NL2005290C2 - New seeding method for deposit of thin selective membrane layers. - Google Patents

New seeding method for deposit of thin selective membrane layers. Download PDF

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Publication number
NL2005290C2
NL2005290C2 NL2005290A NL2005290A NL2005290C2 NL 2005290 C2 NL2005290 C2 NL 2005290C2 NL 2005290 A NL2005290 A NL 2005290A NL 2005290 A NL2005290 A NL 2005290A NL 2005290 C2 NL2005290 C2 NL 2005290C2
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Prior art keywords
palladium
membrane
hydrogen
metal layer
tubular
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NL2005290A
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Dutch (nl)
Inventor
Lucretia Agnes Correia
Johannis Pieter Overbeek
Yvonne Christine Delft
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Stichting Energie
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Priority to NL2005290A priority Critical patent/NL2005290C2/en
Priority to US13/819,586 priority patent/US9156007B2/en
Priority to EP11751663.3A priority patent/EP2611526B1/en
Priority to CN201180042241.7A priority patent/CN103153447B/en
Priority to CA2809232A priority patent/CA2809232C/en
Priority to PCT/NL2011/050578 priority patent/WO2012030212A1/en
Priority to JP2013527028A priority patent/JP6046039B2/en
Application granted granted Critical
Publication of NL2005290C2 publication Critical patent/NL2005290C2/en

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
    • B01D71/02—Inorganic material
    • B01D71/022—Metals
    • B01D71/0223—Group 8, 9 or 10 metals
    • B01D71/02231—Palladium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
    • B01D67/0039—Inorganic membrane manufacture
    • B01D67/0069—Inorganic membrane manufacture by deposition from the liquid phase, e.g. electrochemical deposition
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/22—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by diffusion
    • B01D53/228—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by diffusion characterised by specific membranes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D63/00—Apparatus in general for separation processes using semi-permeable membranes
    • B01D63/06—Tubular membrane modules
    • B01D63/061—Manufacturing thereof
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D63/00—Apparatus in general for separation processes using semi-permeable membranes
    • B01D63/06—Tubular membrane modules
    • B01D63/062—Tubular membrane modules with membranes on a surface of a support tube
    • B01D63/065—Tubular membrane modules with membranes on a surface of a support tube on the outer surface thereof
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D63/00—Apparatus in general for separation processes using semi-permeable membranes
    • B01D63/06—Tubular membrane modules
    • B01D63/066—Tubular membrane modules with a porous block having membrane coated passages
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
    • B01D69/04—Tubular membranes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
    • B01D69/10—Supported membranes; Membrane supports
    • B01D69/105—Support pretreatment
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
    • B01D71/02—Inorganic material
    • B01D71/022—Metals
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2323/00—Details relating to membrane preparation
    • B01D2323/08—Specific temperatures applied
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2325/00—Details relating to properties of membranes
    • B01D2325/04—Characteristic thickness
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2325/00—Details relating to properties of membranes
    • B01D2325/30—Chemical resistance
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2325/00—Details relating to properties of membranes
    • B01D2325/48—Antimicrobial properties

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Inorganic Chemistry (AREA)
  • Manufacturing & Machinery (AREA)
  • Analytical Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Electrochemistry (AREA)
  • Separation Using Semi-Permeable Membranes (AREA)

Description

New seeding method for deposit of thin selective membrane layers
[0001] The present invention pertains to a process for the production of palladium-based layers and membranes for separation of hydrogen, and to the membranes 5 obtained by this process.
Background
[0002] Asymmetric membranes comprising a porous support and a thin dense palladium layer are useful for the separation of hydrogen from other gases such as 10 carbon dioxide and other small molecules such as hydrocarbons and other hydrides. A cost-effective production of palladium-based membranes with electroless plating of porous supports requires the presence of palladium seeds on the porous support. For growing thin dense Pd membranes substantially free of defects, the seeds should be homogeneously distributed over the support in a sufficient amount.
15 [0003] Collins and Way (Ind. Eng. Chem. Res. 1993, 32, 3006-13) use multiple pre-treatments of the support with tin chloride followed by acidic palladium chloride immersion before repeated electroless plating with palladium-amine complex. Li et al. ('Catalysis Today, 56, 2000, 45-51) similarly use tin chloride pre-treatment followed by acidic palladium amine before enhanced electroless plating driven by osmosis. Paglieri 20 et al. (Ind. Eng. Chem. Res. 1999, 38, 1925-1936) proposed an improved seeding procedure of dipping the support into a palladium acetate solution followed by drying and calcining. Zhao et al. (Catalysis Today, 56, 2000, 89-96) used activation by slipcasting with a Pd-modified boehmite sol, followed by drying and calcining. The use of a boehmite sol is also described in CN 1164436 and US2008-176060. A pretreatment 25 with a silica sol is described in KR 2001-045207 and KR 2001-018853. Hou et al. (WO 2005/065806) use a boehmite sol as a pore filler before seeding following the tin chloride procedure. After calcining, γ-alumina is formed in the pores restoring the porous structure of the support. Harold et al. (US 2008/0176060) use two y-alumina layers to sandwich the palladium seeds (layer) applied by electroless plating acting as 30 nuclei for growing palladium in the pores of the top γ-alumina layer also by electroless plating.
[0004] These prior art methods lead to insufficient performance of the membranes thus obtained in terms of stability and hydrogen flux. The tin chloride pre-treatment 2 results in the presence of tin contamination, which affects both the stability of the plating bath and the temperature stability of the palladium membrane. The use of boehmite sols and the like may result in blocking pores and thus reduce separation performance. It may also reduce the maximum application temperature because of 5 limited thermal stability. Also, the prior art methods do not always allow very thin palladium layers to be produced.
[0005] It is therefore an object of the invention to provide a process for producing thin membranes based on palladium, which leads to improved performance of the palladium-based separation layer, and which allows the production of separation 10 membranes having very thin (< 5 μηι) layers of palladium.
Description of the invention
[0006] The invention pertains to a process of producing palladium-based layers, which layers are suitable for hydrogen separation, the process comprising: 15 - pre-treating the porous support by film-coating with a solution of a palladium salt, - drying the support, - reducing the palladium salt to palladium metal, - electroless plating with one or more metal complexes comprising palladium.
In particular, the layers are part of a membrane on a porous support.
20 [0007] The invention furthermore pertains to a palladium-based membrane on porous support, which membrane is suitable for hydrogen separation, said membrane being characterised by a palladium layer at one side having a thickness of between 1 and 10 μΐη.
[0008] The layer or membrane of the invention is anchored in the porous support 25 with palladium seeds up to a depth of 5 pm and no less than 0.5 pm. The palladium membrane has a shiny appearance because of the smoothness of the surface which reduces accumulation of contaminants at the surface.
[0009] The porous support is preferably a tube, but it can also be flat. The support may be any ceramic material such as alumina, zirconia, silica, and stainless steel or the 30 like. The tube can have any length, which may be determined by several factors, such as the heat treatment facilities available and the intended use. Preferable lengths are form 0.4 to 5 meters. Most preferable length is between 0.5 and 2 meters, e.g. about 1 meter. The porosity and pores size of the support is not critical, as long as the pores are 3 sufficiently wide to allow adequate penetration of the treating solutions. Preferably, the pore size is at least 25 nm. More preferably, the support is a macroporous support having pore sizes in the range of 50 nm to 1 gm, most preferably in the range of 100 to 500 nm.
5 [0010] In a preferred embodiment of the process of the invention, the palladium layer is applied on the outside of the tubular porous support, thus resulting in membranes having an outer palladium layer allowing to use higher pressures in the separation process.
[0011] In the process of the invention, the palladium salt used in the pre-treatment 10 solution is a soluble, preferably divalent, palladium salt such as palladium chloride, palladium nitrate, palladium sulphate or palladium selenate. These salts give more homogeneous results than e.g. acetate salts. The preferred salt, also in terms of a homogeneous coverage, is palladium (II) chloride. The concentration of the palladium salt solution can be e.g. between 6 and 24 g Pd per litre (= 56-225 mM), preferably 15 between 12 and 20 g Pd per litre (= 113-188 mM). The treatment can be performed using any coating technique, such as dipping, spraying, brushing etc. An advantageous coating method is film-coating, which allows easy control of impregnation depth and loading.
[0012] The pre-treatment conditions are selected in such a manner that the 20 palladium salt solution penetrates sufficiently into the support, without excessive penetration. This can be achieved by using relatively short contact times, such as with film coating. It is preferred that the palladium penetrates to a depth between 1 and 10 pm, more preferably to no more than 5 pm. The amount and concentration of the solution and the contact time are preferably selected so that the amount of palladium 25 into the pores ranges from 5 to 15 mg per 100 mm tube length, after reduction. Thus a preferred coating rate is between 5 and 100 mm/s, preferably between 15 and 75 mm/s, most preferably between 25 and 60 mm per second. The loading and penetration depth can be further adjusted by varying the palladium concentration in the pre-treatment solution. The loading and penetration depth can be checked e.g. by using Scanning 30 Electron Microscope (SEM) photometry.
[0013] The pre-treatment can be a single coating step, or repeated coating steps, with intermittent partial or complete drying. After the pre-treatment, the pre-treated support is dried at ambient or elevated temperatures, e.g. between 40 and 100 °C.
4
[0014] The next step is activation of the palladium by reducing it to the zerovalent state. This is preferably achieved by treatment with hydrogen-containing gas or other reducing gas at elevated temperatures. The hydrogen-containing may e.g. be pure hydrogen, but also mixtures of hydrogen and inert other gases, such as argon or 5 nitrogen, or another reducing gas. Advantageous conditions for the reduction step include a temperature of between 400 and 700 °C, preferably between 475 and 625 °C. The membranes carrying the reduced palladium seeds are subsequently cooled to ambient temperatures under an inert atmosphere, such as nitrogen.
[0015] Finally on the palladium-seeded supports palladium and/or other metals are 10 deposited, e.g.in an electroless process, following methods known per se for electroless, i.e. autocatalytic, plating using palladium complexes, such as tetra-ammine palladium dichloride (Pd(NH3)4Cl2.2H20), and a stabilising agent such as EDTA and a reducing agent such as hydrazine. Methods of electroless plating are described e.g. by Collins and Way (Ind. Eng. Chem. Res. 1993) and other references cited above under 15 ‘Background’. As a result of the pre-treatment of the invention, the stability of the electroless plating bath is increased, e.g. in that that there is only heterogeneous deposition and no homogeneous deposition. This means that there is only Pd formed on the surface of the support and no crystalline material is formed in the bath itself. Such homogeneous depositing leads to a turbid solution giving way to depositing of irregular 20 agglomerates of material on the support and on the bottom of the bath and consequently depletion of Pd precursor and decreasing plating rate.
[0016] Instead, or especially in addition to palladium, other suitable metals can be used, such as silver, platinum, gold and chromium. Therefore, each time where reference is made to ‘palladium’ in the description above and below, this can be 25 wholly, or preferably partly (alloys), exchanged by other metals, in particular nickel, copper, silver and/or gold. Preferably the palladium content of the plated layer is at least 40 wt.%, more preferably at least 50 wt.%. Specifically advantageous are alloys of 50-95 wt.% of palladium and 5-50 wt.% of other metals. These other metals include one or more metals from the groups 8-11 (VIII and lb), such as nickel, copper, 30 ruthenium, rhodium, platinum, silver and gold, but also metals such as yttrium, cerium, indium, chromium etc. A palladium alloy containing 65-85 wt.% palladium and 15-35 wt.% silver is particularly useful. In all cases the seeds applied in the pretreatment are palladium seeds. Electroless plating of a palladium alloy can be performed using a 5 plating bath containing the relevant metal salts, e.g. palladium chloride or nitrate and silver nitrate in the required ratios.
[0017] When alloy layers are manufactured, it is advantageous to first carry out a palladium plating step and then the further metal or metals can be applied with a second 5 bath. For such a multistep alloy manufacture, it is preferred that the second and optionally further plate bath contains some palladium, e.g. between 2 and 20 wt.%, to facilitate the plating process.
[0018] The palladium-based membranes on a porous support as can be produced by the methods described above are especially suitable for hydrogen separation. The 10 membranes are characterised by a palladium layer at one side having a thickness of between 1 and 10 pm. Preferably, the palladium layer has a thickness of between 2 and 5 pm, most preferably between 2 and 4 pm. Preferably, the palladium layer contains 40-100 wt.% of palladium, more preferably 50-95 wt.% of palladium, and 0-60 wt.%, more preferably 5-50 wt.%, most preferably 10-40 wt.% of other metals as mentioned 15 above, in particular nickel, platinum, copper, silver and/or gold.
[0019] As described above, a preferred embodiment of the membrane is a tubular membrane, more preferably a tubular membrane having the palladium layer at the outside surface. In particular, the tubular membrane has an outer diameter between 5 and 50 mm, preferably between 10 and 25 mm. The hydrogen permeance is at least 20 5.1 O'7 mol/rrf.s.Pa, in particular at least 10-6 mol/m2.s.Pa or even at least 2.10-6 mol/m2.s.Pa.
[0020] The invention further relates to process of separating hydrogen from a gas mixture, comprising subjecting the gas mixture to the membrane as described above. The membrane will selectively allow the passage of hydrogen and thus separate it from 25 other gas molecules, including oxides, such as carbon monoxide, carbon dioxide, and nitrogen oxides, and hydrides such as ammonia, water, hydrocarbons (methane, ethane, ethene, and higher homologues. The membranes obtainable with the process of the invention have the advantage of providing higher selectivities (better separation) at lower thicknesses and consequently higher permeance, thanks to the defect-free thin 30 films produced by the process.
6
Examples Example 1
[0021] A 500 mm tubular asymmetrical macroporous AI2O3 support having two a-alumina layers, outer diameter 14 mm, pore size 0.2 μηι, was film-coated with a 5 solution containing 1.57 g PdCT, 1.025 ml HC1 37% and 63.150 ml of MQ water. The coating rate was 40 mm/sec. The film-coating process was repeated once. The coated tubes were dried at 70°C.
[0022] The dried Pd-seeded tubes were then activated by first slowly heating up to 500°C under a gentle flow of nitrogen followed by a treatment with hydrogen at 500°C.
10 The tubes are weighed to determine the palladium seed load. The Pd load is at least 7 mg per 100 mm support.
[0023] The palladium-seeded tubular membranes were subsequently plated by electroless plating at 55°C with a plate bath solution containing 5.4 g/1 PdCl2, 70 g/1 EDTA (Titriplex), 434 ml/1 NH4OH (25w/o), and 7.5 ml hydrazine (2.05 M) per litre 15 plate bath solution for 2 hours.
[0024] The resulting membranes have a thickness of less than 4 pm, and a high H2/N2 selectivity: the membrane is leak-tight in that no nitrogen flow is measured at a pressure difference across the membrane of 2 bar, and the hydrogen flux (permeance) is 9.5* 10"7 mol/m2.s.Pa. The H2/N2 permselectivity, which is measured by separately 20 measuring pure hydrogen and pure nitrogen permeation, is >1000.
Example 2
[0025] A 500 mm tubular asymmetrical macroporous Al203-Zr02 support having one alumina layer and one zirconia layer, outer diameter 14 mm, pore size 0.2 pm, was film-coated with palladium and subsequently activated as described in Example 1. The 25 palladium seed load was at least 7 mg per 100 mm tube length.
[0026] The palladium-seeded tubular membranes were subsequently plated by electroless plating as described in Example 1. The resulting membranes have a thickness of less than 4 pm, and a high H2/N2 selectivity and are leak-tight. The H2/N2 perm-selectivity is >1000, and the hydrogen flux (permeance) is 1.5* 106 mol/m2.s.Pa.
30

Claims (13)

1. Werkwijze ter vervaardiging van membranen op basis van palladium op een poreuze drager, welke membranen geschikt zijn voor scheiding van waterstof, waarbij men: 5. de poreuze drager voorbehandelt met een oplossing van een palladiumzout door middel van fïlm-coating, - de voorbehandelde drager droogt, - het palladiumzout reduceert tot palladiummetaal, - de voorbehandelde drager electroless bekleedt met een of meer metaalcomplexen 10 die palladium bevatten.Method for the production of palladium-based membranes on a porous support, which membranes are suitable for hydrogen separation, wherein: 5. the porous support is pretreated with a solution of a palladium salt by means of film coating, - the pretreated carrier dries, - the palladium salt reduces to palladium metal, - the pre-treated carrier electroless coated with one or more metal complexes containing palladium. 2. Werkwijze volgens conclusie 1, waarbij het palladiumzout palladiumchloride of palladiumnitraat, bij voorkeur palladiumchloride is.The method of claim 1, wherein the palladium salt is palladium chloride or palladium nitrate, preferably palladium chloride. 3. Werkwijze volgens conclusie 1 of 2, waarbij men palladiumzout reduceert met een waterstof bevattend gas bij een temperatuur tussen 400 en 700 °C.3. Process according to claim 1 or 2, wherein palladium salt is reduced with a hydrogen-containing gas at a temperature between 400 and 700 ° C. 4. Werkwijze volgens een der voorgaande conclusies, waarbij de drager buisvormig is en de hoeveelheid palladium in de voorbehandelde drager 5 tot 12 mg per 100 mm 20 buislengte bedraagt.4. A method according to any one of the preceding claims, wherein the carrier is tubular and the amount of palladium in the pretreated carrier is 5 to 12 mg per 100 mm tube length. 5. Werkwijze volgens een der voorgaande conclusies, waarbij de drager buisvormig is en de snelheid van het fïlm-coaten 15-75 mm buislengte per sec bedraagt.A method according to any one of the preceding claims, wherein the carrier is tubular and the film-coating speed is 15-75 mm pipe length per second. 6. Werkwijze volgens een der voorgaande conclusies, waarbij de penetratie van het palladium in de drager door het fïlm-coaten niet meer dan 5 gm bedraagt.A method according to any one of the preceding claims, wherein the penetration of the palladium into the support by the film coating is no more than 5 µm. 7. Werkwijze volgens een der voorgaande conclusies, waarbij de palladium-concentratie in de voorbehandelingsoplossing tussen 12 en 20 g per 1 bedraagt. 30A method according to any one of the preceding claims, wherein the palladium concentration in the pretreatment solution is between 12 and 20 g per 1. 30 8. Buisvormig membraan op basis van palladium op een poreuze drager, welk membraan geschikt is voor scheiding van waterstof, met het kenmerk dat het membraan aan één zijde een metaallaag met een dikte tussen 1 en 10 μηι heeft, welke metaallaag voor ten minste 40 gew.% uit palladium bestaat.8. A palladium-based tubular membrane on a porous support, which membrane is suitable for hydrogen separation, characterized in that the membrane has on one side a metal layer with a thickness between 1 and 10 μηι, which metal layer comprises at least 40 wt. % consists of palladium. 9. Membraan volgens conclusie 8, waarbij de metaallaag een dikte tussen 2 en 5 μηι 5 heeft.The membrane according to claim 8, wherein the metal layer has a thickness between 2 and 5 μηι 5. 10. Membraan volgens conclusie 8 of 9, waarbij de metaallaag zich aan het buitenoppervlak van het buisvormige membraan bevindt.The membrane of claim 8 or 9, wherein the metal layer is on the outer surface of the tubular membrane. 11. Membraan volgens een der conclusies 8-10, waarbij de metaallaag voor 5-50 gew.% uit een of meer metalen gekozen uit nikkel, platina, koper, zilver en goud bestaat.A membrane according to any one of claims 8-10, wherein the metal layer consists of 5-50% by weight of one or more metals selected from nickel, platinum, copper, silver and gold. 12. Membraan volgens een der conclusies 8-11, dat een waterstofpermeantie van ten 7 2 15 minste 5-10' mol/m .s.Pa heeft.12. A membrane according to any one of claims 8-11, which has a hydrogen permeability of at least 5-10 'mol / m.s.Pa. 13. Werkwijze voor het afscheiden van waterstof uit een gasmengsel, waarbij men het gasmengsel in contact brengt met het membraan volgens een der conclusies 8-12.A method for separating hydrogen from a gas mixture, wherein the gas mixture is brought into contact with the membrane according to any one of claims 8-12.
NL2005290A 2010-08-30 2010-08-30 New seeding method for deposit of thin selective membrane layers. NL2005290C2 (en)

Priority Applications (7)

Application Number Priority Date Filing Date Title
NL2005290A NL2005290C2 (en) 2010-08-30 2010-08-30 New seeding method for deposit of thin selective membrane layers.
US13/819,586 US9156007B2 (en) 2010-08-30 2011-08-26 Seeding method for deposit of thin selective membrane layers
EP11751663.3A EP2611526B1 (en) 2010-08-30 2011-08-26 New seeding method for deposit of thin selective membrane layers
CN201180042241.7A CN103153447B (en) 2010-08-30 2011-08-26 For the new kind crystal method of the selective rete of deposition of thin
CA2809232A CA2809232C (en) 2010-08-30 2011-08-26 New seeding method for deposit of thin selective membrane layers
PCT/NL2011/050578 WO2012030212A1 (en) 2010-08-30 2011-08-26 New seeding method for deposit of thin selective membrane layers
JP2013527028A JP6046039B2 (en) 2010-08-30 2011-08-26 A new seeding method for the deposition of selective thin film layers.

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NL2005290A NL2005290C2 (en) 2010-08-30 2010-08-30 New seeding method for deposit of thin selective membrane layers.
NL2005290 2010-08-30

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Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20080282882A1 (en) * 2006-11-08 2008-11-20 John Charles Saukaitis gas separation membrane comprising a substrate with a layer of coated inorganic oxide particles and an overlayer of a gas-selective material, and its manufacture and use
US20090130477A1 (en) * 2004-01-09 2009-05-21 Bp P.L.C. Metal palladium composite membrane or alloy palladium composite membrane and their preparation methods

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20090130477A1 (en) * 2004-01-09 2009-05-21 Bp P.L.C. Metal palladium composite membrane or alloy palladium composite membrane and their preparation methods
US20080282882A1 (en) * 2006-11-08 2008-11-20 John Charles Saukaitis gas separation membrane comprising a substrate with a layer of coated inorganic oxide particles and an overlayer of a gas-selective material, and its manufacture and use

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
ANWU LI, WEIQIANG LIANG, RONALD HUGHES: "Fabrication of dense palladium compositemembranes for hydrogen separation", CATALYSIS TODAY, vol. 56, 2000, pages 45 - 51, XP002623587 *
STEPHEN N. PAGLIERI, KING Y. FOO, AND J. DOUGLAS WAY: "A New Preparation Technique for Pd/Alumina Membranes withEnhanced High-Temperature Stability", IND. ENG. CHEM. RES., vol. 38, 1999, pages 1925 - 1936, XP002623586 *

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