Nitrogen Permeability Research Articles

A Comprehensive Examination of Low GO-Silica Loading in Pebax1657/PEI Thin Film Nano-composite Membranes for Gas Dehydration

The aim of this study was to assess the effectiveness of blending Pebax1657 polymer with SiO2-GO nanoparticles in the production of TFN membranes for N2 gas dehydration. By utilizing dip coating, nanoparticles were incorporated at varying concentrations. The resulting nanocomposites were subjected to thorough analysis to investigate their chemical structure, physical morphology, surface topology, and thermal stability. This examination encompassed the application of FTIR, SEM, CA, AFM, and TGA techniques. The results demonstrated that the samples displayed good thermal stability and a highly hydrophilic surface. The investigation concluded that the dehydration properties of TFN membranes are influenced by a variety of factors, such as morphology, plasticization, and hydrophilic attributes. The effectiveness of the system is contingent upon the contribution made by each individual nanoparticle. The impact of SiO2 nanoparticles in their pure form is clearly evident in the 0.5 wt% loaded composite membrane membrane. When 0.5% of SiO2 nanoparticles are introduced into the composite membrane, the morphology closely resembles the ideal state due to the non-porous nature of SiO2 and the low concentration of nanoparticles, hence a selectivity of ~560 is experienced. Fortunately this selectivity is beyond the need of the industries. Consequently, there was a reduction in water vapor and nitrogen permeability, resulting in a heightened selectivity ratio. These discoveries hold considerable importance in industrial settings, as they offer a more comprehensive understanding of the topic.

Permeability of porous membrane polymers modified by supercritical carbon dioxide

An approach to predict the gas permeability of membrane polymers after supercritical CO2 treatment is proposed. The approach is based on the connection of the temperatures of secondary relaxation transitions with the effective sizes of mobile free volume elements in the polymers. The correlation between permeability of nitrogen and effective sizes of mobile holes for a set of polymers is established. The effect of supercritical CO2 on the nitrogen permeability of polycarbonate, polysulfone, polyvinylbutyral is analyzed by FTIR spectroscopy of low-molecular weight conformationally-inhomogeneous compounds introduced in the polymers. Membranes were exposed at 40 MPa and 333 K for 4 h through static treatment and dynamic treatment separately. For polyvinylbutyral, the nitrogen permeability did not change after supercritical CO2 modification while for polysulphone, the effective volume of mobile holes increased, but the nitrogen permeability decreased. For polycarbonate after supercritical CO2, the effective volume of mobile holes and the nitrogen permeability increased.

Modeling of multi-mechanisms permeability for hydrogen separation using a membrane process

In gas separation using nanoporous membranes, both operating conditions and membrane properties are key to the process performance. Mathematical modeling is crucial for defining the optimal conditions and properties for the optimization and design of these processes. This research introduces a comprehensive model that integrates surface and pore permeabilities for studying the (PIM-1) membrane performance for H2/N2 separation. The model combines empirical and solution-diffusion models to examine temperature and pressure effects alongside a theoretical approach for assessing how pore size and porosity influence permeability and selectivity. Simulation results indicated that temperature increases from 298 K to 373 K significantly enhanced hydrogen and nitrogen permeability by 13% and 135%, respectively, while the selectivity dropped from 24.6 to 15.3. On the other hand, the pressure effect was less significant compared to the effect. The study also highlighted the critical roles of pore size and porosity in transport mechanisms and membrane performance, showing that increasing the pore size and porosity enhanced permeability and reduced selectivity. Remarkably, PIM-1 membranes with pore sizes of near 1 nm and porosity below 0.1 exceeded the Robeson 2008 upper limit, showcasing improved permeability with good selectivity. This model offers a predictive tool for PIM-1 membrane performance under various conditions, facilitating the design of efficient separation process.

Increasing the efficiency of stimulation of compacted carbonate reservoirs with acid solutions based on methyl acetate

The development of oil and gas deposits in compacted rocks is a promising area of development in the oil and gas industry. The object of research in this paper is the filtration properties of compacted rocks. To develop such deposits, special extraction technologies are required. Compacted carbonate rocks are easily dissolved by most acids, but for effective use, it is necessary that working solutions have very low viscosity and surface tension coefficient. Special filtration equipment has been developed for the research, which allows pumping various liquids and gases through rock samples and measuring permeability at pressures up to 1,000 bar. To determine the effectiveness of the acid solution, three groups of samples were studied: silty sandstone with clay-carbonate cement with a permeability of 0.2–0.95 mD, compacted organogenic-detrital light gray limestone with a permeability of 0.001–0.004 mD, and organogenic-detrital gray limestone with a permeability of 0.04–0.06 mD. In the course of the study, the stimulation fluid was pumped through the samples at a pressure of 200–300 bar and a temperature of 120 °C. The efficiency was determined by the change in nitrogen permeability of the samples before and after the experiments. In general, the studied stimulation fluid allowed increasing the permeability of rocks up to 3–7 times, depending on the rock and research conditions. The solution retains its reactivity for a long time and, due to its low viscosity and surface tension, penetrates deeply into the rock and significantly increases the well treatment radius compared to conventional acid treatments. The use of the developed acid solution for well stimulation will increase the efficiency of hydrocarbon production from compacted reservoirs without the use of hydraulic fracturing

Application of hollow fiber membranes for producing an ultrafiltration permeate from colostrum whey enriched in bioactive compounds

Bovine colostrum whey, despite being a source of bioactive peptides and prebiotic oligosaccharides with dietary and nutraceutical applications, presents significant processing challenges due to its high viscosity, making hollow fiber membranes, with their superior ability to control membrane fouling, well-suited for handling such fluids. The objective of this work was to determine optimal ultrafiltration conditions of a 10 kDa hollow fiber membrane to increase efficiency (i.e., permeate flux), selectively retain whey proteins, and facilitate the permeation of peptides (< 10,000 Da) and oligosaccharides (∼600 Da) from bovine colostrum whey. The impact of feed flow rate (3, 6, 9 L min-1) and transmembrane pressure (1, 2, 3 bar) were evaluated on permeate flux, protein retention, and non-protein nitrogen permeation. Higher permeate fluxes were observed at higher feed flows and moderate transmembrane pressure, demonstrating the ability of turbulence to disrupt the concentration polarization layer at the membrane surface and decrease fouling, as exhibited in the resistance analyses. Higher feed flow significantly increased the cumulative permeate flux during colostrum whey concentration (64.6 ± 0.1 L h-1m-2 at 9 L min-1 vs. 12.5 ± 5.9 L h-1m-2 at 3 L min-1, at continuous diafiltration mode and 2 bar), with continuous diafiltration experiments yielding similar permeate fluxes to the ones achieved in discontinuous mode. Processing scale at 12.7 L (2 bar, 9 L min-1, and continuous diafiltration) enabled 97% protein retention and 95% peptide and oligosaccharide permeation, producing a permeate with 1.3 g L-1 peptide and 0.42 g L-1 oligosaccharide. The results of this study highlight the impact of key ultrafiltration conditions of bovine colostrum whey using a hollow fiber membrane for the effective recovery of peptides and oligosaccharides for subsequent evaluation of their biological properties and commercial applications.

Estimating the Influencing Factors of Gas–Water Relative Permeability in Condensate Gas Reservoirs under High-Temperature and High-Pressure Conditions

The gas–water relative permeability curve plays a crucial role in reservoir simulation and development for condensate gas reservoirs. This paper conducted a series of high-temperature and high-pressure analysis experiments on real gas cores from Wells A and B in Block L of the Yinggehai Basin to investigate the effects of temperature, pressure, and different types of gas media on gas–water seepage. The gas–water relative permeability was simulated in this experiment through variations in temperature, pressure, and gas composition. Temperature has a significant impact on both gas and water relative permeability, particularly on gas relative permeability. As temperature increases, gas relative permeability shows a substantial increase, while water relative permeability remains relatively unchanged. Under the same effective stress, increasing pressure causes downward shifts in both the gas and water relative permeability curves; however, there is a more pronounced decrease in gas relative permeability. Gas composition has minimal influence on the gas–water relative permeability except at higher water saturation where differences become apparent. When water saturation ranges from 80% to 50%, there is no significant variation observed in the measured relative permeability of different displacement gases. However, as water saturation exceeds 80%, distinctions gradually emerge. The relative permeability of nitrogen is approximately 92% lower than that of mixed gas when the bound water saturation reaches 80%. This investigation provides valuable insights into the characteristics of gas–water relative permeability in high-temperature and high-pressure condensate reservoirs within Yinggehai Basin, thereby offering significant contributions to development strategies for similar reservoirs.

Experimental study on permeability evolution of sandstone under cyclic loading

The permeability of a rock mass affects the site selection and construction of underground high-pressure gas storage for compressed-air energy storage. This study investigates the permeability evolution of sandstone under high-pressure gas during the cycle of confining and axial pressures. Nitrogen permeation tests were conducted at different inlet pressures using the steady-state method. The initial steady-state flow, seepage in the circulation, and steady-state flow after circulation were measured continuously in three stages. The effects of the loading and unloading rates and load-holding time on the seepage flow were analyzed. The results indicate that the flow rate and displacement changed with periodic changes in the axial and confining pressures during the cycle. The higher the inlet pressure, the greater was the difference between the peak and trough of the flow in the cycle, and the greater was the difference between the flow after the cycle and the initial flow. When the inlet pressure was 10 MPa, the steady-state flow rate increased from 284 ml/min to 336 ml/min (18%). When the inlet pressure was 2 MPa, the evolution range of the seepage flow in the sample was similar for different load-holding times. The loading and unloading rates had a significant influence on the flow waveform in the circulation process but little influence on the wave height. With an increase in the number of cycles, the porosity of the samples first decreased rapidly and then increased slowly. This study provides a reference for construction and operation of compressed-air energy-storage systems.

High Barrier Properties of Butyl Rubber Composites Containing Liquid Rubber and Graphene Oxide.

The high elasticity and excellent gas barrier properties of rubber composites make them irreplaceable in the field of sealing. Constructing a complicated barrier network to reduce free volume is crucial to improving gas barrier properties. In this research, liquid acrylonitrile-butadiene rubber/γ-Methacryloxypropyl trimethoxy silane (KH570) modified graphene oxide/butyl rubber composites (LNBR/KGO/IIR) were fabricated. A KGO lamellar network was constructed to resist gas diffusion in the IIR matrix. Meanwhile, LNBR macromolecules further occupied the free volume inside the IIR composites, thereby maximizing the retardation of the path of small molecule gas permeation. The modification of GO by KH570 was successfully demonstrated through FTIR and XRD. The grafting rate of KH570 was calculated to be approximately 71.4%. KGO was well dispersed in IIR due to emulsion compounding and the formation of lamellar networks. The 300% modulus, tensile strength and tear strength of KGO/IIR were improved by 43.5%, 39.1% and 14.8%, respectively, compared to those of the IIR composite. In addition, the introduction of LNBR resulted in a 44.2% improvement in the gas barrier performance of nitrogen permeability relative to the original IIR composite.

Effect of ZIF-78 metal-organic framework crystal morphology and defect in resulting polysulfone mixed matrix membranes

BackgroundMixed matrix membranes (MMMs) provide a new possibility for membranes to exceed the tradeoff between permeability and selectivity found in pure polymeric membranes. Factors that enhance gas separation performance in MMMs include filler morphology and aspect ratio. MethodsHigh aspect ratio microporous ZIF-78, a metal-organic framework (MOF) demonstrated in literature to have one of the highest carbon dioxide uptake capacities, was successfully synthesized using a solvothermal method. These particles were incorporated into MMMs in non-defective and systematically defective forms by using two common solvents – chloroform and DMF. Detailed characterization of the various membranes was performed using BET, XRD, SEM, EDS, DSC, TGA, FTIR, and a custom-built gas permeability measurement apparatus. Significant findingsIntroduction of crystals with no apparent defect results in a more tortuous pathway for permeating gas molecules, demonstrated by nitrogen permeation results. Conversely, for carbon dioxide, strong dipole-quadrupole interaction with ZIF-78 creates excellent permeation pathways through the crystal themselves. The defective system possesses more inter-filler free volume which allow all gas components to permeate more easily, in addition to the original mechanism. The gas separation performance of the resulting MMMs in this work displayed a 140 % improvement of CO2 permeability and 129 % improvement of CO2/N2 ideal selectivity over pure polysulfone membranes. This work shows the potential of using deliberately designed fillers to increase performance via special pathways for gas molecules.

Experimental study on the Klinkenberg effect for gas permeability in carboniferous shales, Eastern Qaidam Basin, China

It is crucial to understand the conditions and influencing mechanisms of shale gas slip effect for predicting the productivity of shale gas reservoirs. This study focuses on the Carboniferous Hurleg Formation shales in the eastern Qaidam Basin and conducts gas permeability tests using different gases (He/N2), as well as geochemical and pore-structure tests. The slip behavior of different gases in micro- and nanopores as well as the anisotropy of gas permeability were analyzed and discussed. The results show that helium permeability is 1.81–3.56 times higher than nitrogen permeability, with a greater difference at lower pore pressures. These permeability differences are attributed to variations in gas molecule size and slip effects. Specifically, the slip effect of helium gas has a greater contribution to permeability at lower pore pressures, with a helium slip factor averaging 2.79 times that of nitrogen. The effective pore size of shale, calculated based on the helium slip factor, is 0.74 to 1.51 times larger than when nitrogen is used, with an average of 1.67 times. Helium molecules have smaller diameters and longer average molecular free paths, resulting in a more pronounced slip effect compared to nitrogen. While helium does not adsorb, nitrogen exhibits some adsorption, causing radial expansion during gas penetration. Furthermore, when testing with different gases, the horizontal permeability (S043∥; S052∥) is higher than the vertical permeability (S043⊥; S052⊥). The anisotropy of permeability is controlled by the pore system formed by the arrangement and combination of minerals. Calcium-rich samples (S052) tend to exhibit higher anisotropy compared to calcite-rich samples (S043). The effective pore size in the vertical sample is larger than that in the parallel sample, and the gas slip effect is significantly greater in the vertical sample. These findings provide valuable data for future studies on shale gas slip effects and productivity prediction.

Study on the effects of manifold structure on the gas flow distribution uniformity of anode of PEMFC stack with 140-cell

The gas maldistribution of the large proton exchange membrane fuel cell (PEMFC) stack leads to the deterioration of power performance. This numerical investigation studies the gas flow rate distribution in anode of two U-type stacks (a 15-cell stack and a 140-cell stack) which are composed of the same type of unit fuel cells. The anode gas channels of the two stacks are regarded as porous medium whose characteristic parameters are determined from pressure drop test data. To consider the nitrogen permeation from cathode to anode gas channel during the purging process, an expression of an additional momentum source term is proposed which helps to better fit the simulation results with pressure drop test data. Results show that the anode of the 140-cell stack has a quite good flow distribution uniformity. However, its asymmetric feed header of the manifold structure still has some negative effect. The same 140-cell stack installed with a rotational symmetric feed header is investigated and the simulation result shows that it can reduce the original maximum non-uniformity by about 50%.

Liquid-liquid extraction of phenolic wastewater through a surface modified poly(vinylidene fluoride-co-hexafluoropropylene) hollow fiber membrane contactor and process optimization

BackgroundStrict environmental regulations have been recognized for phenolic wastewater treatment due to toxicity of the phenolic compounds. In this study, solvent extraction of a phenolic wastewater was investigated via a liquid-liquid membrane contactor system. MethodsPorous poly(vinylidene fluoride-co-hexafluoropropylene) (PVDF-HFP) hollow fiber membranes were modified by coating an ultra-thin layer of hydrophobic surface modifying macromolecule (SMM). The membranes were characterized by various tests such as SEM-EDS, nitrogen permeation, overall porosity, contact angle and critical water entry pressure (CEPw). Significant findingsFrom SEM, an open structure with combination of finger-like and sponge-like structure was produced. The membrane exhibited high surface hydrophobicity (water contact angle of 109°) with good wetting resistance, overall porosity of 82% and mean pore size of 18 nm. From response surface methodology (RSM), the maximum phenol extraction flux of 2.02 × 10−3 kg/m2s was estimated by the model at the optimum process variables as phenol concentration of 448 mg/L, feed temperature of 42 °C, aqueous phase flowrate of 196 mL/min and organic phase flowrate of 117 mL/min. The coefficient of determination (R2) of 0.972 showed a close proximity between the model and the experimental data. The membrane showed a reasonable flux that can be a favorable alternative for industrial phenolic wastewater treatment.

Ultra-stable fully-aromatic microporous polyamide membrane for molecular sieving of nitrogen over volatile organic compound

Microporous polymer membranes are promising candidates for industrial membrane-based gas separation because of their high separation performance. However, their relatively low stability due to the local rearrangement of polymer chains during usage remains a problem. Hence, we propose the construction of a fully aromatic polymer structure in a microporous polymer membrane to enhance membrane stability. Four triptycene-based microporous polyamides were synthesized via the polymerization of 2,6,14-triaminotriptycene with aromatic acyl chloride and/or aliphatic acyl chlorides. Their properties were characterized and compared by using nuclear magnetic resonance (NMR) and Brunauer–Emmett–Teller analyses. The synthesized polyamides were fabricated into composite membranes by employing a solution process; their stability was evaluated for the molecular sieving of nitrogen over volatile organic compounds such as cyclohexane. Low-field NMR and X-ray photoelectron spectroscopy were used to investigate the differences in the properties of membranes with different structures at different times. The results showed that the fully aromatic polyamide membrane made from 2,6,14-triaminotriptycene and aromatic acyl chloride displayed constant rejection (99 %) and nitrogen permeability (approximately 50 Barrer) for the molecular sieving of nitrogen over cyclohexane during 100-d experiments, indicating good stability. This approach paves the way for the industrialization of microporous polymer membranes from a theoretical perspective.

Liquid Permeability Determination from Vacuum Imbibition in Tight/Shale Core Plugs

Liquid permeability is a key petrophysical parameter that quantifies the ability of a liquid to flow through porous rock/soil and can be used in determining the efficiency of many subsurface processes, including enhanced hydrocarbon recovery, groundwater transport, carbon dioxide geostorage, underground hydrogen storage, etc. However, it is time-consuming (usually >16–240 h) and challenging to measure the liquid permeability for tight/shale rocks, particularly when the permeability is 100 nD or lower. The objective of this study is to develop a rapid and simple approach to determine liquid (brine or oil) permeability in tight siltstones/shales. Specifically, the developed method is based on the combination of one-dimensional (1D) vacuum imbibition experiments in tight/shale core plugs and a modified Lucas–Washburn model. For our proof-of-concept study, the results have demonstrated that (1) only 44–116 h are required to determine the liquid permeability (98–608 nD) for the analyzed samples from the Montney and Yanchang Formations; and (2) the acquired brine permeability was 28.3–28.5% lower than the slip-corrected nitrogen (N2) permeability derived from the pulse-decay permeability tests. This is the first attempt to determine the absolute permeability of a liquid according to a 1D vacuum imbibition experiment and theory. This study provides a promising technique for the fast characterization of ultratight formation permeability of around 100 nD.

Construction of Nitrogen Content Observer for Fuel Cell Hydrogen Circuit Based on Anode Recirculation Mode

The anode recirculation mode is increasingly being adopted in today’s fuel cell systems. The recycling of hydrogen gas can effectively improve fuel utilization and the wider economy. However, using the purge strategy for the recirculation exhaust has a significant impact on the operational performance and economic efficiency of fuel cell systems.Experiments have shown that, when the purge interval increases from 6 s to 10 s, the recirculation pump power increases by about 20%, the nitrogen content in the exhaust gas increases, and the stack voltage shows a 10 V attenuation. The accumulation of nitrogen permeation in the anode circuit leads to the degradation of the fuel cell performance. Therefore, it is necessary to discharge the accumulated nitrogen through the purge valve in a timely manner. However, opening the exhaust valve with excessively high frequency can result in the unreacted hydrogen being discharged, which reduces the economic efficiency of the fuel cell. This paper is based on the principle of mass conservation and models each subsystem of the anode circuit in the recirculation pump mode of the fuel cell separately, including the proportional valve model, the hydrogen consumption model of the fuel cell, the nitrogen permeation model of the fuel cell, the neural network model of the circulating pump, and the purge valve model. These submodels are integrated to construct a nitrogen content observer for the hydrogen circuit, which can estimate the nitrogen content. The accuracy of the model is validated through experimental data. The estimation error is less than 5.5%. The nitrogen content in the anode circuit can be effectively estimated, providing a model reference for purge operations and improving hydrogen utilization.

Properties of Polysulphones Synthetized for Forming of Porous Hollow-Fiber Membranes

For the first time, for the problem of hollow fiber membranes spinning, polysulfones in a wide range of molecular weights (42 000–184 000 g/mol) were synthesized in such aprotic dipolar solvents as dimethylacetamide, N-methyl-2-pyrollidone, and dimethyl sulfoxide. The dependence of the thermal and mechanical properties of polysulfones on molecular weight characteristics has been studied. A comparison of the mechanical properties of the synthesized PSF, commercial PSF Ultrason S 6010 (BASF, Germany) and PSF-150 (JSC Institute of Plastics, Russia) showed that the synthesized polymers are not inferior to commercial analogues. Some synthesized polymers surpass commercial PSF in terms of elasticity and strength modulus. Based on the study of the spinning solutions dynamic viscosity, promising PSF samples were selected for the formation of porous hollow fiber supports. It was found that hollow-fiber porous support from a PSF sample with a molecular weight of 110 000 g/mol have a high nitrogen permeability of 47.5 m3/m2 · h · bar. Such supports are promising for casting highly permeable composite membranes with a thin selective layer.

Parametric and modelling study of H2O-induced plasticization in PEI-TFC membrane for gas dehydration

Separation of moisture from gaseous mixtures, such as natural gas, humid air in food and goods storage warehouses or in sports halls and so on is of great importance. In this article, the separation of water from a wet gas stream is carried out by a TFC membrane made by interfacial polymerization on the sublayer of porous polyetherimide hollow fibers. Then the key-parameters affecting membrane efficiency is studied. The outcomes show that increasing the concentration of MPD has a substantial effect on enhancing the membrane water vapor flux. Moreover, it is disclose that increasing the concentration of TMC has the greatest effect on reducing nitrogen gas permeability and increasing the selectivity. Our findings reveals that disregarding the very low concentration of water vapor in the feed, shows a great impact on the permeance of each component compared to the pure state. Also, based on the modelling, it is obvious that for nitrogen gas in the entire pressure range, the adsorption mechanism is almost completely controlled by the Henry model, while the Langmuir adsorption mechanism is controlling for water vapor at low pressures, although at high pressures, the Henry mechanism has absolute superiority. Surprisingly, the H2O-induced plasticization impact on nitrogen permeance is more intense than on water vapor permeance. According to the modeling outputs, it is revealed that because D N2 is one to two order of magnitude lower than DH2O, water vapor permeance is much higher than that of nitrogen.

The influence mechanism of effective stress, adsorption effect and Klinkenberg effect on coal seam permeability

Permeability is an important parameter in the process of coalbed methane exploitation. To improve the production efficiency of coalbed methane and explore the control mechanism of the gas flow law in coal, the permeability of helium and nitrogen in the same coal sample was tested under different effective stress (the difference between external stress and pore pressure of coal mass) and pressure by using the seepage device. Based on the gas flow theory, the interaction mechanism of effective stress, adsorption effect and Klinkenberg effect in controlling the permeability has been analyzed. Increasing the gas pressure will enhance the adsorption and deformation ability of coal, causing the reduction of pore size, while it will also cause the reduction of effective stress and stress deformation. There is a certain competition between them under the same external stress condition, which will lead to the change of pore and then affect the permeability of coal seam. The Klinkenberg effect will lead to more complex change factors of permeability, especially in laboratory experiments. Both adsorption deformation and stress deformation will affect the pore structure of coal body, which will also lead to changes in the influence degree of Klinkenberg effect on apparent permeability. Under the influence of adsorption effect, the Klinkenberg effect may be a variable. The experimental results in this work elaborate the microscopic control mechanism of gas permeability change in coal. It can not only provide important guidance for gas injection technology, but also enrich the theory of coal seam gas flow.

Characterization of proven Late Cretaceous Reservoir rocks in the Gulf of Gabes: Integrated case study

Microstructural features control the petrophysical properties of rocks. Of these, pore size is particularly sensitive when non-wetting fluids saturate the reservoir. The pore networks and physical properties (helium, water and mercury saturation porosity, bulk density, nitrogen permeability, P-wave velocity and thermal conductivity) of different rock types from a productive Upper Cretaceous (Coniacian) reservoir in the tunisian offshore are measured on hydrocarbon-washed samples. The facies sampled of Douleb Member are wackestone, packstone and grainstone textures as well as dolostone, dolomitized packstone and anhydrite textures. Based mainly on the results obtained by mercury injection, the porous facies of the Coniacian Douleb Member are characterized by a complex pore system with a large morphological and pore size variability in the rock. Porosity values range from 0.3 to 23.6%, bulk densities vary from 2.05 to 2.92 g.cm−3. The permeability is variable from 3760 mD to values below 0.01 mD (measurement limit of the device). P-wave propagation velocity values range from 2060 to 6084 m.s−1 and thermal conductivity varies from 1.43 to 3.77 W.m−1.K−1. The oil-impregnated facies with the best petrophysical characteristics are mainly the rudist-rich limestones and dolomites of the first unit (U1) of the Douleb Member. The well-sorted grainstones with small rudist debris and peloids have the best reservoir qualities. Porosity is the first order characteristic that controls petrophysical properties. The variability of permeability values around this first-order relationship is attributed to variations in the size of the pore access thresholds and connectivity. The variability in velocities is due to the shape of the voids, while the variability in thermal conductivity measurements is due to the nature of the contacts between the grains.

Method of Liquid-Phase Fluorination of Polymers to Increase the Selectivity of the Air Separation

The one-sided modification of homogeneous polymer films of polyvinyltrimethylsilane (PVTMS), poly(2,6-dimethylphenyl-1,4 oxide) (PPO), and polybenzodioxane (PIM-1) was carried out by liquid-phase fluorination method using a fluorine-nitrogen mixture in perfluorodecalin. The fluorination time ranged from 10 to 60 min. For PPO films the amorphous and β-nanocrystalline phase (48%) was found by X-ray diffraction analysis of the original films. It was shown that fluorination does not significantly affect the degree of PPO crystallinity. The effect of fluorination time on the effective coefficients of permeability, diffusion, and solubility of oxygen and nitrogen has been studied. It was found that the fluorination leads to a decrease in both effective diffusion coefficients and effective gas solubility coefficients, while the resulting increase in permeability selectivity ranged from 30% for PVTMS to a 2 times increase in the case of PPO and PIM-1. It has been noted that this improvement in permeability selectivity is achieved mainly by the solubility selectivity increasing. The permeability of O2/N2 mixture for original and modified films was studied. It was found that the achieved values of the separation factors are close to the ideal selectivity. The results obtained demonstrate the possibility of effective application of the liquid-phase modification method not only for the homogeneous polymer films of the studied polymers treatment, but also for membranes with a selective non-porous layer based on them.