Synthesis of a silicotungstic acid SBA-15 catalyst for selective monoglyceride production
Abstract
The esterification reaction between glycerol and lauric acid was conducted in the presence of commercial Amberlyst IR-120 and synthesized silicotungstic acid (STA)/SBA-15 at 393, 413 and 433 K. The results indicated that STA/SBA-15 was more convenient than Amberlyst IR-120 by means of monoglyceride production. Higher selectivity to monoglyceride obtained in the presence of STA/SBA-15 was due to its mesoporous structure, which induced shape selectivity in favor of monoglyceride. Reaction experiments in the presence of recovered catalysts showed an increase of monoglyceride selectivity, which was due to adsorbed lauric acid inside the mesopores. The selectivity was shown to be altered towards monoglyceride by simply changing the feed ratio and applying washing procedure on the catalyst. Characterization studies conducted on recovered catalysts validated the preservation of catalyst structure and the stability of the catalyst even after utilization for 7 days.
Keywords
Esterification Lauric acid Glycerol Silicotungstic acidNotes
Acknowledgments
The authors wish to extend their sincere appreciation to Prof. Dr. Nuray Oktar for her help and expertise. Supported by Scientific and Technical Research Council of Turkey (TUBITAK 114M005).
Supplementary material
References
- 1.Li B, Ma W, Zuo S, Li X (2011) Preparation of MCM-41 incorporated with lacunary Keggin polyoxometalate and its catalytic performance in esterification. J Colloid Interface Sci 362:42–49CrossRefGoogle Scholar
- 2.Chen T, Che Y, Zhang Y, Zhang J, Wang F, Wang Z (2014) One-pot hydrothermal preparation of SBA-15 supported Keggin-type 12-tungstophosphoric heteropolyacid mesoporous material and its bifunctional catalytic performance. J Porous Mater 21:495–502CrossRefGoogle Scholar
- 3.Dong BB, Zhang BB, Wu HY, Ke Zhang C, Zheng XC (2013) Synthesis, characterization and catalytic evaluation of SBA-15 supported 12 tungstophosphoric acid mesoporous materials in the oxidation of benzaldehyde to benzoic acid. Mater Res Bull 48:2491–2496CrossRefGoogle Scholar
- 4.Yang L, Qi Y, Yuan X, Shen J, Kim J (2005) Direct synthesis, characterization and catalytic application of SBA-15 containing heteropolyacid H3PW12O40. J Mol Catal A 229:199–205CrossRefGoogle Scholar
- 5.Kumar GS, Vishnuvartan M, Palanichamy M, Murugesan V (2006) SBA-15 supported HPW: effective catalytic performance in the alkylation of phenol. J Mol Catal A 260:49–55CrossRefGoogle Scholar
- 6.Liu QY, Wu WL, Wang J, Ren XQ, Wang YR (2004) Characterization of 12-tungstophosphoric acid impregnated on mesoporous silica SBA-15 and its catalytic performance in isopropylation of naphthalene with isopropanol. Microporous Mesoporus Mater 76:51–60CrossRefGoogle Scholar
- 7.Wróblewska A, Makuch E (2014) Regeneration of the Ti-SBA-15 catalyst used in the process of allyl alcohol epoxidation with hydrogen peroxide. J Adv Oxid Technol 17(1):44–52Google Scholar
- 8.Sheng X, Kong J, Zhou Y, Zhang Y, Zhang Z, Zhou S (2014) Direct synthesis, characterization and catalytic application of SBA-15 mesoporous silica with heteropolyacid incorporated into their framework. Microporous Mesoporous Mater 187:7–13CrossRefGoogle Scholar
- 9.Obalı Z, Dogu T (2008) Activated carbon–tungstophosphoric acid catalysts for the synthesis of tert-amyl ethyl ether (TAEE). Chem Eng J 138:548–555CrossRefGoogle Scholar
- 10.Melendez-Ortiz HI, Mercado-Silva A, Garcia-Cerda LA, Castruita G, Perera-Mercado YAJ (2013) Hydrothermal synthesis of mesoporous silica MCM-41 using commercial sodium silicate. J Mex Chem Soc 57(2):73–79Google Scholar
- 11.Brahmkhatri V, Patel A (2011) 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 403:161–172CrossRefGoogle Scholar
- 12.Narkhede N, Brahmkhatri V, Patel A (2014) Efficient synthesis of biodiesel from waste cooking oil using solid acid catalyst comprising 12-tungstosilicic acid and SBA-15. Fuel 135:253–261CrossRefGoogle Scholar
- 13.Chen Y, Cao Y, Suo Y, Zheng GP, Guan XX, Zheng XC (2015) 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 Eng 51:186–192CrossRefGoogle Scholar
- 14.Pires LHO, de Oliveira AN, Monteiro OV Jr, Angelica RS, da Costa CEF, Zamian JR, do Nascimento LAS, Filho GNR (2014) Esterification of a waste produced from the palm oil industry over 12-tungstophosphoric acid supported on kaolin waste and mesoporous materials. Appl Catal B 160–161:122–128CrossRefGoogle Scholar
- 15.Hoo PY, Abdullah AZ (2014) Direct synthesis of mesoporous 12-tungstophosphoric acid SBA-15 catalyst for selective esterification of glycerol and lauric acid to monolaurate. Chem Eng J 250:274–287CrossRefGoogle Scholar
- 16.Degirmenci L, Oktar N, Dogu G (2011) Activated carbon supported silicotungstic acid catalysts for ethyl-tert-butyl ether synthesis. AlChE J 57(11):3171–3181CrossRefGoogle Scholar
- 17.Varisli D, Dogu T, Dogu G (2008) Silicotungstic acid impregnated MCM-41-like mesoporous solid acid catalysts for dehydration of ethanol. Ind Eng Chem Res 47:4071–4076CrossRefGoogle Scholar
- 18.Sawant DP, Vinu A, Jacob NE, Lefebvre F, Halligudi SB (2005) Formation of nanosized zirconia-supported 12-tungstophosphoric acid in mesoporous silica SBA-15: A stable and versatile solid acid catalyst for benzylation of phenol. J Catal 235:341–352CrossRefGoogle Scholar
- 19.Brahmkhatri V, Patel A (2012) Esterification of lauric acid with butanol-1 over H3PW12O40 supported on MCM-41. Fuel 102:72–77CrossRefGoogle Scholar
- 20.Kotwal M, Desphande SS, Srinivas D (2011) Esterification of fatty acids with glycerol over Fe–Zn double-metal cyanide catalyst. Catal Commun 12:1302–1306CrossRefGoogle Scholar
- 21.Hermida L, Abdullah AZ, Mohamed AR (2011) Synthesis of monoglyceride through glycerol esterification with lauric acid over propyl sulfonic acid post-synthesis functionalized SBA-15 mesoporous catalyst. Chem Eng J 174:668–676CrossRefGoogle Scholar
- 22.Sakthivel A, Nakamura R, Komura K, Sugi Y (2007) Esterification of glycerol by lauric acid over aluminium and zirconium containing mesoporous molecular sieves in supercritical carbon dioxide medium. J Supercrit Fluids 42:219–225CrossRefGoogle Scholar
- 23.Barrault J, Bancquart S, Pouilloux Y (2004) Selective glycerol transesterification over mesoporous basic catalysts. Comptes Rendus Chim 7:593–599CrossRefGoogle Scholar
- 24.Osorio-Viana W, Duque-Bernal M, Fontalvo J, Dobrosz-Gomez I, Gomez-Garcia MA (2013) Kinetic study on the catalytic esterification of acetic acid with isoamyl alcohol over Amberlite IR-120. Chem Eng Sci 101:755–763CrossRefGoogle Scholar
- 25.Merchant SQ, Almohammad KA, Al Bassam AAM, Ali SH (2013) Biofuels and additives: Comparative kinetic study of Amberlite IR 120-catalyzed esterification of ethanol with acetic, propanoic and pentanoic acids to produce eco-ethyl-esters. Fuel 111:140–147CrossRefGoogle Scholar
- 26.Ali SH, Al-Rashed O, Azeez FA, Merchant SQ (2011) Potential biofuel additive from renewable sources—kinetic study of formation of butyl acetate by heterogeneously catalyzed transesterification of ethyl acetate with butanol. Bioresour Technol 102:10094–10103CrossRefGoogle Scholar
- 27.Zhou H, Song J, Meng Q, He Z, Jiang Z, Zhou B, Liu H, Han B (2015) Cooperative catalysis of Pt/C and acid resin for the production of 2,5- dimethyltetrahydrofuran from biomass derived 2,5-hexanedione under mild condition. R Soc Chem. doi: 10.1039/C5GC01741F Google Scholar
- 28.Fulvio PF, Pikus S, Jaroinec M (2005) Short-time synthesis of SBA-15 using various silica sources. J Colloid Interface Sci 287:717–720CrossRefGoogle Scholar
- 29.Alhassan Y, Kumar N, Bugaje IM (2015) Catalytic upgrading of waste tire pyrolysis oil via supercritical esterification with deep eutectic solvents (green solvents and catalysts). J Energy Inst. doi: 10.1016/j.joei.2015.05.003 Google Scholar
- 30.D’Anton Reipert EC, Rodrigues CEC, Meirelles AJA (2011) Phase equilibria study of systems composed of refined babassu oil, lauric acid, ethanol, and water at 303.2 K. J Chem Thermodyn 43:1784–1790CrossRefGoogle Scholar
- 31.Dimian AC, Rothenberg G, Schut R (2012) Production of fatty acid alkyl esters. EP 2457648 A1Google Scholar
- 32.Simsek V, Degirmenci L, Murtezaoglu K (2015) Sustainable activity of hydrothermally synthesized mesoporous silicates in acetic acid esterification. Turk J Chem 39:683–696CrossRefGoogle Scholar
- 33.Sarı A, Karaipekli A, Alkan C (2009) Preparation, characterization and thermal properties of lauric acid/expanded perlite as novel form-stable composite phase change material. Chem Eng J 155:899–904CrossRefGoogle Scholar
- 34.Alkan C, Tek Y, Kahraman D (2011) Preparation and characterization of a series of thiourea derivatives as phase change materials for thermal energy storage. Turk J Chem 35:769–777Google Scholar