A Method of Analyzing the Component Reactions of an Overall Reaction: Autothermal Reforming of Acetic Acid Example

Using Excel and its Solver feature, a novel method of analyzing the component reactions of an overall reaction is outlined. As an example, autothermal reforming (300–700 °C) of acetic acid (AA), a significant component of pyrolysis oil, was considered. The overall reaction can be viewed as comprising five individual reactions: reforming, oxidation, water–gas shift, reverse Boudouard, and methanation. A laboratory apparatus was set up in which acetic acid, air, and water were continuously fed to a BASF dual-layer catalytic reactor in plug flow at 1 atm. For this setup, it is easy to construct a material balance in Excel in which five factors, f_i, are defined which represent the fraction of reactant going to each of the individual five reactions. Using the Solver feature of Excel, it can readily be determined which of the five factors f_i produce the best match of the calculated exit gas composition with the measured gas concentrations for CO, CO₂, H₂, CH₄, and O₂. Furthermore, a program such as GasEq or Aspen can then be used to calculate the theoretical equilibrium gas composition at a given condition. Using this equilibrium gas composition and Solver, the individual (f_i)_equilb can be calculated. Thus, the ratio f_i/(f_i)_equilb is an indication of how close each component reaction is to equilibrium. In this way, an idea is gained of which of the individual component reactions need to be improved or inhibited or if operating parameters should be adjusted. For the specific case of autothermal reforming of acetic acid, the steam reforming reaction requires at least 600 °C to approach equilibrium. In contrast, the oxidation reaction goes to equilibrium throughout the temperature range, completely consuming oxygen. The water–gas shift reaction appears to approach equilibrium to the extent of 71–90% throughout the temperature range. The reverse Boudouard reaction is favored at lower temperatures; in fact, coking was predicted and found at the low temperature of 300 °C.