JP4182237B2 - Catalyst for gas-phase catalytic oxidation reaction of isobutane and method for producing alkene and / or oxygen-containing compound using the same - Google Patents
Catalyst for gas-phase catalytic oxidation reaction of isobutane and method for producing alkene and / or oxygen-containing compound using the same Download PDFInfo
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- JP4182237B2 JP4182237B2 JP26690397A JP26690397A JP4182237B2 JP 4182237 B2 JP4182237 B2 JP 4182237B2 JP 26690397 A JP26690397 A JP 26690397A JP 26690397 A JP26690397 A JP 26690397A JP 4182237 B2 JP4182237 B2 JP 4182237B2
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/27—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation
- C07C45/32—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen
- C07C45/33—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen of CHx-moieties
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- B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
Description
【０００１】
【発明の属する技術分野】
本発明は、イソブタンの気相接触酸化反応用触媒の提供並びにこれを用いてなるイソブタンからのイソブチレン、酢酸、アクリル酸、メタクロレイン及び、メタクリル酸等のアルケンおよび含酸素化合物の製造方法に関する。
【０００２】
【従来の技術】
イソブチレンまたはターシャリーブタノールからメタクロレインを経由し、二段階酸化によりメタクリル酸を製造する方法はよく知られており、既に工業化が実施されている。
他方、近年イソブチレンまたはターシャリーブタノールに比べると著しく反応性は乏しいものの、これらと同じ炭素骨格を有し且つ安価であるイソブタンを原料としたメタクロレインおよび／またはメタクリル酸を製造する方法が提案されている。
【０００３】
例えば、特開昭６２−１３２８３２号公報には「リンまたはヒ素を中心元素として、モリブデンを含むヘテロポリ酸を含有する触媒にイソブタンと酸素を交互に接触させ、メタクロレインおよび／またはメタクリル酸を得る方法」、特開平２−４２０３４号公報には「リンおよび／またはヒ素を中心元素として、モリブデンを含むヘテロポリ酸および／またはその塩でＡｇ、Ｚｎ、Ｃｄ、Ｔｉ、Ｚｒ、Ｎｂ、Ｔａ、Ｃｒ、Ｗ、Ｍｎ、Ｆｅ、Ｃｏ、Ｎｉ、Ｒｈ、Ｓｎ、ＢｉおよびＴｅからなる群から選ばれた少なくとも１種を触媒構成元素として含有する触媒に、イソブタンを分子状酸素を含む混合ガスを気相で接触させ、メタクロレインおよび／またはメタクリル酸を得る方法」等が知られている。
特開平５−１７８７７４号公報および特開平５−３３１０８５号公報には、イソブタンを触媒存在下に気相接触酸化して、メタクロレインおよび／またはメタクリル酸を製造するに際し、ピロリン酸ジバナジルを主成分とし、これに他の金属元素を添加し活性、選択性を改良した複合酸化物系触媒を用いることを特徴とする方法が開示されている。
【０００４】
しかしながら、イソブタンはイソブチレンやターシャリーブタノールに比べ反応性が乏しいため、イソブチレンやターシャリーブタノールの酸化条件ではイソブタンの転化率は低い。そこで、酸化反応温度を上げ、転化率を高める方法が考えられるが、リン−モリブデン系ケギン型ヘテロポリ酸系触媒は耐熱性に問題があり、反応温度を上げる方法は採用し難い。他方、ピロリン酸ジバナジルを主成分とする複合酸化物系触媒を用いる場合、必ずしも満足する選択性の改良効果が得られない。また、ピロリン酸ジバナジル系触媒を調製する際、バナジウム原料として五酸化バナジウムを用いるのが一般的であるが、五酸化バナジウムは毒性が強いため、これを使用することは衛生上好ましくないとの問題を有する。
【０００５】
【発明が解決しようとする課題】
かかる状況下において、本発明者らは、イソブタンを複合酸化物系触媒存在下、分子状酸素を用いて、気相接触酸化させることにより、工業的に有用であるイソブチレン、酢酸、アクリル酸、メタクロレイン及び、メタクリル酸等のアルケンおよび／または含酸素化合物を製造することを目的として、鋭意検討した結果、気相接触酸化反応に用いる触媒として、ニオブ−モリブデン−アンチモンを必須成分とする複合酸化物系触媒を用いる場合には、触媒として耐熱性に優れ、且つ転化率、選択性共に優れることを見い出し、本発明を完成するに至った。
【０００６】
【課題を解決するための手段】
すなわち本発明は、焼成後、一般式 ＮｂａＭｏｂＳｂｃＸｄＹｅＯｆ（式中のＮｂはニオブ、Ｍｏはモリブデン、Ｓｂはアンチモン、Ｏは酸素を表し、Ｘはリン、ヒ素、ホウ素、珪素、ゲルマニウムからなる群より選ばれた少なくとも１種の元素、Ｙはカリウム、セシウム、ルビジウム、カルシウム、マグネシウム、タリウム、クロム、マンガン、鉄、コバルト、ニッケル、銅、銀、鉛、ビスマス、アルミニウム、ガリウム、インジウム、スズ、亜鉛、ランタン、セリウム、イットリウム、タングステン、タンタル、ルテニウム、ロジウム、パラジウム、白金、イリジウム、オスミウム、レニウム、ハフニウムからなる群より選ばれた少なくとも１種の元素を表し、また添字ａ、ｂ、ｃ、ｄ及びｅは各元素の原子比を表し、ｂ＝１２としたとき、ａは０を含まない７以下の値、ｃは０を含まない２０以下の値、ｄおよびｅは０を含む６以下の値を表し、ｆは各元素の原子価および原子比によって決まる値を表す）で示される複合酸化物よりなるイソブタンの気相接触酸化反応用触媒を提供するにある。
【０００７】
さらに本発明は、イソブタンを触媒存在下に分子状酸素を用いて気相接触酸化させることによりアルケンおよび／または含酸素化合物を製造する方法に於いて、触媒として一般式 ＮｂａＭｏｂＳｂｃＸｄＹｅＯｆ（式中Ｎｂはニオブ、Ｍｏはモリブデン、Ｓｂはアンチモン、Ｏは酸素を表し、Ｘはリン、ヒ素、ホウ素、珪素、ゲルマニウム、からなる群より選ばれた少なくとも１種の元素、Ｙはカリウム、セシウム、ルビジウム、カルシウム、マグネシウム、タリウム、クロム、マンガン、鉄、コバルト、ニッケル、銅、銀、鉛、ビスマス、アルミニウム、ガリウム、インジウム、スズ、亜鉛、ランタン、セリウム、イットリウム、タングステン、タンタル、ルテニウム、ロジウム、パラジウム、白金、イリジウム、オスミウム、レニウム、ハフニウムからなる群より選ばれた少なくとも１種の元素を表し、また添字ａ、ｂ、ｃ、ｄ及びｅは各元素の原子比を表し、ｂ＝１２としたとき、ａは０を含まない７以下の値、ｃは０を含まない２０以下の値、ｄおよびｅは０を含む６以下の値を表し、ｆは各元素の原子価および原子比によって決まる値を表す。）で示される複合酸化物系触媒であることを特徴とするアルケンおよび／または含酸素化合物の製造方法を提供するにある。
【０００８】
【発明の実施の形態】
以下、本発明をさらに詳細に説明する。
本発明の特徴は、イソブタンを分子状酸素を用いて気相接触酸化させ、イソブチレン、メタクロレイン、メタクリル酸等のアルケンおよび／または含酸素化合物を製造するに際し、適用触媒として一般式 ＮｂａＭｏｂＳｂｃＸｄＹｅＯｆ（式中の記号は前記と同じ）で示されるＮｂ−Ｍｏ−Ｓｂを必須成分とする、即ちｂ＝１２のとき、ａは０＜ａ≦７、好ましくは０＜ａ≦５、ｃは０＜ｃ≦２０、好ましくは０＜ｃ≦１２の原子比よりなる複合酸化物を提供するにある。本発明においては、これらの触媒組成のいずれの成分が欠如しても満足しうる触媒効果、主として選択率の改善効果が得られない。
【０００９】
本発明に用いる触媒調製法に関しては特に制限はない。触媒は公知の種々の方法により調製できる。例えば、モリブデン、ニオブ、アンチモンからなる複合酸化物系触媒は、パラモリブデン酸アンモニウム水溶液に五酸化ニオブと三酸化アンチモンを添加し、蒸発乾固の後、焼成することにより所定の触媒を得ることができる。
モリブデン原料としては、三酸化モリブデン、モリブデン酸、パラモリブデン酸アンモニウム、モリブデン酸ナトリウム等を用いることができる。また、ニオブ、アンチモンおよび上記一般式中Ｘ、Ｙで表した元素をも含め、本発明の触媒構成物質は、触媒調製過程で酸化物に分解され得る化合物、例えば、酸化物、水酸化物、硝酸塩、アンモニウム塩、炭酸塩、塩化物、有機酸塩、アルコキサイド、金属酸アンモニウム塩等として添加使用される。より具体的には、ニオブ原料としては、シュウ酸水素ニオブ、五酸化ニオブ、五塩化ニオブ、ニオブエトキシド等、アンチモン原料としては、三酸化アンチモン、四酸化アンチモン、五酸化アンチモン、酢酸アンチモン、硫酸アンチモン、アンチモンエトキシド等、Ｘ成分としては、リン酸、ピロリン酸、ポリリン酸、ヒ酸、ホウ酸、ホウ酸アンモニウム、二酸化珪素、二酸化ゲルマニウム等、Ｙ成分としては、硝酸カリウム、塩化カリウム、硫酸カリウム、硝酸セシウム、塩化セシウム、硫酸セシウム、水酸化セシウム、硝酸ルビジウム、硫酸ルビジウム、硝酸カルシウム、塩化カルシウム、硫酸カルシウム、酸化カルシウム、硝酸マグネシウム、塩化マグネシウム、硫酸マグネシウム、酸化マグネシウム、水酸化マグネシウム、硝酸タリウム、硝酸クロム、酢酸クロム、硫酸クロム、塩化クロム、乳酸マンガン、硝酸マンガン、シュウ酸マンガン、硫酸マンガン、硝酸鉄、硫酸鉄、シュウ酸鉄アンモニウム、シュウ酸鉄、酢酸コバルト、塩化コバルト、硝酸コバルト、硫酸コバルト、水酸化コバルト、硝酸銅、塩化銅、硫酸銅、安息香酸銀、硝酸銀、炭酸銀、塩化銀、酸化銀、酢酸ビスマス、硝酸ビスマス、酸化ビスマス、酸化アルミニウム、硫酸アルミニウム、硝酸アルミニウム、塩化ガリウム、水酸化ガリウム、硝酸ガリウム、酸化ガリウム、塩化インジウム、硝酸インジウム、酢酸錫、安息香酸錫、塩化錫、蟻酸錫、水酸化錫、硫酸錫、シュウ酸錫、硝酸亜鉛、塩化亜鉛、シュウ酸亜鉛、酸化亜鉛、炭酸ランタン、塩化ランタン、シュウ酸ランタン、硝酸ランタン、硫酸ランタン、酸化セリウム、酢酸セリウム、硝酸セリウム、硝酸イットリウム、蟻酸イットリウム、炭酸イットリウム、硫酸イットリウム、酸化タングステン、タングステン酸、パラタングステン酸アンモニウム、タンタルエトキシド、水酸化タンタル、五酸化タンタル、塩化ルテニウム、酸化ルテニウム、硫酸ルテニウム、塩化ロジウム、酸化ロジウム、硫酸ロジウム、塩化パラジウム、水酸化パラジウム、硝酸パラジウム、塩化白金、塩化イリジウム、酸化イリジウム、塩化オスミウム、酸化オスミウム、塩化レニウム、酸化レニウム、塩化ハフニウム、酸化ハフニウム等が挙げられる。上記一般式中Ｘ、Ｙで表した元素は必須成分ではないが、砒素、ホウ素、ゲルマニウム、鉛、亜鉛、ガリウム等の添加は選択性の向上が、タリウム、クロム、鉄、コバルト、ニッケル、銅、銀、ビスマス、スズ、ランタン、イットリウム、パラジウム、白金、オスミウム、レニウム、ハフニウム等は活性の向上に寄与し得る。
【００１０】
触媒は担体に担持および／または希釈混合した形で用いることができる。担体および／または希釈剤としては、例えばシリカ、アルミナ、シリカ−アルミナ、マグネシア、チタニア、ゼオライト、ジルコニア、シリコン−カーバイト等が挙げられ、担持量や希釈剤と触媒との希釈混合比に制限はない。また、触媒の形状はタブレット、リング、球、押し出し品等限定はない。成型法は圧縮成形、押し出し成形、噴霧乾燥造粒等公知の方法で行うことができる。
【００１１】
反応に供する原料ガス中のイソブタン濃度は、約１モル％〜８５モル％、好ましくは３モル％〜７０モル％である。
【００１２】
分子状酸素のイソブタンに対するモル比は０．０５〜４．０、好ましくは０．１〜３．５が適当である。分子状酸素の供給源としては、空気、純酸素、酸素富化空気などが用いられる。
【００１３】
反応原料ガス中に水蒸気を含有させてもよいが、水蒸気は必ずしも必要としない。
【００１４】
原料ガス中には、貴ガス、窒素、一酸化炭素、二酸化炭素等が含まれていてもよい。また、イソブチレンが原料に含まれていても、イソブチレンはイソブタン同様メタクロレインやメタクリル酸に転換される。
【００１５】
未反応のイソブタンは、燃料として使用することもできるが、回収し再循環することもできる。イソブチレンやメタクロレインも回収、再循環することにより、メタクリル酸に転換できる。また、純酸素或いは酸素富化空気を用いた場合には、未反応の酸素も回収し再利用することが好ましい。
【００１６】
反応温度は２５０〜５５０℃の範囲で選択できるが、好ましくは３００〜５００℃である。反応圧力は減圧から加圧まで幅広く選べるが通常１００〜４００ｋＰａ、好ましくは１００〜２００ｋＰａの範囲である。
【００１７】
本発明の方法は、固定床、移動床、流動床等いずれの反応形式でも実施できる。固定床方式で使用する場合、空間速度に特に制限はないが、空間速度が小さすぎると生産性が低下するため工業的に不利である。また逆に空間速度が大きすぎると、反応活性が低下するため反応温度を高くしなければならない。そこで、通常は４００〜５０００ｈ-1、好ましくは、６００〜２０００-1の範囲である。
【００１８】
生成したアルケン及び各種含酸素化合物は抽出、蒸留等の操作により、各々の生成物に分離精製することができる。
【００１９】
【実施例】
次に実施例により本発明をさらに詳細に説明するが、本発明はこれらに限定されるものではない。転化率（％）および選択率（％）はそれぞれ次式で表す。
イソブタン転化率（％）＝（反応したイソブタンのモル数）÷（供給したイソブタンのモル数）×１００
イソブチレン選択率（％）＝（生成したイソブチレンのモル数）÷（反応したイソブタンのモル数）×１００
メタクロレイン選択率（％）＝（生成したメタクロレインのモル数）÷（反応したイソブタンのモル数）×１００
メタクリル酸選択率（％）＝（生成したメタクリル酸のモル数）÷（反応したイソブタンのモル数）×１００
有効成分の選択率（％）＝（生成したイソブチレンのモル数＋生成したメタクロレインのモル数＋生成したメタクリル酸のモル数）÷（反応したイソブタンのモル数）×１００
また、反応生成物はガスクロマトグラフィーを用いて分析した。
【００２０】
実施例１
イオン交換水６００ｍｌにシュウ酸水素ニオブ｛Ｎｂ（ＨＣ2 Ｏ4 ）5 ・ｎＨ2 Ｏ｝１０２．３７ｇを溶解し、均一な溶液とした（Ａ液）。次いで、イオン交換水７５ｍｌにモリブデン酸アンモニウム｛（ＮＨ4 ）6 Ｍｏ7 Ｏ24 ・４Ｈ2 Ｏ｝５３．１０ｇを添加し撹拌溶解した（Ｂ液）後、Ｂ液をＡ液に全量注入し、さらに三酸化アンチモン｛Ｓｂ2 Ｏ3 ｝３２．８５ｇを撹拌しながら添加した。この混合液を１リットルオートクレーブに移し、１２０℃で１７時間熟成した後、得られたスラリー溶液を２５％アンモニア水を用いｐＨをほぼ中性に調整した。
このようにして得られたスラリー溶液を加熱撹拌しつつ濃縮乾固し、さらに１２０℃にて６時間乾燥し、粉砕、篩別し４〜８メッシュの粒子を得、これを窒素気流中６００℃で２時間焼成してＭｏ12Ｎｂ4.5 Ｓｂ9 Ｏｘの組成を有する触媒を得た。
このようにして得た触媒６ｇを直径１５ｍｍのパイレックスガラス製反応管に充填し、これにイソブタン／酸素／窒素／水蒸気の割合（モル％）が４０／２０／４０／０からなる原料ガスを供給し、反応圧力１５２ｋＰａ、空間速度１０００／ｈｒの条件で酸化反応を検討したところ、反応温度４２１℃においてイソブタン転化率は２．７％、イソブチレン、メタクロレイン及びメタクリル酸への選択率はそれぞれ４３．７％、１３．８％、１．９％であった。反応温度（反応器壁温度）４００℃〜４５０℃の間を詳細に検討した結果、イソブタン転化率５％時の有効成分への選択率は５０．６％であった。
【００２１】
実施例２
イオン交換水１２００ｍｌにシュウ酸水素ニオブ｛Ｎｂ（ＨＣ2 Ｏ4 ）５・ｎＨ2 Ｏ｝２０４．７ｇを溶解し、均一な溶液とした（Ａ液）。次いで、イオン交換水１５０ｍｌにパラモリブデン酸アンモニウム｛（ＮＨ4 ）6 Ｍｏ7 Ｏ24 ・４Ｈ2 Ｏ｝１０５．８４ｇを添加し撹拌溶解した（Ｂ液）後、Ｂ液をＡ液に全量注入し、さらに三酸化アンチモン｛Ｓｂ2 Ｏ3 ｝６５．６１ｇを撹拌しながら添加した。この混合液に２５％アンモニア水入れｐＨをほぼ中性に調整した。
このようにして得られたスラリー溶液を加熱撹拌しつつ濃縮乾固し、さらに１２０℃にて３時間乾燥し、粉砕、篩別し４〜８メッシュの粒子を得、これを窒素気流中６００℃で２時間焼成してＭｏ12Ｎｂ4.5 Ｓｂ9 Ｏｘの組成を有する触媒を得た。
この触媒を用い実施例１と同じ条件で酸化反応を行った。その結果、反応温度４２３℃においてイソブタン転化率は２．７％、イソブチレン、メタクロレイン及びメタクリル酸への選択率はそれぞれ３５．３％、１８．９％、０．４％であった。反応温度（反応器壁温度）４００℃〜４５０℃の間を詳細に検討した結果、イソブタン転化率５％時の有効成分への選択率は４６．５％であった。
【００２２】
実施例３
実施例２の方法において、シュウ酸水素ニオブ｛Ｎｂ（ＨＣ2 Ｏ4 ）5 ・ｎＨ2 Ｏ｝の添加量を変えた他は実施例２と同一方法によりＭｏ12Ｎｂ4 Ｓｂ9 Ｏｘの組成を有する触媒を得た。
この触媒を用い実施例１と同一条件で酸化反応を行った。その結果、反応温度４２４℃においてイソブタン転化率は４．０％、イソブチレン、メタクロレイン及びメタクリル酸への選択率はそれぞれ２５．４％、１７．２％、１．９％であった。反応温度（反応器壁温度）４００℃〜４５０℃の間を詳細に検討した結果、イソブタン転化率５％時の有効成分への選択率は４２．５％であった。
【００２３】
実施例４
実施例２の方法において、シュウ酸水素ニオブ｛Ｎｂ（ＨＣ2 Ｏ4 ）５・ｎＨ2 Ｏ｝の添加量を変えた他は実施例２と同一方法により、Ｍｏ12Ｎｂ3 Ｓｂ9 Ｏｘの組成を有する触媒を得た。
この触媒を用い実施例１と同一条件で酸化反応を行った。その結果、反応温度４２９℃においてイソブタン転化率は３．９％、イソブチレン、メタクロレイン及びメタクリル酸への選択率はそれぞれ１９．７％、１６．２％、０．９％であった。反応温度（反応器壁温度）４００℃〜４５０℃の間を詳細に検討した結果、イソブタン転化率５％時の有効成分への選択率は３４．７％であった。
【００２４】
実施例５
実施例２において得られたスラリー乾燥品を空気中６００℃で２時間焼成してた。
この触媒を用い実施例１と同じ条件で酸化反応を行ったところ、反応温度４０６℃においてイソブタン転化率は４．４％、イソブチレン、メタクロレイン及びメタクリル酸への選択率はそれぞれ１４．４％、１８．２％、３．４％であった。反応温度（反応器壁温度）３５０℃〜４２５℃の間を詳細に検討した結果、イソブタン転化率５％時の有効成分への選択率は３４．５％であった。
【００２５】
実施例６
実施例２の方法において、三酸化アンチモン｛Ｓｂ2 Ｏ3 ｝の添加量を変えた他は実施例２と同一方法によりＭｏ12Ｎｂ4.5 Ｓｂ6 Ｏｘの組成を有する触媒を得た。
この触媒を用い実施例１と同一条件で酸化反応を行った。その結果、反応温度４２９℃においてイソブタン転化率は３．６％、イソブチレン、メタクロレイン及びメタクリル酸への選択率はそれぞれ２８．２％、１５．１％、０．８％であった。反応温度（反応器壁温度）４００℃〜４５０℃の間を詳細に検討した結果、イソブタン転化率５％時の有効成分への選択率は３８．１％であった。
【００２６】
比較例１
イオン交換水４００ｍｌにシュウ酸水素ニオブ｛Ｎｂ（ＨＣ2 Ｏ4 ）5 ・ｎＨ2 Ｏ｝６８．３３ｇを加え撹拌溶解後、バナジウム濃度が２ｍｏｌ／ｌであるシュウ酸バナジル水溶液７５ｍｌを添加し均一な溶液とした（Ａ液）。イオン交換水１５０ｍｌにパラモリブデン酸アンモニウム｛（ＮＨ4 ）6 Ｍｏ7 Ｏ24・４Ｈ2 Ｏ｝１０５．９５ｇを添加し撹拌溶解した（Ｂ液）後、Ａ液をＢ液に全量注入し、スラリー溶液を得た。他方、イオン交換水１００ｍｌに７０％硝酸｛ＨＮＯ3 ｝６７．５９ｇ、酢酸スズ｛Ｓｎ（ＣＨ3 ＣＯ2 ）2 ｝３５．５５ｇを添加し、均一な水溶液を調製した（Ｃ液）。Ｃ液を撹拌しながら上記スラリー溶液に全量注入した。得られたスラリー溶液に２５％アンモニア水を添加し、ｐＨをほぼ中性に調整した。
このようにして得られたスラリー溶液を加熱撹拌しつつ濃縮乾固後、粉砕、篩別し４〜８メッシュの粒子を得、これを窒素気流中６００℃で２時間焼成しＭｏ12Ｎｂ1.5 Ｖ3 Ｓｎ3 Ｏｘの組成を有する触媒を得た。
この触媒を用い実施例１と同一条件で酸化反応を行った。その結果、反応温度３２２℃においてイソブタン転化率は７．３％、イソブチレン、メタクロレイン及びメタクリル酸への選択率はそれぞれ１．６％、３．９％、１．６％であった。反応温度（反応器壁温度）２９０℃〜３５０℃の間を詳細に検討した結果、イソブタン転化率５％時の有効成分への選択率は８．４％であった。
【００２７】
比較例２
イオン交換水１２００ｍｌにパラモリブデン酸アンモニウム｛（（ＮＨ4 ）6 Ｍｏ7 Ｏ24・４Ｈ2 Ｏ）｝２１１．９ｇを添加し、撹拌溶解させたこの溶液に、バナジウム濃度が１ｍｏｌ／ｌであるシュウ酸バナジル水溶液３００ｍｌを添加した。この混合液に２５％アンモニア水を添加しｐＨをほぼ中性に調整した。その後、１２０℃の乾燥機中で水分を蒸発させた。これを窒素気流中６００℃で３時間焼成しＭｏ12Ｖ3 Ｏｘの組成を有する触媒を得た。
この触媒を用い、イソブタン／酸素／窒素／水蒸気の割合（モル％）が２５／１２／３３／３０からなる原料ガスを供給し、反応圧力１５２ｋＰａ、空間速度１０００／ｈｒの条件で酸化反応を検討したところ、反応温度３５３℃においてイソブタン転化率は５．０％、イソブチレン、メタクロレイン及びメタクリル酸への選択率はそれぞれ６．７％、３．１％、０．７％であった。反応器壁温３１０〜３５０℃の間を詳細に検討した結果、イソブタンの転化率５％のときの有効成分への選択率は１０．５％であった。
【００２８】
比較例３
比較例２において得られたスラリー乾燥品を空気中、３５０℃で６時間焼成した。
この触媒を用い比較例１と同じ条件で酸化反応を行った。その結果、反応温度２９１℃においてイソブタン転化率は４．２％、イソブチレン、メタクロレイン及びメタクリル酸への選択率はそれぞれ２．６％、２．４％、０．４％であった。反応器壁温２９０〜３５０℃の間を詳細に検討した結果、イソブタンの転化率５％のときの有効成分への選択率は５．３％であった。
【００２９】
比較例４
イオン交換水３００ｍｌにシュウ酸水素ニオブ｛ Ｎｂ（ＨＣ2 Ｏ4 ）5 ・ｎＨ2 Ｏ｝５８．８７ｇを溶解し、均一な溶液とした（Ａ液）。
他方、イオン交換水３２６ｍｌにメタバナジン酸アンモニウム｛ＮＨ4 ＶＯ3 ｝１５．７１ｇ、パラモリブデン酸アンモニウム｛（（ＮＨ4 ）6 Ｍｏ7 Ｏ24・４Ｈ2 Ｏ）｝７８．９０ｇ、テルル酸｛Ｈ6 ＴｅＯ6 ｝２３．６１ｇを加え５５℃に保持して撹拌溶解し、均一な溶液とした（Ｂ液）。
Ａ液にＢ液を全量注入し沈殿を生成させスラリー溶液とした。このスラリー溶液に２５％アンモニア水入れｐＨをほぼ中性に調整した。
このようにして得られたスラリー溶液を加熱撹拌しつつ濃縮乾固し、さらに１２０℃にて１８時間乾燥し、粉砕、篩別し４〜８メッシュの粒子を得、これを窒素気流中６００℃で２時間焼成しＭｏ12Ｎｂ1.4 Ｖ3.6 Ｔｅ2.8 Ｏｘの組成を有する触媒を得た。
この触媒を用い、比較例１と同一条件で酸化反応を行った。その結果、反応温度３５４℃のとき、イソブタン転化率は４．９％、イソブチレン、メタクロレイン及びメタクリル酸の選択率はそれぞれ４．３％、１３．９％及び１１．８％であった。反応器壁温３３０〜４００℃の間を詳細に検討した結果、イソブタンの転化率５％のときの有効成分への選択率は３０．０％であった。
【００３０】
比較例５
イオン交換水４００ｍｌにヒドロキシルアミン塩酸塩｛ＮＨ2 ＯＨ・ＨＣｌ｝２７．８ｇ、８０％リン酸｛Ｈ3 ＰＯ4 ｝５８．８ｇを溶解し、均一な溶液とした後、ホットスターラーにて８０℃まで加熱した。この溶液に五酸化バナジウム｛Ｖ2 Ｏ5 ｝３６．４ｇを徐々に添加した。五酸化バナジウム添加終了から約６時間撹拌を続け、１２０℃の乾燥機中で１５時間乾燥させ、水分を蒸発させた。得られた乾固物を空気中５００℃で１５時間焼成して（ＶＯ）2 Ｐ2 Ｏ7 の組成を有する触媒を得た。
上記の方法により得た触媒９ｇを直径１５ｍｍのパイレックスガラス製反応管に充填し、これにイソブタン／酸素／窒素／水蒸気の割合（モル％）が４７／３６／１７／０からなる原料ガスを供給し、反応圧力１５２ｋＰａ、空間速度１０００／ｈｒの条件で酸化反応を行ったところ、反応温度３６７℃においてイソブタン転化率は２．１％、イソブチレン、メタクロレイン及びメタクリル酸への選択率はそれぞれ１．７％、２．６％、８．９％であった。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a catalyst for gas-phase catalytic oxidation reaction of isobutane and a method for producing alkenes such as isobutylene, acetic acid, acrylic acid, methacrolein and methacrylic acid and oxygen-containing compounds from isobutane using the catalyst.
[0002]
[Prior art]
A method for producing methacrylic acid from isobutylene or tertiary butanol via methacrolein by two-stage oxidation is well known and has already been industrialized.
On the other hand, in recent years, a method for producing methacrolein and / or methacrylic acid using isobutane as a raw material, which has the same carbon skeleton and is inexpensive, has been proposed, although the reactivity is significantly lower than that of isobutylene or tertiary butanol. Yes.
[0003]
For example, Japanese Patent Application Laid-Open No. 62-132932 discloses a method for obtaining methacrolein and / or methacrylic acid by alternately contacting isobutane and oxygen with a catalyst containing phosphorus or arsenic as a central element and a heteropolyacid containing molybdenum. JP-A-2-42034 discloses a heteropolyacid containing molybdenum and / or a salt thereof containing phosphorus and / or arsenic as a central element and Ag, Zn, Cd, Ti, Zr, Nb, Ta, Cr, W , Mn, Fe, Co, Ni, Rh, Sn, Bi, and a catalyst containing at least one selected from the group consisting of Te and isobutane as a catalytic constituent in contact with a mixed gas containing molecular oxygen in the gas phase To obtain methacrolein and / or methacrylic acid ”.
In JP-A-5-178774 and JP-A-5-331085, in the production of methacrolein and / or methacrylic acid by gas phase catalytic oxidation of isobutane in the presence of a catalyst, divanadyl pyrophosphate is a main component. Also disclosed is a method characterized by using a composite oxide catalyst in which the activity and selectivity are improved by adding another metal element thereto.
[0004]
However, since isobutane is less reactive than isobutylene and tertiary butanol, the conversion of isobutane is low under the oxidation conditions of isobutylene and tertiary butanol. Therefore, a method of increasing the oxidation reaction temperature and increasing the conversion rate is conceivable, but the phosphorus-molybdenum-based Keggin heteropolyacid catalyst has a problem in heat resistance, and a method of increasing the reaction temperature is difficult to adopt. On the other hand, when a composite oxide catalyst mainly composed of divanadyl pyrophosphate is used, a satisfactory selectivity improvement effect cannot always be obtained. Also, when preparing divanadyl pyrophosphate-based catalysts, it is common to use vanadium pentoxide as a vanadium raw material, but vanadium pentoxide is highly toxic, so the use of this is not desirable for hygiene. Have
[0005]
[Problems to be solved by the invention]
Under such circumstances, the present inventors have carried out industrially useful isobutylene, acetic acid, acrylic acid, methacrochromic acid by subjecting isobutane to gas phase catalytic oxidation using molecular oxygen in the presence of a complex oxide catalyst. As a result of intensive studies aimed at producing alkene and / or oxygen-containing compounds such as rain and methacrylic acid, a complex oxide containing niobium-molybdenum-antimony as an essential component as a catalyst used in a gas phase catalytic oxidation reaction In the case of using a system catalyst, it has been found that the catalyst is excellent in heat resistance and excellent in conversion and selectivity, and the present invention has been completed.
[0006]
[Means for Solving the Problems]
That is, the present invention has a general formula NbaMobSbcXdYeOf (where Nb is niobium, Mo is molybdenum, Sb is antimony, O is oxygen, and X is selected from the group consisting of phosphorus, arsenic, boron, silicon, and germanium after firing. At least one element, Y is potassium, cesium, rubidium, calcium, magnesium, thallium, chromium, manganese, iron, cobalt, nickel, copper, silver, lead, bismuth, aluminum, gallium, indium, tin, zinc, lanthanum Represents at least one element selected from the group consisting of cerium, yttrium, tungsten, tantalum, ruthenium, rhodium, palladium, platinum, iridium, osmium, rhenium, hafnium, and the subscripts a, b, c, d and e Represents the atomic ratio of each element, and b = 12. Where a is a value of 7 or less not including 0, c is a value of 20 or less not including 0, d and e are values of 6 or less including 0, and f is determined by the valence and atomic ratio of each element. The present invention provides a catalyst for gas-phase catalytic oxidation reaction of isobutane comprising a composite oxide represented by
[0007]
Furthermore, the present invention relates to a method for producing an alkene and / or an oxygen-containing compound by vapor-phase catalytic oxidation of isobutane with molecular oxygen in the presence of a catalyst, wherein NbaMobSbcXdYeOf (where Nb is niobium) is used as a catalyst. , Mo represents molybdenum, Sb represents antimony, O represents oxygen, X represents at least one element selected from the group consisting of phosphorus, arsenic, boron, silicon, and germanium, Y represents potassium, cesium, rubidium, calcium, Magnesium, thallium, chromium, manganese, iron, cobalt, nickel, copper, silver, lead, bismuth, aluminum, gallium, indium, tin, zinc, lanthanum, cerium, yttrium, tungsten, tantalum, ruthenium, rhodium, palladium, platinum, Iridium, osmium, rhenium, It represents at least one element selected from the group consisting of hafnium, subscripts a, b, c, d and e represent the atomic ratio of each element, and when b = 12, a does not include 0 The following values, c is a value of 20 or less not including 0, d and e are values of 6 or less including 0, and f is a value determined by the valence and atomic ratio of each element. An object of the present invention is to provide a method for producing an alkene and / or oxygen-containing compound, which is an oxide catalyst.
[0008]
DETAILED DESCRIPTION OF THE INVENTION
Hereinafter, the present invention will be described in more detail.
A feature of the present invention is that, in the production of alkenes and / or oxygen-containing compounds such as isobutylene, methacrolein, and methacrylic acid by vapor-phase catalytic oxidation of isobutane with molecular oxygen, a general formula NbaMobSbcXdYeOf (wherein Nb-Mo-Sb represented by the same formula as above), that is, when b = 12, a is 0 <a ≦ 7, preferably 0 <a ≦ 5, and c is 0 <c ≦ The object is to provide a composite oxide having an atomic ratio of 20, preferably 0 <c ≦ 12. In the present invention, even if any component of these catalyst compositions is absent, a satisfactory catalytic effect, mainly a selectivity improvement effect, cannot be obtained.
[0009]
There is no particular limitation on the method for preparing the catalyst used in the present invention. The catalyst can be prepared by various known methods. For example, a composite oxide catalyst composed of molybdenum, niobium, and antimony can be obtained by adding niobium pentoxide and antimony trioxide to an aqueous ammonium paramolybdate solution, evaporating to dryness, and then firing the resulting catalyst. it can.
As the molybdenum raw material, molybdenum trioxide, molybdic acid, ammonium paramolybdate, sodium molybdate, or the like can be used. In addition, the catalyst constituent materials of the present invention including niobium, antimony and the elements represented by X and Y in the above general formula are compounds that can be decomposed into oxides during the catalyst preparation process, such as oxides, hydroxides, It is added and used as nitrate, ammonium salt, carbonate, chloride, organic acid salt, alkoxide, metal acid ammonium salt and the like. More specifically, niobium hydrogen oxalate, niobium pentoxide, niobium pentachloride, niobium ethoxide, etc. as niobium raw materials, antimony trioxide, antimony tetraoxide, antimony pentoxide, antimony acetate, sulfuric acid as antimony raw materials Antimony, antimony ethoxide, etc. X components include phosphoric acid, pyrophosphoric acid, polyphosphoric acid, arsenic acid, boric acid, ammonium borate, silicon dioxide, germanium dioxide, etc. Y components include potassium nitrate, potassium chloride, potassium sulfate , Cesium nitrate, cesium chloride, cesium sulfate, cesium hydroxide, rubidium nitrate, rubidium sulfate, calcium nitrate, calcium chloride, calcium sulfate, calcium oxide, magnesium nitrate, magnesium chloride, magnesium sulfate, magnesium oxide, magnesium hydroxide, thallium nitrate , Chromium nitrate, chromium acetate, chromium sulfate, chromium chloride, manganese lactate, manganese nitrate, manganese oxalate, manganese sulfate, iron nitrate, iron sulfate, ammonium iron oxalate, iron oxalate, cobalt acetate, cobalt chloride, cobalt nitrate , Cobalt sulfate, cobalt hydroxide, copper nitrate, copper chloride, copper sulfate, silver benzoate, silver nitrate, silver carbonate, silver chloride, silver oxide, bismuth acetate, bismuth nitrate, bismuth oxide, aluminum oxide, aluminum sulfate, aluminum nitrate, Gallium chloride, Gallium hydroxide, Gallium nitrate, Gallium oxide, Indium chloride, Indium nitrate, Tin acetate, Tin benzoate, Tin chloride, Tin formate, Tin hydroxide, Tin sulfate, Tin oxalate, Zinc nitrate, Zinc chloride, Shu Zinc acid, zinc oxide, lanthanum carbonate, lanthanum chloride, lanthanum oxalate, lanthanum nitrate, sulfuric acid Tantalum oxide, cerium oxide, cerium acetate, cerium nitrate, yttrium nitrate, yttrium formate, yttrium carbonate, yttrium sulfate, tungsten oxide, tungstic acid, ammonium paratungstate, tantalum ethoxide, tantalum hydroxide, tantalum pentoxide, ruthenium chloride, oxidation Ruthenium, ruthenium sulfate, rhodium chloride, rhodium oxide, rhodium sulfate, palladium chloride, palladium hydroxide, palladium nitrate, platinum chloride, iridium chloride, iridium oxide, osmium chloride, osmium oxide, rhenium chloride, rhenium oxide, hafnium chloride, hafnium oxide Etc. Although the elements represented by X and Y in the above general formula are not essential components, the addition of arsenic, boron, germanium, lead, zinc, gallium, etc. improves selectivity, but thallium, chromium, iron, cobalt, nickel, copper Silver, bismuth, tin, lanthanum, yttrium, palladium, platinum, osmium, rhenium, hafnium, and the like can contribute to the improvement of activity.
[0010]
The catalyst can be used in a form supported on a support and / or diluted and mixed. Examples of the carrier and / or diluent include silica, alumina, silica-alumina, magnesia, titania, zeolite, zirconia, silicon-carbite, and the like, and there are limitations on the loading amount and the dilution mixture ratio of the diluent and the catalyst. Absent. The shape of the catalyst is not limited to tablets, rings, spheres, extruded products and the like. The molding method can be performed by a known method such as compression molding, extrusion molding, or spray drying granulation.
[0011]
The isobutane concentration in the raw material gas used for the reaction is about 1 to 85 mol%, preferably 3 to 70 mol%.
[0012]
The molar ratio of molecular oxygen to isobutane is 0.05 to 4.0, preferably 0.1 to 3.5. Air, pure oxygen, oxygen-enriched air, or the like is used as the molecular oxygen supply source.
[0013]
Although water vapor may be included in the reaction raw material gas, water vapor is not always necessary.
[0014]
The source gas may contain noble gas, nitrogen, carbon monoxide, carbon dioxide and the like. Even if isobutylene is contained in the raw material, isobutylene is converted to methacrolein or methacrylic acid as is isobutane.
[0015]
Unreacted isobutane can be used as fuel, but can also be recovered and recycled. Isobutylene and methacrolein can also be recovered and recycled to convert to methacrylic acid. In addition, when pure oxygen or oxygen-enriched air is used, it is preferable to recover and reuse unreacted oxygen.
[0016]
The reaction temperature can be selected in the range of 250 to 550 ° C, preferably 300 to 500 ° C. The reaction pressure can be widely selected from reduced pressure to increased pressure, but is usually in the range of 100 to 400 kPa, preferably 100 to 200 kPa.
[0017]
The method of the present invention can be carried out in any reaction mode such as a fixed bed, a moving bed, and a fluidized bed. When used in a fixed bed system, the space velocity is not particularly limited, but if the space velocity is too small, the productivity is lowered, which is industrially disadvantageous. On the other hand, if the space velocity is too large, the reaction activity decreases, so the reaction temperature must be increased. Therefore, it is usually in the range of 400 to 5000 h −1 , preferably 600 to 2000 −1 .
[0018]
The produced alkene and various oxygen-containing compounds can be separated and purified into respective products by operations such as extraction and distillation.
[0019]
【Example】
EXAMPLES Next, although an Example demonstrates this invention further in detail, this invention is not limited to these. The conversion rate (%) and the selectivity (%) are expressed by the following equations, respectively.
Isobutane conversion rate (%) = (number of moles of reacted isobutane) ÷ (number of moles of isobutane supplied) × 100
Isobutylene selectivity (%) = (number of moles of isobutylene formed) ÷ (number of moles of reacted isobutane) × 100
Methacrolein selectivity (%) = (number of moles of methacrolein produced) ÷ (number of moles of reacted isobutane) × 100
Methacrylic acid selectivity (%) = (number of moles of methacrylic acid produced) ÷ (number of moles of reacted isobutane) × 100
Active ingredient selectivity (%) = (number of moles of produced isobutylene + number of moles of produced methacrolein + number of moles of produced methacrylic acid) ÷ (number of moles of reacted isobutane) × 100
The reaction product was analyzed using gas chromatography.
[0020]
Example 1
Niobium hydrogen oxalate {Nb (HC 2 O 4 ) 5 · nH 2 O} (102.37 g) was dissolved in 600 ml of ion-exchanged water to obtain a uniform solution (solution A). Next, after adding 53.10 g of ammonium molybdate {(NH 4 ) 6 Mo 7 O 24 · 4H 2 O} to 75 ml of ion-exchanged water and stirring and dissolving (liquid B), the entire amount of liquid B was injected into liquid A, Further, 32.85 g of antimony trioxide {Sb 2 O 3 } was added with stirring. This mixed solution was transferred to a 1 liter autoclave and aged at 120 ° C. for 17 hours, and then the pH of the obtained slurry solution was adjusted to almost neutral using 25% aqueous ammonia.
The slurry solution thus obtained was concentrated to dryness with heating and stirring, further dried at 120 ° C. for 6 hours, pulverized and sieved to obtain particles of 4 to 8 mesh, and this was 600 ° C. in a nitrogen stream. And a catalyst having a composition of Mo 12 Nb 4.5 Sb 9 Ox was obtained.
6 g of the catalyst thus obtained was filled into a Pyrex glass reaction tube having a diameter of 15 mm, and a raw material gas having an isobutane / oxygen / nitrogen / water vapor ratio (mol%) of 40/20/40/0 was supplied thereto. Then, the oxidation reaction was examined under the conditions of a reaction pressure of 152 kPa and a space velocity of 1000 / hr. At a reaction temperature of 421 ° C., the conversion of isobutane was 2.7%, and the selectivity to isobutylene, methacrolein and methacrylic acid was 43. 7%, 13.8% and 1.9%. As a result of examining the reaction temperature (reactor wall temperature) between 400 ° C. and 450 ° C. in detail, the selectivity to the active ingredient when the isobutane conversion was 5% was 50.6%.
[0021]
Example 2
Niobium hydrogen oxalate {Nb (HC 2 O 4 ) 5 · nH 2 O} 204.7 g was dissolved in 1200 ml of ion-exchanged water to obtain a uniform solution (solution A). Next, 105.84 g of ammonium paramolybdate {(NH 4 ) 6 Mo 7 O 24 · 4H 2 O} was added to 150 ml of ion-exchanged water and dissolved by stirring (solution B), and then the entire amount of solution B was injected into solution A. Further, 65.61 g of antimony trioxide {Sb 2 O 3 } was added with stirring. 25% ammonia water was added to this mixed solution, and the pH was adjusted to be almost neutral.
The slurry solution thus obtained was concentrated to dryness while stirring with heating, further dried at 120 ° C. for 3 hours, pulverized and sieved to obtain particles of 4 to 8 mesh, which were obtained at 600 ° C. in a nitrogen stream. And a catalyst having a composition of Mo 12 Nb 4.5 Sb 9 Ox was obtained.
Using this catalyst, an oxidation reaction was carried out under the same conditions as in Example 1. As a result, at a reaction temperature of 423 ° C., the conversion of isobutane was 2.7%, and the selectivity to isobutylene, methacrolein and methacrylic acid was 35.3%, 18.9% and 0.4%, respectively. As a result of examining the reaction temperature (reactor wall temperature) between 400 ° C. and 450 ° C. in detail, the selectivity to the active ingredient when the isobutane conversion was 5% was 46.5%.
[0022]
Example 3
In the method of Example 2, the composition of Mo 12 Nb 4 Sb 9 Ox was changed by the same method as in Example 2 except that the addition amount of niobium hydrogen oxalate {Nb (HC 2 O 4 ) 5 · nH 2 O} was changed. A catalyst having was obtained.
Using this catalyst, an oxidation reaction was carried out under the same conditions as in Example 1. As a result, at a reaction temperature of 424 ° C., the conversion of isobutane was 4.0%, and the selectivity to isobutylene, methacrolein and methacrylic acid was 25.4%, 17.2% and 1.9%, respectively. As a result of examining the reaction temperature (reactor wall temperature) between 400 ° C. and 450 ° C. in detail, the selectivity to the active ingredient when the isobutane conversion was 5% was 42.5%.
[0023]
Example 4
The composition of Mo 12 Nb 3 Sb 9 Ox was the same as in Example 2 except that the amount of niobium hydrogen oxalate {Nb (HC 2 O 4 ) 5 · nH 2 O} was changed in the same manner as in Example 2. A catalyst having was obtained.
Using this catalyst, an oxidation reaction was carried out under the same conditions as in Example 1. As a result, at a reaction temperature of 429 ° C., the conversion of isobutane was 3.9%, and the selectivity to isobutylene, methacrolein and methacrylic acid was 19.7%, 16.2% and 0.9%, respectively. As a result of examining the reaction temperature (reactor wall temperature) between 400 ° C. and 450 ° C. in detail, the selectivity to the active ingredient when the isobutane conversion was 5% was 34.7%.
[0024]
Example 5
The dried slurry obtained in Example 2 was calcined in air at 600 ° C. for 2 hours.
When this catalyst was used for the oxidation reaction under the same conditions as in Example 1, at a reaction temperature of 406 ° C., the conversion of isobutane was 4.4%, and the selectivity to isobutylene, methacrolein and methacrylic acid was 14.4%, 18.2% and 3.4%. As a result of detailed examination of the reaction temperature (reactor wall temperature) between 350 ° C. and 425 ° C., the selectivity to the active ingredient when the isobutane conversion was 5% was 34.5%.
[0025]
Example 6
A catalyst having a composition of Mo 12 Nb 4.5 Sb 6 Ox was obtained in the same manner as in Example 2 except that the amount of antimony trioxide {Sb 2 O 3 } was changed in the method of Example 2.
Using this catalyst, an oxidation reaction was carried out under the same conditions as in Example 1. As a result, at a reaction temperature of 429 ° C., the conversion of isobutane was 3.6%, and the selectivity to isobutylene, methacrolein and methacrylic acid was 28.2%, 15.1% and 0.8%, respectively. As a result of examining the reaction temperature (reactor wall temperature) between 400 ° C. and 450 ° C. in detail, the selectivity to the active ingredient when the isobutane conversion was 5% was 38.1%.
[0026]
Comparative Example 1
After adding 68.33 g of niobium hydrogen oxalate {Nb (HC 2 O 4 ) 5 · nH 2 O} to 400 ml of ion-exchanged water and stirring and dissolving, 75 ml of vanadyl oxalate aqueous solution having a vanadium concentration of 2 mol / l was added to make it uniform. It was set as the solution (A liquid). After adding 105.95 g of ammonium paramolybdate {(NH 4 ) 6 Mo 7 O 24 · 4H 2 O} to 150 ml of ion-exchanged water and stirring and dissolving it (Liquid B), the entire amount of liquid A was injected into liquid B and slurried. A solution was obtained. On the other hand, 70% nitric acid {HNO 3 } 67.59 g and tin acetate {Sn (CH 3 CO 2 ) 2 } 35.55 g were added to 100 ml of ion-exchanged water to prepare a uniform aqueous solution (solution C). The whole amount of the liquid C was poured into the slurry solution while stirring. 25% aqueous ammonia was added to the resulting slurry solution to adjust the pH to almost neutral.
The slurry solution thus obtained was concentrated to dryness with heating and stirring, then pulverized and sieved to obtain particles of 4 to 8 mesh, which were calcined at 600 ° C. for 2 hours in a nitrogen stream, and Mo 12 Nb 1.5 V A catalyst having a composition of 3 Sn 3 Ox was obtained.
Using this catalyst, an oxidation reaction was carried out under the same conditions as in Example 1. As a result, at a reaction temperature of 322 ° C., the conversion of isobutane was 7.3%, and the selectivity to isobutylene, methacrolein and methacrylic acid was 1.6%, 3.9% and 1.6%, respectively. As a result of examining the reaction temperature (reactor wall temperature) between 290 ° C. and 350 ° C. in detail, the selectivity to the active ingredient when the isobutane conversion was 5% was 8.4%.
[0027]
Comparative Example 2
To 1200 ml of ion-exchanged water, 211.9 g of ammonium paramolybdate {((NH 4 ) 6 Mo 7 O 24 · 4H 2 O)} was added and dissolved in the solution with a vanadium concentration of 1 mol / l. 300 ml of an aqueous vanadyl acid solution was added. 25% aqueous ammonia was added to the mixture to adjust the pH to almost neutral. Then, the water | moisture content was evaporated in 120 degreeC drying machine. This was calcined in a nitrogen stream at 600 ° C. for 3 hours to obtain a catalyst having a composition of Mo 12 V 3 Ox.
Using this catalyst, a raw material gas having a ratio of isobutane / oxygen / nitrogen / water vapor (mol%) of 25/12/33/30 was supplied, and the oxidation reaction was examined under the conditions of a reaction pressure of 152 kPa and a space velocity of 1000 / hr. As a result, at a reaction temperature of 353 ° C., the conversion of isobutane was 5.0%, and the selectivity to isobutylene, methacrolein and methacrylic acid was 6.7%, 3.1% and 0.7%, respectively. As a result of detailed examination of the reactor wall temperature of 310 to 350 ° C., the selectivity to the active ingredient when the conversion of isobutane was 5% was 10.5%.
[0028]
Comparative Example 3
The dried slurry obtained in Comparative Example 2 was fired at 350 ° C. for 6 hours in air.
Using this catalyst, an oxidation reaction was performed under the same conditions as in Comparative Example 1. As a result, at a reaction temperature of 291 ° C., the conversion of isobutane was 4.2%, and the selectivity to isobutylene, methacrolein and methacrylic acid was 2.6%, 2.4% and 0.4%, respectively. As a result of examining the reactor wall temperature between 290 and 350 ° C. in detail, the selectivity to the active ingredient when the conversion of isobutane was 5% was 5.3%.
[0029]
Comparative Example 4
58.87 g of niobium hydrogen oxalate {Nb (HC 2 O 4 ) 5 · nH 2 O} was dissolved in 300 ml of ion-exchanged water to obtain a uniform solution (solution A).
On the other hand, ammonium metavanadate {NH 4 VO 3 } 15.71 g, ammonium paramolybdate {((NH 4 ) 6 Mo 7 O 24 · 4H 2 O)} 78.90 g, telluric acid {H 6 TeO 6 } 23.61 g was added and kept at 55 ° C. with stirring and dissolved to obtain a uniform solution (liquid B).
The entire amount of the liquid B was injected into the liquid A to form a precipitate to form a slurry solution. 25% ammonia water was added to the slurry solution and the pH was adjusted to be almost neutral.
The slurry solution thus obtained was concentrated to dryness with heating and stirring, and further dried at 120 ° C. for 18 hours, crushed and sieved to obtain particles of 4 to 8 mesh, which were obtained at 600 ° C. in a nitrogen stream. And a catalyst having a composition of Mo 12 Nb 1.4 V 3.6 Te 2.8 Ox was obtained.
Using this catalyst, an oxidation reaction was performed under the same conditions as in Comparative Example 1. As a result, when the reaction temperature was 354 ° C., the conversion of isobutane was 4.9%, and the selectivities of isobutylene, methacrolein and methacrylic acid were 4.3%, 13.9% and 11.8%, respectively. As a result of examining the reactor wall temperature in the range of 330 to 400 ° C. in detail, the selectivity to the active ingredient when the conversion of isobutane was 5% was 30.0%.
[0030]
Comparative Example 5
Dissolve 27.8 g of hydroxylamine hydrochloride {NH 2 OH · HCl} and 58.8 g of 80% phosphoric acid {H 3 PO 4 } in 400 ml of ion-exchanged water to obtain a uniform solution, and then use a hot stirrer at 80 ° C. Until heated. To this solution, 36.4 g of vanadium pentoxide {V 2 O 5 } was gradually added. Stirring was continued for about 6 hours from the end of the addition of vanadium pentoxide, followed by drying in a dryer at 120 ° C. for 15 hours to evaporate water. The obtained dried product was calcined in air at 500 ° C. for 15 hours to obtain a catalyst having a composition of (VO) 2 P 2 O 7 .
9 g of the catalyst obtained by the above method is filled in a Pyrex glass reaction tube having a diameter of 15 mm, and a raw material gas having an isobutane / oxygen / nitrogen / water vapor ratio (mol%) of 47/36/17/0 is supplied thereto. Then, the oxidation reaction was carried out under conditions of a reaction pressure of 152 kPa and a space velocity of 1000 / hr. As a result, at a reaction temperature of 367 ° C., the conversion of isobutane was 2.1% and the selectivity to isobutylene, methacrolein and methacrylic acid was 1. 7%, 2.6%, and 8.9%.
Claims (2)
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| JP26690397A JP4182237B2 (en) | 1997-09-30 | 1997-09-30 | Catalyst for gas-phase catalytic oxidation reaction of isobutane and method for producing alkene and / or oxygen-containing compound using the same |
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| JP3883755B2 (en) * | 1999-09-17 | 2007-02-21 | 日本化薬株式会社 | Catalyst production method |
| US6762148B2 (en) | 1999-09-17 | 2004-07-13 | Nippon Kayaku Kabushiki Kaisha | Catalyst process of making |
| JP4535611B2 (en) * | 2000-12-27 | 2010-09-01 | 旭化成ケミカルズ株式会社 | Catalyst and method for producing unsaturated nitrile using the same |
| US6919472B2 (en) | 2001-12-21 | 2005-07-19 | Saudi Basic Industries Corporation | Catalyst compositions for the selective conversion of alkanes to unsaturated carboxylic acids, methods of making and methods of using thereof |
| EP1411043A1 (en) * | 2002-10-18 | 2004-04-21 | Rohm And Haas Company | Preparation of unsaturated carboxylic acids and unsaturated carboxylic acid esters from alkanes and/or alkenes |
| US7229946B2 (en) | 2003-03-24 | 2007-06-12 | Saudi Basic Industries Corporation | Catalyst composition for the selective conversion of alkanes to unsaturated carboxylic acids, method of making and method of using thereof |
| JP4501494B2 (en) * | 2004-03-30 | 2010-07-14 | 住友化学株式会社 | Method for producing catalyst for producing methacrylic acid and method for producing methacrylic acid |
| JP4501495B2 (en) * | 2004-03-30 | 2010-07-14 | 住友化学株式会社 | Method for producing catalyst for producing methacrylic acid and method for producing methacrylic acid |
| JP5008271B2 (en) * | 2005-04-26 | 2012-08-22 | 旭化成ケミカルズ株式会社 | Continuous production method of unsaturated carboxylic acid ester using alkane as raw material |
| CN104640627B (en) * | 2012-09-18 | 2017-08-29 | 国立大学法人北海道大学 | Isobutene catalyst for producing and the manufacture method using its isobutene |
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| BE759434A (en) * | 1969-11-25 | 1971-04-30 | Power Gas Ltd | CATALYTIC OXIDATION |
| JPH0733344B2 (en) * | 1986-12-06 | 1995-04-12 | 旭化成工業株式会社 | Method for producing methacrylic acid and / or methacrolein |
| JPH085820B2 (en) * | 1988-04-05 | 1996-01-24 | 旭化成工業株式会社 | Method for producing methacrylic acid and / or methacrolein |
| JPH05177141A (en) * | 1991-12-27 | 1993-07-20 | Tosoh Corp | Preparation of methacrylic acid |
| JPH0710782A (en) * | 1993-06-22 | 1995-01-13 | Sumitomo Chem Co Ltd | Production of isobutylene and methacrolein |
| US5530171A (en) * | 1993-08-27 | 1996-06-25 | Mobil Oil Corporation | Process for the catalytic dehydrogenation of alkanes to alkenes with simultaneous combustion of hydrogen |
| DE4329907A1 (en) * | 1993-09-04 | 1995-03-09 | Basf Ag | Multimetal oxide compositions containing at least the elements antimony and phosphorus and additionally at least one of the two elements Mo, W |
| DE59505944D1 (en) * | 1994-02-22 | 1999-06-24 | Basf Ag | Multimetal oxide materials. |
| JP3855298B2 (en) * | 1996-04-10 | 2006-12-06 | 住友化学株式会社 | Process for producing alkene and / or oxygen-containing compound |
| JP3772389B2 (en) * | 1996-05-10 | 2006-05-10 | 三菱化学株式会社 | Method for producing oxidation catalyst and method for producing methacrylic acid |
| JPH1036311A (en) * | 1996-07-25 | 1998-02-10 | Mitsubishi Chem Corp | Production of alpha, beta-unsaturated carboxylic acid |
| DE19638249A1 (en) * | 1996-09-19 | 1998-03-26 | Basf Ag | Process for producing a catalytically active multimetal oxide mass |
| JPH10128112A (en) * | 1996-10-31 | 1998-05-19 | Sumitomo Chem Co Ltd | Catalyst for vapor phase contact oxidation reaction of isobutane and its preparation |
| JPH10310539A (en) * | 1997-05-09 | 1998-11-24 | Mitsubishi Chem Corp | Vapor-phase, catalytic oxidation of hydrocarbon |
| JPH1142434A (en) * | 1997-05-28 | 1999-02-16 | Mitsubishi Chem Corp | Production of vapor phase catalytic oxidation reaction catalyst of hydrocarbon and vapor phase catalytic oxidation reaction method of hydrocarbon using the same |
| JPH1133403A (en) * | 1997-07-22 | 1999-02-09 | Mitsubishi Rayon Co Ltd | Production of catalyst for synthesis of methacrylic acid and production of methacrylic acid |
| JP3938225B2 (en) * | 1997-08-05 | 2007-06-27 | 旭化成ケミカルズ株式会社 | Catalyst preparation method |
| KR20010023081A (en) * | 1997-08-20 | 2001-03-26 | 스타르크, 카르크 | Method for Producing Multi-Metal Oxide Masses Containing Mo, V and Cu |
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