JPS6012132A - Heat resistant catalyst and use thereof - Google Patents
Heat resistant catalyst and use thereofInfo
- Publication number
- JPS6012132A JPS6012132A JP58118207A JP11820783A JPS6012132A JP S6012132 A JPS6012132 A JP S6012132A JP 58118207 A JP58118207 A JP 58118207A JP 11820783 A JP11820783 A JP 11820783A JP S6012132 A JPS6012132 A JP S6012132A
- Authority
- JP
- Japan
- Prior art keywords
- catalyst
- heat
- resistant catalyst
- lanthanum
- composite oxide
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000003054 catalyst Substances 0.000 title claims abstract description 97
- 229910052746 lanthanum Inorganic materials 0.000 claims abstract description 36
- 238000006243 chemical reaction Methods 0.000 claims abstract description 33
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 claims abstract description 32
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 29
- 239000002131 composite material Substances 0.000 claims abstract description 29
- 230000003197 catalytic effect Effects 0.000 claims abstract description 13
- 229910000873 Beta-alumina solid electrolyte Inorganic materials 0.000 claims abstract description 8
- 239000000919 ceramic Substances 0.000 claims abstract description 4
- 239000007789 gas Substances 0.000 claims description 31
- 238000000034 method Methods 0.000 claims description 29
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 25
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 claims description 21
- 229930195733 hydrocarbon Natural products 0.000 claims description 17
- 150000002430 hydrocarbons Chemical class 0.000 claims description 17
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 16
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 15
- 230000000737 periodic effect Effects 0.000 claims description 13
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 12
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 12
- 229910052725 zinc Inorganic materials 0.000 claims description 12
- 239000011701 zinc Substances 0.000 claims description 12
- 238000002485 combustion reaction Methods 0.000 claims description 11
- 229910052802 copper Inorganic materials 0.000 claims description 9
- 239000010949 copper Substances 0.000 claims description 9
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 8
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 8
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 8
- 229910052804 chromium Inorganic materials 0.000 claims description 8
- 239000011651 chromium Substances 0.000 claims description 8
- 229910052739 hydrogen Inorganic materials 0.000 claims description 8
- 239000001257 hydrogen Substances 0.000 claims description 8
- 229910052759 nickel Inorganic materials 0.000 claims description 8
- 238000000629 steam reforming Methods 0.000 claims description 8
- 229910052720 vanadium Inorganic materials 0.000 claims description 8
- 229910002090 carbon oxide Inorganic materials 0.000 claims description 7
- 238000006356 dehydrogenation reaction Methods 0.000 claims description 7
- 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 7
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims description 6
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 6
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 6
- 229910002091 carbon monoxide Inorganic materials 0.000 claims description 6
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 claims description 6
- 229910052718 tin Inorganic materials 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- 239000004215 Carbon black (E152) Substances 0.000 claims description 5
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 5
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 5
- 229910017052 cobalt Inorganic materials 0.000 claims description 5
- 239000010941 cobalt Substances 0.000 claims description 5
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 5
- 229910052761 rare earth metal Inorganic materials 0.000 claims description 5
- 229910052726 zirconium Inorganic materials 0.000 claims description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 4
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 4
- 229910052684 Cerium Inorganic materials 0.000 claims description 4
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 4
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 claims description 4
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 4
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims description 4
- 150000001342 alkaline earth metals Chemical class 0.000 claims description 4
- 229910052788 barium Inorganic materials 0.000 claims description 4
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 claims description 4
- 229910052791 calcium Inorganic materials 0.000 claims description 4
- 239000011575 calcium Substances 0.000 claims description 4
- 229910052742 iron Inorganic materials 0.000 claims description 4
- 239000011777 magnesium Substances 0.000 claims description 4
- 229910052749 magnesium Inorganic materials 0.000 claims description 4
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 claims description 4
- 229910052712 strontium Inorganic materials 0.000 claims description 4
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 claims description 4
- 229910052719 titanium Inorganic materials 0.000 claims description 4
- 239000010936 titanium Substances 0.000 claims description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 3
- -1 group elements Chemical compound 0.000 claims description 3
- 239000001301 oxygen Substances 0.000 claims description 3
- 229910052760 oxygen Inorganic materials 0.000 claims description 3
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical group [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 3
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 3
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 claims description 2
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 2
- 229910052783 alkali metal Inorganic materials 0.000 claims description 2
- 150000001340 alkali metals Chemical class 0.000 claims description 2
- 229910021529 ammonia Inorganic materials 0.000 claims description 2
- 239000001273 butane Substances 0.000 claims description 2
- 150000002431 hydrogen Chemical class 0.000 claims description 2
- 230000001590 oxidative effect Effects 0.000 claims description 2
- 239000001294 propane Substances 0.000 claims description 2
- 229910052709 silver Inorganic materials 0.000 claims description 2
- 239000004332 silver Substances 0.000 claims description 2
- 239000011135 tin Substances 0.000 claims description 2
- 229910052721 tungsten Inorganic materials 0.000 claims description 2
- 239000010937 tungsten Substances 0.000 claims description 2
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims 4
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 claims 2
- 239000001569 carbon dioxide Substances 0.000 claims 1
- 229910002092 carbon dioxide Inorganic materials 0.000 claims 1
- 150000002910 rare earth metals Chemical class 0.000 claims 1
- 238000009877 rendering Methods 0.000 claims 1
- 239000000126 substance Substances 0.000 claims 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 abstract description 18
- 239000000203 mixture Substances 0.000 abstract description 10
- 150000001875 compounds Chemical class 0.000 abstract description 5
- 239000010953 base metal Substances 0.000 abstract description 4
- 238000010438 heat treatment Methods 0.000 abstract description 4
- 150000004679 hydroxides Chemical class 0.000 abstract description 4
- 229910000510 noble metal Inorganic materials 0.000 abstract description 4
- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum oxide Inorganic materials [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 abstract description 3
- 229910052593 corundum Inorganic materials 0.000 abstract 1
- 230000016615 flocculation Effects 0.000 abstract 1
- 238000005189 flocculation Methods 0.000 abstract 1
- KTUFCUMIWABKDW-UHFFFAOYSA-N oxo(oxolanthaniooxy)lanthanum Chemical compound O=[La]O[La]=O KTUFCUMIWABKDW-UHFFFAOYSA-N 0.000 abstract 1
- 239000007858 starting material Substances 0.000 abstract 1
- 229910001845 yogo sapphire Inorganic materials 0.000 abstract 1
- 239000000843 powder Substances 0.000 description 8
- 230000007423 decrease Effects 0.000 description 7
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 238000010304 firing Methods 0.000 description 6
- 239000000969 carrier Substances 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 150000003839 salts Chemical class 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 description 4
- 229910000505 Al2TiO5 Inorganic materials 0.000 description 3
- 229910052581 Si3N4 Inorganic materials 0.000 description 3
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 230000002776 aggregation Effects 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 238000001354 calcination Methods 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 229910052878 cordierite Inorganic materials 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- JSKIRARMQDRGJZ-UHFFFAOYSA-N dimagnesium dioxido-bis[(1-oxido-3-oxo-2,4,6,8,9-pentaoxa-1,3-disila-5,7-dialuminabicyclo[3.3.1]nonan-7-yl)oxy]silane Chemical compound [Mg++].[Mg++].[O-][Si]([O-])(O[Al]1O[Al]2O[Si](=O)O[Si]([O-])(O1)O2)O[Al]1O[Al]2O[Si](=O)O[Si]([O-])(O1)O2 JSKIRARMQDRGJZ-UHFFFAOYSA-N 0.000 description 3
- 239000012153 distilled water Substances 0.000 description 3
- 238000007654 immersion Methods 0.000 description 3
- FYDKNKUEBJQCCN-UHFFFAOYSA-N lanthanum(3+);trinitrate Chemical compound [La+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O FYDKNKUEBJQCCN-UHFFFAOYSA-N 0.000 description 3
- 150000002739 metals Chemical class 0.000 description 3
- 238000000465 moulding Methods 0.000 description 3
- 229910052763 palladium Inorganic materials 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- AABBHSMFGKYLKE-SNAWJCMRSA-N propan-2-yl (e)-but-2-enoate Chemical compound C\C=C\C(=O)OC(C)C AABBHSMFGKYLKE-SNAWJCMRSA-N 0.000 description 3
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 230000007704 transition Effects 0.000 description 3
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 2
- 239000004480 active ingredient Substances 0.000 description 2
- 238000004220 aggregation Methods 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 238000007084 catalytic combustion reaction Methods 0.000 description 2
- 229910010293 ceramic material Inorganic materials 0.000 description 2
- ZMIGMASIKSOYAM-UHFFFAOYSA-N cerium Chemical compound [Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce] ZMIGMASIKSOYAM-UHFFFAOYSA-N 0.000 description 2
- 150000003841 chloride salts Chemical class 0.000 description 2
- 238000000151 deposition Methods 0.000 description 2
- KZHJGOXRZJKJNY-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Si]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O KZHJGOXRZJKJNY-UHFFFAOYSA-N 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 238000005470 impregnation Methods 0.000 description 2
- 150000002603 lanthanum Chemical class 0.000 description 2
- 229910052863 mullite Inorganic materials 0.000 description 2
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 2
- 239000012495 reaction gas Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 2
- 229910010271 silicon carbide Inorganic materials 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 241001474791 Proboscis Species 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 150000004703 alkoxides Chemical class 0.000 description 1
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- YXEUGTSPQFTXTR-UHFFFAOYSA-K lanthanum(3+);trihydroxide Chemical compound [OH-].[OH-].[OH-].[La+3] YXEUGTSPQFTXTR-UHFFFAOYSA-K 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 150000002823 nitrates Chemical class 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- QGLKJKCYBOYXKC-UHFFFAOYSA-N nonaoxidotritungsten Chemical compound O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1 QGLKJKCYBOYXKC-UHFFFAOYSA-N 0.000 description 1
- 230000009965 odorless effect Effects 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 150000003891 oxalate salts Chemical class 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- GPNDARIEYHPYAY-UHFFFAOYSA-N palladium(ii) nitrate Chemical compound [Pd+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O GPNDARIEYHPYAY-UHFFFAOYSA-N 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000006722 reduction reaction Methods 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 239000010948 rhodium Substances 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- SONJTKJMTWTJCT-UHFFFAOYSA-K rhodium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[Rh+3] SONJTKJMTWTJCT-UHFFFAOYSA-K 0.000 description 1
- YBCAZPLXEGKKFM-UHFFFAOYSA-K ruthenium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[Ru+3] YBCAZPLXEGKKFM-UHFFFAOYSA-K 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 239000010802 sludge Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 229910001930 tungsten oxide Inorganic materials 0.000 description 1
- 229910052845 zircon Inorganic materials 0.000 description 1
- GFQYVLUOOAAOGM-UHFFFAOYSA-N zirconium(iv) silicate Chemical compound [Zr+4].[O-][Si]([O-])([O-])[O-] GFQYVLUOOAAOGM-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Landscapes
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Exhaust Gas Treatment By Means Of Catalyst (AREA)
- Hydrogen, Water And Hydrids (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Catalysts (AREA)
Abstract
Description
【発明の詳細な説明】
〔発明の利用分野〕
本発明は・１５００ｔ：’以下の温度域において安定し
て使用できる耐熱性触媒およびその使用方法に関する。DETAILED DESCRIPTION OF THE INVENTION [Field of Application of the Invention] The present invention relates to a heat-resistant catalyst that can be stably used in a temperature range below 1500 t:' and a method for using the same.
本発明の触媒は、特に８００Ｃ以上の温度で使用するの
に適する。The catalyst of the invention is particularly suitable for use at temperatures above 800C.
触媒を用い高温下で反応を行わせる方法としては、有機
溶剤或は無臭の酸化処理、自動車排ガス処理、高温水蒸
気改質、ｉｉ温脱硝などが知られている。最近になって
大容量のボイラーやガスタービン、航空機用のガスター
ビンなどへ上記の特徴を生かした接触燃焼技術を応用す
る動きが起っている。Known methods for carrying out reactions at high temperatures using catalysts include organic solvent or odorless oxidation treatment, automobile exhaust gas treatment, high temperature steam reforming, and high temperature denitrification. Recently, there has been a movement to apply catalytic combustion technology that takes advantage of the above characteristics to large-capacity boilers, gas turbines, gas turbines for aircraft, etc.
これらの処理法は、反応温度がおよそ６００Ｃ以上であ
シ、条件によっては１４００〜１５００ Ｃにまで達す
る。従って、このような高温域においても触媒活性の低
下が少なく且つ熱的安定性の高い触媒が要求される。In these treatment methods, the reaction temperature is about 600C or higher, and depending on the conditions, it can reach 1400 to 1500C. Therefore, there is a need for a catalyst that exhibits little decrease in catalytic activity even in such a high temperature range and has high thermal stability.
従来、高温用触媒として使用されてきた触媒は、アルミ
ナ、シリカ、シリカ−アルミナ等を担体としてこれに貴
金属、或は卑金属成分を担持したもの、あるいはジルコ
ニア、チタン酸アルミニウム、窒化硅素などのセラミッ
ク材料を担体としてその表面に活性アルミナなどをコー
ティングし貴金属成分を担持させたものなどが使用され
てきた。Catalysts conventionally used as high-temperature catalysts include carriers such as alumina, silica, and silica-alumina on which precious metals or base metal components are supported, or ceramic materials such as zirconia, aluminum titanate, and silicon nitride. It has been used as a carrier, the surface of which is coated with activated alumina or the like to support noble metal components.
しかし、これらの触媒は通常５ｏｏｃ以上になると、担
体の相転移や結晶成長に伴う比表面積の減少、活性成分
の凝集に伴う表面積の減少などが生じ触媒の活性が著し
く劣化する欠点があった。However, these catalysts usually have the disadvantage that when the concentration exceeds 5 ooc, the specific surface area decreases due to phase transition of the carrier and crystal growth, and the surface area decreases due to aggregation of the active ingredients, resulting in a significant deterioration of the catalyst activity.
上記したセラミック材料を用いた触媒は、それ自体の耐
熱性は高いがコーテイング材の耐熱性が低いために触媒
成分が有効に活用されないという欠点もある。Catalysts using the above-mentioned ceramic materials have a high heat resistance, but have a drawback that the catalyst components are not effectively utilized due to the low heat resistance of the coating material.
本発明の目的は、上記した従来技術の欠点を改善し、高
温度の反応条件下においても活性成分の凝集および担体
の比表面積の減少を抑えることができる耐熱性触媒及び
かかる触媒の使用方法を提供することにある。The object of the present invention is to improve the above-mentioned drawbacks of the prior art and to provide a heat-resistant catalyst that can suppress aggregation of active ingredients and a decrease in the specific surface area of a support even under high-temperature reaction conditions, and a method for using such a catalyst. It is about providing.
γあるいはαアルミナは高比表面積を有し、担体やコー
テイング材として多く使用されているが、７００Ｃ以上
特に９００Ｃ以上においてはαアルミナへの相転移及び
結晶粒子径の成長などによシ比表面積が低下し、これに
伴って触媒活性成分である貴金属、卑金属などの粒子の
凝集が起こシ触媒活性が低下する。γ or α alumina has a high specific surface area and is often used as a carrier or coating material, but at temperatures above 700C, especially above 900C, the specific surface area decreases due to phase transition to α alumina and growth of crystal grain size. This causes agglomeration of particles of noble metals, base metals, etc., which are catalytically active components, and the catalytic activity decreases.
本発明者等は、アルミナの上記の様な熱的不安定性を改
良し、担持された触媒成分の粒子が凝集することを防ぐ
ために種々検討した結果、アルミニウムにランタンを添
加して得られるランタンβアルミナ（１１〜１４ Ａｔ
２０ｓ ・Ｌａｗ’ｓ ）担体に触媒活性成分である貴
金属、卑金属などを組合せた触媒が非常に有効であるこ
とを見出した。The present inventors conducted various studies to improve the above-mentioned thermal instability of alumina and prevent the supported catalyst component particles from agglomerating. As a result, the present inventors discovered that lanthanum β obtained by adding lanthanum to aluminum Alumina (11~14 At
It has been found that a catalyst in which a catalytically active component such as a noble metal or a base metal is combined with a carrier is very effective.
本発明は、アルミニウムとランタンの複合酸化物を主成
分とする担体に触媒活性成分を担持してなる耐熱性触媒
である。The present invention is a heat-resistant catalyst in which a catalytically active component is supported on a carrier whose main component is a composite oxide of aluminum and lanthanum.
アルミニウムとランタンの複合酸化物としては、ランタ
ンβアルミナが最も望ましいが、これに限定されるわけ
ではない。As the composite oxide of aluminum and lanthanum, lanthanum β-alumina is most desirable, but it is not limited thereto.
更に、担体はアルミニウムとランタンの複合酸化物のみ
からなることが最も望ましいが、他の相体成分を含んで
もかまわない。Furthermore, although it is most desirable that the carrier consists only of a composite oxide of aluminum and lanthanum, it may contain other phase components.
ランタンβアルミナは、１１′〜１４ Ａ／４０ｓ ・
Ｌａ２Ｏ５よシなる化合！吻である。この麺谷酸化物は
、□それらの水酸化物あるいは酸化物あるいは熱処珈す
ることによシ酸化物を与える化合物を原料として、それ
らの混合物を少なくとも８００Ｃ以上の温度で焼成する
ことによって生成する。Lanthanum β alumina is 11' to 14 A/40s.
A compound like La2O5! It is a proboscis. Mentani oxide is produced by firing a mixture of these hydroxides, oxides, or compounds that give silica oxide when heat-treated at a temperature of at least 800C as raw materials. .
アルミニウムとランタンの複合酸化物よシなる担体に触
媒活性成分を担持した触媒は、１００００以上の高温で
使用しても触媒活性成分の熱による凝集が起シ難く安定
した触媒性能を維持することができる。その理由として
は、アルミニウムとランタンの複合酸化物と触媒活性成
分と−ＸＩ： 弾Ｌ／、相互゛作用を示すことが挙げら
れる。Catalysts in which catalytically active components are supported on a carrier such as a composite oxide of aluminum and lanthanum can maintain stable catalytic performance because the catalytically active components are unlikely to agglomerate due to heat even when used at high temperatures of 10,000 °C or higher. can. The reason for this is that the composite oxide of aluminum and lanthanum interacts with the catalytically active component.
ランタンβアルミナはそれ自体が耐熱性が良く、比表面
積も大きいが、そのほかにこの化合物は活性アルミナか
らαアルミナベの相転移及び結晶成長を抑制する効果が
あることが詳細なＸ線回折、鑞子顕政鏡銭察の結果よシ
明らかになった。従って、ランタンβアルミナのみなら
ず、この複合酸化物を主成分として含むアルミナ担体も
高温で用いる触媒用担体として優れている。Lanthanum β-alumina itself has good heat resistance and a large specific surface area, but detailed X-ray diffraction analysis shows that this compound also has the effect of suppressing the phase transition from activated alumina to α-alumina and crystal growth. The results of the Kensei Mirror Zensai have become clear. Therefore, not only lanthanum β-alumina but also alumina supports containing this composite oxide as a main component are excellent as catalyst supports used at high temperatures.
アルミニウムとランタンの複合酸化物よシなる担体は、
高温条件下での比表面積の低下も少ないことがＮ２吸着
実験によシ明らかとなった。更に上記複合酸層物に担持
さ五た触媒成分であるパラジウムの分散状態を電子顕微
鏡及び−酸化炭素の在学吸着法で調べたところ、１２０
０Ｃで焼成しても高分散状態にあることがわかった。A carrier such as a composite oxide of aluminum and lanthanum is
N2 adsorption experiments have revealed that the specific surface area decreases little under high temperature conditions. Furthermore, when the dispersion state of palladium, which is a catalyst component supported on the composite acid layer, was examined using an electron microscope and a carbon oxide adsorption method, it was found that 120
It was found that even when fired at 0C, it remained in a highly dispersed state.
アルミニウムとランタンの複合酸化物を他のセラミック
スにコーティング或は混合してもよい。The composite oxide of aluminum and lanthanum may be coated or mixed with other ceramics.
例えばαアルミナ、チタニア、ジルコニア、マグネシア
、コージェライト、ムライト、アルミニウムチタネート
などの耐熱性酸化物に加えて使用することもできる。ま
たシリコンカーバイドや窒化硅素のような酸化物以外の
ものにコーティングぶるいは混合しても良い。混合する
場合、アルミニウムとランタンの複合酸化物の量は、担
体全門量の５０％以上を有するようにすることが望まし
い。For example, it can be used in addition to heat-resistant oxides such as alpha alumina, titania, zirconia, magnesia, cordierite, mullite, and aluminum titanate. The coating sieve may also be mixed with materials other than oxides such as silicon carbide and silicon nitride. When mixed, it is desirable that the amount of the composite oxide of aluminum and lanthanum is 50% or more of the total weight of the carrier.
アルミニウムとランタンの複合酸化物を形成するだめの
焼成温度は５ｏｏｃ以上、好ましくは９００Ｃ以上ｘｓ
ｏ６ｃ以上である。焼成温度が８００Ｃ以下ではランタ
ンβアルミナが生成せず、１５００Ｇを超えると焼結が
進行するため好ましくない。The firing temperature for forming a composite oxide of aluminum and lanthanum is 5ooc or higher, preferably 900C or higher
o6c or higher. If the firing temperature is less than 800C, lanthanum β-alumina will not be produced, and if it exceeds 1500G, sintering will proceed, which is not preferable.
上記複合酸化物を含む粉体は種々の形状、例えば球状、
円柱状、リンｒ状、ハニカム状などに成形して使用する
ことができる。また、種々の形状に成形された無機質耐
熱性担体、例えばムライト、コージライト、αアルミナ
、ジルコン、チタン酸アルミニウム、シリコンカーバイ
ド、窒化硅素等のセラミックスに上記複合酸化物を含む
粉体のスラリーをコーティングして使用することもでき
る。The powder containing the above composite oxide has various shapes, such as spherical,
It can be used by forming it into a cylinder shape, a cylindrical shape, a honeycomb shape, etc. In addition, inorganic heat-resistant carriers molded into various shapes, such as ceramics such as mullite, cordierite, α-alumina, zircon, aluminum titanate, silicon carbide, and silicon nitride, are coated with a slurry of powder containing the above complex oxide. It can also be used as
無機質耐熱性担体に担持するＬ記複合酸化物の量は担体
全重量の５％以上、好ましくは５〜３０重量％である。The amount of the compound oxide L supported on the inorganic heat-resistant carrier is 5% or more, preferably 5 to 30% by weight of the total weight of the carrier.
上記のアルミニウムとランタンの複合酸化物を製造する
方法としては、通、常の沈殿法、沈着−。The method for producing the above composite oxide of aluminum and lanthanum is usually a conventional precipitation method or deposition method.
混線法、含浸法などを適用することができ、特に限定さ
れない。−例としてアルミニウム塩とランタン塩の混合
水溶液にアルカリを添加して緊密な共沈物を生成させ、
これを加熱焼成する方法、アルミナおよび／オたはアル
ミナゾルと酸化ランタンおよび／または水酸化ランタン
を緊密に混合し、これを加熱焼成する方法、アルミナに
ランタン塩の溶液を含浸し、これを加熱焼成する方法な
どが挙げられる。A crosstalk method, an impregnation method, etc. can be applied, and there are no particular limitations. -For example, adding an alkali to a mixed aqueous solution of aluminum salt and lanthanum salt to form a tight coprecipitate,
A method of heating and calcining this, a method of intimately mixing alumina and/or alumina sol with lanthanum oxide and/or lanthanum hydroxide, and heating and calcining this, a method of impregnating alumina with a solution of lanthanum salt, and heating and calcining this. Examples include methods to do so.
なお、アルミニウムとランタンを含む水溶液にアルカリ
を加えて両者の緊密な混合物を共沈させてから焼成する
と、比較的低い焼成温度でもアルミニウムとランタンの
複合酸化物が得られるので好ましい方法である。Note that adding an alkali to an aqueous solution containing aluminum and lanthanum to co-precipitate a close mixture of the two and then firing it is a preferred method because a composite oxide of aluminum and lanthanum can be obtained even at a relatively low firing temperature.
アルミニウム原料としては、硝酸塩、硫酸塩。Nitrate and sulfate are aluminum raw materials.
塩化物などの可溶性塩、アルコキシドなどの有機塩、水
酸化物、ｅ化物などが使用できる。一方、ランタン原料
としては、硝酸塩、塩化物、シュウ酸塩などの可溶性塩
、水酸化物、酸化物などが使用できる。ランタンを含有
している混合希土も使用できる。Soluble salts such as chlorides, organic salts such as alkoxides, hydroxides, e-oxides, etc. can be used. On the other hand, as the lanthanum raw material, soluble salts such as nitrates, chlorides, and oxalates, hydroxides, oxides, and the like can be used. Mixed rare earths containing lanthanum can also be used.
触媒活性成分は、最終的に金属又は酸化物の形で担持さ
れる。The catalytically active components are ultimately supported in the form of metals or oxides.
触媒活性成分の担持方法、とじては、含浸浩或は混練法
など９通常行わ、れている方法を適用することができる
。触媒活性成分の原料としては、無機塩や錯塩などを使
！１６・ ７
本発明の触媒は、水素或は−酸化炭素或は炭化水素類の
燃焼反応、悪卑竺去、脱硝反応、高温水蒸気改質反応、
自動車排気ガス浄化などに使用可能である。As the method for supporting the catalytically active component, commonly used methods such as impregnation and kneading methods can be used. Use inorganic salts and complex salts as raw materials for catalytic active components! 16.7 The catalyst of the present invention can be used for combustion reactions of hydrogen or carbon oxides or hydrocarbons, sludge removal, denitrification reactions, high-temperature steam reforming reactions,
It can be used for purifying automobile exhaust gas.
本発明の触媒を水素と一酸化炭素と炭化水素類の少なく
とも１種を燃焼成分とするガスの燃焼反応に使用する場
合には、触媒活性成分として周期律表第種族、マンガン
、クロム、ジルコニウム、希土類元素、錫、亜鉛、銅、
マグネシウム、バリウム、ストロンチウム及びカルシウ
ムなどを用いることが望ましい。かかる燃焼反応に用い
られる。When the catalyst of the present invention is used in a combustion reaction of a gas containing at least one of hydrogen, carbon monoxide, and hydrocarbons as combustion components, the catalyst active components include manganese, chromium, zirconium, rare earth elements, tin, zinc, copper,
It is desirable to use magnesium, barium, strontium, calcium, etc. It is used in such combustion reactions.
炭化水素類としては、エタン、プロパン、ブタン。Hydrocarbons include ethane, propane, and butane.
ペンタンなどがある。反応温度はガスの種類によって異
なる瀘、室温〜１５００１：’の広い温度範囲を適用す
ることができる。燃焼反応を行うときには、前記ガスを
酸素を含むガスの存在下で触媒に接触させる。炭化水素
類がメタンである場合には、反応温度は、４００〜１ｏ
ｏｏ ｃが特に望ましく、触媒活性成分腎仲白傘属金属
を使用することが望ましい。Examples include pentane. The reaction temperature varies depending on the type of gas, and a wide temperature range from room temperature to 15,000 liters can be applied. When performing a combustion reaction, the gas is brought into contact with a catalyst in the presence of a gas containing oxygen. When the hydrocarbon is methane, the reaction temperature is 400 to 1o
ooc is particularly preferred, and it is preferred to use a catalytically active component of the metals of the genus Elena.
本発明の触媒を自動車排ガスなどのように内燃機関の排
ガフの浄化に使〒する場合には・触媒活性成分として周
期律表第種族、マンガン、クロム、？ルコニクム、希よ
類元素、鍋、亜鉛、銅、マグネシウム、バリウム、スト
ロンチウム及びカルシウムの少なくとも１つを用い、１
５０〜１５００Ｃの反応温度で前記排ガス及び酸素を触
媒に箸触させる。触媒活性成分としては、周期律表第種
族から選ばれた金属を使用することが特に望ましい。When the catalyst of the present invention is used to purify exhaust gas from an internal combustion engine, such as automobile exhaust gas, the active components of the catalyst include manganese, chromium, manganese, chromium, etc. ruconicum, rare elements, pot, zinc, copper, magnesium, barium, strontium and calcium;
The exhaust gas and oxygen are brought into contact with the catalyst at a reaction temperature of 50 to 1500C. As the catalytically active component, it is particularly desirable to use metals selected from groups of the periodic table.
このようにすることによシ、排ガス中の一酸化炭素及び
炭化水素を酸化し、窒素酸化物を窒素と水とに変換して
無害化することができる。By doing so, carbon monoxide and hydrocarbons in the exhaust gas can be oxidized, and nitrogen oxides can be converted into nitrogen and water, making them harmless.
本発明の触媒を炭化水素の水蒸気改質に使用する場合に
は、触媒活性成分として周期律表第種族、アルカリ金属
及びアルカリ土類金属から選ばれた少なくとも１つを用
い、４００〜１５００Ｃの温度範囲で反応を行わせて水
素及び−酸化炭素からなるガスを製造する。触媒活性成
分としては、周期律表第■族、特にニッケル、或はニッ
ケルとコバルトの混合物を用いることが望ましい。When the catalyst of the present invention is used for steam reforming of hydrocarbons, at least one selected from groups of the periodic table, alkali metals, and alkaline earth metals is used as the catalytic active component, and the temperature is 400 to 1500C. The reaction takes place within a range to produce a gas consisting of hydrogen and carbon oxide. As the catalytically active component, it is preferable to use Group I of the periodic table, particularly nickel or a mixture of nickel and cobalt.
本発明の触媒をボイラ、ガスタービンなどの排ガス中の
窒素酸化物の還元反応に使用する場合には、還元剤とし
てアンモニアを使用し、５００〜１５００Ｃの温度で反
応を行う。触媒活性成分としては周期律表第■族、アル
カリ土類金属、チタン、ジルコニウム、バナジウム、希
土類元素、■ａ族、ＶＩａ族、マンガン、亜鉛、アルミ
ニウム、錫及び鉛から選ばれた少なくとも１つを用いる
ことが望ましい。When the catalyst of the present invention is used for the reduction reaction of nitrogen oxides in exhaust gas from boilers, gas turbines, etc., ammonia is used as a reducing agent and the reaction is carried out at a temperature of 500 to 1500C. As the catalytic active component, at least one selected from Group Ⅰ of the periodic table, alkaline earth metals, titanium, zirconium, vanadium, rare earth elements, Group Ⅰa, Group VIa, manganese, zinc, aluminum, tin, and lead. It is desirable to use it.
これらは最終的に酸化物の形で担持される。触媒活性成
分の中では、特にタングステン、バナジウム、チタン、
錫、セリウム、鉄、ニッケル、コバルトの少なくとも１
つが好ましい。These are ultimately supported in the form of oxides. Among the catalytic active components, tungsten, vanadium, titanium,
At least one of tin, cerium, iron, nickel, and cobalt
is preferable.
本発明の触媒をメタン化反応に使用する場合には、触媒
活性成分として周期律表第■族、亜鉛、クロム、バナジ
ウム及びセリウムから選ばれた少なくとも１つを用い、
２５０〜４００Ｃの温度で一酸化炭素含有ガスと水素を
触媒に接触させるとよい。触媒活性成分としては周期律
表第■族から選ばれた金属、なかでもニッケルを用いる
ことが特に望ましい。When the catalyst of the present invention is used in a methanation reaction, at least one selected from Group Ⅰ of the periodic table, zinc, chromium, vanadium, and cerium is used as a catalytic active component,
It is preferable to contact the carbon monoxide-containing gas and hydrogen with the catalyst at a temperature of 250 to 400C. As the catalytically active component, it is particularly desirable to use a metal selected from Group I of the Periodic Table, especially nickel.
本発明の触媒を炭化水素類の脱水素反応に使用する場合
には、触媒活性成分としてクロム、亜鉛、バナジウム、
銅、銀、鉄、ニッケル及びコバルトの少なくとも１つを
用い、室温以上且つ１５００１：ｌ’以下の温度で炭化
水素類を触媒に接触させる。炭化水素類がメタノールで
あるときは、触媒活性成分として銅と亜鉛の少なくとも
１つを用いることが望ましい。また、反応温度は３００
〜１ｏｏｏｃにすることが望ましい。When the catalyst of the present invention is used for the dehydrogenation reaction of hydrocarbons, chromium, zinc, vanadium,
Hydrocarbons are brought into contact with a catalyst using at least one of copper, silver, iron, nickel and cobalt at a temperature above room temperature and below 15001:l'. When the hydrocarbon is methanol, it is desirable to use at least one of copper and zinc as the catalytically active component. In addition, the reaction temperature is 300
It is desirable to set it to ~1oooc.
以下に実施例によυ本発明の内容をよシ具体的に説明す
るが、本発明はこれらの実施例に同等限定されるもので
はな仏。 □
実施例 １
硝酸アルミニウム３７５．１ｇと硝酸ランタン２２８ｇ
を蒸留水１ｔに溶解する（Ａｔ／Ｌａ＝９５１５原子比
）。この溶液を攪拌しながら３Ｎアンモニア水を滴下し
ｐＨ７，５まで中和する。得られたアルミニウムとラン
タンの共沈物を充分水洗し乾燥した後粉砕して１ｏｏｏ
ｃで５時間焼成する。得られた粉体をプレス成型機で直
径３ＩＩＯＩ１１長さ３１１ＩＩ＋の円柱状にし担体と
した。The content of the present invention will be explained in more detail with reference to Examples below, but the present invention is not limited to these Examples. □ Example 1 375.1g of aluminum nitrate and 228g of lanthanum nitrate
is dissolved in 1 t of distilled water (At/La=9515 atomic ratio). While stirring this solution, 3N ammonia water is added dropwise to neutralize it to pH 7.5. The obtained coprecipitate of aluminum and lanthanum was thoroughly washed with water, dried, and then ground to give 100
Bake for 5 hours at c. The obtained powder was formed into a cylindrical shape with a diameter of 3IIOI11 and a length of 311II+ using a press molding machine to form a carrier.
一方、前述の方法において硝酸ランタンを添加しない以
外は同様に調製し、アルミナのみから成る比較例担体を
得た。On the other hand, a comparative example carrier consisting only of alumina was obtained by preparing in the same manner as described above except that lanthanum nitrate was not added.
以上の方法で得た２通シの担体のそれぞれに硝酸パラジ
ウム溶液をパラジウムとして１重量％となるように含浸
したのち、１２０Ｃで約５時間乾燥し、その後１２００
ｔ：’で３時間焼成し、実施例１触媒及び比較例１触媒
を調製しメタン燃焼反応について性能評価を行った。下
記組成のガスを空間速度２５．０００ ｈ−１で流通し
、３０時間の連続試験を行なった。Each of the two carriers obtained by the above method was impregnated with a palladium nitrate solution to a concentration of 1% by weight as palladium, dried at 120C for about 5 hours, and then heated at 120C.
After firing at t:' for 3 hours, Example 1 catalyst and Comparative Example 1 catalyst were prepared, and the performance of the methane combustion reaction was evaluated. A continuous test for 30 hours was conducted by flowing a gas having the following composition at a space velocity of 25,000 h-1.
ガス組成
メタン＝３％
空 気：残部
本実験においては反応ガスを５５００に予熱して行なっ
た。メタンの反応率が９０％以上に達すると触媒層の温
度が１２００Ｃ程度に達するので、触媒の高温での耐久
性を評価することができる。Gas composition Methane = 3% Air: Balance In this experiment, the reaction gas was preheated to 5,500 ℃. When the reaction rate of methane reaches 90% or more, the temperature of the catalyst layer reaches about 1200C, so the durability of the catalyst at high temperatures can be evaluated.
実験結果を第１表に示す。The experimental results are shown in Table 1.
第１表から本実施例によ・る触媒は、高温下における触
媒燃焼反応用として好１であることが良くわかる。It is clearly seen from Table 1 that the catalyst according to this example is suitable for catalytic combustion reactions at high temperatures.
実施例１触媒及び比較例２触媒のａｏｈ活性測定後の比
表面積を測定したところ、前者では約５５ｍ”７ｇ、後
者では４ｍ”７ｇであった。また担体上に分散している
パラジウムの表面積を測定した結果、実施例１触媒では
７８ｍ”７ｇ−ｐｄに対し、比較例１触媒では２０ ｍ
’ ／ ｇ−′！ｋｄであった。When the specific surface area of the catalyst of Example 1 and the catalyst of Comparative Example 2 was measured after the AOH activity measurement, the former was about 55 m"7 g, and the latter was about 4 m"7 g. Furthermore, as a result of measuring the surface area of palladium dispersed on the carrier, the catalyst of Example 1 had a surface area of 78 m"7g-pd, while the catalyst of Comparative Example 1 had a surface area of 20 m".
'/g-'! It was kd.
このように比較例１触媒に比べ、実施例１触媒は比表面
積及びｐｄの分散状態が良好であシ、耐熱性触媒として
優れていることがわかる。As described above, it can be seen that, compared to the catalyst of Comparative Example 1, the catalyst of Example 1 has a good specific surface area and a good dispersion state of PD, and is excellent as a heat-resistant catalyst.
実施例 ２
硝酸アルミニウム３７５０ｇと硝酸ランタン４８０ｇを
蒸留水１０／、に溶解する。以下実施例１と同様にして
得られた８００Ｃ焼成粉体１〜に蒸留水２、．５ｔを加
え振動ミルで粉体の平均粒子径が約１μｍになるまで粉
砕し、スラリー状の浸漬液を調製する。この浸漬液に市
販のコージェライト基材から成るハニカム構造体（直径
９０解、長さ７５ＩＩＩ１１）を浸漬した後、浸漬液か
ら取シ出し、圧縮空気を吹付けて過剰に付着した液を除
き、１２０Ｃで乾燥後５００Ｃで１時間熱処理した。こ
の操作を繰返し、最終的に１０００ｔ：’で２時間焼成
した。Example 2 3750g of aluminum nitrate and 480g of lanthanum nitrate are dissolved in 10% of distilled water. Hereinafter, 1 to 800C calcined powder obtained in the same manner as in Example 1, 2 to 2 parts of distilled water, . Add 5 tons of powder and grind with a vibration mill until the average particle size of the powder becomes about 1 μm to prepare a slurry-like immersion liquid. After immersing a commercially available honeycomb structure made of cordierite base material (diameter 90mm, length 75III11) in this immersion liquid, it was taken out from the immersion liquid and compressed air was blown to remove the excess liquid. After drying at 120C, it was heat-treated at 500C for 1 hour. This operation was repeated and finally fired at 1000 t:' for 2 hours.
かくして得られたハニカム構造体は１８．７重量％の複
合酸化物の層を有していた。次いで得られたハニカム構
造体を塩化白金酸と塩化ロジウムを混合した水溶液に浸
漬し、１２０Ｃで乾燥後、６００Ｃ水素気流中で還元し
た。触媒は１．５電歇％の白金と０．４重量％のロジウ
ムを有していた。The honeycomb structure thus obtained had a composite oxide layer of 18.7% by weight. Next, the obtained honeycomb structure was immersed in an aqueous solution containing a mixture of chloroplatinic acid and rhodium chloride, dried at 120C, and then reduced in a hydrogen stream at 600C. The catalyst had 1.5% platinum and 0.4% rhodium by weight.
この触媒を、自動車の排ガス酸化用として用いた。普通
自動車用エンジン（１８００ｃｃ クラス）に触媒コン
バーターとして使用し、１万ｋｍ走行試験を行なった結
果、１０モードでＣＯｌ、Ｏｇ／ｋ ｍ Ｎ ＨＣＯ，
１９ｇ ／ ｋ ｒｎであった。この結果から本発明に
なる耐熱性触媒では内燃機関の排気ガス処理にも使用で
き、高温反応に安定した性能を維持することがわかる。This catalyst was used for oxidizing automobile exhaust gas. It was used as a catalytic converter in a regular automobile engine (1800cc class), and as a result of a 10,000 km driving test, CO1, Og/km N HCO,
It was 19g/krn. These results show that the heat-resistant catalyst of the present invention can be used for exhaust gas treatment of internal combustion engines and maintains stable performance in high-temperature reactions.
実施例 ３
本実施例では本発明になる耐熱性触媒を炭化水素の高温
水蒸気改質反応用に用いた例について述べる。Example 3 This example describes an example in which the heat-resistant catalyst of the present invention was used for a high-temperature steam reforming reaction of hydrocarbons.
実施例１に示した本発明に係る担体１００ｇに硝酸ニッ
ケル水溶液を含没し、１２０Ｃで乾燥後、９００Ｃで２
時間焼成した。このようにして得た触媒はニッケルをＮ
ｉＯに換算して１５皿量％含有していた。100 g of the carrier according to the present invention shown in Example 1 was impregnated with an aqueous nickel nitrate solution, dried at 120C, and then dried at 900C for 2 hours.
Baked for an hour. The catalyst obtained in this way replaces nickel with N
The content was 15% in terms of iO.
上記方法で調製した触媒を反応管に充填し、Ｈ２気流中
、６００Ｃ’で２時間還元した。反応は触媒層入口温度
を５８０ｓ００ｃ、触媒層出口温度を８５０〜９０’Ｄ
Ｃに保ち、圧力１５Ｋｇ／ｘ”でｎ−ブタンの水蒸気改
質反応を行なった。水蒸気／カーボン（モル比） ＝
３．０．空間速度３０００ ｈ−”で行なった。１００
時間の連続試験の結果、ｎ−ブタンの反応率は９９．９
％以上を維持し、反応後、触媒層での炭素析出もほとん
ど認められなかった。反応生成ガスはＨｚ 、ＣＯ，Ｃ
ｏｔ及びＣＨ番であり、これらの成分は触媒層出口の温
度条件下における平衡組成にほぼ等しい割合で存在して
いた。The catalyst prepared by the above method was filled into a reaction tube and reduced at 600 C' for 2 hours in a H2 stream. For the reaction, the temperature at the inlet of the catalyst layer was 580s00c, and the temperature at the outlet of the catalyst layer was 850-90'D.
The steam reforming reaction of n-butane was carried out at a pressure of 15 kg/x'' while maintaining the temperature at
3.0. The space velocity was 3000 h-''.100
As a result of continuous time test, the reaction rate of n-butane was 99.9.
% or more, and almost no carbon deposition was observed in the catalyst layer after the reaction. The reaction product gas is Hz, CO, C
ot and CH numbers, and these components were present in a proportion approximately equal to the equilibrium composition under the temperature conditions at the outlet of the catalyst layer.
本実施例の結果からも明らかなように本発明になる耐熱
性触媒によれば、高温水蒸気改質反応に対しても優れた
性能を示す。As is clear from the results of this example, the heat-resistant catalyst of the present invention exhibits excellent performance even in high-temperature steam reforming reactions.
実施例 ４
本実施例では本発明になる耐熱性触媒を高温脱硝反応用
に用いた例について述べる。Example 4 This example describes an example in which the heat-resistant catalyst of the present invention was used for a high-temperature denitrification reaction.
実施例１と同様の方法で調製した成型前の複合酸化物よ
シ成る粉末５０ｇにメタチタン酸スラリー５００ ｇ
（Ｔｉ０２として１５０ｇ）を混線機により充分混練す
る。その後１５０Ｃで乾燥し、粉砕して４００Ｃで４時
間焼成する。得られた粉末をプレス成型機を用いて直径
３咽、厚さ３ｗＩ＋の円柱状に成型後、タングステン酸
アンモニウムの過酸化水素水溶液に浸漬する。その後６
００Ｃで２時間焼成して触媒を得る。かくして得られた
触媒は酸化タングステンを５重量％富んでいる。500 g of metatitanic acid slurry was added to 50 g of composite oxide powder before molding prepared in the same manner as in Example 1.
(150 g as Ti02) was sufficiently kneaded using a mixer. Thereafter, it is dried at 150C, crushed and fired at 400C for 4 hours. The obtained powder is molded into a cylindrical shape with a diameter of 3 mm and a thickness of 3 wI+ using a press molding machine, and then immersed in an aqueous hydrogen peroxide solution of ammonium tungstate. then 6
Calcinate at 00C for 2 hours to obtain a catalyst. The catalyst thus obtained is enriched with 5% by weight of tungsten oxide.
反応は下記組成のガスを用い、空間速度５０００ｈ−１
、反応温度６０・ＯＣの条件下で１００時間行なった。The reaction was carried out using a gas with the following composition, at a space velocity of 5000 h-1.
The reaction was carried out for 100 hours at a reaction temperature of 60°C.
反応ガス組成
ＮＯｘ ２０（＄＋
ＮＨａ ２００ｐｓｍ
０２ ３％
Ｉ（２０１０％
Ｎ２ 残部
ＮＯＸの除去率は初期で９４．８％１００時間後で９４
．４％であった。以上の結果よシ本発明になる触媒によ
れば高温脱硝反応に対しても浸れた性能を示す。Reaction gas composition NOx 20 ($+ NHa 200 psm 02 3% I (2010% N2 Removal rate of remaining NOX is 94.8% at initial stage, 94% after 100 hours)
．． It was 4%. The above results indicate that the catalyst of the present invention exhibits excellent performance even in high-temperature denitrification reactions.
実施例 ５
本実施例ではＣＯのメタン化反応用触媒に用いた例につ
いて述べる。Example 5 In this example, an example in which the catalyst was used as a catalyst for CO methanation reaction will be described.
実施例工で得た２通シの担体のそれぞれに硝酸ニッケル
を含浸し、５００Ｃで焼成後更に塩化ルテニウムを含浸
し、１０００Ｃで焼成して触媒を調製した。本触媒はＮ
ｉＯａｏ％、ＩＬＬ１３％を含有している。この触媒を
反応管に充填し、ＣＯ５％Ｈｚ１７％、Ｎ２残のガスを
５Ｖ＝１００，０００ｈ”になるように導入し、反応温
度３５０Ｃでメタネーション反応を行った。その結果、
ＣＯのメタン化収率は、本実施例触媒は、比較例触媒に
比べ約１５倍の収量であることがわかった。このように
高温に限らず比較的低温における反応においても本発明
からなる触媒は非常に有効であることがわかる。Each of the two carriers obtained in the example process was impregnated with nickel nitrate, calcined at 500C, further impregnated with ruthenium chloride, and calcined at 1000C to prepare a catalyst. This catalyst is N
Contains iOao% and ILL13%. This catalyst was packed in a reaction tube, and gases containing 5% CO, 17% Hz, and N2 were introduced at 5 V = 100,000 h, and a methanation reaction was carried out at a reaction temperature of 350 C. As a result,
It was found that the CO methanation yield of the catalyst of this example was about 15 times higher than that of the catalyst of the comparative example. It can thus be seen that the catalyst of the present invention is very effective not only in reactions at high temperatures but also in reactions at relatively low temperatures.
実施例 ６ 本実施例ではメタノールの脱水素反応について調べた。Example 6 In this example, the dehydrogenation reaction of methanol was investigated.
実施例１で得た２通シの担体に、硝酸鋼及び硝酸亜鉛溶
液を含浸し、乾燥後１０００Ｃで焼成する。Two sets of carriers obtained in Example 1 are impregnated with nitric acid steel and zinc nitrate solution, dried and fired at 1000C.
Ｃｕ及びｚｎの含有量はそれぞれ２０重電極。The content of Cu and ZN was 20 times each.
１０重量％である。これらの触媒を反応管に充填し、８
００Ｃにした後、メタノールを導入し、脱水素反応を行
わせホルマリンを製造したところ、メタノールの転化率
は９８％以上であシ、ホルマリンへの選択率も従来に比
べ約５倍であった。It is 10% by weight. Fill the reaction tube with these catalysts, and
After reaching 00C, methanol was introduced and a dehydrogenation reaction was performed to produce formalin. The conversion rate of methanol was 98% or more, and the selectivity to formalin was about 5 times higher than that of the conventional method.
以上述べたように本発明によれば、１５００ｃ以下の高
範囲の温度ですぐれた活性を有する耐熱性０発 明 者
加藤明
日立市幸町３丁目１番１号株式
％式％
日立市幸町３丁目１番１号株式
会社日立製作所日立研究所内
０発 明 者 水本守
日立市幸町３丁目１番１号株式
％式％
日立市幸町３丁目１番１号株式
会社日立製作所日立研究所内
一１Ｑ・As described above, according to the present invention, a heat resistant product having excellent activity in a high temperature range of 1500 C or less Inventor: 3-1-1 Saiwai-cho, Ashitachi-shi, Kato Shares: % Formula %: Saiwai-cho, Hitachi City 3-1-1 Hitachi Research Institute, Hitachi, Ltd. 0 Inventor: Mamoru Mizumoto 3-1-1 Saiwai-cho, Hitachi City Stock% formula % Hitachi Research, Hitachi, Ltd. 3-1-1 Saiwai-cho, Hitachi City 1st Q.
Claims (1)
する担体に、触媒活性成分を担持したことを特徴とする
耐熱性触媒。 ２、特許請求の範囲第１項において、前記担体が実質的
に前記複合酸化物のみからなることを特徴とする耐熱性
触媒。 ３、特許請求の範囲第１項において、前記−含酸化物が
セラミックスの表面にコーティングされていることを特
徴とする耐熱性触媒。 ４、特許請求の範囲第１項ないし第３項のいずれか１項
において、前記複合酸化物がランタンβアルミナからな
ることを特徴とする耐熱性触媒。 ５、 アルミニ、ラムとランタンの複合酸化物を主成分
とする担体に触媒活性成分として周期件表第■族、マン
ガン、クロム、ジルコニウム、希土、類元素、錫、亜鉛
、銅、マグネシウム、バリウム、ストロンチウム及びカ
ルシウムの少なくとも１つを担持し次触媒に、水素と一
酸化炭素及び炭化水素類の少なくとも１種を燃焼成分と
するガスと酸素を含むガスを室温〜１５００Ｃの温度で
接触させて前記燃焼成分を酸化することを特徴とする耐
熱性触媒の年月、方法。 ６、特許請求の範囲第５項において、前記炭化水素類カ
メタン、エタン、プロパン、ブタン、ペンタンの少なく
とも１種であることを特徴とする耐熱性触媒の使・用方
法。 ７、特許請求の範囲第６項において、前記炭化水素類が
メタンであシ且つ前記触媒活性成分が白金属金属からな
ることを特徴とする耐熱性触媒の使用方法。 ８、アルミニウムとランタンの複合酸化物を主成分とす
る担体に触媒活性成分として周期律表第■族、マンガン
、クロム、ジルコニウム、希土類元素、錫、亜鉛５、銅
、マグネシウム、バリウム、ストロンチウム及びカルシ
ウムの少なくとも１つを担持した触媒に、内燃機関の排
ガスと酸素を１５０〜１５００Ｃの温度で接触させて前
記排ガス中の−酸化炭素及び炭化水素を酸化し且つ窒素
酸化物を還元することを特徴とする耐熱性触媒の使用方
法。 ９、特許請求の範囲第８項において、前記触媒活性成分
が周期律表第種族から選ばれた少なくとも１種からなる
ことを特徴とする耐熱性触媒の使用方法。 １０、アルミニウムとランタンの複合酸化物を主成分と
する担体に触媒活性成分として周期律表第種族、アルカ
リ金属及びアルカリ土類金属から選ばれた少なくとも１
つを担持した触媒に、炭化水素類と水蒸気を４００〜１
５００Ｃの温度で接触させて水素及び−酸化炭素からな
るガスを製造することを特徴とする水蒸気改質用耐熱性
触媒の使用方法。 １１、特許請求の範囲第１０項において、前記触媒活性
成分が周期律表第種族から選ばれた１種以上からなるこ
とを特徴とする水蒸気改質用耐熱性触媒の使用方法。 １２ アルミニウムとランタンの複合酸化物を主成分と
する担体に触媒活性成分として周期律表第種族、アルカ
リ土類金属、チタン、ジルコニウム、バナジウム、希土
類元素、Ｖａ族、Ｖｉａ族、マンガン、亜鉛、アルミニ
ウム、錫及び鉛から選ばれた少なくとも１つを担持した
触媒に、窒素酸化物を含有する排ガスとアンモニアを５
００〜１５００Ｃの温度で接触させて前記窒素酸化物を
還元、無害化することを特徴とする窒素酸化物還元用耐
熱性触媒の使用方法。 １３、特許請求の範囲第１２項において、前記触媒活性
成分がタングステン、バナジウム、チタン、Ｉｍ、セリ
ウム、鉄、ニッケル、コバルトの少なくとも１つからな
ることを特徴とする窒素酸化物還元用耐熱性触媒の使用
方法。 １４、アルミニウムとランタンの複合酸化物を主成分と
する担体に触媒活性成分として周期律表第種族、亜鉛、
クロム、バナジウム及びセリウムから選ばれた少なくと
も１種を担持した触媒に１−酸化炭素又は二酸化炭素含
有ガスと水素を２５０〜４００Ｃの温度で接触させ前記
−酸化炭素をメタンに変換することを特徴とするメタン
化反応用耐熱性触媒の使用方法。 １５、特許請求の範囲第１４項において、前記触媒活性
成分が周期律表第種族から選ばれた少なくとも１つから
なることを特徴とするメタン化反応用耐熱性触媒の使用
方法。 １６、アルミニウムとランタンの複合酸化物を主成分と
する担体に触媒活性成分としてり四ム、亜鉛、バナジウ
ム、銅、銀、鉄、ニッケル及びコバルトの少なくとも１
つを担持した触媒に、炭化水素類を室温以上、１５００
Ｃ以下の温度で接触させて脱水素を行うことを特徴とす
る脱水素用耐熱性触媒の使用方法。 １７、特許請求の範囲第１６項において、前記炭化水素
類がメタノールであシ且つ３００〜１０００ｔ：’の温
度で前記触媒に接触させることを特徴とする脱水素用耐
熱性触媒の使用方法。 □ １＆特許請求の範囲第１７項において、前記触媒活性成
分が銅と亜鉛の少なくとも１つからなることを特徴とす
る脱水素用耐熱性触媒の使用方法。□[Claims] 1. A heat-resistant catalyst characterized in that a catalytically active component is supported on a carrier whose main component is a composite oxide of aluminum and lanthanum. 2. The heat-resistant catalyst according to claim 1, wherein the carrier consists essentially of the composite oxide. 3. The heat-resistant catalyst according to claim 1, wherein the -oxide-containing substance is coated on the surface of a ceramic. 4. A heat-resistant catalyst according to any one of claims 1 to 3, characterized in that the composite oxide is composed of lanthanum β-alumina. 5. A support mainly composed of composite oxides of aluminum, ram and lanthanum, and catalytically active components such as Group III of the periodic table, manganese, chromium, zirconium, rare earth, group elements, tin, zinc, copper, magnesium, and barium. , a gas containing hydrogen, a gas containing at least one of carbon monoxide and hydrocarbons as combustion components, and a gas containing oxygen are brought into contact with the catalyst supporting at least one of strontium and calcium at a temperature of room temperature to 1500C. Years and methods of heat-resistant catalysts characterized by oxidizing combustion components. 6. A method of using a heat-resistant catalyst according to claim 5, characterized in that the hydrocarbon is at least one of camethane, ethane, propane, butane, and pentane. 7. A method of using a heat-resistant catalyst according to claim 6, wherein the hydrocarbon is methane and the catalytic active component is a platinum metal. 8. A carrier mainly composed of a composite oxide of aluminum and lanthanum, with catalytically active components of group Ⅰ of the periodic table, manganese, chromium, zirconium, rare earth elements, tin, zinc 5, copper, magnesium, barium, strontium, and calcium. A catalyst carrying at least one of the following is brought into contact with the exhaust gas of an internal combustion engine at a temperature of 150 to 1500C to oxidize carbon oxides and hydrocarbons and reduce nitrogen oxides in the exhaust gas. How to use heat-resistant catalysts. 9. The method of using a heat-resistant catalyst according to claim 8, wherein the catalytically active component comprises at least one member selected from Group 1 of the Periodic Table. 10. At least one selected from groups of the periodic table, alkali metals and alkaline earth metals as a catalytic active component on a carrier mainly composed of a composite oxide of aluminum and lanthanum.
Hydrocarbons and water vapor are added to a catalyst supporting 400 to 1
1. A method of using a heat-resistant catalyst for steam reforming, which comprises producing a gas consisting of hydrogen and carbon oxide through contact at a temperature of 500C. 11. The method of using a heat-resistant catalyst for steam reforming according to claim 10, wherein the catalytically active component is comprised of one or more types selected from Groups of the Periodic Table. 12 A carrier whose main component is a composite oxide of aluminum and lanthanum, and catalytically active components including groups of the periodic table, alkaline earth metals, titanium, zirconium, vanadium, rare earth elements, Va group, Via group, manganese, zinc, aluminum. , exhaust gas containing nitrogen oxides and ammonia are added to a catalyst supporting at least one selected from tin and lead.
1. A method for using a heat-resistant catalyst for reducing nitrogen oxides, which comprises reducing and rendering the nitrogen oxides harmless by contacting them at a temperature of 00 to 1500C. 13. The heat-resistant catalyst for reducing nitrogen oxides as set forth in claim 12, wherein the catalytic active component comprises at least one of tungsten, vanadium, titanium, Im, cerium, iron, nickel, and cobalt. How to use. 14. A carrier mainly composed of a composite oxide of aluminum and lanthanum, with zinc,
A catalyst carrying at least one selected from chromium, vanadium, and cerium is brought into contact with a gas containing 1-carbon oxide or carbon dioxide and hydrogen at a temperature of 250 to 400 C to convert the -carbon oxide into methane. How to use a heat-resistant catalyst for methanation reaction. 15. The method of using a heat-resistant catalyst for methanation reaction according to claim 14, wherein the catalytically active component comprises at least one selected from groups of the periodic table. 16. At least one of aluminum, zinc, vanadium, copper, silver, iron, nickel and cobalt as a catalytically active component on a carrier mainly composed of a composite oxide of aluminum and lanthanum.
Hydrocarbons are added to the catalyst supported on the
A method for using a heat-resistant catalyst for dehydrogenation, characterized in that dehydrogenation is carried out by contacting at a temperature of C or lower. 17. A method of using a heat-resistant catalyst for dehydrogenation according to claim 16, characterized in that the hydrocarbon is methanol and is brought into contact with the catalyst at a temperature of 300 to 1000 t:'. □ The method of using a heat-resistant catalyst for dehydrogenation according to claim 17, wherein the catalytically active component comprises at least one of copper and zinc. □
Priority Applications (7)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP58118207A JPH0824843B2 (en) | 1983-07-01 | 1983-07-01 | Heat resistant catalyst and method of using the same |
| KR1019840003812A KR920000149B1 (en) | 1983-07-01 | 1984-07-02 | High temperature stable catalyst and method for using thereof |
| EP84304514A EP0130835B1 (en) | 1983-07-01 | 1984-07-02 | High temperature stable catalyst, process for preparing same and process for conducting chemical reaction using same |
| DE8484304514T DE3482094D1 (en) | 1983-07-01 | 1984-07-02 | AT HIGH TEMPERATURE STABLE CATALYST, METHOD FOR THE PRODUCTION THEREOF AND METHOD FOR CARRYING OUT CHEMICAL REACTIONS USING THE SAME. |
| US06/867,542 US4738946A (en) | 1983-07-01 | 1986-05-28 | High temperature stable catalyst and process for preparing same |
| US07/135,064 US4906176A (en) | 1983-07-01 | 1987-12-18 | High temperature stable catalyst, process for preparing same, and process for conducting chemical reaction using same |
| JP3211854A JP2533703B2 (en) | 1983-07-01 | 1991-08-23 | Catalyst for high temperature steam reforming reaction of hydrocarbon and method of using the same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP58118207A JPH0824843B2 (en) | 1983-07-01 | 1983-07-01 | Heat resistant catalyst and method of using the same |
Related Child Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP3211854A Division JP2533703B2 (en) | 1983-07-01 | 1991-08-23 | Catalyst for high temperature steam reforming reaction of hydrocarbon and method of using the same |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS6012132A true JPS6012132A (en) | 1985-01-22 |
| JPH0824843B2 JPH0824843B2 (en) | 1996-03-13 |
Family
ID=14730847
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP58118207A Expired - Lifetime JPH0824843B2 (en) | 1983-07-01 | 1983-07-01 | Heat resistant catalyst and method of using the same |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0824843B2 (en) |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6022929A (en) * | 1983-07-15 | 1985-02-05 | Hitachi Ltd | Heat resistant carrier for catalyst |
| JPS6135851A (en) * | 1984-07-30 | 1986-02-20 | Hitachi Ltd | Catalyst carrier stable at high temperature and its preparation |
| JPS62262746A (en) * | 1986-04-30 | 1987-11-14 | インタ−ナシヨナル・フユ−エル・セルズ・コ−ポレイシヨン | Steam reforming catalyst |
| JPS63185452A (en) * | 1985-12-12 | 1988-08-01 | フア トン フア クオン シユイエ ユアン | Non-noble metal combustion catalyst and its production |
| US5020351A (en) * | 1990-05-24 | 1991-06-04 | Spiro America Inc. | Apparatus for flattening irregular circumferential surfaces in spirally formed pipe |
| WO2010023919A1 (en) | 2008-08-27 | 2010-03-04 | 株式会社アイシーティー | Exhaust gas purification catalyst and exhaust gas purification method using same |
| US10906816B2 (en) | 2016-07-29 | 2021-02-02 | Sumitomo Chemical Company, Limited | Alumina and method for producing automotive catalyst using same |
| WO2022004778A1 (en) * | 2020-06-30 | 2022-01-06 | 国立研究開発法人科学技術振興機構 | Method for partially oxidizing alkane |
| CN115779900A (en) * | 2022-10-25 | 2023-03-14 | 中船动力(集团)有限公司 | Tail gas CH for natural gas engine of ship 4 Purified oxidation catalyst, method for the production thereof and use thereof |
-
1983
- 1983-07-01 JP JP58118207A patent/JPH0824843B2/en not_active Expired - Lifetime
Cited By (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0435219B2 (en) * | 1983-07-15 | 1992-06-10 | Hitachi Ltd | |
| JPS6022929A (en) * | 1983-07-15 | 1985-02-05 | Hitachi Ltd | Heat resistant carrier for catalyst |
| JPS6135851A (en) * | 1984-07-30 | 1986-02-20 | Hitachi Ltd | Catalyst carrier stable at high temperature and its preparation |
| JPH0435220B2 (en) * | 1984-07-30 | 1992-06-10 | Hitachi Ltd | |
| JPS63185452A (en) * | 1985-12-12 | 1988-08-01 | フア トン フア クオン シユイエ ユアン | Non-noble metal combustion catalyst and its production |
| JPS62262746A (en) * | 1986-04-30 | 1987-11-14 | インタ−ナシヨナル・フユ−エル・セルズ・コ−ポレイシヨン | Steam reforming catalyst |
| US5020351A (en) * | 1990-05-24 | 1991-06-04 | Spiro America Inc. | Apparatus for flattening irregular circumferential surfaces in spirally formed pipe |
| WO2010023919A1 (en) | 2008-08-27 | 2010-03-04 | 株式会社アイシーティー | Exhaust gas purification catalyst and exhaust gas purification method using same |
| KR20110050676A (en) | 2008-08-27 | 2011-05-16 | 아이씨티 코., 엘티디. | Exhaust gas purification catalyst and exhaust gas purification method using same |
| US8465711B2 (en) | 2008-08-27 | 2013-06-18 | Umicore Shokubai Japan Co., Ltd. | Exhaust gas purification catalyst and method for purifying exhaust gas by using same |
| US10906816B2 (en) | 2016-07-29 | 2021-02-02 | Sumitomo Chemical Company, Limited | Alumina and method for producing automotive catalyst using same |
| WO2022004778A1 (en) * | 2020-06-30 | 2022-01-06 | 国立研究開発法人科学技術振興機構 | Method for partially oxidizing alkane |
| CN115734957A (en) * | 2020-06-30 | 2023-03-03 | 国立研究开发法人科学技术振兴机构 | Process for partial oxidation of alkanes |
| CN115779900A (en) * | 2022-10-25 | 2023-03-14 | 中船动力(集团)有限公司 | Tail gas CH for natural gas engine of ship 4 Purified oxidation catalyst, method for the production thereof and use thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0824843B2 (en) | 1996-03-13 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US4906176A (en) | High temperature stable catalyst, process for preparing same, and process for conducting chemical reaction using same | |
| US4793797A (en) | Method of catalytic combustion using heat-resistant catalyst | |
| AU728877B2 (en) | Ammonia oxidation catalyst | |
| US4996180A (en) | Catalyst of copper oxide and ceria | |
| EP0718028B1 (en) | Heat-resistant support for catalysts and the production thereof | |
| JP3999557B2 (en) | Catalyst for partial oxidation of hydrocarbon and method for producing hydrogen-containing gas using the catalyst | |
| JPS63162043A (en) | Catalyst for cleaning exhaust gas | |
| JPH06279027A (en) | Composition based on mixture of zirconium oxide and cerium oxide and method for synthetic production and use thereof | |
| JPH06182201A (en) | Catalyst stable at high temperature, its preparation, and method for effecting chemical reaction using this catalyst | |
| US5108978A (en) | Multifunctional catalysts containing cerium, uranium and at least one other metal, for converting pollutants emitted by internal combustion engines, and their preparation | |
| JPS6138627A (en) | Catalyst stable at high temperature, process for preparing the catalyst, and process for carrying out chemical reaction using the catalyst | |
| EP0604987B1 (en) | Removal of nitrogen oxide from exhaust gas | |
| JPS6012132A (en) | Heat resistant catalyst and use thereof | |
| JPS60222145A (en) | Method for using heat resistant catalyst | |
| US4451580A (en) | Method of preparing a supported catalyst | |
| JPS63190644A (en) | Heat-resistant catalysts and catalyst combustion method using the former | |
| US5171728A (en) | Catalyst for oxidizing carbon-containing compounds and method for the production of the same | |
| JP2533703B2 (en) | Catalyst for high temperature steam reforming reaction of hydrocarbon and method of using the same | |
| JPH0435220B2 (en) | ||
| JP2758616B2 (en) | Heat-resistant catalyst for catalytic combustion and its carrier | |
| JPH0459052A (en) | Catalyst for steam reforming | |
| JPH0435219B2 (en) | ||
| JP2570647B2 (en) | Nitrogen oxide reduction catalyst and nitrogen oxide reduction method | |
| JPH03186347A (en) | Heat-resistant catalyst and catalytic combustion method using the same | |
| JPH0573464B2 (en) |