Applicability of Raman spectroscopy for time-resolved gas composition monitoring during direct methanol synthesis via carbon dioxide hydrogenation was investigated. A series of methanol synthesis experiments with varied reactor conditions was conducted and the reactor outlet stream was analyzed with in-line gas Raman spectroscopy. Concentrations of H2, CO2 and CO were determined directly from the acquired spectral data. For evaluation of methanol and water content a data reconciliation algorithm was developed. The algorithm involves estimation of the occurring chemical reactions' extents by iterative minimization of the difference between concentration values acquired from the experimental data and concentration values computed based on the mass conservation principle. The obtained experimental concentrations were compared and validated against the results of the reactor mathematical modeling, which is based upon a well-established kinetic interpretation of the process. The findings indicate good repeatability and accuracy of the developed gas analysis system, which together with the advantageous temporal resolution of the method, make Raman spectroscopy a promising technique for fast response monitoring of the process.
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