DOE OSTI2017
The need for cleaner energy systems, including CO 2 capture technologies, is driving the current development of new combustion approaches such as chemical looping combustion (CLC). This process is based on using oxygen carrier particles (OCPs) such as iron oxides, copper oxides, calcium sulfates, etc. to provide the oxygen for the combustion process. In order to optimize the overall process performance, it is critical that the properties of the oxygen carriers are well-defined and maintained for their specific purpose during the different stages of the CLC process. One of the critical properties of the oxygen carrier is its oxidation state (e.g., content of Fe 2 O 3 vs. Fe 3 O 4 ) as it affects the fundamental operation of the CLC process. Unfortunately, the ability to make on-line measurements of the oxidation state of oxygen carriers is lacking and new sensors need to be developed. Our goal is to develop a sensor for the on-line analysis of the oxidation state of oxygen carrier particles and to demonstrate its feasibility. Oxygen carrier particles (OCPs) of interest include iron oxides, copper oxides, and calcium sulfate, with particle sizes typically less than 0.5 mm diameter. The expected operating conditions of the sensor include OCP temperatures in the range of 800 °C to 1000 °C, and pressures of about 10 atm. The expected results are to be of a statistical nature, providing relative concentrations of the different oxidation states. These requirements make a strong case for using non-contact, stand-off, pulsed Raman spectroscopy as a sensor for the high-temperature on-line analysis of oxygen carrier particles. In order to achieve our goal, we have set up and tested a pulsed Raman spectroscopy system in combination with a pressurized high-temperature sample chamber, and have taking initial Raman spectra of various materials at high temperature. We are now in the process of optimizing the operating parameters such as laser wavelength, laser intensity, collection optic design, focal spot size, data acquisition, etc. We will also develop an analysis procedure for the interpretation of the Raman spectra. Typical Raman spectra consist of a convolution of background signal and multiple individual spectra. In order to extract relevant information such as the concentration ratio of a material in different oxidation states, we need to process (background subtraction, deconvolution, fitting, etc.) the measured data. In addition, statistical modeling and multivariate calibration need to be performed to correctly analyze the Raman spectra.
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