JP4947753B2 - Catalyst for methacrylic acid synthesis and method for producing methacrylic acid - Google Patents
Catalyst for methacrylic acid synthesis and method for producing methacrylic acid Download PDFInfo
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- 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
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- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
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- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Description
【０００１】
【発明の属する技術分野】
本発明はメタクリル酸合成用触媒の製造方法に関し、より詳しくはメタクロレインを分子状酸素により気相接触酸化してメタクリル酸を合成する際に使用するメタクリル酸合成用触媒の製造方法に関する。
【０００２】
【従来の技術】
メタクロレインを気相接触酸化してメタクリル酸を合成する触媒にはモリブデンおよびリンを含むヘテロポリ酸系触媒が有効であることが広く知られており、触媒の調製方法について数多くの提案がなされている。例えば、特開昭６３−１３０１４３号公報には、モリブデン、リンを含む触媒スラリーを水分含有率が１％程度にまで乾燥させ、得られた固形物を再び水に分散させた後に乾燥処理を行い、続いて成形、焼成して触媒を調製する方法が開示されている。しかし、この方法で得られた触媒は工業触媒としてはメタクリル酸収率がいまだ不充分であり、工業触媒としての使用に際しては更なる収率の向上が望まれている。
【０００３】
【発明が解決しようとする課題】
本発明は、メタクロレインを分子状酸素により気相接触酸化してメタクリル酸を高い収率で製造できるメタクリル酸合成用触媒の製造方法を提供することを目的とする。
【０００４】
【課題を解決するための手段】
上記課題を解決するため、鋭意検討を行った結果、本発明者らは、メタクロレインを分子状酸素により気相接触酸化してメタクリル酸を合成する際に使用する触媒について、高い触媒活性およびメタクリル酸選択性を有する触媒を得ることができる新規調製法を完成させるに至った。
【０００５】
すなわち本発明は、少なくともモリブデンおよびリンを含む水性スラリーから水を部分的に除去して水分含有率が３〜２５重量％の乾燥物とし、この乾燥物を水に分散させて水性スラリーとし、この水性スラリーを乾燥したものを３００〜５００℃で焼成するメタクリル酸合成用触媒の製造方法である。触媒製造の際、乾燥物を分散させる水の質量は乾燥物の質量の１〜１０倍が好ましい。また、メタクリル酸合成用触媒は次の式（１）の組成式で表される複合酸化物が好ましい。
ＭｏaＰbＣｕcＶdＸeＹfＯg （１）
（式中、Ｍｏ、Ｐ、Ｃｕ、ＶおよびＯはそれぞれモリブデン、リン、銅、バナジウムおよび酸素を表し、Ｘはカリウム、ルビジウムおよびセシ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、Ｙは鉄、コバルト、ニッケル、ヒ素、アンチモンおよびビスマスからなる群より選ばれた少なくとも１種の元素を表す。ただし、ａ、ｂ、ｃ、ｄ、ｅ、ｆおよびｇは各元素の原子比を表し、ａ＝１２のとき、０．１≦ｂ≦３、０．０１≦ｃ≦３、０．０１≦ｄ≦３、０．０１≦ｅ≦３、０≦ｆ≦３であり、ｇは前記各成分の原子比を満足するのに必要な酸素の原子比である。）
【０００６】
さらに本発明は、メタクロレインを分子状酸素により気相接触酸化してメタクリル酸を合成するメタクリル酸の製造方法において、前記のメタクリル酸合成用触媒を用いることを特徴とするメタクリル酸の製造方法である。
【０００７】
【発明の実施の形態】
本発明のメタクリル酸合成用触媒は少なくともモリブデンとリンを含有する複合酸化物である。触媒には、ヘテロポリ酸またはヘテロポリ酸塩の構造が含まれていることが好ましい。
【０００８】
また触媒は、モリブデンおよびリン以外にはアルカリ金属を含んでいることが好ましく、これ以外に銅、バナジウム、鉄、コバルト、ニッケル、亜鉛、マグネシウム、カルシウム、ストロンチウム、バリウム、チタン、クロム、タングステン、マンガン、銀、ホウ素、ケイ素、アルミニウム、ガリウム、ゲルマニウム、スズ、鉛、ヒ素、アンチモン、ビスマス、ニオブ、タンタル、ジルコニウム、インジウム、イオウ、セレン、テルル、ランタン、セリウム等を適宜含んでいてもよい。特に次の式（１）の組成式で表される複合酸化物が好ましい。
ＭｏaＰbＣｕcＶdＸeＹfＯg （１）
【０００９】
式（１）中、Ｍｏ、Ｐ、Ｃｕ、ＶおよびＯはそれぞれモリブデン、リン、銅、バナジウムおよび酸素を表し、Ｘはカリウム、ルビジウムおよびセシ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、Ｙは鉄、コバルト、ニッケル、ヒ素、アンチモンおよびビスマスからなる群より選ばれた少なくとも１種の元素を表す。
【００１０】
また式（１）中、ａ、ｂ、ｃ、ｄ、ｅ、ｆおよびｇは各元素の原子比を表している。ａ＝１２のとき、ｂは０．１≦ｂ≦３、好ましくは０．５≦ｂ≦３である。同様にｃは０．０１≦ｃ≦３、好ましくは０．０１≦ｃ≦２である。同様にｄは０．０１≦ｄ≦３、好ましくは０．０１≦ｄ≦２である。同様にｅは０．０１≦ｅ≦３、好ましくは０．１≦ｅ≦３である。同様にｆは０≦ｆ≦３であり、好ましくは０≦ｆ≦２．５である。ｇは前記各成分の原子比を満足するのに必要な酸素の原子比である。
【００１１】
本発明のメタクリル酸合成用触媒は、少なくともモリブデンおよびリンを含む水性スラリー（以下、一次スラリーという。）から水を部分的に除去して水分含有率が３〜２５重量％の乾燥物（以下、一次乾燥物という。）とし、この一次乾燥物を水に分散させて水性スラリーとし、この水性スラリーを乾燥したものを３００〜５００℃で焼成して製造されたものである。
【００１２】
一次スラリーは、触媒の各構成元素の原料（以下、触媒原料という。）を用いて、従来の共沈法、酸化物混合法等により調製する。一次スラリーの調製に用いる触媒原料は特に限定されず、各元素の硝酸塩、炭酸塩、酢酸塩、アンモニウム塩、酸化物、ハロゲン化物等を組み合わせて使用することができる。モリブデン原料としては、例えば、パラモリブデン酸アンモニウム、三酸化モリブデン、モリブデン酸、塩化モリブデン等が使用できる。リン原料としては、例えば、リン酸、リン酸、五酸化リン、リン酸アンモニウム等が使用できる。なお、一次スラリーには必ずしも全ての触媒構成元素を含める必要はなく、少なくともモリブデンとリンを含んでいればよい。従って、この段階で加えなかった触媒原料はこれ以降の別の工程で添加すればよい。
【００１３】
一次スラリーから水を部分的に除去して一次乾燥物とする方法は特に限定されず、例えば、蒸発、ろ過等の操作が挙げられる。なかでも蒸発操作が好ましい。蒸発操作には箱型乾燥機、噴霧乾燥機、ドラムドライヤー、スラリードライヤー等を用いることができる。
【００１４】
得られる一次乾燥物の水分含有率は３〜２５重量％とし、好ましくは５〜２０重量％、特に好ましくは８〜１７重量％とする。一次乾燥物の形態は特に限定されず、例えば、ペースト状、ケーク状、粉末状等が挙げられる。
【００１５】
次に一次乾燥物を水に分散させて水性スラリーを得る。この際、触媒原料を追加することもできる。この際に用いる水の質量は特に限定されないが、一次乾燥物の質量の１〜１０倍が好ましく、１〜７倍がより好ましく、１〜４倍が特に好ましい。
【００１６】
一次スラリーからこの水性スラリーを得る操作（以下、乾燥・分散操作という。）は２度以上繰り返し行ってもよい。すなわち、このスラリーを一次スラリーとして取り扱い、水を部分的に除去して水分含有率が３〜２５重量％の乾燥物とし、この乾燥物に水を加えて水性スラリーを得る操作を1回以上追加することができる。乾燥・分散操作は通常１〜１０回であり、好ましくは１〜５回である。
【００１７】
次に、１または２回以上の乾燥・分散操作により得られた水性スラリー（以下、二次スラリーという。）を乾燥して乾燥物（以下、二次乾燥物という。）を得る。乾燥に際しては箱型乾燥機、噴霧乾燥機、ドラムドライヤー、スラリードライヤー等を用いることができる。二次乾燥物の水分含有率は３％未満にする。
【００１８】
二次乾燥物は３００〜５００℃で焼成する。成形触媒を製造する場合、二次乾燥物をそのまま焼成し、得られる焼成物を成形してもよいが、二次乾燥物を成形してから焼成を行う方が好ましい。成形方法は特に限定はなく、打錠成形、押出成形、造粒等の各種成形法を用いることができる。成形に際しては、成形物の比表面積、細孔容積および細孔分布を再現性よく制御する、機械的強度を高める等の目的で、例えば、硫酸バリウム、硝酸アンモニウム等の無機塩類、グラファイト等の滑剤、セルロース類、でんぷん、ポリビニルアルコール、ステアリン酸等の有機物、シリカゾル、アルミナゾル等の水酸化物ゾル、ウィスカー、ガラス繊維、炭素繊維等の無機質繊維等の添加剤や添加物を適宜添加してもよい。成形物の形状は特に限定されず、例えば、球状、円柱状、リング状、板状等が挙げられる。
【００１９】
二次乾燥物またはその成形物は焼成して触媒とする。焼成の最適条件は用いる触媒原料、触媒組成、調製法によって異なるが、焼成温度は３００〜５００℃、好ましくは３００〜４５０℃である。焼成は、通常、空気等の酸素含有ガス流通下および／または不活性ガス流通下で行う。焼成時間は通常０．５時間以上、好ましくは１〜４０時間である。
【００２０】
焼成により得られる触媒には、前述のようにヘテロポリ酸またはヘテロポリ酸塩の構造が含まれていることが好ましい。
【００２１】
次に、このようにして得られた本発明の触媒を用いてメタクロレインを分子状酸素により気相接触酸化してメタクリル酸を製造する方法について説明する。
【００２２】
気相接触酸化に用いる原料ガスのメタクロレイン濃度は広い範囲で変えることができるが、好ましくは１〜２０容量％、特に好ましくは３〜１０容量％である。原料のメタクロレインには、水、低級飽和アルデヒド等の実質的に反応に影響を与えない不純物が少量含まれている場合があるが、原料ガスにはこのようなメタクロレイン由来の不純物が含まれていてもよい。
【００２３】
原料ガスには分子状酸素が含まれている必要があるが、原料ガス中の分子状酸素の量はメタクロレインの０．４〜４倍モルが好ましく、特に０．５〜３倍モルが好ましい。原料ガスの分子状酸素源には空気を用いるのが工業的に有利であるが、必要に応じて純酸素で富化した空気も使用できる。また原料ガスは、窒素、炭酸ガス等の不活性ガス、水蒸気等で希釈されていることが好ましい。
【００２４】
気相接触酸化の反応圧力は常圧〜数気圧である。反応温度は、通常２００〜４５０℃、好ましくは２５０〜４００℃である。原料ガスと触媒の接触時間は通常１．５〜１５秒、好ましくは２〜７秒である。
【００２５】
【実施例】
以下に本発明を実施例および比較例を用いて説明する。ただし、実施例および比較例中の「部」は重量部を意味する。反応試験分析はガスクロマトグラフィーにより行った。一次および二次乾燥物の水分含有率はケット水分計（島津製作所社製）を用いて測定した。また、原料であるメタクロレインの転化率、生成したメタクリル酸の選択率および収率は以下のように定義される。
メタクロレイン反応率（％）＝（Ｂ／Ａ）×１００
メタクリル酸選択率（％）＝（Ｃ／Ｂ）×１００
メタクリル酸単流収率（％）＝（Ｃ／Ａ）×１００
ここで、Ａは供給したメタクロレインのモル数、Ｂは反応したメタクロレインのモル数、Ｃは生成したメタクリル酸のモル数である。
【００２６】
［実施例１］
パラモリブデン酸アンモニウム１００部を純水２００部に溶解し、そこへメタバナジン酸アンモニウム２．８部、８５重量％リン酸８．２部を純水３０部に溶解した溶液、硝酸銅１．１部を純水３０部に溶解した溶液および硝酸鉄３．８部を純水１０部に溶解した溶液を順次加え、これを攪拌しながら９０℃まで加熱し、液温を９０℃に保ちつつ５時間加熱攪拌した後に、硝酸セシウム９．２部を純水１００部に溶解した溶液をこれに加えて一次スラリーを得た。一次スラリーを加熱攪拌しながら蒸発乾固してペースト状の一次乾燥物を得た。一次乾燥物の水分含有率は１１．７％であった。一次乾燥物１００部を純水４００部に分散して二次スラリーを得た。二次スラリーを過熱攪拌しながら再び蒸発乾固し、得られた固形物を１３０℃で１６時間乾燥させて二次乾燥物を得た。二次乾燥物の水分含有率は１．５重量％であった。この二次乾燥物を粉砕した。こうして得られた粉体１００部にグラファイト３．０部を添加し、続いて打錠成形機により、外径５ｍｍ、内径２ｍｍ、長さ５ｍｍのリング状に成形した。得られた成形物を空気流通下に３８０℃で６時間焼成して触媒を得た。この触媒の酸素を除く元素の組成は、
Ｍｏ１２Ｐ１．５Ｖ０．５Ｃｕ０．１Ｆｅ０．２Ｃｓ１
であった。
【００２７】
この触媒を反応管に充填し、メタクロレイン５％、酸素１０％、水蒸気３０％、窒素５５％（容量％）の混合ガスを反応温度２９０℃、接触時間３．６秒で通じたところ、メタクロレイン反応率８４．１％、メタクリル酸選択率８３．５％、メタクリル酸単流収率７０．２％であった。
【００２８】
［実施例２］
実施例１において、一次乾燥物を得る際の蒸発乾固の時間を短縮し、水分含有率が１８．２重量％の一次乾燥物を得た以外は実施例１と同様に触媒を製造し、同様にしてメタクリル酸を製造したところ、メタクロレイン反応率８３．９％、メタクリル酸選択率８３．４％、メタクリル酸単流収率７０．０％であった。
【００２９】
［実施例３］
実施例１において、一次乾燥物を得る際の蒸発乾固の時間を延長し、水分含有率が６．１重量％の一次乾燥物を得た以外は実施例１と同様に触媒を製造し、同様にしてメタクリル酸を製造したところ、メタクロレイン反応率８４．０％、メタクリル酸選択率８３．０％、メタクリル酸単流収率６９．７％であった。
【００３０】
［実施例４］
実施例１において、一次乾燥物を得る際の蒸発乾固の時間を実施例２よりさらに短縮し、水分含有率が２２．４重量％の一次乾燥物を得た以外は実施例１と同様に触媒を製造し、同様にしてメタクリル酸を製造したところ、メタクロレイン反応率８３．７％、メタクリル酸選択率８３．２％、メタクリル酸単流収率６９．６％であった。
【００３１】
［実施例５］
実施例１において、一次乾燥物を得る際の蒸発乾固の時間を実施例３よりさらに延長し、水分含有率が３．８重量％の一次乾燥物を得た以外は実施例１と同様に触媒を製造し、同様にしてメタクリル酸を製造したところ、メタクロレイン反応率８３．９％、メタクリル酸選択率８２．９％、メタクリル酸単流収率６９．６％であった。
【００３２】
［実施例６］
実施例１において、一次乾燥物を分散させる純水の量を４００部から６００部に変更した点以外は実施例１と同様に触媒を製造し、同様にしてメタクリル酸を製造したところ、メタクロレイン反応率８３．４％、メタクリル酸選択率８３．２％、メタクリル酸単流収率６９．４％であった。
【００３３】
［実施例７］
実施例１において、一次乾燥物を分散させる純水の量を４００部から９００部に変更した点以外は実施例１と同様に触媒を製造し、同様にしてメタクリル酸を製造したところ、メタクロレイン反応率８３．３％、メタクリル酸選択率８３．１％、メタクリル酸単流収率６９．２％であった。
【００３４】
［実施例８］
実施例１において、一次スラリーから二次スラリーを得る操作（乾燥・分散操作）を繰り返し２回行った点以外は実施例１と同様に触媒を製造し、同様にしてメタクリル酸を製造したところ、メタクロレイン反応率８４．２％、メタクリル酸選択率８３．７％、メタクリル酸単流収率７０．５％であった。なお、２回目の乾燥・再溶解操作における一次乾燥物の水分含有率は１１．７重量％であった。
【００３５】
［実施例９］
実施例１において、一次スラリーから二次スラリーを得る操作（乾燥・分散操作）を繰り返し３回行った点以外は実施例１と同様に触媒を製造し、同様にしてメタクリル酸を製造したところ、メタクロレイン反応率８４．４％、メタクリル酸選択率８３．６％、メタクリル酸単流収率７０．６％であった。なお、２回目および３回目の乾燥・再溶解操作における一次乾燥物の水分含有率は各々１１．７重量％、１１．７重量％であった。
【００３６】
［比較例１］
実施例１において、一次乾燥物を純水に分散して乾燥する操作を省略、すなわち一次乾燥物を１３０℃で１６時間乾燥したものを、成形し、焼成して触媒を得た以外は実施例１と同様に触媒を製造し、同様にしてメタクリル酸を製造した。その結果、メタクロレイン反応率８２．４％、メタクリル酸選択率８１．３％、メタクリル酸単流収率６７．０％であり、実施例１に比べて得られる触媒の性能が低いことがわかった。
【００３７】
［比較例２］
実施例１において、一次乾燥物を純水に分散する前に１３０℃で１６時間乾燥した点以外は実施例１と同様に触媒を製造し、同様にしてメタクリル酸を製造した。その結果、メタクロレイン反応率８２．７％、メタクリル酸選択率８１．３％、メタクリル酸単流収率６７．２％であった。なお、一次乾燥物を１３０℃で１６時間乾燥したものの水分含有率は１．５重量％であり、実施例１に比べて得られる触媒の性能が低いことがわかった。
【００３８】
［比較例３］
実施例１において、一次乾燥物を得る際の蒸発乾固の時間を実施例４よりさらに短縮し、水分含有率が３０．５重量％の一次乾燥物を得た以外は実施例１と同様に触媒を製造し、同様にしてメタクリル酸を製造した。その結果、メタクロレイン反応率８２．９％、メタクリル酸選択率８１．４％、メタクリル酸単流収率６７．５％であり、実施例１に比べて得られる触媒の性能が低いことがわかった。
【００３９】
［実施例１０］
パラモリブデン酸アンモニウム１００部、メタバナジン酸アンモニウム４．４２部および硝酸セシウム９．２０部を純水３００部に加熱溶解した。これに８５重量％リン酸８．７１部を純水１０部に溶解した溶液、ついで三酸化アンチモン５．５０部を加え、攪拌しながら９５℃に昇温した後、硝酸銅１．１４部を純水１０部に溶解した溶液を加えた。更にこの混合液を９５℃で１５分間攪拌して一次スラリーを得た。一次スラリーを加熱攪拌しながら蒸発乾固してペースト状の一次乾燥物を得た。一次乾燥物の水分含有率は１３．１％であった。一次乾燥物１００部を純水４００部に分散して二次スラリーを得た。二次スラリーを加熱攪拌しながら再び蒸発乾固し、得られた固形物を１３０℃で１６時間乾燥させて二次乾燥物を得た。二次乾燥物の水分含有率は１．５％であった。この二次乾燥物を実施例１と同様に成形および焼成して触媒を得た。この触媒の酸素を除く元素の組成は、
Ｍｏ１２Ｐ１．６Ｖ０．８Ｃｕ０．１Ｓｂ０．８Ｃｓ１
であった。
【００４０】
この触媒を用いて実施例１と同様に反応を行ったところ、メタクロレイン反応率８４．５％、メタクリル酸選択率８４．８％、メタクリル酸収率７１．７％であった。
【００４１】
［比較例４］
実施例１０において、一次乾燥物を純水に分散して乾燥する操作を省略、すなわち一次乾燥物を１３０℃で１６時間乾燥したものを、成形し、焼成して触媒を得た以外は実施例１０と同様に触媒を製造し、同様にしてメタクリル酸を製造した。その結果、メタクロレイン反応率８２．８％、メタクリル酸選択率８３．７％、メタクリル酸単流収率６９．３％であり、実施例１０に比べて得られる触媒の性能が低いことがわかった。
【００４２】
［比較例５］
実施例１０において、一次乾燥物を純水に分散する前に１３０℃で１６時間乾燥した点以外は実施例１０と同様に触媒を製造し、同様にしてメタクリル酸を製造した。その結果、メタクロレイン反応率８３．０％、メタクリル酸選択率８３．８％、メタクリル酸単流収率６９．６％であった。なお、一次乾燥物を１３０℃で１６時間乾燥したものの水分含有率は１．５重量％であり、実施例１０に比べて得られる触媒の性能が低いことがわかった。
【００４３】
【発明の効果】
本発明のメタクリル酸合成用触媒の製造方法により製造される触媒を用いることにより、メタクロレインを分子状酸素により気相接触酸化してメタクリル酸を高い収率で製造できる。[0001]
BACKGROUND OF THE INVENTION
Relates to a manufacturing method of the present invention is a catalyst for methacrylic acid synthesis, and more particularly relates to a method of manufacturing a catalyze for methacrylic acid synthesis using in the synthesis of methacrylic acid by gas phase catalytic oxidation with molecular oxygen to methacrolein.
[0002]
[Prior art]
It is widely known that heteropolyacid catalysts containing molybdenum and phosphorus are effective as catalysts for synthesizing methacrylic acid by gas-phase catalytic oxidation of methacrolein, and many proposals have been made on catalyst preparation methods. . For example, in Japanese Patent Laid-Open No. 63-130143, a catalyst slurry containing molybdenum and phosphorus is dried to a moisture content of about 1%, and the obtained solid is dispersed again in water, followed by a drying treatment. Subsequently, a method for preparing a catalyst by molding and calcining is disclosed. However, the catalyst obtained by this method is still insufficient in yield of methacrylic acid as an industrial catalyst, and further improvement in yield is desired for use as an industrial catalyst.
[0003]
[Problems to be solved by the invention]
The present invention aims to provide a method for producing a catalyze for methacrylic acid synthesis can be produced at a high methacrylic acid by vapor phase catalytic oxidation yield of methacrolein with molecular oxygen.
[0004]
[Means for Solving the Problems]
As a result of intensive studies to solve the above-mentioned problems, the present inventors have found that a catalyst used for synthesizing methacrylic acid by vapor-phase catalytic oxidation of methacrolein with molecular oxygen has high catalytic activity and methacrylic acid. A new preparation method capable of obtaining a catalyst having acid selectivity has been completed.
[0005]
That is, the present invention partially removes water from an aqueous slurry containing at least molybdenum and phosphorus to obtain a dry product having a water content of 3 to 25% by weight, and the dry product is dispersed in water to form an aqueous slurry. a method for producing a main methacrylic acid synthesis catalyst for baked formed a material obtained by drying an aqueous slurry at 300 to 500 ° C.. In the catalyst production, the mass of water in which the dried product is dispersed is preferably 1 to 10 times the mass of the dried product. The methacrylic acid synthesis catalyst is preferably a composite oxide represented by the following composition formula (1).
Mo a P b Cu c V d X e Y f O g (1)
(Wherein Mo, P, Cu, V and O represent molybdenum, phosphorus, copper, vanadium and oxygen, respectively, X represents at least one element selected from the group consisting of potassium, rubidium and cesium; Y represents iron, cobalt, nickel, arsenic, at least one element selected from antimony and bismuth scan or Ranaru group. However, a, b, c, d , e, f and g are atomic of each element Represents a ratio, and when a = 12, 0.1 ≦ b ≦ 3, 0.01 ≦ c ≦ 3, 0.01 ≦ d ≦ 3, 0.01 ≦ e ≦ 3, 0 ≦ f ≦ 3, g is the atomic ratio of oxygen necessary to satisfy the atomic ratio of each component.
[0006]
Furthermore, the present invention relates to a method for producing methacrylic acid, characterized in that the above-mentioned catalyst for methacrylic acid synthesis is used in the method for producing methacrylic acid by gas phase catalytic oxidation of methacrolein with molecular oxygen to synthesize methacrylic acid. is there.
[0007]
DETAILED DESCRIPTION OF THE INVENTION
The catalyst for synthesizing methacrylic acid of the present invention is a composite oxide containing at least molybdenum and phosphorus. The catalyst preferably contains a heteropolyacid or heteropolyacid salt structure.
[0008]
The catalyst preferably contains an alkali metal other than molybdenum and phosphorus, and besides this, copper, vanadium, iron, cobalt, nickel, zinc, magnesium, calcium, strontium, barium, titanium, chromium, tungsten, manganese Silver, boron, silicon, aluminum, gallium, germanium, tin, lead, arsenic, antimony, bismuth, niobium, tantalum, zirconium, indium, sulfur, selenium, tellurium, lanthanum, cerium, and the like may be contained as appropriate. In particular, a composite oxide represented by the following composition formula (1) is preferable.
Mo a P b Cu c V d X e Y f O g (1)
[0009]
In formula (1), Mo, P, Cu, V and O each represent molybdenum, phosphorus, copper, vanadium and oxygen, and X represents at least one element selected from the group consisting of potassium, rubidium and cesium. , Y represents iron, cobalt, nickel, arsenic, at least one element selected from antimony and bismuth scan or Ranaru group.
[0010]
Moreover, in Formula (1), a, b, c, d, e, f, and g represent the atomic ratio of each element. When a = 12, b is 0.1 ≦ b ≦ 3, preferably 0.5 ≦ b ≦ 3. Similarly, c is 0.01 ≦ c ≦ 3, preferably 0.01 ≦ c ≦ 2. Similarly, d is 0.01 ≦ d ≦ 3, preferably 0.01 ≦ d ≦ 2. Similarly, e is 0.01 ≦ e ≦ 3, preferably 0.1 ≦ e ≦ 3. Similarly, f is 0 ≦ f ≦ 3, and preferably 0 ≦ f ≦ 2.5. g is an atomic ratio of oxygen necessary to satisfy the atomic ratio of each component.
[0011]
The catalyst for synthesizing methacrylic acid of the present invention partially removes water from an aqueous slurry containing at least molybdenum and phosphorus (hereinafter referred to as a primary slurry) and has a moisture content of 3 to 25% by weight (hereinafter referred to as a dry product). This primary dried product is dispersed in water to form an aqueous slurry, and the aqueous slurry is dried and fired at 300 to 500 ° C.
[0012]
The primary slurry is prepared by a conventional coprecipitation method, an oxide mixing method, or the like, using raw materials for the constituent elements of the catalyst (hereinafter referred to as catalyst raw materials). The catalyst raw material used for the preparation of the primary slurry is not particularly limited, and nitrates, carbonates, acetates, ammonium salts, oxides, halides and the like of each element can be used in combination. As the molybdenum raw material, for example, ammonium paramolybdate, molybdenum trioxide, molybdic acid, molybdenum chloride, or the like can be used. Examples of the phosphorus raw material that can be used include phosphoric acid, phosphoric acid, phosphorus pentoxide, and ammonium phosphate. Note that it is not always necessary to include all catalyst constituent elements in the primary slurry, as long as at least molybdenum and phosphorus are included. Therefore, the catalyst raw material not added at this stage may be added in another process thereafter.
[0013]
A method for partially removing water from the primary slurry to obtain a primary dry product is not particularly limited, and examples thereof include operations such as evaporation and filtration. Of these, the evaporation operation is preferred. For the evaporation operation, a box-type dryer, a spray dryer, a drum dryer, a slurry dryer or the like can be used.
[0014]
The water content of the obtained primary dried product is 3 to 25% by weight, preferably 5 to 20% by weight, particularly preferably 8 to 17% by weight. The form of the primary dried product is not particularly limited, and examples thereof include a paste form, a cake form, and a powder form.
[0015]
Next, the primary dry product is dispersed in water to obtain an aqueous slurry. At this time, a catalyst raw material can also be added. Although the mass of the water used in this case is not particularly limited, it is preferably 1 to 10 times, more preferably 1 to 7 times, and particularly preferably 1 to 4 times the mass of the primary dried product.
[0016]
The operation of obtaining this aqueous slurry from the primary slurry (hereinafter referred to as drying / dispersing operation) may be repeated twice or more. That is, this slurry is handled as a primary slurry, and water is partially removed to obtain a dry product having a water content of 3 to 25% by weight. The operation of adding water to the dry product to obtain an aqueous slurry is added one or more times. can do. The drying / dispersing operation is usually 1 to 10 times, preferably 1 to 5 times.
[0017]
Next, the aqueous slurry (hereinafter referred to as secondary slurry) obtained by one or more drying / dispersing operations is dried to obtain a dried product (hereinafter referred to as secondary dried product). For drying, a box dryer, spray dryer, drum dryer, slurry dryer, or the like can be used. The water content of the secondary dried product is less than 3%.
[0018]
The secondary dried product is fired at 300 to 500 ° C. In the case of producing a shaped catalyst, the secondary dried product may be calcined as it is, and the resulting calcined product may be molded. However, it is preferable that the secondary dried product is molded and then calcined. The molding method is not particularly limited, and various molding methods such as tableting molding, extrusion molding, and granulation can be used. In the molding, for the purpose of controlling the specific surface area, pore volume and pore distribution of the molded product with good reproducibility and increasing mechanical strength, for example, inorganic salts such as barium sulfate and ammonium nitrate, lubricants such as graphite, Additives and additives such as celluloses, starches, polyvinyl alcohol, stearic acid and other organic substances, hydroxide sols such as silica sol and alumina sol, whiskers, glass fibers, carbon fibers and other inorganic fibers may be added as appropriate. The shape of the molded product is not particularly limited, and examples thereof include a spherical shape, a cylindrical shape, a ring shape, and a plate shape.
[0019]
The secondary dried product or the molded product thereof is calcined to be a catalyst. The optimum conditions for calcination vary depending on the catalyst raw material, catalyst composition and preparation method used, but the calcination temperature is 300 to 500 ° C, preferably 300 to 450 ° C. Firing is usually performed under a flow of oxygen-containing gas such as air and / or under a flow of inert gas. The firing time is usually 0.5 hours or longer, preferably 1 to 40 hours.
[0020]
The catalyst obtained by calcination preferably contains a heteropolyacid or heteropolyacid salt structure as described above.
[0021]
Next, a method of producing methacrylic acid by vapor-phase catalytic oxidation of methacrolein with molecular oxygen using the catalyst of the present invention thus obtained will be described.
[0022]
The concentration of methacrolein in the raw material gas used for the gas phase catalytic oxidation can be varied within a wide range, but is preferably 1 to 20% by volume, particularly preferably 3 to 10% by volume. The raw material methacrolein may contain a small amount of impurities that do not substantially affect the reaction, such as water, lower saturated aldehydes, etc., but the raw material gas contains such an impurity derived from methacrolein. It may be.
[0023]
The source gas needs to contain molecular oxygen, but the amount of molecular oxygen in the source gas is preferably 0.4 to 4 times mol, more preferably 0.5 to 3 times mol of methacrolein. . Although it is industrially advantageous to use air as the molecular oxygen source of the source gas, air enriched with pure oxygen can also be used if necessary. The source gas is preferably diluted with an inert gas such as nitrogen or carbon dioxide, water vapor or the like.
[0024]
The reaction pressure for gas phase catalytic oxidation is from atmospheric pressure to several atmospheres. The reaction temperature is usually 200 to 450 ° C., preferably 250 to 400 ° C. The contact time between the source gas and the catalyst is usually 1.5 to 15 seconds, preferably 2 to 7 seconds.
[0025]
【Example】
The present invention will be described below with reference to examples and comparative examples. However, “parts” in Examples and Comparative Examples means parts by weight. Reaction test analysis was performed by gas chromatography. The moisture content of the primary and secondary dried products was measured using a ket moisture meter (manufactured by Shimadzu Corporation). Further, the conversion rate of the raw material methacrolein, the selectivity of the produced methacrylic acid and the yield are defined as follows.
Methacrolein reaction rate (%) = (B / A) × 100
Methacrylic acid selectivity (%) = (C / B) × 100
Methacrylic acid single stream yield (%) = (C / A) × 100
Here, A is the number of moles of methacrolein supplied, B is the number of moles of reacted methacrolein, and C is the number of moles of methacrylic acid produced.
[0026]
[Example 1]
A solution in which 100 parts of ammonium paramolybdate is dissolved in 200 parts of pure water and 2.8 parts of ammonium metavanadate and 8.2 parts of 85 wt% phosphoric acid are dissolved in 30 parts of pure water, 1.1 parts of copper nitrate A solution prepared by dissolving 30 parts of pure water and a solution of 3.8 parts of iron nitrate in 10 parts of pure water are sequentially added, heated to 90 ° C. with stirring, and maintained for 5 hours while maintaining the liquid temperature at 90 ° C. After heating and stirring, a solution obtained by dissolving 9.2 parts of cesium nitrate in 100 parts of pure water was added thereto to obtain a primary slurry. The primary slurry was evaporated to dryness with heating and stirring to obtain a paste-like primary dry product. The moisture content of the primary dried product was 11.7%. 100 parts of the primary dried product was dispersed in 400 parts of pure water to obtain a secondary slurry. The secondary slurry was evaporated to dryness again with superheated stirring, and the resulting solid was dried at 130 ° C. for 16 hours to obtain a secondary dried product. The water content of the secondary dried product was 1.5% by weight. This secondary dried product was pulverized. To 100 parts of the powder thus obtained, 3.0 parts of graphite was added, and subsequently formed into a ring shape having an outer diameter of 5 mm, an inner diameter of 2 mm, and a length of 5 mm by a tableting machine. The obtained molded product was calcined at 380 ° C. for 6 hours under air flow to obtain a catalyst. The composition of the elements excluding oxygen in this catalyst is
Mo 12 P 1.5 V 0.5 Cu 0.1 Fe 0.2 Cs 1
Met.
[0027]
When this catalyst was filled in a reaction tube and a mixed gas of 5% methacrolein, 10% oxygen, 30% water vapor and 55% nitrogen (volume%) was passed at a reaction temperature of 290 ° C. and a contact time of 3.6 seconds, The rain reaction rate was 84.1%, the methacrylic acid selectivity was 83.5%, and the methacrylic acid single stream yield was 70.2%.
[0028]
[Example 2]
In Example 1, a catalyst was produced in the same manner as in Example 1 except that the time for evaporation to dryness in obtaining the primary dry product was shortened and a primary dry product having a moisture content of 18.2% by weight was obtained. When methacrylic acid was produced in the same manner, the methacrolein reaction rate was 83.9%, the methacrylic acid selectivity was 83.4%, and the methacrylic acid single stream yield was 70.0%.
[0029]
[Example 3]
In Example 1, a catalyst was produced in the same manner as in Example 1 except that the time for evaporation to dryness in obtaining the primary dry product was extended and a primary dry product having a moisture content of 6.1% by weight was obtained. When methacrylic acid was produced in the same manner, the methacrolein reaction rate was 84.0%, the methacrylic acid selectivity was 83.0%, and the methacrylic acid single-flow yield was 69.7%.
[0030]
[Example 4]
In Example 1, the time for evaporation to dryness in obtaining the primary dry product was further shortened from that in Example 2, and the primary dry product having a moisture content of 22.4% by weight was obtained in the same manner as in Example 1. When the catalyst was produced and methacrylic acid was produced in the same manner, the methacrolein reaction rate was 83.7%, the methacrylic acid selectivity was 83.2%, and the methacrylic acid single-flow yield was 69.6%.
[0031]
[Example 5]
In Example 1, the time for evaporation to dryness in obtaining the primary dried product was further extended from that in Example 3, and the primary dried product having a water content of 3.8% by weight was obtained in the same manner as in Example 1. When the catalyst was produced and methacrylic acid was produced in the same manner, the methacrolein reaction rate was 83.9%, the methacrylic acid selectivity was 82.9%, and the methacrylic acid single-flow yield was 69.6%.
[0032]
[Example 6]
In Example 1, except that the amount of pure water in which the primary dried product was dispersed was changed from 400 parts to 600 parts, a catalyst was produced in the same manner as in Example 1, and methacrylic acid was produced in the same manner. The reaction rate was 83.4%, the selectivity of methacrylic acid was 83.2%, and the single flow rate of methacrylic acid was 69.4%.
[0033]
[Example 7]
In Example 1, except that the amount of pure water in which the primary dried product was dispersed was changed from 400 parts to 900 parts, a catalyst was produced in the same manner as in Example 1, and methacrylic acid was produced in the same manner. The reaction rate was 83.3%, the selectivity of methacrylic acid was 83.1%, and the single flow rate of methacrylic acid was 69.2%.
[0034]
[Example 8]
In Example 1, except that the operation (drying / dispersing operation) for obtaining the secondary slurry from the primary slurry was repeated twice, a catalyst was produced in the same manner as in Example 1, and methacrylic acid was produced in the same manner. The methacrolein reaction rate was 84.2%, the methacrylic acid selectivity was 83.7%, and the methacrylic acid single stream yield was 70.5%. The water content of the primary dried product in the second drying / remelting operation was 11.7% by weight.
[0035]
[Example 9]
In Example 1, except that the operation of obtaining a secondary slurry from the primary slurry (drying / dispersing operation) was repeated three times, a catalyst was produced in the same manner as in Example 1, and methacrylic acid was produced in the same manner. The methacrolein reaction rate was 84.4%, the selectivity of methacrylic acid was 83.6%, and the single flow rate of methacrylic acid was 70.6%. The water content of the primary dried product in the second and third drying / remelting operations was 11.7% by weight and 11.7% by weight, respectively.
[0036]
[Comparative Example 1]
In Example 1, the operation of dispersing and drying the primary dried product in pure water was omitted, that is, except that the primary dried product was dried at 130 ° C. for 16 hours, molded and calcined to obtain a catalyst. A catalyst was produced in the same manner as in Example 1, and methacrylic acid was produced in the same manner. As a result, the methacrolein reaction rate was 82.4%, the methacrylic acid selectivity was 81.3%, and the methacrylic acid single-flow yield was 67.0%. It was found that the performance of the catalyst obtained was lower than that of Example 1. It was.
[0037]
[Comparative Example 2]
In Example 1, a catalyst was produced in the same manner as in Example 1 except that the primary dried product was dried at 130 ° C. for 16 hours before being dispersed in pure water, and methacrylic acid was produced in the same manner. As a result, the methacrolein reaction rate was 82.7%, the methacrylic acid selectivity was 81.3%, and the methacrylic acid single stream yield was 67.2%. In addition, the moisture content of what dried the primary dried material at 130 degreeC for 16 hours is 1.5 weight%, and it turned out that the performance of the catalyst obtained compared with Example 1 is low.
[0038]
[Comparative Example 3]
In Example 1, the time for evaporation to dryness in obtaining the primary dry product was further shortened from that in Example 4, and the primary dry product having a water content of 30.5% by weight was obtained in the same manner as in Example 1. A catalyst was produced and methacrylic acid was produced in the same manner. As a result, the methacrolein reaction rate was 82.9%, the methacrylic acid selectivity was 81.4%, and the methacrylic acid single stream yield was 67.5%. It was found that the performance of the catalyst obtained was lower than that of Example 1. It was.
[0039]
[Example 10]
100 parts of ammonium paramolybdate, 4.42 parts of ammonium metavanadate and 9.20 parts of cesium nitrate were dissolved by heating in 300 parts of pure water. To this was added a solution prepared by dissolving 8.71 parts of 85 wt% phosphoric acid in 10 parts of pure water, then 5.50 parts of antimony trioxide, heated to 95 ° C. with stirring, and then added 1.14 parts of copper nitrate. A solution dissolved in 10 parts of pure water was added. Furthermore, this mixed liquid was stirred at 95 ° C. for 15 minutes to obtain a primary slurry. The primary slurry was evaporated to dryness with heating and stirring to obtain a paste-like primary dry product. The moisture content of the primary dried product was 13.1%. 100 parts of the primary dried product was dispersed in 400 parts of pure water to obtain a secondary slurry. The secondary slurry was evaporated to dryness while stirring with heating, and the obtained solid was dried at 130 ° C. for 16 hours to obtain a secondary dried product. The water content of the secondary dried product was 1.5%. This secondary dried product was molded and calcined in the same manner as in Example 1 to obtain a catalyst. The composition of the elements excluding oxygen in this catalyst is
Mo 12 P 1.6 V 0.8 Cu 0.1 Sb 0.8 Cs 1
Met.
[0040]
When this catalyst was used and reacted in the same manner as in Example 1, the methacrolein reaction rate was 84.5%, the methacrylic acid selectivity was 84.8%, and the methacrylic acid yield was 71.7%.
[0041]
[Comparative Example 4]
In Example 10, the operation of dispersing and drying the primary dried product in pure water was omitted, that is, except that the primary dried product dried at 130 ° C. for 16 hours was molded and calcined to obtain a catalyst. A catalyst was produced in the same manner as in Example 10, and methacrylic acid was produced in the same manner. As a result, the methacrolein reaction rate was 82.8%, the methacrylic acid selectivity was 83.7%, and the methacrylic acid single-flow yield was 69.3%, indicating that the performance of the catalyst obtained was lower than that of Example 10. It was.
[0042]
[Comparative Example 5]
In Example 10, a catalyst was produced in the same manner as in Example 10 except that the primary dried product was dried at 130 ° C. for 16 hours before being dispersed in pure water, and methacrylic acid was produced in the same manner. As a result, the methacrolein reaction rate was 83.0%, the methacrylic acid selectivity was 83.8%, and the single flow yield of methacrylic acid was 69.6%. In addition, the moisture content of what dried the primary dried material at 130 degreeC for 16 hours is 1.5 weight%, and it turned out that the performance of the catalyst obtained compared with Example 10 is low.
[0043]
【Effect of the invention】
By there use a catalyst prepared by the method for producing methacrylic acid synthesis catalyst of the present invention, methacrylic acid can be produced in high yields by vapor phase catalytic oxidation of methacrolein with molecular oxygen.
Claims (3)
ＭｏaＰbＣｕcＶdＸeＹfＯg （１）
（式中、Ｍｏ、Ｐ、Ｃｕ、ＶおよびＯはそれぞれモリブデン、リン、銅、バナジウムおよび酸素を表し、Ｘはカリウム、ルビジウムおよびセシ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、Ｙは鉄、コバルト、ニッケル、ヒ素、アンチモンおよびビスマスからなる群より選ばれた少なくとも１種の元素を表す。ただし、ａ、ｂ、ｃ、ｄ、ｅ、ｆおよびｇは各元素の原子比を表し、ａ＝１２のとき、０．１≦ｂ≦３、０．０１≦ｃ≦３、０．０１≦ｄ≦３、０．０１≦ｅ≦３、０≦ｆ≦３であり、ｇは前記各成分の原子比を満足するのに必要な酸素の原子比である。）The method for producing a methacrylic acid synthesis catalyst according to claim 1 or 2, wherein the methacrylic acid synthesis catalyst is a composite oxide represented by a composition formula of formula (1).
Mo a P b Cu c V d X e Y f O g (1)
(Expressed in the formula, Mo, P, Cu, V and O represent molybdenum, phosphorus, copper, vanadium and oxygen, X represents at least one element selected from potassium, rubidium and cesium or Ranaru group , Y represents iron, cobalt, nickel, arsenic, at least one element selected from antimony and bismuth scan or Ranaru group. However, a, b, c, d , e, f and g are each Represents the atomic ratio of the elements, and when a = 12, 0.1 ≦ b ≦ 3, 0.01 ≦ c ≦ 3, 0.01 ≦ d ≦ 3, 0.01 ≦ e ≦ 3, 0 ≦ f ≦ 3 And g is an atomic ratio of oxygen necessary to satisfy the atomic ratio of each component.)
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| JP4961132B2 (en) * | 2005-11-09 | 2012-06-27 | 三菱レイヨン株式会社 | Method for producing catalyst for producing methacrylic acid, and method for producing methacrylic acid |
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| JP3826413B2 (en) * | 1995-08-17 | 2006-09-27 | 住友化学株式会社 | Method for producing catalyst molded body for synthesis of unsaturated aldehyde and unsaturated carboxylic acid |
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