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Mesoporous materials are promising catalysts for production of biofuels. Herein, H-MCM-41 catalysts with different concentrations of the silica Bindzil binder (10–50 wt%) were prepared and characterized using pulsed-field gradient (PFG) NMR in the powder form and as extrudates. Effective diffusion coefficients (De) are measured in all cases. Diffusivities of n-hexadecane were found smaller for extrudates as compared to the powder catalysts. The estimates of diffusive tortuosity were also determined. PFG NMR data showed one major component that reveals diffusion in interconnected meso- and micropores and one other minor component (1–2%) that may correspond to more isolated pores or may represent complex effects of restricted diffusion. Therefore, several approaches including initial slope analysis of spin-echo attenuation curves, two-component fitting and Laplace inversion were used to discuss different aspects of diffusional transport in the studied H-MCM-41 materials. Correlations between De and the amount of Bindzil, the specific surface area, the micropore volume, the particle size, the total acid sites and the Lewis acid sites are discussed.

The current work focuses on studying the aqueous phase reforming (APR) of pine and birch hydrolysate obtained from waste wood by using organic acids available from biorefineries. Processing of representative synthetic mixtures was utilized in the work in order to support data interpretation related to the influence of different chemical compound and processing parameters on the APR of the actual hydrolysates. It was shown, that hydrogenation of the hydrolysates prior to APR was not feasible in the presence of formic acid, which ruled out one potential processing route. However, it was successfully demonstrated that birch and pine hydrolysates could be directly processed obtaining close to full conversion. The best results were obtained with tailored bimetallic Pd-Pt/sibunit catalyst in a trickle bed reactor system in the temperature range 175 °C–225 °C.

Pulse field gradient NMR technique was used to determine self-diffusivity of heptane and pentadecane at room temperature for microporous catalysts, used both as powders and shaped with a binder extrudates. The results showed that diffusivities increased with increasing specific surface area, micro- and mesopore volume of the studied catalysts. The presence of Bindzil binder together with H-Beta-25 decreased hydrocarbon diffusivities. Self-diffusivities of heptane and pentadecane were smaller for extrudates than for the powder catalysts. The detailed information about mass transfer limitations is needed to further process optimization since effective diffusivity is directly correlated with self-diffusion coefficients. The estimates of the ratio of porosity and tortuosity were also determined. The diffusion measurements with relatively long observation times Δ (20 up to 1000 ms) and catalysts fully immersed in pentadecane revealed that a small portion of sites exhibits very small diffusivities in H-Beta-25-Bindzil extrudates, which is correlated with a low ratio of mesopore to micropore volumes of this material.

Deoxygenation of dilute and concentrated stearic acid over 2% Pd/C beads was performed in a continuous reactor at 300 degrees C and 20 bar pressure of Ar or 5% H-2/Ar. Stable operation was obtained in 5% H-2 atmosphere, with 95% conversion of 10 mol % dilute stearic acid in dodecane and 12% conversion of pure stearic acid. Deactivation took place in H-2-deficient gas atmosphere, probably as a result of the formation of unsaturated products and coking in the pore system. Transient experiments with step changes were performed: 1 h was required for the step change to be visible in liquid sampling, whereas steady states were achieved after a total of 2.5-3 h. Postreaction analysis of the spent catalyst revealed that a deactivation profile was formed downward over the catalyst bed.

Esterification kinetics of propanoic acid with ethanol, 1-propanol and butanol over a fibrous polymer-supported sulphonic acid catalyst (Smopex-101) was studied. Experiments were carried out in a batch reactor operating isothermally at three different temperatures: 60, 70 and 75 degrees C (80 degrees C for butanol) and with different initial molar ratios of propanoic acid and alcohol (1:1, 1:2 and 2:1). The fiber catalyst was active and stable in all the experiments. The experimental results were modeled according to a Langmuir-Hinshelwood model and with an advanced adsorption-based model. The activity coefficients were calculated according to the UNIFAC model. The activation energy of esterification of propanoic acid with ethanol was found to be 52.6 kJ/mol, 49.9 kJ/mol with 1-propanol and 47.3 kJ/mol with butanol. The kinetic model, which includes the adsorption of carboxylic acid and water combined with the activities of the species, explained the experimentally recorded concentrations well., QC 20100525