JPH01210031A - Heat-resistant catalyst and its preparation - Google Patents
Heat-resistant catalyst and its preparationInfo
- Publication number
- JPH01210031A JPH01210031A JP63035325A JP3532588A JPH01210031A JP H01210031 A JPH01210031 A JP H01210031A JP 63035325 A JP63035325 A JP 63035325A JP 3532588 A JP3532588 A JP 3532588A JP H01210031 A JPH01210031 A JP H01210031A
- Authority
- JP
- Japan
- Prior art keywords
- heat
- resistant catalyst
- catalyst
- alkoxide
- resistant
- 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.)
- Pending
Links
- 239000003054 catalyst Substances 0.000 title claims abstract description 144
- 239000000203 mixture Substances 0.000 claims abstract description 45
- 229910052788 barium Inorganic materials 0.000 claims abstract description 15
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 10
- 229910052761 rare earth metal Inorganic materials 0.000 claims abstract description 10
- 229910052712 strontium Inorganic materials 0.000 claims abstract description 9
- 229910052791 calcium Inorganic materials 0.000 claims abstract description 8
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 7
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 5
- 150000004703 alkoxides Chemical class 0.000 claims description 36
- 238000004519 manufacturing process Methods 0.000 claims description 24
- 229910052782 aluminium Inorganic materials 0.000 claims description 23
- 230000007062 hydrolysis Effects 0.000 claims description 21
- 238000006460 hydrolysis reaction Methods 0.000 claims description 21
- -1 aluminum alkoxide Chemical class 0.000 claims description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 17
- 239000000047 product Substances 0.000 claims description 16
- 238000001354 calcination Methods 0.000 claims description 13
- 239000002131 composite material Substances 0.000 claims description 13
- 238000007084 catalytic combustion reaction Methods 0.000 claims description 12
- 150000001875 compounds Chemical class 0.000 claims description 10
- 230000032683 aging Effects 0.000 claims description 9
- 239000007864 aqueous solution Substances 0.000 claims description 8
- 239000013078 crystal Substances 0.000 claims description 8
- 150000004645 aluminates Chemical group 0.000 claims description 6
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical group [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 6
- 125000004432 carbon atom Chemical group C* 0.000 claims description 5
- 229910052804 chromium Inorganic materials 0.000 claims description 5
- 229910052742 iron Inorganic materials 0.000 claims description 5
- 229910000510 noble metal Inorganic materials 0.000 claims description 5
- 239000000243 solution Substances 0.000 claims description 5
- 238000000354 decomposition reaction Methods 0.000 claims description 4
- 229910052802 copper Inorganic materials 0.000 claims description 3
- 229910052697 platinum Inorganic materials 0.000 claims description 3
- 239000002244 precipitate Substances 0.000 claims description 3
- 238000000197 pyrolysis Methods 0.000 claims description 3
- 229910052703 rhodium Inorganic materials 0.000 claims description 3
- 229910052707 ruthenium Inorganic materials 0.000 claims description 3
- 229910052763 palladium Inorganic materials 0.000 claims description 2
- 238000005979 thermal decomposition reaction Methods 0.000 claims description 2
- 230000000694 effects Effects 0.000 abstract description 25
- 238000002485 combustion reaction Methods 0.000 abstract description 5
- 238000006243 chemical reaction Methods 0.000 abstract description 3
- 241000903210 Bryconamericus alpha Species 0.000 abstract 1
- 239000000463 material Substances 0.000 abstract 1
- 238000000034 method Methods 0.000 description 21
- 239000011572 manganese Substances 0.000 description 16
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 14
- 230000007423 decrease Effects 0.000 description 9
- 239000002994 raw material Substances 0.000 description 8
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 7
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 6
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 6
- 239000007789 gas Substances 0.000 description 6
- 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 6
- 229910052751 metal Inorganic materials 0.000 description 6
- 239000002184 metal Substances 0.000 description 6
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 5
- 125000004429 atom Chemical group 0.000 description 4
- IWOUKMZUPDVPGQ-UHFFFAOYSA-N barium nitrate Chemical compound [Ba+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O IWOUKMZUPDVPGQ-UHFFFAOYSA-N 0.000 description 4
- QVQLCTNNEUAWMS-UHFFFAOYSA-N barium oxide Inorganic materials [Ba]=O QVQLCTNNEUAWMS-UHFFFAOYSA-N 0.000 description 4
- 239000000969 carrier Substances 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 238000010304 firing Methods 0.000 description 4
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 4
- 239000007858 starting material Substances 0.000 description 4
- 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 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000004480 active ingredient Substances 0.000 description 3
- 150000001553 barium compounds Chemical class 0.000 description 3
- 229910052746 lanthanum Inorganic materials 0.000 description 3
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 description 3
- 150000002604 lanthanum compounds Chemical class 0.000 description 3
- 229940071125 manganese acetate Drugs 0.000 description 3
- 150000002697 manganese compounds Chemical class 0.000 description 3
- UOGMEBQRZBEZQT-UHFFFAOYSA-L manganese(2+);diacetate Chemical compound [Mn+2].CC([O-])=O.CC([O-])=O UOGMEBQRZBEZQT-UHFFFAOYSA-L 0.000 description 3
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 150000002823 nitrates Chemical class 0.000 description 3
- 238000001556 precipitation Methods 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 238000005245 sintering Methods 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 230000007704 transition Effects 0.000 description 3
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 150000007513 acids Chemical class 0.000 description 2
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 2
- SMZOGRDCAXLAAR-UHFFFAOYSA-N aluminium isopropoxide Chemical compound [Al+3].CC(C)[O-].CC(C)[O-].CC(C)[O-] SMZOGRDCAXLAAR-UHFFFAOYSA-N 0.000 description 2
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 description 2
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 2
- ANBBXQWFNXMHLD-UHFFFAOYSA-N aluminum;sodium;oxygen(2-) Chemical compound [O-2].[O-2].[Na+].[Al+3] ANBBXQWFNXMHLD-UHFFFAOYSA-N 0.000 description 2
- 235000011114 ammonium hydroxide Nutrition 0.000 description 2
- AYJRCSIUFZENHW-UHFFFAOYSA-L barium carbonate Chemical compound [Ba+2].[O-]C([O-])=O AYJRCSIUFZENHW-UHFFFAOYSA-L 0.000 description 2
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000000975 co-precipitation Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 150000004679 hydroxides Chemical class 0.000 description 2
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 description 2
- 238000005470 impregnation Methods 0.000 description 2
- 229910001388 sodium aluminate Inorganic materials 0.000 description 2
- DHEQXMRUPNDRPG-UHFFFAOYSA-N strontium nitrate Chemical compound [Sr+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O DHEQXMRUPNDRPG-UHFFFAOYSA-N 0.000 description 2
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 2
- 239000000725 suspension Substances 0.000 description 2
- FIPWRIJSWJWJAI-UHFFFAOYSA-N Butyl carbitol 6-propylpiperonyl ether Chemical compound C1=C(CCC)C(COCCOCCOCCCC)=CC2=C1OCO2 FIPWRIJSWJWJAI-UHFFFAOYSA-N 0.000 description 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 229910021380 Manganese Chloride Inorganic materials 0.000 description 1
- GLFNIEUTAYBVOC-UHFFFAOYSA-L Manganese chloride Chemical compound Cl[Mn]Cl GLFNIEUTAYBVOC-UHFFFAOYSA-L 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 150000001242 acetic acid derivatives Chemical class 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 229910000272 alkali metal oxide Inorganic materials 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 1
- WDIHJSXYQDMJHN-UHFFFAOYSA-L barium chloride Chemical compound [Cl-].[Cl-].[Ba+2] WDIHJSXYQDMJHN-UHFFFAOYSA-L 0.000 description 1
- 229910001626 barium chloride Inorganic materials 0.000 description 1
- RQPZNWPYLFFXCP-UHFFFAOYSA-L barium dihydroxide Chemical compound [OH-].[OH-].[Ba+2] RQPZNWPYLFFXCP-UHFFFAOYSA-L 0.000 description 1
- 229910001863 barium hydroxide Inorganic materials 0.000 description 1
- AYJRCSIUFZENHW-DEQYMQKBSA-L barium(2+);oxomethanediolate Chemical compound [Ba+2].[O-][14C]([O-])=O AYJRCSIUFZENHW-DEQYMQKBSA-L 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- ZCDOYSPFYFSLEW-UHFFFAOYSA-N chromate(2-) Chemical class [O-][Cr]([O-])(=O)=O ZCDOYSPFYFSLEW-UHFFFAOYSA-N 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 229910052878 cordierite Inorganic materials 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 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 1
- 238000005265 energy consumption Methods 0.000 description 1
- HHFAWKCIHAUFRX-UHFFFAOYSA-N ethoxide Chemical compound CC[O-] HHFAWKCIHAUFRX-UHFFFAOYSA-N 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- VQEHIYWBGOJJDM-UHFFFAOYSA-H lanthanum(3+);trisulfate Chemical compound [La+3].[La+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O VQEHIYWBGOJJDM-UHFFFAOYSA-H 0.000 description 1
- 235000002867 manganese chloride Nutrition 0.000 description 1
- 239000011565 manganese chloride Substances 0.000 description 1
- 229940099607 manganese chloride Drugs 0.000 description 1
- 229940099596 manganese sulfate Drugs 0.000 description 1
- 235000007079 manganese sulphate Nutrition 0.000 description 1
- 239000011702 manganese sulphate Substances 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- NBTOZLQBSIZIKS-UHFFFAOYSA-N methoxide Chemical compound [O-]C NBTOZLQBSIZIKS-UHFFFAOYSA-N 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 229960005235 piperonyl butoxide Drugs 0.000 description 1
- 235000011118 potassium hydroxide Nutrition 0.000 description 1
- 239000012286 potassium permanganate Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- OGHBATFHNDZKSO-UHFFFAOYSA-N propan-2-olate Chemical compound CC(C)[O-] OGHBATFHNDZKSO-UHFFFAOYSA-N 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 235000011121 sodium hydroxide Nutrition 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
Abstract
Description
【発明の詳細な説明】
（産業上の利用分野）
本発明は耐熱性触媒、特に触媒燃焼等の反応に使用され
る耐熱性に優れた高活性の触媒と、その製造方法に関す
るものである。DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention relates to a heat-resistant catalyst, particularly a highly active catalyst with excellent heat resistance used in reactions such as catalytic combustion, and a method for producing the same.
（従来の技術）
触媒燃焼のための触媒は、自動車排ガス中の一酸化炭素
及び炭化水素類の燃焼除去、工場排ガスの除害、脱臭、
無炎燃焼等に今日広く用いられているが、その多くは触
媒の耐熱性が不充分なため、触媒の使用温度を約８００
°Ｃ以下に限定又は制御することで触媒の活性低下を防
ぐなどの特別な配慮の下で使用している。従って、耐熱
性の一段と優れた触媒が渇望されてきた。さらに近年、
ガスタービン、ボイラー及びジェットエンジン等の分野
に於いても、より高温で触媒燃焼を行なうことが注目さ
れるようになり、その要請に答え得る触媒、例えば１２
００℃を越える高温でもなお且つ高い活性を維持する耐
熱性高活性触媒の出現が強く望まれるようになってきた
。(Prior art) Catalysts for catalytic combustion are used to burn and remove carbon monoxide and hydrocarbons from automobile exhaust gas, abate and deodorize factory exhaust gas,
Although it is widely used today for flameless combustion, etc., most of the catalysts have insufficient heat resistance, so the operating temperature of the catalyst is about 800℃.
It is used with special consideration, such as limiting or controlling the temperature below °C to prevent a decrease in catalyst activity. Therefore, a catalyst with even better heat resistance has been desired. Furthermore, in recent years,
In fields such as gas turbines, boilers, and jet engines, catalytic combustion at higher temperatures is attracting attention, and catalysts that can meet this demand, such as 12
There has been a strong desire for a heat-resistant, highly active catalyst that maintains high activity even at high temperatures exceeding 00°C.
耐熱性触媒は通常耐熱性の触媒担体に触媒成分を担持す
ることにより得られる。本発明者等はこの観点から、現
在広く使用されている触媒担体のうち最も耐熱性に優れ
ているアルミナ担体をベースとしながら、遥かに耐熱性
に優れた耐熱性組成物の開発を進め、既にその成果とし
て特願昭６０−１８９９６７号として、ＭｅＯｅ ６Ａ
１ｚ０３（ＭｅはＣａ及び／又はＢａ及び／又はＳｒ）
を主成分として含む組成物が耐熱性に特に優れた触媒担
体となり得ることを示している。Heat-resistant catalysts are usually obtained by supporting catalyst components on a heat-resistant catalyst carrier. From this point of view, the present inventors have proceeded with the development of a heat-resistant composition that has far superior heat resistance, based on alumina carrier, which has the best heat resistance among currently widely used catalyst supports, and has already As a result, MeOe 6A was published as Japanese Patent Application No. 189967/1986.
1z03 (Me is Ca and/or Ba and/or Sr)
This shows that a composition containing as a main component can serve as a catalyst carrier with particularly excellent heat resistance.
また、本発明者等は特願昭６１−１４０２８７号として
、ＭｅＯ・６Ａ１！０２を主成分とする前記組成物がア
ルミニウム及びＭｅで表される金属の複合及び／又は混
合アルコキシドより製造される時、さらに優れた耐熱性
組成物となることを示し、またその好適な製造方法を提
案している。In addition, the present inventors have disclosed in Japanese Patent Application No. 61-140287 that when the composition containing MeO.6A1!02 as a main component is produced from a composite and/or mixed alkoxide of metals represented by aluminum and Me, , it has been shown that a composition with even better heat resistance can be obtained, and a suitable method for producing the same has been proposed.
（発明が解決しようとする問題点）
ＭｅＯ・６Ａ１ｇＯ＋（ＭｅはＣａ、 Ｂａ又はＳｒ）
を主成分とする触媒担体に含浸又はコーティングにより
触媒成分を担持した触媒は、従来のアルミナ担持触媒に
比べれば著しく耐熱性の優れた触媒であるが、１２００
℃を越えるような高温で触媒燃焼反応等の触媒として用
いた場合には、担持した触媒成分の焼結が起り、そのた
めの触媒活性の低下は避けられず、触媒担体の優れた耐
熱性が充分には生かされなかった。(Problem to be solved by the invention) MeO・6A1gO+ (Me is Ca, Ba or Sr)
A catalyst in which a catalyst component is supported by impregnation or coating on a catalyst carrier mainly composed of 1200
When used as a catalyst for catalytic combustion reactions at high temperatures exceeding ℃, sintering of the supported catalyst components occurs, which inevitably reduces the catalytic activity, and the excellent heat resistance of the catalyst support is insufficient. was not kept alive.
本発明はこの欠点を排除し、−層耐熱性及び活性の優れ
た触媒を提供することを目的とする。The present invention aims to eliminate this drawback and provide a catalyst with excellent heat resistance and activity.
（問題点を解決するための手段）
本発明者等はこのような一層耐熱性並びに活性の優れた
触媒を得るため鋭意実験と研究を行った結果、触媒活性
成分と触媒担体成分の特殊な結合物を造ることにより極
めて高活性でしかも耐熱性の優れた触媒が得られること
を見出し、本発明を完成した。即ち、本発明は組成式
％式％
（式中ＡはＣａ、 Ｂａ及びＳｒより成る群から選択し
１種以上の元素、Ｃは希土類元素の中から選択した１種
以上の元素、ＢはＭｎ、 Ｃｏ、 Ｆｅ＋ Ｎｉ、 Ｃ
ｕ及びＣｒより晟る群から選択した１種以上の元素、２
は約０．４以下の数、Ｘは約Ｏ９１〜４の範囲内の数、
ｙはｘ〜２Ｘの範囲内の数、αは元素Ａ、 Ｃ及びＢの
夫々の価数Ｘ、Ｙ及び２及びｘ、 ｙ及び２の数によ
って定まり、
ａ＝ １−− （Ｘ −ｚ （Ｘ−Ｙ） ＋ｘＺ−３
ｙ）で表わされる数を示す）で表わされる組成物を主成
分とすることを特徴とする耐熱性触媒である。(Means for Solving the Problems) The inventors of the present invention have conducted extensive experiments and research in order to obtain a catalyst with further excellent heat resistance and activity, and have found that a special bond between a catalyst active component and a catalyst carrier component has been developed. They discovered that by manufacturing a catalyst, a catalyst with extremely high activity and excellent heat resistance could be obtained, and the present invention was completed. That is, the present invention has a composition formula % (where A is one or more elements selected from the group consisting of Ca, Ba and Sr, C is one or more elements selected from rare earth elements, and B is Mn). , Co, Fe+Ni, C
one or more elements selected from the group consisting of u and Cr, 2
is a number of about 0.4 or less, X is a number within the range of about O91 to 4,
y is a number within the range of x to 2X, α is determined by the respective valences of elements A, C, and B, X, Y, and 2, and the numbers of x, y, and 2, and a= 1−− (X −z ( X-Y) +xZ-3
It is a heat-resistant catalyst characterized by containing as a main component a composition represented by the number represented by y).
本発明の触媒は特に触媒燃焼用触媒に適するものである
が、この用途に限定されるものではなく、高温度を必要
とする他の多くの反応にも使用できる。Although the catalyst of the present invention is particularly suitable as a catalytic combustion catalyst, it is not limited to this use, but can also be used in many other reactions requiring high temperatures.
本発明はさらに、アルミニウムアルコキシド又はアルミ
ニウム及びＡで表わされる金属の複合又は混合アルコキ
ドを原料として用いて本発明の耐熱性組成物を製造する
方法を提供する。このアルコキシド法によれば、固体混
合法、水溶液からの沈殿法等の通常の触媒又は触媒担体
の製造に使用される方法によるよりも、さらに優れた活
性並びに耐熱性をもつ触媒の提供が可能となる。The present invention further provides a method for producing the heat-resistant composition of the present invention using aluminum alkoxide or a composite or mixed alkoxide of aluminum and a metal represented by A as a raw material. According to this alkoxide method, it is possible to provide a catalyst with even better activity and heat resistance than by methods used for producing ordinary catalysts or catalyst carriers, such as solid mixing methods and precipitation methods from aqueous solutions. Become.
本発明の耐熱性触媒中の元素Ａ十元素Ｃの含有量が元素
ＢとＡｌの合計原子数１００原子に対して８．３原子の
場合、Ａ＋−＊ＣｇＢＪｌ＋ｚ−ｙＯｔｑ−ｘ組成物は
最も安定した耐熱性の良い形となるが、Ａ＋Ｃの含有量
はこの割合に限定されるものではなく、（Ａ＋Ｃ）
：（Ｂ＋Ａｌ）の割合は原子比として８．３ ：１０
０に近い値即ち約７〜１０ ： １００の範囲の値をと
ることが特に望ましい。Ａ＋Ｃの割合がこの範囲を越え
て大きい場合はＡＯ又はＡＯ・ＡｌｘＯｓ等、として小
さい場合はＡｌｔｏｚとして触媒中に存在する部分が多
くなり過ぎ、高温下でのそれらの酸化物の焼結に基づ（
比表面積の低下が起り、ひいては触媒活性の低下が起る
ので好ましくない。When the content of elements A and C in the heat-resistant catalyst of the present invention is 8.3 atoms per 100 atoms in total of elements B and Al, the A+-*CgBJl+z-yOtq-x composition is the most stable. However, the content of A+C is not limited to this ratio, and (A+C)
:(B+Al) ratio is 8.3:10 as atomic ratio
Values close to 0, ie in the range of about 7 to 10:100, are particularly desirable. If the ratio of A + C is larger than this range, it will be AO or AO・AlxOs, etc. If it is small, it will be Altoz. (
This is undesirable because it causes a decrease in specific surface area and, in turn, a decrease in catalytic activity.
本発明の耐熱性触媒に含まれるＡ＋−Ｃ−８ｘＡｌｔｚ
−ｙｏ１９−、、。A+-C-8xAltz contained in the heat-resistant catalyst of the present invention
-yo19-,,.
中の助触媒成分Ｃの量を示す２の値を必要以上に大きく
することは、活性の低下、耐熱性の劣化を招くので望ま
しくなく、２の値は約０．４以下とすることが望ましい
。活性成分Ｂの量を示すＸの値は約０．１〜４特に約０
６２〜３の範囲内にあることが望ましい。Ｘが０．１よ
り小さい場合には活性成分Ｂの不足により活性効果が充
分でなく、Ｘが４より大きい場合は、活性元素Ｂを層状
アルミネート構造をとるＡ＋−＊ＣＪＪｌｒｇ−ｙＯ＋
ｖ−を組成物結晶構造中にうまく取り込めず、余った元
素Ｂが単独の酸化物として析出し、焼結による活性低下
を惹き起す原因となる。因みに、本発明者等は、本発明
の耐熱性触媒の主成分であるＡ＋−、Ｃ，Ｂ、Ａｌ＋ｚ
−ｚＣｚＢｘＡｌ１２−＝ｇ組成物がＢａＯ・６ＡｈＯ
３の示すマグネトプランバイト類似構造又はβ−アルミ
ナ類似構造等の層状アルミネート構造をとるものとＸ線
回折結果より推定しており、これが耐熱性を付与するも
のと考えている。It is undesirable to make the value of 2, which indicates the amount of cocatalyst component C in the catalyst, larger than necessary because it causes a decrease in activity and deterioration of heat resistance, and it is desirable that the value of 2 is about 0.4 or less. . The value of X indicating the amount of active ingredient B is about 0.1 to 4, especially about 0.
It is desirable that it be within the range of 62-3. When X is smaller than 0.1, the active effect is insufficient due to the lack of active ingredient B, and when X is larger than 4, active element B has a layered aluminate structure A+-*CJJlrg-yO+
v- cannot be properly incorporated into the crystal structure of the composition, and the remaining element B precipitates as a single oxide, causing a decrease in activity due to sintering. Incidentally, the present inventors have discovered that A+-, C, B, Al+z, which are the main components of the heat-resistant catalyst of the present invention,
-zCzBxAl12-=g composition is BaO.6AhO
It is estimated from the X-ray diffraction results that it has a layered aluminate structure such as the magnetoplumbite-like structure shown in No. 3 or the β-alumina-like structure, and it is believed that this provides heat resistance.
耐熱性組成物Ａ＋−，Ｃ５ＢＸＡｌ＋ｚ−ｙＯｔｖ−べ
を構成するアルミナ並びに元素Ａ、Ｃ及びＢの酸化物の
他に、シリカ及びアルカリ金属酸化物等の耐熱性を与え
る第三成分を、耐熱性触媒中に小量含むことは本発明の
範囲を逸脱するものではない。In addition to the alumina and oxides of elements A, C, and B constituting the heat-resistant composition A+-, C5BXAl+z-yOtv-be, a third component that provides heat resistance such as silica and an alkali metal oxide is added to a heat-resistant catalyst. It does not depart from the scope of the present invention to include small amounts in the composition.
本発明の耐熱性触媒中に含まれるＡ＋−Ｃ−ＢｘＡｌ＋
ｚ−ｙＯｔｖ−ｎで表わされる組成物は、云わば元素へ
の酸化物、元素Ｃの酸化物、元素Ｂの酸化物及びアルミ
ナの四者の複合酸化物である。次に上記の酸化物の夫々
について説明する。A+-C-BxAl+ contained in the heat-resistant catalyst of the present invention
The composition represented by z-yOtv-n is, so to speak, a composite oxide of four elements: an oxide of an element, an oxide of element C, an oxide of element B, and alumina. Next, each of the above oxides will be explained.
本発明の耐熱性触媒中に主成分として含まれる酸化アル
ミニウムの為の出発原料は、固体混合法による場合、一
般に転移性アルミナとして知られるアルミナが好ましい
。The starting material for aluminum oxide contained as a main component in the heat-resistant catalyst of the present invention is preferably alumina, which is generally known as transitional alumina, when a solid mixing method is used.
酸化アルミニウムの為の出発原料は、沈殿法による場合
、通常、硝酸アルミニウム、硫酸アルミニウム又はアル
ミン酸ソーダなどの水溶性の化合物が使用可能である。When the precipitation method is used as the starting material for aluminum oxide, a water-soluble compound such as aluminum nitrate, aluminum sulfate or sodium aluminate can usually be used.
本発明の耐熱性触媒の一つの主成分としての元 。Element as one of the main components of the heat-resistant catalyst of the present invention.
素Ａ及び元素Ｃの酸化物のための出発原料としては、元
素Ａ及びＣの酸化物、水酸化物、炭酸塩、硝酸塩、硫酸
塩などの各種の化合物が使用できる。As starting materials for the oxides of elements A and C, various compounds such as oxides, hydroxides, carbonates, nitrates, and sulfates of elements A and C can be used.
以下本発明に係る元素ＡをＢａ、元素ＣをＬａとして説
明するが、本発明は元素ＡがＢａ以外のＣａ、 Ｓｒの
元素及び元素ＣがＬａ以外の希土類元素についても有効
である。The present invention will be described below assuming that the element A is Ba and the element C is La, but the present invention is also effective when the element A is an element other than Ba such as Ca or Sr, and the element C is a rare earth element other than La.
本発明の耐熱性触媒の主な活性成分である元素Ｂの酸化
物のための出発原料としては元素Ｂの酸化物、水酸化物
、炭酸塩、硝酸塩、硫酸塩、塩化物、醋酸塩などの有機
酸塩、アンミン錯塩等の錯塩、さらに無水クロム酸、マ
ンガン酸塩、クロム酸塩などの元素Ｂの酸及びその塩等
、一般に触媒製造原料として用いら“れる総ての化合物
が使用可能である。以下、本発明に係る元素ＢをＭｎと
して説明するが、本発明はＣｏ、 Ｆｅ、 Ｎｉｔ Ｃ
ｕ及びＣｒについても有効である。Starting materials for the oxide of element B, which is the main active component of the heat-resistant catalyst of the present invention, include oxides, hydroxides, carbonates, nitrates, sulfates, chlorides, acetates, etc. of element B. All compounds that are generally used as raw materials for catalyst production can be used, including organic acid salts, complex salts such as ammine complex salts, as well as element B acids and their salts such as chromic anhydride, manganates, and chromates. Hereinafter, element B according to the present invention will be explained as Mn, but the present invention also includes Co, Fe, Nit C.
This is also valid for u and Cr.
これらのアルミニウム化合物、バリウム化合物、ランタ
ン化合物、マンガン化合物から触媒を製造するにあたっ
ては、共沈法などの沈殿法、固体混合法、混練法、含浸
法など触媒製造時に通常用いられる各種の方法が使用で
きる。In producing catalysts from these aluminum compounds, barium compounds, lanthanum compounds, and manganese compounds, various methods commonly used in catalyst production are used, including precipitation methods such as coprecipitation, solid mixing methods, kneading methods, and impregnation methods. can.
本発明は耐熱性触媒の特殊な製造方法としてアルコキシ
ド法を提起しているが、このアルコキシド法の場合の酸
化アルミニウム及び酸化バリウムの為の原料は、アルミ
ニウム及びバリウムのアルコキシド類である。アルコキ
シドはメトキシド、エトキシド、イソプロポキシド及び
ブトキシド等の炭素数１〜４のアルコキシド類が好まし
い。これらのアルコキシド類は市販のものを使用しても
良いが、金属アルミニウム及び金属バリウムとアルコー
ル類を用いて調製することもできる。The present invention proposes an alkoxide method as a special method for producing heat-resistant catalysts, and the raw materials for aluminum oxide and barium oxide in this alkoxide method are alkoxides of aluminum and barium. The alkoxides are preferably alkoxides having 1 to 4 carbon atoms, such as methoxide, ethoxide, isopropoxide, and butoxide. Commercially available alkoxides may be used, but they can also be prepared using metal aluminum or metal barium and alcohols.
本発明の耐熱性触媒の形状は粉体のままでも良いが、タ
ブレット、リング、球、押出成型形、ハニカム、フオー
ムなど触媒として一般的なあらゆる形状が採用可能であ
る。ハニカム触媒等の場合は、触媒体の全体を本発明の
耐熱性触媒で構成してもよいが、コージェライト等の不
活性成分より成るハニカム骨格上に本発明の耐熱性触媒
をコートして触媒体を構成する方が、より一般的な方法
である。The shape of the heat-resistant catalyst of the present invention may be a powder, but any shape commonly used as a catalyst such as a tablet, ring, sphere, extrusion molding, honeycomb, or foam can be adopted. In the case of a honeycomb catalyst, the entire catalyst body may be composed of the heat-resistant catalyst of the present invention, but the heat-resistant catalyst of the present invention may be coated on the honeycomb skeleton made of an inert component such as cordierite. Configuring the media is a more common method.
本発明の耐熱性触媒は乾燥及び／又は焼成の最終工程又
は中間工程を経て製品とするのが通例であるが、焼成は
必ずしも必要ではなく、時としてこれを行なわない場合
もある。然し、触媒、特に触媒燃焼用の触媒の場合には
、使用最高温度前後の温度での焼成は熱安定性の組成物
を得る為の重要な操作である。例えば本発明の耐熱性触
媒が触媒燃焼用触媒である場合、使用時に１３００°Ｃ
を越える高温に曝されることが当然予想される。このよ
うな場合、１３００°Ｃ又はそれを越える温度で焼成し
ておくことが好ましい。このような高い焼成温度では本
発明によらない組成物例えばＴ−アルミナ担体、シリカ
−アルミナ担体、希土類、アルカリ等の耐熱性向上剤を
加えたアルミナ担体などでは、α−アルミナへの転移が
起り、比表面積の著しい低下とそれに伴う活性特に低温
活性の低下などを避は得ない。The heat-resistant catalyst of the present invention is usually made into a product through a final or intermediate step of drying and/or calcination, but calcination is not always necessary and may sometimes be omitted. However, in the case of catalysts, especially catalysts for catalytic combustion, calcination at temperatures around the maximum temperature of use is an important operation to obtain thermally stable compositions. For example, when the heat-resistant catalyst of the present invention is a catalyst for catalytic combustion, the temperature is 1300°C during use.
It is naturally expected that the product will be exposed to high temperatures exceeding . In such a case, it is preferable to bake at a temperature of 1300°C or higher. At such high calcination temperatures, compositions other than those according to the present invention, such as T-alumina carriers, silica-alumina carriers, alumina carriers to which heat resistance improvers such as rare earth elements and alkalis have been added, undergo a transition to α-alumina. , a significant decrease in specific surface area and an accompanying decrease in activity, particularly low-temperature activity, are unavoidable.
本発明の耐熱性触媒の製造にあたって、９００℃以上の
温度で焼成することが通常の場合好ましいが、１３００
℃を越えるような高温で焼成する場合は、焼成温度と比
表面積の相関関係を予め測定しておき、比表面積を適当
な範囲例えば特定の触媒燃焼用担体では約２ ｔａ”１
ｇ以上の比表面積にしておくことが必要である。In producing the heat-resistant catalyst of the present invention, it is usually preferable to calcinate at a temperature of 900°C or higher;
When firing at a high temperature exceeding ℃, measure the correlation between the firing temperature and the specific surface area in advance, and set the specific surface area to an appropriate range, for example, about 2 ta"1 for a specific catalytic combustion carrier.
It is necessary to keep the specific surface area equal to or larger than g.
本発明の耐熱性触媒は好ましくは水溶性アルミニウム化
合物、水溶性バリウム化合物、水溶性ランタン化合物及
び水溶性マンガン化合物をＡｌ：（Ｂａ＋Ｌａ） ：
Ｍｎの原子比として計算して１００：（７〜１０）
：（０，１〜４）の割合で混合した水溶液より共沈物
の形で混合組成物を生成し、洗浄−濾過又は蒸発乾個の
工程を経て、得た共沈物を約２００〜５００℃で仮焼後
、約１２００−１５００℃で約５〜３０時間焼成するこ
とにより得られる。この場合、水溶性アルミニウム化合
物としては、硝酸アルミニウム、硫酸アルミニウム、塩
化アルミニウム等があり、水溶性バリウム化合物として
は硝酸バリウム、塩化バリウム等があり、水溶性ランタ
ン化合物としては硝酸ランタン、硫酸ランタン、塩化ラ
ンタン等があり、水溶性マンガン化合物としては硫酸マ
ン −ガン、塩化マンガン、硝酸マンガン等がある。こ
の場合の共沈剤としては苛性ソーダ、炭酸ソーダ、苛性
カリ、アンモニア水などが使用可能である。The heat-resistant catalyst of the present invention preferably contains a water-soluble aluminum compound, a water-soluble barium compound, a water-soluble lanthanum compound, and a water-soluble manganese compound in the form of Al: (Ba+La):
Calculated as the atomic ratio of Mn: 100: (7-10)
A mixed composition is produced in the form of a coprecipitate from an aqueous solution mixed at a ratio of: It is obtained by calcining at 1200-1500°C for about 5 to 30 hours. In this case, water-soluble aluminum compounds include aluminum nitrate, aluminum sulfate, aluminum chloride, etc., water-soluble barium compounds include barium nitrate, barium chloride, etc., and water-soluble lanthanum compounds include lanthanum nitrate, lanthanum sulfate, and chloride. Examples include lanthanum, and water-soluble manganese compounds include manganese sulfate, manganese chloride, and manganese nitrate. As the coprecipitant in this case, caustic soda, soda carbonate, caustic potash, aqueous ammonia, etc. can be used.
さらに水溶性の原料として、アルミン酸ソーダ、水酸化
バリウム、過マンガン酸カリなども使用できるが、この
場合の共沈剤としては例えば硝酸ランタン及び硝酸など
の酸が採用される。Further, as water-soluble raw materials, sodium aluminate, barium hydroxide, potassium permanganate, etc. can be used, and in this case, acids such as lanthanum nitrate and nitric acid are used as coprecipitants.
なお前段の仮焼段階を省略しても良い。Note that the previous calcination step may be omitted.
本発明の耐熱性触媒のさらに好ましい製造方法としては
、アルミニウムアルコキシド又はアルミニウム及びバリ
ウムの複合又は混合アルコキシドを原料とするアルコキ
シド法がある。アルコキシドからの酸化物の生成は特に
加水分解を通して行なうことが望ましい。この場合のマ
ンガン及びランタン、場合によってはバリウムの添加の
方法としては、それら元素の硝酸塩等の水溶液の形で加
水分解に必要な水と同時に加える方法がある。A more preferred method for producing the heat-resistant catalyst of the present invention is an alkoxide method using aluminum alkoxide or a composite or mixed alkoxide of aluminum and barium as a raw material. It is particularly desirable to produce oxides from alkoxides through hydrolysis. In this case, manganese and lanthanum, and in some cases barium, can be added in the form of an aqueous solution of nitrates of these elements at the same time as the water necessary for hydrolysis.
アルコキシド分解の方法は、加水分解に限定されるもの
ではなく、熱分解等の方法も採用できる。The method of alkoxide decomposition is not limited to hydrolysis, and methods such as thermal decomposition can also be employed.
また、これら酸化物の全部がアルコキシドより生成する
ものである必要はなく、例えばアルミナ、炭酸バリウム
等をアルコキシドの分解生成物に加えても良い。加水分
解による場合、加水分解は常温で行なうよりも、約５０
〜１００℃に加温して行なうことが望ましい。加水分解
のために添加する水のｐＨの影響は特に認められなかっ
たが、水を添加した後の熟成時間は耐熱性組成物の比表
面積に大きく影響し、熟成時間が長い程比表面積は増加
する。従って熟成時間は少なくとも１時間を越えること
が好ましく、例えば５〜ｌＯ時間の如く、経済的に許容
される範囲で可及的長時間とすることが特に望ましい。Furthermore, it is not necessary that all of these oxides be generated from alkoxides, and for example, alumina, barium carbonate, etc. may be added to the decomposition products of alkoxides. In the case of hydrolysis, the hydrolysis is about 50% lower than when carried out at room temperature.
It is desirable to carry out heating to ~100°C. Although no particular influence of the pH of the water added for hydrolysis was observed, the aging time after adding water greatly affected the specific surface area of the heat-resistant composition, and the longer the aging time, the greater the specific surface area. do. Therefore, it is preferable that the aging time exceeds at least 1 hour, and it is especially preferable that the aging time be as long as possible within an economically acceptable range, for example, 5 to 10 hours.
本発明の耐熱性組成物の比表面積は加水分解に用いる水
の量にも影響されるが、存在するアルコキシドの全量を
水酸化物とアルコールに加水分解するのに必要な水の量
（以下「水の当量」という）以下の水を使用した場合に
於いても、思いがけないほど大きな比表面積が得られる
ことを見出した。水の添加量は従って水の当量以下でも
良いが、０．５当量以下では比表面積は急激に低下する
ので好ましくない。一方、必要以上に多量の水を用いる
ことは処理設備及び消費エネルギー等の過大を招（ので
好ましくなく、約ｌＯ当量以下の範囲とすることが経済
的見地から好ましい。Although the specific surface area of the heat-resistant composition of the present invention is also influenced by the amount of water used for hydrolysis, the amount of water required to hydrolyze the total amount of alkoxide present into hydroxide and alcohol (hereinafter referred to as " It has been found that an unexpectedly large specific surface area can be obtained even when using less than the equivalent amount of water. Therefore, the amount of water added may be less than the equivalent of water, but if it is less than 0.5 equivalent, the specific surface area will sharply decrease, which is not preferable. On the other hand, it is undesirable to use a larger amount of water than necessary because it leads to excessive processing equipment and energy consumption, and it is preferable from an economical point of view to use less than about 1 O equivalent.
従って、水の使用量は通常約０，５〜１０当量である。Therefore, the amount of water used is usually about 0.5 to 10 equivalents.
しかし、水の使用量はこの範囲にのみ限定されるもので
はなく、これほど好適でなければ、この範囲外であって
も良い。However, the amount of water used is not limited to this range, and may be outside this range if it is not so suitable.
本発明のアルコキシド法による耐熱性触媒は、好適な一
製造例では、アルミニウムアルコキシドとバリウムアル
コキシドを、それぞれの中に含まれるＡｌ ： Ｂａ原
子比で１００ニア〜１０の割合で存在するようアルコー
ル類に溶解し、当量比で約０．５〜１０の範囲の量の水
に、マンガン：Ａ１原子比で１〜２：１００となるよう
な割合の硝酸マンガン及び硝酸ランタンを溶解した溶液
を加えて、５０〜１００℃の範囲の温度で加水分解を行
ない、５〜１０時間の熟成の後、蒸発乾個等により溶媒
を除き、得られた分２０成物の混合物を約２００〜５０
０℃で仮焼した後、約９００°Ｃ以上の温度で約５〜３
０時間焼成することにより得られる。なお前段の仮焼段
階は省略する場合もある。In a preferred production example of the heat-resistant catalyst produced by the alkoxide method of the present invention, aluminum alkoxide and barium alkoxide are mixed in alcohol so that the Al:Ba atomic ratio contained in each is between 100 and 10. Adding a solution of manganese nitrate and lanthanum nitrate in a proportion such that the manganese:A1 atomic ratio is 1 to 2:100 in an amount of water in an equivalent ratio of about 0.5 to 10; Hydrolysis is carried out at a temperature in the range of 50 to 100°C, and after aging for 5 to 10 hours, the solvent is removed by evaporation, etc., and the resulting mixture of 20 components is
After calcining at 0°C, about 5 to 3
Obtained by firing for 0 hours. Note that the previous calcination step may be omitted in some cases.
本願発明の耐熱性触媒に低温活性を与えるためには小量
の貴金属特にＰｔ、 Ｒｕ、 Ｒｈ、 Ｐｄ等の白金族
貴金属を更に含浸して担持せしめることが有効である。In order to impart low-temperature activity to the heat-resistant catalyst of the present invention, it is effective to further impregnate and support a small amount of a noble metal, particularly a platinum group noble metal such as Pt, Ru, Rh, or Pd.
このような貴金属担持触媒も本発明に含まれる。Such noble metal supported catalysts are also included in the present invention.
（作 用）
本発明の耐熱性触媒の耐熱性の増加は耐熱性に優れた、
層状アルミネート型結晶構造を持つ複合酸化物Ａ＋−Ｃ
，ＢＸＡｌ Ｉｚ−、Ｏ＋ ＊−１組成物の生成に起因
すると考えられる。即ち、本発明の耐熱性触媒中に於い
て安定な層状アルミネート型結晶構造物Ａｔ−−Ｃ−Ｂ
、ｌＡ１＋ｚ−ｙＯｔｗ−９は遷移アルミナのα−アル
ミナへの転移温度以下の比較的低温度に於いて生成し、
これがアルミナのα−アルミナへの転移及びシンタリン
グを抑制し、より高温度での比表面積及び活性を保持す
ると考えられる。(Function) The increase in heat resistance of the heat-resistant catalyst of the present invention provides excellent heat resistance.
Composite oxide A+-C with layered aluminate crystal structure
, BXAl Iz-, O+ *-1 composition. That is, the stable layered aluminate type crystal structure At--C-B in the heat-resistant catalyst of the present invention
, lA1+z-yOtw-9 is produced at a relatively low temperature below the transition temperature of transition alumina to α-alumina,
It is believed that this suppresses the transformation and sintering of alumina to α-alumina and maintains the specific surface area and activity at higher temperatures.
（実施例） 次に本発明を例につきさらに詳細に説明する。(Example) The invention will now be explained in more detail by way of example.
２隻桝上
窒素雰囲気下、市販のアルミニウムイソプロポキシドと
金属バリウムをイソプロピルアルコール中に８０℃で５
時間かけて溶解し、得られた溶液に酢酸マンガンと硝酸
ランタンを含む水溶液を滴下して加水分解を行なった。Commercially available aluminum isopropoxide and metallic barium were mixed in isopropyl alcohol at 80°C under a nitrogen atmosphere in two tanks.
The mixture was dissolved over time, and an aqueous solution containing manganese acetate and lanthanum nitrate was added dropwise to the resulting solution for hydrolysis.
１２時間熟成の後、得られた懸濁液を８０℃で減圧乾燥
、５００℃で仮焼した後、１３５０℃で５時間焼成を行
い、実施例１の触媒を得た。アルコキシド法によって得
たこの触媒はＢａａ、 ｔＬａｏ、 、、ＭｎＡ１１
ｌｏｔ ｑ４の組成式で表わされる組成を有していた。After aging for 12 hours, the resulting suspension was dried under reduced pressure at 80°C, calcined at 500°C, and then calcined at 1350°C for 5 hours to obtain the catalyst of Example 1. This catalyst obtained by the alkoxide method has Baa, tLao, , MnA11
It had a composition represented by the composition formula of lot q4.
実施例１の触媒のＢＥＴ比表面積は２０．３ｍ”／ｇで
あった。The BET specific surface area of the catalyst of Example 1 was 20.3 m''/g.
共較五１
酸化アルミニウムと炭酸バリウムをボールミル中に供給
し、約２４時間粉砕混合した。これら両原料のモル比＾
１ｔ０３：ＢａＣ０＋は８５．７：１４．３とした。次
いで得られた混合物を１３００℃で５時間焼成して触媒
担体を得た。この触媒担体を酢酸マンガンに含浸した後
、１３００℃で１０時間焼成して比較例１の触媒を得た
。マンガンの担持量は酸化マンガンとして触媒担体の１
０重量％とした。この触媒は担体ＢａＯ’ ６Ａ１ｚＯ
＋にＭｎＯを１０重量％担持したものであった。Co-Comparison 51 Aluminum oxide and barium carbonate were fed into a ball mill and ground and mixed for about 24 hours. Molar ratio of these two raw materials ^
1t03:BaC0+ was set to 85.7:14.3. The resulting mixture was then calcined at 1300° C. for 5 hours to obtain a catalyst carrier. This catalyst carrier was impregnated with manganese acetate and then calcined at 1300° C. for 10 hours to obtain a catalyst of Comparative Example 1. The amount of manganese supported is 1% of the catalyst carrier as manganese oxide.
It was set to 0% by weight. This catalyst is supported by BaO' 6A1zO
10% by weight of MnO was supported on the +.
比較例１の触媒のＢＥＴ比表面積は６．６ｍ”／ｇであ
った。The BET specific surface area of the catalyst of Comparative Example 1 was 6.6 m''/g.
狭可桝上
常圧固定床流通式反応装置によりメタン燃焼活性試験を
行なった。試験に用いたガスはメタン１容量％と空気９
９容量％から成るガスで、空間速度４８０００ｈｒ −
’の流速でこのガスを触媒層に流した。Methane combustion activity tests were conducted using a fixed-bed flow reactor in a narrow chamber at atmospheric pressure. The gases used in the test were methane 1% by volume and air 9%.
With a gas consisting of 9% by volume, the space velocity is 48,000 hr -
This gas was flowed through the catalyst layer at a flow rate of '.
試験の結果を第１表に示した。The test results are shown in Table 1.
施 ２３４ び５
金属バリウムの代りに金属ストロンチウムを用いた他は
実施例１と全く同じ方法により実施例２の触媒を得た。EXAMPLE 5 A catalyst of Example 2 was obtained in exactly the same manner as in Example 1 except that metal strontium was used instead of metal barium.
この触媒はＳｒｏ、ａＬａｏ、ｚＭｎＡｌｌｌｏｌｇ−
（（の組成式で表わされる組成を持ち、ＢＥＴ比表面積
は２３．８＋ｍ”１ｇであった。This catalyst is Sro, aLao, zMnAllolg-
(It had a composition represented by the compositional formula ((), and the BET specific surface area was 23.8+m''1g.
また、硝酸ランタンの使用量を増減すると同時に使用す
る金属ストロンチウムの量を変えた他は実施例２と同様
な方法により、実施例３．４．及び比較例２，３の触媒
を得たが、その組成は夫々Ｓｒｓ、６Ｌａｏ、ａＭｎＡ
ｌ ｔ ＋Ｏ＋ｗ−ｄ ％ Ｓｒａ、ｑｌａａｏ、
ｔＭｎＡｌｔ ｔＯ＋ｑ−ｄ 、ＳｒＭｎＡｌＩＩＯ
Ｉｑ−ｄ 、ＬａＭｎＡｌ＋＋０＋ｗ−ｃｍの組成式で
表わされるものであった。Examples 3.4. The catalysts of Comparative Examples 2 and 3 were obtained, and their compositions were Srs, 6Lao, and aMnA, respectively.
l t +O+w-d % Sra, qlaao,
tMnAlt tO+q−d , SrMnAlIIO
It was expressed by the compositional formula Iq-d, LaMnAl++0+w-cm.
侠貝班主
実施例２．３．４及び比較例２．３の触媒につき使用例
１と同様にして行なった活性試験の結果を第２表に示し
た。Table 2 shows the results of activity tests conducted in the same manner as in Use Example 1 for the catalysts of Main Example 2.3.4 and Comparative Example 2.3.
希土類元素添加の効果は顕著で希土類元素の添加の割合
を示す２の値が０．２迄は添加量の増加に伴って活性は
向上している。然しｚ ＝０．４では逆に活性が低下し
ており、２は約０．４以下とした方が好ましい組成物が
得られる。The effect of adding rare earth elements is remarkable, and the activity improves with increasing amount of addition until the value of 2, which indicates the ratio of addition of rare earth elements, is 0.2. However, when z = 0.4, the activity decreases, and a preferable composition is obtained when 2 is about 0.4 or less.
尖隻斑工
市販のアルミニウムイソプロポキシドをイソプロピルア
ルコール中に溶解し、得られた溶液に硝酸バリウム、硝
酸ランタン及び酢酸マンガンを含む水溶液を滴下して加
水分解を行なった。得られた懸濁液の処理即ち熟成、減
圧乾燥、仮焼、焼成の処理を実施例１触媒と同様に行な
って、実施例５の触媒を得た。この触媒は実施例１触媒
と同じＢａａ、ｙＬａｏ、 ＪｎＡｌ＋ ＋（Ｌ ｑ−
＜の組成を有し、ＢＥＴ比表面積は１８・３ ｖａ”１
ｇであった。また使用例１と同様のメタン燃焼活性試験
を行なったが、実施例５の触媒は実施例１触媒と殆ど同
じ活性を示した。Aluminum isopropoxide commercially available from Sensune Ikko was dissolved in isopropyl alcohol, and an aqueous solution containing barium nitrate, lanthanum nitrate, and manganese acetate was added dropwise to the resulting solution for hydrolysis. The resulting suspension was treated in the same manner as the catalyst of Example 1, including aging, drying under reduced pressure, calcination, and calcination, to obtain the catalyst of Example 5. This catalyst has the same Baa, yLao, JnAl+ + (L q-
It has a composition of <, and a BET specific surface area of 18.3 va”1
It was g. In addition, the same methane combustion activity test as in Use Example 1 was conducted, and the catalyst of Example 5 showed almost the same activity as the catalyst of Example 1.
叉履拠旦
硝酸アルミニウム、硝酸ストロンチウム、硝酸ランタン
及び硝酸マンガンの混合水溶液に、アンモニニア水をｐ
ｉ（８まで滴下し、蒸発乾固して得られた生成物を２０
０℃及び５００℃で夫々２時間仮焼後、１３５０℃で５
時間焼成して実施例６の触媒を得た。Add ammonia water to a mixed aqueous solution of aluminum nitrate, strontium nitrate, lanthanum nitrate, and manganese nitrate.
i (added dropwise to 8 and evaporated to dryness, the resulting product was reduced to 20
After calcination for 2 hours at 0°C and 500°C, 5 hours at 1350°C.
The catalyst of Example 6 was obtained by firing for a period of time.
共沈法によって得られたこの触媒はＳｒｏ、。Ｌａｏ、
２ＭｎＡ１Ｏｔ＊−ａの組成式で表わされる組成を有
し、ＢＥＴ比表面積は１３．８ｍ”１ｇであった。また
、使用例１と同様のメタ活性試験を行なった結果を、次
に示す。This catalyst obtained by coprecipitation method is Sro. Lao,
It had a composition represented by the compositional formula 2MnA1Ot*-a, and had a BET specific surface area of 13.8 m''1 g.Furthermore, the results of a metaactivity test similar to Use Example 1 are shown below.
第３表
（発明の効果）
かくて本発明によれば、触媒として極めて好適な高温で
使用できる耐熱性に極めて優れた触媒が得られる。従っ
て、本発明は産業上極めて有用である。Table 3 (Effects of the Invention) Thus, according to the present invention, a catalyst with extremely excellent heat resistance that can be used at high temperatures and is extremely suitable as a catalyst can be obtained. Therefore, the present invention is extremely useful industrially.
手 続 補 正 書
１昭和６３年 ７月 ４日
特許庁長官 吉 １） 文 毅 殿１、事
件の表示
昭和６３年特許願第３５３２５号
２、発明の名称
耐熱性触媒並びにその製造法
３、補正をする者
事件との関係 特許出願人
東洋シーシーアイ株式会社
４、代理人
５、補正の対象
３、耐熱性触媒中の元素ＡとＣの合計の元素、明細書第
１頁第３行〜第５頁第１２行を下記の通りに訂正する。Procedural amendment
1 July 4, 1988 Director General of the Japan Patent Office Yoshi 1) Moon Takeshi 1, Indication of the case Patent Application No. 35325 of 1988 2, Name of the invention Heat-resistant catalyst and its manufacturing method 3, Person making the amendment Case and Relationship between patent applicant Toyo CCI Corporation 4, agent 5, subject of amendment 3, total element of elements A and C in the heat-resistant catalyst, page 1, line 3 to page 5, line 12 of the specification. Correct as shown below.
「２、特許請求の範囲
１、組成式 Ａ＋−＊ＣＪＪ１＋ｔ−ｚＣｚＢｘＡｌ１
２−４（式中、ＡはＣａ、 Ｂａ及びＳｒより成る群か
ら選択した１種以上の元素、Ｃは希土類元素の中から選
択した１種以上の元素、ＢはＭｎ。"2. Claim 1, Compositional formula A+-*CJJ1+t-zCzBxAl1
2-4 (wherein A is one or more elements selected from the group consisting of Ca, Ba and Sr, C is one or more elements selected from rare earth elements, and B is Mn.
Ｃｏ＋ Ｆｅ、 Ｎｉ、 Ｃｕ及びＣｒより成る群から
選択した１種以上の元素、２は約０．４以下の数、Ｘは
約０．１〜４の範囲内の数、ｙはｘ〜２ｘの範囲内の数
、αは元素Ａ、Ｃ及びＢの夫々の価数Ｘ、Ｙ及びＺ及び
ｘ、 ｙ及び２の数によって定まり、
α＝ １−− （Ｘ −ｚ （Ｘ−Ｙ） ＋ｘＺ−３
ｙ）で表わされる数を示す）で表わされる組成物を主成
分とすることを特徴とする耐熱性触媒。Co+ one or more elements selected from the group consisting of Fe, Ni, Cu and Cr, 2 is a number of about 0.4 or less, X is a number within the range of about 0.1 to 4, y is a number of x to 2x The number α within the range is determined by the valences X, Y and Z of elements A, C and B, and the numbers of x, y and 2, α= 1−− (X −z (X−Y) +xZ− 3
A heat-resistant catalyst characterized by comprising as a main component a composition represented by the number represented by y).
２、 Ｐｔ、 Ｒｕ、 Ｒｈ、 Ｐｄ等の白金族貴金
属を耐熱性触媒上に担持して成る特許請求の範囲１記載
の耐熱性触媒。2. The heat-resistant catalyst according to claim 1, comprising a platinum group noble metal such as Pt, Ru, Rh, Pd, etc. supported on a heat-resistant catalyst.
シトの加水分解生成物及び／又は熱分解生ＢとＡ１の合
計に対する原子比が約７〜１０：１００の範囲にある特
許請求の範囲１又は２記載の耐熱性触媒。3. The heat-resistant catalyst according to claim 1 or 2, wherein the atomic ratio of the hydrolyzed product of Sito and/or the pyrolysis products B and A1 to the total is in the range of about 7 to 10:100.
４、元素ＡがＳｒ、元素ＣがＬａ及び／又はＣｅ。4. Element A is Sr, and element C is La and/or Ce.
元素ＢがＭｎ及び／又はＣｏである特許請求の範囲１，
２又は３記載の耐熱性触媒。Claim 1, wherein element B is Mn and/or Co;
3. The heat-resistant catalyst according to 2 or 3.
５、 ｘが約０．２〜３の範囲の数である特許請求の
範囲１，２．３又は４記載の耐熱性触媒。5. The heat resistant catalyst of claim 1, 2.3 or 4, wherein x is a number in the range of about 0.2 to 3.
６、組成式Ａ＋−＊ＣＪＪ１＋ｇ−ｚＣｚＢｘＡｌ１２
−＜で表わされる組成物中のＡｌ又は元素Ａ及びＡｌの
一部又は全部がアルミニウムアルコキシド又は元素Ａ及
びＡｌの複合及び／又は混合アルコキシドの分解生成物
である特許請求の範囲ｌ。6. Composition formula A+-*CJJ1+g-zCzBxAl12
- Part or all of Al or element A and Al in the composition represented by < is a decomposition product of aluminum alkoxide or a composite and/or mixed alkoxide of element A and Al.
２．３．４又は５記載の耐熱性触媒。The heat-resistant catalyst according to 2.3.4 or 5.
７、組成式Ａ＋−Ｃ，Ｂ、Ａｌ＋ｚ−ｙｏ＋ｑ−〆で表
わされる組成物中のＡｌ又は元素Ａ及びＡ１の一部又は
全部がアルミニウムアルコキシド又は元素Ａ及びＡｌの
複合及び／又は混合アルコキシドである特許請求の範囲
１，２．３．４゜５又は６記載の耐熱性触媒。7. Part or all of Al or elements A and A1 in the composition represented by the composition formula A+-C, B, Al+z-yo+q- is aluminum alkoxide or a composite and/or mixed alkoxide of elements A and Al. The heat-resistant catalyst according to claim 1, 2.3.4.5 or 6.
８、 アルコキシドが炭素数１〜４のアルコキシドであ
る特許請求の範囲１，２，３，４゜５．６又は７記載の
耐熱性触媒。8. The heat-resistant catalyst according to claim 1, 2, 3, 4°5.6 or 7, wherein the alkoxide is an alkoxide having 1 to 4 carbon atoms.
９、組成式Ａ＋−ＣｓＢ、ｔＡ１＋ｇ−ｚＣｚＢｘＡｌ
１２−一で表わされる組成物の一部又は全部を活性元素
Ｂを結晶格子内に取り込んだ層状アルミネート構造の結
晶として有する特許請求の範囲１゜２．３，４，５，６
．７又は８記載の耐熱性触媒。9. Composition formula A+-CsB, tA1+g-zCzBxAl
Claims 1゜2.3, 4, 5, 6 having part or all of the composition represented by 12-1 as a crystal with a layered aluminate structure in which active element B is incorporated into the crystal lattice.
．． 8. The heat-resistant catalyst according to 7 or 8.
１０、耐熱性触媒が触媒燃焼用触媒である特許請求の範
囲１，２，３，４，５，６，７゜８又は９記、載の耐熱
性触媒。10. The heat-resistant catalyst according to claim 1, 2, 3, 4, 5, 6, 7.8 or 9, wherein the heat-resistant catalyst is a catalyst for catalytic combustion.
１１、耐熱性触媒が約１０００°Ｃ以上の温度の触媒燃
焼用触媒である特許請求の範囲ＩＯ記載の耐熱性触媒。11. The heat-resistant catalyst according to claim IO, wherein the heat-resistant catalyst is a catalyst for catalytic combustion at a temperature of about 1000°C or higher.
１２、 水溶性又はアルコール可溶性のアルミニウム化
合物と、Ｃａ、 Ｂａ及びＳｒより成る群から選択した
少なくとも１種の元素Ａの水溶性又はアルコール可溶性
化合物と、希土類元素の中から選択した１種以上の元素
より成る元素Ｃの水溶性又はアルコール可溶性化合物と
、Ｍｎ、 Ｃｏ、 Ｆｅ、 Ｎｉ、 Ｃｕ及びＣｒより
成る群から選択した少な（とも１種の元素Ｂの水溶性又
はアルコール可溶性化合物とを（肛Ａｌ） ： （Ａ＋
Ｃ） ： Ｂ１旦の原子比１００：（７〜１０）：０
．８〜３３．３）： （０〜４）の割合で混合した溶液
からの沈殿物又は加水分解生成物及び／又は熱分解生成
物を、約９００°Ｃ以上の温度で焼成することを特徴と
する耐熱性触媒の製造法。12. A water-soluble or alcohol-soluble aluminum compound, a water-soluble or alcohol-soluble compound of at least one element A selected from the group consisting of Ca, Ba, and Sr, and one or more elements selected from rare earth elements. A water-soluble or alcohol-soluble compound of element C consisting of ) : (A+
C): Atomic ratio of B1: 100:(7-10):0
．． 8-33.3): characterized by calcining the precipitate or hydrolysis product and/or pyrolysis product from the solution mixed in the ratio of (0-4) at a temperature of about 900 ° C or more A method for producing a heat-resistant catalyst.
１３、アルミニウムアルコキシドと元素Ａのアルコキシ
ドとの複合及び／又は混合アルコキシドを、元素Ｃ及び
元素Ｂの化合物の水溶液を用いて加水分解して加水分解
生成物を得る特許請求の範囲１２記載の耐熱性触媒の製
造法。13. Heat resistance according to claim 12, in which a composite and/or mixed alkoxide of aluminum alkoxide and an alkoxide of element A is hydrolyzed using an aqueous solution of a compound of element C and element B to obtain a hydrolysis product. Catalyst manufacturing method.
１４、複合及び／又は混合アルコキシドが炭素数１〜４
のアルコキシドである特許請求の範囲１２又は１３記載
の耐熱性触媒の製造法。14, composite and/or mixed alkoxide has 1 to 4 carbon atoms
14. The method for producing a heat-resistant catalyst according to claim 12 or 13, which is an alkoxide of.
１５、アルコキシド全景を加水分解するのに必 −要
な水の当量の約０．５倍以上の水を加水分解に使用する
特許請求の範囲１２．１３又は１４記載の耐熱性触媒の
製造法。15. The method for producing a heat-resistant catalyst according to claim 12.13 or 14, wherein approximately 0.5 times or more of the equivalent amount of water required to hydrolyze the entire alkoxide is used for hydrolysis.
１６、加水分解を約５０〜１００ ℃の範囲の温度で行
なう特許請求の範囲１２．１３．１４又は１５記載の耐
熱性触媒の製造法。16. A process for producing a heat-resistant catalyst according to claim 12.13.14 or 15, wherein the hydrolysis is carried out at a temperature in the range of about 50 to 100°C.
１７、加水分解の為の水の添加後に約１時間以上の熟成
を行なう特許請求の範囲１２．１３゜１４、１５又は１
６記載の耐熱性触媒の製造法。17. Claim 12.13゜14, 15 or 1 in which aging is carried out for about 1 hour or more after addition of water for hydrolysis.
6. The method for producing a heat-resistant catalyst according to 6.
１８、元素ＡがＳｒ、元素ＣがＬａ及び／又はＣｅ、元
素ＢがＭｎ及び／又はＣｏである特許請求の範囲１２．
１３．１４．１５．１６又は１７記載の耐熱性触媒の製
造法。」
２、明細書第１０頁第１０行の「望ましい。」と「活性
成分」との間に「従って、好ましいＣ： （Ａ＋Ｃ）
の原子比ｚ ： （（１−ｚ）＋ｚ ）の値は（０〜
０．４）：１である。一方、（＾十〇）： （Ｂ＋Ａｆ
）の好ましい原子比は（７〜１０） ： １００である
ので、好ましいＣ： （Ａ＋Ｃ）： （Ｂ＋Ａｊ２）の
原子比は（０〜４）＝（７〜１０） ： １００となる
。」を挿入する。18. Claim 12. Element A is Sr, element C is La and/or Ce, and element B is Mn and/or Co.
13.14.15. The method for producing a heat-resistant catalyst according to 16 or 17. ” 2. On page 10, line 10 of the specification, between “desirable” and “active ingredient,” “Therefore, preferred C: (A+C)
The value of the atomic ratio z: ((1-z)+z) is (0~
0.4):1. On the other hand, (^10): (B+Af
) is (7-10):100, so the preferred atomic ratio of C:(A+C):(B+Aj2) is (0-4)=(7-10):100. ” is inserted.
３、同第１１頁第４〜５行間に「＾＋−、Ｃ，Ｂ、Ａｌ
＋ｚ−ｚＣｚＢｘＡｌ１２−イ組成物が希望するような
りａＯ・６＾２□０．類似構造をとる場合、Ｂ原子はＢ
ａＯ・６Ａ ｆｉ ２０．の結晶格子中のＡｆ原子と置
換していると考えられるので、ｙはＸに近い値となる。3. Between the 4th and 5th lines of page 11, “^+-, C, B, Al
+z-zCzBxAl12-i composition as desired aO.6^2□0. When a similar structure is taken, the B atom is B
aO・6A fi 20. It is thought that the Af atoms in the crystal lattice are substituted, so y has a value close to X.
従って、ｙ・にとすると、好ましいＢＳＣＢ＋八ｌ）の
へ子比Ｘ： （（１＋（１２−ｙ））は（０，１〜４）
：１２、即ち（０，８〜３３．３ ）：１００となる。Therefore, if it is y, then the preferred BSCB+8l) heel ratio X: ((1+(12-y)) is (0,1~4)
:12, that is, (0,8-33.3):100.
」を挿入する。” is inserted.
４、同第１５頁第１１〜１２行の’Ａｌ：Ｂａ＋Ｌａ：
Ｍｎ 」をｒ （Ｍｎ＋＾１）： （Ｂａ＋Ｌａ） ：
Ｍｎ：Ｌａ Ｊと訂正し、同頁第１３行のｒ：（０，１
〜４）」をｒ ： （０，８〜３３．３） ； （０〜
４）」と訂正する。4, 'Al:Ba+La:' on page 15, lines 11-12:
Mn' to r (Mn+^1): (Ba+La):
Corrected Mn: La J, and changed r: (0, 1) in line 13 of the same page.
~4)'' r: (0,8~33.3); (0~
4)” is corrected.
５、同第１８頁第１３〜１５行の「、それぞれの中に含
まれるＡｌ：Ｂａ原子比で１００ニアの割合で存在する
よう」を削除し、
同頁第１６〜１７行の「マンガン：Ａｌ原子比で１〜２
：１００となるような割合の」を削除する。5. Delete "Manganese: so that the atomic ratio of Al:Ba contained in each of them is 100 nia" from lines 13 to 15 on page 18, and replace "Manganese: Al atomic ratio 1-2
:Delete "of the proportion such that it becomes 100."
６、同第１９頁第１行冒頭の「２０」を「解生」と訂正
し、
同頁第４行の「ある。」の後に「この場合、各原料は原
料中のアルミニウム、マンガン、ランタン、バリウムが
原子比として計算して、（Ｍｎ＋八ｌへ： （Ｂａ＋
Ｌａ）：Ｍｎ：Ｌａ＝１００：（７〜１０）： （０
，８〜３３．３）： （０〜４）の範囲内にあるような
量で使用する。」を加入・する。6. On page 19, the number 20 at the beginning of the first line was corrected to read ``Kasei.'' On the fourth line of the same page, after ``Aru.'', it became ``In this case, each raw material is aluminum, manganese, and lanthanum in the raw materials.'' , barium is calculated as an atomic ratio to (Mn+8l: (Ba+
La):Mn:La=100:(7-10):(0
, 8-33.3): Used in an amount within the range of (0-4). ”.
手 続 補 正 書
昭和６３年 ８月 １日
特許庁長官 吉 １） 文 毅 殿１、
事件の表示
昭和６３年特許願第３５３２５号
２、発明の名称
耐熱性触媒並びにその製造法
３、補正をする者
事件との関係 特許出願人
名称 東洋シーシーアイ株式会社
４、代理人
（１）昭和６３年７月４日付は差出しの手続補正書第７
頁第１４行のｒ （１＋ （１２−ｙ） Ｊをｒ ｘ
＋ （１２−Ｙ）Ｊと訂正する。Procedural amendment August 1, 1986 Director General of the Patent Office Yoshi 1) Moon Yi 1,
Display of the case Patent Application No. 35325 of 1988 2, Name of the invention Heat-resistant catalyst and its manufacturing method 3, Person making the amendment Relationship to the case Patent applicant name Toyo CCI Corporation 4, Agent (1) 1988 July 4, 2017 is the 7th amendment to the submission procedure.
Page 14th line r (1+ (12-y) J to r x
+ Correct it as (12-Y)J.
Claims (1)
−＿ｙＯ＿１＿９＿−＿ｄ（式中、ＡはＣａ、Ｂａ及び
Ｓｒより成る群から選択した１種以上の元素、Ｃは希土
類元素の中から選択した１種以上の元素、ＢはＭｎ、Ｃ
ｏ、Ｆｅ、Ｎｉ、Ｃｕ及びＣｒより成る群から選択した
１種以上の元素、ｚは約０．４以下の数、ｘは約０．１
〜４の範囲内の数、ｙはｘ〜２ｘの範囲内の数、αは元
素Ａ、Ｃ及びＢの夫々の価数Ｘ、Ｙ及びＺ及びｘ、ｙ及
びｚの数によって定まり、 α＝１−１／２｛Ｘ−ｚ（Ｘ−Ｙ）＋ｘＺ−３ｙ｝で表
わされる数を示す）で表わされる組成物を主成分とする
ことを特徴とする耐熱性触媒。 ２、Ｐｔ、Ｒｕ、Ｒｈ、Ｐｄ等の白金族貴金属を耐熱性
触媒上に担持して成る特許請求の範囲１記載の耐熱性触
媒。 ３、耐熱性触媒中の元素ＡとＣの合計の元素ＢとＡｌの
合計に対する原子比が約７〜１０：１００の範囲にある
特許請求の範囲１又は２記載の耐熱性触媒。 ４、元素ＡがＳｒ、元素ＣがＬａ及び／又はＣｅ、元素
ＢがＭｎ及び／又はＣｏである特許請求の範囲１、２又
は３記載の耐熱性触媒。 ５、ｘが約０．２〜３の範囲の数である特許請求の範囲
１、２、３又は４記載の耐熱性触媒。 ６、組成式Ａ＿１＿−＿ｚＣ＿ｚＢ＿ｘＡｌ＿１＿２＿
−＿ｙＯ＿１＿９＿−＿ｄで表わされる組成物中のＡｌ
又は元素Ａ及びＡｌの一部又は全部がアルミニウムアル
コキシド又は元素Ａ及びＡｌの複合及び／又は混合アル
コキシドの分解生成物である特許請求の範囲１、２、３
、４又は５記載の耐熱性触媒。 ７、組成式Ａ＿１＿−＿ｚＣ＿ｚＢ＿ｘＡｌ＿１＿２＿
−＿ｙＯ＿１＿９＿−＿ｄで表わされる組成物中のＡｌ
又は元素Ａ及びＡｌの一部又は全部がアルミニウムアル
コキシド又は元素Ａ及びＡｌの複合及び／又は混合アル
コキシドの加水分解生成物及び／又は熱分解生成物であ
る特許請求の範囲１、２、３、４、５又は６記載の耐熱
性触媒。 ８、アルコキシドが炭素数１〜４のアルコキシドである
特許請求の範囲１、２、３、４、５、６又は７記載の耐
熱性触媒。 ９、組成式Ａ＿１＿−＿ｚＣ＿ｚＢ＿ｘＡｌ＿１＿２＿
−＿ｙＯ＿１＿９＿−＿ｄで表わされる組成物の一部又
は全部を活性元素Ｂを結晶格子内に取り込んだ層状アル
ミネート構造の結晶として有する特許請求の範囲１、２
、３、４、５、６、７又は８記載の耐熱性触媒。 １０、耐熱性触媒が触媒燃焼用触媒である特許請求の範
囲１、２、３、４、５、６、７、８又は９記載の耐熱性
触媒。 １１、耐熱性触媒が約１０００℃以上の温度の触媒燃焼
用触媒である特許請求の範囲１０記載の耐熱性触媒。 １２、水溶性又はアルコール可溶性のアルミニウム化合
物と、Ｃａ、Ｂａ及びＳｒより成る群から選択した少な
くとも１種の元素Ａの水溶性又はアルコール可溶性化合
物と、希土類元素の中から選択した１種以上の元素より
成る元素Ｃの水溶性又はアルコール可溶性化合物と、Ｍ
ｎ、Ｃｏ、Ｆｅ、Ｎｉ、Ｃｕ及びＣｒより成る群から選
択した少なくとも１種の元素Ｂの水溶性又はアルコール
可溶性化合物とを、Ａｌ：（Ａ＋Ｃ）：Ｂの原子比１０
０：（７〜１０）：（０．１〜４）の割合で混合した溶
液からの沈殿物又は加水分解生成物及び／又は熱分解生
成物を、約９００℃以上の温度で焼成することを特徴と
する耐熱性触媒の製造法。 １３、アルミニウムアルコキシドと元素Ａのアルコキシ
ドとの複合及び／又は混合アルコキシドを、元素Ｃ及び
元素Ｂの化合物の水溶液を用いて加水分解して加水分解
生成物を得る特許請求の範囲１２記載の耐熱性触媒の製
造法。 １４、複合及び／又は混合アルコキシドが炭素数１〜４
のアルコキシドである特許請求の範囲１２又は１３記載
の耐熱性触媒の製造法。 １５、アルコキシド全量を加水分解するのに必要な水の
当量の約０．５倍以上の水を加水分解に使用する特許請
求の範囲１２、１３又は１４記載の耐熱性触媒の製造法
。 １６、加水分解を約５０〜１００℃の範囲の温度で行な
う特許請求の範囲１２、１３、１４又は１５記載の耐熱
性触媒の製造法。 １７、加水分解の為の水の添加後に約１時間以上の熟成
を行なう特許請求の範囲１２、１３、１４、１５又は１
６記載の耐熱性触媒の製造法。 １８、元素ＡがＳｒ、元素ＣがＬａ及び／又はＣｅ、元
素ＢがＭｎ及び／又はＣｏである特許請求の範囲１２、
１３、１４、１５、１６又は１７記載の耐熱性触媒の製
造法。[Claims] 1. Composition formula A_1_-_zC_zB_xAl_1_2_
-_yO_1_9_-_d (wherein A is one or more elements selected from the group consisting of Ca, Ba and Sr, C is one or more elements selected from rare earth elements, B is Mn, C
o, one or more elements selected from the group consisting of Fe, Ni, Cu and Cr, z is a number of about 0.4 or less, x is about 0.1
a number within the range of ~4, y is a number within the range of x ~ 2x, α is determined by the valences X, Y, and Z of the elements A, C, and B, and the numbers of x, y, and z, α= A heat-resistant catalyst characterized in that the main component is a composition represented by 1-1/2 {X-z(X-Y)+xZ-3y}. 2. The heat-resistant catalyst according to claim 1, comprising a platinum group noble metal such as Pt, Ru, Rh, Pd, etc. supported on a heat-resistant catalyst. 3. The heat-resistant catalyst according to claim 1 or 2, wherein the atomic ratio of the sum of elements A and C to the sum of elements B and Al in the heat-resistant catalyst is in the range of about 7 to 10:100. 4. The heat-resistant catalyst according to claim 1, 2 or 3, wherein element A is Sr, element C is La and/or Ce, and element B is Mn and/or Co. 5. The heat resistant catalyst of claim 1, 2, 3 or 4, wherein x is a number in the range of about 0.2 to 3. 6. Compositional formula A_1_-_zC_zB_xAl_1_2_
Al in the composition represented by -_yO_1_9_-_d
or Claims 1, 2, 3, in which part or all of element A and Al is a decomposition product of aluminum alkoxide or a composite and/or mixed alkoxide of element A and Al.
, 4 or 5. The heat-resistant catalyst according to . 7. Composition formula A_1_-_zC_zB_xAl_1_2_
Al in the composition represented by -_yO_1_9_-_d
or Claims 1, 2, 3, 4, in which part or all of element A and Al is a hydrolysis product and/or thermal decomposition product of aluminum alkoxide or a composite and/or mixed alkoxide of element A and Al. , 5 or 6. 8. The heat-resistant catalyst according to claim 1, 2, 3, 4, 5, 6 or 7, wherein the alkoxide is an alkoxide having 1 to 4 carbon atoms. 9. Composition formula A_1_-_zC_zB_xAl_1_2_
Claims 1 and 2 in which a part or all of the composition represented by -_yO_1_9_-_d is a crystal with a layered aluminate structure in which active element B is incorporated into the crystal lattice.
, 3, 4, 5, 6, 7 or 8. 10. The heat-resistant catalyst according to claim 1, 2, 3, 4, 5, 6, 7, 8 or 9, wherein the heat-resistant catalyst is a catalyst for catalytic combustion. 11. The heat-resistant catalyst according to claim 10, wherein the heat-resistant catalyst is a catalyst for catalytic combustion at a temperature of about 1000° C. or higher. 12. A water-soluble or alcohol-soluble aluminum compound, a water-soluble or alcohol-soluble compound of at least one element A selected from the group consisting of Ca, Ba, and Sr, and one or more elements selected from rare earth elements. a water-soluble or alcohol-soluble compound of element C consisting of;
and a water-soluble or alcohol-soluble compound of at least one element B selected from the group consisting of Co, Fe, Ni, Cu, and Cr in an atomic ratio of Al:(A+C):B of 10.
Calcining the precipitate or hydrolysis product and/or pyrolysis product from the solution mixed in the ratio of 0: (7 to 10): (0.1 to 4) at a temperature of about 900 ° C. or higher. A method for producing characteristically heat-resistant catalysts. 13. Heat resistance according to claim 12, in which a composite and/or mixed alkoxide of aluminum alkoxide and an alkoxide of element A is hydrolyzed using an aqueous solution of a compound of element C and element B to obtain a hydrolysis product. Catalyst manufacturing method. 14, composite and/or mixed alkoxide has 1 to 4 carbon atoms
14. The method for producing a heat-resistant catalyst according to claim 12 or 13, which is an alkoxide of. 15. The method for producing a heat-resistant catalyst according to claim 12, 13 or 14, wherein water is used in the hydrolysis in an amount of about 0.5 times or more the equivalent amount of water required to hydrolyze the entire amount of alkoxide. 16. The method for producing a heat-resistant catalyst according to claim 12, 13, 14 or 15, wherein the hydrolysis is carried out at a temperature in the range of about 50 to 100°C. 17. Claims 12, 13, 14, 15, or 1, in which aging is performed for about 1 hour or more after adding water for hydrolysis.
6. The method for producing a heat-resistant catalyst according to 6. 18. Claim 12, wherein element A is Sr, element C is La and/or Ce, and element B is Mn and/or Co.
17. The method for producing a heat-resistant catalyst according to 13, 14, 15, 16 or 17.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63035325A JPH01210031A (en) | 1988-02-19 | 1988-02-19 | Heat-resistant catalyst and its preparation |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63035325A JPH01210031A (en) | 1988-02-19 | 1988-02-19 | Heat-resistant catalyst and its preparation |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH01210031A true JPH01210031A (en) | 1989-08-23 |
Family
ID=12438666
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP63035325A Pending JPH01210031A (en) | 1988-02-19 | 1988-02-19 | Heat-resistant catalyst and its preparation |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH01210031A (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH04161253A (en) * | 1990-10-25 | 1992-06-04 | Osaka Gas Co Ltd | Composite catalyst for high temperature combustion |
| JP2006239650A (en) * | 2005-03-07 | 2006-09-14 | Denki Kagaku Kogyo Kk | Catalyst carrier and its production method |
| US7442669B2 (en) * | 2002-03-05 | 2008-10-28 | Tda Research, Inc. | Oxidation catalysts comprising metal exchanged hexaaluminate wherein the metal is Sr, Pd, La, and/or Mn |
| DE19707275B4 (en) * | 1996-04-05 | 2011-04-28 | Daihatsu Motor Co., Ltd., Ikeda | Exhaust gas purifying catalyst |
-
1988
- 1988-02-19 JP JP63035325A patent/JPH01210031A/en active Pending
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH04161253A (en) * | 1990-10-25 | 1992-06-04 | Osaka Gas Co Ltd | Composite catalyst for high temperature combustion |
| DE19707275B4 (en) * | 1996-04-05 | 2011-04-28 | Daihatsu Motor Co., Ltd., Ikeda | Exhaust gas purifying catalyst |
| US7442669B2 (en) * | 2002-03-05 | 2008-10-28 | Tda Research, Inc. | Oxidation catalysts comprising metal exchanged hexaaluminate wherein the metal is Sr, Pd, La, and/or Mn |
| JP2006239650A (en) * | 2005-03-07 | 2006-09-14 | Denki Kagaku Kogyo Kk | Catalyst carrier and its production method |
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