The chemical looping gasification uses an oxygen carrier for solid fuel gasification by supplying insufficient lattice oxygen. The effect of gasifying medium on the coal chemical looping gasification with Ca SO4 as ox...The chemical looping gasification uses an oxygen carrier for solid fuel gasification by supplying insufficient lattice oxygen. The effect of gasifying medium on the coal chemical looping gasification with Ca SO4 as oxygen carrier is investigated in this paper. The thermodynamical analysis indicates that the addition of steam and CO2 into the system can reduce the reaction temperature, at which the concentration of syngas reaches its maximum value.Experimental result in thermogravimetric analyzer and a fixed-bed reactor shows that the mixture sample goes through three stages, drying stage, pyrolysis stage and chemical looping gasification stage, with the temperature for three different gaseous media. The peak fitting and isoconversional methods are used to determine the reaction mechanism of the complex reactions in the chemical looping gasification process. It demonstrates that the gasifying medium(steam or CO2) boosts the chemical looping process by reducing the activation energy in the overall reaction and gasification reactions of coal char. However, the mechanism using steam as the gasifying medium differs from that using CO2. With steam as the gasifying medium, parallel reactions occur in the beginning stage, followed by a limiting stage shifting from a kinetic to a diffusion regime. It is opposite to the reaction mechanism with CO2 as the gasifying medium.展开更多
Calcium sulfate(CaSO_(4))has been verified as a promising oxygen carrier(OC)in the chemical looping combustion(CLC)for its high oxygen capacity,abundant reserve and low cost,but its low reactivity and deleterious sulf...Calcium sulfate(CaSO_(4))has been verified as a promising oxygen carrier(OC)in the chemical looping combustion(CLC)for its high oxygen capacity,abundant reserve and low cost,but its low reactivity and deleterious sulfur species emission from the side reactions of CaSO_(4) should be well considered for its wide application in CLC.In order to promote the reactivity of CaSO_(4) and increase its potential to inhibit the gaseous sulfur emission,a CeO_(2)-enhanced CaSO_(4) OC mixed OC of core–shell structure was prepared using the combined template synthesis method.Reaction characteristics of the prepared CaSO_(4)-CeO_(2) mixed OC with a typical lignite was first conducted and systematically investigated,and an improved reactivity of the prepared CaSO_(4)-CeO_(2) mixed OC was demonstrated than its single component CaSO_(4) or CeO_(2) due to the fast transfer and exchange of oxygen from the CaSO_(4) substrate to coal via the doped CeO_(2).Furthermore,the solid products formed from the mixed CaSO_(4)-CeO_(2) OC with the selected coal were collected and analyzed.Especially,evolution and redistribution of the sulfur species of different forms were focused.At the latter reaction stage of YN reaction with the CaSO_(4)-CeO_(2) mixed OC,the SO_(2) emitted from the side reactions of CaSO_(4) was greatly diminished and the doped CeO_(2) was proven effective to directionally fix the SO_(2) released to turn into different solid sulfur compounds,which were determined as Ce_(2)O_(2)S,Ce_(2)S_(3) and Ce_(2)(SO_(4))_(3)·5H_(2)O and formed through the different pathways.In addition,good regeneration of the reduced CaSO_(4)-CeO_(2) mixed OC could be reached in spite of the unavoidable interaction between the included minerals in coal and the reduced mixed OC.Overall,the combined template method-made CaSO_(4)-CeO_(2) mixed OC reported herein was not only endowed with enhanced reactivity for coal conversion,but also owned the potential to directionally fix the gaseous sulfur emission,which is quite applicable as OC for simultaneous decarbonatization and desulfurization in the real CLC process.展开更多
Chemical-looping gasification （CLG） is a novel process for syngas generation from solid fuels, sharing the same basic principles as chemical-looping combustion （CLC）. It also uses oxygen carriers （mainly metal ox...Chemical-looping gasification （CLG） is a novel process for syngas generation from solid fuels, sharing the same basic principles as chemical-looping combustion （CLC）. It also uses oxygen carriers （mainly metal oxide and calcium sulfate） to transfer heat and oxygen to the fuel. In this paper, the primary investigation into the CLG process with CaSO4 as oxygen carrier was carried out by thermodynamic analysis and experiments in the tube reactor. Sulfur-contained gas emission was mainly H2S rather than SO2 in the CLG process, showing some different features from the CLC. The mass and heat balance of CLG processes were calculated thermodynamically to determinate the auto-thermal operating conditions with different CaSO4/C and steam/C molar ratios. It was found that the CaSO4/C molar ratio should be higher than 0.2 to reach auto-thermal balance. The effect of temperature on the reactions between oxygen carrier and coal was investigated based on Gibbs free energy minimum method and ex- perimental results. It indicated that high temperature favored the CLG process in the fuel reactor and part of syngas was consumed to compensate for auto-thermal system.展开更多
基金Supported by the Research and Development Program of the Korea Institute of Energy Research(KIER)(B4-2431-04)the National Natural Science Foundation of China(21276129,20876079)the Natural Science Funds for Distinguished Young Scholar in Shandong Province(JQ200904)
文摘The chemical looping gasification uses an oxygen carrier for solid fuel gasification by supplying insufficient lattice oxygen. The effect of gasifying medium on the coal chemical looping gasification with Ca SO4 as oxygen carrier is investigated in this paper. The thermodynamical analysis indicates that the addition of steam and CO2 into the system can reduce the reaction temperature, at which the concentration of syngas reaches its maximum value.Experimental result in thermogravimetric analyzer and a fixed-bed reactor shows that the mixture sample goes through three stages, drying stage, pyrolysis stage and chemical looping gasification stage, with the temperature for three different gaseous media. The peak fitting and isoconversional methods are used to determine the reaction mechanism of the complex reactions in the chemical looping gasification process. It demonstrates that the gasifying medium(steam or CO2) boosts the chemical looping process by reducing the activation energy in the overall reaction and gasification reactions of coal char. However, the mechanism using steam as the gasifying medium differs from that using CO2. With steam as the gasifying medium, parallel reactions occur in the beginning stage, followed by a limiting stage shifting from a kinetic to a diffusion regime. It is opposite to the reaction mechanism with CO2 as the gasifying medium.
基金supported by the National Natural Science Founda-tion of China(Nos.51776073,51906083)Key Research&Develop-ment program of Henan Province(No.162102210233)+1 种基金North China University of Water Resources and Electric Power Innovative Project(Nos.2019XA014,2019XB058)Scientific Research&Development Project of Ji-Yan Energy Science and Technology Research Institute(NKY2020-05).
文摘Calcium sulfate(CaSO_(4))has been verified as a promising oxygen carrier(OC)in the chemical looping combustion(CLC)for its high oxygen capacity,abundant reserve and low cost,but its low reactivity and deleterious sulfur species emission from the side reactions of CaSO_(4) should be well considered for its wide application in CLC.In order to promote the reactivity of CaSO_(4) and increase its potential to inhibit the gaseous sulfur emission,a CeO_(2)-enhanced CaSO_(4) OC mixed OC of core–shell structure was prepared using the combined template synthesis method.Reaction characteristics of the prepared CaSO_(4)-CeO_(2) mixed OC with a typical lignite was first conducted and systematically investigated,and an improved reactivity of the prepared CaSO_(4)-CeO_(2) mixed OC was demonstrated than its single component CaSO_(4) or CeO_(2) due to the fast transfer and exchange of oxygen from the CaSO_(4) substrate to coal via the doped CeO_(2).Furthermore,the solid products formed from the mixed CaSO_(4)-CeO_(2) OC with the selected coal were collected and analyzed.Especially,evolution and redistribution of the sulfur species of different forms were focused.At the latter reaction stage of YN reaction with the CaSO_(4)-CeO_(2) mixed OC,the SO_(2) emitted from the side reactions of CaSO_(4) was greatly diminished and the doped CeO_(2) was proven effective to directionally fix the SO_(2) released to turn into different solid sulfur compounds,which were determined as Ce_(2)O_(2)S,Ce_(2)S_(3) and Ce_(2)(SO_(4))_(3)·5H_(2)O and formed through the different pathways.In addition,good regeneration of the reduced CaSO_(4)-CeO_(2) mixed OC could be reached in spite of the unavoidable interaction between the included minerals in coal and the reduced mixed OC.Overall,the combined template method-made CaSO_(4)-CeO_(2) mixed OC reported herein was not only endowed with enhanced reactivity for coal conversion,but also owned the potential to directionally fix the gaseous sulfur emission,which is quite applicable as OC for simultaneous decarbonatization and desulfurization in the real CLC process.
基金Supported by the National~ Natural Science Foundation of China （20876079）, the Natural Science Funds for Distinguished Young Scholar in Shandong Province （JQ200904）, and Shandong Province Key Technologies Research and Development Program of China （2008GG 10006010, 2009GG 10007001）.
文摘Chemical-looping gasification （CLG） is a novel process for syngas generation from solid fuels, sharing the same basic principles as chemical-looping combustion （CLC）. It also uses oxygen carriers （mainly metal oxide and calcium sulfate） to transfer heat and oxygen to the fuel. In this paper, the primary investigation into the CLG process with CaSO4 as oxygen carrier was carried out by thermodynamic analysis and experiments in the tube reactor. Sulfur-contained gas emission was mainly H2S rather than SO2 in the CLG process, showing some different features from the CLC. The mass and heat balance of CLG processes were calculated thermodynamically to determinate the auto-thermal operating conditions with different CaSO4/C and steam/C molar ratios. It was found that the CaSO4/C molar ratio should be higher than 0.2 to reach auto-thermal balance. The effect of temperature on the reactions between oxygen carrier and coal was investigated based on Gibbs free energy minimum method and ex- perimental results. It indicated that high temperature favored the CLG process in the fuel reactor and part of syngas was consumed to compensate for auto-thermal system.
