CN112955418A - 基于钙铁石的多晶熔合产品 - Google Patents
基于钙铁石的多晶熔合产品 Download PDFInfo
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- CN112955418A CN112955418A CN201980061668.8A CN201980061668A CN112955418A CN 112955418 A CN112955418 A CN 112955418A CN 201980061668 A CN201980061668 A CN 201980061668A CN 112955418 A CN112955418 A CN 112955418A
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- 229910052791 calcium Inorganic materials 0.000 claims abstract description 39
- 229910052712 strontium Inorganic materials 0.000 claims abstract description 39
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 33
- 229910052742 iron Inorganic materials 0.000 claims abstract description 32
- 239000000203 mixture Substances 0.000 claims abstract description 30
- 229910052802 copper Inorganic materials 0.000 claims abstract description 13
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 12
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 7
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 7
- 229910052688 Gadolinium Inorganic materials 0.000 claims abstract description 4
- 229910052777 Praseodymium Inorganic materials 0.000 claims abstract description 4
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 4
- 229910052733 gallium Inorganic materials 0.000 claims abstract description 4
- 229910052598 goethite Inorganic materials 0.000 claims abstract description 4
- AEIXRCIKZIZYPM-UHFFFAOYSA-M hydroxy(oxo)iron Chemical compound [O][Fe]O AEIXRCIKZIZYPM-UHFFFAOYSA-M 0.000 claims abstract description 4
- 229910052738 indium Inorganic materials 0.000 claims abstract description 4
- 229910052746 lanthanum Inorganic materials 0.000 claims abstract description 4
- 229910052749 magnesium Inorganic materials 0.000 claims abstract description 4
- 229910052706 scandium Inorganic materials 0.000 claims abstract description 4
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 4
- 239000000843 powder Substances 0.000 claims description 51
- 239000002245 particle Substances 0.000 claims description 46
- 239000007858 starting material Substances 0.000 claims description 35
- 238000000034 method Methods 0.000 claims description 32
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 31
- 239000001301 oxygen Substances 0.000 claims description 31
- 239000007788 liquid Substances 0.000 claims description 29
- 230000003197 catalytic effect Effects 0.000 claims description 20
- 239000003054 catalyst Substances 0.000 claims description 17
- 238000002844 melting Methods 0.000 claims description 15
- 230000008018 melting Effects 0.000 claims description 15
- 230000008569 process Effects 0.000 claims description 11
- 239000007787 solid Substances 0.000 claims description 11
- 239000012528 membrane Substances 0.000 claims description 7
- 239000000446 fuel Substances 0.000 claims description 5
- 238000000926 separation method Methods 0.000 claims description 5
- 238000001816 cooling Methods 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 2
- 239000011344 liquid material Substances 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 claims 1
- 239000000047 product Substances 0.000 description 75
- 239000011575 calcium Substances 0.000 description 44
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 42
- 239000000126 substance Substances 0.000 description 25
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 21
- 239000012530 fluid Substances 0.000 description 18
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 17
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 15
- 229910002091 carbon monoxide Inorganic materials 0.000 description 15
- 238000006243 chemical reaction Methods 0.000 description 15
- 229910002092 carbon dioxide Inorganic materials 0.000 description 12
- 229910000018 strontium carbonate Inorganic materials 0.000 description 11
- 239000001569 carbon dioxide Substances 0.000 description 10
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 10
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 9
- 229910000019 calcium carbonate Inorganic materials 0.000 description 9
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 9
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 description 9
- LEDMRZGFZIAGGB-UHFFFAOYSA-L strontium carbonate Chemical compound [Sr+2].[O-]C([O-])=O LEDMRZGFZIAGGB-UHFFFAOYSA-L 0.000 description 9
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 8
- 150000001875 compounds Chemical class 0.000 description 8
- 239000010949 copper Substances 0.000 description 8
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 7
- 238000002360 preparation method Methods 0.000 description 6
- 229910002406 SrFeO2.5 Inorganic materials 0.000 description 5
- 239000011324 bead Substances 0.000 description 5
- 238000002441 X-ray diffraction Methods 0.000 description 4
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 4
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 4
- 238000005266 casting Methods 0.000 description 4
- 239000013078 crystal Substances 0.000 description 4
- 239000006185 dispersion Substances 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 239000001307 helium Substances 0.000 description 4
- 229910052734 helium Inorganic materials 0.000 description 4
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 4
- 229910052697 platinum Inorganic materials 0.000 description 4
- 239000002243 precursor Substances 0.000 description 4
- IATRAKWUXMZMIY-UHFFFAOYSA-N strontium oxide Inorganic materials [O-2].[Sr+2] IATRAKWUXMZMIY-UHFFFAOYSA-N 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- 239000002019 doping agent Substances 0.000 description 3
- 238000010891 electric arc Methods 0.000 description 3
- 239000008187 granular material Substances 0.000 description 3
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- 150000004679 hydroxides Chemical class 0.000 description 3
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- 238000007792 addition Methods 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 238000007664 blowing Methods 0.000 description 2
- 238000001354 calcination Methods 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 239000000470 constituent Substances 0.000 description 2
- 239000010431 corundum Substances 0.000 description 2
- 229910052593 corundum Inorganic materials 0.000 description 2
- 230000001186 cumulative effect Effects 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 229910052731 fluorine Inorganic materials 0.000 description 2
- 238000000227 grinding Methods 0.000 description 2
- 125000001475 halogen functional group Chemical group 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- NWAHZABTSDUXMJ-UHFFFAOYSA-N platinum(2+);dinitrate Chemical compound [Pt+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O NWAHZABTSDUXMJ-UHFFFAOYSA-N 0.000 description 2
- 238000007873 sieving Methods 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 238000007711 solidification Methods 0.000 description 2
- 230000008023 solidification Effects 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- 229910001018 Cast iron Inorganic materials 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 229910000608 Fe(NO3)3.9H2O Inorganic materials 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 241000764238 Isis Species 0.000 description 1
- -1 M and M' elements Chemical compound 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 229960004543 anhydrous citric acid Drugs 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000000071 blow moulding Methods 0.000 description 1
- ICSSIKVYVJQJND-UHFFFAOYSA-N calcium nitrate tetrahydrate Chemical compound O.O.O.O.[Ca+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ICSSIKVYVJQJND-UHFFFAOYSA-N 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 238000002447 crystallographic data Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
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- 230000002349 favourable effect Effects 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 239000012634 fragment Substances 0.000 description 1
- 238000005469 granulation Methods 0.000 description 1
- 230000003179 granulation Effects 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- BDAGIHXWWSANSR-NJFSPNSNSA-N hydroxyformaldehyde Chemical compound O[14CH]=O BDAGIHXWWSANSR-NJFSPNSNSA-N 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000011872 intimate mixture Substances 0.000 description 1
- 150000002506 iron compounds Chemical class 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000010309 melting process Methods 0.000 description 1
- 238000003801 milling Methods 0.000 description 1
- 239000004570 mortar (masonry) Substances 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 238000010606 normalization Methods 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 1
- 238000004445 quantitative analysis Methods 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 229910002076 stabilized zirconia Inorganic materials 0.000 description 1
- 238000007655 standard test method Methods 0.000 description 1
- 150000003438 strontium compounds Chemical class 0.000 description 1
- DHEQXMRUPNDRPG-UHFFFAOYSA-N strontium nitrate Inorganic materials [Sr+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O DHEQXMRUPNDRPG-UHFFFAOYSA-N 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 238000000844 transformation Methods 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- RIUWBIIVUYSTCN-UHFFFAOYSA-N trilithium borate Chemical compound [Li+].[Li+].[Li+].[O-]B([O-])[O-] RIUWBIIVUYSTCN-UHFFFAOYSA-N 0.000 description 1
- 238000004876 x-ray fluorescence Methods 0.000 description 1
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- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/01—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics
- C04B35/26—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on ferrites
- C04B35/2683—Other ferrites containing alkaline earth metals or lead
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- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/01—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics
- C04B35/26—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on ferrites
- C04B35/2608—Compositions containing one or more ferrites of the group comprising manganese, zinc, nickel, copper or cobalt and one or more ferrites of the group comprising rare earth metals, alkali metals, alkaline earth metals or lead
- C04B35/2633—Compositions containing one or more ferrites of the group comprising manganese, zinc, nickel, copper or cobalt and one or more ferrites of the group comprising rare earth metals, alkali metals, alkaline earth metals or lead containing barium, strontium or calcium
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- 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
- B01J23/78—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 alkali- or alkaline earth metals
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/653—Processes involving a melting step
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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
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/90—Selection of catalytic material
- H01M4/9016—Oxides, hydroxides or oxygenated metallic salts
- H01M4/9025—Oxides specially used in fuel cell operating at high temperature, e.g. SOFC
- H01M4/9033—Complex oxides, optionally doped, of the type M1MeO3, M1 being an alkaline earth metal or a rare earth, Me being a metal, e.g. perovskites
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- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
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- H01M4/9075—Catalytic material supported on carriers, e.g. powder carriers
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- C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
- C04B2235/3205—Alkaline earth oxides or oxide forming salts thereof, e.g. beryllium oxide
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- C04B2235/3205—Alkaline earth oxides or oxide forming salts thereof, e.g. beryllium oxide
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- C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
- C04B2235/3205—Alkaline earth oxides or oxide forming salts thereof, e.g. beryllium oxide
- C04B2235/3215—Barium oxides or oxide-forming salts thereof
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- C04B2235/3217—Aluminum oxide or oxide forming salts thereof, e.g. bauxite, alpha-alumina
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Abstract
一种基于钙铁石的多晶熔合产品,其95重量%以上的重量由元素Ca,Sr,Fe,O,M和M'组成,所述元素的含量由式XyMzFetM’uO2.5定义,其中原子指数使得0.76≤y≤1.10,z≤0.21,0.48≤t≤1.10和u≤0.52,0.95≤y+z≤1.10,和0.95≤t+u≤1.10,X为Ca或Sr或Ca和Sr的混合物,M是选自由La,Ba及其混合物形成的组中的元素,M'是选自由Ti,Cu,Gd,Mn,Al,Sc,Ga,Mg,Ni,Zn,Pr,In,Co形成的组中的元素及其混合物,Ti和Cu的原子指数之和小于或等于0.1。
Description
本发明涉及一种化学式为XyMzFetM'uO2.5的基于钙铁石(brownmillerite)的多晶材料,其中X为Ca或Sr或Ca和Sr的混合物,特别是用于需要氧气传输的应用,特别是用作氧气分离的膜的应用,例如用于固体氧化物燃料电池(SOFC)的电极,用作催化剂载体,或甚至用作催化剂。
通式为CaFeO2.5和SrFeO2.5的产品通常分别称为“钙铁钙铁石”和“锶铁钙铁石”,CaFeO2.5 或SrFeO2.5钙铁石相任选地掺杂有掺杂剂M和/或M',为了改善离子传导率和/或烧结能力和/或热和/或化学稳定性。掺杂剂M特别地可以是Ba,La或这些元素的混合物,并且掺杂剂M'可以是Ti,Cu,Gd,Mn,Al,Sc,Ga,Mg,Ni,Zn,Pr,In,Co或这些元素的混合物。
这些钙铁石通常通过以下方法制备:
-溶胶-凝胶,特别是通过Pechini方法,
-固体烧结合成,
-自燃。
如Ceretti 等人在"Influence of Phase Transformations on Crystal Growth of Stoichiometric Brownmillerite Oxides: Sr 2 ScGaO 5 and Ca 2 Fe 2 O 5 "(Ceretti etal., Crystals, Vol.6, 2016, pp 146)中所述,通过浮区法制备的CaFeO2.5钙铁石单晶,也是已知的。
最后,使用这些材料作为催化剂载体是已知的。
需要在尽可能低的反应温度下实现非常高的转化率。
本发明的目的是至少部分地满足该需求。
根据本发明,该目的是通过基于钙铁石的多晶熔合产品来实现的,所述熔合产品的重量的95%以上由元素Ca,Sr,Fe,O,M和M'组成,其中所述熔合产品中的所述元素由式XyMzFetM'uO2.5定义,其中原子指数使得0.76 ≤ y ≤ 1.10, z ≤ 0.21, 0.48 ≤ t ≤1.10, u ≤ 0.52, 0.95 ≤ y + z ≤ 1.10, 和0.95 ≤ t + u ≤ 1.10,X是Ca或Sr或Ca和Sr的混合物,M选自元素La,Ba及其混合物,M'选自元素Ti,Cu,Gd,Mn,Al,Sc,Ga,Mg,Ni,Zn,Pr,In,Co及其混合物,Ti和Cu的原子指数之和小于或等于0.1。
换句话说,上式中Ti和Cu对指数u的总贡献小于或等于0.1。
当然,0 ≤ z和0 ≤ u。
在一个实施方案中,除Ca, Sr, Fe, M和M’之外的所述元素以氧化物的形式按重量计大于95重量%,大于99重量%,或者甚至基本上100重量%。
出人意料的是,已证明此类产品非常适合于构成催化剂载体,从而使得可以在低温下获得高转化率。包含本发明的产品或由本发明的产品组成的催化载体特别值得注意的是,在用于将CO氧化为CO2的反应中,达到转化率等于50%所需的温度***地小于通过熔融以外的其他方法获得的具有相同组成的载体以达到该相同程度所需的温度。该性质甚至似乎构成根据本发明的产品的标志。
在熔融然后冷却的作用下,Ca, Sr, Fe, M, M'和O元素以至少一种钙铁石相,或甚至其他含钙和/或铁和/或锶(尤其地FeO, CaO, CaCO3, Fe, Fe2O3和SrCO3)的次要相的形式结合在一起。
优选地,根据本发明的产品还包括以下可选特征中的一个,并且优选地,其具有多个:
- 0.85 ≤ y ≤ 1.05 和/或 z ≤ 0.15 和/或 0.75 ≤ t ≤ 1.05 和/或 u≤ 0.25,
- 一个或多个钙铁石相的含量(即,基于熔合产品中存在的所有结晶相的一个或多个钙铁石相的重量百分比)大于50%,更优选大于55%,
- z = 0,
- u = 0,
- z = 0和u = 0,
- 元素M'选自Ti, Cu, Ni, Co, Mn及其混合物,
- 在式XyMzFetM'uO2.5中,如果x表示式 (Ca(1-x)Srx)yMzFetM'uO2.5中Sr的比例且(1-x)表示Ca的相对比例,0 < x ≤ 0.1, 0.9 ≤ y ≤ 1.05, 0.1≥ z ≥ 0.01, y + z ≤1.1, t ≥ 0.8, 0.01 ≤ u ≤ 0.2, t + u ≤ 1.1,以及除Ca,Sr,Fe,M,M'和O以外的元素的总重量含量小于3%,以基于产品重量的百分比计,
-在式XyMzFetM'uO2.5中,如果x表示式(Ca(1-x)Srx)yMzFetM'uO2.5中Sr的比例且(1-x)表示Ca的相对比例,x = 0, 0.9 ≤ y ≤ 1.05, 0.1≥ z ≥ 0.01, y + z ≤ 1.1, t ≥0.8, 0.01 ≤ u ≤ 0.2, t + u ≤ 1.1,以及除了Ca,Sr,Fe,M,M'和O以外的元素的总重量含量小于3%,以基于产品重量的百分比计,
-在式XyMzFetM'uO2.5中,如果x表示式(Ca(1-x)Srx)yMzFetM'uO2.5中Sr的比例且(1-x)表示Ca的相对比例,1 > x ≥ 0.9, 0.9 ≤ y ≤ 1.05, 0.1≥ z ≥ 0.01, y + z ≤1.1, t ≥ 0.8, 0.01 ≤ u ≤ 0.2, t + u ≤ 1.1,以及除了Ca,Sr,Fe,M,M'和O以外的元素的总重量含量小于3%,以基于产品重量的百分比计,
- 在式XyMzFetM'uO2.5中,如果x表示式(Ca(1-x)Srx)yMzFetM'uO2.5中Sr的比例和和(1-x)表示Ca的相对比例,x = 1, 0.9 ≤ y ≤ 1.05, 0.1≥ z ≥ 0.01, y + z ≤ 1.1, t≥ 0.8, 0.01 ≤ u ≤ 0.2, t + u ≤ 1.1,以及除了Ca,Sr,Fe,M,M'和O以外的元素的总重量含量小于3%,以基于产品重量的百分比计。
本发明还涉及一种粉末,包含大于90重量%或甚至100重量%的在如上所述的熔合产品中的颗粒。这种粉末的中值粒度D50大于0.1μm且小于4mm。
有利地,这些任选的特性改善了催化性能,使得根据本发明的产品特别适合在任选研磨之后用作催化剂载体或催化剂。
本发明还涉及一种粉末,包含按重量计大于90%,或甚至大于95%,或甚至基本上100%的在本发明产品中的颗粒。
本发明还涉及包括以下步骤的制备方法:
a)混合起始材料,以形成适合在步骤c)结束时获得本发明产品的起始原料,
b)熔融起始原料直至获得液体物质,
c)冷却所述液体物质直至完全固化,从而获得根据本发明的熔合产品。
本发明还涉及可以通过根据本发明的方法获得的产品。
最后,本发明涉及选自氧分离膜,催化膜,用于固体氧化物燃料电池的电极,催化剂载体,催化剂,该催化剂包含下述物质或由下述物质组成:根据本发明的产品,或根据本发明的粉末或可通过本发明方法制备的产品或可通过本发明的方法制备的产品。
根据第一方面,本发明涉及一种催化载体或催化剂,该催化剂包含下述物质或由下述物质组成:如上所述的熔合产品,或如上所述的粉末,或由如上所述的方法制备的产品。
根据另一方面,本发明涉及一种氧分离膜,其包含下述物质或由下述物质组成:如上所述的熔合产品,或如上所述的粉末,或由如上所述的方法制备的产品。
根据另一方面,本发明涉及一种用于固体氧化物燃料电池SOFC的电极,其包含下述物质或由下述物质组成:如上所述的熔合产品,或如上所述的粉末,或由如上所述的方法制备的产品。
在化学式由式XyMzFetM'uO2.5示出的产品与式XyMzFetM'uO2.5的相之间应加以区分,其中该式表示所述相的晶体学结构。
在根据本发明的产品中,各种相都是可能的,尤其是式XyMzFetM'uO2.5的一个或多个相,特别是CaFeO2.5和SrFeO2.5。
ICDD(“国际衍射数据中心”("International Center for Diffraction Data"))文件00-018-0286和01-070-5778使得可以识别分别与CaFeO2.5钙铁石相和SrFeO2.5钙铁石相对应的衍射峰的角度范围。
根据本发明的产品的粉末的X射线图,基于根据存在于根据本发明的产品中的所有可检测的结晶相,以重量百分数确定钙铁石相和可能的次生相的含量,根据例如在出版物中描述的常规RIR(参考强度比)方法进行检测:"A standard test method for the determination of RIR values by x-ray diffraction", Walter N. Schreiner,Powder Diffraction, Vol. 10, No. 1, March 1995 or "The Use of Reference Intensity Ratios in X-Ray Quantitative Analysis", Robert L. Snyder, PowderDiffraction, Vol. 7, No. 4, December 1992。
使用DIFFRAC EVA软件并通过如上所述RIR方法对获得的图案进行处理并确定产品中存在的相。根据所使用的程序,优化了各相的强度,以使其尽可能与实验衍射图相对应。 RIR方法是使用ICDD文件执行的,该文件具有可用于所有可检测相(例如上面提到的那些相)的可能的最佳质量的信号,并且尤其具有I/Icorundum之比的值,即相对于用作标准品的刚玉样品,产品中存在的结晶相的ICDD文件的信号强度之间的比率。
为了确定产品中钙铁石相的总含量,根据本发明考虑通过RIR方法基于相应相的ICDD文件测定存在的钙铁石相的含量的总和。尤其,如果存在的一个或多个钙铁石相对应于通式[Ca(1-x)Srx]yMzFetM'uO2.5,且x≠0和x≠1,则所有相的累积贡献具有根据在11°和12°之间的衍射角2θ的峰,将考虑在所述一个或多个钙铁石相的平面[020]上的反射特性。因此,根据该测量,钙铁石相的含量考虑到了以钙铁石晶体形式的所有Ca(1-x)SrxFeO2.5相,其中0≤x≤1,其中元素M和/或M'可以存在。同样,对于钙铁石以外的其他相(称为次生相)的贡献和含量,根据与上述相同的程序并通过RIR方法确定。除了CaFeO2.5和SrFeO2.5钙铁石相以外,次生相是可通过X射线衍射检测的相。其中,FeO, Fe2O3, SrCO3, CaCO3, Fe,SrFeO2.75, SrFeO2.875或CaO可能是X射线衍射图确定的次生相,特别是当产品XyMzFetM'uO2.5不包含或基本不包含元素M和M'。
这些相的检测和鉴定是通过所述产品的X射线衍射图进行的,例如通过Panalytical公司的X’Pert PRO衍射仪装置获得的,该装置配有铜XRD管。使用该设备在5°至80°的角度范围2θ内以0.017°的步进和60秒/步的计数时间获取衍射图。前透镜包括一个1/4°固定使用的可编程发散狭缝,一个0.04 rad的Soller狭缝,一个等于10 mm的掩模和一个1/2°的固定防散射狭缝。样品围绕其自身的轴旋转以限制优先方向。后透镜包括一个1/4°固定使用的可编程防散射狭缝,0.04 rad的Soller狭缝和Ni滤镜。
术语“熔合产品”是指通过将液态物质形式的起始原料熔融,然后使所述液态物质固化而获得的产品。
术语“颗粒”尤其是指穿过具有正方形网眼且具有等于10mm的开口的筛子的固体物体。
术语“块(block)”旨在表示不是颗粒的固体物体。
粉末的术语“中值粒度”,用D50表示,是指在粉末的粒度的累积粒度分布曲线上,对应于50%重量百分比的粒度,粒度以递增的顺序分类。可以通过使用激光粒度分析仪测量的粒度分布来确定中值粒度。
术语“杂质”是指不可避免的成分,它们是无意地和必然地与起始材料一起引入的,或者是由与这些成分反应而产生的。杂质不是必需的成分,而仅仅是可容忍的。
术语“元素的最稳定的氧化物”旨在表示在热力学上在20℃下最稳定的所述元素的氧化物。
术语化合物或元素的“前体”旨在表示能够在实施根据本发明的制备方法期间分别提供所述化合物或元素的组分。
除非另有说明,和特别是在式XyMzFetM'uO2.5和[Ca(1-x)Srx]yMzFetM'uO2.5中,其中指数x,y,z,t,u和2.5是原子指数,所有根据本发明的成分的含量是基于产品表示的重量百分比。
除非另外指出,否则术语“包含一个”或“包括一个”旨在表示“包含至少一个”。
优选通过以下方法获得本发明的熔合产品:将起始原料熔融,将液体物质铸造,优选在模具中或以细流的形式铸造,然后固化。
现在详细描述根据本发明的方法的实施例。
根据本发明的产品的化学性质和钙铁石相的量,特别是钙铁石相的含量,特别取决于步骤a)中制备的起始原料的组成。
能够制备根据本发明的熔合产品的原料由下述的化合物形成:钙和/或锶的化合物,铁的化合物,以及任选地元素M和/或M',特别地呈氧化物/或碳酸盐和/或氢氧化物形式,和/或钙和/或锶,铁和M和/或M'元素的前体的化合物。起始原料的组成可通过添加氧化物或氧化物的混合物和/或前体来调节,特别地CaO, CaCO3, SrO, SrCO3, Fe2O3,元素M的一种或多种氧化物,元素M'的一种或多种氧化物,元素M的一种或多种碳酸盐,元素M'的一种或多种碳酸盐,元素M的一种或多种氢氧化物,元素M'的一种或多种氢氧化物。氧化物和/或碳酸盐和/或氢氧化物的使用改善了形成钙铁石相及其电中性所需的氧利用率,并因此是优选的。
优选地,将铁,M和M'中的至少一种或甚至全部元素以氧化物的形式引入起始原料中。在一个特定的实施方案中,使用氧化物粉末来提供铁,M和M'元素,并且使用碳酸盐粉末来提供钙元素和/或锶元素。
优选地,提供钙和/或锶,铁,M和M'元素的化合物选自CaO, CaCO3, SrO, SrCO3,Fe2O3,元素M的一种或多种氧化物,元素M'的一种或多种氧化物,元素M的一种或多种碳酸盐,元素M'的一种或多种碳酸盐。
优选地,提供钙和/或锶,铁,M和/或M'元素的化合物一起按重量百分比计占起始原料的成分的大于90%,优选地大于99%。优选地,这些化合物与杂质一起表示起始原料的成分的100%。
优选地,除了提供钙和/或锶,铁,M和/或M'元素的那些化合物之外,没有化合物被故意地引入起始原料中,或者甚至除了CaO, CaCO3, SrO, SrCO3, Fe2O3,元素M的一种或多种氧化物,元素M'的一种或多种氧化物,元素M的一种或多种碳酸盐,元素M'的一种或多种碳酸盐之外,没有其他化合物被故意地引入起始原料中。在一个实施方案中,CaO, CaCO3,SrO, SrCO3, Fe2O3,元素M的一种或多种氧化物,元素M'的一种或多种氧化物,元素M的一种或多种碳酸盐,元素M'的一种或多种碳酸盐,及其前体占起始原料的99重量%以上。
起始原料中钙和/或锶,铁,元素M和元素M'的含量主要包含在制备的熔合产品中。如果依靠熔融条件,依靠它们的常识或简单的常规试验,一部分组分在熔融步骤中能够挥发,本领域技术人员知道如何根据他们希望在熔合产品中的含量以及所使用的熔融条件来调节起始原料中这些成分的量。
为了增加钙铁石含量,优选起始原料中钙,锶,铁,M和M'元素的摩尔比例接近于期望制备的钙铁石熔合产品的摩尔比例。
为了制备根据本发明的熔合产品,在起始原料中,优选钙,锶,铁,M和M'元素的摩尔含量分别为c,s,f,m和n,以摩尔百分比计,基于含量c,s,f,m和n的总和,以遵守以下条件:
· k1. [(1-x)*y]/(x*y) ≤ c / s ≤ k2. [(1-x)*y]/(x*y), 和/或
· k'1. u/t ≤ n / f ≤ k'2. u/t, 和/或
· k''1. z/t ≤ m / f ≤ k''2. z/t, 和/或
· k'''1. [(1-x)*y]/t ≤ c/ f ≤ k'''2. [(1-x)*y]/t, 和/或
· k''''1. (x*y)/t ≤ s/ f ≤ k''''2. (x*y)/t,
其中
- x,y,z,t和u可以采用本说明中定义的值,特别是0 ≤ x ≤ 1, 0.76 ≤ y ≤1.10, z ≤ 0.21, 0.48 ≤ t ≤ 1.10, u ≤ 0.52, 0.95 ≤ y + z ≤ 1.10, 和0.95≤ t + u ≤ 1.10,和
- k1 ≥ 0.9, 优选 ≥ 0.95, 和/或
- k'1 ≥ 0.9, 优选 ≥ 0.95, 和/或
- k''1 ≥ 0.9, 优选 ≥ 0.95, 和/或
- k'''1 ≥ 0.9, 优选 ≥ 0.95, 和/或
- k''''1 ≥ 0.9, 优选 ≥ 0.95, 和/或
- k2 ≤ 1.1, 优选 ≤ 1.05, 和/或
- k'2 ≤ 1.1, 优选 ≤ 1.05, 和/或
- k''2 ≤ 1.1, 优选 ≤ 1.05, 和/或
- k'''2 ≤ 1.1, 优选 ≤ 1.05, 和/或
- k''''2 ≤ 1.1, 优选 ≤ 1.05。
当然,这些值k1, k'1, k''1, k'''1, k''''1, k2, k'2, k''2, k'''2 和k''''2是在既定的工作条件下采用的那些,也就是说在不同组成之间的过渡步骤之外以及在启动步骤之外要采用的那些。这是因为,如果所需产品与用于制备先前产品的起始原料相比,起始原料的组成发生变化,则必须考虑炉中先前产品的残留物。然而,本领域技术人员知道如何相应地调节起始原料。
起始原料中使用的粉末的粒度可以是熔融过程中通常遇到的那些。
起始材料的紧密混合物可以在混合器中进行。然后将该混合物倒入熔融炉中。
在步骤b)中,起始原料被熔融。
例如,可以使用包括两个电极的Heroult电弧炉,并且其罐的直径约为0.8 m,并且可以容纳约180 kg的熔融液体。优选地,能量在1500和2800kWh/T之间,优选地在1600和2300kWh/T之间。
但是,可以设想所有已知的炉子,例如感应炉,等离子炉或其他类型的Heroult炉,只要它们能够获得液体物质即可。
也可以在热处理炉中,优选在电炉中,在坩埚中进行熔融。
优选地,使用电弧炉或感应炉,优选电弧炉。实际上,电熔合可以以有利的产率制备大量的熔合产品。
优选地,不使用等离子炬,也不使用热风枪。特别地,使用等离子炬或热风枪的方法并不总是能够产生熔融颗粒。即使在熔融的情况下,它们通常也不能产生尺寸大于200微米,和至少大于500微米的熔融颗粒。
熔融可以在还原性,中性或含氧的环境中进行,优选在含氧的环境中,更优选在空气中进行。
在步骤b)结束时,起始原料为液体物质的形式,其可以包含少量固体颗粒,但是其量不足以使它们能够构成所述物质。根据定义,为了保持其形状,必须在容器内盛装液体物质。
在第一实施方案中,步骤c)包括以下步骤:
c1)以液滴的形式分散液体物质,
c2)通过与流体,优选为含氧流体接触,使这些液滴固化,从而获得熔合颗粒。
通过简单地调节起始原料的组成,常规的分散方法,特别是通过吹塑或喷雾干燥,因此使得可以从液体物质开始制备出具有大于50%,优选大于60%,优选大于70%,优选大于80%,优选大于90%,或甚至大于95%的钙铁石相含量的颗粒。。在步骤c)结束时,特别是根据该第一实施方案制备的根据本发明的熔合产品可以是具有小于5mm,或甚至小于1mm,或者甚至小于500 µm,或甚至小于200 µm,或甚至小于100 µm的尺寸的颗粒的形式。
在步骤c1)中,将熔融液体的细流分散为液滴,该熔融液体的温度优选地高于根据本发明的产品的熔点,优选地高于1400℃。
分散可通过吹气稀的液体物质而产生。然而,可以设想本领域技术人员已知的用于喷雾干燥液体物质的任何其他方法。
在步骤c1)中,使所述液体物质与流体,优选为含氧流体,优选为气体,优选为空气接触。含氧流体优选具有大于20体积%的氧体积含量。
在步骤c2)中,通过与含氧流体,优选为气体,优选为空气接触,将液滴转化为固体颗粒。含氧流体优选具有大于20体积%的氧体积含量。
优选地,该方法适于使得熔融液滴一形成就与含氧流体接触。再次优选地,分散体(步骤c1))和固化(步骤c2))基本上是同时的,液体物质由能够冷却和固化该液体的含氧流体,优选气体,优选空气分散。
优选地,至少在液滴完全固化之前保持与含氧流体的接触。
在环境温度下可以吹气。
在步骤c2)结束时,根据分散条件,通常获得尺寸在0.01mm至5mm之间的固体颗粒。
在第二实施方案中,步骤c)包括以下步骤:
c1')将液态物质铸造在模具中;
c2')通过冷却铸造在模具中的液态物质直至获得至少部分固化的块来进行固化;
c3')从模具中取出块。
在步骤c1')中,将液体物质铸造在能够承受熔融液体浴的模具中。优选地,使用由石墨制成的模具,由铸铁制成的模具或如在US 3 993 119中所定义的模具。在感应炉的情况下,转弯被认为构成了模具。铸造优选在空气下进行。
在步骤c2')中,冷却铸造在模具中的液态物质,直到获得至少部分固化的块为止。
优选地,在固化过程中,使液体物质与流体,优选为含氧流体,优选为气态流体,优选与空气接触。一旦进行铸造,就可以进行这种接触。然而,优选仅在铸造之后才开始进行这种接触。出于实际原因,与含氧流体的接触优选仅在从模具中取出之后开始,优选在从模具中取出之后尽可能早地开始。
含氧流体优选包含按体积计至少20%的氧。
优选地,保持与含氧流体的接触,直到块完全固化为止。
在步骤c3')中,将块从模具中移出。为了促进液体物质与含氧流体接触,优选在完全固化之前,尽可能快地从模具中取出块。因此,固化然后在步骤c3')中继续。
优选地,一旦块具有足够的刚度以基本上保持其形状,就将其从模具中取出,然后立即开始与含氧流体接触。
在完全固化之后,在步骤d)之后获得能够提供根据本发明的颗粒粉末的块。
在任选的步骤d)中,将获得的熔合产品压碎和/或研磨以减小碎片的尺寸,优选直至中值粒度D50小于4mm,小于3mm,小于2mm,小于1mm,小于0.5mm,小于0.25mm,小于0.1mm,和优选大于0.1μm的熔合颗粒粉末为止。
可以使用所有类型的破碎机和研磨机来减小碎块的尺寸。特别地,当寻求具有小于1μm的中值粒度D50的熔合颗粒的粉末时,在空气喷射磨机或球磨机中进行了第一研磨操作之后,可以使用碾磨机。优选地,当在湿介质中进行研磨时,不使用水。优选地,使用醇,优选地,乙醇和/或丙醇。
当寻求中值粒度D50大于1μm的熔合颗粒粉末时,优选使用空气喷射研磨机或球磨机。
然后根据需要的用途,例如通过筛分,特别是通过筛分来进行粒度选择,使得所获得的颗粒粉末尤其具有大于0.1μm且小于4mm的中值粒度。
熔合颗粒的粉末还可以经历,特别是在步骤d)之后,用于形成喷雾干燥的颗粒,附聚物或聚集体的另外的步骤。
可以使用本领域技术人员已知的所有技术,特别是浆料或造粒的喷雾干燥。
根据本发明的产品,特别是根据本发明的方法制备的产品,可以具有以下一种或多种特征的组成:
-优选地,钙铁石相的含量,即一个或多个钙铁石相的重量百分比基于熔合产品中存在的所有结晶相,大于50%,优选地大于55%,优选地大于60%,优选大于70%,优选大于80%,优选大于85%,或者甚至大于90%,或者甚至大于95%,或者甚至大于98%;
- 优选, y ≥ 0.8, 优选 y ≥ 0.85, 优选 y ≥ 0.9 和/或 y ≤ 1.05, 优选y ≤ 1;
- 优选, z ≤ 0.2, 优选 z ≤ 0.15, 优选 z ≤ 0.1 和/或 z ≥ 0.01;
- 在一个实施方案中, z = 0;
- 优选, y + z ≤ 1.1, 优选 y + z ≤ 1.05;
- 优选, t ≥ 0.5, 优选 t ≥ 0.55, 优选 t ≥ 0.6, 优选 t ≥ 0.65, 优选t ≥ 0.7, 优选 t ≥ 0.75, 优选 t ≥ 0.8, 优选 t ≥ 0.85, 优选 t ≥ 0.90, 和/或 t ≤ 1.05, 优选 t ≤ 1;
- 优选 u ≤ 0.5, 优选 u ≤ 0.45, 优选 u ≤ 0.4, 优选 u ≤ 0.35, 优选u ≤ 0.3, 优选 u ≤ 0.25, 优选 u ≤ 0.2, 优选 u ≤ 0.15, 优选 u ≤ 0.1, 优选u ≤ 0.08, 优选 u ≤ 0.05 和/或 u ≥ 0.01;
- 在一个实施方案中, u = 0;
- 在一个实施方案中, z = 0 和u = 0;
优选, t + u ≤ 1.1, 优选 t + u ≤ 1.05;
-优选地,X = Ca(1-x)Srx,其中0≤x≤1。优选地,x≤0.1,优选地x≤0.05,有利地改善钙铁石相的稳定性,特别是在催化过程中使用,或优选x≥0.9,优选x≥0.95,有利地提高了其催化性能。在一个实施方案中,0 <x <1。在另一个替换实施方案中,x = 0。在另一个实施方案中,x = 1;
-在一个特定的实施方案中,元素M的总原子比例z的大于80%,优选大于85%,优选大于90%,优选大于95%由单一原子物种组成;
- 优选地,元素M'选自Ti, Cu, Ni, Co, Mn及其混合物;
- 优选地,Ti和Cu的原子指数之和小于或等于0.08,优选地小于或等于0.07,优选地小于或等于0.05;
-在一个具体实施方案中,元素M'的总原子比例u的大于80%,优选大于85%,优选大于90%由一种或两种原子种类组成,优选仅由一种原子种类组成;
- 优选地,除Ca, Sr, Fe, M, M'和O以外的元素的总重量含量小于4%,优选小于3%,优选小于2%,优选小于1%,优选小于0.7%,优选小于0.4%,基于产品重量百分比计;
- 在一个实施方案中, x=0, y=1, z=0, t=1 和u= 0;
- 在一个实施方案中,x=1, y=1, z=0, t=1 和u= 0;
- 在一个实施方案中,0<x<1, y=1, z=0, t=1 和u=0。
可将M和/或M'引入待熔融的起始原料中,作为起始原料中痕量。原子指数z和u考虑了这些加入。
在一个特定实施方案中:
- x ≤ 0.1, 优选x ≤ 0.05, 和x > 0, 和
- y ≥ 0.9 和y ≤ 1.05, 优选y ≤ 1, 和
- z ≤ 0.1 和z ≥ 0.01, 和
- y + z ≤ 1.1, 优选y + z ≤ 1.05, 和
- t ≥ 0.8, 优选t ≥ 0.85, 优选t ≥ 0.90 和t ≤ 1.05, 优选t ≤ 1, 和
- u ≤ 0.2, 优选u ≤ 0.15, 优选u ≤ 0.1, 优选u ≤ 0.08, 优选u ≤0.07, 优选u ≤ 0.05 和u ≥ 0.01, 和
- t + u ≤ 1.1, 优选y + z ≤ 1.05,并且
- 除了Ca, Sr, Fe, M, M'和O之外的元素的总重量含量小于3%,优选小于2%,优选小于1%,优选小于0.7%,优选小于0.4%,基于产品重量百分比计。
在一个特定实施方案中:
- x = 0, 和
- y ≥ 0.9 和y ≤ 1.05, 优选y ≤ 1, 和
- z ≤ 0.1 和z ≥ 0.01, 和
- y + z ≤ 1.1, 优选y + z ≤ 1.05, 和
- t ≥ 0.8, 优选t ≥ 0.85, 优选t ≥ 0.90 和t ≤ 1.05, 优选t ≤ 1, 和
- u ≤ 0.2, 优选u ≤ 0.15, 优选u ≤ 0.1, 优选u ≤ 0.08, 优选u ≤0.07, 优选u ≤ 0.05 和u ≥ 0.01, 和
- t + u ≤ 1.1, 优选y + z ≤ 1.05,并且
- 除了Ca, Sr, Fe, M, M'和O以外的元素的总重量含量小于3%,优选小于2%,优选小于1%,优选小于0.7%,优选小于0.4%,基于产品重量百分比计。
在一个特定实施方案中:
- x≥0.9,优选x≥0.95,和
- y≥0.9且y≤1.05,优选y≤1,和
- z≤0.1和z≥0.01,以及
- y + z≤1.1,最好y + z≤1.05,以及
- t≥0.8,优选t≥0.85,优选t≥0.90且t≤1.05,优选t≤1,和
- u≤0.2,优选地u≤0.15,优选地u≤0.1,优选地u≤0.08,优选地u≤0.07,优选地u≤0.05和u≥0.01,和
- t + u≤1.1,最好y + z≤1.05,并且
- 除了Ca,Sr,Fe,M,M′和O以外的元素的总重量含量小于3%,优选小于2%,优选小于1%,优选小于0.7%,优选小于0.4%,基于产品重量百分比计。
在一个特定实施方案中:
- x = 1,并且
- y≥0.9且y≤1.05,优选y≤1,和
- z≤0.1和z≥0.01,以及
- y + z≤1.1,最好y + z≤1.05,以及
- t≥0.8,优选t≥0.85,优选t≥0.90且t≤1.05,优选t≤1,和
- u≤0.2,优选地u≤0.15,优选地u≤0.1,优选地u≤0.08,优选地u≤0.07,优选地u≤0.05和u≥0.01,和
- t + u≤1.1,最好y + z≤1.05,并且
- 除了Ca,Sr,Fe,M,M′和O以外的元素的总重量含量小于3%,优选小于2%,优选小于1%,优选小于0.7%,优选小于0.4%,基于产品重量百分比计。
根据本发明的熔合产品的原子指数的测定以下列方式进行:
除氧以外的各元素的重量含量通过化学分析来测定。氧的重量含量Qo被认为构成了100%的剩余部分。Ca,Sr,Fe,M和M'以外的元素(如果存在)以其最稳定的氧化物形式表示,如果不是,或以元素形式表示。例如,钠的量以Na2O的形式表示,和氯或氟的量分别等于Cl或F的重量含量。从氧的重量含量Qo中减去以最稳定的氧化物Q'o的形式表示除Ca,Sr,Fe,M和M'以外的元素的重量含量所需的氧量。Qo-Q'o和Ca,Sr,Fe,M和M'的重量含量转换为摩尔数。 Qo-Q'o的摩尔数标准化为2.5。Ca,Sr,Fe,M和M'的摩尔数乘以允许所述标准化为2.5的因子,这使得可以确定式[Ca(1-x)Srx]yMzFetM'uO2.5的指数x, y, z, t和u。
根据本发明的熔合产品可以有利地具有变化的尺寸。因此,它非常适合工业生产。
根据本发明的产品可以特别地为颗粒形式。
本发明还涉及一种粉末,其包含按重量计大于90%,或甚至大于95%,或甚至基本上100%的颗粒,作为根据本发明的产品。粉末的中值粒度优选大于0.1μm和/或小于4mm,小于3mm,小于2mm,小于1mm,小于0.5mm,小于0.25mm,小于0.1mm。
在一个特定的实施方案中,粉末的中值粒度在0.5μm至50μm之间。
在一个实施方案中,根据本发明的粉末包括喷雾干燥的材料,其通常为颗粒形式,和/或根据本发明的颗粒的聚集体和/或附聚物。
根据本发明的产品,特别是粉末形式的产品,或通过本发明的方法制备或可以通过本发明的方法制备的产品可以有利地用于制备氧气分离膜,催化膜,用于固体氧化物燃料电池的电极,催化剂载体,催化剂。
实施例
给出以下实施例仅用于说明目的,并不限制本发明。
作为比较例的实施例1和2的产品以下列方式化学制备。
对于实施例1和2中的每一个,将下表1中定义的盐的混合物引入蒸馏水中,并且通过添加无水柠檬酸将pH保持在1以下。
实施例 | Ca(NO<sub>3</sub>)<sub>2</sub>.4H<sub>2</sub>O | Sr(NO<sub>3</sub>)<sub>2</sub> | Fe(NO<sub>3</sub>)<sub>3</sub>.9H<sub>2</sub>O |
1(*) | 1.76 | - | 3.04 |
2(*) | - | 1.15 | 2.20 |
(*): 本发明范围之外
表1。
在使用磁力搅拌器搅拌3小时后,通过添加氨水使pH达到等于3的值,然后使混合物达到110℃以蒸发掉水。当凝胶开始形成时,加入1 ml乙二醇。在使用磁力搅拌器搅拌30分钟之后,通过加热板将形成的凝胶在等于370℃的温度下保持该温度等于2小时。然后将如此获得的粉末在空气中在电炉中于600℃下煅烧6小时,升温速率达到该温度等于100℃/h。
实施例3和4的熔合产品以下列方式制备。
首先在混合机中充分混合以下初始的起始材料:
-对于实施例3和4,一种氧化铁粉末,其包含大于99重量%的Fe2O3,其中值粒度等于0.34μm;
-对于实施例3,一种粉末,其包含按重量计大于99%的碳酸钙CaCO3,其中值粒度等于1.85μm;
-对于实施例4,一种粉末,其包含按重量计大于99%的碳酸锶SrCO3,其中值粒度等于4.3μm。
对于实施例3和实施例4,在下表2中定义起始原料,以重量百分比计:
实施例 | CaCO<sub>3</sub> | SrCO<sub>3</sub> | Fe<sub>2</sub>O<sub>3</sub> |
3 | 55.6 | - | 44.4 |
4 | - | 64.9 | 35.1 |
表2。
对于每个实施例,将重量为5kg的起始原料倒入Heroult电弧熔融炉中。然后根据熔融以120伏的电压和基本上等于2000kWh/T的施加能量将其熔融,以完全均匀地熔融所有混合物。
然后,当熔融完成时,将熔融液体铸造以形成细流。
在环境温度和3 bar的超压下吹入压缩的干燥空气,使细流破裂并将熔融液体分散成液滴。
吹气冷却了这些液滴并将它们凝结成熔合颗粒的形式。
实施例3和4的熔合颗粒被容纳在容器中。
对在1000℃下2小时的煅烧样品进行化学分析。
通过X射线荧光对要分析的产品的珠子进行化学分析,该产品是通过将所述产品与硼酸锂熔合而制备。
在干磨后,中值粒度小于40 µm的样品进行钙铁石相含量的测定。
比表面积通过在《美国化学学会杂志》 (Journal of American ChemicalSociety 60 (1938), pages 309 to 316)中所述的BET(Brunauer Emmet Teller)方法进行测量。
使用Horiba公司的Partica LA-950激光粒度分析仪测量中值粒度。
下表3和表4总结了获得的结果。
(*): 本发明范围之外
表3
实施例 | 钙铁石相含量 | 次生相 |
1(*) | 95 | CaO / Fe<sub>2</sub>O<sub>3</sub> / CaCO<sub>3</sub> |
2(*) | 43 | SrFeO<sub>2.75</sub> / SrFeO<sub>2.875</sub> / SrCO<sub>3</sub> / Fe |
3 | 97 | Fe<sub>2</sub>O<sub>3</sub> / FeO / Fe |
4 | 58 | SrFeO<sub>2.75</sub> / SrFeO<sub>2.875</sub> / SrCO<sub>3</sub> / Fe |
(*): 本发明范围之外
表4。
实施例3和4的产品的X射线衍射图在低角度下没有显示出非晶相存在的光晕(halo)特性。
然后将实施例的产品在广口瓶研磨机中以等于60 rpm的转速研磨72小时,广口瓶的体积等于0.9升,向其中引入1.4千克掺有3重量%MgO的氧化锆制成的圆珠(cylpebs),其具有等于12.7mm的尺寸,和650g实施例的产品。分离圆珠后,然后将40 g回收的粉末在减磨机中以1000 rpm的速度研磨75分钟,该罐的体积等于0.89升,还包含680 g的3 mol%钇稳的氧化锆的珠(680 g of beads of zirconia yttriated at 3 mol%),其中值粒度等于0.8毫米,以及200毫升异丙醇。下表5总结了所得粉末的特性。
实施例 | 中值粒度 (µm) | 比表面积 (m<sup>2</sup>/g) |
1(*) | 0.56 | 12 |
2(*) | 0.56 | 13 |
3 | 1.2 | <1 |
4 | 1 | <1 |
(*): 本发明范围之外
表5。
在本发明之外以及在本发明之外的实施例1和2的粉末以及根据本发明的实施例3和4的粉末被用于制备催化体系中作为催化剂载体,铂被用作催化剂,铂的重量基本上等于0.99重量%,基于催化剂载体和铂的重量。
通过用硝酸铂Pt(NO3)2溶液浸渍每个实施例的粉末来进行催化体系的制备。该方法易于实施,是本领域技术人员众所周知的。将粉末悬浮在硝酸铂溶液中后,将其在环境温度下于超声浴中放置30分钟。将各种浸渍的粉末在旋转蒸发仪中于47℃在130 mbar的压力下干燥3小时。然后将浸渍过的各种粉末在空气中于500℃下煅烧,该温度下保持时间等于2小时,升温速率等于10℃/min,下降速率不受控制。
煅烧后,将粉末在手压机上压实以形成粒料。然后用研杵和研钵将沉淀粉碎,将得到的粉末过筛,以回收相应的催化体系,该体系对应于未通过筛孔等于125 µm的方形孔筛的粉末部分,并通过筛孔为方形的筛子,筛孔等于250 µm。
然后,在石英固定床流通式开放式反应器中,在大气压下,对每个催化***进行一氧化碳氧化为二氧化碳的反应(CO + ½ O2 → CO2)的催化测试根据下列步骤:将200 mg催化体系(在本例中,实施例1 *,2 *,3和4的粉末用铂浸渍)中放入反应器中。减少粉末的第一步是在一个循环中注入10 l/h的40%氢气和60%体积氩气的混合物流,循环具有的升温速率等于10℃/min,直至温度等于300℃并在此温度下保持1小时。在氦气下以炉子的惯性速率降低温度至环境温度。
进行第一个催化循环,包括以等于2℃/min的速率增加到等于350℃的温度,在350℃保持10分钟,然后在氦气下以反应器的惯性速率降低温度至环境温度。在升温和固定在350℃的过程中,将6000 ppm的CO和10000 ppm的稀释在氦气中的氧气的反应混合物以等于10 l/h的总流速注入到反应器中。降温是在氦气下进行的,氦气流量等于1 l/h。
一氧化碳到二氧化碳的转化率,以%表示,定义为已反应的一氧化碳的量与引入反应器中的一氧化碳的量的比,已反应的一氧化碳的量等于引入反应器中的一氧化碳的量减去离开反应器的未反应的一氧化碳的量。在整个催化循环中,通过装有热导检测器的微型气相色谱仪(配备有两个平行柱)以每235秒采样的速率对离开反应器的未反应一氧化碳的量和离开反应器的二氧化碳的量进行测量。
在相同条件下进行第二催化循环,然后进行第三催化循环。
下表6将获得的结果分组在一起:
在催化***中用作催化剂载体的粉末 | 在第一循环中达到一氧化碳向二氧化碳的转化率等于50%的温度(℃) | 在第三循环中达到一氧化碳向二氧化碳的转化率等于50%的温度(℃) |
Ex1(*) | 221 | 240 |
Ex2(*) | 202 | 247 |
Ex3 | 187 | 201 |
Ex4 | 197 | 196 |
(*): 本发明范围之外对比实施例
表 6。
X = Ca的实施例1(本发明之外)和实施例3(根据本发明)的比较显示,关于在第一循环中达到一氧化碳向二氧化碳的转化率等于50%的温度,对于实施例3为187℃和对于实施例1为221℃,在第三循环中达到一氧化碳向二氧化碳的转化率等于50%的温度,对于实施例3为201℃和对于实施例1为240℃。
X = Sr的实施例2(本发明之外)和实施例4(根据本发明)的比较显示,关于在第一循环中达到一氧化碳向二氧化碳的转化率等于50%的温度,对于实施例4为197℃和对于实施例2为202℃,在第三循环中达到一氧化碳向二氧化碳的转化率等于50%的温度,对于实施例4为196℃和对于实施例2为247℃。
这些结果表明,在较低的温度下,通过由衍生自根据本发明的多晶熔合产品的粉末得到的催化体系,可以实现一氧化碳向二氧化碳的高转化率,因此相对于比本发明之外的实施例的粉末更低的温度下可以得到非常好的转化率。
如目前明显可知,根据本发明的粉末可以改善催化性能。
当然,本发明不限于通过说明性和非限制性示例提供的所描述的实施例。
特别地,对于本领域技术人员而言显而易见的是,如上所述,将根据本发明的另一种阳离子元素M和/或M'引入所述结构,将产生与上述那些相同的催化性能,条件是所获得的熔合产品保持该相同的钙铁石结构。
Claims (17)
1.基于钙铁石的多晶熔合产品,其重量的95%以上由元素Ca,Sr,Fe,O,M和M'组成,所述元素的含量由式XyMzFetM’uO2.5定义,其中原子指数使得0.76 ≤ y ≤ 1.10, z ≤0.21, 0.48 ≤ t ≤ 1.10和u ≤ 0.52, 0.95 ≤ y + z ≤ 1.10,和0.95 ≤ t + u ≤1.10,X为Ca或Sr或Ca和Sr的混合物,M选自元素La、Ba及其混合物,M'选自元素Ti、Cu、Gd、Mn、Al、Sc、Ga、Mg、Ni、Zn、Pr、In、Co及其混合物,Ti和Cu的原子指数之和小于或等于0.1。
2.根据权利要求1所述的熔合产品,其中0.85 ≤ y ≤ 1.05和/或z ≤ 0.15和/或0.75 ≤ t ≤ 1.05和/或u ≤ 0.25。
3.根据前述权利要求中任一项所述的熔合产品,其中,所述钙铁石相的含量大于50%。
4.根据前述权利要求中任一项所述的熔合产品,其中z = 0。
5.根据前述权利要求中任一项所述的熔合产品,其中,u = 0。
6.根据前述权利要求中任一项所述的熔合产品,其中z = 0且u = 0。
7.根据权利要求1至4中任一项所述的熔合产品,其中,所述元素M'选自Ti、Cu、Ni、Co、Mn及其混合物。
8.根据权利要求1至3和7中任一项所述的熔合产品,其式为XyMzFetM'uO2.5,其中,如果x表示式 (Ca(1-x)Srx)yMzFetM'uO2.5中Sr的比例且(1-x)表示Ca的相对比例,0 < x ≤ 0.1,0.9 ≤ y ≤ 1.05, 0.1≥ z ≥ 0.01, y + z ≤ 1.1, t ≥ 0.8, 0.01 ≤ u ≤ 0.2,t + u ≤ 1.1,以及除Ca,Sr,Fe,M,M'和O以外的元素的总重量含量小于3%,以基于产品重量的百分比计。
9.根据权利要求1至3和7之一所述的熔合产品,其式为XyMzFetM'uO2.5,其中,如果x表示式(Ca(1-x)Srx)yMzFetM'uO2.5中Sr的比例且(1-x)表示Ca的相对比例,x = 0, 0.9 ≤ y ≤1.05, 0.1≥ z ≥ 0.01, y + z ≤ 1.1, t ≥ 0.8, 0.01 ≤ u ≤ 0.2, t + u ≤1.1,以及除了Ca,Sr,Fe,M,M'和O以外的元素的总重量含量小于3%,以基于产品重量的百分比计。
10.根据权利要求1至3和7之一所述的熔合产品,其中,如果x表示式(Ca(1-x)Srx)yMzFetM'uO2.5中Sr的比例且(1-x)表示Ca的相对比例,1 > x ≥ 0.9, 0.9 ≤ y ≤ 1.05,0.1≥ z ≥ 0.01, y + z ≤ 1.1, t ≥ 0.8, 0.01 ≤ u ≤ 0.2, t + u ≤ 1.1,以及除了Ca,Sr,Fe,M,M'和O以外的元素的总重量含量小于3%,以基于产品重量的百分比计。
11.根据权利要求1至3和7之一所述的熔合产品,其中,如果x表示式(Ca(1-x)Srx)yMzFetM'uO2.5中Sr的比例和和(1-x)表示Ca的相对比例,x = 1, 0.9 ≤ y ≤ 1.05, 0.1≥z ≥ 0.01, y + z ≤ 1.1, t ≥ 0.8, 0.01 ≤ u ≤ 0.2, t + u ≤ 1.1,以及除了Ca,Sr,Fe,M,M'和O以外的元素的总重量含量小于3%,以基于产品重量的百分比计。
12.粉末,包含大于90重量%的在前述权利要求中任一项所述的熔合产品中的颗粒。
13.根据前述权利要求所述的粉末,其中值粒度D50大于0.1μm且小于4mm。
14.根据权利要求1至11中任一项所述的制备熔合产品的方法,其包括以下步骤:
a. 混合起始材料,以形成适合在步骤c)结束时获得本发明所述产品的起始原料,
b. 熔融起始原料,直到获得液体物质为止,
c. 冷却直至所述液体物质完全固化,从而获得本发明所要求的熔合产品。
15.催化载体或催化剂,其包含下述物质或由下述物质组成:权利要求1至11中任一项所述的熔合产品,或权利要求12至13中任一项所述的粉末或通过权利要求14所述方法制备的产品。
16.氧分离膜,该氧分离膜包含下述物质或由下述物质组成:权利要求1至11中任一项所述的熔合产品,或权利要求12至13中任一项所述的粉末,或通过权利要求14所述方法制备的产品。
17.用于固体氧化物燃料电池SOFC的电极,其包含下述物质或由下述物质组成:权利要求1至11中任一项所述的熔合产品,或权利要求12至13中任一项所述的粉末,或通过权利要求14所述方法制备的产品。
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