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Alkoxylation of α−pinene, β−pinene and limonene was performed in the presence of SBA-15-occluded tungstophosphoric acid (HPW). The HPW was immobilised in SBA-15 using the sol-gel method. The catalysts were characterised by N 2 adsorption, FT-IR, Raman spectroscopy, X-Ray diffraction, ICP-AES and TEM. A series of catalysts with different heteropolyacid loadings ranging from 1.8 to 19.3 wt. % were prepared. PW4-SBA-15 (with 10.8 wt. %) exhibited the highest catalytic activity for the alkoxylation of α-pinene with ethanol. An approximately 53% selectivity to α-terpinyl ethyl ether was observed over the PW-SBA-15 catalysts. PW4-SBA-15 was also used as a catalyst for the alkoxylation of other terpenes, including β-pinene and limonene. The PW4-SBA-15 catalyst exhibited high catalytic stability for the alkoxylation of α-pinene with ethanol. PW4-SBA-15 was also used as a catalyst for the esterification of free fatty acids (i.e., palmitic, stearic and oleic acids) with ethanol. Good catalytic activity was observed for the PW4-SBA-15 catalyst with the different substrates used in the esterifications. [ABSTRACT FROM AUTHOR]

Abstract: The acetylation of glycerol was carried out over dodecatungstophosphoric acid (PW) supported on activated carbon, being the monoacetin, diacetin and triacetin the reaction products. A series of catalysts, with different heteropolyacid loading (from 3.5 to 6.5wt.%), were prepared. It was observed that the catalytic activity increases with the amount of PW immobilized on the activated carbon, being the PW2_AC (with 4.9wt.%) the most active sample. However, at high loading of heteropolyacid on the activated carbon, a decrease on the catalytic activity was observed, which can be probably explained due to some hindrance in the activated carbon porous system. All catalysts exhibited good values of selectivity to the diacetin. Catalytic stability of the PW2_AC was also studied by performing consecutives batch runs with the same catalyst sample. After the third batch, it was observed that the catalytic activity stabilized. [Copyright &y& Elsevier]

Abstract: The acetalisation of glycerol was studied using heteropolyacids, immobilized in silica, as catalysts, at 70°C. The main product of glycerol acetalisation was solketal. The tungstophosphoric (PW), molybdophosphoric (PMo), tungstosilisic (SiW) and molybdosilisic (SiMo) acids were immobilized in silica by sol–gel method. It was observed that the catalytic activity decreases in the series: PW_S>SiW_S>PMo_S>SiMo_S. All catalysts exhibited good values of selectivity to solketal (about 98% near complete conversion). The effect of different parameters, such as catalyst loading, molar ratio of glycerol to acetone and temperature on the glycerol acetalisation, over PW_S catalyst, was studied. Catalytic stability of the PW_S, SiW_S, PMo_S and SiMo_S catalysts was evaluated by performing consecutive batch runs with the same catalyst sample. After the third batch, it was observed a stabilisation of the initial activity. [Copyright &y& Elsevier]

Abstract: The esterification of glycerol with acetic acid was carried out over dodecatungstophosphoric acid (PW) immobilized into a silica matrix. The products of glycerol acetylation were monoacetin, diacetin and triacetin. The immobilization of PW into silica was carried out by two different techniques: sol–gel and impregnation methods. The catalysts prepared by sol–gel method will be denoted as PW-in-S while the catalysts prepared by impregnation will be denoted as PW-on-S. The catalysts were characterized by nitrogen adsorption at 77K, FTIR, XDR and ICP-AES. A series of PW immobilized into silica with different PW loading were prepared. It was observed that the catalytic activity increases with the amount of PW immobilized into silica, either by the sol–gel method or by the impregnation method. High values of selectivity to diacetin were obtained with all catalyst. The effect of various parameters, such as, reaction temperature, catalyst loading, molar ratio of glycerol to acetic acid and reusability of PW-in-S2 were studied to optimize the reaction conditions. The catalytic stability of the PW-in-S2 was evaluated by performing consecutives batch runs with the same catalyst sample. It was observed a stabilization of the catalytic activity. [Copyright &y& Elsevier]

Abstract: The esterification of glycerol with acetic acid was carried out over dodecamolybdophosphoric acid (PMo) encaged in the USY zeolite. The products of glycerol acetylation were monoacetin, diacetin and triacetin. A series of PMo encaged in the NaUSY zeolite with different PMo loading from 0.6 to 5.4wt.% were prepared. It was observed that the catalytic activity increases with the amount of PMo immobilized in the NaUSY zeolite, being the PMo3_NaUSY (with 1.9wt.%) the most active sample. However, at high loading of heteropolyacid encaged in the NaUSY zeolite, a decrease on the catalytic activity was observed, which can be explained, probably, due to the internal diffusion limitations. Good values of selectivity to diacetin were obtained with all the catalyst. Catalytic stability of the PMo3_NaUSY was evaluated by performing consecutives batch runs with the same catalyst sample. After the second batch, it was observed a stabilization of the catalytic activity. [Copyright &y& Elsevier]

Abstract: The esterification of palmitic acid with methanol was studied using tungstophosphoric acid (PW), molibdophosphoric acid (PMo) and tungstosilicic acid (SiW) immobilized by sol–gel technique on silica, at 60°C. It was observed that the catalytic activity decreases in the series: PW-silica>SiW-silica>PMo-silica. A series of PW immobilized on silica with different PW loadings from 2.5wt.% to 8.4wt.% were prepared. It was observed that the PW-silica2 (with 4.2wt.%) shows the highest catalytic activity on esterification of palmitic acid with methanol. Catalytic stability of the PW-silica2 was evaluated by performing consecutive batch runs with the same catalyst sample. After the second batch it was observed a stabilisation of the initial activity. In order to study the heteropolyacid lixiviation, a posterior catalytic experiment was carried out. The PW-silica2 was put in contact with methanol, without palmitic acid, during 72h. After this period, the catalyst was separated from methanol by centrifugation, and the palmitic acid was added to the reaction mixture. It was observed that the reaction only occurs in the heterogeneous phase. The PW-silica2 was also used as catalyst in esterification of others fatty acids: oleic and stearic acid. It was also observed a good catalytic activity of PW-silica2 for the different substrates used in the esterifications. [Copyright &y& Elsevier]

Abstract: A polyvinylalcohol/molybdophosphoric acid (PVA/HPMo) membrane crosslinked with succinic acid was modified by treatment with acetic anhydride in order to improve its hydrophobic properties, and was used as catalyst in the hydration reaction of α-pinene. The increase of membrane hydrophobicity with acetylation is documented not only by the water droplet contact angle but also by the sorption coefficients of α-pinene and water. The introduction of acetyl groups improves the membrane transport properties, as reflected by pinene diffusivity calculated from permeation data. A kinetic-diffusion model was developed assuming that the reaction product α-terpineol affects the transport of water and α-pinene across the acetylated PVA membranes. When membrane acetylation increases, the model predicted kinetic constants for hydration and isomerization reactions decrease, although the initial water diffusivity increases. These results suggest that the increase of catalytic activity may be due to an improvement of water transport across the membrane. [Copyright &y& Elsevier]

• Acetalization of glycerol with pentanal was performed over molybdophosphoric acid (HPMo) encaged in USY zeolite. • High catalytic activity with low amount of HPMo@Y was observed. • High selectivity to (2-butyl-1,3-dioxolan-4-yl) methanol product. • Good catalytic activity after the forth use. Dodecamolydbophosphoric acid (HPMo) immobilized on USY zeolite was used as a catalyst for the acetalization of glycerol with pentanal at 70 °C. Catalysts were prepared with different amounts of heteropolyacid, and the most active sample was the HPMo2@Y catalyst (1.1 wt.%). The products of glycerol acetalization with pentanal were (2-butyl-1,3-dioxolan-4-yl)methanol, a five-member ring compound, and 2-butyl-1,3-dioxan-5-ol, a six-member ring compound. Good values of selectivity for the five-member ring compound (80–85%) were obtained with all materials. The reaction conditions were optimized using HPMo2@Y as a catalyst. The optimal conditions were determined to be 70 °C reaction temperature with 0.3 g catalyst and a 1:2.5 M ratio of glycerol to pentanal. The catalytic stability of HPMo2@Y was studied. The acetalization of glycerol with pentanal was performed using the same sample. High catalytic activity for HPMo2@Y was observed. [ABSTRACT FROM AUTHOR]

Abstract: Tungstophosphoric acid (PW), molybdophosphoric acid (PMo) and tungstosilicic acid (SiW) immobilized on SBA-15 were used, as catalysts, in the esterification of palmitic acid with methanol, at 60°C. Catalysts were characterized by N2 adsorption, FTIR, X-ray diffraction, ICP-AES and TEM. All catalysts exhibited high catalytic activity in palmitic acid esterification with methanol. It was observed that the catalytic activity decreases in the follow series: PW1-SBA-15>SiW-SBA-15>PMo-SBA-15. A series of PW immobilized on SBA-15 with different PW loadings from 2.7wt% to 8.3wt% were prepared. It was observed high catalytic activity with low amount of tungstophosphoric acid immobilized on SBA-15. In order to optimize the reaction conditions, the effect of different parameters, such as catalyst loading, carbon length of the alcohol and temperature, molar ratio of fatty acid to methanol in the presence of PW3-SBA-15 were studied. PW3-SBA-15 catalyst can be separated from reaction system for re-use. It was observed a small leaching of the PW from SBA-15 to liquid phase. PW3-SBA-15 catalyst was also used in the esterification of stearic and oleic acid with methanol. High catalytic activity was observed. [ABSTRACT FROM AUTHOR]

Abstract: The methoxylation of α-pinene was studied using heteropolyacids immobilized on silica as catalysts, at 60°C, being the α-terpinyl methyl ether the main product. Tungstophosphoric acid (PW), molybdophosphoric acid (PMo), tungstosilicic acid (SiW) and molybdosilicic acid (SiMo) were immobilized on silica by sol–gel method. It was observed that the catalytic activity of the silica-supported heteropolyacids decreases in the series: PW2_S>SiW_S>PMo_S>SiMo_S. A series of PW immobilized on silica with different PW loading were prepared. It was observed that the catalytic activity increases with the amount of PW immobilized on silica. However, at high amount of PW on silica, a decrease of the catalytic activity was observed. Good values of selectivity to α-terpinyl methyl ether (about 60% near complete conversion) were obtained with all catalysts. Catalytic stability of the PW2_S was evaluated by performing consecutive batch runs with the same catalyst sample. After the third batch it was observed a stabilisation of the initial activity. A kinetic model was developed assuming that the α-pinene is consumed according to the parallel reaction network. It was observed that the kinetic model fits the experimental concentration data quite well. [Copyright &y& Elsevier]