Monitoring of technical oils in supercritical CO2 under continuous flow conditions by NIR spectroscopy and multivariate calibration

Metal parts and residues from machining processes are usually polluted with cutting or grinding oil and have to be cleaned before further use. Supercritical carbon dioxide can be used for extraction processes and precision cleaning of metal parts, as developed at Forschungszentrum Karlsruhe. For optimizing and efficiently conducting the extraction process, in-line analysis of oil concentration is desirable. Therefore, a monitoring method using fiber-optic NIR spectroscopy in combination with PLS calibration has been developed. In an earlier paper we have described the instrumental set-up and a calibration model using the model compound squalane in the spectral range of the CH combination bands from 4900 to 4200 cm−1. With this model only poor prediction results were obtained if applied to technical oil samples in supercritical CO2. In this paper we describe a new calibration model, which was set up for the squalane/carbon dioxide system covering the 323–353 K temperature and the 16–35.6 MPa pressure range. Here, calibration data in the spectral range from 6100 to 5030 cm−1 have been used. This range includes the 5100 cm−1 CO2 band of the Fermi triad as well as the hydrocarbon 1st overtone CH stretching bands, where spectral features of oil compounds and squalane are more similar to each other. ot mean-squared error of prediction obtained with this model is 4 mg cm−3 for carbon dioxide and 0.4 mg cm−3 for squalane, respectively. The utilizability of the newly developed PLS calibration model for predicting the oil concentration and CO2 density of solutions of technical oils in supercritical carbon dioxide has been tested. Three types of “real world” cutting and grinding oil formulations were used in these experiments. The calibration proved to be suitable for determining the technical oil concentration with an error of 1.1 mg cm−3 and the CO2 density with an error of 6 mg cm−3. Therefore, it seems possible to apply this in-line analytical approach on the basis of a cost-effective and time-saving model compound calibration for the surveillance of real world de-oiling and other extraction process based on supercritical carbon dioxide, and furthermore to establish an automated process termination criterion based on this technique.