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1.
On-site hydrogen production via catalytic ammonia decomposition presents an attractive pathway to realize H2 economy and to mitigate the risk associated with storing large amounts of H2. This work reports the synthesis and characterization of a dual-layer hollow fiber catalytic membrane reactor for simultaneous NH3 decomposition and H2 permeation application. Such hollow fiber was synthesized via single-step co-extrusion and co-sintering method and constitutes of 26 μm-thick mixed protonic-electronic conducting Nd5.5Mo0.5W0.5O11.25-δ (NMW) dense H2 separation layer and Nd5.5Mo0.5W0.5O11.25-δ-Ni (NMW-Ni) porous catalytic support. This dual-layer NMW/NMW-Ni hollow fiber exhibited H2 permeation flux of 0.26 mL cm−2 min−1 at 900 °C when 50 mL min−1 of 50 vol% H2 in He was used as feed gas and 50 mL min−1 N2 was used as sweep gas. Membrane reactor based on dual-layer NMW/NMW-Ni hollow fiber achieved NH3 conversion of 99% at 750 °C, which was 24% higher relative to the packed-bed reactor with the same reactor volume. Such higher conversion was enabled by concurrent H2 extraction out of the membrane reactor during the reaction. This membrane reactor also maintained stable NH3 conversion and H2 permeation flux as well as structure integrity over 75 h of reaction at 750 °C.  相似文献   

2.
This study was investigated to utilize innovatively oil-free diaphragm pump to forcibly desorb the hydrogen from the small pilot MgH2–TiH2 based hydride reactor below the theoretical temperature of 278 °C. Active MgH2-0.1TiH2 composites were prepared using ball milling. Their hydrogenation performances at 25–300 °C were measured under a constant H2 flow mode using a modified Sieverts apparatus. The dehydrogenation rates at 250–350 °C with or without diaphragm pump were investigated to examine whether the pilot reactors could be integrated with a proton exchange membrane fuel cell (PEMFC) for power generation. At a H2 flow rate of 25 ml min−1 g−1, the reactors exhibited excellent hydrogenation, achieving gravimetric hydrogen storage capacities of 2.9–5.2 wt% (excluding the weight of the reactors) at 25–300 °C after 22 min. All hydrided MgTi–based reactors could be dehydrogenated at 250 °C at an average rate of 5 ml min−1 g−1 under vacuum. This is the first demonstration of Mg-based reactors that were hydrogenated at 100 °C and dehydrogenated at 250 °C to power a small PEMFC, yielding a measured conversion efficiency of 18%.  相似文献   

3.
Mixed proton and electron conductor ceramic composites are among the most promising materials for hydrogen separation membrane technology especially if designed in an asymmetrical configuration (thin membrane supported onto a thicker porous substrate). However a precise processing optimization is needed to effectively obtain planar and crack free asymmetrical membranes with suitable microstructure and composition without affecting their hydrogen separation efficiency. This work highlights for the first time the most critical issues linked to the tape casting process used to obtain BaCe0.65Zr0.20Y0.15O3-δ – Ce0.8Gd0.2O2-δ (BCZY-GDC) asymmetrical membranes for H2 separation. The critical role of the co-firing process, sintering aid and atmosphere was critically investigated. The optimization of the production strategy allowed to obtain asymmetric membranes constituted by a dense 20 μm-thick ceramic-ceramic composite layer supported by a porous (36%) 750 μm-thick BCZY-GDC substrate. The asymmetric membranes here reported showed H2 fluxes (0.47 mL min−1 cm−2 at 750 °C) among the highest obtained for an all-ceramic membrane.  相似文献   

4.
In this study, the hydrogen permeation behavior of a Pd93–Cu7 alloy membrane deposited on ceria-modified porous nickel support (PNS) was evaluated. PNS, which has an average pore size of 600 nm, was modified by alumina sol. Alumina sol was prepared using precursors that had a mean particle size of 300 nm. Alumina-modified PNS was further treated with ceria sol modification to produce a smoother surface morphology and narrow surface pores. A 7 μm thick Pd93–Cu7 alloy membrane was made on an alumina-modified PNS and a ceria-finished membrane was fabricated by magnetron sputtering followed by Cu-reflow at 700 °C for 2 h. SEM analysis showed that the membrane deposited on a ceria-finished PNS contained more clear grain boundaries than the membrane deposited on the alumina-modified PNS. The membrane was mounted in a stainless steel permeation cell with a gold-plated stainless steel O-ring. Permeation tests were then conducted using pure hydrogen and helium at temperatures ranging from 673 to 773 K and feed side pressures ranging from 100 to 400 kPa. These tests showed that the membrane had a hydrogen permeation flux of 2.8 × 10−1 mol m−2 s−1 with H2/He selectivity of >50,000 at a temperature of 773 K and pressure difference of 400 kPa.  相似文献   

5.
Palladium–copper (PdCu) alloy layers with 150 nm thickness were prepared by one-step electroplating on both sides of a vanadium foil. The entire process, including pretreatment, washing, and electroplating, was complete in <5 min. The PdCu layer had a high surface coverage and almost completely covered the vanadium foil. The composition difference between the center and the edges was within 3 at%, and the alloy composition was controlled to nearly the target composition (50:50). Peel tests revealed that the as-electroplated layer had sufficient adhesion for practical applications. XRD analysis confirmed the successful formation of a face-centered cubic (FCC) PdCu alloy. In-situ XRD analysis performed under a hydrogen atmosphere revealed the structural change of PdCu from FCC to body-centered cubic (BCC) immediately after the temperature reached 300 °C. The hydrogen permeability of electroplated PdCu/V/PdCu at 200–300 °C (1–3 × 10−8 mol m−1 s−1 Pa−1/2) was considerably higher than that of the 10 μm-thick electroplated BCC PdCu.  相似文献   

6.
《Journal of power sources》2006,159(2):1291-1295
Composite membranes consisting of Ni metal and Ba(Zr0.1Ce0.7Y0.2)O3 (or Ni–BZCY7) have been developed for separation of hydrogen from gas mixtures to replace Ni–BCY20 (Ni–BaCe0.8Y0.2O3), which has poor stability in CO2 and H2O-containing atmosphere. Hydrogen fluxes through these cermet membranes were measured as a function of temperature, membrane thickness, and partial pressure of hydrogen in various atmospheres. Results indicated that the Ni–BZCY7 membrane is chemically stable and display high hydrogen permeability. A maximum flux of 0.805 cm3 min−1 cm2 was obtained for a dense cermet membrane of 266-μm-thick at 900 °C using 100% H2 as the feed gas and 100 ppm H2/N2 as the sweep gas. The stable performance of Ni–BZCY7 cermet membrane during exposure to a wet gas containing 30% CO2 for about 80 h indicated that it is promising for practical applications.  相似文献   

7.
Palladium composite membrane with excellent stability was successfully prepared using the electroless plating (ELP) route on a porous stainless steel (PSS) support for hydrogen separation. In order to modify the average pore size of PSS support and to prevent inter-metallic diffusion, the NaY zeolite layer was coated on the PSS support with the seeding and secondary growth method. A high-temperature membrane module was designed by Solid work software and fabricated from 316 L stainless steel with a knife-edge seal. The microstructures and morphologies of the samples were analyzed using XRD, BET, AFM, FESEM and EDX techniques. Permeation experiments were carried out with binary mixtures of H2/N2 with various ratios (90/10, 75/25 and 50/50) and pure H2 and N2 at different temperatures (350, 400 and 450 °C) and feed pressures (200–400 kPa). Hydrogen permeation tests showed that the membrane with a thickness of about 7 μm had a hydrogen permeance of 6.2 × 10−4 mol m−2 s−1 Pa−0.5 with an ideal H2/N2 selectivity of 736, at 450 °C. In addition, the results of stability tests revealed that the membrane could remain stable during a long-term operation by varying temperature and feed gases.  相似文献   

8.
BaHf0.8Ln0.2O3-δ doped with rare earth elements with different ionic radii (Ln = Yb, Y, Dy and Gd) as candidate materials for solid oxide fuel cells and H2 separation membrane have been prepared. Their phase composition, sinterability, chemical stability and conductivity were studied systematically. The rare earth elements are successfully incorporated into the main phase crystal lattice of barium hafnate to generate a single perovskite phase. The relative density of all samples sintered at 1600 °C reaches above 90%, and Y-doped BaHfO3 has the highest relative density (94.7%) and the biggest grain size (about 1 μm) among all samples. The conductivities of the samples firstly increase and then decrease with the increase of the doped ion radius. Among all samples the conductivity of BaHf0.8Y0.2O3-δ is the highest and reaches 6.02 × 10−3 S cm−1 in wet air at 700 °C, which is attributed to the good sinterability and suitable crystal structure (tolerance factor and free volume). All samples also show excellent chemical stability in the test atmospheres, including saturated H2O steam, pure H2 and CO2, 200 ppm H2S/Ar and boiling water. The Pt/BaHf0.8Y0.2O3-δ electrolyte/Pt single cell was fabricated with a 530 μm-thick disk and its electrochemical properties were tested. The peak power density reaches 10.21 mW cm−2 at 700 °C, which is comparable to similar fuel cells reported. These results suggest that BaHf0.8Y0.2O3-δ is a promising electrolyte candidate for proton-conducting fuel cells.  相似文献   

9.
This study uses a palladium membrane to separate hydrogen from an H2/CO2 (90/10 vol%) gas mixture. Three different operating parameters of temperature (320–380 °C), total pressure difference (2–3.5 atm), and vacuum degree (15–49 kPa) on hydrogen are taken into account, and the experiments are designed utilizing a central composite design (CCD). Analysis of variance (ANOVA) is also used to analyze the importance and suitability of the operating factors. Both the H2 flux and CO2 (impurity) concentration on the permeate side are the targets in this study. The ANOVA results indicate that the influences of the three factors on the H2 flux follow the order of vacuum degree, temperature, and total pressure difference. However, for CO2 transport across the membrane, the parameters rank as total pressure difference > vacuum degree > temperature. The predictions of the maximum H2 flux and minimum CO2 concentration by the response surface methodology are close to those by experiments. The maximum H2 flux is 0.2163 mol s?1 m?2, occurring at 380 °C, 3.5 atm total pressure difference, and 49 kPa vacuum degree. Meanwhile, the minimum CO2 concentration in the permeate stream is t 643.58 ppm with the operations of 320 °C, 2 atm total pressure difference, and 15 kPa vacuum degree. The operation with a vacuum can significantly intensify H2 permeation, but it also facilitates CO2 diffusion across the Pd membrane. Therefore, a compromise between the H2 flux and the impurity in the treated gas should be taken into account, depending on the requirement of the gas product.  相似文献   

10.
《Journal of power sources》2006,158(1):137-142
Sulfonic-functionalized heteropolyacid–SiO2 nanoparticles were synthesized by grafting and oxidizing of a thiol-silane compound onto the heteropolyacid–SiO2 nanoparticle surface. The surface functionalization was confirmed by solid-state NMR spectroscopy. The composite membrane containing the sulfonic-functionalized heteropolyacid–SiO2 nanoparticles was prepared by blending with Nafion® ionomer. TG–DTA analysis showed that the composite membrane was thermally stable up to 290 °C. The DMFC performance of the composite membrane increased the operating temperature from 80 to 200 °C. The function of the sulfonic-functionalized heteropolyacid–SiO2 nanoparticles was to provide a proton carrier and act as a water reservoir in the composite membrane at elevated temperature. The power density was 33 mW cm−2 at 80 °C, 39 mW cm−2 at 160 °C and 44 mW cm−2 at 200 °C, respectively.  相似文献   

11.
This work presents the use of doped CeO2 particles with palladium as intermediate barrier for the preparation of fully dense Pd films by Electroless Pore-Plating. The use of doped ceria particles instead of non-doped ones clearly helps to reduce the final palladium thickness required to prepare a fully dense membrane over porous stainless steel supports from 15 to 9 μm (average values by gravimetric analyses), thus saving around 40% of total palladium required in the process. Pure hydrogen permeation tests reveal a consequent increase in the H2 flux in the range 15–30%, depending on the operation mode. Thus, a H2 permeance of 6.26·10−4 mol m−2 s−1 Pa−0.5 at 400 °C and ΔP = 1 bar is reached, maintaining a really high H2/N2 ideal separation factor (≥10,000) and an activation energy within the typical range for these type of membranes, Ea = 13.1 kJ mol−1. Permeation of binary H2/N2 gas mixtures and the effect of feeding the mixture from the inner or the outer side of the membrane have been also studied. A significant concentration-polarization effect was observed, being higher when the gas is fed from the inner to the outer side of the membrane. This effect becomes more relevant for the membrane prepared with doped CeO2, instead of raw CeO2, due to its lower Pd thickness and higher relative influence of the surface processes. However, it should be emphasized that higher H2 permeance values were obtained for the entire set of experiments when using the Pd-membranes containing doped ceria. Finally, long-term permeation tests for more than 850 h with pure gases at T = 400 °C and ΔP = 1 bar were also carried out, demonstrating a suitable mechanical stability of membranes at these operating conditions.  相似文献   

12.
CH3OH steam reforming is an attractive way to produce hydrogen with high efficiency. In this study, CuO.xAl2O3 (x = 1, 2, 3, and 4) were fabricated based on the solid-state route, and the calcined samples were employed in methanol steam reforming at atmospheric pressure and in the temperature range of 200–450 °C. The results revealed that all samples have a high BET area (173–275 m2 g−1), and their crystallinity was reduced by increasing the alumina content in the catalyst formulation. The catalytic activity tests showed that the CH3OH conversion and H2 selectivity decreased by rising the Al2O3·CuO molar ratio. The methanol conversion enhanced from 13% to 85% by increasing the reaction temperature from 200 °C to 450 °C over the CuO·Al2O3 catalyst, due to the higher reducibility of this catalyst at lower temperatures compared to other prepared samples. The influence of calcination temperature (300–500 °C), GHSV (28,000–48000 ml h−1. g−1cat), feed ratio (C:W = 1:1 to 1:9), and reduction temperature (250–450 °C) was also determined on the yield of the chosen sample. The results revealed that the maximum methanol conversion decreased from 90 to 79% by raising the calcination temperature from 300 to 500 °C due to the reduction of surface area and sintering of species at high calcination temperatures.  相似文献   

13.
We examine the interplay between cathode catalyst layer (CL) porosity/thickness on mass transport limitations in single cell fuel cells comprised of Pt/C-based CLs fabricated via ultrasonic spray deposition onto polymer electrolyte membranes. We determine that the pore size distribution remains unchanged as CL thickness increases from 3.8 to 11.8 μm, but porosity decreases with increasing CL thickness. The decrease in porosity results in an increase in mass transport resistance for thicker CLs, but does not result in an increase in charge transfer resistance for the oxygen reduction reaction. We found that a fuel cell comprising a 7.5 μm-thick cathode CL delivers the highest performance (1 A cm−2 at 0.60 V at 80 °C in H2|Air at a relative humidity of 50% under ambient pressure). We attribute this high performance to the CL striking an optimal balance between solid and void networks, with the solid networks facilitating transport of H+/e to the Pt electrocatalyst, and the void network ensuring adequate transport of O2 to, and H2O away from, the Pt electrocatalyst.  相似文献   

14.
The present study investigates the optimization of hydrogen (H2) production with in-situ catalytic adsorption (ICA) steam gasification by using a pilot-scale fluidized bed gasifier. Two important response variables i.e. H2 composition (in percent volume fraction, %) and H2 yield (in g kg−1 of biomass) are optimized with respect to five process variables such as temperature (600 °C–750 °C), steam to biomass mass ratio (1.5–2.5), adsorbent to biomass mass ratio (0.5–1.5), superficial velocity (0.15 m s−1–0.26 m s−1) and biomass particle size (350 μm–2 mm). The optimization study is carried out based on Response Surface Methodology (RSM) using Central Composite Rotatable Design (CCRD) approach. The adsorbent to biomass mass ratio is found to be the most significant process variables that influenced the H2 composition, whereas temperature and biomass particle size are found to be marginally significant. For H2 yield, temperature is the most significant process variables followed by steam to biomass mass ratio, adsorbent to biomass mass ratio and biomass particle size. The optimum process conditions are found to be at 675 °C, steam to biomass mass ratio of 2.0, adsorbent to biomass mass ratio of 1.0, superficial velocity of 0.21 m s−1 that is equivalent to 4 times the minimum fluidization velocity, and 1.0 mm–2.0 mm of biomass particle size. The theoretical response variables predicted by the developed model fit well with the experimental results.  相似文献   

15.
The objective of this study was to evaluate the effects of hydraulic retention time (HRT) (8–1 h) on H2 production from sugarcane juice (5000 mg COD L−1) in mesophilic (30 °C, AFBR-30) and thermophilic (55 °C, AFBR-55) anaerobic fluidized bed reactors (AFBRs). At HRTs of 8 and 1 h in AFBR-30, the H2 production rates were 60 and 116 mL H2 h−1 L−1, the hydrogen yields were 0.60 and 0.10 mol H2 mol−1 hexose, and the highest bacterial diversities were 2.47 and 2.34, respectively. In AFBR-55, the decrease in the HRT from 8 to 1 h increased the hydrogen production rate to 501 mL H2 h−1 L−1 at the HRT of 1 h. The maximum hydrogen yield of 1.52 mol H2 mol−1 hexose was observed at the HRT of 2 h and was associated with the lowest bacterial diversity (0.92) and highest bacterial dominance (0.52).  相似文献   

16.
In this work, a sol-gel Ni–Mo2C–Al2O3 catalyst is employed for the first time in the glycerol steam reforming for syngas production. Catalyst stability and activity are investigated in the temperature range of 550 °C–700 °C and time on stream up to 30 h. As reaction temperature increases, from 550 °C to 700 °C, H2 yield boosts from 22% to 60%. The stability test, carried out at milder conditions (600 °C and Gas-Hourly Space-Velocity (GHSV) of 50,000 mL h−1.gcat−1), shows high catalyst stability, up to 30 h, with final conversion, H2 yield, and H2/CO ratio of 95%, 53% and 1.95, respectively. Both virgin and spent catalysts have been characterized by a multitude of techniques, e.g., Atomic-Absorption spectroscopy, Raman spectroscopy, N2-adsorption-desorption, and Transmission Electron Microscopy (TEM), among others. Regarding the spent catalysts, carbon deposits’ morphology becomes more graphitic as the reaction temperature increases, and the total coke formation is mitigated by increasing reaction temperature and lowering GHSV.  相似文献   

17.
A series of Cu0.1-xNixCe0.9O2-y catalysts with different Cu/Ni molar ratios were prepared by the ball milling method. The obtained catalytic materials were characterized by XRD, H2-TPR, BET, XPS and Ramen and the effects of different Cu/Ni content on the structure, properties and CO catalytic oxidation performance of the catalysts were explored. The results evidenced the formation of Cu–Ni–Ce mixed oxide solid solution in all ternary catalysts. In addition, there is a synergistic interaction between Cu and Ni in ternary catalysts, resulting in more oxygen vacancies and improved reduction performance, and hence demonstrating better CO catalytic oxidation activity in the ternary catalysts than binary ones. Under a GHSV of 60000 mL·gcat−1·h−1, the required reaction temperature for reaching less than 10 ppm CO is lowed from 160 °C with Cu0·1Ce0·9O2-y to 130 °C with Cu0·07Ni0·03Ce0·9O2-y.  相似文献   

18.
Dimethyl ether (DME) partial oxidation (PO) was studied over 1 wt% Rh/Ce0.75Zr0.25O2 catalyst at temperatures 300–700 °C, O2:C molar ratio of 0.25 and GHSV 10000 h−1. The catalyst was active and stable under reaction conditions. Complete conversion of DME was reached at 500 °C, but equilibrium product distribution was observed only at T ≥ 650 °C. High concentration of CH4 and low contents of CO and H2 were observed at 500–625 °C 75 cm3 of composite catalyst 0.24 wt% Rh/Ce0.75Zr0.25O2/Al2O3/FeCrAl showed excellent catalytic performance in DME PO at O2:C molar ratio of 0.29 and inlet temperature 840 °C which corresponded to carbon-free region. 100% DME conversion was reached at GHSV of 45,000 h−1. The produced syngas contained (vol. %): 33.4 H2, 34.8 N2, 22.7 CO, 3.6 CO2 and 1.6 CH4. Composite catalyst demonstrated the specific syngas productivity (based on CO and H2) in DME PO of 42.8 m3·Lcat−1·h−1 (STP) and the syngas productivity of more than 3 m3·h−1 (STP) that was sufficient for 3 kWe SOFC feeding. PO of natural gas and liquified petroleum gas can be carried out over the same catalyst with similar productivity, realizing the concept of multifuel hydrogen generation. The syngas composition obtained via DME PO was shown to be sufficient for YSZ-based SOFC feeding.  相似文献   

19.
BaCe0·7Zr0.1Gd0.2O3-δ (BCZG) powder is synthesized by a citrate sol-gel method, and different amounts of Li2CO3 are introduced to lower the sintering temperature. The densification temperature of BCZG ceramic is decreased drastically to 1250 °C by using Li2CO3 as sintering aid. BCZG with 2.5 wt% of Li2CO3 (BCZG-2.5L) can not only remarkably promote the sintering process of BCZG but also enhance its electrical conductivity. The total ionic conductivity of BCZG-2.5L attains to 1.9 × 10−2 S cm−1 at 600 °C in a wet H2 atmosphere. Ammonia synthesis at atmospheric pressure is conducted on (2K, 10Fe)/Ni-BCZG | BCZG-2.5L | Ni-BCZG electrolytic cell with an applied voltage of 0.2–1.6 V at a temperature of 450–600 °C. The highest NH3 formation rate of 1.87 × 10−10 mol s−1 cm−2 and the highest current efficiency of 0.53% is achieved at 500 °C with an applied voltage of 0.8 V.  相似文献   

20.
By choosing a triple block polymer, poly(styrene-b-(ethylene-co-butylene)-b-styrene) (SEBS), as the backbone and adopting a long side-chain double-cation crosslinking strategy, a series of SEBS-based anion-exchange membranes (AEMs) was successively synthesized by chloromethylation, quaternization, crosslinking, solution casting, and alkalization. The 70C16-SEBS-TMHDA membrane showed high OH conductivity (72.13 mS/cm at 80 °C) and excellent alkali stability (only 10.86% degradation in OH conductivity after soaking in 4-M NaOH for 1700 h at 80 °C). Furthermore, the SR was only 9.3% at 80 °C and the peak power density of the H2/O2 single cell was up to 189 mW/cm2 at a current density of 350 mA/cm2 at 80 °C. By introducing long flexible side chains into a polymer SEBS backbone, the structure of the hydrophilic–hydrophobic microphase separation in the membrane was constructed to improve the ionic conductivity. Additionally, network crosslinked structure improved dimensional stability and mechanical properties.  相似文献   

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