Accuracy Enhancement of LIBS-XRF Coal Quality Analysis Through Spectral Intensity Correction and Piecewise Modeling

Abstract

The combination of laser-induced breakdown spectroscopy and energy dispersive X-ray fluorescence spectroscopy in the coal quality analysis was reported formerly. But in the practical test of the prototype instrument in the real power plant, the X-ray fluorescence signals suffered from intensity fluctuations over long-time measurements. The long-term signal fluctuations cause lower efficiency on the establishment of the calibration model and relatively larger root-mean-squared error of prediction (RMSEP) for unknown samples. Therefore, the spectral intensity correction was performed in the measurements; a randomly selected sample was measured several times in the whole measurements, including the modeling samples and unknown samples, recording the signal fluctuations and searching for a set of factors suitable for the intensity correction of a full-spectrum–based partial least square calibration model. In addition, as the signals of the coal samples of the power plant showed the potential of classification, the piecewise models were also established in case of further enhancement of the model or prediction accuracy. The RMSEPs of the calorific value, ash, volatile, and sulfur were lowered from 0.68 MJ/kg, 1.62%, 0.32%, and 0.24% to 0.51 MJ/kg, 1.34%, 0.16%, and 0.14% after spectral intensity correction, respectively. The piecewise modeling with spectral intensity correction achieved similar RMSEP for volatile and sulfur prediction but with more accurate models. The spectral intensity correction showed the ability to reduce the long-term signal fluctuation, and piecewise modeling also showed more efficiency in the model establishments for volatile and ash determination.