Preparations of metal impregnated porous inorganic membranes for hydrogen separation by multi-step pore modifications

In this research, porous inorganic membranes for hydrogen separation were prepared with α-alumina support by multi-step pore modification method. Porous inorganic membranes were made by three consecutive steps: sol-gel method,in-situ hydrolysis of tetraethylorthosilicate (TEOS) and soaking and vapor deposition (SVD) method. In order to enhance the hydrogen selectivity, we used nickel (Ni) and palladium (Pd) particles in the first and final pore modification steps. Although both nickel and palladium induced surface diffusion, palladium was shown more effective for hydrogen selective adsorption than nickel. This multi-step method produced porous membranes with a moderate hydrogen selectivity and excellent hydrogen permeability at high temperature up to 773 K and at transmembrane pressure (ΔP) as high as 310 kPa. The separation factor of hydrogen relative to nitrogen was maintained at about 7 even when the transmembrane pressure was 70 kPa, and the hydrogen permeability was still much higher than that of non-porous polymeric membranes. Furthermore, the distributions of nickel and palladium within the intermediate layer formed at the membrane cross-section were examined by scanning electron microscopy (SEM) and energy dispersive X-ray analysis.     

Robust super-hydrophobic inorganic nanoparticles modified layered structure Si2N2O membrane for membrane distillation

Robust super-hydrophobic ceramic membranes consisting of layered structure Si₂N₂O grains and organosilane-derived inorganic nanoparticles were successfully fabricated and employed for membrane distillation. First, phase inversion and sintering method were used to prepare porous Si₂N₂O membranes. The slurry composition and sintering temperature were optimized to obtain a pure phase Si₂N₂O membrane with high bending strength, tailored average pore size, and high permeability. Then, the Si₂N₂O membranes were modified with organosilane-derived inorganic nanoparticles through ammonolysis and pyrolysis reactions. Due to the micro and nano-hierarchical rough structures and the presence of -Si-CH₃ groups, the membranes showed super-hydrophobicity with a water contact angle of 152 ± 1°. Finally, the membranes were applied to desalinate seawater by sweeping gas membrane distillation. A stable water flux of 76 ± 0.9 L/(m² day) with a salt rejection of > 99% was recorded during 30 h distillation test at 75 °C, demonstrating the stability and durability of the membranes.     

Hydrogen generation and purification in a composite Pd hollow fiber membrane reactor: Experiments and modeling

“Pd nanopore” composite membranes are a novel class of H₂ permselective membranes in which a thin layer of Pd is grown within the pores of a supported nanoporous layer. In this work, Pd nanopore membranes and conventional Pd top-layer membranes were used in the generation of high-purity H₂ from the catalytic decomposition of anhydrous NH₃. An effective 4 μm thick Pd nanopore membrane and 13 μm thick Pd top-layer membrane were synthesized on 2 mm O.D. α-Al₂O₃ hollow fibers. The permeation features of the membranes were determined and the membranes were then employed in a single fiber packed-bed membrane reactor in which Ni-catalyzed NH₃ decomposition served as the test reaction, with conditions spanning a range of conditions (500–600 °C; 3–5 bar total retentate pressure; 60–1200 scc/h g cat space velocity). The NH₃ conversions in both the PBMRs were approximately 10% higher than in a packed-bed reactor (PBR) under similar conditions. The increase in conversion with the PBMR was attributed to the removal of H₂, which has an inhibitory effect on the forward kinetics of the reaction as per the Temkin-Pyzhev type rate mechanism. Reactor productivities in the range of 2 mol/s m³ (at 85% H₂ utilization) to 7 mol/s m³ (at 50% H₂ utilization) were obtained. The permeate stream purity exceeded 99.2% H₂. A two-dimensional pseudo-homogeneous model was successfully used to simulate the experimental results and to interpret the findings. Permeation and kinetic parameters were estimated in permeation and PBR experiments, respectively. Without any data fitting the PBMR model predictions demonstrated very good agreement with experimental trends. Together with an analysis of the characteristic times, the model determined that transverse transport of hydrogen in the catalyst bed limited PBMR performance. The model was used to determine the rate limiting step and to suggest ways in which the reactor productivities could be further improved.     

用膜分离技术从合成氨弛放气中回收氢气

论述了中空纤维氮氢分离膜的应用以及从合成氨驰放气中回收氢。     

膜分离-变压吸附联合工艺生产燃料电池氢气

将膜分离技术和变压吸附两种气体分离与净化技术相结合．充分发挥了两种工艺模式的优点．使得装置整体性能指标在稳定性、产品品质和氧气回收率上均有优异的表现,最终使得单位原料气的获利大幅挺高。另外,联合工艺具有广泛的适应性,能够灵活采用各种运行模式以适用于各种不同的气源。     

CFD modelling of inorganic membrane modules for gas mixture separation

This work is aimed at investigating the capability of a computational fluid dynamics (CFD) approach to reliably predict the fluid dynamic and the separation performances of inorganic membranes modules for gas mixture separation.The simulations are based on the numerical solution of the Navier-Stokes equations on the three dimensional domain representing quite closely the selected module geometry. The membrane is modelled as a selective layer, which allows the permeation of different components as a function of the transport mechanism and the driving force.The computational strategy is strictly evaluated by comparing the results with available experimental data. The simulation predictions show fairly good agreement with the measured permeation data and allow to recognise the critical local fluid dynamic features of the separation module.     

Hydrogen recovery from cyclohexane as a chemical hydrogen carrier using a palladium membrane reactor

A palladium membrane reactor was applied to recover the hydrogen from cyclohexane as one of the promising chemical hydrogen carriers. The operation conditions of the palladium membrane reactor to obtain a higher hydrogen recovery were predicted by computer simulation. As a result, it was shown that the hydrogen recovery rate becomes higher as the pressure on the hydrogen permeation side is lowered below atmospheric pressure or as the reaction pressure increases. This was confirmed experimentally. As the perm-side pressure was lowered, the conversion as well as the hydrogen recovery rate at 573 K was found to increase. About 80% of the hydrogen contained in cyclohexane, depending on the operation condition was successfully recovered.     

Fabrication of Pd-Nb bimetallic doped organosilica membranes by different metal doping routes for H2/CO2 separation

Monometallic doping has proved its superiority in improving either permselectivity or H2 permeability of organosilica membranes for H2/CO2 separation,but it is still challenging to break the trade-off effect.Herein,we report a series of Pd-Nb bimetallic doped 1,2-bis(triethoxysilyl)ethane (Pd-Nb-BTESE,PNB) membranes with different metal doping routes for simultaneously improving H2 permeance and H2/CO2 permselectivity by the synergetic effects of Pd and Nb.The doped Pd can exist in the BTESE network as nanoparticles while the doped Nb is incorporated into BTESE network forming Nb-O-Si covalent bonds.The metal doping routes signif-icantly influence the microstructure of PNB networks and gas separation performance of the PNB membranes.We found that the PNB membrane with Pd doping priority (PNB-Pd) exhibited the highest surface area and pore volume,comparing with Nb doping priority (PNB-Nb) or Pd-Nb simultaneous doping (PNB-PdNb).The PNB-Pd membrane could not only exhibit an excellent H2 permeance of ～ 10-6 mol· m-2· s-1· Pa-1 but also a high H2/CO2 permselectivity of 17.2.Our findings may provide novel insights into preparation of bimetallic doped organosilica membranes with excellent H2/CO2 separation performance.     

Efficient separation scheme for binary mixture of CO2 and H2S using aromatic components

Separating a mixture of CO₂ and H₂S into two products through distillation is both difficult and complicated because of similar relative volatility between the two gasses, particularly when a CO₂ concentration exceeds 80%. Therefore, the separation process can involve many separating stages. However, adding a solvent (agent) to the distillation column during the separation process makes this procedure easier.

In this study, different solvents (ethylbenzene, o-xylene, m-xylene, and toluene) and operating conditions (temperature, pressure, and reflux ratio) for separating CO₂ from H₂S have been simulated through distillation using Aspen HYSYS software. Furthermore, four different aromatic compounds (solvents) for different concentrations (from 0 to 40 mol%) have been evaluated to increase the CO₂/H₂S relative volatility, reducing the quantity of the solvent required and energy consumption.

m-xylene was found to be the best solvent for separating CO₂ from H₂S because of the significant effect on relative volatility, the low quantity required for high CO₂ recovery, and the low energy for generating the solvent.     

无机膜回收分子筛催化剂过程阻力的研究与测定

介绍了无机膜回收分子筛催化剂过程中的膜污染机理及影响因素,阐述了滤饼层的形成是膜污染的主要来源,同时对膜阻力进行了测定。得出实验所用的无机微滤膜在23℃、错流过滤速度2 m/s、操作压力为0.1 MPa的操作条件下过滤分子筛催化剂过程中所产生的总阻力Rt为3.26×1012m-1,污染所产生的阻力Rf为2.733×1012m-1,组件自身的阻力Rm为5.27×1011m-1,Rf约为Rm的5倍,是导致膜通量下降的主要原因。     

Polyurethane-SAPO-34 mixed matrix membrane for CO2/CH4 and CO2/N2 separation

SAPO-34 nanocrystals (inorganic filler) were incorporated in polyurethane membranes and the permeation properties of CO₂, CH_4, and N₂ gases were explored. In this regard, the synthesized PU-SAPO-34 mixed matrix membranes (MMMs) were characterized via SEM, AFM, TGA, XRD and FTIR analyses. Gas permeation properties of PU-SAPO-34 MMMs with SAPO-34 contents of 5 wt%, 10 wt% and 20 wt% were investigated. The permeation results revealed that the presence of 20 wt% SAPO-34 resulted in 4.45%, 18.24% and 40.2% reductions in permeability of CO_2, CH_4, and N₂, respectively, as compared to the permeability of neat polyurethane membrane. Also, the findings showed that at the pressure of 1.2 MPa, the incorporation of 20 wt% SAPO-34 into the polyurethane membranes enhanced the selectivity of CO₂/CH₄ and CO₂/N₂, 14.43 and 37.46%, respectively. In this research, PU containing 20 wt% SAPO-34 showed the best separation performance. For the first time, polynomial regression (PR) as a simple yet accurate tool yielded a mathematical equation for the prediction of permeabilities with high accuracy (R² > 99%).     

Screening and design of COF-based mixed-matrix membrane for CH4/N2 separation

Membrane separation is a high-efficiency, energy-saving, and environment-friendly separation technology. Covalent organic framework (COF)-based mixed-matrix membranes (MMMs) have broad application prospects in gas separation and are expected to provide new solutions for coal-bed methane purification. Herein, a high-throughput screening method is used to calculate and evaluate COF-based MMMs for CH₄/N₂ separation. General design rules are proposed from thermodynamic and kinetic points of view using the computation-ready, experimental COFs. From our database containing 471,671 generated COFs, 5 COF membrane materials were screened with excellent membrane selectivities, which were then used as the filler of MMMs for separation performance evaluation. Among them, BAR-NAP-Benzene_CF₃ combined with polydimethylsiloxane and styrene-b-butadiene-b-styrene show high CH₄ permeability of 4.43×10^-13 mol·m·s^-1·Pa^-1·m^-2 and high CH₄/N₂ selectivity of 9.54, respectively. The obtained results may provide reasonable information for the design of COF-based membranes for the efficient separation of CH₄/N₂.     

Preparation of a tubular palladium membrane by photocatalytic deposition

A novel photocatalytic deposition method for the preparation of a thin tubular palladium membrane is presented in this paper. The membrane is prepared on a porous asymmetric TiO₂ support by photocatalytic reaction of palladium ion, followed by electroless plating. Gas permeation results show that the membrane exhibits increased hydrogen permeance with the increase of temperature. The hydrogen permeance and selectivity to nitrogen at 773 K are about 1.43×l0⁻⁶ mol m⁻² s⁻¹ Pa⁻¹ and 17, respectively, when the pressure in the feed side is 0.1 MPa. The activation energy of hydrogen permeation is 11.06 kJ/mol at the temperature range of 573–773 K.     

Application of O3 and O3/H2O2 as post-treatment processes for color removal in swine wastewater from a membrane filtration system

This study was aimed to evaluate the use of ozone (O₃) alone and peroxone (a combination of ozone and hydrogen peroxide; O₃/H₂O₂) as post-treatment processes for color removal in swine wastewater from a membrane filtration system. Results showed that the application of ozone-alone process or the peroxone process could reduce both capital and operating costs compared to reverse osmosis (RO) treatment. Of the two oxidation processes, the ozone-alone process was the most effective for treating nanofiltration (NF)-filtered wastewater, while the peroxone process was the most effective for treating ultrafiltration (UF)-filtered wastewater.     

Glycerol removal from biodiesel using membrane separation technology

Membrane separation technology was used to remove free glycerol from biodiesel in order to meet the ASTM D6751 and EN 14214 standards. Fatty acid methyl esters (FAME) produced from canola oil and methanol were purified using ultra-filtration. The effect of different materials present in the transesterification reaction, such as water, soap, and methanol, on the final free glycerol separation was studied. A modified polyacrylonitrile (PAN) membrane, with 100 kD molecular weight cut-off was used in all runs. Tests were performed at 25 °C and 552 kPa operating pressure. The free glycerol content in the feed, retentate and permeate of the membrane system was analyzed using gas chromatography according to ASTM D6584. Results showed low concentrations of water had a considerable effect in removing glycerol from the FAME even at approx. 0.08 mass%. This is four orders of magnitude less than the amount of water required in a conventional biodiesel purification process using water washing. It is suggested that the mechanism of separation of free glycerol from FAME was due to the removal of an ultrafine dispersed glycerol-rich phase present in the untreated FAME. This was confirmed by the presence of particulates in the untreated FAME. The size of the particles and the free glycerol separation both increased with increasing water content of the FAME. The trends of separation and particle size vs. water content in the FAME phase were very similar and exhibited a sudden increase at 0.08 mass% water in the untreated FAME. This supports the conclusion that water increased the size of the distributed glycerol phase in the untreated FAME leading to its separation by the ultra-filtration membrane. The technology for the removal of free glycerol from biodiesel was found to use 2.0 g of water per L of treated FAME (0.225 mass% water) vs. the current 10 L of water per L of treated FAME.     

Economic comparison of several membrane configurations for H2/N2 separation

Several one- and two-stage membrane systems were compared for use in separating H₂/N₂ mixtures from coal gasification processes. Computer models of cross flow membrane modules were used in the evaluations. The processing cost, determined by a discounted cash flow analysis of capital and operating expenses, was used as the basis for the comparison. Membrane properties were those of a poly[etherimide] composite membrane. Hydrogen mole fractions from 34% to 97% in the feed and from 80% to 99.9% in the product (permeate) were examined; in all cases it was required that 95% of the feed H₂ be recovered. Four configurations were evaluated: single module (SM), single module with recycle (SMR), two-module series (SER), and two-stage cascade (CAS). The results showed that for conditions where SM was capable of performing the separation the optimum recycle rate in SMR was zero, and thus SMR and SM were identical. In some conditions, SER also reduced to SM. In general, SM is best for easy separations (where the feed and product compositions are similar), CAS is best for difficult separations (where feed and product compositions are very different), and SER is best for separations of moderate difficulty; in this example, where the H₂ recovery is fixed, SMR is never the best configuration. In some circumstances, it is economically better to treat only a portion of the feed in the membrane system, but to a higher purity than is required, and then to mix the overconcentrated stream with the untreated feed to make a product stream of the desired purity.     

Pervaporative separation of butanol using a composite PDMS/PEI hollow fiber membrane

In the study, the separation and purification of butanol was carried out using the composite hollow fiber membrane having the active layer of polydimethylsiloxane (PDMS) on the macroporous support of polyetherimide (PEI). The pervaporation results with the initial butanol concentration showed a trade-off between flux and separation factor. However, both the flux and the separation factor increased as the operating temperature increased. The pervaporation results showed the butanol flux and the separation factor were higher than those of the reported results. In this study, butanol was concentrated by the pervaporation as a feasibility study for the biofuel applications.     

Hydrogen production by methanol steam reforming carried out in membrane reactor on Cu/Zn/Mg-based catalyst

The methanol steam reforming (MSR) reaction was studied by using both a dense Pd-Ag membrane reactor (MR) and a fixed bed reactor (FBR). Both the FBR and the MR were packed with a new catalyst based on CuOAl₂O₃ZnOMgO, having an upper temperature limit of around 350 °C. A constant sweep gas flow rate in counter-current mode was used in MR and the experiments were carried out by varying the water/methanol feed molar ratio in the range 3/1–9/1 and the reaction temperature in the range 250–300 °C. The catalyst shows high activity and selectivity towards the CO₂ and the H₂ formation in the temperature range investigated. Under the same operative conditions, the MR shows higher conversions than FBR and, in particular, at 300 °C and H₂O/CH₃OH molar ratio higher than 5/1 the MR shows complete methanol conversion.     

氢气的分离与纯化技术的发展

本文在叙述了氢气的来源和传统的分离与纯化技术的基础上,论述了 PSA 法Prism 法、低温法、金属氢化物法等在氢气的分离与纯化方面的开发现状、工艺过程、分离原理及其发展前景。     

Synergistic extraction and separation of mixture of lanthanum and neodymium by hollow fiber supported liquid membrane

Separation of lanthanum and neodymium by supported liquid membrane has been studied. Synergistic extraction and recovery of lanthanum and neodymium with thenoyltrifluoroacetone (HTTA) in benzene have been found by the addition of Trioctylamine (TOA). Results indicate that percentage of extraction is highly dependent on pH of feed solution, which the maximum value is 2.5. When TOA was added to HTTA, the percentage of extraction and recovery considerably increased due to synergism. Lanthanum can be extracted and recovered more than neodymium because of the adduct formation constant,β ₁ . Theβ ₁ values decreased with an increase in atomic number of lanthanide and showed a difference between lanthanum and neodymium. Percentage of extraction and recovery is enhanced when the HTTA concentration is increased, but its difference is larger when TOA concentration is increased. Finally, multi-column module of supported hollow fiber membrane was used and the percentage and difference of extraction and recovery was found to be more increased due to resident time.