A Comparative Thermodynamic Study of Equilibrium Conditions for Carbon Deposition from Catalytic C–H–O Reformates

The importance of carbon deposition occurring during catalytic fuel reforming is briefly described along with former studies on the process. Thermodynamic fundamentals of modeling the critical conditions of the deposition equilibrium are presented. Computational results of ternary C–H–O diagrams with the threshold lines between the carbon deposition and deposition-free regions are discussed for two new pressure levels of 3 and 30 bar and a temperature range from 200 to 1000 °C. The process pressure does not affect the temperature range typical for the type of deposited carbon allotrope; either graphite, multi-walled carbon nanotubes, or single-walled carbon nanotubes in bundles. However, pressure has a profound influence on the location of the threshold lines for carbon deposition. Three reforming processes of two hydrocarbon fuels are analyzed; catalytic partial oxidation, and wet and dry reforming. Chord lines representing varied compositions of process mixtures are introduced to the ternary diagrams. The intersection points of the chord lines with the threshold lines are used in a novel interpretation of the functions of the oxygen-to-carbon critical ratio against temperature and pressure, which can be used in avoiding carbon deposition in catalytic reforming of natural gas and liquefied petroleum gas.