磷石膏玻璃态胶凝材料及制品的研究
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摘要
磷石膏是化工厂用磷灰石与硫酸作用湿法生产磷酸时的副产品，磷石膏有许多可以加以肯定的重要性质，其两个主要优点为二水化合物含量高(常达90％)和材料的细度细，可以省去天然石膏用来破碎和磨细的费用。但是磷石膏中存在着杂质，这些杂质包括磷酸、各种磷酸盐、氟化物、有机成分、铝的化合物和可溶性盐，这些物质影响磷石膏制品的强度和凝结性能，也给磷石膏的利用带来了困难。
本论文根据材料化学原理，采用生石灰作碱性激发剂，一方面可以中和磷石膏中的酸性物质，同时它又是矿渣的强力激发剂，而选用的早强剂则使其能够与上述物料体系中的成分反应生成早强型水化产物钙矾石。
本论文通过实验确定了磷石膏玻璃态胶凝材料的组成体系和最佳配合比，探讨了影响胶凝材料性能的主要工艺参数，借助XRD、SEM和热导式量热仪等现代测试手段对磷石膏玻璃态胶凝材料的水化动力学；水化产物；硬化机理和硬化体的微观结构进行了分析。并对胶凝材料的应用进行了实验室试验。
本研究由于不需要对磷石膏进行水洗、煅烧等预处理，在复合激发剂作用下可直接与矿渣、砂等作用，生产出28天抗压强度大于30MPa环保型胶凝材料和各种不同的建筑制品，不仅节能，而且不产生二次污染。其成果具有重要的应用价值和社会效益。
论文通过对磷石膏玻璃态胶凝材料的LCA评价，可以判定该材料具有良好的环境协调性。
Phosphogypsum is the by-product of the production of phosphoric acid by wet process with apatite and sulphuric acid. Phosphogypsum has many excellent properties, the most distinguished two merits are the high content of dihydrate(commonly 90%) and the good fineness, it can save the cost of crushing and grinding. However, there are many impurities in phosphogypsum which includes the phosphoric acid, various kinds of phosphates, fluorides, organic ingredients, aluminous compounds and soluble salts. All these foreign matters bring influence to the strength and setting property of the phosphogypsum product, and also bring difficulty to the application of it.
Based on the principles of material chemistry, this paper uses the lime hydrate as the alkali activator. It can not only neutralize acids in phosphogypsum but also work as the powerful activator to the slag. And the chosen accelerator enable it to react with the components in above material system to generate accelerated hydration product--ettringite.
In this paper, the components system and optimum mix proportion of phosphogypsum cementing material are designed by experiments. The main technological factors influencing the properties of the cementing material are explored. With advanced testing methods of XRD, SEM, thermoelectric conduction calorimeter,etc, the hydration kinetics and hydration products, the hardening mechanism and the microstructure of hardened pastes are analyzed. The application of cementitious materials is carried out in laboratory.
The study in this paper doesn't require such pretreatments as water scrubing and burning of phosphogypsum. And under the action of compound activators, it can react directly with slag and sand to produce environment-protecting cementing material with 28d compressive strength above 30Mpa and various kinds of construction products. It is energy saving and it won't bring the secondary pollution. The result has great value of application and social benefits.
According to the LCA evaluation of the glass-phosphogypsum cementing material, it can be determined that this material has excellent property in environment conditioning.
本论文根据材料化学原理，采用生石灰作碱性激发剂，一方面可以中和磷石膏中的酸性物质，同时它又是矿渣的强力激发剂，而选用的早强剂则使其能够与上述物料体系中的成分反应生成早强型水化产物钙矾石。
本论文通过实验确定了磷石膏玻璃态胶凝材料的组成体系和最佳配合比，探讨了影响胶凝材料性能的主要工艺参数，借助XRD、SEM和热导式量热仪等现代测试手段对磷石膏玻璃态胶凝材料的水化动力学；水化产物；硬化机理和硬化体的微观结构进行了分析。并对胶凝材料的应用进行了实验室试验。
本研究由于不需要对磷石膏进行水洗、煅烧等预处理，在复合激发剂作用下可直接与矿渣、砂等作用，生产出28天抗压强度大于30MPa环保型胶凝材料和各种不同的建筑制品，不仅节能，而且不产生二次污染。其成果具有重要的应用价值和社会效益。
论文通过对磷石膏玻璃态胶凝材料的LCA评价，可以判定该材料具有良好的环境协调性。
Phosphogypsum is the by-product of the production of phosphoric acid by wet process with apatite and sulphuric acid. Phosphogypsum has many excellent properties, the most distinguished two merits are the high content of dihydrate(commonly 90%) and the good fineness, it can save the cost of crushing and grinding. However, there are many impurities in phosphogypsum which includes the phosphoric acid, various kinds of phosphates, fluorides, organic ingredients, aluminous compounds and soluble salts. All these foreign matters bring influence to the strength and setting property of the phosphogypsum product, and also bring difficulty to the application of it.
Based on the principles of material chemistry, this paper uses the lime hydrate as the alkali activator. It can not only neutralize acids in phosphogypsum but also work as the powerful activator to the slag. And the chosen accelerator enable it to react with the components in above material system to generate accelerated hydration product--ettringite.
In this paper, the components system and optimum mix proportion of phosphogypsum cementing material are designed by experiments. The main technological factors influencing the properties of the cementing material are explored. With advanced testing methods of XRD, SEM, thermoelectric conduction calorimeter,etc, the hydration kinetics and hydration products, the hardening mechanism and the microstructure of hardened pastes are analyzed. The application of cementitious materials is carried out in laboratory.
The study in this paper doesn't require such pretreatments as water scrubing and burning of phosphogypsum. And under the action of compound activators, it can react directly with slag and sand to produce environment-protecting cementing material with 28d compressive strength above 30Mpa and various kinds of construction products. It is energy saving and it won't bring the secondary pollution. The result has great value of application and social benefits.
According to the LCA evaluation of the glass-phosphogypsum cementing material, it can be determined that this material has excellent property in environment conditioning.
引文
[1] Lutz R. Preparation of Phosphate Acid Gypsum for Further Processing to Make Building Materials. Zement-Kalk-Gips. 1995(2): 98-102
[2] Soroka I. Effect of phosphogypsum on Properties of Portland cement. American Ceramic Bulletin. 1982,63(12): 1502-1505
[3] Lmez H, Erdem E. The Effects of PG on Setting and Mechanical Properties of Cement. Cement and Concrete Research. 1989,19:378-384
[4] Tabikh A, Miller F M. The Nature of Phosphogypsum Impurities and Their Influence on Cement Hydration. Cement and Concrete Research. 1971,1:663-667
[5] Mehta P k, James R. Utilization of Phosphogypsum in Portland Cement Industry. Cement and Concrete Research. 1977,7:537-544
[6] 彭家惠，等．磷石膏颗粒级配、结构与性能研究．武汉理工大学学报，2001，23(1)：6-11
[7] 魏超平．磷石膏综合利用现状调查与探讨．新型建筑材料．1994(2)：30-33
[8] 徐翠云．磷石膏的开发利用现状．矿产保护与利用，2000，2：53-54
[9] 席美云．磷石膏的综合利用．环境科学与技术，2001，95(3)：10-13
[10] 郑小莲．从云南省磷硫资源状况看磷石膏的综合利用．昆明理工大学学报，2000，25 (4)：32-36
[11] 林芳辉，彭家惠，季建新．以粉煤灰为改性组份的石膏粉煤灰胶凝材料研究．粉煤灰综合利用，1997，3：27-32
[12] 周一鹏．二水石膏矿渣制品．建工材料，1981，5：4-8
[13] 张东翔，黄晓军，王刚．稻草纤维磷石膏板的工艺研究．新型建筑材料，2001，2：6-8
[14] 潘恒．磷石膏制砖工艺探讨．贵州化工，2000，25(4)：48-51 [15] 彭志辉，等．二水磷石膏粉煤灰复合胶凝材料研究．粉煤灰综合利用，2001，1：3-6
[16] 陈德玉，谭克锋，刘广儒．磷石膏矿渣胶凝材料性能的研究．西南工学院学报，1998，13(2)：5-9
[17] 李东国．磷石膏开发利用的前景和途径．节能，1998，8：45-46
[18] 康志国．磷石膏的综合利用．河北化工，1997，2：57-58
[19] 卢忠远．利用磷石膏生产陶瓷装饰材料．重庆环境科学，1997，19(3)：48-49
[20] 苑金生．磷石膏在建材工业中的应用．广东建材，1993，2；39-40
[21] 青发纯，吕萍．蒸压磷石膏砖的研制．新型建筑材料，1992，11：22-24
[22] 林芳辉，彭家惠，雷伟．脱硫石膏粉煤灰胶凝材料的研究．新型建筑材料，1994，3：1821
[23] 唐修仁，包文星．用磷石膏生产α-半水石膏的研究．新型建筑材料，1994，4：11-14
[24] 沈礼善．磷石膏制白水泥．现代化工，1994，8：44
[25] 杨林，等．磷石膏生产水泥的工艺特点及发展动态．水泥技术，1997(5)：21-23
[26] 张丕兴．以粉煤灰和磷石膏为原料低温烧制贝里特硫铝酸盐水泥，山西建材，1998(4)：27-28
[27] 刘心中，等．磷石膏、粉煤灰胶凝材料的研究．化工矿物与加工，2001(7)：12-14
[28] 周玉昆．磷石膏综合利用新技术．化工环保，1994，14：78-81
[29] 马隆．用粒化高炉矿渣对磷石膏进行改性．水泥，2000(10)：52
[30] 张丕兴．磷石膏低碱水泥及其水化特性，硅酸盐通报，1996(2)：19-24
[31] Mehta P K, Brady J R. Utilization of phosphogypsum in Portland cement industry. Cem Coner Res, 1997. 7:537-544
[32] Olmez H, Yilmaz V T. Infrared study on the erfinement of phosphogypusum for cements. Cem Coner Res, 1998, 18:449-454
[33] 姚永发，等．磷酸磷铵重钙技术与设计手册．北京：化学工业出版杜，1997
[34] 袁润章．胶凝材料学．武汉：武汉工业大学出版社，1998
[35] 向才旺．建筑石膏及其制品．北京：中国建材工业出版社，1998
[36] 刘朝荣．工业技术应用数理统计方法．武汉：湖北科学技术出版社，1985
[37] 王天民．生态环境材料．天津：天津大学出版社，2000．12
[38] Frederico Neto "Market based mechanisms for controlling global emissions of greenhouse gases" Natural Resources Forum Vol 19,No.3,1995
[39] 山本良一“环境材料—迈向21世纪的新材料研究”工业材料，104期，95年8月
[40] 刘江龙等“论环境(协调)材料”环境科学进展，Vol．4，No．1，1996
[41] 山本良一．“材料之环境负担性的评价”，工业材料，104期，95年8月
[42] Terrie K.Boguski etc "LCA Methodology" Environmental Life circle assessment:Copyright 1996 by The McGraw—Hill Companies, Inc.
(43) Jurgen Giegrich "Valuation as a step in impact assessment: Methods and case study" Environmental Life circle assessment: Copyright 1996 by The McGraw-Hill Companies, Inc.
(44) 甘应爱等，《运筹学》清华大学出版社 1990年
(45) Agis Veroutis and Vital Aelion "Design for environment: An implementation framework": Total Quality Environmental management volume 5． no 4 Summer 1996
(46) Keith A.weitz "Developing a decision support tool for Life circle cost assessment" Total Quality Environmental management volume 4． no 1 Summer 1994
(47) Gregory A.Keoleian ,Ph.D "Life circle design" Environmental Life circle assessment: Copyright 1996 by The McGraw-Hill Companies, Inc.
(48) Michael Lenox and John R.Ehrenfeld, "Design for environment: A new framework for strategic decisions" Total Quality Environmental management volume 4． no 4 Summer 1995
(49) 杨南如，无机非金属材料测试方法，武汉：武汉工业大学出版社, 1990． 8
(50) 陈福广，等，新型墙体材料手册，北京：中国建材工业出版社, 2000． 1
[2] Soroka I. Effect of phosphogypsum on Properties of Portland cement. American Ceramic Bulletin. 1982,63(12): 1502-1505
[3] Lmez H, Erdem E. The Effects of PG on Setting and Mechanical Properties of Cement. Cement and Concrete Research. 1989,19:378-384
[4] Tabikh A, Miller F M. The Nature of Phosphogypsum Impurities and Their Influence on Cement Hydration. Cement and Concrete Research. 1971,1:663-667
[5] Mehta P k, James R. Utilization of Phosphogypsum in Portland Cement Industry. Cement and Concrete Research. 1977,7:537-544
[6] 彭家惠，等．磷石膏颗粒级配、结构与性能研究．武汉理工大学学报，2001，23(1)：6-11
[7] 魏超平．磷石膏综合利用现状调查与探讨．新型建筑材料．1994(2)：30-33
[8] 徐翠云．磷石膏的开发利用现状．矿产保护与利用，2000，2：53-54
[9] 席美云．磷石膏的综合利用．环境科学与技术，2001，95(3)：10-13
[10] 郑小莲．从云南省磷硫资源状况看磷石膏的综合利用．昆明理工大学学报，2000，25 (4)：32-36
[11] 林芳辉，彭家惠，季建新．以粉煤灰为改性组份的石膏粉煤灰胶凝材料研究．粉煤灰综合利用，1997，3：27-32
[12] 周一鹏．二水石膏矿渣制品．建工材料，1981，5：4-8
[13] 张东翔，黄晓军，王刚．稻草纤维磷石膏板的工艺研究．新型建筑材料，2001，2：6-8
[14] 潘恒．磷石膏制砖工艺探讨．贵州化工，2000，25(4)：48-51 [15] 彭志辉，等．二水磷石膏粉煤灰复合胶凝材料研究．粉煤灰综合利用，2001，1：3-6
[16] 陈德玉，谭克锋，刘广儒．磷石膏矿渣胶凝材料性能的研究．西南工学院学报，1998，13(2)：5-9
[17] 李东国．磷石膏开发利用的前景和途径．节能，1998，8：45-46
[18] 康志国．磷石膏的综合利用．河北化工，1997，2：57-58
[19] 卢忠远．利用磷石膏生产陶瓷装饰材料．重庆环境科学，1997，19(3)：48-49
[20] 苑金生．磷石膏在建材工业中的应用．广东建材，1993，2；39-40
[21] 青发纯，吕萍．蒸压磷石膏砖的研制．新型建筑材料，1992，11：22-24
[22] 林芳辉，彭家惠，雷伟．脱硫石膏粉煤灰胶凝材料的研究．新型建筑材料，1994，3：1821
[23] 唐修仁，包文星．用磷石膏生产α-半水石膏的研究．新型建筑材料，1994，4：11-14
[24] 沈礼善．磷石膏制白水泥．现代化工，1994，8：44
[25] 杨林，等．磷石膏生产水泥的工艺特点及发展动态．水泥技术，1997(5)：21-23
[26] 张丕兴．以粉煤灰和磷石膏为原料低温烧制贝里特硫铝酸盐水泥，山西建材，1998(4)：27-28
[27] 刘心中，等．磷石膏、粉煤灰胶凝材料的研究．化工矿物与加工，2001(7)：12-14
[28] 周玉昆．磷石膏综合利用新技术．化工环保，1994，14：78-81
[29] 马隆．用粒化高炉矿渣对磷石膏进行改性．水泥，2000(10)：52
[30] 张丕兴．磷石膏低碱水泥及其水化特性，硅酸盐通报，1996(2)：19-24
[31] Mehta P K, Brady J R. Utilization of phosphogypsum in Portland cement industry. Cem Coner Res, 1997. 7:537-544
[32] Olmez H, Yilmaz V T. Infrared study on the erfinement of phosphogypusum for cements. Cem Coner Res, 1998, 18:449-454
[33] 姚永发，等．磷酸磷铵重钙技术与设计手册．北京：化学工业出版杜，1997
[34] 袁润章．胶凝材料学．武汉：武汉工业大学出版社，1998
[35] 向才旺．建筑石膏及其制品．北京：中国建材工业出版社，1998
[36] 刘朝荣．工业技术应用数理统计方法．武汉：湖北科学技术出版社，1985
[37] 王天民．生态环境材料．天津：天津大学出版社，2000．12
[38] Frederico Neto "Market based mechanisms for controlling global emissions of greenhouse gases" Natural Resources Forum Vol 19,No.3,1995
[39] 山本良一“环境材料—迈向21世纪的新材料研究”工业材料，104期，95年8月
[40] 刘江龙等“论环境(协调)材料”环境科学进展，Vol．4，No．1，1996
[41] 山本良一．“材料之环境负担性的评价”，工业材料，104期，95年8月
[42] Terrie K.Boguski etc "LCA Methodology" Environmental Life circle assessment:Copyright 1996 by The McGraw—Hill Companies, Inc.
(43) Jurgen Giegrich "Valuation as a step in impact assessment: Methods and case study" Environmental Life circle assessment: Copyright 1996 by The McGraw-Hill Companies, Inc.
(44) 甘应爱等，《运筹学》清华大学出版社 1990年
(45) Agis Veroutis and Vital Aelion "Design for environment: An implementation framework": Total Quality Environmental management volume 5． no 4 Summer 1996
(46) Keith A.weitz "Developing a decision support tool for Life circle cost assessment" Total Quality Environmental management volume 4． no 1 Summer 1994
(47) Gregory A.Keoleian ,Ph.D "Life circle design" Environmental Life circle assessment: Copyright 1996 by The McGraw-Hill Companies, Inc.
(48) Michael Lenox and John R.Ehrenfeld, "Design for environment: A new framework for strategic decisions" Total Quality Environmental management volume 4． no 4 Summer 1995
(49) 杨南如，无机非金属材料测试方法，武汉：武汉工业大学出版社, 1990． 8
(50) 陈福广，等，新型墙体材料手册，北京：中国建材工业出版社, 2000． 1