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MAGNETIC MESOPOROUS SILICA NANOCOMPOSITE DECORATED WITH HETEROPOLY TUNGSTIC ACID AS HIGHLY EFFICIENT AND STABLE CATALYST FOR BIODIESEL PRODUCTION

Year 2020, Volume: 21 Issue: 2, 335 - 349, 15.06.2020
https://doi.org/10.18038/estubtda.657085

Abstract

A multifunctional heterogeneous acid catalyst named as spFe3O4@SBA-15@HPW was prepared, which consists of versatile properties such as magnetic separability, high conversion efficiency and reusability. This catalyst was characterized by XRD, FT-IR, VSM, TEM and SEM/EDX techniques with respect to structural, morphological and magnetic properties. The catalyst showed higher catalytic activity than the commercial catalysts such as Amberlyst-15 and Dowex 50Wx4 and also heteropoly tungstic acid (HPW) alone in terms of conversion of oleic acid for biodiesel production by the esterification of oleic acid with methanol. The experimental data were correlated by pseudo-first-order homogeneous and Eley-Rideal heterogeneous models, and the results demonstrate the suitability of Eley-Rideal mechanism.

References

  • [1] Chen Y, Cao Y, Suo Y, Zheng G P, Guan X X, Zheng X C. Mesoporous solid acid catalysts of 12-tungstosilicic acid anchored to SBA-15: Characterization and catalytic properties for esterification of oleic acid with methanol. J Taiwan Inst Chem E 2015; 51: 186-192.
  • [2] Kozhevnikov I V, Kloetstra K R, Sinnema A, Zandbergen H W, van Bekkum H. Study of catalysts comprising heteropoly acid H3PW12O40 supported on MCM-41 molecular sieve and amorphous silica. J Mol Catal A Chem 1996; 114: 287-298.
  • [3] Gagea B C, Lorgouilloux Y, Altintas Y, Jacobs P A, Martens J A. Bifunctional conversion of n-decane over HPW heteropoly acid incorporated into SBA-15 during synthesis. J Catal 2009; 265: 99-108.
  • [4] Qiu J, Wang G, Zhang Y, Zeng D, Chen Y. Direct synthesis of mesoporous H3PMo12O40/SiO2 and its catalytic performance in oxidative desulfurization of fuel oil. Fuel 2015; 147: 195-202.
  • [5] Abdalla Z E A, Li B, Tufail A. Direct synthesis of mesoporous (C19H42N)4H3(PW11O39)/SiO2 and its catalytic performance in oxidative desulfurization. Colloids Surf A Physicochem Eng Asp 2009; 341: 86-92.
  • [6] Yan X M, Mei Z, Mei P, Yang Q. Self-assembled HPW/silica–alumina mesoporous nanocomposite as catalysts for oxidative desulfurization of fuel oil. J Porous Mater 2014; 21: 729-737.
  • [7] Wang X S, Huang Y B, Lin Z J, Cao R. Phosphotungstic acid encapsulated in the mesocages of amine-functionalized metal–organic frameworks for catalytic oxidative desulfurization. Dalton Trans 2014; 43: 11950-11958.
  • [8] Yue D, Lei J, Peng Y, Li J, Du X. Hierarchical ordered meso/macroporous H3PW12O40/SiO2 catalysts with superior oxidative desulfurization activity. J Porous Mater 2018; 25: 727-734.
  • [9] Patil C R, Rode C V. Synthesis of diesel additives from fructose over PWA/SBA-15 catalyst. Fuel 2018; 217: 38-44.
  • [10] Li S, Zhai S R, Zhang J M, Xiao Z Y, An Q D, Li M H, Song X W. Magnetic and Stable H3PW12O40-Based Core@shell Nanomaterial towards the Esterification of Oleic Acid with Methanol. Eur J Inorg Chem 2013; 5428-5435.
  • [11] Kralj S, Makovec D, Campelj S, Drofenik M. Producing ultra-thin silica coatings on iron-oxide nanoparticles to improve their surface reactivity. J Magn Magn Mater 2010; 322: 1847-1853.
  • [12] Mrowczynski R, Nan A, Liebscher J. Magnetic nanoparticle-supported organocatalysts-an efficient way of recycling and reuse. RSC Adv 2014; 4: 5927–5952.
  • [13] Wang Y T, Fang Z, Yang X X. Biodiesel production from high acid value oils with a highly active and stable bifunctional magnetic acid. Appl Energy 2017; 204: 702–714.
  • [14] Hoo P Y, Abdullah A Z. Direct synthesis of mesoporous 12-tungstophosphoric acid SBA-15 catalyst for selective esterification of glycerol and lauric acid to monolaurate. Chem Eng J 2014; 250: 274–287.
  • [15] Li B, Ma W, Liu J, Han C, Zuo S, Li X. Synthesis of the well-ordered hexagonal mesoporous silicate incorporated with phosphotungstic acid through a novel method and its catalytic performance on the oxidative desulfurization reaction. Catal Commun 2011; 13: 101–105.
  • [16] Souza K C, Salazar-Alvarez G, Ardisson J D, Macedo W A A, Sousa E M B. Mesoporous silica–magnetite nanocomposite synthesized by using a neutral surfactant. Nanotechnology 2008; 19: 185603.
  • [17] Brahmkhatri V, Patel A. 12-Tungstophosphoric acid anchored to SBA-15: An efficient, environmentally benign reusable catalysts for biodiesel production by esterification of free fatty acids Appl Catal A Gen 2011; 403: 161– 172.
  • [18] Masteri-Farahani M, Modarres M. Wells-Dawson heteropoly acid immobilized inside the nanocages of SBA-16 with ship-in-a-bottle method: A new recoverable catalyst for the epoxidation of olefins. J Mol Catal A Chem 2016; 417: 81-88.
  • [19] Chen Y, Zhang X, Dong M, Wu Y, Zheng G, Huang J, Guan X, Zheng X. MCM-41 immobilized 12-silicotungstic acid mesoporous materials: Structural and catalytic properties for esterification of levulinic acid and oleic acid. J Taiwan Inst Chem E 2016; 61: 147-155.
  • [20] Frattini L, Isaacs M A, Parlett C M A, Wilson K, Kyriakou G. Support enhanced α-pinene isomerization over HPW/SBA-15. Appl Catal B Environ 2017; 200: 10-18.
  • [21] Brigante M, Pecini E, Avena M. Magnetic mesoporous silica for water remediation: Synthesis, characterization and application as adsorbent of molecules and ions of environmental concern. Micro Meso Mater 2016; 230: 1-10.
  • [22] Groen J C, Peffer L A A, Perez-Ramirez J. Pore size determination in modified micro-and mesoporous materials. Pitfalls and limitations in gas adsorption data analysis. Micro Meso Mater 2003; 60: 1-17.
  • [23] Fazaeli R, Aliyan H. Production of Biodiesel through Esterification of Palmitic Acid Using 12-Tungestoposphoric Acid Supported on Nanocavity of Aluminium Incorporated Mesoporous SBA-15. Russ J Appl Chem 2015; 88: 676-681.
  • [24] Xiong J, Zhu W, Ding W, Yang L, Chao Y, Li H, Zhu F, Li H. Phosphotungstic Acid Immobilized on Ionic Liquid-Modified SBA-15: Efficient Hydrophobic Heterogeneous Catalyst for Oxidative Desulfurization in Fuel. Ind Eng Chem Res 2014; 53: 19895-19904.
  • [25] Dashtian K, Zare-Dorabei R. Synthesis and characterization of functionalized mesoprous SBA-15 decorated with Fe3O4 nanoparticles for removal of Ce(III) ions from aqueous solution: ICP–OES detection and central composite design optimization. J Colloid Interface Sci 2017; 494: 114-123.
  • [26] Nicola R, Costişor O, Muntean S G, Nistor M A, Putz A M, Ianaşi C, Lazau R, Almasy L, Sacarescu L. Mesoporous magnetic nanocomposites: a promising adsorbent for the removal of dyes from aqueous solutions. J Porous Mater 2020; 27: 413-428.
  • [27] Ilgen O. Investigation of reaction parameters, kinetics and mechanism of oleic acid esterification with methanol by using Amberlyst 46 as a catalyst. Fuel Process Tech 2014; 124: 134-139.
Year 2020, Volume: 21 Issue: 2, 335 - 349, 15.06.2020
https://doi.org/10.18038/estubtda.657085

Abstract

References

  • [1] Chen Y, Cao Y, Suo Y, Zheng G P, Guan X X, Zheng X C. Mesoporous solid acid catalysts of 12-tungstosilicic acid anchored to SBA-15: Characterization and catalytic properties for esterification of oleic acid with methanol. J Taiwan Inst Chem E 2015; 51: 186-192.
  • [2] Kozhevnikov I V, Kloetstra K R, Sinnema A, Zandbergen H W, van Bekkum H. Study of catalysts comprising heteropoly acid H3PW12O40 supported on MCM-41 molecular sieve and amorphous silica. J Mol Catal A Chem 1996; 114: 287-298.
  • [3] Gagea B C, Lorgouilloux Y, Altintas Y, Jacobs P A, Martens J A. Bifunctional conversion of n-decane over HPW heteropoly acid incorporated into SBA-15 during synthesis. J Catal 2009; 265: 99-108.
  • [4] Qiu J, Wang G, Zhang Y, Zeng D, Chen Y. Direct synthesis of mesoporous H3PMo12O40/SiO2 and its catalytic performance in oxidative desulfurization of fuel oil. Fuel 2015; 147: 195-202.
  • [5] Abdalla Z E A, Li B, Tufail A. Direct synthesis of mesoporous (C19H42N)4H3(PW11O39)/SiO2 and its catalytic performance in oxidative desulfurization. Colloids Surf A Physicochem Eng Asp 2009; 341: 86-92.
  • [6] Yan X M, Mei Z, Mei P, Yang Q. Self-assembled HPW/silica–alumina mesoporous nanocomposite as catalysts for oxidative desulfurization of fuel oil. J Porous Mater 2014; 21: 729-737.
  • [7] Wang X S, Huang Y B, Lin Z J, Cao R. Phosphotungstic acid encapsulated in the mesocages of amine-functionalized metal–organic frameworks for catalytic oxidative desulfurization. Dalton Trans 2014; 43: 11950-11958.
  • [8] Yue D, Lei J, Peng Y, Li J, Du X. Hierarchical ordered meso/macroporous H3PW12O40/SiO2 catalysts with superior oxidative desulfurization activity. J Porous Mater 2018; 25: 727-734.
  • [9] Patil C R, Rode C V. Synthesis of diesel additives from fructose over PWA/SBA-15 catalyst. Fuel 2018; 217: 38-44.
  • [10] Li S, Zhai S R, Zhang J M, Xiao Z Y, An Q D, Li M H, Song X W. Magnetic and Stable H3PW12O40-Based Core@shell Nanomaterial towards the Esterification of Oleic Acid with Methanol. Eur J Inorg Chem 2013; 5428-5435.
  • [11] Kralj S, Makovec D, Campelj S, Drofenik M. Producing ultra-thin silica coatings on iron-oxide nanoparticles to improve their surface reactivity. J Magn Magn Mater 2010; 322: 1847-1853.
  • [12] Mrowczynski R, Nan A, Liebscher J. Magnetic nanoparticle-supported organocatalysts-an efficient way of recycling and reuse. RSC Adv 2014; 4: 5927–5952.
  • [13] Wang Y T, Fang Z, Yang X X. Biodiesel production from high acid value oils with a highly active and stable bifunctional magnetic acid. Appl Energy 2017; 204: 702–714.
  • [14] Hoo P Y, Abdullah A Z. Direct synthesis of mesoporous 12-tungstophosphoric acid SBA-15 catalyst for selective esterification of glycerol and lauric acid to monolaurate. Chem Eng J 2014; 250: 274–287.
  • [15] Li B, Ma W, Liu J, Han C, Zuo S, Li X. Synthesis of the well-ordered hexagonal mesoporous silicate incorporated with phosphotungstic acid through a novel method and its catalytic performance on the oxidative desulfurization reaction. Catal Commun 2011; 13: 101–105.
  • [16] Souza K C, Salazar-Alvarez G, Ardisson J D, Macedo W A A, Sousa E M B. Mesoporous silica–magnetite nanocomposite synthesized by using a neutral surfactant. Nanotechnology 2008; 19: 185603.
  • [17] Brahmkhatri V, Patel A. 12-Tungstophosphoric acid anchored to SBA-15: An efficient, environmentally benign reusable catalysts for biodiesel production by esterification of free fatty acids Appl Catal A Gen 2011; 403: 161– 172.
  • [18] Masteri-Farahani M, Modarres M. Wells-Dawson heteropoly acid immobilized inside the nanocages of SBA-16 with ship-in-a-bottle method: A new recoverable catalyst for the epoxidation of olefins. J Mol Catal A Chem 2016; 417: 81-88.
  • [19] Chen Y, Zhang X, Dong M, Wu Y, Zheng G, Huang J, Guan X, Zheng X. MCM-41 immobilized 12-silicotungstic acid mesoporous materials: Structural and catalytic properties for esterification of levulinic acid and oleic acid. J Taiwan Inst Chem E 2016; 61: 147-155.
  • [20] Frattini L, Isaacs M A, Parlett C M A, Wilson K, Kyriakou G. Support enhanced α-pinene isomerization over HPW/SBA-15. Appl Catal B Environ 2017; 200: 10-18.
  • [21] Brigante M, Pecini E, Avena M. Magnetic mesoporous silica for water remediation: Synthesis, characterization and application as adsorbent of molecules and ions of environmental concern. Micro Meso Mater 2016; 230: 1-10.
  • [22] Groen J C, Peffer L A A, Perez-Ramirez J. Pore size determination in modified micro-and mesoporous materials. Pitfalls and limitations in gas adsorption data analysis. Micro Meso Mater 2003; 60: 1-17.
  • [23] Fazaeli R, Aliyan H. Production of Biodiesel through Esterification of Palmitic Acid Using 12-Tungestoposphoric Acid Supported on Nanocavity of Aluminium Incorporated Mesoporous SBA-15. Russ J Appl Chem 2015; 88: 676-681.
  • [24] Xiong J, Zhu W, Ding W, Yang L, Chao Y, Li H, Zhu F, Li H. Phosphotungstic Acid Immobilized on Ionic Liquid-Modified SBA-15: Efficient Hydrophobic Heterogeneous Catalyst for Oxidative Desulfurization in Fuel. Ind Eng Chem Res 2014; 53: 19895-19904.
  • [25] Dashtian K, Zare-Dorabei R. Synthesis and characterization of functionalized mesoprous SBA-15 decorated with Fe3O4 nanoparticles for removal of Ce(III) ions from aqueous solution: ICP–OES detection and central composite design optimization. J Colloid Interface Sci 2017; 494: 114-123.
  • [26] Nicola R, Costişor O, Muntean S G, Nistor M A, Putz A M, Ianaşi C, Lazau R, Almasy L, Sacarescu L. Mesoporous magnetic nanocomposites: a promising adsorbent for the removal of dyes from aqueous solutions. J Porous Mater 2020; 27: 413-428.
  • [27] Ilgen O. Investigation of reaction parameters, kinetics and mechanism of oleic acid esterification with methanol by using Amberlyst 46 as a catalyst. Fuel Process Tech 2014; 124: 134-139.
There are 27 citations in total.

Details

Primary Language English
Journal Section Articles
Authors

Beyhan Erdem 0000-0002-1803-9400

Kübra Bilgin 0000-0001-6765-8227

Publication Date June 15, 2020
Published in Issue Year 2020 Volume: 21 Issue: 2

Cite

AMA Erdem B, Bilgin K. MAGNETIC MESOPOROUS SILICA NANOCOMPOSITE DECORATED WITH HETEROPOLY TUNGSTIC ACID AS HIGHLY EFFICIENT AND STABLE CATALYST FOR BIODIESEL PRODUCTION. Eskişehir Technical University Journal of Science and Technology A - Applied Sciences and Engineering. June 2020;21(2):335-349. doi:10.18038/estubtda.657085