FUEL ETHANOL QUALITY: METHODS OF ANALYSIS AND REFERENCE MATERIALS

Stradiotto, Nelson Ramos ; Zanoni, Maria Valnice Boldrin ; Fraga, Isabel Cristina Serta ; Borges, Paulo Paschoal

Resumo:

Biofuels constitute a viable alternative in relation to fuel derived from petrol and can be considered as important source of energy in the future. The participation of biofuel in the energetic matrix depends of a complex array of factors involving many production aspects (raw material and technology) and from the sustainability (social, economic and environmental), of this energy source. Since the start of Proalcool program the quality of ethanol was always connected with performance of engine working with hydrated alcohol and playing an important role in its sustainability economic. Afterwards, ethanol quality was considered a priority factor for environmental sustainability, mainly when it compared with other vehicles working with other fuels. More recently, ethanol quality plays a decisive role on the possibility of becoming a commodity in the international market. The validation of biofuels is markedly dependent of three basic factors: normalized specifications; official methods of analysis, and certified reference materials. The normalized specifications are a set of characteristics required to secure that the biofuel has the final destination as previously defined. The official methods are the tools necessary to construct a correct evaluation of the normalized specification of the fuel. The credited reference materials are tools utilized in the validation and official method control of fuel analysis.

Download (PDF)

29 downloads

DOI: 10.5151/9788521208228-SUGARCANEBIOETHANOL_68

Referências bibliográficas
  • [1] Firmino, MF, Saczk AA, Okumura LL, Stradiotto NR, Analytical methods employed at quality control of fuel ethanol. Energy Andamp; Fuels 2009; on line.
  • [2] Bruning IMRA, Malm EB. Identificação e quantificação das impurezas presentes no etanol. Bol Tec Petrobras 1982; 25:217-28.
  • [3] Pereira EA, Tavares MFF, Stevanato A and Cardoso AA. Evaluation of inorganic and organic contaminants in alcohol fuel by capillary electrophoresis. Quím Nova 2006; 29:66-71.
  • [4] Munoz RAA, Richter EM, Jesus DP, Lago CL, Angnes L. Determination of inorganic ions in ethanol fuel by capillary electrophoresis. J Braz Chem Soc 2004; 15:523-6.
  • [5] Okumura LL, Saczk AA, De Oliveira MF, Zanoni MVB and Stradiotto NR. Rapid and sensitive method for the determination of acetaldehyde in fuel ethanol by high-performance liquid chromatography with UV–Vis detection. Anal Bioanal Chem 2005; 381:1619–24.
  • [6] Saczk AA, Okumura LL, De Oliveira MF, Zanoni MVB and Stradiotto NR. Determination of aldehydes and ketones in fuel ethanol by high-performance liquid chromatography with electrochemical detection. Chromatographia 2006; 63:45–51.
  • [7] Vilar RBC, Da Silva R, Schossler P,Veses RC, Piatnicki CMS, Samios D et al. Preliminary characterization of anhydrous ethanol used in Brazil as automotive fuel. J. Chrom. A 2003; 985:367-73.
  • [8] Pereira EA, Tavares MFF, Stevanato A and Cardoso AA. Indirect determination of chloride and sulfate ions in alcohol fuel by capillary electrophoresis. Anal Bioanal Chem 2004; 380:178-82.
  • [9] Okumura LL, Saczk AA, De Oliveira MF, Zanoni MVB and Stradiotto NR. Determination of acetaldehyde in fuel ethanol by high-performance liquid chromatography with electrochemical detection. Anal Sci 2005; 21:441-4.
  • [10] SaintPierre TD, Tormen L, Frescura VLA, Curtius AJ. The direct analysis of fuel ethanol by ICP-MS using a flow injection system coupled to an ultrasonic nebulizer for sample introduction. J Anal Atom Spectrom 2006; 21:1340–4.
  • [11] De Oliveira AP, De Moraes M, Neto JAG, Lima EC. Simultaneous determination of Al, As, Cu, Fe, Mn, and Ni in fuel ethanol by GFAAS. Atom Spectrosc 2002; 23:39-43.
  • [12] Roldan PS, Alcantara IL, Castro GR, Rocha JC, Padilha CCF, Padilha PM. Determination of Cu, Ni, and Zn in fuel ethanol by FAAS after enrichment in column packed with 2-aminothiazole-modified silica gel. Anal Bioanal Chem 2003; 375:574-7.
  • [13] Teixeira LSG, Brasileiro JF, Borges JR MM, Cordeiro PWL. Simultaneous spectrophotometric determination of iron and copper using ferroin reagents. Quim Nova 2006; 29:741-5.
  • [14] De Oliveira FS, Korn M. Spectrophotometric determination of sulphate in automotive fuel ethanol by sequential injection analysis using dimethylsulphonazo (III) reaction. Talanta 2006; 68:992-9.
  • [15] Teixeira LSG, Leão ES, Dantas AF, Pinheiro HCL, Costa ACS, Andrade JB. Determination of formaldehyde in Brazilian alcohol fuels by flow-injection solid phase spectrophotometry. Talanta 2004; 64:711-15.
  • [16] De Oliveira AP, De Moraes M, Neto JAG, Lima EC. Direct determination of Al, As, Cu, Fe, Mn, and Ni in fuel ethanol by simultaneous GFAAS using integrated platforms pretreated with W-Rh permanent modifier together with Pd plus Mg modifier. Atom Spectrosc 2002; 23:190-5.
  • [17] Padilha PM, Padilha CCF, Rocha JC. Flame AAS determination of metal ions in fuel ethanol after preconcentration on acid carboxymethylcellulose. Quim Anal 1999; 18:299-303.
  • [18] Gomes LAM, Padilha PM, Moreira JC, Filho NLD, Gushikem Y. Determination of metal ions in fuel ethanol after preconcentration on 5-amino-1,3,4-thiadiazole-2-thiol modified silica gel. J Braz Chem Soc 1998; 9:494-8.
  • [19] Teixeira LSG, Bezerra MA, Lemos VA, Santos HC, Jesus DS, Costa ACS. Determination of Copper, Iron, Nickel, and Zinc in Ethanol Fuel by Flame Atomic Absorption Spectrometry Using On-Line Preconcentration System. Sep Sci Tech 2005; 40: 2555-65.
  • [20] Teixeira LSG, Bezerra MA, Lemos VA, Santos HC, Jesus DS, Costa ACS. Determiantion of copper, iron, nickel and zinc in ethanol fuel by flame atomic absorption spectrometry using on-line preconcentration system. Sep. Sci Tech. 2005; 40:2555-65.
  • [21] Moreira JC and Gushikem Y. Preconcentration of metal-ions on silica-gel modified with 3(1-imidazolyl) propyl groups. Anal Chim Acta 1985; 176:263-7.
  • [22] Filho NLD, Gushikem Y, Polito WL, Moreira JC and Ehirim EO. Sorption and preconcentration of metal ions in ethanol solution with a silica gel surface chemically modified with benzimidazole. Talanta 1995; 42:1625-30.
  • [23] De Oliveira AP, Okumura LL, Neto JAG, De Moraes M. Evaluation of analyte additions method for sodium determination in fuel ethanol by flame atomic emission spectrometry. Eclet Quim 2002. 27:285-91.
  • [24] Curtius AJ, Giacomelli MBO, Silva JBB, SaintPierre TD. Use of iridium plus rhodium as permanent modifier to determine As, Cd and Pb in acids and ethanol by electrothermal atomic absorption spectrometry. Microchem J 2004; 77:151-6.
  • [25] SaintPierre TD, Frescura VLA, Curtius AJ. The development of a method for the determination of trace elements in fuel alcohol by ETV-ICP-MS using isotope dilution calibration. Talanta 2006; 68:957–62.
  • [26] Oliveira FS, Leite BCO, Andrade MVAS, Korn M. Determination of total aldehydes in fuel ethanol by MBTH method –SIA. J Braz Chem Soc 2005; 16:87-92.
  • [27] Aleixo LM, Rath S, Godinho OES. Determination of total sulphur in ethanol by reduction using Raney nickel and detection by cathodic stripping voltammetry. Analyst 1988; 113:1427-9.
  • [28] Takeuchi RM, Santos AL, Padilha PM and Stradiotto NR. Copper determination in ethanol fuel by differential pulse anodic stripping voltammetry at a solid paraffin-based carbon paste electrode modified with 2-aminothiazole organofunctionalized silica. Talanta 2007; 71:771-7.
  • [29] Avelar HM, Barbeira PJS. Conductometric determination of total acidity and chloride content in automotive fuel ethanol. Fuel 2007; 86:299-302.
  • [30] De Oliveira MF, Saczk AA, Okumura LL, Fernandes AP, De Moraes M, Stradiotto NR. Simultaneous determination of zinc, copper, lead, and cadmium in fuel ethanol by anodic stripping voltammetry using a glassy carbon–mercury-film electrode. Anal Bioanal Chem 2004; 380:135-40.
  • [31] Rodgher VS, Okumura LL, Saczk AA, Stradiotto NR and Zanoni MVB. Electroanalysis and determination of acetaldehyde in fuel ethanol using the reaction with 2,4-dinitrophenylhydrazine. J Anal Chem 2006; 61:889-95.
  • [32] Romanini, DC, Trindade MAG, Zanoni MVB. A simple electroanalytical method for the analysis of the dye solvent orange 7 in fuel ethanol. Fuel 2009; 88:105–109.
  • [33] Rodgher VS, Stradiotto NR and Zanoni MVB. Electroanalysis of acetaldehyde derivatized with hydrazine and determination in fuel ethanol by square wave voltammetry. Quim Nova 2006; 29:662-5.
  • [34] Saczk AA, De Oliveira MF, Okumura LL and Stradiotto NR. Voltammetric behavior of 2-furfuraldehide reduction in ethanol using glassy carbon electrode. Eclet Quim 2002; 27:141-51.
  • [35] Tartarotti FO, De Oliveira MF, Balbo VR and Stradiotto NR. Determination of nickel in fuel ethanol using a carbon paste modified electrode containing dimethylglyoxime. Microchim Acta 2006; 155:397–401.
  • [36] Bergamini MF, Santos AL, Stradiotto NR. Lead ions determination in ethanol fuel by differential pulse anodic stripping voltammetry using a carbon paste electrode modified with ion-exchange resin Amberlite IR120. Eclet Quím 2006; 31:45-52.
  • [37] Takeuchi RM, Santos AL, Padilha PM and Stradiotto NR. A solid paraffin-based carbon paste electrode modified with 2-aminothiazole organofunctionalized silica for differential pulse adsorptive stripping analysis of nickel in ethanol fuel. Anal Chim Acta 2007; 584:295-301.
  • [38] De Oliveira MF, Saczk AA, Okumura LL, Stradiotto NR. Determination of zinc in fuel alcohol by anodic stripping voltammetry. Eclet Quim 2002; 27:153-60.
  • [39] Munoz RAA, Angnes L. Simultaneous determination of copper and lead in ethanol fuel by anodic stripping voltammetry. Microchem J 2004. 77:157-62.
  • [40] Mattos CS, Carmo DR, De Oliveira MF and Stradiotto NR. Voltammetric determination of total iron in fuel ethanol using a 1,10 fenantroline/nafion carbon paste-modified electrode. Int J Electrochem Sci 2008; 3:338-45.
  • [41] Neves EFA, Neto GO and Serrano SHP. A new type of precipitating agent for copper membrane-electrode. Anal Lett 1987; 20:1363-77.
  • [42] Moreira JR, Goldemberg J, The alcohol program, Energy Policy, 1999; 27: 229-245.
  • [43] Lima LR, Marcondes AA, Álcool Carburante uma Estratégia Brasileira, Curitiba, UFPR, 2002. [44] Futuro para o mercado do álcool e açúcar. Available at: Andlt;http://www.biodieselbr.com/energia/alcool/mercado-etanol.htmAndgt;, 30 September, 2009.
  • [45] White paper on internationally compatible biofuel standards. Tripartite task force: Brazil, European Union Andamp; United States of America, Dec. 31, 2007. Available at: www.inmetro.gov.br/painelsetorial/biocombustiveis/whitepaper.pdf.
  • [46] Bioetanol de caña de azúcar: energía para el desarrollo sostenible. Coordinación BNDES y CGEE, Rio de Janeiro: BNDES, 2008.
  • [47] Biofuels and other renewable energy in the transport sector (2009). Available at: Andlt;http://ec.europa.eu/energy/renewables/biofuels/biofuels_en.htmAndgt;, 30 August, 2009.
  • [48] Energy independency and Security Act of 2007. Available at: Andlt;http://www.govtrack.us/congress/billtext.xpd?bill=h110-6Andgt;, 30 August, 2009.
  • [49] Inmetro, Material de Referência Certificado de Bioetanol. Available at: Andlt;http://www.inmetro.gov.br/metcientifica/MRC/material_bioetanol.pdfAndgt;, 30 September, 2009.
  • [50] VIM, International Vocabulary of Metrology – Basic and general concepts and associated terms, 2008.
  • [51] Emons H, Fajgelj A, Van Der Veen, A.M.H., Watters, R., New definitions on reference materials, Accred.Qual. Assur., 10, pp. 576-578, 2006.
  • [52] ABNT ISO Guia 31:2004, Materiais de Referência – Conteúdo de certificados e rótulos. Segunda edição.
  • [53] ABNT ISO Guia 34:2004, Requisitos gerais para a competência de produtores de materiais de referência. Primeira edição.
  • [54] ISO Guide 35:2006, Reference materials – General and statistical principles for certification. Third edition.
  • [55] Richter W, Primary methods of measurement in chemical analysis, Accred Qual Assur 1997; 2: 354-359.
  • [56] Máriássy M, Vyskocil L, Mathiasová A, Link to the SI via primary direct methods, Accred Qual Assur 2000; 5:437-440.
  • [57] Fraga ICS, Rodrigues JM, Borges PP, Araújo TO, Cunha VS, Os conceitos envolvendo materiais de referência, Metrologia Andamp; Instrumentação, abril/maio, 2009; 40-43.
  • [58] ABNT ISO Guia 30:2000, Termos e definições relacionados com materiais de referência. Primeira edição.
  • [59] ABNT ISO Guia 32:2000, Calibração em química analítca e uso de materiais de referência certificados. Primeira edição.
  • [60] ABNT ISO Guia 33:2002, Utilização de materiais de referência certificados. Primeira edição.
  • [61] ABNT NBR ISO/IEC 17025:2005, Requisitos gerais para a competência de laboratórios de ensaio e calibração.
  • [62] Guia para a Expressão da Incerteza de Medição, 3 edição brasileira, ABNT / Inmetro, SERIFA comunicação: Rio de Janeiro, 2003.
  • [63] Linsinger TPJ, Pauwels J, Van der Veen AMH, Schimmel H, Lamberty A, Homogeneity and stability of reference materials, Accred Qual Assur 2001; 6: 20-25.
  • [64] Pauwels J, Van der Veen AMH, Lamberty A, Schimmel H, Evaluation of uncertainty of reference materials, Accred Qual Assur 2000; 5: 95-99.
  • [65] Van der Veen AMH, Linsinger TPJ, Schimmel H, Lamberty A, Pauwels J, Uncertainty calculations in the certification of reference materials. 4. Characterisation and certification, Accred Qual Assur 2001; 6: 290-294.
  • [66] Van der Veen AMH, Linsinger T, Pauwels J, Uncertainty calculations in the certification of reference materials. 2. Homogeneity study, Accred Qual Assur 2001; 6: 26-30.
  • [67] Van der Veen AMH, Pauwels J, Uncertainty calculations in the certification of reference materials. 1. Principles of analysis of variance, Accred Qual Assur 2000; 5: 464-469.
  • [68] Lamberty A, Schimmel H, Pauwels J, The study of the stability of reference materials by isochronous measurements, Fresenius J Anal Chemistry 1997; 360:359-361.
  • [69] Van der Veen AMH, Linsinger TPJ, Lamberty A, Pauwels J, Uncertainty calculations in the certification of reference materials. 3. Stability study, Accred Qual Assur 2001; 6: 257-263.
  • [70] International Laboratory Accreditation Cooperation, ILAC G12 Guidelines for the Requirements for the Competence of Reference Materials Producer, ILAC, 2000.
  • [71] Guidelines for feasibility studies on certified reference materials, European Commission, EUR 20574 EN, 2002.
  • [72] Resolução ANP n. 36, de 16 de dezembro de 2005.
  • [73] American Society for Testing and Material (ASTM) Standard, D4806:1998, Denatured fuel ethanol for blending with gasoline, for use as automotive spark-ignition engine fuel.
Como citar:

STRADIOTTO, Nelson Ramos; ZANONI, Maria Valnice Boldrin; FRAGA, Isabel Cristina Serta; BORGES, Paulo Paschoal; "FUEL ETHANOL QUALITY: METHODS OF ANALYSIS AND REFERENCE MATERIALS", p. 813-828. Sugarcane bioethanol — R&D for Productivity and Sustainability. São Paulo: Blucher, None.
ISBN: 9788521208228, DOI 10.5151/9788521208228-SUGARCANEBIOETHANOL_68