CN106999915A - 用于一氧化二氮分解的铑催化剂、其制备及其用途 - Google Patents
用于一氧化二氮分解的铑催化剂、其制备及其用途 Download PDFInfo
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- CN106999915A CN106999915A CN201580065651.1A CN201580065651A CN106999915A CN 106999915 A CN106999915 A CN 106999915A CN 201580065651 A CN201580065651 A CN 201580065651A CN 106999915 A CN106999915 A CN 106999915A
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- catalyst
- hal
- aryl
- zirconium dioxide
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- 239000003054 catalyst Substances 0.000 title claims abstract description 94
- GQPLMRYTRLFLPF-UHFFFAOYSA-N Nitrous Oxide Chemical compound [O-][N+]#N GQPLMRYTRLFLPF-UHFFFAOYSA-N 0.000 title claims abstract description 64
- 239000010948 rhodium Substances 0.000 title claims abstract description 34
- 239000001272 nitrous oxide Substances 0.000 title claims abstract description 31
- 229910052703 rhodium Inorganic materials 0.000 title claims abstract description 22
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 title claims abstract description 16
- 238000000354 decomposition reaction Methods 0.000 title claims description 7
- 238000002360 preparation method Methods 0.000 title description 6
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims abstract description 37
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 claims abstract description 27
- 239000000853 adhesive Substances 0.000 claims abstract description 21
- 230000001070 adhesive effect Effects 0.000 claims abstract description 21
- 150000003377 silicon compounds Chemical class 0.000 claims abstract description 21
- 239000000843 powder Substances 0.000 claims abstract description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 17
- 238000000034 method Methods 0.000 claims abstract description 14
- 125000003118 aryl group Chemical group 0.000 claims abstract description 13
- 125000003710 aryl alkyl group Chemical group 0.000 claims abstract description 11
- 238000001354 calcination Methods 0.000 claims abstract description 11
- 125000002252 acyl group Chemical group 0.000 claims abstract description 7
- 125000003342 alkenyl group Chemical group 0.000 claims abstract description 7
- 125000000304 alkynyl group Chemical group 0.000 claims abstract description 7
- 229910052794 bromium Inorganic materials 0.000 claims abstract description 6
- 229910052801 chlorine Inorganic materials 0.000 claims abstract description 6
- 125000000753 cycloalkyl group Chemical group 0.000 claims abstract description 6
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- 229910052736 halogen Inorganic materials 0.000 claims abstract description 6
- 229910052740 iodine Inorganic materials 0.000 claims abstract description 6
- 125000000392 cycloalkenyl group Chemical group 0.000 claims abstract 3
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- 125000000217 alkyl group Chemical group 0.000 claims description 14
- 238000002156 mixing Methods 0.000 claims description 12
- 238000004898 kneading Methods 0.000 claims description 11
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- 239000000654 additive Substances 0.000 claims description 9
- 239000004088 foaming agent Substances 0.000 claims description 8
- 229910052750 molybdenum Inorganic materials 0.000 claims description 7
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 5
- 239000011733 molybdenum Substances 0.000 claims description 5
- 230000007704 transition Effects 0.000 claims description 5
- 238000007598 dipping method Methods 0.000 claims description 3
- 229910052747 lanthanoid Inorganic materials 0.000 claims description 2
- 150000002602 lanthanoids Chemical class 0.000 claims description 2
- 230000000737 periodic effect Effects 0.000 claims description 2
- 125000005843 halogen group Chemical group 0.000 claims 2
- 238000001035 drying Methods 0.000 abstract description 6
- 238000004519 manufacturing process Methods 0.000 abstract description 5
- 150000002367 halogens Chemical class 0.000 abstract description 4
- 239000000463 material Substances 0.000 abstract 3
- 125000000547 substituted alkyl group Chemical group 0.000 abstract 2
- XJKVPKYVPCWHFO-UHFFFAOYSA-N silicon;hydrate Chemical compound O.[Si] XJKVPKYVPCWHFO-UHFFFAOYSA-N 0.000 abstract 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 12
- 239000000243 solution Substances 0.000 description 12
- -1 alkoxy silane Chemical compound 0.000 description 11
- 229910017604 nitric acid Inorganic materials 0.000 description 9
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 8
- 229910052751 metal Inorganic materials 0.000 description 8
- 239000002184 metal Substances 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 7
- 239000007789 gas Substances 0.000 description 7
- 229910052760 oxygen Inorganic materials 0.000 description 7
- 239000000047 product Substances 0.000 description 7
- 239000000377 silicon dioxide Substances 0.000 description 7
- 239000002912 waste gas Substances 0.000 description 7
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 6
- 239000002585 base Substances 0.000 description 6
- 239000003638 chemical reducing agent Substances 0.000 description 6
- 229910044991 metal oxide Inorganic materials 0.000 description 6
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- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 5
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- 239000003795 chemical substances by application Substances 0.000 description 5
- 150000001875 compounds Chemical class 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 5
- 229910052710 silicon Inorganic materials 0.000 description 5
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 4
- 239000011651 chromium Substances 0.000 description 4
- 229910052681 coesite Inorganic materials 0.000 description 4
- 229910052906 cristobalite Inorganic materials 0.000 description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 4
- 229920001296 polysiloxane Polymers 0.000 description 4
- VXNYVYJABGOSBX-UHFFFAOYSA-N rhodium(3+);trinitrate Chemical compound [Rh+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VXNYVYJABGOSBX-UHFFFAOYSA-N 0.000 description 4
- 239000010703 silicon Substances 0.000 description 4
- 229910052682 stishovite Inorganic materials 0.000 description 4
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- OERNJTNJEZOPIA-UHFFFAOYSA-N zirconium nitrate Chemical compound [Zr+4].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O OERNJTNJEZOPIA-UHFFFAOYSA-N 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 3
- 229910021529 ammonia Inorganic materials 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 229910052804 chromium Inorganic materials 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 3
- 229910052742 iron Inorganic materials 0.000 description 3
- 150000002739 metals Chemical class 0.000 description 3
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 3
- 229910052707 ruthenium Inorganic materials 0.000 description 3
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 2
- 229910002651 NO3 Inorganic materials 0.000 description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 2
- 239000002202 Polyethylene glycol Substances 0.000 description 2
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 2
- 229920004482 WACKER® Polymers 0.000 description 2
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- 239000000969 carrier Substances 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 description 2
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 description 2
- 238000005660 chlorination reaction Methods 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 238000006356 dehydrogenation reaction Methods 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- JBKVHLHDHHXQEQ-UHFFFAOYSA-N epsilon-caprolactam Chemical compound O=C1CCCCCN1 JBKVHLHDHHXQEQ-UHFFFAOYSA-N 0.000 description 2
- 229910052737 gold Inorganic materials 0.000 description 2
- 239000010931 gold Substances 0.000 description 2
- 238000000227 grinding Methods 0.000 description 2
- 229910052741 iridium Inorganic materials 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 125000000962 organic group Chemical group 0.000 description 2
- 229910052763 palladium Inorganic materials 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
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- 229920001223 polyethylene glycol Polymers 0.000 description 2
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- 229910052709 silver Inorganic materials 0.000 description 2
- 229910009112 xH2O Inorganic materials 0.000 description 2
- XJUNLJFOHNHSAR-UHFFFAOYSA-J zirconium(4+);dicarbonate Chemical compound [Zr+4].[O-]C([O-])=O.[O-]C([O-])=O XJUNLJFOHNHSAR-UHFFFAOYSA-J 0.000 description 2
- ZNEMGFATAVGQSF-UHFFFAOYSA-N 1-(2-amino-6,7-dihydro-4H-[1,3]thiazolo[4,5-c]pyridin-5-yl)-2-[5-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]-1,3,4-oxadiazol-2-yl]ethanone Chemical compound NC=1SC2=C(CN(CC2)C(CC=2OC(=NN=2)C=2C=NC(=NC=2)NC2CC3=CC=CC=C3C2)=O)N=1 ZNEMGFATAVGQSF-UHFFFAOYSA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- 125000000882 C2-C6 alkenyl group Chemical group 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 1
- 101000801643 Homo sapiens Retinal-specific phospholipid-transporting ATPase ABCA4 Proteins 0.000 description 1
- 229910021638 Iridium(III) chloride Inorganic materials 0.000 description 1
- 229910015667 MoO4 Inorganic materials 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 229920001131 Pulp (paper) Polymers 0.000 description 1
- 102100033617 Retinal-specific phospholipid-transporting ATPase ABCA4 Human genes 0.000 description 1
- 229910019891 RuCl3 Inorganic materials 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- 229910003910 SiCl4 Inorganic materials 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
- 125000002777 acetyl group Chemical group [H]C([H])([H])C(*)=O 0.000 description 1
- 239000001361 adipic acid Substances 0.000 description 1
- 235000011037 adipic acid Nutrition 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910001413 alkali metal ion Inorganic materials 0.000 description 1
- 229910001420 alkaline earth metal ion Inorganic materials 0.000 description 1
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- 230000002902 bimodal effect Effects 0.000 description 1
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- 239000001569 carbon dioxide Substances 0.000 description 1
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- 229920002678 cellulose Polymers 0.000 description 1
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- 230000008859 change Effects 0.000 description 1
- IJOOHPMOJXWVHK-UHFFFAOYSA-N chlorotrimethylsilane Chemical compound C[Si](C)(C)Cl IJOOHPMOJXWVHK-UHFFFAOYSA-N 0.000 description 1
- 239000000567 combustion gas Substances 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 229910052593 corundum Inorganic materials 0.000 description 1
- 239000004148 curcumin Substances 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
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- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 239000005431 greenhouse gas Substances 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
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- 238000002329 infrared spectrum Methods 0.000 description 1
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- 229910000765 intermetallic Inorganic materials 0.000 description 1
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(III) nitrate Inorganic materials [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- ARYZCSRUUPFYMY-UHFFFAOYSA-N methoxysilane Chemical class CO[SiH3] ARYZCSRUUPFYMY-UHFFFAOYSA-N 0.000 description 1
- JLUFWMXJHAVVNN-UHFFFAOYSA-N methyltrichlorosilane Chemical compound C[Si](Cl)(Cl)Cl JLUFWMXJHAVVNN-UHFFFAOYSA-N 0.000 description 1
- 239000000206 moulding compound Substances 0.000 description 1
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 229910000069 nitrogen hydride Inorganic materials 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 150000003961 organosilicon compounds Chemical class 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- HZBAVWLZSLOCFR-UHFFFAOYSA-N oxosilane Chemical compound [SiH2]=O HZBAVWLZSLOCFR-UHFFFAOYSA-N 0.000 description 1
- 238000001935 peptisation Methods 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
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- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 150000002910 rare earth metals Chemical class 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- SVOOVMQUISJERI-UHFFFAOYSA-K rhodium(3+);triacetate Chemical compound [Rh+3].CC([O-])=O.CC([O-])=O.CC([O-])=O SVOOVMQUISJERI-UHFFFAOYSA-K 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- FZHAPNGMFPVSLP-UHFFFAOYSA-N silanamine Chemical compound [SiH3]N FZHAPNGMFPVSLP-UHFFFAOYSA-N 0.000 description 1
- 150000004756 silanes Chemical class 0.000 description 1
- FDNAPBUWERUEDA-UHFFFAOYSA-N silicon tetrachloride Chemical compound Cl[Si](Cl)(Cl)Cl FDNAPBUWERUEDA-UHFFFAOYSA-N 0.000 description 1
- 239000010944 silver (metal) Substances 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
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- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
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- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
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- 229910001845 yogo sapphire Inorganic materials 0.000 description 1
- 229910003158 γ-Al2O3 Inorganic materials 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
- B01J23/46—Ruthenium, rhodium, osmium or iridium
- B01J23/464—Rhodium
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/86—Catalytic processes
- B01D53/8621—Removing nitrogen compounds
- B01D53/8625—Nitrogen oxides
- B01D53/8628—Processes characterised by a specific 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
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
- B01J21/066—Zirconium or hafnium; Oxides or hydroxides thereof
-
- 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
- B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
- B01J21/08—Silica
-
- 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
- B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/24—Chromium, molybdenum or tungsten
- B01J23/28—Molybdenum
-
- 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
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Abstract
本发明涉及一种用于分解一氧化二氮的催化剂、用于生产所述催化剂的方法及其用途。该催化剂包含催化剂载体上的铑,并且催化剂载体由以下生产:将二氧化锆粉末与作为粘合剂的硅化合物和水混合以形成可捏和物质,使该物质均化,将该物质模制为模制品,干燥和煅烧。粘合剂选自通式(I)‑(VI)的硅化合物:(Hal)xSiR4‑x (I)、(Hal)xSi(OR1)4‑x (II)、(Hal)xSi(NR1R2)4‑x (III)、RxSi(OR1)4‑x (IV)、RxSi(NR1R2)4‑x (V)、(R1O)xSi(NR1R2)4‑x (VI),其中Hal彼此独立地表示卤素(F、Cl、Br或I),R彼此独立地表示H或任选取代的烷基、链烯基、炔基、环烷基、环烯基、芳基烷基或芳基,R1和R2彼此独立地表示H或任选取代的烷基、酰基、芳基烷基或芳基,并且x表示0‑4。
Description
本发明涉及一种用于一氧化二氮分解的催化剂及其制备方法和用途。
一氧化二氮(N2O)是分子全球变暖潜能约为二氧化碳的310倍的温室气体。最大比例的人为一氧化二氮来源于农业,但化学制造,包括硝酸和己二酸的生产中也释放相当大量的N2O。已知各种催化方法用于减少化学制造过程中的一氧化二氮排放。一种方式是借助还原剂选择性催化还原一氧化二氮,另一种方式是将其直接催化分解成氧和氮。使用还原剂意味着所使用的催化剂即使在相对低的温度下也具有足够的活性。合适的方法和体系可商购(DE 10001539 B4、EP 1269040 B1、EP 1257347 B1、EP 1370342 B1、EP 1372827 B1、EP 1497014 B1、US 7,462,340 B2、US 7,744,839 B2、WO 2009/021586 A1,Perbandt等,Chem.Eng.Techn.2013,第85卷,第5期,第705-709页)。一氧化二氮的直接催化分解的优点是不会由于还原剂而产生费用,也不会由于未耗用还原剂或还原剂的副反应而产生排放。然而,已知用于硝酸工厂的废气料流中的催化剂,例如在没有还原剂的情况下在400℃以下的温度下不具有足够的活性。
JP 05-103953描述了在与烃混合的废气料流中同时耗尽含氮气体(NO、NO2=NOx)和N2O并且然后在催化剂上通过的方法。催化剂由作为载体的各种金属氧化物上的一种或多种元素Cu、Ag、Cr、Fe、Co、Ni、Ru、Rh和Ir组成。
JP 2010242614描述了一种从内燃机的废气料流中除去一氧化二氮的方法,其中使包含1-10当量CO(相对于N2O)的废气在催化剂上通过。该催化剂包含在金属氧化物载体(Al2O3、TiO2或CeO2)上的贵金属(Pt与Pd或Rh),所述载体可以包含二氧化锆或二氧化硅作为另外的组分。
JP 2007152263公开了一种DeNOx催化剂,除了碱金属和碱土金属或稀土金属之外,其还包含以下元素中的一种:Ni、Cu、Co、Fe、Ag、Ru、Rh、Pt、Au、Pd或Ir。载体由孔体积为0.1-0.6ml/g的多孔金属氧化物组成。金属氧化物是二氧化钛、氧化铝、二氧化硅或二氧化锆。
各种金属氧化物上载Rh在文献中已知为用于一氧化二氮分解的催化剂。然而,在工业设施的废气料流(存在少量的水和氧气)中占主导的条件下,所研究的大多数体系没有足够的活性。
Christoforou等(Catalysis Letters 2002,第79卷,第137-147页)描述了用于一氧化二氮分解的催化剂,其中各种金属已经浸渍在氧化载体上。氧化铝载体上的Ru和Rh催化剂显示最佳的转化率。含有其他载体如SiO2或ZrO2上的Rh的催化剂显示较低的转化率。
DE 10 2011 111 307描述了用于在含氧气体中分解N2O的催化剂。该催化剂包含具有储氧特性的氧化物或混合氧化物(例如CeO2或CeO2-ZrO2)上的Rh金属。这些催化剂确实在180-300℃下显示活性,但仅在废气中的N2O浓度非常低(<1ppm)下。
DE 10 2009 023 877公开了包含多孔载体材料上的活性金属组分的负载催化剂,以及其在处理机动车燃料废气中的用途。
EP 1 503 855公开了包含基于二氧化锆的载体的催化剂及其在脱氢中的用途。经由其中使用硅化合物作为粘合剂的特定方法制备载体。该催化剂包含一种或多种来自过渡族VIII或VI的元素,其具有或不具有其他元素。当用于脱氢时,这些催化剂显示出比不包含通过该特定方法制备的载体的相当组合物的催化剂更好的性能。
本发明的目的是提供一种用于在废气料流中在比现有技术催化剂所允许的明显更低的温度下(优选在400℃以下)无需添加还原剂(同时废气料流也应可包含氧和/或少量的水)而分解一氧化二氮的催化剂。
发现该目的通过包含含有SiO2和ZrO2的特定载体上的铑(Rh)的一氧化二氮分解催化剂实现。
因此,本发明提供一种包含催化剂载体上的铑的一氧化二氮分解催化剂,其中催化剂载体通过以下方式得到:将二氧化锆粉末与作为粘合剂的硅化合物、任选地致孔剂(porogen)、任选地酸、水和任选地其他添加剂混合以形成可捏和组合物,使组合物均化,将组合物成形成成形制品,干燥和煅烧,其中粘合剂选自通式(I)-(VI)的硅化合物,
(Hal)xSiR4-x (I)
(Hal)xSi(OR1)4-x (II)
(Hal)xSi(NR1R2)4-x (III)
RxSi(OR1)4-x (IV)
RxSi(NR1R2)4-x (V)
(R1O)xSi(NR1R2)4-x (VI)
其中
Hal在每次出现时独立地为卤素(F、Cl、Br或I),
R在每次出现时独立地为H或者取代或未取代的烷基、链烯基、炔基、环烷基、环烯基、芳基烷基或芳基,
R1和R2在每次出现时各自独立地为H或者取代或未取代的烷基、酰基、芳基烷基或芳基,和
x为0-4。
本发明的一个优选实施方案使用粒度为0.2-50μm的二氧化锆粉末制备催化剂载体。本发明的另一优选实施方案使用具有通常10-400m2/g,更优选50-150m2/g的高BET比表面积的二氧化锆粉末制备催化剂载体。
本发明的另一优选实施方案使用基本单斜二氧化锆粉末制备催化剂载体。基本单斜二氧化锆粉末为85-100重量%,优选90-100重量%的单斜二氧化锆,其如EPA 0 716883所述,可以通过以下方式用氨沉淀锆盐而得到:将硝酸锆或氯化锆溶液加入氨水溶液中,pH从14降至6,并将沉淀产物洗去,干燥并煅烧。为此,第一步使用碳酸锆和盐酸制备浓度非常高(通常2-5摩尔%)的氯化锆溶液,或者使用优选碳酸锆和硝酸制备浓度非常高(通常2-5摩尔%)的硝酸锆溶液。将该溶液通常在20-60℃的温度下在pH控制下混入最初添加的氨水溶液(约15摩尔%的NH3)中,条件是混合步骤在6-8的pH下结束且pH值不能降至6以下。随后,后续搅拌时间通常为30-600分钟。
例如,在压滤机上洗出沉淀产物以使其基本不含铵盐,并干燥和在300-600℃,优选400-500℃的温度和0.05-1巴的压力下空气煅烧。
由此得到的基本单斜二氧化锆偶尔还将包含少量的四方或立方的多晶型物。可以通过在0.2-0.9巴的水蒸气分压下煅烧之前的干燥步骤,将四方或立方的多晶型物的比例降低到x射线检测极限以下。干燥步骤例如在120℃下进行约16小时。
本发明催化剂的载体通过使用硅化合物作为粘合剂而制备。合适的粘合剂包括例如单体、低聚或聚合的硅烷、烷氧基硅烷、芳氧基硅烷、酰氧基硅烷、肟基硅烷、卤代硅烷、氨基氧硅烷、氨基硅烷、酰胺基硅烷、硅氮烷或聚硅氧烷,例如如Ullmann's Encyclopedia ofIndustrial Chemistry,第A24卷,第21-56页中所描述。它们更具体地包括以下通式(I)-(VI)的单体硅化合物:
(Hal)xSiR4-x (I)
(Hal)xSi(OR1)4-x (II)
(Hal)xSi(NR1R2)4-x (III)
RxSi(OR1)4-x (IV)
RxSi(NR1R2)4-x (V)
(R1O)xSi(NR1R2)4-x (VI)
其中
Hal在每次出现时独立地为卤素(F、Cl、Br或I),
R在每次出现时独立地为H或者取代或未取代的烷基、链烯基、炔基、环烷基、环烯基、芳基烷基或芳基,
R1和R2在每次出现时各自独立地为H或者取代或未取代的烷基、酰基、芳基烷基或芳基,和
x为0-4。
R、R1和R2可以各自为H,烷基,优选C1-C6烷基,其可以是线性或支化的。烷基R尤其为甲基、乙基、正丙基、异丙基、正丁基、仲丁基或叔丁基,特别是甲基或乙基。R、R1和R2各自还可以是芳基,优选苯基或芳基烷基,优选苄基。
R还可以是链烯基,优选C2-C6链烯基,尤其是乙烯基或烯丙基,或者炔基,优选乙炔基。
R1和R2各自还可以是酰基,优选C2-C6酰基,尤其是乙酰基。
合适的通式(I)的硅化合物的实例是例如SiCl4、MeSiCl3、Me2SiCl2和Me3SiCl。
合适的通式(IV)的硅化合物是例如Si(OEt)4、MeSi(OEt)3、Me2Si(OEt)2和Me3SiOEt。
合适的通式(V)的化合物是例如Me3Si(NMeCOMe)和Me3Si(NMeCOCH2C6H5)。
(MeO)3SiNMe2是合适的通式(VI)的化合物的实例。
合适的低聚和聚合的有机硅化合物的实例是甲基聚硅氧烷和乙基聚硅氧烷。
非常特别优选的含硅粘合剂是甲基聚硅氧烷,例如来自Wacker的产品。
用作粘合剂的硅化合物在室温下通常是液体。结果,在混合步骤中用硅化合物将高表面积的二氧化锆均匀地润湿,其结果是硅化合物将二氧化锆颗粒包裹并部分饱和。这导致二氧化锆颗粒之间的结合显著增强,并且所得到的成形催化剂载体制品具有非常好的机械稳定性。当成形的催化剂载体制品经历煅烧时,整体中的含硅粘合剂的有机结构部分烧尽而形成二氧化硅(SiO2),其以非常细分散状态存在于二氧化锆基体中。含硅粘合剂的有机结构部分的燃烧导致额外的孔形成。因为粘合剂在二氧化锆基质中形成均匀的分布,所以这些额外的孔的分布同样非常均匀。结果,催化剂载体的总孔隙率增加。此外,SiO2的存在使二氧化锆稳定以防止热烧结。这种稳定效果的强度随着二氧化硅分布的均匀性而增加。
本发明催化剂的载体材料包含通常约1-20重量%,优选约3-10重量%的SiO2。
制备本发明催化剂的方法包括将二氧化锆粉末与含硅粘合剂、任选地致孔剂、任选地酸、水和任选地其他添加剂混合以形成可捏和组合物的第一步骤。优选
a)50-98重量%的二氧化锆粉末,
b)2-50重量%,更优选5-20重量%的硅化合物作为粘合剂,
c)0-48重量%,更优选0-10重量%的致孔剂,和
d)0-48重量%,更优选0-10重量%的其他添加剂,
其中组分a)-d)的总和为100重量%。
为了得到可捏和组合物,通常将水加入二氧化锆粉末和硅化合物的混合物中。还可以向混合物中加入酸。可捏和组合物的胶溶由该酸引起。合适的酸包括例如硝酸和乙酸;优选硝酸。
本发明的一个优选实施方案使用致孔剂制备催化剂载体。合适的致孔剂包括例如聚氧化烯如聚氧化乙烯、碳水化合物如纤维素和糖、天然纤维、纸浆或合成聚合物如聚乙烯醇。
本发明的另一优选实施方案使用其他添加剂制备催化剂载体。其他添加剂包括例如熟悉的影响流变性的化合物,例如羟甲基纤维素或聚氧化烯。
为了制备用于本发明催化剂的载体,将所涉及的组分在常规混合装置中混合均匀。合适的混合装置包括例如捏和机、研磨机(muller)、混合研磨机,其确保最初不均匀的可捏和组合物的良好的混合和均化。催化剂载体模塑组合物随后被模制成成形制品,例如挤出成线料或中空载体。
然后通常将成形的催化剂载体制品干燥。干燥例如在90-120℃的温度下进行10-100小时。干燥的成形催化剂载体制品随后被煅烧。煅烧通常在300-800℃,优选400-600℃的温度下进行0.5-6小时。煅烧优选在空气中和在大气压下进行。
本发明催化剂包含优选以基于最终催化剂量为0.01-1.00重量%的在催化剂载体上的铑。本发明具有另一实施方案,其中催化剂载体上的催化剂除了铑之外还包含周期表中过渡族III(包括镧系元素)和/或过渡族VI和/或VIII的其他元素。在本发明的一个优选实施方案中,除了铑之外催化剂载体上的催化剂还包含铁、铬和/或钼,更优选钼。在本发明的一个特别优选的实施方案中,催化剂在催化剂载体上包含0.01-1.00重量%的铑和0.01-0.50重量%的钼。
铑和任选存在的其他元素通常通过用所述金属的合适化合物的水溶液浸渍而施加。合适的化合物溶解在水中,通过煅烧可转化成相应的金属氧化物。金属化合物也可以通过喷涂而施用。合适的金属盐包括例如金属的硝酸盐、乙酸盐和氯化物,但金属的复合阴离子也是可能的。优选使用硝酸铑或乙酸铑以施加铑,使用Cr(NO3)3或(NH4)2CrO4以施加铬。
通常将用所述金属盐溶液浸渍的催化剂载体在350-650℃的温度下煅烧0.5-6小时。
本发明还提供一种制备上述一氧化二氮分解催化剂的方法,其包括用含铑溶液浸渍通过以下方式得到的催化剂载体:将二氧化锆粉末与作为粘合剂的硅化合物、任选地致孔剂、任选地酸、水和任选地其他添加剂混合以形成可捏和组合物,使组合物均化,将组合物成形成成形制品,干燥和煅烧,其中粘合剂选自通式(I)-(VI)的硅化合物,
(Hal)xSiR4-x (I)
(Hal)xSi(OR1)4-x (II)
(Hal)xSi(NR1R2)4-x (III)
RxSi(OR1)4-x (IV)
RxSi(NR1R2)4-x (V)
(R1O)xSi(NR1R2)4-x (VI)
其中
Hal在每次出现时独立地为卤素(F、Cl、Br或I),
R在每次出现时独立地为H或者取代或未取代的烷基、链烯基、炔基、环烷基、环烯基、芳基烷基或芳基,
R1和R2在每次出现时各自独立地为H或者取代或未取代的烷基、酰基、芳基烷基或芳基,和
x为0-4,
然后干燥并煅烧。
本发明还提供了使用上述催化剂分解一氧化二氮的方法。在该方法中,催化剂优选在250-700℃,优选300-430℃,更优选在350-425℃的操作温度下使用。在催化剂上通过的气流优选包含至多20 000ppm的N2O,更优选包含至多5000ppm的N2O,并且还可以包含至多2000ppm的NOx、至多1%的H2O和/或至多5%的O2。
本发明的另一优选实施方案是在硝酸或己内酰胺的生产中使用上述催化剂分解一氧化二氮的方法。
以下实施例说明本发明。
实施例:
实施例1:催化剂载体的制备
将3680g ZrO2粉末在450℃下加热3小时,然后与262.6g甲氧基硅烷(来自Wacker的Silres MSE100)、110.4g聚氧化乙烯(Alkox E100)、110.4g65重量%HNO3和1270g水研磨混合20分钟。将得到的捏塑组合物螺杆挤出成3mm外径的线料,并将线料在120℃下干燥,然后在560℃下加热4小时。得到的载体具有95m2/g的BET表面积和0.36ml/g的孔隙率(使用水银孔率法测定),并且在20nm和450nm处具有最大值的双峰孔径分布。载体具有35N的切割阻力。
实施例2:催化剂(Rh/ZrO2/SiO2)的制备
将3.37g硝酸铑水溶液(13.7重量%,来自Haereus,对应于0.461g Rh)用水配至101ml。首先将230g载体材料(来自实施例1的1.5mm线料)装入烧瓶中,加入浸渍溶液,随后静置30分钟,其中每隔5分钟振荡。然后在旋转蒸发器中除去上清液。随后在125℃下真空干燥16小时,然后在旋转管式炉中以540℃/4h/100l(S.T.P.)/h N2煅烧,随后用空气钝化。该线料包含0.20重量%的Rh。
实施例3和4:
类似于实施例2的制备,分别使用8.65g和11.13g硝酸铑溶液(34重量%,BASFItalia)。该线料分别包含0.32重量%和0.42重量%的Rh。
实施例5:催化剂(Mo/Rh/ZrO2/SiO2)的制备
将3.37g硝酸铑溶液(13.7重量%,来自Haereus,对应于0.461g Rh)和4.61ml Mo-ICP溶液(来自ABCR,在5%HNO3中的1g Mo,对应于0.0461g Mo)混合并用水配至101ml。首先将230g载体材料(来自实施例1的1.5mm线料)装入烧瓶中,加入浸渍溶液,随后静置30分钟,其中每隔5分钟振荡。此后,在水喷射泵真空(20毫巴)中在85℃的水浴温度下除去水上清液。随后在125℃下真空干燥16小时,然后在旋转管式炉中以540℃/4h/100l(S.T.P.)/h N2煅烧,随后用空气钝化。该线料具有0.20重量%的Rh含量和0.02重量%的Mo含量。
实施例6:
与实施例5类似制备,使用0.231g Mo(在10ml的2M HNO3中0.39gH2MoO4)和3.37g硝酸铑溶液(13.7重量%,来自Haereus,对应于0.461gRh),用水配至101ml。该线料具有0.20重量%的Rh含量和0.10重量%的Mo含量。
对比实施例1-5:
用47ml前体溶液浸渍110g载体材料。其余程序类似于实施例2。所用的前体是:IrCl3xH2O(用9ml HCl溶解)、Pd(NO3)2、RuCl3xH2O、Fe(NO3)3x9H2O、Pt-A溶液(胺稀释的氢氧化铂(H2Pt(OH)6)水溶液)。
对比实施例6-11:
重复实施例2以制备催化剂,不同的是实施例1的载体被以下载体替代:具有4.2重量%Si的四方ZrO2(Saint-Gobain NorPro SZ61152),具有5.0重量%Si的单斜ZrO2(Saint-Gobain Norpro SZ31107),纯的主要是单斜的ZrO2、SiO2、γ-Al2O3和CeO2。
一氧化二氮分解:
将23g(20ml)催化剂与用于热电偶的3mm内管一起装入内径为25mm的垂直立式230ml管式反应器中。催化剂的填充在管的中心1-1.5mm的石英玻璃碎片层之间。使用电炉加热管式反应器,并借助热电偶在催化剂床的中心测量催化剂床中的温度。将由3%O2、1000ppm N2O、3000ppm H2O、96.6%N2组成的气体混合物在8巴的压力和20,000h-1的GHSV下在催化剂上通过,并使用红外光谱分析反应气体。
表1包括根据实施例2-6(B2-B6)的本发明催化剂和对比实施例1-11(VB1-VB11)的结果。
表1:X=N2O转化率
根据本发明得到的ZrO2/SiO2载体上的Rh比该载体上的其他金属具有更高的转化率。根据本发明得到的ZrO2/SiO2载体上的Rh比其他载体上的Rh具有更高的转化率。
用气体混合物中的1000ppm NO重复一氧化二氮分解操作。
气体混合物中存在的NOx明显地降低N2O的分解。然而,本发明催化剂比包含其他金属的催化剂具有明显更高的转化率。
添加少量的钼也对气体混合物中的NOx的催化剂性能产生积极的影响。包含0.10重量%或0.20重量%的Mo的催化剂在相同温度下比仅包含Rh的催化剂具有更高的转化率。
显示催化剂分析的表
Claims (10)
1.一种在催化剂载体上包含铑的一氧化二氮分解催化剂,其中催化剂载体通过以下方式得到:将二氧化锆粉末与作为粘合剂的硅化合物、任选地致孔剂、任选地酸、水和任选地其他添加剂混合以形成可捏和组合物,使组合物均化,将组合物成形成成形制品,干燥和煅烧,其中粘合剂选自通式(I)-(VI)的硅化合物,
(Hal)xSiR4-x (I)
(Hal)xSi(OR1)4-x (II)
(Hal)xSi(NR1R2)4-x (III)
RxSi(OR1)4-x (IV)
RxSi(NR1R2)4-x (V)
(R1O)xSi(NR1R2)4-x (VI)
其中
Hal在每次出现时独立地为卤素(F、Cl、Br或I),
R在每次出现时独立地为H或者取代或未取代的烷基、链烯基、炔基、环烷基、环烯基、芳基烷基或芳基,
R1和R2在每次出现时各自独立地为H或者取代或未取代的烷基、酰基、芳基烷基或芳基,和
x为0-4。
2.根据权利要求1的催化剂,其中催化剂载体通过在水和任选地酸存在下混合以下组分以形成可捏和组合物而制备:
a)50-98重量%的二氧化锆粉末,
b)2-50重量%的作为粘合剂的硅化合物,
c)0-48重量%的致孔剂,和
d)0-48重量%的其他添加剂,
其中组分a)-d)的总和为100重量%。
3.根据权利要求1或2的催化剂,其中二氧化锆粉末基本由单斜二氧化锆组成。
4.根据权利要求1-3中任一项的催化剂,其中二氧化锆粉末的粒度为0.2-50μm。
5.根据权利要求1-4中任一项的催化剂,其中二氧化锆粉末的BET比表面积为10-400m2/g。
6.根据权利要求1-5中任一项的催化剂,其中催化剂载体上的催化剂还包含周期表的包括镧系元素在内的过渡族III和/或过渡族VI和/或VIII的其他元素。
7.根据权利要求1-5中任一项的催化剂,其中催化剂载体上的催化剂还包含钼。
8.一种制备一氧化二氮分解催化剂的方法,其包括用含铑溶液浸渍通过以下方式得到的催化剂载体:将二氧化锆粉末与作为粘合剂的硅化合物、任选地致孔剂、任选地酸、水和任选地其他添加剂混合以形成可捏和组合物,使组合物均化,将组合物成形成成形制品,干燥和煅烧,其中粘合剂选自通式(I)-(VI)的硅化合物,
(Hal)xSiR4-x (I)
(Hal)xSi(OR1)4-x (II)
(Hal)xSi(NR1R2)4-x (III)
RxSi(OR1)4-x (IV)
RxSi(NR1R2)4-x (V)
(R1O)xSi(NR1R2)4-x (VI)
其中
Hal在每次出现时独立地为卤素(F、Cl、Br或I),
R在每次出现时独立地为H或者取代或未取代的烷基、链烯基、炔基、环烷基、环烯基、芳基烷基或芳基,
R1和R2在每次出现时各自独立地为H或者取代或未取代的烷基、酰基、芳基烷基或芳基,和
x为0-4,
然后干燥并煅烧。
9.使用根据权利要求1-7中任一项的催化剂分解一氧化二氮的方法。
10.根据权利要求9的方法,其中在催化剂上通过的气体料流包含至多20 000ppm的N2O,含有或不含至多2000ppm的NOx,至多1%的H2O和/或至多5%的O2。
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- 2015-11-24 US US15/535,270 patent/US10286381B2/en not_active Expired - Fee Related
- 2015-11-24 DK DK15800799.7T patent/DK3227019T3/en active
- 2015-11-24 EP EP15800799.7A patent/EP3227019B1/de not_active Not-in-force
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Also Published As
Publication number | Publication date |
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US20180078922A1 (en) | 2018-03-22 |
US10286381B2 (en) | 2019-05-14 |
WO2016087269A1 (de) | 2016-06-09 |
DK3227019T3 (en) | 2019-04-23 |
US20190134611A1 (en) | 2019-05-09 |
US10695750B2 (en) | 2020-06-30 |
EP3227019B1 (de) | 2019-01-09 |
CA2969588A1 (en) | 2016-06-09 |
EP3227019A1 (de) | 2017-10-11 |
PL3227019T3 (pl) | 2019-07-31 |
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