Abstract
A novel carbon solid acid catalyst was prepared by incomplete hydrothermal carbonization of β-cyclodextrin into small polycyclic aromatic carbon sheets, followed by the introduction of –SO3H groups via sulfonation with sulfuric acid. The physical and chemical properties of the catalyst were characterized in detail. The catalyst simultaneously catalyzed esterification and transesterification reactions to produce biodiesel from high free fatty acid (FFA) containing oils (55.2 %). For the as-prepared catalyst, 90.82 % of the oleic acid was esterified after 8 h, while the total transesterification yield of high FFA containing oils reached 79.98 % after 12 h. By contrast, the obtained catalyst showed comparable activity to biomass (such as sugar, starch, etc.)-based carbon solid acid catalyst while Amberlyst-15 resulted in significantly lower levels of conversion, demonstrating its relatively high catalytic activity for simultaneous esterification and transesterification. Moreover, as the catalyst can be regenerated, it has the potential for use in biodiesel production from oils with a high FFA content.
This is a preview of subscription content, log in via an institution to check access.
Similar content being viewed by others
References
Steinfeld JI (2006) Energy futures and green chemistry: competing for carbon. Sust Sci 1:123–126
Ma FR, Hanna MA (1999) Biodiesel production: a review. Bioresour Technol 70:1–15
Meher LC, Sagar DV, Naik SN (2006) Technical aspects of biodiesel production by transesterification—a review. Renew Sust Energ Rev 10:248–268
Lotero E, Liu YJ, Lopez DE, Suwannakarn K, Bruce DA, Goodwin JG (2005) Synthesis of biodiesel via acid catalysis. Ind Eng Chem Res 44:5353–5363
Okuhara T (2002) Water-tolerant solid acid catalysts. Chem Rev 102:3641–3665
Van Rhijn WM, De Vos DE, Sels BF, Bossaert WD, Jacobs PA (1998) Sulfonic acid functionalised ordered mesoporous materials as catalysts for condensation and esterification reactions. Chem Commun (3):317–318
Harmer MA, Farneth WE, Sun Q (1998) Towards the sulfuric acid of solids. Adv Mater 10:1255–1257
Yadav GD, Nair JJ (1999) Sulfated zirconia and its modified versions as promising catalysts for industrial processes. Microporous Mesoporous Mat 33:1–48
Harmer MA, Sun Q, Vega AJ, Farneth WE, Heidekum A, Hoelderich WF (2000) Nafion resin-silica nanocomposite solid acid catalysts. Microstructure-processing-property correlations. Green Chem 2:7–14
Soldi RA, Oliveira ARS, Ramos LP, Cesar-Oliveira MAF (2009) Soybean oil and beef tallow alcoholysis by acid heterogeneous catalysis. Appl Catal A-Gen 361:42–48
Caetano CS, Guerreiro L, Fonseca IM, Ramos AM, Vital J, Castanheiro JE (2009) Esterification of fatty acids to biodiesel over polymers with sulfonic acid groups. Appl Catal A-Gen 359:41–46
Hara M (2010) Biodiesel Production by amorphous carbon bearing So(3)H, COOH and phenolic OH groups, a solid bronsted acid catalyst. Top Catal 53:805–810
Chen G, Fang BS (2011) Preparation of solid acid catalyst from glucose-starch mixture for biodiesel production. Bioresour Technol 102:2635–2640
Devi B, Gangadhar KN, Prasad PSS, Jagannadh B, Prasad RBN (2009) A glycerol-based carbon catalyst for the preparation of biodiesel. Chem Sus Chem 2:617–620
Liang XZ, Yang JG (2009) Synthesis of a novel carbon based strong acid catalyst through hydrothermal carbonization. Catal Lett 132:460–463
Lou WY, Zong MH, Duan ZQ (2008) Efficient production of biodiesel from high free fatty acid-containing waste oils using various carbohydrate-derived solid acid catalysts. Bioresour Technol 99:8752–8758
Okamura M, Takagaki A, Toda M, Kondo JN, Domen K, Tatsumi T, Hara M, Hayashi S (2006) Acid-catalyzed reactions on flexible polycyclic aromatic carbon in amorphous carbon. Chem Mat 18:3039–3045
Zong MH, Duan ZQ, Lou WY, Smith TJ, Wu H (2007) Preparation of a sugar catalyst and its use for highly efficient production of biodiesel. Green Chem 9:434–437
Shin Y, Wang LQ, Bae IT, Arey BW, Exarhos GJ (2008) Hydrothermal syntheses of colloidal carbon spheres from cyclodextrins. J Phys Chem C 112:14236–14240
da Silva CAS, Sanaiotti G, Lanza M, Follegatti-Romero LA, Meirelles AJA, Batista EAC (2010) Mutual solubility for systems composed of vegetable oil plus ethanol plus water at different temperatures. J Chem Eng Data 55:440–447
Geng L, Wang Y, Yu G, Zhu YX (2011) Efficient carbon-based solid acid catalysts for the esterification of oleic acid. Catal Comm 13:26–30
Furukawa S, Uehara Y, Yamasaki H (2010) Variables affecting the reactivity of acid-catalyzed transesterification of vegetable oil with methanol. Bioresour Technol 101:3325–3332
Furuta S, Matsuhashi H, Arata K (2004) Biodiesel fuel production with solid superacid catalysis in fixed bed reactor under atmospheric pressure. Catal Commun 5:721–723
Mo X, Lopez DE, Suwannakarn K, Liu Y, Lotero E, Goodwin JG, Lu CQ (2008) Activation and deactivation characteristics of sulfonated carbon catalysts. J Catal 254:332–338
Acknowledgments
The authors are grateful to the support from Natural Science Foundation of Guangdong (No. S2011040001667), National Natural Science Foundation of China (No. 21306061), National High Technology Research and Development Program 863 (No. 2009AA064401) and Fundamental Research Funds for the Central Universities (No. 11612328).
Author information
Authors and Affiliations
Corresponding author
About this article
Cite this article
Fu, Xb., Chen, J., Song, Xl. et al. Biodiesel Production Using a Carbon Solid Acid Catalyst Derived from β-Cyclodextrin. J Am Oil Chem Soc 92, 495–502 (2015). https://doi.org/10.1007/s11746-015-2621-8
Received:
Revised:
Accepted:
Published:
Issue Date:
DOI: https://doi.org/10.1007/s11746-015-2621-8