JPH05131137A - Oxidizing catalyst - Google Patents
Oxidizing catalystInfo
- Publication number
- JPH05131137A JPH05131137A JP3294506A JP29450691A JPH05131137A JP H05131137 A JPH05131137 A JP H05131137A JP 3294506 A JP3294506 A JP 3294506A JP 29450691 A JP29450691 A JP 29450691A JP H05131137 A JPH05131137 A JP H05131137A
- Authority
- JP
- Japan
- Prior art keywords
- oxide
- zirconium
- catalyst
- composite oxide
- titanium
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Withdrawn
Links
- 239000003054 catalyst Substances 0.000 title claims abstract description 42
- 230000001590 oxidative effect Effects 0.000 title abstract 5
- 239000002131 composite material Substances 0.000 claims abstract description 22
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims abstract description 15
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 claims abstract description 10
- 239000000463 material Substances 0.000 claims abstract description 10
- 239000010936 titanium Substances 0.000 claims abstract description 10
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims abstract description 9
- 229910052726 zirconium Inorganic materials 0.000 claims abstract description 9
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 8
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 8
- 229910052761 rare earth metal Inorganic materials 0.000 claims abstract description 7
- 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 6
- 229910052878 cordierite Inorganic materials 0.000 claims abstract description 6
- 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 claims abstract description 6
- 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 claims abstract description 5
- 229910052863 mullite Inorganic materials 0.000 claims abstract description 5
- 229910052593 corundum Inorganic materials 0.000 claims abstract 2
- 229910001845 yogo sapphire Inorganic materials 0.000 claims abstract 2
- 238000007254 oxidation reaction Methods 0.000 claims description 17
- 230000003647 oxidation Effects 0.000 claims description 16
- 229910010413 TiO 2 Inorganic materials 0.000 claims description 10
- 238000000465 moulding Methods 0.000 claims description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 abstract description 9
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 abstract description 5
- 229910002091 carbon monoxide Inorganic materials 0.000 abstract description 5
- 229930195733 hydrocarbon Natural products 0.000 abstract description 4
- 150000002430 hydrocarbons Chemical class 0.000 abstract description 4
- 229910052739 hydrogen Inorganic materials 0.000 abstract description 4
- 239000001257 hydrogen Substances 0.000 abstract description 4
- 125000004435 hydrogen atom Chemical class [H]* 0.000 abstract description 4
- 239000004215 Carbon black (E152) Substances 0.000 abstract description 3
- 239000011248 coating agent Substances 0.000 abstract description 2
- 238000000576 coating method Methods 0.000 abstract description 2
- 239000007864 aqueous solution Substances 0.000 description 12
- 239000007789 gas Substances 0.000 description 12
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 8
- 241000264877 Hippospongia communis Species 0.000 description 7
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 6
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 239000000395 magnesium oxide Substances 0.000 description 6
- 239000002244 precipitate Substances 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 238000000034 method Methods 0.000 description 5
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 4
- 235000011114 ammonium hydroxide Nutrition 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 239000011572 manganese Substances 0.000 description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 239000004480 active ingredient Substances 0.000 description 3
- 239000000969 carrier Substances 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
- 239000000843 powder Substances 0.000 description 3
- 239000001294 propane Substances 0.000 description 3
- PMTRSEDNJGMXLN-UHFFFAOYSA-N titanium zirconium Chemical compound [Ti].[Zr] PMTRSEDNJGMXLN-UHFFFAOYSA-N 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 229910021193 La 2 O 3 Inorganic materials 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 239000010953 base metal Substances 0.000 description 2
- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium(3+);trinitrate Chemical compound [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000010304 firing Methods 0.000 description 2
- 229910052746 lanthanum Inorganic materials 0.000 description 2
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 description 2
- 239000011777 magnesium Substances 0.000 description 2
- 229910052748 manganese Inorganic materials 0.000 description 2
- IPJKJLXEVHOKSE-UHFFFAOYSA-L manganese dihydroxide Chemical compound [OH-].[OH-].[Mn+2] IPJKJLXEVHOKSE-UHFFFAOYSA-L 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
- 229910052763 palladium Inorganic materials 0.000 description 2
- 229910052697 platinum Inorganic materials 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- LLZRNZOLAXHGLL-UHFFFAOYSA-J titanic acid Chemical compound O[Ti](O)(O)O LLZRNZOLAXHGLL-UHFFFAOYSA-J 0.000 description 2
- 150000003609 titanium compounds Chemical class 0.000 description 2
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 2
- 150000003755 zirconium compounds Chemical class 0.000 description 2
- OERNJTNJEZOPIA-UHFFFAOYSA-N zirconium nitrate Chemical compound [Zr+4].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O OERNJTNJEZOPIA-UHFFFAOYSA-N 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 238000007084 catalytic combustion reaction Methods 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 238000009841 combustion method Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- JEGUKCSWCFPDGT-UHFFFAOYSA-N h2o hydrate Chemical compound O.O JEGUKCSWCFPDGT-UHFFFAOYSA-N 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 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 1
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 description 1
- 239000001095 magnesium carbonate Substances 0.000 description 1
- 229910000021 magnesium carbonate Inorganic materials 0.000 description 1
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 1
- -1 magnesium hydroxide Chemical class 0.000 description 1
- 239000000347 magnesium hydroxide Substances 0.000 description 1
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 1
- GEYXPJBPASPPLI-UHFFFAOYSA-N manganese(III) oxide Inorganic materials O=[Mn]O[Mn]=O GEYXPJBPASPPLI-UHFFFAOYSA-N 0.000 description 1
- PLDDOISOJJCEMH-UHFFFAOYSA-N neodymium oxide Inorganic materials [O-2].[O-2].[O-2].[Nd+3].[Nd+3] PLDDOISOJJCEMH-UHFFFAOYSA-N 0.000 description 1
- 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 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 1
- DUNKXUFBGCUVQW-UHFFFAOYSA-J zirconium tetrachloride Chemical compound Cl[Zr](Cl)(Cl)Cl DUNKXUFBGCUVQW-UHFFFAOYSA-J 0.000 description 1
Landscapes
- Exhaust Gas Treatment By Means Of Catalyst (AREA)
- Catalysts (AREA)
- Gas Burners (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は酸化触媒、例えば水素、
一酸化炭素、炭化水素などのガスを燃焼させるための酸
化触媒に関し、特に各種可燃性ガスの中で最も酸化され
にくいメタンを低温、高いガス流量／触媒容積比の条件
下で高効率で酸化することができ、しかも１０００℃以
上の高温においても優れた耐熱性を有する酸化触媒に関
する。This invention relates to oxidation catalysts such as hydrogen,
Regarding an oxidation catalyst for burning gases such as carbon monoxide and hydrocarbons, methane, which is the most difficult to oxidize among various combustible gases, is highly efficiently oxidized under conditions of low temperature and high gas flow rate / catalyst volume ratio The present invention relates to an oxidation catalyst that can be processed and has excellent heat resistance even at a high temperature of 1000 ° C. or higher.
【０００２】[0002]
【従来の技術】一酸化炭素、水素、あるいは炭化水素等
の可燃性ガスを酸化触媒の存在下で燃焼させる接触燃焼
法は、主として自動車排ガスの浄化を目的に研究され、
多くの酸化触媒が開発されている。その主なものは白金
のような貴金属、銅や鉄のような卑金属の酸化物を活性
成分とし、各活性成分を粒状やハニカム状等に成形した
り、あるいはアルミナやチタニア等の担体に直接担持さ
せたものである。2. Description of the Related Art A catalytic combustion method of burning a combustible gas such as carbon monoxide, hydrogen, or hydrocarbon in the presence of an oxidation catalyst has been studied mainly for purifying automobile exhaust gas.
Many oxidation catalysts have been developed. The main ones are oxides of noble metals such as platinum and base metals such as copper and iron as active ingredients, and each active ingredient is formed into granules or honeycombs, or directly loaded on a carrier such as alumina or titania. It was made.
【０００３】一方、最近では低ＮＯｘ燃焼法開発の一環
として、プロパン、低熱量ガス、オイル等を燃焼させる
酸化触媒が研究されている。この触媒はハニカム型のコ
ージュライトやムライト等のセラミックスを基材とし、
この基材にγ−Ａｌ2 Ｏ3 （ガンマアルミナ）、ジルコ
ニア、マグネシア、α−Ａｌ2 Ｏ3 （アルファアルミ
ナ）等の担体をウォシュコートし、活性成分としてＰ
ｔ、Ｐｔ＋Ｐｄ、Ｐｄ、Ｐｔ＋Ｒｈ等の貴金属、あるい
はコバルト、ニッケル、マンガン等の卑金属の酸化物を
担持させたものである。On the other hand, recently, as part of the development of the low NOx combustion method, an oxidation catalyst for burning propane, low calorific gas, oil, etc. has been studied. This catalyst is based on ceramics such as honeycomb type cordierite and mullite,
A carrier such as γ-Al 2 O 3 (γ-alumina), zirconia, magnesia, α-Al 2 O 3 (alpha-alumina) is wash-coated on this base material, and P is used as an active ingredient.
An oxide of a noble metal such as t, Pt + Pd, Pd, Pt + Rh, or a base metal such as cobalt, nickel, or manganese is supported.
【０００４】上記のような従来の酸化触媒は一酸化炭素
やプロパンに対しては高活性を示すものの、より安定な
メタンに対してはいずれも性能が悪く、現在のところメ
タンに対してはその酸化性能において多くの問題点を残
している。Although the conventional oxidation catalysts as described above show high activity with respect to carbon monoxide and propane, they have poor performance with respect to more stable methane, and at present, with respect to methane. Many problems remain in the oxidation performance.
【０００５】また最近では１０００℃前後でも耐熱性が
ある触媒として、アルミニウムとランタンの複合酸化物
を主成分とする担体に、触媒活性成分を担持した触媒
（特開昭６０−１２１３２号公報）、又はアルカリ土類
金属元素とアルミニウムの複合酸化物を主成分とする触
媒（特開昭６２−１５３１５８号公報）などが提案され
ている。Further, recently, as a catalyst having heat resistance even at around 1000 ° C., a catalyst having a catalytically active component supported on a carrier containing a composite oxide of aluminum and lanthanum as a main component (JP-A-60-12132), Alternatively, a catalyst containing a composite oxide of an alkaline earth metal element and aluminum as a main component (JP-A-62-153158) has been proposed.
【０００６】[0006]
【発明が解決しようとする課題】従来の触媒は１０００
℃以上で使用すると担体が熱によりシンタリングし比表
面積が急激に低下するため実用上使用することができな
い。The conventional catalyst is 1000
If it is used at a temperature of ℃ or above, the carrier will be sintered by heat and the specific surface area will be drastically reduced.
【０００７】本発明は上記技術水準に鑑み、高温下でも
耐熱性の優れた酸化触媒を提供しようとするものであ
る。In view of the above-mentioned state of the art, the present invention aims to provide an oxidation catalyst having excellent heat resistance even at high temperatures.
【０００８】[0008]
【課題を解決するための手段】本発明は （１）希土類元素の酸化物を担持したジルコニウム及び
チタニウムの複合酸化物にマンガン酸化物を含有させて
なることを特徴とする酸化触媒。Means for Solving the Problems The present invention (1) is an oxidation catalyst characterized by containing a manganese oxide in a zirconium-titanium composite oxide carrying a rare earth element oxide.
【０００９】（２）ジルコニウム及びチタニウムの複合
酸化物をハニカム状に成型してなることを特徴とする上
記第（１）項の酸化触媒。(2) The oxidation catalyst according to item (1), which is formed by molding a composite oxide of zirconium and titanium into a honeycomb shape.
【００１０】（３）コージェライト、ムライト又はＭｇ
Ｏ，Ａｌ2 Ｏ3 ，ＴｉＯ2 よりなる結晶性複合酸化物の
うちから選択されるハニカム状耐熱基材に上記第（１）
項の触媒をコーティングしてなることを特徴とする酸化
触媒である。(3) Cordierite, mullite or Mg
The honeycomb-shaped heat-resistant base material selected from the crystalline composite oxides of O, Al 2 O 3 and TiO 2 has the above-mentioned (1)
An oxidation catalyst characterized by being coated with the catalyst according to the item.
【００１１】[0011]
【作用】本発明にいうジルコニウム及びチタニウムの複
合酸化物とは、ＺｒＯ2 ：ＴｉＯ2 の重量比で５：９５
〜９５：５の組成を有する非晶質（一部は結晶化してい
るものの全体としては非晶質）のもので下記方法で製造
される。The composite oxide of zirconium and titanium referred to in the present invention means that the weight ratio of ZrO 2 : TiO 2 is 5:95.
It is an amorphous material having a composition of ˜95: 5 (a part of which is crystallized but is amorphous as a whole) and is manufactured by the following method.
【００１２】 チタニウムの化合物及びジルコニウム
の化合物の水溶液にアンモニア水又は炭酸ソーダ水溶液
などの塩基性の沈殿剤を添加して生成する沈殿を洗浄し
た後乾燥し、５００℃以上で焼成する。A basic precipitant such as ammonia water or an aqueous solution of sodium carbonate is added to an aqueous solution of a titanium compound and a zirconium compound to wash a precipitate, which is then dried and calcined at 500 ° C. or higher.
【００１３】 チタニウムの水酸化物または酸化物を
ジルコニウムの化合物の水溶液に混合した後、沈殿剤を
添加して生成する沈殿を洗浄した後乾燥し、５００℃以
上で焼成する。After mixing titanium hydroxide or oxide with an aqueous solution of a zirconium compound, a precipitant is added to wash the resulting precipitate, which is dried and calcined at 500 ° C. or higher.
【００１４】 ジルコニウムの水酸化物または酸化物
をチタニウムの化合物の水溶液に混合した後、沈殿剤を
添加して生成する沈殿を洗浄した後乾燥し、５００℃以
上で焼成する。After mixing a hydroxide or oxide of zirconium with an aqueous solution of a titanium compound, a precipitating agent is added to wash the resulting precipitate, which is then dried and calcined at 500 ° C. or higher.
【００１５】以上の方法で調製したジルコニウム及びチ
タニウムの複合酸化物はバインダーを添加してハニカム
状に成型したり、又は複合酸化物のスラリーにコージェ
ライト、ムライト又はＭｇＯ，Ａｌ2 Ｏ3 ，ＴｉＯ2 よ
りなる結晶性複合酸化物のうちから選択されるハニカム
状耐熱基材を浸漬してウォッシュコートし、５００℃以
上で焼付けることによりハニカム状の担体にすることが
できる。The composite oxide of zirconium and titanium prepared by the above method is added with a binder to be formed into a honeycomb shape, or a slurry of the composite oxide is formed into cordierite, mullite or MgO, Al 2 O 3 , TiO 2. A honeycomb heat-resistant base material selected from the crystalline composite oxides may be dipped into the honeycomb heat-resistant base material, wash-coated, and baked at 500 ° C. or higher to obtain a honeycomb-shaped carrier.
【００１６】なお、上記のＭｇＯ，Ａｌ2 Ｏ3 ，ＴｉＯ
2 よりなる結晶性複合酸化物とはマグネシア、炭酸マグ
ネシウム、水酸化マグネシウムのようなＭｇ化合物、ア
ルミナ、水酸化アルミニウムのようなＡｌ化合物及びア
ナターゼ又はルチル型酸化チタンのようなＴｉ化合物の
混合物を、１３００〜１７００℃で焼成して結晶化する
ことによって得られた低膨張性のものを意味する。The above MgO, Al 2 O 3 and TiO
The crystalline complex oxide consisting of 2 is a mixture of magnesia, magnesium carbonate, a Mg compound such as magnesium hydroxide, alumina, an Al compound such as aluminum hydroxide and a Ti compound such as anatase or rutile titanium oxide, It means a low-expansion product obtained by firing at 1300 to 1700 ° C. and crystallization.
【００１７】次に、このようにして得られたジルコニウ
ム及びチタニウムの複合酸化物又はハニカム状の担体に
希土類元素の酸化物を担持する場合には、希土類元素の
硝酸塩水溶液に担体を浸漬後焼成すればよい。希土類元
素の酸化物の一例としてはＬａ2 Ｏ3 、ＣｅＯ2 、Ｎｄ
2 Ｏ3 などがあり、その担持量はジルコニウム及びチタ
ニウムの複合酸化物１００重量部当たり１〜３０重量部
（以下重量％と略す）の範囲が好ましい。Next, when the rare earth element oxide is carried on the zirconium-titanium composite oxide or honeycomb-shaped support thus obtained, the support is immersed in an aqueous solution of a rare earth element nitrate and then baked. Good. Examples of rare earth element oxides include La 2 O 3 , CeO 2 , and Nd.
2 O 3 and the like, and the supported amount thereof is preferably in the range of 1 to 30 parts by weight (hereinafter abbreviated as “wt%”) per 100 parts by weight of the zirconium and titanium composite oxide.
【００１８】希土類元素の酸化物を担持したジルコニウ
ム及びチタニウムの複合酸化物にマンガン酸化物を含有
させる量としては触媒全重量１００重量部当たりマンガ
ン酸化物１〜５０重量部の範囲が好ましい。複合酸化物
にマンガン酸化物を含有させる方法としては硝酸マンガ
ン水溶液に複合酸化物の粉末を添加したスラリーに、沈
殿剤を添加して生成する沈殿を洗浄した後乾燥し５００
℃以上で焼成する方法などが用いられる。The amount of the manganese oxide contained in the zirconium-titanium composite oxide supporting the rare earth element oxide is preferably in the range of 1 to 50 parts by weight per 100 parts by weight of the total catalyst. As a method of containing manganese oxide in the composite oxide, a precipitation agent is added to a slurry prepared by adding powder of the composite oxide to an aqueous solution of manganese nitrate, and the precipitate formed is washed and then dried.
For example, a method of firing at a temperature of ℃ or higher is used.
【００１９】以上のようにして得られた触媒は水素、一
酸化炭素、炭化水素ガス等のガスの酸化反応に対し優れ
た活性、耐久性を示した。The catalyst obtained as described above exhibited excellent activity and durability against the oxidation reaction of hydrogen, carbon monoxide, hydrocarbon gas and the like.
【００２０】以下、実施例により本発明を具体的に説明
する。The present invention will be specifically described below with reference to examples.
（例１）硝酸ジルコニウムと塩化チタンの混合水溶液に
炭酸ソーダ水溶液を添加して得られる沈殿を濾過、水
洗、乾燥後５００℃で焼成して複合酸化物１（Ｚｒ
Ｏ2 ：ＴｉＯ2 の重量比 ５０：５０）を得た。Example 1 A precipitate obtained by adding an aqueous solution of sodium carbonate to a mixed aqueous solution of zirconium nitrate and titanium chloride was filtered, washed with water, dried, and then baked at 500 ° C. to form a complex oxide 1 (Zr
A weight ratio of O 2 : TiO 2 of 50:50) was obtained.
【００２１】水酸化チタンＴｉ（ＯＨ）4粉末を水に添
加し、さらに塩化ジルコニウム水溶液を添加した溶液に
アンモニア水を添加して得られる沈殿を濾過、水洗し乾
燥後１０００℃で焼成してＺｒＯ2 ：ＴｉＯ2 比の異な
る複合酸化物２（ＺｒＯ2 ：ＴｉＯ2 の重量比 ９０：
１０）、複合酸化物３（ＺｒＯ2 ：ＴｉＯ2 の重量比２
０：８０）及び複合酸化物４（ＺｒＯ2 ：ＴｉＯ2 の重
量比 １０：９０）を得た。Titanium hydroxide Ti (OH) 4 powder was added to water, and ammonia water was added to a solution containing an aqueous solution of zirconium chloride to obtain a precipitate, which was filtered, washed with water, dried and calcined at 1000 ° C. to obtain ZrO 2. 2 : Compound oxide 2 having a different TiO 2 ratio (weight ratio of ZrO 2 : TiO 2 90:
10), complex oxide 3 (ZrO 2 : TiO 2 weight ratio 2
0:80) and composite oxide 4 (ZrO 2 : TiO 2 weight ratio 10:90) were obtained.
【００２２】複合酸化物１〜４を硝酸ランタンの水溶液
に浸漬し５００℃で焼成することによりＬａ2 Ｏ3 を５
重量％（複合酸化物１００重量部当たり５重量部）担持
した担体１〜４を調製した。硝酸マンガン水溶液に担体
１〜４を各々添加した後、アンモニア水を添加し水酸化
マンガンを生成させ、水洗・乾燥後５００℃で焼成し、
Ｍｎ2 Ｏ3 を１５重量％（触媒全重量当たり）含有する
触媒１〜４を調製した。The composite oxides 1 to 4 were dipped in an aqueous solution of lanthanum nitrate and calcined at 500 ° C. to prepare La 2 O 3
Carriers 1 to 4 supported by weight% (5 parts by weight per 100 parts by weight of complex oxide) were prepared. After adding each of the carriers 1 to 4 to the manganese nitrate aqueous solution, ammonia water is added to generate manganese hydroxide, which is washed with water, dried, and calcined at 500 ° C.
Catalysts 1-4 containing 15 wt% Mn 2 O 3 (based on total catalyst weight) were prepared.
【００２３】これらの触媒を表１の条件（可燃ガスを空
気で希釈）で活性評価を行い、その結果を表２に示す。The activity of these catalysts was evaluated under the conditions shown in Table 1 (flammable gas was diluted with air), and the results are shown in Table 2.
【表１】 [Table 1]
【表２】 [Table 2]
【００２４】（例２）例１で調製した複合酸化物３を硝
酸ランタン、硝酸セリウム、又は硝酸ネオジウムの各水
溶液に浸漬し、５００℃で焼成することによりＬａ2 Ｏ
3 を１０重量％担持した担体５、ＣｅＯ2 を１重量％担
持した担体６及びＮｄ2 Ｏ3 を３０重量％担持した担体
７を調製した。硝酸マンガン水溶液に担体５〜７を各々
添加した後、アンモニア水を添加し水酸化マンガンを生
成させ、水洗・乾燥後５００℃で焼成しＭｎ2 Ｏ3 を４
０重量％（以下、触媒全重量当たり）含有する触媒５
（担体５を使用）、Ｍｎ2 Ｏ3 を５重量％含有する触媒
６（担体６を使用）、Ｍｎ 2 Ｏ3 を１０重量％含有する
触媒７（担体７を使用）を調製した。(Example 2) The composite oxide 3 prepared in Example 1 was mixed with glass.
Lanthanum acid, cerium nitrate, or neodymium nitrate water
La by immersing in the solution and baking at 500 ° C2O
310% by weight of carrier 5, CeO21% by weight
Carrier 6 and Nd2O3Carrier carrying 30% by weight of
7 was prepared. Carriers 5 to 7 are added to the manganese nitrate aqueous solution.
After the addition, aqueous ammonia is added to produce manganese hydroxide.
Mn, washed with water, dried and baked at 500 ° C2O34
Catalyst 5 containing 0% by weight (hereinafter, based on the total weight of the catalyst)
(Using carrier 5), Mn2O3Containing 5% by weight of
6 (using carrier 6), Mn 2O3Contains 10% by weight
Catalyst 7 (using carrier 7) was prepared.
【００２５】これらの触媒をプロパン又はメタノールを
含有する空気を原料として、反応温度８００℃、ガス空
塔速度１０，０００ｈ-1の条件で活性評価を行い、その
結果を表３に示す。The activity of these catalysts was evaluated using air containing propane or methanol as a raw material under the conditions of a reaction temperature of 800 ° C. and a gas superficial velocity of 10,000 h −1 , and the results are shown in Table 3.
【表３】 [Table 3]
【００２６】（例３）直径１インチで、１平方インチ当
たり２００個の開口部（２００セル）を有するハニカム
状のコージェライト（２ＭｇＯ・２Ａｌ2 Ｏ3 ・５Ｓｉ
Ｏ2 ）基材又はＭｇＯ，Ａｌ2 Ｏ3 ，ＴｉＯ2 よりなる
結晶性複合酸化物（ＭｇＯ・４Ａｌ2 Ｏ3 ・６Ｔｉ
Ｏ2 ）基材を用い、触媒３の粉末を上記基材にウォッシ
ュコートし、１０００℃で焼付けて触媒８、９を得た。
触媒３のコート量はハニカム担体１００重量部当たり４
０重量部であった。Example 3 A cordierite (2MgO.2Al 2 O 3 .5Si) having a diameter of 1 inch and having 200 openings (200 cells) per square inch.
O 2 ) base material or crystalline complex oxide (MgO.4Al 2 O 3 .6Ti) composed of MgO, Al 2 O 3 , and TiO 2.
Using the O 2 ) base material, the powder of the catalyst 3 was wash-coated on the base material and baked at 1000 ° C. to obtain catalysts 8 and 9.
The coating amount of the catalyst 3 is 4 per 100 parts by weight of the honeycomb carrier.
It was 0 part by weight.
【００２７】これらの触媒及びさらに１１００℃で１０
００時間焼成した触媒を、メタン３％（残部空気）含有
ガスを用い、ガス空塔速度３００，０００ｈ-1、触媒層
入口ガス温度７００℃の条件で活性評価を行い表４の結
果を得た。These catalysts and additionally 10 at 1100 ° C.
The catalyst calcined for 00 hours was subjected to activity evaluation using a gas containing 3% of methane (remainder air) at a gas superficial velocity of 300,000 h −1 and a catalyst layer inlet gas temperature of 700 ° C., and the results in Table 4 were obtained. ..
【表４】 [Table 4]
【００２８】[0028]
【発明の効果】以上詳述したように本発明によれば、活
性が高くかつ耐熱性に優れた酸化触媒を提供できる。As described above in detail, according to the present invention, an oxidation catalyst having high activity and excellent heat resistance can be provided.
Claims (3)
ウム及びチタニウムの複合酸化物にマンガン酸化物を含
有させてなることを特徴とする酸化触媒。1. An oxidation catalyst comprising a complex oxide of zirconium and titanium supporting an oxide of a rare earth element and manganese oxide.
物をハニカム状に成型してなることを特徴とする請求項
１記載の酸化触媒。2. The oxidation catalyst according to claim 1, which is formed by molding a composite oxide of zirconium and titanium into a honeycomb shape.
Ａｌ2 Ｏ3 ，ＴｉＯ 2 よりなる結晶性複合酸化物のうち
から選択されるハニカム状耐熱基材に請求項１記載の触
媒をコーティングしてなることを特徴とする酸化触媒。3. Cordierite, mullite or MgO,
Al2O3, TiO 2Of the crystalline composite oxide consisting of
The honeycomb-shaped heat-resistant base material selected from
An oxidation catalyst characterized by being coated with a medium.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP3294506A JPH05131137A (en) | 1991-11-11 | 1991-11-11 | Oxidizing catalyst |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP3294506A JPH05131137A (en) | 1991-11-11 | 1991-11-11 | Oxidizing catalyst |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH05131137A true JPH05131137A (en) | 1993-05-28 |
Family
ID=17808663
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP3294506A Withdrawn JPH05131137A (en) | 1991-11-11 | 1991-11-11 | Oxidizing catalyst |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH05131137A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2025028423A1 (en) * | 2023-08-03 | 2025-02-06 | 株式会社村田製作所 | Organic matter decomposition catalyst, honeycomb structure, decomposition method for organic matter, and organic matter decomposition device |
-
1991
- 1991-11-11 JP JP3294506A patent/JPH05131137A/en not_active Withdrawn
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2025028423A1 (en) * | 2023-08-03 | 2025-02-06 | 株式会社村田製作所 | Organic matter decomposition catalyst, honeycomb structure, decomposition method for organic matter, and organic matter decomposition device |
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| Date | Code | Title | Description |
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