JPS6135851A - Catalyst carrier stable at high temperature and its preparation - Google Patents
Catalyst carrier stable at high temperature and its preparationInfo
- Publication number
- JPS6135851A JPS6135851A JP59159980A JP15998084A JPS6135851A JP S6135851 A JPS6135851 A JP S6135851A JP 59159980 A JP59159980 A JP 59159980A JP 15998084 A JP15998084 A JP 15998084A JP S6135851 A JPS6135851 A JP S6135851A
- Authority
- JP
- Japan
- Prior art keywords
- alumina
- composite oxide
- rare earth
- catalyst carrier
- high temperatures
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000003054 catalyst Substances 0.000 title claims abstract description 123
- 238000002360 preparation method Methods 0.000 title description 8
- 239000002131 composite material Substances 0.000 claims abstract description 68
- 229910000873 Beta-alumina solid electrolyte Inorganic materials 0.000 claims abstract description 49
- 239000002243 precursor Substances 0.000 claims abstract description 32
- 229910052746 lanthanum Inorganic materials 0.000 claims abstract description 31
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 claims abstract description 27
- 229910052761 rare earth metal Inorganic materials 0.000 claims abstract description 26
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 18
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000000203 mixture Substances 0.000 claims description 42
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 38
- 238000000034 method Methods 0.000 claims description 26
- 239000013078 crystal Substances 0.000 claims description 20
- 229910052779 Neodymium Inorganic materials 0.000 claims description 17
- QEFYFXOXNSNQGX-UHFFFAOYSA-N neodymium atom Chemical compound [Nd] QEFYFXOXNSNQGX-UHFFFAOYSA-N 0.000 claims description 13
- 229910052777 Praseodymium Inorganic materials 0.000 claims description 12
- PUDIUYLPXJFUGB-UHFFFAOYSA-N praseodymium atom Chemical compound [Pr] PUDIUYLPXJFUGB-UHFFFAOYSA-N 0.000 claims description 11
- 239000011259 mixed solution Substances 0.000 claims description 8
- 229910052751 metal Inorganic materials 0.000 claims description 7
- 239000002184 metal Substances 0.000 claims description 7
- 150000003839 salts Chemical class 0.000 claims description 7
- 229910052684 Cerium Inorganic materials 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 6
- 229910052804 chromium Inorganic materials 0.000 claims description 5
- 239000011651 chromium Substances 0.000 claims description 5
- 229910052712 strontium Inorganic materials 0.000 claims description 5
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 4
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 claims description 4
- 239000003513 alkali Substances 0.000 claims description 3
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 claims 3
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 15
- 238000006243 chemical reaction Methods 0.000 description 38
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 24
- 239000007789 gas Substances 0.000 description 22
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 20
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 15
- 238000010304 firing Methods 0.000 description 15
- 239000002245 particle Substances 0.000 description 13
- 239000000243 solution Substances 0.000 description 13
- 239000000969 carrier Substances 0.000 description 11
- 239000000843 powder Substances 0.000 description 11
- 230000007423 decrease Effects 0.000 description 10
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 8
- 238000010586 diagram Methods 0.000 description 8
- 238000012360 testing method Methods 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- 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 7
- 238000002441 X-ray diffraction Methods 0.000 description 7
- 239000010410 layer Substances 0.000 description 7
- 238000001179 sorption measurement Methods 0.000 description 7
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 6
- 239000004480 active ingredient Substances 0.000 description 6
- 230000003197 catalytic effect Effects 0.000 description 6
- 238000002485 combustion reaction Methods 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 238000005470 impregnation Methods 0.000 description 6
- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum oxide Inorganic materials [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 description 6
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical group [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 6
- 229910052789 astatine Inorganic materials 0.000 description 5
- 238000000975 co-precipitation Methods 0.000 description 5
- 239000012153 distilled water Substances 0.000 description 5
- 238000000465 moulding Methods 0.000 description 5
- 239000007858 starting material Substances 0.000 description 5
- 239000002253 acid Substances 0.000 description 4
- 239000011248 coating agent Substances 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
- 239000006185 dispersion Substances 0.000 description 4
- 239000001257 hydrogen Substances 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 4
- 238000007254 oxidation reaction Methods 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 description 4
- 229910000505 Al2TiO5 Inorganic materials 0.000 description 3
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- 230000010718 Oxidation Activity Effects 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- 229910000831 Steel Inorganic materials 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 3
- 235000011114 ammonium hydroxide Nutrition 0.000 description 3
- 239000010953 base metal Substances 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 238000001354 calcination Methods 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 230000003247 decreasing effect Effects 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 239000000295 fuel oil Substances 0.000 description 3
- 229910002804 graphite Inorganic materials 0.000 description 3
- 239000010439 graphite Substances 0.000 description 3
- 238000007654 immersion Methods 0.000 description 3
- FYDKNKUEBJQCCN-UHFFFAOYSA-N lanthanum(3+);trinitrate Chemical compound [La+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O FYDKNKUEBJQCCN-UHFFFAOYSA-N 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- CFYGEIAZMVFFDE-UHFFFAOYSA-N neodymium(3+);trinitrate Chemical compound [Nd+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O CFYGEIAZMVFFDE-UHFFFAOYSA-N 0.000 description 3
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 3
- 229910000510 noble metal Inorganic materials 0.000 description 3
- KTUFCUMIWABKDW-UHFFFAOYSA-N oxo(oxolanthaniooxy)lanthanum Chemical compound O=[La]O[La]=O KTUFCUMIWABKDW-UHFFFAOYSA-N 0.000 description 3
- YWECOPREQNXXBZ-UHFFFAOYSA-N praseodymium(3+);trinitrate Chemical compound [Pr+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O YWECOPREQNXXBZ-UHFFFAOYSA-N 0.000 description 3
- AABBHSMFGKYLKE-SNAWJCMRSA-N propan-2-yl (e)-but-2-enoate Chemical compound C\C=C\C(=O)OC(C)C AABBHSMFGKYLKE-SNAWJCMRSA-N 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 239000012495 reaction gas Substances 0.000 description 3
- 239000010959 steel Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 230000007704 transition Effects 0.000 description 3
- HGINCPLSRVDWNT-UHFFFAOYSA-N Acrolein Chemical compound C=CC=O HGINCPLSRVDWNT-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 2
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 2
- 229910052581 Si3N4 Inorganic materials 0.000 description 2
- 241000270666 Testudines Species 0.000 description 2
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical compound C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 238000004220 aggregation Methods 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 229910002090 carbon oxide Inorganic materials 0.000 description 2
- 239000000919 ceramic Substances 0.000 description 2
- 229910010293 ceramic material Inorganic materials 0.000 description 2
- ZMIGMASIKSOYAM-UHFFFAOYSA-N cerium Chemical compound [Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce] ZMIGMASIKSOYAM-UHFFFAOYSA-N 0.000 description 2
- 150000001805 chlorine compounds Chemical class 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 238000006356 dehydrogenation reaction Methods 0.000 description 2
- KZHJGOXRZJKJNY-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Si]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O KZHJGOXRZJKJNY-UHFFFAOYSA-N 0.000 description 2
- 238000001493 electron microscopy Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 239000003779 heat-resistant material Substances 0.000 description 2
- 239000008240 homogeneous mixture Substances 0.000 description 2
- 150000004679 hydroxides Chemical class 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 description 2
- NNPPMTNAJDCUHE-UHFFFAOYSA-N isobutane Chemical compound CC(C)C NNPPMTNAJDCUHE-UHFFFAOYSA-N 0.000 description 2
- 238000006317 isomerization reaction Methods 0.000 description 2
- 238000004898 kneading Methods 0.000 description 2
- 238000011068 loading method Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 229910052863 mullite Inorganic materials 0.000 description 2
- 150000002823 nitrates Chemical class 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- GPNDARIEYHPYAY-UHFFFAOYSA-N palladium(ii) nitrate Chemical compound [Pd+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O GPNDARIEYHPYAY-UHFFFAOYSA-N 0.000 description 2
- 229910052697 platinum Chemical group 0.000 description 2
- 238000000634 powder X-ray diffraction Methods 0.000 description 2
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 2
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 2
- 229910010271 silicon carbide Inorganic materials 0.000 description 2
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 2
- 238000005245 sintering Methods 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 239000002344 surface layer Substances 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical class [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 229910002483 Cu Ka Inorganic materials 0.000 description 1
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 1
- 229910017583 La2O Inorganic materials 0.000 description 1
- -1 Lanthanum aluminate Chemical class 0.000 description 1
- 229910020785 La—Ce Inorganic materials 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- 150000001206 Neodymium Chemical class 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000004703 alkoxides Chemical class 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 description 1
- 239000011609 ammonium molybdate Substances 0.000 description 1
- 235000018660 ammonium molybdate Nutrition 0.000 description 1
- 229940010552 ammonium molybdate Drugs 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000007084 catalytic combustion reaction Methods 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 1
- 229910001981 cobalt nitrate Inorganic materials 0.000 description 1
- 238000009841 combustion method Methods 0.000 description 1
- 239000000306 component Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 1
- 238000010908 decantation Methods 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 238000004817 gas chromatography Methods 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
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- FBAFATDZDUQKNH-UHFFFAOYSA-M iron chloride Chemical compound [Cl-].[Fe] FBAFATDZDUQKNH-UHFFFAOYSA-M 0.000 description 1
- 239000001282 iso-butane Substances 0.000 description 1
- YXEUGTSPQFTXTR-UHFFFAOYSA-K lanthanum(3+);trihydroxide Chemical compound [OH-].[OH-].[OH-].[La+3] YXEUGTSPQFTXTR-UHFFFAOYSA-K 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 1
- PLDDOISOJJCEMH-UHFFFAOYSA-N neodymium oxide Inorganic materials [O-2].[O-2].[O-2].[Nd+3].[Nd+3] PLDDOISOJJCEMH-UHFFFAOYSA-N 0.000 description 1
- UTWHRPIUNFLOBE-UHFFFAOYSA-H neodymium(3+);tricarbonate Chemical compound [Nd+3].[Nd+3].[O-]C([O-])=O.[O-]C([O-])=O.[O-]C([O-])=O UTWHRPIUNFLOBE-UHFFFAOYSA-H 0.000 description 1
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 1
- QGLKJKCYBOYXKC-UHFFFAOYSA-N nonaoxidotritungsten Chemical compound O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1 QGLKJKCYBOYXKC-UHFFFAOYSA-N 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 150000003891 oxalate salts Chemical class 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- MMKQUGHLEMYQSG-UHFFFAOYSA-N oxygen(2-);praseodymium(3+) Chemical class [O-2].[O-2].[O-2].[Pr+3].[Pr+3] MMKQUGHLEMYQSG-UHFFFAOYSA-N 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000001103 potassium chloride Substances 0.000 description 1
- 235000011164 potassium chloride Nutrition 0.000 description 1
- 229910003447 praseodymium oxide Inorganic materials 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 150000002910 rare earth metals Chemical group 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 239000010948 rhodium Substances 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- SONJTKJMTWTJCT-UHFFFAOYSA-K rhodium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[Rh+3] SONJTKJMTWTJCT-UHFFFAOYSA-K 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- YBCAZPLXEGKKFM-UHFFFAOYSA-K ruthenium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[Ru+3] YBCAZPLXEGKKFM-UHFFFAOYSA-K 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 229930192474 thiophene Natural products 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910001930 tungsten oxide Inorganic materials 0.000 description 1
- 238000005292 vacuum distillation Methods 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Abstract
Description
【発明の詳細な説明】
〔発明の利用分野〕
本発明は高温で安定な触媒用担体およびその調製方法に
関する。本発明で使用される担体は広い温度範囲で可い
られ、特に８００ｔｌｌ’以上の温度においても安定で
比表面積を維持することができる。DETAILED DESCRIPTION OF THE INVENTION [Field of Application of the Invention] The present invention relates to a catalyst carrier that is stable at high temperatures and a method for preparing the same. The carrier used in the present invention can be used in a wide temperature range, and is stable and can maintain its specific surface area even at temperatures of 800 tll' or higher.
触媒を用いて高温下で反応を行わせるものに、有機溶媒
の酸化除去、悪臭処理、自動車排ガス浄化、高温脱硝な
どがある。また最近、大容量のボイラーやガスタービン
、航空機用のガスタ−ビンなどへ触媒燃焼技術を応用す
る動きが起っている。Examples of reactions that use catalysts to carry out reactions at high temperatures include oxidative removal of organic solvents, odor treatment, automobile exhaust gas purification, and high-temperature denitrification. Recently, there has been a movement to apply catalytic combustion technology to large-capacity boilers, gas turbines, gas turbines for aircraft, etc.
これらの方法では、反応温度がおよそ６００Ｃ以上であ
り、条件によっては１４００〜１５００ｔ：’にまで達
する。従ってこの様な高温域においても触媒活性の低下
が少なく、且つ熱的安定性の高い触媒が要求される。In these methods, the reaction temperature is about 600C or higher, and depending on the conditions, it can reach up to 1400 to 1500t:'. Therefore, there is a need for a catalyst that exhibits little decrease in catalytic activity even in such a high temperature range and has high thermal stability.
従来高温用触媒として使用されてきた触媒は、アルミナ
、シリカ、シリカ−アルミナ等を担体としてこれに貴金
属、或は卑金属成分を担持したもの、或はジルコニア、
チタン酸アルミニウム、コージェライト、窒化硅素など
のセラミック材料を担体としてその表面に活性アルミナ
などをコーテインクし、貴金属成分を担持させたものな
どが使用されてきた。Catalysts conventionally used as high-temperature catalysts include alumina, silica, silica-alumina, etc. as carriers on which precious metals or base metal components are supported, zirconia,
Ceramic materials such as aluminum titanate, cordierite, and silicon nitride are used as carriers, and activated alumina is coated on the surface of the carrier to support noble metal components.
しかし、これらの触媒は通常８００Ｃ以上になると、担
体の結晶構造の変化（例えばアルミナの場合ｒｍからα
型への相転位）や結晶成長に伴う比表面積の減少が起こ
り、これに伴って活性成分の凝集による活性点の減少が
生じ、触媒活性が失われてしまう欠点があった。上記し
たセラミックス材料を用いた触媒は、セラミックス自体
の耐熱性は高いが、コーテイング材の耐熱性が低いため
に触媒成分が有効に活用されないという欠点がある。However, when these catalysts are heated to 800C or higher, the crystal structure of the support changes (for example, in the case of alumina, from rm to α
However, the specific surface area decreases due to crystal growth (phase transition to a type) and crystal growth, resulting in a decrease in the number of active sites due to aggregation of active ingredients, resulting in a loss of catalytic activity. Catalysts using the above-mentioned ceramic materials have a drawback that, although the ceramic itself has high heat resistance, the coating material has low heat resistance, so that the catalyst components are not effectively utilized.
従来、アルミナと希土類からなる担体を用いた触媒とし
ては、下記に記載されているものが知られている。Conventionally, the catalysts described below are known as catalysts using a carrier made of alumina and rare earth elements.
ω 米国特許３，９９３，５７２ 希土類と白金族か
らなる触媒成分
偉） 米国特許３，９６６．３９１ 高温安定触媒を
用いた燃焼方法
（３）米国特許３，９５６，１８８ 高温安定触媒の
組成と調製方法
（４）米国特許３，８９９，４４４ 排ガス処理用触
媒（５） 米国特許３，８６７．３１２ 排ガス処
理用触媒（６）米国特許３，７１４，０７１ 高温で
高強度をもつ低密度アルミナ粒子
（７）米国特許４，０５６，４８９ 高温安定触媒組
成物及びその調製法
（８）米国特許４，０２１，１８５ 高温で安定な触
媒の組成と調製法
（９）米国特許４，２２０，５５９ 高温安定触媒α
Ｏ米国特許４，０６１，５９４ 高温で安定なアルミ
ナベースの担体
また従来の高温担体として米国特許３，９７８，００４
゜＆９５６，１８６，３，９３１，０５０．＆８９＆１
８３，３，８９４，１４０゜＆８８亀４４５，３，８８
０，７７５．λ８６７．３０９．八８１９，５３６゜４
．３７４，８１９．４３６９，１３０，４，３１８，８
９４，４，２３亀１８０１４２０６．０８７，４，１７
７．１６３，４．１５＆５８０，４，１７０，５７３゜
４．０５４，６４２ などに記載されているものがあ
る。ω U.S. Patent 3,993,572 Catalyst component consisting of rare earth and platinum group) U.S. Patent 3,966,391 Combustion method using high-temperature stable catalyst (3) U.S. Patent 3,956,188 Composition and preparation of high-temperature stable catalyst Method (4) U.S. Patent 3,899,444 Catalyst for exhaust gas treatment (5) U.S. Patent 3,867.312 Catalyst for exhaust gas treatment (6) U.S. Patent 3,714,071 Low-density alumina particles with high strength at high temperatures ( 7) U.S. Patent No. 4,056,489 High-temperature stable catalyst composition and method for preparing the same (8) U.S. Patent No. 4,021,185 Composition and preparation method of catalyst stable at high temperature (9) U.S. Patent No. 4,220,559 High-temperature stability Catalyst α
O U.S. Pat. No. 4,061,594 High temperature stable alumina-based supports and conventional high temperature supports U.S. Pat. No. 3,978,004
゜&956,186,3,931,050. &89&1
83,3,894,140°&88 turtle 445,3,88
0,775. λ867.309. 8819,536゜4
．． 374,819.4369,130,4,318,8
94,4,23 turtle 18014206.087,4,17
7.163, 4.15&580, 4,170,573°4.054,642, etc.
これらの中で入９６６．３９１，４，１７０，５７３゜
４．０６１，５９４ は本発明と関連していると思わ
れる。Among these, entry 966.391,4,170,573°4.061,594 is considered to be relevant to the present invention.
米国特許３，９６６．３９１ではＬａ （ＮＯａ ）ａ
、 Ｃｒｙｓ 。In U.S. Patent 3,966.391, La (NOa)a
, Crys.
Ｓｒ （Ｎｏ３）ａ を含む溶液にアルミナ粉末を加
えて含浸法でこれらの成分を担持し、１１０ｍ；で、乾
燥後、１２００Ｃで２時間焼成している。この触媒は炭
化油の燃焼に用いる。Alumina powder was added to a solution containing Sr (No3)a to support these components by an impregnation method, dried at 110 m, and then fired at 1200 C for 2 hours. This catalyst is used for combustion of carbonized oil.
米国特許４，１７０，５７３ではＬａ（Ｎｏ３）ａ
をアルミナ粉末に含浸し、１６０℃、１６時間乾燥後、
１２５０Ｃで１時間焼成した後、Ｃｅ （ＮＯｓ）ａ
溶液を含浸後１６０Ｇで１６時間乾燥する。その後ｐｔ
ｃｔ４溶液を含浸し４２７〜６．４９Ｃで焼成してＰｔ
Ｌａ−Ｃｅ ｋＬｚｏｓ触媒を得ている。In U.S. Patent 4,170,573, La(No3)a
was impregnated with alumina powder and dried at 160℃ for 16 hours.
After baking at 1250C for 1 hour, Ce(NOs)a
After impregnation with the solution, dry at 160G for 16 hours. Then pt.
Pt was impregnated with ct4 solution and fired at 427-6.49C.
A La-Ce kLzos catalyst is obtained.
米国特許４，０６１，５９４では６００Ｃでオートクレ
ーブ処理したアルミナを５００Ｃで焼成し、Ｌａ（Ｎｏ
３）３ を含浸した後、Ｌａ＊Ｏｓ Ａｔｇ ｏｓ を
つくり、これに白金族を含浸して１０００〜１２００Ｃ
で焼成している。In US Pat. No. 4,061,594, alumina autoclaved at 600C is fired at 500C, and La (No.
3) After impregnating 3, make La*Os Atgos, impregnate it with platinum group and heat it to 1000-1200C.
It is fired in
ジャーナル オブ ソリッド ステート ケミストリー
（Ｊｏｕｒｎａｌ ｏｆ ３ｏ１ｉｄ １３ｔａｔｅＣ
ｈｅｍｉｓｔｒｙ） １９．１９３−２０４ （１９７
６）ではランタンβ−アルミナの結晶についての研究な
行つているが、該結晶の触媒用担体に関する記述はない
。Journal of Solid State Chemistry (Journal of 3o1id 13tateC
hemistry) 19.193-204 (197
6), studies are conducted on crystals of lanthanum β-alumina, but there is no description regarding catalyst supports for these crystals.
本発明の目的は、耐熱性の高い触媒用担体及び調製方法
を提供することにある。An object of the present invention is to provide a highly heat-resistant catalyst carrier and a preparation method.
ｒ−或はη−などのアルミナは高比表面積を有し、担体
やコーティング剤として現在広く用いられているが、８
０（Ｉ’以上特に９００Ｃ以上においてはα−アルミナ
への相転移及び結晶粒子の成長によシ焼結体となり比表
面積が著しく低下し、これに伴って触媒活性成分である
貴金属、卑金属などの粒子が凝集し、触媒活性が低下す
る。本発明者らは、この様なアルミナの熱的不安定性の
改良及び触媒活性成分の凝集を防ぐため鋭意研究を行っ
てきた。その結果ランタンβ−アルミナ（Ｌａ＊Ｏａ
・１１〜１４ＡｔｓＯｓ）、 ７’ラセ；ｔシ’）ムｌ
ｊ −アルミナ（ＰｒｉＯｓ ・１１〜１４ＡｔｓＯｍ
）、ネオジウムβ−アルミナ（Ｎｄ＊Ｏｓ・１１〜１４
ＡｔｓＯｓ） （以後該担体をＬ−β−アルミナと記
述する）担体に触媒活性成分である貴金属、卑金属など
を担持した触媒が非常に有効であることを見出した。Alumina such as r- or η- has a high specific surface area and is currently widely used as a carrier or coating agent.
0(I' or higher, especially at 900C or higher, the phase transition to α-alumina and the growth of crystal grains result in a sintered body with a marked decrease in specific surface area, and along with this, the catalytic active components such as noble metals and base metals) The particles aggregate and the catalyst activity decreases.The present inventors have conducted extensive research to improve the thermal instability of alumina and prevent the aggregation of catalytically active components.As a result, lanthanum β-alumina (La*Oa
・11~14AtsOs), 7'race;tshi')mul
j - Alumina (PriOs ・11~14AtsOm
), neodymium β-alumina (Nd*Os・11~14
AtsOs) (hereinafter the carrier will be referred to as L-β-alumina) It has been found that a catalyst in which a noble metal, base metal, etc. as a catalytically active component is supported on a carrier is very effective.
本発明はアルミニウムとランタンの複合酸化物からなる
耐熱性担体である。The present invention is a heat-resistant carrier made of a composite oxide of aluminum and lanthanum.
アルミニウムとランタンの複合酸化物はランタンβ−ア
ルミナとその前駆体の混合物からなシ、該前駆体は１０
００Ｃで２時間加熱した時ランタンβ−アルミナに変り
得るものである。また上記複合酸化物は本質的にランタ
ンβ−アルミナの前駆体からなる場合でも良い。The composite oxide of aluminum and lanthanum is made of a mixture of lanthanum β-alumina and its precursor, and the precursor is 10
It can be converted to lanthanum β-alumina when heated at 00C for 2 hours. Further, the above composite oxide may essentially consist of a precursor of lanthanum β-alumina.
本発明からなる担体は、ランタン、ネオジウム。The carrier of the present invention is lanthanum or neodymium.
プラセオジウムの少なくとも一つとアルミニウムを含む
複合酸化物であシ該複合酸化物は比表面積ｘｏｍ’／ｇ
以上を有し、かつクロム、ストロンチウム、セリウムが
１重量膚以下で、Ｌ−β−アルミナ及び１０００ｔ：’
で１０時間以内で加熱した時にＬ−β−アルミナに変り
得る前駆体あるいは本質的にＬ−β−アルミナの前駆体
の混合物からなる。A composite oxide containing at least one praseodymium and aluminum, and the composite oxide has a specific surface area xom'/g
or more, and chromium, strontium, and cerium are less than 1% by weight, and L-β-alumina and 1000t:'
It consists of a precursor or a mixture of precursors that are essentially L-β-alumina, which can be converted to L-β-alumina when heated at a temperature of up to 10 hours.
以下本発明の詳細を述べる。本発明においてＬ−β−ア
ルミナは前述したように、ＬａｚＯｓ・１１〜１４．Ａ
ｔｚＯｓ 、 Ｐ ｒｘｏｓ ・１１〜１４ ＡｔｇＯ
ａ ｒ Ｎ（ｈＯｓ・１１〜１４Ａｔｇｏｓの化学式で
示される複合酸化物である。これらの複合酸化物はｋｌ
とＬａ、 Ｎｄ。The details of the present invention will be described below. In the present invention, L-β-alumina is LazOs 11-14. A
tzOs, P rxos ・11-14 AtgO
a r N (hOs・11~14Atgos) These composite oxides are kl
and La, Nd.
Ｐｒの水酸化物、酸化物の混合物ｔ−５ｏｏｃ以上の温
度で熱処理することによって得られる。この担体に触媒
活性成分を担持した触媒は１０００Ｃ以上の温度で使用
しても、触媒活性成分は熱により凝集しに＜＜、高活性
を維持できる。これはアルミニウムとランタン又はネオ
ジウム、又はプラセオジウムの複合酸化物と触媒活性成
分との間における相互作用が強く働らいているためであ
る。A mixture of hydroxide and oxide of Pr is obtained by heat-treating the mixture at a temperature of t-5ooc or higher. Even when a catalyst in which a catalytically active component is supported on a carrier is used at a temperature of 1000 C or higher, the catalytically active component does not aggregate due to heat and can maintain high activity. This is because there is a strong interaction between aluminum and the composite oxide of lanthanum, neodymium, or praseodymium and the catalytic active component.
複合酸化物はＬ−β−アルミナとその前駆体の混合物又
は該前駆体からなる。該複合酸化物は優れ九耐熱性を有
し、高比表面積をもつ。Ｘ線回折及び電子顕微鏡観察か
ら、この複合酸化物はアルミナの相転移が抑制され結晶
成長を起こしにくいものであることがわかった。また窒
素吸着量から求めた本発明の担体の比表面積は、高温に
してもその減少が非常に少ない。上記担体に活性成分と
してパラジウムあるいは白金を担持した場合、これら活
性成分の分散状態（結晶粒子径）を電子顕微鏡及びＣＯ
の化学吸着量から調べた結果１２００Ｃで焼成した場合
でも、粒子径は小さく高分散されていることがわかった
。The composite oxide consists of a mixture of L-β-alumina and its precursor, or the precursor thereof. The composite oxide has excellent heat resistance and a high specific surface area. From X-ray diffraction and electron microscopy observations, it was found that this composite oxide suppresses the phase transition of alumina and is resistant to crystal growth. Further, the specific surface area of the carrier of the present invention determined from the amount of nitrogen adsorption shows very little decrease even at high temperatures. When palladium or platinum is supported as an active ingredient on the above carrier, the dispersion state (crystal particle size) of these active ingredients can be observed using an electron microscope and CO2.
As a result of investigating the chemical adsorption amount, it was found that even when fired at 1200C, the particle size was small and highly dispersed.
ＡｔとＬａ又は、Ｎｄ、又はｐｒの複合酸化物をセラミ
ックスの成形体にコーティング、あるいは両者の粉末を
混合して担体とすることもできる。A composite oxide of At and La, Nd, or pr may be coated on a ceramic molded body, or powders of both may be mixed to form a carrier.
例えば耐熱性のあるα−アルミナ、チタニア、ジルコニ
ア、マグネシア、コージェライト、ムライ゛ト、チタン
酸アルミニウムなどの酸化物と上記複合酸化物を混合し
て使用することができる。またシリコンナイトライド、
シリコンカーバイトなどの非酸化物系の耐熱性材料と混
合して使用できる。For example, the above composite oxide can be used in combination with a heat-resistant oxide such as α-alumina, titania, zirconia, magnesia, cordierite, mullite, or aluminum titanate. Also silicon nitride,
Can be used in combination with non-oxide heat-resistant materials such as silicon carbide.
また上記耐熱性の材料からなる成形体に本発明からなる
複合酸化物をコーティングして使用できる。Further, a molded article made of the above-mentioned heat-resistant material can be coated with the composite oxide of the present invention.
この場合、ＡＬとＬａ又はＮ ｄ ｓ又はｐｒからなる
複合酸化物は全担体の少なくとも５０係以上であること
が望ましい。In this case, it is desirable that the composite oxide consisting of AL and La or N d s or pr accounts for at least 50% of the total support.
本発明者らは次の様な事実を明らかにした（以後は説明
を簡単にするため、ＬａＫ限って記述する）。The present inventors have revealed the following facts (hereinafter, only LaK will be described for simplicity of explanation).
α）Ｌａ、Ｐｒ、Ｎｄは高温加熱するとアルミーナ担体
の安定化に対し効果をもたらすが、同じ希土類でもＣｅ
は安定化に対する効果がない。さらにＣｒ、Ｚｒ、Ｓｒ
、Ｃａ、Ｎａなどをアルミナに添加すると、１２００ｔ
：’以上で焼成した場合に結晶成長を促進する。この現
象が起こると担体の比表面積は著しく減少してしまう。α) La, Pr, and Nd have an effect on stabilizing the alumina support when heated at high temperatures, but even with the same rare earths, Ce
has no effect on stabilization. Furthermore, Cr, Zr, Sr
, Ca, Na, etc. are added to alumina, 1200t
: 'Promotes crystal growth when fired at a temperature higher than '. When this phenomenon occurs, the specific surface area of the carrier decreases significantly.
・（２） この複合酸化物は少なくと
も１０ｍ’／ｇの比表面積をもち、無定形あるいはこれ
に近い結晶状態にあるＬ−β−アルミナまたは１４００
ｔ：’で２時間加熱した時にＬ−β−アルミナに変り得
るＬ−β−アルミナの前駆体の状態で存在する。複合酸
化物におけるアルミナの化学形態はα−，ｒ −。・(2) This composite oxide has a specific surface area of at least 10 m'/g, and is made of L-β-alumina or 1400 alumina, which is in an amorphous or nearly crystalline state.
It exists in the state of a precursor of L-β-alumina that can be converted to L-β-alumina when heated at t:' for 2 hours. The chemical forms of alumina in composite oxides are α-, r-.
θ−１η−＠ ｋ Ｉ ｘ ｌρ−１δ−以外であり、
比表面積は望ましくは２０〜１００ｍ’／ｇを有する。other than θ−1η−@ k I x lρ−1δ−,
The specific surface area desirably ranges from 20 to 100 m'/g.
（３）複合酸化物におけるＬ−β−アルミナの含有率は
１５〜９５重量−である。出発原料（焼成前）における
ｋＬｍＯｓ に対するＬａｚＯｓのモル比（Ｌ ａｘ
Ｏｓ ／ＡＬｉ Ｏｘ ）は、１／９９でＬ−β−ア
ルミナの含有率は１５重量％である。(3) The content of L-β-alumina in the composite oxide is 15 to 95% by weight. The molar ratio of LazOs to kLmOs in the starting material (before calcination) (L ax
Os /ALi Ox ) is 1/99, and the L-β-alumina content is 15% by weight.
ＬａｚＯａ ／Ａｔ２０ｇ ＝ ２ ｏ／ ８０ （モ
Ａ比）、（０時、Ｌ−β−Ａｔｚ０３の含有率は９５重
量％である。LazOa/At20g = 2 o/80 (MoA ratio), (at 0 o'clock, the content of L-β-Atz03 is 95% by weight.
同様にＬａ２Ｏ３／ＡｔｇＯｓ ＝ １０ ／ ９０で
は、Ｌ−β−アルミナは９０重量％、ＬａｚＯａ ／Ａ
ｔ＊Ｏａ ＝５／９５では６４重量％、ＬａｚＯｓｌＡ
１２０ｇ ＝２／９８では２７重量％である。Similarly, when La2O3/AtgOs = 10/90, L-β-alumina is 90% by weight and LazOa/A
t*Oa = 5/95, 64% by weight, LazOslA
If 120g = 2/98, it is 27% by weight.
複合酸化物における主成分はＬ−β−アルミナとその前
駆体又は前駆体であり、少なくとも５０重量％以上を含
む。The main components in the composite oxide are L-β-alumina and its precursor or precursor, and contain at least 50% by weight.
Ｌ二β−アルミナは粉末Ｘ線回折において、Ｃｕ−Ｋａ
線を用いた場合、ブラッグ角２θが１８．９°■、２０
．１°■、３２３°■、３４．０゜■、３６．２’■、
３９．４°■、４０．９°［相］。In powder X-ray diffraction, L2β-alumina shows Cu-Ka
When using a line, the Bragg angle 2θ is 18.9°■, 20
．． 1°■, 323°■, 34.0°■, 36.2'■,
39.4°■, 40.9° [phase].
４２８°■、 ４５．１′Ｄ＠、 ｓ ｓ、ｏ６＠ 、
６７．４゜■（丸で囲んだ番号は相対強度を示す）の
位置にピークをもつ。１２００Ｃで焼成した複合酸化物
の場合、第３ｂ図、第３Ｃ図に示すように１＆９’。428°■, 45.1'D@, s s, o6@,
There is a peak at a position of 67.4°■ (the circled number indicates the relative intensity). In the case of a composite oxide fired at 1200C, 1 &9' as shown in Figures 3b and 3C.
２０．１’ 、 ３２．．３°、 ３４０’ 、 ３
６．２°。20.1', 32. ．． 3°, 340', 3
6.2°.
４２．８°、４’５．１°、５８．０°、６７．４°に
ピークをもっている。このことは該複合酸化物が、Ｌ−
β−アルミナを含有していることを示している。It has peaks at 42.8°, 4'5.1°, 58.0°, and 67.4°. This means that the composite oxide is L-
This indicates that it contains β-alumina.
第３ｂ図、第３Ｃ図に示すＸ線回折図は、第３ａ図、第
３ｄ図に比べてピークが弱く、シかもブロードであるこ
とから、この複合酸化物はＬ−β−アルミナとα−、γ
−、θ−９η−１に一９δ−１Ｘ−、ρ−以外の形態を
有するＬ−β−アルｉすの前駆体を含み、この前駆体は
無定形であることがわかる。第３ｂ図、第３Ｃ図におい
て、黒丸で示したピークは３２３°、３６．２°、４２
．８°。The X-ray diffraction diagrams shown in Figures 3b and 3C have weaker peaks and broader peaks than those in Figures 3a and 3d, indicating that this composite oxide is composed of L-β-alumina and α- , γ
-, θ-9η-1, -9δ-1X-, ρ- It can be seen that this precursor contains an L-β-alis precursor having a form other than -, θ-9η-1, and is amorphous. In Figures 3b and 3C, the peaks indicated by black circles are 323°, 36.2°, and 42°.
．． 8°.
４５．１°、６７．４°である。They are 45.1° and 67.4°.
（４）α−、γ−、θ−９δ−９η−１ｋＩ ｘ１ρ
−の様な形態をもつアルミナ担体にランタン。(4) α-, γ-, θ-9δ-9η-1kI x1ρ
Lanthanum on an alumina carrier with a form similar to -.
プラセオジウム、ネオジウム塩の溶液を含浸し、１００
０〜１２００Ｃで２時間焼成した場合、Ｌ−β−アルミ
ナの量は充分生成しない。Impregnated with a solution of praseodymium and neodymium salts, 100
When calcined at 0 to 1200C for 2 hours, a sufficient amount of L-β-alumina is not produced.
本発明によると高温で安定な担体は複合酸化物からなっ
ている。本発明の担体はノ・二カム構造をとり得る。本
発明の担体は触媒活性成分を担持する担体と担体を支持
するための支持体とから成ることもできる。この場合支
持体として金属板、金網、海綿状金属から選ぶことがで
きる。また活性成分が担持されている複合酸化物を担体
の表面にコーティングして用いることもできる。According to the present invention, the carrier that is stable at high temperatures is made of a composite oxide. The carrier of the present invention may have a two-cam structure. The carrier of the present invention can also consist of a carrier supporting a catalytically active component and a support for supporting the carrier. In this case, the support can be selected from metal plates, wire mesh and spongy metal. Further, a composite oxide carrying an active ingredient may be coated on the surface of a carrier.
本発明の担体を調製する望ましい方法は、アルばニウム
塩と、ランタン、プラセオジウムあるいはネオジウムか
ら選ばれた希土類元素の１つ以上との塩の混合溶液にア
ルカリを添加して得られる共沈物を濾過して分離し、成
形した後、１ｏｏｏｔ：’以上の温度で焼成する。この
焼成でＡｔとＬａ。A preferred method for preparing the support of the present invention is to prepare a coprecipitate obtained by adding an alkali to a mixed solution of an albium salt and a salt of one or more rare earth elements selected from lanthanum, praseodymium or neodymium. After filtration, separation, and molding, it is fired at a temperature of 100:' or higher. This firing produces At and La.
Ｎｄ、ｐｒの複合酸化物が生成する。即ち、少なくとも
１０ｍ”／ｇ以上の比表面積をもつ複合酸化物となシ、
該複合酸化物は、α−，ｒ−、θ−１η−１ｋ ｌＸ
Ｓρ−１δ−以外のアルミナ構造をもつものであり、こ
れは、１００ＯＣ以上で２時間以内で加熱した時にＬ−
β−アルミナに変りうる前駆体、あるいはＬ−β−アル
ミナとこの前駆体の混合物である。A composite oxide of Nd and pr is generated. That is, the composite oxide must have a specific surface area of at least 10 m"/g or more,
The complex oxide has α-, r-, θ-1η-1k lX
It has an alumina structure other than Sρ-1δ-, and when heated at 100OC or higher for less than 2 hours, L-
It is a precursor that can be converted into β-alumina, or a mixture of L-β-alumina and this precursor.
更に本発明からなる触媒用担体は、アルミニウムとラン
タン、ネオジウム又はプラセオジウムの酸化物あるいは
塩の微粉末を乾式、湿式法で均一に混合し８００Ｃ以上
望ましくは１０００Ｃ以上で焼成し、Ｌ−β−アルミナ
の前駆体又はＬ−β−アルミナを調製することができる
。Furthermore, the catalyst carrier of the present invention can be obtained by uniformly mixing fine powders of aluminum and lanthanum, neodymium, or praseodymium oxides or salts by a dry or wet method, and calcining the mixture at a temperature of 800C or more, preferably 1000C or more, to obtain L-β-alumina. A precursor of L-β-alumina can be prepared.
焼成温度が８００Ｃ以下であると、Ｌ−β−アルミナの
前駆体の生成が認められない。When the firing temperature is 800C or less, no L-β-alumina precursor is observed to be produced.
本発明の担体は次の様な方法で調製される。The carrier of the present invention is prepared by the following method.
α）複合酸化物の出発原料即ちＡｔと、Ｌａ。α) Starting materials for the composite oxide, namely At and La.
Ｎｄ、ｐｒの少なくとも１つとの塩の均−温合物を例え
ば８００Ｃ以下の温度で焼成する。次いで９００Ｃ以上
の温度で焼成し、１００ＯＣ以上で１０時間以内で加熱
するとＬ−β−アルミナ及びその前駆体の混合物をつく
る。A homogeneous mixture of salt with at least one of Nd and pr is fired at a temperature of, for example, 800C or lower. The mixture is then calcined at a temperature of 900C or higher and heated at a temperature of 100OC or higher within 10 hours to form a mixture of L-β-alumina and its precursor.
Ｃ） 複合酸化物の出発原料を予め８００Ｃ以下の温度
で焼成する。次いで、複合酸化物の前駆体忙活性成分を
含む溶浸を含浸する。あるいは担体上に該複合酸化物と
活性成分が含まれているものをコーティングする。これ
を９００〜１５００ｔｌｌ’で一定時間焼成して、Ｌ−
β−アルミナの前駆体及びこれとＬ−β−アルミナとの
混合物を形成させる。C) The starting material of the composite oxide is fired in advance at a temperature of 800C or less. Next, a precursor of the composite oxide is impregnated with an infiltrate containing an active component. Alternatively, a carrier containing the complex oxide and the active ingredient is coated. This is fired at 900 to 1500 tll' for a certain period of time, and L-
A precursor of β-alumina and a mixture thereof with L-β-alumina are formed.
ＡｔとＬａの複合酸化物を形成させるための焼成温度は
９００Ｃ以上望ましくは１０００ｔ：’以上が良い。も
し焼成温度が９００Ｃ以下であると、望ましい複合酸化
物が形成されない。The firing temperature for forming a composite oxide of At and La is preferably 900 C or higher, preferably 1000 t:' or higher. If the firing temperature is below 900C, the desired composite oxide will not be formed.
本発明の複合酸化物の結晶は無定形に近く、またはＬ−
β−アルミナに近い構造をもつ。この構造については、
その焼成温度、焼成時間で決まる。The crystals of the composite oxide of the present invention are nearly amorphous, or L-
It has a structure similar to β-alumina. For this structure,
It is determined by the firing temperature and firing time.
温度が高くなると、複合酸化物中のＬ−β−アルミナの
割合は多くなる。As the temperature increases, the proportion of L-β-alumina in the composite oxide increases.
複合酸化物の前駆体が１５００Ｃで１時間以上加熱され
ると、複合酸化物の結晶成長が著しく起とシ、比表面積
が減少してしまう。９００Ｃで加熱した場合でも望まし
い複合酸化物を得るＫは１００時間あるいはそれ以上加
熱すれば良い。焼成条件は実用見地から選ぶと良い。望
ましい焼成条件は１０００Ｃで少なくとも１時間から１
４００Ｃで０．５ｈあるいはそれ以下が良い。焼成する
ときの圧力はそれほど重要な要素ではない。最も望まし
い焼成条件は１１００ｔ：’で１０時間から１３００Ｃ
’で０．５〜２Ｑ間で、圧力が１００〜／ｃｒＩ以下で
ある。If the composite oxide precursor is heated at 1500C for more than 1 hour, crystal growth of the composite oxide will occur significantly, resulting in a decrease in the specific surface area. Even when heated at 900C, a desired composite oxide can be obtained by heating K for 100 hours or more. Firing conditions should be selected from a practical standpoint. Desirable firing conditions are 1000C for at least 1 hour to 1 hour.
0.5 hours or less at 400C is good. Pressure during firing is not a very important factor. The most desirable firing conditions are 1100t:' and 1300C for 10 hours.
' is between 0.5 and 2Q, and the pressure is 100~/crI or less.
複合酸化物からなる粉末は種々の形状、例えば球状９円
柱状６円筒状、リング状、ハニカム状などにして用いる
。また複合酸化物を含む粉体を種種の形状をもつ金属板
、金網、海綿状金属、あるいは無機質の耐熱性基材、例
えばムライト、コージェライト、α−アルミナ、ジルコ
ニア、アルミニウムチタネート、シリコンカーバイト、
シリコンカイトライドなどにコーティングして使用する
ことができる。この場合、複合酸化物のコーテイング量
は全担体に対して少なくとも５重量％、望ましくは５〜
３０重量係重量−。アルミニウムとランタンの複合酸化
物は通常の沈殿法、沈着法。The powder made of the composite oxide is used in various shapes, such as spherical, 9 cylindrical, 6 cylindrical, ring, and honeycomb shapes. Powders containing composite oxides can also be used in metal plates with various shapes, wire mesh, spongy metal, or inorganic heat-resistant substrates such as mullite, cordierite, α-alumina, zirconia, aluminum titanate, silicon carbide,
It can be used by coating silicon kitride, etc. In this case, the coating amount of the composite oxide is at least 5% by weight, preferably 5 to 5% by weight based on the total carrier.
30 weight ratio -. Composite oxides of aluminum and lanthanum can be produced using conventional precipitation and deposition methods.
混練法、含浸法などで調製できる。これらの方法の中で
、共沈法は均密な複合酸化物が生成できることから最も
適している。It can be prepared by kneading method, impregnation method, etc. Among these methods, the coprecipitation method is the most suitable because it can produce a homogeneous composite oxide.
更に共沈法はＬ−β−アルミナ及びその前駆体の生成に
対し最も有効な方法である。Furthermore, the coprecipitation method is the most effective method for producing L-β-alumina and its precursors.
複合酸化物は共沈法あるいはアルミナ又はアルミナゾル
と、酸化ランタンあるいは水酸化ランクンの均一な混合
物を焼成することによシ得られ、またアルミナにランタ
ンの水溶液を含浸し加熱することＫよっても得られる。Composite oxides can be obtained by coprecipitation or by firing a homogeneous mixture of alumina or alumina sol and lanthanum oxide or lanthanum hydroxide, or by impregnating alumina with an aqueous solution of lanthanum and heating it. .
アルミニウムとう゛ンタンの混合溶液にアルカリを添加
し均一な共沈殿物を調製することが望ましく、この方法
によれば、比較的低い温度でも目的とするアルミニウム
とランタンの複合酸化物が得られる。It is desirable to add an alkali to a mixed solution of aluminum and lanthanum to prepare a uniform coprecipitate. According to this method, the desired composite oxide of aluminum and lanthanum can be obtained even at a relatively low temperature.
本発明において、アルミニウムの出発原料としては硝酸
塩、硫酸塩゛、塩化物、アルコキシドなどの有機塩、水
酸化物、酸化物などが用いられる。In the present invention, organic salts such as nitrates, sulfates, chlorides, alkoxides, hydroxides, oxides, etc. are used as starting materials for aluminum.
ランタン、ネオジウム、プラセオジウムの出発原料とし
ては、硝酸塩、塩化物、しゆう酸塩などの水溶性塩、水
酸化物、酸化物などが用いられる。As starting materials for lanthanum, neodymium, and praseodymium, water-soluble salts such as nitrates, chlorides, and oxalates, hydroxides, and oxides are used.
またランタツ、ネオジウム、プラセオジウムを含みセリ
ウムを含まない混合粘土でも良い。Also, a mixed clay containing lantern, neodymium, and praseodymium but not containing cerium may be used.
触媒活性成分は、金属あるいは金属酸化物で担体に担持
される。この場合活性成分は通常の方法例えば含浸法、
混線法などによって担体に担持される。The catalytically active component is supported on a metal or metal oxide carrier. In this case, the active ingredient can be added in the usual manner, e.g. by impregnation,
It is supported on a carrier by a crosstalk method or the like.
本発明の担体を有する触媒は、水素、−酸化炭素、炭化
水素、アルコールなどの燃料の燃焼反応。The catalyst having a carrier of the present invention is suitable for combustion reactions of fuels such as hydrogen, carbon oxides, hydrocarbons, and alcohols.
悪臭除去、脱硝反応、自動車排ガス処理などに用いられ
る。Used for odor removal, denitrification reactions, automobile exhaust gas treatment, etc.
Ｌａ２Ｏ３Ａ−ｔ２０ｓ担体の調製
Ｉ、ａ２０３−Ａｚ４０ｓ 系担体の調製法を第１図
に示す。Ｌａ （ＮＯｓ）ｓとＡｔ（ＮＯｘ）ｓの混合
溶液にアンモニア水を滴下し、沈殿物を水洗し乾燥する
。Preparation I of La2O3A-t20s carrier The method for preparing the a203-Az40s carrier is shown in FIG. Aqueous ammonia is added dropwise to a mixed solution of La (NOs)s and At(NOx)s, and the precipitate is washed with water and dried.
５００Ｃで予備焼成した後、グラファイトを１重量％添
加し直径３鰭、長さ３Ｉ＋ｌｌ１１の円柱状に成型する
。次いで７００ｔ：’で２時間予備焼成する。比較のた
めＡｔ＊Ｏｓ のみ、あるいはＬａｇ’ｓ のみの場合
も同様にして調製した。Ｌａ＊Ｏｓ を５モル％、ｋ
Ｌｘｏｓを９５モル係含む場合をＬ ａ２０３ ・Ａ
Ｌ＊Ｏｓ（５／９５ ）で以後記述する。７００Ｃ焼成
におけるＬａ２０ｓＡｔ＊Ｏａ （５／ ９５ ）担体
では、比表面積が１３０ｍ’／ｇ、細孔容積（含水率か
ら測定）は０．４ ｒｄ／ ｇであった。After preliminarily firing at 500C, 1% by weight of graphite is added and molded into a cylindrical shape with a diameter of 3 fins and a length of 3I+ll11. Then, it is pre-fired at 700 t:' for 2 hours. For comparison, samples containing only At*Os or only Lag's were prepared in the same manner. La*Os 5 mol%, k
The case containing 95 mol of Lxos is L a203 ・A
It will be described hereafter as L*Os (5/95). The La20sAt*Oa (5/95) support fired at 700C had a specific surface area of 130 m'/g and a pore volume (measured from water content) of 0.4 rd/g.
ｐｄ触媒の調製
硝酸パラジウム溶液を上記担体に含浸法で担持した。ｐ
ｄ含有量は１重量％である。Ｐｄを担持した後、５００
Ｃで３０分間予備焼成した後、１２００ｔ：’で２時間
焼成した。Preparation of PD Catalyst A palladium nitrate solution was supported on the above carrier by an impregnation method. p
The d content is 1% by weight. After loading Pd, 500
After preliminarily firing at C for 30 minutes, it was fired at 1200 t:' for 2 hours.
実験装置
触媒の活性については内径１８＋＋ｏｓの石英管を用い
て通常の流通方式でメタンの酸化活性を調べたメタン０
．１係を含む空気を触媒層に導入し、等温条件下でメタ
ン反応率を測定した。また触媒の耐久性を調べるため、
メタン３憾を含む空気を、５００Ｃに予熱し、触媒層に
導入して約１１５００に保持した（断熱温度は１２００
Ｃ以上）。触媒量は８−で、空間速度はａ ｏ ｏ ｏ
ｏ ｈ−１とした。メタンの濃度はガスクロマトグラ
フによシ行った。担体の結晶構造はＸ線回折及び透過盤
電子顕微鏡で調べた。担体に担持されたｐｄの分散状態
は、Ｃｏの化学吸着量で調べ、比表面積はＮ２の吸着よ
シ求めた。Experimental Equipment Regarding the activity of the catalyst, the methane oxidation activity was investigated using a normal flow method using a quartz tube with an inner diameter of 18++ os.
．． Air containing Part 1 was introduced into the catalyst layer, and the methane reaction rate was measured under isothermal conditions. In addition, to examine the durability of the catalyst,
Air containing methane was preheated to 500C, introduced into the catalyst layer, and maintained at approximately 11500C (the adiabatic temperature was 1200C).
C or higher). The amount of catalyst is 8-, and the space velocity is a o o o
o h-1. The concentration of methane was determined by gas chromatography. The crystal structure of the carrier was investigated by X-ray diffraction and transmission disc electron microscopy. The dispersion state of PD supported on the carrier was determined by the chemical adsorption amount of Co, and the specific surface area was determined by the amount of N2 adsorption.
Ｌ’ＪＯｓ Ａｔ２Ｑ３系担体の比表面積と結晶構造Ｌ
ａを０．２，５，１０，２０，５０，７５゜１００−６
ルｌ含むＬａｚＯａ ・ＡｔｚＯｓ 系担体を調製し
、予め７００Ｃで焼成した。これを１０００ｃ（曲線１
１）、１２００ｔｌ：’（曲線１２ ）、１４００ｔ：
’（曲線１３）で２時間焼成した。第２図に比表面積の
測定結果を示す。比表面積は］［、ａが２〜５モル係含
むとき忙最大値を示すことがわかる。１２００Ｃで焼成
した場合、Ｌａ５ｈｓ ・Ａｔ２０ｇ（２／ ９８ ）
で３３ｍ”／ ｇｓ （５／ ９５ ）で３７ぜ７ｇ
であった。これに対してｋｔｚｏｓ 単独では５．６ｍ
’／ｇであった。Ｌａ含有量が１０〜１００モル係に増
えると、比表面積は次第に減少する。この結果から、Ｌ
ａｚＯａをＡｔ２０３に少量添加すると熱的安定性が著
しく増加する。Specific surface area and crystal structure L of L'JOs At2Q3-based carrier
a to 0.2, 5, 10, 20, 50, 75°100-6
A LazOa .AtzOs-based carrier containing 100% chloride was prepared and preliminarily calcined at 700C. This is 1000c (curve 1
1), 1200tl:' (curve 12), 1400t:
' (Curve 13) for 2 hours. Figure 2 shows the measurement results of specific surface area. It can be seen that the specific surface area shows a maximum value when a contains 2 to 5 moles. When fired at 1200C, La5hs・At20g (2/98)
33m”/gs (5/95) and 37ze 7g
Met. On the other hand, ktzos alone is 5.6m.
'/g. When the La content increases from 10 to 100 moles, the specific surface area gradually decreases. From this result, L
Adding a small amount of azOa to At203 significantly increases thermal stability.
ＬａｚＯａ Ａ１２ｏｓ 系担体の結晶構造をＸ線回折
で調べた。第３ａ図〜第３ｄ図は、１２００ｔ：’で２
時間加熱した担体のＸ線回折図を示したものである。Ａ
１２ｏｓ単独ではα−ＡｔｚＯａに帰属するピークが認
められ、ＬａｚＯａ ・Ａｔ＊０３ （５／ ９５ ）
ではランタン−β−ｋＬｚｏｓ （Ｌａｓｈｓ ・１１
Ａｔｚ０３）に帰属する４つのピークが認められた。Ｌ
ａｚＯａ−ｋＬｚｏｓ（５０／ ５０ ）ではＬ ａ
Ａ １０ ｓ が生成した。The crystal structure of the LazOa A12os-based carrier was investigated by X-ray diffraction. Figures 3a to 3d show 1200t:' and 2
This figure shows an X-ray diffraction pattern of a carrier heated for a certain period of time. A
When 12os was used alone, a peak belonging to α-AtzOa was observed, and LazOa・At*03 (5/95)
So, lanthanum-β-kLzos (Lashs ・11
Four peaks belonging to Atz03) were observed. L
azOa-kLzos (50/50) is La
A 10 s was generated.
ランタン−β−ＡＬ＊ Ｏｎに帰属するピークは弱く、
ブロードでめり結晶成長は僅かであることがわかる。従
って、得られた複合酸化物はランタン−β−Ａｔ２０ｍ
の前駆体あるいはランタン−β−Ａｌｔｏｓ に近い
形態のものであることが考えられる。The peak attributed to lanthanum-β-AL*On is weak;
It can be seen that the crystal growth is slight in the broad spectrum. Therefore, the obtained composite oxide is lanthanum-β-At20m
It is thought that it is a precursor of lanthanum-β-Altos or a form similar to lanthanum-β-Altos.
１０００Ｃで２時間加熱した場合、この複合酸化物は明
確なピークは認められず、無定形を示しているが、これ
はランタン−β−アルミナの前駆体と考えられる。この
前駆体は１４００Ｃで２時間焼成するとランタン−β−
Ａｔ２０３ に転換する。ペロブスカイト構造をもつラ
ンタンアルミネート（Ｌ ａ Ａｔｏ ｓ ）は強いピ
ークを示している。Ｌａ２Ｏ３／Ａｔｇｏｓ （１０／
９０ ）の場合、ランタン−β−ＡｌｔｏｓとＩ＋ａ
ＡＺＯｓの混合物が生成している。When heated at 1000 C for 2 hours, this composite oxide showed no clear peak and was amorphous, but this is considered to be a precursor of lanthanum-β-alumina. When this precursor is calcined at 1400C for 2 hours, lanthanum-β-
Convert to At203. Lanthanum aluminate (L a Ato s ) with a perovskite structure shows a strong peak. La2O3/Atgos (10/
90), lanthanum-β-Altos and I+a
A mixture of AZOs is produced.
第４図に８００〜１４００Ｃで焼成したＬａ２Ｏ３・Ａ
ｔｚＯｓ系酸化物の生成条件についてＸ線回折で調べた
結果を示した。ランタン−β−アルミナ及びその類似物
は１４００Ｃ焼成の場合Ｌａが２〜３０モル係で生成し
ていることがわかる。ＬａＡｔＯｓは低い温度で容易に
生成する。Figure 4 shows La2O3・A fired at 800-1400C.
The results of an investigation using X-ray diffraction regarding the conditions for the formation of tzOs-based oxides are shown. It can be seen that when lanthanum-β-alumina and its analogs are fired at 1400C, La is produced at a concentration of 2 to 30 moles. LaAtOs is easily produced at low temperatures.
Ａ４ｘＯｓ単独では１２００Ｕで焼成するとα−ｋｌｔ
ｏｓ の″非常に強いピークが認められるが、Ｌａ２Ｏ
５・ｋＬｘＯｓ （２／ ９８ ） ％ではθ−１ｋ−
ｋｔ＊Ｏｓ Ｋ帰属する非常に弱いピークが認められる
。これらの結果から、Ａｌｔｏｓ に少量のＬａ５ｈｓ
を添加することによシ、α−ｋＬｚＯｓの成長を抑制し
ていることがわかる。When A4xOs alone is fired at 1200U, α-klt
A very strong peak of os is observed, but La2O
At 5・kLxOs (2/98)%, θ-1k-
kt*Os A very weak peak attributed to K is observed. From these results, it is clear that a small amount of La5hs is added to Altos.
It can be seen that the addition of .alpha.-kLzOs suppresses the growth of .alpha.-kLzOs.
Ｒ，℃、Ｒｏｐｐ等らはランタン−β−Ａｔ２０ｔはＬ
ａｚＯａ ・Ａ４０ｇ （８，３／ ９、７ ）の混合
物を１４００Ｃ以上に加熱すると１ａＡｔＯａ を経
て生成することを報告している（ Ｊ、 Ａｍ、 Ｃｅ
ｒ、 ３ｏｃ、 Ｉ ６３１４１６（１９８０））。R, °C, Ropp et al.
It has been reported that when a mixture of 40 g (8,3/9,7) of azOa and A is heated above 1400 C, 1aAtOa is formed (J, Am, Ce
r, 3oc, I 631416 (1980)).
本発明において１００ＯＣの様に低温で２時間焼成した
場合でも、ランタン−β−に１２０Ｂ の生成が認めら
れるのは、その調製法の相違即ち本発明では共沈法であ
り％ Ｂｒ０ｐｐらは酸化物同士の混合物から調製した
ためと思われる。共沈法は両酸化物の混合が充分性われ
ている。Ｌａ２’ｓ・ＡＬｚＯｓ担体の粒子径を電子顕
微鏡で調べた。代表的なものとして、１２００Ｃで焼成
した囚ｋｔｚＯｓ 単独、■Ｌａ２Ｏ５” ＡｔｚＯｓ
（５／ ９５ ）を調べた結果、α−ｋｔｚ０３ は５
００〜１５００人に達するのに対し、Ｌａ２Ｏ５’ Ａ
ｔｚＯｓ（５／ ９５ ）では１００〜．３’００人で
あった。Ｌａ２Ｏ５ｊ Ａ１２０Ｂ（５０／ ５０ ）
即ちＬ ａ Ａ １０ ｇでは約１０００人であった。In the present invention, even when calcined at a low temperature such as 100OC for 2 hours, the formation of 120B is observed in lanthanum-β- due to the difference in the preparation method, that is, the coprecipitation method used in the present invention, and %Br0pp and other oxides. This is probably because it was prepared from a mixture of the two. The coprecipitation method ensures sufficient mixing of both oxides. The particle size of the La2's/ALzOs carrier was examined using an electron microscope. Typical examples are ktzOs alone fired at 1200C, ■La2O5” AtzOs
As a result of examining (5/95), α-ktz03 is 5
00-1500 people, whereas La2O5' A
tzOs (5/95) is 100~. There were 3'00 people. La2O5j A120B (50/50)
That is, 10 g of L a A was about 1000 people.
５ｃｈａｐｅｒらはＬａ２Ｏ５はｒ −ＡｔｚＯｓ
のシンタリングを防止するが、これは担体の表面層にＬ
ａＡｔＯｓが生成すると報告している（ Ｈ，８ｃｈａ
ｐｅｒ、ｅｔ、 ａｌ。5chaper et al. La2O5 is r-AtzOs
This prevents sintering of L on the surface layer of the carrier.
It has been reported that aAtOs is generated (H,8cha
per, et, al.
Ａｐｐｌｉｅｄ Ｃａｔａｌｙｓｉｓ、 ７．２１１
（１９８３））。しかし本発明ではシンタリングの防止
はランタン−β−Ａｔ２０ｇ の生成によるもので、Ｌ
ａ Ａ １０ ａの生成のためではない。この相違は
、調製法に起因するものと思われる。即ち、５ｃｈａｐ
ｅｒらは、成型したｒ −Ａ１２０Ｂ にＬａ（Ｎｏ
３）ｓ 溶液を含浸する方法を採用しているからであ
る。含浸法では、担体の表面層でＬ ａ ｚ Ｏｓ 濃
度が高くなるので、１、ａＡｔＯｓが容易に生成するた
めである。Applied Catalysis, 7.211
(1983)). However, in the present invention, the prevention of sintering is due to the production of 20 g of lanthanum-β-At.
Not for the production of a A 10 a. This difference seems to be due to the preparation method. That is, 5 chap
er et al. added La (No.
3) This is because a method of impregnating with s solution is adopted. This is because in the impregnation method, the concentration of L azOs becomes high in the surface layer of the carrier, so that 1.aAtOs is easily generated.
Ｐ ｄ −Ｌａ２Ｏ５・ＡＪ４０３触媒の活性Ｐｄ触媒
のＣＨ４酸化活性を調べるため、ＣＨａ倉０．１％含む
空気を用いて２５０〜７００Ｃの温度で酸化率を測定し
た。これらの測定は、等温条件で行った。第５図は種々
のＬａ／ｈｔの組成比をもつ担体にＰｄを担持した触媒
の活性を調べた結果を示したものである。Ｐ ｄ Ｌ
ａｚＯｓ・Ａｌｔｏｓ（５／９５ ）の触媒が最高の活
性を示すＣ曲線２４）。Ｐｄ Ａ４０ｓ触媒（曲線２
１）は活性が最も低い。Ｐ ｄ Ｌａ２’ｓ ・Ａｌ
ｔｏｓ （２／ ９８ ）は曲線２５で示したように、
（１０／９０）（曲線２３）の場合とほぼ同様であるこ
とがわかる。Activity of Pd-La2O5.AJ403 Catalyst In order to investigate the CH4 oxidation activity of the Pd catalyst, the oxidation rate was measured at a temperature of 250 to 700C using air containing 0.1% CHa. These measurements were performed under isothermal conditions. FIG. 5 shows the results of investigating the activity of catalysts in which Pd was supported on carriers having various La/ht composition ratios. PdL
C curve 24) in which the azOs/Altos (5/95) catalyst shows the highest activity. Pd A40s catalyst (curve 2
1) has the lowest activity. P d La2's ・Al
tos (2/98) is as shown by curve 25,
It can be seen that this is almost the same as in the case of (10/90) (curve 23).
Ｐｄ ＬａｚＯｓ・Ａｔ２Ｏｓ （５ｏ／ ５０ ）
ｉｄｇ２図テ示したように比表面積は低いにも拘らず
曲線２２で示すように活性は比較的高いことがわかる。Pd LazOs・At2Os (5o/50)
As shown in Figure 2, although the specific surface area is low, the activity is relatively high as shown by curve 22.
担体上に担持されたｐｄの分散状態を調べるためＣＯ吸
着によりＰｄ表面積を求めた。２５０Ｃでｌ（ｅ処理し
た後、２０（ｌでＣＯ吸着量を測定した。第６図はＬａ
含有量の異なる担体に担持したｐｄの表面積を求めた結
果を示したものである。In order to investigate the dispersion state of PD supported on the carrier, the Pd surface area was determined by CO adsorption. After treatment at 250C and 20C, the amount of CO adsorption was measured at 20L.
This figure shows the results of determining the surface area of PD supported on carriers with different contents.
Ｐｄ表面積はＬａが５〜１０モルチ迄は増加し、５０モ
ル嗟では０に迄減少する。電子顕微鏡でｐｄ触媒の粒子
径を観察した。その結果％ ｋ４０ｓ単独の担体に担持
されたＰｄの粒子径は１５００〜２０００人であり、Ｌ
ａ２ｈｓ ・Ａｔ１Ｏｓ（５／ ９５ ）に担持された
ｐｄ粒子径は３００〜８００人でめった。担体の結晶粒
子が成長することにより、Ｐｄ粒子も凝集する。いわゆ
る地震効果が起っている。The Pd surface area increases when La increases from 5 to 10 mol, and decreases to 0 at 50 mol. The particle size of the PD catalyst was observed using an electron microscope. As a result, the particle size of Pd supported on the carrier of %k40s alone was 1500 to 2000, and L
The pd particle size supported on a2hs/At1Os (5/95) was found to be between 300 and 800 people. As the crystal particles of the carrier grow, the Pd particles also aggregate. A so-called seismic effect is occurring.
ランタン−β−Ａｔ２０ｇ に担持されたＰｄ触媒の耐
久性
ｐｄ燃焼触媒の耐久性を調べるため、メタン３ｖｏ１％
を含む空気で触媒層に５００Ｃで導入し、メタンを１１
５０Ｃで燃焼させた。Ｐｄ−Ｌａ１ｅｓ・ＡｔｚＯｓ（
５／ ９５ ）及びｐｄ−Ａｔ２０３触媒の２種類につ
いて、１００時間の連続テストを行った。Durability of Pd catalyst supported on 20 g of lanthanum-β-At In order to investigate the durability of the Pd combustion catalyst, 3 vol.
was introduced into the catalyst layer at 500C, and methane was heated to 11
It was burned at 50C. Pd-La1es・AtzOs(
5/95) and pd-At203 catalysts were subjected to a continuous test for 100 hours.
この場合、Ｐｄ−ＡｔｘＯａ触媒は、１０００ｔ：’で
焼成したものを使用した。これは１２００Ｇで焼成する
と、ガスの温度を５００Ｃにしても着火しないためであ
る。耐久試験を第７図に示した。Ｐｄ−ＬａｚＯｓ ・
Ａｌｔｏｓ（５／ ９５ ）では曲線３２で示したよう
に９９．５１以上のメタン反応率を示すが、Ｐ ｄ−Ａ
ｔａＯｓでは曲線３１で示したように９９．５係から９
８４以下に低下している。In this case, the Pd-AtxOa catalyst used was one calcined at 1000 t:'. This is because when fired at 1200G, no ignition occurs even if the gas temperature is 500C. The durability test is shown in Figure 7. Pd-LazOs・
Altos (5/95) shows a methane reaction rate of 99.51 or higher as shown by curve 32, but P d-A
In taOs, as shown by curve 31, from 99.5 to 9
It has decreased to below 84.
耐久試験後の触媒を種々の方法で調べた。ＢＥＴ比表面
積、Ｐｄ表面積の測定結果を第１表に示した。After the durability test, the catalyst was examined using various methods. The measurement results of BET specific surface area and Pd surface area are shown in Table 1.
第 １ 表−
ｐ ｄ −ｋＬ＊ｏｓ触媒では、これらの表面積は著し
く減少するのに対し、Ｐｄ−Ｌａ１ｅｓ ＃ ＡｔｚＯ
ｓ （５／９５）触媒では比較的小さい。耐久試験後の
両触媒の活性について、０．１％のメタンで用いて３０
０〜７００Ｃの等温条件下で反応率を調べた結果、Ｐ
ｄ ＬａｚＯｓ ６ ｋｌｚｏｓ （５／ ９５ ）
では速度定数が１５〜２０係低下していたのに対し、Ｐ
ｄ−Ａ４０ｓでは５０〜８０饅低下していた。また電子
顕微鏡観察から、耐久試験後のｐ ｄ −ｋｔｚｃｈ触
媒では、担体上のＰｄ粒子径が３０００〜５０００人に
まで達していた。Table 1 - For p d -kL*os catalysts, these surface areas are significantly reduced, whereas for Pd-La1es #AtzO
s (5/95) catalyst is relatively small. Regarding the activity of both catalysts after durability test, 30
As a result of investigating the reaction rate under isothermal conditions of 0 to 700C, P
d LazOs 6 klzos (5/95)
In contrast, the rate constant decreased by a factor of 15 to 20 in P
In d-A40s, it decreased by 50-80. Further, observation using an electron microscope revealed that in the p d -ktzch catalyst after the durability test, the Pd particle size on the carrier reached 3000 to 5000 particles.
以後本発明の例を具体的に記述するが、本発明はこれら
の実施例”に何等限定されるものではない。Examples of the present invention will be specifically described below, but the present invention is not limited to these examples in any way.
実施例１
硝酸アルミニウム３７５．１ｇと硝酸ランタン２２８ｇ
を蒸留水１ｔに溶解する（Ｌａ／Ａｔ＝５／９５）。こ
の溶液を攪拌しながら３Ｎアンモニア水を滴下し、ｐＨ
７，５まで中和する。得られたアルミニウムとランタン
の共沈物を充分水洗し、乾燥した後、粉砕して１０００
Ｃで５時間焼成した。得られた粉末をプレス成型機で直
径３ ｗｘ 、長さ３■の円柱状にし担体とした。Example 1 375.1g of aluminum nitrate and 228g of lanthanum nitrate
is dissolved in 1 t of distilled water (La/At=5/95). While stirring this solution, 3N ammonia water was added dropwise to adjust the pH.
Neutralize to 7.5. The obtained coprecipitate of aluminum and lanthanum was thoroughly washed with water, dried, and then ground to a
It was fired at C for 5 hours. The obtained powder was formed into a cylindrical shape with a diameter of 3 wx and a length of 3 cm using a press molding machine to form a carrier.
一方前述の方法において、硝酸ランタンを添加しない以
外は同様に調製し、アルミナのみから成る比較例担体を
得た。On the other hand, a comparative example carrier consisting only of alumina was obtained by preparing in the same manner as described above except that lanthanum nitrate was not added.
上記した２種類の担体に硝酸パラジウム溶液をＰｄとし
て１重量部含浸した後、１２０Ｃで５時間乾燥し、その
後１２００Ｃで３時間焼成し、実施例、比較例１の触媒
を得た。この触媒のメタン酸化活性について調べた。下
記組成のガスを空間速度２５０００ ｈ’″ｌで流し、
１０００時間の連続試験を行った。The two types of carriers described above were impregnated with 1 part by weight of Pd in a palladium nitrate solution, dried at 120C for 5 hours, and then calcined at 1200C for 3 hours to obtain catalysts of Examples and Comparative Example 1. The methane oxidation activity of this catalyst was investigated. A gas having the following composition is flowed at a space velocity of 25000 h'''l,
A continuous test was conducted for 1000 hours.
ガス組成： メタン ３嗟
空気 残
本実験では反応ガスを５００Ｃに予熱した６メタンの反
応率が９０係以上に達すると、触媒層の温度は約１２０
０Ｃに達するので、触媒の高温での耐久性を評価できる
。第２表にその結果を示す。Gas composition: Methane 3 Mo. In this experiment, the reaction gas was preheated to 500 C. When the reaction rate of 6 methane reached 90 coefficient or higher, the temperature of the catalyst layer was about 120 C.
Since the temperature reaches 0C, the durability of the catalyst at high temperatures can be evaluated. Table 2 shows the results.
第２表
実施例１で得られた触媒は高温耐久性に優れていること
がわかる。実施例１及び比較例１の触媒の１００時間試
験後の比表面積を測定したところ、それぞれ２３．５ｒ
ｒ？／ｇ 、 ５．６ｒｒ？／ｇであった。またｐｄの
表面積は実施例１では３７ｔｒ？／ｇ−、Ｐｄ。It can be seen that the catalyst obtained in Example 1 in Table 2 has excellent high-temperature durability. When the specific surface areas of the catalysts of Example 1 and Comparative Example 1 were measured after a 100-hour test, they were 23.5 r.
r? /g, 5.6rr? /g. Also, the surface area of PD is 37tr in Example 1? /g-, Pd.
１３．６ｍ”／ｇ−Ｐｄであった。この様に比較例触媒
に比べて、実施例触媒は比表面積及びＰｄの分散状態が
良好であシ耐熱性触媒として優れていることがわかる。13.6 m''/g-Pd. Thus, compared to the comparative example catalyst, it can be seen that the example catalyst has a better specific surface area and a better dispersion state of Pd, and is therefore superior as a heat-resistant catalyst.
実施例２
硝酸アルミニウム３７５０ｇと硝酸ランタン４８０ｇを
蒸留水１０／、に溶解する。以下実施例１と同様にして
得られた５ｏｏｃ焼成粉体ＩＫｇに蒸留水２．５ｔを加
え振動ミルで粉体の平均粒子径が約１μｍになるまで粉
砕し、スラリー状の浸漬液を調製する。この浸漬液に市
販のコージライト基材から成るハニカム構造体（直径９
０ｍ、長さ７５ｍ）を浸漬した後、浸漬液から取シ出し
、圧縮空気を吹付けて過剰に付着した液を除き、１２０
Ｃ’で乾燥後５００Ｃで１時間熱処理した。この操作を
繰返し、最終的に１０００ｔ：’で２時間焼成した。か
くして得られたハニカム構造体は、１８．７重量憾の複
合酸化物の層を有していた。このハニカム担体の比表面
積は１１５ｙｌ？／ｇであった。次いで得られたハニカ
ム構造体を塩化白金酸と塩化ロジウムを混合した水溶液
に浸漬し、１２０Ｃで乾燥後、６００Ｃ水素気流中で還
元した。触媒は、５重量係のｉ金と０．４重量係のロジ
ウムを有していた。Example 2 3750g of aluminum nitrate and 480g of lanthanum nitrate are dissolved in 10% of distilled water. Below, 2.5 tons of distilled water is added to 500 kg of calcined powder obtained in the same manner as in Example 1, and pulverized with a vibration mill until the average particle size of the powder becomes approximately 1 μm to prepare a slurry-like immersion liquid. . A honeycomb structure made of a commercially available cordierite base material (diameter 9
0 m, length 75 m), remove it from the immersion liquid, blow compressed air to remove excess liquid, and remove it from the immersion liquid.
After drying at C', heat treatment was performed at 500C for 1 hour. This operation was repeated and finally fired at 1000 t:' for 2 hours. The honeycomb structure thus obtained had a composite oxide layer weighing 18.7 kg. Is the specific surface area of this honeycomb carrier 115yl? /g. Next, the obtained honeycomb structure was immersed in an aqueous solution containing a mixture of chloroplatinic acid and rhodium chloride, dried at 120C, and then reduced in a hydrogen stream at 600C. The catalyst had 5 parts by weight of gold and 0.4 parts by weight of rhodium.
この触媒を、自動車の排ガス酸化用として用いた。普通
自動車用エンジン（１８００ｃｃクラス）に触媒コンバ
ーターとして使用し、１万一走行試験を行なった結果、
１０モードでＣＯ１，Ｏｇ ／Ｉｎ。This catalyst was used for oxidizing automobile exhaust gas. As a result of using it as a catalytic converter in a regular car engine (1800cc class) and conducting a 10-day driving test,
CO1, Og/In in 10 mode.
ＨＣｏ、１９ｇ／−であった。この結果から本発明にな
る耐熱性担体を用いた触媒では内燃機関の排気ガス処理
にも使用でき、高温反応に安定した性能を維持すること
がわかる。HCo, 19g/-. These results show that the catalyst using the heat-resistant carrier of the present invention can be used for exhaust gas treatment of internal combustion engines and maintains stable performance in high-temperature reactions.
実施例３
本実施例では本発明になる耐熱性担体を高温脱硝反応用
触媒に用いた例について述べる。Example 3 This example describes an example in which the heat-resistant carrier of the present invention is used as a catalyst for high-temperature denitrification reaction.
実施例１と同様の方法で調製した成型前の複合酸化物よ
り成る粉末５０ｇにメタチタン酸スラリー５００ｇ（Ｔ
ｉ（ｈとして１５０ｇ）を混線機により充分混練する。500 g of metatitanic acid slurry (T
i (150 g as h) was sufficiently kneaded using a mixer.
その後１５０Ｃで乾燥し、粉砕して４００Ｃで４時間焼
成する。得られた粉末をプレス成型機を用いて直径３■
、厚さ３ｍｌの円柱状に成型後、タングステン酸アンモ
ニウムの過酸化水素水溶液に浸漬する。その後６００Ｃ
で２時間焼成して触媒を得る。かくして得られた触媒は
酸化タングステンを５重量嗟含んでいる。Thereafter, it is dried at 150C, crushed and fired at 400C for 4 hours. The obtained powder is molded into a diameter of 3cm using a press molding machine.
After molding into a cylindrical shape with a thickness of 3 ml, it was immersed in an aqueous hydrogen peroxide solution of ammonium tungstate. Then 600C
Calcinate for 2 hours to obtain a catalyst. The catalyst thus obtained contains 5 parts by weight of tungsten oxide.
反応は下記組成のガスを用い、空間速度５０００１１−
１１反反応度６００Ｃの条件下で１００時間行なった。The reaction uses a gas with the following composition, and the space velocity is 500011-
The reaction was carried out for 100 hours at a reaction rate of 600C.
反応ガス組成
ＮＯｘ ２００１ｐｌ
ＮＨｓ ２００胛
０２ ３％
Ｎ２０ １０俤
Ｎ２ 残部
ＮＯｘの除去率は初期で９４．８％、１００時間後で９
４．４１であった。以上の結果よシ本発明になる担体を
用いた触媒によれば高温脱硝反応に対しても優れた性能
を示す。Reaction gas composition NOx 2001 pl NHs 200 yen 02 3% N20 10 yen N2 The removal rate of the remaining NOx was 94.8% at the initial stage and 9 after 100 hours.
It was 4.41. As can be seen from the above results, the catalyst using the carrier of the present invention exhibits excellent performance even in high-temperature denitrification reactions.
実施例４
本実施例ではＣＯのメタン化反応用触媒に用いた例につ
いて述べる。Example 4 In this example, an example in which the catalyst was used as a catalyst for CO methanation reaction will be described.
実施例１と比較例１で得た成型後の担体に硝酸ニッケル
を含浸し、５００Ｃで焼成後更に塩化ルテニウムを含浸
後、１００ＯＣで焼成し完成触媒を得た。本触媒はＮｉ
０３０、Ｒｕ３％を含有している。この触媒を反応管に
充填し、ＣＯ５４゜Ｈｚ ｌ ７ 俤、Ｈｚ残のガスを
８Ｖ＝１０００００ｈ−１になるように導入し、反応温
度３５０Ｃでメタネーション反応を行った。その結果、
ＣＯのメタン化収率は、本実施例触媒は、本比較例触媒
に比べ約１５倍の収量で返ることがわかった。このよう
に高温に限らず比較的低温における反応においても本発
明の担体を有する触媒は非常に有効であることがわかる
。The molded supports obtained in Example 1 and Comparative Example 1 were impregnated with nickel nitrate, calcined at 500C, further impregnated with ruthenium chloride, and calcined at 100OC to obtain finished catalysts. This catalyst is Ni
030, containing 3% Ru. This catalyst was filled in a reaction tube, CO was introduced at 54° Hz l 7 , and the remaining gas at 8 V = 100000 h −1 was introduced to carry out methanation reaction at a reaction temperature of 350 C. the result,
It was found that the CO methanation yield of the catalyst of this example was about 15 times that of the catalyst of this comparative example. Thus, it can be seen that the catalyst having the carrier of the present invention is very effective not only in reactions at high temperatures but also at relatively low temperatures.
実施例５
本実施例ではメタノールの脱水素用反応について調べた
。Example 5 In this example, a methanol dehydrogenation reaction was investigated.
実施例１で述べた成型後の担体に硝酸鋼及び硝酸亜鉛溶
液を含浸し、乾燥後１０００Ｃで焼成する。The molded carrier described in Example 1 is impregnated with nitrate steel and zinc nitrate solution, dried and then fired at 1000C.
Ｃｕ及びｚｎの含有量はそれぞれ２０重量％。The contents of Cu and zn were each 20% by weight.
１０重量％である。該触媒を反応管に充填し、８００１
：ｌ’にした後、メタノールを導入し、脱水素反応を行
わせてホルマリンを製造したところ、メタノールの転化
率は、９８俤以上であり、ホルマリンへの選択率も従来
に比べ約５倍であった。It is 10% by weight. The catalyst was filled into a reaction tube, and 8001
:1', then methanol was introduced and a dehydrogenation reaction was performed to produce formalin.The conversion rate of methanol was over 98 yen, and the selectivity to formalin was about 5 times that of the conventional method. there were.
実施例６
硝酸アルミニウム５００ｇと硝酸ネオジム３０．７ｇを
蒸留水５ｔに溶解した。この溶液を攪拌しながら３Ｎア
ンモニア水を滴下しｐＨ８まで中和した。得られたアル
ミニウムとネオジムの共沈物をデカンテーションにより
蒸留水を用いて充分洗浄した後、ろ過し１５０Ｃで１昼
夜乾燥した。６０メツシユ以下に粉砕し、５００Ｕで２
時間焼成した後、グラファイトを０．５重量俤加え、プ
レス成型機を用いて直径３ ｍ 、厚さ３１ＩＩｉｌ＋
の円柱状に成型した。この担体囚の組成はＮｄ２０ｇ
５モル係。Example 6 500 g of aluminum nitrate and 30.7 g of neodymium nitrate were dissolved in 5 tons of distilled water. While stirring this solution, 3N ammonia water was added dropwise to neutralize it to pH 8. The resulting coprecipitate of aluminum and neodymium was thoroughly washed by decantation with distilled water, filtered, and dried at 150C for one day and night. Grind to 60 mesh or less, 2 with 500U
After firing for an hour, 0.5 weight of graphite was added and molded using a press molding machine to a diameter of 3 m and a thickness of 31 II +
It was molded into a cylindrical shape. The composition of this carrier prisoner is 20g of Nd.
5 mole person.
ＡｔｚＯａ９５モル係である。この担体を１２００Ｃで
２時間焼成し、比表面積をＮ２ガス吸着によるＢ Ｅ、
Ｔ法で測定した。また、担体の結晶構造は粉末Ｘ線回折
法で調べた。その結果を第３表に示す。AtzOa is 95 moles. This support was calcined at 1200C for 2 hours, and the specific surface area was determined by B E by N2 gas adsorption.
Measured by T method. Further, the crystal structure of the carrier was investigated by powder X-ray diffraction. The results are shown in Table 3.
実施例７
硝酸アルミニウムと硝酸ネオジムの割合を変えた以外は
実施例６と同様にして調製し、担体■。Example 7 A carrier ■ was prepared in the same manner as in Example 6 except that the ratio of aluminum nitrate and neodymium nitrate was changed.
０．０を得た。得られた担体はそれぞれ次の組成を有す
る。■： ＮｄｚＯｓ ２モルチ、 ｋＬｘｏｓ
９８モル％、 （Ｑ ： ＮｄｚＯｓ １０モル％、
Ａｌｔｏｓ ９０モル％、 Ｑ）） ： ＮｄｚＯｓ
２０モル％、 ＡｔｔＯ蓋 ８０モル係。これらの
担体の比表面積及び生成物の形態を実施例６と同様な方
法で測定した。結果を第３表に示す。I got 0.0. The obtained carriers each have the following composition. ■: NdzOs 2molti, kLxos
98 mol%, (Q: NdzOs 10 mol%,
Altos 90 mol%, Q)): NdzOs
20 mol%, AttO lid 80 mol. The specific surface area of these carriers and the morphology of the products were measured in the same manner as in Example 6. The results are shown in Table 3.
第３表
実施例８
硝酸アルミニウム５００ｇと硝酸プラセオジム３０、５
ｇを原料とし、実施例６と同様の方法で調製し、ｐｒ
、ｏ３５モに’Ａ＊ ｋｔｚｏ３９５Ｔ−Ａ／４から成
る担体■を得た。また硝酸アルミニウムと硝酸プラセオ
ジムの割合を変え、担体［Ｆ］、０）、８を得た。得ら
ｉｔた担体はそれぞれ次の組成を有する。Table 3 Example 8 Aluminum nitrate 500g and praseodymium nitrate 30,5
g as a raw material, prepared in the same manner as in Example 6, and pr
, a carrier (■) consisting of 'A* ktzo395T-A/4 was obtained on o35 mo. Further, carriers [F], 0) and 8 were obtained by changing the ratio of aluminum nitrate and praseodymium nitrate. The obtained carriers each had the following composition.
（Ｆ’）： Ｐｒｚ０３ ２モル％、 ＡｔｚＯａ
９８−ｒ−ルｌ、 ｆ３）： Ｐ ｒ２０ｇ １０
モル％ ＋ ＡＺ２０３９０ モル％ ＋ ＠： ｐｒ
２ｏ３ ２０ モｋ ％ 、 ＡｔｘＯｓ ８０ モ
ル％。これらの担体の比表面積及び生成物の形態を調べ
た結果を第４表に示す。(F'): Prz03 2 mol%, AtzOa
98-r-ru, f3): P r20g 10
Mol% + AZ20390 Mol% + @: pr
2o3 20 mole%, AtxOs 80 mole%. Table 4 shows the results of examining the specific surface area and product morphology of these carriers.
第４表
実棒例９
硝酸アルミニウム５００ｇと硝酸ネオジム１８．６ｇと
硝酸プラセオジム１８．５ｇを原料とし実施例６と同様
の方法で、Ｎｄ２０３３ モに％ 、 Ｐｒ５Ｏｓ３モ
ル’Ａ 、 ＡｔｚＯｓ ９４モル係の割合で含む担
体（Ｉ）を調製した。この担体の比表面積は２３．０ｙ
νｇであった。また結晶構造を調べたところ、主にネオ
ジム−β−アルミナとプラセオジム−β−アルミナから
成ることが確認された。この結果からもわかるようにこ
れらのβ−アルミナを含有する担体は高温においても高
比表面積を有している。Table 4 Actual Bar Example 9 Using 500 g of aluminum nitrate, 18.6 g of neodymium nitrate, and 18.5 g of praseodymium nitrate as raw materials, the same method as in Example 6 was carried out to produce a mixture of Nd2033%, Pr5Os3mol'A, and AtzOs 94%. A carrier (I) containing: The specific surface area of this carrier is 23.0y
It was νg. Further, when the crystal structure was examined, it was confirmed that it mainly consists of neodymium-β-alumina and praseodymium-β-alumina. As can be seen from this result, these carriers containing β-alumina have a high specific surface area even at high temperatures.
実施例１０
アルミナゾル（アルミナ含有率９．８１）５００ｇと炭
酸ネオジム１２．．３ｇをライカイ機にて２時間混練し
た後、１５（ｌで１昼夜乾燥した。６０メツシユ以下に
粉砕し、５００Ｃで２時間焼成した後、グラファイトを
０．５重量％加え、プレス成鳳機を用いて直径３■、厚
さ３ｍ＋の円柱状に成減した。との担体の組成はＮｄ２
Ｏ５４モル％、ｋＬ＊０９６モル饅である。この担体を
１００ＯＣまたは１２００Ｃで、２時間焼成し、比表面
積を測定したところ、それぞれ９ ａｓｍ”／ｇ、 ２
、６ｍ”／ｇであった。Example 10 500g of alumina sol (alumina content 9.81) and neodymium carbonate 12. ．． After kneading 3g in a Laikai machine for 2 hours, it was dried in 15L for 1 day and night. It was ground to 60 mesh or less and fired at 500C for 2 hours, then 0.5% by weight of graphite was added and a press forming machine was used. The composition of the carrier was Nd2.
O54 mol%, kL*096 mol. This carrier was calcined at 100OC or 1200C for 2 hours and the specific surface area was measured to be 9 asm''/g, 2
, 6 m''/g.
実施例６〜１０で調製した担体を用いたｐｄ触媒の耐久
試験を行ったところ、８００〜１４００Ｃで優れた性能
を示した。When the PD catalyst using the supports prepared in Examples 6 to 10 was tested for durability, it showed excellent performance at 800 to 1400C.
以上の様に本発明の担体を有する触媒は高温においても
比表面積が大きく、低温は言うに及ばず高温における化
学反応に対しても適用できることがわかる。As described above, it can be seen that the catalyst having the carrier of the present invention has a large specific surface area even at high temperatures, and can be applied to chemical reactions not only at low temperatures but also at high temperatures.
実施例１１
実施例１に示した本発明に係る担体にモリブデン酸アン
モニウム及び硝酸ニッケルの混合溶液を含浸し、乾燥後
５００Ｃで５時間焼成する。本触媒の組成はＭｏ０ｓ１
５重量％、Ｎｉ０５重量係である。この触媒４０−を内
径１５ｍの反応管に充填し、約１ｔ／―の流速で水素を
流通して４５０Ｃで５時間還元した。還元後、４００℃
、１０気圧の条件で、Ｈ２を３００ｄ／−の流速、また
ｎ−ヘキサンにチオフェンを８として１００重量胛添加
、した合成原料を１００ｄ／ｈの流速で触媒上に供給し
た。反応後のｎ−ヘキサンキの硫黄濃度をガスクロマト
グラフで測定したところ、１００時間後においてもＳと
して０．１重量−以下であった。Example 11 The carrier according to the present invention shown in Example 1 is impregnated with a mixed solution of ammonium molybdate and nickel nitrate, dried and then calcined at 500C for 5 hours. The composition of this catalyst is Mo0s1
5% by weight, based on the weight of Ni05. This catalyst 40- was packed into a reaction tube with an inner diameter of 15 m, and hydrogen was passed through it at a flow rate of about 1 t/- to reduce the reaction at 450C for 5 hours. After reduction, 400℃
, under conditions of 10 atm, H2 was supplied at a flow rate of 300 d/-, and synthetic raw materials prepared by adding 100 weight of thiophene to n-hexane were supplied onto the catalyst at a flow rate of 100 d/h. When the sulfur concentration of n-hexane after the reaction was measured using a gas chromatograph, it was found to be 0.1 weight or less as S even after 100 hours.
実施例１２
実施例１に示した本発明に係る担体に塩化白金酸溶液を
含浸し、乾燥後９００ｃで２時間焼成する。本触媒のｐ
ｔ含有量は１％である。この触媒５ｃｃ を反応管に
充填し、悪臭成分の代表としてメチルエチルケトン、ト
ルエン、ホルマリンの三成分をそれぞれ１００Ｆ含むガ
スを空気とともに触媒層に導入する。反応温度５００ｃ
において、触媒層出口の前記有機物を測定したところ、
メチルエチルケトン０．４Ｆ、）ルエン０．３Ｆ、ホル
マリン０．８Ｆであり、本触媒は悪臭成分を除去するの
に非常に有効であることがわかった。Example 12 The carrier according to the present invention shown in Example 1 is impregnated with a chloroplatinic acid solution, dried and then calcined at 900c for 2 hours. p of this catalyst
The t content is 1%. A reaction tube was filled with 5 cc of this catalyst, and a gas containing 100F each of three components, methyl ethyl ketone, toluene, and formalin as representative malodorous components, was introduced into the catalyst layer together with air. Reaction temperature 500c
When the organic matter at the outlet of the catalyst layer was measured,
Methyl ethyl ketone: 0.4F, toluene: 0.3F, formalin: 0.8F, and it was found that this catalyst is very effective in removing malodorous components.
実施例１３
実施例ＩＫ示した本発明に係る担体の微粉末とβスズ酸
スラリーを混線・乾燥して５００ｔｒで３ｈ焼成した触
媒１ｇを重質油２０ｇＫ添加しこれをオートクレーブ内
に充填し、１００Ｋｇ／ｄ。Example 13 1 g of catalyst obtained by mixing and drying the fine powder of the carrier according to the present invention shown in Example IK and β-stannic acid slurry and calcining it at 500 tr for 3 hours was added with 20 g of heavy oil, which was then filled into an autoclave to produce 100 kg. /d.
４００ＣでＨ２を流しながら３０分間反応させた。The reaction was carried out at 400C for 30 minutes while flowing H2.
反応終了後生成物を減圧蒸留によシ各留分に分離した。After the reaction was completed, the product was separated into various fractions by vacuum distillation.
その結果、下表に示すように本触媒は重質油の軽質化に
優れた性能を示すことがわかる。As a result, as shown in the table below, it can be seen that this catalyst exhibits excellent performance in lightening heavy oil.
沸点範囲 組 成
〜２００９憾
２００〜３５０Ｃ３９係
３５０〜５５０ｔ：’ ３７俤残
１５チ
実施例１４
実施例１に示した本発明に係る担体に塩化鋼の溶液を含
浸し、５００Ｃで２時間焼成した。本触媒の組成はＣｕ
２Ｑ ２０重量係である。この触媒を用いてプロピレン
の酸化反応を行った。触媒２〇−に反応ガスとしてＣ５
Ｈｓ ２５俤、０ｚ１０係。Boiling point range Composition ~2009 200~350C39 350~550t: '37 remaining
15th Example 14 The carrier according to the present invention shown in Example 1 was impregnated with a solution of chlorinated steel and fired at 500C for 2 hours. The composition of this catalyst is Cu
2Q 20 weight section. An oxidation reaction of propylene was carried out using this catalyst. C5 as a reaction gas to catalyst 20-
Hs 25 yen, 0z10 person in charge.
Ｎ２残の組成から成るガスを温度４５０Ｃで導入し、生
成ガスを分析した。その結果、Ｃ３Ｈ６の転化率は９８
係で、アクロレインへの選択率は８８係であった。この
ように本触媒の酸化率は非常に高いことがわかる。A gas having a composition of N2 residue was introduced at a temperature of 450C, and the produced gas was analyzed. As a result, the conversion rate of C3H6 was 98
The selectivity to acrolein was 88. It can thus be seen that the oxidation rate of this catalyst is extremely high.
実施例１５
実施例１に示した本発明に係る担体に硝酸コバルト、硝
酸第２鉄の混合液を含浸し、８００Ｃで５時間焼成した
。本触媒の組成はＣＯＯ１２％。Example 15 The carrier according to the present invention shown in Example 1 was impregnated with a mixed solution of cobalt nitrate and ferric nitrate, and calcined at 800C for 5 hours. The composition of this catalyst is COO12%.
Ｆｅ＊Ｏａ ８％である。この触媒４０−にＣＯ４０
％、Ｈ２６０係から成るガスを３００Ｇ、５０Ｋｇ／
ｃｒＡの条件で反応させたところ［℃、Ｏ＋Ｈｚ ］の
転化率は８８俤であった。また生成物の分析から選択率
を調べたところ、Ｃ１”Ｃｓまでのガス成分は４８％、
ガソリン留分２１％、含酸素化合物１２俤１重質油２９
チであった。以上の結果から本触媒はＣＯとＨ２から有
機化合物と合成するのに適していることがわかった。Fe*Oa is 8%. CO40 to this catalyst 40-
%, gas consisting of H260 300G, 50Kg/
When the reaction was carried out under the conditions of crA, the conversion rate [°C, O+Hz] was 88 degrees. In addition, when we checked the selectivity from the analysis of the product, the gas component up to C1"Cs was 48%,
Gasoline fraction 21%, oxygenated compounds 12 yen 1 heavy oil 29
It was Chi. From the above results, it was found that this catalyst is suitable for synthesizing organic compounds from CO and H2.
実施例１６
実施例１に示した本発明に係る担体に、硝酸銅と硝酸亜
鉛の混合溶液を含浸し、５００ｔ：’で２時間焼成した
。本触媒に水素７５チ、−酸化炭素２５憾から成る混合
ガスを温度３００℃、圧力１００〜／−で導入し、生成
ガスを分析したところ［ＣＯ＋Ｈｚ ］の転化率は９０
％でメタノールの選択率は９２チであった。以上のこと
から、本触媒はＣＯとＨ２からメタノールを合成するの
に適していることがわかる。Example 16 The carrier according to the present invention shown in Example 1 was impregnated with a mixed solution of copper nitrate and zinc nitrate, and fired at 500 t:' for 2 hours. A mixed gas consisting of 75 parts hydrogen and 25 parts carbon oxide was introduced into this catalyst at a temperature of 300°C and a pressure of 100~/-, and the resulting gas was analyzed, and the conversion rate of [CO+Hz] was 90.
% methanol selectivity was 92%. From the above, it can be seen that this catalyst is suitable for synthesizing methanol from CO and H2.
実施例１７
実施例１に示しだ本発明に係る担体に硝酸ニッケル溶液
を含浸し、５００Ｇで２時間焼成する。Example 17 The carrier according to the invention shown in Example 1 is impregnated with a nickel nitrate solution and calcined at 500G for 2 hours.
本触媒の組成はＮｉ０１５重量係である。本触媒を用い
てノルマルブタンの異性化反応を温度１００Ｃで行った
ところ、イソブタンへの収率が６９俤であった。このよ
うに本触媒は異性化反応に対して有効であることがわか
る。The composition of this catalyst is based on the weight of Ni015. When the isomerization reaction of n-butane was carried out at a temperature of 100C using this catalyst, the yield to isobutane was 69 yen. Thus, it can be seen that the present catalyst is effective for isomerization reactions.
実施例１８ 実施例１に示した本発明に係る担体に塩化鉄。Example 18 Iron chloride was used as the carrier according to the present invention shown in Example 1.
塩化カリウム、塩化鋼の混合溶液を含浸し、乾燥後、７
００ｔ：’で２時間焼成した。本触媒の組成は、Ｆｅ＋
Ｏ＋ ２０重量％、に２０２％、Ｃｕ０２ｍである。After impregnating with a mixed solution of potassium chloride and chlorinated steel and drying, 7
00t:' for 2 hours. The composition of this catalyst is Fe+
O+ 20% by weight, 202% Cu02m.
本触媒に７５４Ｈ２および２５４Ｎｚを温度５５ （１
，圧力２５０ Ｋｇ／ｃｄの条件下で接触させたとζろ
、［Ｈ２＋Ｎｚ ：）の転化率は９５係であった。この
実験から、本発明の担体を有する触媒はＮ２の水素化に
よるアンモニア合成に有効であることがわかる。754H2 and 254Nz were applied to this catalyst at a temperature of 55 (1
, the conversion rate of [H2+Nz:) was 95 when contacted under conditions of a pressure of 250 Kg/cd. This experiment shows that the catalyst having the support of the present invention is effective for ammonia synthesis by hydrogenation of N2.
以上詳細に説明したように、本発明による担体は高温で
の比表面積が大きく且つ安定である。このため本発明の
担体を有する触媒は、高温化学反応プロセスにおいて顕
著な触媒活性を発揮することができる。As explained in detail above, the carrier according to the present invention has a large specific surface area and is stable at high temperatures. Therefore, the catalyst having the support of the present invention can exhibit remarkable catalytic activity in high-temperature chemical reaction processes.
第１図は本発明の一実施例に係るＬａ２ｏ３−Ａｔ２Ｏ
ａ第２Ｏａ系担法を示す工程図、第２図はり、ａ２０ｓ
ＡｔａＯｓ系担体の組成と比表面積との関係を示す
特性図、第３ａ図〜第３ｄ図はＬａｚＯｓ−ｋＬｘｏｓ
系担体の結晶構造を示すＸ線回折図、第４図はＬａ２
ｈｓ Ａｔｚ０３系担体の組成と焼成温度の関係を示
す特性図、第５図はＰ ｄ ＬａｚＯｓ・ＡＬｚＯｓ
触媒を用いたＣＨ４酸化反応における反応温度とＣＨ４
転化率との関係を示す特性図、第６図はＰ ｄ Ｌａ
２０ａ ＨＡｔ２０ａ触媒における担体の組成とＰｄ表
面積の関係を示す特性図、第７図はＰｄ−Ｉ、ａｚ０３
・Ａｔ２０ａ触媒を用いたメタン燃焼における燃焼時間
とＣＨ４転化率との関係を示す特性図である。
／Ｉ、ノ２．／３ ＝−＝・しａ−Ｏａ’ＡノｚＯｓ
”ｒ’ｕ本２ｘ、２３，２４．λ’ ・・山ｆｄ−し
ａ２０３−ＡｌｚＯａ ｈ気☆」しう２ ・・ ・−Ｐ
ｄ−ＬａｘＯＢ ・ＡｌｚＯｓ ｈ”４−平 １ 図
第 ２ 図
ＬａＩＬ（Ｌ＋ρす、七ル２FIG. 1 shows La2o3-At2O according to an embodiment of the present invention.
a2 Process diagram showing the Oa system loading method, Figure 2 beam, a20s
Characteristic diagrams showing the relationship between the composition and specific surface area of the AtaOs-based carrier, Figures 3a to 3d are LazOs-kLxos
X-ray diffraction diagram showing the crystal structure of the system carrier, Figure 4 is La2
hs A characteristic diagram showing the relationship between the composition of Atz03-based carrier and firing temperature, Figure 5 is P d LazOs/ALzOs
Reaction temperature and CH4 in CH4 oxidation reaction using catalyst
A characteristic diagram showing the relationship with conversion rate, Figure 6 is P d La
20a Characteristic diagram showing the relationship between carrier composition and Pd surface area in HAt20a catalyst, Figure 7 shows Pd-I, az03
- It is a characteristic diagram showing the relationship between combustion time and CH4 conversion rate in methane combustion using At20a catalyst. /I, ノ2. /3 =-=・shia-Oa'AノzOs
``r'u book 2x, 23, 24.λ'...Mountain fd-shia203-AlzOa hki☆'' Shiu 2... ・-P
d-LaxOB ・AlzOs h"4-Hei 1 Figure 2 Figure LaIL (L+ρS, 7L 2
Claims (1)
た希土類元素の１種以上と、アルミニウムの複合酸化物
を含み、該複合酸化物が少なくとも１０ｍ＾２／ｇ以上
の比表面積を有し、かつ該複合酸化物は実質的に前記希
土類元素β−アルミナと１０００℃以上で２時間以内で
加熱した時に該β−アルミナに変り得る前駆体であるこ
とを特徴とする高温で安定な触媒用担体。 ２、特許請求の範囲第１項において、前記複合酸化物中
の希土類元素は酸化物として１〜２０モル％であり、残
部はアルミナであることを特徴とする高温で安定な触媒
用担体。 ３、特許請求の範囲第１項において、前記複合酸化物中
の希土類元素は酸化物として３〜１０モル％であり、残
部はアルミナであることを特徴とする高温で安定な触媒
用担体。 ４、特許請求の範囲第１項において、前記複合酸化物は
２０〜１００ｍ＾２／ｇの比表面積を有することを特徴
とする高温で安定な触媒用担体。 ５、特許請求の範囲第１項において、担体構造がハニカ
ム構造よりなることを特徴とする高温で安定な触媒用担
体。 ６、特許請求の範囲第１項において、担体の支持体を有
することを特徴とする高温で安定な触媒用担体。 ７、特許請求の範囲第６項において、前記支持体が金属
板、金網、海綿状金属から選ばれることを特徴とする高
温で安定な触媒用担体。 ８、ランタン、ネオジウム、プラセオジウムから選ばれ
た希土類元素の１種以上と、アルミニウムの複合酸化物
を含み、該複合酸化物は１０ｍ＾２／ｇ以上の比表面積
を有し、クロム、ストロンチウム、セリウムの含有量は
１重量％以下であり、前記希土類元素は酸化物として１
〜２０モル％、残部がアルミナであり、実質的に前記希
土類元素β−アルミナとこれらの前駆体の混合物から成
ることを特徴とする高温で安定な触媒用担体。 ９、特許請求の範囲第８項において、前記希土類元素は
酸化物として３〜１０モル％であり、残部はアルミナで
あることを特徴とする高温で安定な触媒用担体。 １０、特許請求の範囲第８項において、前記複合酸化物
が２０〜１００ｍ＾２／ｇの比表面積を有することを特
徴とする高温で安定な触媒用担体。 １１、ランタン、ネオジウム、プラセオジウムから選ば
れた希土類元素の１種以上と、アルミニウムの複合酸化
物を含み、該複合酸化物は１０ｍ＾２／ｇ以上の比表面
積を有し、アルミナのα−、γ−、θ−、η−、ｋ−、
ｘ−、ρ−、δ−以外の結晶構造をもち、かつクロム、
ストロンチウム、セリウムは１重量％以下であり、前記
希土類元素β−アルミナおよび１０００℃、２時間以内
の加熱で、該β−アルミナに変り得るこれらの前駆体の
混合物からなり、前記希土類元素は酸化物として１〜２
０モル％、残部がアルミナであることを特徴とする高温
で安定な触媒用担体。 １２、特許請求の範囲第１１項において、前記複合酸化
物中の希土類元素が酸化物として３〜１０モル％、残部
がアルミナであることを特徴とする高温で安定な触媒用
担体。 １３、特許請求の範囲第１１項において、前記複合酸化
物の比表面積が２０〜１００ｍ＾２／ｇであることを特
徴とする高温で安定な触媒用担体。 １４、ランタン、ネオジウム、プラセオジウムから選ば
れた希土類元素の１種以上と、アルミニウムの複合酸化
物であり、該複合酸化物は１０ｍ＾２／ｇ以上の比表面
積を有し、クロム、ストロンチウム、セリウムの含有量
は１重量％以下であり、実質的に前記希土類元素β−ア
ルミナと１０００℃で２時間以内の加熱でこれらの複合
酸化物に変り得る前駆体の混合物からなり、該複合酸化
物は希土類元素が酸化物として１〜２０モル％、残部が
アルミナであることを特徴とする高温で安定な触媒用担
体。 １５、特許請求の範囲第１４項において、複合酸化物は
希土類元素が酸化物として３〜１０モル％、残部がアル
ミナであることを特徴とする高温で安定な触媒用担体。 １６、特許請求の範囲第１４項において、前記複合酸化
物の比表面積が２０〜１００ｍ＾２／ｇであることを特
徴とする高温で安定な触媒用担体。 １７、アルミニウム塩とランタン、ネオジウム、プラセ
オジウムから選ばれた希土類元素の少なくとも１つの塩
の混合溶液にアルカリを添加して、該混合物の共沈物を
沈殿させ、該共沈物を分離した後、種々の形状に成型し
、１０００℃以上の温度で焼成してアルミニウムと前記
希土類元素との複合酸化物からなり、少なくとも１０ｍ
＾２／ｇの比表面積をもち、前記希土類元素β−アルミ
ナと１０００℃で２時間以内の加熱で該β−アルミナに
変り得る前駆体あるいは実質的にその前駆体の混合物を
得ることを特徴とする高温で安定な触媒用担体の調製方
法。[Claims] 1. Contains a composite oxide of aluminum and one or more rare earth elements selected from lanthanum, neodymium, and praseodymium, and the composite oxide has a specific surface area of at least 10 m^2/g or more. and the composite oxide is substantially a precursor of the rare earth element β-alumina that can be converted into the β-alumina when heated at 1000° C. or higher within 2 hours. Carrier for use. 2. A catalyst carrier stable at high temperatures according to claim 1, wherein the rare earth element in the composite oxide is 1 to 20 mol % as an oxide, and the remainder is alumina. 3. A catalyst carrier stable at high temperatures according to claim 1, wherein the rare earth element in the composite oxide is 3 to 10 mol % as an oxide, and the remainder is alumina. 4. A catalyst carrier stable at high temperatures, as set forth in claim 1, wherein the composite oxide has a specific surface area of 20 to 100 m^2/g. 5. A catalyst carrier stable at high temperatures, as set forth in claim 1, wherein the carrier structure has a honeycomb structure. 6. A catalyst carrier which is stable at high temperatures and is characterized by having a carrier support according to claim 1. 7. A catalyst carrier stable at high temperatures according to claim 6, wherein the support is selected from a metal plate, a wire mesh, and a spongy metal. 8. Contains a composite oxide of aluminum and one or more rare earth elements selected from lanthanum, neodymium, and praseodymium, and the composite oxide has a specific surface area of 10 m^2/g or more, and contains chromium, strontium, and cerium. The content of the rare earth element is 1% by weight or less, and the rare earth element is 1% by weight as an oxide.
20 mol %, the balance being alumina, and comprising essentially a mixture of the rare earth element β-alumina and a precursor thereof. 9. A catalyst carrier stable at high temperatures according to claim 8, wherein the rare earth element is present in an amount of 3 to 10 mol % as an oxide, and the remainder is alumina. 10. A catalyst carrier stable at high temperatures, as set forth in claim 8, wherein the composite oxide has a specific surface area of 20 to 100 m^2/g. 11. Contains a composite oxide of aluminum and one or more rare earth elements selected from lanthanum, neodymium, and praseodymium, the composite oxide has a specific surface area of 10 m^2/g or more, γ-, θ-, η-, k-,
Has a crystal structure other than x-, ρ-, δ-, and chromium,
Strontium and cerium are contained in an amount of 1% by weight or less, and are composed of a mixture of the rare earth element β-alumina and a precursor thereof that can be converted into the β-alumina by heating at 1000°C within 2 hours, and the rare earth element is an oxide. as 1~2
A catalyst carrier that is stable at high temperatures and is characterized by having 0 mol% and the balance being alumina. 12. A catalyst carrier stable at high temperatures according to claim 11, wherein the rare earth element in the composite oxide is 3 to 10 mol % as an oxide, and the balance is alumina. 13. A catalyst carrier stable at high temperatures, as set forth in claim 11, wherein the composite oxide has a specific surface area of 20 to 100 m^2/g. 14. A composite oxide of aluminum and one or more rare earth elements selected from lanthanum, neodymium, and praseodymium, and the composite oxide has a specific surface area of 10 m^2/g or more, and contains chromium, strontium, and cerium. The content of is 1% by weight or less, and is substantially composed of a mixture of the rare earth element β-alumina and a precursor that can be converted into these composite oxides by heating at 1000°C within 2 hours, and the composite oxide is A catalyst carrier stable at high temperatures, characterized by containing 1 to 20 mol% of a rare earth element as an oxide, and the balance being alumina. 15. A catalyst carrier stable at high temperatures according to claim 14, wherein the composite oxide contains 3 to 10 mol% of rare earth elements as oxides, and the balance is alumina. 16. A catalyst carrier stable at high temperatures, as set forth in claim 14, wherein the composite oxide has a specific surface area of 20 to 100 m^2/g. 17. Adding an alkali to a mixed solution of an aluminum salt and at least one salt of a rare earth element selected from lanthanum, neodymium, and praseodymium to precipitate a coprecipitate of the mixture, and separating the coprecipitate, It is molded into various shapes and fired at a temperature of 1000°C or higher to form a composite oxide of aluminum and the rare earth element, and is made of a composite oxide of at least 10m.
A precursor having a specific surface area of ^2/g and which can be converted into β-alumina by heating with the rare earth element β-alumina at 1000°C within 2 hours, or a mixture of substantially the precursor thereof, is obtained. A method for preparing a catalyst carrier that is stable at high temperatures.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP59159980A JPS6135851A (en) | 1984-07-30 | 1984-07-30 | Catalyst carrier stable at high temperature and its preparation |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP59159980A JPS6135851A (en) | 1984-07-30 | 1984-07-30 | Catalyst carrier stable at high temperature and its preparation |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS6135851A true JPS6135851A (en) | 1986-02-20 |
| JPH0435220B2 JPH0435220B2 (en) | 1992-06-10 |
Family
ID=15705370
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP59159980A Granted JPS6135851A (en) | 1984-07-30 | 1984-07-30 | Catalyst carrier stable at high temperature and its preparation |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS6135851A (en) |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS63134058A (en) * | 1986-11-27 | 1988-06-06 | Cataler Kogyo Kk | Catalyst for cleaning exhaust gas |
| JPS63134551A (en) * | 1986-11-25 | 1988-06-07 | 東ソー株式会社 | Alumina base sintered body and manufacture |
| JPS63139044A (en) * | 1986-12-01 | 1988-06-10 | 東ソー株式会社 | Alumina-zirconia base sintered body and manufacture |
| JPH01281145A (en) * | 1987-12-22 | 1989-11-13 | Rhone Poulenc Chim | Catalyst carrier material |
| WO2007049778A1 (en) * | 2005-10-24 | 2007-05-03 | Toyota Jidosha Kabushiki Kaisha | Catalyst support and catalyst for exhaust-gas purification |
| JP2007252988A (en) * | 2006-03-20 | 2007-10-04 | Catalysts & Chem Ind Co Ltd | Catalyst for carbon monoxide methanation and methanation method of carbon monoxide using the catalyst |
| CN103949239A (en) * | 2014-04-10 | 2014-07-30 | 北京工业大学 | Preparation method of rare earth element-doped ZnO loaded bentonite composite photocatalyst |
| US10906816B2 (en) | 2016-07-29 | 2021-02-02 | Sumitomo Chemical Company, Limited | Alumina and method for producing automotive catalyst using same |
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|---|---|---|---|---|
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| JPS63134058A (en) * | 1986-11-27 | 1988-06-06 | Cataler Kogyo Kk | Catalyst for cleaning exhaust gas |
| JPS63139044A (en) * | 1986-12-01 | 1988-06-10 | 東ソー株式会社 | Alumina-zirconia base sintered body and manufacture |
| JPH01281145A (en) * | 1987-12-22 | 1989-11-13 | Rhone Poulenc Chim | Catalyst carrier material |
| WO2007049778A1 (en) * | 2005-10-24 | 2007-05-03 | Toyota Jidosha Kabushiki Kaisha | Catalyst support and catalyst for exhaust-gas purification |
| US7776783B2 (en) | 2005-10-24 | 2010-08-17 | Toyota Jidosha Kabushiki Kaisha | Catalyst carrier and exhaust gas purification catalyst |
| JP2007252988A (en) * | 2006-03-20 | 2007-10-04 | Catalysts & Chem Ind Co Ltd | Catalyst for carbon monoxide methanation and methanation method of carbon monoxide using the catalyst |
| CN103949239A (en) * | 2014-04-10 | 2014-07-30 | 北京工业大学 | Preparation method of rare earth element-doped ZnO loaded bentonite composite photocatalyst |
| US10906816B2 (en) | 2016-07-29 | 2021-02-02 | Sumitomo Chemical Company, Limited | Alumina and method for producing automotive catalyst using same |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0435220B2 (en) | 1992-06-10 |
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