JPS6138626A - Carrier for catalyst - Google Patents
Carrier for catalystInfo
- Publication number
- JPS6138626A JPS6138626A JP59159981A JP15998184A JPS6138626A JP S6138626 A JPS6138626 A JP S6138626A JP 59159981 A JP59159981 A JP 59159981A JP 15998184 A JP15998184 A JP 15998184A JP S6138626 A JPS6138626 A JP S6138626A
- Authority
- JP
- Japan
- Prior art keywords
- carrier
- alumina
- neodymium
- praseodymium
- oxide
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000003054 catalyst Substances 0.000 title claims description 21
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 32
- 229910052779 Neodymium Inorganic materials 0.000 claims abstract description 15
- 239000000203 mixture Substances 0.000 claims abstract description 15
- QEFYFXOXNSNQGX-UHFFFAOYSA-N neodymium atom Chemical compound [Nd] QEFYFXOXNSNQGX-UHFFFAOYSA-N 0.000 claims abstract description 13
- 229910000873 Beta-alumina solid electrolyte Inorganic materials 0.000 claims abstract description 11
- PLDDOISOJJCEMH-UHFFFAOYSA-N neodymium(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Nd+3].[Nd+3] PLDDOISOJJCEMH-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000002131 composite material Substances 0.000 claims abstract description 10
- 229910052777 Praseodymium Inorganic materials 0.000 claims abstract description 8
- PUDIUYLPXJFUGB-UHFFFAOYSA-N praseodymium atom Chemical compound [Pr] PUDIUYLPXJFUGB-UHFFFAOYSA-N 0.000 claims abstract description 7
- MMKQUGHLEMYQSG-UHFFFAOYSA-N oxygen(2-);praseodymium(3+) Chemical compound [O-2].[O-2].[O-2].[Pr+3].[Pr+3] MMKQUGHLEMYQSG-UHFFFAOYSA-N 0.000 claims abstract description 6
- 229910003447 praseodymium oxide Inorganic materials 0.000 claims abstract description 6
- 238000000034 method Methods 0.000 abstract description 14
- 229910052782 aluminium Inorganic materials 0.000 abstract description 5
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 abstract description 5
- 230000003197 catalytic effect Effects 0.000 abstract description 5
- 238000010438 heat treatment Methods 0.000 abstract description 3
- 150000001213 Praseodymium Chemical class 0.000 abstract description 2
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 abstract description 2
- 238000001354 calcination Methods 0.000 abstract 2
- 150000001206 Neodymium Chemical class 0.000 abstract 1
- 229910052593 corundum Inorganic materials 0.000 abstract 1
- 229910003443 lutetium oxide Inorganic materials 0.000 abstract 1
- 239000002244 precipitate Substances 0.000 abstract 1
- 229910001845 yogo sapphire Inorganic materials 0.000 abstract 1
- 238000010304 firing Methods 0.000 description 9
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 8
- 239000000969 carrier Substances 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 7
- 239000000463 material Substances 0.000 description 6
- 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 5
- 230000007423 decrease Effects 0.000 description 5
- 229910052761 rare earth metal Inorganic materials 0.000 description 5
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 4
- 239000011248 coating agent Substances 0.000 description 4
- 238000000576 coating method Methods 0.000 description 4
- 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 4
- 230000000694 effects Effects 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 description 4
- 229910052863 mullite Inorganic materials 0.000 description 4
- 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 4
- 239000000843 powder Substances 0.000 description 4
- -1 rare earth salts Chemical class 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 239000000377 silicon dioxide Substances 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 238000002441 X-ray diffraction Methods 0.000 description 3
- 229910052804 chromium Inorganic materials 0.000 description 3
- 239000011651 chromium Substances 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 229910052878 cordierite Inorganic materials 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- JSKIRARMQDRGJZ-UHFFFAOYSA-N dimagnesium dioxido-bis[(1-oxido-3-oxo-2,4,6,8,9-pentaoxa-1,3-disila-5,7-dialuminabicyclo[3.3.1]nonan-7-yl)oxy]silane Chemical compound [Mg++].[Mg++].[O-][Si]([O-])(O[Al]1O[Al]2O[Si](=O)O[Si]([O-])(O1)O2)O[Al]1O[Al]2O[Si](=O)O[Si]([O-])(O1)O2 JSKIRARMQDRGJZ-UHFFFAOYSA-N 0.000 description 3
- 229910000510 noble metal Inorganic materials 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
- 238000000746 purification Methods 0.000 description 3
- 229910000505 Al2TiO5 Inorganic materials 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 229910052684 Cerium Inorganic materials 0.000 description 2
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 238000007084 catalytic combustion reaction Methods 0.000 description 2
- 150000003841 chloride salts Chemical class 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000012153 distilled water Substances 0.000 description 2
- 239000010439 graphite Substances 0.000 description 2
- 229910002804 graphite Inorganic materials 0.000 description 2
- 150000004679 hydroxides Chemical class 0.000 description 2
- 150000001247 metal acetylides Chemical class 0.000 description 2
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical compound O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- ZLGIGTLMMBTXIY-UHFFFAOYSA-K praseodymium(3+);trihydroxide Chemical compound [OH-].[OH-].[OH-].[Pr+3] ZLGIGTLMMBTXIY-UHFFFAOYSA-K 0.000 description 2
- 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 2
- 150000003839 salts Chemical class 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
- 238000005245 sintering Methods 0.000 description 2
- 238000000629 steam reforming Methods 0.000 description 2
- 150000003568 thioethers Chemical class 0.000 description 2
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 2
- 229910001887 tin oxide Inorganic materials 0.000 description 2
- 229910052721 tungsten Inorganic materials 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- 229910052692 Dysprosium Inorganic materials 0.000 description 1
- 229910052691 Erbium Inorganic materials 0.000 description 1
- 229910052693 Europium Inorganic materials 0.000 description 1
- 229910052688 Gadolinium Inorganic materials 0.000 description 1
- 229910052689 Holmium Inorganic materials 0.000 description 1
- 229910052765 Lutetium Inorganic materials 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- 241001201614 Prays Species 0.000 description 1
- 229910052581 Si3N4 Inorganic materials 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 229910052771 Terbium Inorganic materials 0.000 description 1
- 229910052769 Ytterbium Inorganic materials 0.000 description 1
- YKTSYUJCYHOUJP-UHFFFAOYSA-N [O--].[Al+3].[Al+3].[O-][Si]([O-])([O-])[O-] Chemical compound [O--].[Al+3].[Al+3].[O-][Si]([O-])([O-])[O-] YKTSYUJCYHOUJP-UHFFFAOYSA-N 0.000 description 1
- 150000001242 acetic acid derivatives Chemical class 0.000 description 1
- 239000004480 active ingredient Substances 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 229910000287 alkaline earth metal oxide Inorganic materials 0.000 description 1
- 150000004703 alkoxides Chemical class 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000010953 base metal Substances 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
- 239000011247 coating layer Substances 0.000 description 1
- 239000000571 coke Substances 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000010908 decantation Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000006356 dehydrogenation reaction Methods 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 239000011872 intimate mixture Substances 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000003350 kerosene Substances 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 229910052746 lanthanum Inorganic materials 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 238000002715 modification method Methods 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
- 229910052759 nickel Inorganic materials 0.000 description 1
- 150000002823 nitrates Chemical class 0.000 description 1
- 150000004767 nitrides Chemical class 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 150000003891 oxalate salts Chemical class 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000000634 powder X-ray diffraction Methods 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 150000002910 rare earth metals Chemical class 0.000 description 1
- 238000006722 reduction reaction Methods 0.000 description 1
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
Landscapes
- Compounds Of Alkaline-Earth Elements, Aluminum Or Rare-Earth Metals (AREA)
- Catalysts (AREA)
- Compositions Of Oxide Ceramics (AREA)
Abstract
Description
【発明の詳細な説明】
〔発明の利用分野〕
本発明は触媒用担体に係シ、特に高温においても安定し
て使用できる触媒用担体に関する。DETAILED DESCRIPTION OF THE INVENTION [Field of Application of the Invention] The present invention relates to a catalyst carrier, and particularly to a catalyst carrier that can be stably used even at high temperatures.
従来、触媒用担体としては活性アルミナ、チタニア、シ
リカ、シリカ・アルミナなどの物質が一般的に用いられ
ている。しかし、これらの担体に適当な触媒活性成分を
担持して触媒化したのち、高温で行われる反応、例えば
、炭化水素類や水素の接触燃焼反応、自動車の排ガス浄
化、高温水蒸気改質反応などに使用すると、主に担体の
熱劣化が原因で触媒性能が低下する欠点があった。一方
、比較。的耐熱性の良いα−アルミナ、ムライト、コ−
ジライト、シリコンカーバイドなどを材料とした担体は
一般に比表面積が小さく、高々１ｍ”／ｇ程度であるた
め、触媒活性成分、例えば貴金属を高分散担持すること
は困難で、その結果、活性の低い触媒しか得られないと
いう欠点があった。そのため最高９００Ｃ付近で使用さ
れる自動車排ガス浄化用触媒の例全とると、コージライ
ト、ムライト等のハニカム担体の表面を活性アルミナで
コーティングし、そのコーティング層に貴金属等を担持
して使用している。しかし、反応温度が１０００Ｃ以上
になる場合は、コーテイング材である活性アルミナの焼
結や結晶化あるいは相転移が進み、比表面積が減少する
。その結果、担体上の触媒活性成分の凝集が進み、性能
が低下する。Conventionally, materials such as activated alumina, titania, silica, and silica/alumina have been commonly used as catalyst carriers. However, after catalyzing appropriate catalytic active components on these carriers, reactions that take place at high temperatures, such as catalytic combustion reactions of hydrocarbons and hydrogen, automobile exhaust gas purification, and high-temperature steam reforming reactions, etc. When used, there was a drawback that catalyst performance deteriorated mainly due to thermal deterioration of the carrier. On the other hand, comparison. α-alumina, mullite, and coke with good heat resistance
Supports made of dirite, silicon carbide, etc. generally have a small specific surface area, about 1 m''/g at most, so it is difficult to support catalytically active components, such as noble metals, in a highly dispersed manner, and as a result, the catalyst has low activity. Therefore, in all examples of automobile exhaust gas purification catalysts used at temperatures around 900C, the surface of a honeycomb carrier such as cordierite or mullite is coated with activated alumina, and the coating layer is coated with activated alumina. It is used to support noble metals, etc. However, if the reaction temperature exceeds 1000C, sintering, crystallization, or phase transition of activated alumina, which is the coating material, progresses and the specific surface area decreases.As a result, Agglomeration of the catalytically active components on the carrier progresses, resulting in decreased performance.
このような活性アルミナの欠点を改良する方法として、
アルミナ粉末とマグネンア粉末との混合物を高温で焼成
したマグネシア・アルミナゾルを担体とする方法（特公
昭５７−３４１９）、アルミナにクロム、タングステン
、セリウム等を加えた担体（特開昭５Ｏ−９９（ｉ８Ｂ
）、アルミナに高級アルカリ土類と三酸化モリブデン、
ジルコニア。As a way to improve these drawbacks of activated alumina,
A method using magnesia/alumina sol prepared by firing a mixture of alumina powder and magnenia powder at high temperature as a carrier (Japanese Patent Publication No. 57-3419), a method using a carrier containing chromium, tungsten, cerium, etc. to alumina (Japanese Patent Publication No. 50-99 (i8B
), alumina with high alkaline earth and molybdenum trioxide,
Zirconia.
シリカ、酸化錫、ランタナとシリカ、ランタナと酸化錫
を加えた担体（特開昭５４−１１７３８７）などが知ら
れている。上記したアルミナの改質法はそれぞれ利点は
あるが、耐熱性の面で充分ではない。Known carriers include silica, tin oxide, lanthana and silica, and lanthana and tin oxide (Japanese Unexamined Patent Publication No. 117387/1987). Although each of the above alumina modification methods has advantages, they are not sufficient in terms of heat resistance.
本発明の目的は高温でも安定して使用できる触媒用担体
を提供するにある。An object of the present invention is to provide a catalyst carrier that can be used stably even at high temperatures.
一般に活性アルミナは高比表面積を有しカサ密度も低い
ため、触媒用担体や担体のコーテイング材として広く使
用されているが、高温ではδ−アルミナ、θ−アルミナ
等の遷移減アルミナを経て特に１０００〜１２００ｔ：
’においてはα−アルミナへ転移する。これに伴い比表
面積も大きく減少する。In general, activated alumina has a high specific surface area and a low bulk density, so it is widely used as a catalyst carrier or carrier coating material. ~1200t:
', it transforms to α-alumina. Along with this, the specific surface area also decreases significantly.
本発明者らはアルミナの上記の様な熱的不安定性を改良
するため種々検討した結果、本発明の触媒用担体に至っ
た。The present inventors conducted various studies to improve the above-mentioned thermal instability of alumina, and as a result, they arrived at the catalyst carrier of the present invention.
本発明の担体は、ネオジム（Ｎｄ）とプラセオジム（Ｐ
ｒ）から選ばれた少なくとも１つとアルミニウムとの複
合酸化物を主成分として含有し、該複合酸化物の少くと
も一部分はＬｎｚＯｓ ・１１〜１４ＡｔｚＯａ
（但しＬｎはＮｄとｐｒの少なくとも１つ、組成はモル
比）の組成を持ついわゆるβ−アルミナの形態を有して
いることを特徴とする。これらの希土類元素を含むβ−
アルミナはそれ自体が耐熱性が高く、比表面積が大きい
が、そのほかにこの化合物は遷移型アルミナからα−ア
ルミナへの相転移および結晶成長を抑制する効果のある
ことが詳細なＸ線回折、電子顕微鏡観察の結果から明ら
かになった。The carrier of the present invention comprises neodymium (Nd) and praseodymium (P).
contains as a main component a composite oxide of at least one selected from r) and aluminum, and at least a portion of the composite oxide is LnzOs 11-14AtzOa
(However, Ln is characterized by having a so-called β-alumina form having a composition of at least one of Nd and pr, the composition being a molar ratio). β- containing these rare earth elements
Alumina itself has high heat resistance and a large specific surface area, but detailed X-ray diffraction and electron This became clear from the results of microscopic observation.
担体中におけるこれらのβ−アルミナの含有量は１０重
量％以上であることが好ましく、それ以下では効果が充
分でなく、高温での比表面積の低下が大きい。The content of β-alumina in the carrier is preferably 10% by weight or more; if it is less than that, the effect is not sufficient and the specific surface area decreases significantly at high temperatures.
酸化ネオジムおよび／または酸化プラセオジムとアルミ
ナを含有する担体において、その組成比は酸化ネオジム
および／または酸化プラセオジムが２〜２０モル％、ア
ルミナが８０〜９８モル％の範囲であることが好ましい
。この範囲をはずれると高温での比表面積の低下が大き
い。In the carrier containing neodymium oxide and/or praseodymium oxide and alumina, the composition ratio thereof is preferably in the range of 2 to 20 mol% of neodymium oxide and/or praseodymium oxide and 80 to 98 mol% of alumina. Outside this range, the specific surface area decreases significantly at high temperatures.
さらに本発明になる触媒用担体のもう一つの特徴は、１
０００Ｃの温度において２時間の焼成徒歩くともａｏｍ
’／ｇ以上、特に１２００Ｃの温度において２時間の焼
成後、少くとも１０ｍ’／ｇ以上の比表面積を有するこ
とにある。このように高温においても高比表面積を有す
ることによシ、触媒活性成分を高分散に担持することが
でき、高活性な触媒を得ることが可能となる。Furthermore, another feature of the catalyst carrier of the present invention is 1.
Baking for 2 hours at a temperature of 000C
It is to have a specific surface area of at least 10 m'/g, especially at least 10 m'/g after firing for 2 hours at a temperature of 1200C. By having such a high specific surface area even at high temperatures, the catalytically active component can be supported in a highly dispersed manner, making it possible to obtain a highly active catalyst.
本発明の担体を製造する方法としては、通常の沈殿法、
沈着法、混線法、含浸法などが利用できるカ、酸化ネオ
ジムおよび／マタは酸化プラセオジムとアルミナの緊密
な混合物を調製しておくとβ−アルミナが生成し易く、
このことがら共沈法は特に好ましい方法である。−例を
挙げると、アルミニウム塩とネオジムおよび／またはプ
ラセオジム塩の混合水溶液に適当な沈殿剤を添加して緊
゛密な共沈物を生成させ、これを加熱焼成する方法でお
る。そのｔｌかにアルミナゾルとネオジムおよび／また
はプラセオジムの水酸化物を緊密に混練し、これを加熱
焼成する方法、アルミナ微粉末にこれら希土類塩の溶液
を含浸し、これを加熱焼成する方法、希土類塩の溶液中
にアルミナ微粉末を懸濁させたのち適当な沈殿剤を加え
て、ネオジムおよび／またはプラセオジムの水酸化物を
沈着させる方法など、多くの方法が可能である。The method for producing the carrier of the present invention includes a conventional precipitation method,
For neodymium oxide and/or praseodymium oxide, which can be used by the deposition method, cross-wire method, impregnation method, etc., β-alumina can be easily formed by preparing an intimate mixture of praseodymium oxide and alumina.
For this reason, the coprecipitation method is a particularly preferred method. - For example, a suitable precipitant is added to a mixed aqueous solution of aluminum salt and neodymium and/or praseodymium salt to form a tight coprecipitate, which is then heated and calcined. A method of closely kneading alumina sol and neodymium and/or praseodymium hydroxide and heating and firing the same, a method of impregnating fine alumina powder with a solution of these rare earth salts and heating and firing it, a rare earth salt Many methods are possible, including a method in which neodymium and/or praseodymium hydroxide is deposited by suspending fine alumina powder in a solution of alumina and then adding a suitable precipitating agent.
アルミニウム原料としては、硝酸塩、硫酸塩。Nitrate and sulfate are aluminum raw materials.
塩化物などの可溶性塩、アルコキシドなどの有機化合物
、水酸化物、酸化物などが使用できる。一方、ネオジム
およびプラセオジム原料としては、硝酸塩、塩化物、シ
ュウ酸塩、酢酸塩などの可溶性塩、炭識塩、水酸化物、
酸化物などが使用できる。ネオジムおよび／またはプラ
セオジムを含有している混合粘土や、希土類鉱物も使用
できる。Soluble salts such as chlorides, organic compounds such as alkoxides, hydroxides, oxides, etc. can be used. On the other hand, neodymium and praseodymium raw materials include soluble salts such as nitrates, chlorides, oxalates, acetates, carbonates, hydroxides,
Oxides etc. can be used. Mixed clays containing neodymium and/or praseodymium and rare earth minerals can also be used.
本発明になる担体は主成分としてネオジムおよび／また
はプラセオジムとアルミニウムとの複合酸化物を含有し
ているが、これら成分の含有量の合計が担体全重量の５
０重量％以上であることが望ましい。ただし本発明にな
る担体をハニカム担体などのコーテイング材として使用
する場合には、コーテイング材中の含有量が５０重量％
以上であれば良く、ハニカム基材も含んだ全体の担体中
の含有量は５０％未満であっても良い。本発明になる触
媒用担体の主成分以外に含有しても良い成分の例として
はＩム族のＬｊ、Ｎａ、に、ＩＩム族のＢ ｅ＋＋Ｍ＆
ｔ、Ｃ＋ａ、Ｓ ｒ 、 Ｂ ａ ％ ＩＶＡ族のＳｉ
、（）ｅ。The carrier of the present invention contains a composite oxide of neodymium and/or praseodymium and aluminum as a main component, and the total content of these components is 5% of the total weight of the carrier.
It is desirable that the amount is 0% by weight or more. However, when the carrier according to the present invention is used as a coating material such as a honeycomb carrier, the content in the coating material is 50% by weight.
The content in the entire carrier including the honeycomb base material may be less than 50%. Examples of components that may be contained in addition to the main components of the catalyst carrier of the present invention include Lj, Na, of the I-Mu group, Be++M& of the II-Mu group, etc.
t, C+a, S r , B a % IVA group Si
, ()e.
Ｓｎ、 Ｉｂ族のＣｕ、Ａｇ、ＩＩｂ族のＺｎ、ｌｌ
ｂ族（ＤＳＣ，Ｙ％ ■ｂ族ＯＴ ｉ、 ＺｒＸＶｂ族
＋７）Ｖ。Sn, Cu of group Ib, Ag, Zn of group IIb, ll
Group b (DSC, Y% ■ Group b OT i, ZrXV group +7)V.
Ｎｂ、’ｒａ、Ｖｌｂ族のＣｒ、ＭＯ，Ｗ、■ｂ族のＭ
ｎ％■ｂ族のＦｅ、Ｃ０１Ｎｉなどのうちから選ばれた
１種以上の酸化物、炭化物、硫化物、窒化物などが挙げ
られる。もちろんこれらの成分から成る複合酸化物、た
とえば、コージライト、ムライト、スボジュメン、チタ
ン酸アルミニウム。Nb, 'ra, Cr of Vlb group, MO, W, M of ■b group
Examples include one or more oxides, carbides, sulfides, and nitrides selected from n%■b group Fe, CO1Ni, and the like. Of course, there are complex oxides made of these components, such as cordierite, mullite, subodumene, and aluminum titanate.
アルミニウムシリケートなどから選ばれた１種以上を含
むことも可能である。また、Ｎｄ、Ｐｒ以外の希土類元
素、すなわち、Ｃｅ、Ｌａ、Ｐｍｐ８ｍ、Ｅｕ、Ｇｄ、
Ｔｂ、Ｄｙ、Ｈｏ、Ｅｒ。It is also possible to include one or more selected from aluminum silicate and the like. In addition, rare earth elements other than Nd and Pr, such as Ce, La, Pmp8m, Eu, Gd,
Tb, Dy, Ho, Er.
’Ｉ’ｍ、Ｙｂ、Ｌｕの１種以上の酸化物を含むことも
もちろん可能である。Of course, it is also possible to include one or more oxides of 'I'm, Yb, and Lu.
本発明になる担体は通常、種々の形状、例えば球状２円
柱状、リング状、ハニカム状などに成型して使用される
。あるいは種々のの形状に成型された担体、例えば、ム
ライト、コージライト、α−アルミナ、ジルコニア、チ
タン酸アルミニウム炭化珪素、窒化珪素などのハニカム
状担体の表面に本発明になる担体組成物をコーティング
して１更用することもできる。The carrier according to the present invention is usually used after being molded into various shapes, such as spherical, bicylindrical, ring, and honeycomb shapes. Alternatively, the carrier composition of the present invention may be coated on the surface of a carrier formed into various shapes, such as a honeycomb carrier such as mullite, cordierite, α-alumina, zirconia, aluminum titanate silicon carbide, or silicon nitride. It can also be used again.
本発明になる担体の焼成は８００Ｃ以上、好ましくは１
ｏｏｏｃ以上；１５００Ｃ未満で行われる。焼成温度が
５ｏｏｃ未満では、β−アルミナ構造が充分に形成され
ず、アルミナのみの担体と比較して効果が顕著でない。The carrier of the present invention is fired at 800C or higher, preferably at 1
oooc or more; carried out at less than 1500C. If the firing temperature is less than 5ooc, the β-alumina structure will not be sufficiently formed, and the effect will not be as remarkable as compared to a support made only of alumina.
ただし、焼成温度が８００Ｃ未満でも、使用温度が５ｏ
ｏｃ以上にな。However, even if the firing temperature is less than 800C, the operating temperature is 5o
More than oc.
る場合には使用中にβ−アルミナ構造が形成されるので
差しつかえない。焼成温度が１５００Ｃ以上（なると焼
結が進み、比表面積も大きく低下するので好ましくない
。This is not a problem if a β-alumina structure is formed during use. If the firing temperature is 1500C or higher, sintering progresses and the specific surface area decreases significantly, which is not preferable.
本発明になる担体を触媒化する場合の活性成分としては
、ｐｔ、ｐｄ、）ｌ、ｈなどの貴金属、Ｆｅ。Active components for catalyzing the support of the present invention include noble metals such as pt, pd, )l, and h, and Fe.
ＣＯ，Ｎｉ、Ｃｕ、Ｃｒ、Ｍｒ、Ｖ、Ｍｏ、Ｗ。CO, Ni, Cu, Cr, Mr, V, Mo, W.
ｆ３ｎなどの卑金属、あるいはこれらの酸化物、硫化物
、炭化物などが使用でき特に限定されない。Base metals such as f3n, or their oxides, sulfides, carbides, etc. can be used without any particular limitation.
活性成分はその対象とする反応に対し最適なものを選ぶ
ことができる。The active ingredient can be selected to be optimal for the target reaction.
本発明になる担体を用いた触媒は高温下で行われる反応
、特に８０００以上で行われる反応に効果がある。反応
の種類は特に限定されないが、例を挙げれば、ＬＮＧ、
ＬＰＧ、Ｃｏ；Ｈｚ 、灯油などの燃料の接触燃焼反応
、内燃機関の排ガス浄化、悪臭除去、通常の化学プラン
トで用いる酸化反応、還元反応、脱水素反応、水添反応
、水蒸気改質反応などがある。The catalyst using the carrier according to the present invention is effective in reactions carried out at high temperatures, especially reactions carried out at temperatures of 8,000 or higher. The type of reaction is not particularly limited, but examples include LNG,
Catalytic combustion reactions of fuels such as LPG, Co; Hz, kerosene, exhaust gas purification of internal combustion engines, odor removal, oxidation reactions, reduction reactions, dehydrogenation reactions, hydrogenation reactions, steam reforming reactions used in ordinary chemical plants, etc. be.
以下、実施例によυ本発明の内容をよシ具体的に説明す
るが、本発明は本実施例に同等限定されるものではない
。Hereinafter, the content of the present invention will be explained in more detail with reference to Examples, but the present invention is not limited to the Examples.
実施例１
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、５００Ｃで２
時間焼成した後、グラファイトを０．５重量％加え、プ
レス成型機を用いて直径３闘、厚さ３調の円柱状（成型
した。この担体（Ａ）の組成はＮｄ２０３５モル％、Ａ
ｔ２０３９５モル％である。この担体を】２００Ｃ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。その結果を表１に示す。Example 1 500 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 the solution 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 and heat at 500C for 2
After firing for an hour, 0.5% by weight of graphite was added and molded into a cylindrical shape with a diameter of 3mm and thickness of 3mm using a press molding machine.The composition of this carrier (A) was 2035 mol% of Nd, A
t20395 mol%. This carrier] at 200C
B, E, and T are baked for a time and the specific surface area is determined by N2 gas adsorption.
, measured by the method. Further, the crystal structure of the carrier was investigated by powder X-ray diffraction method. The results are shown in Table 1.
比較例１
実施例１において硝酸ネオジムを添加しないほかは実施
例１と同様に調製し、アルミナのみから成る比較例担体
１を得た。比表面積及びＸ線回折結果を表１に示す。Comparative Example 1 Comparative example carrier 1 consisting only of alumina was prepared in the same manner as in Example 1 except that neodymium nitrate was not added. Table 1 shows the specific surface area and X-ray diffraction results.
表１から明らかなように比較例担体１では、１２００１
：：焼成ではα−アルミナの結晶構造を有しておシ、比
表面積も小さい。これに対してネオジムを添加した実施
例担体（Ａ）では、ネオジムβ−アルミナが生成してお
シ、比表面積も大きい。As is clear from Table 1, in Comparative Example Carrier 1, 12001
:: When fired, it has an α-alumina crystal structure and has a small specific surface area. On the other hand, in the example carrier (A) to which neodymium was added, neodymium β-alumina was produced and the specific surface area was large.
実施例２
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１と同様にして調製し、担体（Ｂ）。Example 2 A carrier (B) was prepared in the same manner as in Example 1 except that the ratio of aluminum nitrate and neodymium nitrate was changed.
（Ｃ）、 （Ｄ）を得た。得られた担体はそれぞれ次の
組成を有する。（Ｂ ） ： ＮｄｚＯｓ ２モル％。(C) and (D) were obtained. The obtained carriers each have the following composition. (B): 2 mol% of NdzOs.
ｋｔ２０ｇ ９８モル％、（Ｃ） ： Ｎｄ２Ｏ３１０
モル％、 ｋｔｚＯｓ ９０モル％、（Ｄ） ：Ｎｄ
ｇＯｓ ２０モル％、 ＡＬｚ Ｏｓ ８０モル％。こ
れらの担体の比表面積及び生成物の形態を実施例１と同
様な方法で測定した。結果を表１に示す。kt20g 98mol%, (C): Nd2O310
Mol%, ktzOs 90mol%, (D): Nd
gOs 20 mol%, ALzOs 80 mol%. The specific surface area of these carriers and the morphology of the products were measured in the same manner as in Example 1. The results are shown in Table 1.
実施例３
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１と同様の方法で調製し、Ｐｒ２
Ｏ３５モル％、 ＡｔｚＯｓ ９５モ＃％から成る担体
（Ｅ）を得た。比表面積の測定結果及びＸ線回折の結果
を表２に示す。Example 3 500 g of aluminum nitrate and 30.5 g of praseodymium nitrate
Using Pr2g as a raw material, prepared in the same manner as in Example 1, Pr2
A carrier (E) consisting of 35 mol% O and 95 mol% AtzOs was obtained. Table 2 shows the measurement results of specific surface area and the results of X-ray diffraction.
実施例４
硝酸アルミニウムと硝酸プラセオジムの割合を変えた以
外は実施例１と同様にして調製し、担体（Ｆ）、（Ｇ）
、（Ｈ） を得た。得られた担体はそれぞれ次の組成
を有する。（Ｆ ） ： Ｐｒａｙｓ ２モル％＊ Ａ
ｔ２０３９’８ モ／ｌｚ％、（Ｇ）：ＰｒｚＯｓ１０
モル％、 ＡＬｚＯｓ ９’０モル％、（Ｈ）：ｐ ｒ
２０３２０モル％＋ Ａｔ＊０３８０ 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表２
に示す。Example 4 Carriers (F) and (G) were prepared in the same manner as in Example 1 except that the ratio of aluminum nitrate and praseodymium nitrate was changed.
, (H) was obtained. The obtained carriers each have the following composition. (F): Prays 2 mol%*A
t2039'8 mo/lz%, (G): PrzOs10
Mol%, ALzOs 9'0 mol%, (H):pr
20320 mol% + At*0380 mol%. Table 2 shows the results of examining the specific surface area and product morphology of these carriers.
Shown below.
実施例５
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１８．５ ｇを原料とし実施例１と同
様の方法で、Ｎｄ２Ｏ３ ３モル％、Ｐｒｔ０３３モア
ｕ％、Ａｔ２０３９４モル％の割合で含む担体（Ｉ）を
調製した。この担体の比表面積は２＆Ｏｍ”７ｇ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。Example 5 Using 500 g of aluminum nitrate, 18.6 g of neodymium nitrate, and 18.5 g of praseodymium nitrate as raw materials, a carrier containing 3 mol% of Nd2O3, u% of Prt033, and 394 mol% of At20 was prepared in the same manner as in Example 1. I) was prepared. The specific surface area of this carrier was 2&Om"7g. 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 these results, these β Al
The carrier containing Mina has a high specific surface area even at high temperatures.
実施例６
アルミナゾル（アルミナ含有率９．８％）５００ｇと炭
酸ネオジム１２３ｇをライカイ機にて２時間混練した後
、１５０ｔ：’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、プレス成型機を用いて直径３ｗｔｇ
５厚さ３ｍｓ＋の円柱状に成型した。この担体の組成は
Ｎｄ１Ｏｓ ４モル％、ｋｔｔ ０３９６モル％である
。この担体を１ｏｏｏｃまたは１２０（ｌで２時間焼成
し、比表面積を測定したところ、それぞれ９６．５ｍ’
／ｇ、 ２１．６ｍ”７ｇであった。Example 6 500 g of alumina sol (alumina content 9.8%) and 123 g of neodymium carbonate were kneaded for 2 hours in a Laikai machine, and then dried at 150 t:' for 1 day and night. After grinding to 60 mesh or less and firing at 500C for 2 hours, 0.5% by weight of graphite was added, and a diameter of 3wtg was formed using a press molding machine.
5 It was molded into a cylindrical shape with a thickness of 3 ms+. The composition of this carrier is 4 mol% of Nd1Os and 0396 mol% of ktt. This carrier was calcined for 2 hours at 1oooc or 120 (l), and the specific surface area was measured to be 96.5 m', respectively.
/g, 21.6m"7g.
本発明による触媒用担体は高温においても安定に使用で
き、高温反応用触媒の担体として適している。The catalyst carrier according to the present invention can be used stably even at high temperatures, and is suitable as a catalyst carrier for high-temperature reactions.
Claims (1)
つとアルミニウムの複合酸化物を含み、該複合酸化物の
少くとも一部分はＬｎ＿２Ｏ＿３・１１〜１４Ａｌ＿２
Ｏ＿３（但しＬｎはネオジムとプラセオジムの少なくと
も１つ、組成はモル比）の組成を持つβ−アルミナの形
態を有していることを特徴とする触媒用担体。 ２、特許請求の範囲第１項において、前記複合酸化物の
組成比は、酸化ネオジムと酸化プラセオジムの少なくと
も１つが２〜２０モル％、アルミナが８０〜９８モル％
の範囲にあることを特徴とする触媒用担体。 ３、特許請求の範囲第１項において、前記複合酸化物は
１２００℃の温度において２時間の焼成後、少くとも１
０ｍ＾２／ｇ以上の比表面積を有していることを特徴と
する触媒用担体。 ４、特許請求の範囲第１項において、前記Ｌｎ＿２Ｏ＿
３・１１〜１４Ａｌ＿２Ｏ＿３の含有量が担体全重量の
１０重量％以上であることを特徴とする触媒用担体。 ５、特許請求の範囲第１項において、前記複合酸化物の
含有量が担体全重量の５０重量％以上であることを特徴
とする触媒用担体。[Claims] 1. At least one selected from neodymium and praseodymium
At least a portion of the composite oxide contains Ln_2O_3・11~14Al_2
A catalyst carrier characterized in that it has a form of β-alumina having a composition of O_3 (wherein Ln is at least one of neodymium and praseodymium, the composition is a molar ratio). 2. In claim 1, the composition ratio of the composite oxide is 2 to 20 mol% of at least one of neodymium oxide and praseodymium oxide, and 80 to 98 mol% of alumina.
A catalyst carrier characterized by being in the range of. 3. In claim 1, the composite oxide has at least 1
A catalyst carrier having a specific surface area of 0 m^2/g or more. 4. In claim 1, the Ln_2O_
3. A catalyst carrier characterized in that the content of 11-14Al_2O_3 is 10% by weight or more based on the total weight of the carrier. 5. The catalyst carrier according to claim 1, wherein the content of the composite oxide is 50% by weight or more based on the total weight of the carrier.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP59159981A JPS6138626A (en) | 1984-07-30 | 1984-07-30 | Carrier for catalyst |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP59159981A JPS6138626A (en) | 1984-07-30 | 1984-07-30 | Carrier for catalyst |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPS6138626A true JPS6138626A (en) | 1986-02-24 |
Family
ID=15705393
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP59159981A Pending JPS6138626A (en) | 1984-07-30 | 1984-07-30 | Carrier for catalyst |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS6138626A (en) |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| JPH04228422A (en) * | 1990-06-13 | 1992-08-18 | Rhone Poulenc Chim | Composition based on alumina used as catalyst, its manufacture, catalyst and manufacture of catalyst |
| WO2003057318A1 (en) * | 2002-01-14 | 2003-07-17 | K.U. Leuven Research And Development | Catalytic destruction of halogenated hydrocarbons |
| WO2013136821A1 (en) | 2012-03-14 | 2013-09-19 | エヌ・イーケムキャット株式会社 | Catalyst composition for exhaust gas cleaning and catalyst for automobile exhaust gas cleaning |
| WO2014002667A1 (en) | 2012-06-28 | 2014-01-03 | エヌ・イーケムキャット株式会社 | Catalyst composition for exhaust gas purification and exhaust gas purifying catalyst for automobiles |
| WO2018147408A1 (en) | 2017-02-13 | 2018-08-16 | エヌ・イーケムキャット株式会社 | Exhaust gas purifying catalyst composition, method for producing same and exhaust gas purifying catalyst for automobiles |
-
1984
- 1984-07-30 JP JP59159981A patent/JPS6138626A/en active Pending
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| JPH04228422A (en) * | 1990-06-13 | 1992-08-18 | Rhone Poulenc Chim | Composition based on alumina used as catalyst, its manufacture, catalyst and manufacture of catalyst |
| JPH0813685B2 (en) * | 1990-06-13 | 1996-02-14 | ローヌ−プーラン・シミ | Alumina-based composition used for catalyst, method for producing the same, catalyst and method for producing the catalyst |
| WO2003057318A1 (en) * | 2002-01-14 | 2003-07-17 | K.U. Leuven Research And Development | Catalytic destruction of halogenated hydrocarbons |
| WO2013136821A1 (en) | 2012-03-14 | 2013-09-19 | エヌ・イーケムキャット株式会社 | Catalyst composition for exhaust gas cleaning and catalyst for automobile exhaust gas cleaning |
| US9339793B2 (en) | 2012-03-14 | 2016-05-17 | N.E. Chemcat Corporation | Catalyst composition for exhaust gas cleaning and catalyst for automobile exhaust gas cleaning |
| WO2014002667A1 (en) | 2012-06-28 | 2014-01-03 | エヌ・イーケムキャット株式会社 | Catalyst composition for exhaust gas purification and exhaust gas purifying catalyst for automobiles |
| US9339794B2 (en) | 2012-06-28 | 2016-05-17 | N.E. Chemcat Corporation | Catalyst composition for exhaust gas purification and exhaust gas purifying catalyst for automobiles |
| WO2018147408A1 (en) | 2017-02-13 | 2018-08-16 | エヌ・イーケムキャット株式会社 | Exhaust gas purifying catalyst composition, method for producing same and exhaust gas purifying catalyst for automobiles |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP2818171B2 (en) | Catalyst for steam reforming reaction of hydrocarbon and method for producing the same | |
| US4738946A (en) | High temperature stable catalyst and process for preparing same | |
| US4808564A (en) | Catalyst for the purification of exhaust gases | |
| AU692207B2 (en) | Composition precursor and cerium and zirconium mixed oxide based composition, method for its preparation and use thereof | |
| US3867312A (en) | Exhaust gas catalyst support | |
| JPH09187649A (en) | Catalytic combustion method including consecutive plural catalytic zone | |
| JPH0852352A (en) | Oxidative catalyst withstanding high temperature,method for preparation thereof and method for combustion using said catalyst | |
| JP4151820B2 (en) | Exhaust gas purification catalyst | |
| PL188449B1 (en) | Ammonia oxidation catalyst | |
| JPH06182201A (en) | Catalyst stable at high temperature, its preparation, and method for effecting chemical reaction using this catalyst | |
| JPS6138626A (en) | Carrier for catalyst | |
| JPS6138627A (en) | Catalyst stable at high temperature, process for preparing the catalyst, and process for carrying out chemical reaction using the catalyst | |
| JPS60238146A (en) | Heat resistant carrier composition | |
| KR970001520B1 (en) | Carrier material for a catalyst and a process for making such a carrier material | |
| JPS60222145A (en) | Method for using heat resistant catalyst | |
| JP4771681B2 (en) | Method for producing noble metal-containing heat-resistant oxide | |
| JPH0445452B2 (en) | ||
| JPH0435220B2 (en) | ||
| JPS6022929A (en) | Heat resistant carrier for catalyst | |
| JPH0824843B2 (en) | Heat resistant catalyst and method of using the same | |
| JP2533703B2 (en) | Catalyst for high temperature steam reforming reaction of hydrocarbon and method of using the same | |
| JP2758616B2 (en) | Heat-resistant catalyst for catalytic combustion and its carrier | |
| JP2000051700A (en) | Exhaust emission purifying catalyst and its production | |
| JPS6253737A (en) | Catalyst for purifying exhaust gas and preparation thereof | |
| JPS60222148A (en) | Preparation of heat resistant carrier |