Synthesis of magnetic carbonaceous acid derived from waste garlic peel for biodiesel production via esterification

Abstract

Waste biomass-supported magnetic solid acids have particular advantages in catalyst separation. First, a novel magnetic carbonaceous catalyst was synthesized from waste garlic peel (GP) via in situ impregnation before conducting carbonization at 450–600°C and sulfonation at 105°C. The physical and chemical properties of the synthesized catalysts were characterized. It was found that the magnetism of the catalyst increased with the carbonization temperature. The optimized catalyst, carbonized at 600°C (C600-S), possessed an excellent magnetization value of 12.5 emu/g, with a specific surface area of 175.1 m²/g, a pore volume of 0.16 cm³/g, and an acidic property of 0.74 mmol/g -SO₃H density. By optimizing the esterification conditions to produce biodiesel, an oleic acid conversion of 94.5% was achieved at w(catalyst dosage) = 10% (w is mass fraction), a molar ratio of n(methanol): n(oleic acid) = 10: 1 (n is the amount of substance), and a reaction for 4 h at 90°C. Further, for catalyst regeneration, it was found that sulfuric acid treatment was more effective for improving the esterification activity than solvent washing, with which a conversion of more than 76% was achieved after the third run.

Graphical abstract

Keywords

garlic peel (GP) / magnetic carbonaceous acid / esterification / biodiesel

References

[1] Zhang Y, Niu S, Lu C. . Catalytic performance of NaAlO₂/γ-Al₂O₃ as heterogeneous nanocatalyst for biodiesel production: optimization using response surface methodology. Energy Conversion and Management, 2020, 203 : 112263

[2] Fauziyah M, Widiyastuti W, Setyawan H. Sulfonated carbon aerogel derived from coir fiber as high performance solid acid catalyst for esterification. Advanced Powder Technology, 2020, 31( 4): 1412– 1419

[3] Hazmi B, Rashid U, Ibrahim M L. . Synthesis and characterization of bifunctional magnetic nano-catalyst from rice husk for production of biodiesel. Environmental Technology and Innovation, 2021, 21 : 101296

[4] Nazir M H, Ayoub M, Zahid I. . Development of lignin based heterogeneous solid acid catalyst derived from sugarcane bagasse for microwave assisted-transesterification of waste cooking oil. Biomass and Bioenergy, 2021, 146 : 105978

[5] Zhang Q, Luo Q, Wu Y. . Construction of a Keggin heteropolyacid/Ni-MOF catalyst for esterification of fatty acids. RSC Advances, 2021, 11( 53): 33416– 33424

[6] Akkarawatkhoosith N, Kaewchada A, Ngamcharussrivichai C. . Biodiesel production via interesterification of palm oil and ethyl acetate using ion-exchange resin in a packed-bed reactor. BioEnergy Research, 2020, 13( 2): 542– 551

[7] Al-Qaysi K, Nayebzadeh H, Saghatoleslami N. Comprehensive study on the effect of preparation conditions on the activity of sulfated silica–titania for green biofuel production. Journal of Inorganic and Organometallic Polymers and Materials, 2020, 30( 10): 3999– 4013

[8] Zavarize D G, de Oliveira J D. Brazilian açaí berry seeds: an abundant waste applied in the synthesis of carbon-based acid catalysts for transesterification of low free fatty acid waste cooking oil. Environmental Science and Pollution Research International, 2021, 28( 17): 21285– 21302

[9] Roy M, Mohanty K. Valorization of de-oiled microalgal biomass as a carbon-based heterogeneous catalyst for a sustainable biodiesel production. Bioresource Technology, 2021, 337 : 125424

[10] Balasubramaniam S, Ninomiya S, Sasaki M. . Carbon-based solid acid catalyst derived from Undaria pinnatifida and its application in esterification. Algal Research, 2021, 55 : 102272

[11] Sahu O. Characterisation and utilization of heterogeneous catalyst from waste rice-straw for biodiesel conversion. Fuel, 2021, 287 : 119543

[12] Wang A, Li H, Pan H. . Efficient and green production of biodiesel catalyzed by recyclable biomass-derived magnetic acids. Fuel Processing Technology, 2018, 181 : 259– 267

[13] Quah R V, Tan Y H, Mubarak N M. . Magnetic biochar derived from waste palm kernel shell for biodiesel production via sulfonation. Waste Management (New York, N.Y.), 2020, 118 : 626– 636

[14] Li J, Liang X. Magnetic solid acid catalyst for biodiesel synthesis from waste oil. Energy Convertion and Management, 2017, 141 : 126– 132

[15] Guo Y, Liu W, Wu B. . Modification of garlic skin dietary fiber with twin-screw extrusion process and in vivo evaluation of Pb binding. Food Chemistry, 2018, 268 : 550– 557

[16] Reddy J P, Rhim J W. Extraction and characterization of cellulose microfibers from agricultural wastes of onion and garlic. Journal of Natural Fibers, 2018, 15( 4): 465– 473

[17] Veerakumar P, Thanasekaran P, Lin K C. . Biomass derived sheet-like carbon/palladium nanocomposite: an excellent opportunity for reduction of toxic hexavalent chromium. ACS Sustainable Chemistry & Engineering, 2017, 5( 6): 5302– 5312

[18] Zhang Q, Han K, Li S. . Synthesis of garlic skin-derived 3D hierarchical porous carbon for high-performance supercapacitors. Nanoscale, 2018, 10( 5): 2427– 2437

[19] Wei W, Wu J, Shao Q. . Biodiesel production using a biomass-based solid acid catalyst synthesized from agricultural residue garlic peel. Waste and Biomass Valorization, 2022, 13( 8): 3597– 3609

[20] Dehkhoda A M, West A H, Ellis N. Biochar based solid acid catalyst for biodiesel production. Applied Catalysis A, General, 2010, 382( 2): 197– 204

[21] Chen T, Peng L, Yu X. . Magnetically recyclable cellulose-derived carbonaceous solid acid catalyzed the biofuel 5-ethoxymethylfurfural synthesis from renewable carbohydrates. Fuel, 2018, 219 : 344– 352

[22] Liu F, Ma X, Li H. . Dilute sulfonic acid post functionalized metal organic framework as a heterogeneous acid catalyst for esterification to produce biodiesel. Fuel, 2020, 266 : 117149

[23] Krishnan S G, Pua F, Syed Jaafar S N. Synthesis and characterization of local biomass supported magnetic catalyst for esterification reaction. Materials Today: Proceedings, 2020, 31 : 161– 165

[24] Gardy J, Osatiashtiani A, Céspedes O. . A magnetically separable SO₄/Fe-Al-TiO₂ solid acid catalyst for biodiesel production from waste cooking oil. Applied Catalysis B: Environmental, 2018, 234 : 268– 278

[25] Malins K, Brinks J, Kampars V. . Esterification of rapeseed oil fatty acids using a carbon-based heterogeneous acid catalyst derived from cellulose. Applied Catalysis A, General, 2016, 519 : 99– 106

[26] Jenie S N A, Kristiani A. . Sulfonated magnetic nanobiochar as heterogeneous acid catalyst for esterification reaction. Journal of Environmental Chemical Engineering, 2020, 8( 4): 103912

[27] Zhang F, Tian X, Fang Z. . Catalytic production of Jatropha biodiesel and hydrogen with magnetic carbonaceous acid and base synthesized from Jatropha hulls. Energy Conversion and Management, 2017, 142 : 107– 116

[28] Wan H, Wu Z, Chen W. . Heterogenization of ionic liquid based on mesoporous material as magnetically recyclable catalyst for biodiesel production. Journal of Molecular Catalysis A Chemical, 2015, 398 : 127– 132

[29] Ma Z, Xing X, Qu Z. . Activity of microporous lignin-derived carbon-based solid catalysts used in biodiesel production. International Journal of Biological Macromolecules, 2020, 164 : 1840– 1846

[30] Zhang F, Fang Z, Wang Y. Biodiesel production direct from high acid value oil with a novel magnetic carbonaceous acid. Applied Energy, 2015, 155 : 637– 647

[31] Li H, Liu F, Ma X. . An efficient basic heterogeneous catalyst synthesis of magnetic mesoporous Fe@C support SrO for transesterification. Renewable Energy, 2020, 149 : 816– 827

[32] Xie W, Wang H. Grafting copolymerization of dual acidic ionic liquid on core-shell structured magnetic silica: a magnetically recyclable Brönsted acid catalyst for biodiesel production by one-pot transformation of low-quality oils. Fuel, 2021, 283 : 118893

[33] Wang Y, Fang Z, Yang X. Biodiesel production from high acid value oils with a highly active and stable bifunctional magnetic acid. Applied Energy, 2017, 204 : 702– 714

[34] Araujo R O, Chaar J D S, Queiroz L S. . Low temperature sulfonation of acai stone biomass derived carbons as acid catalysts for esterification reactions. Energy Conversion and Management, 2019, 196 : 821– 830

[35] Zhang B, Gao M, Geng J. . Catalytic performance and deactivation mechanism of a one-step sulfonated carbon-based solid-acid catalyst in an esterification reaction. Renewable Energy, 2021, 164 : 824– 832

[36] Ning Y, Niu S, Han K. . Catalytic capability of phosphotungstic acid supported on bamboo activated carbon in esterification for biodiesel production with density functional theory. Biomass and Bioenergy, 2020, 143 : 105873

[37] Li H, Wang J, Ma X. . Carbonized MIL−100(Fe) used as support for recyclable solid acid synthesis for biodiesel production. Renewable Energy, 2021, 179 : 1191– 1203

[38] Mo X, López D E, Suwannakarn K. . Activation and deactivation characteristics of sulfonated carbon catalysts. Journal of Catalysis, 2008, 254( 2): 332– 338

[39] Fraile J M, García-Bordejé E, Roldán L. Deactivation of sulfonated hydrothermal carbons in the presence of alcohols: Evidences for sulfonic esters formation. Journal of Catalysis, 2012, 289 : 73– 79

[40] Dechakhumwat S, Hongmanorom P, Thunyaratchatanon C. . Catalytic activity of heterogeneous acid catalysts derived from corncob in the esterification of oleic acid with methanol. Renewable Energy, 2020, 148 : 897– 906

[41] Ballotin F C, da Silva M J, Lago R M. . Solid acid catalysts based on sulfonated carbon nanostructures embedded in an amorphous matrix produced from bio-oil: esterification of oleic acid with methanol. Journal of Environmental Chemical Engineering, 2020, 8( 2): 103674

[42] Ibrahim S F, Asikin-Mijan N, Ibrahim M L. . Sulfonated functionalization of carbon derived corncob residue via hydrothermal synthesis route for esterification of palm fatty acid distillate. Energy Conversion and Management, 2020, 210 : 112698

Acknowledgments

The project was financially supported by the Natural Science Foundation of Shandong Province, China (Grant Nos. ZR2020QE210 and ZR2021QE066) and the Undergraduate Training Program for Innovation and Entrepreneurship Program of Shandong Province (2021).

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