WO2000059613A1 - Catalytic membrane reactor materials for the separation of oxygen from air - Google Patents
Catalytic membrane reactor materials for the separation of oxygen from air Download PDFInfo
- Publication number
- WO2000059613A1 WO2000059613A1 PCT/US2000/009251 US0009251W WO0059613A1 WO 2000059613 A1 WO2000059613 A1 WO 2000059613A1 US 0009251 W US0009251 W US 0009251W WO 0059613 A1 WO0059613 A1 WO 0059613A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- oxygen
- membrane
- metal oxide
- elements
- group
- Prior art date
Links
- 239000001301 oxygen Substances 0.000 title claims abstract description 126
- 229910052760 oxygen Inorganic materials 0.000 title claims abstract description 126
- 239000012528 membrane Substances 0.000 title claims abstract description 112
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 title claims abstract description 105
- 239000000463 material Substances 0.000 title claims abstract description 58
- 238000000926 separation method Methods 0.000 title claims abstract description 21
- 230000003197 catalytic effect Effects 0.000 title claims abstract description 11
- 239000007789 gas Substances 0.000 claims abstract description 59
- 229910003455 mixed metal oxide Inorganic materials 0.000 claims abstract description 51
- 238000000034 method Methods 0.000 claims abstract description 47
- 239000000203 mixture Substances 0.000 claims abstract description 29
- 229910044991 metal oxide Inorganic materials 0.000 claims abstract description 26
- 150000004706 metal oxides Chemical class 0.000 claims abstract description 26
- 229910052747 lanthanoid Inorganic materials 0.000 claims abstract description 15
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 13
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims abstract description 12
- 229910052733 gallium Inorganic materials 0.000 claims abstract description 12
- 150000002602 lanthanoids Chemical class 0.000 claims abstract description 11
- 229910052742 iron Inorganic materials 0.000 claims abstract description 10
- 230000007935 neutral effect Effects 0.000 claims abstract description 9
- 229910052738 indium Inorganic materials 0.000 claims abstract description 7
- 230000007704 transition Effects 0.000 claims abstract description 7
- 230000003647 oxidation Effects 0.000 claims description 51
- 238000007254 oxidation reaction Methods 0.000 claims description 51
- 230000009467 reduction Effects 0.000 claims description 40
- -1 oxygen anions Chemical class 0.000 claims description 25
- 239000003054 catalyst Substances 0.000 claims description 20
- 239000010409 thin film Substances 0.000 claims description 17
- 229910052712 strontium Inorganic materials 0.000 claims description 9
- 239000000843 powder Substances 0.000 claims description 8
- 229910052788 barium Inorganic materials 0.000 claims description 7
- 239000011261 inert gas Substances 0.000 claims description 7
- 239000011230 binding agent Substances 0.000 claims description 3
- 238000005245 sintering Methods 0.000 claims description 3
- 229910052684 Cerium Inorganic materials 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 238000003825 pressing Methods 0.000 claims description 2
- 230000004907 flux Effects 0.000 abstract description 11
- 230000002950 deficient Effects 0.000 abstract description 6
- 229910052727 yttrium Inorganic materials 0.000 abstract description 4
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 abstract description 4
- 238000004519 manufacturing process Methods 0.000 abstract description 3
- 229910052751 metal Inorganic materials 0.000 description 18
- 239000002184 metal Substances 0.000 description 16
- 239000000758 substrate Substances 0.000 description 16
- 238000002441 X-ray diffraction Methods 0.000 description 8
- 150000002500 ions Chemical class 0.000 description 8
- 239000007858 starting material Substances 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- 230000004913 activation Effects 0.000 description 6
- 229910052791 calcium Inorganic materials 0.000 description 5
- UBEWDCMIDFGDOO-UHFFFAOYSA-N cobalt(II,III) oxide Inorganic materials [O-2].[O-2].[O-2].[O-2].[Co+2].[Co+3].[Co+3] UBEWDCMIDFGDOO-UHFFFAOYSA-N 0.000 description 5
- 238000000151 deposition Methods 0.000 description 5
- 230000008021 deposition Effects 0.000 description 5
- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum oxide Inorganic materials [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 description 5
- 150000002739 metals Chemical class 0.000 description 5
- 229910000018 strontium carbonate Inorganic materials 0.000 description 5
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 4
- 229910010293 ceramic material Inorganic materials 0.000 description 4
- 239000004020 conductor Substances 0.000 description 4
- QZQVBEXLDFYHSR-UHFFFAOYSA-N gallium(III) oxide Inorganic materials O=[Ga]O[Ga]=O QZQVBEXLDFYHSR-UHFFFAOYSA-N 0.000 description 4
- 239000012535 impurity Substances 0.000 description 4
- 229910052746 lanthanum Inorganic materials 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- 238000001354 calcination Methods 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 229910052802 copper Inorganic materials 0.000 description 3
- 239000002019 doping agent Substances 0.000 description 3
- 239000010408 film Substances 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 229930195733 hydrocarbon Natural products 0.000 description 3
- 150000002430 hydrocarbons Chemical class 0.000 description 3
- 229910052749 magnesium Inorganic materials 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 229910052709 silver Inorganic materials 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- 229910052688 Gadolinium Inorganic materials 0.000 description 2
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 150000001450 anions Chemical class 0.000 description 2
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 238000005336 cracking Methods 0.000 description 2
- 230000003247 decreasing effect Effects 0.000 description 2
- 230000001419 dependent effect Effects 0.000 description 2
- 239000010432 diamond Substances 0.000 description 2
- 238000003618 dip coating Methods 0.000 description 2
- 238000010304 firing Methods 0.000 description 2
- 238000000462 isostatic pressing Methods 0.000 description 2
- 238000011068 loading method Methods 0.000 description 2
- 230000007774 longterm Effects 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 238000003801 milling Methods 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 239000012766 organic filler Substances 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 238000000197 pyrolysis Methods 0.000 description 2
- 229910052705 radium Inorganic materials 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- 238000004528 spin coating Methods 0.000 description 2
- 239000007921 spray Substances 0.000 description 2
- 238000005118 spray pyrolysis Methods 0.000 description 2
- 239000000725 suspension Substances 0.000 description 2
- 238000010345 tape casting Methods 0.000 description 2
- 229940083957 1,2-butanediol Drugs 0.000 description 1
- RZVAJINKPMORJF-UHFFFAOYSA-N Acetaminophen Chemical compound CC(=O)NC1=CC=C(O)C=C1 RZVAJINKPMORJF-UHFFFAOYSA-N 0.000 description 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- 229910052692 Dysprosium Inorganic materials 0.000 description 1
- 229910052691 Erbium Inorganic materials 0.000 description 1
- 229910052693 Europium Inorganic materials 0.000 description 1
- 229910052689 Holmium Inorganic materials 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 229910052765 Lutetium Inorganic materials 0.000 description 1
- 229910052779 Neodymium Inorganic materials 0.000 description 1
- 229910052777 Praseodymium Inorganic materials 0.000 description 1
- 229910052772 Samarium Inorganic materials 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- 229910052771 Terbium Inorganic materials 0.000 description 1
- 229910052775 Thulium Inorganic materials 0.000 description 1
- 229910052769 Ytterbium Inorganic materials 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 229910052790 beryllium Inorganic materials 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052795 boron group element Inorganic materials 0.000 description 1
- 244000309464 bull Species 0.000 description 1
- BMRWNKZVCUKKSR-UHFFFAOYSA-N butane-1,2-diol Chemical compound CCC(O)CO BMRWNKZVCUKKSR-UHFFFAOYSA-N 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 239000012018 catalyst precursor Substances 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 230000005591 charge neutralization Effects 0.000 description 1
- 238000001311 chemical methods and process Methods 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 229910052593 corundum Inorganic materials 0.000 description 1
- 238000005137 deposition process Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 229910052741 iridium Inorganic materials 0.000 description 1
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 229910001092 metal group alloy Inorganic materials 0.000 description 1
- 229910001960 metal nitrate Inorganic materials 0.000 description 1
- 150000002926 oxygen Chemical class 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 239000012466 permeate Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229920002037 poly(vinyl butyral) polymer Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000012704 polymeric precursor Substances 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 1
- 239000003380 propellant Substances 0.000 description 1
- 239000005297 pyrex Substances 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 150000002910 rare earth metals Chemical class 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 229910052706 scandium Inorganic materials 0.000 description 1
- 239000000565 sealant Substances 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- 238000007873 sieving Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 229910002076 stabilized zirconia Inorganic materials 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 229910001845 yogo sapphire Inorganic materials 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B13/00—Oxygen; Ozone; Oxides or hydroxides in general
- C01B13/02—Preparation of oxygen
- C01B13/0229—Purification or separation processes
- C01B13/0248—Physical processing only
- C01B13/0251—Physical processing only by making use of membranes
- C01B13/0255—Physical processing only by making use of membranes characterised by the type of membrane
-
- 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
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01D53/32—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 electrical effects other than those provided for in group B01D61/00
- B01D53/326—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 electrical effects other than those provided for in group B01D61/00 in electrochemical cells
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01D67/0039—Inorganic membrane manufacture
- B01D67/0041—Inorganic membrane manufacture by agglomeration of particles in the dry state
- B01D67/00411—Inorganic membrane manufacture by agglomeration of particles in the dry state by sintering
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- B01D71/024—Oxides
- B01D71/0271—Perovskites
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J12/00—Chemical processes in general for reacting gaseous media with gaseous media; Apparatus specially adapted therefor
- B01J12/007—Chemical processes in general for reacting gaseous media with gaseous media; Apparatus specially adapted therefor in the presence of catalytically active bodies, e.g. porous plates
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
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- B01J19/2475—Membrane reactors
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- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/83—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with rare earths or actinides
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/33—Electric or magnetic properties
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- B01J35/50—Catalysts, in general, characterised by their form or physical properties characterised by their shape or configuration
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- B01J8/00—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
- B01J8/008—Details of the reactor or of the particulate material; Processes to increase or to retard the rate of reaction
- B01J8/009—Membranes, e.g. feeding or removing reactants or products to or from the catalyst bed through a membrane
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B17/00—Sulfur; Compounds thereof
- C01B17/02—Preparation of sulfur; Purification
- C01B17/04—Preparation of sulfur; Purification from gaseous sulfur compounds including gaseous sulfides
- C01B17/0404—Preparation of sulfur; Purification from gaseous sulfur compounds including gaseous sulfides by processes comprising a dry catalytic conversion of hydrogen sulfide-containing gases, e.g. the Claus process
- C01B17/046—Preparation of sulfur; Purification from gaseous sulfur compounds including gaseous sulfides by processes comprising a dry catalytic conversion of hydrogen sulfide-containing gases, e.g. the Claus process without intermediate formation of sulfur dioxide
- C01B17/0465—Catalyst compositions
-
- 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
- C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
- C01B3/32—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air
- C01B3/34—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents
- C01B3/36—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents using oxygen or mixtures containing oxygen as gasifying agents
-
- 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
- C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
- C01B3/32—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air
- C01B3/34—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents
- C01B3/38—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents using catalysts
- C01B3/386—Catalytic partial combustion
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01C—AMMONIA; CYANOGEN; COMPOUNDS THEREOF
- C01C3/00—Cyanogen; Compounds thereof
- C01C3/02—Preparation, separation or purification of hydrogen cyanide
- C01C3/0208—Preparation in gaseous phase
- C01C3/0212—Preparation in gaseous phase from hydrocarbons and ammonia in the presence of oxygen, e.g. the Andrussow-process
- C01C3/0216—Preparation in gaseous phase from hydrocarbons and ammonia in the presence of oxygen, e.g. the Andrussow-process characterised by the catalyst used
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- 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
- H01M8/10—Fuel cells with solid electrolytes
- H01M8/12—Fuel cells with solid electrolytes operating at high temperature, e.g. with stabilised ZrO2 electrolyte
- H01M8/1231—Fuel cells with solid electrolytes operating at high temperature, e.g. with stabilised ZrO2 electrolyte with both reactants being gaseous or vaporised
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- 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
- H01M8/10—Fuel cells with solid electrolytes
- H01M8/12—Fuel cells with solid electrolytes operating at high temperature, e.g. with stabilised ZrO2 electrolyte
- H01M8/124—Fuel cells with solid electrolytes operating at high temperature, e.g. with stabilised ZrO2 electrolyte characterised by the process of manufacturing or by the material of the electrolyte
- H01M8/1246—Fuel cells with solid electrolytes operating at high temperature, e.g. with stabilised ZrO2 electrolyte characterised by the process of manufacturing or by the material of the electrolyte the electrolyte consisting of oxides
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- 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
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- 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
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Definitions
- Oxygen-deficient oxides of this invention are derived from brownmillerite materials which have the general structure A 2 B 2 0 5 .
- the materials of this invention maintain high oxygen anion conductivities at relatively low membrane operating conditions ranging from about 700°C to 900°C.
- the metal elements at the B-site in the brownmillerite structure are selected to provide mixed ion- and electron- conducting materials and particularly to provide material that conduct oxygen anions and electrons.
- the materials of this invention have the general formula:
- x and x' are greater than 0; y and y' are greater than 0; x + x' is less than or equal to 2; y + y' is less than or equal to 2; z is a number that makes the metal oxide charge neutral;
- A is an element selected from the lanthanide elements and yttrium;
- A' is an element selected from the Group 2 elements;
- B is an element selected from the group consisting of Al, Ga, In or mixtures thereof.
- the lanthanide metals include the f block lanthanide metals: La, Ce, Pr, Nd,
- Yttrium has properties similar to the f block lanthanide metals and is also included herein in the definition of lanthanide metals.
- A is preferably La or Gd, with La more preferred.
- Group 2 metal elements of the Periodic Table (also designated Group lla) are Be, Mg, Ca, Sr, Ba, and Ra.
- the preferred Group 2 elements for the A' element of the materials of this invention are Ca, Sr and Ba and Sr is most preferred.
- the more preferred B elements are Ga and Al, with Ga more preferred.
- the d block transition elements include Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, and Zn.
- B' and B" elements are Mg, Fe and Co, with Fe and Co being more preferred as B' and B", respectively.
- Mixed metal oxides in which B" and B" are Fe and Co are particularly preferred for membranes having high oxygen flux rates.
- the value of z in the above formula depends upon the values of x, x', y and y' and the oxidation states of the A, A', A" , B, B' and B" elements.
- the value of z is such that the mixed metal oxide material is charge neutral. In preferred materials, 0 ⁇ z ⁇ 1.
- Electronically- and ionically-conducting membranes employed in the oxygen- separation reactors of this invention comprise mixed metal oxides of the above formula.
- Substantially gas-impermeable membranes having both electronic and ionic conductivity are formed by initially preparing mixed metal oxide powders by repeatedly calcining and milling the powders of individual metal oxides or the corresponding carbonates (or other metal precursors) in the desired stoichiometric ratios.
- the resulting mixed metal oxide is then pressed and sintered into dense membranes of various shapes, including disks and open-one-ended tubes. These membranes are then employed to construct catalytic membrane reactors, particularly for oxygen separation processes.
- the purity of the product oxygen produced in reactors of this invention is generally greater than about 90% and preferably greater than about 99%.
- the presence of the mixed metal oxide of desired stoichiometry (as in the given formulas) in a repeatedly calcined and milled mixed metal oxide can be assessed by X-ray diffraction studies. Further, the presence of distinct phases of metal oxides or other metal species that may be present in the mixed metal oxides materials of this invention can be detected by X-ray diffraction techniques by the observation of peaks not assignable with the predominate mixed metal oxide of desired stoichiometry.
- the level of distinct phase material that can be detected depends upon the resolution and sensitivity of the X-ray diffractometer employed and upon the identity and number of the distinct phases present. It is believed that greater than about 4% by weight of another phase can be detected by the X-ray diffraction method employed (Figs. 1-5)
- a catalytic reactor of this invention comprises an oxidation zone and a reduction zone separated by the substantially gas-impermeable catalytic membrane which comprises the electronically and ionically conducting mixed metal oxides of the above formula.
- the membrane Once in the reactor, the membrane has an oxidation surface in contact with the oxidation zone of the reactor and a reduction surface in contact with the reduction zone of the reactor.
- Electronic conduction in the reactor is provided through the membrane material which is a mixed ion and electron conductor (i.e., conducts both electrons and ions, such as oxygen anions).
- a reactor also comprises passages for admission of oxygen-containing gas, such as air, into the reactor reduction zone and admission of an oxygen-depleted gas, inert gas or reduced gas into the oxidation zone of the reactor.
- a vacuum can alternatively be applied to the oxidation zone to remove separated oxygen from the oxidation zone. Oxygen removed in this way can be collected and concentrated, if desired.
- the reactor also has gas exit passages from the reduction and oxidation zones.
- a plurality of membrane reactors can be provided in series or in parallel (with respect to gas flow through the reactor) to form a multi-membrane reactor to enhance speed or efficiency of oxygen separation.
- an oxygen-containing gas such as air, is introduced into the reduction zone of the reactor in contact with the reduction surface to the catalytic membrane. Oxygen is reduced to oxygen anion at the reduction surface and the anion is conducted through the membrane to the oxidation surface.
- the oxygen anion is re-oxidized to oxygen which is released into the oxidation zone of the reactor.
- oxygen anion can be employed to oxidize a reduced gas (e.g., a hydrocarbon gas) at the oxidation surface of the membrane.
- Membrane materials of this invention conduct electrons as well as anions. (Membrane materials that also conduct electrons allow charge neutralization of the membrane during operation.) Gases in the reactor can be under ambient or atmospheric pressure or they can be placed under higher or lower pressure (e.g., a vacuum can be applied) than ambient conditions.
- the membrane is heated typically at a temperature above about 700°C and more typically from about 700°C to about 1100°C.
- Preferred materials of this invention can be efficiently operated at temperatures that are generally lower than those currently used in the art, at from about 700°C to about 900°C.
- the oxidation surface, or the reduction surface or both surfaces (or parts of those surfaces) of the membrane can be coated with an oxidation catalyst or reduction catalyst, respectively, or both.
- a preferred catalyst for either or both surfaces of the membrane is La 08 Sr 02 Co0 3 . z where z is a number that makes the oxide charge neutral.
- An oxygen flux of about 1 ml/min-cm 2 or higher can be obtained through a 1 mm- thick membrane at ambient pressure and at an operating temperature of about 900°C. These high flux rates can be maintained for long-term operation, e.g., up to about 700 h of operation.
- Membrane materials as described herein can be employed in a method for oxygen separation from an oxygen-containing gas.
- a reactor as described above, is provided with a substantially gas-impermeable membrane which separates an oxidation and reduction zone.
- Oxygen is reduced at the reducing surface of the membrane, the resulting oxygen anions are then transported across the membrane to the reduction surface where oxygen anions are re-oxidized to form oxygen which is released into the oxidation zone for collection.
- This method can be employed to generate high purity oxygen (greater than about 90% purity) or very high purity oxygen (greater than about 99% purity) or to generate oxygen-enriched gases (e.g., oxygen in an inert gas).
- Figure 1 is an x-ray diffractometer scan for calcined mixed metal oxide having the formula 4 05 +z .
- Figure 2 is an x-ray diffractometer scan for calcined mixed metal oxide having the formula La 0 gS 7 Ga 06 Fe ⁇ ⁇ O Q 3 0 5+Z .
- Figure 3 is an x-ray diffractometer scan for calcined mixed metal oxides having the formula La 04 Sr 1 7 AI 06 Fe 1 ⁇ O ⁇ OS ⁇ .
- Figure 4 is an x-ray diffractometer scan for calcined mixed metal oxides of formula La 04 Sr 1 6 Ga 06 Fe 1 2 Co 02 O 5+z .
- Figure 5 is an x-ray diffractometer scan for calcined and sintered mixed metal oxides of formula La 04 S 6 AI 06 Fe ⁇ 2 Co 02 0 5+z .
- Brownmillerites are generally referred to as having the formula A 2 B 2 0 5 .
- Brownmillerite is considered to be derived from the perovskite structure by removal of 1/6 of the oxygen atoms.
- Solid state compositions based on the brownmillerite parent compound Ba 2 ln 2 0 5 and useful in this invention are formed by introducing dopants or substitutents into the B-site of the lattice to lower the order-disorder phase transition. Higher oxygen anion conductivity is generally found to correlate with the disordered phase. Clear correlations exist between perovskite-related crystallographic and thermodynamic parameters with empirical parameters relating to the activation energy (E a ) for ionic transport. Lower values of E a favor higher ionic conduction.
- E a activation energy
- ⁇ S m is the activation entropy
- C is the fraction of available sites occupied by mobile ions
- ⁇ is the jump distance
- Z is the number of jump directions
- u 0 is the molar volume
- e is the electronic charge.
- the exponential term is related to the activation energy.
- Membrane materials of this invention can be used for oxygen separation or oxygen enrichment, i.e., for decreasing the oxygen concentration in one gas stream and increasing or enriching the oxygen concentration in another gas stream.
- Oxygen-containing gas includes air, oxygen in nitrogen, oxygen in inert gases and contaminated oxygen.
- Oxygen from the oxygen-containing gas can be transferred in the reactors of this invention, in principle, to any gas in which it is desired to increase oxygen concentration, in particular an inert gas, nitrogen, a reduced gas (i.e., hydrocarbon-containing gas) can be introduced into the oxidation zone of the reactor.
- a reduced gas i.e., hydrocarbon-containing gas
- a vacuum or partial vacuum can be applied to the oxidation zone to collect separated oxygen.
- the separated oxygen can also be used to oxidize a reduced gas in the oxidation zone, i.e., to form oxygenated hydrocarbons.
- This invention provides a method for separating oxygen from oxygen- containing gases and/or for oxygen enrichment of oxygen-deficient gases in which it is desired to increase the level of oxygen.
- the method employs a reactor having two chambers or zones (an oxidation zone and a reduction zone) separated by a substantially gas impermeable membrane.
- a substantially gas impermeable membrane may not be completely impermeable to small gaseous species such as hydrogen gas and may allow a low level of leakage of other gases. It is particularly important that the membrane be impermeable to gases from which oxygen is to be separated, such as nitrogen. Preferred membranes are formed without substantial cracking and gas leakage.
- the membrane is capable of transporting oxygen ions and also conducts electrons.
- the membrane is fabricated from an ion-conducting and electron-conducting mixed metal oxide of this invention having the formula given above.
- the oxygen-containing gas is introduced into one chamber, the reduction zone, in contact with the reduction surface of the membrane.
- a differential oxygen partial pressure is established between the two chambers or zones, with oxygen partial pressure higher in the reduction zone.
- the differential partial pressure can be established by introducing an oxygen-deficient gas or a reduced gas into the oxidation zone which has a lower concentration of oxygen than in the oxygen- containing gas.
- the oxygen-deficient gas can be an inert gas such as helium.
- a partial or full vacuum can be applied to the oxidation zone to remove transported oxygen.
- Gas pressure in the zones may be ambient or higher or lower than ambient to achieve the desired differential oxygen partial pressure.
- the membrane is heated to a temperature that facilitates oxygen anion transport and also facilitates electron transport. Oxygen is transported across the membrane to enrich the oxygen content of the oxygen-deficient or reduced gas. Oxygen can be concentrated from the oxygen-enriched gas exiting the oxidation zone.
- the membranes of this invention are heated, typically to at least about 700°C. At lower temperatures, e.g., at 600°C, ionic conductivity of the 1 mm thick membrane is typically too low for practical operation.
- the oxygen-separation reactors of this invention can be combined with other known methods for gas purification or gas separation to provide desired levels of purity in gas streams.
- the gas stream output of oxygen-separation reactors can be introduced as product gas streams for other reactors.
- Mixed metal oxide materials useful for preparation of ionically- and electronically-conductive membranes include, among others:
- La 03 Sr 1 7 AI 06 Fe 1 0 . rn Co rn O 5+z where m is 0, 0.1 , 0.15, 0.20, 0.25, 0.30,
- Mixed metal oxide materials of this invention are substantially single-phase in that they are predominately (greater than about 90% by weight) comprised of a single-phase mixed metal oxide of the formula given above.
- the purity of the materials can be determined by X-ray diffraction methods which are believed to detect the presence of greater than about 4% by weight of other phases.
- the materials formed on mixing, calcining and milling individual metal oxide powders may contain minor amounts (up to about 10% by weight) of other metal oxides that form distinct phases, but which do not contribute significantly to the electronic and ionic conductivity of the material as a whole.
- additional metal oxide phases may be formed unintentionally due to inaccuracies in the amounts of starting materials added because, for example, the starting materials may contain nonvolatile impurities (e.g., starting metal oxides may contain low levels of metal carbonates) or volatile impurities (e.g., water) that alter the relative stoichiometries of component metals.
- additional metal oxide phases may be selectively introduced into the mixed metal oxide material by preparing off-stoichiometric
- the diffractometer employed can detect greater than about 4% by weight of other phases (as determined by adding increasing amounts of SrAI 2 0 4 impurity). Small arrows on the scans indicate peaks believed to be indicative of second phases.
- the shoulder peak at about 32 is believed to be due to (Sr, La) 2 AI0 4 .
- the peaks between 28-30 are believed to be due to Sr(Fe, Al) 2 0 4 .
- the peaks at 34 and 41 have not as yet been identified.
- Group 2 elements Mg, Ca, Sr, Ba and Ra are believed to be in the 2+ oxidation state.
- Group 13 elements Al, Ga, and In are believed to be in the 3+ oxidation state.
- Lanthanides (including lanthanum and yttrium) are believed to be in the 3+ oxidation state.
- the transition metals in these materials are expected to be of mixed valence (i.e., a mixture of oxidation states) dependent upon the amount of oxygen present and the temperature.
- Membranes useful in the oxygen separation method of this invention can be dense, substantially gas impermeable sintered materials in any desired shape, including membrane disks, open tubes, one-open-ended tubes, etc., that can be adapted to form a gas-tight seal between the two zones or chambers discussed above.
- the membrane can be sealed between the two zone or chambers with a gas tight seal employing approriately selected adhesive or sealant.
- Membranes can be formed by isostatic pressing of mixed metal oxide materials of this invention into dense substantially gas-impermeably membranes.
- substantially gas-impermeable membranes can be formed by forming dense thin films of ionically and electronically conducting mixed metal oxide on porous substrate materials.
- Porous substrates can have any desired shape including disks, tubes or one-open-ended tubes.
- Porous substrates (which allow passage of gas through the substrate) can include various metal oxide materials including metal-oxide stabilized zirconia, titania, alumina, magnesia, or silica, mixed metal oxide materials exhibiting ion and/or electronic conduction or metal alloys, particularly those that minimally react with oxygen.
- the substrate material should be inert to oxygen or facilitate the desired transport of oxygen. More preferred substrates are those that have a thermal expansion coefficient (over the operational temperatures of the reactor) that is matched to that of the mixed metal oixde ion/elelctron conducting material.
- Thin films (about 10-300 ⁇ m thick) of the mixed metal oxides of this invention are formed on the porous substrate by a variety of techniques, including tape casting, dip coating or spin coating.
- a presently preferred two component membrane is prepared by forming dense thin films of the mixed metal oxides of this invention on a porous substrate formed from the same mixed metal oxide material.
- the oxidation and reduction surfaces of the membranes of this invention can optionally be provided with an oxidation catalyst, a reduction catalyst or both.
- Oxidation and reduction catalysts can be selected from mixed metal oxides having the formula:
- a preferred oxidation/reduction catalyst is La 08 Sr 02 Co0 3 _ ⁇ , where ⁇ is a number that makes the metal oxide charge neutral.
- Alternative catalysts include: A 2 Co 2 . b M b 0 5+b/2 , where 0 ⁇ b ⁇ 0.2, A is Ba, Sr, Ca or mixtures thereof and M is Fe, Ni, Cu, Ag or mixtures thereof; and metals dispersed onto ceramic material, particularly where the metal is Ag, Pd, Pt, Ir, Rh, Ru or mixtures thereof.
- Catalysts can be deposited on the membrane surface by any known deposition process.
- a preferred process is the deposition of the catalysts on the sintered membrane surfaces by spray pyrolysis.
- Stoichiometric aqueous metal nitrate (or other metal precursor) solutions (having the stoichiometry of the desired metal oxide catalyst, for example, can be spray pyrolyzed by heating to about 700°C using air as the spray pyrolysis propellant to avoid oxygen depletion during deposition.
- the pyrolyzed spray is uniformly deposited onto a heated (e.g., to 500°C ) sintered membrane, for example using an air brush device.
- Other solvents that do not interfere with deposition or react with the catalyst can be employed in the pyrolysis solution.
- Catalyst loading is varied by adjusting the concentration of the catalyst (or catalyst precursor) in the pyrolysis solution. Catalyst loading will typically be about 0.001 to about 0.1 g/cm 2 and preferably about 0.01 gr/cm 2 .
- Example 1 Preparation of Mixed Metal Oxides Starting materials for preparation of mixed metal oxides were obtained from commercial sources and typically were employed without further purification. Higher purity mixed metal oxides can be obtained by initial removal of volatile impurities (e.g., H 2 0, by heating starting materials under vacuum). For specific examples below, La 2 0 3 , SrC0 3 , Ga 2 0 3 , Al 2 0 3 and Co 3 0 4 were obtained from Alfa/Aesar at purities indicated below. Fe 2 0 3 was obtained from Aldrich.
- volatile impurities e.g., H 2 0, by heating starting materials under vacuum.
- La 2 0 3 , SrC0 3 , Ga 2 0 3 , Al 2 0 3 and Co 3 0 4 were obtained from Alfa/Aesar at purities indicated below.
- Fe 2 0 3 was obtained from Aldrich.
- brownmillerite-derived ceramic materials of this invention were in general prepared from powders using standard solid state synthesis techniques.
- the resulting powders were mixed with polyvinyl butyral binder and pressed and sintered in air at 1150°C - 1450°C for 4-12 hours into dense disks and dense open-one-end tubes.
- Materials containing Ga are preferably sintered at lower temperatures in this range, up to about 1225 °C .
- X-ray diffraction of sintered membranes show material to be substantially single-phase containing small amounts (less than about 10%) of second phases.
- Membranes were prepared as in A above.
- An X-ray diffraction scan of calcined .,Co 03 O 5+x is provided in Fig. 2.
- An open-one-end membrane tube (about 1.0 mm m thick) prepared from La 0 3 Sr 1 7 Ga 06 Fe 1 .,Co 0 35 O 5+x as described in Example 1C was incorporated into a membrane reactor with a Pyrex seal used to isolate the air from the permeate chamber.
- a slurry of La 08 Sr 02 CoO 3 . x (in 1 , 2-butanediol) was applied on both the anode (oxidation) and cathode (reduction) sides of the membrane to serve as both oxidation and reduction catalysts. Gas flows on both sides of the membrane were under ambient pressure.
- Air flow on the cathode side of the reactor was held at 600 ml/min, and the He flow on the anode side was fixed at 400 ml/min. Under these conditions, an oxygen flux of 0.9 ml/min-cm 2 was maintained at 900°C for 700 h of operation. This is equivalent to an oxygen ion conductivity of 0.7 S/cm. An activation energy of less than 0.5eV was calculated from temperature dependent measurements. Oxygen conductivity is calculated from oxygen flux (or permeation) according to the equation: where J is the oxygen permeation in ml/min-cm 3 , d is membrane thickness in cm, T is temperature in K, P' and P" are the oxygen partial pressures on opposite sides of the membrane.
- Table 1 provides oxygen permeation data for dense membranes (about 0.8- 1.0 mm thick) prepared by isostatic pressing of mixed metal oxide materials of this invention.
- Membranes were prepared as open-one-ended tubes.
- the partial pressure of oxygen on the cathode side was 0.21 atm (0 2 in air) and on the anode side was maintained at 0.02 atm. He flow on the anode side was adjusted to maintain the constant oxygen partial pressure of 0.02 atm. In both cases gas flows were at ambient pressure. Maintenance of the constant partial pressures of oxygen on either side of the membrane allows comparison of data among different membrane materials.
- Table 1 also lists ion conductivities which are calculated using the equation above. The values of oxygen permeation and calculated conductivity given in the table at those measured after operation in a reactor for the time listed in Table 1.
- Figures 6 and 7 are graphs comparing oxygen flux or permeation (ml/min-cm 2 ) as a function of time at 900°C for several different membrane materials.
- Figure 6 compares oxygen flux as a function of time using membranes prepared from La 0 aS ⁇ 7 Ga 06 Fe ⁇ 4 .
- Figure 7 compares oxygen flux as a function of time using membranes prepared from La 04 Sr., 6 Ga 06 Fe., 4 . y Co y 0 5+z where 0.0 ⁇ y ⁇ 0.4, indicating that the amount of Co is varied.
- Membranes for oxygen separation reactors can be prepared by coating a substrate with a thin film (about 10-about 300 ⁇ m thick) of a mixed metal oxide material of this invention.
- a porous substrate material can be coated with a dense thin film of these materials to provide a substantially gas impermeable membrane.
- thin films are applied to selected substrates by methods known in the art, including tape casting, dip coating or spin coating.
- Presently preferred thin film-coated membranes are prepared using a porous membrane as a substrate where the porous membrane is made of a mixed metal oxide of the same or similar composition to the ion and electron conduction mixed metal oxide that will comprise the thin film.
- Porous membranes of the mixed metal oxides of this invention can be prepared in a variety of ways, for example, by combining the metal oxide with an organic filler (up to about 20% by weight), such as cellulose or starch particles of a selected size range 9e.g. about 20 ⁇ m particles), shaping or pressing the desired membrane and sintering.
- an organic filler up to about 20% by weight
- the organic filler is destroyed and removed on sintering leaving desired pores of a selected size in the membrane.
- Thin films are preferably uniformly thick and crack-free on firing. Uniform deposition of films can for example be obtained by use of colloidal suspensions of the metal oxide in a selected solvent. The suspension is applied to the porous substrate by conventional coating or casting methods to give a uniform deposition which on firing gives a film of uniform thickness.
- An alternative method for applying thin films is the use of co-polymeric precursors which comprise metal oxide incorporated into the polymer.
- Flat membranes or tubular membranes can be prepared having dense thin films of the metal oxide mixed ion and electron conductors of this invention.
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Abstract
Description
Claims
Priority Applications (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP00920206A EP1183092A4 (en) | 1999-04-06 | 2000-04-06 | Catalytic membrane reactor materials for the separation of oxygen from air |
AU40784/00A AU4078400A (en) | 1999-04-06 | 2000-04-06 | Catalytic membrane reactor materials for the separation of oxygen from air |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
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US09/286,829 | 1999-04-06 | ||
US09/286,829 US6165431A (en) | 1993-12-08 | 1999-04-06 | Methods for separating oxygen from oxygen-containing gases |
Publications (1)
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WO2000059613A1 true WO2000059613A1 (en) | 2000-10-12 |
Family
ID=23100349
Family Applications (1)
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PCT/US2000/009251 WO2000059613A1 (en) | 1999-04-06 | 2000-04-06 | Catalytic membrane reactor materials for the separation of oxygen from air |
Country Status (4)
Country | Link |
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US (1) | US6165431A (en) |
EP (1) | EP1183092A4 (en) |
AU (1) | AU4078400A (en) |
WO (1) | WO2000059613A1 (en) |
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US6596054B2 (en) * | 2001-07-23 | 2003-07-22 | Advanced Technology Materials, Inc. | Method for carbon monoxide reduction during thermal/wet abatement of organic compounds |
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FR2862005A1 (en) * | 2003-11-06 | 2005-05-13 | Air Liquide | Composite material e.g. useful as a mixed conductor material in catalytic membrane reactors for producing synthesis gas comprises a doped ceramic oxide component and a ceramic, metal or alloy component |
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US8337724B2 (en) | 2003-11-06 | 2012-12-25 | L'air Liquide Societe Anonyme Pour L'etude Et L'exploitation Des Procedes Georges Claude | Addition of (A) blocking agent(s) in a ceramic membrane for blocking crystalline growth of grains during atmospheric sintering |
DE102009047795A1 (en) * | 2009-09-30 | 2011-03-31 | Siemens Aktiengesellschaft | Device for separating gases through a membrane that separates a high pressure region from a low pressure region, comprises an arrangement for modifying the active cross-section of the gas arranged above the membrane |
Also Published As
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EP1183092A4 (en) | 2004-11-03 |
AU4078400A (en) | 2000-10-23 |
EP1183092A1 (en) | 2002-03-06 |
US6165431A (en) | 2000-12-26 |
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