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流化床燃煤固硫灰渣水化研究 【作者】宋远明 【导师】钱觉时

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#UXcrF)~0流化床燃煤固硫灰渣水化研究水利论文6fQ@#^*}T t:f"G

#nZ9L|K$x3C!{!G!k0作者】宋远明 【导师钱觉时
x/~d*[6x2d l bP0【作者基本信息】重庆大学,材料科学与工程,2007年,博士水利论文j:}\$n G#K:C7Sv

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L)TLS(gA3d-[g0【中文摘要】 流化床燃煤固硫技术是为了适应环境保护的要求而发展起来的先进煤燃烧技术,但由于目前对其副产物,即流化床燃煤固硫灰渣(以下简称固硫灰渣)的特性了解有限,在一定程度上影响了其资源化利用,甚至影响到了该技术的进一步推广。固硫灰渣用于建材领域是其最重要的资源化利用途径之一,而固硫灰渣的水化特性与这一用途密切相关。固硫灰渣均含有烧粘土质矿物和固硫矿物(主要为游离CaO和Ⅱ-CaSO4),这两种物质在水化过程中发挥的主要作用是不同的,因此对它们的水化特性分别进行研究。本文研究了固硫灰渣与水化有关的物化特性;用化学动力学方法研究了固硫灰渣中烧粘土质矿物的火山灰水化反应特性,并研究了其水化特性对固硫灰渣水硬性的影响;利用XRD、SEM和EDS等微观分析手段对固硫灰渣中固硫矿物的水化产物特性进行研究,并对因固硫矿物水化而引起的膨胀特性及机理进行研究。为使研究结果更具代表性,采用11种不同CaO、SO3含量的固硫灰渣进行研究,并与煤粉炉粉煤灰进行对比。固硫灰渣与粉煤灰颗粒形貌差异主要取决于它们生成温度的不同。固硫灰渣[SiO4]和[AlO6]聚合度在CaO含量较低时与粉煤灰比较接近,而在CaO含量较高时则低...更多于粉煤灰。目前主要采用氢氧化钙变化量法和化学结合水量法研究火山灰质掺合料的火山灰水化反应动力学,而本研究首次采用了活性组分变化量法。该法不但可以反映出活性SiO2、Al2O3火山灰反应能力差异,还可得到火山灰反应速率常数和表观活化能等有用的动力学参数。在燃煤灰渣-Ca(OH)2-水系统中,固硫灰渣和粉煤灰的活性SiO2、Al2O3火山灰反应均符合一级反应动力学模型;火山灰反应速率常数与温度的关系符合阿累尼乌斯定律。固硫灰渣的火山灰水化反应速率明显高于粉煤灰,反应能垒则低于粉煤灰。采用密度分离法研究固硫灰渣的矿物组成,并在此基础上得出:烧粘土质矿物和游离CaO、Ⅱ-CaSO4间发生的火山灰反应可使固硫灰渣具有明显的水硬性,而且水硬速率较快。如不采取限制措施,固硫灰渣硬化体中的钙矾石在90 d龄期时会分解为二水石膏和石灰石;游离CaO含量会影响钙矾石的结晶形态,这两种因素对固硫灰渣膨胀特性均有较大影响。研究结果证实,固硫灰渣的膨胀性能主要与钙矾石的含量和结晶形态有关。  还原水利论文+P tE(I@ B#^)K`?[P'c f E

`0N _V-B&l#Zi7q d0【英文摘要】 Fluidized bed combustion (FBC) technology is advanced because it can meet the demand of environment protection, but the byproducts, namely FBC ashes, are still something new to most people. As a result, the utilization of them and even the further promotion of the technology are seriously hampered. The utilization in building materials is very important for FBC ashes, closely related to the hydration properties of them. The sulphur-fixing products, mainly free lime andⅡ-CaSO4, and calcined clay minerals in FBC ashes play the different roles in the hydration process, studied respectively in this thesis. The physico-chemical properties relating to hydration of FBC ashes are analyzed. The chemical kinetics method is introduced in to study the pozzolanic hydration properties of the calcined clay minerals in FBC ashes. This paper also deals with the effect of the hydration properties of the calcined clay minerals on the hydraulic properties of FBC ashes. The hydration products from the sulp...更多hur-fixing products are studied by XRD, SEM and EDS, and the expansion properties and mechanism are also investigated.Eleven FBC ashes with different content of free lime and SO3 are adopted to make the study representative, by contrast with Pulverized Coal Combustion fly (PF) ashes. The difference between the morphology of FBC ashes and that of PF ashes is controlled by the combustion temperature. The polymerization degree of [SiO4] and [AlO6] of FBC ashes decreases with the CaO content. The polymerization degree of [SiO4] and [AlO6] of FBC ashes with lower CaO content is close to that of PF ashes.All the present studies on the pozzolanic reaction kinetics of pozzolans regard the active components as a whole and model the reaction kinetics by the change of Ca(OH)2 or chemically combined water content. For the first time, the method of the change of active components content is used to investigate the pozzolanic reaction kinetics of FBC ashes and PF ashes. The new method can differentiate the pozzolanic reactivity of active SiO2 and Al2O3, and obtain the useful parameters, such as reaction rate constant and activation energy. The pozzolanic reaction of active SiO2 and Al2O3 of FBC ashes and PF ashes follows apparent first-order kinetics, and the relationship between the pozzolanic reaction rate constant and temperature conforms to the Arrehenius Law. The reaction rate of FBC ashes is greater than that of PF ashes, while it is just the contrary for the energy barrier. Density separation is used to study the mineral phases of FBC ashes. On this basis, this work confirms that the pozzolanic reaction among calcined clay minerals, free lime and anhydrite can enable the hydraulic properties of FBC ashes to be obvious and fast.If contact with air is not restricted, the ettringite formed earlier will decompose at 90 d, its place being taken by gypsum and calcite, and free lime can affect the crystal morphology of ettringite in FBC ashes pastes, which have a great influence on the expansion properties of FBC ashes. The work confirms that the expansion properties of FBC ashes depend mainly on the content and crystal morphology of ettringite.  还原

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j'ojR Y.tS.J4o0【中文关键词】 流化床; 固硫灰渣; 水化特性; 烧粘土质矿物; 固硫矿物
S(J2I4]ki!}%Sd0【英文关键词】 Fluidized bed combustion; FBC ashes; hydration properties; calcined clay minerals; sulphur-fixing products水利论文T"P5TEoEPU

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TAG: 流化床 水化 燃煤 灰渣 钱觉时
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