Quantification of animal fat biodiesel in soybean biodiesel and B20 diesel blends using near infrared spectroscopy and synergy interval support vector regression.

In this work, multivariate calibration based on partial least squares (PLS) and support vector regression (SVR) using the whole spectrum and variable selection by synergy interval (siPLS and siSVR) were applied to NIR spectra for the determination of animal fat biodiesel content in soybean biodiesel and B20 diesel blends. For all models, prediction errors, bias test for systematic errors and permutation test for trends in the residuals were calculated. The siSVR produced significantly lower prediction errors compared to the full spectrum methods and siPLS, with a root mean squares error (RMSEP) of 0.18%(w/w) (concentration range: 0.00%-69.00%(w/w)) in the soybean biodiesel blend and 0.10%(w/w) in the B20 diesel (concentration range: 0.00%-13.80%(w/w)). Additionally, in the models for the determination of animal fat biodiesel in blends with soybean diesel, PLS and SVR showed evidence of systematic errors, and PLS/siPLS presented trends in residuals based on the permutation test. For the B20 diesel, PLS presented evidence of systematic errors, and siPLS presented trends in the residuals.

[1]  S. Engelsen,et al.  Interval Partial Least-Squares Regression (iPLS): A Comparative Chemometric Study with an Example from Near-Infrared Spectroscopy , 2000 .

[2]  P. Geladi,et al.  Linearization and Scatter-Correction for Near-Infrared Reflectance Spectra of Meat , 1985 .

[3]  Maria Fernanda Pimentel,et al.  Infrared spectroscopy and multivariate calibration to monitor stability quality parameters of biodiesel , 2010 .

[4]  Richard G. Brereton,et al.  Introduction to multivariate calibration in analytical chemistry , 2000 .

[5]  José C. Menezes,et al.  Multivariate near infrared spectroscopy models for predicting the oxidative stability of biodiesel: Effect of antioxidants addition , 2012 .

[6]  Selmo Q. Almeida,et al.  Characterization of beef tallow biodiesel and their mixtures with soybean biodiesel and mineral diesel fuel. , 2010 .

[7]  Qing-Song Xu,et al.  Support vector machines and its applications in chemistry , 2009 .

[8]  R. Brereton,et al.  Self-Organizing Maps and Support Vector Regression as aids to coupled chromatography: illustrated by predicting spoilage in apples using volatile organic compounds. , 2011, Talanta: The International Journal of Pure and Applied Analytical Chemistry.

[9]  Bernhard Schölkopf,et al.  A tutorial on support vector regression , 2004, Stat. Comput..

[10]  Marco Flôres Ferrão,et al.  Simultaneous determination of quality parameters of biodiesel/diesel blends using HATR-FTIR spectra and PLS, iPLS or siPLS regressions , 2011 .

[11]  Maria Fernanda Pimentel,et al.  Screening analysis to detect adulteration in diesel/biodiesel blends using near infrared spectrometry and multivariate classification. , 2011, Talanta.

[12]  Hilko van der Voet,et al.  Comparing the predictive accuracy of models using a simple randomization test , 1994 .

[13]  Jerry Workman,et al.  Practical guide to interpretive near-infrared spectroscopy , 2007 .

[14]  Nathalie Dupuy,et al.  Evaluation of multiblock NIR/MIR PLS predictive models to detect adulteration of diesel/biodiesel blends by vegetal oil , 2011 .

[15]  R. Nogueira,et al.  Validation of model of multivariate calibration: an application to the determination of biodiesel blend levels in diesel by near‐infrared spectroscopy , 2012 .

[16]  Qing-Song Xu,et al.  Generalized PLS regression , 2001 .

[17]  I. Fortes,et al.  Multivariate Calibration by Variable Selection for Blends of Raw Soybean Oil/Biodiesel from Different Sources Using Fourier Transform Infrared Spectroscopy (FTIR) Spectra Data , 2008 .

[18]  A. A. Gomes,et al.  Determination of biodiesel content in biodiesel/diesel blends using NIR and visible spectroscopy with variable selection. , 2011, Talanta.

[19]  Ronei J. Poppi,et al.  Determination of diesel quality parameters using support vector regression and near infrared spectroscopy for an in-line blending optimizer system , 2012 .

[20]  Patrícia Valderrama,et al.  Variable selection, outlier detection, and figures of merit estimation in a partial least-squares regression multivariate calibration model. A case study for the determination of quality parameters in the alcohol industry by near-infrared spectroscopy. , 2007, Journal of agricultural and food chemistry.

[21]  Pedro Felizardo,et al.  Multivariate near infrared spectroscopy models for predicting methanol and water content in biodiesel. , 2007, Analytica chimica acta.

[22]  A. Höskuldsson PLS regression methods , 1988 .

[23]  Dazhou Zhu,et al.  The performance of ν-support vector regression on determination of soluble solids content of apple by acousto-optic tunable filter near-infrared spectroscopy , 2007 .

[24]  Corinna Cortes,et al.  Support-Vector Networks , 1995, Machine Learning.

[25]  J. Rubim,et al.  A comparative study of diesel analysis by FTIR, FTNIR and FT-Raman spectroscopy using PLS and artificial neural network analysis , 2005 .

[26]  S. D. Jong SIMPLS: an alternative approach to partial least squares regression , 1993 .

[27]  L. Stragevitch,et al.  Prediction of properties of diesel/biodiesel blends by infrared spectroscopy and multivariate calibration , 2010 .

[28]  M. J. C. Pontes,et al.  Using near-infrared overtone regions to determine biodiesel content and adulteration of diesel/biodiesel blends with vegetable oils. , 2012, Analytica chimica acta.

[29]  J. Kalivas,et al.  Interrelationships of multivariate regression methods using eigenvector basis sets , 1999 .

[30]  Vladimir Vapnik,et al.  An overview of statistical learning theory , 1999, IEEE Trans. Neural Networks.

[31]  Martin Andersson,et al.  A comparison of nine PLS1 algorithms , 2009 .

[32]  S. Wold,et al.  PLS-regression: a basic tool of chemometrics , 2001 .