流化床燃煤固硫灰渣中无水石膏作用研究
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摘要
流化床燃煤固硫技术是符合节能环保发展方向的先进煤燃烧技术,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,缺乏基础资料,导致这一技术的推广应用因固硫灰渣没有成熟和经济的综合利用途径而受到严重影响。
固硫灰渣本质上是烧粘土质矿物,用于建材领域是其最重要的资源化利用途径之一,固硫灰渣中含有大量的固硫矿物——无水石膏,无水石膏既可以激发固硫灰渣的火山灰活性,又会带来无法控制的膨胀,使固硫灰渣具有很多独特的性能,阻碍了其建材资源化利用。本论文围绕固硫灰渣中的无水石膏展开,利用XRD、SEM和EDS等微观分析手段系统研究了固硫灰渣中无水石膏的微观形貌和分布规律;利用化学手段分析了无水石膏在固硫灰渣水化过程中的作用;在此基础上,研究了固硫灰渣中的无水石膏对其活性及活性行为的影响,提出了基于消除无水石膏影响的固硫灰渣活性评价方法;最后,研究了如何抑制固硫灰渣中无水石膏的膨胀,提出了建材资源化利用的方向。
本论文有以下研究成果:(1)通过XRD和化学分析手段证明了固硫灰渣中含硫矿物几乎都以Ⅱ型无水石膏形式存在;(2)利用密度分离和筛分方法研究固硫灰渣中无水石膏的形貌和分布规律,发现无水石膏在固硫灰渣中分布不均匀,易富集在粒径小、密度大的固硫灰渣颗粒中;(3)通过SEM和EDS能谱分析发现固硫灰和固硫渣中都不同程度存在有致密和疏松的两种类型颗粒。固硫灰致密颗粒表面结晶较好的突出物主要是无水石膏及一定含量的粘土矿物,疏松颗粒主要是未燃烧的炭;固硫渣致密颗粒表面结晶较好的突出物主要是无水石膏,疏松颗粒表面结晶较好的柱状颗粒主要是粘土矿物,还吸附了少量的无水石膏;(4)通过反应速率常数K和溶解曲线的测试,表明850℃煅烧2h的无水石膏与固硫灰渣中的无水石膏溶解性能和反应活性相似,可以外掺入固硫灰渣以研究不同无水石膏含量对其性能的影响;(5)通过系统的pH值、钙矾石和化学结合水的定量测试,证明固硫灰渣中的无水石膏会积极参与并影响固硫灰渣中烧粘土矿物的水化,从而影响活性行为和膨胀性能;(6)固硫灰渣中的无水石膏含量对其火山灰活性的高低没有影响,但可以明显影响其活性行为。当无水石膏在系统中的含量在2~4% (以SO3含量计)范围内时,固硫灰渣的活性行为表现最好,小于这一范围,无水石膏对固硫灰渣的火山灰活性激发效果差,大于这一范围,过量的无水石膏会在水化后期生成延迟钙矾石和二水石膏,破坏已经形成的强度结构,都不利于固硫灰渣的活性行为表现;(7)提出的基于消除无水石膏影响的固硫灰渣活性评价方法,即“水泥熟料胶砂28d抗压强度比方法”,强调通过控制石膏含量来控制系统SO3含量,通过胶砂流动度来控制用水量,可以真实反映固硫灰渣可应用的火山灰活性。该方法要求固硫灰渣含硫量应在11.6%(以SO3含量计)以内,我国固硫灰渣平均含硫量为7.8%(以SO3含量计),绝大部分适用于此方法;(8)无水石膏是导致固硫灰渣水化膨胀的主要因素。试验表明选择能够促进无水石膏溶解和水化的外加剂可在一定程度上抑制固硫灰渣中无水石膏的膨胀,掺入1%的CaCl2或Na2CO3后,可使28d胶砂线性膨胀率降低约19%;控制固硫灰渣掺量和胶凝体系中的SO3含量,固硫灰渣可以作为水泥混凝土的混合材使用,选择SO3含量在11.6%以下的固硫灰渣,以30%的掺量与水泥熟料组成的胶凝材料自由线性膨胀率不超过基准水泥,28天抗压强度可达到基准水泥的90%,且安定性、凝结时间、抗冻融、抗碳化等性能均符合要求;(9)热养护能消除固硫灰渣中无水石膏的膨胀,用70%的固硫灰渣和30%的水泥熟料混合,通过蒸压养护后,固硫灰渣水泥熟料制品强度是自然养护条件下试件的2~3倍,28天胶砂抗压强度达到25MPa。蒸压后净浆水化产物中没有钙矾石生成,有托贝莫来石生成,水化产物结晶更完善,最大线性膨胀率仅为直接水中养护净浆的1/7左右,在5×10-4以下,且随龄期变化很小。
Fluidized bed combustion (FBC for short) technology is one of the advanced coal combustion technology that meets the demands of energy conversation and environmental protection. However, further application of this technology was blocked due to the basic research deficiency and limited understand to the characteristics of FBC ashes—the byproduct of the technology, leading to lack of effective ways to utilize the ashes.
FBC ashes can be widely used in building materials for they are one kind of incinerated-clay minerals essentially. Nonetheless, FBC ashes containing a lot of solid sulfides—anhydrite, which can not only activate the pozzalanic activity of FBC ashes, but also cause expansion out of control, adding many special characteristics to the ashes that hampered their utilization as building materials.
This thesis is focus on anhydrite solidified in FBC ashes. Micro-morphology and particle distribution of anhydrite were investigated by X-ray diffraction (XRD), electron scanning microscope (SEM) and energy dispersive scanning (EDS); the function that anhydrite played during hydration of FBC ashes was studied by chemical analysis.
Based on which, the influence on activity and activation behavior of FBC ashes with the change of anhydrite were studied and a method to evaluate activation of FBC ashes was proposed aimed at eliminating disadvantage influence of anhydrite. Besides, the restraint of anhydrate expansion in FBC ashes was studied and a way of their utilization as building materials was put forward.
The results are listed as follows: (1) XRD and chemical analysis results testified that the sulphates mineral solidified in FBC ashes is mainlyⅡ-anhydrite. (2) Micro-morphology and particle distribution of anhydrite in FBC ashes was studied through new methods of density-separation and sieving. The anhydrite in FBC ashes are concentrated in particles of FBC ashes with small size and high density. (3) SEM and EDS analysis results showed that the compacted and loose particles are co-existed both in FBC fly ashes and bed ashes. The protrudent crystals on the surface of compacted particles of FBC fly ashes are mainly anhydrite and some clay minerals while loose particles are mainly unburnt carbon; and for FBC bed ashes, the protrudent crystals on the surface of compacted particles are mainly anhydrite while the column crystals on the surface of loose particles are clay minerals as well as some absorbed anhydrite. (4) The results of reaction rate constant K and dissolution curve showed that the reactive activity and dissolution capability of anhydrite calcined at 850℃for 2h are similar to that of anhydrite solidified in FBC ashes. Anhydrite calcined at 850℃for 2h can be added to FBC ashes to investigate the influence on anhydrite properties of FBC ashes with different dosage. (5) The results of pH value and content of ettringite and chemical combined water indicated that anhydrite takes part in the hydration process and effects the hydration of FBC ashes as well as activation behavior and expansion properties. (6) Although the content of anhydrite had no effect on the degree of FBC ashes’activity, it obviously influenced the activation behavior of FBC ashes. When the content of anhydrite was at the range of 2~4% (SO3), the pozzolanic activity of FBC ashes was most effectively activated. While content of anhydrate was below this rage, the activating effect became worse, and if anhydrite was excessive, the delay-ettringite and dihydrate gypsum formed at later age would reduce the strength because of uncontrolled expansion. (7) A method aimed at eliminating disadvantage influence of anhydrite was proposed to evaluate activation of FBC ashes, namely the 28d compressive strength ratio of cement clinker mortar. This new method can value activity of available FBC ashes objectively, in which the content of SO3 and water content were respectively controlled by gypsum content and mortar fluidity. This method is adapted to FBC ashes with content of SO3 below 11.6%. The average content of SO3 in domestic FBC ashes is 7.8%, which meets the sulphur content demand mentioned above. (8) Anhydrite was the main factor that leads to expansion of FBC ashes during hydration. Additives can restrain the expansion through promoting the dissolution and hydration of anhydrite, such as CaCl2 and Na2O3. The linear expansion ratio of FBC ashes mortar can reduce by 19% after adding 1% of CaCl2 or Na2CO3.The results also showed that, FBC ashes can be used as additive for cement and concrete under restricted amount. (9) The expansion of anhydrite was eliminated by way of autoclave curing, which explored a new way for utilization of FBC ashes. The linear expansion ratio of FBC ashes pastes was below 5×10-4 after autoclave curing. There was tobermorite formed when FBC ashes pastes being autoclave cured, and no ettringite can be found.
固硫灰渣本质上是烧粘土质矿物,用于建材领域是其最重要的资源化利用途径之一,固硫灰渣中含有大量的固硫矿物——无水石膏,无水石膏既可以激发固硫灰渣的火山灰活性,又会带来无法控制的膨胀,使固硫灰渣具有很多独特的性能,阻碍了其建材资源化利用。本论文围绕固硫灰渣中的无水石膏展开,利用XRD、SEM和EDS等微观分析手段系统研究了固硫灰渣中无水石膏的微观形貌和分布规律;利用化学手段分析了无水石膏在固硫灰渣水化过程中的作用;在此基础上,研究了固硫灰渣中的无水石膏对其活性及活性行为的影响,提出了基于消除无水石膏影响的固硫灰渣活性评价方法;最后,研究了如何抑制固硫灰渣中无水石膏的膨胀,提出了建材资源化利用的方向。
本论文有以下研究成果:(1)通过XRD和化学分析手段证明了固硫灰渣中含硫矿物几乎都以Ⅱ型无水石膏形式存在;(2)利用密度分离和筛分方法研究固硫灰渣中无水石膏的形貌和分布规律,发现无水石膏在固硫灰渣中分布不均匀,易富集在粒径小、密度大的固硫灰渣颗粒中;(3)通过SEM和EDS能谱分析发现固硫灰和固硫渣中都不同程度存在有致密和疏松的两种类型颗粒。固硫灰致密颗粒表面结晶较好的突出物主要是无水石膏及一定含量的粘土矿物,疏松颗粒主要是未燃烧的炭;固硫渣致密颗粒表面结晶较好的突出物主要是无水石膏,疏松颗粒表面结晶较好的柱状颗粒主要是粘土矿物,还吸附了少量的无水石膏;(4)通过反应速率常数K和溶解曲线的测试,表明850℃煅烧2h的无水石膏与固硫灰渣中的无水石膏溶解性能和反应活性相似,可以外掺入固硫灰渣以研究不同无水石膏含量对其性能的影响;(5)通过系统的pH值、钙矾石和化学结合水的定量测试,证明固硫灰渣中的无水石膏会积极参与并影响固硫灰渣中烧粘土矿物的水化,从而影响活性行为和膨胀性能;(6)固硫灰渣中的无水石膏含量对其火山灰活性的高低没有影响,但可以明显影响其活性行为。当无水石膏在系统中的含量在2~4% (以SO3含量计)范围内时,固硫灰渣的活性行为表现最好,小于这一范围,无水石膏对固硫灰渣的火山灰活性激发效果差,大于这一范围,过量的无水石膏会在水化后期生成延迟钙矾石和二水石膏,破坏已经形成的强度结构,都不利于固硫灰渣的活性行为表现;(7)提出的基于消除无水石膏影响的固硫灰渣活性评价方法,即“水泥熟料胶砂28d抗压强度比方法”,强调通过控制石膏含量来控制系统SO3含量,通过胶砂流动度来控制用水量,可以真实反映固硫灰渣可应用的火山灰活性。该方法要求固硫灰渣含硫量应在11.6%(以SO3含量计)以内,我国固硫灰渣平均含硫量为7.8%(以SO3含量计),绝大部分适用于此方法;(8)无水石膏是导致固硫灰渣水化膨胀的主要因素。试验表明选择能够促进无水石膏溶解和水化的外加剂可在一定程度上抑制固硫灰渣中无水石膏的膨胀,掺入1%的CaCl2或Na2CO3后,可使28d胶砂线性膨胀率降低约19%;控制固硫灰渣掺量和胶凝体系中的SO3含量,固硫灰渣可以作为水泥混凝土的混合材使用,选择SO3含量在11.6%以下的固硫灰渣,以30%的掺量与水泥熟料组成的胶凝材料自由线性膨胀率不超过基准水泥,28天抗压强度可达到基准水泥的90%,且安定性、凝结时间、抗冻融、抗碳化等性能均符合要求;(9)热养护能消除固硫灰渣中无水石膏的膨胀,用70%的固硫灰渣和30%的水泥熟料混合,通过蒸压养护后,固硫灰渣水泥熟料制品强度是自然养护条件下试件的2~3倍,28天胶砂抗压强度达到25MPa。蒸压后净浆水化产物中没有钙矾石生成,有托贝莫来石生成,水化产物结晶更完善,最大线性膨胀率仅为直接水中养护净浆的1/7左右,在5×10-4以下,且随龄期变化很小。
Fluidized bed combustion (FBC for short) technology is one of the advanced coal combustion technology that meets the demands of energy conversation and environmental protection. However, further application of this technology was blocked due to the basic research deficiency and limited understand to the characteristics of FBC ashes—the byproduct of the technology, leading to lack of effective ways to utilize the ashes.
FBC ashes can be widely used in building materials for they are one kind of incinerated-clay minerals essentially. Nonetheless, FBC ashes containing a lot of solid sulfides—anhydrite, which can not only activate the pozzalanic activity of FBC ashes, but also cause expansion out of control, adding many special characteristics to the ashes that hampered their utilization as building materials.
This thesis is focus on anhydrite solidified in FBC ashes. Micro-morphology and particle distribution of anhydrite were investigated by X-ray diffraction (XRD), electron scanning microscope (SEM) and energy dispersive scanning (EDS); the function that anhydrite played during hydration of FBC ashes was studied by chemical analysis.
Based on which, the influence on activity and activation behavior of FBC ashes with the change of anhydrite were studied and a method to evaluate activation of FBC ashes was proposed aimed at eliminating disadvantage influence of anhydrite. Besides, the restraint of anhydrate expansion in FBC ashes was studied and a way of their utilization as building materials was put forward.
The results are listed as follows: (1) XRD and chemical analysis results testified that the sulphates mineral solidified in FBC ashes is mainlyⅡ-anhydrite. (2) Micro-morphology and particle distribution of anhydrite in FBC ashes was studied through new methods of density-separation and sieving. The anhydrite in FBC ashes are concentrated in particles of FBC ashes with small size and high density. (3) SEM and EDS analysis results showed that the compacted and loose particles are co-existed both in FBC fly ashes and bed ashes. The protrudent crystals on the surface of compacted particles of FBC fly ashes are mainly anhydrite and some clay minerals while loose particles are mainly unburnt carbon; and for FBC bed ashes, the protrudent crystals on the surface of compacted particles are mainly anhydrite while the column crystals on the surface of loose particles are clay minerals as well as some absorbed anhydrite. (4) The results of reaction rate constant K and dissolution curve showed that the reactive activity and dissolution capability of anhydrite calcined at 850℃for 2h are similar to that of anhydrite solidified in FBC ashes. Anhydrite calcined at 850℃for 2h can be added to FBC ashes to investigate the influence on anhydrite properties of FBC ashes with different dosage. (5) The results of pH value and content of ettringite and chemical combined water indicated that anhydrite takes part in the hydration process and effects the hydration of FBC ashes as well as activation behavior and expansion properties. (6) Although the content of anhydrite had no effect on the degree of FBC ashes’activity, it obviously influenced the activation behavior of FBC ashes. When the content of anhydrite was at the range of 2~4% (SO3), the pozzolanic activity of FBC ashes was most effectively activated. While content of anhydrate was below this rage, the activating effect became worse, and if anhydrite was excessive, the delay-ettringite and dihydrate gypsum formed at later age would reduce the strength because of uncontrolled expansion. (7) A method aimed at eliminating disadvantage influence of anhydrite was proposed to evaluate activation of FBC ashes, namely the 28d compressive strength ratio of cement clinker mortar. This new method can value activity of available FBC ashes objectively, in which the content of SO3 and water content were respectively controlled by gypsum content and mortar fluidity. This method is adapted to FBC ashes with content of SO3 below 11.6%. The average content of SO3 in domestic FBC ashes is 7.8%, which meets the sulphur content demand mentioned above. (8) Anhydrite was the main factor that leads to expansion of FBC ashes during hydration. Additives can restrain the expansion through promoting the dissolution and hydration of anhydrite, such as CaCl2 and Na2O3. The linear expansion ratio of FBC ashes mortar can reduce by 19% after adding 1% of CaCl2 or Na2CO3.The results also showed that, FBC ashes can be used as additive for cement and concrete under restricted amount. (9) The expansion of anhydrite was eliminated by way of autoclave curing, which explored a new way for utilization of FBC ashes. The linear expansion ratio of FBC ashes pastes was below 5×10-4 after autoclave curing. There was tobermorite formed when FBC ashes pastes being autoclave cured, and no ettringite can be found.
引文
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