View More View Less
  • 1 QuiCSI Team, LMC and LQAA, Institute of Chemistry, University of Brasília, C.P. 4478, Brasilia, DC, 70904-970, Brazil
  • 2 Federal Institute of Technologic Education of Rio Verde, C.P. 66, Rio Verde, GO, 75910-970, Brazil
Restricted access

Abstract

Biofuel has been obtained by cracking of soybean (Glycine sp.) oil, which is characterized by acidity index, density, cetane index, copper corrosion, carbon residue, fulgor point, and heat of combustion. In order to evaluate the quality of biofuel as well as detect its adulteration with vegetable oil, partial least squares regression calibration models based on thermogravimetric (TG) analysis were used as a precise and an accurate method. Thirty mixtures of biofuel/diesel/vegetable oil standards were prepared. Twenty of them were used for calibration, and ten for validation. The results have shown that the thermogravimetric analysis, PLS/TG, presented the best performance for the detection of vegetable oil contamination with a root mean square error of prediction (RMSEC% w/w) of 0.23, with a relative error of prediction of 3.6%, corroborating with the success of TG analysis application to determine the quality of biofuels and diesel/biofuel blends, showing that the TG analysis is an excellent tool to control quality of biofuels.

  • 1.

    Faria, EA, Ramalho, HF, Marques, JS, Suarez, PAZ, Prado, AGS. 2008. Tetramethylguanidine covalently bonded onto silica gel surface as an efficient and reusable catalyst for transesterification of vegetable oil. Appl Catal A. 338:7278 .

    • Crossref
    • Search Google Scholar
    • Export Citation
  • 2.

    Bulkatov, AN, Lebedev, YN, Nikolaev, AB, Zil'berberg, IA, Lozhkin, YP. 2002. The primary crude oil refining plant all Samotlor Refinery. Chem Technol Fuels Oils. 38:2730 .

    • Crossref
    • Search Google Scholar
    • Export Citation
  • 3.

    Faria, EA, Marques, JS, Dias, IM, Andrade, RDA, Suarez, PAZ, Prado, AGS. 2009. Nanosized and reusable SiO2/ZrO2 catalyst for highly efficient biodiesel production by soybean transesterification. J Braz Chem Soc. 20 9 17321737 .

    • Crossref
    • Search Google Scholar
    • Export Citation
  • 4.

    Suarez, PAZ, Moser, BR, Sharma, BK, Erhan, SZ. 2009. Comparing the lubricity of biofuels obtained from pyrolysis and alcoholysis of soybean oil and their blends with petroleum diesel. Fuel. 88:11431147 .

    • Crossref
    • Search Google Scholar
    • Export Citation
  • 5.

    Monteiro, MR, Ambrozin, ARP, Liao, LM, Ferreira, AG. 2008. Critical review on analytical methods for biodiesel characterization. Talanta. 77:593605 .

    • Crossref
    • Search Google Scholar
    • Export Citation
  • 6.

    Chang, CC, Wan, SW. 1947. Chinas motor fuels from tung oil. Ind Eng Chem Res. 39:15431546 .

  • 7.

    Fortes, ICP, Baugh, PJ. 1999. Study of analytical on-line pyrolysis of oils from Macauba fruit (Acrocomia sclerocarpa M.) via GC/MS. J Braz Chem Soc. 10:469474 .

    • Crossref
    • Search Google Scholar
    • Export Citation
  • 8.

    Fortes, ICP, Baugh, PJ. 1994. Study of calcium soap pyrolysates derived from macauba fruit (Acrocomia sclerocarpa M.)—derivatization and analysis by GC/MS and CI-MS. J Anal Appl Pyrolysis. 29:153156 .

    • Crossref
    • Search Google Scholar
    • Export Citation
  • 9.

    Idem, RO, Katikaneni, SPR, Bakhshi, NN. 1996. Thermal cracking of Canola oil: reaction products in the presence and absence of steam. Energy Fuels. 10:11501155 .

    • Crossref
    • Search Google Scholar
    • Export Citation
  • 10.

    Bacaud, R, Besson, M, Brodzki, D, Bussière, P, Charcosset, H, Diega-Mariadassou, G, Oberson, M, Sharma, BK. 1989. On the occurrence and role of SnO2, SnS and FeSn2 in coal hydroliquefaction experiments using tin-based catalysts. Hyperfine Interact. 46:583589 .

    • Crossref
    • Search Google Scholar
    • Export Citation
  • 11.

    Prado, AGS, Pescara, IC, Evangelista, SM, Holanda, MS, Andrade, RA, Suarez, PAZ, Zara, LF. 2011. Adsorption and preconcentration of divalent metal ions in fossil fuels and biofuels: gasoline, diesel, biodiesel, diesel-like and ethanol by using chitosan microspheres and thermodynamic approach. Talanta. 84:759765 .

    • Crossref
    • Search Google Scholar
    • Export Citation
  • 12.

    Doll, KM, Sharma, BK, Suarez, PAZ, Erhan, SZ. 2008. Comparing biofuels obtained from pyrolysis, of soybean oil or soapstock, with traditional soybean biodiesel: density, kinematic viscosity, and surface tensions. Energy Fuels. 22:20612066 .

    • Crossref
    • Search Google Scholar
    • Export Citation
  • 13.

    DeOliveira, E, Quirino, RL, Suarez, PAZ, Prado, AGS. 2006. Heats of combustion of biofuels obtained by pyrolysis and by transesterification and of biofuel/diesel blends. Thermochim Acta. 450:8790 .

    • Crossref
    • Search Google Scholar
    • Export Citation
  • 14.

    M De Luca Oliverio, F, Ioele, G, Ragno, G. 2009. Multivariate calibration techniques applied to derivative spectroscopy data for the analysis of pharmaceutical mixtures. Chem Int Lab Syst. 96:1421 .

    • Crossref
    • Search Google Scholar
    • Export Citation
  • 15.

    Carneiro, RL, Braga, JWB, Poppia, RJ, Tauler, R. 2008. Multivariate curve resolution of pH gradient flow injection mixture analysis with correction of the Schlieren effect. Analyst. 133:774783 .

    • Crossref
    • Search Google Scholar
    • Export Citation
  • 16.

    T de Nardo Shiroma-Kian, C, Halim, Y, Francis, D, Rodriguez-Saona, LE. 2009. Rapid and simultaneous determination of lycopene and beta-carotene contents in tomato juice by infrared spectroscopy. J Agric Food Chem. 57:11051112 .

    • Crossref
    • Search Google Scholar
    • Export Citation
  • 17.

    Monteiro, MR, Ambrozin, ARP, Santos, MS, Boffo, EF, Pereira-Filho, ER, Lião, LM, Ferreira, AG. 2008. Evaluation of biodiesel-diesel blends quality using H-1 NMR and chemometrics. Talanta. 78:660664 .

    • Crossref
    • Search Google Scholar
    • Export Citation
  • 18.

    Valderrama, P, Poppi, RJ. 2008. Bilinear least squares (BLLS) and molecular fluorescence in the quantification of the propranolol enantiomers. Anal Chim Acta. 623:3845 .

    • Crossref
    • Search Google Scholar
    • Export Citation
  • 19.

    Brereton, RG. 2000. Introduction to multivariate calibration in analytical chemistry. Analyst. 125:21252154 .

  • 20.

    Pappa, A, Mikedi, K, Tzamtzis, N, Statheropoulos, M. 2003. Chemometric methods for studying the effects of chemicals on cellulose pyrolysis by thermogravimetry-mass spectrometry. J Anal Appl Pyrolysis. 67:221235 .

    • Crossref
    • Search Google Scholar
    • Export Citation
  • 21.

    Kokot, S, Yang, P. 1995. Comparison of thermogravimetric and differential scanning calorimetric results for cellulosic fabrics by chemometrics. Anal Chim Acta. 304:297305 .

    • Crossref
    • Search Google Scholar
    • Export Citation
  • 22.

    Hughes, J, Shanks, R, Cerezo, F. 2004. Characterisation of the comonomer composition and distribution of copolymers using chemometric techniques. J Therm Anal Calorim. 76:10691078 .

    • Crossref
    • Search Google Scholar
    • Export Citation
  • 23.

    McCall, RD, Sharma, HSS, Kernaghan, K. 2007. Analysis of a cellulose cross-linking treatment of linen fabric using thermogravimetry. Thermochim Acta. 460:18 .

    • Crossref
    • Search Google Scholar
    • Export Citation
  • 24.

    Awaja, F, Bhargava, S. 2006. The prediction of clay contents in oil shale using DRIFTS and TGA data facilitated by multivariate calibration. Fuel. 85:13961402 .

    • Crossref
    • Search Google Scholar
    • Export Citation
  • 25.

    Svinninga, K, Høskuldsson, A, Justnes, H. 2008. Prediction of compressive strength up to 28 days from microstructure of Portland cement. Cem Concr Compos. 30:138151 .

    • Crossref
    • Search Google Scholar
    • Export Citation
  • 26.

    Norgaard, L, Saudland, A, Wagner, J, Nielsen, J, Munck, P, Engelsen, LSB. 2000. Interval partial least-squares regression (iPLS): a comparative chemometric study with an example from near-infrared spectroscopy. Spectroscopy. 54:413419 .

    • Crossref
    • Search Google Scholar
    • Export Citation
  • 27.

    Martens, H, Naes, T. 1989 Multivariate calibration Wiley New York.

  • 28.

    Thomas, EV. 1994. A primer on multivariate calibration. Anal Chem. 66:795A804A .

  • 29.

    Olivieri, AC, Faber, NM, Ferré, J, Boqué, R, Kalivas, JH, Mark, H. 2006. Uncertainty estimation and ures of merit for multivariate calibration. Pure Appl Chem. 78:633661 .

    • Crossref
    • Search Google Scholar
    • Export Citation
  • 30.

    Miller-Ihli, NJ, O'Haver, TC. 1984. Calibration and curve fitting for extended range AAS. Spectrochim Acta B. 39:16031614 .

  • 31.

    Faber, NM, Song, XH, Hopke, PK. 2003. Sample-specific standard error of prediction for partial least squares regression. Trends Anal Chem. 22:330334 .

    • Crossref
    • Search Google Scholar
    • Export Citation
  • 32.

    H Van Der Voet 1999. Pseudo-degrees of freedom for complex predictive models: the example of partial least squares. J Chemom. 13:195208 .

    • Crossref
    • Search Google Scholar
    • Export Citation
  • 33.

    ISO 11843-2, Capability of detection. Geneva, Switzerland: International Standards Organization; 2000.

  • 34.

    Ortiz, MC, Sarabia, LA, Herrero, A, Sánchez, MS, Sanz, MB, Rueda, ME, Giménez, D, Meléndez, ME. 2003. Capability of detection of an analytical method evaluating false positive and false negative (ISO 11843) with partial least squares. Chem Int Lab Syst. 69:2126 .

    • Crossref
    • Search Google Scholar
    • Export Citation
  • 35.

    Oliveira, JS, Montalvão, RS, Daher, LO, Suarez, PAZ, Rubim, JC. 2006. Determination of methyl ester contents in biodiesel blends by FTIR-ATR and FTNIR spectroscopies. Talanta. 69:12781282 .

    • Crossref
    • Search Google Scholar
    • Export Citation
  • 36.

    Lima, DG, Soares, VCD, Ribeiro, EB, Carvalho, DA, Cardoso, ECV, Rassi, FC, Mundim, KC, Rubim, JC, Suarez, PAZ. 2004. Diesel-like fuel obtained by pyrolysis of vegetable oils. J Anal Appl Pyrolysis. 71:987991 .

    • Crossref
    • Search Google Scholar
    • Export Citation
  • 37.

    Andrade RDA , Faria EA, Silva AM, Araujo WC, Jaime, Costa KP, Prado AGS. Heat of combustion of biofuels mixed with fossil diesel oil. J Therm Anal Calorim. 2011, in press.

    • Search Google Scholar
    • Export Citation
  • 38.

    Ramalho, VC, Jorge, N. 2006. Antioxidants used in oils, fats and fatty foods. Quim Nova. 29:755760 .

  • 39.

    Garcia, CC, Franco, PIBM, Zuppa, TO, Antoniosi Filho, NR, Leles, MIG. 2007. Thermal stability studies of some cerrado plant oils. J Therm Anal Calorim. 87:645648 .

    • Crossref
    • Search Google Scholar
    • Export Citation
  • 40.

    Rudnik, E, Szczucinska, A, Gwardiak, H, Szulc, A, Winiarska, A. 2001. Comparative studies of oxidative stability of linseed oil. Thermochim Acta. 370:135139 .

    • Crossref
    • Search Google Scholar
    • Export Citation

Monthly Content Usage

Abstract Views Full Text Views PDF Downloads
Nov 2020 2 3 0
Dec 2020 3 0 0
Jan 2021 1 0 0
Feb 2021 0 0 0
Mar 2021 0 0 0
Apr 2021 0 0 0
May 2021 0 0 0