An automatic PNA analyser for the under 200°C fraction contained in a higher boiling product

Summary We present a modified circuit for the PNA-analyser, which allows analysis for paraffins, naphthenes and aromatics in the under 200°C fraction of a sample having a final boiling point above 200°C. The modified separation scheme gives, in addition, improved type separation. By the introduction of adapted instrumentation the analyser has been suited to fully automated serial analysis. The new concept will eventually be commercialized.A glossary of abbreviations has been included at the end of this paper.     

Stepwise Engineering the Pore Aperture of a Cage-like MOF for the Efficient Separation of Isomeric C4 Paraffins under Humid Conditions

The separation of isomeric C4 paraffins is an important task in the petrochemical industry, while current adsorbents undergo a trade-off relationship between selectivity and adsorption capacity. In this work, the pore aperture of a cage-like Zn-bzc (bzc=pyrazole-4-carboxylic acid) is tuned by the stepwise installation methyl groups on its narrow aperture to achieve both molecular-sieving separation and high n-C₄H₁₀ uptake. Notably, the resulting Zn-bzc-2CH₃ (bzc-2CH₃=3,5-dimethylpyrazole-4-carboxylic acid) can sensitively capture n-C₄H₁₀ and exclude iso-C₄H₁₀, affording molecular-sieving for n-C₄H₁₀/iso-C₄H₁₀ separation and high n-C₄H₁₀ adsorption capacity (54.3 cm³ g⁻¹). Breakthrough tests prove n-C₄H₁₀/iso-C₄H₁₀ can be efficiently separated and high-purity iso-C₄H₁₀ (99.99 %) can be collected. Importantly, the hydrophobic microenvironment created by the introduced methyl groups greatly improves the stability of Zn-bzc and significantly eliminates the negative effect of water vapor on gas separation under humid conditions, indicating Zn-bzc-2CH₃ is a new benchmark adsorbent for n-C₄H₁₀/iso-C₄H₁₀ separation.     

Coverage dependence of neopentane trapping dynamics on Pt(111)

Adsorption probabilities for neopentane on Pt(111) were measured directly using supersonic molecular-beam techniques at coverages ranging from zero to monolayer saturation, incident translational energies between 18 and 110 kJ mol⁻¹ and incident angles between 0° and 60° at a surface temperature of 105 K. The adsorption probability was found to increase with coverage up to near monolayer saturation at all incident translational energies and incident angles. The coverage dependence of the adsorption probability predicted by a modified Kisliuk model with enhanced trapping into the second layer exhibits good quantitative agreement with the experimental values. The angular dependence of the adsorption probability decreases with increasing coverage, suggesting that the effective corrugation of the gas–surface interaction potential increases with the adsorbate coverage. The initial adsorption probability into the second layer onto the covered surface decreases from 0.95 to 0.75 with increasing energy over the energy range studied, and exhibits total energy scaling. A comparison with second-layer trapping data of simpler molecules onto covered Pt(111) indicates that the structural complexity of adsorbed neopentane molecules facilitates collisional energy transfer during adsorption.     

A rapid multidimensional liquid-gas chromatography method for the analysis of mineral oil saturated hydrocarbons in vegetable oils

The present paper describes an investigation directed toward the development of a rapid heart-cutting LC-GC method for the analysis of mineral oil saturated hydrocarbons contained in vegetable oils. The automated LC-GC experiments were carried out by using a system equipped with a syringe-type interface, capable of both heart-cutting and comprehensive (LC × GC) two-dimensional analysis. The first dimension separation was achieved on a 100 mm × 3 mm ID × 5 μm d(p) silica column, operated under isocratic conditions (hexane). A single 30-s cut, corresponding to a 175 μL volume, was transferred to a programmed temperature vaporizer. After the large volume injection, the target analytes were separated in a rapid manner (~9 min) using a 15 m × 0.1mm ID × 0.1 μm micro-bore GC capillary. The overall LC-GC run time enables the analysis of ca. 4 samples/hour. Quantification was performed by using external calibration, in the 1-200 mg/kg range. The method was validated in terms of linearity, precision, limits of detection and quantification, and accuracy. A series of commercial samples were subjected to analysis. Various degrees of contamination were found in all samples, in the 7.6-180.6 mg/kg range.     

Solid-phase extraction versus solid-phase microextraction for the determination of chlorinated paraffins in water using gas chromatography-negative chemical ionisation mass spectrometry

Solid-phase extraction (SPE) and solid-phase microextraction (SPME) were evaluated for the analysis of short-chain chlorinated paraffins (SCCPs) in water samples using gas chromatography coupled to negative chemical ionisation mass spectrometry (GC-NCI-MS). For SPE optimisation, four commercially available SPE cartridges were tested and several SPE parameters, such as the elution solvent, elution volume and breakthrough volume were studied. The best results were obtained with Varian Bond Elut-C18. In order to achieve a high selectivity in the determination of SCCPs, GC-NCI-MS was used. Quality parameters of the optimised SPE and SPME procedures were determined, and the best results were obtained for the SPE/GC-NCI-MS method with LODs of 5 and 20 ng l(-1) for tap and river water, respectively. This method was successfully applied to the analysis of SCCPs in river water samples at concentrations below the microg l(-1) level.     

Improvement in thermal conductivity of paraffin by adding high aspect-ratio carbon-based nano-fillers

Molecular dynamics simulations have been utilized to study thermal conductivity of liquid and solid mixtures of paraffin and carbon-based high aspect-ratio nano-additives, i.e. carbon nanotubes and graphene. In agreement with existing experimental data, we observe high enhancement in thermal conductivity through adding these graphitic nano-additives into paraffin, particularly in the solid phase. We demonstrate that this significant improvement is mainly achieved by the enhancement in thermal conductivity of the matrix itself. This is caused by carbon nanotubes and graphene promoting ordering of the matrix molecules which consequently leads to improvement of its thermal conductivity.     

Light mirror reflection combined with heating/cooling curves as a method of studying phase transitions in transparent and opaque petroleum products: Apparatus and theory

A portable low weight low cost apparatus “Phasafot” and method for determining pour and cloud points of petroleum products, as well as precipitation and melting temperatures of paraffins in both transparent (diesel fuels), semi-transparent (lube oils) and opaque (crude oils) samples are described. The method consists in illuminating the surface of a sample with an oblique light beam and registering the intensity of specularly reflected light while heating/cooling the sample in the temperature range of its structural transitions. The mirror reflection of a light beam from an ideally smooth liquid surface falls in intensity when the surface becomes rough (dim) due to crystal formation. Simultaneous recording of the temperature ramp curve and the mirror reflection curve enables the determination of the beginning and end of crystallization of paraffins in both transparent and opaque petroleum products. Besides, their rheological properties can be accurately determined by rocking or tilting the instrument while monitoring the sample movement via its mirror reflection.