Biodiesel content determination in diesel fuel blends using near infrared (NIR) spectroscopy and support vector machines (SVM).

This work verifies the potential of support vector machine (SVM) algorithm applied to near infrared (NIR) spectroscopy data to develop multivariate calibration models for determination of biodiesel content in diesel fuel blends that are more effective and appropriate for analytical determinations of this type of fuel nowadays, providing the usual extended analytical range with required accuracy. Considering the difficulty to develop suitable models for this type of determination in an extended analytical range and that, in practice, biodiesel/diesel fuel blends are nowadays most often used between 0 and 30% (v/v) of biodiesel content, a calibration model is suggested for the range 0-35% (v/v) of biodiesel in diesel blends. The possibility of using a calibration model for the range 0-100% (v/v) of biodiesel in diesel fuel blends was also investigated and the difficulty in obtaining adequate results for this full analytical range is discussed. The SVM models are compared with those obtained with PLS models. The best result was obtained by the SVM model using the spectral region 4400-4600 cm(-1) providing the RMSEP value of 0.11% in 0-35% biodiesel content calibration model. This model provides the determination of biodiesel content in agreement with the accuracy required by ABNT NBR and ASTM reference methods and without interference due to the presence of vegetable oil in the mixture. The best SVM model fit performance for the relationship studied is also verified by providing similar prediction results with the use of 4400-6200 cm(-1) spectral range while the PLS results are much worse over this spectral region.

[1]  Gerhard Knothe,et al.  Determining the blend level of mixtures of biodiesel with conventional diesel fuel by fiber-optic near-infrared spectroscopy and 1H nuclear magnetic resonance spectroscopy , 2001 .

[2]  Chih-Jen Lin,et al.  LIBSVM: A library for support vector machines , 2011, TIST.

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

[4]  W. Fragoso,et al.  Flow-batch technique for the simultaneous enzymatic determination of levodopa and carbidopa in pharmaceuticals using PLS and successive projections algorithm. , 2008, Talanta.

[5]  Roman M. Balabin,et al.  Motor oil classification by base stock and viscosity based on near infrared (NIR) spectroscopy data , 2008 .

[6]  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 .

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

[8]  Maria Fernanda Pimentel,et al.  Determination of biodiesel content when blended with mineral diesel fuel using infrared spectroscopy and multivariate calibration , 2006 .

[9]  A. Olivieri,et al.  Sustained prediction ability of net analyte preprocessing methods using reduced calibration sets. Theoretical and experimental study involving the spectrophotometric analysis of multicomponent mixtures. , 2001, The Analyst.

[10]  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.

[11]  Joel C Rubim,et al.  Determination of methyl ester contents in biodiesel blends by FTIR-ATR and FTNIR spectroscopies. , 2006, Talanta.

[12]  G. G. Stokes "J." , 1890, The New Yale Book of Quotations.

[13]  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.

[14]  J. Riu,et al.  Validation of bias in multianalyte determination methods. Application to RP-HPLC derivatizing methodologies , 2000 .

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

[16]  C. Pasquini Near Infrared Spectroscopy: fundamentals, practical aspects and analytical applications , 2003 .

[17]  Daniel Svozil,et al.  Introduction to multi-layer feed-forward neural networks , 1997 .

[18]  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 .

[19]  Lutgarde M. C. Buydens,et al.  Evolutionary optimisation : a tutorial , 1998 .

[20]  M. A. Herrador,et al.  Intra-laboratory testing of method accuracy from recovery assays. , 1999, Talanta.

[21]  Alexander Smola Introduction to Large Margin Classifiers , 2000 .

[22]  Shijin Shuai,et al.  Characteristics of carbonyl compounds emission from a diesel-engine using biodiesel–ethanol–diesel as fuel , 2006 .

[23]  Roman M. Balabin,et al.  Gasoline classification using near infrared (NIR) spectroscopy data: comparison of multivariate techniques. , 2010, Analytica chimica acta.

[24]  B. Kowalski,et al.  Partial least-squares regression: a tutorial , 1986 .

[25]  R. Poppi,et al.  Diesel Oil Quality Parameter Determinations Using Support Vector Regression and near Infrared Spectroscopy for Hydrotreating Feedstock Monitoring , 2012 .

[26]  L. E. Borges,et al.  Determination of Lubricant Base Oil Properties by near Infrared Spectroscopy Using Different Sample and Variable Selection Methods , 2004 .

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

[28]  J. Mandel,et al.  Study of Accuracy in Chemical Analysis Using Linear Calibration Curves , 1957 .

[29]  G. Jacobs,et al.  Fischer–Tropsch synthesis: 14C labeled 1-alkene conversion using supercritical conditions with Co/A12O3 , 2005 .

[30]  C. Pasquini,et al.  A low cost short wave near infrared spectrophotometer: application for determination of quality parameters of diesel fuel. , 2010, Analytica chimica acta.

[31]  Haiying Tang,et al.  Fuel properties and precipitate formation at low temperature in soy-, cottonseed-, and poultry fat-based biodiesel blends , 2008 .

[32]  Chih-Jen Lin,et al.  A Practical Guide to Support Vector Classication , 2008 .

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

[34]  D. Faedo,et al.  Effects of 30% v/v biodiesel/diesel fuel blend on regulated and unregulated pollutant emissions from diesel engines , 2011 .

[35]  W. Yuan,et al.  Predicting the dynamic and kinematic viscosities of biodiesel–diesel blends using mid- and near-infrared spectroscopy , 2012 .

[36]  Alexander J. Smola,et al.  Learning with kernels , 1998 .

[37]  R. A. Klamt,et al.  Sunflower biodiesel production and application in family farms in Brazil , 2010 .

[38]  Andrew G. Glen,et al.  APPL , 2001 .

[39]  G. Knothe Dependence of biodiesel fuel properties on the structure of fatty acid alkyl esters , 2005 .

[40]  C. Boshui,et al.  Effect of cold flow improvers on flow properties of soybean biodiesel , 2010 .

[41]  K. Raja Gopal,et al.  A review on biodiesel production, combustion, emissions and performance , 2009 .

[42]  Bernhard Schölkopf,et al.  Experimentally optimal v in support vector regression for different noise models and parameter settings , 2004, Neural Networks.

[43]  Xianming Shi,et al.  Emission characteristics using methyl soyate-ethanol-diesel fuel blends on a diesel engine , 2005 .

[44]  M. A. Fazal,et al.  Biodiesel feasibility study: An evaluation of material compatibility; performance; emission and engine durability , 2011 .

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

[46]  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 .

[47]  Jorge M. Marchetti,et al.  A summary of the available technologies for biodiesel production based on a comparison of different feedstock's properties , 2012 .

[48]  Roman M. Balabin,et al.  Comparison of linear and nonlinear calibration models based on near infrared (NIR) spectroscopy data for gasoline properties prediction , 2007 .

[49]  Jie Yang,et al.  Support Vector Machine In Chemistry , 2004 .

[50]  L. Buydens,et al.  Comparing support vector machines to PLS for spectral regression applications , 2004 .

[51]  Bernhard Schölkopf,et al.  New Support Vector Algorithms , 2000, Neural Computation.

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

[53]  T. Alleman,et al.  Quality analysis of wintertime B6B20 biodiesel blend samples collected in the United States , 2011 .