加压流化床气化条件下煤灰熔融特性的实验研究
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摘要
煤炭在我国一次能源的生产和消费结构中一直占主导地位,随着能源消费的持续增长,环境问题的逐渐显现,煤炭的清洁利用越来越受人们的关注。煤炭气化是发展煤炭洁净转化的主要技术之一,其中压力流化床煤炭气化以其煤种适应性强,污染物排放低等特点成为煤炭气化技术的一个重要发展方向。
煤灰熔融特性是动力用煤和气化用煤的一项重要的质量指标,直接决定着煤炭燃烧气化过程排渣方式的选择,是影响煤炭燃烧和气化运行的一个重要因素。本课题拟针对压力下煤灰的熔融特性和烧结特性开展一系列实验和理论研究,希望为煤炭气化系统设计和运行提供一定的帮助。
首先,归纳分析了不同气氛下煤灰碱金属化合物对煤灰熔融特性的影响实验结果,发现不同气氛、不同煤灰化学成分对煤灰的熔融性的影响不同,煤灰熔融温度不仅与Fe_2O_3和CaO总含量有关,而且与其CaO/Fe_2O_3摩尔比也有关。
其次,利用压力热天平分析仪和X射线衍射分析仪,对不同压力、不同气氛煤灰矿物质的转变情况进行实验研究,研究表明压力会影响煤灰矿物质化学反应平衡,压力抑制方解石、硫酸钙和钾云母的分解,促进石英的相变,以及莫来石、钙长石和铁尖晶石等矿物质的生成,对煤灰熔融特性影响复杂。
然后,利用搭建的压差法实验台,对课题目标煤进行了烧结特性的实验研究,分析了主要煤灰化学成分对煤灰烧结特性的影响规律,以及气氛条件对煤灰烧结特性的影响规律,结果显示,煤灰中的CaO、Na_2O成分降低了煤灰烧结温度,与氧化性气氛相比,还原性气氛降低了煤灰烧结温度,其降低程度与煤灰中Fe_2O_3含量有关。
最后,利用热力学计算软件对不同压力、不同气氛下煤灰矿物质反应过程进行模拟计算,分析了各种工况下,煤灰各矿物质生成情况,从理论上对各种气化条件下煤灰矿物质反应情况进行研究。计算表明,随着加热过程的进行,煤灰逐渐由低温矿物质转变为高温矿物质;压力条件能够抑制硫酸钙的分解反应,促进莫来石、钙长石和堇青石的生成以及石英的相变;还原性气氛主要通过和煤灰中的含铁化合物反应来改变煤灰的矿物质组分,进而影响煤灰的熔融特性。
Coal is the dominant energy in the energy production and consumption structure of our country. With continued growth in energy consumption, environmental issues appear gradually, and the clean use of coal is concerned by increasing people. Coal gasification is the development of clean coal technologies, and pressurized fluidized bed coal gasification with its coal adaptability, and low emissions is to be an important development direction.
The fusibility of coal ash is an important characteristic in pulverized coal combustion and coal gasification, which determines how to utilize coal resources in coal combustion or gasification. But there are some operation problems such as bed fusion, bed agglomeration and deposition in fluidized gasification technology, the paper mainly did experimental and theoretical research on coal ash fusibility which is important to solving these problems.
Firstly, analyzed the influences of coal ash characteristics and atmosphere on coal ash fusibility, the results shows the fusion temperature is not only concerned with the sum of CaO and Fe_2O_3, but also with the ratio of CaO and Fe_2O_3;
Secondly, experiments on the pressure thermal-balance apparatus and XRD, analyzed the influences of pressure and atmosphere on the mineral transformation in the coal. The results shows that the pressure will influence the balance of ash mineral chemical reactions suppress calcite, sulfuric acid Calcium and potassium mica decomposition and promote the transformation of quartz and mullite, calcium and iron spinel. The impact of pressure on the fusibility of coal ashes is complex.
Then, analyzed the sintering temperature of coal ashes which is adding additives alter the proportion of alkaline oxides under different atmospheres. The results show the sintering temperature under coal gasification condition is lower than that under oxidizing atmosphere. And with the increase of Fe_2O_3, CaO, Na_2O content, the sintering temperature decreases.
At last, we used the calculation software-FACTSage to simulate the influences of pressure and atmosphere on the mineral transformation in the coal ashes. Calculation shows that, with the heating process, the low-temperature minerals gradually transformed into high-temperature minerals; pressure suppress calcium sulfate decomposition and promote the transformation of mullite, anorthite, and cordierite. Reducing atmosphere, mainly through reacting with iron compounds, change the ash mineral components, thereby affecting the fusibility of coal ashes.
煤灰熔融特性是动力用煤和气化用煤的一项重要的质量指标,直接决定着煤炭燃烧气化过程排渣方式的选择,是影响煤炭燃烧和气化运行的一个重要因素。本课题拟针对压力下煤灰的熔融特性和烧结特性开展一系列实验和理论研究,希望为煤炭气化系统设计和运行提供一定的帮助。
首先,归纳分析了不同气氛下煤灰碱金属化合物对煤灰熔融特性的影响实验结果,发现不同气氛、不同煤灰化学成分对煤灰的熔融性的影响不同,煤灰熔融温度不仅与Fe_2O_3和CaO总含量有关,而且与其CaO/Fe_2O_3摩尔比也有关。
其次,利用压力热天平分析仪和X射线衍射分析仪,对不同压力、不同气氛煤灰矿物质的转变情况进行实验研究,研究表明压力会影响煤灰矿物质化学反应平衡,压力抑制方解石、硫酸钙和钾云母的分解,促进石英的相变,以及莫来石、钙长石和铁尖晶石等矿物质的生成,对煤灰熔融特性影响复杂。
然后,利用搭建的压差法实验台,对课题目标煤进行了烧结特性的实验研究,分析了主要煤灰化学成分对煤灰烧结特性的影响规律,以及气氛条件对煤灰烧结特性的影响规律,结果显示,煤灰中的CaO、Na_2O成分降低了煤灰烧结温度,与氧化性气氛相比,还原性气氛降低了煤灰烧结温度,其降低程度与煤灰中Fe_2O_3含量有关。
最后,利用热力学计算软件对不同压力、不同气氛下煤灰矿物质反应过程进行模拟计算,分析了各种工况下,煤灰各矿物质生成情况,从理论上对各种气化条件下煤灰矿物质反应情况进行研究。计算表明,随着加热过程的进行,煤灰逐渐由低温矿物质转变为高温矿物质;压力条件能够抑制硫酸钙的分解反应,促进莫来石、钙长石和堇青石的生成以及石英的相变;还原性气氛主要通过和煤灰中的含铁化合物反应来改变煤灰的矿物质组分,进而影响煤灰的熔融特性。
Coal is the dominant energy in the energy production and consumption structure of our country. With continued growth in energy consumption, environmental issues appear gradually, and the clean use of coal is concerned by increasing people. Coal gasification is the development of clean coal technologies, and pressurized fluidized bed coal gasification with its coal adaptability, and low emissions is to be an important development direction.
The fusibility of coal ash is an important characteristic in pulverized coal combustion and coal gasification, which determines how to utilize coal resources in coal combustion or gasification. But there are some operation problems such as bed fusion, bed agglomeration and deposition in fluidized gasification technology, the paper mainly did experimental and theoretical research on coal ash fusibility which is important to solving these problems.
Firstly, analyzed the influences of coal ash characteristics and atmosphere on coal ash fusibility, the results shows the fusion temperature is not only concerned with the sum of CaO and Fe_2O_3, but also with the ratio of CaO and Fe_2O_3;
Secondly, experiments on the pressure thermal-balance apparatus and XRD, analyzed the influences of pressure and atmosphere on the mineral transformation in the coal. The results shows that the pressure will influence the balance of ash mineral chemical reactions suppress calcite, sulfuric acid Calcium and potassium mica decomposition and promote the transformation of quartz and mullite, calcium and iron spinel. The impact of pressure on the fusibility of coal ashes is complex.
Then, analyzed the sintering temperature of coal ashes which is adding additives alter the proportion of alkaline oxides under different atmospheres. The results show the sintering temperature under coal gasification condition is lower than that under oxidizing atmosphere. And with the increase of Fe_2O_3, CaO, Na_2O content, the sintering temperature decreases.
At last, we used the calculation software-FACTSage to simulate the influences of pressure and atmosphere on the mineral transformation in the coal ashes. Calculation shows that, with the heating process, the low-temperature minerals gradually transformed into high-temperature minerals; pressure suppress calcium sulfate decomposition and promote the transformation of mullite, anorthite, and cordierite. Reducing atmosphere, mainly through reacting with iron compounds, change the ash mineral components, thereby affecting the fusibility of coal ashes.
引文
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[1]A.Y.Al-Otoom,L.K.Elliott,T.F.Wall,et al.Measruement of the Sintering Kinetics of Coal Ash.Energy&Fuels,2000,(14):994-995
[2]孙亦禄.煤灰中矿物杂质对锅炉的危害.北京:水利电力出版社,1994.
[3]D.Mason.Fuel process Technol,1992,30:215-226
[4]B.Skrifvars,et al.Energy& Fuel,1997,(11):843-848
[5]王泉清.曾蒲君.煤灰熔融性研究现状与分析.煤炭转化,1997,20(2):32
[6]K.K.Vassilev S V.Influence of mineral and chemical composition of coal ashes on their fusibility.Fuel Processing Technology,1995,4(5):27
[7]陈兖.刘新兵.煤灰熔融性的研究.煤化工,1995,(2):48-52
[8]姚星一,王文森.煤灰熔点与化学成分的关系.燃料化学学报,1965,6(2):151
[9]R.P.Winegartner E C,1975,97(3):395-401.
[10]G.V.Fuel,1987,66(9):1230-1239
[11]二宫善彦.平户端惠.煤炭熔融特性的基础研究.燃料协会志,1988,68(5):393-401
[12]刘桂建,王俊新.煤中矿物质及其燃烧后的变化分析.煤炭转化,2004,27(3):68
[13]李梅,张洪,孙明.高岭石对煤炭燃烧特性影响的研究.煤炭转化,2004,27(3):68
[14]王泉海,邱建荣.煤粉燃烧过程中铁矿物质迁移特征的研究进展.燃烧科技与技术,2002,6(8):567
[15]川井隆夫,柴田次进.水曜会志,1985,30(5):325
[16]H.Kahraman,Reifenstein.Mineralogical changes in selected Australian and overseas coals in boiler simulation test and improved ash fusion test.18th Annual International Pittsburgh Coal Conference,2001,70(6):746-762
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