To get deep understanding of the reaction mechanism of coal pyrolysis in hydrogen plasma, the decomposition reaction pathways of aliphatic hydrocarbons and cycloalkanes, which are two main components in volatiles from...To get deep understanding of the reaction mechanism of coal pyrolysis in hydrogen plasma, the decomposition reaction pathways of aliphatic hydrocarbons and cycloalkanes, which are two main components in volatiles from coal, were investigated. Methane and cyclohexane were chosen as the model compounds. Density functional theory was employed, and many reaction pathways were involved. Calculations were carried out in Gaussian 09 at the B3LYP/6-31G（d,p） level of the theory. The results indicate that the main pyrolysis products of methane and cyclohexane in hydrogen plasma are both hydrogen and acetylene, and the participation of active hydrogen atoms makes dehydrogenation reactions more favorable. H2 mainly comes from dehydrogenation process, while many reaction pathways are responsible for acetylene formation. During coal pyrolysis in hydrogen plasma, three main components in volatiles like aliphatic hydrocarbons, cycloalkanes and aromatic hydrocarbons lead to the formation of hydrogen and acetylene, but their contributions to products distribution are different.展开更多
Coal pyrolysis is a fundamental reaction in the thermal processing and utilization of coal.Investigating the behavior and kinetics of coal pyrolysis is crucial for optimizing,designing,and developing a composite riser...Coal pyrolysis is a fundamental reaction in the thermal processing and utilization of coal.Investigating the behavior and kinetics of coal pyrolysis is crucial for optimizing,designing,and developing a composite riser for the staged pyrolysis gasification process of pulverized coal.In this study,the non-isothermal pyrolysis behavior and kinetics of coal were examined at different heating rates(30,50,100,300,500,700,and 900℃/min)using thermogravimetry(TG)coupled with Fourier-transform infrared spectroscopy.Analysis of the TG/derivative TG(TG/DTG)curves indicated that coal pyrolysis mainly occurred between 300℃ and 700℃.Higher heating rates led to more volatiles being released from the coal,and a higher temperature was required to achieve rapid pyrolysis.Kinetic analysis showed that both the model-free methods(Friedman,Flynn-Wall-Ozawa,and Kissinger-Akahira-Sunose)and the model-based method(Coats-Redfern)effectively describe the coal pyrolysis process.The change in the Ea values between the two kinetic models was consistent throughout the pyrolysis process,and the most probable mechanism was the F2 model(secondary chemical reaction).In addition,the heating rate did not change the overall reaction order of the pyrolysis process;however,a higher heating rate resulted in a decrease in the Ea value during the initial pyrolysis stage.展开更多
Various semicokes were obtained from medium-low temperature pyrolysis of Dongrong long flame coal.The proximate analysis,calorific value and Hardgrove grindability index(HGI) of semicokes were determined,and the ignit...Various semicokes were obtained from medium-low temperature pyrolysis of Dongrong long flame coal.The proximate analysis,calorific value and Hardgrove grindability index(HGI) of semicokes were determined,and the ignition temperature,burnout temperature,ignition index,burnout index,burnout ratio,combustion characteristic index of semicokes were measured and analyzed using thermogravimetry analysis(TGA).The effects of pyrolysis temperature,heating rate,and pyrolysis time on yield,composition and calorific value of long flame coal derived semicokes were investigated,especially the influence of pyrolysis temperature on combustion characteristics and grindability of the semicokes was studied combined with X-ray diffraction(XRD) analysis of semicokes.The results show that the volatile content,ash content and calorific value of semicokes pyrolyzed at all process parameters studied meet the technical specifications of the pulverized coal-fired furnaces(PCFF) referring to China Standards GB/T 7562-1998.The pyrolysis temperature is the most influential factor among pyrolysis process parameters.As pyrolysis temperature increases,the yield,ignition index,combustion reactivity and burnout index of semicokes show a decreasing tend,but the ash content increases.In the range of 400 and 450 °C,the grindability of semicokes is rational,especially the grindability of semicokes pyrolyzed at 450 °C is suitable.Except for the decrease of volatile content and increase of ash content,the decrease of combustion performance of semicokes pyrolyzed at higher temperature should be attributed to the improvement of the degree of structural ordering and the increase of aromaticity and average crystallite size of char.It is concluded that the semicokes pyrolyzed at the temperature of 450 °C is the proper fuel for PCFF.展开更多
基金supported by the National High Technology Research and Development Program of China(2009AA044701)the Program for Zhejiang Leading Team of S&T Innovation(2013TD07)
文摘To get deep understanding of the reaction mechanism of coal pyrolysis in hydrogen plasma, the decomposition reaction pathways of aliphatic hydrocarbons and cycloalkanes, which are two main components in volatiles from coal, were investigated. Methane and cyclohexane were chosen as the model compounds. Density functional theory was employed, and many reaction pathways were involved. Calculations were carried out in Gaussian 09 at the B3LYP/6-31G（d,p） level of the theory. The results indicate that the main pyrolysis products of methane and cyclohexane in hydrogen plasma are both hydrogen and acetylene, and the participation of active hydrogen atoms makes dehydrogenation reactions more favorable. H2 mainly comes from dehydrogenation process, while many reaction pathways are responsible for acetylene formation. During coal pyrolysis in hydrogen plasma, three main components in volatiles like aliphatic hydrocarbons, cycloalkanes and aromatic hydrocarbons lead to the formation of hydrogen and acetylene, but their contributions to products distribution are different.
基金the financial support from the National Natural Science Foundation of China(Grant No.21576293 and 21576294)。
文摘Coal pyrolysis is a fundamental reaction in the thermal processing and utilization of coal.Investigating the behavior and kinetics of coal pyrolysis is crucial for optimizing,designing,and developing a composite riser for the staged pyrolysis gasification process of pulverized coal.In this study,the non-isothermal pyrolysis behavior and kinetics of coal were examined at different heating rates(30,50,100,300,500,700,and 900℃/min)using thermogravimetry(TG)coupled with Fourier-transform infrared spectroscopy.Analysis of the TG/derivative TG(TG/DTG)curves indicated that coal pyrolysis mainly occurred between 300℃ and 700℃.Higher heating rates led to more volatiles being released from the coal,and a higher temperature was required to achieve rapid pyrolysis.Kinetic analysis showed that both the model-free methods(Friedman,Flynn-Wall-Ozawa,and Kissinger-Akahira-Sunose)and the model-based method(Coats-Redfern)effectively describe the coal pyrolysis process.The change in the Ea values between the two kinetic models was consistent throughout the pyrolysis process,and the most probable mechanism was the F2 model(secondary chemical reaction).In addition,the heating rate did not change the overall reaction order of the pyrolysis process;however,a higher heating rate resulted in a decrease in the Ea value during the initial pyrolysis stage.
基金support from the Allocated Section of the Basic Fund for the Scientific Research and Operation of Central Universities of China (No.2009KH10)
文摘Various semicokes were obtained from medium-low temperature pyrolysis of Dongrong long flame coal.The proximate analysis,calorific value and Hardgrove grindability index(HGI) of semicokes were determined,and the ignition temperature,burnout temperature,ignition index,burnout index,burnout ratio,combustion characteristic index of semicokes were measured and analyzed using thermogravimetry analysis(TGA).The effects of pyrolysis temperature,heating rate,and pyrolysis time on yield,composition and calorific value of long flame coal derived semicokes were investigated,especially the influence of pyrolysis temperature on combustion characteristics and grindability of the semicokes was studied combined with X-ray diffraction(XRD) analysis of semicokes.The results show that the volatile content,ash content and calorific value of semicokes pyrolyzed at all process parameters studied meet the technical specifications of the pulverized coal-fired furnaces(PCFF) referring to China Standards GB/T 7562-1998.The pyrolysis temperature is the most influential factor among pyrolysis process parameters.As pyrolysis temperature increases,the yield,ignition index,combustion reactivity and burnout index of semicokes show a decreasing tend,but the ash content increases.In the range of 400 and 450 °C,the grindability of semicokes is rational,especially the grindability of semicokes pyrolyzed at 450 °C is suitable.Except for the decrease of volatile content and increase of ash content,the decrease of combustion performance of semicokes pyrolyzed at higher temperature should be attributed to the improvement of the degree of structural ordering and the increase of aromaticity and average crystallite size of char.It is concluded that the semicokes pyrolyzed at the temperature of 450 °C is the proper fuel for PCFF.
