Olefin/paraffin gas separations with 6FDA-based polyimide membranes

Pure gas permeation and sorption experiments were carried out for the gases ethylene, ethane, propylene and propane using polyimides based on 4,4′-(hexafluoroisopropylidene) diphthalic anhydride (6FDA). Composite membranes and free films were used. Experiments were performed at 308 K and feed pressures up to 17 atm for ethylene and ethane and 9 atm for propylene and propane. Mixed gas permeation experiments were carried out with 50 : 50 olefin/paraffin feed mixtures. For all investigated polyimides, the ideal ethylene/ethane separation factor ranged between 3.3 and 4.4 and the ideal propylene/propane separation factor ranged between 10 and 16 at a feed pressure of 3.8 atm and 308 K. In mixed gas permeation experiments, up to 20% lower selectivity was found for the ethylene/ethane separation and up to 50% reduced selectivity for the propylene/propane separation compared to the ideal selectivity. The influence of feed temperature on separation and permeation properties will be discussed based on pure gas permeability data at 298 and 308 K.     

Modified poly(phenylene oxide) membranes for the separation of carbon dioxide from methane

Two types of poly(phenylene oxide) (PPO) membranes were prepared: one by chemical modification through sulfonation using chlorosulfonic acid and another by physical incorporation with a heteropolyacid (HPA), viz., phosphotungstic acid. These membranes were tested for the separation of CO₂/CH₄ mixtures. Fourier transform infrared spectroscopy (FTIR) and X-ray diffraction techniques were used to confirm the modified structure of PPO as well as to understand its interactions with gaseous molecules. Scanning electron microscopy (SEM) was used to investigate the membrane morphology. Thermal stability of the modified polymers was assessed by differential scanning calorimetry (DSC), while the tensile strength was measured to evaluate their mechanical stability. Both chemical and physical modifications did not adversely affect the thermally and mechanical stabilities. Experiments with pure CO₂ and CH₄ gases showed that CO₂ selectivity (27.2) for SPPO increased by a factor of 2.2, while the PPO–HPA membrane exhibited 1.7 times increase in selectivity with a reasonable permeability of 28.2 Barrer. An increase in flux was observed for the binary CO₂/CH₄ mixture permeation with an increasing feed concentration (5–40 mol%) of CO₂. An enhancement in feed pressure from 5 to 40 kg/cm² resulted in reduced CO₂ permeability and selectivity due to the competitive sorption of methane. Both the modified PPO membranes were found to be promising for enrichment of methane despite exhibiting lower permeability values than the pristine PPO membrane.     

Effect of copolymer type and composition on separation characteristics of pervaporation membranes—A case study with separation of acetone–water mixtures

Five different copolymer membranes, i.e. copolymer of acrylonitrile with 2-hydroxyethyl methacrylate (PANHEMA), vinyl acetate (PANVAC) and methyl methacrylate (PANMMA) and styrene with vinyl acetate PSTYVAC) and methyl methacrylate (PSTYMMA) were synthesized, each with two different copolymer compositions (i.e. PANHEMA-1, PANHEMA-2, etc.). The copolymer membranes were synthesized on the basis of their relative solubility parameters with respect to acetone and hydrophilicity with respect to water. These membranes were used for pervaporative dehydration of acetone over the entire concentration range of 0–100 wt% water as well as acetone separation over 0–44 wt% acetone in feed. The acrylonitrile copolymers showed water selectivity with maximum water flux and selectivity for PANHEMA-2 copolymer (29.3 g/(m² h), 16.73, respectively, for 2.5 wt% water in feed) while the styrene copolymers showed maximum acetone selectivity with reasonable acetone flux for PSTYMMA-1 copolymer (7.12 g/(m² h), 12.61, respectively, for 1.6 wt% acetone in feed) membrane. The influence of one permeant on permeation of the other permeant was also studied in terms of permeation factor.     

Application of the radioactive ionisation detector to the determination of permanent gases by gas chromatography and some uses in studies of chemical kinetics

It has been found possible to determine volumes of hydrogen, methane, and carbon dioxide within the range 0.1–10 ml at S.T.P. and carbon monoxide and nitrogen within the range 0.1–0.4ml at S.T.P. with an accuracy of around 5 % in a gas chromatograph using the radioactive ionisation detector, provided that the detector temperature and the rate of carrier gas flow through the column are maintained between stated limits. Results of experiments on the sensitivity of the instrument to oxygen, sulphur dioxide, ethane, propane and n-pentane are also reported. Particular attention has been directed towards selecting the most suitable parameter of the response peaks for use in quantitative analysis.

Some particular applications of the argon chromatograph in studies of chemical kinetics involving permanent gases are described, and a method for the removal of corrosive gases from mixtures to be analysed is discussed.     

Transport properties of alkanes through ceramic thin zeolite MFI membranes

Polycrystalline randomly oriented defect free zeolite layers on porous α-Al₂O₃ supports are prepared with a thickness of less than 5 μm by in situ crystallisation of silicalite-1. The flux of alkanes is a function of the sorption and intracrystalline diffusion. In mixtures of strongly and weakly adsorbing gases and a high loadings of the strongly adsorbing molecule in the zeolite poze, the flux of the weakly adsorbing molecule is suppressed by the sorption and the mobility of the strongly adsorbing molecule resulting in pore-blocking effects. The separation of these mixtures is mainly based on the sorption and completely different from the permselectivity. At low loadings of the strongly adsorbing molecules the separation is based on the sorption and the diffusion and is the same as the permselectivity. Separation factors for the isomers of butane (n-butane/isobutane) and hexane (hexane/2,2-dimethylbutane) are respectively high (10) and very high (> 2000) at 200°C. These high separation factors are a strong evidence that the membrane shows selectivity by size-exclusion and that transport in pores larger than the zeolite MFI pores (possible defects, etc) can be neglected.     

Transport of organic vapors through poly(1-trimethylsilyl-1-propyne)

Poly(1-trimethylsilyl-1-propyne) [PTMSP], a high-free-volume glassy polymer, has the highest gas permeability of any known synthetic polymer. In contrast to conventional, low-free-volume, glassy polymers, PTMSP is more permeable to large, condensable organic vapors than to permanent gases. The organic-vapor/permanent-gas selectivity of PTMSP based on pure gas measurements is low. In organic-vapor/permanent-gas mixtures, however, the selectivity of PTMSP is much higher because the permeability of the permanent gas is reduced dramatically by the presence of the organic vapor. For example, in n-butane/methane mixtures, as little as 2 mol% n-butane (relative n-butane pressure 0.16) lowers the methane permeability 10-fold from the pure methane permeability. The result is that PTMSP shows a mixed-gas n-butane/methane selectivity of 30. This selectivity is the highest ever observed for this mixture and is completely unexpected for a glassy polymer. In addition, the gas mixture n-butane permeability of PTMSP is considerably higher than that of any known polymer, including polydimethylsiloxane, the most vapor-permeable rubber known. PTMSP also shows high mixed-gas selectivities and vapor permeabilities for the separation of chlorofluorocarbons from nitrogen. The unusual vapor permeation properties of PTMSP result from its very high free volume - more than 20% of the total volume of the material. The free volume elements appear to be connected, forming the equivalent of a finely microporous material. The large amount of condensable organic vapor sorbed into this finely porous structure causes partial blocking of the small free-volume elements, reducing the permeabilities of the noncondensable permanent gases from their pure gas values.     

Continuous dynamic-gravimetric preparation of calibration gas mixtures for air pollution measurements

 The preparation of calibration gas mixtures for air pollution measurements by the dynamic-gravimetric method was investigated using sulphur dioxide in nitrogen as a model. The target mole fraction was 200×10^–9 mol/mol, with the option of also getting smaller mole fractions. Thermal mass flow meters calibrated with reference mass flows were used to measure the dilution gas flow (nitrogen). The relative standard uncertainty of the dilution gas flows between 10 mg/s (approx. 500 ml/min) and 40 mg/s (approx. 2000 ml/min) was 0.15%. The mass flow of the target component measured as the permeation rate was determined via the quasi-continuous observation of the loss in the permeation tube mass during the measuring time. A magnetic coupling system and an adapted microbalance were used for this purpose. The results presented show permeation rates measured over the lifetime of a tubular permeation source. The measurement cycles took between 3 days and 7 h at least. The relative standard uncertainty of the mixture composition did not exceed 2%. First comparisons with gas mixtures prepared by the static-gravimetric method show compatibility. The applicability of the system is not restricted to the SO₂/N₂ mixture. It can also be used for preparing other gas mixtures in this field of application. Received: 26 April 2000 / Accepted: 12 September 2000     

Properties of oxygen permeation and partial oxidation of methane in La0.6Sr0.4CoO3−δ (LSC)–La0.7Sr0.3Ga0.6Fe0.4O3−δ (LSGF) membrane

The oxygen separation membrane having perovskite structure for the partial oxidation of methane to synthesis gas was prepared. La_0.7Sr_0.3Ga_0.6Fe_0.4O_3−δ (LSGF) perovskite membrane coated with La_0.6Sr_0.4CoO_3−δ (LSC) (M1), and the one side of M1 membrane coated with NiO (M2) was prepared to examine the partial oxidation of methane. The single oxygen permeations of the LSC + LSGF (M1) membrane and NiO coated membrane (M2) were measured. The oxygen permeation flux in M1 membrane was higher than that of M1 membrane at 850 °C.

The partial oxidation experiment of methane using the prepared membranes was examined at 850 °C. The value of CH₄ conversion and CO selectivity of M2 membrane was higher than that of M1 membrane.

NiO/NiAl₂O₄ catalyst was used to improve the methane conversion, and the partial oxidation experiment of methane with M1 membrane was examined at 850 °C. The CH₄ conversion was 88%, and CO selectivity was 100%.     

Synthesis and characterization of silicalite-1/carbon-graphite membranes

Silicalite-1/carbon-graphite composite membranes have been prepared using a standard hydrothermal synthesis method and characterized by XRD, SEM, TGA, BET and permeation experiments. Single gas permeation fluxes and binary mixtures separation and selectivity data are reported for methane, ethane and propane using the composite membranes. Carbon-graphite oxidized for 4 h prior to membrane preparation had the most promising separation properties. The permeation fluxes for the binary mixtures reflect that of the single component flux ratios. At 20 degrees C the membranes show high separation selectivity toward lighter component in binary mixtures. Single gas permeances for methane and ethane were found to decrease with increasing temperatures while that of propane fluctuates.     

Ti–Ni–Pd dense membranes—The effect of the gas mixtures on the hydrogen permeation

In this experimental work the influence of co-existing gases on the hydrogen permeation through a Ti–Ni–Pd membrane was studied. It was found that nitrogen, carbon dioxide and helium do not influence the hydrogen permeation through the dense membrane. However, carbon monoxide influences the hydrogen flux at each temperature investigated (400–500 °C). The results show that for low CO concentration (i.e. at H₂ upstream >80%), the hydrogen flux through the membrane decreases faster than linearly, while, at H₂ upstream <80%, the slope is linear but smaller than the theoretical one.     

Development of a new gas sensor for binary mixtures based on the permselectivity of polymeric membranes: Application to carbon dioxide/methane and carbon dioxide/helium mixtures

Membrane-based gas sensors were developed and used for determining the composition on bi-component mixtures in the 0-100% range, such as oxygen/nitrogen and carbon dioxide/methane (biogas). These sensors are low cost and are aimed at a low/medium precision market.The paper describes the use of this sensor for two gas mixtures: carbon dioxide/methane and carbon dioxide/helium. The membranes used are poly(dimethylsiloxane) (PDMS) and Teflon-AF hollow fibers. The response curves for both sensors were obtained at three different temperatures. The results clearly indicate that the permeate pressure of the sensors relates to the gas mixture composition at a given temperature. The data is represented by a third order polynomial. The sensors enable quantitative carbon dioxide analysis in binary mixtures with methane or helium. The response of the sensors is fast (less than 50 s), continuous, reproducible and long-term stable over a period of 2.3×10⁷ s (9 months). The absolute sensitivity of the sensors depends on the carbon dioxide feed concentration ranging from 0.03 to 0.13 MPa.     

Diffusion of methane and carbon dioxide in carbon molecular sieve membranes by multinuclear pulsed field gradient NMR

Carbon molecular sieve (CMS) membranes are promising materials for energy efficient separations of light gases. In this work, we report a detailed microscopic study of carbon dioxide and methane self-diffusion in three CMS membrane derived from 6FDA/BPDA(1:1)-DAM and Matrimid polymers. In addition to diffusion of one-component sorbates, diffusion of a carbon dioxide/methane mixture was investigated. Self-diffusion studies were performed by the multinuclear (i.e., (1)H and (13)C) pulsed field gradient (PFG) NMR technique which combines the advantages of high field (17.6 T) NMR and high magnetic field gradients (up to 30 T/m). Diffusion measurements were carried out at different temperatures and for a broad range of the root-mean-square displacements of gas molecules inside the membranes. The diffusion data obtained from PFG NMR are compared with the corresponding results of membrane permeation measurements reported previously for the same membrane types. The observed differences between the transport diffusivities and self-diffusion coefficients of carbon dioxide and methane are discussed.     

Gas permeation through water-swollen hydrogel membranes

This work deals with water-swollen hydrogel membranes for potential CO₂ separation applications, with an emphasis on elucidating the role of water in the membrane for gas permeation. A series of hydrogel membranes with a wide range of water contents (0.9–10 g water/g polymer) were prepared from poly(vinyl alcohol), chitosan, carboxyl methyl cellulose, alginic acid and poly(vinylamine), and the permeation of CO₂, H₂, He and N₂ through the membranes at different pressures (200–800 kPa) was studied. The gas permeabilities through the dry dense membranes were measured as well to evaluate the resistance of the polymer matrix in the hydrogel membranes. It was shown that the gas permeability in water-swollen membrane is lower than the gas permeability in water, and the selectivity of the water-swollen membranes to a pair of gases is close to the ratios of their permeabilities in water. The permeability of the water-swollen membranes increases with an increase in the swelling degree of the membrane, and the membrane permeability tends to level off when the water content is sufficiently high. A resistance model was proposed to describe gas permeation through the hydrogel membranes, where the immobilized water retained in the polymer matrix was considered to form transport passageways for gas permeation through the membrane. It was shown that the permeability of hydrogel membranes was primarily determined by the water content in the membrane. The model predictions were consistent with the experimental data for various hydrogel membranes with a wide range of water contents (0.4–10 g water/g polymer).     

Gas transport property of polyallylamine–poly(vinyl alcohol)/polysulfone composite membranes

Polyallylamine (PAAm) was synthesized by free radical polymerization and characterized by Fourier transform infrared resonance (FT-IR) spectroscopy, hydrogen nuclear magnetic resonance (¹H NMR) spectroscopy and differential scanning calorimetry (DSC). The composite membranes were prepared by using PAAm–poly(vinyl alcohol) (PVA) blend polymer as the separation layer and polysulfone (PSF) ultrafiltration membranes as the support layer. The surface and cross-section morphology of the membrane was inspected by environmental scanning electron microscopy (ESEM). The gas transport property of the membranes, including gas permeance, flux and selectivity, were investigated by using pure CO₂, N₂, CH₄ gases and CO₂/N₂ gas mixture (20 vol% CO₂ and 80 vol% N₂) and CO₂/CH₄ gas mixture (10 vol% CO₂ and 90 vol% CH₄). The plots of gas permeance or flux versus feed gas pressure imply that CO₂ permeation through the membranes follows facilitated transport mechanism whereas N₂ and CH₄ permeation follows solution–diffusion mechanism. Effect of PAAm content in the separation layer on gas transport property was investigated by measuring the membranes with 0–50 wt% PAAm content. With increasing PAAm content, gas permeance increases initially, reaches a maximum, and then decreases gradually. For CO₂/N₂ gas mixture, the membranes with 10 wt% PAAm content show the highest CO₂ permeance of about 1.80 × 10⁻⁵ cm³ (STP) cm⁻² s⁻¹ KPa⁻¹ and CO₂/N₂ selectivity of 80 at 0.1 MPa feed gas pressure. For CO₂/CH₄ gas mixture, the membranes with 20 wt% PAAm content display the highest CO₂ permeance of about 1.95 × 10⁻⁵ cm³ (STP) cm⁻² s⁻¹ KPa⁻¹ and CO₂/CH₄ selectivity of 58 at 0.1 MPa feed gas pressure. In order to explore the possible reason of gas permeance varying with PAAm content, the crystallinity of PVA and PAAm–PVA blend polymers was measured by X-ray diffraction (XRD) spectra. The experimental results show an inverse relationship between crystallinity and gas permeance, e.g., a minimum crystallinity and a maximum CO₂ permeance are obtained at 20 wt% PAAm content, indicating that the possibility of increasing CO₂ permeance with PAAm content due to the increase of carrier concentration could be weakened by the increase of crystallinity.     

Starch-Enhanced Synthesis of Oxygenates from Methane and Carbon Dioxide Using Dielectric-Barrier Discharges

In this work, starch has been used to enhance the oxygenate formation directly from methane and carbon dioxide using dielectric-barrier discharges (DBDs). The use of starch inhibits the formation of liquid hydrocarbons and significantly increases the selectivity of oxygenates. Oxygenates produced include primarily formaldehyde, methanol, ethanol, formic acid, and acetic acid. The total selectivity is about 10–40% with conversion of methane and carbon dioxide of about 20%. Lower methane feed concentration favors the production of oxygenates, and higher feed flow rate leads to higher selectivity of oxygenates in the presence of starch.     

Comparative study of the separation of methanol–methyl acetate mixtures by pervaporation and vapor permeation using a commercial membrane

In the present study, the permeation behavior of methanol and methyl acetate in the pervaporation (PV) experiments are compared with those in vapor permeation (VP) experiments using a PVA-based composite membrane. Experiments have been carried out to study the selectivity and mass transport flux of the systems under varying operations conditions of feed temperature (40–60 °C) and feed methanol concentrations (2–34 wt%). The selected membrane was found to be methanol selective. Results show higher permeation flux but a similar separation factor for methanol in PV than in VP. For PV operation, the resulting separation factor at 60 °C shows a monotonous decrease (6.4–4.1) as the alcohol concentration in the feed mixture increases (2.3–34 wt%), whereas the total flux increases from 0.97 to 7.9 kg m⁻² h⁻¹. Based on the solution-diffusion theory, a mathematical model that describes satisfactorily the permeation fluxes of methanol and methyl acetate in both the PV and VP processes has been applied. The fluxes of both permeants can be explained by the solution-diffusion model with variable diffusion coefficients dependent on MeOH concentration in the membrane. Both PV and VP processes can be described with the same model but using different fitting parameters.     

Preparation and characterization of a composite PDMS membrane on CA support

Polydimethylsiloxane (PDMS) is the most commonly used membrane material for the separation of condensable vapors from lighter gases. In this study, a composite PDMS membrane was prepared and its gas permeation properties were investigated at various upstream pressures. A microporous cellulose acetate (CA) support was initially prepared and characterized. Then, PDMS solution, containing crosslinker and catalyst, was cast over the support. Sorption and permeation of C₃H₈, CO₂, CH₄, and H₂ in the prepared composite membrane were measured. Using sorption and permeation data of gases, diffusion coefficients were calculated based on solution‐diffusion mechanism. Similar to other rubbery membranes, the prepared PDMS membrane advantageously exhibited less resistance to permeation of heavier gases, such as C₃H₈, compared to the lighter ones, such as CO₂, CH₄, and H₂. This result was attributed to the very high solubility of larger gas molecules in the hydrocarbon‐based PDMS membrane in spite of their lower diffusion coefficients relative to smaller molecules. Increasing feed pressure increased permeability, solubility, and diffusion coefficients of the heavier gases while decreased those of the lighter ones. At constant temperature (25°C), empirical linear relations were proposed for permeability, solubility, and diffusion coefficients as a function of transmembrane pressure. C₃H₈/gas solubility, diffusivity, and overall selectivities were found to increase with increasing feed pressure. Ideal selectivity values of 9, 30, and 82 for C₃H₈ over CO₂, CH₄, and H₂, respectively, at an upstream pressure of 8 atm, confirmed the outstanding separation performance of the prepared membrane. Copyright © 2009 John Wiley & Sons, Ltd.     

Studies on phenol permeation through supported liquid membranes containing functionalized polyorganosiloxanes

In this study, the functionalized, linear, hydrophobic fluid organosiloxane polymers, namely, methylhydrosiloxane–dimethylsiloxane copolymers supported on a polypropylene microporous flat sheet membrane (Celgard 2502 and 2402) have been tested as supported liquid membranes (SLMs) for phenol recovery from aqueous phases into a 0.1 M NaOH phase. The functionalized polymers include, Me₃SiO[MeSi(OR)O]_x[Me₂SiO]_ySiMe₃ (containing x = 15–18, 25–35 and 50–55 mol% of R, where R is –(CH₂)_nNMe₂ (n = 3 or 4 or 6) or –(CH₂)₂OEt pendent organofunctional groups. The functionalities, R, tested were derived from the commercially available 3-dimethylamino-1-propanol and 2-ethoxyethanol as well as newly synthesized 4-dimethylamino-1-butanol and 6-dimethylamino-1-hexanol which have been made for the purpose of this study.

The study showed that phenol permeation expressed as permeate flux through the membranes increases with the larger number of carbon spacers in the alkyl chain of the aminoalcohol pendent, larger porosity of the polypropylene support films, higher mol% of the methylhydrosiloxane portion functionalized and faster flow rates of both the feed and the receiving phases. Phenol permeation was enhanced significantly when the mol% of the methylhydrosiloxane portion was 50–55 or 25–35 with 6-dimethylamino-1-hexanol functionality supported on Celgard 2502.     

Gas transport properties of poly(ethylene oxide-co-epichlorohydrin) membranes

Gas permeation properties of crosslinked membranes prepared from a series of poly(ethylene oxide-co-epichlorohydrin) (P(EO/EP)) copolymers with different contents of ethylene oxide are determined by using the constant-volume and pressure-increase method. In addition to the chemical composition, the transport properties are related to the main characteristics of copolymers like the glass transition temperature, crystallinity and crosslinking ratio. Permeation measurements of He, H₂, N₂, O₂, CO₂ and CH₄ show that the permeabilities are nearly constant up to an EO content of about 75–80 mol%, then increase rapidly up to a maximum around 90 mol% of EO in the copolymers. The same behavior is observed for the diffusion coefficient and the CO₂ sorption coefficient. The presence of an optimal EO composition is explained by the competition between crystalline and amorphous EO sequences. The copolymers present very high CO₂ permeability and selectivity respect to other permanent gases even in gas mixtures and under high pressures.     

Supported Pd-perovskite catalyst for CNG engines'' exhaust gas treatment

Perovskite-type oxides of the series La_1−xA_xMn_1−yB_yO₃ (A = Sr; B = Fe or Co) were prepared by solution combustion synthesis and characterized by X-ray diffraction, specific surface analysis, transmission electron microscopy and field emission scanning electron microscopy techniques. Their activity towards the combustion of methane was evaluated in a temperature programmed combustion microreactor. The LaMn_0.9Fe_0.1O₃ catalyst was found to provide the best performance. The half-conversion temperature of methane over the LaMn_0.9Fe_0.1O₃ catalyst was 398 °C with a W/F = 0.12 g s/cm³ and a methane feed concentration of 0.4 vol% under oxygen excess. Via temperature programmed oxygen desorption (TPD) analysis as well as catalytic combustion runs, the prevalent activity of the LaMn_0.9Fe_0.1O₃ catalyst could be explained by its higher and increased capability to desorb suprafacial, weakly chemisorbed oxygen species. Further catalyst development allowed to maximise the catalytic activity of this compound by promoting it with CeO₂ (1:1 molar ratio) and with 1 wt% Pd. This promoted catalyst was lined on cordierite monoliths in a γ-Al₂O₃-supported form (catalyst weight percentage: 15 wt%) and then tested in a lab-scale test rig under realistic conditions for compressed natural gas-vehicles' exhaust gas treatment. Half methane conversion was achieved at 340 °C (gas high space velocity = 10 000 h⁻¹), nearly the same but with a fourfold lower amount of the expensive noble metal than that used in commercial 4wt%Pd–γ-Al₂O₃ catalysts.