WO2005065806A1 - A metal palladium composite membrane or alloy palladium composite membrane and their preparation methods - Google Patents
A metal palladium composite membrane or alloy palladium composite membrane and their preparation methods Download PDFInfo
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- WO2005065806A1 WO2005065806A1 PCT/GB2005/000041 GB2005000041W WO2005065806A1 WO 2005065806 A1 WO2005065806 A1 WO 2005065806A1 GB 2005000041 W GB2005000041 W GB 2005000041W WO 2005065806 A1 WO2005065806 A1 WO 2005065806A1
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- Prior art keywords
- palladium
- porous
- pore
- composite membrane
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- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 title claims abstract description 169
- 239000012528 membrane Substances 0.000 title claims abstract description 111
- 229910052763 palladium Inorganic materials 0.000 title claims abstract description 78
- 239000002131 composite material Substances 0.000 title claims abstract description 63
- 238000002360 preparation method Methods 0.000 title claims abstract description 29
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 20
- 239000002184 metal Substances 0.000 title claims abstract description 20
- 229910045601 alloy Inorganic materials 0.000 title abstract description 10
- 239000000956 alloy Substances 0.000 title abstract description 10
- 239000000758 substrate Substances 0.000 claims abstract description 92
- 239000011148 porous material Substances 0.000 claims abstract description 75
- 238000000034 method Methods 0.000 claims abstract description 54
- 239000000945 filler Substances 0.000 claims abstract description 40
- 230000008569 process Effects 0.000 claims abstract description 19
- 238000007747 plating Methods 0.000 claims abstract description 10
- 239000000084 colloidal system Substances 0.000 claims description 29
- 229910001252 Pd alloy Inorganic materials 0.000 claims description 21
- 239000000919 ceramic Substances 0.000 claims description 18
- 239000002244 precipitate Substances 0.000 claims description 18
- 206010061619 Deformity Diseases 0.000 claims description 13
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 12
- 239000002245 particle Substances 0.000 claims description 11
- 238000012805 post-processing Methods 0.000 claims description 11
- 238000007772 electroless plating Methods 0.000 claims description 9
- 239000000126 substance Substances 0.000 claims description 9
- 239000003513 alkali Substances 0.000 claims description 8
- 239000010935 stainless steel Substances 0.000 claims description 8
- 229910001220 stainless steel Inorganic materials 0.000 claims description 8
- 238000004140 cleaning Methods 0.000 claims description 6
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- -1 sols Substances 0.000 claims description 4
- ZGTMUACCHSMWAC-UHFFFAOYSA-L EDTA disodium salt (anhydrous) Chemical compound [Na+].[Na+].OC(=O)CN(CC([O-])=O)CCN(CC(O)=O)CC([O-])=O ZGTMUACCHSMWAC-UHFFFAOYSA-L 0.000 claims description 3
- 229910017849 NH2—NH2 Inorganic materials 0.000 claims description 3
- 229910002666 PdCl2 Inorganic materials 0.000 claims description 3
- 229910021626 Tin(II) chloride Inorganic materials 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 3
- 239000000499 gel Substances 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 claims description 3
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 claims description 3
- AXZWODMDQAVCJE-UHFFFAOYSA-L tin(II) chloride (anhydrous) Chemical compound [Cl-].[Cl-].[Sn+2] AXZWODMDQAVCJE-UHFFFAOYSA-L 0.000 claims description 3
- 229910052759 nickel Inorganic materials 0.000 claims description 2
- 239000005373 porous glass Substances 0.000 claims description 2
- 230000003213 activating effect Effects 0.000 claims 1
- 230000001235 sensitizing effect Effects 0.000 claims 1
- 238000005406 washing Methods 0.000 claims 1
- 239000001257 hydrogen Substances 0.000 description 52
- 229910052739 hydrogen Inorganic materials 0.000 description 52
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 44
- 239000000243 solution Substances 0.000 description 37
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 33
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 30
- 238000005034 decoration Methods 0.000 description 23
- 230000004907 flux Effects 0.000 description 21
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 18
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 12
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 11
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 10
- 239000012153 distilled water Substances 0.000 description 10
- 239000012716 precipitator Substances 0.000 description 10
- 230000015572 biosynthetic process Effects 0.000 description 9
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 8
- 150000002431 hydrogen Chemical class 0.000 description 8
- 229910000029 sodium carbonate Inorganic materials 0.000 description 8
- 229910000069 nitrogen hydride Inorganic materials 0.000 description 7
- 229910001868 water Inorganic materials 0.000 description 7
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 6
- 229910052593 corundum Inorganic materials 0.000 description 6
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 6
- 229910001845 yogo sapphire Inorganic materials 0.000 description 6
- 229910001316 Ag alloy Inorganic materials 0.000 description 5
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 description 5
- 238000000197 pyrolysis Methods 0.000 description 5
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 4
- JLDSOYXADOWAKB-UHFFFAOYSA-N aluminium nitrate Chemical compound [Al+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O JLDSOYXADOWAKB-UHFFFAOYSA-N 0.000 description 4
- 229910000019 calcium carbonate Inorganic materials 0.000 description 4
- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium(3+);trinitrate Chemical compound [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 3
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 229910000027 potassium carbonate Inorganic materials 0.000 description 3
- 238000000746 purification Methods 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 3
- 239000008279 sol Substances 0.000 description 3
- 229910003158 γ-Al2O3 Inorganic materials 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- 229910021502 aluminium hydroxide Inorganic materials 0.000 description 2
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 2
- 125000004429 atom Chemical group 0.000 description 2
- 238000001354 calcination Methods 0.000 description 2
- 239000003638 chemical reducing agent Substances 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 229910052681 coesite Inorganic materials 0.000 description 2
- 239000012141 concentrate Substances 0.000 description 2
- 229910052906 cristobalite Inorganic materials 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 239000000446 fuel Substances 0.000 description 2
- 229910001679 gibbsite Inorganic materials 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 239000003607 modifier Substances 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- SWELZOZIOHGSPA-UHFFFAOYSA-N palladium silver Chemical compound [Pd].[Ag] SWELZOZIOHGSPA-UHFFFAOYSA-N 0.000 description 2
- 230000035699 permeability Effects 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 229910052682 stishovite Inorganic materials 0.000 description 2
- 229910052905 tridymite Inorganic materials 0.000 description 2
- BYFGZMCJNACEKR-UHFFFAOYSA-N Al2O Inorganic materials [Al]O[Al] BYFGZMCJNACEKR-UHFFFAOYSA-N 0.000 description 1
- 229910001020 Au alloy Inorganic materials 0.000 description 1
- 240000008100 Brassica rapa Species 0.000 description 1
- 229910002668 Pd-Cu Inorganic materials 0.000 description 1
- 206010070834 Sensitisation Diseases 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 239000007853 buffer solution Substances 0.000 description 1
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 1
- 239000000920 calcium hydroxide Substances 0.000 description 1
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- GHLITDDQOMIBFS-UHFFFAOYSA-H cerium(3+);tricarbonate Chemical compound [Ce+3].[Ce+3].[O-]C([O-])=O.[O-]C([O-])=O.[O-]C([O-])=O GHLITDDQOMIBFS-UHFFFAOYSA-H 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000006356 dehydrogenation reaction Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 238000005504 petroleum refining Methods 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 230000008313 sensitization Effects 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 239000001509 sodium citrate Substances 0.000 description 1
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical compound O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 229910006636 γ-AlOOH Inorganic materials 0.000 description 1
Classifications
-
- 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
- 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
- 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
- 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
- B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
- B01D67/0081—After-treatment of organic or inorganic membranes
- B01D67/0083—Thermal after-treatment
-
- 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
- B01D69/02—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor characterised by their properties
-
- 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
-
- 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
- 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
- B01D69/106—Membranes in the pores of a support, e.g. polymerized in the pores or voids
-
- 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
- B01D69/108—Inorganic support material
-
- 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
- B01D69/12—Composite membranes; Ultra-thin membranes
- B01D69/1213—Laminated layers
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
- C01B3/50—Separation of hydrogen or hydrogen containing gases from gaseous mixtures, e.g. purification
- C01B3/501—Separation of hydrogen or hydrogen containing gases from gaseous mixtures, e.g. purification by diffusion
- C01B3/503—Separation of hydrogen or hydrogen containing gases from gaseous mixtures, e.g. purification by diffusion characterised by the membrane
- C01B3/505—Membranes containing palladium
-
- 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
- B01D2323/081—Heating
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/12—All metal or with adjacent metals
- Y10T428/12479—Porous [e.g., foamed, spongy, cracked, etc.]
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/249921—Web or sheet containing structurally defined element or component
- Y10T428/249953—Composite having voids in a component [e.g., porous, cellular, etc.]
- Y10T428/249981—Plural void-containing components
Definitions
- a metal palladium composite membrane or alloy palladium composite membrane and their preparation methods The present invention relates to a metal palladium - or alloy palladium - composite membrane which exhibits a high permeable hydrogen flux and high hydrogen selectivity for separation or purification.
- the present invention further relates to a preparation method for producing these said metal or alloy palladium composite membranes.
- Palladium membranes or alloy palladium membranes have been the subject of many studies, due largely to their unmatched potential as hydrogen selective membranes for separation or purification and membrane reactors for hydrogenation /dehydrogenation reactions. However, these studies show that improvement regarding hydrogen peraieability in pure and composite membranes is necessary, as the measured hydrogen permeation flux throughout the studies remained very low.
- Another significant problem found in membrane studies is, under 275°C, pure palladium membrane is susceptible to cracking during the phase transformation due to the amount of hydrogen absorbed. This phenomenon is often termed 'hydrogen embrittlement'.
- an alloy palladium membrane such as Pd-Ag alloy membrane, Pd-Cu alloy membrane or Pd-Au alloy membrane.
- Membranes can either exist as a pure or as a composite membrane.
- a pure palladium membrane, that is an unsupported palladium membrane, is well known in the public domain.
- the corresponding thickness of the membrane must be greater than 200 microns in order to ensure enough mechanical strength to sustain the reaction; consequently this specified membrane thickness results in a low hydrogen permeable flux and a very high production cost.
- composite membranes are preferred, that is a supported palladium membrane where the palladium membrane layer is connected to a porous substrate support, hence reducing the required thickness of the palladium membrane layer and consequently reducing the expense and improving the hydrogen permeation flux, whilst still maintaining the mechanical strength of the whole membrane.
- conventional composite membranes exist in three defined layers; palladium/palladium alloy membrane layer, the surface substrate support and an intermediate layer interconnecting the previous two layers. Indeed, in order to obtain a thin palladium/palladium alloy membrane layer on porous substrates, an intermediate layer is usually introduced in the prior art, which results in a three-layer composite membrane. However this three layer formation again presents the major problem of a low hydrogen permeation flux.
- the present invention concentrates on the aforementioned problems, of the low hydrogen permeable flux and high production costs and proposes a technique for forming a palladium composite membrane directly onto the surface of a porous substrate support without use of an intermediate layer between the membrane and the support. This technique will create a two layer composite membrane as opposed to the conventional three layer composite membrane.
- the present invention concentrates on a simple and easy to operate method to modify the porous substrate by preoccupying the pore channels or disfigurements of the substrate surface. Then it becomes possible to produce a thin dense palladium membrane using an electroless plating preparation method.
- the known preparation method for the conventional three layer palladium palladium alloy composite membrane comprises of a method wherein the porous substrate support is first subjected to 'Surface decoration' in order to overcome the problems associated with the existence of large pores and disfigurement at the surface. These said defects arise due to the non-homogeneous nature of both the surface and of the pore distribution of the support and as a result make it difficult to form a dense palladium membrane on the surface of the support which consequently reduces the membranes' permeable hydrogen selectivity.
- Surface decoration is used to avoid the existence of the large pores and defects and can be performed by either: a) Using a porous surface modifier such as ⁇ -Al 2 0 3 , to coat a thin layer over the substrate surface through coating or moulding in order to produce an intermediate layer. b) Using a porous material, which has a smaller pore-diameter than the pore channels of the substrate support, such as ⁇ -Al 2 0 3 , Zr0 2 , Si0 2 or Ce0 2 to fill in the large pore channels or disfigurements of the substrate surface.
- a porous surface modifier such as ⁇ -Al 2 0 3
- Zr0 2 Zr0 2
- porous materials such as ⁇ -Al 2 O 3 were used to coat a thin intermediate layer over the channels of substrate surface through coating or moulding.
- the palladium plating solution enters into the pore channels, resulting in palladium deposition in the channels of the substrate, thus effectively causing a second resistance to hydrogen permeation and lowering the hydrogen permeation flux.
- porous materials which have a smaller pore- diameter than the pore channels of the substrate support, such as ⁇ -Al 2 0 , ZrO 2 , Si0 2 or CeO 2 are used to fill in the large pore channels or disfigurements of the substrate surface before electroless plating.
- the objective of this present invention is to provide a new efficient surface decoration method of the porous substrate support, for preparation of a two layer palladium or palladium alloy composite membrane that exhibits a high hydrogen permeable flux.
- the present invention is essentially a two layer metal palladium composite membrane consisting of a porous substrate support and a palladium membrane.
- the metal palladium composite membrane is characterized in that the palladium metal substantially exists on the outer surface of the porous substrate support with little or no presence in the pore channels of the substrate.
- This invention also includes a two layer palladium alloy composite membrane, consisting of a porous substrate support and a palladium alloy membrane.
- the palladium alloy composite membrane is characterized in that the palladium alloy membrane substantially exists on the outer surface of the porous substrate support with little or no presence in the pore channels of the substrate. According to the preparation procedure of present invention there is 'little or no presence' of palladium in the pore channels of the support because our pore filler preoccupies the pore channels of porous substrate which prevents the palladium plating solution from entering the substrate.
- the present invention relates to both of these aforementioned two layer composite membranes which are both obtainable by the following preparation process. According to a preferred embodiment of the present invention the process proceeds by the following consecutive steps; 1.
- the porous substrate support is rinsed with a dilute solution of hydrochloric acid, washed, rinsed with a dilute solution of sodium hydroxide, and then washed with distilled water, rinsed with a solvent like CC1 , and dried under ambient conditions.
- the porous substrate support prepared as above is then immersed in a solution of pore filler under vacuum conditions for 20min.
- the excess pore filler residing on the substrate surface is preferably removed by mechanical cleaning e.g. wiping the substrate surface, and then washed with distilled water. According to a preferred embodiment of the present invention this method of decoration is repeated 5-6 times.
- the porous substrate support is sensitized in SnCl 2 solution and activated in PdCl 2 solution, respectively.
- this process is repeated 4 times.
- the Pd° atoms, formed in the reduction of Pd 2+ by Sn 2+ adsorb over the substrate surface and form nuclei for further Pd growth. 4.
- Pd 2+ existed in the chemical plating solution as metastable metal complex ion continuously being reduced to Pd° by reducing agent hydrazine.
- Pd nuclei gradually become large to form the dense palladium membrane. 5.
- the porous substrate is then subjected to post-processing where the pore fillers residing in the pore-channels of the porous substrate are removed or reduced in volume through either heating or physical/chemical dissolving.
- the Pd membrane is then dried at 200°C in nitrogen for 60min, and then calcined at 500°C for 120min.
- Figure 1 represents a schematic description of the preparation steps procedure and of the resulting membrane.
- Substrate modification The modification of porous support involves preoccupying the channels of the porous substrate by pore fillers, for example Al(OH) 3 , which can be removed or partly removed by post-processing.
- Palladium nuclei formation Palladium nuclei will be formed by the sensitization and activation technique.
- Membrane formation Palladium or palladium alloy membrane are formed by electroless plating method.
- Modifier decomposition The pore fillers, for example Al(OH) 3 are decomposed to porous A1 2 0 3 which will keep the channels of the substrate open, which form free passages for H 2 permeation.
- the pore fillers are substances that * are capable of preoccupying the channels of the porous substrate and optionally the disfigurements of the substrate surface during the decoration technique step, and » prevent palladium ingress inside the pores during the preparation.
- the said pore fillers are then removed or partly removed by postprocessing, e.g.. heat treatment (preferably pyrolysis) and/or physical dissolution.
- the said pore fillers can preferably be gels sols, colloids or precipitates. They are preferably Chosen amongst Al-sol, Si-sol, Ti-sol, Zr-sol and/or Ce-sol.
- the pore fillers used according to the present invention are characterised by a particle size lower than 0.2 micron, preferably lower than 0.1 micron, most preferably lower than 0.05 micron.
- the chemical particles which could be processed such as pyrolysis
- porous tiny particles as pore fillers or which could evidently shrink its volume by pyrolysis process such as gel, sol, colloid, precipitate
- pore filler Al-sol, Si-sol, Ti-sol, hydroxide colloid, alkali carbonate colloid, carbonate precipitate, etal.
- porous substrate membrane was suspended in the sol, colloid, or precipitates solution of said pore fillers, the tiny particles of pore fillers entered the pore channel of porous substrate, especially the big channel or the disfigurement, such will decorate the substrate surface and will benefit the formation of dense palladium membrane. Due to the pyrolysis process after palladium membrane formation made the pore fillers shrink its volume and decomposed to porous materials, which provide the free passages for hydrogen permeating the membrane, metal palladium composite membrane derived from modified porous substrate will have high hydrogen permeable flux.
- the material used for the porous substrate support of the metal palladium composite membrane or alloy palladium composite membrane is selected from one of the following porous materials; porous stainless steel, porous nickel, porous glass or porous ceramics.
- the preferred materials used for the support are porous stainless steel and porous ceramics.
- the characteristics of the present invention are as follows; i. Simple technology. In this invention, vacuum is the only condition needed for pore filler particles entering the pore channels of porous substrate. Both the operation and technology are very simple. ii. Wide application. This invention is not limited to the substrate membrane decoration for metal palladium/palladium alloy composite membrane preparation; it can also be applied for the decoration of any porous substrates for other metal membranes.
- the pore fillers are those which do not react with the plating solution. iii. Low production cost.
- cheap pore fillers which could be decomposed by pyrolysis, are used such as sol, colloid, or precipitate.
- the raw materials used are inexpensive, the preparation technology is simple, and easy to perform, therefore the production cost of the process is low. Examples
- Porous substrate surface decoration substrate is alumina porous ceramic tube.
- Porous substrate was first rinsed with the dilute solution of hydrochloric acid and the dilute solution of sodium hydroxide, and then washed with distilled water, rinsed with CCI 4 , and then dried.
- the rinsed alumina porous ceramic tube were im erged in the above colloid solution at vacuum condition, colloid particles will enter the pore channels and the surface disfigurements of alumina porous ceramic tube.
- the excess surface pore filler residing on the surface of the support was then removed by mechanical cleaning.
- Palladium composite membrane preparation Porous substrates after decoration were sensitized in SnCl 2 solution and activated in PdCl 2 solution, respectively. The above steps were repeatedly 4 times.
- Pd° atoms formed in the reduction of Pd 2+ by Sn 2+ adsorbed over the substrate surface.
- Immerging the porous substrate into the electroless plating solution whose typical composition is [Pd(NH 3 ) 2 ]Cl 2 (4g l), EDTA-2Na (65g/l), NH 2 -NH 2 H 2 O(0.6g/l), NH 3 - FI 2 O(28%) (300 ml/1), pH - 10, 50°C.
- Pd 2+ existed in the electroless plating solution as metastable metal complex ion continuously being reduced to Pd° by reducing agent hydrazine.
- Pd° gradually became large enough to form a dense palladium membrane.
- Example 2 Colloid preparation: it is the same as that in example 1.
- Porous substrate surface decoration substrate is porous stainless steel tube.
- Porous substrate surface decoration substrate is alumina porous ceramic tube. Porous substrate was first rinsed with the dilute solution of hydrochloric acid and the dilute solution of sodium hydroxide, and then washed with distilled water, rinsed with CC1 , and then dried.
- Example 4 Colloid preparation C0 2 is injected into the Ca(OH) 2 solution to form CaC0 3 precipitate, which were rinsed 5 times with distilled water.
- Porous substrate surface decoration substrate is alumina porous ceramic tube. Porous substrate was first rinsed with the dilute solution of hydrochloric acid and the dilute solution of sodium hydroxide, and then washed with distilled water, rinsed with CC1 , and then dried. The rinsed alumina porous ceramic tube were immerged in the above CaCO 3 precipitate suspending liquid at vacuum condition, CaC0 3 precipitate particles will enter the pore channels and the surface disfigurements of alumina porous ceramic tube. The excess surface pore filler residing on the surface of the support was then removed by mechanical cleaning.
- Palladium composite membrane preparation the procedures are the same as those in example 1. Post processing method is the same as that in example 1. Palladium composite membrane, prepared by chemical plating method and porous alumina ceramic substrate modified by CaC0 3 precipitate, exhibit a 66 m 3 m "2 -h " -bar " 1 of hydrogen permeable flux and a 3800 of hydrogen permeation selectivity (H 2 /N 2 ).
- Porous substrate surface decoration ⁇ -AlOOH sol, derived from SB powder, is being as surface pore filler, substrate is alumina porous ceramic tube.
- Porous substrate was first rinsed with the dilute solution of hydrochloric acid and the dilute solution of sodium hydroxide, and then washed with distilled water, rinsed with CC1 , and then dried.
- the rinsed alumina porous ceramic tube were immerged in the above Al-sol solution at vacuum condition, AIOOH particles will enter the pore channels and the surface disfigurements of alumina porous ceramic rube under the vacuum conditions.
- the excess surface pore filler residing on the surface of the support was then removed by mechanical cleaning.
- Palladium composite membrane preparation the procedures are the same as those in example 1.
- Post processing method is the same as that in example 1.
- Palladium composite membrane prepared by chemical plating method and porous alumina ceramic substrate modified by ⁇ - AIOOH sol, exhibit a 58 m 3 m "2 h "1 -bar "1 of hydrogen permeable flux and a 3800 of hydrogen permeation selectivity (H 2 /N 2 ).
- Palladium-silver alloy composite membrane preparation First, the procedures are the same as those in example 1. Then, palladium composite membrane obtained is immerged into the chemical plating solution containing silver which component is
- Example 7 Porous substrate surface decoration: porous ⁇ -Al 2 ⁇ 3 is suspended in distilled water, substrate is alumina porous ceramic mbe. Porous alumina porous ceramic t ⁇ be were immerged in the above suspending liquid at vacuum condition, porous ⁇ -Al 2 ⁇ 3 particles will enter the pore channels and the surface disfigurements of alumina porous ceramic tube under the vacuum conditions. Such decorates the substrate. It is the same surface decoration with Ce ⁇ 2, Ti ⁇ 2 , and Zr02 instead of ⁇ -Al 2 0 3 .
- Palladium composite membrane preparation the procedures are the same as those in example 1. Table 7 lists the hydrogen permeability of palladium composite membrane prepared with different pore fillers ( ⁇ -Al 2 O 3 , CeO 2 , Ti ⁇ 2, Zr ⁇ 2 ) which modified the porous alumina ceramic tube.
- Example 8 (for comparison) Porous substrate surface decoration: substrate is porous stainless steel mbe. Surface decoration method is the same as that shown in example 7. Palladium composite membrane preparation: the procedure is the same as that in example 1. Table 8 lists the hydrogen permeability of palladium composite membrane prepared with different pore fillers ( ⁇ -Al 2 O 3 , Ce ⁇ 2 , Ti0 2 , Zr0 2 ) which modified the porous stainless steel mbe.
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Abstract
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Priority Applications (13)
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AU2005203910A AU2005203910B2 (en) | 2004-01-09 | 2005-01-07 | A metal palladium composite membrane or alloy palladium composite membrane and their preparation methods |
BRPI0506744-8A BRPI0506744A (en) | 2004-01-09 | 2005-01-07 | palladium metal composite membrane or palladium alloy composite membrane and its preparation methods |
EA200601293A EA011051B1 (en) | 2004-01-09 | 2005-01-07 | A metal palladium composite membrane or alloy palladium composite membrane and their preparation method |
CN200580007843.3A CN1929900A (en) | 2004-01-09 | 2005-01-07 | Metallic palladium composite membrane or alloy palladium composite membrane and method for their preparations |
EP20050701811 EP1701779B1 (en) | 2004-01-09 | 2005-01-07 | Preparation method of a metal palladium composite membrane or alloy palladium composite membrane |
CA 2552485 CA2552485A1 (en) | 2004-01-09 | 2005-01-07 | A metal palladium composite membrane or alloy palladium composite membrane and their preparation methods |
DE200560022670 DE602005022670D1 (en) | 2004-01-09 | 2005-01-07 | METHOD OF MANUFACTURING A METAL PALLADIUM COMPOSITE MEMBRANE OR PALLADIUM ALLOY COMPOSITE MEMBRANE |
JP2006548385A JP4528785B2 (en) | 2004-01-09 | 2005-01-07 | Metal palladium composite membrane or alloy palladium composite membrane and method for producing the same |
AT05701811T ATE476249T1 (en) | 2004-01-09 | 2005-01-07 | PRODUCTION PROCESS OF A METAL-PALLADIUM COMPOSITE MEMBRANE OR PALLADIUM ALLOY COMPOSITE MEMBRANE |
US10/585,516 US8052775B2 (en) | 2004-01-09 | 2005-01-07 | Process for the preparation of a two-layer metal palladium or palladium alloy composite membrane |
PL05701811T PL1701779T3 (en) | 2004-01-09 | 2005-01-07 | Preparation method of a metal palladium composite membrane or alloy palladium composite membrane |
MXPA06007876A MXPA06007876A (en) | 2004-01-09 | 2005-01-07 | A metal palladium composite membrane or alloy palladium composite membrane and their preparation methods. |
TNP2006000215A TNSN06215A1 (en) | 2004-01-09 | 2006-07-07 | A metal palladium composite membrane or alloy palladium composite membrane and their preparation methods |
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BR (1) | BRPI0506744A (en) |
CA (1) | CA2552485A1 (en) |
DE (1) | DE602005022670D1 (en) |
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ES (1) | ES2350356T3 (en) |
MX (1) | MXPA06007876A (en) |
PL (1) | PL1701779T3 (en) |
SG (1) | SG149057A1 (en) |
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WO2010100432A2 (en) | 2009-03-06 | 2010-09-10 | Institute Of Metal Research, Chinese Academy Of Sciences | Sealing technology |
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WO2010096988A1 (en) * | 2009-02-26 | 2010-09-02 | 南京工业大学 | Process for preparing supported palladium or palladium alloy membrane |
WO2010100432A2 (en) | 2009-03-06 | 2010-09-10 | Institute Of Metal Research, Chinese Academy Of Sciences | Sealing technology |
WO2012030212A1 (en) | 2010-08-30 | 2012-03-08 | Stichting Energieonderzoek Centrum Nederland | New seeding method for deposit of thin selective membrane layers |
US9156007B2 (en) | 2010-08-30 | 2015-10-13 | Stichting Energieonderzoek Centrum Nederland | Seeding method for deposit of thin selective membrane layers |
Also Published As
Publication number | Publication date |
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CA2552485A1 (en) | 2005-07-21 |
AU2005203910A1 (en) | 2005-07-21 |
CN1640530A (en) | 2005-07-20 |
US8052775B2 (en) | 2011-11-08 |
UA92314C2 (en) | 2010-10-25 |
ES2350356T3 (en) | 2011-01-21 |
PL1701779T3 (en) | 2011-05-31 |
TNSN06215A1 (en) | 2007-12-03 |
ZA200605552B (en) | 2008-04-30 |
EA011051B1 (en) | 2008-12-30 |
AU2005203910B2 (en) | 2010-05-27 |
JP4528785B2 (en) | 2010-08-18 |
BRPI0506744A (en) | 2007-05-15 |
EP1701779B1 (en) | 2010-08-04 |
EA200601293A1 (en) | 2007-04-27 |
KR20060121927A (en) | 2006-11-29 |
MXPA06007876A (en) | 2007-03-01 |
ATE476249T1 (en) | 2010-08-15 |
JP2007517655A (en) | 2007-07-05 |
EP1701779A1 (en) | 2006-09-20 |
CN1327942C (en) | 2007-07-25 |
US20090130477A1 (en) | 2009-05-21 |
DE602005022670D1 (en) | 2010-09-16 |
SG149057A1 (en) | 2009-01-29 |
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