JP3318351B2 - Catalyst for combustion of hydrocarbons - Google Patents
Catalyst for combustion of hydrocarbonsInfo
- Publication number
- JP3318351B2 JP3318351B2 JP16340692A JP16340692A JP3318351B2 JP 3318351 B2 JP3318351 B2 JP 3318351B2 JP 16340692 A JP16340692 A JP 16340692A JP 16340692 A JP16340692 A JP 16340692A JP 3318351 B2 JP3318351 B2 JP 3318351B2
- Authority
- JP
- Japan
- Prior art keywords
- catalyst
- zirconium
- lanthanum
- combustion
- composite 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.)
- Expired - Fee Related
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Description
【０００１】[0001]
【産業上の利用分野】本発明は炭化水素の燃焼用触媒に
関するものであり、特にボイラー、航空機用ジェットエ
ンジン、自動車用ガスタービン、発電用ガスタービンな
どの高温燃焼器に使用可能な燃焼活性が高く、耐熱性に
優れた炭化水素の燃焼用触媒に関するものである。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a catalyst for combustion of hydrocarbons, and more particularly to a catalyst having a combustion activity usable for high-temperature combustors such as boilers, jet engines for aircraft, gas turbines for automobiles and gas turbines for power generation. The present invention relates to a hydrocarbon combustion catalyst having high heat resistance.
【０００２】[0002]
【従来の技術】炭化水素を酸素の存在下、炭酸ガスと水
蒸気に完全酸化させる触媒としては白金、パラジウムな
どの白金族金属をアルミナ、シリカ等の無機耐熱材料を
担体として担持させた触媒が最も活性が高いとされ広く
使用されている。さらに、燃焼活性および耐熱性を改良
するために広く研究され、種々の触媒も提案されてい
る。例えば、特開昭６０−２２２１４５号公報に示され
ているように、アルミナにＬａなどの希土類元素を添加
して耐熱性を改良する方法が提案されている。2. Description of the Related Art As a catalyst for completely oxidizing hydrocarbons into carbon dioxide gas and water vapor in the presence of oxygen, a catalyst in which a platinum group metal such as platinum or palladium is supported as a carrier on an inorganic heat-resistant material such as alumina or silica is most used. It is widely used because of its high activity. In addition, various studies have been made to improve combustion activity and heat resistance, and various catalysts have been proposed. For example, as disclosed in JP-A-60-222145, a method for improving heat resistance by adding a rare earth element such as La to alumina has been proposed.
【０００３】また、最近ではジルコニアの触媒作用が注
目され、ジルコニアも燃焼触媒の担体として用いること
が検討され、そして、ジルコニアの場合には耐熱衝撃性
が低いことから、Ｍｇ，Ｃａ，Ｙなどを添加した安定化
ジルコニアについての研究が行われている。しかし、こ
れらのアルミナ、シリカ、ジルコニア等の無機耐熱材料
を担体とした触媒を高温燃焼に用いた場合、燃焼活性は
著しく低下してしまうことや、触媒活性金属として使用
される白金、パラジウムなどの白金属金属は高価である
という問題点がある。[0003] Recently, attention has been paid to the catalytic action of zirconia, and the use of zirconia as a carrier for a combustion catalyst has been studied. In the case of zirconia, Mg, Ca, Y, etc. are used because of their low thermal shock resistance. Studies have been conducted on added stabilized zirconia. However, when a catalyst using an inorganic heat-resistant material such as alumina, silica, and zirconia as a carrier is used for high-temperature combustion, the combustion activity is significantly reduced, and platinum and palladium used as catalytically active metals such as platinum and palladium are used. There is a problem that white metal is expensive.
【０００４】[0004]
【発明が解決しようとする問題点】一般に燃焼活性は触
媒活性金属の分散性に依存し、また、触媒活性金属の分
散性は担体表面積に依存すると考えられている。このよ
うな観点から、高温燃焼用触媒の開発には高温でも大き
な表面積を有し、耐熱性に優れた触媒担体の開発が重要
となっている。本発明は、上記従来技術の問題点を解決
し、触媒燃焼方式の高温燃焼器などに用いる高温でも高
い活性を有し、耐熱性に優れた炭化水素の燃焼用触媒を
提供することを目的とする。It is generally believed that the combustion activity depends on the dispersibility of the catalytically active metal, and the dispersibility of the catalytically active metal depends on the surface area of the carrier. From such a viewpoint, development of a catalyst carrier having a large surface area even at a high temperature and excellent in heat resistance is important for the development of a catalyst for high-temperature combustion. An object of the present invention is to solve the above-mentioned problems of the prior art and to provide a hydrocarbon combustion catalyst having high activity even at a high temperature used for a catalytic combustion type high temperature combustor and having excellent heat resistance. I do.
【０００５】[0005]
【課題を解決するための手段】本発明者らは炭化水素の
燃焼用触媒について鋭意研究した結果、特定の温度で焼
成して得られる特定の複合酸化物を触媒活性成分とする
ことにより燃焼活性が高く、かつ耐熱性に優れた炭化水
素の燃焼用触媒が得られることを見出し、この知見に基
づいて本発明を達成することができた。Means for Solving the Problems The present inventors have conducted intensive studies on catalysts for combustion of hydrocarbons, and found that a specific composite oxide obtained by calcining at a specific temperature is used as a catalytically active component to produce a catalyst having a combustion activity. The present inventors have found that a hydrocarbon combustion catalyst having high heat resistance and excellent heat resistance can be obtained, and the present invention has been achieved based on this finding.
【０００６】すなわち、本発明はランタンとジルコニウ
ムをＬａ／Ｚｒモル比が３／７〜７／３となるように混
合した混合物を空気中で温度７００〜１４００℃未満で
焼成したことによって得られるランタンとジルコニウム
との複合酸化物Ｌａ2 Ｚｒ2Ｏ7 を触媒活性成分とする
炭化水素の燃焼用触媒に関する。That is, the present invention relates to a lanthanum obtained by calcining a mixture of lanthanum and zirconium at a La / Zr molar ratio of 3/7 to 7/3 in air at a temperature of 700 to less than 1400 ° C. The present invention relates to a hydrocarbon combustion catalyst comprising La 2 Zr 2 O 7 as a catalyst active component.
【０００７】本発明でいうランタンとジルコニウムとの
複合酸化物Ｌａ2 Ｚｒ2 Ｏ7 は触媒活性成分として用い
られる。The composite oxide La 2 Zr 2 O 7 of lanthanum and zirconium referred to in the present invention is used as a catalytically active component.
【０００８】本発明で用いるジルコニウム塩としては、
水酸化物、塩化物、硝酸塩等が好ましい。The zirconium salt used in the present invention includes:
Hydroxides, chlorides, nitrates and the like are preferred.
【０００９】本発明で用いるランタン塩としては、塩化
物、炭酸塩、酢酸塩、硝酸塩、硫酸塩等が好ましい。The lanthanum salt used in the present invention is preferably chloride, carbonate, acetate, nitrate, sulfate and the like.
【００１０】本発明においてランタンとジルコニウムの
混合割合は、Ｌａ／Ｚｒモル比として３／７〜７／３が
好ましい。好ましくは２／３〜３／２の混合割合であ
る。さらに好ましくは１／１の割合である。Ｌａ／Ｚｒ
モル比が３／７未満であると、ランタンと未反応のジル
コニウム酸化物が生成し活性を低下させる。Ｌａ／Ｚｒ
（モル比）が３／７を越えるとジルコニアの触媒作用が
損なわれてしまうことや、耐熱衝撃性に若干の問題が生
じる。In the present invention, the mixing ratio of lanthanum and zirconium is preferably 3/7 to 7/3 in terms of La / Zr molar ratio. Preferably, the mixing ratio is 2/3 to 3/2. More preferably, the ratio is 1/1. La / Zr
When the molar ratio is less than 3/7, lanthanum and unreacted zirconium oxide are generated, and the activity is reduced. La / Zr
If (molar ratio) exceeds 3/7, the catalytic action of zirconia will be impaired and some problems will occur in thermal shock resistance.
【００１１】本発明において触媒担体として少量のアル
ミナ、シリカ、マグネシア、チタニア等の耐火性無機酸
化物を含んでもよい。In the present invention, the catalyst carrier may contain a small amount of a refractory inorganic oxide such as alumina, silica, magnesia and titania.
【００１２】本発明の触媒調製法について述べる。ジル
コニウム塩を水中に溶解させ、これにＬａ／Ｚｒモル比
が３／７〜７／３となるように所定量のランタン塩を加
えて撹拌させる。生成物を蒸発乾固させた後空気中で３
００〜６００℃、３０分〜３時間乾燥させる。さらに空
気中で焼成してランタンとジルコニウムとの複合酸化物
Ｌａ2 Ｚｒ2 Ｏ7 として触媒活性成分を製造する。The catalyst preparation method of the present invention will be described. A zirconium salt is dissolved in water, and a predetermined amount of a lanthanum salt is added thereto and stirred so that the La / Zr molar ratio becomes 3/7 to 7/3. After evaporating the product to dryness,
Dry at 00-600 ° C for 30 minutes to 3 hours. Further, the catalyst is calcined in the air to produce a catalytically active component as a composite oxide La 2 Zr 2 O 7 of lanthanum and zirconium.
【００１３】焼成温度は７００〜１４００℃未満、好ま
しくは１０００〜１３００℃の範囲で焼成して、触媒担
体を製造する。７００℃未満の温度で焼成した場合に
は、ランタンと未反応のジルコニウム酸化物が生成し、
燃焼活性を低下させることがある。The sintering temperature is from 700 to less than 1400 ° C., preferably from 1000 to 1300 ° C. to produce a catalyst carrier. When calcined at a temperature lower than 700 ° C., lanthanum and unreacted zirconium oxide are generated,
Combustion activity may be reduced.
【００１４】触媒担体の形状は押し出し品、錠剤、球
粒、顆粒、粉末、ハニカム構造等のいずれのものも所望
の大きさにして用いることができる。As the shape of the catalyst carrier, any of extruded products, tablets, spheres, granules, powders, honeycomb structures and the like can be used in a desired size.
【００１５】本発明でいう炭化水素とは、高温燃焼器の
燃料として用いることのできる、メタン、プロパン、ブ
タンあるいは都市ガス、天然ガス、灯油、軽油等であ
る。The hydrocarbon in the present invention is methane, propane, butane or city gas, natural gas, kerosene, light oil, etc., which can be used as a fuel for a high-temperature combustor.
【００１６】[0016]
【実施例】以下、本発明を実施例により詳細に説明する
が、本発明はこれらの実施例のみに限定されるものでは
ない。 実施例−１ 本発明に触媒活性成分として使用されるランタンとジル
コニウムとの複合酸化物Ｌａ2 Ｚｒ2 Ｏ7 は、以下の方
法で製造される。水酸化ジルコニウムＺｒ（ＯＨ）4 を
２５ｇ、水に溶解させたスラリー中に、硝酸ランタンＬ
ａ（ＮＯ3 ）3 ・６Ｈ2 Ｏを６８ｇ（Ｌａ／Ｚｒモル比
＝１／１）添加し１時間撹拌した後、蒸発乾固させる。
これを空気中で５００℃２時間乾燥した後、空気中で１
０００℃２時間焼成してランタン・ジルコニウムとの複
合酸化物Ａを得た。得られた複合酸化物のＸ線回折パタ
ーンをＣｕ−Ｋα線で測定した結果、複合酸化物はＬａ
2 Ｚｒ2 Ｏ7 であった。EXAMPLES Hereinafter, the present invention will be described in detail with reference to examples, but the present invention is not limited to these examples. Composite oxide La 2 Zr 2 O 7 of lanthanum and zirconium to be used as a catalyst active component in Example 1 the present invention is produced by the following method. In a slurry of 25 g of zirconium hydroxide Zr (OH) 4 dissolved in water, lanthanum nitrate L was added.
68 g (La / Zr molar ratio = 1/1) of a (NO 3 ) 3 .6H 2 O was added, stirred for 1 hour, and evaporated to dryness.
This was dried in air at 500 ° C. for 2 hours, and then dried in air.
Calcination was performed at 000 ° C. for 2 hours to obtain a composite oxide A with lanthanum / zirconium. As a result of measuring the X-ray diffraction pattern of the obtained composite oxide with Cu-Kα ray, the composite oxide was La
2 Zr 2 O 7 .
【００１７】実施例−２ 水酸化ジルコニウムＺｒ（ＯＨ）4 を２５ｇ、水に溶解
させたスラリー中に、硝酸ランタンＬａ（ＮＯ3 ）3 ・
６Ｈ2 Ｏを６８ｇ（Ｌａ／Ｚｒモル比＝１／１）添加し
１時間攪拌した後、蒸発乾固させる。これを空気中で５
００℃２時間乾燥した後、空気中で１２００℃２時間焼
成してランタン・ジルコニウム複合酸化物Ｂを得た。得
られた複合酸化物の実施例−１と同様の条件で測定した
Ｘ線回折パターンは、Ｌａ2 Ｚｒ2 Ｏ7 であった。Example 2 A slurry prepared by dissolving 25 g of zirconium hydroxide Zr (OH) 4 in water was mixed with lanthanum nitrate La (NO 3 ) 3.
68 g of 6H 2 O (La / Zr molar ratio = 1/1) was added, and the mixture was stirred for 1 hour and evaporated to dryness. This in the air 5
After drying at 00 ° C. for 2 hours, it was calcined in air at 1200 ° C. for 2 hours to obtain a lanthanum-zirconium composite oxide B. The X-ray diffraction pattern of the obtained composite oxide measured under the same conditions as in Example 1 was La 2 Zr 2 O 7 .
【００１８】比較例−１ 水酸化ジルコニウムＺｒ（ＯＨ）4 を空気中で５００℃
２時間焼成した後、さらに空気中で１０００℃２時間焼
成してジルコニウム酸化物粉末Ｃを得た。得られたジル
コニウム酸化物の実施例−１と同様の条件で測定したＸ
線回折パターンは、単斜晶のＺｒＯ2 であった。Comparative Example 1 Zirconium hydroxide Zr (OH) 4 was heated at 500 ° C. in air.
After firing for 2 hours, the powder was further fired in air at 1000 ° C. for 2 hours to obtain zirconium oxide powder C. X of the obtained zirconium oxide measured under the same conditions as in Example-1
The line diffraction pattern was monoclinic ZrO 2 .
【００１９】比較例−２ 実施例−１において水酸化ジルコニウムＺｒ（ＯＨ）4
を２５ｇ、水に溶解させたスラリー中に、硝酸ランタン
Ｌａ（ＮＯ3 ）3 ・６Ｈ2 Ｏを７．５ｇ（Ｌａ／Ｚｒモ
ル比＝１／９）添加した以外は同様の方法によってラン
タン・ジルコニウ複合酸化物Ｄを得た。得られた複合酸
化物の実施例−１と同様の条件で測定したＸ線回折パタ
ーンは、Ｌａ2 Ｚｒ2 Ｏ7 の他に未反応の単斜晶ＺｒＯ
2 が検出された。Comparative Example 2 Zirconium hydroxide Zr (OH) 4 in Example 1.
Of lanthanum nitrate La (NO 3 ) 3 .6H 2 O was added to a slurry of 25 g of lanthanum zirconium in a slurry prepared by dissolving 25 g of lanthanum zirconium in water. A composite oxide D was obtained. An X-ray diffraction pattern of the obtained composite oxide measured under the same conditions as in Example 1 shows that unreacted monoclinic ZrO besides La 2 Zr 2 O 7.
2 has been detected.
【００２０】以上実施例−１、実施例−２および比較例
−１、比較例−２で得た触媒を円筒型燃焼器に０．３ｇ
充填し、１容量％のメタンを含有するメタン−空気混合
気体を１時間当り９リッター導入して燃焼活性を測定し
た。メタン転化率は入口ガス中のメタン濃度と出口ガス
中のメタン濃度差から求めた。表１にメタン転化率１０
％および９０％となる反応温度を示す。The catalyst obtained in Example 1, Example 2, Comparative Example 1, and Comparative Example 2 was charged into a cylindrical combustor in an amount of 0.3 g.
The combustion activity was measured by charging and introducing 9 liters of a methane-air gas mixture containing 1% by volume of methane per hour. The methane conversion was determined from the difference between the methane concentration in the inlet gas and the methane concentration in the outlet gas. Table 1 shows the methane conversion rate of 10
% And 90% reaction temperature.
【００２１】[0021]
【表１】 [Table 1]
【００２２】実施例および比較例から明らかなように、
ランタンとジルコニウムをＬａ／Ｚｒモル比が３／７〜
７／３となるように混合した混合物を空気中で７００〜
１４００℃未満で焼成したことによって得られるランタ
ンとジルコニウムとの複合酸化物Ｌａ2 Ｚｒ2 Ｏ7 を触
媒活性成分とする炭化水素の燃焼用触媒は、他の金属を
触媒活性金属として用いることなしに、複合酸化物Ｌａ
2 Ｚｒ2 Ｏ7 自身で高い燃焼活性を示し、また、耐熱性
が優れていることがわかる。As is clear from the examples and comparative examples,
La / Zr molar ratio of lanthanum and zirconium is 3/7 ~
The mixture mixed so as to be 7/3 is mixed with air in air at 700 to
A hydrocarbon combustion catalyst containing a composite oxide La 2 Zr 2 O 7 of lanthanum and zirconium obtained by calcining at a temperature lower than 1400 ° C. as a catalytically active component can be used without using other metals as catalytically active metals. , Composite oxide La
2 Zr 2 O 7 itself shows high combustion activity, also it can be seen that the heat resistance is excellent.
【００２３】[0023]
【発明の効果】ランタンとジルコニウムをＬａ／Ｚｒモ
ル比が３／７〜７／３となるように混合した混合物を空
気中で温度７００〜１４００℃で焼成したことによって
得られるランタンとジルコニウムとの複合酸化物Ｌａ2
Ｚｒ2 Ｏ7 を触媒活性成分とすることにより、燃焼活性
が高く、耐熱性に優れ、かつ安価な炭化水素の燃焼用触
媒が得られる。The mixture of lanthanum and zirconium at a La / Zr molar ratio of 3/7 to 7/3 is calcined in air at a temperature of 700 to 1400 ° C. to obtain a mixture of lanthanum and zirconium. Composite oxide La 2
By using Zr 2 O 7 as a catalytically active component, an inexpensive hydrocarbon combustion catalyst having high combustion activity, excellent heat resistance, and low heat resistance can be obtained.
───────────────────────────────────────────────────── フロントページの続き (56)参考文献 特開 昭62−168544（ＪＰ，Ａ) 特開 昭61−33233（ＪＰ，Ａ) 特開 昭63−305938（ＪＰ，Ａ) 特開 平６−154605（ＪＰ，Ａ) (58)調査した分野(Int.Cl.7，ＤＢ名) B01J 21/00 - 38/74 ──────────────────────────────────────────────────続 き Continuation of the front page (56) References JP-A-62-168544 (JP, A) JP-A-61-33233 (JP, A) JP-A-63-305938 (JP, A) 154605 (JP, A) (58) Fields investigated (Int. Cl. 7 , DB name) B01J 21/00-38/74
Claims (1)
ル比が３／７〜７／３となるように混合した混合物を空
気中で温度７００〜１４００℃未満で焼成したことによ
って得られるランタンとジルコニウムとの複合酸化物Ｌ
ａ2 Ｚｒ2 Ｏ7 を触媒活性成分とする炭化水素の燃焼用
触媒。1. A lanthanum and zirconium obtained by calcining a mixture of lanthanum and zirconium at a La / Zr molar ratio of 3/7 to 7/3 in air at a temperature of 700 to less than 1400 ° C. Composite oxide L
combustion catalyst for hydrocarbon to the a 2 Zr 2 O 7 and the catalytically active component.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP16340692A JP3318351B2 (en) | 1992-06-01 | 1992-06-01 | Catalyst for combustion of hydrocarbons |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP16340692A JP3318351B2 (en) | 1992-06-01 | 1992-06-01 | Catalyst for combustion of hydrocarbons |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH06142508A JPH06142508A (en) | 1994-05-24 |
| JP3318351B2 true JP3318351B2 (en) | 2002-08-26 |
Family
ID=15773292
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP16340692A Expired - Fee Related JP3318351B2 (en) | 1992-06-01 | 1992-06-01 | Catalyst for combustion of hydrocarbons |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3318351B2 (en) |
-
1992
- 1992-06-01 JP JP16340692A patent/JP3318351B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JPH06142508A (en) | 1994-05-24 |
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