Raman spectroscopy of oxygen carrier particles in harsh environments

Abstract

Fossil fuel combustion processes generate CO2, a greenhouse gas of considerable concern. To reduce this emission, the National Energy Technology Laboratory (NETL) is evaluating alternative combustion approaches, including chemical looping combustion (CLC). This technique generates relatively pure CO2, suitable for subsequent capture and storage. CLC uses oxygen-carrier particles (OCPs) such as iron oxides, copper oxides, calcium sulfates, etc. to provide oxygen for the combustion process. Optimization of the overall combustion process requires knowledge of the oxidation state (e.g., content of Fe2O3 vs. Fe3O4) of the OCPs during the different stages of the CLC process. Unfortunately, the ability to make on-line measurements of the oxidation state of OCPs in harsh environments is lacking and new sensors need to be developed. We are evaluating non-contact, stand-off Raman spectroscopy to determine the relative concentrations of the oxidized and reduced forms of OCPs at temperatures between 800 °C and 1000 °C, and pressures of about 10 atm. Using cw and pulsed Raman spectroscopy, in combination with a pressurized high-temperature sample chamber, we have optimized the operating parameters such as laser wavelength, laser intensity, collection optic design, focal spot size, etc. and measured Raman spectra of various OCP materials at high temperatures. To extract from the Raman spectra relevant information such as the concentration ratio of a material in different oxidation states, the measured data needs to be processed, and statistical modeling and multivariate calibration need to be performed.