JPH0952045A - Catalyst powder, combustion catalyst and combustor - Google Patents
Catalyst powder, combustion catalyst and combustorInfo
- Publication number
- JPH0952045A JPH0952045A JP7208124A JP20812495A JPH0952045A JP H0952045 A JPH0952045 A JP H0952045A JP 7208124 A JP7208124 A JP 7208124A JP 20812495 A JP20812495 A JP 20812495A JP H0952045 A JPH0952045 A JP H0952045A
- Authority
- JP
- Japan
- Prior art keywords
- catalyst
- catalyst powder
- active component
- catalytically active
- 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.)
- Withdrawn
Links
- 239000003054 catalyst Substances 0.000 title claims abstract description 300
- 239000000843 powder Substances 0.000 title claims abstract description 184
- 238000002485 combustion reaction Methods 0.000 title claims abstract description 136
- 229910003445 palladium oxide Inorganic materials 0.000 claims abstract description 73
- 239000001301 oxygen Substances 0.000 claims abstract description 59
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 59
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 44
- 239000000463 material Substances 0.000 claims abstract description 32
- 239000000446 fuel Substances 0.000 claims abstract description 27
- 239000004020 conductor Substances 0.000 claims abstract description 25
- JQPTYAILLJKUCY-UHFFFAOYSA-N palladium(ii) oxide Chemical compound [O-2].[Pd+2] JQPTYAILLJKUCY-UHFFFAOYSA-N 0.000 claims abstract 10
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 99
- 239000007789 gas Substances 0.000 claims description 80
- 239000000126 substance Substances 0.000 claims description 65
- 239000002245 particle Substances 0.000 claims description 49
- 229910052763 palladium Inorganic materials 0.000 claims description 38
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 claims description 28
- 239000010948 rhodium Substances 0.000 claims description 26
- 229910052703 rhodium Inorganic materials 0.000 claims description 26
- 239000002737 fuel gas Substances 0.000 claims description 22
- 238000002156 mixing Methods 0.000 claims description 18
- 229910000420 cerium oxide Inorganic materials 0.000 claims description 16
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 claims description 15
- -1 oxygen ion Chemical class 0.000 claims description 15
- 238000007254 oxidation reaction Methods 0.000 claims description 11
- 239000011148 porous material Substances 0.000 claims description 10
- 239000012466 permeate Substances 0.000 claims description 6
- 229910052727 yttrium Inorganic materials 0.000 claims description 6
- 229910052675 erionite Inorganic materials 0.000 claims description 5
- 229910052747 lanthanoid Inorganic materials 0.000 claims description 4
- 150000002602 lanthanoids Chemical class 0.000 claims description 4
- 230000003647 oxidation Effects 0.000 claims description 4
- 229910052706 scandium Inorganic materials 0.000 claims description 4
- 230000001590 oxidative effect Effects 0.000 claims description 3
- 239000007800 oxidant agent Substances 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 53
- 238000006243 chemical reaction Methods 0.000 abstract description 30
- 239000011248 coating agent Substances 0.000 abstract description 4
- 238000000576 coating method Methods 0.000 abstract description 4
- 230000000717 retained effect Effects 0.000 abstract 1
- HBEQXAKJSGXAIQ-UHFFFAOYSA-N oxopalladium Chemical compound [Pd]=O HBEQXAKJSGXAIQ-UHFFFAOYSA-N 0.000 description 66
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 48
- 230000003197 catalytic effect Effects 0.000 description 41
- 238000007873 sieving Methods 0.000 description 30
- 239000000567 combustion gas Substances 0.000 description 27
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 26
- 230000000052 comparative effect Effects 0.000 description 25
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 19
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 18
- 238000000034 method Methods 0.000 description 17
- 239000000203 mixture Substances 0.000 description 17
- 229910052751 metal Inorganic materials 0.000 description 16
- 239000002184 metal Substances 0.000 description 16
- 239000002585 base Substances 0.000 description 14
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 10
- 229910052759 nickel Inorganic materials 0.000 description 9
- 229910052697 platinum Inorganic materials 0.000 description 9
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 8
- 230000007423 decrease Effects 0.000 description 8
- 239000012071 phase Substances 0.000 description 8
- 238000010248 power generation Methods 0.000 description 8
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 7
- 229910052749 magnesium Inorganic materials 0.000 description 7
- 239000011777 magnesium Substances 0.000 description 7
- 239000002002 slurry Substances 0.000 description 7
- 238000012360 testing method Methods 0.000 description 7
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 6
- 150000001875 compounds Chemical class 0.000 description 6
- 238000010586 diagram Methods 0.000 description 6
- 239000003345 natural gas Substances 0.000 description 6
- 125000004430 oxygen atom Chemical group O* 0.000 description 6
- 238000005245 sintering Methods 0.000 description 6
- 239000000919 ceramic Substances 0.000 description 5
- 239000003426 co-catalyst Substances 0.000 description 5
- 238000009841 combustion method Methods 0.000 description 5
- 238000005470 impregnation Methods 0.000 description 5
- 229910044991 metal oxide Inorganic materials 0.000 description 5
- 150000004706 metal oxides Chemical class 0.000 description 5
- 229910000510 noble metal Inorganic materials 0.000 description 5
- 229910001233 yttria-stabilized zirconia Inorganic materials 0.000 description 5
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 4
- 229910052779 Neodymium Inorganic materials 0.000 description 4
- 229910052777 Praseodymium Inorganic materials 0.000 description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 4
- 229910017052 cobalt Inorganic materials 0.000 description 4
- 239000010941 cobalt Substances 0.000 description 4
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 4
- 229910052878 cordierite Inorganic materials 0.000 description 4
- 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 4
- 229910052742 iron Inorganic materials 0.000 description 4
- 229910052746 lanthanum Inorganic materials 0.000 description 4
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 description 4
- 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 description 4
- 238000003801 milling Methods 0.000 description 4
- QEFYFXOXNSNQGX-UHFFFAOYSA-N neodymium atom Chemical compound [Nd] QEFYFXOXNSNQGX-UHFFFAOYSA-N 0.000 description 4
- 238000007747 plating Methods 0.000 description 4
- PUDIUYLPXJFUGB-UHFFFAOYSA-N praseodymium atom Chemical compound [Pr] PUDIUYLPXJFUGB-UHFFFAOYSA-N 0.000 description 4
- 238000000638 solvent extraction Methods 0.000 description 4
- 238000004544 sputter deposition Methods 0.000 description 4
- 229910052720 vanadium Inorganic materials 0.000 description 4
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 229910052684 Cerium Inorganic materials 0.000 description 3
- 206010021143 Hypoxia Diseases 0.000 description 3
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 3
- 229910052788 barium Inorganic materials 0.000 description 3
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 3
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 description 3
- 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 3
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 description 3
- 230000002950 deficient Effects 0.000 description 3
- 230000006866 deterioration Effects 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 238000010574 gas phase reaction Methods 0.000 description 3
- 229930195733 hydrocarbon Natural products 0.000 description 3
- 150000002430 hydrocarbons Chemical class 0.000 description 3
- 230000006872 improvement Effects 0.000 description 3
- 239000011812 mixed powder Substances 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 description 3
- 229910052726 zirconium Inorganic materials 0.000 description 3
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 2
- 229910021078 Pd—O Inorganic materials 0.000 description 2
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 238000010793 Steam injection (oil industry) Methods 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 239000013543 active substance Substances 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 238000007084 catalytic combustion reaction Methods 0.000 description 2
- 239000003245 coal Substances 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 230000003247 decreasing effect Effects 0.000 description 2
- 238000010790 dilution Methods 0.000 description 2
- 239000012895 dilution Substances 0.000 description 2
- 230000005611 electricity Effects 0.000 description 2
- 239000003546 flue gas Substances 0.000 description 2
- 238000002309 gasification Methods 0.000 description 2
- 239000003779 heat-resistant material Substances 0.000 description 2
- 150000004687 hexahydrates Chemical class 0.000 description 2
- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 description 2
- 230000007774 longterm Effects 0.000 description 2
- YIXJRHPUWRPCBB-UHFFFAOYSA-N magnesium nitrate Chemical compound [Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O YIXJRHPUWRPCBB-UHFFFAOYSA-N 0.000 description 2
- 239000000395 magnesium oxide Substances 0.000 description 2
- 150000001247 metal acetylides Chemical class 0.000 description 2
- 150000004767 nitrides Chemical class 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 239000011164 primary particle Substances 0.000 description 2
- 238000010298 pulverizing process Methods 0.000 description 2
- 238000010405 reoxidation reaction Methods 0.000 description 2
- 229910052707 ruthenium Inorganic materials 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 239000011163 secondary particle Substances 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- 239000010935 stainless steel Substances 0.000 description 2
- 229910052712 strontium Inorganic materials 0.000 description 2
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 description 2
- 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 1
- 229910002080 8 mol% Y2O3 fully stabilized ZrO2 Inorganic materials 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 229910052692 Dysprosium Inorganic materials 0.000 description 1
- 229910052691 Erbium Inorganic materials 0.000 description 1
- 229910052693 Europium Inorganic materials 0.000 description 1
- 229910052689 Holmium Inorganic materials 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- 229910052773 Promethium Inorganic materials 0.000 description 1
- 206010037660 Pyrexia Diseases 0.000 description 1
- 229910052772 Samarium Inorganic materials 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- 229910052771 Terbium Inorganic materials 0.000 description 1
- 229910052775 Thulium Inorganic materials 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 229910052769 Ytterbium Inorganic materials 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 239000004480 active ingredient Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
- 229910052797 bismuth Inorganic materials 0.000 description 1
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000010531 catalytic reduction reaction Methods 0.000 description 1
- DRVWBEJJZZTIGJ-UHFFFAOYSA-N cerium(3+);oxygen(2-) Chemical class [O-2].[O-2].[O-2].[Ce+3].[Ce+3] DRVWBEJJZZTIGJ-UHFFFAOYSA-N 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 239000010987 cubic zirconia Substances 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 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 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 230000008034 disappearance Effects 0.000 description 1
- 238000010494 dissociation reaction Methods 0.000 description 1
- 230000005593 dissociations Effects 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- KBQHZAAAGSGFKK-UHFFFAOYSA-N dysprosium atom Chemical compound [Dy] KBQHZAAAGSGFKK-UHFFFAOYSA-N 0.000 description 1
- 238000007772 electroless plating Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- UYAHIZSMUZPPFV-UHFFFAOYSA-N erbium Chemical compound [Er] UYAHIZSMUZPPFV-UHFFFAOYSA-N 0.000 description 1
- OGPBJKLSAFTDLK-UHFFFAOYSA-N europium atom Chemical compound [Eu] OGPBJKLSAFTDLK-UHFFFAOYSA-N 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- KJZYNXUDTRRSPN-UHFFFAOYSA-N holmium atom Chemical compound [Ho] KJZYNXUDTRRSPN-UHFFFAOYSA-N 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 238000009434 installation Methods 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- GJKFIJKSBFYMQK-UHFFFAOYSA-N lanthanum(3+);trinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[La+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O GJKFIJKSBFYMQK-UHFFFAOYSA-N 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 229910052863 mullite Inorganic materials 0.000 description 1
- 229910000480 nickel oxide Inorganic materials 0.000 description 1
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 1
- PXHVJJICTQNCMI-OUBTZVSYSA-N nickel-60 atom Chemical group [60Ni] PXHVJJICTQNCMI-OUBTZVSYSA-N 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 description 1
- BPUBBGLMJRNUCC-UHFFFAOYSA-N oxygen(2-);tantalum(5+) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Ta+5].[Ta+5] BPUBBGLMJRNUCC-UHFFFAOYSA-N 0.000 description 1
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- VQMWBBYLQSCNPO-UHFFFAOYSA-N promethium atom Chemical compound [Pm] VQMWBBYLQSCNPO-UHFFFAOYSA-N 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 239000012495 reaction gas Substances 0.000 description 1
- 230000036632 reaction speed Effects 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000006722 reduction reaction Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- KZUNJOHGWZRPMI-UHFFFAOYSA-N samarium atom Chemical compound [Sm] KZUNJOHGWZRPMI-UHFFFAOYSA-N 0.000 description 1
- SIXSYDAISGFNSX-UHFFFAOYSA-N scandium atom Chemical compound [Sc] SIXSYDAISGFNSX-UHFFFAOYSA-N 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 238000003746 solid phase reaction Methods 0.000 description 1
- 229910052596 spinel Inorganic materials 0.000 description 1
- 239000011029 spinel Substances 0.000 description 1
- 239000013589 supplement Substances 0.000 description 1
- 230000000153 supplemental effect Effects 0.000 description 1
- 230000002459 sustained effect Effects 0.000 description 1
- 229910001936 tantalum oxide Inorganic materials 0.000 description 1
- GZCRRIHWUXGPOV-UHFFFAOYSA-N terbium atom Chemical compound [Tb] GZCRRIHWUXGPOV-UHFFFAOYSA-N 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 238000011144 upstream manufacturing Methods 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
- NAWDYIZEMPQZHO-UHFFFAOYSA-N ytterbium Chemical compound [Yb] NAWDYIZEMPQZHO-UHFFFAOYSA-N 0.000 description 1
- RUDFQVOCFDJEEF-UHFFFAOYSA-N yttrium(III) oxide Inorganic materials [O-2].[O-2].[O-2].[Y+3].[Y+3] RUDFQVOCFDJEEF-UHFFFAOYSA-N 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
Landscapes
- Catalysts (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、触媒粉末、燃焼触
媒および燃焼触媒を備えた燃焼器に係り、特にガスター
ビン等の高温条件下において使用可能な、活性が高く、
耐久性を有する触媒粉末および燃焼触媒、そして、燃焼
触媒を備えて窒素酸化物の発生を抑制可能とした燃焼器
に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a catalyst powder, a combustion catalyst, and a combustor equipped with the combustion catalyst.
The present invention relates to a durable catalyst powder and a combustion catalyst, and a combustor provided with the combustion catalyst and capable of suppressing the generation of nitrogen oxides.
【０００２】[0002]
【従来の技術】近年、石油資源の枯渇化に伴い、代替エ
ネルギーが要求される一方、エネルギー資源の効率的な
利用に多くの関心が払われている。そして、これらの要
求に応える手段として、例えば燃料として天然ガスを用
いるガスタービン・スチームタービン複合サイクル発電
システム、あるいは石炭ガス化ガスタービン・スチーム
タービン複合サイクル発電システムが開発されている。
また、これらの発電システムは、化石燃料を使用する従
来のスチームタービン・発電システムに比較して発電効
率が高いので、将来、使用量の増加が予想される天然ガ
スや石炭ガス化ガスなどの燃料を有効に電力に変換でき
る発電システムとして期待されている。2. Description of the Related Art In recent years, with depletion of petroleum resources, alternative energy has been demanded, and much attention has been paid to efficient use of energy resources. As means for meeting these demands, for example, a gas turbine / steam turbine combined cycle power generation system or a coal gasification gas turbine / steam turbine combined cycle power generation system using natural gas as a fuel has been developed.
In addition, these power generation systems have higher power generation efficiency than conventional steam turbines and power generation systems that use fossil fuels, so fuels such as natural gas and coal gasification gas whose usage is expected to increase in the future. Is expected as a power generation system that can effectively convert electricity into electricity.
【０００３】ところで、ガスタービン発電システムに使
用されているガスタービン燃焼器においては、一般的
に、燃料と空気との混合物をスパークプラグによって着
火し、燃焼を行う均一系反応（気相燃焼）の燃焼方式が
採られている。By the way, in a gas turbine combustor used in a gas turbine power generation system, generally, a mixture of fuel and air is ignited by a spark plug to perform combustion, and a homogeneous reaction (gas phase combustion) occurs. The combustion method is adopted.
【０００４】図２１はガスタービン燃焼器の要部構成例
を断面的に示したもので、２７は筐体、２８は燃料ノズ
ル、２９はスパークプラグ（着火素子）、３０は燃焼用
気体（例えば空気）供給口、３１は冷却用空気供給口で
あり、また希釈用空気供給口３２等を側壁に備え、かつ
所要の燃焼ガスをタービンノズル３４に供給する燃焼ガ
ス供給路３３を有している。そして、図２１に示す燃焼
器においては、燃料ノズル２８から噴射された燃料ガス
が燃焼用気体供給口３０から供給された空気等と混合さ
れ、スパークプラグ２９によって着火され燃焼する。こ
の燃焼に伴い、冷却用空気供給口３１および希釈用空気
供給口３２から所要の空気が供給され、所定の温度（タ
ービン入り口温度）まで冷却された燃焼ガスが、タービ
ンノズル３４を介してタービン内に噴射されるという機
能を果たしている。FIG. 21 is a sectional view showing an example of the construction of the main part of a gas turbine combustor. 27 is a casing, 28 is a fuel nozzle, 29 is a spark plug (ignition element), 30 is a combustion gas (for example, (Air) supply port, 31 is a cooling air supply port, has a dilution air supply port 32 and the like on its side wall, and has a combustion gas supply passage 33 for supplying a required combustion gas to the turbine nozzle 34. . Then, in the combustor shown in FIG. 21, the fuel gas injected from the fuel nozzle 28 is mixed with the air supplied from the combustion gas supply port 30 and ignited by the spark plug 29 to burn. Along with this combustion, required air is supplied from the cooling air supply port 31 and the dilution air supply port 32, and the combustion gas cooled to a predetermined temperature (turbine inlet temperature) passes through the turbine nozzle 34 into the turbine. It has the function of being injected into.
【０００５】しかしながら、ガスタービン燃焼器は燃焼
用気体として空気を使用するため、燃焼時に生成する窒
素酸化物（ＮＯｘ）による環境汚染が問題となってい
る。すなわち、窒素酸化物の生成は、燃焼温度が１５０
０℃を越えると急激に増加するが、ガスタービン燃焼器
内では燃焼濃度分布が存在し部分的に１５００℃を越え
る高温部が存在するため、ガスタービン燃焼器における
窒素酸化物の大量発生・生成は不可避的なものとなって
いる。最新のＬＮＧ火力発電プラントでは、燃焼器の蒸
気噴射と接触還元方式の排煙脱硝装置によりＮＯｘを１
０ｐｐｍ以下にすることが可能となっているが、これら
従来方式では排煙脱硝装置による発電コストの上昇と蒸
気噴射によるプラント効率の低下が避けられないことか
ら、より本質的な低ＮＯｘ化技術の確立が望まれてき
た。However, since the gas turbine combustor uses air as a combustion gas, environmental pollution due to nitrogen oxides (NOx) generated during combustion is a problem. That is, nitrogen oxide is produced at a combustion temperature of 150.
Although it rapidly increases when the temperature exceeds 0 ° C, there is a combustion concentration distribution in the gas turbine combustor and there is a high temperature part that exceeds 1500 ° C. Therefore, large amounts of nitrogen oxides are generated and generated in the gas turbine combustor. Is inevitable. In the latest LNG thermal power plant, NOx is reduced to 1 by the combustor steam injection and the catalytic reduction type flue gas denitration device.
Although it is possible to reduce the amount to 0 ppm or less, these conventional methods cannot avoid the increase in power generation cost due to the flue gas denitration device and the decrease in plant efficiency due to steam injection, and therefore, the more essential NOx reduction technology. The establishment has been desired.
【０００６】これに対して、均一系反応（気相燃焼）に
代えて、触媒を用いた不均一系反応による燃焼方式が提
案されている。この提案された触媒を用いる燃焼方式に
よれば、比較的低温で燃焼の開始が可能となり、燃焼温
度の上昇を緩慢にし、燃焼器内の最高温度を窒素酸化物
が急激に発生する１５００℃程度以下に維持することが
できるので、燃焼用気体として空気を用いた場合でも、
窒素酸化物の生成を低減できるという利点がある。On the other hand, instead of the homogeneous reaction (gas phase combustion), a combustion method by a heterogeneous reaction using a catalyst has been proposed. According to the proposed combustion method using a catalyst, it becomes possible to start combustion at a relatively low temperature, the increase in combustion temperature is slowed down, and the maximum temperature in the combustor is about 1500 ° C at which nitrogen oxides are rapidly generated. Since it can be maintained below, even when using air as the combustion gas,
There is an advantage that the generation of nitrogen oxides can be reduced.
【０００７】しかし、ガスタービン燃焼器のように燃焼
温度が１３００℃以上に設定される場合には、燃焼触媒
の温度も１３００℃以上となるため、高温における燃焼
触媒の強度あるいは性能の低下、または損傷が問題とな
っている。However, when the combustion temperature is set to 1300 ° C. or higher as in a gas turbine combustor, the temperature of the combustion catalyst also rises to 1300 ° C. or higher, so that the strength or performance of the combustion catalyst decreases at high temperatures, or Damage is a problem.
【０００８】こうした問題に対処するため、例えば特公
平２−４５７７２号公報に記載されているように、触媒
を用いて不均一系反応および気相反応を連続させる燃焼
方式が提案されている。この燃焼方法によれば、触媒部
分が比較的低温で燃焼を行うことができるため、触媒活
性成分の揮発消失または劣化、あるいは触媒活性成分を
担持する担体の劣化等が抑制され、燃焼触媒の強度ある
いは性能の劣化および損傷が低減されて信頼性の向上し
た燃焼器を得ることができる。In order to deal with such a problem, for example, as disclosed in Japanese Patent Publication No. 2-45772, a combustion system has been proposed in which a heterogeneous reaction and a gas phase reaction are continuously conducted using a catalyst. According to this combustion method, since the catalyst portion can burn at a relatively low temperature, volatilization disappearance or deterioration of the catalytically active component, deterioration of the carrier carrying the catalytically active component, etc. are suppressed, and the strength of the combustion catalyst is reduced. Alternatively, a combustor with reduced performance deterioration and damage and improved reliability can be obtained.
【０００９】この燃焼方法による触媒活性成分として、
白金あるいはパラジウム等の貴金属が使用される。貴金
属を触媒活性成分とする燃焼触媒としては、例えばガス
タービンでの使用温度下において触媒成分の凝集あるい
は粗大化を防止するために、直径数マイクロメータ以下
の比較的大きいジルコニア粒子等のセラミック粒子に含
浸法あるいは無電解メッキ法等により貴金属を担持させ
た触媒成分を耐熱性のハニカム基材上に被着、担持させ
たものが使用されており、耐久性も向上している。As a catalytically active component by this combustion method,
Noble metals such as platinum or palladium are used. As a combustion catalyst having a noble metal as a catalytically active component, for example, in order to prevent agglomeration or coarsening of the catalyst component at a temperature used in a gas turbine, a relatively large ceramic particle such as zirconia particles having a diameter of several micrometers or less is used. A catalyst component supporting a noble metal by an impregnation method or an electroless plating method is used by being deposited and supported on a heat-resistant honeycomb substrate, and the durability is also improved.
【００１０】こうした燃焼触媒の中でも、今後需要が見
込まれているメタン等を主成分とする燃料を酸化反応に
より燃焼させるには、低温度から酸化反応を開始するパ
ラジウムを触媒活性成分として含有している燃焼触媒の
使用が特に好ましい。Among these combustion catalysts, in order to burn the fuel whose main component is methane, which is expected to be in the future, by oxidation reaction, palladium which starts the oxidation reaction from low temperature is contained as a catalytically active component. The use of combustion catalysts is particularly preferred.
【００１１】パラジウムは酸化状態（ＰｄＯ）のときは
触媒活性が高く、金属（Ｐｄ）のときは触媒活性が低い
という特性を有している。図２２に示すように、酸化パ
ラジウムは酸素分圧と雰囲気温度によって支配される平
衡によって９００℃以上で酸素を放出して金属（Ｐｄ）
となる。前述したように、パラジウム（Ｐｄ）は酸化パ
ラジウム（ＰｄＯ）に比較して触媒活性が低いため、酸
素解離開始温度での触媒活性をピークに触媒活性が頭打
ちになり、燃焼触媒はある程度の温度以上に上昇しな
い。燃焼触媒がある程度の温度以上とならない点はパラ
ジウム系触媒の利点である。一方、他の貴金属、たとえ
ば白金を触媒として使用する場合には、燃焼触媒の高温
化に伴って触媒活性が増加するため燃焼用ガスの温度や
燃焼用ガスの濃度に起因する僅かの温度上昇によって触
媒活性の上昇、さらには触媒設置領域の温度上昇を招い
て温度暴走を生じ、その結果、耐熱性構造基材等の融
解、破損を生じる恐れがある。したがって、酸化パラジ
ウムを触媒活性成分とする燃焼触媒を、触媒領域と触媒
領域の下流に触媒を設置しない気相反応部とからなる燃
焼方式に適用すると、燃焼温度を制御しやすいという特
性を発揮する。Palladium has a characteristic that it has a high catalytic activity in the oxidation state (PdO) and a low catalytic activity in the case of a metal (Pd). As shown in FIG. 22, palladium oxide releases oxygen at 900 ° C. or higher due to the equilibrium governed by the oxygen partial pressure and the ambient temperature to form metal (Pd).
Becomes As described above, since the catalytic activity of palladium (Pd) is lower than that of palladium oxide (PdO), the catalytic activity reaches a peak at the catalytic activity at the oxygen dissociation start temperature, and the combustion catalyst has a certain temperature or higher. Does not rise to It is an advantage of the palladium-based catalyst that the temperature of the combustion catalyst does not rise above a certain temperature. On the other hand, when other precious metals such as platinum are used as a catalyst, the catalytic activity increases as the temperature of the combustion catalyst increases, so that a slight temperature rise due to the temperature of the combustion gas or the concentration of the combustion gas causes There is a risk that the catalyst activity will rise and the temperature in the catalyst installation region will rise, causing temperature runaway, and as a result, the heat-resistant structural base material and the like will melt and break. Therefore, when a combustion catalyst containing palladium oxide as a catalytically active component is applied to a combustion system consisting of a catalyst region and a gas phase reaction unit in which a catalyst is not installed downstream of the catalyst region, it exhibits the property of easily controlling the combustion temperature. .
【００１２】しかしながら、ガスタービン燃焼器のよう
に燃焼負荷（酸化反応量）が大きい場合には、長期間に
わたる連続運転中に酸化パラジウムが燃焼反応（燃料の
酸化反応）によって還元され、平衡的には酸化パラジウ
ムであるべき温度領域でも活性の低いパラジウム（Ｐ
ｄ）の割合が増加し、触媒活性が低下して触媒温度が低
下する。触媒温度が低下すると、触媒領域の下流に設置
されている気相反応部で失火が発生し、ガスタービンの
運転が困難となる。However, when the combustion load (oxidation reaction amount) is large as in a gas turbine combustor, palladium oxide is reduced by the combustion reaction (fuel oxidation reaction) during long-term continuous operation, resulting in equilibrium. Is palladium (P
The ratio of d) increases, the catalytic activity decreases, and the catalyst temperature decreases. When the catalyst temperature decreases, misfire occurs in the gas-phase reaction section installed downstream of the catalyst area, making it difficult to operate the gas turbine.
【００１３】一般に、酸化パラジウムを触媒活性成分と
する燃焼触媒の触媒反応は、触媒表面に酸素が解離吸着
したＰｄ−Ｏの酸化物状態で炭化水素類を酸化し、酸化
パラジウム自身は還元されて金属（Ｐｄ）となり、金属
（Ｐｄ）は再び酸化されてＰｄ−Ｏの酸化物状態を生成
し、これを繰り返して炭化水素類を酸化するレドックス
反応である。通常の炭化水素類の酸化反応では反応量が
多くないためレドックスサイクルが触媒表面上で円滑に
進行する。しかし、ガスタービン燃焼器のように燃焼負
荷（酸化反応量）が大きい反応系では、レドックスサイ
クルのバランスが崩れて触媒表面に解離吸着したＰｄ−
Ｏの酸素が容易に消費されるとともに、燃焼触媒の内側
に存在しているバルクの酸化パラジウム（ＰｄＯ）の酸
素が触媒表面に移動して燃料の酸化に使用されていると
考えられる。In general, the catalytic reaction of a combustion catalyst containing palladium oxide as a catalytically active component oxidizes hydrocarbons in the Pd-O oxide state in which oxygen is dissociated and adsorbed on the catalyst surface, and palladium oxide itself is reduced. It becomes a metal (Pd), and the metal (Pd) is oxidized again to generate an oxide state of Pd-O, which is a redox reaction in which hydrocarbons are oxidized by repeating this. Since the reaction amount is not large in the ordinary hydrocarbon oxidation reaction, the redox cycle proceeds smoothly on the catalyst surface. However, in a reaction system with a large combustion load (oxidation reaction amount) such as a gas turbine combustor, the balance of the redox cycle is disturbed and Pd- which is dissociated and adsorbed on the catalyst surface is adsorbed.
It is considered that the oxygen of O is easily consumed, and the oxygen of bulk palladium oxide (PdO) existing inside the combustion catalyst moves to the catalyst surface and is used for the oxidation of fuel.
【００１４】すなわち、酸化反応の初期状態では、燃焼
触媒中のパラジウムのほとんどが酸化パラジウムである
ため高い触媒活性を呈するが、燃焼反応の進行に伴って
バルクの酸化パラジウム（ＰｄＯ）の酸素が消費される
ため触媒表面に金属（Ｐｄ）の割合が増加し、触媒活性
が低下するという問題があった。That is, in the initial state of the oxidation reaction, most of the palladium in the combustion catalyst is palladium oxide and thus exhibits a high catalytic activity, but oxygen of bulk palladium oxide (PdO) is consumed as the combustion reaction progresses. Therefore, there is a problem that the ratio of metal (Pd) increases on the surface of the catalyst and the catalytic activity decreases.
【００１５】[0015]
【発明が解決しようとする課題】本発明は、上記従来例
に鑑みてなされたもので、高温下においても長期間にわ
たり高い活性を保持し、また高い活性を発揮する触媒粉
末を提供することを目的とする。SUMMARY OF THE INVENTION The present invention has been made in view of the above-mentioned conventional examples, and it is an object of the present invention to provide a catalyst powder which retains high activity for a long period of time even at high temperature and exhibits high activity. To aim.
【００１６】また、本発明は、高温下においても長期間
にわたり所定の活性を保持する燃焼触媒を提供すること
を目的とする。Another object of the present invention is to provide a combustion catalyst which retains a predetermined activity for a long period of time even at a high temperature.
【００１７】さらに、本発明は、高温下においても長期
間にわたり所定の活性を保持する燃焼触媒を有する、窒
素酸化物の発生を抑制可能な燃焼器を提供することを目
的とする。A further object of the present invention is to provide a combustor capable of suppressing the generation of nitrogen oxides, which has a combustion catalyst that retains a predetermined activity for a long period of time even at high temperatures.
【００１８】[0018]
【課題を解決するための手段】本発明において、第１の
触媒粉末は、触媒活性成分を酸化物担体に担持してなる
触媒粉末であって、前記触媒活性成分は少なくとも酸化
パラジウムを含有し、前記酸化物担体は８００℃以上で
少なくとも２．０×１０-2／Ωｃｍ以上の酸素イオン伝
導度を有しており、前記酸化物担体の少なくとも一部の
表面を電子導電材で被覆したことを特徴としている。In the present invention, the first catalyst powder is a catalyst powder in which a catalytically active component is supported on an oxide carrier, and the catalytically active component contains at least palladium oxide, The oxide carrier has an oxygen ion conductivity of at least 2.0 × 10 −2 / Ωcm or more at 800 ° C. or higher, and at least a part of the surface of the oxide carrier is coated with an electronic conductive material. It has a feature.
【００１９】本発明は、燃料の燃焼時において、触媒活
性の高い金属酸化物である例えば酸化パラジウムから奪
われる酸素を酸素イオンの動きやすい酸化物担体側から
供給して補い、一方、酸化物担体側からの供給に相当す
る酸素は酸化物担体に気相中から電子導電材を通じて供
給することによりパラジウムの再酸化速度の遅れを解消
し、常に触媒活性の高い酸化物状態、すなわち酸化パラ
ジウムを維持するものである。According to the present invention, during combustion of fuel, oxygen deprived from a metal oxide having a high catalytic activity, such as palladium oxide, is supplied from the oxide carrier side where oxygen ions are easy to move to supplement the oxygen. Oxygen corresponding to the supply from the side eliminates the delay in the reoxidation rate of palladium by supplying it to the oxide carrier through the electron conductive material from the gas phase, and always maintains the oxide state with high catalytic activity, that is, palladium oxide. To do.
【００２０】つまり、本発明の触媒粉末においては、燃
料の燃焼時にレドックスサイクル反応（燃焼）で触媒粉
末に酸素が欠乏すると、酸化物担体に付加された電子導
電材の表面で酸素が解離し、酸化物担体を通じて酸素の
欠乏している触媒活性成分に酸素が供給される。その結
果、触媒活性成分は常に触媒活性の高い酸化物状態に保
たれ、長期にわたって触媒活性が維持されるのである。That is, in the catalyst powder of the present invention, when the catalyst powder is deficient in oxygen by the redox cycle reaction (combustion) during the combustion of fuel, oxygen is dissociated on the surface of the electron conductive material added to the oxide carrier, Oxygen is supplied to the catalytically active component depleted of oxygen through the oxide carrier. As a result, the catalytically active component is always kept in an oxide state with high catalytic activity, and the catalytic activity is maintained for a long period of time.
【００２１】図１はこうして得られる触媒粉末１の一部
を模式的に拡大して示したもので、２は酸化パラジウ
ム、３は電子導電材であり、４は酸化パラジウム２およ
び電子導電材３を担持する酸化物担体である。５は電子
導電材３と酸化物担体４と酸素およびメタン等の可燃性
ガスの存在する気相との接触領域である界面、６は酸化
パラジウム２と酸化物担体４との接触領域である界面で
ある。FIG. 1 is a schematic enlarged view of a part of the catalyst powder 1 thus obtained. 2 is palladium oxide, 3 is an electronic conductive material, and 4 is palladium oxide 2 and electronic conductive material 3. Is an oxide carrier that supports. 5 is an interface which is a contact region between the electron conductive material 3, the oxide carrier 4 and a gas phase in which a combustible gas such as oxygen and methane exists, and 6 is an interface which is a contact region between the palladium oxide 2 and the oxide carrier 4. Is.
【００２２】そして、図１に示す界面５、酸化物担体４
の内部、界面６、酸化パラジウム２の４つの領域におい
ては、以下のように反応が進行すると考えられる。Then, the interface 5 and the oxide carrier 4 shown in FIG.
It is considered that the reaction proceeds in the following manner in the four regions of the inside, the interface 6, and the palladium oxide 2.
【００２３】（界面５）電子導電材３を介し、以下の反
応により酸素が気相中より酸化物担体４の内部にある酸
素空孔に取り込まれる。(Interface 5) Oxygen is taken from the gas phase into the oxygen vacancies inside the oxide carrier 4 through the electron conductive material 3 by the following reaction.
【００２４】１／２Ｏ2 （気相中）＋２ｅ- （電子導電
材３）→Ｏ2-（酸化物担体４の内部） （酸化物担体４の内部）酸化物担体４の内部に界面５か
ら酸素が取り込まれるのに対し、界面６に接した酸化パ
ラジウム２では燃焼反応の進行に伴い酸素の欠乏が顕著
となっている。この欠乏が原動力となり、界面５から取
り込まれた酸素が酸素イオンとして界面５から界面６に
移動する。1 / 2O 2 (in gas phase) + 2e − (electron conductive material 3) → O 2 − (inside oxide carrier 4) (inside oxide carrier 4) Inside the oxide carrier 4 from the interface 5 While oxygen is taken in, in the palladium oxide 2 in contact with the interface 6, oxygen deficiency is remarkable as the combustion reaction progresses. This deficiency serves as a driving force, and oxygen taken in from the interface 5 moves from the interface 5 to the interface 6 as oxygen ions.
【００２５】（界面６）酸素の欠乏が顕著となってお
り、還元状態の（酸化）パラジウム２に対し、以下の反
応により酸化物担体４の内部より酸素イオンが供給され
る。(Interface 6) Oxygen deficiency is remarkable, and oxygen ions are supplied from the inside of the oxide carrier 4 to the reduced (oxidized) palladium 2 by the following reaction.
【００２６】Ｏ2-（酸化物担体４の内部）＋Ｐｄ（（酸
化）パラジウム２）→ＰｄＯ（酸化パラジウム２）＋２
ｅ- （酸化パラジウム２） ＰｄＯが、メタンとの燃焼反応に関与する。O 2− (inside the oxide carrier 4) + Pd ((palladium oxide) 2) → PdO (palladium oxide 2) +2
e − (palladium oxide 2) PdO participates in the combustion reaction with methane.
【００２７】上記４つの領域での反応を介し、気相〜電
子導電材３〜酸化物担体４〜還元状態の（酸化）パラジ
ウム２へと酸素の供給が順次行われることにより、酸化
パラジウム２の再酸化速度の遅れが解消され燃焼時の触
媒活性に持続性が得られる。触媒活性成分を酸化物担体
に担持させるには、後述の如くメッキ法、スパッタ法、
含浸法、供沈法等が挙げられる。Oxygen is sequentially supplied to the gas phase, the electron conductive material 3, the oxide carrier 4, and the reduced (oxidized) palladium 2 through the reactions in the above four regions, whereby the palladium oxide 2 The delay in the reoxidation rate is eliminated, and the catalyst activity during combustion is sustained. In order to support the catalytically active component on the oxide carrier, the plating method, the sputtering method, and the
An impregnation method, a precipitation method, etc. are mentioned.
【００２８】本発明においては、触媒活性成分と酸化物
担体の混合比は特に限定はされないが、一般的に触媒活
性成分を全体の１〜７０質量％（更に好ましくは１０〜
６０質量％，残りが酸化物担体）程度に選択される。こ
こで、触媒活性成分が少なすぎると活性点不足となり、
十分な活性が発揮できない。また、逆に多すぎると、酸
化物担体によるシンタリング防止効果がなくなるため、
速やかにシンタリングして金属の表面積が低下し触媒活
性は低下する。さらに、触媒活性成分および酸化物担体
の平均粒度は、０．０１〜１００μｍ程度が好ましく、
０．１〜１０μｍ程度がより好ましい。触媒粉末を触媒
活性成分と酸化物担体のミリングにより作成した場合に
は、０．０１〜１００μｍ以下の粒径の１次粒子が凝集
し、この程度の大きさの粒径を有する２次粒子を生成し
ていることが好ましい。In the present invention, the mixing ratio of the catalytically active component and the oxide carrier is not particularly limited, but generally 1 to 70% by mass (more preferably 10 to 10% by mass) of the catalytically active component.
60% by mass and the balance is oxide support). Here, if the catalytically active component is too small, the active sites become insufficient,
Not able to exert sufficient activity. On the other hand, if the amount is too large, the effect of preventing oxides from sintering is lost.
Sintering quickly reduces the surface area of the metal and reduces the catalytic activity. Further, the average particle size of the catalytically active component and the oxide carrier is preferably about 0.01 to 100 μm,
It is more preferably about 0.1 to 10 μm. When the catalyst powder is prepared by milling a catalytically active component and an oxide carrier, primary particles having a particle size of 0.01 to 100 μm or less are aggregated, and secondary particles having a particle size of this size are produced. It is preferably generated.
【００２９】触媒粉末（あるいは触媒活性成分と酸化物
担体とを含有する粉末）の酸化物担体に電子導電材を付
加する方法としては、メッキ、スパッタ、含浸による方
法等が挙げられる。Examples of the method of adding the electron conductive material to the oxide carrier of the catalyst powder (or the powder containing the catalytically active component and the oxide carrier) include plating, sputtering, and impregnation.
【００３０】酸化物担体に電子導電材をどの程度付加す
るかは触媒系によって相違するが、おおよそ以下のよう
に規定される。すなわち、単位時間当たりに、酸化物担
体あるいは電子導電材の付加部分から触媒活性成分中に
供給される酸素原子の合計量が、触媒粉末中でのレドッ
クスサイクル反応により消費される酸素原子の量よりも
多くなる、あるいは同量であるようにすればよい。The degree to which the electron conductive material is added to the oxide carrier varies depending on the catalyst system, but is roughly defined as follows. That is, per unit time, the total amount of oxygen atoms supplied from the oxide carrier or the additional portion of the electron conductive material into the catalytically active component is more than the amount of oxygen atoms consumed by the redox cycle reaction in the catalyst powder. It may be increased or the same amount.
【００３１】本発明による、酸化物担体を構成する酸化
物としては、８００℃以上で少なくとも２．０×１０-2
／Ωｃｍ以上の酸素イオン伝導度を有することが好まし
い。特に、組成式（１−ｘ−ｙ）ＺｒＯ2 −ｘＳｃ2 Ｏ
3 −ｙＡ2 Ｏ3 （０＜ｘ＋ｙ≦０．１６、ｘ＞０、ｙ＞
０、ＡはＹ、Ｓｃおよびランタノイド元素からなる群よ
り選択される少なくとも１つ以上の元素）で示される物
質が好ましい。また、ジルコニウム、ビスマス、セリウ
ム、ニッケル、コバルト、マンガン、バナジウム、鉄、
マグネシウム、ストロンチウム、バリウム、イットリウ
ム、ランタン、プラセオジム、ネオジムの少なくとも１
種類以上の元素を含有する酸化物であって、上記の酸素
イオン伝導度を有するものが挙げられる。The oxide constituting the oxide carrier according to the present invention is at least 2.0 × 10 -2 at 800 ° C. or higher.
It preferably has an oxygen ion conductivity of / Ωcm or more. In particular, the composition formula (1-x-y) ZrO 2 -xSc 2 O
3- yA 2 O 3 (0 <x + y ≦ 0.16, x> 0, y>
0 and A are preferably substances represented by at least one element selected from the group consisting of Y, Sc and lanthanoid elements). Also, zirconium, bismuth, cerium, nickel, cobalt, manganese, vanadium, iron,
At least one of magnesium, strontium, barium, yttrium, lanthanum, praseodymium, and neodymium
Examples thereof include oxides containing more than one kind of element and having the above-mentioned oxygen ion conductivity.
【００３２】また、電子導電材とは、比抵抗が１．０×
１０-3Ωｃｍ以下のものであり、他には、例えば白金、
ニッケルを使用することが可能である。The electronic conductive material has a specific resistance of 1.0 ×
10 -3 [Omega] cm are those below the other, for example platinum,
It is possible to use nickel.
【００３３】また、本発明による第２の触媒粉末は、触
媒活性成分として少なくとも酸化パラジウムを含有した
触媒粉末において、前記触媒活性成分の少なくとも一部
の表面を、燃料物質は透過せず酸素分子は透過する細孔
径を有する選択的透過性材で被覆したことを特徴として
いる。Further, the second catalyst powder according to the present invention is a catalyst powder containing at least palladium oxide as a catalytically active component, wherein at least a part of the surface of the catalytically active component is not permeated by the fuel substance and oxygen molecules are not permeated. It is characterized in that it is coated with a selectively permeable material having a pore size for permeation.
【００３４】したがって、触媒活性成分である酸化パラ
ジウムは、分子ふるい効果を有する物質で被覆され、酸
素分子は到達できるが反応（燃料）物質は到達できない
領域を有している。この領域では、触媒活性成分が反応
（燃料）物質と反応しないので常に酸化雰囲気にあり、
レドックスサイクル反応（燃焼）で触媒活性成分に酸素
が欠乏しても、酸素は触媒活性成分のバルク内を拡散し
て速やかに触媒粉末に対して供給される。そして、触媒
活性成分の反応領域は常に酸素欠乏から免れるため、長
期にわたって触媒活性が維持される。Therefore, the catalytically active component palladium oxide is coated with a substance having a molecular sieving effect, and has a region where oxygen molecules can reach but a reaction (fuel) substance cannot reach. In this region, the catalytically active component does not react with the reaction (fuel) material, so it is always in an oxidizing atmosphere,
Even if the catalytically active component is deficient in oxygen in the redox cycle reaction (combustion), oxygen diffuses in the bulk of the catalytically active component and is rapidly supplied to the catalyst powder. Further, the reaction area of the catalytically active component is always protected from oxygen deficiency, so that the catalytic activity is maintained for a long time.
【００３５】本発明においては、触媒活性成分である金
属酸化物の表面を部分的に分子ふるい効果を持つ物質で
被覆している。この被覆の形態を示す例として、図６〜
図１５に断面を示した。図６〜図１５において、触媒粉
末１１は酸化パラジウム８および分子ふるい効果を有す
る物質９とから構成されている。In the present invention, the surface of the metal oxide which is the catalytically active component is partially covered with a substance having a molecular sieving effect. As an example showing the form of this coating, FIG.
The cross section is shown in FIG. 6 to 15, the catalyst powder 11 is composed of palladium oxide 8 and a substance 9 having a molecular sieving effect.
【００３６】また、本発明の触媒粉末は、図１６〜図１
８に断面あるいは一部断面を示したように耐熱性担体に
担持させてもよい。図１６において、触媒粉末７は触媒
活性成分である酸化パラジウム８、分子ふるい効果を有
する物質９、耐熱性担体１０より構成されている。図１
７に示す触媒粉末７においては、触媒粉末７は耐熱性担
体１０と耐熱性担体１０に担持された酸化パラジウム８
および酸化パラジウム８を被覆する分子ふるい効果を有
する物質９、図１８においては、触媒粉末７は耐熱性担
体１０と耐熱性担体１０に担持された酸化パラジウム８
と分子ふるい効果を有する物質９とから構成されてい
る。The catalyst powder of the present invention is shown in FIGS.
It may be supported on a heat-resistant carrier as shown in the cross section or partial cross section in FIG. In FIG. 16, the catalyst powder 7 is composed of palladium oxide 8 which is a catalytically active component, a substance 9 having a molecular sieving effect, and a heat resistant carrier 10. FIG.
In the catalyst powder 7 shown in FIG. 7, the catalyst powder 7 is a heat-resistant carrier 10 and palladium oxide 8 supported on the heat-resistant carrier 10.
18 and the substance 9 having a molecular sieving effect which coats the palladium oxide 8; in FIG. 18, the catalyst powder 7 is the heat-resistant carrier 10 and the palladium oxide 8 supported on the heat-resistant carrier 10.
And a substance 9 having a molecular sieving effect.
【００３７】図６〜図１８に示すように、「被覆」の意
味は、分子ふるい効果を有する物質９を薄い膜として酸
化パラジウム８の表面につけるというだけでなく、主た
る触媒活性成分である酸化パラジウム８と外部雰囲気と
の間に分子ふるい効果を持つ物質９が存在してさえいれ
ばよい。As shown in FIGS. 6 to 18, the meaning of “coating” is not only to attach the substance 9 having a molecular sieving effect to the surface of the palladium oxide 8 as a thin film, but also to oxidize the main catalytically active component. It suffices that the substance 9 having a molecular sieving effect is present between the palladium 8 and the external atmosphere.
【００３８】分子ふるい効果を有する物質とは、その物
質が内部に有する細孔内を酸素は拡散できるが、反応
（燃料）物質は拡散できない物質である。すなわち、酸
素分子径以上で反応（燃焼）物質分子径以下の細孔径を
有する物質である。例えば、燃料がメタンの場合、ゼオ
ライトの一種であるエリオナイトがこれに該当する例と
して挙げられる。しかしながら、上述の特性を有するも
のであればエリオナイトに限定されるものではない。ま
た、分子ふるいの細孔径を調整することにより、他の反
応系への応用も可能である。そして、分子ふるい効果を
有する物質は、必要に応じて適宜決定されるものであ
る。A substance having a molecular sieving effect is a substance capable of diffusing oxygen in the pores of the substance but not diffusing a reaction (fuel) substance. That is, it is a substance having a pore size not less than the molecular size of oxygen and not more than that of the reaction (combustion) substance. For example, when the fuel is methane, erionite, which is a type of zeolite, can be cited as an example corresponding to this. However, it is not limited to erionite as long as it has the above-mentioned characteristics. In addition, by adjusting the pore size of the molecular sieve, it can be applied to other reaction systems. Then, the substance having the molecular sieving effect is appropriately determined as necessary.
【００３９】耐熱性担体を構成する物質（耐熱性物質）
としては、酸化物または窒化物あるいは炭化物等のセラ
ミックスが挙げられる。金属を担体とすると、燃焼用の
空気と反応して金属担体自体が酸化し、最終的に酸化物
担体となる場合があるが、酸化しないものは金属担体と
して使用可能である。これらの中で、金属酸化物、特に
遷移金属元素の酸化物は、触媒粉末との間で酸素のやり
とりを行って触媒性能を向上させる助力となりうるので
好ましい。特に、酸化物の中ではジルコニア（Ｚｒ
Ｏ2 ）が望ましく、さらにイットリア（Ｙ2 Ｏ3 ）によ
る安定化を行った立方晶系ジルコニアが望ましい。ま
た、耐熱性物質は、上記した物質の２種類以上の併用系
での使用も可能である。さらに、分子ふるい効果を有す
る物質自身を耐熱性担体とすることで、他に耐熱性担体
としての物質を使用しないことも可能である。Substance that constitutes the heat-resistant carrier (heat-resistant substance)
Examples thereof include ceramics such as oxides, nitrides, and carbides. When a metal is used as the carrier, it may react with the air for combustion to oxidize the metal carrier itself and finally become an oxide carrier, but a substance that does not oxidize can be used as the metal carrier. Of these, metal oxides, particularly oxides of transition metal elements, are preferable because they can assist exchange of oxygen with the catalyst powder to improve catalyst performance. In particular, among oxides, zirconia (Zr
O 2 ) is desirable, and cubic zirconia stabilized by yttria (Y 2 O 3 ) is more desirable. The heat-resistant substance can also be used in a combination system of two or more of the above substances. Furthermore, by using a substance having a molecular sieving effect itself as a heat resistant carrier, it is possible not to use any other substance as a heat resistant carrier.
【００４０】触媒活性成分と耐熱性物質の混合比は特に
限定はされないが、一般的に触媒活性成分を全体の１〜
７０質量％（好ましくは１０〜６０質量％、更にガスタ
ービン燃焼器用では好ましくは４０〜６０質量％，残り
が耐熱性物質）程度に選択される。ここで、触媒活性成
分が少なすぎると、活性点不足となり、十分な活性が発
揮できない。また、逆に多すぎると、耐熱性担体による
シンタリング防止効果が無くなるため、速やかにシンタ
リングして金属の表面積が低下し、触媒活性は低下す
る。The mixing ratio of the catalytically active component and the heat-resistant substance is not particularly limited, but generally the catalytically active component is contained in the total amount of 1 to
The amount is selected to be about 70% by mass (preferably 10 to 60% by mass, more preferably 40 to 60% by mass for a gas turbine combustor, the rest being a heat resistant substance). Here, if the amount of the catalytically active component is too small, the active sites become insufficient and sufficient activity cannot be exhibited. On the other hand, when the amount is too large, the effect of preventing sintering by the heat-resistant carrier is lost, so that the surface is rapidly reduced by sintering and the catalytic activity is reduced.
【００４１】さらに、分子ふるい効果を有する物質で被
覆された酸化パラジウムおよび耐熱性物質で構成される
触媒粉末の平均粒度は、０．０１〜１００μｍ程度が好
ましいが、より好ましくは０．１〜１０μｍ程度であ
る。触媒粉末を触媒活性成分と耐熱性物質のミリングに
より作成した場合には、０．０１〜１μｍ以下の粒径の
１次粒子が凝集し、この程度の大きさの粒径を有する２
次粒子を生成していることが好ましい。Further, the average particle size of the catalyst powder composed of palladium oxide coated with a substance having a molecular sieving effect and a heat resistant substance is preferably about 0.01 to 100 μm, more preferably 0.1 to 10 μm. It is a degree. When the catalyst powder is prepared by milling the catalytically active component and the heat-resistant substance, the primary particles having a particle size of 0.01 to 1 μm or less are aggregated and have a particle size of this size.
It is preferable to generate secondary particles.
【００４２】本発明に係る触媒粉末の製造に関しては、
初めに触媒活性成分および耐熱性物質を含有する粉末を
作成した後、分子ふるい効果のある物質で触媒活性物質
を被覆して製造してもよいし、あらかじめ分子ふるい効
果のある物質で触媒活性成分を被覆した後に耐熱性物質
に担持してもよい。触媒活性成分および耐熱性物質を含
有する物質とは、両者の混合粉末であっても良いし、耐
熱性物質の粒子に触媒活性成分の粒子が担持（被着）さ
れた形態の粉末、あるいは触媒活性成分の粒子に耐熱性
物質の粒子が担持（被着）された形態の粉末、またはこ
れらの混合体であってもよい。Regarding the production of the catalyst powder according to the present invention,
It is also possible to first prepare a powder containing a catalytically active component and a heat-resistant substance, and then coat the catalytically active substance with a substance having a molecular sieving effect to produce it. It may be supported on a heat resistant material after being coated. The substance containing the catalytically active component and the heat-resistant substance may be a mixed powder of both, or a powder of a form in which particles of the catalytically active component are supported (adhered) on particles of the heat-resistant substance, or a catalyst. It may be a powder in which particles of a heat-resistant substance are carried (adhered) on particles of an active ingredient, or a mixture thereof.
【００４３】触媒粉末（あるいは触媒活性成分と耐熱性
物質を含有する粉末）を分子ふるい効果を有する物質で
被覆する方法としては、ミリングによる機械的混合、粉
末混合後加圧成型し再び粉砕する方法、触媒活性成分の
塩の水溶液中に分子ふるい効果を持つ物質を分散させた
後にアルカリを加えて共沈させる方法、水熱合成などで
触媒粉末の表面上に結晶成長させる方法、含浸・スパッ
タ等により分子ふるい効果を持つ物質の外表面上に触媒
粉末を担持する方法等が挙げられる。The method of coating the catalyst powder (or the powder containing the catalytically active component and the heat-resistant substance) with the substance having the molecular sieving effect includes mechanical mixing by milling, mixing the powders, press-molding and then pulverizing again. , A method of dispersing a substance having a molecular sieving effect in an aqueous solution of a salt of a catalytically active component and then coprecipitating by adding an alkali, a method of growing crystals on the surface of a catalyst powder by hydrothermal synthesis, impregnation / sputtering, etc. Then, a method of supporting a catalyst powder on the outer surface of a substance having a molecular sieving effect can be mentioned.
【００４４】分子ふるい効果を有する物質を触媒活性物
質にどの程度被覆するかは触媒系によって相違するが、
おおよそ以下のように規定される。すなわち、単位時間
当たりに、耐熱性担体から触媒活性成分中に移動してく
る酸素原子と、分子ふるい効果を有する物質で被覆した
部分から触媒粉末に供給される酸素原子の合計量が、耐
熱性担体にも分子ふるい効果を有する物質にも接してお
らず反応（燃焼）が起こっている領域において、レドッ
クスサイクル反応により消費される酸素原子の量よりも
多くなる、あるいは同量であるようにすればよい。The extent to which the substance having the molecular sieving effect is coated on the catalytically active substance depends on the catalyst system.
It is roughly defined as follows. That is, the total amount of oxygen atoms transferred from the heat-resistant carrier into the catalytically active component per unit time and the oxygen atoms supplied to the catalyst powder from the portion coated with the substance having a molecular sieving effect is The amount of oxygen atoms consumed by the redox cycle reaction should be greater than or equal to the amount of oxygen atoms consumed in the region where reaction (combustion) occurs without contact with the carrier or the substance having the molecular sieving effect. Good.
【００４５】さらに、本発明の第３の触媒粉末は、少な
くともロジウムを含有する触媒活性成分をセリウム酸化
物担体に担持した触媒粉末と、少なくとも酸化パラジウ
ムを含有する触媒活性成分を酸化物担体に担持した触媒
粉末とを共に含有することを特徴としている。Furthermore, the third catalyst powder of the present invention comprises a cerium oxide carrier carrying a catalyst active component containing at least rhodium, and an oxide carrier carrying a catalyst active component containing at least palladium oxide. It is characterized by containing together with the catalyst powder.
【００４６】本発明は、燃焼器等の運転中にパラジウム
系触媒が触媒活性を有するＰｄＯから触媒活性を殆ど有
しないＰｄに還元されて触媒活性が低下することを防止
するために、少なくともセリウム酸化物担体に少なくと
もロジウムを含有する触媒活性成分を担持した触媒粉末
と酸化物担体に少なくとも酸化パラジウムを含有する触
媒活性成分を担持した触媒粉末の両者を共存させて、高
い触媒活性を持続させるものである。According to the present invention, in order to prevent the palladium-based catalyst from being reduced from PdO having a catalytic activity to Pd having almost no catalytic activity during the operation of the combustor or the like to lower the catalytic activity, at least cerium oxide is used. In order to maintain a high catalytic activity, both a catalyst powder carrying a catalytically active component containing at least rhodium on a carrier and a catalyst powder carrying a catalytically active component containing at least palladium oxide on an oxide carrier are allowed to coexist. is there.
【００４７】つまり、燃料の燃焼時において、少なくと
もセリウム酸化物担体に少なくともロジウムを含有する
触媒活性成分を担持した触媒粉末に酸素が雰囲気中から
取り込まれ、レドックスサイクル反応（燃焼）により酸
素の欠乏した隣接する酸化物担体に担持されたパラジウ
ムに対して酸素が供給される。そして、パラジウムはＰ
ｄから触媒活性の高いＰｄＯに酸化され、常に触媒活性
を有する酸化パラジウムの状態が維持されるために、触
媒活性の低下が防止される。That is, during combustion of the fuel, oxygen was taken in from the atmosphere into the catalyst powder in which at least the cerium oxide carrier carried the catalytically active component containing at least rhodium, and was deficient in oxygen by the redox cycle reaction (combustion). Oxygen is supplied to the palladium loaded on the adjacent oxide carrier. And palladium is P
Since d is oxidized from Pd to PdO having a high catalytic activity and the state of palladium oxide having a catalytic activity is always maintained, the catalytic activity is prevented from lowering.
【００４８】一般に、パラジウム系触媒にロジウムや白
金などの貴金属元素を添加することにより、触媒の性能
を改善することは行われている。しかし、これらの貴金
属を単に添加あるいは混合しただけでは、本発明の効果
は得られない。すなわち、酸化物担体に少なくとも酸化
パラジウムを含有する触媒活性成分を担持した触媒粉末
と、少なくともセリウム酸化物担体に少なくともロジウ
ムを含有する触媒活性成分を担持した触媒粉末とが共存
することによって、初めて効果が現れる。この時、ロジ
ウムがセリウム酸化物担体に担持されていること及び酸
化パラジウムが酸化物担体に担持されていることが必要
である。酸化パラジウム、ロジウム、セリウムを含有す
る酸化物、その他の酸化物が単に混合されている系で
は、本発明の効果は持続しない。Generally, the performance of the catalyst has been improved by adding a noble metal element such as rhodium or platinum to the palladium-based catalyst. However, the effect of the present invention cannot be obtained by simply adding or mixing these noble metals. That is, the catalyst powder carrying a catalytically active component containing at least palladium oxide on the oxide carrier and the catalyst powder carrying at least a catalytically active component containing at least rhodium on the cerium oxide carrier coexist with each other. Appears. At this time, it is necessary that rhodium is supported on the cerium oxide carrier and palladium oxide is supported on the oxide carrier. The effect of the present invention does not last in a system in which oxides containing palladium oxide, rhodium, cerium, and other oxides are simply mixed.
【００４９】本発明においては、酸化物担体に少なくと
もパラジウムを含有する触媒活性成分を担持した触媒粉
末と、少なくともセリウム酸化物担体に少なくともロジ
ウムを含有する触媒活性成分を担持した触媒粉末とが共
存しており、これらの混合比は反応系により適宜決定さ
れるが、通常、１０：９０〜９０：１０程度、好ましく
は４０：６０〜７０：３０にするとよい。In the present invention, a catalyst powder having an oxide carrier carrying a catalytically active component containing at least palladium and a catalyst powder having at least a cerium oxide carrier carrying a catalytically active component containing at least rhodium coexist. Although the mixing ratio of these is appropriately determined depending on the reaction system, it is usually about 10:90 to 90:10, preferably 40:60 to 70:30.
【００５０】本発明に係る少なくともセリウム酸化物担
体を構成する酸化物としては、例えば、セリウム酸化
物、あるいはジルコニウム、ニッケル、コバルト、マン
ガン、バナジウム、鉄、マグネシウム、ストロンチウ
ム、バリウム、イットリウム、ランタン、プラセオジ
ム、ネオジムの少なくとも１種類以上の元素を含むセリ
ウム酸化物を挙げることができる。これらのセリウム酸
化物に担持するロジウムは、単体でも他の触媒活性成分
を含んでいても良い。本発明に関る、酸化物担体に少な
くともパラジウムを含有する触媒活性成分を担持した触
媒粉末においては、酸化物担体を構成する酸化物とし
て、例えばジルコニウム、アルミニウム、希土類元素、
ニッケル、コバルト、マンガン、バナジウム、鉄、マグ
ネシウム、バリウム、ランタン、プラセオジム、ネオジ
ムの少なくとも１種類以上の元素の酸化物を挙げること
ができるが、これらに限定されるものではない。これら
の触媒粉末においては、ロジウム及びパラジウムの担持
量は酸化物担体に対して１〜７０質量％程度が好まし
く、特に１０〜６０質量％が望ましい。Examples of the oxide constituting at least the cerium oxide carrier according to the present invention include cerium oxide, zirconium, nickel, cobalt, manganese, vanadium, iron, magnesium, strontium, barium, yttrium, lanthanum, praseodymium. , Cerium oxide containing at least one element of neodymium. The rhodium supported on these cerium oxides may be a single substance or may contain other catalytically active components. In the catalyst powder according to the present invention, which carries a catalytically active component containing at least palladium on an oxide carrier, as an oxide constituting the oxide carrier, for example, zirconium, aluminum, a rare earth element,
Examples thereof include, but are not limited to, oxides of at least one element selected from nickel, cobalt, manganese, vanadium, iron, magnesium, barium, lanthanum, praseodymium, and neodymium. In these catalyst powders, the supported amount of rhodium and palladium is preferably about 1 to 70% by mass, and particularly preferably 10 to 60% by mass with respect to the oxide carrier.
【００５１】本発明に係る触媒粉末は、特に、粒径を
０．０１〜１００μｍとすることにより、触媒効果の持
続性が向上する。また、触媒粉末は、多孔質層（たとえ
ば、アルミナ、ジルコニア、チタニア、マグネシア等）
に分散させて、反応ガスとの接触を保つようにすること
が好ましい。The catalyst powder according to the present invention has a particle size of 0.01 to 100 μm, whereby the sustainability of the catalytic effect is improved. The catalyst powder is a porous layer (eg, alumina, zirconia, titania, magnesia, etc.)
It is preferable to disperse it in order to maintain contact with the reaction gas.
【００５２】本発明の第１〜第３の触媒粉末において、
粉末とは、最大径が１ｍｍ以下であれば粒状、塊状、球
状、りん片状、針状、棒状の他、不規則形状でもよく、
またこれらの混合物でもよい。In the first to third catalyst powders of the present invention,
The powder may be in the form of granules, lumps, spheres, flakes, needles, rods, or irregular shapes as long as the maximum diameter is 1 mm or less,
Also, a mixture of these may be used.
【００５３】本発明の第１〜第３のパラジウム系触媒の
場合、触媒活性成分である酸化パラジウムあるいは金属
状態である金属パラジウム以外の成分に、助触媒として
ニッケル、マグネシウム、チタン、バナジウム、クロ
ム、マンガン、鉄、コバルト、銅、亜鉛、モリブデン、
ルテニウム、ロジウム、銀、白金、金、ランタノイドを
含む希土類（スカンジウム、イットリウム、ランタン、
セリウム、プラセオジウム、ネオジム、プロメチウム、
サマリウム、ユーロピウム、ガドニウム、テルビウム、
ジスプロシウム、ホルミウム、エルビウム、ツリウム、
イッテルビウム、ルテニウム）、または、これらの金属
の酸化物等を加えてもよい。特にニッケルまたはその酸
化物を加えた場合には触媒活性の向上が大きい。In the case of the first to third palladium-based catalysts of the present invention, nickel, magnesium, titanium, vanadium, chromium as a cocatalyst is added to a component other than palladium oxide which is a catalytically active component or metallic palladium which is in a metal state. Manganese, iron, cobalt, copper, zinc, molybdenum,
Ruthenium, rhodium, silver, platinum, gold, rare earths including lanthanoids (scandium, yttrium, lanthanum,
Cerium, praseodymium, neodymium, promethium,
Samarium, europium, gadnium, terbium,
Dysprosium, holmium, erbium, thulium,
Ytterbium, ruthenium), or oxides of these metals may be added. Especially when nickel or its oxide is added, the catalytic activity is greatly improved.
【００５４】触媒活性成分を耐熱性物質（酸化物または
窒化物あるいは炭化物等のセラミックス）に担持させる
には、単に両者の粉末を混ぜ合わせるだけでもよいが、
触媒活性成分および耐熱性物質の接触が密になり、接触
面積も増えて良好な接触を維持するために両者の相互作
用が高まることから、ボールミルを用いてミリングする
のが好ましい。混合の際、通常、雰囲気条件は特に限定
されない。また、含浸法、メッキ法（例えば、塩化錫水
溶液による処理および塩化パラジウム水溶液で処理し、
析出させた錫粒子をパラジウム粒子で置換してメッキ核
を析生（生成）させる手法）、スパッタ法、共沈法等に
よっても得ることができる。In order to support the catalytically active component on the heat resistant substance (ceramics such as oxides, nitrides or carbides), both powders may be simply mixed.
Since the contact between the catalytically active component and the heat-resistant substance becomes dense and the contact area also increases to enhance the interaction between the two in order to maintain good contact, it is preferable to perform milling using a ball mill. At the time of mixing, the atmosphere conditions are not particularly limited. Further, an impregnation method, a plating method (for example, treatment with an aqueous tin chloride solution and treatment with an aqueous palladium chloride solution,
It can also be obtained by a method of substituting the deposited tin particles with palladium particles to precipitate (generate) plating nuclei), a sputtering method, a coprecipitation method, or the like.
【００５５】助触媒を添加する場合には、触媒活性成分
と耐熱性物質の混合時に、同時に添加してもよいし、混
合後に改めて添加してもよい。また、耐熱性物質に触媒
活性成分が担持（被着）された触媒粉末の調製時に触媒
活性成分と同時に添加しても良いし、調製後に改めて添
加してもよい。なお、本発明は、元来触媒燃焼器用の触
媒粉末を得ることを主目的としているが、触媒燃焼器用
以外の燃焼触媒としてもまた、同様の効果を発揮するこ
とができる。When the cocatalyst is added, it may be added at the same time as the catalytically active component and the heat-resistant substance are mixed, or may be added again after the mixing. Further, it may be added at the same time as the catalyst active component at the time of preparation of the catalyst powder in which the catalyst active component is supported (deposited) on the heat resistant material, or may be added again after the preparation. Although the present invention primarily aims to obtain a catalyst powder for a catalytic combustor, the same effect can be exhibited by a combustion catalyst other than that for a catalytic combustor.
【００５６】また、本発明の燃焼触媒は、多数のガス流
路を有する耐熱性構造基材と、前記耐熱性構造基材のガ
ス流路内壁面に被着・担持された触媒粉末とを有してな
り、前記触媒粉末は、（ａ）触媒活性成分を酸化物担体
に担持してなる触媒粉末であって、前記触媒活性成分は
少なくとも酸化パラジウムを含有し、前記酸化物担体は
８００℃以上で少なくとも２．０×１０-2／Ωｃｍ以上
の酸素イオン伝導度を有しており、前記酸化物担体の少
なくとも一部の表面を電子導電材で被覆したことを特徴
とする触媒粉末、（ｂ）触媒活性成分として少なくとも
酸化パラジウムを備えた触媒粉末において、前記触媒活
性成分の少なくとも一部の表面を燃料物質は透過せず酸
素分子は透過する細孔径を有する選択的透過性材で被覆
したことを特徴とする触媒粉末、（ｃ）少なくともロジ
ウムを含有する触媒活性成分をセリウム酸化物担体に担
持した触媒粉末と、少なくとも酸化パラジウムを含有す
る触媒活性成分を酸化物担体に担持した触媒粉末とを共
に含有することを特徴とする触媒粉末からなる群より選
択された、少なくとも１種以上であることを特徴として
いる。Further, the combustion catalyst of the present invention comprises a heat resistant structural base material having a large number of gas flow paths, and a catalyst powder adhered to and carried on the gas flow path inner wall surface of the heat resistant structural base material. The catalyst powder is (a) a catalyst powder in which a catalytically active component is supported on an oxide carrier, the catalytically active component contains at least palladium oxide, and the oxide carrier is 800 ° C. or higher. And has an oxygen ion conductivity of at least 2.0 × 10 −2 / Ωcm or more, and at least a part of the surface of the oxide carrier is coated with an electronic conductive material. ) In a catalyst powder having at least palladium oxide as a catalytically active component, at least a part of the surface of the catalytically active component is coated with a selectively permeable material having a pore size that does not permeate the fuel substance but permeates oxygen molecules. Featuring And (c) a catalyst powder having a cerium oxide carrier carrying a catalytically active component containing at least rhodium, and a catalyst powder having an oxide carrier carrying a catalytically active component containing at least palladium oxide. It is characterized by being at least one or more selected from the group consisting of catalyst powders.
【００５７】金属酸化物系触媒の粉末を被着・担持させ
る耐久性基材としては、たとえば、耐熱セラミック製、
もしくは耐熱耐酸化金属製の板またはパイプ、あるいは
開口部が正方形、長方形、三角形あるいは六角形等に仕
切られたハニカム等が挙げられる。耐久性基材をガス流
路に配置してガス流路を兼用する場合には、ハニカム状
の構造であることが望ましい。Examples of the durable base material on which the powder of the metal oxide catalyst is adhered and carried are, for example, heat-resistant ceramics,
Alternatively, a plate or pipe made of heat-resistant and oxidation-resistant metal, or a honeycomb in which openings are partitioned into squares, rectangles, triangles, hexagons, or the like can be given. When the durable base material is arranged in the gas flow path and also serves as the gas flow path, it is desirable that the structure is a honeycomb structure.
【００５８】また、ガスタービン用の燃焼器に使用する
場合には、耐熱性構造基材の構成材料として、１２００
℃程度の高温酸化性雰囲気中で安定性を有する材質、た
とえば、コーラジェライト、ムライト、α−アルミナ、
ジルコニアスピネル、チタニアなどのセラミック、もし
くはステンレス鋼等の使用が望ましい。When it is used in a combustor for a gas turbine, it is used as a constituent material of the heat resistant structural base material, 1200
A material having stability in a high temperature oxidizing atmosphere of about ℃, for example, cola gellite, mullite, α-alumina,
It is preferable to use ceramics such as zirconia spinel and titania, or stainless steel.
【００５９】ハニカム構造を有する耐熱性構造基材の多
数個のガス流路内壁面に対して触媒粉末を被着・担持さ
せるには、ガス流路内壁面に触媒粉末を含むスラリーを
塗布し、その後焼結することにより行われる。また、本
発明の触媒粉末を耐久性基材に被着・担持する際には、
焼結に先だって特願平０６−１８９３３４あるいは０７
−０１５６０４に記載された前処理（熱処理）を触媒粉
末に対して行ってもよい。In order to deposit and carry the catalyst powder on a large number of gas flow passage inner wall surfaces of the heat resistant structural substrate having a honeycomb structure, a slurry containing the catalyst powder is applied to the gas flow passage inner wall surfaces, Then, it is performed by sintering. Further, when the catalyst powder of the present invention is adhered to and carried on a durable substrate,
Prior to sintering, Japanese Patent Application No. 06-189334 or 07
The pretreatment (heat treatment) described in 015604 may be performed on the catalyst powder.
【００６０】また、全てのガス流路に触媒粉末を塗布せ
ず、隣り合う流路の一方（例えば市松模様の黒に当たる
部分に相当する領域）には触媒粉末を塗布しないことも
可能である。この方法としては、予め触媒粉末を塗布し
ない流路の端を蓋しておき、塗布できない状態にした後
で塗布を行い、塗布後に蓋を除去すればよい。It is also possible that the catalyst powder is not applied to all the gas flow passages, and the catalyst powder is not applied to one of the adjacent flow passages (for example, the area corresponding to the black portion of the checkered pattern). As a method for this, the end of the flow path to which the catalyst powder is not applied is covered in advance, application is performed after the state where the catalyst powder cannot be applied, and the cover is removed after application.
【００６１】さらに、本発明の燃焼器は、燃料ガス供給
口と、空気供給口と、前記燃料ガス供給口から供給され
る燃料ガスおよび空気供給口から供給される酸素含有ガ
スを混合するガス混合部と、前記ガス混合部から流出す
る混合ガス流路に配置された燃焼触媒とを具備してなる
燃焼器であって、前記燃焼触媒が多数のガス流路を有す
る耐熱性構造基材と、前記耐熱性構造基材のガス流路内
壁面に被着・担持された触媒粉末とを有してなり、前記
触媒粉末は、（ａ）触媒活性成分を酸化物担体に担持し
てなる触媒粉末であって、前記触媒活性成分は少なくと
も酸化パラジウムを含有し、前記酸化物担体は８００℃
以上で少なくとも２．０×１０-2／Ωｃｍ以上の酸素イ
オン伝導度を有しており、前記酸化物担体の少なくとも
一部の表面を電子導電材で被覆したことを特徴とする触
媒粉末、（ｂ）触媒活性成分として少なくとも酸化パラ
ジウムを備えた触媒粉末において、前記触媒活性成分の
少なくとも一部の表面を燃料物質は透過せず酸素分子は
透過する細孔径を有する選択的透過性材で被覆したこと
を特徴とする触媒粉末、（ｃ）少なくともロジウムを含
有する触媒活性成分をセリウム酸化物担体に担持した触
媒粉末と、少なくとも酸化パラジウムを含有する触媒活
性成分を酸化物担体に担持した触媒粉末とを共に含有す
ることを特徴とする触媒粉末からなる群より選択され
た、少なくとも１種以上であることを特徴としている。Further, the combustor of the present invention is a gas mixture for mixing a fuel gas supply port, an air supply port, a fuel gas supplied from the fuel gas supply port and an oxygen-containing gas supplied from the air supply port. And a heat-resistant structural base material having a plurality of gas flow paths, wherein the combustion catalyst comprises a combustion catalyst arranged in a mixed gas flow path flowing out of the gas mixing section, The catalyst powder adhered to and supported on the inner wall surface of the gas flow path of the heat-resistant structural base material, wherein the catalyst powder is (a) a catalyst powder having a catalytically active component supported on an oxide carrier. The catalytically active component contains at least palladium oxide, and the oxide carrier has a temperature of 800 ° C.
As described above, the catalyst powder has an oxygen ion conductivity of at least 2.0 × 10 −2 / Ωcm or more, and at least a part of the surface of the oxide carrier is coated with an electronic conductive material, ( b) In a catalyst powder having at least palladium oxide as a catalytically active component, at least a part of the surface of the catalytically active component is coated with a selectively permeable material having a pore size that does not allow fuel substances to permeate but oxygen molecules. And (c) a catalyst powder having a cerium oxide carrier supporting a catalytically active component containing at least rhodium, and a catalyst powder having an oxide carrier supporting a catalytically active component containing at least palladium oxide. And at least one selected from the group consisting of catalyst powders containing at least one of the above.
【００６２】燃焼触媒は多数のガス流路を有する耐熱性
構造基材のガス流路内壁面に被着・担持された金属酸化
物を触媒活性成分とし、また、触媒活性成分以外の物質
を担体としており、触媒活性成分を還元雰囲気下で一度
還元後に酸化してもよい。そして、燃焼触媒の上流で燃
料と空気などの酸素含有ガスを予め混合して燃焼触媒に
供給して燃焼させることによって、触媒活性が長期に渡
って持続し、窒素酸化物の発生を抑制した燃焼器を得る
ことができる。The combustion catalyst has a metal oxide adhered and supported on the inner wall surface of the gas flow passage of the heat-resistant structural base material having a large number of gas passages as a catalytically active component, and a substance other than the catalytically active component as a carrier. However, the catalytically active component may be reduced once in a reducing atmosphere and then oxidized. Then, by mixing a fuel and an oxygen-containing gas such as air in advance upstream of the combustion catalyst and supplying the mixture to the combustion catalyst for combustion, the catalytic activity is maintained for a long period of time, and combustion that suppresses the generation of nitrogen oxides. You can get a vessel.
【００６３】つまり、本発明に係る燃焼触媒および燃焼
器においては、高圧ガス発生領域に配置された触媒粉末
が長期間にわたり触媒活性を維持するため、例えばガス
タービンの燃焼器に利用することにより、ガスタービン
の駆動用高温ガスを効率よく生成・利用することが可能
となり、排気のクリーン化を長期持続することが可能に
なる。That is, in the combustion catalyst and combustor according to the present invention, the catalyst powder arranged in the high-pressure gas generation region maintains the catalytic activity for a long period of time. The high temperature gas for driving the gas turbine can be efficiently generated and used, and the exhaust gas can be kept clean for a long time.
【００６４】[0064]
【発明の実施の形態】以下に、本発明の実施例を図面を
用いて詳細に説明する。なお、以下の実施例において、
各図に共通する部分には、同一符号を付して重複する説
明は省略することとする。また、本発明は以下の実施例
に限定されるものではない。Embodiments of the present invention will be described below in detail with reference to the drawings. In the following examples,
The parts common to each figure are denoted by the same reference numerals, and duplicate description will be omitted. The present invention is not limited to the examples below.
【００６５】（実施例１）粒径１μｍのＺｒＯ2 粉末
と、粒径１μｍのＳｃ2 Ｏ3 粉末と、粒径１μｍのＹ2
Ｏ3 粉末とを組成式：０．９２ＺｒＯ2 −ｘＳｃ2 Ｏ3
−（０．０８‐ｘ）Ｙ2 Ｏ3 （０＜ｘ≦０．０８）で表
される化合物において、ｘ＝０．０１、０．０２、０．
０４、０．０８の各組成となるように秤量して混合し、
大気中において１６００℃、１０時間焼成して化合物を
得た。得られたｘ＝０．０１、０．０２、０．０４、
０．０８の各組成の化合物をそれぞれ粉砕により粒径１
μｍの粒子とし、これを酸化物担体４とした。この酸化
物担体４と粒径０．３μｍの金属パラジウム粉末とを
１：１の重量比で秤取し、１０時間粉砕・混合してパラ
ジウム触媒粉末とした。次いで、パラジウム触媒粉末を
電子導電材料である白金ペ−ストに浸漬し、瀘過したも
のを大気中で乾燥した後、１０００℃で３０分焼成し
た。Example 1 ZrO 2 powder having a particle size of 1 μm, Sc 2 O 3 powder having a particle size of 1 μm, and Y 2 having a particle size of 1 μm
O 3 powder and composition formula: 0.92ZrO 2 -xSc 2 O 3
In the compound represented by — (0.08-x) Y 2 O 3 (0 <x ≦ 0.08), x = 0.01, 0.02, 0.
Weigh and mix so that each composition is 04, 0.08,
The compound was obtained by baking in air at 1600 ° C. for 10 hours. The obtained x = 0.01, 0.02, 0.04,
Particle size of 1 by crushing each compound of 0.08
Particles having a size of μm were used as the oxide carrier 4. The oxide carrier 4 and metallic palladium powder having a particle size of 0.3 μm were weighed at a weight ratio of 1: 1 and pulverized and mixed for 10 hours to obtain a palladium catalyst powder. Next, the palladium catalyst powder was immersed in a platinum paste, which was an electronic conductive material, and the filtered material was dried in the air and then baked at 1000 ° C. for 30 minutes.
【００６６】図２および図３は、こうして得られた触媒
粉末１の構造を模式的に示したものであり、図４は、図
３の触媒粉末１の一部断面を示した図である。電子導電
材３は、図２に示されるように酸化物担体４の一部に付
加してもよく、また図３に示されるように酸化物担体４
の全体に付加してもよい。その後、触媒粉末１に水を添
加してスラリ−化し、直径３０ｍｍ、長さ１７０ｍｍ、
６．４５ｃｍ2 （１ｉｎｃｈ2 ）あたり１００個の燃焼
ガス流路を区画・形成して構成されるコージェライト製
ハニカムに塗布した後、９００℃で２４時間焼成して図
５に示すような燃焼触媒１３とした。2 and 3 schematically show the structure of the catalyst powder 1 thus obtained, and FIG. 4 is a diagram showing a partial cross section of the catalyst powder 1 of FIG. The electronic conductive material 3 may be added to a part of the oxide carrier 4 as shown in FIG. 2, or the oxide carrier 4 as shown in FIG.
May be added to the whole. After that, water is added to the catalyst powder 1 to form a slurry, and the diameter is 30 mm and the length is 170 mm.
After being applied to a cordierite honeycomb constituted by partitioning and forming 100 combustion gas passages per 6.45 cm 2 (1 inch 2 ), it is fired at 900 ° C. for 24 hours and then burned as shown in FIG. It was set to 13.
【００６７】次に、これらのハニカム型の燃焼触媒１３
をガスタービン燃焼器を模擬した燃焼器１２に組み込み
（装着）、燃焼試験を行った。すなわち、図５に要部構
成例を断面的に示したように、燃焼用気体供給口１４か
ら供給される燃焼用気体（たとえば空気）が流れるガス
供給路１５、前記ガス供給路１５の壁面に設置され、ガ
ス供給路１５を流れる燃焼用気体に燃料ガスを混合して
燃焼作用を進める燃焼ガス供給口１６、ガス供給路１５
を流れる混合系ガスに補給用燃料ガスを供給する補給燃
料供給口１７とを具備する燃焼器１２において、ガス供
給路１５にこれらのハニカム型の燃焼触媒１３を装着し
て燃焼試験を行った。Next, these honeycomb type combustion catalysts 13
Was installed (installed) in a combustor 12 simulating a gas turbine combustor, and a combustion test was conducted. That is, as shown in a cross-sectional view of a configuration example of a main part in FIG. 5, a gas supply path 15 through which a combustion gas (for example, air) supplied from the combustion gas supply port 14 flows and a wall surface of the gas supply path 15 are provided. The combustion gas supply port 16 and the gas supply path 15 which are installed and which promote combustion by mixing the fuel gas with the combustion gas flowing through the gas supply path 15.
In a combustor 12 having a refueling fuel supply port 17 for supplying a refueling fuel gas to the mixed system gas flowing through the gas, a honeycomb type combustion catalyst 13 was attached to the gas supply passage 15 and a combustion test was conducted.
【００６８】（比較例１）一方、対照として、酸化物担
体４に８ｍｏｌ％イットリア安定化ジルコニア（８ＹＳ
Ｚ）粉末（粒径１μｍ）を用いて電子導電材３を付加せ
ずに実施例１と同一の条件で作成した燃焼触媒１３を用
意した。Comparative Example 1 On the other hand, as a control, 8 mol% yttria-stabilized zirconia (8YS) was added to the oxide carrier 4.
Z) A combustion catalyst 13 prepared using the powder (particle size 1 μm) under the same conditions as in Example 1 without adding the electronic conductive material 3 was prepared.
【００６９】燃焼実験は、全圧を０．７ＭＰａとし、メ
タン３％を含む空気を２ｍ3 ／分の流量で流し、触媒入
口温度が５００℃になるように温度コントロールしなが
ら連続運転させることにより実施された。実施例１にお
ける燃焼触媒１３の触媒活性は運転１００時間後もほと
んど変化しなかったのに対し、比較例１の燃焼触媒１３
は５時間後には活性が低下し、燃焼が維持できなかっ
た。また、反応後の触媒粉末を取り出し、Ｘ線分析した
ところ、実施例１の燃焼触媒１３では、酸化パラジウム
の回折ピークのみが検出され、金属パラジウムはほとん
ど存在しなかったのに対し、比較例１の燃焼触媒１３で
は、金属パラジウムが大部分を占め、酸化パラジウムの
回折ピークはわずかしか検出されなかった。In the combustion experiment, the total pressure was 0.7 MPa, the air containing 3% of methane was flowed at a flow rate of 2 m 3 / min, and the catalyst inlet temperature was controlled to 500 ° C. by continuously operating the temperature. It was implemented. While the catalytic activity of the combustion catalyst 13 in Example 1 hardly changed after 100 hours of operation, the combustion catalyst 13 of Comparative Example 1
The activity decreased after 5 hours and combustion could not be maintained. In addition, when the catalyst powder after the reaction was taken out and subjected to X-ray analysis, in the combustion catalyst 13 of Example 1, only the diffraction peak of palladium oxide was detected and metallic palladium was hardly present, whereas Comparative Example 1 In the combustion catalyst 13 of No. 1, metallic palladium accounted for the majority, and only a few diffraction peaks of palladium oxide were detected.
【００７０】さらに、触媒活性の持続性は、Ｓｃ2 Ｏ3
の添加割合を増加させるに伴い（すなわち、ｘが０．０
１から０．０２、０．０４、０．０８と増加するに従
い）向上が認められた。Further, the sustainability of the catalytic activity depends on Sc 2 O 3
With increasing the addition ratio (that is, x is 0.0
Improvement was recognized) (as it increased from 1 to 0.02, 0.04, 0.08).
【００７１】また、実施例１で用いた酸化物担体４の酸
素イオン伝導度をペレット（同じ固相反応の条件で得た
粉末を、円柱形（直径１５ｍｍ、長さ１ｍｍ）に成型し
たもの）を用いて、複素インピ−ダンス法にて８００℃
で測定した。この場合についても酸素イオン伝導度が、
同じくＳｃ2 Ｏ3 の添加割合の増加に伴い、比較例１で
用いている酸化物担体４（８ＹＳＺ）の２．０×１０-2
／Ωｃｍから上昇してゆく傾向が見られた。Further, the oxygen ion conductivity of the oxide carrier 4 used in Example 1 was pelletized (the powder obtained under the same solid-phase reaction conditions was molded into a cylindrical shape (diameter 15 mm, length 1 mm)). By complex impedance method at 800 ℃
It was measured at. Also in this case, the oxygen ion conductivity is
Similarly, as the proportion of Sc 2 O 3 added increased, 2.0 × 10 −2 of the oxide carrier 4 (8YSZ) used in Comparative Example 1 was used.
The tendency was to increase from / Ωcm.
【００７２】（実施例２）粒径１μｍのＺｒＯ2 粉末
と、粒径１μｍのＳｃ2 Ｏ3 粉末と、粒径１μｍ程度の
Ａ2 Ｏ3 とを、組成式：（１‐ｘ‐ｙ）ＺｒＯ2 −ｘＳ
ｃ2 Ｏ3 −ｙＡ2 Ｏ3 （０＜ｘ＋ｙ≦０．１６、ｘ＞
０、ｙ＞０、ＡはＹ、Ｓｃ、ランタノイド元素からなる
群より選択される少なくとも１つ以上の元素）で表され
る化合物が、（ｘ、ｙ）＝（０．０１、０．０２）、
（０．０２、０．０４）、（０．０３、０．０６）、
（０．０４、０．０８）、（０．０６、０．１０）、
（０．０８、０．１０）、（０．１０、０．２０）の各
組成となるように秤量して混合し、大気中において１６
００℃、１０時間焼成して化合物を得た。Example 2 A ZrO 2 powder having a particle size of 1 μm, a Sc 2 O 3 powder having a particle size of 1 μm, and A 2 O 3 having a particle size of about 1 μm were used as a composition formula: (1-xy). ZrO 2 -xS
c 2 O 3 -yA 2 O 3 (0 <x + y ≦ 0.16, x>
0, y> 0, A is Y, Sc, at least one or more elements selected from the group consisting of lanthanoid elements), and a compound represented by (x, y) = (0.01, 0.02) ,
(0.02, 0.04), (0.03, 0.06),
(0.04, 0.08), (0.06, 0.10),
(0.08, 0.10) and (0.10, 0.20) were weighed and mixed so that the respective compositions would be 16 in the air.
The compound was obtained by baking at 00 ° C. for 10 hours.
【００７３】得られた（ｘ、ｙ）＝（０．０１、０．０
２）、（０．０２、０．０４）、（０．０３、０．０
６）、（０．０４、０．０８）、（０．０６、０．１
０）、（０．０８、０．１０）、（０．１０、０．２
０）の各組成の化合物を、それぞれ粉砕により粒径１μ
ｍの粒子とし、これを酸化物担体４とした。この酸化物
担体４と粒径０．３μｍの金属パラジウム粉末とを１：
１の重量比で秤取し、１０時間粉砕・混合してパラジウ
ム触媒粉末とした。次いで、パラジウム触媒粉末を電子
導電材料である白金ペ−ストに浸漬し、瀘過したものを
大気中で乾燥したのち、１０００℃で３０分焼成した。Obtained (x, y) = (0.01, 0.0
2), (0.02, 0.04), (0.03, 0.0
6), (0.04, 0.08), (0.06, 0.1
0), (0.08, 0.10), (0.10, 0.2
The compound of each composition of 0) was pulverized to a particle size of 1 μm.
Particles of m were used as the oxide carrier 4. The oxide carrier 4 and metallic palladium powder having a particle size of 0.3 μm were mixed with each other in a ratio of 1:
The palladium catalyst powder was obtained by weighing in a weight ratio of 1 and pulverizing and mixing for 10 hours. Next, the palladium catalyst powder was dipped in a platinum paste which was an electronic conductive material, and the filtered material was dried in the air and then baked at 1000 ° C. for 30 minutes.
【００７４】こうして得られた触媒粉末１の構造は、実
施例１において示された図２、図３および図４と同様で
ある。その後、触媒粉末１に水を添加してスラリ−化
し、直径３０ｍｍ、長さ１７０ｍｍ、６．４５ｃｍ
2 （１ｉｎｃｈ2 ）あたり１００個の燃焼ガス流路を区
画・形成して構成されるコージェライト製ハニカムに塗
布した後、９００℃で２４時間焼成して燃焼触媒１３と
した。The structure of the catalyst powder 1 thus obtained is similar to that shown in FIGS. 2, 3 and 4 shown in the first embodiment. Then, water is added to the catalyst powder 1 to form a slurry, and the diameter is 30 mm, the length is 170 mm, and the length is 6.45 cm.
After being applied to a cordierite honeycomb constituted by partitioning and forming 100 combustion gas flow paths per 2 (1 inch 2 ), the combustion catalyst 13 was obtained by firing at 900 ° C. for 24 hours.
【００７５】燃焼実験は、比較例１の燃焼触媒１３を対
照とし、全圧を０．７ＭＰａ、メタン３％を含む空気を
２ｍ3 ／分の流量で流し、触媒入口温度が５００℃にな
るように温度コントロールしながら連続運転させること
により実施された。実施例２における燃焼触媒１３の触
媒活性の持続性は、（ｘ、ｙ）＝（０．０８、０．１
０）、（０．１０、０．２０）の組成を除いた上記
（ｘ、ｙ）のどの組成の酸化物担体４を用いたもので
も、比較例１の燃焼触媒１３と比較して燃焼時における
触媒活性の持続性に向上が認められた。In the combustion experiment, the combustion catalyst 13 of Comparative Example 1 was used as a control, air having a total pressure of 0.7 MPa and 3% methane was flowed at a flow rate of 2 m 3 / min, and the catalyst inlet temperature was 500 ° C. It was carried out by continuously operating while controlling the temperature. The sustainability of the catalytic activity of the combustion catalyst 13 in Example 2 is (x, y) = (0.08, 0.1
0) and (0.10, 0.20) except for the composition of the oxide carrier 4 of any of the above (x, y), when compared with the combustion catalyst 13 of Comparative Example 1 during combustion Improvement in the sustainability of the catalytic activity was observed.
【００７６】なお、（ｘ、ｙ）＝（０．０８、０．１
０）、（０．１０、０．２０）の組成の酸化物担体４を
用いた燃焼触媒１３の触媒活性に持続性がなかったこと
から明らかなように、ジルコニアに対する添加酸化物
（先の組成式におけるＳｃ2 Ｏ3あるいはＡ2 Ｏ3 ）の
量がｘ＋ｙにして０．１６を越える組成のもので酸化物
担体４を作成した場合には、比較例１の燃焼触媒１３以
上に高い触媒活性をもつ燃焼触媒１３は得られないこと
がわかった。Note that (x, y) = (0.08, 0.1
0) and (0.10, 0.20), the catalytic activity of the combustion catalyst 13 using the oxide carrier 4 has no sustaining activity. When the oxide carrier 4 is made of a composition in which the amount of Sc 2 O 3 or A 2 O 3 ) in the formula is more than 0.16 in x + y, the catalytic activity higher than that of the combustion catalyst 13 of Comparative Example 1 is obtained. It was found that the combustion catalyst 13 having the
【００７７】（実施例３）粒径０．３μｍの金属パラジ
ウム粉末に、金属パラジウム粉末の１０重量％に相当す
る平均粒径１μｍに予備粉砕しておいたエリオナイトを
加えた。次いで、空気雰囲気下において遊星ボールミル
を用いて４５０回転／分の回転を与え、１時間粉砕・混
合した。この後、平均粒径１μｍの８ｍｏｌ％イットリ
ア安定化ジルコニア粉末を金属パラジウム粉末と等重量
秤取して上述の１時間粉砕・混合した混合物に加え、さ
らに４５０回転／分の回転を与えて５時間粉砕・混合し
た。図１６は、こうして得られた触媒粉末７の構造を模
式的に示したものである。Example 3 To metal palladium powder having a particle size of 0.3 μm, erionite preliminarily pulverized to an average particle size of 1 μm corresponding to 10% by weight of the metal palladium powder was added. Then, the mixture was pulverized and mixed for 1 hour by applying a rotation of 450 rpm with a planetary ball mill in an air atmosphere. Then, an 8 mol% yttria-stabilized zirconia powder having an average particle diameter of 1 μm was weighed in an equal weight with the metal palladium powder, pulverized and mixed for 1 hour as described above, and the mixture was further rotated at 450 rpm for 5 hours. It was crushed and mixed. FIG. 16 schematically shows the structure of the catalyst powder 7 thus obtained.
【００７８】（比較例２）エリオナイトに代えて、ほと
んど細孔を持たない平均粒径１μｍの８ｍｏｌ％イット
リア安定化ジルコリニア粉末を使用する以外には、実施
例３とまったく同様にして触媒粉末を得た。Comparative Example 2 A catalyst powder was prepared in the same manner as in Example 3 except that 8 mol% yttria-stabilized zirco linear powder having an average particle size of 1 μm and having almost no pores was used in place of erionite. Obtained.
【００７９】燃焼実験は、実施例３の触媒粉末と、比較
例１の触媒粉末を各々１００ｍｇとり、内径５ｍｍのス
テンレス管にそれぞれ詰め、全圧を０．７ＭＰａとし、
メタン３％を含む空気を１０ｌ／分（標準状態換算）の
流量で流し、触媒粉末部の温度が８００℃程度になるよ
うに温度コントロールしながら５時間反応させて実施し
た。In the combustion experiment, 100 mg each of the catalyst powder of Example 3 and the catalyst powder of Comparative Example 1 was placed in a stainless steel tube having an inner diameter of 5 mm and the total pressure was 0.7 MPa.
Air containing 3% of methane was caused to flow at a flow rate of 10 l / min (converted to the standard state), and the reaction was carried out for 5 hours while controlling the temperature so that the temperature of the catalyst powder portion was about 800 ° C.
【００８０】触媒出口のＣＯ2 濃度をモニターしたとこ
ろ、実施例３では３％であった。一方、比較例２では最
初は３％であったが、徐々に減少して５時間後には２％
になり、燃焼がおこりにくくなっていることが確認され
た。When the CO 2 concentration at the catalyst outlet was monitored, it was 3% in Example 3. On the other hand, in Comparative Example 2, it was 3% at first, but gradually decreased to 2% after 5 hours.
It was confirmed that combustion was less likely to occur.
【００８１】反応後の触媒粉末を取り出しＸ線分析した
ところ、実施例３の触媒粉末では、酸化パラジウムの回
折ピークのみが検出され、金属パラジウムはほとんど存
在しなかった。しかし、比較例２の触媒粉末では、金属
パラジウムが大部分を占め、酸化パラジウムの回折ピー
クはわずかしか検出されなかった。なお、実施例３およ
び比較例２においては、耐熱性担体として８ｍｏｌ％イ
ットリア安定化ジルコニア粉末を用いたが、耐熱性担体
としてアルミナ、シリカ、チタニア、ランタニア、セリ
ア、酸化ニッケル、酸化タンタル、マグネシアやこれら
の混合物を用いた場合においてもほぼ同様の結果を示し
た。When the catalyst powder after the reaction was taken out and subjected to X-ray analysis, in the catalyst powder of Example 3, only the diffraction peak of palladium oxide was detected, and metallic palladium was almost absent. However, in the catalyst powder of Comparative Example 2, metallic palladium accounted for the majority, and only a small diffraction peak of palladium oxide was detected. In Example 3 and Comparative Example 2, although 8 mol% yttria-stabilized zirconia powder was used as the heat resistant carrier, alumina, silica, titania, lanthania, ceria, nickel oxide, tantalum oxide, magnesia, etc. were used as the heat resistant carrier. Similar results were obtained when these mixtures were used.
【００８２】（実施例４）実施例３および比較例２に相
当する触媒粉末を水酸化アルミニウムとともに共沈さ
せ、スラリーを得た。得られたスラリーを直径３０ｍ
ｍ、長さ１７０ｍｍ、６．４５ｃｍ2 （１ｉｎｃｈ2 ）
あたり１００個の燃焼ガス流路を区画・形成して構成さ
れるコージェライト製ハニカム型に塗布し、空気中にお
いて７００℃で６時間焼成して２種類のハニカム型の燃
焼触媒１３を得た。(Example 4) A catalyst powder corresponding to Example 3 and Comparative Example 2 was coprecipitated with aluminum hydroxide to obtain a slurry. Diameter of the obtained slurry is 30 m
m, length 170 mm, 6.45 cm 2 (1 inch 2 ).
Each of them was applied to a cordierite honeycomb type constituted by partitioning and forming 100 combustion gas flow paths, and fired in air at 700 ° C. for 6 hours to obtain two types of honeycomb type combustion catalysts 13.
【００８３】次に、これらのハニカム型の燃焼触媒１３
をガスタービン燃焼器を模擬した燃焼器１２に組み込み
（装着）、燃焼試験を行った。すなわち、図５に要部構
成例を断面的に示したように、燃焼用気体供給口１４か
ら供給される燃焼用気体（例えば空気）が流れるガス供
給路１５、前記ガス供給路１５の壁面に設置され、ガス
供給路１５を流れる燃焼用気体に燃料ガスを混合して燃
焼作用を進める燃焼ガス供給口１６、ガス供給路１５を
流れる混合系ガスに補給用燃料ガスを供給する補給燃料
供給口１７とを具備する燃焼器１２において、ガス供給
路１５にこれらのハニカム型の燃焼触媒１３を装着して
燃焼試験を行った。Next, these honeycomb-type combustion catalysts 13
Was installed (installed) in a combustor 12 simulating a gas turbine combustor, and a combustion test was conducted. That is, as shown in the cross-sectional view of the main part configuration example in FIG. 5, the gas supply passage 15 through which the combustion gas (eg, air) supplied from the combustion gas supply port 14 flows, and the wall surface of the gas supply passage 15 A combustion gas supply port 16 that is installed and that promotes combustion by mixing a fuel gas with a combustion gas that flows through the gas supply passage 15, and a supplementary fuel supply port that supplies supplemental fuel gas to a mixed gas that flows through the gas supply passage 15 In the combustor 12 including the fuel cell 17, the honeycomb type combustion catalyst 13 was attached to the gas supply passage 15 and a combustion test was performed.
【００８４】燃焼試験は、０．７ＭＰａの圧力下におい
て、４５０℃まで予備加熱した空気を燃焼用気体供給口
１４から、２．０Ｎ−ｍ3 ／分の流量で流す一方、天然
ガス濃度が２．５％程度となるように燃料ガスを燃料ガ
ス供給口１６からガス供給路１５へ流し、ハニカム型の
燃焼触媒１３を通過させて触媒燃焼を行い、ハニカム型
の燃焼触媒１３の出口でのガス温度をそれぞれ測定する
ことにより行われた。その結果、反応開始直後は、両者
ともにハニカム型の燃焼触媒１３の出口でのガス温度は
約９００℃であったが、５時間経過後の測定では実施例
３の触媒粉末を用いた燃焼触媒１３の場合、反応開始直
後と同様に約９００℃を維持していたのに対し、比較例
２の触媒粉末を用いた燃焼触媒１３の場合には約８５０
℃と低下していた。In the combustion test, air preheated to 450 ° C. was flowed from the combustion gas supply port 14 at a flow rate of 2.0 N-m 3 / min under a pressure of 0.7 MPa, while the natural gas concentration was 2%. The fuel gas is made to flow from the fuel gas supply port 16 to the gas supply passage 15 so as to be about 0.5%, and the catalytic combustion is performed by passing through the honeycomb-type combustion catalyst 13, and the gas at the outlet of the honeycomb-type combustion catalyst 13 is discharged. This was done by measuring the temperature respectively. As a result, immediately after the start of the reaction, the gas temperature at the outlet of the honeycomb type combustion catalyst 13 was about 900 ° C., but the combustion catalyst 13 using the catalyst powder of Example 3 was measured after 5 hours. In the case of, the combustion temperature was maintained at about 900 ° C just after the start of the reaction, whereas in the case of the combustion catalyst 13 using the catalyst powder of Comparative Example 2, about 850 ° C.
It was as low as ℃.
【００８５】次に、燃料ガスを加えた後の天然ガス濃度
が４％となるように設定し、ハニカム型の燃焼触媒１３
の下流でスパークプラグ１８によって着火して燃料ガス
を完全燃焼させた。触媒温度に関しては、パラジウムの
自己温度制御性により触媒温度の異常な上昇が防止さ
れ、実施例３および比較例２の触媒粉末を用いたハニカ
ム型の燃焼触媒１３の出口でのガス温度は燃料ガス濃度
が２．５％の場合と同様にそれぞれ約９００℃および約
８５０℃となった。また、燃焼試験中の窒素酸化物の発
生濃度を測定したところ、実施例３の触媒粉末を用いた
ハニカム型の燃焼触媒１３の出口での窒素酸化物濃度は
約２ｐｐｍに維持されていた。また、ハニカム型の燃焼
触媒１３内への炎の逆火も起こらなかった。一方、比較
例２の触媒粉末を用いたハニカム型の燃焼触媒１３の出
口での窒素酸化物濃度は、約２．５ｐｐｍであった。Next, the natural gas concentration after adding the fuel gas is set to 4%, and the honeycomb type combustion catalyst 13 is set.
The spark plug 18 ignited the fuel gas downstream thereof to completely burn the fuel gas. Regarding the catalyst temperature, the self-temperature controllability of palladium prevents the catalyst temperature from rising abnormally, and the gas temperature at the outlet of the honeycomb-type combustion catalyst 13 using the catalyst powder of Example 3 and Comparative Example 2 is the fuel gas. Similar to the case where the concentration was 2.5%, the temperature was about 900 ° C and about 850 ° C, respectively. Further, when the generated concentration of nitrogen oxides was measured during the combustion test, the concentration of nitrogen oxides at the outlet of the honeycomb-type combustion catalyst 13 using the catalyst powder of Example 3 was maintained at about 2 ppm. Further, flame backfire did not occur in the honeycomb-type combustion catalyst 13. On the other hand, the nitrogen oxide concentration at the outlet of the honeycomb-type combustion catalyst 13 using the catalyst powder of Comparative Example 2 was about 2.5 ppm.
【００８６】さらに、燃料ガスを加えた後の天然ガス濃
度が３％となるように設定し、燃料ガスがハニカム型の
燃焼触媒１３を通過する際に触媒燃焼を起こさせ、か
つ、ハニカム型の燃焼触媒１３の下流に設置されている
補給燃料供給口１７から、ハニカム型の燃焼触媒１３の
下流での天然ガス濃度を１％増加させるだけの補給用燃
料ガスを供給してよく混合した後、スパークプラグ１８
によって着火して完全燃焼させた。触媒温度に関して
は、実施例３および比較例２の触媒粉末を用いたハニカ
ム型の燃焼触媒１３の出口でのガス温度は、燃料ガス濃
度が２．５％の場合と同様にそれぞれ約９００℃および
約８５０℃となった。また、ハニカム型の燃焼触媒１３
の出口での窒素酸化物の濃度を測定したところ、実施例
３の触媒粉末を用いた場合では約３ｐｐｍに維持されて
いた。また、比較例２の触媒粉末を用いた場合では、ハ
ニカム型の燃焼触媒１３の出口での窒素酸化物の濃度は
約３．５ｐｐｍであり、燃焼器用出口側のガス温度（気
相燃焼後のガス温度）は共に１２５０℃であった。Further, the natural gas concentration after adding the fuel gas is set to be 3%, catalytic combustion is caused when the fuel gas passes through the honeycomb type combustion catalyst 13, and the honeycomb type From the supplementary fuel supply port 17 installed downstream of the combustion catalyst 13, a supplementary fuel gas for increasing the natural gas concentration in the downstream of the honeycomb type combustion catalyst 13 by 1% is supplied and well mixed, Spark plug 18
It was ignited and completely burned. Regarding the catalyst temperature, the gas temperature at the outlet of the honeycomb-type combustion catalyst 13 using the catalyst powders of Example 3 and Comparative Example 2 was about 900 ° C. and the same as when the fuel gas concentration was 2.5%. It reached about 850 ° C. Further, the honeycomb type combustion catalyst 13
When the concentration of nitrogen oxides at the outlet of was measured, it was maintained at about 3 ppm when the catalyst powder of Example 3 was used. When the catalyst powder of Comparative Example 2 was used, the concentration of nitrogen oxides at the outlet of the honeycomb-type combustion catalyst 13 was about 3.5 ppm, and the gas temperature on the outlet side for the combustor (after gas phase combustion The gas temperatures were both 1250 ° C.
【００８７】（実施例５）９水塩の硝酸アルミニウム１
５０質量部、６水塩の硝酸ランタン１４質量部、６水塩
の硝酸ニッケル４０質量部および６水塩の硝酸マグネシ
ウム６０質量部との混合水溶液に炭酸カリウムを適量加
えてｐＨを約９に調整し、これらの金属塩を同時に共沈
後、水洗・瀘過・乾燥して混合粉末を得た。(Example 5) Aluminum nitrate of 9-hydrate 1
50 parts by mass, 14 parts by mass of hexahydrate lanthanum nitrate, 40 parts by mass of hexahydrate of nickel nitrate and 60 parts by mass of hexahydrate of magnesium nitrate are added to an aqueous solution of an appropriate amount of potassium carbonate to adjust the pH to about 9. Then, after coprecipitating these metal salts at the same time, they were washed with water, filtered and dried to obtain a mixed powder.
【００８８】一方、平均粒径０．６μｍの８ｍｏｌ％イ
ットリア安定化ジルコニア粒粉末１５質量部に、平均粒
径０．０１μｍのパラジウム粉末５質量部と平均粒径
０．０１μｍのマグネシウムおよびニッケルの助触媒粉
末とを各２．５質量部づつ担持させた平均粒径０．８μ
ｍの二重構造を有するパラジウム触媒粉末および平均粒
径０．６μｍのセリア粒子１０質量部に、平均粒径０．
０１μｍのロジウム粉末５質量部と平均粒径０．０１μ
ｍのマグネシウムおよびニッケルの助触媒粉末とを各
２．５質量部づつ担持させた平均粒径０．８μｍの二重
構造を有するロジウム触媒粉末を用意した。On the other hand, to 15 parts by mass of 8 mol% yttria-stabilized zirconia powder having an average particle size of 0.6 μm, 5 parts by mass of palladium powder having an average particle size of 0.01 μm and magnesium and nickel having an average particle size of 0.01 μm were used. An average particle size of 0.8μ, each supporting 2.5 parts by mass of catalyst powder
m to the palladium catalyst powder having a double structure and 10 parts by mass of ceria particles having an average particle size of 0.6 μm, an average particle size of 0.
5 parts by mass of 01 μm rhodium powder and 0.01 μm average particle size
A rhodium catalyst powder having a double structure having an average particle diameter of 0.8 μm was prepared by supporting 2.5 parts by mass of magnesium and nickel co-catalyst powder, respectively.
【００８９】次いで、前述した混合粉末４５質量部、パ
ラジウム触媒粉末３０質量部およびロジウム触媒粉末２
５質量部とを混合し、水を加えて十分にミリングしてス
ラリーとし、このスラリーを直径３０ｍｍ、長さ１７０
ｍｍ、６．４５ｃｍ2 （１ｉｎｃｈ2 ）あたり１００個
の燃焼ガス流路を区画・形成して構成されるコージェラ
イト製ハニカムに塗布して乾燥後、９００℃で焼成して
ハニカム型の燃焼触媒１３を得た。得られたハニカム型
の燃焼触媒１３の触媒層（耐熱性構造基材に触媒粉末を
保持する層）は、アルミニウム、ランタンの酸化物およ
び複合酸化物から構成されていた。Next, 45 parts by mass of the above-mentioned mixed powder, 30 parts by mass of palladium catalyst powder and 2 parts of rhodium catalyst powder.
5 parts by mass are mixed, water is added and milled sufficiently to form a slurry, and the slurry is 30 mm in diameter and 170 mm in length.
mm, 6.45 cm 2 (1 inch 2 ) is applied to a cordierite honeycomb constituted by partitioning and forming 100 combustion gas passages, dried, and fired at 900 ° C. to form a honeycomb-type combustion catalyst 13 Got The catalyst layer of the resulting honeycomb-type combustion catalyst 13 (the layer that holds the catalyst powder on the heat-resistant structure base material) was composed of aluminum oxide, lanthanum oxide, and composite oxide.
【００９０】図１９は、このハニカム型の燃焼触媒１３
の一部を模式的に拡大した断面図である。１９はハニカ
ム型の耐熱性構造基材、２０はハニカム型の耐熱性構造
基材１９の上に形成された触媒層、２１は耐熱性酸化物
担体２２であるジルコニアの上に触媒活性成分２３とし
てパラジウムおよび助触媒を担持し触媒層２０に埋設・
担持されたパラジウム触媒粉末、２４は耐熱性酸化物担
体２２´であるセリアの上に触媒活性成分２５としてロ
ジウムおよび助触媒を担持し触媒層２０に埋設・担持さ
れたロジウム触媒粉末、２６は触媒層２０に埋設・担持
された助触媒成分である。FIG. 19 shows this honeycomb type combustion catalyst 13.
FIG. 3 is a schematic enlarged cross-sectional view of a part of FIG. Reference numeral 19 is a honeycomb-type heat-resistant structural base material, 20 is a catalyst layer formed on the honeycomb-type heat-resistant structural base material, and 21 is a catalytically active component 23 on zirconia which is a heat-resistant oxide support 22. Embedded in catalyst layer 20 carrying palladium and co-catalyst
Supported palladium catalyst powder, 24 is rhodium catalyst powder which is embedded / supported in the catalyst layer 20 by supporting rhodium and a cocatalyst as the catalytically active component 25 on ceria which is the heat-resistant oxide carrier 22 ', and 26 is a catalyst. It is a co-catalyst component embedded and carried in the layer 20.
【００９１】（比較例３）実施例５で用いたロジウム触
媒粉末２４に代わり、平均粒径０．６μｍのアルミナ粉
末１０質量部に、平均粒径０．０１μｍの白金粉末を５
質量部、平均粒径０．０１μｍのマグネシウムおよびニ
ッケルの助触媒粉末を各２．５質量部づつ担持させた平
均粒径０．８μｍの二重構造を有する白金触媒粉末２５
質量部を用いる以外には、実施例５と同様の条件でハニ
カム型の燃焼触媒１３を得た。Comparative Example 3 Instead of the rhodium catalyst powder 24 used in Example 5, 10 parts by mass of alumina powder having an average particle size of 0.6 μm and 5 parts of platinum powder having an average particle size of 0.01 μm were used.
25 parts by weight, platinum catalyst powder 25 having a double structure having an average particle size of 0.8 μm and supporting 2.5 parts by mass of each of magnesium and nickel promoter powders having an average particle size of 0.01 μm
A honeycomb-type combustion catalyst 13 was obtained under the same conditions as in Example 5 except that the parts by mass were used.
【００９２】（比較例４）実施例５で用いたロジウム触
媒粉末２４に代えて、実施例５で用いたパラジウム触媒
粉末２１を用いて実施例５と同様にハニカム型の燃焼触
媒１３を得た。Comparative Example 4 A honeycomb type combustion catalyst 13 was obtained in the same manner as in Example 5 except that the palladium catalyst powder 21 used in Example 5 was used instead of the rhodium catalyst powder 24 used in Example 5. .
【００９３】（比較例５）実施例５で用いたパラジウム
触媒粉末２１およびロジウム触媒粉末２４に代わり、触
媒活性成分のみから成る平均粒径０．８μｍの触媒粒子
（パラジウム粉末およびロジウム粉末）を触媒層２０に
直接担持させた以外は、実施例５と同様の条件でハニカ
ム型の燃焼触媒１３を得た。(Comparative Example 5) Instead of the palladium catalyst powder 21 and the rhodium catalyst powder 24 used in Example 5, catalyst particles (palladium powder and rhodium powder) having an average particle diameter of 0.8 μm and containing only catalytically active components were used as catalysts. A honeycomb-type combustion catalyst 13 was obtained under the same conditions as in Example 5, except that the layer 20 was directly supported.
【００９４】（実施例６）図５において示すように、上
記実施例５、比較例３、比較例４および比較例５におい
て構成した各ハニカム型の燃焼触媒１３を燃焼器１２に
組み込み、燃焼試験により特性評価を行った。試験方法
は、図５に要部構造の断面図を示したように、燃焼用気
体供給口１４から供給される予め加熱された空気と燃焼
ガス供給口１５から供給される燃料ガスとを均一に混合
してハニカム型の燃焼触媒１３に供給し、燃焼時間と触
媒出口温度との関係を調べることにより実施された。そ
の結果を、図２０に示した。(Embodiment 6) As shown in FIG. 5, each honeycomb-type combustion catalyst 13 constructed in the above-mentioned Embodiment 5, Comparison 3, Comparison 4 and Comparison 5 was incorporated into a combustor 12, and a combustion test was conducted. The characteristics were evaluated by. As shown in the sectional view of the main part structure in FIG. 5, the test method makes uniform the preheated air supplied from the combustion gas supply port 14 and the fuel gas supplied from the combustion gas supply port 15. It was carried out by mixing and supplying it to the honeycomb-type combustion catalyst 13 and examining the relationship between the combustion time and the catalyst outlet temperature. The result is shown in FIG.
【００９５】図２０から明らかなように、実施例５のハ
ニカム型の燃焼触媒１３の場合は、触媒温度が高く燃焼
が安定している結果を示した。しかしながら、比較例
３、比較例４および比較例５のハニカム型の燃焼触媒１
３の場合には、時間の経過とともに触媒温度が低下する
結果を示した。As is apparent from FIG. 20, in the case of the honeycomb-type combustion catalyst 13 of Example 5, the results show that the catalyst temperature is high and combustion is stable. However, the honeycomb-type combustion catalysts 1 of Comparative Examples 3, 4 and 5
In the case of 3, the result shows that the catalyst temperature decreases with the passage of time.
【００９６】比較例３の場合は、初期活性は高いが長期
使用中にパラジウムと白金が反応して、それぞれの役割
を果たさなくなったためである。In the case of Comparative Example 3, the initial activity is high, but palladium and platinum react with each other during long-term use, and they no longer play their respective roles.
【００９７】また、比較例４による結果は、パラジウム
触媒粉末のみを単独に用いた場合には、燃焼が進むにつ
れてＰｄＯがＰｄに還元されることにより、触媒活性の
低下がもたらされたものと考えられる。The results of Comparative Example 4 indicate that when only the palladium catalyst powder was used alone, PdO was reduced to Pd as combustion progressed, resulting in a decrease in catalytic activity. Conceivable.
【００９８】さらに、比較例５による結果は、触媒活性
成分が耐熱性酸化物担体の上に担持されていないため、
触媒活性成分であるパラジウムとロジウムが急激にシン
タリングして特性を失ってしまうことおよび燃焼が進む
につれてＰｄＯがＰｄに還元されることにより、触媒活
性の低下がもたらされたものと考えられる。Further, the results of Comparative Example 5 show that the catalytically active component is not supported on the heat-resistant oxide carrier,
It is considered that the catalytic activity is lowered due to the fact that palladium and rhodium, which are catalytically active components, suddenly sinter and lose their properties, and PdO is reduced to Pd as combustion progresses.
【００９９】なお、本発明は、同等の効果を発揮するな
らば本実施例に限定されるものではない。たとえば、燃
焼触媒１３に関しては、材質あるいは燃焼ガス流路の閉
口部の形状の変更、あるいは触媒粉末を被着・担持させ
る燃焼ガス流路の領域、または燃焼ガス流路の位置もし
くは内壁面の位置などによって触媒粉末の被着・担持量
や助触媒の種類・添加料を調整する等が行われる。さら
に、触媒粉末の使用方法についても、ガスタービン用の
燃焼器に限るものではなく、反応中に触媒バルクの酸素
が奪われて失活してしまう系の改善に適用できることは
明らかである。The present invention is not limited to this embodiment as long as the same effect is exhibited. For example, regarding the combustion catalyst 13, the material or the shape of the closed portion of the combustion gas flow passage is changed, or the region of the combustion gas flow passage on which the catalyst powder is deposited and carried, or the position of the combustion gas flow passage or the position of the inner wall surface. The amount of catalyst powder deposited and supported, the type of co-catalyst, and the amount of additives are adjusted according to the conditions. Further, the method of using the catalyst powder is not limited to the combustor for the gas turbine, and it is obvious that it can be applied to the improvement of the system in which oxygen in the catalyst bulk is deprived during the reaction and deactivated.
【０１００】[0100]
【発明の効果】以上説明したとおり、本願発明によれ
ば、次のような効果が得られる。As described above, according to the present invention, the following effects can be obtained.
【０１０１】（１）燃焼負荷（反応速度）の大きい、例
えばガスタービン用触媒燃焼器での使用に際しても、触
媒活性成分に酸素が供給されることにより、触媒活性成
分は常に触媒活性の高い酸化物状態に維持される。その
ため、高温下においても長期間にわたり高い活性を保持
し、また高い活性を発揮する触媒粉末を提供することが
できる。(1) Even when used in a catalytic combustor for a gas turbine having a large combustion load (reaction speed), oxygen is supplied to the catalytically active component, so that the catalytically active component is always oxidized with high catalytic activity. Maintained in physical condition. Therefore, it is possible to provide a catalyst powder that retains high activity for a long period of time even at high temperatures and exhibits high activity.
【０１０２】（２）また、常に触媒活性の高い酸化物状
態に維持される触媒粉末を耐熱性構造基材に被着・担持
したため、高温下においても長期間にわたり所定の活性
を保持する燃焼触媒を提供することができる。(2) Further, since the catalyst powder, which is always maintained in an oxide state having a high catalytic activity, is adhered to and carried on the heat-resistant structural base material, the combustion catalyst retains a predetermined activity for a long time even at a high temperature. Can be provided.
【０１０３】（３）さらに、常に触媒活性の高い酸化物
状態に維持される触媒粉末で燃焼触媒を構成し、ガスタ
ービン等の燃焼器に燃焼触媒を組み込んだため、高温下
においても長期間にわたり所定の活性を保持し、窒素酸
化物の発生を抑制可能な燃焼器を提供することができ
る。(3) Further, since the combustion catalyst is composed of the catalyst powder which is always maintained in the oxide state having high catalytic activity, and the combustion catalyst is incorporated in the combustor such as the gas turbine, it is possible to maintain a high temperature for a long time. It is possible to provide a combustor which retains a predetermined activity and can suppress the generation of nitrogen oxides.
【図１】触媒粉末１の一部を模式的に拡大して示した
図。FIG. 1 is a diagram schematically showing a part of a catalyst powder 1 in an enlarged manner.
【図２】触媒粉末１の構造を模式的に示した図。FIG. 2 is a diagram schematically showing the structure of catalyst powder 1.
【図３】触媒粉末１の他の構造を模式的に示した図。FIG. 3 is a diagram schematically showing another structure of the catalyst powder 1.
【図４】図３における触媒粉末１の一部断面を示した
図。4 is a diagram showing a partial cross section of catalyst powder 1 in FIG.
【図５】燃焼触媒１３を組み込んだ（装着した）ガスタ
ービン燃焼器を模擬した燃焼器１２の要部構成例を断面
的に示した図。FIG. 5 is a cross-sectional view showing a configuration example of a main part of a combustor 12 simulating a gas turbine combustor in which a combustion catalyst 13 is incorporated (installed).
【図６】触媒活性成分である酸化パラジウム８の表面を
分子ふるい効果を有する物質９で被覆した形態を示した
断面図。FIG. 6 is a cross-sectional view showing a form in which the surface of palladium oxide 8 which is a catalytically active component is coated with a substance 9 having a molecular sieving effect.
【図７】触媒活性成分である酸化パラジウム８の表面を
分子ふるい効果を有する物質９で被覆した他の形態を示
した断面図。FIG. 7 is a cross-sectional view showing another form in which the surface of palladium oxide 8 which is a catalytically active component is coated with a substance 9 having a molecular sieving effect.
【図８】触媒活性成分である酸化パラジウム８の表面を
分子ふるい効果を有する物質９で被覆した他の形態を示
した断面図。FIG. 8 is a cross-sectional view showing another form in which the surface of palladium oxide 8 which is a catalytically active component is coated with a substance 9 having a molecular sieving effect.
【図９】触媒活性成分である酸化パラジウム８の表面を
分子ふるい効果を有する物質９で被覆した他の形態を示
した断面図。FIG. 9 is a cross-sectional view showing another form in which the surface of palladium oxide 8 which is a catalytically active component is coated with a substance 9 having a molecular sieving effect.
【図１０】触媒活性成分である酸化パラジウム８の表面
を分子ふるい効果を有する物質９で被覆した他の形態を
示した断面図。FIG. 10 is a cross-sectional view showing another form in which the surface of palladium oxide 8 which is a catalytically active component is coated with a substance 9 having a molecular sieving effect.
【図１１】触媒活性成分である酸化パラジウム８の表面
を分子ふるい効果を有する物質９で被覆した他の形態を
示した断面図。FIG. 11 is a cross-sectional view showing another embodiment in which the surface of palladium oxide 8 which is a catalytically active component is coated with a substance 9 having a molecular sieving effect.
【図１２】触媒活性成分である酸化パラジウム８の表面
を分子ふるい効果を有する物質９で被覆した他の形態を
示した断面図。FIG. 12 is a cross-sectional view showing another form in which the surface of palladium oxide 8 which is a catalytically active component is coated with a substance 9 having a molecular sieving effect.
【図１３】触媒活性成分である酸化パラジウム８の表面
を分子ふるい効果を有する物質９で被覆した他の形態を
示した断面図。FIG. 13 is a cross-sectional view showing another form in which the surface of palladium oxide 8 which is a catalytically active component is coated with a substance 9 having a molecular sieving effect.
【図１４】触媒活性成分である酸化パラジウム８の表面
を分子ふるい効果を有する物質９で被覆した他の形態を
示した断面図。FIG. 14 is a cross-sectional view showing another form in which the surface of palladium oxide 8 which is a catalytically active component is coated with a substance 9 having a molecular sieving effect.
【図１５】触媒活性成分である酸化パラジウム８の表面
を分子ふるい効果を有する物質９で被覆した他の形態を
示した断面図。FIG. 15 is a cross-sectional view showing another form in which the surface of palladium oxide 8 which is a catalytically active component is coated with a substance 9 having a molecular sieving effect.
【図１６】触媒粉末７の構造を模式的に示した断面図。16 is a sectional view schematically showing the structure of catalyst powder 7. FIG.
【図１７】触媒粉末７の他の構造の一部を模式的に示し
た断面図。FIG. 17 is a sectional view schematically showing a part of another structure of the catalyst powder 7.
【図１８】触媒粉末７の他の構造の一部を模式的に示し
た断面図。FIG. 18 is a cross-sectional view schematically showing a part of another structure of the catalyst powder 7.
【図１９】ハニカム型の燃焼触媒１３の一部を模式的に
拡大した断面図。FIG. 19 is a schematic enlarged cross-sectional view of a part of a honeycomb-type combustion catalyst 13.
【図２０】燃焼時間と触媒出口温度との関係を示した
図。FIG. 20 is a graph showing the relationship between combustion time and catalyst outlet temperature.
【図２１】従来のガスタービン燃焼器の要部構成例を断
面的に示した図。FIG. 21 is a cross-sectional view showing a configuration example of a main part of a conventional gas turbine combustor.
【図２２】酸素分圧と雰囲気温度によって支配されるパ
ラジウムの状態を示した図。FIG. 22 is a diagram showing a state of palladium controlled by oxygen partial pressure and ambient temperature.
１……触媒粉末 ２……酸化パラジウム ３……電子導電材 ４……酸化物担体 ７……触媒粉末 ８……酸化パラジウム ９……分子ふるい効果を有する物質 １０……耐熱性担体 １１……触媒粉末 １２……燃焼器 １３……燃焼触媒 １９……耐熱性構造基材 ２０……触媒層 ２１……パラジウム触媒粉末 ２４……ロジウム触媒粉末 ２６……助触媒成分 1 ... Catalyst powder 2 ... Palladium oxide 3 ... Electronic conductive material 4 ... Oxide carrier 7 ... Catalyst powder 8 ... Palladium oxide 9 ... Substance having molecular sieving effect 10 ... Heat-resistant carrier 11 ... Catalyst powder 12 ... Combustor 13 ... Combustion catalyst 19 ... Heat-resistant structural base material 20 ... Catalyst layer 21 ... Palladium catalyst powder 24 ... Rhodium catalyst powder 26 ... Co-catalyst component
───────────────────────────────────────────────────── フロントページの続き (72)発明者 羽中田 佳男 神奈川県川崎市幸区小向東芝町１番地 株 式会社東芝研究開発センター内 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Yoshio Hanakata 1 Komukai Toshiba-cho, Saiwai-ku, Kawasaki-shi, Kanagawa Toshiba Research & Development Center
Claims (8)
触媒粉末であって、 前記触媒活性成分は少なくとも酸化パラジウムを含有
し、 前記酸化物担体は８００℃以上で少なくとも２．０×１
０-2／Ωｃｍ以上の酸素イオン伝導度を有しており、 前記酸化物担体の少なくとも一部の表面を電子導電材で
被覆したことを特徴とする触媒粉末。1. A catalyst powder in which a catalytically active component is supported on an oxide carrier, wherein the catalytically active component contains at least palladium oxide, and the oxide carrier is at least 2.0 × 1 at 800 ° C. or higher.
A catalyst powder having an oxygen ion conductivity of 0 −2 / Ωcm or more, wherein at least a part of the surface of the oxide carrier is coated with an electron conductive material.
ＺｒＯ2 −ｘＳｃ2Ｏ3 −ｙＡ2 Ｏ3 （０＜ｘ＋ｙ≦
０．１６、ｘ＞０、ｙ＞０、ＡはＹ、Ｓｃおよびランタ
ノイド元素からなる群より選択される少なくとも１つ以
上の元素）で示される物質からなることを特徴とする請
求項１に記載の触媒粉末。2. The oxide carrier has a compositional formula (1-x-y).
ZrO 2 -xSc 2 O 3 -yA 2 O 3 (0 <x + y ≦
0.16, x> 0, y> 0, A is a substance represented by at least one element selected from the group consisting of Y, Sc and lanthanoid elements). Catalyst powder.
ウムを含有した触媒粉末において、 前記触媒活性成分の少なくとも一部の表面を、燃料物質
は透過せず酸素分子は透過する細孔径を有する選択的透
過性材で被覆したことを特徴とする触媒粉末。3. A catalyst powder containing at least palladium oxide as a catalytically active component, wherein at least a part of the surface of the catalytically active component has a pore size such that a fuel substance does not permeate but oxygen molecules permeate therethrough. A catalyst powder coated with a material.
ることを特徴とする請求項３に記載の触媒粉末。4. The catalyst powder according to claim 3, wherein the selectively permeable material is erionite.
分をセリウム酸化物担体に担持した触媒粉末と、少なく
とも酸化パラジウムを含有する触媒活性成分を酸化物担
体に担持した触媒粉末とを共に含有することを特徴とす
る触媒粉末。5. A catalyst powder comprising a cerium oxide carrier carrying a catalytically active component containing at least rhodium, and a catalyst powder carrying an oxide carrier carrying a catalytically active component containing at least palladium oxide. Characteristic catalyst powder.
性成分をセリウム酸化物担体に担持した触媒粉末および
前記少なくとも酸化パラジウムを含有する触媒活性成分
を酸化物担体に担持した触媒粉末の粒径が、０．１μｍ
〜１０μｍであることを特徴とする請求項５に記載の触
媒粉末。6. The particle size of the catalyst powder in which the catalytically active component containing at least rhodium is carried on a cerium oxide carrier and the particle size of the catalyst powder in which the catalytically active component containing at least palladium oxide is carried on an oxide carrier are 0. .1 μm
It is -10 micrometers, The catalyst powder of Claim 5 characterized by the above-mentioned.
と、前記耐熱性構造基材のガス流路内壁面に被着・担持
された触媒粉末とを有してなり、 前記触媒粉末は、 （ａ）触媒活性成分を酸化物担体に担持してなる触媒粉
末であって、前記触媒活性成分は少なくとも酸化パラジ
ウムを含有し、前記酸化物担体は８００℃以上で少なく
とも２．０×１０-2／Ωｃｍ以上の酸素イオン伝導度を
有しており、前記酸化物担体の少なくとも一部の表面を
電子導電材で被覆したことを特徴とする触媒粉末、 （ｂ）触媒活性成分として少なくとも酸化パラジウムを
備えた触媒粉末において、前記触媒活性成分の少なくと
も一部の表面を燃料物質は透過せず酸素分子は透過する
細孔径を有する選択的透過性材で被覆したことを特徴と
する触媒粉末、 （ｃ）少なくともロジウムを含有する触媒活性成分をセ
リウム酸化物担体に担持した触媒粉末と、少なくとも酸
化パラジウムを含有する触媒活性成分を酸化物担体に担
持した触媒粉末とを共に含有することを特徴とする触媒
粉末、 からなる群より選択された、少なくとも１種以上である
ことを特徴とする燃焼触媒。7. A catalyst powder comprising: a heat resistant structural base material having a large number of gas flow paths; and a catalyst powder adhered to and supported on the gas flow path inner wall surface of the heat resistant structural base material. Is (a) a catalyst powder in which a catalytically active component is supported on an oxide carrier, wherein the catalytically active component contains at least palladium oxide, and the oxide carrier is at least 2.0 × 10 8 at 800 ° C. or higher. -2 / Ωcm or more oxygen ion conductivity, characterized in that at least part of the surface of the oxide carrier is coated with an electronic conductive material, (b) at least oxidation as a catalytically active component In a catalyst powder comprising palladium, a catalyst powder characterized in that at least a part of the surface of the catalytically active component is coated with a selectively permeable material having a pore size that allows oxygen molecules to pass therethrough but does not permeate a fuel substance, (C) small A catalyst powder characterized by containing both a catalyst powder in which a catalytically active component containing rhodium is supported on a cerium oxide carrier, and a catalyst powder in which a catalytically active component containing at least palladium oxide is supported on an oxide carrier. A combustion catalyst comprising at least one selected from the group consisting of:
料ガス供給口から供給される燃料ガスおよび空気供給口
から供給される酸素含有ガスを混合するガス混合部と、
前記ガス混合部から流出する混合ガス流路に配置された
燃焼触媒とを具備してなる燃焼器であって、 前記燃焼触媒が多数のガス流路を有する耐熱性構造基材
と、前記耐熱性構造基材のガス流路内壁面に被着・担持
された触媒粉末とを有してなり、 前記触媒粉末は、 （ａ）触媒活性成分を酸化物担体に担持してなる触媒粉
末であって、前記触媒活性成分は少なくとも酸化パラジ
ウムを含有し、前記酸化物担体は８００℃以上で少なく
とも２．０×１０-2／Ωｃｍ以上の酸素イオン伝導度を
有しており、前記酸化物担体の少なくとも一部の表面を
電子導電材で被覆したことを特徴とする触媒粉末、 （ｂ）触媒活性成分として少なくとも酸化パラジウムを
備えた触媒粉末において、前記触媒活性成分の少なくと
も一部の表面を燃料物質は透過せず酸素分子は透過する
細孔径を有する選択的透過性材で被覆したことを特徴と
する触媒粉末、 （ｃ）少なくともロジウムを含有する触媒活性成分をセ
リウム酸化物担体に担持した触媒粉末と、少なくとも酸
化パラジウムを含有する触媒活性成分を酸化物担体に担
持した触媒粉末とを共に含有することを特徴とする触媒
粉末、 からなる群より選択された、少なくとも１種以上である
ことを特徴とする燃焼器。8. A fuel gas supply port, an air supply port, and a gas mixing section for mixing the fuel gas supplied from the fuel gas supply port and the oxygen-containing gas supplied from the air supply port.
A combustor comprising a combustion catalyst arranged in a mixed gas flow channel flowing out from the gas mixing section, wherein the combustion catalyst has a heat resistant structural base material having a large number of gas flow channels, and the heat resistance. And a catalyst powder deposited and carried on the inner wall surface of the gas flow path of the structural base material, wherein the catalyst powder is (a) a catalyst powder having a catalytically active component carried on an oxide carrier. The catalytically active component contains at least palladium oxide, the oxide carrier has an oxygen ion conductivity of at least 2.0 × 10 −2 / Ωcm or more at 800 ° C. or higher, and at least the oxide carrier has (B) a catalyst powder having at least palladium oxide as a catalytically active component, wherein at least a part of the surface of the catalytically active component is a fuel substance. Not transparent The elementary molecule is coated with a selectively permeable material having a permeating pore diameter, (c) a catalyst powder in which a cerium oxide carrier carries a catalytically active component containing at least rhodium, and at least an oxidant. A combustor comprising at least one selected from the group consisting of a catalyst powder containing a catalyst active component containing palladium and a catalyst powder supported on an oxide carrier. .
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP7208124A JPH0952045A (en) | 1995-08-15 | 1995-08-15 | Catalyst powder, combustion catalyst and combustor |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP7208124A JPH0952045A (en) | 1995-08-15 | 1995-08-15 | Catalyst powder, combustion catalyst and combustor |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH0952045A true JPH0952045A (en) | 1997-02-25 |
Family
ID=16551041
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP7208124A Withdrawn JPH0952045A (en) | 1995-08-15 | 1995-08-15 | Catalyst powder, combustion catalyst and combustor |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0952045A (en) |
-
1995
- 1995-08-15 JP JP7208124A patent/JPH0952045A/en not_active Withdrawn
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