JPH01104345A - Oxygen-deficient perovskite catalyst - Google Patents
Oxygen-deficient perovskite catalystInfo
- Publication number
- JPH01104345A JPH01104345A JP62260166A JP26016687A JPH01104345A JP H01104345 A JPH01104345 A JP H01104345A JP 62260166 A JP62260166 A JP 62260166A JP 26016687 A JP26016687 A JP 26016687A JP H01104345 A JPH01104345 A JP H01104345A
- Authority
- JP
- Japan
- Prior art keywords
- catalyst
- oxygen
- reaction
- deficient
- deficient perovskite
- 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 59
- 229910052760 oxygen Inorganic materials 0.000 title claims abstract description 23
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 title claims abstract description 22
- 239000001301 oxygen Substances 0.000 title claims abstract description 22
- 230000002950 deficient Effects 0.000 title claims abstract description 18
- 229910052761 rare earth metal Inorganic materials 0.000 claims abstract description 5
- 229910052723 transition metal Inorganic materials 0.000 claims abstract description 5
- 229910052692 Dysprosium Inorganic materials 0.000 claims description 2
- 229910052691 Erbium Inorganic materials 0.000 claims description 2
- 229910052693 Europium Inorganic materials 0.000 claims description 2
- 229910052688 Gadolinium Inorganic materials 0.000 claims description 2
- 229910052689 Holmium Inorganic materials 0.000 claims description 2
- 229910052777 Praseodymium Inorganic materials 0.000 claims description 2
- 229910052772 Samarium Inorganic materials 0.000 claims description 2
- 229910052775 Thulium Inorganic materials 0.000 claims description 2
- 229910052802 copper Inorganic materials 0.000 claims description 2
- 229910052742 iron Inorganic materials 0.000 claims description 2
- 229910052746 lanthanum Inorganic materials 0.000 claims description 2
- 229910052748 manganese Inorganic materials 0.000 claims description 2
- 229910052759 nickel Inorganic materials 0.000 claims description 2
- 229910052727 yttrium Inorganic materials 0.000 claims description 2
- 229910052771 Terbium Inorganic materials 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 abstract description 22
- 239000000203 mixture Substances 0.000 abstract description 14
- 238000001354 calcination Methods 0.000 abstract description 3
- 238000005504 petroleum refining Methods 0.000 abstract description 3
- 238000010298 pulverizing process Methods 0.000 abstract description 3
- 238000003786 synthesis reaction Methods 0.000 abstract description 3
- 238000011282 treatment Methods 0.000 abstract description 3
- 239000002912 waste gas Substances 0.000 abstract description 3
- 238000002156 mixing Methods 0.000 abstract description 2
- 239000002994 raw material Substances 0.000 abstract description 2
- 230000009257 reactivity Effects 0.000 abstract description 2
- -1 carbonate compound Chemical class 0.000 abstract 1
- 150000002894 organic compounds Chemical class 0.000 abstract 1
- 230000000694 effects Effects 0.000 description 16
- 238000000354 decomposition reaction Methods 0.000 description 13
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 10
- 150000001875 compounds Chemical class 0.000 description 7
- 238000010304 firing Methods 0.000 description 5
- AYJRCSIUFZENHW-UHFFFAOYSA-L barium carbonate Chemical compound [Ba+2].[O-]C([O-])=O AYJRCSIUFZENHW-UHFFFAOYSA-L 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- 238000007254 oxidation reaction Methods 0.000 description 4
- MWUXSHHQAYIFBG-UHFFFAOYSA-N Nitric oxide Chemical compound O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 3
- 238000002485 combustion reaction Methods 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 239000007921 spray Substances 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 2
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 239000013065 commercial product Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 150000002430 hydrocarbons Chemical class 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 239000010453 quartz Substances 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- 241000251730 Chondrichthyes Species 0.000 description 1
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- 229910017061 Fe Co Inorganic materials 0.000 description 1
- 241000899793 Hypsophrys nicaraguensis Species 0.000 description 1
- 229910052765 Lutetium Inorganic materials 0.000 description 1
- 101100477492 Mus musculus Sinhcaf gene Proteins 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 150000003841 chloride salts Chemical class 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000004108 freeze drying Methods 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum oxide Inorganic materials [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 150000002823 nitrates Chemical class 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- KTUFCUMIWABKDW-UHFFFAOYSA-N oxo(oxolanthaniooxy)lanthanum Chemical compound O=[La]O[La]=O KTUFCUMIWABKDW-UHFFFAOYSA-N 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 235000015320 potassium carbonate Nutrition 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000000779 smoke Substances 0.000 description 1
- LEDMRZGFZIAGGB-UHFFFAOYSA-L strontium carbonate Chemical compound [Sr+2].[O-]C([O-])=O LEDMRZGFZIAGGB-UHFFFAOYSA-L 0.000 description 1
- 229910000018 strontium carbonate Inorganic materials 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Landscapes
- Exhaust Gas Treatment By Means Of Catalyst (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
Description
【発明の詳細な説明】
（技術分野）
この発明は酸素欠陥型ペロブスカイト触媒に関するもの
である。さらに詳しくは、この発明は、反応活性に優れ
た特異選択反応性を有する酸素欠陥型のペロブスカイト
化合物触媒に関するものである。DETAILED DESCRIPTION OF THE INVENTION (Technical Field) This invention relates to an oxygen-deficient perovskite catalyst. More specifically, the present invention relates to an oxygen-deficient perovskite compound catalyst having excellent reaction activity and specific selective reactivity.
（背景技術）
ペロブスカイト化合物は、近年、その触媒としての機能
について注目されはじめている。特に、酸素欠陥を持つ
ペロブスカイトは、その欠陥部が活性点となって様々な
反応について特異選択的な活性を示すことが明らかにな
ってきており、有機合成反応、石油精製、廃ガス処理な
どの多様な分野において今後の発展が注目されている。(Background Art) In recent years, perovskite compounds have begun to attract attention for their functions as catalysts. In particular, it has become clear that perovskites with oxygen vacancies act as active sites and exhibit specific and selective activity in various reactions, making them useful for organic synthesis reactions, petroleum refining, waste gas treatment, etc. Future developments in a variety of fields are attracting attention.
たとえば、Ｌ ａ Ｓ ｒ Ｃｏ Ｏ３−Ｙから
なる１−××
ペロブスカイト触媒は、Ｎｏ（酸化窒素）の分解反応や
炭化水素のＭ１ヒ反応に著しく高い活性を示すことが知
られている。For example, a 1-xx perovskite catalyst composed of L a S r Co O3-Y is known to exhibit significantly high activity in the decomposition reaction of No (nitrogen oxide) and the M1 reaction of hydrocarbons.
しかしながら、これらのぺＤブスカイト触媒については
、その活性は高いものの、反応の選択性が低いために実
用に供することができないという問題があった。たとえ
ば、上記の
ｔ、ａ Ｓｒ Ｃｏ０３−ｙの触媒は、炭化水素
の１−ｘ ｘ
完全燃焼の触媒としては優れた活性を示すが、メタンか
らのエタン、あるいはエチレンの合成などの部分酸化反
応のための触媒としては選択性が低いため実用的ではな
い。However, although these pebuskite catalysts have high activity, there is a problem in that they cannot be put to practical use due to low reaction selectivity. For example, the above t, a Sr Co03-y catalyst shows excellent activity as a catalyst for the complete combustion of 1-x It is not practical as a catalyst for this purpose due to its low selectivity.
また、Ｎｏの分解反応に用いる場合などは、高い温度で
反応させることが必要となり、実用的には有利ではない
という問題もある。ＮＯの分解触媒としては他にＳ ’
ｒ Ｆ ｅ Ｏ３−ｘの組成からなる触媒も知られてい
るが、この場合も同様の問題かある。Furthermore, when used in the decomposition reaction of No, it is necessary to carry out the reaction at a high temperature, which is not advantageous in practical terms. In addition to the NO decomposition catalyst, S'
A catalyst having a composition of r F e O3-x is also known, but this case also has similar problems.
なお、Ｎｏ分解触媒や燃焼触媒としてはＰｔ。Note that Pt is used as the No decomposition catalyst and combustion catalyst.
Ｉ ｒ等のけ金属からなるものか知られているが、これ
らは燃焼触媒としては強力であるが、部分酸化反応には
用いることができず、またＮｏの分解反応触媒としては
初期活性は高いが反応中に表面か酸化し失活してしまう
ため触媒寿命は著しく短く実用的ではない。しかもこれ
らの貴金属は非常に高価であるという問題を有している
。It is known that these are made of metals such as Ir, but although they are powerful as combustion catalysts, they cannot be used for partial oxidation reactions, and they have high initial activity as catalysts for decomposition reactions of No. Since the surface of the catalyst is oxidized and deactivated during the reaction, the catalyst life is extremely short and is not practical. Moreover, these precious metals have the problem of being extremely expensive.
このような＄情に鑑みて、この発明の発明者は、酸素欠
陥型へロブスカイト化合物の触媒としての活性の大きさ
に着目し、かつその反応選択性の向上と、より低い反応
温度の実現について鋭意検討してきた。その結果、従来
の酸素欠陥型へロブスカイト１ヒ合物とは異なるＡ 、
Ａ ’ ２ Ｂ３０□−６の組成を有する酸素欠陥型
へロブスカイト化合物か高い活性とともに良好な選択性
を有することを見出してこの発明を完成した。In view of these circumstances, the inventors of the present invention focused on the high activity of oxygen-deficient helovskite compounds as catalysts, and sought to improve the reaction selectivity and realize lower reaction temperatures. I have been seriously considering it. As a result, we found that A, which is different from the conventional oxygen-deficient helobskite monomer compounds,
The inventors completed this invention by discovering that an oxygen-deficient helovskite compound having a composition of A'2B30□-6 has high activity and good selectivity.
（発明の目的）
この発明は、以上の通りの事情を踏まえてなされたもの
であり、従来のペロブスカイト触媒の欠点を改善し、よ
り低い反応温度においても高活性、高選沢性を有する新
しいタイプの酸素欠陥型ペロブスカイト化合物触媒を提
供することを目的としている。(Objective of the Invention) This invention was made in light of the above circumstances, and it improves the drawbacks of conventional perovskite catalysts and develops a new type that has high activity and high selectivity even at lower reaction temperatures. The purpose of the present invention is to provide an oxygen-deficient perovskite compound catalyst.
（発明の開示）
この発明の酸素欠陥型ペロブスカイト触媒は、上記の「
１的を実現するために、
Ａ１Ａ′２Ｂ３０７−α
（ＡはＹ、希土類元素から選択される１種または２種以
上の元素、Ａ′は２価の元素の１種または２種以上の元
素、Ｂは遷移金属元素の１種または２種以上を示し、０
≦α≦１を示す）
の組成からなることを特徴としている。(Disclosure of the Invention) The oxygen-deficient perovskite catalyst of the present invention is characterized by the above-mentioned “
In order to realize the first objective, A1A'2B307-α (A is Y, one or more elements selected from rare earth elements, A' is one or more divalent elements, B represents one or more transition metal elements, and 0
≦α≦1).
このＡ１Ａ′２Ｂ３０７−ａの組成からなるペロブスカ
イト触媒は、Ａサイトの周囲に酸素空孔を有し、また、
ｔ１５０〜９５０°Ｃ稈度の温度範囲においてさらに酸
素が脱け、この欠陥部が活性サイトとして１１１用する
。この組成のらのは、池の酸素欠陥型ペロブスカイト触
媒に比べて、良好な活性と選択性を有している。この触
媒は、低温域において存在する酸素空孔と高温域で出現
する酸素空孔との２種類の空孔が存在するため、その相
互作用によって優れた作用を示すものと考えられる。This perovskite catalyst having the composition A1A'2B307-a has oxygen vacancies around the A site, and
Oxygen is further eliminated in the temperature range of t150 to 950°C, and this defective part serves as an active site 111. This composition of RANO has better activity and selectivity than Ike's oxygen-deficient perovskite catalyst. Since this catalyst has two types of vacancies: oxygen vacancies that exist in the low temperature range and oxygen vacancies that appear in the high temperature range, it is thought that the catalyst exhibits excellent effects due to the interaction between them.
コノ発明の酸素欠陥型へロブスカイト化合物触媒の組成
であるＡサイトは、Ｙ、希土類元素の１種または２種以
上から選択する。この場合、たとえば、Ｙ、Ｌａ、Ｐｒ
、Ｐｍ、Ｓｍ、Ｅｕ、Ｇｄ。The A site, which is the composition of the oxygen-deficient herovskite compound catalyst of the Kono invention, is selected from one or more of Y and rare earth elements. In this case, for example, Y, La, Pr
, Pm, Sm, Eu, Gd.
’Ｔ’ｂ、Ｄｙ、Ｈｏ、Ｅｒ、Ｔｍ、Ｌｕなどの元素が
好ま−しいものとして例示される。Ａ′サイトについて
は２価の元素の１種または２種以上を用いるが、好まし
いものとしては、Ｂａ、Ｓｒ、Ｃａなどが例示される。Preferred examples include elements such as 'T'b, Dy, Ho, Er, Tm, and Lu. For the A' site, one or more divalent elements are used, and preferred examples include Ba, Sr, and Ca.
Ｂサイトとしては、遷移金属元素の１種または２種以上
のものを用いる。たとえば、Ｍｎ、Ｃｕ。As the B site, one or more transition metal elements are used. For example, Mn, Cu.
Ｎｉ、Ｆｅ、Ｃｏが好ましいものとして例示される。Preferred examples include Ni, Fe, and Co.
もちろん、これらの例示した元素にこの発明の触媒の組
成は何ら限定されるものではない。Of course, the composition of the catalyst of the present invention is not limited to these exemplified elements.
この発明の触媒は、一般的には、原料とする酸化物、炭
酸塩化合物等を混合した後に、８５０〜１２００℃で焼
成し、次いでボールミル等の粉砕機で粉砕したものを用
いることができる。また、硝酸塩、＾ＦＰｉ塩、塩化物
等の混合水溶液から水酸化物、炭酸塩の形態で共沈させ
たものを熱分解して焼成させる方法、もしくは、同様の
混合水溶液をスプレードライヤーや凍結乾煙法を用いて
均一に乾固した混合物を熱分解し、焼成する方法は、低
温での短時間焼成によりペロブスカイトが生成するため
に高比表面積のものが得られ、有利な方法である。The catalyst of the present invention can generally be prepared by mixing raw materials such as oxides and carbonate compounds, calcining the mixture at 850 to 1200°C, and then pulverizing the mixture using a pulverizer such as a ball mill. Alternatively, a method of co-precipitating a mixed aqueous solution of nitrates, ^FPi salts, chlorides, etc. in the form of hydroxides and carbonates and pyrolyzing and calcining them, or a similar mixed aqueous solution using a spray dryer or freeze-drying. The method of thermally decomposing and firing a mixture that has been uniformly dried using the smoke method is an advantageous method because a perovskite is produced by short-time firing at a low temperature, so that a product with a high specific surface area can be obtained.
比表面積については、１０ｒ＃／ｇを超える場合には易
焼結性のペロブスカイトとなり、高温反応において粒成
長が激しく、結局は■粉になってしまう。このため、１
〜１０ｔｄ／ｌｒの比表面積を持ち、粒径がそろってい
るものが好ましく用いられる。Regarding the specific surface area, if it exceeds 10 r#/g, it becomes an easily sinterable perovskite, and grains grow violently in high-temperature reactions, eventually turning into powder. For this reason, 1
Those having a specific surface area of ~10 td/lr and having uniform particle sizes are preferably used.
この発明の酸素欠陥型ペロブスカイト触媒は、石油精製
、有機合成反応、廃ガス処理などに効果的に用いること
ができるものであり、たとえば、ＮＯの分解、炭化水素
の部分酸化などに好適に用いることができる０反応の活
性は大きく、選択性も良好である。さらには触媒の寿命
も長い。The oxygen-deficient perovskite catalyst of the present invention can be effectively used in petroleum refining, organic synthesis reactions, waste gas treatment, etc., and can be suitably used, for example, in NO decomposition, hydrocarbon partial oxidation, etc. The activity of the 0 reaction that can be achieved is large and the selectivity is also good. Furthermore, the life of the catalyst is also long.
次に実施例を示してさらに評しくこの発明の触媒につい
て説明する。もちろんこの発明は、以下の実施例によっ
て限定されるものではない。Next, the catalyst of the present invention will be described in more detail with reference to Examples. Of course, this invention is not limited to the following examples.
実施ｐＡ１
次の（１）〜（８）のこの発明の酸素欠陥型へロブス力
、イト触奴を製造した。Implementation pA1 Oxygen-deficient type Helobus force and Ito-tactile cells according to the following (1) to (8) of the present invention were manufactured.
（１）ＹＢａ Ｃｏ３０７−ａ
Ｙ ＯとＢａＣ０およびＣｏｏを
２３ ３゜
０．５：２ ： ３の割合で混合し、９５０℃で４０時
間焼成した後に、ボールミルで８時間粉砕してＦ！ｌＩ
造した。(1) YBa Co307-a YO, BaC0 and Coo were mixed at a ratio of 233°0.5:2:3, fired at 950°C for 40 hours, and then ground in a ball mill for 8 hours to obtain F! lI
Built.
（２） Ｅ ｒ Ｂ ａ ２ Ｃｕ ３０７−ａＥｒ
ＯとＢ ａ ＣＯ３およびＣｕＯを０．５： ２ ：
３の割合で混合し、９５０°Ｃで４０時間焼成したも
のをボールミルで８時間粉砕して製造した。(2) E r B a 2 Cu 307-aEr
O and B a CO3 and CuO at 0.5:2:
The mixture was mixed at a ratio of 3 to 3, baked at 950°C for 40 hours, and then ground in a ball mill for 8 hours.
（３）ＹＢａ２Ｃｕ３０７−ａ
Ｙ （Ｎ ０３ ） ３とＢａ（Ｎｏ３）２．およびＣ
ｕ （Ｎ Ｏ３）を１＝２：３の割合で水に溶−解した
後にｏｆｆを調整しつつＫ ２ ＣＯ３を滴下した。得
られた炭酸塩の混合物を８５０℃で６時間焼成して触媒
とした。(3) YBa2Cu307-a Y (N 03 ) 3 and Ba (No3) 2. and C
After dissolving u (N O3) in water at a ratio of 1=2:3, K2CO3 was added dropwise while adjusting off. The obtained carbonate mixture was calcined at 850° C. for 6 hours to obtain a catalyst.
（４）ＬａＳｒ Ｃｏ３０７−ａ
Ｌａ （Ｎｏ ） 、 Ｓ ｒ （ＮＯ３） ２
。(4) LaSr Co307-a La (No), S r (NO3) 2
.
ＣＯ（Ｎ ０３ ） ３を１：２：３のモル比で水に溶
解し、スプレードライヤーで噴霧乾燥し、それを９００
℃で１０時間焼成して製造した。CO(N 03 ) 3 was dissolved in water in a molar ratio of 1:2:3, spray-dried with a spray dryer, and
It was produced by firing at ℃ for 10 hours.
（Ｓ） Ｅ ｕ Ｂ ａ２ Ｃ０３０７−ａＥｕ Ｏ
、ＢａＣＯ３、Ｃｏｏを１：２：３のモル比で混合し、
９００°Ｃで３０時間焼成したものを８時間ボールミル
で粉砕して製造した。(S) E u B a2 C0307-aEu O
, BaCO3, and Coo are mixed in a molar ratio of 1:2:3,
It was produced by firing at 900°C for 30 hours and pulverizing it in a ball mill for 8 hours.
（６）ＳｒｎＢａ２ （Ｃｕ 、、 （、，３）０
７−αｉ
Ｓｍ Ｏ、ＢａＣＯ３，ＣｕＯ，ＮｉＯを１ ： ２
： ２．７： ０．３のモル比で混合し、９５０
℃で２０時間焼成したものをボールミルで８時間粉砕し
て製造した。(6) SrnBa2 (Cu,, (,,3)0
7-αi SmO, BaCO3, CuO, NiO in 1:2
: Mixed at a molar ratio of 2.7:0.3, 950
It was produced by firing at ℃ for 20 hours and grinding it in a ball mill for 8 hours.
（７） ＧｄＢａ２（Ｃｕ １．５Ｍｎ １．５） ０
７−。(7) GdBa2 (Cu 1.5Mn 1.5) 0
7-.
Ｇｄ （Ｎｏ３）３．Ｂａ （Ｎｏ３）２゜Ｃｕ（Ｎ０
３）２９Ｍｎ（ＮＯ３）２を１＝２： １．５：
ｉ、ｓのモル比で水に溶解し、スプレードライヤーで乾
燥した後９００℃で１０時間焼成して製造した。Gd (No3)3. Ba (No3)2゜Cu(N0
3) 29Mn(NO3)2 1=2: 1.5:
It was prepared by dissolving it in water at a molar ratio of i and s, drying it with a spray dryer, and then baking it at 900°C for 10 hours.
Ｓｒ ）・
（８） ＨＯ（Ｂ ａ １．５ ０．５（Ｆｅ
Ｃｏ ）０
０．６ ２．４ ７−α
Ｈｏ Ｏ、ＢａＣ０、ＳｒＣＯ３゜
Ｆｅ Ｏ、Ｃｏｏを、１ ： １．５： ０．５
：０．６： ２．４のモル比で混合し、９５０℃で４
０時間焼成した後に、ボールミルで８時間粉砕して製造
した。Sr )・(8) HO(B a 1.5 0.5(Fe
Co )0 0.6 2.4 7-α Ho O, BaC0, SrCO3°Fe O, Coo, 1: 1.5: 0.5
:0.6:2.4 molar ratio and at 950℃
After baking for 0 hours, the product was ground in a ball mill for 8 hours.
実施例 ２ 実施例１で製造した触媒をＮＯの分解に用髪）た。Example 2 The catalyst prepared in Example 1 was used for the decomposition of NO.
触媒粉末は石英管に充填し、Ｈｅで希釈したＮ。The catalyst powder was packed into a quartz tube and diluted with He.N.
ガ３をこの石英管内に流通させて反応を行った。A reaction was carried out by flowing Moga 3 into this quartz tube.
反応生成ガスはガスクロマトグラフィー〇二よって分析
した。The reaction product gas was analyzed by gas chromatography 02.
反応条件は次の通りとした。The reaction conditions were as follows.
・反応温度 ６００〜９００℃
・ＳＶ １５００ｈｒ”（３％Ｎ Ｏ／ １−Ｉ ｅ
ガス）・触媒 ２．５ｇ
なお、触媒活性の測定評価は、定常的な活性を得るため
に、反応開始後１０時間以上経過した後に行った。・Reaction temperature 600-900℃ ・SV 1500hr" (3%N O / 1-I e
Gas)・Catalyst 2.5 g In order to obtain steady activity, the measurement and evaluation of catalyst activity was carried out after 10 hours or more had elapsed from the start of the reaction.
また、比鮫のために、市販の００３０４．０．５％Ｉ”
ｔ／ＡＩ ０ 、 ０．５％Ｉ ｒ ／ Ａ ｌ
２０３の各触媒についても同様にしてその活性を評価し
た。 反応の結果を示したものが次の表−１である。
この表−１から明らかなように、この発明の触媒（１）
〜（８）においては、低温度においてら、また８００〜
９００℃の高温度においても、極めて高いＮＯ分解率を
示している。Also, for Japanese sharks, commercially available 00304.0.5% I"
t/AI 0 , 0.5%I r /A l
The activity of each catalyst No. 203 was evaluated in the same manner. The following Table 1 shows the results of the reaction.
As is clear from this Table-1, the catalyst (1) of the present invention
~(8), at low temperature, and at 800~
It shows an extremely high NO decomposition rate even at a high temperature of 900°C.
また、第１図には、反応経過時間（ｈ「）による分解率
の変化を、触媒試料（６）と、比較例１および比較例２
について示している。この第１図から明らかなように、
従来の触媒の場合には１時間後にはＮＯ分解率は急速に
低下し、６時間後には初期の１７１０にまで低下するが
、この発明の触媒（６）の場合には、１０時間以上経過
してら活性の低下は見られない。触媒は高活性であり、
その寿命にも優れている。In addition, Fig. 1 shows the change in decomposition rate depending on the elapsed reaction time (h'') for catalyst sample (6), Comparative Example 1, and Comparative Example 2.
It shows about. As is clear from this figure 1,
In the case of the conventional catalyst, the NO decomposition rate rapidly decreases after 1 hour and drops to the initial level of 1710 after 6 hours, but in the case of the catalyst (6) of the present invention, the NO decomposition rate decreases rapidly after 1 hour. No decrease in Tera activity was observed. The catalyst is highly active;
Its longevity is also excellent.
実施例 ３
実施例１で製造した触媒（２）（３）を用いてメタン（
ＣＨ４）の部分酸化反応を行った。Example 3 Methane (
A partial oxidation reaction of CH4) was performed.
表−１ 反応条件は次の通りとした。Table-1 The reaction conditions were as follows.
・反応温度 ７００℃
・ガス流量
ＨＣ！ ／ ＣＨ４／ ０２ ＝ １０／１０１０．５
（ｍ１７分）・触媒層 １ｇ
メタンからエタンおよびエチレンへの転化率は、触媒ｆ
２） （ＥｒＢａ Ｃｕ Ｏ）の場合、各２ ３
７−α
々２．０％、１，０％であり、触媒（３）（ＹＢａ
Ｃｕ Ｏ）の場合には、１．７／Ｌ；１２ ３７−α
０．７％であった。・Reaction temperature 700℃ ・Gas flow rate HC! / CH4/ 02 = 10/1010.5
(m17 minutes)・Catalyst layer 1g The conversion rate of methane to ethane and ethylene is the catalyst f
2) In the case of (ErBa Cu O), each 2 3
7-α is 2.0% and 1.0%, respectively, and catalyst (3) (YBa
In the case of CuO), it was 1.7/L; 12 37-α 0.7%.
これに対して従来の０，５％Ｐ ｔ ／ Ａ Ｉ ２０
３（市販品）触媒の場合には各々０％、０％であった。In contrast, the conventional 0.5% P t / AI 20
In the case of catalyst No. 3 (commercial product), they were 0% and 0%, respectively.
Ｌａ２Ｏ３（市販品）触媒の場合には、各々１．５％、
０．３％であった。In the case of La2O3 (commercial product) catalyst, 1.5% each,
It was 0.3%.
メタンリッチの条Ｐｔ＝におけるこの反応の結果からも
、この発明の触媒がメタンの部分酸化反応の選択性に優
れていることがわかる。The results of this reaction in a methane-rich strip Pt= also show that the catalyst of the present invention has excellent selectivity for the partial oxidation reaction of methane.
第１図は、この発明の触媒と従来の触媒とのＮｏ分解活
性の経時変化を示した反応経過時間・ＮＯ分解率の相関
図である。
代理人 弁理士 西 澤 利 大筒 １
図
反応経過時間FIG. 1 is a correlation diagram of elapsed reaction time and NO decomposition rate showing the change over time in the No decomposition activity of the catalyst of the present invention and a conventional catalyst. Agent Patent Attorney Toshi Nishizawa Otsutsu 1
Figure reaction elapsed time
Claims (4)
希土類元素から選択される１種または２種以上の元素、
Ａ′は２価の元素の１種または２種以上の元素、Ｂは遷
移金属元素の１種または２種以上を示し、０≦α≦１を
示す） の組成からなることを特徴とする酸素欠陥型ペロブスカ
イト触媒。(1) A_1A_2'B_3O_7_-_α (A is Y,
One or more elements selected from rare earth elements,
A' is one or more divalent elements, B is one or more transition metal elements, and 0≦α≦1. Defected perovskite catalyst.
うちの１種または２種以上からなる特許請求の範囲第（
１）項記載の酸素欠陥型ペロブスカイト触媒。(2) The B-site element consists of one or more of Mn, Cu, Ni, Fe, and Co.
The oxygen-deficient perovskite catalyst described in item 1).
Ｅｕ、Ｇｄ、Ｔｂ、Ｄｙ、Ｈｏ、Ｅｒ、Ｔｍのうちの１
種または２種以上からなる特許請求の範囲第（１）項記
載の酸素欠陥型ペロブスカイト触媒。(3) A site element is Y, La, Pr, Pm, Sm,
One of Eu, Gd, Tb, Dy, Ho, Er, Tm
The oxygen-deficient perovskite catalyst according to claim (1), which comprises one or more species.
または２種以上からなる特許請求の範囲第（１）項記載
の酸素欠陥型ペロブスカイト触媒。(4) The oxygen-deficient perovskite catalyst according to claim (1), wherein the A' site element is one or more of Ba, Sr, and Ca.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62260166A JPH01104345A (en) | 1987-10-15 | 1987-10-15 | Oxygen-deficient perovskite catalyst |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62260166A JPH01104345A (en) | 1987-10-15 | 1987-10-15 | Oxygen-deficient perovskite catalyst |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH01104345A true JPH01104345A (en) | 1989-04-21 |
| JPH0586257B2 JPH0586257B2 (en) | 1993-12-10 |
Family
ID=17344238
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP62260166A Granted JPH01104345A (en) | 1987-10-15 | 1987-10-15 | Oxygen-deficient perovskite catalyst |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH01104345A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH01266851A (en) * | 1988-04-19 | 1989-10-24 | Res Dev Corp Of Japan | Y-ba-co compound oxide catalyst |
| US5851501A (en) * | 1995-05-09 | 1998-12-22 | Daimler-Benz Ag | Process for absorbing and desorbing nitrogen oxides in exhaust gases |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6430644A (en) * | 1987-07-24 | 1989-02-01 | Matsushita Electric Ind Co Ltd | Nox decomposition catalyst |
| JPS6430629A (en) * | 1987-07-24 | 1989-02-01 | Matsushita Electric Ind Co Ltd | Burner |
| JPS6430630A (en) * | 1987-07-24 | 1989-02-01 | Matsushita Electric Ind Co Ltd | Burner |
| JPS6430631A (en) * | 1987-07-24 | 1989-02-01 | Matsushita Electric Ind Co Ltd | Burner |
| JPS6430645A (en) * | 1987-07-24 | 1989-02-01 | Matsushita Electric Ind Co Ltd | Nox decomposition catalyst |
| JPS6430642A (en) * | 1987-07-24 | 1989-02-01 | Matsushita Electric Ind Co Ltd | Catalyst for purifying exhaust gas |
| JPS6430648A (en) * | 1987-07-24 | 1989-02-01 | Matsushita Electric Ind Co Ltd | Nox decomposition catalyst |
| JPS6430573A (en) * | 1987-07-24 | 1989-02-01 | Matsushita Electric Ind Co Ltd | Tobacco filter |
| JPS6430641A (en) * | 1987-07-24 | 1989-02-01 | Matsushita Electric Ind Co Ltd | Catalyst for purifying exhaust gas |
| JPS6430649A (en) * | 1987-07-24 | 1989-02-01 | Matsushita Electric Ind Co Ltd | Nox decomposition catalyst |
| JPS6430627A (en) * | 1987-07-24 | 1989-02-01 | Matsushita Electric Ind Co Ltd | Air filter |
| JPS6430643A (en) * | 1987-07-24 | 1989-02-01 | Matsushita Electric Ind Co Ltd | Catalyst for purifying exhaust gas |
| JPS6430628A (en) * | 1987-07-24 | 1989-02-01 | Matsushita Electric Ind Co Ltd | Burner |
| JPS6430647A (en) * | 1987-07-24 | 1989-02-01 | Matsushita Electric Ind Co Ltd | Catalyst for purifying exhaust gas |
-
1987
- 1987-10-15 JP JP62260166A patent/JPH01104345A/en active Granted
Patent Citations (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6430644A (en) * | 1987-07-24 | 1989-02-01 | Matsushita Electric Ind Co Ltd | Nox decomposition catalyst |
| JPS6430629A (en) * | 1987-07-24 | 1989-02-01 | Matsushita Electric Ind Co Ltd | Burner |
| JPS6430630A (en) * | 1987-07-24 | 1989-02-01 | Matsushita Electric Ind Co Ltd | Burner |
| JPS6430631A (en) * | 1987-07-24 | 1989-02-01 | Matsushita Electric Ind Co Ltd | Burner |
| JPS6430645A (en) * | 1987-07-24 | 1989-02-01 | Matsushita Electric Ind Co Ltd | Nox decomposition catalyst |
| JPS6430642A (en) * | 1987-07-24 | 1989-02-01 | Matsushita Electric Ind Co Ltd | Catalyst for purifying exhaust gas |
| JPS6430648A (en) * | 1987-07-24 | 1989-02-01 | Matsushita Electric Ind Co Ltd | Nox decomposition catalyst |
| JPS6430573A (en) * | 1987-07-24 | 1989-02-01 | Matsushita Electric Ind Co Ltd | Tobacco filter |
| JPS6430641A (en) * | 1987-07-24 | 1989-02-01 | Matsushita Electric Ind Co Ltd | Catalyst for purifying exhaust gas |
| JPS6430649A (en) * | 1987-07-24 | 1989-02-01 | Matsushita Electric Ind Co Ltd | Nox decomposition catalyst |
| JPS6430627A (en) * | 1987-07-24 | 1989-02-01 | Matsushita Electric Ind Co Ltd | Air filter |
| JPS6430643A (en) * | 1987-07-24 | 1989-02-01 | Matsushita Electric Ind Co Ltd | Catalyst for purifying exhaust gas |
| JPS6430628A (en) * | 1987-07-24 | 1989-02-01 | Matsushita Electric Ind Co Ltd | Burner |
| JPS6430647A (en) * | 1987-07-24 | 1989-02-01 | Matsushita Electric Ind Co Ltd | Catalyst for purifying exhaust gas |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH01266851A (en) * | 1988-04-19 | 1989-10-24 | Res Dev Corp Of Japan | Y-ba-co compound oxide catalyst |
| US5851501A (en) * | 1995-05-09 | 1998-12-22 | Daimler-Benz Ag | Process for absorbing and desorbing nitrogen oxides in exhaust gases |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0586257B2 (en) | 1993-12-10 |
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