JPH01135537A - Oxidation catalyst of combustible gas - Google Patents
Oxidation catalyst of combustible gasInfo
- Publication number
- JPH01135537A JPH01135537A JP62291954A JP29195487A JPH01135537A JP H01135537 A JPH01135537 A JP H01135537A JP 62291954 A JP62291954 A JP 62291954A JP 29195487 A JP29195487 A JP 29195487A JP H01135537 A JPH01135537 A JP H01135537A
- Authority
- JP
- Japan
- Prior art keywords
- group
- earth metal
- metal
- catalyst
- metals
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000003054 catalyst Substances 0.000 title claims abstract description 40
- 230000003647 oxidation Effects 0.000 title claims abstract description 12
- 238000007254 oxidation reaction Methods 0.000 title claims abstract description 12
- 229910052751 metal Inorganic materials 0.000 claims abstract description 18
- 239000002184 metal Substances 0.000 claims abstract description 18
- 229910052802 copper Inorganic materials 0.000 claims abstract description 9
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims abstract description 8
- 150000001342 alkaline earth metals Chemical class 0.000 claims abstract description 6
- 229910052804 chromium Inorganic materials 0.000 claims abstract description 6
- 229910052761 rare earth metal Inorganic materials 0.000 claims abstract description 6
- 150000002910 rare earth metals Chemical class 0.000 claims abstract description 6
- 229910044991 metal oxide Inorganic materials 0.000 claims abstract description 5
- 229910052684 Cerium Inorganic materials 0.000 claims abstract description 3
- 229910052688 Gadolinium Inorganic materials 0.000 claims abstract description 3
- 229910052779 Neodymium Inorganic materials 0.000 claims abstract description 3
- 229910052777 Praseodymium Inorganic materials 0.000 claims abstract description 3
- 229910052772 Samarium Inorganic materials 0.000 claims abstract description 3
- 229910052788 barium Inorganic materials 0.000 claims abstract description 3
- 229910052741 iridium Inorganic materials 0.000 claims abstract description 3
- 229910052746 lanthanum Inorganic materials 0.000 claims abstract description 3
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 3
- 229910052762 osmium Inorganic materials 0.000 claims abstract description 3
- 229910052763 palladium Inorganic materials 0.000 claims abstract description 3
- 229910052697 platinum Inorganic materials 0.000 claims abstract description 3
- 229910052707 ruthenium Inorganic materials 0.000 claims abstract description 3
- 229910052791 calcium Inorganic materials 0.000 claims abstract 2
- 229910052749 magnesium Inorganic materials 0.000 claims abstract 2
- 229910052703 rhodium Inorganic materials 0.000 claims abstract 2
- 229910052712 strontium Inorganic materials 0.000 claims abstract 2
- 150000002739 metals Chemical class 0.000 claims description 12
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 6
- 239000010949 copper Substances 0.000 claims description 6
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 4
- 239000011651 chromium Substances 0.000 claims description 4
- 229910017052 cobalt Inorganic materials 0.000 claims description 4
- 239000010941 cobalt Substances 0.000 claims description 4
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 4
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 claims description 3
- 150000004706 metal oxides Chemical class 0.000 claims description 3
- 239000002131 composite material Substances 0.000 abstract description 4
- 229910052742 iron Inorganic materials 0.000 abstract description 3
- 229910052748 manganese Inorganic materials 0.000 abstract description 3
- 230000001105 regulatory effect Effects 0.000 abstract 2
- 239000007789 gas Substances 0.000 description 12
- 230000000694 effects Effects 0.000 description 9
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 8
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 description 8
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 7
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 6
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 6
- 229910002091 carbon monoxide Inorganic materials 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
- 239000007864 aqueous solution Substances 0.000 description 5
- 230000003197 catalytic effect Effects 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 4
- 229930195733 hydrocarbon Natural products 0.000 description 4
- 150000002430 hydrocarbons Chemical class 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- 229910000029 sodium carbonate Inorganic materials 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 239000004215 Carbon black (E152) Substances 0.000 description 3
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 description 3
- 238000001354 calcination Methods 0.000 description 3
- 229910000423 chromium oxide Inorganic materials 0.000 description 3
- 229910000428 cobalt oxide Inorganic materials 0.000 description 3
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical compound [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 description 3
- 238000002485 combustion reaction Methods 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 3
- 229910000480 nickel oxide Inorganic materials 0.000 description 3
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 3
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 description 3
- 229910000831 Steel Inorganic materials 0.000 description 2
- IWOUKMZUPDVPGQ-UHFFFAOYSA-N barium nitrate Chemical compound [Ba+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O IWOUKMZUPDVPGQ-UHFFFAOYSA-N 0.000 description 2
- ZCCIPPOKBCJFDN-UHFFFAOYSA-N calcium nitrate Chemical compound [Ca+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ZCCIPPOKBCJFDN-UHFFFAOYSA-N 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
- 239000013078 crystal Substances 0.000 description 2
- 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 2
- YIXJRHPUWRPCBB-UHFFFAOYSA-N magnesium nitrate Chemical compound [Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O YIXJRHPUWRPCBB-UHFFFAOYSA-N 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 239000010959 steel Substances 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
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 1
- 239000005751 Copper oxide Substances 0.000 description 1
- 241000264877 Hippospongia communis Species 0.000 description 1
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical group CC(C)O KFZMGEQAYNKOFK-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
- 235000003434 Sesamum indicum Nutrition 0.000 description 1
- 244000000231 Sesamum indicum Species 0.000 description 1
- 150000004703 alkoxides Chemical class 0.000 description 1
- SMZOGRDCAXLAAR-UHFFFAOYSA-N aluminium isopropoxide Chemical compound [Al+3].CC(C)[O-].CC(C)[O-].CC(C)[O-] SMZOGRDCAXLAAR-UHFFFAOYSA-N 0.000 description 1
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 1
- 239000010953 base metal Substances 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
- 229910000431 copper oxide Inorganic materials 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 230000002427 irreversible effect Effects 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- 229910001960 metal nitrate Inorganic materials 0.000 description 1
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 1
- LFLZOWIFJOBEPN-UHFFFAOYSA-N nitrate, nitrate Chemical compound O[N+]([O-])=O.O[N+]([O-])=O LFLZOWIFJOBEPN-UHFFFAOYSA-N 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- OGHBATFHNDZKSO-UHFFFAOYSA-N propan-2-olate Chemical compound CC(C)[O-] OGHBATFHNDZKSO-UHFFFAOYSA-N 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
Landscapes
- Catalysts (AREA)
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明は一酸化炭素、水素、炭化水素ガスなどの可燃性
ガスの酸化触媒に関するものであって、とくに本発明の
触媒は内燃機関の排ガスのような苛酷な条件下に使用し
て耐久性の高い性質を示す触媒に関する。[Detailed Description of the Invention] [Field of Industrial Application] The present invention relates to an oxidation catalyst for combustible gases such as carbon monoxide, hydrogen, and hydrocarbon gases, and in particular, the catalyst of the present invention relates to an oxidation catalyst for combustible gases such as carbon monoxide, hydrogen, and hydrocarbon gases. It relates to a catalyst that exhibits highly durable properties when used under severe conditions such as.
内燃機関、例えば自動車の排ガス中には一酸化炭素をは
じめ窒素酸化物、炭化水素などいわゆる公害性物質が多
量に含有されているが、とりわけ−酸化炭素の発生源は
自動車排ガスであって、血液中のへモクロピンと結合し
、回復不能な一酸化炭素へモクロピンとなってしまうの
で、その浄化対策は早くから進められてきている。Exhaust gas from internal combustion engines, such as automobiles, contains large amounts of so-called polluting substances such as carbon monoxide, nitrogen oxides, and hydrocarbons. Because it combines with the hemoclopin inside and turns into moclopin, which becomes irreversible carbon monoxide, measures to purify it have been underway for a long time.
その、主なるものはエンジン改良方式、排気マニホール
ドリアクター、サーマルリアクターおよび触媒コンバー
タ一方式などであるが、末だ満足すべき成果をあげてい
るとは言い難ｈ０ことに触媒方式にあっては白金のよう
な貴金属、銅や鉄のような卑金属の酸化物を触媒成分と
し、そのものを粒状、ハニカム状等に成形したものや、
それら触媒成分物質をアルミナ、チタニアなどの担体に
直接浸漬担持させたものがあるが、これら触媒は性能、
寿命、耐熱性など現在までのところ多くの問題点を残し
ている。The main ones are engine improvement systems, exhaust manifold reactors, thermal reactors, and single-type catalytic converters, but it cannot be said that they have achieved satisfactory results. Oxides of noble metals such as copper and base metals such as iron are used as catalyst components, and these are formed into granules, honeycombs, etc.
There are catalysts in which these catalyst components are directly immersed and supported on carriers such as alumina and titania, but these catalysts have
To date, many problems remain, such as lifespan and heat resistance.
従来、担体として使用されるアルミナは約６００℃まで
は耐熱性がありｒ型の結晶構造で安定であるがチタニア
に比べて性能が若干劣る。Conventionally, alumina used as a support has heat resistance up to about 600° C. and is stable with an r-type crystal structure, but its performance is slightly inferior to that of titania.
又、チタニアは５００℃以上では結晶構造が触媒活性を
有するアナターゼ型からμチｙ型に次第に変化してゆき
耐熱性に難点がある。さらにジルコニアは熱的にも極め
て安定であシ、触媒にした時の性能も優れているが、価
格が高くジルコニアだけを成型して担体に使用するには
経済性が成り立たない。Further, at temperatures above 500° C., titania has a problem in heat resistance because its crystal structure gradually changes from an anatase type having catalytic activity to a μ-chiy type. Furthermore, zirconia is extremely stable thermally and has excellent performance when used as a catalyst, but it is expensive and it is not economical to mold only zirconia and use it as a carrier.
又、触媒活性成分として使用される金属酸化物の中には
高温下で溶融したり担体と反応して触媒活性を低下させ
るものもある。Furthermore, some metal oxides used as catalytically active components melt at high temperatures or react with the carrier, reducing the catalytic activity.
〔発明の目的〕
本発明は上記技術水準に鑑み、耐熱性に優れ、苛酷な条
件下で使用しても安定に酸化触媒として作用する性能を
有する酸化触媒を提供しようとするものである。[Object of the Invention] In view of the above-mentioned state of the art, the present invention aims to provide an oxidation catalyst that has excellent heat resistance and has the ability to stably act as an oxidation catalyst even when used under severe conditions.
本発明者らは、Ａｔとアルカリ土類金属および希土類金
属からなる複合酸化物担体にマンガン、コバルト、銅、
クロム、■族金属のうち少なくとも一種の金属酸化物を
担持させると、担体の有する＃熱性がさらに向上し、苛
酷な条件下で使用しても安定に酸化触媒としての性能を
有することを見い出し、本発明を完成するに至った。The present inventors have discovered that manganese, cobalt, copper,
It has been discovered that when at least one metal oxide among chromium and group II metals is supported, the thermal properties of the support are further improved, and the support has stable performance as an oxidation catalyst even when used under severe conditions. The present invention has now been completed.
すなわち、本発明はＭバアルカリ土類金属二希土類金属
の原子比が１００：α５〜１００：１５〜１００である
複合酸化物担体に、マンガン、コバルト、銅、クロム、
または■族金属のうち少なくとも１種の金属、酸化物を
担持させてなることを特徴とする可燃性ガスの酸化触媒
である。That is, the present invention provides manganese, cobalt, copper, chromium,
Alternatively, the present invention is an oxidation catalyst for combustible gas, characterized in that it supports at least one metal or oxide among group (3) metals.
本発明においてアルカリ土類金属としてはＣａ、Ｍｆ、
８ｒ及びＢａのいずれか１種以上の金属が用いられ、希
土類金属としてはＬａ、Ｃｅ、Ｐｒ、Ｎｄ、Ｐｍ。In the present invention, the alkaline earth metals include Ca, Mf,
One or more metals of 8r and Ba are used, and the rare earth metals include La, Ce, Pr, Nd, and Pm.
Ｓｍ及びＧｄのいずれか１種以上の゛金属が用いられる
。また■族金属としてはＦｅ 、Ｃｏ 、Ｎｉ 、Ｒｕ
、Ｒｈ。One or more metals selected from Sm and Gd are used. Group III metals include Fe, Co, Ni, and Ru.
, Rh.
Ｐｄ、Ｏｓ、Ｉｒ及びＰｔのいずれか１種以上の金属が
用いられる。One or more metals selected from Pd, Os, Ir, and Pt are used.
本発明において、ｋＡとアルカリ土類金属と希土類金属
の複合酸化物よりなる担体は、目的とする金属の原子比
になるように調製した硝酸アルミニウムと各金属硝酸塩
の水溶液に炭酸ナトリウムなどを滴下して共沈させた水
酸化物、あるいはア〜コキＶド法、すなわちアルミニウ
ムイソプロポキシドと各金属イソプロポキシドの２−プ
ロパノ−〃溶液を加水分解して得られる水酸化物、を焼
成するととＫよって得られる。In the present invention, a support made of a composite oxide of kA, an alkaline earth metal, and a rare earth metal is prepared by adding sodium carbonate or the like dropwise to an aqueous solution of aluminum nitrate and each metal nitrate prepared to have the desired atomic ratio of the metals. When calcining the hydroxide co-precipitated by the method, or the hydroxide obtained by hydrolyzing a 2-propano solution of aluminum isopropoxide and each metal isopropoxide, It is obtained by K.
次に、このようにして得られた担体にマンガン、コバμ
ト、銅、クロムまたは■族金属の酸化物を担持させる方
法は従来から用いられている方法でよく、例えば、これ
らの金属の硝酸塩水溶液に担体を浸漬後焼成すればよい
。これら酸化物の担体への担持量は複合酸化物担体１０
０重量部に対して（Ｌ１〜５０重電部が好ましい。Next, the carrier obtained in this way was coated with manganese and
The method for supporting the oxides of copper, copper, chromium, or group II metals may be any conventionally used method, for example, by immersing the support in an aqueous nitrate solution of these metals and then firing. The amount of these oxides supported on the support is 10
With respect to 0 parts by weight (L1 to 50 parts by weight is preferable).
本発明触媒を利用することによシ、内燃機関の排ガス、
焼結炉の排ガスなどのように一酸化炭素、水素、炭化水
素ガスなどの可燃性がヌを触媒酸化して有害成分の除去
を容易に行うことができる。By using the catalyst of the present invention, exhaust gas from an internal combustion engine,
Harmful components can be easily removed by catalytically oxidizing combustible gases such as carbon monoxide, hydrogen, and hydrocarbon gases such as exhaust gas from a sintering furnace.
以上のようＫして得られた触媒は一酸化炭素、水素、炭
化水素ガスなど可燃性ガスを酸化する反応に対し３００
〜１５００℃の温度領域で長時間にわたり高い触媒活性
を示した。The catalyst obtained by K as described above has a 300%
It showed high catalytic activity for a long time in the temperature range of ~1500°C.
以下、実施例によシ本発明を具体的に説明する。Hereinafter, the present invention will be specifically explained using Examples.
〔実施例１〕
ＣＨｓ）ｓ をＢａ ： ｋｌ ： Ｌａ＝１ ：
２５ ： ／ （原子比）の割合で２−プロパノ−
μ液に加え攪拌した後、水を添加して上記アルコキシド
を加水分解し得られた水酸化物を５５（ＩＣで焼成した
。仁のようにして得られた担体をそれぞれ硝酸コバルト
水溶液、硝酸マンガン水溶液、硝酸調水溶液、硝酸ニッ
ケル水溶液、硝酸クロム水溶液、硝酸鉄水溶液に浸漬し
、酸化コバルト、酸化マンガン、酸化銅、酸化ニッケｙ
、峻化クロム、酸化鉄が各々５ ｗｔ％になるように担
持し、その後、６０Ｑ℃で焼成した触媒１，２，５，４
，５゜６を調製した。[Example 1] CHs)s Ba: kl: La=1:
2-propano- in the ratio of 25: / (atomic ratio)
After adding to μ solution and stirring, water was added to hydrolyze the alkoxide and the resulting hydroxide was calcined with 55 (IC). Cobalt oxide, manganese oxide, copper oxide, nickel oxide
Catalysts 1, 2, 5, and 4 were prepared by supporting 5 wt% of each of chromium oxide and iron oxide, and then calcining them at 60Q°C.
, 5°6 was prepared.
これらの触媒の活性評価を表１に示す条件で実施し、そ
の結果を表２に示す。The activity of these catalysts was evaluated under the conditions shown in Table 1, and the results are shown in Table 2.
表を
表２
〔実施例２〕
硝酸カルシウムと硝酸アルミニウムおよび硝酸ランタン
をＣａ ：Ａｔ：Ｌａ＝１ ：２５ ： １ （原子比
）の割合で水に加え、攪拌した後、徐々に炭酸ナトリウ
ム水溶液を上記水溶液中１ｃｐＨ＝７に到達するまで滴
下する。このように共沈法により得られた水酸化物を洗
浄し５５０℃で焼成した。このようにして得られた担体
を実施例１と同様にして、酸化コバＡ／）、酸化マンガ
ン、酸化鋼、酸化ニッケル、酸化クロム、酸化鉄がそれ
ぞれ５ ｖｔＸになるように担持した触ｖ＆７゜８．９
．１０，１１．１２を調製して、表１に示すような活性
評価を行い、表５のような結果が得られた。Table 2 [Example 2] Calcium nitrate, aluminum nitrate, and lanthanum nitrate were added to water at a ratio of Ca:At:La=1:25:1 (atomic ratio), and after stirring, a sodium carbonate aqueous solution was gradually added. 1 c in the above aqueous solution is added dropwise until pH=7 is reached. The hydroxide thus obtained by the coprecipitation method was washed and calcined at 550°C. The thus obtained carrier was treated in the same manner as in Example 1, and was loaded with 5 vtX of cobalt oxide A/), manganese oxide, steel oxide, nickel oxide, chromium oxide, and iron oxide at a concentration of 5 vtX each. 8.9
．． 10, 11.12 were prepared and the activity evaluations shown in Table 1 were performed, and the results shown in Table 5 were obtained.
表五
〔実施例３〕
硝酸マグネシウムと硝酸アルミニウムと硝酸ランタン及
び硝酸ストロンチウムと硝酸アルミニウムと硝酸セリウ
ムを各々ＭＹ ： ＡＬ ： Ｌａ ：１：３４：２．
Ｓｒ：Ａｔ：Ｃｅ＝２：５５：１（原子比）の割合で水
に加え、攪拌した後、徐々に炭酸ナトリウム水溶液を上
記水溶液中にＴ）Ｈ＝７に到達するまで滴下する。以後
実施例２と同様にして担体を調製して酸化コバルト、酸
化マンガン、酸化鋼、酸化ニッケル、酸化クロム、酸化
鉄をそれぞれ所定量担持した触媒１３゜１４ 、１５
、１．６ 、１７．１８ 、１９ 、２０ 。Table 5 [Example 3] Magnesium nitrate, aluminum nitrate, lanthanum nitrate, strontium nitrate, aluminum nitrate, and cerium nitrate, respectively, MY:AL:La:1:34:2.
After adding to water at a ratio of Sr:At:Ce=2:55:1 (atomic ratio) and stirring, an aqueous sodium carbonate solution is gradually added dropwise into the aqueous solution until T)H=7 is reached. Thereafter, a carrier was prepared in the same manner as in Example 2, and catalysts 13, 14 and 15 were prepared in which predetermined amounts of cobalt oxide, manganese oxide, steel oxide, nickel oxide, chromium oxide, and iron oxide were supported, respectively.
, 1.6 , 17.18 , 19 , 20 .
２１．２２，２３．２４を調製して表１に示すような活
性評価を行い表４に示すような結果が得られた。21.22 and 23.24 were prepared and evaluated for their activity as shown in Table 1, and the results shown in Table 4 were obtained.
〔実施例４〕
硝酸バリウムと硝酸アルミニウム゛と硝酸ツンタ、ンを
各々ｚｏ：ｓｏ：ｚ、４ｏ：ｓｏ：１ｏ。[Example 4] Barium nitrate, aluminum nitrate, and nitrate nitrate were zo:so:z and 4o:so:1o, respectively.
１：５０：３０，４０：５０：４Ｇ（原子比）の割合で
水に加え、攪拌した後、徐々に炭酸ナトリウム水溶液を
上記水溶液中にｐＨ＝７に到達するまで滴下する。以後
、実施例２と同様にして担体を調製して酸化マンガンを
各担体に２ｗｔ％担持した触媒２５．２６，２７．２８
を調製して、表１１Ｃ示すような活性評価を行い、表５
に示すような結果が得られた。After adding to water in the ratio of 1:50:30, 40:50:4G (atomic ratio) and stirring, an aqueous sodium carbonate solution is gradually added dropwise into the aqueous solution until pH=7 is reached. Thereafter, supports were prepared in the same manner as in Example 2, and catalysts 25.26 and 27.28 were prepared in which 2 wt% of manganese oxide was supported on each support.
was prepared and subjected to activity evaluation as shown in Table 11C, and Table 5
The results shown are obtained.
表翫
〔実施例５〕
本発明触媒の一酸化炭素以外の可燃性ガスを酸化する反
応についての効果をみるために、実施例１のコバルト触
［１を用いて表６の条件で触媒活性を評価した結果を表
７に示す。[Example 5] In order to examine the effect of the catalyst of the present invention on the reaction of oxidizing combustible gases other than carbon monoxide, the catalytic activity was tested using the cobalt catalyst [1 of Example 1] under the conditions shown in Table 6. The evaluation results are shown in Table 7.
表６
表７
〔実施例６〕
本発明の酸化触媒の耐熱性をテストし従来の触媒と比較
するためにアルミナ担体にコバ／Ｉ／）を担持した触媒
２９、アルミナ・バリウム複合酸化物担体３０及び実施
例３に記す触媒１３゜１４の＃＃熱テストを実施した。Table 6 Table 7 [Example 6] In order to test the heat resistance of the oxidation catalyst of the present invention and compare it with conventional catalysts, catalyst 29 was prepared by supporting Koba/I/) on an alumina carrier, and alumina/barium composite oxide carrier 30 Thermal tests of catalysts 13 and 14 described in Example 3 were carried out.
耐熱テストとして１０００℃で１０００時間、１４００
℃で１０００時間空気中で焼成した後、表１に示す条件
で触媒の活性評価を行い１表８に示す結果が得られた。As a heat resistance test, 1000 hours at 1000℃, 1400℃
After calcination in air for 1000 hours at °C, the activity of the catalyst was evaluated under the conditions shown in Table 1, and the results shown in Table 8 were obtained.
表８
なお、触［１〜１２及び触媒１５〜２８においても上記
同様の耐熱性試験を実施し、表１に示す条件で触媒の活
性評価を行った結果どの触媒ともＣＯ酸化率９０Ｘ前後
と耐熱性テスト前と同様な結果が得られた。Table 8 In addition, heat resistance tests similar to those described above were carried out for catalysts 1 to 12 and catalysts 15 to 28, and the activity of the catalysts was evaluated under the conditions shown in Table 1. As a result, the CO oxidation rate of all catalysts was around 90X. The results were similar to those before the sex test.
実施例においては粒状触媒につ調て説明しであるが、触
媒の形状を特に限定するものではなく、ハニカム状、板
状などの触媒形状で用いて良いことは言うまでもない。Although the examples focus on granular catalysts, the shape of the catalyst is not particularly limited, and it goes without saying that honeycomb-like, plate-like, and other catalyst shapes may be used.
上記実施例に示すように本発明触媒はＣｏ。 As shown in the above examples, the catalyst of the present invention is Co.
Ｈ！、ＣＨ４いずれの可燃性ガスとも比較的低温にて燃
焼除去することができ、さらに耐熱性を有すためガスタ
ービン等の高温用燃焼触媒として十分利用できる。H! , CH4 can be burned and removed at a relatively low temperature, and furthermore, it has heat resistance, so it can be fully used as a high-temperature combustion catalyst for gas turbines and the like.
Claims (2)
１００：０．５〜１００：０．５〜１００である複合酸
化物担体に、マンガン、コバルト、銅、クロム、または
VIII族金属のうち少なくとも１種の金属酸化物を担持さ
せてなることを特徴とする可燃性ガスの酸化触媒。(1) Manganese, cobalt, copper, chromium, or
A combustible gas oxidation catalyst characterized by supporting at least one metal oxide among group VIII metals.
らなる群のうちの１種以上の金属であり、希土類金属が
Ｌａ、Ｃｅ、Ｐｒ、Ｎｄ、Ｐｍ、Ｓｍ及びＧｄからなる
群のうちの１種以上の金属であり、VIII族金属がＦｅ、
Ｃｏ、Ｎｉ、Ｒｕ、Ｒｈ、Ｐｄ、Ｏｓ、Ｉｒ及びＰｔか
らなる群のうちの１種以上の金属である特許請求の範囲
（１）記載の可燃性ガスの酸化触媒。(2) The alkaline earth metal is one or more metals from the group consisting of Ca, Mg, Sr, and Ba, and the rare earth metal is one or more metals from the group consisting of La, Ce, Pr, Nd, Pm, Sm, and Gd. one or more metals, and the group VIII metal is Fe,
The combustible gas oxidation catalyst according to claim (1), which is one or more metals from the group consisting of Co, Ni, Ru, Rh, Pd, Os, Ir, and Pt.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62291954A JP2563393B2 (en) | 1987-11-20 | 1987-11-20 | Combustible gas oxidation catalyst |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62291954A JP2563393B2 (en) | 1987-11-20 | 1987-11-20 | Combustible gas oxidation catalyst |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH01135537A true JPH01135537A (en) | 1989-05-29 |
| JP2563393B2 JP2563393B2 (en) | 1996-12-11 |
Family
ID=17775615
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP62291954A Expired - Lifetime JP2563393B2 (en) | 1987-11-20 | 1987-11-20 | Combustible gas oxidation catalyst |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2563393B2 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH02131400A (en) * | 1988-11-07 | 1990-05-21 | Diesel Kiki Co Ltd | Device for detecting load of generator |
| JP2006511333A (en) * | 2002-12-20 | 2006-04-06 | 本田技研工業株式会社 | Alkali-containing catalyst formulation for hydrogen production at medium and low temperatures |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS60222145A (en) * | 1984-04-20 | 1985-11-06 | Hitachi Ltd | Method for using heat resistant catalyst |
-
1987
- 1987-11-20 JP JP62291954A patent/JP2563393B2/en not_active Expired - Lifetime
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS60222145A (en) * | 1984-04-20 | 1985-11-06 | Hitachi Ltd | Method for using heat resistant catalyst |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH02131400A (en) * | 1988-11-07 | 1990-05-21 | Diesel Kiki Co Ltd | Device for detecting load of generator |
| JP2006511333A (en) * | 2002-12-20 | 2006-04-06 | 本田技研工業株式会社 | Alkali-containing catalyst formulation for hydrogen production at medium and low temperatures |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2563393B2 (en) | 1996-12-11 |
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