Comparison of Hexane Vapour Permeation in Two Different Polymeric Membranes via an Innovative In-line FID Detection Method

This manuscript presents a novel method for the analysis of vapour permeation through polymeric membranes based on in-line analysis of the permeate with an FID detector. The hexane vapour permeation was studied for two commercially available membranes, namely low-density polyethylene (LDPE) and thin-film-composite polyamide (PA) membrane. The hexane permeation was studied at temperatures of 25–45 °C, hexane vapour activity in the range of 0.2–0.8 and trans-membrane pressures of 5–50 kPa. Two fundamentally different membranes were chosen to demonstrate the potential and sensitivity of the permeation apparatus. Upon increasing the temperature from 25 to 45 °C, the flux in LDPE was found to increase almost fourfold over the whole activity range. The nonlinear increase of the flux with activity indicates plasticization of the polymer by hexane. Contrarily, the flux in the PA membrane increases almost linearly with activity, with only a minor upward curvature. Since the PA is far away from any phase transition, it is less temperature-dependent than LDPE. The activation energy for permeation demonstrates that the temperature dependence in the LDPE membrane is dominated by changes in diffusion, whereas it is dominated by changes in solubility in the PA membrane. This work is licensed under a Creative Commons Attribution 4.0 International License

Diffusion Measurements of Hydrocarbons in Zeolites with Pulse-Field Gradient Nuclear Magnetic Resonance Spectroscopy

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 Delta (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

Effect of the Preparation of Pt-Modified Zeolite Beta-Bentonite Extrudates on Their Catalytic Behavior in n-Hexane Hydroisomerization

Four different types of shaped catalysts with controlled deposition of platinum and the same composition were prepared by extrusion of beta zeolite agglomerated with bentonite as an aluminosilicate clay binder. The catalysts were characterized using mechanical strength tests; scanning electron microscopy for morphology; transmission electron microscopy for porosity and periodicity; nitrogen physisorption for surface area, pore volume, and pore size distribution; and Fourier transform infrared spectroscopy using pyridine as a probe molecule to elucidate the presence, strength, and amount of Bronsted and Lewis acid sites. Elemental analysis was carried out using energy-dispersive X-ray microanalysis. Activity and selectivity of catalysts in the isomerization of n-hexane were evaluated using a fixed bed reactor at 200-350 degrees C. At low temperature, the performance of metal/acid bifunctional shaped catalysis was strongly affected by the metal-to-acid site ratio. This ratio and the total acidity were strongly influenced by the preparation method of the shaped catalysts, while the textural properties were comparable. The highest conversion of n-hexane and selectivity to C-6 isomers (comprising all branched isomers, such as methyl pentane and dimethylbutane) was obtained with extrudates prepared via in situ synthesis with platinum located on the zeolite. The extrudates prepared in this way have the highest metal-to-acid site ratio and their closest proximity, albeit the lowest mechanical strength

Diffusion measurements of hydrocarbons in zeolites with pulse-field gradient nuclear magnetic resonance spectroscopy

Abstract 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

Diffusion measurements of hydrocarbons in H-MCM-41 extrudates with pulsed-field gradient nuclear magnetic resonance spectroscopy

Abstract 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