Combined Steam Reforming of Methane and Formic Acid To Produce Syngas with an Adjustable H2:CO Ratio

Syngas is an important intermediate in the chemical process industry. It is used for the production of hydrocarbons, acetic acid, oxo-alcohols, and other chemicals. Depending on the target product and stoichiometry of the reaction, an optimum (molar) ratio between hydrogen and carbon monoxide (H₂:CO) in the syngas is required. Different technologies are available to control the H₂:CO molar ratio in the syngas. The combination of steam reforming of methane (SRM) and the water-gas shift (WGS) reaction is the most established approach for syngas production. In this work, to adjust the H₂:CO ratio, we have considered formic acid (FA) as a source for both hydrogen and carbon monoxide. Using thermochemical equilibrium calculations, we show that the syngas composition can be controlled by cofeeding formic acid into the SRM process. The H₂:CO molar ratio can be adjusted to a value between one and three by adjusting the concentration of FA in the reaction feed. At steam reforming conditions, typically above 900 K, FA can decompose to water and carbon monoxide and/or to hydrogen and carbon dioxide. Our results show that cofeeding FA into the SRM process can adjust the H₂:CO molar ratio in a single step. This can potentially be an alternative to the WGS process.