Modeling and multivariate analysis of the production process of alpha-hydroxy acids and hydrogen by electro-oxidation of glycerol / Modelagem e análise multivariada do processo de produção de alfa-hidroxiácidos e hidrogênio por eletro-oxidação de glicerol

Eduardo Dória Silva, Nelson Medeiros de Lima Filho, Humberto Dória Silva

Abstract


The electro-oxidation of alkaline solutions of glycerol to obtain alpha-hydroxy acids and hydrogen is a sustainable procedure of a renewable nature, with the raw material derived from the co-production of biodiesel. The system is composed of a stirred tank electrochemical reactor built "ad-hoc" with a cell separated by ceramic where oxygen is generated to produce acids and hydrogen. The present studies were conducted by controlling the variables: temperature (0C), molar ratio (mol/mol) and current density (mA/cm2), based on experimental design and cyclic voltammogram. The empirical model and multivariate analysis were obtained through data collected by HPLC with a refractive index detector. This analysis presents the conversion of glycerol to tartronic and oxalic acid associated with the current density corresponding to factor1. Factor2 reveals the productivity of glyceric acid and glycolic acid related to molar ratio. The accumulated percentage of the two factors were more than 75% representative.  The empirical model built from experimental planning had  an error of less than 5%. The best phenomenological model experienced had an average error of less than 7%. From this model, the amount of hydrogen generated in the NTP was calculated.


Keywords


glycerol electro-oxidation, alpha hydroxy acids, hydrogen, empirical and phenomenological modeling, multivariate analysis

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BARROS NETO, B.; SCARMINIO, I. S.; BRUNS, R. E. Como fazer experimentos. 3 ed. Campinas, SP: Editora UNICAMP. 2007.

CIRIMINNA, R; PINA, C. D,; ROSSI, M.; PAGLIAGO, M. Understanding the glycerol market. Eur. J. Lipid Sci. Technol. v. 116. p. 1432-1439. 2014.

COEURET, F. Introduction a La Ingeniería Electroquímica. Universidad de Rennes. Editorial Reverté, S. A. Barcelona, Espanha. 1992.

FARNETTI, E., CROTTI, C. Selective oxidation of glycerol to formic acid catalyzed by iron salts. Catalysis Communications, v. 84, p. 1-4, 2016.

FERNANDEZ, P.; MARTINS, M. E.; CAMARA, A,C. New insights about the electro-oxidation of glycerol on platinum nanoparticles supported on multi-walled carbon nanotubes. Electrochimica Acta, v. 66, p. 180-187, 2012.

GARCIA, A. C; FERREIRA, E. B; BARROS, V. V. S; LINARES, J. J; TREMILIOSI-FILHO, G. Pt/Ag/MnOx/C as a promising electrocalalyst for glycerol electro-oxidation in alcaline médium. Journal of Electroanalytical Chemistry. v. 793. p. 188-196. 2017.

GIL, S.; MARCHENA, M; SÁNCHEZ-SILVA, L.; ROMERO, A.; SÁNCHEZ, P.; VALVERDE, J. L. Effect of the operations on the selective oxidation of glycerol with catalysts based on Au supported on carbonaceous materials. Chemical Engineering Journal, v. 178, p. 423-435. 2011.

GOMES, J. F; TREMILIOS-FILHO, G. Spectroscopic studies of the glycerol electro-oxidation on polycrystalline Au and Pt surfaces in acid and alkaline media. Electrocatal, v.2, p. 96-105, 2011.

LERTTHAHAN, P.; YONGPRAPAT, S.; THERDTHIANWONG, A.; THERDTHIANWONG, S. Pt-modified Au/C catalysts for direct glycerol electro-oxidation in an alkaline medium. International Journal of Hydrogen Energy. 2016.

LIANG D.; GAO, J.; WANG, J.; CHEN, P.; HOU, Z.; ZHEN, X. Selective oxidation of glycerol in a base-free aqueous solution over different sized Pt catalysts. Catalysis Communications, 2009.

MELLE, G. B; MACHADO, E. G; MASCARO, L. H; SITTA, E. Effect of mass transport on the glycerol electro-oxidation. Electrochimica Acta. v.296. p. 972-979. 2019.

ROQUET, I.; BELGSIR, E. M.; LÉGER, J. M.; LAMY, C. Kinetics and mechanisms of the electrocatalytic oxidation of glycerol as investigated by chromatographic analysis of the reaction products: potential and pH effects. Electrochimica Acta, v. 39, n. 16, p. 2387-2394. 1994.

SIMÕES M.; BARANTON, S.; COUTANCEAU, C. Electro-oxidation of glycerol at Pd based nano-catalysts for an application in alkaline fuel cells for chemicals and energy cogeneration. Applied Catalysis B: Environmental, v. 93, p. 354-362, 2010.

SIMÕES M;, BARANTON S;, COUTANCEAU C. Electrochemical valorization of glycerol. ChemSusChem. v. 5. 2106-2124. 2012.

SILVA, E. D.; LIMA FILHO, N. M. Avaliação do processo de eletro-oxidação aplicado à produção de alfa-hidroxiácidos. Congresso Brasileiro de Engenharia Química. Anais. 2016. Fortaleza, Ce.

VON FRAUNHOFER, J. A.; BANKS, C. H. Potentiostat and its applications. Butterworth & Co. Publishers Ltd. London. 1972.

ZHOU, Y.; SHEN, Y. Selective electro-oxidation of glycerol over Pd and Pt@Pd nanocubes. Electrochemistry Communications. v. 90, p. 106-110. 2018.




DOI: https://doi.org/10.34117/bjdv6n2-046

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