Abstract
The modeling of carbon deposition from C-H-O reformates has usually employed thermodynamic data for graphite, but has rarely employed such data for impure filamentous carbon. Therefore, electrochemical data for the literature on the chemical potential of two types of purified carbon nanotubes (CNTs) are included in the study. Parameter values determining the thermodynamic equilibrium of the deposition of either graphite or CNTs are computed for dry and wet reformates from natural gas and liquefied petroleum gas. The calculation results are presented as the atomic oxygen-to-carbon ratio (O/C) against temperature (200 to 100 °C) for various pressures (1 to 30 bar). Areas of O/C for either carbon deposition or deposition-free are computed, and indicate the critical O/C values below which the deposition can occur. Only three types of deposited carbon were found in the studied equilibrium conditions: Graphite, multi-walled CNTs, and single-walled CNTs in bundles. The temperature regions of the appearance of the thermodynamically stable forms of solid carbon are numerically determined as being independent of pressure and the analyzed reactants. The modeling indicates a significant increase in the critical O/C for the deposition of CNTs against that for graphite. The highest rise in the critical O/C, of up to 290% at 30 bar, was found for the wet reforming process.
Highlights
Renewed interest in the use of fuel cells as more efficient and less carbon-intensive energy solutions has caused the wet and dry reforming of lower hydrocarbons to gain attention
The modeling indicates a significant increase in the critical oxygen-to-carbon ratio (O/C) for the deposition of carbon nanotubes (CNTs) against that for graphite
The highest rise in the critical O/C, of up to 290% at 30 bar, was found for the wet reforming process
Summary
Renewed interest in the use of fuel cells as more efficient and less carbon-intensive energy solutions has caused the wet and dry reforming of lower hydrocarbons to gain attention. The water steam (wet) reforming process is highly endothermic and is usually carried out in a fixed bed catalytic reactor [2]. The process involves many intermediate reaction steps and several paths can lead to the desired product formation [3]. This makes the selection of an appropriate catalyst and its configuration difficult in order to provide high performance of the reactor with respect to the hydrogen production [4]. Most experimental studies of wet reforming have indicated that the O/C ratio should be higher than 2.5 to avoid carbon formation [2,6]
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