Catalysis Today, Vol.172, No.1, 34-40, 2011
Evaluation of sulfated tin oxides in the esterification reaction of free fatty acids
Sulfated tin oxides (SO(4)(2-)/SnO(2)) with different SO(4)(2-) contents (0.15, 0.3 and 0.45 wt%) were synthesized from hydroxylated tin oxide obtained by the precipitation method, followed by ion exchange of the OH groups with SO(4)(2-) species using a sulfuric acid solution. In samples annealed at 673, 773 and 873 K the characterization of the solids was made by XRD, FT-IR and nitrogen adsorption. The strength and number of acid sites were determined by titration with n-butylamine using Hammett indicators an acid strength of Ho < -8.2 was found. Sulfated tin oxides were tested in the esterification reaction of free fatty acids with ethanol (molar ratio 1:10), at 353 K. XRD profiles showed that the sulfating inhibits the SnO(2) crystal growth. The SO(4) species remained strongly bonded at the SnO(2) surface stabilizing its crystallite size against sintering and it acts as a structure porogen director mediating nanoparticle growth and assembly yielding a mesostructured form of SnO(2) with wormhole morphology and high thermal stability. The conversion of oleic acid increases with the increase of surface acidity showing a maximum when the sulfate content and calcination temperature were 0.3 wt% and 773 K, respectively. Regeneration through heating the SO(4)(2-)/SnO(2) with the highest activity for 4 h allows it for reuse without losing of its catalytic activity. Published by Elsevier B.V.
Keywords:XRD sulfated tin oxides;Solid superacid;Acidity of Hammett;Esterification of free fatty acids;Sulfated tin oxides acidity