CN103752315B - A kind of metal phase carrier load type catalyst and its production and use - Google Patents
A kind of metal phase carrier load type catalyst and its production and use Download PDFInfo
- Publication number
- CN103752315B CN103752315B CN201410018008.0A CN201410018008A CN103752315B CN 103752315 B CN103752315 B CN 103752315B CN 201410018008 A CN201410018008 A CN 201410018008A CN 103752315 B CN103752315 B CN 103752315B
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- Prior art keywords
- phase carrier
- catalyst
- metal
- metal phase
- reaction
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- 239000003054 catalyst Substances 0.000 title claims abstract description 168
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 153
- 239000002184 metal Substances 0.000 title claims abstract description 147
- 238000004519 manufacturing process Methods 0.000 title description 6
- 238000006243 chemical reaction Methods 0.000 claims abstract description 95
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims abstract description 69
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims abstract description 43
- 229910002092 carbon dioxide Inorganic materials 0.000 claims abstract description 24
- 229910044991 metal oxide Inorganic materials 0.000 claims abstract description 23
- 150000004706 metal oxides Chemical class 0.000 claims abstract description 23
- 230000000694 effects Effects 0.000 claims abstract description 21
- 239000001569 carbon dioxide Substances 0.000 claims abstract description 20
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 12
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 11
- 238000003786 synthesis reaction Methods 0.000 claims abstract description 11
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 86
- 229910052782 aluminium Inorganic materials 0.000 claims description 64
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 64
- 239000000835 fiber Substances 0.000 claims description 53
- 239000002245 particle Substances 0.000 claims description 36
- 229910052759 nickel Inorganic materials 0.000 claims description 34
- 239000007864 aqueous solution Substances 0.000 claims description 32
- 238000005470 impregnation Methods 0.000 claims description 30
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 26
- 239000004411 aluminium Substances 0.000 claims description 25
- 239000000843 powder Substances 0.000 claims description 24
- 238000005245 sintering Methods 0.000 claims description 24
- 238000000034 method Methods 0.000 claims description 21
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims description 16
- 238000005275 alloying Methods 0.000 claims description 16
- 229910002091 carbon monoxide Inorganic materials 0.000 claims description 16
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 15
- 239000007787 solid Substances 0.000 claims description 15
- 230000008569 process Effects 0.000 claims description 13
- 239000000725 suspension Substances 0.000 claims description 13
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 12
- 235000011121 sodium hydroxide Nutrition 0.000 claims description 12
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 11
- 238000001035 drying Methods 0.000 claims description 11
- 150000003839 salts Chemical class 0.000 claims description 9
- 229910052684 Cerium Inorganic materials 0.000 claims description 7
- 229910052799 carbon Inorganic materials 0.000 claims description 7
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 claims description 7
- 239000006262 metallic foam Substances 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 6
- 229910045601 alloy Inorganic materials 0.000 claims description 5
- 239000000956 alloy Substances 0.000 claims description 5
- 239000011777 magnesium Substances 0.000 claims description 5
- 229910000570 Cupronickel Inorganic materials 0.000 claims description 4
- 239000002671 adjuvant Substances 0.000 claims description 4
- 229910000272 alkali metal oxide Inorganic materials 0.000 claims description 4
- YOCUPQPZWBBYIX-UHFFFAOYSA-N copper nickel Chemical compound [Ni].[Cu] YOCUPQPZWBBYIX-UHFFFAOYSA-N 0.000 claims description 4
- 229910052742 iron Inorganic materials 0.000 claims description 4
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 claims description 3
- 238000005984 hydrogenation reaction Methods 0.000 claims description 3
- 229910052750 molybdenum Inorganic materials 0.000 claims description 3
- 239000011733 molybdenum Substances 0.000 claims description 3
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 2
- 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 claims description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 2
- 229910052791 calcium Inorganic materials 0.000 claims description 2
- 239000011575 calcium Substances 0.000 claims description 2
- 229910052746 lanthanum Inorganic materials 0.000 claims description 2
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 claims description 2
- 229910052749 magnesium Inorganic materials 0.000 claims description 2
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 claims description 2
- CHWRSCGUEQEHOH-UHFFFAOYSA-N potassium oxide Chemical compound [O-2].[K+].[K+] CHWRSCGUEQEHOH-UHFFFAOYSA-N 0.000 claims description 2
- 229910001950 potassium oxide Inorganic materials 0.000 claims description 2
- 229910052708 sodium Inorganic materials 0.000 claims description 2
- 239000011734 sodium Substances 0.000 claims description 2
- 230000002194 synthesizing effect Effects 0.000 claims description 2
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 2
- 229910052721 tungsten Inorganic materials 0.000 claims description 2
- 239000010937 tungsten Substances 0.000 claims description 2
- 240000007594 Oryza sativa Species 0.000 claims 1
- 235000007164 Oryza sativa Nutrition 0.000 claims 1
- 235000009566 rice Nutrition 0.000 claims 1
- 238000002360 preparation method Methods 0.000 abstract description 21
- 230000003197 catalytic effect Effects 0.000 abstract description 15
- 230000008901 benefit Effects 0.000 abstract description 6
- 239000000126 substance Substances 0.000 abstract description 4
- 230000035699 permeability Effects 0.000 abstract description 2
- 239000010410 layer Substances 0.000 description 30
- 239000007789 gas Substances 0.000 description 25
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 21
- 229960004424 carbon dioxide Drugs 0.000 description 20
- 229910052739 hydrogen Inorganic materials 0.000 description 20
- 239000001257 hydrogen Substances 0.000 description 20
- JLDSOYXADOWAKB-UHFFFAOYSA-N aluminium nitrate Chemical compound [Al+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O JLDSOYXADOWAKB-UHFFFAOYSA-N 0.000 description 18
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 18
- 229910052760 oxygen Inorganic materials 0.000 description 17
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 16
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 15
- 239000006260 foam Substances 0.000 description 14
- 239000002994 raw material Substances 0.000 description 14
- 229910052802 copper Inorganic materials 0.000 description 13
- 239000010949 copper Substances 0.000 description 13
- 229910052593 corundum Inorganic materials 0.000 description 11
- 229910001845 yogo sapphire Inorganic materials 0.000 description 11
- 229920000914 Metallic fiber Polymers 0.000 description 10
- 229910002651 NO3 Inorganic materials 0.000 description 10
- 239000012153 distilled water Substances 0.000 description 10
- 238000011010 flushing procedure Methods 0.000 description 10
- 229910000480 nickel oxide Inorganic materials 0.000 description 10
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 description 10
- 230000001681 protective effect Effects 0.000 description 10
- 239000000377 silicon dioxide Substances 0.000 description 10
- UGJMSCJZPQXPKR-UHFFFAOYSA-N dialuminum oxonickel oxygen(2-) Chemical compound [Ni]=O.[O-2].[Al+3].[O-2].[O-2].[Al+3] UGJMSCJZPQXPKR-UHFFFAOYSA-N 0.000 description 9
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 8
- 239000000969 carrier Substances 0.000 description 7
- 238000006555 catalytic reaction Methods 0.000 description 7
- 239000003795 chemical substances by application Substances 0.000 description 7
- 230000003647 oxidation Effects 0.000 description 7
- 238000007254 oxidation reaction Methods 0.000 description 7
- FFBHFFJDDLITSX-UHFFFAOYSA-N benzyl N-[2-hydroxy-4-(3-oxomorpholin-4-yl)phenyl]carbamate Chemical compound OC1=C(NC(=O)OCC2=CC=CC=C2)C=CC(=C1)N1CCOCC1=O FFBHFFJDDLITSX-UHFFFAOYSA-N 0.000 description 6
- 238000007598 dipping method Methods 0.000 description 6
- 239000008246 gaseous mixture Substances 0.000 description 6
- 238000005259 measurement Methods 0.000 description 6
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(II) nitrate Inorganic materials [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 6
- 230000003287 optical effect Effects 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- 238000012546 transfer Methods 0.000 description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 5
- 229920003043 Cellulose fiber Polymers 0.000 description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 239000001301 oxygen Substances 0.000 description 5
- 235000012239 silicon dioxide Nutrition 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- 239000003708 ampul Substances 0.000 description 4
- 125000004429 atom Chemical group 0.000 description 4
- 238000009826 distribution Methods 0.000 description 4
- 238000004993 emission spectroscopy Methods 0.000 description 4
- 150000002431 hydrogen Chemical class 0.000 description 4
- 239000000395 magnesium oxide Substances 0.000 description 4
- 239000010453 quartz Substances 0.000 description 4
- 230000004044 response Effects 0.000 description 4
- 229910003158 γ-Al2O3 Inorganic materials 0.000 description 4
- 238000005804 alkylation reaction Methods 0.000 description 3
- 239000008187 granular material Substances 0.000 description 3
- 238000013112 stability test Methods 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 2
- KKCBUQHMOMHUOY-UHFFFAOYSA-N Na2O Inorganic materials [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- ZCCIPPOKBCJFDN-UHFFFAOYSA-N calcium nitrate Chemical compound [Ca+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ZCCIPPOKBCJFDN-UHFFFAOYSA-N 0.000 description 2
- 229910002090 carbon oxide Inorganic materials 0.000 description 2
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000004744 fabric Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- YIXJRHPUWRPCBB-UHFFFAOYSA-N magnesium nitrate Chemical compound [Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O YIXJRHPUWRPCBB-UHFFFAOYSA-N 0.000 description 2
- 239000011572 manganese Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 2
- 238000004088 simulation Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- 229910002422 La(NO3)3·6H2O Inorganic materials 0.000 description 1
- 229910020350 Na2WO4 Inorganic materials 0.000 description 1
- GCNLQHANGFOQKY-UHFFFAOYSA-N [C+4].[O-2].[O-2].[Ti+4] Chemical compound [C+4].[O-2].[O-2].[Ti+4] GCNLQHANGFOQKY-UHFFFAOYSA-N 0.000 description 1
- SHPBBNULESVQRH-UHFFFAOYSA-N [O-2].[O-2].[Ti+4].[Zr+4] Chemical compound [O-2].[O-2].[Ti+4].[Zr+4] SHPBBNULESVQRH-UHFFFAOYSA-N 0.000 description 1
- GNKOIJKKCGYZHM-UHFFFAOYSA-N [W+4].[O-2].[Na+] Chemical compound [W+4].[O-2].[Na+] GNKOIJKKCGYZHM-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 229910000287 alkaline earth metal oxide Inorganic materials 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 238000002453 autothermal reforming Methods 0.000 description 1
- XXLDWSKFRBJLMX-UHFFFAOYSA-N carbon dioxide;carbon monoxide Chemical compound O=[C].O=C=O XXLDWSKFRBJLMX-UHFFFAOYSA-N 0.000 description 1
- RVYIIQVVKDJVBA-UHFFFAOYSA-N carbon monoxide;methane Chemical compound C.O=[C] RVYIIQVVKDJVBA-UHFFFAOYSA-N 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 238000005187 foaming Methods 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 230000002779 inactivation Effects 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Inorganic materials O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 description 1
- AMWRITDGCCNYAT-UHFFFAOYSA-L manganese oxide Inorganic materials [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Inorganic materials O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 238000011017 operating method Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 229910001404 rare earth metal oxide Inorganic materials 0.000 description 1
- 239000012495 reaction gas Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000002407 reforming Methods 0.000 description 1
- 238000006057 reforming reaction Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Inorganic materials [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 description 1
- 229910001948 sodium oxide Inorganic materials 0.000 description 1
- XMVONEAAOPAGAO-UHFFFAOYSA-N sodium tungstate Chemical compound [Na+].[Na+].[O-][W]([O-])(=O)=O XMVONEAAOPAGAO-UHFFFAOYSA-N 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 238000005728 strengthening Methods 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
- 230000001839 systemic circulation Effects 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/02—Boron or aluminium; Oxides or hydroxides thereof
- B01J21/04—Alumina
-
- 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
-
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/40—Catalysts, in general, characterised by their form or physical properties characterised by dimensions, e.g. grain size
-
- 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
-
- 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
- C01B2203/02—Processes for making hydrogen or synthesis gas
- C01B2203/0205—Processes for making hydrogen or synthesis gas containing a reforming step
- C01B2203/0227—Processes for making hydrogen or synthesis gas containing a reforming step containing a catalytic reforming step
- C01B2203/0238—Processes for making hydrogen or synthesis gas containing a reforming step containing a catalytic reforming step the reforming step being a carbon dioxide reforming step
-
- 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
- C01B2203/02—Processes for making hydrogen or synthesis gas
- C01B2203/0205—Processes for making hydrogen or synthesis gas containing a reforming step
- C01B2203/0227—Processes for making hydrogen or synthesis gas containing a reforming step containing a catalytic reforming step
- C01B2203/0244—Processes for making hydrogen or synthesis gas containing a reforming step containing a catalytic reforming step the reforming step being an autothermal reforming step, e.g. secondary reforming processes
-
- 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
- Y02P20/141—Feedstock
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Health & Medical Sciences (AREA)
- General Health & Medical Sciences (AREA)
- Combustion & Propulsion (AREA)
- Inorganic Chemistry (AREA)
- Catalysts (AREA)
Abstract
A kind of metal phase carrier load type catalyst and preparation method thereof and for catalytic CO or (with) carbon dioxide prepares methane and the purposes of methane synthesis gas reaction.Described metal phase carrier load type catalyst includes activity component metal oxide and the auxiliary agent metal oxides being carried on metal phase carrier, and has below formula: xM1O‑yM2O/ZT, wherein M1O represents activity component metal oxide, M2O represents that auxiliary agent metal oxides, ZT represent metal phase carrier, and x represents the mass percent of catalyst shared by activity component metal oxide, and y represents that auxiliary agent metal oxides accounts for the mass percent of catalyst.The advantages such as catalyst of the present invention has that high activity, high stability, excellent heat conductivity, permeability be high, easy to use, life-span length, preparation are simple, can effectively solve the heat effect difficult problem in putting by force in chemical field/endothermic reaction, can be as methanation and the catalyst of methane synthesis gas reaction.
Description
Technical field
The invention belongs to catalysis technical field, relate to a kind of catalyst and its production and use, specifically a kind of with
Metal phase carrier load type catalyst and its production and use, this catalyst can be used for catalytic CO or (with) two
Carbonoxide hydrogenation reacts with synthesizing methane and reforming of methane on Ni-Ce.
Background technology
Natural gas is a kind of safe and clean high-grade energy, and main component is methane (CH4), have that calorific value is high, it is little to pollute
Etc. advantage, have a wide range of applications at generating, chemical industry and the aspect such as civilian.Since Sabatier and Senderens in 1902
First, after utilizing carbon monoxide and hydrogen to synthesize methane on nickel-base catalyst, methanation reaction quickly grows and extensively applies
At gas purification process.
Methanation process it is crucial that exploitation efficient catalyst.The multiple methanation catalyst of teaching in prior art, such as
Chinese patent 200610021836.5,201010223996.4 and Chinese patent ZL88105142.x.In short, prior art
Methanation catalyst substantially use oxide as carrier, such as alchlor, silicon dioxide, titanium dioxide, titanium dioxide
Zirconium etc..
On the one hand, the methanation of carbon monoxide, carbon dioxide methanation and carbon monoxide carbon dioxide methanation altogether, all
It is strongly exothermic process, and the heat conductivility of oxide material is poor, in course of reaction, therefore easily form " focus " the most anti-
Answer device temperature runaway, thus cause the sintering of catalyst inactivation of prior art even to cause work safety accident.In actual production not
Obtain the operating procedure not using reaction gas systemic circulation than the reaction that combines multistage with intersegmental cooling, to solve asking of reactor temperature runaway
Topic, but bring the problems such as high energy consumption, efficiency are low.On the other hand, in prior art, in order to eliminate at fixed bed reactors
Middle gas internal diffusion and the restriction of external diffusion, need to use the less catalyst granules of particle diameter and bigger gas flow rate.But
These measures can cause the pressure drop of bed two ends to increase, and the problem bringing energy consumption and secure context is unfavorable to producing.
Additionally, methane synthesis gas is one of important channel realizing methane chemical utilization, steam reformation, portion are developed at present
Divide the process for preparing synthetic gas such as oxidation, CO 2 reformation and self-heating recapitalization, but above-mentioned technique all exists stronger heat effect (by force
Heat absorption or strongly exothermic) problem, the thermodynamic study for them shows, it occurs side reaction carbon distribution the most at low temperatures.Thing
In reality, owing in traditional fixed bed reaction pipe, effective heat transfer coefficient is the most relatively low, even if tube wall temperature is up to 800 DEG C, bed
Still suffering from cold spot in Ceng, carbon distribution is difficult to avoid that.
Metal phase carrier structure catalyst is owing to its specific surface area is big, the transmission advantages such as performance is good, bed pressure drop is low, at environment
Catalysis and Environmental capacity field have been applied.Utilize this excellent transmission performance, metal phase carrier structure catalyst is applied
In putting by force in chemical field/endothermic reaction, energy utilization efficiency can be increased substantially, it is achieved Process integration, reach
Purpose to process intensification.And all there is strong heat effect in methanation reaction, methane synthesis gas reaction, the most existing skill
Art has existed metal phase carrier structure methanation catalyst and the trial of methane synthetic gas catalyst.But, these are existing
The catalyst of technology exists that fusing point is low, chemism is high, catalysis activity is not enough, preparation is complicated, preparation process is polluted more serious
Etc. defect.
Summary of the invention
It is an object of the invention to provide one and there is high catalytic activity, high stability, superior thermal conductivity, easy to use, system
Catalyst of advantage such as standby simple and its preparation method and application, with the standby reaction of methane being applicable to there is strong heat effect and
The reaction of methane synthesis gas.
For achieving the above object, the invention provides a kind of metal phase carrier load type catalyst, including being carried on metal
The activity component metal oxide of phase carrier and auxiliary agent metal oxides also have formula xM1O-yM2O/ZT, wherein M1O
Represent activity component metal oxide, M2O represents that auxiliary agent metal oxides, ZT represent metal phase carrier, and x represents activity
The mass percent of catalyst shared by component metals oxide, y represents that auxiliary agent metal oxides accounts for the mass percent of catalyst.
As further preferred scheme, in the catalyst of the present invention, activity component metal oxide M1Catalyst matter shared by O
Amount percent x is 1～15%, auxiliary agent metal oxides M2Shared by O, catalyst quality percent y is 1～15%, and remaining is
Metal phase carrier ZT.In various embodiments, the value of x, y can be 1,3,5,6,7.5,9,10,13,15,
The purpose of the present invention can be realized.
As further preferred version, described metal phase carrier is metallic nickel, metallic copper, metallic iron or metal copper-nickel alloy.
As further preferred version, described metal phase carrier is a diameter of 4～150 microns, a length of 2～10 millimeters
Fiber, by the three-dimensional porous structure monoblock type metal fiber carrier of this fiber sintering or three-dimensional porous structure monoblock type metal
Foam carrier.
As further preferred version, the activity component metal oxide M in the catalyst of the present invention1O is nickel and ferrum
At least one in oxide.
As further preferred version, auxiliary agent metal oxides M in the catalyst of the present invention2O be aluminum, cerium, lanthanum,
Molybdenum, manganese, tungsten, magnesium, calcium, sodium, potassium oxide at least one.
Another aspect provides the preparation method of a kind of catalyst, comprise the steps:
1. with the suspension incipient impregnation metal containing aluminium powder (preferred particle size superfine aluminium power between 1-10 micron)
Phase carrier (" incipient impregnation " means that the suspension containing aluminium powder is identical with the volume of metal phase carrier to be impregnated), then
It is dried process, after making aluminum particle be dispersed in metal phase carrier surface, at 550～650 DEG C, makes aluminum particle and metal
Phase carrier top layer carries out solid-solid alloying reaction (such as reaction 1～10 hour), and (reaction such as can be at high-purity protective atmosphere
In carry out, such as purity is equal to or higher than 99.999% nitrogen, hydrogen, argon or helium, it is also possible to carry out in a vacuum), obtain table
Layer alloyed metal (AM) phase carrier (in different embodiments of the invention, the temperature of solid-solid alloying reaction can be 550,
570,600,630,650 DEG C, the response time can be 1,2,3,5,7,8,10 hours shorter or longer, all
The purpose of the present invention can be realized)；
2. product step 1. prepared is 5 by concentration at a temperature of room temperature to 60 DEG C～the hydrochloric acid of 20% or sodium hydroxide
Aqueous solution carries out taking out aluminum and processes (such as 1～6 hour), after drying in distilled water flushing, air, obtains top layer porous
Metal phase carrier (in different embodiments of the invention, the temperature of this step can be 20,30,40,50,60 DEG C,
The concentration of hydrochloric acid or sodium hydrate aqueous solution can be 5,5.5,7,10,14,18,20%, takes out the aluminum process time permissible
Be 1,2,4,5,6 hours shorter or longer, the purpose of the present invention can be realized)；
3. the product 2. step prepared, room temperature or quite under the conditions of incipient impregnation in containing active component M1 metallic element
Salt and adjuvant component M2 metallic element salt aqueous solution (dipping herein can be 2. step is prepared product dipping
At the same time in the same solution containing active component and adjuvant component, it is also possible to be that product step 2. prepared is successively respectively only
The first solution containing a kind of component impregnates, then impregnates in the second solution containing another kind of component), after drying in
300～600 DEG C of roastings (such as 0.5～2 hour), i.e. obtain described metal phase carrier metal phase carrier load type catalyst (
In different embodiments, the sintering temperature of this step can be 300,350,400,500,600 DEG C, and roasting time can be
0.5,1,1.5,2 hours shorter or longer, the purpose of the present invention can be realized).
As further preferred scheme, the particle diameter of the aluminium powder used in the alloying process of metal phase carrier top layer is 1～3 micron,
The mass ratio of aluminium powder/metal phase carrier is 0.5～10/100(in different embodiments, and the mass ratio of aluminium powder/metal phase carrier can
To be 0.5/100,1/100,3/100,5/100,8/100,10/100, the purpose of the present invention can be realized).
Another aspect of the present invention is to be used for described metal phase carrier load type catalyst from carbon monoxide and/or titanium dioxide
Carbon Hydrogenation is for methane.
Another aspect of the present invention is to be used for from methane for synthesis gas, especially by described metal phase carrier load type catalyst
It it is the catalyst preparing synthesis gas as methane-CO 2 reformation or methane self-heating recapitalization.
Compared with prior art, the metal phase carrier load type catalyst that the present invention provides have Stability Analysis of Structures, heat conductivity good,
Permeability advantages of higher, in use has and is prone to molding, is prone to filling, the advantage such as easily stored, and its preparation method letter
List, raw material are easy to get, structure-controllable.Compare conventional oxide carrier load type catalyst granules and fill the prior art of fixed bed,
The macroporosity of the monoblock type metal phase carrier load type catalyst of the present invention can be substantially reduced the pressure drop at bed two ends, and it is high
Heat conductivity so that in bed temperature be more uniformly distributed, can fully meet the catalytic performance requirement of synthesis gas methanation reaction.
Accompanying drawing explanation
Nickel oxide-aluminium oxide catalyst that sintering metal nickel that Fig. 1 is made in embodiment 1 is fiber-loaded
10NiO-10Al2O3The optical photograph of/8-Ni-SMF-450.
Nickel oxide-aluminium oxide catalyst that sintering metal nickel that Fig. 2 is made in embodiment 1 is fiber-loaded
10NiO-10Al2O3The SEM photograph of/8-Ni-SMF-450.
Nickel oxide-aluminium oxide catalyst that sintering metal nickel that Fig. 3 is made in embodiment 1 is fiber-loaded
10NiO-10Al2O3The XRD spectra of/8-Ni-SMF-450.
The ferric oxide-alumina catalyst that metallic copper that Fig. 4 is made in embodiment 3 is fiber-loaded
10Fe2O3-5Al2O3The optical photograph of/30-Cu-fiber-300.
The ferric oxide-alumina catalyst that metallic copper that Fig. 5 is made in embodiment 3 is fiber-loaded
10Fe2O3-5Al2O3The SEM photograph of/30-Cu-fiber-300.
The carrier loaded nickel oxide of metal foam nickel-alumina-silica cerium catalyst that Fig. 6 is made in embodiment 8
10NiO-5Al2O3-5CeO2The optical photograph of/Ni-foam-600.
The carrier loaded nickel oxide of metal foam nickel-alumina-silica cerium catalyst that Fig. 7 is made in embodiment 8
10NiO-5Al2O3-5CeO2The SEM photograph of/Ni-foam-600.
Nickel oxide that metallic nickel that Fig. 8 is made in embodiment 6 is fiber-loaded and magnesia catalyst
8NiO-8Al2O3-2MgO/8-Ni-SMF-600 and comparative example beaded catalyst 10NiO-5MgO/ γ-Al2O3In reactor
Temperature Distribution comparison diagram.
Fig. 9 is the 5NiO-5Al that embodiment 5 prepares2O3-2.5CeO2/ 8-Ni-SMF-500 catalyst carbon monoxide methane
Change 1000 hours stability test results of reaction.
Figure 10 is the 5NiO-5Al that embodiment 5 prepares2O3-2.5CeO2/ 8-Ni-SMF-500 catalyst carbon monoxide first
3000 hours stability test results of alkylation reaction.
Figure 11 is the 5NiO-5Al that embodiment 5 prepares2O3-2.5CeO2/ 8-Ni-SMF-500 catalyst carbon dioxide first
1000 hours stability test results of alkylation reaction.
Detailed description of the invention
Below in conjunction with embodiment, the invention will be further elaborated, its objective is content for a better understanding of the present invention.Cause
This cited case is not limiting as protection scope of the present invention.
Embodiment 1
The present embodiment provides the preparation of the nickel oxide-aluminium oxide catalyst of a kind of sintrered nickel metal fiber carrier load.
1. a diameter of 8 microns, the nickel metallic fiber 15 grams of a length of 2～5 millimeters and a length of 0.1～1 millimeter of fiber are weighed
2.5 grams and 1.5 liters water of cellulose fiber join in blender, transfer to paper machine after being sufficiently stirred for the most scattered fiber pulp
In, add water to 8.5 liters, stirring, draining aftershaping；In 500 DEG C of roastings 1 hour in air atmosphere after to be dried；Again
Hydrogen sinters 1 hour in 950 DEG C, the thickness of product is controlled at 1 millimeter by compacting, obtain sintering metal nickel fine
Dimension carrier, is expressed as 8-Ni-SMF；
2. sintering metal nickel fiber carrier step 1. prepared is cut into a diameter of 16 millimeters of disks and weighs 5 grams and be placed in
In 50 milliliters of beakers.At room temperature, pipette containing 0.1 gram of aluminium powder (matter of aluminium powder/metal phase carrier that particle diameter is 1～3 micron
Amount ratio is 2/100) suspension incipient impregnation metal phase carrier and dry make aluminum particle be dispersed in metal phase carrier surface
After, make aluminum particle carry out solid-solid alloying reaction 2 with metal phase carrier top layer in high-purity protective atmosphere at 600 DEG C
Hour, obtain top layer alloyed metal (AM) phase carrier；
3. product step 2. prepared, carries out taking out aluminum with the sodium hydrate aqueous solution that concentration is 15% at room temperature to 60 DEG C
Process 1 hour, dry in distilled water flushing, air, obtain the metal phase carrier of top layer porous；
4. 3 grams of the carrier that 3. step prepares is weighed, with isopyknic Ni (NO containing 1.528 grams and 1.305 grams3)2·6H2O
With Al (NO3)3·9H2The aqueous solution of O, at room temperature incipient impregnation carrier, 450 DEG C of roastings in air after 100 DEG C of drying
Burn 2 hours, i.e. obtain the nickel oxide-aluminium oxide catalyst of described sintrered nickel metal fiber carrier load；Through plasma electric
Sense linking atom emission spectrometry is learnt, in the catalyst prepared by the present embodiment, and Al2O3Weight content be 10.4%；
Measuring through temperature programmed reduction working curve method and learn, in the catalyst prepared by the present embodiment, the weight content of NiO is
9.5%；Catalyst prepared by the present embodiment is expressed as 10NiO-10Al2O3/ 8-Ni-SMF-450(mantissa herein " 450 "
Represent that during step is 4., the sintering temperature of catalyst is 450 DEG C, lower same).
10NiO-10Al2O3The optical photograph of/8-Ni-SMF-450 is shown in that Fig. 1, scanning electron microscope (SEM) photo are shown in Fig. 2, X
X ray diffraction (XRD) figure is shown in Fig. 3.
Learn through macroscopic measurement: the integral catalyzer 10NiO-10Al of this enforcement preparation2O3In/8-Ni-SMF-450, sintering
Percent by volume shared by W metal fibre structure catalyst backbone is 5%, and porosity is 95%.
The diameter of the nickel metallic fiber used in the present embodiment the 1. step can be 4 microns, and remaining condition is constant, and gained is catalyzed
Agent is expressed as 10NiO-10Al2O3/4-Ni-SMF-450。
In the present embodiment the 2. step, the quality of aluminium powder can be 0.025～0.10g or 0.10～0.50g, and remaining condition is constant.
In the present embodiment the 2. step, solid-solid alloying reaction temperature can be 550～600 DEG C or 600～650 DEG C, solid-solid alloy
The change response time can be 1～2 hour or 2～10 hours, and remaining condition is constant.
In the present embodiment the 3. step, concentration of sodium hydroxide solution can be 5～15% or 15～20%, and remaining condition is constant.
Taking out aluminum in the present embodiment the 3. step and process the time can be 1～6 hour, and remaining condition is constant.
In the present embodiment the 4. step, sintering temperature can be 600 DEG C, and remaining condition is constant, and gained catalyst is expressed as
10NiO-10Al2O3/8-Ni-SMF-600。
In the present embodiment the 4. step, roasting time can be 0.5～2 hour, and remaining condition is constant.
In the present embodiment the 4. step, Ni (NO in the aqueous solution of 3 grams of carriers of incipient impregnation3)2·6H2O and
Al(NO3)3·9H2The content of O can be 0.146 gram and 1.864 grams, or 2.183 grams and 0.124 gram, or 0.719 gram and
1.228 grams, remaining condition is constant, and obtained catalyst is expressed as 1NiO-15Al2O3/ 8-Ni-SMF-450,
15NiO-1Al2O3/ 8-Ni-SMF-450,5NiO-10Al2O3/8-Ni-SMF-450。
Embodiment 2
The present embodiment provides the preparation of a kind of nickel oxide-aluminium oxide catalyst sintering the load of red copper metal fiber carrier.
1. a diameter of 8 microns, the red copper metallic fiber 15 grams of a length of 2～5 millimeters and a length of 0.1～1 millimeter of fibre are weighed
2.5 grams and 1.5 liters water of cellulose fiber join in blender, transfer to papermaking after being sufficiently stirred for the most scattered fiber pulp
In machine, add water to 8.5 liters, stirring, draining aftershaping；In 250 DEG C of roastings 1 hour in air atmosphere after to be dried；
Sinter 1 hour in 900 DEG C in hydrogen again, obtain sintering metal red copper fiber carrier, be expressed as 8-Cu-SMF；
2. sintering metal red copper fiber carrier step 1. prepared is cut into a diameter of 16 millimeters of disks and weighs 5 grams and be placed in
In 50 milliliters of beakers.At room temperature, the suspension incipient impregnation metal containing 0.4 gram of aluminium powder that particle diameter is 1～3 micron is pipetted
Phase carrier and be dried make aluminum particle be dispersed in metal phase carrier surface after, in high-purity protective atmosphere, at 600 DEG C, make aluminium powder
Granule carries out solid-solid alloying reaction 2 hours with metal phase carrier top layer, obtains top layer alloyed metal (AM) phase carrier；
3. product step 2. prepared, carries out taking out aluminum with the aqueous hydrochloric acid solution that concentration is 20% at room temperature to 60 DEG C and processes
6 hours, after distilled water flushing, air are dried, obtain the metal phase carrier of top layer porous；
4. 3 grams of the carrier that 3. step prepares is weighed, with isopyknic Ni (NO containing 1.438 grams and 0.614 gram3)2·6H2O
With Al (NO3)3·9H2The aqueous solution of O, at room temperature incipient impregnation carrier, 300 DEG C of roastings in air after 100 DEG C of drying
Burn 2 hours, i.e. obtain the nickel oxide-aluminium oxide catalyst of described sintering red copper metal fiber carrier load.
Learn through plasma inductance linking atom emission spectrometry, in the catalyst prepared by the present embodiment, the weight of NiO
Content is 9.6%, Al2O3Weight content be 5.3%；Catalyst prepared by the present embodiment is expressed as
10NiO-5Al2O3/8-Cu-SMF-300。
Learn through macroscopic measurement: the integral catalyzer 10NiO-5Al of this enforcement preparation2O3In/8-Cu-SMF-300, sintering
Percent by volume shared by Ni metal fibre structure catalyst backbone is 38%, and porosity is 62%.
In the present embodiment the 1. step, the diameter of red copper metallic fiber can be 30 microns, and remaining condition is constant, gained catalyst
It is expressed as 10NiO-5Al2O3/30-Cu-SMF-300。
Embodiment 3
The present embodiment provides the preparation of a kind of red copper fiber carrier load ferric oxide-alumina catalyst.
1. a diameter of 30 microns, the red copper metallic fiber (being expressed as Cu-fiber) 15 grams of a length of 5～10 millimeters are weighed,
At room temperature, pipette the suspension incipient impregnation metal phase carrier containing 0.075 gram of aluminium powder that particle diameter is 1～3 micron and be dried
After making aluminum particle be dispersed in metal phase carrier surface, high-purity protective atmosphere makes at 600 DEG C aluminum particle and metal phase
Carrier top layer carries out solid-solid alloying reaction 2 hours, obtains top layer alloyed metal (AM) phase carrier；
2. product step 1. prepared, carries out taking out aluminum with the aqueous hydrochloric acid solution that concentration is 5% at room temperature to 60 DEG C and processes
1 hour, after distilled water flushing, air are dried, obtain the metal phase carrier of top layer porous；
3. 3 grams of the carrier that 2. step prepares is weighed, with isopyknic Fe (NO containing 1.489 grams and 0.614 gram3)3·9H2O
With Al (NO3)3·9H2The aqueous solution of O, at room temperature incipient impregnation carrier, 300 DEG C of roastings in air after 100 DEG C of drying
Burn 2 hours, i.e. obtain the ferric oxide-alumina catalyst of described red copper metal fiber carrier load.
Learn through plasma inductance linking atom emission spectrometry, in the catalyst prepared by the present embodiment, Fe2O3Weight
Amount content is 10.6%, Al2O3Weight content be 4.8%；Catalyst prepared by the present embodiment is expressed as
10Fe2O3-5Al2O3/ 30-Cu-fiber-300(mantissa herein " 300 " represents that the sintering temperature of step 3. middle catalyst is 300 DEG C,
Lower same).
10Fe2O3-5Al2O3The optical photograph of/30-Cu-fiber-300 is shown in that Fig. 4, scanning electron microscope (SEM) photo are shown in Fig. 5.
In the present embodiment the 1. step, the diameter of red copper metallic fiber can be 150 microns (being expressed as 150-Cu-fiber), remaining
Condition is constant, and gained catalyst is expressed as 10Fe2O3-5Al2O3/150-Cu-fiber-300。
Embodiment 4
The present embodiment provides the preparation of a kind of ferrous metal fiber carrier load nickel oxide-aluminium oxide catalyst.
1. a diameter of 80 microns, the ferrous metal fiber (being expressed as 80-Fe-fiber) 5 grams of a length of 5～10 millimeters are weighed,
At room temperature, pipette the suspension incipient impregnation metal phase carrier containing 0.2 gram of aluminium powder that particle diameter is 1～3 micron and be dried make
After aluminum particle is dispersed in metal phase carrier surface, aluminum particle is made to carry mutually with metal at 600 DEG C in high-purity protective atmosphere
Surface layer carries out solid-solid alloying reaction 2 hours, obtains top layer alloyed metal (AM) phase carrier；
2. product step 1. prepared, carries out taking out aluminum with the sodium hydrate aqueous solution that concentration is 5% at room temperature to 60 DEG C
Process 1 hour, after distilled water flushing, air are dried, obtain the metal phase carrier of top layer porous；
3. 3 grams of the carrier that 2. step prepares is weighed, with isopyknic Ni (NO containing 0.745 gram and 0.614 gram3)2·6H2O
With Al (NO3)3·9H2The aqueous solution of O, at room temperature incipient impregnation carrier, 400 DEG C of roastings in air after 100 DEG C of drying
Burn 2 hours, i.e. obtain the nickel oxide-aluminium oxide catalyst of described metallic iron fiber carrier load.
Learn through plasma inductance linking atom emission spectrometry, in the catalyst prepared by the present embodiment, the weight of NiO
Content is 5.2%, Al2O3Weight content be 5.3%；Catalyst prepared by the present embodiment is expressed as
5NiO-5Al2O3/80-Fe-fiber-400。
In the present embodiment, metallic fiber used can be the copper-nickel alloy fiber (being expressed as 80-BT-fiber) of 80 microns, remaining condition
Constant, gained catalyst is expressed as 5NiO-5Al2O3/80-BT-fiber-400。
Embodiment 5
The present embodiment provides the system of a kind of sintrered nickel metal fiber carrier load nickel oxide-alumina-rare earth oxide catalyst
Standby.
1. a diameter of 8 microns, the nickel metallic fiber 15 grams of a length of 2～5 millimeters and a length of 0.1～1 millimeter of fiber are weighed
2.5 grams and 1.5 liters water of cellulose fiber join in blender, transfer to paper machine after being sufficiently stirred for the most scattered fiber pulp
In, add water to 8.5 liters, stirring, draining aftershaping；In 500 DEG C of roastings 1 hour in air atmosphere after to be dried；Again
Hydrogen sinters 1 hour in 950 DEG C, the thickness of product is controlled at 1 millimeter by compacting, obtain sintering metal nickel fine
Dimension carrier, is expressed as 8-Ni-SMF；
2. sintering metal nickel fiber carrier step 1. prepared is cut into a diameter of 16 millimeters of disks and weighs 5 grams and be placed in 50
In milliliter beaker.At room temperature, pipette containing 0.1 gram of aluminium powder (mass ratio of aluminium powder/metal phase carrier that particle diameter is 1～3 micron
Be 2/100) suspension incipient impregnation metal phase carrier and be dried make aluminum particle be dispersed in metal phase carrier surface after,
Aluminum particle is made to carry out solid-solid alloying reaction 2 hours with metal phase carrier top layer in high-purity protective atmosphere at 650 DEG C,
Obtain top layer alloyed metal (AM) phase carrier；
3. product step 2. prepared, carries out taking out at aluminum with the sodium hydrate aqueous solution that concentration is 5% at room temperature to 60 DEG C
Manage 6 hours, after distilled water flushing, air are dried, obtain the metal phase carrier of top layer porous；
4. weigh 3 grams of the carrier that 3. step prepares, contain 0.596 gram, 0.698 gram and 0.211 gram with isopyknic
Ni(NO3)2·6H2O、Al(NO3)3·9H2O and Ce (NO3)3·6H2The aqueous solution of O, at room temperature incipient impregnation carrier,
100 DEG C are dried dried 500 DEG C of roastings 2 hours in air, i.e. obtain the nickel oxide of described nickel metal fiber carrier load
-alumina-silica cerium catalyst, wherein NiO, Al2O3And CeO2Weight content in the catalyst is respectively 5%, 5%
With 2.5%, catalyst is expressed as 5NiO-5Al2O3-2.5CeO2/8-Ni-SMF-500。
Learn through macroscopic measurement: the integral catalyzer 5NiO-5Al of this enforcement preparation2O3-2.5CeO2In/8-Ni-SMF-500,
Percent by volume shared by metallic nickel fibre structure catalyst backbone is 22%, and porosity is 78%.
In the present embodiment the 4. step, Ni (NO in the aqueous solution of 3 grams of carriers of incipient impregnation3)2·6H2O、
Al(NO3)3·9H2O and Ce (NO3)3·6H2The content of O can be 0.719 gram, 0.614 gram and 0.500 gram, or 1.528
Gram, 0.652 gram and 0.510 gram, remaining condition is constant, prepare catalyst be expressed as 5NiO-5Al2O3-5CeO2/
8-Ni-SMF-500,10NiO-5Al2O3-5CeO2/8-Ni-SMF-500。
In the present embodiment the 4. step, the salt for the aqueous solution rare earth elements of 3 grams of carriers of incipient impregnation can be
La(NO3)3·6H2O, its content can be 0.120 gram or 0.230 gram, and remaining condition is constant, and the catalyst prepared is expressed as
5NiO-5Al2O3-2.5La2O3/ 8-Ni-SMF-500,5NiO-5Al2O3-5La2O3/8-Ni-SMF-500。
Embodiment 6
The present embodiment provides a kind of nickel metal fiber carrier load different content oxidation nickel-alumina-alkaline earth oxide agent
Preparation.
1. a diameter of 8 microns, the nickel metallic fiber 15 grams of a length of 2～5 millimeters and a length of 0.1～1 millimeter of fiber are weighed
2.5 grams and 1.5 liters water of cellulose fiber join in blender, transfer to paper machine after being sufficiently stirred for the most scattered fiber pulp
In, add water to 8.5 liters, stirring, draining aftershaping；In 500 DEG C of roastings 1 hour in air atmosphere after to be dried；Again
Hydrogen sinters 1 hour in 950 DEG C, the thickness of product is controlled at 1 millimeter by compacting, obtain sintering metal nickel fine
Dimension carrier, is expressed as 8-Ni-SMF；
2. sintering metal nickel fiber carrier step 1. prepared is cut into a diameter of 16 millimeters of disks and weighs 5 grams and be placed in
In 50 milliliters of beakers.At room temperature, pipette containing 0.025 gram of aluminium powder that particle diameter is 1～3 micron (aluminium powder/metal phase carrier
Mass ratio is 0.5/100) suspension incipient impregnation metal phase carrier and be dried make aluminum particle be dispersed in metal phase carrier
Behind surface, aluminum particle and metal phase carrier top layer is made to carry out solid-solid alloying in high-purity protective atmosphere at 500 DEG C anti-
Answer 2 hours, obtain top layer alloyed metal (AM) phase carrier；
3. product step 2. prepared, carries out taking out aluminum with the sodium hydrate aqueous solution that concentration is 5% at room temperature to 60 DEG C
Process 1 hour, after distilled water flushing, air are dried, obtain the metal phase carrier of top layer porous；
4. weigh 3 grams of the carrier that 3. step prepares, contain 1.222 grams, 1.043 grams and 0.510 gram with isopyknic
Ni(NO3)2·6H2O、Al(NO3)3·9H2O and Mg (NO3)2·6H2The aqueous solution of O, at room temperature incipient impregnation carrier,
100 DEG C are dried dried 600 DEG C of roastings 2 hours in air, i.e. obtain the nickel oxide of described nickel metal fiber carrier load
-alumina-silica Mg catalyst, wherein NiO, Al2O3It is respectively 8%, 8% with MgO weight content in the catalyst
With 2%, catalyst is expressed as 8NiO-8Al2O3-2MgO/8-Ni-SMF-600。
Learn through macroscopic measurement: the integral catalyzer 8NiO-8Al of this enforcement preparation2O3In-2MgO/8-Ni-SMF-600,
Percent by volume shared by metallic nickel fibre structure catalyst backbone is 28%, and porosity is 72%.
In the present embodiment the 4. step, in the aqueous solution of 5 grams of carriers of incipient impregnation, the salt of alkali earth metal can be
Ca(NO3)2·4H2O, its content is 0.519 gram, and remaining condition is constant, and the catalyst prepared is expressed as
8NiO-8Al2O3-2CaO/8-Ni-SMF-600。
Embodiment 7
The present embodiment provides the system of a kind of sintrered nickel metal fiber carrier load oxidation nickel-alumina-alkali metal oxide catalyst
Standby.
1. a diameter of 8 microns, the nickel metallic fiber 15 grams of a length of 2～5 millimeters and a length of 0.1～1 millimeter of fiber are weighed
2.5 grams and 1.5 liters water of cellulose fiber join in blender, transfer to paper machine after being sufficiently stirred for the most scattered fiber pulp
In, add water to 8.5 liters, stirring, draining aftershaping；In 500 DEG C of roastings 1 hour in air atmosphere after to be dried；Again
Hydrogen sinters 1 hour in 950 DEG C, the thickness of product is controlled at 1 millimeter by compacting, obtain sintering metal nickel fine
Dimension carrier, is expressed as 8-Ni-SMF；
2. sintering metal nickel fiber carrier step 1. prepared is cut into a diameter of 16 millimeters of disks and weighs 5 grams and be placed in
In 50 milliliters of beakers.At room temperature, pipette containing 0.025 gram of aluminium powder that particle diameter is 1～3 micron (aluminium powder/metal phase carrier
Mass ratio is 0.5/100) suspension incipient impregnation metal phase carrier and be dried make aluminum particle be dispersed in metal phase carrier
Behind surface, aluminum particle and metal phase carrier top layer is made to carry out solid-solid alloying in high-purity protective atmosphere at 550 DEG C anti-
Answer 2 hours, obtain top layer alloyed metal (AM) phase carrier；
3. product step 2. prepared, carries out taking out aluminum with the sodium hydrate aqueous solution that concentration is 5% at room temperature to 60 DEG C
Process 1 hour, after distilled water flushing, air are dried, obtain the metal phase carrier of top layer porous；
4. weigh 3 grams of the carrier that 3. step prepares, contain 1.222 grams, 1.043 grams and 0.110 gram with isopyknic
Ni(NO3)2·6H2O、Al(NO3)3·9H2O and NaNO3Aqueous solution, at room temperature incipient impregnation carrier, 100 DEG C of bakings
Dried 600 DEG C of roastings 2 hours in air, i.e. obtain the oxidation nickel-alumina of described nickel metal fiber carrier load-
Sodium oxide catalyst, wherein NiO, Al2O3And Na2O weight content in the catalyst is respectively 8%, 8% and 2%,
Catalyst is expressed as 8NiO-8Al2O3-2Na2O/8-Ni-SMF-600。
Learn through macroscopic measurement: the integral catalyzer 8NiO-8Al of this enforcement preparation2O3-2Na2In O/8-Ni-SMF-600,
Percent by volume shared by metallic nickel fibre structure catalyst backbone is 28%, and porosity is 72%.
In the present embodiment the 4. step, in the aqueous solution of 3 grams of carriers of incipient impregnation, the salt of alkali earth metal can be
KNO3, its content is 0.090 gram, and remaining condition is constant, and the catalyst prepared is expressed as
8NiO-8Al2O3-2K2O/8-Ni-SMF-600。
Embodiment 8
The present embodiment provides the preparation of the carrier loaded nickel oxide of a kind of metal foam nickel-alumina-silica cerium catalyst.
1. weighing nickel foam metal (being expressed as Ni-foam) 5 grams, at room temperature, pipetting containing particle diameter is 1～10 micron
The suspension incipient impregnation metal phase carrier of 0.3 gram of aluminium powder after being dried and making aluminum particle be dispersed in metal phase carrier surface,
Aluminum particle is made to carry out solid-solid alloying reaction 2 hours with metal phase carrier top layer in high-purity protective atmosphere at 600 DEG C,
Obtain top layer alloyed metal (AM) phase carrier；
2. product step 1. prepared, carries out taking out aluminum with the sodium hydrate aqueous solution that concentration is 15% at room temperature to 60 DEG C
Process 1 hour, after distilled water flushing, air are dried, obtain the metallic nickel foam carrier of top layer porous；
3. weigh 3 grams of the carrier that 2. step prepares, contain 1.528 grams, 0.652 gram and 0.450 gram with isopyknic
Ni(NO3)2·6H2O、Al(NO3)3·9H2O and Ce (NO3)3·6H2The aqueous solution of O, room temperature volumetric dipping carrier, 100 DEG C
After drying in air 600 DEG C of roastings 2 hours, i.e. obtain nickel oxide-alumina-silica that described nickel foam is carrier loaded
Cerium catalyst, wherein NiO, Al2O3And CeO2Weight content in the catalyst is respectively 10%, 5% and 5%, and this is urged
Agent is expressed as 10NiO-5Al2O3-5CeO2/Ni-foam-600。
10NiO-5Al prepared by the present embodiment2O3-5CeO2The optical photograph of/Ni-foam-600 catalyst and scanning electron microscope
(SEM) photo is shown in Fig. 6, Fig. 7 respectively.
Learn through macroscopic measurement: the integral catalyzer 10NiO-5Al of this enforcement preparation2O3-5CeO2In/Ni-foam-600,
Percent by volume shared by metallic nickel foam framework is 20%, and porosity is 80%.
In the present embodiment, metal foaming material can be that foam copper-nickel alloy (being expressed as BT-foam), foam copper (are expressed as
Cu-foam), foamed iron (being expressed as Fe-foam), remaining condition is constant, and obtained catalyst is expressed as
10NiO-5Al2O3-5CeO2/BT-foam-600、10NiO-5Al2O3-5CeO2/Cu-foam-600、10NiO
-5Al2O3-5CeO2/Fe-foam-600。
Embodiment 9
The present embodiment provides the preparation of the carrier loaded nickel oxide of a kind of metal foam nickel-alumina-silica Mn catalyst.
1. weighing 5 grams of nickel foam (being expressed as Ni-foam) metal, at room temperature, pipetting containing particle diameter is 1～10 micron
The suspension incipient impregnation metal phase carrier of 0.3 gram of aluminium powder after being dried and making aluminum particle be dispersed in metal phase carrier surface,
Aluminum particle is made to carry out solid-solid alloying reaction 2 hours with metal phase carrier top layer in high-purity protective atmosphere at 600 DEG C,
Obtain top layer alloyed metal (AM) phase carrier；
2. product step 1. prepared, carries out taking out aluminum with the sodium hydrate aqueous solution that concentration is 15% at room temperature to 60 DEG C
Process 1 hour, after distilled water flushing, air are dried, obtain the metallic nickel foam carrier of top layer porous；
3. weigh 3 grams of the carrier that 2. step prepares, contain 1.528 grams, 0.652 gram and 0.250 gram with isopyknic
Ni(NO3)2·6H2O、Al(NO3)3·9H2O and Mn (NO3)2·4H2The aqueous solution of O, room temperature volumetric dipping carrier,
100 DEG C dry after in air 600 DEG C of roastings 2 hours, i.e. obtain the oxidation nickel-alumina that described nickel foam is carrier loaded
-manganese oxide catalyst, wherein NiO, Al2O3And MnO2Weight content in the catalyst is respectively 10%, 5% and 5%,
This catalyst is expressed as 10NiO-5Al2O3-5MnO2/Ni-foam-600。
In the present embodiment the 3. step, the aqueous solution for 3 grams of carriers of incipient impregnation can be containing 1.528 grams, 0.652 gram
Ni (NO with 0.250 gram3)2·6H2O、Al(NO3)3·9H2O and Mo (NO3)3.5H2The aqueous solution of O, room temperature volumetric
Dipping carrier, 100 DEG C dry after in air 600 DEG C of roastings 2 hours, remaining condition is constant, i.e. obtains described nickel bubble
The carrier loaded nickel oxide of foam-alumina-silica molybdenum catalyst, wherein NiO, Al2O3And MoO3Weight in the catalyst
Content is respectively 10%, 5% and 5%, and this catalyst is expressed as 10NiO-5Al2O3-5MoO3/Ni-foam-600。
In the present embodiment the 3. step, first with isopyknic Ni (NO containing 1.528 grams and 0.652 gram3)2·6H2O and
Al(NO3)3·9H2The aqueous solution of O, room temperature volumetric 3 grams of carriers of dipping, after 100 DEG C dry, contain 0.230 with isopyknic
Gram Na2WO4·2H2After the aqueous solution of O incipient impregnation again, dry and 600 DEG C of roastings 2 hours in air in 100 DEG C,
Remaining condition is constant, i.e. obtains the carrier loaded nickel oxide of described nickel foam-alumina-silica tungsten-sodium oxide catalyst, its
Middle NiO, Al2O3、WO3And Na2O weight content in the catalyst is respectively 10%, 5%, 4% and 1%, and this is urged
Agent is expressed as 10NiO-5Al2O3-4WO3-1Na2O/Ni-foam-600。
Inventors herein have recognized that, the present invention with the gained catalyst such as the mutually carrier loaded NiO of porous metals at catalytic performance and
Al all it is substantially better than on heat conductivility2O3NiO base catalyst Deng oxide carrier load.Present inventor is presented herein below
The catalyst for contrast experiment done.
Comparative example 1
Weigh the Ni (NO of 1.438g3)2·6H2Mg (the NO of O and 1.198g3)2·6H2O be dissolved in 4 milliliters of water are made into water-soluble
Liquid, is at room temperature dried γ-Al by 3.0g2O3Impregnated in the nickel nitrate of preparation with equi-volume impregnating and magnesium nitrate mixing is water-soluble
In liquid after 12 hours, dried at 120 DEG C, in 550 DEG C of roastings 2 hours in air atmosphere, i.e. obtain MgO modification
The nickel oxide catalyst of alumina load, wherein NiO and MgO weight content in the catalyst is respectively 10% and 5%,
It is expressed as 10NiO-5MgO/ γ-Al2O3。
Application examples 1
Fixed bed reactors are investigated catalyst of the present invention under the conditions of differential responses to the methanation of carbon monoxide reaction
Catalytic performance, reaction raw materials be the mol ratio of carbon monoxide and hydrogen, carbon monoxide and hydrogen be 1:3.Fixed bed reactors
Be internal diameter be that the quartz ampoule of 16 millimeters, carbon monoxide and hydrogen mixed before entering reaction tube, mix homogeneously
Rear entrance beds reacts.Product gas-phase product after cold-trap condenses enters chromatograph, utilizes conductance cell to detect
Device (TCD) is analyzed.
Should the 10NiO-10Al for preparing in embodiment 1 of use-case2O3Carry out on/8-Ni-SMF-450 catalyst, catalyst amount
Being 0.482 gram, volume is about 1.25 milliliters, and the reaction condition used and conversion ratio and selectivity are listed in table 1 respectively.
Table 1 reaction temperature, gas hourly space velocity prepare catalyst 10NiO-10Al to embodiment 12O3/ 8-Ni-SMF-450 is catalyzed CO
The impact of methanation performance
| Reaction temperature (DEG C) | Unstripped gas air speed (h-1) | CO conversion ratio (%) | CH4Selectivity (%) |
| 250 | 2500 | 85.9 | 91.5 |
| 250 | 5000 | 91.9 | 86.8 |
| 250 | 10000 | 96.7 | 84.3 |
| 400 | 2500 | 99.3 | 92.8 |
| 400 | 5000 | 99.1 | 90.7 |
| 400 | 10000 | 98.2 | 86.8 |
| 550 | 2500 | 84.1 | 80.8 |
| 550 | 5000 | 83.6 | 82.5 |
| 550 | 10000 | 75.3 | 78.4 |
Application examples 2
Fixed bed reactors are investigated catalyst of the present invention under the conditions of differential responses to carbon dioxide methanation reaction
Catalytic performance, reaction raw materials be the mol ratio of carbon dioxide and hydrogen, carbon dioxide and hydrogen be 1:4.Fixed bed reactors
Be internal diameter be that the quartz ampoule of 16 millimeters, carbon dioxide and hydrogen mixed before entering reaction tube, mix homogeneously
Rear entrance beds reacts.Product gas-phase product after cold-trap condenses enters chromatograph, utilizes conductance cell to detect
Device (TCD) is analyzed.
Should the 10NiO-10Al for preparing in embodiment 1 of use-case2O3Carry out on/8-Ni-SMF-450 catalyst, catalyst amount
Being 0.482 gram, volume is about 1.25 milliliters, and the reaction condition used and conversion ratio and selectivity are listed in table 2 respectively.
Table 2 reaction temperature, gas hourly space velocity prepare catalyst 10NiO-10Al to embodiment 12O3/ 8-Ni-SMF-450 is catalyzed CO2
The impact of methanation performance
| Reaction temperature (DEG C) | Unstripped gas air speed (h-1) | CO2Conversion ratio (%) | CH4Selectivity (%) |
| 250 | 2500 | 52.7 | 99.65 |
| 250 | 5000 | 46.2 | 99.85 |
| 250 | 10000 | 35.5 | 99.92 |
| 400 | 2500 | 91.3 | 99.6 |
| 400 | 5000 | 81.8 | 99.0 |
| 400 | 10000 | 76.5 | 97.4 |
| 550 | 2500 | 72.6 | 82.1 |
| 550 | 5000 | 67.2 | 75.6 |
| 550 | 10000 | 64.6 | 69.5 |
Application examples 3
Reaction unit, reaction raw materials, catalyst amount are with application examples 1.
Should use-case at gas hourly space velocity 5000h-1Under the conditions of reaction temperature 350 DEG C, investigate an oxygen of embodiment catalyst
Changing carbon methanation catalyst reactivity worth, result is listed in table 3.
The each embodiment of table 3 and the methanation of carbon monoxide catalytic performance of comparative example catalyst
Application examples 4
Fixed bed reactors are investigated the catalyst of the present invention at different conditions to carbon monoxide and carbon dioxide first altogether
The catalytic performance of alkylation reaction, reaction raw materials is the gaseous mixture of carbon monoxide, carbon dioxide, methane and hydrogen, carbon monoxide,
The mol ratio of carbon dioxide, methane and hydrogen is 17:20:10:53.Fixed bed reactors be internal diameter be the stone of 16 millimeters
Ying Guan, carbon monoxide, carbon dioxide, methane and hydrogen mixed before entering reaction tube, enter and urge after mix homogeneously
Agent bed reacts.Product gas-phase product after cold-trap condenses enters chromatograph, utilizes thermal conductivity cell detector (TCD)
It is analyzed.
Should the 10NiO-5Al for preparing in embodiment 2 of use-case2O3Carry out on/8-Cu-SMF-300 catalyst, catalyst amount
Being 1.053 grams, volume is about 1.61 milliliters, and the reaction condition used and conversion ratio are listed in table 4 respectively.Carbon dioxide
Conversion ratio is that negative value represents that carbon dioxide does not convert, newly-generated partial CO 2.
Table 4 reaction temperature, gas hourly space velocity prepare catalyst 10NiO-5Al to embodiment 22O3/ 8-Cu-SMF-300 catalytic performance
Impact
| Reaction temperature (DEG C) | Unstripped gas air speed (h-1) | CO conversion ratio (%) | CO2Conversion ratio (%) |
| 350 | 5000 | 95.4 | -8.9 |
| 350 | 10000 | 91.8 | -7.8 |
| 350 | 15000 | 87.4 | -6.0 |
| 450 | 5000 | 82.8 | -4.0 |
| 450 | 10000 | 75.2 | -2.0 |
| 450 | 15000 | 66.5 | 1.7 |
| 550 | 5000 | 33.5 | 9.0 |
| 550 | 10000 | 24.3 | 14.1 |
| 550 | 15000 | 17.0 | 18.4 |
Application examples 5
Fixed bed reactors are investigated the catalyst of the present invention at different conditions to methane and carbon dioxide reforming reaction
Catalytic performance, reaction raw materials is the gaseous mixture of carbon dioxide and methane, and methane, the mol ratio of carbon dioxide are 1:1.Gu
Fixed bed reactor be internal diameter be the quartz ampoule of 16 millimeters, methane and carbon dioxide mixed before entering reaction tube,
Enter beds after mix homogeneously to react.Product gas-phase product after cold-trap condenses enters chromatograph, utilizes heat
Lead pool detector (TCD) to be analyzed.
Should the 5NiO-5Al for preparing in embodiment 5 of use-case2O3-2.5CeO2Carry out on/8-Ni-SMF-500 catalyst, catalysis
Agent consumption is 1.216 grams, and volume is about 1.92 milliliters, and the reaction condition used and conversion ratio are listed in table 5 respectively.
Table 5 reaction temperature, gas hourly space velocity are to embodiment 5 catalyst 5NiO-5Al2O3-2.5CeO2/ 8-Ni-SMF-500 catalytic
The impact of energy
| Reaction temperature (DEG C) | Unstripped gas air speed (h-1) | CH4Conversion ratio (%) | CO2Conversion ratio (%) |
| 750 | 3000 | 72.0 | 74.3 |
| 750 | 6000 | 59.9 | 72.6 |
| 750 | 9000 | 42.8 | 62.2 |
| 800 | 3000 | 87.0 | 91.8 |
| 800 | 6000 | 84.8 | 86.7 |
| 800 | 9000 | 68.9 | 80.7 |
| 850 | 3000 | 93.6 | 95.4 |
| 850 | 6000 | 93.2 | 94.4 |
| 850 | 9000 | 88.5 | 92.1 |
Application examples 6
Fixed bed reactors have been investigated the catalysis at different conditions to methane autothermal reforming reaction of the catalyst of the present invention
Performance, reaction raw materials is the gaseous mixture of methane, steam and oxygen, and the mol ratio of methane, steam and oxygen is 3:10:2.
Fixed bed reactors be internal diameter be the quartz ampoule of 16 millimeters, methane, steam and oxygen are entering the advance of reaction tube
Row mixing, enters beds and reacts after mix homogeneously.Product gas-phase product after cold-trap condenses enters chromatograph,
Thermal conductivity cell detector (TCD) is utilized to be analyzed.
Should the 8NiO-8Al for preparing in embodiment 6 of use-case2O3Carry out on-2MgO/8-Ni-fiber-600 catalyst, catalyst
Consumption is 1.139 grams, and volume is about 1.76 milliliters, and the reaction condition used and conversion ratio and selectivity are listed in table 6 respectively.
Table 6 reaction temperature, gas hourly space velocity are to embodiment 6 catalyst 8NiO-8Al2O3-2MgO/8-Ni-fiber-600 catalytic performance
Impact
| Reaction temperature (DEG C) | Unstripped gas air speed (h-1) | CH4Conversion ratio (%) | CO selectivity (%) |
| 650 | 3000 | 74.3 | 93.6 |
| 650 | 6000 | 70.6 | 92.9 |
| 650 | 9000 | 64.8 | 92.4 |
| 750 | 3000 | 88.2 | 95.2 |
| 750 | 6000 | 85.3 | 94.9 |
| 750 | 9000 | 81.9 | 95.1 |
| 850 | 3000 | 96.8 | 97.8 |
| 850 | 6000 | 94.3 | 97.2 |
| 850 | 9000 | 92.4 | 96.4 |
Application examples 7
The present embodiment is that strengthening reaction is moved heat, disappears by the high-termal conductivity of the catalyst by the CFD simulation comparative illustration present invention
Excellent effect except high temperature hotspot.
Reaction unit, reaction raw materials, catalyst amount are with application examples 1.
Should the 8NiO-8Al for preparing in embodiment 6 of use-case2O3Carry out on-2MgO/8-Ni-fiber-600 catalyst, reaction temperature
Spend 350 DEG C, gas hourly space velocity 10000h-1, the mol ratio of carbon monoxide and hydrogen be 1:3, CO conversion is 95%,
Methane selectively is 91%.Under the same reaction conditions, comparative example 1 made catalyst 10NiO-5MgO/ γ-Al2O3On,
CO conversion is 98%, methane selectively is 85%.Utilize CFD software fluent that the temperature in reactor is divided
Cloth carries out numerical simulation, grain bed (10NiO-5MgO/ γ-Al2O3) and metal fabric structures catalyst
(8NiO-8Al2O3-2MgO/8-Ni-fiber-600) Temperature Distribution in reactor is shown in Fig. 8.As seen from Figure 8, the present invention
Catalyst is owing to having good heat conductivity, and the hot(test)-spot temperature at beds center is only 110 DEG C；But, traditional oxygen
The hot(test)-spot temperature at compound carried catalyst bed center is up to 400 DEG C.
Application examples 8
Reaction unit, reaction raw materials, catalyst amount are with application examples 1.
Should the 5NiO-5Al for preparing in embodiment 5 of use-case2O3-2.5CeO2On/8-Ni-SMF-500 catalyst, with an oxidation
The mol ratio of carbon and hydrogen be the gaseous mixture of 1:3 be raw material, investigated catalytic CO methanation reaction 1000 hours
Stability, result is shown in Fig. 9.
Application examples 9
Reaction unit, reaction raw materials are with application examples 1, catalyst amount 10.4 milliliters.
Should the 5NiO-5Al for preparing in embodiment 5 of use-case2O3-2.5CeO2On/8-Ni-SMF-500 catalyst, with an oxidation
The mol ratio of carbon and hydrogen be the gaseous mixture of 1:3 be raw material, at 330 DEG C of reaction temperatures and 5000h-1Under gas hourly space velocity, examine
Having examined 3000 hours stability of catalytic CO methanation reaction, result is shown in Figure 10.As seen from Figure 10, the present invention
Catalyst has reaction stability and the activity and selectivity of excellence to the methanation of carbon monoxide.
Application examples 10
Reaction unit, reaction raw materials are with application examples 1, catalyst amount 10.2 milliliters.
Should the 5NiO-5Al for preparing in embodiment 5 of use-case2O3-2.5CeO2Carry out on/8-Ni-SMF-500 catalyst, with two
The mol ratio of carbonoxide and hydrogen be the gaseous mixture of 1:4 be raw material, at 320 DEG C of reaction temperatures and 5000h-1Under gas hourly space velocity,
Having investigated 1000 hours stability of catalysis carbon dioxide methanation, result is shown in Figure 11.As seen from Figure 11, present invention catalysis
Agent has reaction stability and the activity and selectivity of excellence to carbon dioxide methanation.
Claims (10)
1. a metal phase carrier load type catalyst, including be carried on metal phase carrier activity component metal oxide and
Auxiliary agent metal oxides also has formula xM1O-yM2O/ZT, wherein M1O represents activity component metal oxide, M2O
Representing auxiliary agent metal oxides, ZT represents metal phase carrier, and x represents the quality of catalyst shared by activity component metal oxide
Percent, y represents that auxiliary agent metal oxides accounts for the mass percent of catalyst；It is characterized in that:
Activity component metal oxide M1O is at least one in the oxide of nickel and ferrum；
Auxiliary agent metal oxides M2O be aluminum, cerium, lanthanum, molybdenum, manganese, tungsten, magnesium, calcium, sodium, potassium oxide in extremely
Few one；
The method preparing described metal phase carrier load type catalyst comprises the steps:
1. with the suspension incipient impregnation metal phase carrier containing aluminium powder and be dried make aluminum particle be dispersed in metal phase carrier table
Behind face, make aluminum particle carry out solid-solid alloying reaction with metal phase carrier top layer at 550～650 DEG C, obtain table
Layer alloyed metal (AM) phase carrier；
2. the top layer alloyed metal (AM) phase carrier 1. step prepared, below 60 DEG C at a temperature of be 5～20% by concentration
Hydrochloric acid or sodium hydrate aqueous solution carry out taking out aluminum and process, through rinsing, drying, the metal obtaining top layer porous carries mutually
Body；
The metal phase carrier of the top layer porous 3. step 2. prepared, incipient impregnation is in containing active component M1Metallic element
Salt and adjuvant component M2The aqueous solution of the salt of metallic element, roasting at 300～600 DEG C after drying, i.e. obtain described
Metal phase carrier load type catalyst.
Catalyst the most according to claim 1, it is characterised in that: described mass percent x is 1～15%, described
Mass percent y is 1～15%, and remaining composition of described catalyst is described metal phase carrier.
Catalyst the most according to claim 1, it is characterised in that: described metal phase carrier ZT is metallic nickel, metal
Copper, metallic iron or metal copper-nickel alloy.
Catalyst the most according to claim 1, it is characterised in that: described metal phase carrier is a diameter of 4～150 micro-
Rice, the fiber of a length of 2～10 millimeters or by the three-dimensional porous structure monoblock type metal fiber carrier of this fiber sintering
Or three-dimensional porous structure monoblock type metallic foam support.
Catalyst the most according to claim 4, it is characterised in that: the metallic framework of described metal phase carrier accounts for described
The percent by volume of metal phase carrier is 5～40%, remaining for porosity.
6. for the method preparing the metal phase carrier load type catalyst as according to any one of claim 1-5,
Described method comprises the steps:
1. with the suspension incipient impregnation metal phase carrier containing aluminium powder and be dried make aluminum particle be dispersed in metal phase carrier table
Behind face, make aluminum particle carry out solid-solid alloying reaction with metal phase carrier top layer at 550～650 DEG C, obtain table
Layer alloyed metal (AM) phase carrier；
2. the top layer alloyed metal (AM) phase carrier 1. step prepared, below 60 DEG C at a temperature of be 5～20% by concentration
Hydrochloric acid or sodium hydrate aqueous solution carry out taking out aluminum and process, through rinsing, drying, the metal obtaining top layer porous carries mutually
Body；
The metal phase carrier of the top layer porous 3. step 2. prepared, incipient impregnation is in containing active component M1Metallic element
Salt and adjuvant component M2The aqueous solution of the salt of metallic element, after drying, roasting at 300～600 DEG C, i.e. obtains
Described metal phase carrier load type catalyst.
Catalyst method the most according to claim 6, it is characterised in that in described metal phase carrier top layer alloying
During, the particle diameter of described aluminium powder is 1～10 micron, and the mass ratio of aluminium powder/metal phase carrier is 0.5～10/100.
8. by described in claim 1 or that according to claim 6 prepared by method metal phase carrier load type catalyst
It is used as the purposes of the catalyst of the reaction of carbon monoxide and/or hydrogenation of carbon dioxide synthesizing methane.
9. by described in claim 1 or metal phase carrier load type catalyst that according to claim 6 prepared by method
It is used as the methane purposes for the catalyst of the reaction of synthesis gas.
Purposes the most according to claim 9, it is characterised in that: described methane for the reaction of synthesis gas be methane-
CO 2 reformation or methane self-heating recapitalization prepare the reaction of synthesis gas.
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| CN103752315B (en) * | 2014-01-15 | 2016-08-10 | 易高环保能源研究院有限公司 | A kind of metal phase carrier load type catalyst and its production and use |
| CN105289649B (en) * | 2014-05-28 | 2022-03-15 | 易高环保能源研究院有限公司 | Metal phase carrier supported catalyst and preparation method and application thereof |
| JP6830543B2 (en) | 2017-01-31 | 2021-02-17 | クラリアント・プロドゥクテ・（ドイチュラント）・ゲゼルシャフト・ミト・ベシュレンクテル・ハフツング | Manganese-doped nickel-methaneation catalyst |
| WO2018141646A1 (en) | 2017-01-31 | 2018-08-09 | Clariant Produkte (Deutschland) Gmbh | Nickel methanation catalysts doped with iron and manganese |
| CN107597133B (en) * | 2017-10-15 | 2020-07-31 | 华东师范大学 | Self-supporting nickel oxide-based catalyst and preparation method and application thereof |
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| JP6881393B2 (en) * | 2018-06-08 | 2021-06-02 | 株式会社豊田中央研究所 | Methane production equipment, control method of methane production equipment, and methane production method |
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| CN109225190B (en) * | 2018-09-04 | 2021-06-15 | 华东师范大学 | Self-supporting hydrogenation catalyst and preparation method and application thereof |
| CN111203210A (en) * | 2018-11-22 | 2020-05-29 | 中国石油化工股份有限公司 | Supported catalyst, preparation method thereof and method for preparing olefin by oxidative coupling of methane |
| CN111318281A (en) * | 2018-12-13 | 2020-06-23 | 中国科学院大连化学物理研究所 | Catalyst carrier and catalyst for preparing methane through carbon dioxide hydrogenation reaction, and preparation method and application thereof |
| CN110029383B (en) * | 2019-03-15 | 2020-08-18 | 浙江工贸职业技术学院 | Degradable zinc-copper foam biological material |
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| CN115970746A (en) * | 2022-12-22 | 2023-04-18 | 浙江大学 | Method for improving activity of low-temperature methanation reaction by establishing hydrophobization catalytic system |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1154944A (en) * | 1996-01-17 | 1997-07-23 | 中国科学院大连化学物理研究所 | Nickel based catalyst for prepn. of synthetic gas by methane direct oxidation |
| CN1168298A (en) * | 1996-06-19 | 1997-12-24 | 中国科学院大连化学物理研究所 | Catalyst for producing synthetic gas through the reaction between low-carbon alkane and carbon dioxide and its use |
| CN101703933A (en) * | 2009-11-06 | 2010-05-12 | 山西大学 | Bimetal methanation catalyst and preparation method thereof |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS60209254A (en) * | 1984-04-03 | 1985-10-21 | Mitsubishi Heavy Ind Ltd | Catalyst for manufacturing gas containing methane |
| CN1179789C (en) * | 2001-09-19 | 2004-12-15 | 川化集团有限责任公司 | Catalyst for producing synthetic gas by partial oxidation of methane |
| US20110313187A1 (en) * | 2009-02-09 | 2011-12-22 | Christof Wilhelm Wigbers | Method for improving the catalytic activity of monolithic catalysts |
| CN103157475B (en) * | 2013-03-22 | 2015-10-28 | 北京神雾环境能源科技集团股份有限公司 | For the Catalysts and its preparation method of coke-stove gas tri-reforming |
| CN103752315B (en) * | 2014-01-15 | 2016-08-10 | 易高环保能源研究院有限公司 | A kind of metal phase carrier load type catalyst and its production and use |
-
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-
2015
- 2015-01-08 WO PCT/CN2015/000020 patent/WO2015106634A1/en active Application Filing
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1154944A (en) * | 1996-01-17 | 1997-07-23 | 中国科学院大连化学物理研究所 | Nickel based catalyst for prepn. of synthetic gas by methane direct oxidation |
| CN1168298A (en) * | 1996-06-19 | 1997-12-24 | 中国科学院大连化学物理研究所 | Catalyst for producing synthetic gas through the reaction between low-carbon alkane and carbon dioxide and its use |
| CN101703933A (en) * | 2009-11-06 | 2010-05-12 | 山西大学 | Bimetal methanation catalyst and preparation method thereof |
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