Monte Carlo simulation of hydrogen absorption in palladium and palladium–silver alloys

A modified Monte Carlo (MC) simulation was performed to investigate the hydrogen absorption behavior in Pd and Pd–Ag alloys of the composition Pd_xAg_1−x (x=0.7–0.8) under H₂ pressure (0.1 MPa) at different temperatures. The present method employed can consider the dissociative adsorption of hydrogen molecule and the subsequent absorption of hydrogen atom by formalizing the relationship between the pressure of hydrogen molecule and hydrogen atom. The potential parameters were determined to reproduce the solution enthalpy of hydrogen in pure metals. The results are in good agreement with experimental findings as well as previous theoretical studies. We confirmed that our method is useful to simulate the absorption of hydrogen in metals and alloys.     

Selective permeation and separation of steam from water–methanol–hydrogen gas mixtures through mordenite membrane

Separation properties of a mordenite membrane for water–methanol–hydrogen mixtures were studied in the temperature range from 423 to 523 K under pressurized conditions. The mordenite membrane was prepared on the outer surface of a porous alumina tubular support by a secondary-growth method. It was found that water was selectively permeated through the membrane. The separation factor of water/hydrogen and water/methanol were 49–156 and 73–101, respectively. Even when only hydrogen was fed at 0.5 MPa, its permeance was as low as 10⁻⁹ mol m⁻² s⁻¹ Pa⁻¹ up to 493 K, possibly suggesting that water pre-adsorbed in the micropores of mordenite hindered the permeation of hydrogen. The hydrogen permeance dramatically increased to 6.5 × 10⁻⁷ mol m⁻² s⁻¹ Pa⁻¹ at 503 K and reached to 1.4 × 10⁻⁶ mol m⁻² s⁻¹ Pa⁻¹ at 523 K because of the formation of cracks in the membrane. However, the membrane was thermally stabilized in the presence of steam and/or methanol.     

Effects of Thermal Treatment on Gas Transport Through Porous Silica Membranes

Abstract

The effects of thermal treatment from 180°C to 1150°C on the gas transport properties of porous silica membranes were systematically studied for various gases. The permeance of all gases, except for CO₂, has a maximum at 800°C. The CO₂ permeance was constant from 180°C to 600°C and then decreased monotonically. Membranes thermally treated at 1150°C did not exhibit any gas permeation because of pore collapse. The gas transport behavior follows a combination of Knudsen diffusion and surface diffusion for all gases tested except for carbon dioxide. The permeation of carbon dioxide is strongly affected by capillary condensation. We propose a new transport model composed of two components; that is, the Knudsen diffusion factor, α, and the surface diffusion factor, β. A transition was observed for α and β at around 800–900°C, which is close to the strain point of the membrane. This transition treatment temperature can be correlated with the changes in gas permeance. The model allows qualitative evaluation of gas transport through porous membranes regardless of their actual microporous structures.     

Alumina-supported cobalt-molybdenum catalyst for slurry phase Fischer–Tropsch synthesis

An evaluative investigation of the Fischer–Tropsch performance of two catalysts (20%Co/Al₂O₃ and 10%Co:10%Mo/Al₂O₃) has been carried out in a slurry reactor at 2 MPa and 220–260 °C. The addition of Mo to the Co-catalyst significantly increased the acid-site strength suggesting strong electron withdrawing character in the Co-Mo catalyst. Analysis of steady-state rate data however, indicates that the FT reaction proceeds via a similar mechanism on both catalysts (carbide mechanism with hydrogenation of surface precursors as the rate-determining step). Although chain growth, , on both catalysts were comparable (  0.6), stronger CH₂ adsorption on the Co-Mo catalyst and lower surface concentration of hydrogen adatoms as a result of increased acid-site strength was responsible for the lower individual hydrocarbons production rate compared to the Co catalyst. The activation energy, E, for Co (96.6 kJ mol⁻¹), is also smaller than the estimate for the Co-Mo catalyst (112 kJ mol⁻¹). Transient hydrocarbon rate profiles on each catalyst are indicative of first-order processes, however the associated surface time constants are higher for alkanes than alkenes on individual catalysts. Even so, for each homologous class, surface time constants for paraffins are greater for Co-Mo than Co, indicative that the adsorption of CH₂ species on the Co-Mo surface is stronger than on the monometallic Co catalyst.     

Constant concentration method of measuring hydrogen permeation from a hydrogen mixture with Pd membrane

The conventional flow method of measuring hydrogen permeation flux was found to be inaccurate and inadequate to obtain a consistent value of hydrogen flux and permeance because of changing hydrogen concentration along the palladium membrane tube in a hydrogen mixture. We designed a new method in which the hydrogen concentration was kept constant in the retentate. This constant concentration method was a more accurate measurement of hydrogen permeation flux in all of the possible hydrogen mixtures: H₂ + Y with Y = Ar, N₂ and CH₄ and various hydrogen concentrations under different pressure. Permselectivity of the hydrogen mixture was measured under this constant concentration method and was compared with both the conventional flow-through method and separate flow measurement of pure component gases. All three methods gave a different value of permselectivity for the same composite mixture.This method enables us to measure hydrogen flux and permeance accurately in the corresponding composition of the mixture. We found that even with the same partial hydrogen pressure differential for Sieverts’ equation, the hydrogen flux and permeance decreased dramatically with the lowering of hydrogen concentration in the feed.     

Pervaporation via silicon-based membranes: Correlation and prediction of performance in pervaporation and gas permeation

Pervaporation (PV) is a membrane technology that holds great promise for industrial applications. To better understand the PV mechanism, PV dehydrations of various types of organic solvents (methanol, ethanol, iso-propanol, tert-butanol, and acetone) were performed on five types of organosilica and two types of silicon carbide-based membranes, all with different pore sizes. Water permeance was dependent on the types of organic aqueous solutions, which suggested that organic solvents penetrated the pores and hindered the permeation of water. In addition, water permeance of various types of membranes in PV was well correlated with hydrogen permeance in single-gas permeation. Furthermore, a clear correlation was obtained between the permeance ratio in PV and that in single-gas permeation, which was confirmed via the modified-gas translation model. These correlations make it possible to use single-gas permeation properties to predict PV performance.     

High flux mesoporous MCM-48 membranes: Effects of support and synthesis conditions on membrane permeance and quality

This communication reports experimental efforts to synthesize defect-free mesoporous MCM-48 membranes with improved gas flux. We demonstrate a facile and inexpensive method of synthesizing defect-free supported MCM-48 membranes with improved N₂ and CO₂ permeance (>2 × 10⁻⁷ mol/m² s Pa) employing asymmetric supports for the membrane synthesis which contain layers of macropores possessing different pore sizes. The membranes prepared on asymmetric -alumina supports displayed higher gas permeance than those fabricated on symmetric supports (N₂ permeance <10⁻⁷ mol/m² s Pa) as confirmed by unsteady-state gas permeation experiments. Further improvement in gas permeance was achieved by covering one face and the sides of the support with a ceramic tape during membrane synthesis.     

Catalysis with homogeneous membranes loaded with nanoscale metallic clusters and their preparation

Catalytically powerful, non-porous membranes were manufactured from two highly gas permeable poly(amide imides) consisting of structures with moieties of 3,3'-dimethylnaphthidine and hexafluoroisopropylidene (6F) or hexafluoroisopropylidene 2,2-bis(phthalic acid anhydride) (6FDA) and 6F. The catalysts are pure precious metals or precious metal alloys dispersed on a nanoscale uniformly throughout the membrane. The membranes are characterized by electron microscopy, gas permeability, hydrogen uptake and, as a model reaction, the decomposition of nitrous oxide by hydrogen to nitrogen and water catalyzed by Pd/Ag. The permeance to hydrogen and nitrous oxide is round 2–10^-6 cm³ (STP) /cm²·s·cmHg for membranes of 40–50μm in thickness.     

Abatement of volatile organic compounds: oxidation of ethanal over niobium oxide-supported palladium-based catalysts

Niobium-supported palladium-based catalysts (Pd, Pd–Cu and Pd–Au) were employed in the oxidation of ethanal. The catalysts were prepared according to original methods by either multi-steps (anchoring of complexes, calcination and reduction) or one-step (photoassisted reduction) procedures. The oxidation of ethanal was carried out in gas phase in a dynamic-differential reactor at 300 °C at atmospheric pressure. The activity/selectivity of the catalysts depend on (i) the catalyst preparation; (ii) the presence of a second metal. Addition of Au or Cu decreases the catalysts deactivation and the best performance in total oxidation was obtained with Pd–Au/Nb₂O₅ prepared by photoassisted reduction. As shown by in situ IR spectroscopy of adsorbed CO, this peculiarity may be ascribed to Au→Pd electron donation, which prevents the surface oxidation of palladium particles.     

Computerized Solution of the Dynamic Sorption Process for a Ternary System in a Heterophase Medium

A mathematical model equation for the ternary adsorption–reaction process was developed and illustrated for the catalytic dehydrogenation of cyclohexane to benzene with the adsorption of hydrogen atoms as a monomolecular species on platinum–rhenium/alumina catalyst in inert and active carrier gases using pulse and continuous flow techniques. An optimization routine of the Nelder–Mead simplex method was used to estimate the surface reaction rate constant and adsorption equilibrium constant at different temperatures. These constants were then used to determine activation energies and adsorption equilibrium energies for cyclohexane dehydrogenation in inert (argon, helium) and active (hydrogen) carrier gases using pulse and continuous flow techniques. Numerical solutions for the ternary adsorption–reaction scheme were compared with the binary adsorption–reaction case where hydrogen adsorption is ignored. The predicted results for the ternary adsorption–reaction revealed that hydrogen adsorption during cyclohexane dehydrogenation is significant.     

Hydrogen generation and separation using Gd0.2Ce0.8O1.9−δ–Gd0.08Sr0.88Ti0.95Al0.05O3±δ mixed ionic and electronic conducting membranes

Decomposition of steam under a chemical driving force at moderate temperatures offers a simple and economical way to generate hydrogen. A significant amount of hydrogen can be generated and separated by splitting steam and removing the oxygen using Gd_0.2Ce_0.8O_1.9−δ (GDC)–Gd_0.08Sr_0.88Ti_0.95Al_0.05O_3±δ (GSTA) mixed oxygen ionic and electronic conducting membranes. Hydrogen generation experiments for the self-supported thick membranes and porous supported thin membranes were conducted at different oxygen partial pressure gradients across the membrane established using H₂–H₂O mixture gas. Experimental results indicate that the hydrogen generation from steam using GDC–GSTA MIEC membranes at elevated temperatures is mainly controlled by the bulk diffusion of oxygen for the self-supported thick membranes, while the permeation process for the porous supported thin membranes is mixed controlled, i.e. the hydrogen generation/oxygen permeation process is controlled by the surface exchange reactions and bulk diffusion of oxygen through the MIEC membrane. A mathematical model for the calculation of the area specific hydrogen generation rate is proposed in this paper based on the measured oxygen partial pressures, gas compositions, and gas flow rates of the inlet and outlet gases on feed side of the membrane, as well as the permeation area of the membrane.     

Electrodeposition of palladium–silver in a Lewis basic 1-ethyl-3-methylimidazolium chloride-tetrafluoroborate ionic liquid

The electrodeposition of palladium–silver alloys was investigated in a basic 1-ethyl-3-methylimidazolium chloride/tetrafluoroborate ionic liquid containing Pd(II) and Ag(I). Cyclic voltammetry experiments showed that the reduction of Ag(I) occurs prior to the reduction Pd(II). Both electrodeposition processes require nucleation overpotential. Energy-dispersive spectroscopy data indicated that the composition of the Pd–Ag alloys could be varied by deposition potential and concentrations of Pd(II) and Ag(I) in the solution. The Pd content in the deposited Pd–Ag alloy increased with decreasing deposition potential and the Pd mole fraction in the plating bath. At potentials where the deposition of both Pd and Ag was mass-transport limited, the Pd/Ag ratio in the electrodeposited alloys was slightly less than the Pd(II)/Ag(I) ratio in the ionic liquid due to the smaller diffusion coefficient of Pd(II). Scanning electron micrographs of the electrodeposits showed that in general, the Pd–Ag alloys were nodular and become more compact upon increasing the temperature up to 120 °C.     

Comparison of parameters calculated from the BET and Freundlich isotherms obtained by nitrogen adsorption on activated carbons: A new method for calculating the specific surface area

The empirical linear relationship between the BET surface area S_BET and the Freundlich constant K_F, calculated from nitrogen adsorption isotherms of activated carbons, S_BET = a₀K_F is mathematically demonstrated. This correlation exists in the relative pressure domain in which the BET equation is valid, whatever the value of c for the BET equation and for values of the Freundlich exponent, , between 0 and 0.2. This study allows to determine the correlation factor a₀ = 1/a with . From this result, a new expression, depending of and K_F, can be deduced for calculating the specific surface area.     

Gas permeation properties in a composite mesoporous alumina ceramic membrane

In this study, the effect of different chemical interactions on the gas permeation properties were investigated in the composite mesoporous ceramic membrane prepared with γ-alumina on the surface of a macroporous ceramic membrane. In the permeation results, the gas permeance of the strongly adsorbing gas species increased in the mesoporous ceramic membranes. It is considered that the permeation of the adsorbing gas species increased through preferential adsorption on the membrane pore surface. It was shown in this study that the modified mesoporous ceramic membrane could increase the permeation performance in the presence of the adsorbing gas species due to the surface diffusion mechanism.     

Ceramic Supported PDMS and PEGDA Composite Membranes for CO2 Separation

Composite membranes have attracted increasing attentions owing to their potential applications for CO2 separation. In this work, ceramic supported polydimethylsiloxane （PDMS） and poly （ethylene glycol） diacrylate （PEGDA） composite membranes were prepared. The microstructure and physicochemical properties of the compos- ite membranes were characterized. Preparation conditions were systematically optimized. The gas separation performance of the as-prepared membranes was studied by pure gas and binary gas permeation measurement of CO〉 N2 and H〉 Experiments showed that PDMS, as silicone rubber, exhibited larger permeance and lower separation factors. Conversely, PEGDA composite membrane presented smaller gas permeance but higher ideal selectivity for CO2/N2. Compared to the performance of those membranes using polymeric supports or freestanding membranes, the two kinds of ceramic supported composite membranes exhibited higher gas permeance and acceptable selectivity. Therefore, the ceramic supported composite membrane can be expected as a candidate for CO2 separation from light gases.     

加压和超临界流体在多孔膜中的渗透

考察加压和超临界流体在多孔膜中渗透过程的各种影响因素并进行模型分析,对深入认识过程的传质机理、开发普遍适用的数学模型有重要意义。首先实验测定了不同温度、压力和压差条件下,He、N2和CO2在多孔陶瓷膜中的渗透率,考察了各主要影响因素。以二项尘气模型为基础,考虑到流体枯度随压力的变化,特别是近临界区流体枯度可能出现的突变,对模型进行了修正,建立了新的模型表达式。理论分析与实验结果表明,加压和超临界条件下,由于He的粘度变化甚微,其渗透过程仍然符合二项尘气模型,而对于N2需要考虑粘度随压力变化对渗透率计算结果的影响。由于近临界区相交的作用,CO2在多孔膜中的渗透过程出现奇异现象;而在低压和高压条件下,本研究建立的渗透模型与实验结果十分吻合。     

Micropore size estimation on gas separation membranes: A study in experimental and molecular dynamics

The effect of the gas molecular size and its affinity to the pore surface on gas permeation properties through the ceramic membranes was studied by both the gas permeation experiments and gas permeation simulations using a nonequilibrium molecular dynamics (MD) technique. A modified gas permeation model equation based on the gas translation (GT) mechanism was presented. MD simulation revealed that the effective diffusion length in a micropore depended on the gas molecular size, and the pre‐exponential coefficient of a modified GT model equation showed good correlation with the kinetic diameter of the gas molecules. Also presented is a simple method to estimate the mean pore size of microporous membranes. The estimated pore sizes were consistent with observed kinetic diameter dependencies of gas permeance for real silica membranes. The pore size of a Deca‐Dodecasil 3R (DDR) zeolite membrane was also reasonably estimated at ～0.4 nm from the reported gas permeation data. © 2012 American Institute of Chemical Engineers AIChE J, 59: 2179–2194, 2013     

Hydrogen permeation through sol–gel-coated iron during galvanostatic charging

One-layer sol–gel silica–zirconia and two-layer silica–zirconia and zirconia coatings were deposited on one side of iron membranes by spin-coating, densified in air and annealed up to 800 °C in vacuum. Hydrogen permeation through the membranes, coated and uncoated, polarised cathodically under galvanostatic control in 0.1 M NaOH solution was studied using the electrochemical permeation technique. During the initial period, the effect of the sol–gel coatings was insignificant. However, the coatings quite efficiently prevented the iron surface become more active to hydrogen entry during a long-lasting cathodic polarisation. In addition, the electrochemical-corrosion behaviour of the coated iron and the effect of the sol–gel coatings on the effective diffusivity of hydrogen in the coated membranes were studied. On the basis of the polarisation curves and the hydrogen permeation data it was proved that the sol–gel coatings blocked the iron surface for the hydrogen evolution reaction and, consequently, for the hydrogen entry into iron. The effective coating coverage was determined by comparison of the hydrogen fluxes permeating the coated and uncoated membranes. Finally the real concentration of hydrogen beneath the uncoated iron sites and the amount of hydrogen stored in a membrane were evaluated.     

The Effects of H2O, CO and CO2 on the H2 Permeance and Surface Characteristics of 1 mm Thick Pd80wt%Cu Membranes

The hydrogen permeance of 1 mm-thick Pd_80wt%Cu foils was measured in the presence of equimolar mixtures of H₂ with CO, CO₂ or H₂O over the temperature and total pressure ranges of 623–1,173 K and 0.62–2.86 MPa, respectively. In all cases, permeance losses at 623 and 738 K were very modest. At higher temperatures, more significant decreases in membrane permeance were observed with the highest reduction of about 50% occurring when macroscopic carbon deposition occurred on the membrane surface during H₂–CO exposure at 908 K. The more worrisome effects of exposure to these gases, however, were the micron-scale surface defects observed at 908 and 1,038 K. Although the 1 mm thick disk membranes retained their mechanical integrity, such defects could cause catastrophic failure of ultra-thin, Pd–Cu membranes (1–5 μm thick) deposited on porous substrates.