CN114477298A - Composite oxide and preparation method and application thereof - Google Patents
Composite oxide and preparation method and application thereof Download PDFInfo
- Publication number
- CN114477298A CN114477298A CN202011162004.1A CN202011162004A CN114477298A CN 114477298 A CN114477298 A CN 114477298A CN 202011162004 A CN202011162004 A CN 202011162004A CN 114477298 A CN114477298 A CN 114477298A
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- Prior art keywords
- composite oxide
- source
- oxide
- reaction
- acid salt
- Prior art date
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- 239000002131 composite material Substances 0.000 title claims abstract description 80
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- 238000006243 chemical reaction Methods 0.000 claims abstract description 49
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 41
- 239000001257 hydrogen Substances 0.000 claims abstract description 41
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 41
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 38
- 239000001301 oxygen Substances 0.000 claims abstract description 38
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 38
- 238000004519 manufacturing process Methods 0.000 claims abstract description 30
- 239000000203 mixture Substances 0.000 claims abstract description 17
- 239000000126 substance Substances 0.000 claims abstract description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 36
- 238000000034 method Methods 0.000 claims description 29
- -1 inorganic acid salt Chemical class 0.000 claims description 25
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical group O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 16
- 238000003756 stirring Methods 0.000 claims description 16
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 13
- 229910052593 corundum Inorganic materials 0.000 claims description 13
- 239000000446 fuel Substances 0.000 claims description 13
- 229910001845 yogo sapphire Inorganic materials 0.000 claims description 13
- 238000002485 combustion reaction Methods 0.000 claims description 12
- 238000002156 mixing Methods 0.000 claims description 12
- 229910017970 MgO-SiO2 Inorganic materials 0.000 claims description 11
- 229910052681 coesite Inorganic materials 0.000 claims description 10
- 229910052906 cristobalite Inorganic materials 0.000 claims description 10
- 239000000377 silicon dioxide Substances 0.000 claims description 10
- 229910052682 stishovite Inorganic materials 0.000 claims description 10
- 229910052905 tridymite Inorganic materials 0.000 claims description 10
- 229910003112 MgO-Al2O3 Inorganic materials 0.000 claims description 8
- 239000007864 aqueous solution Substances 0.000 claims description 8
- 239000003054 catalyst Substances 0.000 claims description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims description 4
- 230000035484 reaction time Effects 0.000 claims description 4
- 229910002974 CaO–SiO2 Inorganic materials 0.000 claims description 3
- 229910002651 NO3 Inorganic materials 0.000 claims description 3
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 3
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 2
- 239000004449 solid propellant Substances 0.000 claims description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims 3
- 230000000694 effects Effects 0.000 abstract description 4
- 238000001035 drying Methods 0.000 description 57
- 239000010936 titanium Substances 0.000 description 33
- 239000008367 deionised water Substances 0.000 description 26
- 229910021641 deionized water Inorganic materials 0.000 description 26
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 22
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 description 22
- 239000002002 slurry Substances 0.000 description 18
- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium(3+);trinitrate Chemical compound [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 description 16
- 238000001914 filtration Methods 0.000 description 15
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 14
- 235000011114 ammonium hydroxide Nutrition 0.000 description 14
- 230000007935 neutral effect Effects 0.000 description 14
- 239000000243 solution Substances 0.000 description 14
- 230000032683 aging Effects 0.000 description 13
- 238000010438 heat treatment Methods 0.000 description 13
- 238000001556 precipitation Methods 0.000 description 13
- 238000005406 washing Methods 0.000 description 13
- 238000005303 weighing Methods 0.000 description 13
- 239000000463 material Substances 0.000 description 10
- DCKVFVYPWDKYDN-UHFFFAOYSA-L oxygen(2-);titanium(4+);sulfate Chemical compound [O-2].[Ti+4].[O-]S([O-])(=O)=O DCKVFVYPWDKYDN-UHFFFAOYSA-L 0.000 description 9
- 238000006722 reduction reaction Methods 0.000 description 9
- 229910000348 titanium sulfate Inorganic materials 0.000 description 9
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 8
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 8
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 6
- 238000001354 calcination Methods 0.000 description 6
- 229910002092 carbon dioxide Inorganic materials 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 6
- YIXJRHPUWRPCBB-UHFFFAOYSA-N magnesium nitrate Chemical compound [Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O YIXJRHPUWRPCBB-UHFFFAOYSA-N 0.000 description 6
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 5
- SFBLKWGYRDDITM-UHFFFAOYSA-J [Ti+4].[O-]S([O-])=O.[O-]S([O-])=O Chemical compound [Ti+4].[O-]S([O-])=O.[O-]S([O-])=O SFBLKWGYRDDITM-UHFFFAOYSA-J 0.000 description 5
- 239000007789 gas Substances 0.000 description 5
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 4
- ZCCIPPOKBCJFDN-UHFFFAOYSA-N calcium nitrate Chemical compound [Ca+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ZCCIPPOKBCJFDN-UHFFFAOYSA-N 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- 239000001569 carbon dioxide Substances 0.000 description 4
- 239000000969 carrier Substances 0.000 description 4
- VGBWDOLBWVJTRZ-UHFFFAOYSA-K cerium(3+);triacetate Chemical compound [Ce+3].CC([O-])=O.CC([O-])=O.CC([O-])=O VGBWDOLBWVJTRZ-UHFFFAOYSA-K 0.000 description 4
- 239000003245 coal Substances 0.000 description 4
- 230000018044 dehydration Effects 0.000 description 4
- 238000006297 dehydration reaction Methods 0.000 description 4
- PVFSDGKDKFSOTB-UHFFFAOYSA-K iron(3+);triacetate Chemical compound [Fe+3].CC([O-])=O.CC([O-])=O.CC([O-])=O PVFSDGKDKFSOTB-UHFFFAOYSA-K 0.000 description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 3
- 239000004115 Sodium Silicate Substances 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 description 3
- 238000000975 co-precipitation Methods 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 230000007547 defect Effects 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- 238000002309 gasification Methods 0.000 description 3
- 150000004677 hydrates Chemical class 0.000 description 3
- 229910052742 iron Inorganic materials 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002243 precursor Substances 0.000 description 3
- 238000000746 purification Methods 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 230000009257 reactivity Effects 0.000 description 3
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 3
- 229910052911 sodium silicate Inorganic materials 0.000 description 3
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 description 2
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 2
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 2
- 159000000021 acetate salts Chemical class 0.000 description 2
- 238000007605 air drying Methods 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 230000001351 cycling effect Effects 0.000 description 2
- 239000002737 fuel gas Substances 0.000 description 2
- 239000000499 gel Substances 0.000 description 2
- 239000005431 greenhouse gas Substances 0.000 description 2
- 150000004679 hydroxides Chemical class 0.000 description 2
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 239000003345 natural gas Substances 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 238000007493 shaping process Methods 0.000 description 2
- 239000000725 suspension Substances 0.000 description 2
- 229940073455 tetraethylammonium hydroxide Drugs 0.000 description 2
- LRGJRHZIDJQFCL-UHFFFAOYSA-M tetraethylazanium;hydroxide Chemical compound [OH-].CC[N+](CC)(CC)CC LRGJRHZIDJQFCL-UHFFFAOYSA-M 0.000 description 2
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 2
- 238000004846 x-ray emission Methods 0.000 description 2
- FJLUATLTXUNBOT-UHFFFAOYSA-N 1-Hexadecylamine Chemical compound CCCCCCCCCCCCCCCCN FJLUATLTXUNBOT-UHFFFAOYSA-N 0.000 description 1
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonium chloride Substances [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 1
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 1
- 229910052684 Cerium Inorganic materials 0.000 description 1
- 239000006004 Quartz sand Substances 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- 150000001242 acetic acid derivatives Chemical class 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000004480 active ingredient Substances 0.000 description 1
- SMZOGRDCAXLAAR-UHFFFAOYSA-N aluminium isopropoxide Chemical compound [Al+3].CC(C)[O-].CC(C)[O-].CC(C)[O-] SMZOGRDCAXLAAR-UHFFFAOYSA-N 0.000 description 1
- 229940115440 aluminum sodium silicate Drugs 0.000 description 1
- VXAUWWUXCIMFIM-UHFFFAOYSA-M aluminum;oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Al+3] VXAUWWUXCIMFIM-UHFFFAOYSA-M 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 229910052925 anhydrite Inorganic materials 0.000 description 1
- 238000001636 atomic emission spectroscopy Methods 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052793 cadmium Inorganic materials 0.000 description 1
- 239000001110 calcium chloride Substances 0.000 description 1
- 229910001628 calcium chloride Inorganic materials 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- ZMIGMASIKSOYAM-UHFFFAOYSA-N cerium Chemical compound [Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce] ZMIGMASIKSOYAM-UHFFFAOYSA-N 0.000 description 1
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 238000005049 combustion synthesis Methods 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 238000005469 granulation Methods 0.000 description 1
- 230000003179 granulation Effects 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 238000005216 hydrothermal crystallization Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 229910052746 lanthanum Inorganic materials 0.000 description 1
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 229910001629 magnesium chloride Inorganic materials 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 150000002823 nitrates Chemical class 0.000 description 1
- 229910052755 nonmetal Inorganic materials 0.000 description 1
- 238000000643 oven drying Methods 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 238000003980 solgel method Methods 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000001694 spray drying Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G49/00—Compounds of iron
- C01G49/009—Compounds containing, besides iron, two or more other elements, with the exception of oxygen or hydrogen
-
- 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
- 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
-
- 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
- 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
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/03—Precipitation; Co-precipitation
- B01J37/031—Precipitation
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/082—Decomposition and pyrolysis
-
- 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
- C01B3/40—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 characterised by the catalyst
-
- 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
- B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/10—Catalysts for performing the hydrogen forming reactions
- C01B2203/1041—Composition of the catalyst
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/10—Catalysts for performing the hydrogen forming reactions
- C01B2203/1041—Composition of the catalyst
- C01B2203/1082—Composition of support materials
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/12—Feeding the process for making hydrogen or synthesis gas
- C01B2203/1205—Composition of the feed
- C01B2203/1211—Organic compounds or organic mixtures used in the process for making hydrogen or synthesis gas
- C01B2203/1235—Hydrocarbons
- C01B2203/1241—Natural gas or methane
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
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Abstract
The invention discloses a composite oxide and a preparation method and application thereof. The formula CeFe for the composition of the composite oxidexTiyOδ‑αWherein x =5 to 35, y =1 to 25, and δ is a positive number representing a value at which oxygen in the composite oxide reaches a valence equilibrium, and α =0 to δ/2. The method for producing a composite oxide includes a step of bringing a Ce source, an Fe source, and a Ti source into contact with each other to cause a reaction, thereby obtaining a composite oxide. The composite oxide used as an oxygen carrier for chemical looping hydrogen production has the advantages of high activity, good stability, high hydrogen yield and the like.
Description
Technical Field
The invention relates to a composite oxide, a preparation method and application thereof, in particular to a composite oxide, a preparation method and application thereof in chemical-looping combustion.
Background
At present, the industrial large-scale hydrogen production method mainly comprises the hydrogen production by natural gas steam conversion and the hydrogen production by coal gasification. The hydrogen production by natural gas steam conversion is a strong endothermic reaction, part of fuel is required to be combusted to provide heat energy required by the reaction, the reaction is generally carried out in a tubular reactor (or a conversion tube), the hydrogen production efficiency of unit volume is low, a large-scale device needs to be built, and the equipment investment is high; the coal gasification hydrogen production is that crude synthesis gas obtained after partial oxidation and gasification of coal is subjected to shift reaction to obtain shift gas with high hydrogen content, and then the shift gas is subjected to acid gas removal and purification, and then hydrogen purification is carried out to obtain industrial hydrogen. Hydrogen purification often employs a pressure swing adsorption process, which results in a partial loss of hydrogen. The carbon in the raw material of the hydrogen production process is finally CO2And (3) the hydrogen is discharged in a form, a large amount of carbon dioxide is mixed in the discharged gas in the hydrogen production by steam conversion and the hydrogen production by coal, and the condition is provided for CCS after the carbon dioxide is not separated easily. The development direction of large-scale hydrogen production technology in the future is a novel hydrogen production method with the characteristics of high efficiency, high hydrogen purity and greenhouse gas emission reduction effect.
The chemical ring hydrogen production technology is a novel and environment-friendly green hydrogen production technology, and is a hydrogen production technology which utilizes oxygen atoms in an oxygen carrier to replace oxygen to oxidize fuel and produce hydrogen at the same time. It uses oxidation-reduction reaction as principle, selects proper oxygen carrier to implement hydrogen preparation between two reactors alternatively and circularly, and the oxygen carrier can be reacted with fuel of methane and CO to produce CO in fuel reactor2And water vapor, and carbon dioxide can be enriched by condensation and dehydration; in the oxidation reactor, the oxygen carrier is oxidized by water vapor and hydrogen is released. The method is a new environment-friendly technology for capturing carbon dioxide and producing hydrogen, and has great significance for solving the increasingly prominent greenhouse gas emission problem and preparing hydrogen as a clean energy source. Oxygen carriers and reactors are the key points for chemical looping hydrogen production. The oxygen carrier generally adopts iron oxide as an active component, the iron oxide is loaded on a carrier, and the problem of carbon deposition caused by the reaction of the iron oxide and carbon-containing fuel at high temperature is seriousThis aspect has yet to be intensively studied in terms of carbon capture efficiency and hydrogen production efficiency.
CN106669685A discloses an oxygen carrier and a preparation method and application thereof. The preparation method comprises the following steps: (1) NaAlO is added2Mixing NaOH, silica gel, Cetyl Trimethyl Ammonium Bromide (CTAB), isomeric hexadecylamine (CA), tetraethyl ammonium hydroxide (TEAOH) and water according to a certain proportion to form gel, and carrying out hydrothermal crystallization, drying and roasting on a gel system to obtain a material A; (2) dispersing the material A prepared in the step (1) in distilled water to prepare a suspension, adding titanium dioxide sol into the suspension, and filtering, drying and roasting to prepare a carrier; (3) and (3) loading lanthanum and/or cerium, nickel and/or cobalt on the carrier prepared in the carrier step (2) to prepare the oxygen carrier.
CN103374431A discloses an oxygen carrier which is CeO2-Al2O3As carrier, NiO as active component, and CeO as carrier2-Al2O3CeO in2Wrapping in Al2O3Surface of (C) CeO2The content of the active component NiO in the oxygen carrier is 1-20%, preferably 1-10% by weight of the final oxygen carrier, and the pore diameter of the oxygen carrier is 10-100 nm.
CN102382706A TiO with cavity structure2As a carrier, Fe2O3As an active ingredient, TiO2Support and Fe2O3The mass percentage of the active components is 50-95% and 5-50%.
CN101486941A provides a method for preparing an iron-based oxygen carrier, which organically combines a sol-gel method and a combustion synthesis method by taking iron and aluminum nitrate as raw materials and urea as fuel to prepare nano-scale Fe with excellent sintering resistance2O3/Al2O3An oxygen carrier.
Oxygen carrier as medium is circulated between two reactors to continuously transfer oxygen in air (water vapor) reactor and heat generated by reaction to fuel reactor for reduction reactionThe nature of the body directly affects the operation of the entire chemical looping combustion/hydrogen production. Thus, high performance oxygen carriers are realized with CO2The key of the chemical ring combustion/hydrogen production technology of the enrichment characteristic. At present, the oxygen carrier mainly studied is a metal oxygen carrier, including Fe, Ni, Co, Cu, Mn, Cd, etc., and the carriers mainly include: al (Al)2O3、TiO2、MgO、SiO2YSZ, etc., and also small amounts of non-metal oxides such as CaSO4And the like. In the chemical looping combustion/hydrogen production process, the oxygen carrier is in a continuous oxygen loss-gaining state, so the activity of oxygen in the oxygen carrier is very important. In contrast, in the prior art, oxygen carriers generally have the defects of limited oxygen carrying rate, low cycling reactivity, incapability of bearing high reaction temperature, low hydrogen production rate and the like.
Disclosure of Invention
Aiming at the defects of the prior art and the defects of the prior art, the invention discloses a composite oxide and a preparation method and application thereof. The composite oxide used as an oxygen carrier for chemical looping hydrogen production has the advantages of high activity, good stability, high hydrogen yield and the like.
A composite oxide, composition formula CeFexTiyOδ-αWherein x =5 to 35, y =1 to 25, and δ is a positive number representing a value at which oxygen in the composite oxide reaches a valence equilibrium, and α =0 to δ/2.
In the context of the present specification, the term "value at which oxygen in the composite oxide reaches a valence equilibrium" refers to a value required for forming an electrically neutral composite oxide when Ce in the composite oxide is +3 valent, Fe is +3 or +2 valent, Ti is +4 valent, O is-2 valent, and α = 0.
According to the invention, x =5-35, preferably 10-30, more preferably 15-25, further preferably 18-24.
According to the invention, y =1-25, preferably 3-20, more preferably 5-15.
According to the invention, α =0 to δ/2, preferably 0 to δ/4, more preferably 0.
According to the present invention, the composite oxide may be a supported composite oxide (for convenience of description, also simply referred to as a composite oxide in the present specification), that is, a composite oxide is supported on a carrier.
According to the invention, as the support, an inorganic refractory oxide is preferred. Examples of the inorganic refractory oxide include SiO2、Al2O3、MgO-SiO2、MgO-Al2O3、Al2O3-SiO2、CaO-SiO2And CaO-MgO-SiO2Etc., among which SiO is preferred2、Al2O3、MgO-SiO2、MgO-Al2O3Or a combination thereof.
According to the present invention, the ratio of the complex oxide to the carrier is not particularly limited, and is generally 0.01 to 5: 1, preferably 0.5 to 4: 1, and more preferably 1 to 3:1 in terms of a weight ratio.
According to the present invention, the composite oxide can be produced by the following production method.
According to the present invention, the production method includes a step of bringing a Ce source, an Fe source, and a Ti source into contact with each other to react with each other to obtain a composite oxide.
According to the invention, the Ce source, the Fe source and the Ti source are used in such relative amounts that the obtained composite oxide has the formula CeFexTiyOδ-α(α =0, hereinafter referred to as a composite oxide a) in which x =5 to 35, y =1 to 25, and δ is a positive number, represents a value at which oxygen in the composite oxide reaches a valence equilibrium (as described above).
According to the invention, x =5-35, preferably 10-30, more preferably 15-25, further preferably 18-24.
According to the invention, y =1-25, preferably 3-20, more preferably 5-15.
According to the invention, α =0 to δ/2, preferably 0 to δ/4, more preferably 0.
According to the present invention, the contacting may be performed in any manner as long as the Ce source, the Fe source, and the Ti source can react with each other to cause a chemical reaction, thereby producing the composite oxide a, and for example, the sources may be mixed with each other in the form of a solution or a melt one after another or simultaneously.
According to the present invention, the contacting may be performed in the presence of a support, thereby obtaining a supported composite oxide a (also referred to as a composite oxide a).
According to the invention, as the support, an inorganic refractory oxide or a precursor thereof is preferred. Examples of the inorganic refractory oxide include SiO2、Al2O3、MgO-SiO2、MgO-Al2O3、Al2O3-SiO2、CaO-SiO2And CaO-MgO-SiO2Etc., among which SiO is preferred2、Al2O3、MgO-SiO2、MgO-Al2O3Or a combination thereof. The precursor of the inorganic refractory oxide has a meaning generally used in the art, and means any material that can be converted into the inorganic refractory oxide during the process for producing the composite oxide of the present invention (for example, by the firing step described below), and examples thereof include aluminum nitrate, aluminum chloride, aluminum sulfate, aluminum isopropoxide, sodium silicate, ethyl orthosilicate, silica sol, magnesium nitrate, magnesium chloride, calcium nitrate, calcium chloride, and the like, with aluminum nitrate, aluminum chloride, aluminum sulfate, sodium silicate, ethyl orthosilicate, magnesium nitrate, calcium nitrate, and more preferably aluminum nitrate, aluminum sulfate, sodium silicate, and magnesium nitrate.
According to the present invention, the amount of the carrier used at this time is not particularly limited, but it is preferable that the carrier is used in an amount such that the weight ratio of the composite oxide a to the carrier (in terms of the inorganic refractory oxide) is 0.01 to 5: 1, preferably 0.5 to 4: 1, more preferably 1 to 3: 1.
According to the present invention, as the Ce source, for example, oxides, hydroxides, inorganic acid salts and organic acid salts of Ce (including hydrates of these compounds) may be cited, among which water-soluble inorganic acid salts and water-soluble organic acid salts of Ce are preferable, and nitrate and acetate salts of Ce such as Ce (NO) are more preferable3)3Or a hydrate thereof.
According to the present invention, as the Fe source, there may be mentioned, for example, an oxide, a hydroxide, an inorganic acid salt and an organic acid salt of Fe (including those of the compounds)Hydrates) of Fe, among which water-soluble inorganic acid salts and water-soluble organic acid salts of Fe are preferable, nitrates and acetates of Fe are more preferable, such as Fe (NO)3)3Or a hydrate thereof.
According to the present invention, as the Ti source, for example, oxides, hydroxides, inorganic acid salts and organic acid salts (including hydrates of these compounds) of Ti are cited, among which water-soluble inorganic acid salts and water-soluble organic acid salts of Ti are preferable, and sulfate and acetate salts of Ti, such as Ti2(SO4)3Or a hydrate thereof.
According to a preferred embodiment of the present invention, the Ce source, the Fe source, and the Ti source are provided in the form of aqueous solutions, and the complex oxide a is obtained by mixing these aqueous solutions (sequentially or simultaneously) and reacting them, optionally in the presence of the carrier.
According to the invention, the reaction of the Ce source, the Fe source, the Ti source is preferably carried out in the presence of stirring.
According to the present invention, the reaction conditions of the Ce source, the Fe source, and the Ti source when the reaction is performed are generally: the pH value of the reaction system is 7-10, preferably 7.5-9, the reaction temperature is 60-90 ℃, preferably 70-80 ℃, and the reaction time is 1-12 hours, preferably 3-10 hours.
After production, the composite oxide a of the present invention may be formed into a suitable particle form, such as a strip form, a flake form, a column form, a spherical form, a zigzag form, etc., according to a technique known in the art, if necessary. For example, the composite oxide A is mixed with a binder (preferably pseudoboehmite) and kneaded to form a desired product.
The production method according to the present invention optionally includes, although not necessarily, a step of partially reducing the complex oxide a (α = 0) so that α becomes more than 0 to δ/2, preferably more than 0 to δ/4, and in this case, the complex oxide is also referred to as a complex oxide B.
According to the present invention, the manner of carrying out the partial reduction is not limited at all, as long as a part of the metal elements in the composite oxide a can be brought into a reduced valence state (ratio)Such as Ce0、Fe2+Or Ti0Etc.) can be prepared. The present invention is also not specific to the kind of the metal element in which the partial reduction occurs.
According to the invention, by this partial reduction, it is possible to obtain a composition of formula CeFexTiyOδ-αThe complex oxide B represented by (1) wherein α is more than 0 to δ/2, preferably more than 0 to δ/4, and the other symbols are as defined above.
According to the present invention, as the partial reduction method, for example, a method of bringing the composite oxide a into contact with a reducing agent (for example, hydrogen gas) under appropriate reaction conditions to cause a reduction reaction can be exemplified. Examples of the reaction conditions include: the reaction temperature is 60-600 ℃, the reaction pressure is 15-1500psia, and the reaction time is sufficient to partially reduce the composite oxide a to a value of more than 0 to δ/2 (preferably more than 0 to δ/4) (for example, 0.5-12 hours, but sometimes not limited thereto).
According to the present invention, the composition of the complex oxide (including complex oxide a and complex oxide B) can be identified by atomic emission spectrometry (ICP) or X-ray fluorescence spectrometry (XRF).
According to a preferred embodiment of the present invention, the co-precipitation reaction (neutralization reaction) of the Ce source, the Fe source, and the Ce source is carried out by the contact, thereby obtaining a composite oxide a.
According to the process of the present invention, the Ce source, the Fe source, and the Ti source are provided in the form of aqueous solutions, and an aqueous slurry is obtained by mixing these aqueous solutions (sequentially or simultaneously) to cause a coprecipitation reaction thereof, optionally in the presence of the carrier.
For example, the Ce source, the Fe source, and the Ti source are separately dissolved in water to prepare respective aqueous solutions, these aqueous solutions and an optional carrier are added (preferably, the carrier is added first) to a reaction system (e.g., a reaction vessel) in a predetermined amount sequentially or simultaneously with stirring, the pH of the reaction system is adjusted to 7 to 10 (preferably, 7.5 to 9, for example, using an aqueous ammonia solution), and the coprecipitation is carried out at a reaction temperature of 60 to 90 ℃ (preferably, 70 to 80C) for 1 to 12 hours (preferably, 3 to 10 hours, thereby obtaining the aqueous slurry.
Then, the composite oxide a can be obtained by dehydrating, optionally molding, drying, and calcining the aqueous slurry.
According to the present invention, the dehydration may be carried out in a manner known in the art, and examples thereof include an evaporation dehydration method, a filtration dehydration method and the like.
According to the invention, the shaping can be carried out in a manner known in the art (e.g. extrusion, granulation), advantageously obtaining a composite oxide a having a suitable granular morphology (e.g. in the form of bars, tablets, cylinders, spheres, etc.).
According to the present invention, the drying may be performed according to a method known in the art, and examples thereof include a spray drying method, a vacuum drying method, a hot oven drying method, and the like. The drying and the shaping may be carried out as one step, as required. The drying conditions include, for example, a drying temperature of 60 to 180 ℃, preferably 100 to 150 ℃, and a drying time of 4 to 48 hours, preferably 6 to 36 hours, and more preferably 8 to 24 hours.
According to the invention, the dried aqueous slurry is completely converted into the composite oxide a by the calcination, while the precursor of the inorganic refractory oxide (when used) is converted into the inorganic refractory oxide. Examples of the conditions for the calcination include a calcination temperature of 600-1200 deg.C, preferably 700-1100 deg.C, more preferably 800-1050 deg.C, and a calcination time of 3-12 hours, preferably 4-10 hours. The calcination may be carried out in an oxygen-containing atmosphere (such as air), as required.
According to the invention, it also relates to the use of the aforementioned composite oxides of the invention as chemical looping combustion catalysts. Specifically, the present invention relates to a method for producing hydrogen by chemical looping combustion, which comprises a step of producing hydrogen by chemical looping combustion using the composite oxide of the present invention as a catalyst.
According to the invention, the reaction conditions of the chemical looping combustion are: the reaction temperature of the composite oxide in the fuel is 500-800 ℃, the reaction temperature of the composite oxide in the water vapor is 500-800 ℃, and the used fuel can be solid fuel or gaseous fuel.
The invention is the CeFe for carrying the composite oxidexTiyOδ-αWherein x =5 to 35, y =1 to 25, and δ is a positive number representing a value at which oxygen in the composite oxide reaches a valence equilibrium, and α =0 to δ/2. The oxygen carrier has the advantages of high oxygen carrying rate, stable cycling reactivity, capability of bearing higher reaction temperature, high hydrogen production efficiency and the like, and is simple in preparation process, good in repeatability and suitable for industrial production.
Detailed Description
The following detailed description of the embodiments of the present invention is provided, but it should be noted that the scope of the present invention is not limited by the embodiments, but is defined by the appended claims.
All publications, patent applications, patents, and other references mentioned in this specification are herein incorporated by reference in their entirety. Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. In case of conflict, the present specification, including definitions, will control.
When the specification describes materials, methods, components, devices, or apparatus as "known to one of ordinary skill in the art" or "known conventionally in the art" or the like, that term means that the specification includes those conventionally used in the art at the time of filing the present application, but also includes those not currently used, but which will become known in the art to be suitable for a similar purpose.
In addition, all ranges mentioned in this specification are inclusive of their endpoints unless explicitly stated otherwise. Further, when a range, one or more preferred ranges, or a plurality of upper preferable values and lower preferable values, are given for an amount, concentration, or other value or parameter, it is to be understood that all ranges formed from any pair of any upper range limit or preferred value and any lower range limit or preferred value are specifically disclosed, regardless of whether such pairs of values are individually disclosed.
Finally, unless otherwise expressly indicated, all percentages, parts, ratios, etc. referred to in this specification are by weight unless otherwise generally recognized by those skilled in the art.
Example 1
Weighing a certain amount of ferric nitrate, cerium nitrate and titanium sulfate, dissolving in deionized water, heating to 70 ℃, then slowly dropwise adding concentrated ammonia water into the solution under the stirring condition, ensuring the pH value of the slurry to be 7.5, standing and aging for 3 hours after complete precipitation, filtering, repeatedly washing with deionized water to be neutral, drying the obtained sample, roasting, and drying at the drying temperature of 100 ℃ for 24 hours. The roasting temperature is 580 ℃ and the roasting time is 8 hours. The composition formula of the obtained final composite oxide is CeFe18Ti5O39Denoted as C1.
Example 2
Weighing a certain amount of ferric nitrate, cerium nitrate and titanium sulfate, dissolving in deionized water, heating to 80 ℃, then slowly dropwise adding concentrated ammonia water into the solution under the stirring condition, ensuring the pH value of the slurry to be 9, standing and aging for 10 hours after complete precipitation, filtering, repeatedly washing with deionized water until the slurry is neutral, drying the obtained sample, roasting, and drying at the drying temperature of 150 ℃ for 8 hours. The roasting temperature is 680 ℃ and the roasting time is 4 hours. Obtaining the final composite oxide composition of formula CeFe24Ti15O68This is denoted C2.
Example 3
Weighing a certain amount of ferric nitrate, cerium nitrate and titanium sulfate, dissolving in deionized water, heating to 75 ℃, then slowly dropwise adding concentrated ammonia water into the solution under the stirring condition, ensuring the pH value of the slurry to be 8.3, standing and aging for 6 hours after complete precipitation, filtering, repeatedly washing with deionized water to be neutral, drying the obtained sample, roasting, and drying at the drying temperature of 120 ℃ for 12 hours. The roasting temperature is 600 ℃ and the roasting time is 6 hours. Obtaining the final composite oxide composition of formula CeFe20Ti10O52This is denoted C3.
Example 4
Weighing a certain amount of ferric acetate, cerium acetate and titanium sulfite, dissolving in deionized water, heating to 75 ℃, then slowly dropwise adding concentrated ammonia water into the solution under the stirring condition, ensuring the pH value of the slurry to be 8.3, standing and aging for 6 hours after complete precipitation, filtering, repeatedly washing with deionized water to be neutral, drying the obtained sample, roasting, and drying at the drying temperature of 120 ℃ for 12 hours. The roasting temperature is 600 ℃, and the roasting time is 6 hours. Obtaining the final composite oxide composition of formula CeFe20Ti10O52And (4) showing. Mixing the composite oxide with Al2O3Uniformly mixing the materials according to the mass ratio of 1:1, extruding the materials into strips, forming the strips, drying and roasting the strips, wherein the drying temperature is 100 ℃, the drying time is 24 hours, the roasting temperature is 800 ℃, the roasting time is 10 hours, and the obtained sample is recorded as C4
Example 5
Weighing a certain amount of ferric acetate, cerium acetate and titanium sulfite, dissolving in deionized water, heating to 75 ℃, then slowly dropwise adding concentrated ammonia water into the solution under the stirring condition, ensuring the pH value of the slurry to be 8.3, standing and aging for 6 hours after complete precipitation, filtering, repeatedly washing with deionized water to be neutral, drying the obtained sample, roasting, and drying at the drying temperature of 120 ℃ for 12 hours. The roasting temperature is 600 ℃, and the roasting time is 6 hours. Obtaining the final composite oxide composition of formula CeFe20Ti10O52And (4) showing. Mixing the composite oxide with MgO-Al2O3Uniformly mixing the materials according to the mass ratio of 2:1, extruding the materials into strips, forming the strips, drying and roasting the strips, wherein the drying temperature is 150 ℃, the drying time is 8 hours, the roasting temperature is 1050 ℃, the roasting time is 4 hours, and the obtained sample is marked as C5.
Example 6
Weighing a certain amount of ferric acetate, cerium acetate and titanium sulfate, dissolving in deionized water, heating to 75 ℃, slowly dropwise adding concentrated ammonia water into the solution under the stirring condition to ensure that the pH value of the slurry is 8.3, standing and aging for 6 hours after complete precipitation, filtering, repeatedly washing with deionized water to be neutral, drying and roasting the obtained sample at the drying temperature of 120 DEG CThe drying time was 12 hours. The roasting temperature is 600 ℃ and the roasting time is 6 hours. Obtaining the final composite oxide composition of formula CeFe20Ti10O52And (4) showing. Mixing the composite oxide with MgO-Al2O3Uniformly mixing the materials according to the mass ratio of 3:1, extruding the materials into strips, forming the strips, drying and roasting the strips after air drying, wherein the drying temperature is 120 ℃, the drying time is 12 hours, the roasting temperature is 900 ℃, the roasting time is 6 hours, and the obtained sample is marked as C6.
Example 7
Weighing a certain amount of ferric nitrate, cerous nitrate and titanium sulfite to be dissolved in deionized water, and adding a carrier SiO after the ferric nitrate, the cerous nitrate and the titanium sulfite are completely dissolved2Then heating to 75 ℃, slowly dropwise adding concentrated ammonia water into the solution under the stirring condition to ensure that the pH value of the slurry is 8.3, standing and aging for 6 hours after complete precipitation, filtering, repeatedly washing with deionized water to be neutral, drying the obtained sample, roasting, and drying at 120 ℃ for 12 hours. The roasting temperature is 1000 ℃ and the roasting time is 6 hours. The final composition is obtained as CeFe20Ti10O52 - SiO2The sample of (A) is C7, the CeFe20Ti10O52Composite oxide and carrier SiO2The mass ratio of (A) to (B) is 1: 1.
Example 8
Weighing a certain amount of ferric nitrate, cerous nitrate and titanium sulfate, dissolving in deionized water, and adding MgO-SiO carrier after the ferric nitrate, cerous nitrate and titanium sulfate are completely dissolved2Then heating to 75 ℃, slowly dropwise adding concentrated ammonia water into the solution under the stirring condition to ensure that the pH value of the slurry is 8.3, standing and aging for 6 hours after complete precipitation, filtering, repeatedly washing with deionized water to be neutral, drying the obtained sample, roasting, and drying at 120 ℃ for 12 hours. The roasting temperature is 900 ℃ and the roasting time is 6 hours. The final composition is obtained as CeFe20Ti10 O52/ MgO-SiO2The sample of (1) is denoted as C8, the CeFe20Ti10O52With a carrier MgO-SiO2The mass ratio of (A) to (B) is 1: 1.
Example 9
Weighing a certain amountDissolving ferric nitrate, cerium nitrate and titanium sulfate in deionized water, heating to 75 ℃, then slowly dropwise adding concentrated ammonia water into the solution under the stirring condition to ensure that the pH value of the slurry is 8.3, standing and aging for 6 hours after complete precipitation, filtering, repeatedly washing with the deionized water to be neutral, drying the obtained sample, roasting, wherein the drying temperature is 120 ℃, and the drying time is 12 hours. The roasting temperature is 600 ℃ and the roasting time is 6 hours. Obtaining the final composite oxide composition of formula CeFe20Ti10O52And (4) showing. The obtained composite oxide was partially reduced at a pressure of 1000psia and a temperature of 400 ℃ for 4 hours to obtain a sample represented by the formula CeFe20Ti10O10This is denoted C9.
Example 10
Weighing a certain amount of ferric acetate, cerium acetate and titanium sulfite, dissolving in deionized water, heating to 75 ℃, slowly dropwise adding concentrated ammonia water into the solution under the stirring condition, ensuring the pH value of the slurry to be 8.3, standing and aging for 6 hours after complete precipitation, filtering, repeatedly washing with deionized water to be neutral, drying the obtained sample, roasting, and drying at the drying temperature of 120 ℃ for 12 hours. The roasting temperature is 600 ℃ and the roasting time is 6 hours. Obtaining the final composite oxide composition of formula CeFe20Ti10O52And (4) showing. Mixing the composite oxide with Al2O3Uniformly mixing the raw materials according to the mass ratio of 2:1, extruding the mixture into strips, forming the strips, drying and roasting the strips after air drying, wherein the drying temperature is 120 ℃, the drying time is 12 hours, the roasting temperature is 900 ℃, the roasting time is 6 hours, the obtained composite oxide is partially reduced for 2 hours under the conditions that the pressure is 1000psia and the temperature is 600 ℃, and the obtained sample is represented by the formula CeFe20Ti10O20/Al2O3This is denoted C10.
Comparative example 1
Weighing a certain amount of ferric nitrate and titanium sulfate, dissolving in deionized water, heating to 70 ℃, slowly dropwise adding concentrated ammonia water into the solution under the stirring condition to ensure that the pH value of the slurry is 7.5, standing and aging for 3 hours after complete precipitation, filtering, repeatedly washing with deionized water to be neutral, drying and roasting the obtained sample at the drying temperature of 100 ℃, and drying for 24 hours. The roasting temperature is 580 ℃ and the roasting time is 8 hours. The final composite oxide was obtained and was designated as C11.
Comparative example 2
Weighing a certain amount of ferric nitrate and cerium nitrate, dissolving in deionized water, heating to 70 ℃, slowly dropwise adding concentrated ammonia water into the solution under the stirring condition to ensure that the pH value of the slurry is 7.5, standing and aging for 3 hours after complete precipitation, filtering, repeatedly washing with deionized water to be neutral, drying the obtained sample, roasting at the drying temperature of 100 ℃, and drying for 24 hours. The roasting temperature is 580 ℃ and the roasting time is 8 hours. The final composite oxide was obtained and was designated as C12.
Example 1
Weighing a certain amount of ferric nitrate, cerium nitrate and titanium sulfate, dissolving in deionized water, heating to 70 ℃, then slowly dropwise adding concentrated ammonia water into the solution under the stirring condition, ensuring the pH value of the slurry to be 7.5, standing and aging for 3 hours after complete precipitation, filtering, repeatedly washing with deionized water to be neutral, drying the obtained sample, roasting, and drying at the drying temperature of 100 ℃ for 24 hours. The roasting temperature is 580 ℃ and the roasting time is 8 hours. The composition formula of the obtained final composite oxide is CeFe18Ti5O39This is denoted C1.
The performance evaluation of the catalyst prepared in the above examples was carried out as follows. The catalyst evaluation test is carried out in a continuous flow fixed bed reactor, and 3ml of oxygen carrier is mixed with quartz sand with the same mesh number according to the volume ratio of 1: 1. The fuel gas is methane (10 vol% CH)4，90vol%N2) The flow rate is 220ml/min, the reaction temperature is 900 ℃, and the reaction pressure is normal pressure. After 5 minutes of reduction, nitrogen was switched to maintain the temperature at 900 ℃ for 20 minutes. Then water is introduced, gasified first and then enters a preheater, the temperature of which is maintained at 300 ℃, and then enters the reactor. After the reaction is completed, the water introduction is stopped, the air introduction is started, the flow rate is 25ml/min, and the temperature is kept at 90 DEG0 ℃ is used. After 10 minutes of reaction, nitrogen was again switched to the reaction mixture, and the temperature was kept constant. Then introducing fuel gas, and the reaction condition is identical to the above-mentioned reduction reaction condition. Adopting 7890 gas chromatography on-line analysis, 5A molecular sieve column and PorapakQ column, TCD detection. The results of the performance evaluation are shown in Table 1.
TABLE 1 reactivity of the catalysts
*1: CH circulation 50 times4Average conversion of (d);
*2: CH circulation 100 times4Average conversion of (d);
*3: when the circulation is 100 times, the single time is H2Average value of the yield.
Claims (21)
1. A composite oxide characterized by: the formula CeFe for the composition of the composite oxidexTiyOδ-αWherein x =5 to 35, y =1 to 25, and δ is a positive number representing a value at which oxygen in the composite oxide reaches a valence equilibrium, and α =0 to δ/2.
2. The oxide according to claim 1, wherein: the x is 10 to 30, preferably 15 to 25, and further preferably 18 to 24.
3. The oxide according to claim 1, wherein: said y is from 3 to 20, preferably from 5 to 15.
4. The oxide according to claim 1, wherein: alpha is 0 to delta/4, preferably 0.
5. The oxide according to claim 1, wherein: the composite oxide is supported on a carrier.
6. An oxide according to claim 5, wherein: the carrier is SiO2、Al2O3、MgO-SiO2、MgO-Al2O3、Al2O3-SiO2、CaO-SiO2、CaO-MgO-SiO2Or combinations thereof, preferably SiO2、Al2O3、MgO-SiO2、MgO-Al2O3Or a combination thereof.
7. An oxide according to claim 5, wherein: the weight ratio of the composite oxide to the carrier is 0.01-5: 1, preferably 0.5-4: 1, and more preferably 1-3: 1.
8. A process for the preparation of an oxide according to any one of claims 1 to 7, characterized in that: the method comprises the step of contacting a Ce source, an Fe source and a Ti source to react to obtain the composite oxide.
9. The method of claim 8, wherein: the contacting may be performed in the presence of a support, thereby supporting the composite oxide on the support.
10. The method of claim 8, wherein: the Ce source is oxide, hydroxide, inorganic acid salt or organic acid salt of Ce, preferably water-soluble inorganic acid salt and water-soluble organic acid salt of Ce, and more preferably nitrate and acetate of Ce.
11. The method of claim 8, wherein: the Fe source is an oxide, a hydroxide, an inorganic acid salt or an organic acid salt of Fe, preferably a water-soluble inorganic acid salt and a water-soluble organic acid salt of Fe, and more preferably a nitrate and an acetate of Fe.
12. The method of claim 8, wherein: the Ti source is Ti oxide, Ti hydroxide, Ti inorganic acid salt or Ti organic acid salt, preferably Ti water-soluble inorganic acid salt and Ti water-soluble organic acid salt, more preferably Ti sulfate and Ti acetate.
13. The method of claim 8, wherein: the Ce source, the Fe source, and the Ti source are provided in the form of aqueous solutions, and the composite oxide is obtained by mixing these aqueous solutions one after another or simultaneously, optionally in the presence of the carrier, to react them.
14. The method of claim 8, wherein: the reaction of the Ce source, the Fe source, the Ti source is carried out in the presence of stirring.
15. The method of claim 8, wherein: the reaction conditions of the Ce source, the Fe source and the Ti source during the reaction are as follows: the pH value of the reaction system is 7-10, preferably 7.5-9, the reaction temperature is 60-90 ℃, preferably 70-80 ℃, and the reaction time is 1-12 hours, preferably 3-10 hours.
16. The method of claim 8, wherein: the composite oxide is shaped into a strip, a sheet, a column, a sphere or a sawtooth shape as required.
17. The method of claim 8, wherein: comprising the step of partially reducing the composite oxide α =0 to a value of α of more than 0 to δ/2, preferably more than 0 to δ/4.
18. The method of claim 17, wherein: the reduction conditions were as follows: the reaction temperature is 60-600 ℃, the reaction pressure is 15-1500psia, and the reaction time is sufficient to partially reduce the composite oxide a to a value of more than 0 to δ/2 (preferably more than 0 to δ/4) (for example, 0.5-12 hours, but sometimes not limited thereto).
19. The composite oxide as claimed in any one of claims 1 to 7 as a chemical looping combustion catalyst.
20. A method for producing hydrogen by chemical looping combustion is characterized in that: the composite oxide is used as a catalyst for producing hydrogen by chemical looping combustion, wherein the composite oxide is any one of 1-7.
21. The method of claim 20, wherein: the reaction conditions of the chemical looping combustion are as follows: the reaction temperature of the composite oxide in the fuel is 500-800 ℃, the reaction temperature of the composite oxide in the water vapor is 500-800 ℃, and the used fuel is solid fuel or gaseous fuel.
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