Transesterification of palm oil using KF and NaNO3 catalysts supported on spherical millimetric γ-Al2O3

The use of spherical millimetric gamma-alumina (γ-Al2O3) as a catalyst support for the production of biodiesel from palm oil is demonstrated. The catalyst support was produced using a dripping method, and KF and NaNO3 catalysts were loaded on the support using the impregnation method. X-ray diffraction (XRD) analysis showed the formation of Na2O and NaAlO2 phases on the NaNO3/γ-Al2O3 catalyst and the formation of K2O and KAlF4 on the KF/γ-Al2O3 catalyst, which were possibly the active sites for the transesterification reaction. The highest number and strength of basic sites generated from the solid phase reaction of the KF/γ-Al2O3 catalyst loaded with 0.24 g kF/g γ-Al2O3 and the NaNO3/γ-Al2O3 catalyst loaded with 0.30 g NaNO3/g γ-Al2O3 were confirmed by temperature programmed desorption of CO2 (CO2-TPD) analysis. The nitrogen adsorption–desorption isotherms also revealed a mesoporous structure of the catalysts. The biodiesel yield was comparable to that produced from smaller catalysts, and this result indicated the potential of the macrospherical catalysts

Alkali- and nitrate-free synthesis of highly active Mg-Al hydrotalcite-coated alumina for FAME production

Mg-Al hydrotalcite coatings have been grown on alumina via a novel alkali- and nitrate-free impregnation route and subsequent calcination and hydrothermal treatment. The resulting Mg-HT/AlO catalysts significantly outperform conventional bulk hydrotalcites prepared via co-precipitation in the transesterification of C-C triglycerides for fatty acid methyl ester (FAME) production, with rate enhancements increasing with alkyl chain length. This promotion is attributed to improved accessibility of bulky triglycerides to active surface base sites over the higher area alumina support compared to conventional hydrotalcites wherein many active sites are confined within the micropores

Facile route to conformal hydrotalcite coatings over complex architectures:a hierarchically ordered nanoporous base catalyst for FAME production

An alkali- and nitrate-free hydrotalcite coating has been grafted onto the surface of a hierarchically ordered macroporous-mesoporous SBA-15 template via stepwise growth of conformal alumina adlayers and their subsequent reaction with magnesium methoxide. The resulting low dimensional hydrotalcite crystallites exhibit excellent per site activity for the base catalysed transesterification of glyceryl triolein with methanol for FAME production

Kinetic modeling studies of heterogeneously catalyzed biodiesel synthesis reactions

The heterogeneously catalyzed transesterification reaction for the production of biodiesel from triglycerides was investigated for reaction mechanism and kinetic constants. Three elementary reaction mechanisms Eley-Rideal (ER), Langmuir-Hinshelwood-Hougen-Watson (LHHW), and Hattori with assumptions, such as quasi-steady-state conditions for the surface species and methanol adsorption, and surface reactions as the rate-determining steps were applied to predict the catalyst surface coverage and the bulk concentration using a multiscale simulation framework. The rate expression based on methanol adsorption as the rate limiting in LHHW elementary mechanism has been found to be statistically the most reliable representation of the experimental data using hydrotalcite catalyst with different formulations

Heterogeneous catalysis for sustainable biodiesel production via esterification and transesterification

Concern over the economics of accessing fossil fuel reserves, and widespread acceptance of the anthropogenic origin of rising CO2 emissions and associated climate change from combusting such carbon sources, is driving academic and commercial research into new routes to sustainable fuels to meet the demands of a rapidly rising global population. Here we discuss catalytic esterification and transesterification solutions to the clean synthesis of biodiesel, the most readily implemented and low cost, alternative source of transportation fuels to meet future societal demands

Catalysing sustainable fuel and chemical synthesis

Concerns over the economics of proven fossil fuel reserves, in concert with government and public acceptance of the anthropogenic origin of rising CO2 emissions and associated climate change from such combustible carbon, are driving academic and commercial research into new sustainable routes to fuel and chemicals. The quest for such sustainable resources to meet the demands of a rapidly rising global population represents one of this century’s grand challenges. Here, we discuss catalytic solutions to the clean synthesis of biodiesel, the most readily implemented and low cost, alternative source of transportation fuels, and oxygenated organic molecules for the manufacture of fine and speciality chemicals to meet future societal demands

Catalytic conversion of lignin to low molecular weight compounds

Nowadays lignocellulosic materials represent the higher renewable natural resource in the world. These materials consist of 34–50% cellulose, 19–34% hemicellulose and 11–30% lignin. Unlike cellulose, lignin is a three-dimensional aromatic polymer including three main phenylpropane units, namely p-coumaril, coniferyl and sinapyl alcohol which are linked by C-O-C or C-C bonds. To valorize this material it is necessary to achieve its depolymerization to monomers or dimers that typically results from the cleavage of β-O-4 linkages. Literature already reported several approaches to depolymerize lignin using both homogeneous and heterogeneous catalysts. Yuan et all have considered a homogeneous route in this scope using NaOH as catalyst. This solution is however by far non-green leading to no-recyclable wastes. Heterogeneous catalysts offer an alternative. The use of noble metals like Pt or Rh supported on carbon, at 473 K, under H2 pressure, was shown to yield over 50% in monomers and dimers . Cheaper metals as copper represent a more versatile route but the reported example uses high energetic supercritical conditions. The use of inexpensive metals such as Ni may offer another alternative. In this study we propose an inexpensive route presenting results obtained using as active species, nickel in different environments such as NiOx, (NiAl)Ox, (NiMgAl)Ox thus looking also for the effect of basicity in this reaction. These materials were prepared using specific protocols and characterized by several techniques like: XRD, DRIFT, BET, and TEM. The catalysts were tested in autoclave conditions at different temperature (423-473K) under H2 pressure. The lignin was extracted from Miscanthus plants into formic acid / acetic acid / water mixture. Since it is not soluble in water its solubilization was achieved in an [BMIM]OAc ionic liquid, selected from a screening of a series of ILs. On the other side, the analysis of the reaction products is a complicate issue in this chemistry. This was carried out with a chromatographic system equipped with a Detector Triple Quad LC/MS, and a MS Ion Source type, working simultaneously in both APCI and ESI modes. The analysis of the reaction products indicated both polar and less polar compounds with a m/z signal varying from 80 till 900. The population of the different class molecules was carefully analyzed as a function of the nature of the catalyst and the reaction conditions. The higher extent of lignin depolymerization was around 54% and was obtained using a (NiAl)Ox catalyst. Under these conditions the predominant class was that with m/z of 200-300 a.u. Finally the stability of the catalysts was checked looking for their separation and recyclability in several successive cycles