No abstract

In this paper, a review is presented of the evolution of different catalytic systems and operating conditions used in the selective hydrogenation of acids and esters of fatty acids to obtain fatty alcohols, which have broad industrial applications in the oleochemical industry. In addition, the current status of the different technologies used industrially (Lurgi, Davy and Henkel) for obtaining fatty alcohols, as well as major global sources of raw materials for the oleochemical industry are put forward. Finally, the reaction mechanisms of the selective hydrogenation process of oleic acid and methyl oleate to obtain the corresponding unsaturated alcohol as well as the new catalysts proposed by researchers are described.

No abstract

No abstract

A simple method for the almost complete removal of glycerol from methanol-free biodiesel streams coming out from industrial transesterification reactors is presented. The method is posed as a “dry” alternative to the conventional “wet” methods involving water washing. It is based on the use of silica beds and relies on the adsorption at room temperature to retain the small amounts of glycerol dissolved in the solutions of fatty acid methyl esters and adjust their content to the quality standards for biodiesel fuel. Fresh silica has a great processing capacity and the breakthrough of the bed depends mainly on the feed rate, the concentration of glycerol, and the mass of adsorbent. In the case of the silica gel used, the saturation capacity was found to be 0.13 g of glycerol per gram of silica. If the particle diameter is 1−1.5 mm, the breakthrough and saturation point almost coincide and the full capacity of the bed is used. However, industrial adsorption units with 1/8 in. silica beads suffer from mass-transfer limitations inside the pellet pores, and for this particle size, the breakthrough point (C/C 0 = 0.01) is located at about one-half of the time of full saturation. For a glycerol concentration of 0.11−0.25% typical of biodiesel streams issuing from gravity settling tanks and an entrance velocity of 11 cm min-1, a 2 m high silica bed with 1/8 in. beads has a breakthrough point of 8 h and a net processing capacity of 0.01−0.02 m3 biodiesel kgsilica -1. The breakthrough curves were studied using approximate solutions to the set of differential equations. Assuming a linear isotherm gives erroneous results; fitting the experimental breakthrough curves produces underestimated values of the Henry's adsorption constant and of the mass-transfer resistances. Modeling the high dilution regime with the UNIFAC method gives more realistic values of the Henry's constant (1.1 m3 kg-1). The experimentally measured saturation capacity is close to the monolayer capacity (13−15% w/w). These values give a Langmuir isotherm which can be fairly well approximated by a square irreversible isotherm. Accordingly, breakthrough curves were fairly well predicted using an irreversible isotherm, a shrinking-core adsorption model, and common correlations for the mass-transfer coefficients. The silica bed was succesfully regenerated eluting 4 bed volumes of methanol and drying in a nitrogen stream for 1 h. Temperature programmed oxidation tests of fresh, regenerated, and glycerol impregnated silica pellets indicated that desorption of glycerol was practically complete. In the industrial practice, the eluted volume can be recycled to the transesterification reactors with no waste of products or reactants. Evaporation of the adsorbed methanol during drying of the bed produced a decrease of the bed temperature and about 200 kJ kgsilica -1 should be provided in order to maintain the temperature.

Zirconia-supported vanadium oxide systems, with V2O5 loadings ranging from V/Zr ) 0.033-0.270 atom ratios (0.2-2 monolayers), were prepared by impregnation of a porous ZrO2 substrate with ammonium metavanadate solutions. The surface structures of air-calcined samples were elucidated by Raman and X-ray photoelectron spectroscopic techniques and thermal desorption methods. Some insight into how the bulk structures of these materials developed upon thermal treatment was derived from the X-ray diffraction patterns and temperature-programmed reduction. At low V content, surface-dispersed vanadium oxide species were formed, which produced the transformation of the ZrO2 support from the tetragonal phase into the monoclinic one. At higher vanadium oxide contents, a solid-state reaction between V2O5 and ZrO2 occurred, with subsequent formation of the ZrV2O7 phase, this being the major V-containing phase. The reactivity of these surface structures was examined by looking at their performance for the oxidation of o-xylene to phthalic anhydride. Activity tests indicated that surface vanadium oxide species were more active for the oxidation of o-xylene but had a lower selectivity to phthalic anhydride.

Biodiesel obtained by transesterification of soy oil with methanol was isomerized in the liquid phase at 125-275°C using solid acid catalysts. The purpose of this work was to improve the cold flow properties of biodiesel by inhibiting the formation of crystals. Crystallization was analyzed by means of the measurement of the cloud point of the fuel. Tested catalysts were SO 4 2--ZrO 2 and H-mordenite. At a temperature of reaction (T r ) lower than 125°C, the catalytic activity was negligible. At T r > 200°C, the reaction rate was greatly accelerated, but the cetane number was also decreased and the amount of coke deposits was greatly increased. While reacting biodiesel at 150-200°C, a small decrease (4-6.5°C) of the cloud point was obtained without a meaningful decrease of the cetane index. Best results were obtained with SO 4 2--ZrO 2 at 125°C. Isomerization had both positive and negative effects on fuel properties: it reduced the cloud point but also increased the viscosity and decreased the cetane index. Due to the different reactivity between the saturated fraction (estearates, palmitates) and the unsaturated one (linoleates, linolenoates, oleates), an adequate control of the degree of isomerization was only possible by performing a previous fractionation step. A good combination was obtained by reacting the saturates rich fraction at 200°C over H-mordenite and the unsaturated rich fraction at 150°C over SO 4 2--ZrO 2 . The fuel obtained by mixing both reacted fractions had a cetane index of 49.5 and a cloud point of -2°C. However, this combined approach yields only a little benefit compared to those obtained with the single reaction over SO 4 2--ZrO 2 at 125°C.

No abstract