利用二水石膏制备粉刷石膏的研究
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摘要
我国每年排放化学石膏1亿吨以上,绝大多数都堆积弃用,不仅占用了大量的土地,而且污染环境。因此综合利用工业副产石膏对生态环境保护有着十分重要的意义。在目前工业固体废弃物综合利用中,建材行业占90%以上,在建设节约型社会中有其特殊地位,是发展循环经济中的重要一环。利用化学石膏生产石膏建材是资源综合利用的有效途径之一,而且石膏建材同其他水泥建材相比,具有节能、环保、保温隔热的优势,显著提升了建筑物的质量和功能,是一种生态环保建材。
从工业废石膏的资源化利用和建筑节能出发,本文提出两种新的制备粉刷石膏的制备方法,即以二水石膏掺矿渣、水泥、外加剂等制备二水石膏型粉刷石膏,以及二水石膏—无水石膏混合相掺矿渣、水泥、外加剂等制备二水石膏-无水石膏混合相型粉刷石膏。打破了传统二水石膏必须经煅烧脱水成半水石膏或无水石膏才能做粉刷石膏的老思路,开辟了一条二水石膏无需煅烧,直接利用的新途径。系统研究了各种硫铝酸盐水泥、复合促凝剂、保水剂等外加剂以及石膏的预处理等因素对石膏基复合胶凝材料和粉刷石膏性能的影响,并在此基础上探讨石膏、矿渣、水泥等的水化机理。
本文通过实验,获得了一些重要结果,结果表明:
(1)磷石膏因含有游离酸,须经过石灰中和处理。处理后的陈化时间对复合材料的性能也产生较大的影响,陈化时间最好要大于7天。
(2)硫铝酸盐水泥、复合促凝剂掺量对二水磷石膏粉刷料的凝结时间有很大影响,对早期强度影响也较大。随着硫铝酸盐水泥、复合促凝剂掺量的增加,凝结时间逐渐缩短,早期强度和后期强度也得到提升,但是当硫铝酸盐水泥、复合促凝剂掺量过大时,材料的强度又呈现下降趋势。
(3)用磷石膏制备粉刷石膏的配比为,磷石膏:矿渣:水泥(质量百分比)=60:30:10,其他外加剂外掺计量,当硫铝酸盐水泥掺量为10%,石灰掺量为1.5%,复合促凝剂掺量为2.5%,MC掺量为0.1%,PVA掺量为0.5%时,粉刷石膏的性能最优,3d抗折达3.1 MPa,抗压强度达12.7MPa,28d粘结强度为1.0 MPa,抗折强度达到粉刷石膏标准要求,粘结强度、抗压强度远高于标准要求。
(4)用脱硫石膏-氟石膏混合相石膏制备粉刷石膏的最佳配比为脱硫石膏:氟石膏:矿渣:普通硅酸盐水泥(质量百分比)=35:35:20:10,其他添加剂外掺计量,硫铝酸盐水泥掺量为5%,石灰掺量为2%,促凝剂掺量为2%,MC掺量为0.1%,PVA掺量为0.3%时粉刷石膏的性能最优。3d抗折强度为3.6 MPa,抗压强度为12.2 MPa,28d粘结强度为1.1 MPa。
Most of China’s emissions of chemical gypsum, estimated higher than 100,000,000 tons annualy, are stacked and abandoned. Thus not only occupies vast land, also pollutes the enviroment seriously. Therefore, comprehensive utilization of industrial by-product gypsum is of great significance for the protection of ecological environment. In the current recycling of the industrial solid waste, the field of building materials accounts for more than 90% , which therefore enjoys a special status to build a conservation-oriented society and develop sustainable economy. Utilization of chemical gypsum to produce gypsum-based building materials has proved to be effective. In addition, compared with cement-based building materials, the gypsum-based building materials are charactrized by energy-saving, enviormentally friendness and good thermal insulation. Due to the considerable improvement of both quality and fuction of buildings by the use of gypsum-based building materials, it is a type of eco-friendly building materials.
For the purpose of utilization of the wasted industrial gypsum and energy reduction, two innovative methods to make wall plaster were put forward in this thesis. Dihydrate gypsum and dihydrate–anhydrite composite, were blended with a certain amount of blast slag,ordinary cement,addtives to make wall plaster,respectively. This is beyond the traditional method of production of wall plaster, which always experiences a process of calcining of dihydrate gypsum to obtain anhydrate or hemihydrate gypsum. Systematic investigation on influence of sulphoaluminate cement,composite setting accelerator,water-retaining agent(etc.) and pretreatment of gypsum on properties of wall plaster were conducted. The hydration mechanism of gypsum,blast slag and cement were also discussed.
Based on the experimental results, some important findings were obtained and showed in the following:
(1) Phosphogypsum must be neutralized with lime prior to use due to the existence of free acid. The slaking time affects the properties of the manufatured composite wall plaster radically and at least seven days of slaking proved to be needed.
(2) The dosage of sulphoaluminate cement and composite setting accelerator influences the setting time and early strength of the wall plaster considerably. The setting time reduces and the strength improves with the increase of the dosage of sulphoaluminate cement and composite setting accelerator. However, the strength decreases if excessive sulphoaluminate cement and composite setting accelerator were added.
(3) When phosphogypsum is involved to make wall plaster,the optimum mix proportion can be expressed as phosphogypsum: slag: ordinary cement (mass percent)= 60:30:10. In addition, 10% sulphoaluminate cement,1.5% lime,2.5% composite setting accelerator, 0.1%methyl cellulose(MC),0.5% polyvinyl alcohol(PVA) were added. The flexural ,compressive strength at the age of 3 days and the bonding strength at the age of 28 days achieved 3.1MPa,12.7MPa,and 1.0MPa,respectively. The flexural strength can meet the technical requirement specified in the gypsum specification. The bonding strength and compressive strength is considerably higher than the indexes required.
(4) When desulfogypsum-fluorogypsum is involved to make wall plaster,the optimum mix proportion can be expressed as desulfogypsum:fluorogypsum slag: ordinary cement(mass percent) = 35:35:20:10. In addition, 5% sulphoaluminate cement,2% lime,2% composite setting accelerator, 0.1% MC, 0.3% PVA were added. The flexural ,compressive strength at the age of 3 days and the bonding strength at the age of 28 days achieved 3.6MPa,12.2MPa,and 1.1MPa,respectively.
从工业废石膏的资源化利用和建筑节能出发,本文提出两种新的制备粉刷石膏的制备方法,即以二水石膏掺矿渣、水泥、外加剂等制备二水石膏型粉刷石膏,以及二水石膏—无水石膏混合相掺矿渣、水泥、外加剂等制备二水石膏-无水石膏混合相型粉刷石膏。打破了传统二水石膏必须经煅烧脱水成半水石膏或无水石膏才能做粉刷石膏的老思路,开辟了一条二水石膏无需煅烧,直接利用的新途径。系统研究了各种硫铝酸盐水泥、复合促凝剂、保水剂等外加剂以及石膏的预处理等因素对石膏基复合胶凝材料和粉刷石膏性能的影响,并在此基础上探讨石膏、矿渣、水泥等的水化机理。
本文通过实验,获得了一些重要结果,结果表明:
(1)磷石膏因含有游离酸,须经过石灰中和处理。处理后的陈化时间对复合材料的性能也产生较大的影响,陈化时间最好要大于7天。
(2)硫铝酸盐水泥、复合促凝剂掺量对二水磷石膏粉刷料的凝结时间有很大影响,对早期强度影响也较大。随着硫铝酸盐水泥、复合促凝剂掺量的增加,凝结时间逐渐缩短,早期强度和后期强度也得到提升,但是当硫铝酸盐水泥、复合促凝剂掺量过大时,材料的强度又呈现下降趋势。
(3)用磷石膏制备粉刷石膏的配比为,磷石膏:矿渣:水泥(质量百分比)=60:30:10,其他外加剂外掺计量,当硫铝酸盐水泥掺量为10%,石灰掺量为1.5%,复合促凝剂掺量为2.5%,MC掺量为0.1%,PVA掺量为0.5%时,粉刷石膏的性能最优,3d抗折达3.1 MPa,抗压强度达12.7MPa,28d粘结强度为1.0 MPa,抗折强度达到粉刷石膏标准要求,粘结强度、抗压强度远高于标准要求。
(4)用脱硫石膏-氟石膏混合相石膏制备粉刷石膏的最佳配比为脱硫石膏:氟石膏:矿渣:普通硅酸盐水泥(质量百分比)=35:35:20:10,其他添加剂外掺计量,硫铝酸盐水泥掺量为5%,石灰掺量为2%,促凝剂掺量为2%,MC掺量为0.1%,PVA掺量为0.3%时粉刷石膏的性能最优。3d抗折强度为3.6 MPa,抗压强度为12.2 MPa,28d粘结强度为1.1 MPa。
Most of China’s emissions of chemical gypsum, estimated higher than 100,000,000 tons annualy, are stacked and abandoned. Thus not only occupies vast land, also pollutes the enviroment seriously. Therefore, comprehensive utilization of industrial by-product gypsum is of great significance for the protection of ecological environment. In the current recycling of the industrial solid waste, the field of building materials accounts for more than 90% , which therefore enjoys a special status to build a conservation-oriented society and develop sustainable economy. Utilization of chemical gypsum to produce gypsum-based building materials has proved to be effective. In addition, compared with cement-based building materials, the gypsum-based building materials are charactrized by energy-saving, enviormentally friendness and good thermal insulation. Due to the considerable improvement of both quality and fuction of buildings by the use of gypsum-based building materials, it is a type of eco-friendly building materials.
For the purpose of utilization of the wasted industrial gypsum and energy reduction, two innovative methods to make wall plaster were put forward in this thesis. Dihydrate gypsum and dihydrate–anhydrite composite, were blended with a certain amount of blast slag,ordinary cement,addtives to make wall plaster,respectively. This is beyond the traditional method of production of wall plaster, which always experiences a process of calcining of dihydrate gypsum to obtain anhydrate or hemihydrate gypsum. Systematic investigation on influence of sulphoaluminate cement,composite setting accelerator,water-retaining agent(etc.) and pretreatment of gypsum on properties of wall plaster were conducted. The hydration mechanism of gypsum,blast slag and cement were also discussed.
Based on the experimental results, some important findings were obtained and showed in the following:
(1) Phosphogypsum must be neutralized with lime prior to use due to the existence of free acid. The slaking time affects the properties of the manufatured composite wall plaster radically and at least seven days of slaking proved to be needed.
(2) The dosage of sulphoaluminate cement and composite setting accelerator influences the setting time and early strength of the wall plaster considerably. The setting time reduces and the strength improves with the increase of the dosage of sulphoaluminate cement and composite setting accelerator. However, the strength decreases if excessive sulphoaluminate cement and composite setting accelerator were added.
(3) When phosphogypsum is involved to make wall plaster,the optimum mix proportion can be expressed as phosphogypsum: slag: ordinary cement (mass percent)= 60:30:10. In addition, 10% sulphoaluminate cement,1.5% lime,2.5% composite setting accelerator, 0.1%methyl cellulose(MC),0.5% polyvinyl alcohol(PVA) were added. The flexural ,compressive strength at the age of 3 days and the bonding strength at the age of 28 days achieved 3.1MPa,12.7MPa,and 1.0MPa,respectively. The flexural strength can meet the technical requirement specified in the gypsum specification. The bonding strength and compressive strength is considerably higher than the indexes required.
(4) When desulfogypsum-fluorogypsum is involved to make wall plaster,the optimum mix proportion can be expressed as desulfogypsum:fluorogypsum slag: ordinary cement(mass percent) = 35:35:20:10. In addition, 5% sulphoaluminate cement,2% lime,2% composite setting accelerator, 0.1% MC, 0.3% PVA were added. The flexural ,compressive strength at the age of 3 days and the bonding strength at the age of 28 days achieved 3.6MPa,12.2MPa,and 1.1MPa,respectively.
引文
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