Monitoring of technical oils in supercritical CO(2) 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 4200cm(-1). With this model only poor prediction results were obtained if applied to technical oil samples in supercritical CO(2). In this paper we describe a new calibration model, which was set up for the squalane/carbon dioxide system covering the 323-353K temperature and the 16-35.6MPa pressure range. Here, calibration data in the spectral range from 6100 to 5030cm(-1) have been used. This range includes the 5100cm(-1) CO(2) 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. The root mean-squared error of prediction obtained with this model is 4mgcm(-3) for carbon dioxide and 0.4mgcm(-3) for squalane, respectively. The utilizability of the newly developed PLS calibration model for predicting the oil concentration and CO(2) 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 1.1mgcm(-3) and the CO(2) density with an error of 6mgcm(-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.
Bürck
J
J
Institut für Instrumentelle Analytik (IFIA), Forschungszentrum Karlsruhe, GmbH in der Helmholtz-Gemeinschaft, P.O. Box 3640, D-76021 Karlsruhe, Germany.
Wiegand
G
G
Roth
S
S
Mathieu
H
H
Krämer
K
K