Assessment the activity of magnetic KOH/Fe3O4@Al2O3 core–shell nanocatalyst in transesterification reaction: effect of Fe/Al ratio on structural and performance

Kazemifard, Sina; Nayebzadeh, Hamed; Saghatoleslami, Naser; Safakish, Ebrahim

doi:10.1007/s11356-018-3249-7

Research Article
Published: 24 September 2018

Assessment the activity of magnetic KOH/Fe₃O₄@Al₂O₃ core–shell nanocatalyst in transesterification reaction: effect of Fe/Al ratio on structural and performance

Sina Kazemifard¹,
Hamed Nayebzadeh ORCID: orcid.org/0000-0001-9813-5189²,
Naser Saghatoleslami¹ &
Ebrahim Safakish¹

Environmental Science and Pollution Research volume 25, pages 32811–32821 (2018)Cite this article

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Abstract

Recently, biodiesel production using heterogeneous catalysts has been of great concern. However, simple separation of these catalysts from product mixtures is a problem of the process. In this study, series of magnetic KOH/Fe₃O₄@Al₂O₃ core–shell nanocatalysts were synthesized via the incipient wetness impregnation method and the effect of weight ratio of Fe₃O₄-to-Al₂O₃ (0.15–0.35) on the catalytic performance was assessed. The samples were characterized by XRD, FTIR, BET-BJH, VSM, SEM, TEM, and EDX analyses and their basicity was measured by the Hammett indicator method. The results revealed that although the magnetic KOH/Fe₃O₄@Al₂O₃ nanocatalyst with 25 wt% of Fe₃O₄ showed less activity as compared to those with 15 wt% of Fe3O4, it exhibited higher surface area and appropriate magnetic properties. The sample presented superparamagnetic properties with the magnetic strength of 1.25 emu/g that was simply recovered by using an external magnetic field. The nanocatalyst converted 98.8% of canola oil to biodiesel under reflux condition at the best operational conditions of 12 M ratio of methanol/oil, 4 wt% of catalyst and 6 h of reaction time. Moreover, the nanocatalyst showed high reusability such that it was reused several times without appreciable loss of its catalytic activity.

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References

Ahangaran F, Hassanzadeh A, Nouri S (2013) Surface modification of Fe₃O₄@SiO₂ microsphere by silane coupling agent Int Nano Lett 3:1–5 doi:https://doi.org/10.1186/2228-5326-3-23
Castro CS, Garcia Júnior LCF, Assaf JM (2014) The enhanced activity of Ca/MgAl mixed oxide for transesterification. Fuel Process Technol 125:73–78. https://doi.org/10.1016/j.fuproc.2014.03.024
CAS Article Google Scholar
Chang Y-P, Chang P-H, Lee Y-T, Lee T-J, Lai Y-H, Chen S-Y (2014) Morphological and structural evolution of mesoporous calcium aluminate nanocomposites by microwave-assisted synthesis. Microporous Mesoporous Mater 183:134–142. https://doi.org/10.1016/j.micromeso.2013.09.013
CAS Article Google Scholar
da Costa Evangelista JP, Gondim AD, Souza LD, Araujo AS (2016) Alumina-supported potassium compounds as heterogeneous catalysts for biodiesel production: a review. Renew Sust Energ Rev 59:887–894. https://doi.org/10.1016/j.rser.2016.01.061
CAS Article Google Scholar
Dall'Oglio EL, PTd SJ, Oliveira PTJ, LGd V, Parizotto CA, Kuhnen CA (2014) Use of heterogeneous catalysts in methylic biodiesel production induced by microwave irradiation. Química Nova 37:411–417
CAS Article Google Scholar
Dantas J, Leal E, Mapossa AB, Cornejo DR, Costa ACFM (2017) Magnetic nanocatalysts of Ni_0.5Zn_0.5Fe₂O₄ doped with Cu and performance evaluation in transesterification reaction for biodiesel production. Fuel 191:463–471. https://doi.org/10.1016/j.fuel.2016.11.107
CAS Article Google Scholar
Dussan KJ, Cardona CA, Giraldo OH, Gutiérrez LF, Pérez VH (2010) Analysis of a reactive extraction process for biodiesel production using a lipase immobilized on magnetic nanostructures. Bioresour Technol 101:9542–9549. https://doi.org/10.1016/j.biortech.2010.07.044
CAS Article Google Scholar
Evangelista JPC, Chellappa T, Coriolano ACF, Fernandes Jr VJ, Souza LD, Araujo AS (2012) Synthesis of alumina impregnated with potassium iodide catalyst for biodiesel production from rice bran oil Fuel Process Technol 104:90–95 doi:https://doi.org/10.1016/j.fuproc.2012.04.028
CAS Article Google Scholar
Feyzi M, Norouzi L (2016) Preparation and kinetic study of magnetic Ca/Fe₃O₄@SiO₂ nanocatalysts for biodiesel production. Renew Energy 94:579–586. https://doi.org/10.1016/j.renene.2016.03.086
CAS Article Google Scholar
Gawande MB, Goswami A, Asefa T, Guo H, Biradar AV, Peng DL, Zboril R, Varma RS (2015) Core–shell nanoparticles: synthesis and applications in catalysis and electrocatalysis. Chem Soc Rev 44:7540–7590. https://doi.org/10.1039/C5CS00343A
CAS Article Google Scholar
Ghafuri H, Rashidizadeh A, Ghorbani B, Talebi M (2015) Nano magnetic sulfated zirconia (Fe₃O₄@ZrO₂/SO₄ ²⁻): an efficient solid acid catalyst for the green synthesis of [small alpha]-aminonitriles and imines. New J Chem 39:4821–4829. https://doi.org/10.1039/C5NJ00314H
CAS Article Google Scholar
Guo P, Huang F, Zheng M, Li W, Huang Q (2012) Magnetic solid base catalysts for the production of biodiesel. J Am Oil Chem Soc 89:925–933. https://doi.org/10.1007/s11746-011-1979-5
CAS Article Google Scholar
Hájek M, Skopal F, Čapek L, Černoch M, Kutálek P (2012) Ethanolysis of rapeseed oil by KOH as homogeneous and as heterogeneous catalyst supported on alumina and CaO. Energy 48:392–397. https://doi.org/10.1016/j.energy.2012.06.052
CAS Article Google Scholar
Hashemzehi M, Saghatoleslami N, Nayebzadeh H (2016a) Microwave-assisted solution combustion synthesis of spinel-type mixed oxides for esterification reaction. Chem Eng Commun 204:415–423. https://doi.org/10.1080/00986445.2016.1273831
CAS Article Google Scholar
Hashemzehi M, Saghatoleslami N, Nayebzadeh H (2016b) A study on the structure and catalytic performance of Zn_xCu_1−xAl₂O₄ catalysts synthesized by the solution combustion method for the esterification reaction. Comptes Rendus Chimie 19:955–962. https://doi.org/10.1016/j.crci.2016.05.006
CAS Article Google Scholar
Hojjat M, Nayebzadeh H, Khadangi-Mahrood M, Rahmani-Vahid B (2016) Optimization of process conditions for biodiesel production over CaO–Al₂O₃/ZrO₂ catalyst using response surface methodology. Chem Pap 71:689–698. https://doi.org/10.1007/s11696-016-0096-1
CAS Article Google Scholar
Hu S, Guan Y, Wang Y, Han H (2011) Nano-magnetic catalyst KF/CaO–Fe3O4 for biodiesel production. Appl Energy 88:2685–2690. https://doi.org/10.1016/j.apenergy.2011.02.012
CAS Article Google Scholar
Komintarachat C, Chuepeng S (2009) Solid acid catalyst for biodiesel production from waste used cooking oils. Ind Eng Chem Res 48:9350–9353. https://doi.org/10.1021/ie901175d
CAS Article Google Scholar
Liu S, Ma J, Guan L, Li J, Wei W, Sun Y (2009) Mesoporous CaO–ZrO₂ nano-oxides: a novel solid base with high activity and stability. Microporous Mesoporous Mater 117:466–471. https://doi.org/10.1016/j.micromeso.2008.07.026
CAS Article Google Scholar
Liu C, Lv P, Yuan Z, Yan F, Luo W (2010) The nanometer magnetic solid base catalyst for production of biodiesel. Renew Energy 35:1531–1536. https://doi.org/10.1016/j.renene.2009.10.009
CAS Article Google Scholar
Liu C-H, Huang C-C, Wang Y-W, Lee D-J, Chang J-S (2012) Biodiesel production by enzymatic transesterification catalyzed by Burkholderia lipase immobilized on hydrophobic magnetic particles. Appl Energy 100:41–46. https://doi.org/10.1016/j.apenergy.2012.05.053
CAS Article Google Scholar
Liu Q, Xin R, Li C, Xu C, Yang J (2013) Application of red mud as a basic catalyst for biodiesel production. J Environ Sci 25:823–829. https://doi.org/10.1016/S1001-0742(12)60067-9
CAS Article Google Scholar
Liu Y, Zhang P, Fan M, Jiang P (2016) Biodiesel production from soybean oil catalyzed by magnetic nanoparticle MgFe₂O₄@CaO. Fuel 164:314–321. https://doi.org/10.1016/j.fuel.2015.10.008
CAS Article Google Scholar
Ma G, Hu W, Pei H, Jiang L, Ji Y, Mu R (2014) Study of KOH/Al₂O₃ as heterogeneous catalyst for biodiesel production via in situ transesterification from microalgae. Environ Technol 36:622–627. https://doi.org/10.1080/09593330.2014.954629
CAS Article Google Scholar
Ma G, Hu W, Pei H, Jiang L, Ji Y, Mu R (2015) Study of KOH/Al₂O₃ as heterogeneous catalyst for biodiesel production via in situ transesterification from microalgae. Environ Technol 36:622–627. https://doi.org/10.1080/09593330.2014.954629
CAS Article Google Scholar
Macedo AL et al (2016) A mesoporous SiO₂/Fe₂O₃/KI heterogeneous magnetic catalyst for the green synthesis of biodiesel. J Braz Chem Soc 27:2290–2299
CAS Google Scholar
Mandić V, Kurajica S (2015) The influence of solvents on sol–gel derived calcium aluminate. Mater Sci Semicond Process 38:306–313. https://doi.org/10.1016/j.mssp.2015.01.004
CAS Article Google Scholar
Marinkovic Milos M., I. SN, Vasic Marija B., Ljupkovic Radomir B., Rancic Sofija M., Spalovic Boban R., R. ZA (2016) Synthesis of biodiesel from sunflower oil over potassium loaded alumina as heterogeneous catalyst: the effect of process parameters Hemijska industrija 70
Mehrasbi MR, Mohammadi J, Peyda M, Mohammadi M (2017) Covalent immobilization of Candida antarctica lipase on core-shell magnetic nanoparticles for production of biodiesel from waste cooking oil. Renew Energy 101:593–602. https://doi.org/10.1016/j.renene.2016.09.022
CAS Article Google Scholar
Mutreja V, Singh S, Ali A (2011) Biodiesel from mutton fat using KOH impregnated MgO as heterogeneous catalysts. Renew Energy 36:2253–2258. https://doi.org/10.1016/j.renene.2011.01.019
CAS Article Google Scholar
Nayebzadeh H, Saghatoleslami N, Tabasizadeh M (2016) Optimization of the activity of KOH/calcium aluminate nanocatalyst for biodiesel production using response surface methodology. J Taiwan Inst Chem Eng 68:379–386. https://doi.org/10.1016/j.jtice.2016.09.041
CAS Article Google Scholar
Noiroj K, Intarapong P, Luengnaruemitchai A, Jai-In S (2009) A comparative study of KOH/Al₂O₃ and KOH/NaY catalysts for biodiesel production via transesterification from palm oil. Renew Energy 34:1145–1150
CAS Article Google Scholar
Rahmani Vahid B, Haghighi M (2016) Urea-nitrate combustion synthesis of MgO/MgAl₂O₄ nanocatalyst used in biodiesel production from sunflower oil: influence of fuel ratio on catalytic properties and performance. Energy Convers Manag 126:362–372. https://doi.org/10.1016/j.enconman.2016.07.050
CAS Article Google Scholar
Rahmani Vahid B, Saghatoleslami N, Nayebzadeh H, Maskooki A (2012) Preparation of nano-size Al-promoted sulfated zirconia and the impact of calcination temperature on its catalytic activity. Chem Biochem Eng Q 26:71–77
Google Scholar
Shahraki H, Entezari MH, Goharshadi EK (2015) Sono-synthesis of biodiesel from soybean oil by KF/γ-Al₂O₃ as a nano-solid-base catalyst. Ultrason Sonochem 23:266–274. https://doi.org/10.1016/j.ultsonch.2014.09.010
CAS Article Google Scholar
Shao GN, Sheikh R, Hilonga A, Lee JE, Park Y-H, Kim HT (2013) Biodiesel production by sulfated mesoporous titania–silica catalysts synthesized by the sol–gel process from less expensive precursors. Chem Eng J 215–216:600–607. https://doi.org/10.1016/j.cej.2012.11.059
CAS Article Google Scholar
Shokuhi Rad A, Hoseini Nia M, Ardestani F, Nayebzadeh H (2016) Esterification of waste chicken fat: sulfonated MWCNT toward biodiesel production Waste and Biomass Valorization:1–9 doi:https://doi.org/10.1007/s12649-016-9732-9
Article Google Scholar
Shu Q, Zhang Q, Xu G, Nawaz Z, Wang D, Wang J (2009) Synthesis of biodiesel from cottonseed oil and methanol using a carbon-based solid acid catalyst. Fuel Process Technol 90:1002–1008. https://doi.org/10.1016/j.fuproc.2009.03.007
CAS Article Google Scholar
Umdu ES, Seker E (2012) Transesterification of sunflower oil on single step sol–gel made Al₂O₃ supported CaO catalysts: effect of basic strength and basicity on turnover frequency. Bioresour Technol 106:178–181. https://doi.org/10.1016/j.biortech.2011.11.135
CAS Article Google Scholar
Wang P, Huang W, Zhang G, Gao Z, Tang Y, Sun K, Zhang X (2015) The facile preparation of Cu–Zn–Al oxide composite catalysts with high stability and performance for the production of dimethyl ether using modified aluminum alkoxide. J Ind Eng Chem 26:243–250. https://doi.org/10.1016/j.jiec.2014.12.001
CAS Article Google Scholar
Xie W, Peng H, Chen L (2006) Transesterification of soybean oil catalyzed by potassium loaded on alumina as a solid-base catalyst. Appl Catal A Gen 300:67–74. https://doi.org/10.1016/j.apcata.2005.10.048
CAS Article Google Scholar
Ye B, Qiu F, Sun C, Li Y, Yang D (2014) Biodiesel production from soybean oil using heterogeneous solid base catalyst. J Chem Technol Biotechnol 89:988–997. https://doi.org/10.1002/jctb.4190
CAS Article Google Scholar
Yiping Y, Zhang W, Yan L, Houfang J, CUI C-s (2015) Transesterification of soybean oil using KOH/γ-Al2O3 catalyst synthesized by sol-gel method. Paper presented at the 17th International Symposium on Relations between Homogeneous and Heterogeneous Catalysis (ISHHC17), Utrecht, Netherlands, 2015-07-12
Zhang C, Wang H, Liu F, Wang L, He H (2013) Magnetic core–shell Fe₃O₄@C-SO₃H nanoparticle catalyst for hydrolysis of cellulose. Cellulose 20:127–134. https://doi.org/10.1007/s10570-012-9839-5
CAS Article Google Scholar

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Funding

The authors received financial support from the Ferdowsi University of Mashhad (grant number: 32390) and the Iran Nanotechnology Initiative Council (grant number: 81401).

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Affiliations

Department of Chemical Engineering, Faculty of Engineering, Ferdowsi University of Mashhad, P.O.Box 9177948974, Mashhad, Iran
Sina Kazemifard, Naser Saghatoleslami & Ebrahim Safakish
Young Researchers and Elite Club, Shahr-e-Qods Branch, Islamic Azad University, P.O.Box 3754113115, Tehran, Iran
Hamed Nayebzadeh

Authors

Sina Kazemifard
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Hamed Nayebzadeh
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Naser Saghatoleslami
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Ebrahim Safakish
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Correspondence to Hamed Nayebzadeh.

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Responsible editor: Philippe Garrigues

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Kazemifard, S., Nayebzadeh, H., Saghatoleslami, N. et al. Assessment the activity of magnetic KOH/Fe₃O₄@Al₂O₃ core–shell nanocatalyst in transesterification reaction: effect of Fe/Al ratio on structural and performance. Environ Sci Pollut Res 25, 32811–32821 (2018). https://doi.org/10.1007/s11356-018-3249-7

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Received: 19 April 2018
Accepted: 14 September 2018
Published: 24 September 2018
Issue Date: November 2018
DOI: https://doi.org/10.1007/s11356-018-3249-7

Keywords

Core–shell nanoparticle
Magnetic nanocatalyst
Alumina
Biodiesel
Transesterification