生物质流化床燃烧粘结特性及控制研究
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摘要
生物质含有高含量的碱金属元素和营养元素。在流化床中的燃烧过程中,大部分的碱金属元素会固留在生物质灰中。生物质灰中的碱金属元素容易与床料中富含的SiO2发生反应生成低熔点的物质,低熔点物质的生成使流化床床层发生粘结现象。粘结发生时,床内流态化会被破坏,随着粘结块的进一步形成与增加,可能引起整个流化床的流态化停滞,导致锅炉被迫停炉,从而造成严重的经济损失。本论文围绕生物质流态化燃烧粘结现象展开深入的研究,期望发现解决这一瓶颈的科学依据,研究生物质灰与典型床料(石英、河砂)发生粘结的反应机理,建立流化床颗粒粘结数学模型,寻求预测生物质流化床粘结发生的方法,探索抑制生物质流化床内燃烧粘结的新技术,为流化床燃烧技术在生物质燃料直接燃烧领域的应用奠定理论基础。
探索利用热重差示扫描量热分析法(TG/DSC)研究麦秆灰以及麦秆灰与石英混合物的高温熔融特性。通过引入模型化合物分析得出：麦秆灰以及麦秆灰与石英混合物在620～700℃的温度范围内存在KCl和CaCl2混合物的共熔反应,熔融的KC;和CaCl2在800℃～900℃的温度区间开始转移到气相中。在空气气氛中,麦秆灰中的K2CO3与SiO2发生化学反应,生成硅酸钾,在901℃～1039℃的温度区间麦秆灰中的硅酸钾发生熔融。麦秆灰与石英混合物相对于单独的麦秆灰,KCl和CaCl2的熔融峰的温度区间无明显区别,而硅酸盐的初始熔融温度明显降低。硅酸钾发生了熔融是麦秆灰与石英混合物出现粘结现象的主要原因。
利用热重差示扫描量热分析法、偏光显微镜、扫描电镜-能谱分析技术和多相平衡计算等多种分析手段研究麦秆灰和河砂混合物的高温粘结机理得出：麦秆灰与河砂的混合物在850℃出现轻微的粘结,900℃时粘结明显,粘结物主要成分为硅酸盐,其主要成份为K20-SiO2-Na2O-Al2O3-CaOo粘结物中钾元素和钙元素的聚集是造成粘结的重要原因。麦秆灰与河砂混合物的粘结现象,不能归结为麦秆灰的熔融使得河砂颗粒粘结在一起,而是化学反应和熔融行为综合作用的结果。高温下麦秆灰与河砂发生反应产生低熔点的硅酸盐是造成麦杆灰与河砂混合物粘结的直接原因。
以生物质流化床内燃烧粘结发生的力平衡模型为基础,建立了描述生物质流化床内燃烧流化失败过程的数学模型,并利用FactS age多相平衡模型计算床层温度下生物质灰和床料混合物中液态相的比例和成分,结合Urbain的硅酸盐粘度计算模型,得到生物质流化床燃烧粘结失流过程的数学模型。从粘结力和破坏力的物理意义出发,得到粘结力和破坏力随着运行时间、床层温度、床料粒径、生物质灰以及床料成分的变化规律。利用力学平衡模型最终得到失流时间关于床层温度、床料粒径、生物质灰以及床料成分的函数表达式。结果表明：模型计算结果与实验结果具有较好的一致性。
应用FactSage软件中Equilib模块计算在一定温度范围内生物质灰和不同床料多相平衡时物相变化、液态相质量分数和液态相成分,并应用偏光显微镜-能谱分析实验对计算结果进行验证,建立以多相平衡计算模型为基础,偏光显微镜-能谱分析实验为验证的系统预测方法,预测不同床料下生物质流化床燃烧粘结趋势。多相平衡计算模型计算结果表明：相对于河砂,粘土、高岭土、石煤灰都能够有效的抑制生物质流化床燃烧粘结现象。应用多相平衡计算模型计算得到了麦秆灰和不同床料多相平衡时液态相成分和比例,计算结果与偏光显微镜-能谱分析结果基本一致。
在5kW鼓泡床实验装置上进行了不同床料下麦秆燃烧粘结特性实验。结果表明：相对于石英,高岭土、流化床燃煤炉渣、煤矸石灰渣、高炉渣都能有效的抑制生物质流化床燃烧粘结现象的发生。流化床燃煤炉渣和煤矸石灰渣作为床料,能够明显抑制生物质流化床内的燃烧粘结现象。高含量的铝元素、较高含量的硫元素、高含量的碱土金属元素和较低含量的碱金属元素有利于粘结物的熔点的提高,进而阻止了床层大面积的粘结。
High content of potassium in biomass ash leads to agglomeration in the fluidized bed during combustion, which eventually propagates to partial or total defluidization of the reactor, and then subsequently unscheduled shut down of the boiler. In this thesis, intensive research on the agglomeration phenomenon is conducted with the expectation to find out the scientific basis to solve such problem. The reaction mechanism of agglomeration caused by biomass ash and typical bed materials is analyzed. A mathematical model is established to describe the agglomeration process in bio-fuel fired fluidized bed combustor. A method forecasting the agglomeration is proposed to explore new technology of counteracting agglomeration in bio-fuel fluidized bed.
Melting behavior of wheat stalk ash and its mixture with quartz at high temperature was investigated with thermogravimetric analysis (TG) and differential scanning calorimetry (DSC). Model compounds were introduced for analysis, finding that there is eutectic reaction between KC1and CaCl2in wheat stalk ash and its mixture with quartz at the temperature from620℃to700℃. The molten KCl and CaCl2transfer to gas phase when the temperature ranges from800℃to900℃. At the air atmosphere, K2CO3in wheat stalk ash can react with SiO2, forming potassium silicate, the part of which in the wheat stalk melts at the temperature from901℃to1039℃. Compared with the wheat stalk ash, there is no obvious difference for the range of melting temperatures of CaCl2and KCl in the mixture of wheat stalk ash and quartz, but the initial melt temperature of silicate decreases markedly. The Melting of potassium silicate is the main reason for the agglomeration of the mixture of wheat straw ash and quartz.
Melting behavior of wheat stalk ash and its mixture with quartz at high temperature was investigated with TG/DSC, polarized light microscopy, scanning electron microscopy and energy dispersive X-ray (SEM-EDX)and Multi-phase equilibrium calculation. No agglomeration is detected below850℃. At the temperature ranging from900℃tolOOO℃, however, obvious agglomeration is observed and the agglomerates solidify further as the temperature increases. The presence of potassium and calcium causes a sticky sand surface that induces agglomeration. The main components of the agglomerate surface are K2O-SiO2-Na2O-Al2O3-CaO. The agglomeration is not caused by the melting behavior of wheat stalk ash itself but due to the comprehensive results of chemical reaction and the melting behavior at high temperatures. The formation of molten silicates will directly lead to the agglomeration of the mixture of wheat straw ash and river sands.
Based on the balance mechanism of the adhesive force caused by liquid bonding between two particles and the breaking force induced by bubbles in the fluidized bed, a mathematical model is established to describe the agglomeration process in bio-fuel fired fluidized bed combustor, which considers the modified Urbain model and chemical equilibrium calculation using FactSage modeling. This model accounts for the evolvement of the adhesive and breaking forces, and clearly demonstrates that the different compositions of ash, the increasing matter of liquid phase and the fluidization velocity cause defluidization in fluidized bed. In this model, it is hypothesized that the bonding stress between two particles is proportional to the mass fraction of liquid phase and inversely proportional to the diameter of particles. Viscosity of liquid phase is put forward for the first time. The defluidization time calculated by this model shows good agreement with that from the experimental data.
Multiphase equilibrium calculation is performed by the FactSage to identify the melting behavior of biomass ash blended with different bed materials. The proportion and the composition of liquid phase and solid phase at different temperatures were predicted by the Equilib module of the FactSage. The calculation results are verified by polarized light microscopyand energy dispersive X-ray. A prediction method based on multiphase equilibrium calculation is set up and tested by polarized light microscopyand energy dispersive X-ray experiments. The calculation results of multiphase equilibrium show that compared with river sands, the bed materials, the clay, kaolin and stone coal ash can counteract agglomeration, which is consistent with the experimental results.
The characteristics of bed agglomeration during combustion of wheat stalk pellet in a bench scale bubbling fluidized bed with four kinds of bed materials are investigated with the data from scanning electron microscopy(SEM) and energy dispersive X-ray(EDX) and multiphase equilibrium calculation. The bed materials include kaolin, coal gangue ash, fluidized bed coal slag and blast furnace slag. The results indicate that compared with the commonly used silica sands, all of the four kinds of bed materials can reduce the agglomeration of biomass ash. Especially, coal gangue ash and fluidized bed coal slag can effectively counteract the agglomeration. The high content of aluminum, sulfur and alkaline, and low content of alkali are conducive to improve the melting point of coating layer covered by the surface of the bed material pellets to prevent them from growing. Therefore, further bed agglomeration and defluisization can be prevented.
探索利用热重差示扫描量热分析法(TG/DSC)研究麦秆灰以及麦秆灰与石英混合物的高温熔融特性。通过引入模型化合物分析得出：麦秆灰以及麦秆灰与石英混合物在620～700℃的温度范围内存在KCl和CaCl2混合物的共熔反应,熔融的KC;和CaCl2在800℃～900℃的温度区间开始转移到气相中。在空气气氛中,麦秆灰中的K2CO3与SiO2发生化学反应,生成硅酸钾,在901℃～1039℃的温度区间麦秆灰中的硅酸钾发生熔融。麦秆灰与石英混合物相对于单独的麦秆灰,KCl和CaCl2的熔融峰的温度区间无明显区别,而硅酸盐的初始熔融温度明显降低。硅酸钾发生了熔融是麦秆灰与石英混合物出现粘结现象的主要原因。
利用热重差示扫描量热分析法、偏光显微镜、扫描电镜-能谱分析技术和多相平衡计算等多种分析手段研究麦秆灰和河砂混合物的高温粘结机理得出：麦秆灰与河砂的混合物在850℃出现轻微的粘结,900℃时粘结明显,粘结物主要成分为硅酸盐,其主要成份为K20-SiO2-Na2O-Al2O3-CaOo粘结物中钾元素和钙元素的聚集是造成粘结的重要原因。麦秆灰与河砂混合物的粘结现象,不能归结为麦秆灰的熔融使得河砂颗粒粘结在一起,而是化学反应和熔融行为综合作用的结果。高温下麦秆灰与河砂发生反应产生低熔点的硅酸盐是造成麦杆灰与河砂混合物粘结的直接原因。
以生物质流化床内燃烧粘结发生的力平衡模型为基础,建立了描述生物质流化床内燃烧流化失败过程的数学模型,并利用FactS age多相平衡模型计算床层温度下生物质灰和床料混合物中液态相的比例和成分,结合Urbain的硅酸盐粘度计算模型,得到生物质流化床燃烧粘结失流过程的数学模型。从粘结力和破坏力的物理意义出发,得到粘结力和破坏力随着运行时间、床层温度、床料粒径、生物质灰以及床料成分的变化规律。利用力学平衡模型最终得到失流时间关于床层温度、床料粒径、生物质灰以及床料成分的函数表达式。结果表明：模型计算结果与实验结果具有较好的一致性。
应用FactSage软件中Equilib模块计算在一定温度范围内生物质灰和不同床料多相平衡时物相变化、液态相质量分数和液态相成分,并应用偏光显微镜-能谱分析实验对计算结果进行验证,建立以多相平衡计算模型为基础,偏光显微镜-能谱分析实验为验证的系统预测方法,预测不同床料下生物质流化床燃烧粘结趋势。多相平衡计算模型计算结果表明：相对于河砂,粘土、高岭土、石煤灰都能够有效的抑制生物质流化床燃烧粘结现象。应用多相平衡计算模型计算得到了麦秆灰和不同床料多相平衡时液态相成分和比例,计算结果与偏光显微镜-能谱分析结果基本一致。
在5kW鼓泡床实验装置上进行了不同床料下麦秆燃烧粘结特性实验。结果表明：相对于石英,高岭土、流化床燃煤炉渣、煤矸石灰渣、高炉渣都能有效的抑制生物质流化床燃烧粘结现象的发生。流化床燃煤炉渣和煤矸石灰渣作为床料,能够明显抑制生物质流化床内的燃烧粘结现象。高含量的铝元素、较高含量的硫元素、高含量的碱土金属元素和较低含量的碱金属元素有利于粘结物的熔点的提高,进而阻止了床层大面积的粘结。
High content of potassium in biomass ash leads to agglomeration in the fluidized bed during combustion, which eventually propagates to partial or total defluidization of the reactor, and then subsequently unscheduled shut down of the boiler. In this thesis, intensive research on the agglomeration phenomenon is conducted with the expectation to find out the scientific basis to solve such problem. The reaction mechanism of agglomeration caused by biomass ash and typical bed materials is analyzed. A mathematical model is established to describe the agglomeration process in bio-fuel fired fluidized bed combustor. A method forecasting the agglomeration is proposed to explore new technology of counteracting agglomeration in bio-fuel fluidized bed.
Melting behavior of wheat stalk ash and its mixture with quartz at high temperature was investigated with thermogravimetric analysis (TG) and differential scanning calorimetry (DSC). Model compounds were introduced for analysis, finding that there is eutectic reaction between KC1and CaCl2in wheat stalk ash and its mixture with quartz at the temperature from620℃to700℃. The molten KCl and CaCl2transfer to gas phase when the temperature ranges from800℃to900℃. At the air atmosphere, K2CO3in wheat stalk ash can react with SiO2, forming potassium silicate, the part of which in the wheat stalk melts at the temperature from901℃to1039℃. Compared with the wheat stalk ash, there is no obvious difference for the range of melting temperatures of CaCl2and KCl in the mixture of wheat stalk ash and quartz, but the initial melt temperature of silicate decreases markedly. The Melting of potassium silicate is the main reason for the agglomeration of the mixture of wheat straw ash and quartz.
Melting behavior of wheat stalk ash and its mixture with quartz at high temperature was investigated with TG/DSC, polarized light microscopy, scanning electron microscopy and energy dispersive X-ray (SEM-EDX)and Multi-phase equilibrium calculation. No agglomeration is detected below850℃. At the temperature ranging from900℃tolOOO℃, however, obvious agglomeration is observed and the agglomerates solidify further as the temperature increases. The presence of potassium and calcium causes a sticky sand surface that induces agglomeration. The main components of the agglomerate surface are K2O-SiO2-Na2O-Al2O3-CaO. The agglomeration is not caused by the melting behavior of wheat stalk ash itself but due to the comprehensive results of chemical reaction and the melting behavior at high temperatures. The formation of molten silicates will directly lead to the agglomeration of the mixture of wheat straw ash and river sands.
Based on the balance mechanism of the adhesive force caused by liquid bonding between two particles and the breaking force induced by bubbles in the fluidized bed, a mathematical model is established to describe the agglomeration process in bio-fuel fired fluidized bed combustor, which considers the modified Urbain model and chemical equilibrium calculation using FactSage modeling. This model accounts for the evolvement of the adhesive and breaking forces, and clearly demonstrates that the different compositions of ash, the increasing matter of liquid phase and the fluidization velocity cause defluidization in fluidized bed. In this model, it is hypothesized that the bonding stress between two particles is proportional to the mass fraction of liquid phase and inversely proportional to the diameter of particles. Viscosity of liquid phase is put forward for the first time. The defluidization time calculated by this model shows good agreement with that from the experimental data.
Multiphase equilibrium calculation is performed by the FactSage to identify the melting behavior of biomass ash blended with different bed materials. The proportion and the composition of liquid phase and solid phase at different temperatures were predicted by the Equilib module of the FactSage. The calculation results are verified by polarized light microscopyand energy dispersive X-ray. A prediction method based on multiphase equilibrium calculation is set up and tested by polarized light microscopyand energy dispersive X-ray experiments. The calculation results of multiphase equilibrium show that compared with river sands, the bed materials, the clay, kaolin and stone coal ash can counteract agglomeration, which is consistent with the experimental results.
The characteristics of bed agglomeration during combustion of wheat stalk pellet in a bench scale bubbling fluidized bed with four kinds of bed materials are investigated with the data from scanning electron microscopy(SEM) and energy dispersive X-ray(EDX) and multiphase equilibrium calculation. The bed materials include kaolin, coal gangue ash, fluidized bed coal slag and blast furnace slag. The results indicate that compared with the commonly used silica sands, all of the four kinds of bed materials can reduce the agglomeration of biomass ash. Especially, coal gangue ash and fluidized bed coal slag can effectively counteract the agglomeration. The high content of aluminum, sulfur and alkaline, and low content of alkali are conducive to improve the melting point of coating layer covered by the surface of the bed material pellets to prevent them from growing. Therefore, further bed agglomeration and defluisization can be prevented.
引文
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