CN1701047A - 飞灰的处理方法 - Google Patents
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Abstract
一种处理用于制备砂浆和混凝土的飞灰的方法。本发明的特征在于在第一步中,飞灰与高活性且干燥的水泥混合物剧烈混合,其中所述混合物通过使普通水泥与微填料以及可能的减水剂混合并研磨所述混合物而得到,在第二步中,将如此得到的共混物在振动研磨设备中内磨,以使最终产品的粒度达到在45μm筛子上的保留量低于15wt%。
Description
技术领域
本发明涉及一种处理飞灰的方法,所述飞灰可用于制备混凝土、砂浆和其它包含水泥和飞灰的混合物。按本发明方法生产的飞灰明显提高了混凝土的性能,并能替代更多的标准普通水泥,这将产生明显的经济和环境效益。
背景技术
飞灰是燃煤电力装置的副产品,每年在世界范围内大量产生。
飞灰通常含有约85%玻璃状的无定形组分。按照ASTM C 618,飞灰分为两类即C类和F类。F类飞灰通常含有大于70wt%的二氧化硅、氧化铝和氧化铁类,而C类飞灰通常含70-50%。F类飞灰作为烟煤燃烧的副产品产生,而C类飞灰具有较高的钙含量,其作为亚烟煤燃烧的副产品而产生。
1988年,在美国大约产生了84,000,000吨的煤灰,其以飞灰(大约60.7%)、底灰(大约16.7%)、炉渣(5.9%)和废气脱硫(16.7%)的形式存在,例如参见Tyson于1990的“Coal Combustion By Product Utilization”,Seminar,Pittsburgh,第15页。在每年生产的约50,000,000吨飞灰中,只有约10%用于混凝土中,参见ACI Committee 226,1987,“Use of FlyAsh In Concrete”,ACI 226.3R-87,ACI J.Proceedings 84:381-409),而剩余部分主要作为废物堆积在垃圾堆中。
更全面的研究表明,与不含飞灰的普通水泥混凝土相比,含大量飞灰的混凝土表现出更长时间的强度进展、较低的水和气体渗透性、较高的氯离子阻力等。
与此同时,含大量飞灰的混凝土具有明显的缺点:较长的固化时间,并且在0-28天期间具有非常慢的强度进展,这使用于替代普通水泥的飞灰量平均降低15-20%。
已经作了许多努力来提高含大量飞灰的混凝土的性能;例如参见Malhotra的Concrete International J.第21卷,第5期,1999年5月,第61-66页。按照Malhotra,通过明显增加粘合剂(水泥+微填料)的含量并明显降低混合水的量,这种混凝土的强度进展可以得到改善,但是这种方法需要增加减水混合物的量以保持混凝土混合物可接受的稠度,这明显增加了混凝土的成本。
为了通过研磨飞灰而提高其凝硬性,开发了多种涉及研磨飞灰的方法,这些方法增加了粒径约为11微米的飞灰颗粒的量,同时引入氧化钙,参见美国专利US 6,038,987、US 5,714,002、US 5,714,003、US 5,383,521和US 5,121,795。所提到的这些已知方法均不能明显改善飞灰作为混凝土组分的性能,且极大地增加了火山灰添加剂的费用。
发明内容
本发明涉及一种处理用于制备砂浆和混凝土的飞灰的方法,其特征在于在第一步中,飞灰与高活性且干燥的水泥混合物剧烈混合,其中通过使普通水泥与微填料以及可能的减水剂混合并研磨该混合物而得到所述水泥混合物,在第二步中,将这样得到的共混物在振动研磨设备中内磨,以使最终产品的粒度达到在45μm的筛子上的保留量小于15wt%。
按照一个优选的实施方案,所述研磨设备的振动循环具有2-30mm的振幅和800-2000rpm的振动频率。
因此本发明涉及一种处理可用于制备砂浆和混凝土的飞灰的方法,其中所述飞灰首先与高活性且干燥的水泥混合物剧烈混合,其中通过将普通水泥与微填料以及可能的减水剂彻底混合而得到所述水泥混合物,然后将所述共混物在振动研磨设备中内磨。
在振动循环具有2-30mm的振幅和800-2000rpm的振动频率的研磨设备中,使飞灰与高活性水泥混合物内磨会产生多种效果。
所述效果首先是提高最终产品的细度,使飞灰颗粒的平均粒度降低,从而在45μm的筛子上的保留量小于15wt%;其次,飞灰颗粒的表面会发生附加变形;第三,高活性水泥混合物中的硅酸三钙和硅酸二钙在飞灰颗粒表面的分布更均匀。这些效果提高了与氢氧化钙反应的凝硬性活性,同时使处理后的飞灰产生内部水力学活性。
本发明方法的另一个优点是研磨处理可能会释放由脲处理的煤产生的飞灰表面所捕集的氨,这一优点用于减少NOX的排放。飞灰中氨的存在使其不适合用于混凝土或砂浆中。
本发明的这一优点在于所提出的飞灰处理减少了锅炉条件对与锅炉条件相关的飞灰特性的影响,并降低了煤的粉碎程度。
前述高活性的干燥水泥混合物是按欧洲专利申请说明书EP 0696262和美国专利US 5,804,175所述方法得到的水泥混合物,或者按照相应方法处理从而使耐压强度相当于EP 0696262和US 5,804,175中所述数值而得到的水泥混合物。
按照一个优选的实施方案,在所述内磨过程中,减水剂以约0.1-0.3wt%的量以粉末形式加入。
按照另一个优选的实施方案,在飞灰-水泥混合物中,以混合物的总重量计,所述飞灰以约20-70wt%的量替代水泥。
欧洲专利说明书EP 0696262和美国专利US 5,804,175均描述了制备水泥的方法,该方法可用于产生用于制备灰浆、砂浆、混凝土和其它水泥基材料的水泥,而这些材料对减水剂含量具有较高的承受力,具有较高的机械强度,并且具有较高的密度和较快的强度进展。这种方法包括对水泥和下述两组分中至少一个组分的混合物进行机械-化学处理:第一个组分为含有二氧化硅的微填料,第二个组分为以减水剂形式存在的聚合物。在第一个阶段中,水泥和第一和/或第二组分干态混合,其中第一和/或第二组分颗粒被吸附在水泥颗粒上。在第一阶段中得到的混合物在第二阶段中在研磨机内用振动研磨介质进行处理,其中所述混合物中的颗粒受到大量的以极快频率改变方向的冲击力作用,因此造成水泥颗粒表面特性的改变,改变形式为相当大幅度地增加了表面能和化学活性。在第二阶段中的处理时间应该是足够的,使得侧面长度为20mm的、在振动下完全压实的、在密封条件下在+20℃下固化的水泥灰浆方块具有至少60MPa的一天耐压强度。
因而在本申请中引入欧洲专利EP 0 696 262。
按照一个优选的实施方案,飞灰和高活性水泥混合物的共混物含有约99-90wt%的飞灰。
另外,本发明涉及一种制备用于生产成形混凝土元件或构件的混凝土混合物的方法,所述方法包括如下步骤:首先按照上述方法制备处理过的飞灰,其次使所述共混的水泥与砂子和/或尺寸较大的集料和水混合,和第三步铸塑形成成形的元件或构件并使其硬化。
在这一方面,以混合物的总量计,优选所述飞灰在飞灰-水泥混合物中以约20-70wt%的量替代水泥。
部分结合如下表格,在下文将更为详细地描述本发明,其中表1和表2分别表示了参比普通水泥、按本发明方法处理过的F类和C类飞灰替代20wt%和40wt%普通水泥的砂浆的强度进展。
所述表格含有以类似量替代普通水泥的砂浆的数据,其中仅以传统方式通过与其它砂浆组分内混而加入飞灰。按照ASTM C 109、ASTM C-311和ASTM C-192实施实验。
按照所得到的结果,与传统共混物相比,以20%和40%用F类飞灰替代普通水泥而制备的砂浆显示出明显增强的强度,不管是长期效果还是短期效果都是如此。用20%替代的砂浆在硬化后约3天达到纯普通水泥的强度水平,并且显示固化28天后其强度高约11%。用40%替代的砂浆固化28天后几乎达到纯普通水泥砂浆的强度。
用按本发明方法处理的C类飞灰制备的砂浆表现出类似的强度进展改进趋势。与纯普通水泥砂浆相比,替代20%普通水泥的砂浆其强度经过3天就表现出更优的强度,并且经过28天硬化后其强度高约12%。
应用Gilmore设备按照ASTM C 266测量含有粘合剂的处理过的飞灰和参比普通水泥灰浆的固化时间。数据表明:处理后飞灰的水泥灰浆的固化时间与参比普通水泥一致:初始固化时间2:20-2:40小时,最终固化时间3:40-3:55小时。
已经发现在振动研磨设备中使F类和C类飞灰与高活性水泥混合物内磨,其中所述研磨设备的振动循环的振幅为2-30mm、振动频率为800-2000rpm,将使最终产品的细度达到在45μm筛子上的保留量低于5wt%。这导致所述飞灰表面明显改变,造成更多的变形且吸附高活性水泥混合物颗粒。这种改变将会导致飞灰的化学活性改善,并且导致含飞灰的复合物的性能得到改善。
按照第一个实施方案,所述飞灰主要由F类飞灰组成。
按照第二个实施方案,所述飞灰主要由C类飞灰组成。
按照第三个实施方案,所述飞灰主要由F类飞灰和C类飞灰的共混物组成。
按照第四个实施方案,所述飞灰主要由F类飞灰、C类飞灰和/或褐煤飞灰的共混物组成。
实施例
在下述实验中应用如下材料:按照EN-197或按照ASTM C 150第I类的标准普通水泥CEMI 42.5、F类飞灰和C类飞灰。
F类飞灰和C类飞灰的细度分别以在45微米筛子上的保留量为21wt%和19.5wt%表示。
所述飞灰与高活性干燥水泥混合物干态混合,所述水泥混合物按欧洲专利说明书EP 0696262生产并含99%普通水泥(PC)及2%的F类飞灰。所述组分的混合用旋转速率为280rpm的″Tonimix″混合器(德国制造)实施,持续3分钟以得到均匀的共混物。飞灰和高活性水泥混合物的含量分别为95wt%和5wt%。
上述混合物的内磨在一个振幅为10mm且振动频率为1500rpm的Humboldt Palla 20U(Humboldt,德国)振动研磨机中实施,从而使最终产品的细度达到45微米的分数为约2.5wt%。
按照实验结果,参见表1-2,按照本发明方法处理的C类和F类飞灰表现出明显的性能改进。这可能会导致飞灰在混凝土中的利用增加,并且会导致在混凝土中飞灰更大程度地替代普通水泥。这将对水泥和混凝土工业的环境状况有明显影响。
表1 F类飞灰的砂浆试验
水泥类型 | 耐压强度,MPa;固化时间,天 | |||
1 | 3 | 7 | 28 | |
参比普通水泥 | 10.2 | 26.5 | 30.0 | 38.6 |
80%PC+20%飞灰* | 8.5 | 25.0 | 32.5 | 43.1 |
60%PC+40%飞灰* | 6.4 | 19.5 | 24.1 | 36.2 |
80%PC+20%飞灰** | 6.5 | 20.0 | 23.6 | 35.8 |
60%PC+40%飞灰** | 3.8 | 15.0 | 17.7 | 29.6 |
*)按本发明方法处理的飞灰
**)在混合器中以传统方式加入的飞灰
表2 C类飞灰的砂浆试验
水泥类型 | 耐压强度,MPa;固化时间,天 | |||
1 | 3 | 7 | 28 | |
参比普通水泥 | 10.2 | 26.5 | 30.0 | 38.6 |
80%PC+20%飞灰* | 9.5 | 27.0 | 35.3 | 46.2 |
60%PC+40%飞灰* | 7.4 | 21.5 | 27.2 | 38.2 |
80%PC+20%飞灰** | 7.5 | 22.0 | 28.3 | 39.8 |
60%PC+40%飞灰** | 4.8 | 17.0 | 19.7 | 32.6 |
*)按本发明方法处理的飞灰
**)在混合器中以传统方式加入的飞灰
由于明显降低了普通渣块(Portland clinker)含量,应用这种混合水泥可以明显降低二氧化碳和其它“温室”气体的排放水平,其降低量可能超过50%,并且还会明显降低普通渣块生产所需要的能量。
Claims (11)
1.一种处理用于制备砂浆和混凝土的飞灰的方法,其特征在于,在第一步中,使飞灰与高活性且干燥的水泥混合物剧烈混合,其中所述混合物通过使普通水泥与微填料以及可能的减水剂混合并研磨所述混合物而得到,在第二步中,将如此得到的共混物在振动研磨设备中内磨,以使最终产品的细度达到在45μm筛子上的保留量低于15wt%。
2.权利要求1的方法,其特征在于,所述研磨设备的振动循环的振幅为2-30mm、振动频率为800-2000rpm。
3.权利要求1或2的方法,其特征在于,所述飞灰和高活性水泥混合物的共混物含有约99-90wt%的飞灰。
4.权利要求1、2或3的方法,其特征在于,所述飞灰主要由F类飞灰组成。
5.权利要求1、2或3的方法,其特征在于,所述飞灰主要由C类飞灰组成。
6.权利要求1、2或3的方法,其特征在于,所述飞灰主要由F类飞灰和C类飞灰的共混物组成。
7.权利要求1、2或3的方法,其特征在于,所述飞灰主要由F类飞灰、C类飞灰和/或褐煤飞灰的共混物组成。
8.权利要求1、2、3、4、5、6或7的方法,其特征在于,在所述内磨过程中,减水剂以约0.1-0.3wt%的量以粉末形式引入。
9.制备权利要求7的混合物的方法,其特征在于,以混合物的总重量计,所述飞灰替代飞灰-水泥混合物中约20-70wt%的水泥。
10.前述权利要求任一项的方法,其特征在于,所述高活性水泥通过欧洲专利说明书EP 0696262中所述的方法得到。
11.制备用于生产混凝土构件和元件的混凝土混合物的方法,其特征在于,该方法包括权利要求1-6中任一项的步骤,并且接下来将所述飞灰和水泥混合物与砂子和/或尺寸较大的集料和水、以及可能的夹带空气和减水的混合物混合。
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CN101407380B (zh) * | 2007-08-30 | 2011-02-16 | 私立淡江大学 | 垃圾焚化飞灰再生利用作为水泥材料的方法 |
CN101965318B (zh) * | 2007-11-12 | 2013-03-27 | 普洛希多企业公司 | 处理火山灰质材料的方法 |
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CN110420961A (zh) * | 2019-05-14 | 2019-11-08 | 广州环投环境服务有限公司 | 一种飞灰填埋工艺 |
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US20040089202A1 (en) | 2004-05-13 |
PT1558544E (pt) | 2012-05-29 |
KR100988543B1 (ko) | 2010-10-20 |
US6818058B2 (en) | 2004-11-16 |
MXPA05004695A (es) | 2005-11-04 |
BR0315436A (pt) | 2005-09-20 |
RU2331598C2 (ru) | 2008-08-20 |
EP1558544A1 (en) | 2005-08-03 |
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