The thermodynamics analysis and experimental validation for complicated systems in CO_2 hydrogenation process

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.

Physicochemical principles of hydrogen metallurgy in blast furnace

Based on the stoichiometric method and the free energy minimization method,an ideal model for the reduction of iron oxides by carbon and hydrogen under blast furnace conditions was established,and the reduction efficiency and theoretical energy consumption of the all-carbon blast furnace and the hydrogen-rich blast furnace were compared.The results show that after the reduction reaction is completed at the bottom of the blast furnace,the gas produced by reduction at 1600℃still has a certain excessive reduction capacity,which is due to the hydrogen brought in by the hydrogen-rich blast as well as the excess carbon monoxide generated by the reaction of the coke and the oxygen brought in by the blast.During the process of the gas with excessive reduction capacity rising from the bottom of the blast furnace and gas reduction process,the excessive reduction capacity of the gas gradually decreases with the increase in the dydrogen content in the blast.In the all-carbon blast furnace,the excess gas reduction capacity is the strongest,and the total energy consumption per ton of iron reduction is the lowest.This shows that,for the current operation mode of the blast furnace,adding hydrogen in the blast furnace cannot reduce the consumption of carbon required for reduction per ton of iron,but rather increases the consumption of carbon.