利用城市垃圾焚烧飞灰煅烧水泥熟料的研究
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摘要
飞灰是城市生活垃圾经高温焚烧后在烟气净化装置中收集到的残余物,富集高毒性的重金属离子和二嗯英类有机污染物,被国家列入危险废弃物名录,规定需进行固化／稳定化后准予安全填埋。但飞灰的安全填埋不仅占用土地,成本高且厂址难寻,而且不能完全排除二次污染的潜在威胁,已成为制约飞灰综合利用的技术瓶颈。因此,寻找适合我国国情的飞灰无害化处置与资源化利用的基础研究与应用技术已成为近年来探索热点之一。
利用水泥回转窑处理危险工业废弃物在工业发达国家已有近30年的历史,它不仅能够利用废弃物生产熟料,而且能彻底销毁有毒有害的危险废弃物,被全球公认为是利用率高,范围广和效果好的处理危险废弃物的行业之一。
本论文采用XRD和f-CaO等现代分析测试手段探讨利用飞灰配料煅烧水泥熟料的可行性。在验证其可行性后,研究飞灰掺量对烧成熟料性能的影响,确定出飞灰最大掺量。然后采用XRD、SEM及IR等分析测试手段研究利用飞灰烧制水泥熟料的性能及其水化性能,并探讨含重金属离子水泥熟料的水化机理。最后通过熟料对重金属离子的固化率和熟料水化后重金属离子的浸出毒性评价飞灰制品对环境的影响。在这些实验的基础上,得出主要结论如下：
1.利用飞灰配料烧成的水泥熟料矿物特征衍射峰与普通硅酸盐水泥熟料完全相似,没有发现其它新的特征衍射峰。利用飞灰配制的水泥生料易烧性好,熟料中f-CaO含量基本在2%以下,达到水泥企业出厂熟料中f-CaO需控制的范围要求。
2.煅烧温度和飞灰掺量对水泥生料易烧性影响显著：随着煅烧温度的提高,水泥熟料中f-CaO含量逐渐减少；随着飞灰掺量的增加,水泥熟料中f-CaO含量先减小后增大。当飞灰掺量为5.2%时,水泥熟料矿物组成和空白样相比变化不大；当飞灰掺量达到10.9%时,水泥熟料中C3S矿物相对含量明显增大,f-CaO含量最低,易烧性最好。
3.掺有10.9%飞灰的水泥熟料与空白样相比,早期强度有所降低而后期强度略有提高。从XRD和SEM可以看出,掺有10.9%的飞灰熟料后期水化更充分,试样中残留的硅酸盐矿物较少,生成的水化产物C-S-H较多,浆体结构更加致密。
4.重金属氧化物的掺杂对水泥熟料水化影响显著,PbO的掺入显著降低熟料中硅酸盐矿物的含量,阻止水化反应进程；Cr2O3阻止C2S向C3S的转变,提高熟料中C2S含量但降低C3S的含量,促进后期水化；Ni2O3的掺入提高熟料中硅酸盐矿物相对含量,促进早期水化。
5.在实验室条件下烧制水泥熟料对重金属离子的固化率高达80%左右,其中铅的固化率略低且烧成熟料中检测不到Ni。利用飞灰烧制的水泥水化28d后毒性浸出浓度远远低于国家规定危险废弃物浸出液最高允许的排放标准,对环境几乎没有影响。
The Fly Ash is residue collected from the gas refining equipment when the Municipal Solid Wastes are sintering at high temperature. Because it contains virulent heavy metal ions and dioxin-like organic pollutants, it is listed as hazardous waste, which need to be solidification/stabilization before satisfying the standard of security landfill. However, the safety of landfill not only occupies the land and costs more, but also doesn't completely rule out the potential threat of secondary contamination, as a bottleneck restricting the utilization of fly ash. Therefore, the reseach for disposal and application technology of fly ash fitting China's national conditions has become a hot topic in recent years.
There are nearly 30 years for disposaling of hazardous industrial waste in cement klin in the industrialized countries. It is not only able to make use of waste, but also can completely elimination of toxic waste, which has been widely considered as a high utilization, broad scope and good effect of disposal of hazardous waste industry.
First, we consider the feasibility of using the fly ash sintered the cement clinker byXRD、SEM、f-CaO and other modern analytical methods. After we make it sure, We study the influence of the content of fly ash to the sinterd clinker and confirm its largest dosage. Second, we research on the properties of sinterd clinker by using XRD、SEM、IR and so on, and discuss the curing mechanism of heavy metal ions in the hydration. Finally, we measure how much the clinker solidify heavy metal ions and leaching toxicity of heavy metal ions when it hydrates, and evaluate the environmental impact of fly ash product. In these experiments, some main conclusions can be considerated as follows:
1. They are similar to the characteristic peaks in both the Ordinary Portland cement clinker and the sintered cement clinker by using fly ash. And there are any new peaks in samples. The burnability of samples are very good, because the content of f-CaO of the samples are all less then 2%, which are in the range of requirements that should be controlled in cement factory.
2. Both calcination temperature and fly ash dosage play great influence on the burnability of the samples:with the calcination temperature increased, the content of f-CaO of samples are decreased; With the fly ash dosage increased, the content of f-CaO of samples are decreased first and increased later. As the content of fly ash is up to 5.2%, the cement clinker composition changes little; However, the content of C3S of the sample is larger than that of blank sample, and the content of f-CaO of the sample is the lowest, when it raise to 10.9%.
3. Comparing with the blank sample, the early strength of the sample mixed with 10.9%fly ash is dropped slightly, but the late strength are increased. From XRD and SEM we can see, the sample, which the content of fly ash is 10.9%, hydrates more fully late than the blank sample. There are less silicate mineral but more C-S-H in hydration product, and the mortar is more compact.
4. Metal oxide doping plays a great important role on the hydration of the cement clinker. PbO significantly reduced the relative content of silicate minerals in cement clinker and prevent hydration process; Cr2O3 prevents C2S from transforming to C3S, so it increases the content of C2S but decreases that of C3S in cement clinker, which promote the post-hydration; Ni2O3 can increase the relative content of silicate minerals in cement clinker, and promote early hydration.
5. Under laboratory conditions, the solidification rate of heavy metal irons are up to 80%in cement clinkers. The curing rate of Pb is slightly low and Ni cann't be tested in cement clinkers. When the sample hydrates after 28d, the leaching toxicity is far less than the maximum allowable discharge standards, indicating it has little impact on the environment.
利用水泥回转窑处理危险工业废弃物在工业发达国家已有近30年的历史,它不仅能够利用废弃物生产熟料,而且能彻底销毁有毒有害的危险废弃物,被全球公认为是利用率高,范围广和效果好的处理危险废弃物的行业之一。
本论文采用XRD和f-CaO等现代分析测试手段探讨利用飞灰配料煅烧水泥熟料的可行性。在验证其可行性后,研究飞灰掺量对烧成熟料性能的影响,确定出飞灰最大掺量。然后采用XRD、SEM及IR等分析测试手段研究利用飞灰烧制水泥熟料的性能及其水化性能,并探讨含重金属离子水泥熟料的水化机理。最后通过熟料对重金属离子的固化率和熟料水化后重金属离子的浸出毒性评价飞灰制品对环境的影响。在这些实验的基础上,得出主要结论如下：
1.利用飞灰配料烧成的水泥熟料矿物特征衍射峰与普通硅酸盐水泥熟料完全相似,没有发现其它新的特征衍射峰。利用飞灰配制的水泥生料易烧性好,熟料中f-CaO含量基本在2%以下,达到水泥企业出厂熟料中f-CaO需控制的范围要求。
2.煅烧温度和飞灰掺量对水泥生料易烧性影响显著：随着煅烧温度的提高,水泥熟料中f-CaO含量逐渐减少；随着飞灰掺量的增加,水泥熟料中f-CaO含量先减小后增大。当飞灰掺量为5.2%时,水泥熟料矿物组成和空白样相比变化不大；当飞灰掺量达到10.9%时,水泥熟料中C3S矿物相对含量明显增大,f-CaO含量最低,易烧性最好。
3.掺有10.9%飞灰的水泥熟料与空白样相比,早期强度有所降低而后期强度略有提高。从XRD和SEM可以看出,掺有10.9%的飞灰熟料后期水化更充分,试样中残留的硅酸盐矿物较少,生成的水化产物C-S-H较多,浆体结构更加致密。
4.重金属氧化物的掺杂对水泥熟料水化影响显著,PbO的掺入显著降低熟料中硅酸盐矿物的含量,阻止水化反应进程；Cr2O3阻止C2S向C3S的转变,提高熟料中C2S含量但降低C3S的含量,促进后期水化；Ni2O3的掺入提高熟料中硅酸盐矿物相对含量,促进早期水化。
5.在实验室条件下烧制水泥熟料对重金属离子的固化率高达80%左右,其中铅的固化率略低且烧成熟料中检测不到Ni。利用飞灰烧制的水泥水化28d后毒性浸出浓度远远低于国家规定危险废弃物浸出液最高允许的排放标准,对环境几乎没有影响。
The Fly Ash is residue collected from the gas refining equipment when the Municipal Solid Wastes are sintering at high temperature. Because it contains virulent heavy metal ions and dioxin-like organic pollutants, it is listed as hazardous waste, which need to be solidification/stabilization before satisfying the standard of security landfill. However, the safety of landfill not only occupies the land and costs more, but also doesn't completely rule out the potential threat of secondary contamination, as a bottleneck restricting the utilization of fly ash. Therefore, the reseach for disposal and application technology of fly ash fitting China's national conditions has become a hot topic in recent years.
There are nearly 30 years for disposaling of hazardous industrial waste in cement klin in the industrialized countries. It is not only able to make use of waste, but also can completely elimination of toxic waste, which has been widely considered as a high utilization, broad scope and good effect of disposal of hazardous waste industry.
First, we consider the feasibility of using the fly ash sintered the cement clinker byXRD、SEM、f-CaO and other modern analytical methods. After we make it sure, We study the influence of the content of fly ash to the sinterd clinker and confirm its largest dosage. Second, we research on the properties of sinterd clinker by using XRD、SEM、IR and so on, and discuss the curing mechanism of heavy metal ions in the hydration. Finally, we measure how much the clinker solidify heavy metal ions and leaching toxicity of heavy metal ions when it hydrates, and evaluate the environmental impact of fly ash product. In these experiments, some main conclusions can be considerated as follows:
1. They are similar to the characteristic peaks in both the Ordinary Portland cement clinker and the sintered cement clinker by using fly ash. And there are any new peaks in samples. The burnability of samples are very good, because the content of f-CaO of the samples are all less then 2%, which are in the range of requirements that should be controlled in cement factory.
2. Both calcination temperature and fly ash dosage play great influence on the burnability of the samples:with the calcination temperature increased, the content of f-CaO of samples are decreased; With the fly ash dosage increased, the content of f-CaO of samples are decreased first and increased later. As the content of fly ash is up to 5.2%, the cement clinker composition changes little; However, the content of C3S of the sample is larger than that of blank sample, and the content of f-CaO of the sample is the lowest, when it raise to 10.9%.
3. Comparing with the blank sample, the early strength of the sample mixed with 10.9%fly ash is dropped slightly, but the late strength are increased. From XRD and SEM we can see, the sample, which the content of fly ash is 10.9%, hydrates more fully late than the blank sample. There are less silicate mineral but more C-S-H in hydration product, and the mortar is more compact.
4. Metal oxide doping plays a great important role on the hydration of the cement clinker. PbO significantly reduced the relative content of silicate minerals in cement clinker and prevent hydration process; Cr2O3 prevents C2S from transforming to C3S, so it increases the content of C2S but decreases that of C3S in cement clinker, which promote the post-hydration; Ni2O3 can increase the relative content of silicate minerals in cement clinker, and promote early hydration.
5. Under laboratory conditions, the solidification rate of heavy metal irons are up to 80%in cement clinkers. The curing rate of Pb is slightly low and Ni cann't be tested in cement clinkers. When the sample hydrates after 28d, the leaching toxicity is far less than the maximum allowable discharge standards, indicating it has little impact on the environment.
引文
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