RI 5913 Calculated Equilibrium Gas Composition Of Water-Carbon Dioxide Mixtures Over Iron At Pressures Of 1 To 30 Atmospheres And Temperatures Of 800° To 1,300° K. ? Summary And Conclusions

The Bureau of Mines has been studying a modified steam-iron process using coal-derived producer gas for making either hydrogen plus carbon monoxide or methane. To provide a guide for this experimental study, compositions of equilibrium product gases for the reaction of steam plus carbon dioxide with iron were calculated and are discussed in this report. The calculations, which are described in this report, are based on thermodynamic data in the literature and cover temperatures from 800° to 1,300° K., pressures from 1 to 30 atmospheres, and hydrogen-to-carbon atomic ratios in the gas of 4 to 12. The equilibrium gas compositions are discussed in regard to making hydro-gen, carbon monoxide, and methane in the oxidation step of the modified steam-iron process. From the viewpoint of thermodynamics alone, assuming the reactions reach equilibrium, the discussion considers the effects of temperature, pressure, and composition of feed gas upon the composition of the product gas, the degree of oxidation of the iron, and the possible deposition of carbon. The results indicated the following: (1) Nearly all the carbon can be converted to methane at low temperatures (800° to 900° K.) and high pressures (over 20 atmospheres); (2) to obtain high yields of synthesis gas, high temperatures are required. For example, at 30 atmospheres, a temperature over 1,200° K. is required to convert 60 percent of the steam plus carbon dioxide to hydrogen plus carbon monoxide. Lower temperatures may be used at lower pressures) (3) oxidation of the iron increases with increasing pressure and decreases with increasing temperature; and (4) process conditions favoring carbon deposition were found within the range of variables studied, but it is thermodynamically possible to operate the oxidation process with steam and carbon dioxide outside this range of carbon deposition.