Abstract Effects of phosphorus addition to HZSM-5 on ethanol conversion to propylene were evaluated. Catalysts were characterized by XRF, XRD, nitrogen adsorption, 27Al and 31P MAS NMR, n-propylamine and ammonia TPD. Increasing P content decreased the strength and density of acid total sites. Ethanol dehydration was carried out in a fixed bed reactor operating at atmospheric pressure. Conversion was around 100% for all catalysts. 1.2 wt% of P catalyst showed the highest propylene yield, and was used to evaluate temperature and ethanol partial pressure effects on the product distribution. The highest propylene accumulated productivity was obtained for an ethanol partial pressure of 0.4 atm. Propylene formation was favored in the temperature range 475-500 °C. Significant changes in the product distribution as a function of time on stream were observed at higher temperatures, suggesting stronger catalyst deactivation. The ethylene yield decreased up to 500 °C, rising significantly at 550 °C, possibly due to heavier product cracking reactions.

Abstract The high octane number of pyrolysis gasoline (PYGAS) explains its insertion in the gasoline pool. However, its use is troublesome due to the presence of gum-forming chemicals which, in turn, can be removed via hydrogenation. The use of Langmuir-Hinshelwood kinetic models was evaluated for hydrogenation of styrene, a typical gum monomer, using Pd/9%Nb2O5-Al2O3 as catalyst. Kinetic models accounting for hydrogen dissociative and non-dissociative adsorption were considered. The availability of one or two kinds of catalytic sites was analyzed. Experiments were carried out in a semi-batch reactor at constant temperature and pressure in the absence of transport limitations. The conditions used in each experiment varied between 16 - 56 bar and 60 - 100 ºC for pressure and temperature, respectively. The kinetic models were evaluated using MATLAB and EMSO software. Models using adsorption of hydrogen and organic molecules on the same type of site fitted the data best.

Pyrolysis gasoline - PYGAS - is an intermediate boiling product of naphtha steam cracking with a high octane number and high aromatic/unsaturated contents. Due to stabilization concerns, PYGAS must be hydrotreated in two stages. The first stage uses a mild trickle-bed conversion for removing extremely reactive species (styrene, dienes and olefins) prior to the more severe second stage where sulfured and remaining olefins are hydrogenated in gas phase. This work addresses the reaction network and two-phase kinetic model for the first stage of PYGAS upgrading. Nonlinear estimation was used for model tuning with kinetic data obtained in bench-scale trickle-bed hydrogenation with a commercial Pd/Al2O3 catalyst. On-line sampling experiments were designed to study the influence of variables - temperature and spatial velocity - on the conversion of styrene, dienes and olefins.

The synthesis of ethyl hexadecanoate was carried out by esterification of palmitic acid with ethanol in a solvent-free system. A commercial immobilized lipase (Lipozyme RM-IM) was mixed with the reagents, in a 15 mL closed batch reactor with constant stirring and coupled with a condenser. The effects of palmitic acid/ethanol molar ratio (0.16 to 1.84), reaction temperature (65 to 75ºC) and enzyme concentration (0.48 to 5.52% w/w) on the initial reaction rate of ethyl hexadecanoate were determined using central composite design 2³ with six central points. Statistical analysis indicated that the enzyme concentration and palmitic acid/ethanol molar ratio had been found to be the most significant variables affecting the initial reaction rate. The best result was obtained under the following experimental conditions: palmitic acid/ethanol molar ratio of 0.50, temperature of 67ºC, and enzyme concentration of 4.50% (w/w).