半焦孔隙结构和加压燃烧特性的试验研究
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摘要
不断发展的第二代增压流化床燃烧联合循环(PFBC-CC)发电技术是洁净煤技术(CCT)在理念上的更新和完善,是洁净煤技术发展的新阶段。实施煤热解、气化、燃烧的分级转化和综合利用,就是根据煤不同形态的特点,采用优化和集成的概念,达到既能使用常规的技术脱除煤利用过程中的污染物,又能实现其高效转化和清洁利用的目的。半焦加压燃烧是第二代PFBC-CC技术的重要组成部分。因此本课题直接选用了常压工业流化床和中试规模增压喷动流化床气化炉半焦,对原煤和半焦进行了孔隙结构和表面形态的测定和分析,对半焦的加压燃烧特性进行了系统地试验研究,并在中试规模热输入1MWt增压流化床燃烧室内进行了半焦燃烧的验证试验。
用氮气等温吸附(77K)法测量了原煤和加压、常压部分气化后半焦的BET比表面积,并通过BJH法计算了孔比表面积、比孔容、孔径和孔分布。结果表明,原煤在转化为半焦的过程中,孔隙结构变得发达,比表面积、孔比表面积和孔容积明显增大。实验发现半焦的孔比表面积和孔容积分布曲线存在两个明显的峰值,第一个尖峰对应的孔径稍小于2nm,表明微孔的比表面积大大增加;第二个尖峰对应的孔径在3.8nm左右,说明中孔的比表面积增加很快以至于出现了中孔的扩展。加压气化后的半焦孔隙结构更加发达,加压气化比常压气化更能促进半焦孔隙的生成和发展。
从气化条件、半焦颗粒粒径、半焦工业分析成分三方面定性分析了影响半焦孔隙结构的因素。常压喷动流化床气化中,挥发分析出和热解反应对半焦孔隙的发展和生成起到主导作用;加压气化过程中,碳的气化反应对半焦孔隙的生成和发展有明显的促进作用。在一定的气化工况下,煤焦可能存在一个合适的颗粒尺寸范围,使得挥发分的析出比较彻底,煤焦气化反应进行得比较充分,半焦颗粒的比表面积、孔比表面积和孔容积都能得到充分的发展。本实验中,对常压气化该合适的粒径范围是1mm～1.5mm,对加压气化为0.5mm～1mm。利用扫描电镜,得到了不同粒径原煤和半焦样品的表观结构图像,进一步证实了加压半焦比常压半焦有更为发达的孔隙结构。
在小型加压试验台上,分别对原煤和两种半焦进行了系统的燃烧特性试验研究;在大型增压流化床燃烧试验台上,进行了半焦加压燃烧的验证试验。研究结果表明:系统压力对煤和半焦的燃烧有不同的影响。随系统压力的增加,炉膛温度逐渐升高,燃烧效率也相应增大;在压力接近于0.5MPa左右时,压力增加,煤的燃烧效率增加减缓,但半焦的燃烧效率仍然增加显著。这一结果对第二代PFBC燃烧室内半焦的燃烧有指导意义。在较低的系统压力下,过量空气系数对半焦燃烧效率有较大的影响;在较高的系统压力下,压力对燃烧的影响占主导因素,过量空气系数的合适范围以不超过1.5为宜。压力下,初始静止床层高度对半焦的燃烧效率有较大影响。对喷动流化床,随静止床高的增加,燃烧效率呈先增大后减小的趋势,对一定的试验装置,存在一个合适的静止床层高度的范围。本文实验条件下,静止床层高度在280～320mm之间比较合适。床层温度受燃料给料量、过量空气系数、炉膛压力、静止床层高度、空气预热温度等工况参数的综合影响,进而影响半焦的燃烧效率。床层温度提高时,燃烧反应速度加快,颗粒燃烧较完全,有利于提高燃烧效率。在小型试验台上,当系统压力为0.5MPa时,半焦的燃烧效率达到94.73%,在大型试验台上,半焦的燃烧效率达到99.20%,充分证明了半焦加压燃烧的优越性。
The developing 2~(nd) generation Pressurized Fluidized Bed Combustion Combined Cycle (PFBC-CC) power generation technology features the state of the art among the current Clean Coal Technologies (CCT) in a new concept of challenging the traditional coal complete gasification. Recognizing the fact that wild gasification of coal in fluidized bed gasifiers hinders the further promotion of gasification efficiency, a new concept is proposed that the coal is gasified in a carbonator first and then is burnt in a higher efficient combustor of PFB that is an optical way to utilize the coals with complete utilization and friendly environmental effect. In a result, the re-combustion of gasified coal-chars play a very important role in the 2nd PFBC-CC technologies for pursuing higher overall power generation efficiency. For the purpose of evaluating the effects of coal-char combustion and studying the coal-char combustion characteristic and providing the data base of designing parameters for industrialized PFBC boiler, the gasified coal-chars from both an industrial atmospheric fluidized bed gasifier and a pilot scale pressurized spouted fluidized bed gasifier were collected for better understanding the superficial features of the coal-chars and its pore structures. The pressurized combustion characteristic of coal-chars was systematically conducted in a bench-scale pressurized fluidized bed combustor. The effects of operational conditions on coal-char combustion efficiency were also experimentally tested. Finally, the coal-chars were fed into a pilot scale of heat input 1 MWt pressurized fluidized bed combustor to verify its utility combustion effects.
The coal and coal-char samples from atmosphere and pressurized partial gasification were measured by nitrogen adsorption at 77K. Their specific surface areas were determined based on BET model. The average pore size, total pore volumes, pore specific surface areas and pore size distributions were statistically obtained by using BJH theory. The results showed that more abundant pores and larger specific areas and pore volumes were formed after partial gasification. Two peaks were found in distribution curves of the coal-char pore specific surface area and pore volume; the first peak corresponds to a pore diameter of a little less than 2 nm, the second of about 3.8 nm. Such a result implies quick increase of the specific surface areas of less than middle pores and forming a lot of larger than middle pores. It was concluded that gasification at elevated pressure could largely accelerate the pore formation and its further development comparing to gasification at atmospheric condition.
The influential factors on pore structure of coal-chars were discussed based on the analytical results such as operating condition, coal-char size and coal-char proximate analysis. In atmospheric gasification process, devolatilization of volatile matters and pyrolysis played a leading role to form the abundant pore structure of coal-chars. While in pressurized gasification process, it was the gasification reaction of char that played an additional and dominant positive impact on promoting formation and development of the coal-char pore structure. An assumption could be derived from the variation of coal-char sizes that there maybe exist an optimal coal-char size range that made abundant porosity and bigger pore specific areas to enhance the gasification reaction. In this study, the optimal range of particle size is about 1mm～1.5mm for atmospheric gasification and about 0.5mm～1mm for pressurized gasification. Moreover, applying the Scanning Electron Microscope (SEM) technique into viewing the microscopic surface configuration ofcoal-chars, it further confirmed that the pressurized gasified coal-chars have more developed pore structures than the atmospheric gasified coal-chars.
The systematical experiments on pressurized combustion characteristic were done in a bench scale test facility for two kinds of gasified coal-chars along with bituminous coal from which the coal-chars were produced. The same cola-chars were also tested in a pilot scale PFBC test rig to verify their utility combustion effect. The results showed that the system pressure and combustion temperature exerted different impacts on combustion of coal and coal-chars. Generally, the combustion temperature and efficiency increased with increasing of the system pressure. When pressure approached to 0.5MPa, the combustion efficiency of coal increased slowly but the combustion efficiency of coal-char continued going up which represented potential advantages of coal-char combustion for the 2nd generation pressurized fluidized bed combustion system because it is usually run at higher pressure much more than the experimental pressure. Under operational condition of low pressure, excess air coefficient affected the coal-char combustion efficiency more; however, under operational condition of a little higher pressure of the test case, the pressure turned to pay a dominant affection to the combustion efficiency. The optimal excess air coefficient was better less than 1.5 for most test runs. At elevated pressure, the combustion efficiency also varied greatly with changes of initial stationary height of bed material in the bench scale spouted fluidized bed. It increased first and then decreased with ever increasing of the initial stationary height, which showed that there existed an optimal height of 280～320mm in the operation condition of this paper. The combustion temperature was dependent on many run parameters such as coal feeding rate, excess air coefficient, system pressure, initial bed height, air temperature, and so on, which directly affected the combustion efficiency of coal-chars. Higher temperature made the coal-chars burnt completely as a result of speeding up the combustion reactions between air and coal-chars and thus benefited the combustion efficiency. At the system pressure of 0.5MPa, the coal-char combustion efficiency reached 94.73% in the bench scale pressurized spouted fluidized bed test facility and 99.20% in the pilot scale 1 MWt PFBC test rig, which indicated the advantage of coal-char combustion at elevated pressure.
用氮气等温吸附(77K)法测量了原煤和加压、常压部分气化后半焦的BET比表面积,并通过BJH法计算了孔比表面积、比孔容、孔径和孔分布。结果表明,原煤在转化为半焦的过程中,孔隙结构变得发达,比表面积、孔比表面积和孔容积明显增大。实验发现半焦的孔比表面积和孔容积分布曲线存在两个明显的峰值,第一个尖峰对应的孔径稍小于2nm,表明微孔的比表面积大大增加;第二个尖峰对应的孔径在3.8nm左右,说明中孔的比表面积增加很快以至于出现了中孔的扩展。加压气化后的半焦孔隙结构更加发达,加压气化比常压气化更能促进半焦孔隙的生成和发展。
从气化条件、半焦颗粒粒径、半焦工业分析成分三方面定性分析了影响半焦孔隙结构的因素。常压喷动流化床气化中,挥发分析出和热解反应对半焦孔隙的发展和生成起到主导作用;加压气化过程中,碳的气化反应对半焦孔隙的生成和发展有明显的促进作用。在一定的气化工况下,煤焦可能存在一个合适的颗粒尺寸范围,使得挥发分的析出比较彻底,煤焦气化反应进行得比较充分,半焦颗粒的比表面积、孔比表面积和孔容积都能得到充分的发展。本实验中,对常压气化该合适的粒径范围是1mm～1.5mm,对加压气化为0.5mm～1mm。利用扫描电镜,得到了不同粒径原煤和半焦样品的表观结构图像,进一步证实了加压半焦比常压半焦有更为发达的孔隙结构。
在小型加压试验台上,分别对原煤和两种半焦进行了系统的燃烧特性试验研究;在大型增压流化床燃烧试验台上,进行了半焦加压燃烧的验证试验。研究结果表明:系统压力对煤和半焦的燃烧有不同的影响。随系统压力的增加,炉膛温度逐渐升高,燃烧效率也相应增大;在压力接近于0.5MPa左右时,压力增加,煤的燃烧效率增加减缓,但半焦的燃烧效率仍然增加显著。这一结果对第二代PFBC燃烧室内半焦的燃烧有指导意义。在较低的系统压力下,过量空气系数对半焦燃烧效率有较大的影响;在较高的系统压力下,压力对燃烧的影响占主导因素,过量空气系数的合适范围以不超过1.5为宜。压力下,初始静止床层高度对半焦的燃烧效率有较大影响。对喷动流化床,随静止床高的增加,燃烧效率呈先增大后减小的趋势,对一定的试验装置,存在一个合适的静止床层高度的范围。本文实验条件下,静止床层高度在280～320mm之间比较合适。床层温度受燃料给料量、过量空气系数、炉膛压力、静止床层高度、空气预热温度等工况参数的综合影响,进而影响半焦的燃烧效率。床层温度提高时,燃烧反应速度加快,颗粒燃烧较完全,有利于提高燃烧效率。在小型试验台上,当系统压力为0.5MPa时,半焦的燃烧效率达到94.73%,在大型试验台上,半焦的燃烧效率达到99.20%,充分证明了半焦加压燃烧的优越性。
The developing 2~(nd) generation Pressurized Fluidized Bed Combustion Combined Cycle (PFBC-CC) power generation technology features the state of the art among the current Clean Coal Technologies (CCT) in a new concept of challenging the traditional coal complete gasification. Recognizing the fact that wild gasification of coal in fluidized bed gasifiers hinders the further promotion of gasification efficiency, a new concept is proposed that the coal is gasified in a carbonator first and then is burnt in a higher efficient combustor of PFB that is an optical way to utilize the coals with complete utilization and friendly environmental effect. In a result, the re-combustion of gasified coal-chars play a very important role in the 2nd PFBC-CC technologies for pursuing higher overall power generation efficiency. For the purpose of evaluating the effects of coal-char combustion and studying the coal-char combustion characteristic and providing the data base of designing parameters for industrialized PFBC boiler, the gasified coal-chars from both an industrial atmospheric fluidized bed gasifier and a pilot scale pressurized spouted fluidized bed gasifier were collected for better understanding the superficial features of the coal-chars and its pore structures. The pressurized combustion characteristic of coal-chars was systematically conducted in a bench-scale pressurized fluidized bed combustor. The effects of operational conditions on coal-char combustion efficiency were also experimentally tested. Finally, the coal-chars were fed into a pilot scale of heat input 1 MWt pressurized fluidized bed combustor to verify its utility combustion effects.
The coal and coal-char samples from atmosphere and pressurized partial gasification were measured by nitrogen adsorption at 77K. Their specific surface areas were determined based on BET model. The average pore size, total pore volumes, pore specific surface areas and pore size distributions were statistically obtained by using BJH theory. The results showed that more abundant pores and larger specific areas and pore volumes were formed after partial gasification. Two peaks were found in distribution curves of the coal-char pore specific surface area and pore volume; the first peak corresponds to a pore diameter of a little less than 2 nm, the second of about 3.8 nm. Such a result implies quick increase of the specific surface areas of less than middle pores and forming a lot of larger than middle pores. It was concluded that gasification at elevated pressure could largely accelerate the pore formation and its further development comparing to gasification at atmospheric condition.
The influential factors on pore structure of coal-chars were discussed based on the analytical results such as operating condition, coal-char size and coal-char proximate analysis. In atmospheric gasification process, devolatilization of volatile matters and pyrolysis played a leading role to form the abundant pore structure of coal-chars. While in pressurized gasification process, it was the gasification reaction of char that played an additional and dominant positive impact on promoting formation and development of the coal-char pore structure. An assumption could be derived from the variation of coal-char sizes that there maybe exist an optimal coal-char size range that made abundant porosity and bigger pore specific areas to enhance the gasification reaction. In this study, the optimal range of particle size is about 1mm～1.5mm for atmospheric gasification and about 0.5mm～1mm for pressurized gasification. Moreover, applying the Scanning Electron Microscope (SEM) technique into viewing the microscopic surface configuration ofcoal-chars, it further confirmed that the pressurized gasified coal-chars have more developed pore structures than the atmospheric gasified coal-chars.
The systematical experiments on pressurized combustion characteristic were done in a bench scale test facility for two kinds of gasified coal-chars along with bituminous coal from which the coal-chars were produced. The same cola-chars were also tested in a pilot scale PFBC test rig to verify their utility combustion effect. The results showed that the system pressure and combustion temperature exerted different impacts on combustion of coal and coal-chars. Generally, the combustion temperature and efficiency increased with increasing of the system pressure. When pressure approached to 0.5MPa, the combustion efficiency of coal increased slowly but the combustion efficiency of coal-char continued going up which represented potential advantages of coal-char combustion for the 2nd generation pressurized fluidized bed combustion system because it is usually run at higher pressure much more than the experimental pressure. Under operational condition of low pressure, excess air coefficient affected the coal-char combustion efficiency more; however, under operational condition of a little higher pressure of the test case, the pressure turned to pay a dominant affection to the combustion efficiency. The optimal excess air coefficient was better less than 1.5 for most test runs. At elevated pressure, the combustion efficiency also varied greatly with changes of initial stationary height of bed material in the bench scale spouted fluidized bed. It increased first and then decreased with ever increasing of the initial stationary height, which showed that there existed an optimal height of 280～320mm in the operation condition of this paper. The combustion temperature was dependent on many run parameters such as coal feeding rate, excess air coefficient, system pressure, initial bed height, air temperature, and so on, which directly affected the combustion efficiency of coal-chars. Higher temperature made the coal-chars burnt completely as a result of speeding up the combustion reactions between air and coal-chars and thus benefited the combustion efficiency. At the system pressure of 0.5MPa, the coal-char combustion efficiency reached 94.73% in the bench scale pressurized spouted fluidized bed test facility and 99.20% in the pilot scale 1 MWt PFBC test rig, which indicated the advantage of coal-char combustion at elevated pressure.
引文
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