KR100614974B1 - 다공성 수소분리막 및 그 제조방법 - Google Patents
다공성 수소분리막 및 그 제조방법 Download PDFInfo
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- KR100614974B1 KR100614974B1 KR1020040056479A KR20040056479A KR100614974B1 KR 100614974 B1 KR100614974 B1 KR 100614974B1 KR 1020040056479 A KR1020040056479 A KR 1020040056479A KR 20040056479 A KR20040056479 A KR 20040056479A KR 100614974 B1 KR100614974 B1 KR 100614974B1
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- Prior art keywords
- hydrogen
- metal powder
- separation membrane
- powder
- hydrogen separation
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- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 101
- 239000001257 hydrogen Substances 0.000 title claims abstract description 101
- 239000012528 membrane Substances 0.000 title claims abstract description 64
- 238000000926 separation method Methods 0.000 title claims abstract description 57
- 125000004435 hydrogen atom Chemical class [H]* 0.000 title abstract 4
- 238000002360 preparation method Methods 0.000 title description 2
- 229910052751 metal Inorganic materials 0.000 claims abstract description 78
- 239000002184 metal Substances 0.000 claims abstract description 78
- 239000000843 powder Substances 0.000 claims abstract description 74
- 239000002245 particle Substances 0.000 claims abstract description 38
- 239000010419 fine particle Substances 0.000 claims abstract description 8
- 238000001179 sorption measurement Methods 0.000 claims abstract description 8
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 52
- 150000002431 hydrogen Chemical class 0.000 claims description 44
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical group [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 24
- 238000004519 manufacturing process Methods 0.000 claims description 15
- 238000000034 method Methods 0.000 claims description 13
- 229910052763 palladium Inorganic materials 0.000 claims description 12
- 229910052782 aluminium Inorganic materials 0.000 claims description 8
- 238000003825 pressing Methods 0.000 claims description 7
- 229910052737 gold Inorganic materials 0.000 claims description 5
- 239000011812 mixed powder Substances 0.000 claims description 5
- 229910052697 platinum Inorganic materials 0.000 claims description 5
- 230000002829 reductive effect Effects 0.000 claims description 5
- 229910052703 rhodium Inorganic materials 0.000 claims description 5
- 229910052707 ruthenium Inorganic materials 0.000 claims description 5
- 229910052710 silicon Inorganic materials 0.000 claims description 5
- 229910052709 silver Inorganic materials 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 4
- 238000000748 compression moulding Methods 0.000 claims 2
- 238000001354 calcination Methods 0.000 claims 1
- 238000000465 moulding Methods 0.000 abstract description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 54
- 229910052757 nitrogen Inorganic materials 0.000 description 27
- 239000007789 gas Substances 0.000 description 21
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 17
- 238000005245 sintering Methods 0.000 description 13
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 12
- 238000000576 coating method Methods 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 10
- 239000003112 inhibitor Substances 0.000 description 10
- 239000011248 coating agent Substances 0.000 description 7
- 238000005259 measurement Methods 0.000 description 5
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 238000009826 distribution Methods 0.000 description 4
- 238000001878 scanning electron micrograph Methods 0.000 description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 3
- 229910021536 Zeolite Inorganic materials 0.000 description 3
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 238000010304 firing Methods 0.000 description 3
- 239000011859 microparticle Substances 0.000 description 3
- 230000035699 permeability Effects 0.000 description 3
- 238000000746 purification Methods 0.000 description 3
- 239000010457 zeolite Substances 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 229910002092 carbon dioxide Inorganic materials 0.000 description 2
- 239000001569 carbon dioxide Substances 0.000 description 2
- 229910002091 carbon monoxide Inorganic materials 0.000 description 2
- 238000012512 characterization method Methods 0.000 description 2
- 239000003638 chemical reducing agent Substances 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 230000003247 decreasing effect Effects 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 239000012153 distilled water Substances 0.000 description 2
- 238000005485 electric heating Methods 0.000 description 2
- 239000000446 fuel Substances 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 150000002430 hydrocarbons Chemical class 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000001651 catalytic steam reforming of methanol Methods 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 229910052681 coesite Inorganic materials 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 229910052906 cristobalite Inorganic materials 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000000635 electron micrograph Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- -1 hydrogen ions Chemical class 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 239000006193 liquid solution Substances 0.000 description 1
- 238000001755 magnetron sputter deposition Methods 0.000 description 1
- 239000013335 mesoporous material Substances 0.000 description 1
- 239000012229 microporous material Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000004570 mortar (masonry) Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000036961 partial effect Effects 0.000 description 1
- 239000005518 polymer electrolyte Substances 0.000 description 1
- 238000009702 powder compression Methods 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000002407 reforming Methods 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 239000000344 soap Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000000629 steam reforming Methods 0.000 description 1
- 229910052682 stishovite Inorganic materials 0.000 description 1
- 229910052905 tridymite Inorganic materials 0.000 description 1
- 238000003466 welding Methods 0.000 description 1
Images
Classifications
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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
-
- 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
- B01D67/0041—Inorganic membrane manufacture by agglomeration of particles in the dry state
-
- 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
- B01D67/0041—Inorganic membrane manufacture by agglomeration of particles in the dry state
- B01D67/00413—Inorganic membrane manufacture by agglomeration of particles in the dry state by agglomeration of nanoparticles
-
- 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
- B01D67/0076—Pretreatment of inorganic membrane material prior to membrane formation, e.g. coating of metal powder
-
- 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
- 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
- B01D71/02232—Nickel
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/06—Combination of fuel cells with means for production of reactants or for treatment of residues
- H01M8/0662—Treatment of gaseous reactants or gaseous residues, e.g. cleaning
- H01M8/0687—Reactant purification by the use of membranes or filters
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2257/00—Components to be removed
- B01D2257/10—Single element gases other than halogens
- B01D2257/108—Hydrogen
-
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2323/00—Details relating to membrane preparation
- B01D2323/10—Specific pressure applied
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2323/00—Details relating to membrane preparation
- B01D2323/12—Specific ratios of components used
-
- 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
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
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- 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
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
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- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- General Chemical & Material Sciences (AREA)
- Analytical Chemistry (AREA)
- Thermal Sciences (AREA)
- Physics & Mathematics (AREA)
- Nanotechnology (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Life Sciences & Earth Sciences (AREA)
- Sustainable Development (AREA)
- Sustainable Energy (AREA)
- Electrochemistry (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
Abstract
Description
압력차(psi) | 수소(㎖/㎠.min.atm) | 질소(㎖/㎠.min.atm) | 선택도(H2/N2) |
2.2 | 33.6 | 1.0 | 32.0 |
5.0 | 18.0 | 1.8 | 9.7 |
7.3 | 13.8 | 1.9 | 7.3 |
14.7 | 10.5 | 1.7 | 6.0 |
압력차(psi) | 수소(㎖/㎠.min.atm) | 질소(㎖/㎠.min.atm) | 선택도(H2/N2) |
2.2 | 181 | 15 | 11.5 |
5.0 | 121 | 24 | 4.8 |
7.3 | 97 | 22 | 4.2 |
14.7 | 84 | 26 | 3.2 |
압력차(psi) | 수소(㎖/㎠.min.atm) | 질소(㎖/㎠.min.atm) | 선택도(H2/N2) |
2.2 | 45.1 | 2.1 | 21.5 |
5.0 | 26.3 | 2.7 | 9.5 |
7.3 | 20.1 | 2.8 | 7.1 |
14.7 | 15.8 | 3.4 | 4.6 |
압력차(psi) | H2/N2 | H2/CO2 | H2/CH4 | H2/C3H8 |
2.2 | 21.5 | 43.0 | 8.6 | 21.5 |
5.0 | 9.5 | 14.2 | 5.7 | 9.5 |
7.3 | 7.1 | 9.1 | 4.3 | 7.1 |
14.7 | 4.6 | 6.7 | 3.4 | 4.6 |
누센확산 | 3.7 | 4.7 | 1.8 | 4.7 |
압력차(psi) | 수소(㎖/㎠.min.atm) | 질소(㎖/㎠.min.atm) | 선택도(H2/N2) |
2.2 | 58.8 | 4.2 | 14.0 |
5.0 | 35.5 | 5.5 | 6.4 |
7.3 | 29.8 | 5.9 | 5.0 |
14.7 | 24.8 | 6.7 | 3.6 |
압력차(psi) | 수소(㎖/㎠.min.atm) | 질소(㎖/㎠.min.atm) | 선택도(H2/N2) |
2.2 | 73.5 | 3.1 | 23.3 |
5.0 | 41.1 | 3.7 | 11.1 |
7.3 | 33.0 | 3.7 | 8.7 |
14.7 | 17.9 | 3.7 | 4.7 |
Claims (11)
- 수소에 대한 흡착특성을 가지는 미세입자를 압착성형하여 제조되는 수소분리막에 있어서, 상기 미세입자는 평균입경이 0.01∼0.5㎛인 제1금속분말 0.5∼50 중량% 및 평균입경이 0.8∼10㎛인 제2금속분말 50∼99.5 중량%로 구성됨을 특징으로 하는 수소분리막
- 삭제
- 삭제
- 제 1항에 있어서, 제1금속분말은 표면에 Al, Si, Pt, Pd, Ru, Rh, Au, Ag의 군에서 선택되는 적어도 1종의 금속이 코팅되어진 것임을 특징으로 하는 수소분리막
- 제 1항에 있어서, 제2금속분말은 전처리로서 200∼500℃ 수소분위기에서 환원시킨 것임을 특징으로 하는 수소분리막
- 제 1항에 있어서, 제1금속분말 또는 제2금속분말은 니켈분말인 것을 특징으로 하는 수소분리막
- 수소에 대한 흡착특성을 가지는 미세입자를 포함하는 수소분리막의 제조방법에 있어서, 평균입경이 0.01∼0.5㎛인 제1금속분말 0.5∼50 중량% 및 평균입경이 0.8∼10㎛인 제2금속분말 50∼99.5 중량%를 혼합하는 단계; 상기 혼합분말을 소정의 압력하에 가압성형하는 단계; 및 상기 성형체를 수소분위기에서 소성하는 단계를 포함함을 특징으로 하는 수소분리막의 제조방법
- 제 7항에 있어서, 압착성형은 1∼20톤/㎠의 압력하에 수행되어짐을 특징으로 하는 수소분리막의 제조방법
- 제 7항에 있어서, 제1금속분말은 표면에 Al, Si, Pt, Pd, Ru, Rh, Au, Ag의 군에서 선택되는 적어도 1종의 금속이 코팅되어진 것임을 특징으로 하는 수소분리막의 제조방법
- 제 7항에 있어서, 제2금속분말은 전처리로서 200∼500℃ 수소분위기에서 환원시킨 것임을 특징으로 하는 수소분리막
- 제 7항에 있어서, 제1금속분말 또는 제2금속분말은 니켈분말인 것을 특징으로 하는 수소분리막
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Cited By (2)
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WO2013015566A2 (ko) | 2011-07-22 | 2013-01-31 | 한국에너지기술연구원 | 수소 분리막 보호층 및 이의 코팅방법 |
KR101424340B1 (ko) | 2012-09-03 | 2014-07-31 | 박광희 | 다공성 촉매 분리막의 제조 방법 |
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KR100982913B1 (ko) * | 2008-05-19 | 2010-09-20 | 한양대학교 산학협력단 | 하이브리드형 복합 입자를 이용한 다공성 니켈 멤브레인의제조방법 |
KR101222476B1 (ko) * | 2008-12-11 | 2013-01-15 | 한국기계연구원 | 소결체 |
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JP2002355537A (ja) * | 2001-05-29 | 2002-12-10 | Daido Steel Co Ltd | 水素透過膜及びその製造方法 |
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WO2013015566A2 (ko) | 2011-07-22 | 2013-01-31 | 한국에너지기술연구원 | 수소 분리막 보호층 및 이의 코팅방법 |
KR101424340B1 (ko) | 2012-09-03 | 2014-07-31 | 박광희 | 다공성 촉매 분리막의 제조 방법 |
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