Thermodynamic analysis was applied to study combined partial oxidation and carbon dioxide reforming of methane in view of carbon formation. The equilibrium calculations employing the Gibbs energy minimization were per...Thermodynamic analysis was applied to study combined partial oxidation and carbon dioxide reforming of methane in view of carbon formation. The equilibrium calculations employing the Gibbs energy minimization were performed upon wide ranges of pressure （1-25 atm）, temperature （600-1300 K）, carbon dioxide to methane ratio （0-2） and oxygen to methane ratio （0-1）. The thermodynamic results were compared with the results obtained over a Ru supported catalyst. The results revealed that by increasing the reaction pressure methane conversion decreased. Also it was found that the atmospheric pressure is the preferable pressure for both dry reforming and partial oxidation of methane and increasing the temperature caused increases in both activity of carbon and conversion of methane. The results clearly showed that the addition of O2 to the feed mixture could lead to a reduction of carbon deposition.展开更多
Catalytic conversion of COinto chemicals and fuels is an alternative to alleviate climate change and ocean acidification.The catalytic reduction of COby Hcan lead to the formation of various products:carbon monoxide,c...Catalytic conversion of COinto chemicals and fuels is an alternative to alleviate climate change and ocean acidification.The catalytic reduction of COby Hcan lead to the formation of various products:carbon monoxide,carboxylic acids,aldehydes,alcohols and hydrocarbons.In this paper,a comprehensive thermodynamics analysis of COhydrogenation is conducted using the Gibbs free energy minimization method.The results show that COreduction to CO needs a high temperature and H/COratio to achieve a high COconversion.However,synthesis of methanol from COneeds a relatively high pressure and low temperature to minimize the reverse water-gas shift reaction.Direct COhydrogenation to formic acid or formaldehyde is thermodynamically limited.On the contrary,production of CHfrom COhydrogenation is the thermodynamically easiest reaction with nearly 100%CH4 yield at moderate conditions.In addition,complex reactions with more than one product are also calculated in this work.Among the considered carboxylic acids（HCOOH,CHCOOH and CHCOOH）,propionic acid dominates in the product stream（selectivity above 90%）.The same trend can also be found in the hydrogenation of COto aldehydes and alcohols with the major product of propionaldehyde and butanol,respectively.In the process of COhydrogenation to alkenes,low temperature,high pressure,and high Hpartial pressure favor the COconversion.CHis the most thermodynamically favorable among all considered alkynes under different temperatures and pressures.The thermodynamic calculations are validated with experimental results,suggesting that the Gibbs free energy minimization method is effective for thermodynamically understanding the reaction network involved in the COhydrogenation process,which is helpful for the development of high-performance catalysts.展开更多
基金supported by University of Kashan(Grant No.158426/5)
文摘Thermodynamic analysis was applied to study combined partial oxidation and carbon dioxide reforming of methane in view of carbon formation. The equilibrium calculations employing the Gibbs energy minimization were performed upon wide ranges of pressure （1-25 atm）, temperature （600-1300 K）, carbon dioxide to methane ratio （0-2） and oxygen to methane ratio （0-1）. The thermodynamic results were compared with the results obtained over a Ru supported catalyst. The results revealed that by increasing the reaction pressure methane conversion decreased. Also it was found that the atmospheric pressure is the preferable pressure for both dry reforming and partial oxidation of methane and increasing the temperature caused increases in both activity of carbon and conversion of methane. The results clearly showed that the addition of O2 to the feed mixture could lead to a reduction of carbon deposition.
基金funded by the National Research Foundation(NRF)Prime Minister’s Office,Singapore under its Campus for Research Excellence and Technological Enterprise(CREATE)Program
文摘Catalytic conversion of COinto chemicals and fuels is an alternative to alleviate climate change and ocean acidification.The catalytic reduction of COby Hcan lead to the formation of various products:carbon monoxide,carboxylic acids,aldehydes,alcohols and hydrocarbons.In this paper,a comprehensive thermodynamics analysis of COhydrogenation is conducted using the Gibbs free energy minimization method.The results show that COreduction to CO needs a high temperature and H/COratio to achieve a high COconversion.However,synthesis of methanol from COneeds a relatively high pressure and low temperature to minimize the reverse water-gas shift reaction.Direct COhydrogenation to formic acid or formaldehyde is thermodynamically limited.On the contrary,production of CHfrom COhydrogenation is the thermodynamically easiest reaction with nearly 100%CH4 yield at moderate conditions.In addition,complex reactions with more than one product are also calculated in this work.Among the considered carboxylic acids（HCOOH,CHCOOH and CHCOOH）,propionic acid dominates in the product stream（selectivity above 90%）.The same trend can also be found in the hydrogenation of COto aldehydes and alcohols with the major product of propionaldehyde and butanol,respectively.In the process of COhydrogenation to alkenes,low temperature,high pressure,and high Hpartial pressure favor the COconversion.CHis the most thermodynamically favorable among all considered alkynes under different temperatures and pressures.The thermodynamic calculations are validated with experimental results,suggesting that the Gibbs free energy minimization method is effective for thermodynamically understanding the reaction network involved in the COhydrogenation process,which is helpful for the development of high-performance catalysts.
