• 한국표면공학회지
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• 제50권2호
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• pp.98-107
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• 2017

Pd-based membranes have been widely used in hydrogen purification and separation due to their high hydrogen diffusivity and infinite selectivity. However, it has been difficult to fabricate thin and dense Pd-based membranes on a porous stainless steel(PSS) support. In case of a conventional PSS support having the large size of surface pores, it was required to use complex surface treatment and thick Pd coating more than $6{\mu}m$ on the PSS was required in order to form pore free surface. In this study, we could fabricate thin and dense Pd membrane with only $3{\mu}m$ Pd layer on a new PSS support manufactured by metal injection molding(MIM). The PSS support had low surface roughness and mean pore size of $5{\mu}m$. Pd membrane were prepared by advanced Pd sputter deposition on the modified PSS support using fine polishing and YSZ vacuum filling surface treatment. At temperature $400^{\circ}C$ and transmembrane pressure difference of 1 bar, hydrogen flux and selectivity of $H_2/N_2$ were $11.22ml\;cm^{-2}min^{-1}$ and infinity, respectively. Comparing with $6{\mu}m$ Pd membrane, $3{\mu}m$ Pd membrane showed 2.5 times higher hydrogen flux which could be due to the decreased Pd layer thickness from $6{\mu}m$ to $3{\mu}m$ and an increased porosity. It was also found that pressure exponent was changed from 0.5 on $6{\mu}m$ Pd membrane to 0.8 on $3{\mu}m$ Pd membrane.

• 한국수소및신에너지학회논문집
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• 제32권4호
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• pp.219-227
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• 2021

Hydrogen isotopes, which are used as raw materials in fusion reaction, participate in the reaction only in small amount, and most of them are released together with impurities. In order to recover and reuse only hydrogen isotopes from this exhaust gas, a recovery process is required, and most of the hydrogen isotopes can be recovered using a Pd Membrane. In this study, the recovery rate of hydrogen isotopes was measured through the first and second stage Pd membrane experiments. In the case of the experiment using a single stage Pd membrane, about 99.2%, and in the case of the first stage and second stage Pd membrane connection experiments, a recovery rate of 99.9% or more was obtained. Therefore, the recovery rate of Pd membrane process applied to hydrogen can be applied to hydrogen isotopes. In addition, the simulation model was established using aspen custom modeler, a commercial software, and the validity of the simulation was checked by applying the references and experimental data. The simulation results based on the experimental data showed a difference of 2% or less.

• 한국표면공학회지
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• 제45권6호
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• pp.248-256
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• 2012

A Pd-based hydrogen membranes for hydrogen purification and separation need high hydrogen perm-selectivity. The surface roughness of the support is important to coat the pinholes free and thin-film membrane over it. Also, The pinholes drastically decreased the hydrogen perm-selectivity of the Pd-based composite membrane. In order to remove the pinholes, we introduced various surface pre-treatment such as alumina powder packing, nickel electro-plating and micro-polishing pre-treatment. Especially, the micro-polishing pretreatment was very effective in roughness leveling off the surface of the porous nickel support, and it almost completely plugged the pores. Fine Ni particles filled surface pinholes with could form open structure at the interface of Pd alloy coating and Ni support by their diffusion to the membrane and resintering. In this study, a $4{\mu}m$ surface pore-free Pd-Cu-Ni ternary alloy membrane on a porous nickel substrate was successfully prepared by micro-polishing, high temperature sputtering and Cu-reflow process. And $H_2$ permeation and $N_2$ leak tests showed that the Pd-Cu-Ni ternary alloy hydrogen membrane achieved both high permeability of $13.2ml{\cdot}cm^{-2}{\cdot}min^{-1}{\cdot}atm^{-1}$ permation flux and infinite selectivity.

• Membrane and Water Treatment
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• 제9권6호
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• pp.463-471
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• 2018

The present paper deals with the liquid-liquid extraction and flat sheet supported liquid membrane studies of Pd(II) separation from nitric acid medium using a novel synthesized ligand, namely, N,N,N',N'-tetraethyl-2,2-thiodiethanthiodiglycolamide (TETEDGA). The effect of various diluents and stripping reagents on the extraction of Pd(II) was studied. The liquid-liquid extraction studies showed complete extraction of Pd(II) in ~ 5 min. The influence of nitric acid and TETEDGA concentration on the distribution of Pd(II) has been investigated. The increase in nitric acid concentration resulted in increase in extraction of Pd(II). Stoichiometry of the extracted species was found to be $Pd(NO_3)_2{\cdot}TETEDGA$ by slope analysis method. Extraction studies with SSCD solution showed negligible uptake of Pt, Cr, Ni, and Fe, thus showing very high selectivity and extractability of TETEDGA for Pd(II). The flat sheet supported liquid membrane studies showed quantitative transport of Pd(II), ~99%, from the feed ($3M\;HNO_3$) to the strippant (0.02 M thiourea diluted in $0.4M\;HNO_3$) using 0.01 M TETEDGA as a carrier diluted in n-dodecane. Extraction time was ~160 min. Parameters such as feed acidity, TETEDGA concentration in membrane phase, membrane porosity etc. were optimized to achieve maximum transport rate. Permeability coefficient value of $2.66{\times}10^{-3}cm/s$ was observed using TETEDGA (0.01 M) as carrier, at 3 M, $HNO_3$ feed acidity across $0.2{\mu}m$ PTFE as membrane. The membrane was found to be stable over five runs of the operation.

• 멤브레인
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• 제28권5호
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• pp.297-306
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• 2018

본 총설은 분리막기술이 적용된 수소생산에 대한 개론으로, 특히, 암모니아를 수소운반체로 이용하는 수소생산에 대한 연구결과를 중점적으로 서술하였다. 암모니아를 수소운반체로 적용한 수소생산은 추가적인 탄소생성이 없다는 점 외에 여러 측면에 있어 이점이 있다. 많은 연구들이 고순도 수소 분리 및 생산을 위한 분리막 개발을 위해 진행되고 있으며, 이들 중 팔라듐을 기본으로 한 분리막(예를 들어, 다공성 세라믹 또는 다공성 금속 지지체와 팔라듐 합금의 얇은 선택층으로 이루어진 분리막)에 대한 연구가 활발하다. 반면에, 효율적인 암모니아 분해를 위해서는 주로 루테늄 촉매가 적용되고 있으며, 루테늄과 지지체 및 촉진제로 이루어진 루테늄에 기반을 둔 촉매에 대한 연구발표가 다수 존재한다. 수소생산을 위한 분리막 반응기 형태로는 충전층, 유동층, 그리고 마이크로반응기 등이 있으며, 이들의 최적화 및 원활한 물질전달 연구는 현재진행형이다. 또한, 높은 암모니아 분해율, 고순도 수소생산 및 높은 수소생산율을 얻기 위해 분리막과 촉매의 다양한 조합에 대한 연구 및 분리막과 촉매의 역할을 동시에 구현할 수 있는 분리막에 대한 연구가 발표되고 있다.

• 센서학회지
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• 제21권4호
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• pp.283-286
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• 2012

This paper presents the optical hydrogen sensor based on transparent 3C-SiC membrane and photovoltaic effect. Gasochromic materials of Pd and Pd/$WO_3$ were deposited by sputter on 3C-SiC membrane for gas sensing area. Gasochromic materials change to transparency by exposure to hydrogen. The variations of light intensity by hydrogen generate the photovoltaic of P-N junction between N-type 3C-SiC and P-type Si. Single layer of Pd shows higher photovoltaic compared with Pd/$WO_3$. However, phase transition from ${\alpha}$ to ${\beta}$ is shown at 6 %. Pd/$WO_3$ structure show the more linear response to hydrogen range of 2 % ~10 %. Also, almost 2 times fast response and recovery characteristics are shown at Pd/$WO_3$. These fast performances are come from the fact that Pd promoted the chemical reaction between hydrogen and $WO_3$.

• 한국막학회:학술대회논문집
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• 한국막학회 2003년도 The 4th Korea-Italy Workshop
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• pp.25-28
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• 2003

Low cost composite metallic membranes for the hydrogen separation and production have been prepared by using thin Pd-Ag foils reinforced by metallic (stainless steel and nickel) structures. Especially, “supported membranes” have been obtained by a diffusion welding procedure in which Pd-Ag thin foils have been joined with perforated metals (nickel) and expanded metals (stainless steel): in these membranes the thin palladium foil assures both the high hydrogen permeability and the perm-selectivity while the metallic support provides the mechanical strength. A second studied method of producing "laminated membranes" consists of coating non-noble metal sheets with very thin palladium layers by diffusion welding and cold-rolling. Palladium thin coatings over these metals reduce the activation energy of the hydrogen adsorption process and make them permeable to the hydrogen. In this case, the dense non-noble metal has been used as a support structure of the thin Pd-Ag layers coated over its surfaces: a proper thickness of the metal assures the mechanical strength, the absence of defects (cracks, micro-holes) and the complete hydrogen selectivity of the membrane. membrane.

• 한국신재생에너지학회:학술대회논문집
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• 한국신재생에너지학회 2007년도 추계학술대회 논문집
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• pp.79-79
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• 2007

• 대한금속재료학회지
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• 제46권5호
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• pp.296-303
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• 2008

Hydrogen permeation through dense palladium-based membranes has attracted the attention of many scientists largely due to their unmatched potential as hydrogen-selective membranes for membrane reactor applications. Although it is well known that the permeation mechanism of hydrogen through Pd involves various processes such as dissociative adsorption, transitions to and from the bulk Pd, diffusion within Pd, and recombinative desorption, it is still unclear which process mainly limits hydrogen permeation at a given temperature and hydrogen partial pressure. In this study, we report an all-electron density-functional theory study of hydrogen permeation through Pd membrane (using VASP code). Especially, we focus on the variation of the energy barrier of the penetration process from the surface to the bulk with hydrogen coverage, which means the large reduction of the fracture stress in the brittle crack propagation considering Griffith's criterion. It is also found that the penetration energy barrier from the surface to the bulk largely decreases so that it almost vanishes at the coverage 1.25, which means that the penetration process cannot be the rate determining process.

• 한국수소및신에너지학회논문집
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• 제14권1호
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• pp.17-23
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• 2003

$H_2$ permeation flux though a $100{\mu}m-thick$ Pd-Ru (6wt%) membrane was measured at various temperatures and pressures. The permeation flux followed the Sievert's law and thus the rate-limiting step of the hydrogen permeation was the bulk atomic diffusion step. The activation energy of the permeation flux was obtained at 17.9 kJ/mol and this value is consistent with those published previously. While no degradation of the permeation flux wasfound in the membrane exposed to the $O_2$ and $CO_2$ environments for 100 hours, the membrane exposed to $N_2$ environment for 100 hours showed the degradation in the $H_2$ permeation flux. The $H_2$ permeation was decreased as the exposure temperature to $N_2$, environment was increased. The $H_2$ permeation flux was fully recovered after the membrane was kept in the $H_2$ environment for certain time. The permeation flux degradation might be caused by the formation of metal nitride on the membrane surface.