High-Pressure Kinetic Interactions between CO and H₂ during Syngas Catalytic Combustion on PdO

Abstract

The catalytic combustion of H2/CO/O2/N2 mixtures over PdO was investigated at pressures 3 to 10 bar, H2:CO volumetric ratios 1:5 to 3:1, and global equivalence ratios ψ = 0.13 and 0.23. The catalyst surface temperatures were controlled to 540-690 K, a range especially important for hybrid hetero-/homogeneous combustion approaches with large gas turbines at idle or part-load operation and for microreactors with recuperative small-scale turbines. In situ Raman measurements determined the major gas-phase species concentrations over the catalyst boundary layers in a channel-flow reactor, thermocouples monitored the surface temperatures, and surface characterization identified the catalyst oxidation state (PdO) and surface morphology. A 2-D CFD code with a detailed catalytic reaction mechanism simulated the experiments. Simulations and measurements of the combustion of the individual fuel components revealed pressure dependencies ~p0.74 and ~p0.10 for the CO and H2 reactivities, respectively, at the investigated equivalence ratios. In the combustion of H2/CO blends, transition temperatures (TTRAN) were identified, below (above) which H2 inhibited (promoted) chemically the oxidation of CO. The transition temperatures decreased with increasing H2:CO volumetric ratio, pressure, and equivalence ratio. Sensitivity analysis indicated that the H2 and O2 adsorption reactions had the larger inhibiting effect on CO oxidation, particularly at lower pressures. Comparisons with other noble metals showed that the PdO transition temperatures were higher than those on Pt and Rh. Even though this behavior favored Pt and Rh for the ignition of syngas in practical catalytic burners, the H2 and CO kinetic coupling (H2 inhibition) was considerably weaker on PdO at T < TTRAN, thus rendering PdO also potentially suitable for low temperature syngas ignition.

Department(s)

Mechanical and Aerospace Engineering

Comments

Support was provided by the Swiss National Science Foundation (SNSF) under project 200021_179019.

Keywords and Phrases

High-Pressure Syngas Catalytic Combustion on PdO; in Situ Raman Measurements; Inhibition of CO Oxidation by H 2; Pressure Effect on CO and H Kinetic Coupling 2; Transition Temperatures in CO Oxidation

International Standard Serial Number (ISSN)

1540-7489

Document Type

Article - Journal

Document Version

Citation

File Type

text

Language(s)

English

Rights

© 2022 Elsevier, All rights reserved.

Publication Date

01 Jan 2022

Share

 
COinS