Gas permeation properties of polyamide membrane prepared by interfacial polymerization

Interfacial polymerization technique has been widely employed to prepare reverse osmosis (RO) and nanofiltration (NF) membranes. The present study explores the possibility of preparing a polyamide membrane by interfacial polymerization and its utilization for the separation of CO₂ and H₂S from CH₄. A novel ultraporous substrate of polysulfone (PSF) was prepared by phase inversion technique from a solution containing 18% PSF and 4% propionic acid in dimethyl formamide (DMF) solvent. Thin film composite (TFC) polyamide membrane was synthesized on PSF substrate from the reaction between meta-phenylene diamine in an aqueous media and isophthaloyl chloride in hexane. The membrane prepared was characterized by Fourier transform infrared spectroscopy (FTIR), X-ray diffraction (XRD), differential scanning calorimetry (DSC) and scanning electron microscopy (SEM) to study intermolecular interactions, crystallinity, thermal stability and surface morphology, respectively. Gas permeabilities of pure CO₂, H₂S, CH₄, O₂, and N₂ gases were measured using the indigenously built permeation cell incorporated into a high-pressure gas separation manifold. At the feed pressure of 1 MPa, the membrane exhibited permeances of 15.2 GPU for CO₂ and 51.6 GPU for H₂S with selectivities of 14.4 and 49.1 for CO₂/CH₄ and H₂S/CH₄ systems, respectively. The observed N₂ permeance of 0.95 GPU was close to that of CH_4. The corresponding O₂ permeance was 5.13 GPU with a reasonably high O₂/N₂ selectivity of 5.4. The effect of feed pressure on polyamide membrane performance was examined. Further, molecular dynamics (MD) simulations were employed to compute the cohesive energy density (CED), solubility parameter (δ) and sorption of CO₂, H₂S, CH₄, O₂, and N₂ gases in polyamide membrane to corroborate theoretical study with experimentally determined gas transport properties.     

Thermodynamische Stoffdaten für Biogase

Thermodynamic analysis of apparatus designed for biogas and biogas production calls for the thermodynamic properties of these gases. In this paper newly fitted functions of the isobaric specific heat capacity c_p ^iG =c_p(T) are presented for the species nitrogen N₂, methane CH₄, carbondioxide CO₂, carbonmonoxide CO, water H₂O, sulfurdioxide SO₂, hydrogen H₂, oxygen O₂, sulfur hydrogen H₂S und Argon Ar. Equations for mixtures of these ideal gases are given and their application is shown by means of an example.     

Residual gases in Hgl2 crystal growth ampoules

Gases evolve in sealed borosilicate glass ampoules containing Hgl₂, which influence the crystallization of Hgl₂. It was found by mass spectroscopy that they are mainly H₂, H₂O, CH₄, CO, CO₂ and NO. The composition of gases depended on the mode of Hgl₂ preparation. The amount of gases evolved covered the range (2–12)×10^–7 mol/g Hgl₂. The Hgl₂ vapour transport rate in ampoules containing different samples of mercuric iodide was measured. Other ampoules filled with Hgl₂ were degassed and preheated in various ways which influenced the Hgl₂ crystallization rate. On the basis of the experiments carried out a procedure was elaborated permitting a 35-fold increase of the Hgl₂ vapour transport rate under identical thermal conditions.     

Mixed matrix membrane development

This article looks at two types of mixed matrix membranes that have been developed by UOP LLC. The first type includes adsorbent—polymers such as silicalite—cellulose acetate (CA), NaXCA and AgXCA mixed matrix membrane. The silicalite—CA has a CO₂/H₂ selectivity of 5.15±2.20. In contrast, the cellulose acetate membrane has a CO₂/H₂ selectivity of 0.77±0.06. The second type of mixed matrix membrane has a polyethyleneglycol silicone rubber structure. This has a high selectivity for polar gases such as SO₂, NH₃ and H₂S.     

In Situ Detecting Thermal Stability of Solid Electrolyte Interphase (SEI)

Solid electrolyte interphase (SEI) plays an important role in regulating the interfacial ion transfer and safety of Lithium-ion batteries (LIBs). It is unstable and readily decomposed releasing much heat and gases and thus triggering thermal runaway. Herein, in situ heating X-ray photoelectron spectroscopy is applied to uncover the inherent thermal decomposition process of the SEI. The evolution of the composition, nanostructure, and the released gases are further probed by cryogenic transmission electron microscopy, and gas chromatography. The results show that the organic components of SEI are readily decomposed even at room temperature, releasing some flammable gases (e.g., H₂, CO, C₂H₄, etc.). The residual SEI after heat treatment is rich in inorganic components (e.g., Li₂O, LiF, and Li₂CO₃), provides a nanostructure model for a beneficial SEI with enhanced stability. This work deepens the understanding of SEI intrinsic thermal stability, reveals its underlying relationship with the thermal runaway of LIBs, and enlightens to enhance the safety of LIBs by achieving inorganics-rich SEI.     

CO2 and H2 detection with a CHx/porous silicon-based sensor

There has been great interest in the last years in gas sensors based on porous silicon (PS). Recently, a gas sensing device based on a hydrocarbon CH_x/porous silicon structure has been fabricated. The porous samples were coated with hydrocarbon groups deposited in a methane argon plasma. We have experimentally demonstrated that the structure can be used for detecting a low concentration of ethylene, ethane and propane gases [Gabouze N, Belhousse S, Cheraga H. Phy State Solidi (C), in press].In this paper, the CH_x/PS/Si structure has been used as a sensing material to detect CO₂ and H₂ gases. The sensitivity of the devices, response time and impedance response to different gas exposures (CO₂, H₂) have been investigated.The results show that current-voltage and impedance-voltage characteristics are modified by the gas reactivity on the PS/CH_x surface and the sensor shows a rapid and reversible response to low concentrations of the gases studied at room temperature.     

Scale formation mechanisms of martensitic steels in high CO2/H2O-containing gases simulating oxyfuel environments

Abstract

In oxyfuel power plants, metallic components will be exposed to service environments containing high amounts of CO₂ and water vapour. Therefore, the oxidation behaviour of a number of martensitic 9–12%Cr steels in a model gas mixture containing 70% CO₂–30% H₂O was studied in the temperature range 550–700°C. The results were compared with the behaviour in air, Ar–CO₂ and Ar–H₂O. It was found that in the CO₂- and/or H₂O-rich gases, the mentioned steels tended to form iron-rich oxide scales with significantly higher growth rates than the Cr-rich surface scales formed during air exposure. The iron-rich scales were formed as a result of a decreased flux of chromium in the bulk alloy toward the surface because of enhanced internal oxidation of chromium in the H₂O-containing gases and carbide formation in the CO₂-rich gases. Additionally, the presence of water vapour in the exposure atmosphere led to buckling of the outer haematite layer, apparently as a result of compressive oxide growth stresses. The Fe-base oxide scales formed in CO₂(–H₂O)-rich gases appeared to be permeable to CO₂ molecules resulting in substantial carburization of the steel.     

Synthesis and characterization of CdO-doped nanocrystalline ZnO:TiO2-based H2S gas sensor

This paper reports the preparation and gas-sensing characteristic of ZnO:TiO₂-based hydrogen sulfide (H₂S) gas sensor with different mol% of CdO by polymerized complex method. The structural and gas-sensing properties of ZnO:TiO₂ materials have been characterized using X-ray diffraction and gas-sensing measurement. The electrical resistance response of the sensor based on the materials was investigated at different operating temperatures and different gas concentrations. The sensor with 10 mol% CdO-doped ZnO:TiO₂ shows excellent electrical resistance response toward H₂S gas. The cross sensitivity was also checked for reducing gases like CH₄, CO and H₂ gas. The selectivity and sensitivity of ZnO:TiO₂-based H₂S gas sensor were improved by the addition of 10 mol% of CdO at an operating temperature of 250 °C.     

Nanocrystalline Pt-doped TiO2 thin films prepared by spray pyrolysis for hydrogen gas detection

Nanostructured pure and Pt-doped TiO₂ thin films were prepared by chemical spray pyrolysis technique. Aqueous solution of TiCl₃·6H₂O (0·01 M) was chosen as the starting solution for the preparation of pure TiO₂ thin film. Aqueous solutions of PtCl₆·6H₂O (0·01 M) and TiCl₃·6H₂O (0·01 M) were mixed in volume % of 1 : 99, 2·5 : 97·5 and 5 : 95 respectively to obtain Pt-doped TiO₂ thin films. The solutions were sprayed onto quartz substrate heated at 350 °C temperature to obtain the films. These thin films were fired for one hour at 550 °C. The sensing performance of these films was tested for various gases such as LPG, H₂, CO₂, ethanol, NH₃ and Cl₂ (1000 ppm). The Pt-doped TiO₂ (1 : 99) was observed to be most sensitive (572) to H₂ at 400 °C with high selectivity against other gases. Its response time was short (10 s) and recovery was also fast (14 s). To understand the reasons behind the gas-sensing performance of the films, their structural and microstructral properties were studied using X-ray diffraction and electron microscopy (FE–SEM and TEM), respectively. Thicknesses of all these samples were determined using Surface Profiler. The results are interpreted.     

Gas hydrate occurrences in the Qilian Mountain permafrost,Qinghai Province,China

Four scientific experimental wells were drilled in the Qilian Mountain permafrost of Qinghai Province, China, in 2008 and 2009. Gas hydrate was obtained from three of four wells and its related anomalous phenomena were observed in all the four wells. Raman spectroscopy was used in the laboratory to evaluate the type of clathrates recovered from these sites, including structures containing large and small cages of hydrocarbon gases. Gas hydrate and associated anomalies occur mainly in fractured mudstone, oily shale, siltstone, and fine-grained sandstone. Secondary occurrences were also present in the pore space of fine to medium grained sandstone in a zone between 133 and 396 mbs. This interval was vertically discontinuous and horizontally did not appear to correlate between wells. Gas hydrate occurrences in these wells are not solely related to lithology and are strongly controlled by fissures in the Qilian Mountain permafrost. Gas geochemical characteristics reveal that gas hydrate is primarily composed of CH₄, with secondary components of C₂H₆, C₃H₈, and CO₂. Raman spectra analysis indicates a sII gas hydrate structure. Gas composition and carbon and hydrogen isotope geochemistry show that gases from gas hydrate are mainly thermogenic with a biogenic fraction. In the study area, gas hydrate and its related anomalous phenomena are confined to the gas hydrate stability zone which is constrained by permafrost pressure and temperature conditions. Core observations indicate that individual gas hydrate occurrences are controlled by fissures. It is speculated that, when hydrocarbon gases reach the gas hydrate stability zone, they form into gas hydrate that occurred preferably in fissures beneath the permafrost.     

Mixed waste ferrite as a novel sorbent for carbon dioxide derived from flue gases

Ferrite is a potential sorbent for flue gases such as CO₂, H₂S and SO₂. This paper discusses the adsorption and decomposition of CO₂ into carbon by hydrogen-activated waste ferrites prepared from Berkeley Pit acid mine water (Butte, MT). The decomposition effectiveness of these waste ferrites was studied at 300 °C and compared with the synthetic magnetite obtained from ferrous sulfate solution in our laboratory. The decomposition was measured by two methods: indirectly by measuring the adsorption rate of CO₂ and directly by analysing the carbon deposited on the samples. The results indicated that the mixed waste ferrite had good affinity for the adsorption and decomposition. The CO₂ decomposition data of both sorbents fitted the first-order reaction kinetics. Even though the surface area of the magnetite was higher than that of waste ferrite, the CO₂ decomposition rate of the waste ferrite was estimated to be 2.5 times higher than that of magnetite under identical conditions. The carbon analysis deposited on the sample indicated that the CO₂ was 100% decomposed into carbon and other carbon/hydrogen compounds by the waste ferrite, whereas the conversion was 43% by the magnetite. In terms of specific adsorption of carbon, ferrite was three to five times more efficient than magnetite.     

Gas sorption by barium films

The various experimental data about gas sorption are analyzed on the basis of a previously described adsorption-diffusion theory of gas-metal interaction. Thereby is obtained some new information about the mechanism of the sorption of different gases (N₂, H₂, CO, CO₂, O₂) by barium films at low pressure and kinetic equations are deduced for the calculation gettering rates.     

Electrochemical Behaviour of Ce0.9Gd0.1O2−δ SOFC‐Anodes

In order to compare the electrochemical performance of Ce_0.9Gd_0.1O_2−δ (CGO) in various fuels, impedance spectroscopy measurements were carried out in the atmospheres containing H₂, CO, CO₂, CH₄, N₂ at various compositions, in the temperature range 650°C to 850°C. Ohmic loss and polarization resistance were derived from impedance spectroscopy measurements. The stability at different temperatures of the anode was also investigated in 9%H₂/91%N₂ humidified with 3% H₂O. The microstructure of the anode before and after degradation test was analysed by SEM. These investigations indicated similarities in the impedance and the activation enthalpies in hydrogen/water, methane/water and CO/CO₂ atmospheres. No indications of methane cracking leading to carbon formation were found.     

Preparation and Properties of Thin HfO<Subscript>2</Subscript> Films

HfO₂ layers were grown on silicon by metalorganic chemical vapor deposition using (C₅H₅)₂Hf(CH₃)₂, (C₅H₅)₂Hf(N(C₂H₅)₂)₂, and Hf(dpm)₄ as volatile precursors and were characterized by x-ray diffraction, x-ray photoelectron spectroscopy, and IR spectroscopy. The films were shown to consist of monoclinic HfO₂ and to contain hafnium silicide and silicate at the HfO₂/Si interface. The presence of hafnium silicide was attributed to oxygen deficiency produced by argon ion milling. Hafnium silicate was formed as a result of the reaction between hafnium and silicon oxides during annealing. Current-voltage and capacitance-voltage measurements on Al/HfO₂/Si test structures were used to determine the dielectric permittivity and electrical resistivity of the films: ? = 15–20, ρ ～ 10¹⁵ cm.     

Gas Storage in Fullerenes

Abstract

Fullerenes and in particular C₆₀ have been shown to store effectively a wide range of gases from simple monatomic rare gases to diatomics and polyatomics. A review of the research in this area conducted at ANSTO is given. The trapping of Ar, Kr, Xe, and CO₂ are discussed in detail whilst preliminary results pertaining to N₂O, CH₄, CF₄, C₂H₆ and SF₆ are also reported. A range of techniques have been used to elucidate both the structure of the new fullerene intercalated solid and the trapped gas itself. The preponderant techniques used, include infra-red absorption spectroscopy (IR), X-ray powder diffraction a (XRD), neutron powder diffraction (NRD), transmission electron microscopy (TEM), and thermal gravimetric analysis (TGA).     

Effect of treating atmosphere in plasma post-oxidation of nitrocarburized AISI 5115 steel

In this study quenched and tempered AISI 5115 steel was plasma-nitrided and nitrocarburized at 550 °C for 5 h in atmospheres of 80% N₂ balanced with various amounts of CO₂ and H₂ gases. The amount of CO₂ varied from 0 to 10 vol%. The highest amount of ε phases was formed in the compound layer after treating in atmosphere containing 7 vol% CO₂. Optimized compound layer was post-oxidized for 1 h at 450 °C under O₂/H₂ volume ratios of 1/1 and 3/1 as well as 100% oxygen. The treated samples were characterized using metallographic techniques, XRD, SEM, roughness measurement and potentiodynamic methods. The results showed that the growth rate of the oxide layer increased with increasing O₂ in the oxidizing gas mixture. X-ray diffraction analysis of oxidized layers confirmed the formation of highest amount of magnetite at post-oxidation in an atmosphere with the O₂/H₂ volume ratio of 1/1. Electrochemical polarization tests proved the enhancement of corrosion resistance by plasma post-oxidation and the highest corrosion resistance obtained after oxidizing under an O₂/H₂ volume ratio of 1/1.     

Mg/Ca decorated on carbon-doped boron nitride sheet: Application for gas adsorption

Through first-principles calculations, we investigate the adsorption of alkaline-earth(AE) metal (Mg/Ca) on carbon doped hexagonal boron nitride (h-BN) sheet, as well as its potential application as a sensor for gas molecules H₂, H₂O, CO, CO₂, O₂, and NO. With carbon substitution of nitrogen, Mg and Ca were energetically favorable to doped on the BN sheet with binding energies of 1.464 and 2.047 eV, respectively, due to the strong binding between AE atoms and substrate. With the Mg/Ca dopant, the binding interaction between gas molecules and the moderated BN sheet becomes stronger. For all the studied gases, the overall process of adsorption was found to be exothermic, moreover, NO, H₂O, and O₂ are chemisorbed while CO, H₂, and CO₂ are physisorbed. After adsorption, the electronic structures of systems are also affected judging from the electronic density of the state calculation.     

Thermophilic biofiltration of H2S and isolation of a thermophilic and heterotrophic H2S-degrading bacterium, Bacillus sp. TSO3

Thermophilic biofiltration of H₂S-containing gas was studied at 60 °C using polyurethane (PU) cubes and as a packing material and compost as a source of thermophilic microorganisms. The performance of biofilter was enhanced by pH control and addition of yeast extract (YE). With YE supplement and pH control, H₂S removal efficiency remained above 95% up to an inlet concentration of 950 ppmv at a space velocity (SV) of 50 h⁻¹ (residence time = 1.2 min). H₂S removal efficiency strongly correlated with the inverse of H₂S inlet concentrations and gas flow rates. Thermophilic, sulfur-oxidizing bacteria, TSO3, were isolated from the biofilter and identified as Bacillus sp., which had high similarity value (99%) with Bacillus thermoleovorans. The isolate TSO3 was able to degrade H₂S without a lag period at 60 °C in liquid cultures as well as in the biofilter. High H₂S removal efficiencies were sustained with a periodic addition of YE. This study demonstrated that an application of thermophilic microorganism for a treatment of hot gases may be an economically attractive option since expensive pre-cooling of gases to accommodate mesophilic processes is not required.     

XPS investigation on AISI 420 stainless steel corrosion in oil and gas well environments

The corrosion behaviour of 13Cr-martensitic stainless steel (AISI 420) was investigated in CO₂-H₂S-Cl^– environments typical of oil and gas wells under different CO₂ and H₂S partial pressures. The corrosion tests indicated that the AISI 420 steel was highly corrosion resistant to CO₂-induced phenomena (general corrosion and carbonate S.C.C.), while in the H₂S environment a high S.S.C.C. (Sulphide Stress Corrosion Cracking) susceptibility and high corrosion rates were found. Moreover, CO₂ in CO₂-H₂S-Cl^– systems inhibited general corrosion and S.S.C.C. phenomena by favouring the formation of a protective film. By means of X-ray photoelectron spectroscopy (XPS) the chemical nature of the films grown on AISI 420 in different environmental conditions was investigated and the following statements were drawn out:

Decomposition mechanism of organic compounds by DC water plasmas at atmospheric pressure

The purpose of this paper is to investigate the decomposition mechanism of organic compounds by water plasmas. The plasma torch can generate 100%-steam by DC discharge without a commercially available steam generator. Methanol or ethanol used as a model substance of water-soluble organic compounds was mixed with water for plasma supporting gas. The main gases after the decomposition were H₂, CO, and CO₂. The 50 wt.% of carbon was transformed into solid carbon in 5 mol%-ethanol decomposition, while the solid-carbon formation from 5 mol%-methanol was negligible. Larger amount of solid-carbon formation from ethanol decomposition indicates the different mechanism between methanol and ethanol decomposition.