性试验，获得了制备泡沫材料的优化方案。最后，对材料的力学性能(抗折强度、抗压强度)、物理性能(密度、吸水率、收缩率、导热系数)、微观结构进行了综合分析。
研究结果表明：当采用磷酸5％(体积百分比)，废砂7％，助熔剂(A)2％，烧结温度1050℃，保温1h的工艺方案可以制备出性能较优的磷酸盐泡沫陶瓷，其性能为：密度0.902g／cm~3，抗折强度2.1Mpa，抗压强度9.875Mpa，导热系数0.05W／m．K。
用粉煤灰制备磷酸盐泡沫陶瓷不仅为粉煤灰的综合利用开辟了一条新的技术路线，而且所制备的磷酸盐泡沫陶瓷可以广泛应用于冶金、化工、节能、建筑等领域，具有较好的经济效益和社会效益。
Coal Ash is one kind of industry solid waste sent off by power plants. Presently about 1. 5 trillion tons of Coal Ash is disposed annually in the world. If it isn' t processed timely and effectively, it will occupy large amount of land and infield, heavily pollute the environment, have a great influence on the climates and damage the balance of ecosystem. So large-scale reclamation of fly ash has been the focus of the world.
On the basis of such traditional technology about utilization of fly ash as sinter brick, concrete full of bubble and porous glass etc, by drawing their good qualities and abandoning their weakness, one kind of new technology about fly ash reclamation named foam ceramics of phosphate made from coal ash, was developed.
This study was developed through two steps: First, to develop the solid ceramics of phosphate. Such factors as the amount of phosphoric acid and meltable additives and the agglomeration crafts including the highest temperature, the time of heat preservation at the temperature, and the velocity of temperature rising and falling were individually researched. Moreover, the relationship of them was systematically studied. Thus, the optimal craft was gained. Secondly, to develop the foam ceramics of phosphate by appending appropriate kind and amount of foaming agent on the basis of the solid one. By orthonormal experiment the best craft of foam ceramics was gained. Finally, the material was analysed in the view of mechanical property including bending and tension strength, physical property including density, water assimilating percentage, shrinkage percentage and thermal conductivity and microstructure.
It was shown that the best parameters was phosphoric acid 5%(volume amount), waste sand 7%, Meltable additive (A) 2%, the temperature 1050*C and the time of preservation Ih. The properties of the final material was the density:0. 902g/cm3, bending-strength:2. IMpa, tension-strength:9. 875Mpa, thermal conductivity 0. 05W/m k.
To prepare the foaming ceramics of phosphate made from the coal ash, not only open up a new technological road of fly ash utilizing, but also
the product could be widely used in the field of metallic, chemical engineering , energy saving engineering and building etc. So it can bring better economic and social benefits.
本文综合考虑了诸如粉煤灰烧结砖、粉煤灰加气混凝土、粉煤灰泡沫玻璃这些传统的粉煤灰利用技术，取其所长，弃其所短，开发了一种粉煤灰综合利用的新技术——粉煤灰质磷酸盐泡沫陶瓷。
粉煤灰质磷酸盐泡沫陶瓷的研究经历了两个过程：第一步，研究了粉煤灰质磷酸盐陶瓷的制备技术。考察了磷酸用量、助熔剂用量、烧结工艺(包括烧结温度、保温时间、升温速度及降温速度)等因素对材料性能的影响，并系统地考察了这些因素的相互关联性，获得了制各本体材料的优化方案。第二步，在本体材料的基础上通过添加适当种类和数量的发泡剂，对材料进行泡沫化处理，通过多因素的关联性试验，获得了制备泡沫材料的优化方案。最后，对材料的力学性能(抗折强度、抗压强度)、物理性能(密度、吸水率、收缩率、导热系数)、微观结构进行了综合分析。
研究结果表明：当采用磷酸5％(体积百分比)，废砂7％，助熔剂(A)2％，烧结温度1050℃，保温1h的工艺方案可以制备出性能较优的磷酸盐泡沫陶瓷，其性能为：密度0.902g／cm~3，抗折强度2.1Mpa，抗压强度9.875Mpa，导热系数0.05W／m．K。
用粉煤灰制备磷酸盐泡沫陶瓷不仅为粉煤灰的综合利用开辟了一条新的技术路线，而且所制备的磷酸盐泡沫陶瓷可以广泛应用于冶金、化工、节能、建筑等领域，具有较好的经济效益和社会效益。
Coal Ash is one kind of industry solid waste sent off by power plants. Presently about 1. 5 trillion tons of Coal Ash is disposed annually in the world. If it isn' t processed timely and effectively, it will occupy large amount of land and infield, heavily pollute the environment, have a great influence on the climates and damage the balance of ecosystem. So large-scale reclamation of fly ash has been the focus of the world.
On the basis of such traditional technology about utilization of fly ash as sinter brick, concrete full of bubble and porous glass etc, by drawing their good qualities and abandoning their weakness, one kind of new technology about fly ash reclamation named foam ceramics of phosphate made from coal ash, was developed.
This study was developed through two steps: First, to develop the solid ceramics of phosphate. Such factors as the amount of phosphoric acid and meltable additives and the agglomeration crafts including the highest temperature, the time of heat preservation at the temperature, and the velocity of temperature rising and falling were individually researched. Moreover, the relationship of them was systematically studied. Thus, the optimal craft was gained. Secondly, to develop the foam ceramics of phosphate by appending appropriate kind and amount of foaming agent on the basis of the solid one. By orthonormal experiment the best craft of foam ceramics was gained. Finally, the material was analysed in the view of mechanical property including bending and tension strength, physical property including density, water assimilating percentage, shrinkage percentage and thermal conductivity and microstructure.
It was shown that the best parameters was phosphoric acid 5%(volume amount), waste sand 7%, Meltable additive (A) 2%, the temperature 1050*C and the time of preservation Ih. The properties of the final material was the density:0. 902g/cm3, bending-strength:2. IMpa, tension-strength:9. 875Mpa, thermal conductivity 0. 05W/m k.
To prepare the foaming ceramics of phosphate made from the coal ash, not only open up a new technological road of fly ash utilizing, but also
the product could be widely used in the field of metallic, chemical engineering , energy saving engineering and building etc. So it can bring better economic and social benefits.
引文
[1]李庆繁，李光复．高掺量粉煤灰烧结砖有关技术的商榷[J]．新型建筑材料，2002，(10)：57-60
[2]韩怀强，蒋挺大．粉煤灰利用技术[M]．北京：化学工业出版社，2001
[3]王福元，吴正严．粉煤灰利用手册[M]．北京：中国电力出版社，1997
[4]钱觉时．粉煤灰特性与粉煤灰混凝土[M]．北京：科学出版社，2002
[5]J.C. Qian, E. E. Lachowski and F. P. Glasser. Microstructure and chemical variation in class F fly ash glass[J]. In: Materials Research Society Symposia Proceedings, 1988, 113(10): 45-54
[6]王将军，孙立军．高钙粉煤灰的界定[J]，粉煤灰综合利用．2002，(05)：27-29
[7]L. Barbieri. T. Manfredini, Y. Queralt, M. Romero, and J. Ma. Rincon, Vitrific ation of Fly Ash from Thermal Power Stations. Glass Technol, 1997, 38(5): 65-170
[8]煤炭科学研究总院等．煤质分析应用技术指南[M]．北京：中国标准出版社，1991
[9]程光甫，宋存义．粉煤灰性能的基本分析[J]．粉煤灰综合利用，1992，(01)：27-30
[10]李国栋．结构因素对活性激发的影响[J]．粉煤灰综合利用，1998，(03)：3-5
[11]吴任宇．粉煤灰的危害及综合利用[J]．江西石油化工，1996，(01)：54-56
[12]华振明．固体废物的处理与处置[M]．北京：高等教育出版社，1998
[13]吕庆荣，王广才，吴家白等．化工部自备电厂粉煤灰综合利用技术考察报告[J]．化工设备与防腐蚀，1998，(01)：25-30
[14]E.E. Berry and E.J. Anthony. Properties and environmental considera tions related to AFBC solid results[J]. in. Materials Research Society Symposia Proceedings, 1987, 86(9)49-58
[15]袁荣和．粉煤灰及其在建筑业的开发利用[J]．安庆石化，1991，(02)：13
[16]沈旦申，昌镇恶．粉煤灰优质混凝土[M]．上海：上海科学出版社，1992
[17]炳林，百敏．治理三废与保护环境[M]．北京：科学出版社，1982
[18]刘守庆，张召述，董占能．用蒸压法制备新型粉煤灰水泥的研究[J]．再生资源研究，2003，(03)：19-22
[19]吴正直．粉煤灰房建材料的开发与应用[M]．北京：中国建材工业出版社，2003
[20]邵靖邦．国外免烧粉煤灰陶粒生产技术[J]．粉煤灰综合利用，1996，(04)：52
[21]I. Queralt, X. Querol, A. Lopez-Soler, and F. Plana. Use of Coal Fly Ash for Ceramics: a Case Study from a Spanish Large Power Station[J]. Fuel, 1997, 76(8): 787-91
[22]张永林．磷酸盐浇注料在工业炉上的合理应用[J]．工业炉，2000，22(04)：27-30
[23]邹伟斌，李实，肖生展．提高磷酸盐耐火材料工作寿命的技术途径[J]．中国建材装备，1997，(02)：40-42
[24]华南工学院，南京化工学院，武汉建筑材料工业学院．陶瓷工艺学[M]．北京：中国建筑工业出版社，1981
[25]Xinwen Zhu, Dongliang Jiang, Shouhong Tan, and Zhaoquan Zhang. Imp rovement in the Strut Thickness of Reticulated Porous Ceramics[J].J. Am. Ceram. Soc, 2001, 84(7): 1654-56
[26]J. Ma. Rincon. Glasses and Glass-Ceramics for Nuclear Waste Management, 2nded. Centro de Investigaciones Energeticas Medioambientales Tecnologicas SEVC, Spain. 1995,25(7): 307-14
[27]吴庆祝，刘永先，李福工等．泡沫陶瓷及其应用[J]．陶瓷，2002，(02)：12-15
[28]J. Saggio-Woyaansky and C.E. Scottetal. Processing of Porous Cerami cs[J]. Am. Ceram. Soc. Bull, 1992, 71(11): 1674-82
[29]W. Brockmeyer, L. S. Aubrey, and J.E. Dore. Ceramic Materials[J].U.S. Pat. No. 4004 933, Jan. 25,1977
[30]韩行禄．不定形耐火材料[M]．北京：冶金工业出版社，2001
[31]陈嘉甫，谭光薰．磷酸盐的生产与应用[M]．成都：成都科技大学出版社，1989
[32]张召述，周新涛，宋红敏．用铸造废砂制备磷酸盐泡沫陶瓷的研究[J]．铸造，2003，52(08)：564-567
[33]张俊．磷精细化学品生产工艺[M]．昆明：云南科技出版社，1998
[34]胡彭生．型砂(第二版)[M]．上海：上海科学技术出版社，1994
[35]曲远方．无机非金属材料专业实验[M]．天津：天津大学出版社，2003
[36]殷念祖．烧结砖瓦工艺[M]．北京：中国建筑工业出版社，1983
[37]王培铭．无机非金属材料学[M]．上海：同济大学出版社，1998
[38]F. E. G. Ravault. Production of Porous Ceramic Materials[J]. U. S. Pat. No. 4004 933, Jan, 25,1977
[39]Chandra S. Ray. Comment on "Influence of Fe~(3+)/Fe~(2+) Ratio on the Crystallization of Iron-Rich Glasses Made With Industrial Wastes" [J]. J. Am. Ceram. Soc. 2001. 84(11): 2740-41
[40]C. S. Ray. X. Fang, M. Karabulut, G. K. Marasinghe, and D. E. Day, "Effect of Melting Temperature and Time on Iron Valance and Crystallizatio-of Iron Phosphate Glass" J. Non-Cryst. Solids, 1999 249: 1-16
[41]周新涛，张召述，陈贤智．玻璃基废弃物复合材料泡沫化工艺研究[J]．新型建筑材料，2003，(08)：46-49
[42]F. Y. Wang, Ceramic Fabrication Processes, Academic Press, 1976, 32(5): 24-30
[43]W. E. Worrall, Clays and Ceramic Raw Materials, Apllied Science Publishers, LTD, 1975, 17(02): 80-84
[44]B. Jaffe, W. R. Cook Jr and H. Jaffe, Piezoeleemric Ceramics, Academic Press, 1971 42(2): 101-105
[45]H 舒尔兹编，黄照柏译．陶瓷物理及化学原理[M]．北京：建筑工业出版社，1975
[46]M. D. Bakker and J. G. Laguros. Reaction products in fly ash concretes.In: Materials Research Society Symposia Proceedings, 1985, 43(11): 73-83
[47]R. A. Kruger. Fly ash beneticiation-creating new opportunities in market place. In: International Ash Utilization Symposium, 1995, 21.(10): 15-23
[48]祁景玉．X射线结构分析[M]．上海：同济大学出版社，2003
[2]韩怀强，蒋挺大．粉煤灰利用技术[M]．北京：化学工业出版社，2001
[3]王福元，吴正严．粉煤灰利用手册[M]．北京：中国电力出版社，1997
[4]钱觉时．粉煤灰特性与粉煤灰混凝土[M]．北京：科学出版社，2002
[5]J.C. Qian, E. E. Lachowski and F. P. Glasser. Microstructure and chemical variation in class F fly ash glass[J]. In: Materials Research Society Symposia Proceedings, 1988, 113(10): 45-54
[6]王将军，孙立军．高钙粉煤灰的界定[J]，粉煤灰综合利用．2002，(05)：27-29
[7]L. Barbieri. T. Manfredini, Y. Queralt, M. Romero, and J. Ma. Rincon, Vitrific ation of Fly Ash from Thermal Power Stations. Glass Technol, 1997, 38(5): 65-170
[8]煤炭科学研究总院等．煤质分析应用技术指南[M]．北京：中国标准出版社，1991
[9]程光甫，宋存义．粉煤灰性能的基本分析[J]．粉煤灰综合利用，1992，(01)：27-30
[10]李国栋．结构因素对活性激发的影响[J]．粉煤灰综合利用，1998，(03)：3-5
[11]吴任宇．粉煤灰的危害及综合利用[J]．江西石油化工，1996，(01)：54-56
[12]华振明．固体废物的处理与处置[M]．北京：高等教育出版社，1998
[13]吕庆荣，王广才，吴家白等．化工部自备电厂粉煤灰综合利用技术考察报告[J]．化工设备与防腐蚀，1998，(01)：25-30
[14]E.E. Berry and E.J. Anthony. Properties and environmental considera tions related to AFBC solid results[J]. in. Materials Research Society Symposia Proceedings, 1987, 86(9)49-58
[15]袁荣和．粉煤灰及其在建筑业的开发利用[J]．安庆石化，1991，(02)：13
[16]沈旦申，昌镇恶．粉煤灰优质混凝土[M]．上海：上海科学出版社，1992
[17]炳林，百敏．治理三废与保护环境[M]．北京：科学出版社，1982
[18]刘守庆，张召述，董占能．用蒸压法制备新型粉煤灰水泥的研究[J]．再生资源研究，2003，(03)：19-22
[19]吴正直．粉煤灰房建材料的开发与应用[M]．北京：中国建材工业出版社，2003
[20]邵靖邦．国外免烧粉煤灰陶粒生产技术[J]．粉煤灰综合利用，1996，(04)：52
[21]I. Queralt, X. Querol, A. Lopez-Soler, and F. Plana. Use of Coal Fly Ash for Ceramics: a Case Study from a Spanish Large Power Station[J]. Fuel, 1997, 76(8): 787-91
[22]张永林．磷酸盐浇注料在工业炉上的合理应用[J]．工业炉，2000，22(04)：27-30
[23]邹伟斌，李实，肖生展．提高磷酸盐耐火材料工作寿命的技术途径[J]．中国建材装备，1997，(02)：40-42
[24]华南工学院，南京化工学院，武汉建筑材料工业学院．陶瓷工艺学[M]．北京：中国建筑工业出版社，1981
[25]Xinwen Zhu, Dongliang Jiang, Shouhong Tan, and Zhaoquan Zhang. Imp rovement in the Strut Thickness of Reticulated Porous Ceramics[J].J. Am. Ceram. Soc, 2001, 84(7): 1654-56
[26]J. Ma. Rincon. Glasses and Glass-Ceramics for Nuclear Waste Management, 2nded. Centro de Investigaciones Energeticas Medioambientales Tecnologicas SEVC, Spain. 1995,25(7): 307-14
[27]吴庆祝，刘永先，李福工等．泡沫陶瓷及其应用[J]．陶瓷，2002，(02)：12-15
[28]J. Saggio-Woyaansky and C.E. Scottetal. Processing of Porous Cerami cs[J]. Am. Ceram. Soc. Bull, 1992, 71(11): 1674-82
[29]W. Brockmeyer, L. S. Aubrey, and J.E. Dore. Ceramic Materials[J].U.S. Pat. No. 4004 933, Jan. 25,1977
[30]韩行禄．不定形耐火材料[M]．北京：冶金工业出版社，2001
[31]陈嘉甫，谭光薰．磷酸盐的生产与应用[M]．成都：成都科技大学出版社，1989
[32]张召述，周新涛，宋红敏．用铸造废砂制备磷酸盐泡沫陶瓷的研究[J]．铸造，2003，52(08)：564-567
[33]张俊．磷精细化学品生产工艺[M]．昆明：云南科技出版社，1998
[34]胡彭生．型砂(第二版)[M]．上海：上海科学技术出版社，1994
[35]曲远方．无机非金属材料专业实验[M]．天津：天津大学出版社，2003
[36]殷念祖．烧结砖瓦工艺[M]．北京：中国建筑工业出版社，1983
[37]王培铭．无机非金属材料学[M]．上海：同济大学出版社，1998
[38]F. E. G. Ravault. Production of Porous Ceramic Materials[J]. U. S. Pat. No. 4004 933, Jan, 25,1977
[39]Chandra S. Ray. Comment on "Influence of Fe~(3+)/Fe~(2+) Ratio on the Crystallization of Iron-Rich Glasses Made With Industrial Wastes" [J]. J. Am. Ceram. Soc. 2001. 84(11): 2740-41
[40]C. S. Ray. X. Fang, M. Karabulut, G. K. Marasinghe, and D. E. Day, "Effect of Melting Temperature and Time on Iron Valance and Crystallizatio-of Iron Phosphate Glass" J. Non-Cryst. Solids, 1999 249: 1-16
[41]周新涛，张召述，陈贤智．玻璃基废弃物复合材料泡沫化工艺研究[J]．新型建筑材料，2003，(08)：46-49
[42]F. Y. Wang, Ceramic Fabrication Processes, Academic Press, 1976, 32(5): 24-30
[43]W. E. Worrall, Clays and Ceramic Raw Materials, Apllied Science Publishers, LTD, 1975, 17(02): 80-84
[44]B. Jaffe, W. R. Cook Jr and H. Jaffe, Piezoeleemric Ceramics, Academic Press, 1971 42(2): 101-105
[45]H 舒尔兹编，黄照柏译．陶瓷物理及化学原理[M]．北京：建筑工业出版社，1975
[46]M. D. Bakker and J. G. Laguros. Reaction products in fly ash concretes.In: Materials Research Society Symposia Proceedings, 1985, 43(11): 73-83
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