JP3629719B2 - Reversible ionization and non-ionization processes for hydroformylation catalysts - Google Patents

Description

｛式（１）において、Ｒ^１は、直鎖状、分岐状もしくは環状アルキル基又はフェニル基もしくはナフチル基（これらは必要に応じ水酸基、ハロゲンなどの他の置換基で置換されていてもよい）などの炭素数１〜１０の炭化水素基であり、Ｒ^２は水素原子、メチル、エチル、イソプロピル、シクロペンチルなどの炭素数１〜５のアルキル基、ニトロ基又はクロロ、ブロモなどのハロゲン原子であり、ｍは１、２又は３であり、ｎは０又は１であり、ｘは０、１又は２であり、ｙ及びｚは独立的に０、１、２又は３であり、但し、ｘとｙとｚとの和は３であり、そしてＸ^１及びＸ^２は独立的に水素原子又は−ＮＲ^３Ｒ^４（ここで、Ｒ^３及びＲ^４は独立的に、メチル、エチル、プロピル、イソプロピル、ブチルなどの炭素数１〜４のアルキル基である）であり、但し、ｙとｚとが共に０ではない場合Ｘ^１及びＸ^２は同時に水素原子ではなく、ｙが０の場合Ｘ^２は−ＮＲ^３Ｒ^４であり、ｚが０の場合Ｘ^１は−ＮＲ^３Ｒ^４である｝；
【００３３】
【化７】

｛式（２）において、Ｒ^５及びＲ^６は独立的に水素原子、メチル、エチル、イソプロピル、シクロペンチルなどの炭素数１〜５のアルキル基、ニトロ基又はクロロ、ブロモなどのハロゲン原子であり、ｍ及びｎは式（１）で定義した通りであり、ｐは１、２又は３であり、ｑは０又は１であり、ａ、ｂ、ｃ及びｄは独立的に０、１又は２であり、但し、ａとｂの和が２であり且つｃとｄの和が２であり、Ｚはメチレン、エチレン、シクロヘキシレンなどの環状、非環状の２価の炭素数１〜１０の炭化水素基であり、そしてＸ^３、Ｘ^４、Ｘ^５及びＸ^６は独立的に水素原子又は−ＮＲ^３Ｒ^４（ここで、Ｒ^３及びＲ^４は式（１）で定義した通りである）であり、但し、ａとｂとｃとｄとがともに１の場合Ｘ^３、Ｘ^４、Ｘ^５及びＸ^６は同時に水素原子ではなく、ａが０の場合Ｘ^４、Ｘ^５及びＸ^６の少なくとも一つは−ＮＲ^３Ｒ^４であり、ｂが０の場合Ｘ^３、Ｘ^５及びＸ^６の少なくとも一つは−ＮＲ^３Ｒ^４であり、ｃが０の場合Ｘ^３、Ｘ^４及びＸ^６の少なくとも一つは−ＮＲ^３Ｒ^４であり、ｄが０の場合Ｘ^３、Ｘ^４及びＸ^５の少なくとも一つは−ＮＲ^３Ｒ^４である｝；
【００３４】
【化８】

｛式（３）において、Ｒ^７及びＲ^９は独立的に水素原子、メチル、エチル、イソプロピルなどの炭素数１〜６のアルキル基又はフェニル基であり、Ｒ^８及びＲ^１０は独立的に水素原子、メチル、エチル、イソプロピルなどの炭素数１〜６のアルキル基、ニトロ基又はクロロ、ブロモなどのハロゲン原子であり、ｒ及びｓは独立的に０、１、２又は３であり、ｅは１、２又は３であり、ｆは０、１又は２であり、但し、ｅとｆとの和は３であり、Ｘ^７は−ＮＲ^３Ｒ^４（ここで、Ｒ^３及びＲ^４は式（１）で定義した通りである）である｝；及び
【００３５】
【化９】

｛式（４）において、Ｒ^５、Ｒ^６、ｍ、ｎ、ｐ、ｑ、ａ、ｂ、ｃ、ｄ、Ｘ^３、Ｘ^４、Ｘ^５、Ｘ^６及びＺは式（２）で定義した通りである｝。
【００３６】
これらの式（１）〜（４）のなかでより好ましい具体的な有機リン化合物としては以下の式（５）〜（２２）のものを例示することができる。
【００３７】
【化１０】
Ｐ［ＣＨ_２Ｎ（Ｃ_２Ｈ_５）_２］_３ （５）
（Ｃ_４Ｈ_９）_２ＰＣＨ_２Ｎ（ＣＨ_３）_２ （６）
（Ｃ_４Ｈ_９）_２ＰＣＨ_２ＣＨ_２Ｎ（ＣＨ_３）_２ （７）
Ｐ［ＣＨ_２ＣＨ_２ＣＨ_２Ｎ（ＣＨ_３）_２］_３ （８）
Ｐ［ＣＨ_２ＣＨ_２ＣＨ_２Ｎ（Ｃ_２Ｈ_５）_２］_３ （９）
Ｐ［ＣＨ_２ＣＨ_２Ｎ（ｔ−Ｃ_４Ｈ_９）_２］_３ （１０）
（Ｃ_８Ｈ_１７）Ｐ［ＣＨ_２Ｎ（ＣＨ_３）_２］_２ （１１）
（Ｃ_６Ｈ_１３）_２ＰＣＨ_２ＣＨ_２ＣＨ_２Ｎ（ＣＨ_３）_２ （１２）
（Ｃ_６Ｈ_５）_２ＰＣＨ_２Ｎ（ＣＨ_３）_２ （１３）
（Ｃ_６Ｈ_５）_２ＰＣＨ_２ＣＨ_２Ｎ（ＣＨ_３）_２ （１４）
Ｐ［ＣＨ_２ＣＨ_２Ｃ_６Ｈ_４Ｎ（ＣＨ_３）_２］_３ （１５）
Ｐ［Ｃ_６Ｈ_４Ｎ（ＣＨ_３）_２］_３ （１６）
Ｐ［Ｃ_６Ｈ_４ＣＨ_２Ｎ（ＣＨ_３）_２］_３ （１７）
Ｃ_６Ｈ_５Ｐ［Ｃ_６Ｈ_４Ｎ（ＣＨ_３）_２］_２ （１８）
Ｃ_６Ｈ_５Ｐ［Ｃ_６Ｈ_４ＣＨ_２Ｎ（ＣＨ_３）_２］_２ （１９）
Ｃ_６Ｈ_５Ｐ［ＣＨ_２ＣＨ_２ＣＨ_２Ｎ（ＣＨ_３）_２］_２ （２０）
（Ｃ_６Ｈ_５）_２Ｐ［Ｃ_６Ｈ_４Ｎ（ＣＨ_３）_２］ （２１）
（Ｃ_６Ｈ_５）_２Ｐ［Ｃ_６Ｈ_４ＣＨ_２Ｎ（ｉ−Ｃ_３Ｈ_７）_２］ （２２）
【００３８】
本発明の可逆的イオン化方法及び非イオン化方法で使用するヒドロホルミル化用触媒においては、有機リン化合物の使用量が少なすぎると触媒の安定性が損なわれ、また、多すぎると反応速度が低下するので、ロジウム原子換算で成分（ａ）のロジウム化合物１グラム原子に対して、リン原子換算で成分（ｂ）の有機リン化合物を好ましくは１〜１００００グラム原子、より好ましくは１０〜１０００グラム原子使用する。
【００３９】
なお、本発明において、成分（ｂ）の有機リン化合物を成分（ａ）のロジウム化合物に対して過剰に用いた場合には、ロジウム化合物に配位していない有機リン化合物も存在することになるが、触媒をリサイクル使用する際のヒドロホルミル化反応条件をできるだけ一定に保持するために、ロジウム化合物に配位していない有機リン化合物を、ヒドロホルミル化用触媒と同じ相に存在させることが好ましい。このためには、ロジウム化合物に配位していない有機リン化合物を、ロジウム化合物に配位した有機リン化合物と同様に可逆的にイオン化又は非イオン化することが好ましい。
【００４０】
本発明の可逆的イオン化方法においては、このような成分からなる触媒に水と炭酸ガスとを反応させて有機リン化合物配位子の第３級アミン残基をアンモニウムカーボネートに変換することにより触媒をイオン化するが、この場合、反応温度が高すぎると、イオン化速度より炭酸ガスの遊離速度の方が速くなり、また反応温度が低すぎるとイオン化速度が遅すぎるので、１０〜５０℃の範囲で行うことが好ましい。また、炭酸ガスの圧力には特に制限はないが、１〜５０気圧の範囲で行うことが操作性の点から好ましい。
【００４１】
このようにイオン化した触媒は、本発明の可逆的非イオン化方法において、その有機リン化合物配位子のアンモニウムカーボネートに変換された第３級アミン残基から、公知の方法により炭酸ガスを遊離させることにより可逆的に非イオン化する。例えば、イオン化した触媒を７０〜１００℃に水性相中で加熱したり、触媒を減圧条件下に置いたりすることにより行うことができる。
【００４２】
次に、このように可逆的にイオン化あるいは非イオン化できるヒドロホルミル化用触媒の存在下で、エチレン性不飽和化合物を、一酸化炭素と水素と反応させて対応するアルデヒドを製造するための本発明のヒドロホルミル化方法を、１）エチレン性不飽和化合物及び相当する生成物が非水溶性（非極性）である場合と、２）エチレン性不飽和化合物及び相当する生成物が水溶性（極性）である場合とに分けて詳細に説明する。
【００４３】
１）エチレン性不飽和化合物及び相当する生成物が非水溶性（非極性）である場合。
【００４４】
１−ａ） まず、非水溶性のエチレン性不飽和化合物を、イオン化していない前述した成分（ａ）のロジウム化合物と成分（ｂ）の有機リン化合物とからなるヒドロホルミル化用触媒の存在下で、一酸化炭素と水素とヒドロホルミル化反応させて対応するアルデヒドに変換する。具体的には、撹拌型反応槽又は気泡型反応槽などの中に非水溶性エチレン性不飽和化合物とヒドロホルミル化用触媒とを仕込み、この容器中に、水素と一酸化炭素との混合反応ガス［Ｈ _２ ／ＣＯ（好ましくはモル比＝約０．５〜５）］を、一般に１〜３００気圧、好ましくは５〜１００気圧の圧力で導入し、一般に２０〜１６０℃、好ましくは５０〜１４０℃の温度に加熱撹拌する。この場合、ヒドロホルミル化用触媒は、成分（ａ）及び（ｂ）をヒドロホルミル化反応系に別個に導入し、その系の中で両者を反応させて錯体とすることにより調製することが好ましい。また、このような反応は、連続方式又はバッチ方式で行なうことができる。
【００４５】
また、ヒドロホルミル化反応におけるヒドロホルミル化用触媒の使用量は、少なすぎると反応速度が遅すぎ、また、多すぎると反応速度を効果的に速めることができず、かえって触媒コストが増大しすぎることとなるので、好ましくは反応液１リットル当たりロジウム原子換算で０．００１〜１０ミリグラム原子、より好ましくは０．００５〜５ミリグラム原子の濃度範囲となるようにする。
【００４６】
なお、有機リン化合物の反応液中での濃度を、ロジウム化合物の種類にもよるが、単座の場合には反応液１リットル当りリン原子換算で０．１〜５００ミリグラム原子の濃度範囲とすることが好ましく、０．５〜２００ミリグラム原子の濃度範囲とすることがより好ましい。また、２座以上の有機リン化合物の場合は、ロジウム原子に対して０．１〜５倍モルの範囲で使用することが好ましい。
【００４７】
このヒドロホルミル化反応において、不活性な非水溶性有機溶媒を使用することができる。例えば、ベンゼン、トルエン、キシレンなどの芳香族化合物、ヘキサン、オクタン、シクロヘキサンなどの脂肪族炭化水素、ジエチルエーテル、ジフェニルエーテルなどのエーテル類、シクロヘキサノン、メチルイソブチルケトンのようなケトン類、ジオクチルフタレート、酢酸エチルなどのエステル類、シクロヘキサノンなどのようなケトン類を適宜選択して使用することができる。
【００４８】
１−ｂ） 次に、前述の本発明の可逆的イオン化方法によりヒドロホルミル化反応混合物中のヒドロホルミル化用触媒に水の存在下で炭酸ガスを作用させてイオン化（極性化）し、そのイオン化した触媒を抽剤としての水性媒体に抽出する。これにより非水溶性の生成物と触媒とを容易に分離することができ、生成物の分離と触媒の回収とを容易に行うことができる。また、触媒の回収を抽出という手段で行うことにより、生成物の分離時に触媒が生成物の共存下で加熱されることはなくなるので、加熱により触媒が劣化したり、加熱により生成物やその分解物で触媒が被毒することを回避でき、触媒寿命を延ばすことができるようになる。
【００４９】
このような水性媒体としては水を好ましく使用することができ、その使用量は反応混合物の１／１０〜１０／１容量倍、好ましくは１／５〜５／１容量倍である。
【００５０】
更に、層分離を促進するためにベンゼン、トルエンなどの芳香族炭化水素類、ヘキサン、シクロヘキサンなどの脂肪族炭化水素類などを添加することができる。
【００５１】
また、触媒の劣化防止のために、水性媒体での抽出操作を炭酸ガス加圧下（好ましくは１〜５０気圧）で１０〜５０℃の温度で行うことが好ましい。
【００５２】
１−ｃ） 次に、前述の本発明の可逆的非イオン化方法により、水性層に含有されている触媒から炭酸ガスを遊離させて非イオン化（非極性化）し、非水溶性有機媒体に触媒を抽出する。このとき、非水溶性有機媒体として原料の非水溶性エチレン性不飽和化合物を使用することにより、簡便にヒドロホルミル化反応を再び行うことが可能となり、触媒のリサイクル使用を容易に実現できる。
【００５３】
非水溶性有機媒体の使用量は一般に反応混合物の１／１０〜１０／１容量倍、好ましくは１／５〜５／１容量倍である。また、炭酸ガス遊離を促進させるために触媒の非イオン化及び非水溶性有機媒体での抽出を７０〜１１０℃の温度で行うことが好ましい。あるいは、減圧下で行うこともできる。
【００５４】
なお、分離したヒドロホルミル化生成物（アルデヒド）は、晶析、蒸留などの通常の手段により単離することができる。
【００５５】
２）エチレン性不飽和化合物及び相当する生成物が水溶性（非極性）である場合。
【００５６】
２−ａ） まず、水溶性のエチレン性不飽和化合物を、前述の本発明の可逆的イオン化方法によりイオン化された、成分（ａ）のロジウム化合物と成分（ｂ）の有機リン化合物とからなるヒドロホルミル化用触媒の存在下で、一酸化炭素と水素とヒドロホルミル化反応させて対応するアルデヒドに変換する。具体的には、撹拌型反応槽又は気泡型反応槽などの中に水溶性エチレン性不飽和化合物とイオン化されていないヒドロホルミル化用触媒と水とを仕込み、この容器中に炭酸ガスを導入して触媒のイオン化を行い、次いで、水素と一酸化炭素との混合反応ガスを導入することにより行うことができる。この場合、ヒドロホルミル化反応の条件は、前述の非水溶性のエチレン性不飽和化合物のヒドロホルミル化反応において説明した通りである。但し、使用する溶媒としては、非水溶性のものではなくジメチルスルホキシド、スルホラン、低級アルコール、アセトンなどの水溶性有機溶媒を使用することができる。
【００５７】
また、ヒドロホルミル化反応中に触媒が非イオン化されることを抑制するために気相部の炭酸ガス分圧を０．１気圧以上１００気圧以下に保つことが望ましい。
【００５８】
２−ｂ） 次に、前述した本発明の可逆的非イオン化方法により、ヒドロホルミル化反応混合物中の触媒から炭酸ガスを遊離させて非イオン化し、その触媒を非水溶性有機媒体に抽出する。なお、触媒の非イオン化操作と抽出操作は同時に平行して行うことができる。
【００５９】
このような抽出により水溶性のヒドロホルミル化生成物と触媒とを容易に分離することができ、生成物の分離と触媒の回収とを容易に行うことができる。また、触媒の回収を抽出という手段で行うことにより、生成物の分離時に触媒が生成物の共存下で加熱されることはなくなるので、加熱により触媒が劣化したり、加熱により生成物やその分解物で触媒が被毒することを回避でき、触媒寿命を延ばすことができるようになる。
【００６０】
このような非水溶性有機媒体としては、ベンゼン、トルエン、キシレン、クメンなどの芳香族炭化水素類、ヘキサン、オクタン、シクロヘキサン、メチルシクロヘキサンなどの脂肪族炭化水素類を例示することができ、その使用量は反応混合物の１／１０〜１０／１容量倍、好ましくは１／５〜５／１容量倍である。
【００６１】
更に、層分離を促進させるために水を添加することができる。
【００６２】
また、炭酸ガスの遊離を促進させるために、触媒の非イオン化及び非水溶性有機媒体での抽出を７０〜１１０℃の温度で行うことが好ましい。あるいは、減圧下で行うこともできる。
【００６３】
２−ｃ） 次に、非水溶性有機媒体に抽出された触媒を、前述した本発明の可逆的イオン化方法によりイオン化し、そのイオン化された触媒を水性媒体に抽出する。このとき、水性媒体に水溶性エチレン性不飽和化合物を溶解しておくことにより、簡便にヒドロホルミル化反応を再び行うことが可能となり、触媒のリサイクル使用を容易に実現できる。
【００６４】
水性媒体の使用量は一般に反応混合物の１／１０〜１０／１容量倍、好ましくは１／５〜５／１容量倍である。
【００６５】
なお、抽出により分離したヒドロホルミル化生成物（アルデヒド）は、更に、晶析、蒸留などの通常の手段により精製することができる。
【００６６】
本発明において、ヒドロホルミル化反応の対象となるエチレン性不飽和化合物としては、直鎖、分岐又は環状の炭素数２以上の末端あるいは内部オレフィン、例えば、エチレン、プロピレン、１−ブテン、１−ペンテン、１−ヘキセン、１−ヘプテン、１−オクテン、１−ノネン、２−ブテン、イソブテン、２−オクテン、１，７−オクタジエン、ビニルシクロヘキセン、ジシクロペンタジエン、シクロオクタジエン、ブタジエン重合物、イソプレン重合物などの不飽和脂肪族炭化水素類、スチレン、α−メチルスチレン、β−メチルスチレン、アルキル基核置換スチレン、ジビニルベンゼンなどのスチレン類、アリルアルコール、メタリルアルコール、クロチルアルコール、２−ブテン−１，４−ジオ−ル、３−メチル−３−ブテン−１−オール、７−オクテン−１−オール、２，７−オクタジエノールなどの不飽和アルコール類、ビニルアセテート、アリルアセテート、メチルアクリレート、メチルメタクリレート、７−オクテン−１−アールなどの官能基を含有するオレフィン類、アリルスルホン酸ソーダ、スチレンスルホン酸ソーダのような無機塩残基を有するオレフィン類など、広範囲のエチレン性不飽和化合物を例示することができる。
【００６７】
また、本発明の二つの態様のヒドロホルミル化反応においては、触媒をイオン化或いは非イオン化して触媒を選択的に抽出できるようにして、ヒドロホルミル化反応混合物を生成物含有層と触媒成分含有層とに分離するが、この分離時に、窒素ガスなどの不活性ガスや、一酸化炭素／水素混合ガスの存在下で行うこともできる。また、触媒を抽出する際に、十分に層分離しない場合には、その層分離を促進させるために遠心分離操作を併用することが好ましい。
【００６８】
なお、ヒドロホルミル化反応と触媒の回収とを繰り返す間に、触媒の損失量が無視し得ない水準に達することもあるが、触媒成分を追加することにより反応速度を容易に維持することができる。
【００６９】
【作用】
本発明のヒドロホルミル化方法においては、ヒドロホルミル化反応を促進させる触媒能を有するロジウム化合物に、第３級アミン残基と第３級リン残基とをそれぞれ少なくとも一つ有する有機リン化合物が配位して安定化されたものをヒドロホルミル化用触媒として使用する。
【００７０】
一方、本発明の可逆性イオン化方法により、この有機リン化合物の第３級アミン残基を、それに水と炭酸ガスを反応させることによりイオン化してアンモニウムカーボネートに変換する。また、本発明に可逆的非イオン化方法により、イオン化した触媒のアンモニウムカーボネート残基から炭酸ガスを遊離させることにより第３級アミンに変換し非イオン化する。こうして、ヒドロホルミル化用触媒を可逆的にイオン化あるいは非イオン化することが可能となる。従って、ヒドロホルミル化用触媒を非水溶性有機媒体に溶解あるいは抽出したり、水性媒体に溶解あるいは抽出したりすることを自由に行うことができる。
【００７１】
従って、本発明のヒドロホルミル化方法では、このヒドロホルミル化用触媒の可逆的イオン化方法あるいは非イオン化方法を利用することにより、エチレン性不飽和化合物が水溶性または非水溶性のいずれであっても、使用するエチレン性不飽和化合物の性質に応じて触媒をイオン化又は非イオン化して、均一な溶液中で触媒をエチレン性不飽和化合物に接触させることが可能となる。
【００７２】
また、反応終了後には、触媒をヒドロホルミル化反応時と逆のイオン状態とすることにより、ヒドロホルミル化反応混合物から触媒を選択的に抽出分離回収すること、及び生成物を分離することが同時に可能となる。
【００７３】
更に、抽出液中の触媒のイオン状態を逆にすること、即ちヒドロホルミル化反応時と同じイオン状態として、エチレン性不飽和化合物を含有する媒体に触媒を抽出することにより、その抽出物をそのまま一酸化炭素と水素とヒドロホルミル化反応させることが可能となる。こうして、触媒のリサイクル使用が簡便に行うことが可能となる。従って、エチレン性不飽和化合物からヒドロホルミル化反応により対応するアルデヒドを低い製造コストで工業的に有利に製造することが可能となる。
【００７４】
【実施例】
本発明を以下の実施例により更に具体的に説明するが、本発明はこれらの実施例に限定されるものではない。
【００７５】
実施例１
ガス導入口およびサンプリング口を備えた内容３００ｍｌの電磁撹拌式オートクレーブに、ジカルボニルアセチルアセトナートロジウム２．５８ｍｇ（０．０１ｍｍｏｌ）、トリ（ｐ−Ｎ，Ｎ−ジメチルアミノメチルフェニル）ホスフィン４３３ｍｇ（１ｍｍｏｌ）、アリルスルホン酸ナトリウム２０ｇ（０．１３９ｍｏｌ）及び水９０ｇを空気に触れないように仕込み、オートクレーブ内に炭酸ガスを１０ｋｇ／ｃｍ^２Ｇの圧力になるまで供給し、均一な溶液とした。
【００７６】
次いで、オートクレーブ内に水素／一酸化炭素＝１／１の混合ガスを連続的に供給し、全圧を６０ｋｇ／ｃｍ^２Ｇにした。その圧力を保ちながら、反応混合物を撹拌し、２０分かけて内温を８０℃にあげた。この状態で５時間ヒドロホルミル化反応を行った。その結果、ヒドロホルミル化物（４−スルホブタナールナトリウム塩及び３−スルホ−２−メチルプロパナールナトリウム塩の混合物）の収率は３８％であった。
【００７７】
次いで、オートクレーブ内の反応混合液を空気に触れないように還流装置の付いた内容１リットルの三ッ口フラスコに圧送し、更にトルエン１００ｇを空気に触れないように加え、この三ッ口フラスコの内温を９０℃に保ちながら窒素ガスを１リットル／ｈｒで流し、炭酸ガスを遊離させながら２時間撹拌した。撹拌を停止して反応混合物を２層に分離し、その下層の水性層を抜き取った。
【００７８】
残った上層の触媒を含むトルエン層にアリルスルホン酸ナトリウム２０ｇ（０．１３９ｍｏｌ）及び水９０ｇを追加した。得られた混合液を空気に触れないようにしてオートクレーブ内に仕込み、オートクレーブ内を炭酸ガスで置換し、更に炭酸ガスで１０ｋｇ／ｃｍ^２Ｇの圧力に保ちながら、２０℃で１時間撹拌した。撹拌を停止し、あらかじめ水素／一酸化炭素＝１／１の混合ガスで置換された内容１リットルの分液ロートに圧送し、静置して２層に分離し、下層の水溶液を空気に触れないようにオートクレーブに移し、第１回目と同じ反応条件でヒドロホルミル化反応を行った。その結果、ヒドロホルミル化物の収率は４３％であった。
【００７９】
実施例２
ガス導入口およびサンプリング口を備えた内容３００ｍｌの電磁撹拌式オートクレーブに、ジカルボニルアセチルアセトナートロジウム２．５８ｍｇ（０．０１ｍｍｏｌ）、トリ（ｐ−Ｎ，Ｎ−ジメチルアミノメチルフェニル）ホスフィン１．０８ｇ（２．５ｍｍｏｌ）及び１−オクテン７０ｇを空気に触れないようにして仕込み、オートクレーブ内の圧力を水素／一酸化炭素＝２／１の混合ガスで２０ｋｇ／ｃｍ^２Ｇの圧力とした。その圧力を保ちながら、１５リットル／ｈｒでオフガスを流し、撹拌しながら２０分かけて内温を９０℃にあげた。この状態で５時間ヒドロホルミル化反応を行った。原料である１−オクテンの転換率は９２％であり、ヒドロホルミル化選択率は９５％であった。また、生成アルデヒドの直鎖率は８０％であった。
【００８０】
次いで、オートクレーブ内の水素／一酸化炭素混合ガスを、その内圧が大気圧と同じになるまで放出した。その後、オートクレーブに水２００ｍｌを空気に触れないように仕込み、その中を炭酸ガスで置換し、更に炭酸ガスで１０ｋｇ／ｃｍ^２Ｇの圧力に保ちながら、２５℃で３時間撹拌した。撹拌を停止した後、混合液を分離槽に空気に触れないように移して２層に分離させた。
【００８１】
下層の水溶液を、還流装置の付いた内容１リットルの三ッ口フラスコに空気に触れないように移し、更に１−オクテン７０ｇを追加した。この三ッ口フラスコの内温を８０℃に保ち、窒素ガスを２リットル／ｈで流し、炭酸ガスを遊離させながら２時間撹拌した。撹拌を停止して反応混合物を２層に分離させた。そして、空気に触れないように上層の触媒成分を含む１−オクテンをオートクレーブに移し、第１回目と同じ反応条件でヒドロホルミル化反応を行った。その結果、原料の１−オクテンの転換率は８６％であり、ヒドロホルミル化選択率は９５％であった。また、生成アルデヒドの直鎖率は８０％であった。
【００８２】
実施例３
ガス導入口およびサンプリング口を備えた内容３００ｍｌの電磁撹拌式オートクレーブに、ジカルボニルアセチルアセトナートロジウム１．９３５ｍｇ（０．００７５ｍｍｏｌ）、トリ（ｐ−Ｎ，Ｎ−ジメチルアミノメチルフェニル）ホスフィン１６２．４ｍｇ（０．３７５ｍｍｏｌ）及び７−オクテン−１−アール６４ｇ（１０ｗｔ％のｎ−オクタナールを含む）を空気に触れないように仕込み、オートクレーブの圧力を水素／一酸化炭素＝１／１の混合ガスで９０ｋｇ／ｃｍ^２Ｇの圧力とした。その圧力を保ちながら２０分かけて内温を１００℃にあげた。この状態で３０分ヒドロホルミル化反応を行った。その結果、原料の７−オクテン−１−アールの転換率は７９％であった。
【００８３】
次いで、オートクレーブ内の水素／一酸化炭素混合ガスを、その内圧が大気圧と同じになるまで放出した。その後、オートクレーブに水１００ｍｌを空気に触れないように仕込み、その中を炭酸ガスで置換し、更に炭酸ガスで１２ｋｇ／ｃｍ^２Ｇの圧力に保ちながら、２０℃で３時間撹拌した。撹拌を停止した後、混合液を水素／一酸化炭素雰囲気に保った分離槽に空気に触れないように移し、遠心分離処理（１００００Ｇ、１０分間）を施して２層に分離した。
【００８４】
下層の水溶液を、還流装置の付いた内容１リットルの三ッ口フラスコに空気に触れないように移し、更に７−オクテン−１−アール６４ｇ（１０ｗｔ％のｎ−オクタナールを含む）を追加した。この三ッ口フラスコの内温を９０℃に保ち、窒素ガスを１リットル／ｈｒで流し、炭酸ガスを遊離させながら２時間撹拌した。撹拌を停止して反応混合物を２層に分離させた。そして、空気に触れないように上層の触媒成分を含む７−オクテン−１−アールをオートクレーブに移し、第１回目と同じ反応条件でヒドロホルミル化反応を行った。原料の７−オクテン−１−アールの転換率は６６％であった。
【００８５】
実施例４
ガス導入口およびサンプリング口を備えた内容３００ｍｌの電磁撹拌式オートクレーブに、ジカルボニルアセチルアセトナートロジウム１．５４８ｍｇ（０．００６ｍｍｏｌ）、トリ（ｐ−Ｎ，Ｎ−ジメチルアミノメチルフェニル）ホスフィン２６０ｍｇ（０．６ｍｍｏｌ）、７−オクテン−１−アール１０２ｇ（１０ｗｔ％のｎ−オクタナールを含む）を空気に触れないように仕込み、オートクレーブ内の圧力を水素／一酸化炭素＝１／１の混合ガスで３０ｋｇ／ｃｍ^２Ｇの圧力とした。その圧力を保ち、撹拌しながら３０分かけて内温を９０℃にあげた。この状態で６時間ヒドロホルミル化反応を行った。原料の７−オクテン−１−アールの転換率は９６％であった。
【００８６】
次いで、オートクレーブ内の水素／一酸化炭素混合ガスを、その内圧が大気圧と同じになるまで放出した。そして、水１２０ｍｌを空気に触れないようにオートクレーブに仕込み、その中を炭酸ガスで置換し、更に炭酸ガスで６ｋｇ／ｃｍ^２Ｇの圧力に保ちながら、３０℃で２時間撹拌した。撹拌を停止した後、混合液を水素／一酸化炭素雰囲気に保った分離槽に空気に触れないように移し、遠心分離処理（１００００Ｇ、１０分間）を施して２層に分離させた。
【００８７】
下層の水溶液を、還流装置の付いた内容１リットルの三ッ口フラスコに空気に触れないように移し、更に７−オクテン−１−アール１０２ｇ（１０ｗｔ％のｎ−オクタナールを含む）を追加した。この三ッ口フラスコの内温を１００℃に保ち、窒素ガスを１リットル／ｈｒで流し、炭酸ガスを遊離させながら１時間撹拌した。撹拌を停止して反応混合物を２層に分離させた。空気に触れないように上層の触媒成分を含む原料の７−オクテン−１−アールをオートクレーブに移し、第１回目と同じ反応条件でヒドロホルミル化反応を行った。原料の７−オクテン−１−アールの転換率は８１％であった。
【００８８】
実施例５
ガス導入口およびサンプリング口を備えた内容３００ｍｌの電磁撹拌式オートクレーブに、ジカルボニルアセチルアセトナートロジウム１．２９ｍｇ（０．００５ｍｍｏｌ）、トリ（ｐ−Ｎ，Ｎ−ジメチルアミノメチルフェニル）ホスフィン４３．３ｍｇ（０．１ｍｍｏｌ）及び７−オクテン−１−アール８５ｇ（１０ｗｔ％のｎ−オクタナールを含む）を空気に触れないように仕込み、オートクレーブ内の圧力を水素／一酸化炭素＝１／１の混合ガスで３０ｋｇ／ｃｍ^２Ｇの圧力とした。撹拌しながら３０分かけて内温を１００℃にあげた。この状態で３時間ヒドロホルミル化反応を行った。原料の７−オクテン−１−アールの転換率は８９％であった。
【００８９】
次いで、オートクレーブ内の水素／一酸化炭素混合ガスを、その内圧が大気圧と同じになるまで放出した。その後、水５０ｍｌを空気に触れないようにオートクレーブに仕込み、その中を炭酸ガスで置換し、更に炭酸ガスで１０ｋｇ／ｃｍ^２Ｇの圧力に保ちながら、４０℃で５時間撹拌した。撹拌を停止した後、混合液を水素／一酸化炭素雰囲気に保った分離槽に、空気に触れないように移し、遠心分離処理（１００００Ｇ、１０分間）を施し、２層に分離させた。
【００９０】
下層の水溶液を、還流装置の付いた内容１リットルの三ッ口フラスコに空気に触れないように移し、更に７−オクテン−１−アール８５ｇ（１０ｗｔ％のｎ−オクタナールを含む）を追加した。この三ッ口フラスコの内温を８０℃に保ち、窒素ガスを１リットル／ｈｒで流し、炭酸ガスを遊離させながら１時間撹拌した。撹拌を停止して反応混合物を２層に分離させた。そして、空気に触れないようにして上層の触媒成分を含む原料（７−オクテン−１−アール）をオートクレーブに移し、第１回目と同じ反応条件でヒドロホルミル化反応を行った。原料の７−オクテン−１−アールの転換率は６１％であった。
【００９１】
実施例６
ガス導入口およびサンプリング口を備えた内容３００ｍｌの電磁撹拌式オートクレーブに、ジカルボニルアセチルアセトナートロジウム１．２９ｍｇ（０．００５ｍｍｏｌ）、トリ（ｐ−Ｎ，Ｎ−ジメチルアミノメチルフェニル）ホスフィン１．０８ｇ（２．５ｍｍｏｌ）及び２，７−オクタジエノール８５ｇを空気に触れないように仕込み、オートクレーブ内の圧力を水素／一酸化炭素＝３／１の混合ガスで１５ｋｇ／ｃｍ^２Ｇの圧力とした。その圧力を保ちながら、１５リットル／ｈｒでオフガスを流し、撹拌しながら２０分かけて内温を８５℃にあげた。この状態で４．５時間ヒドロホルミル化反応を行った。原料である２，７−オクタジエノールの転換率は６２％であり、９−ヒドロキシ−７−ノネン−１−アールの収率は４３％であった。
【００９２】
次いで、オートクレーブ内の水素／一酸化炭素混合ガスを、その内圧が大気圧と同じになるまで放出した。その後、水１００ｍｌを空気に触れないようにオートクレーブに仕込み、その中を炭酸ガスで置換し、更に炭酸ガスで１５ｋｇ／ｃｍ^２Ｇの圧力に保ちながら、２０℃で３時間撹拌した。撹拌を停止した後、混合液を水素／一酸化炭素雰囲気に保った分離槽に空気に触れないように移し、遠心分離処理（１００００Ｇ、３０分間）を施し、２層に分離した。
【００９３】
下層の水溶液を、還流装置の付いた内容１リットルの三ッ口フラスコに空気に触れないように移し、更に２，７−オクタジエノール８５ｇを追加した。この三ッ口フラスコの内温を８０℃に保ち、窒素ガスを１リットル／ｈｒで流し、炭酸ガスを遊離させながら２時間撹拌した。撹拌を停止して反応混合物を２層に分離させた。そして、空気に触れないように上層の触媒成分を含む原料の２，７−オクタジエノールをオートクレーブに移し、第１回目と同じ反応条件でヒドロホルミル化反応を行った。原料の２，７−オクタジエノールの転換率は５８％で、９−ヒドロキシ−７−ノネン−１−アールの収率は４０％であった。
【００９４】
実施例７
ガス導入口およびサンプリング口を備えた内容３００ｍｌの電磁撹拌式オートクレーブに、ジカルボニルアセチルアセトナートロジウム１．５４８ｍｇ（０．００６ｍｍｏｌ）、トリ（ｐ−Ｎ，Ｎ−ジメチルアミノメチルフェニル）ホスフィン２６０ｍｇ（０．６ｍｍｏｌ）及び２，７−オクタジエノール１０２ｇを空気に触れないように仕込み、オートクレーブ内の圧力を水素／一酸化炭素＝３／１の混合ガスで３０ｋｇ／ｃｍ^２Ｇの圧力とした。その圧力を保ちながら、１５リットル／ｈｒでオフガスを流し、撹拌しながら２０分かけて内温を１００℃にあげた。この状態で４時間ヒドロホルミル化反応を行った。原料の２，７−オクタジエノールの転換率は７０％であり、９−ヒドロキシ−７−ノネン−１−アールの収率は４４％であった。
【００９５】
次いで、オートクレーブ内の水素／一酸化炭素混合ガスを、その内圧が大気圧と同じになるまで放出した。そして水６０ｍｌを空気に触れないようにオートクレーブに仕込み、その中を炭酸ガスで置換し、更に、炭酸ガスで１０ｋｇ／ｃｍ^２Ｇの圧力に保ちながら、内温を３５℃に保ちながら１時間撹拌した。撹拌を停止した後、混合液を水素／一酸化炭素雰囲気に保った分離槽に空気に触れないように移し、遠心分離処理（１００００Ｇ、３０分間）を施して２層に分離させた。
【００９６】
下層の水溶液を、還流装置の付いた内容１リットルの三ッ口フラスコに空気に触れないように移し、更に、２，７−オクタジエノール１０２ｇを追加した。この三ッ口フラスコの内温を９０℃に保ち、ヘリウムガスを１リットル／ｈｒで流し、炭酸ガスを遊離させながら１時間撹拌した。撹拌を停止して、反応混合物を２層に分離した。そして、空気に触れないように上層の触媒成分を含む原料の２，７−オクタジエノールをオートクレーブに移し、第１回目と同じ反応条件でヒドロホルミル化反応を行った。原料の２，７−オクタジエノールの転換率は６５％であった。また、９−ヒドロキシ−７−ノネン−１−アールの収率は４１％であった。
【００９７】
実施例８
ガス導入口およびサンプリング口を備えた内容３００ｍｌの電磁撹拌式オートクレーブに、ジカルボニルアセチルアセトナートロジウム１．２９ｍｇ（０．００５ｍｍｏｌ）、トリ（ｐ−Ｎ，Ｎ−ジメチルアミノメチルフェニル）ホスフィン４３．３ｍｇ（０．１ｍｍｏｌ）及びスチレン９１ｇを空気に触れないように仕込み、オートクレーブ内の圧力を水素／一酸化炭素＝１／１の混合ガスで９０ｋｇ／ｃｍ^２Ｇの圧力とした。その圧力を保ち、撹拌しながら２０分かけて内温を１１０℃にあげた。この状態で６時間ヒドロホルミル化反応を行った。原料のスチレンの転換率は７２％であり、ヒドロホルミル化選択率は９８％であった。また、生成アルデヒドの直鎖率は２０％であった。
【００９８】
次いで、オートクレーブ内の水素／一酸化炭素混合ガスを、その内圧が大気圧と同じになるまで放出した。そして、水２５ｍｌとｎ−ヘキサン５０ｍｌとを空気に触れないようにオートクレーブに仕込み、その中を炭酸ガスで置換し、更に、炭酸ガスで６ｋｇ／ｃｍ^２Ｇの圧力に保ち、２５℃で１時間撹拌した。撹拌を停止した後、混合液を炭酸ガス雰囲気に保った分離槽に空気に触れないように移し、２層に分離させた。
【００９９】
下層の水溶液を、還流装置の付いた内容１リットルの三ッ口フラスコに空気に触れないように移し、更にスチレン９１ｇを追加した。この三ッ口フラスコの内温を９０℃に保ち、窒素ガスを１リットル／ｈｒで流し、炭酸ガスを遊離させながら１時間撹拌した。撹拌を停止して反応混合物を２層に分離させた。空気に触れないように上層の触媒成分を含む原料のスチレンをオートクレーブに移し、第１回目と同じ反応条件でヒドロホルミル化反応を行った。原料のスチレンの転換率は５５％であり、ヒドロホルミル化選択率は９８％であった。また、生成アルデヒドの直鎖率は２０％であった。
【０１００】
実施例９
ガス導入口およびサンプリング口を備えた内容３００ｍｌの電磁撹拌式オートクレーブにジカルボニルアセチルアセトナートロジウム２．５８ｍｇ（０．０１ｍｍｏｌ）、トリ（ｐ−Ｎ，Ｎ−ジメチルアミノメチルフェニル）ホスフィン２１７ｍｇ（０．５ｍｍｏｌ）、２−ブテン−１，４−ジオール４４ｇ（０．５ｍｏｌ）及び水５９ｇを空気に触れないように仕込み、オートクレーブ内に炭酸ガスを１０ｋｇ／ｃｍ^２Ｇの圧力になるまで供給し、均一な溶液とした。
【０１０１】
次いで、オートクレーブ内に水素／一酸化炭素＝１／１の混合ガスを連続的に供給し、全圧を８０ｋｇ／ｃｍ^２Ｇの圧力とした。その圧力を保ちながら、３０分かけて内温を６０℃にあげた。この状態で１０時間ヒドロホルミル化反応を行った。その結果、ヒドロホルミル化生成物として２−ホルミル−１，４−ブタンジオールが収率３０％で得られた。
【０１０２】
次いで、オートクレーブ内の反応液をただちに冷却し、空気に触れないように還流装置の付いた内容１リットルの三ッ口フラスコに圧送し、更に、トルエン２００ｍｌと水１００ｍｌとを空気に触れないように仕込み、窒素ガスを１リットル／ｈｒで流しながらこの三ッ口フラスコの内温を室温から９０℃になるまで毎時３０℃の速度で昇温し、９０℃になってから更に１時間炭酸ガスを遊離させながら撹拌した。撹拌を停止して反応混合物を２層に分離させ、下層の水溶液を抜き取った。
【０１０３】
残った上層の触媒を含むトルエン層に２−ブテン−１，４−ジオール４４ｇ （０．５ｍｏｌ）及び水５９ｇを追加した。得られた混合液を空気に触れないようにオートクレーブ内に仕込み、オートクレーブ内を炭酸ガスで置換し、更に、炭酸ガスで１２ｋｇ／ｃｍ^２Ｇの圧力に保ちながら、２５℃で２時間撹拌した。撹拌を停止し、予め水素／一酸化炭素＝１／１の混合ガスで置換された内容１リットル分液ロートに圧送し、静置して２層に分離させた。下層の水溶液を空気に触れないようにオートクレーブに移し、第１回目と同じ反応条件でヒドロホルミル化反応を行った。その結果、２−ホルミル−１，４−ブタンジオールが収率２４％で得られた。
【０１０４】
実施例１０
ガス導入口およびサンプリング口を備えた内容３００ｍｌの電磁撹拌式オートクレーブにジカルボニルアセチルアセトナートロジウム１．２９ｍｇ（０．００５ｍｍｏｌ）、トリ（ｐ−Ｎ，Ｎ−ジメチルアミノメチルフェニル）ホスフィン２１７ｍｇ（０．５ｍｍｏｌ）、２−ブテン−１，４−ジオール４４ｇ（０．５ｍｏｌ）及び水５９ｇを空気に触れないように仕込み、オートクレーブ内に炭酸ガスを１０ｋｇ／ｃｍ^２Ｇの圧力になるまで供給し、均一な溶液とした。
【０１０５】
次いで、オートクレーブ内に水素／一酸化炭素＝１／１の混合ガスを連続的に供給し、全圧を１２０ｋｇ／ｃｍ^２Ｇの圧力にした。その圧力を保ち且つ撹拌しながら３０分かけて内温を６０℃にあげた。この状態で６時間ヒドロホルミル化反応を行った。その結果、ヒドロホルミル化物として２−ホルミル−１，４−ブタンジオールが収率１０％で得られた。
【０１０６】
次いで、オートクレーブ内の反応液をただちに冷却し、空気に触れないように還流装置の付いた内容１リットルの三ッ口フラスコに圧送し、更に、１−オクテン１６８ｇを空気に触れないように仕込み、窒素ガスを１リットル／ｈｒで流しながらこの三ッ口フラスコの内温を室温から９０℃になるまで毎時３０℃の速度で昇温し、９０℃になってから更に１時間、炭酸ガスを遊離させながら撹拌した。撹拌を停止して反応混合物を２層に分離させ、下層の水溶液を抜き取った。
【０１０７】
残った上層の触媒を含む１−オクテンを、空気に触れないように、ガス導入口およびサンプリング口を備えた内容５００ｍｌの電磁撹拌式オートクレーブに仕込み、その雰囲気を水素／一酸化炭素＝１／１の混合ガスで置換し、更に、１２０ｋｇ／ｃｍ^２Ｇの圧力に保ち、撹拌しながら２０分かけて内温を１１０℃にあげた。この状態で４時間ヒドロホルミル化反応を行った。原料の１−オクテンの転換率は９１％であり、ヒドロホルミル化選択率は９８％であった。また、生成アルデヒドの直鎖率は６０％であった
【０１０８】
【発明の効果】
本発明によれば、エチレン性不飽和化合物が水溶性であるか非水溶性であるかに関わらず、多量の非水性極性溶媒を使用せずに工業的に十分な反応速度でエチレン性不飽和化合物をヒドロホルミル化してアルデヒドを製造でき、しかも容易に触媒を高収率で回収でき、回収した触媒をリサイクル使用することができる。[0001]
[Industrial application fields]
The present invention relates to reversible use of a catalyst for hydroformylation used in the hydroformylation reaction of an ethylenically unsaturated compound, carbon monoxide and hydrogen to produce the corresponding aldehyde. The present invention relates to an ionization method or a nonionization method. The present invention also relates to a hydroformylation method using the reversible ionization method or non-ionization method.
[0002]
[Prior art]
A reaction in which an ethylenically unsaturated compound, hydrogen, and carbon monoxide are reacted in the presence of a catalyst to convert them into an aldehyde is called a hydroformylation reaction or an oxo reaction, and this reaction can be used to produce an aldehyde. It has become extremely valuable industrially.
[0003]
The catalyst used in such a hydroformylation reaction is generally a cobalt compound or a rhodium compound, but the latter rhodium compound is superior to the former cobalt compound in terms of catalytic activity and the property of selectively producing an aldehyde. It is known to be excellent.
[0004]
Examples of such rhodium compounds include rhodium salts such as rhodium oxide, rhodium complex compounds such as rhodium carbonyl, etc., and these may be used alone, but rather improve the stability of these compounds, In order to improve the catalytic activity or the like, it is used in a complexed form modified with a ligand such as an organic phosphorus compound, an organic arsenic compound, or an organic antimony compound.
[0005]
Among these ligands, organophosphorus compounds are preferably used in terms of toxicity and production costs, but depending on the type of raw material ethylenically unsaturated compound and target aldehyde, among organophosphorus compounds The bonding state of the phosphorus atom and the type of substituent bonded to the phosphorus atom are properly used. In other words, compounds such as tertiary phosphines and phosphites, the number of phosphorus atoms that are monodentate or bidentate, and the type of substituents that are alkyl-substituted or phenyl-substituted are properly used. It has been.
[0006]
From this point of view, an example of using an organophosphorus compound as a ligand for a hydroformylation catalyst comprising a rhodium compound is as follows:
(A) The rhodium compound is modified with a tertiary phosphine when the linear aldehyde is selectively produced (Japanese Patent Publication No. 45-10730);
(B) The rhodium compound is modified with a bidentate tertiary phosphine when a linear or branched aldehyde is selectively produced from an olefin having a functional group such as methyl methacrylate or allyl alcohol (Bull, Chem, Soc, Jpn., 50, 2351 (1977); JP-A-54-106407);
(C) In order to increase the reaction rate when producing an aldehyde compound from a highly sterically hindered branched olefin such as 3-methyl-3-buten-1-ol, a rhodium compound is substituted with an alkyl group at the 2-position of the phenyl group. Modification with substituted triphenyl phosphite (Japanese Patent Laid-Open No. 62-201881)
Etc. have been proposed.
[0007]
By the way, the rhodium compound is very expensive, and when it is industrially used as a hydroformylation catalyst, it is necessary to recover and recycle it. For this reason, as a method for recovering general hydroformylation catalysts including the catalysts for hydroformylation proposed in the prior arts (A) to (C) described above, a reaction mixture after completion of the hydroformylation reaction is conventionally used. The product was heated and the product and unreacted raw material were distilled and separated from the reaction mixture, and the hydroformylation catalyst was recovered as an evaporation residue.
[0008]
However, when the hydroformylation catalyst is recovered in this way, there is a problem that the catalyst deteriorates and its life is shortened due to heating when the product is distilled from the reaction mixture. In particular, when the boiling point of the product is high, the shortening of the catalyst life becomes remarkable. In addition, due to the heating, the product decomposes or condenses, generating a catalyst poison as a by-product or accumulating high-boiling compounds, which makes it impossible to recycle the catalyst.
[0009]
In order to solve such a problem, a rhodium catalyst having a sulfonated or carboxylated water-soluble triarylphosphine as a ligand when hydroformylating an aliphatic olefin having 2 to 12 carbon atoms is used. It has been proposed to use a hydroformylation reaction in an aqueous phase and separate the product from the catalyst by decantation (Japanese Patent Laid-Open No. 60-228439). In addition, it has been proposed to use a water-soluble dinuclear complex as a hydroformylation catalyst (Japanese Patent Laid-Open No. 61-97295).
[0010]
In addition, the hydroformylation reaction is performed using an ionic metal complex catalyst having a water-soluble organophosphorus compound having a trisulfonated salt residue as a ligand in the presence of a non-aqueous polar solvent, and the reaction is performed in a hydrocarbon solvent. It has been proposed to recover the catalyst as a solution of a non-aqueous polar solvent by extracting the product from the mixture (JP-A-62-145038).
[0011]
In addition, hydroformylation reaction is performed using an ionic metal complex catalyst having a water-soluble organic phosphorus compound having a monosulfonated salt residue as a ligand in the presence of a non-aqueous polar solvent, and water is used as an extractant. It has been proposed to recover the catalyst as an aqueous solution by extracting the catalyst from the reaction mixture (EP 0350922).
[0012]
[Problems to be solved by the invention]
However, in the methods described in JP-A-60-228439 and JP-A-61-97295, hydroformyl is produced at a reaction rate which is industrially satisfactory due to the low solubility of the raw material olefin in the aqueous phase. There was a problem that it was not possible.
[0013]
In the method described in JP-A-62-145038, a phosphorus compound as a ligand having a trisulfonated salt residue is very difficult to dissolve in ordinary hydrocarbon olefins. There was a problem that it was necessary to use a non-aqueous polar solvent. Further, even if a large amount of non-aqueous solvent is used, the solubility of the organophosphorus compound in such a solvent is not sufficient, so that the molar ratio of phosphorus / rhodium cannot be increased,ConditionThere is a problem that it is difficult to selectively produce the aldehyde.
[0014]
In the method described in EP 0350922, a non-aqueous polar solvent must be used because an organic phosphorus compound as a ligand having a monosulfonated salt residue is difficult to dissolve in ordinary olefins. There was a problem. In addition, since the solubility of the organophosphorus compound in such a non-aqueous polar solvent is not sufficient, in order to increase the molar ratio of phosphorus / rhodium, a large amount of the non-aqueous polar solvent is used so that the productivity is clearly reduced. There was a problem that had to be used.
[0015]
As described above, the prior art method barely dissolves a polar phosphorus ligand that is inherently difficult to dissolve in a nonpolar raw material and a nonpolar product using a polar solvent. There was a limit to the amount of ingredients used.
[0016]
Furthermore, the hydroformylation reaction in the prior art described above is industrially limited to the case where the raw material and the product are organic compounds not containing an inorganic salt residue, and ethylenically unsaturated having an inorganic salt residue. When the corresponding aldehyde is produced from the compound, there is a problem that it cannot be applied because it is extremely difficult to recycle the catalyst. This is because the ethylenically unsaturated compounds having most inorganic salt residues and their hydroformylation products (aldehydes) are solid, so it is virtually impossible to separate them from the catalyst by distillation. It is. Also, separation by extraction is substantially impossible as will be described below.
[0017]
That is, since an ethylenically unsaturated compound having an inorganic salt residue is soluble only in a polar solvent such as water or methanol, a hydroformylation catalyst used for hydroformylating such an ethylenically unsaturated compound is not suitable. As the ligand, only a phosphorus ligand substituted with a polar group such as a sulfonate residue can be used. Here, when a polar solution mainly composed of water or methanol is used to extract and recover the hydroformylation catalyst coordinated with such a phosphorus ligand from the reaction mixture, the hydroformylation product is also water-soluble. For this reason, both the catalyst and the product cannot be extracted and separated.
[0018]
On the other hand, it is conceivable to use a non-polar phosphorus ligand so that the catalyst can be extracted from the reaction mixture containing the water-soluble hydroformylation product. However, such a non-polar phosphorus ligand does not dissolve to a sufficient extent to industrially carry out the hydroformylation reaction in a solution containing water or methanol as a main component in this case. was there.
[0019]
The present invention solves the above-mentioned problems of the prior art, and the ethylenically unsaturated compound has an industrially sufficient reaction rate without using a large amount of non-aqueous solvent regardless of the polarity of the ethylenically unsaturated compound. It is an object of the present invention to produce aldehydes by hydroformylating and to easily recover the catalyst in a high yield and to recycle the recovered catalyst.
[0020]
[Means for Solving the Problems]
In order to achieve the above-mentioned object, the present inventors dissolved a hydroformylation catalyst in a reaction solution when reacting an ethylenically unsaturated compound, carbon monoxide, and hydrogen, and only the catalyst after completion of the reaction. It is only necessary to be able to extract, and to that end, it is only necessary to make the polarity of the catalyst different between the reaction and the extraction, so that the polarity of the catalyst can be reversibly changed. In order to change the polarity, it is sufficient that the ligand of the rhodium compound has such a function. Further, in order to realize such a function in the ligand, at least one first ligand is included in the ligand. It has been found that an organic phosphorus compound having a tertiary amine residue is used, and the tertiary amine residue can be nonionized by ammonium ionization with carbon dioxide gas and water, or by liberation of carbon dioxide gas. This has led to the completion of the present invention.
[0021]
That is, the present invention is used for hydroformylation comprising the following components (a) and (b) used in a hydroformylation reaction in which an ethylenically unsaturated compound is reacted with carbon monoxide and hydrogen to convert it to the corresponding aldehyde. catalyst:
(A) a rhodium compound; and
(B) An organophosphorus compound having at least one tertiary amine residue and tertiary phosphorus residue each having coordination ability to the rhodium compound
Wherein the catalyst is ionized by bringing the catalyst into contact with water and carbon dioxide gas and reacting it, and the tertiary amine residue of the organophosphorus compound is converted to ammonium carbonate. A reversible ionization method for a hydroformylation catalyst is provided.
[0022]
The present invention also relates to a method for reversibly deionizing a hydroformylation catalyst reversibly ionized by the above method, wherein the ionized catalyst is released by releasing carbon dioxide from the ionized catalyst. A method for reversible deionization of a catalyst for hydroformylation, characterized by deionizing the catalyst.
[0023]
The present invention also relates to a hydroformylation method in which a water-insoluble ethylenically unsaturated compound is reacted with carbon monoxide and hydrogen in the presence of a hydroformylation catalyst to produce an aldehyde. In order to separate the catalyst from the product, the catalyst in the reaction mixture is ionized by the reversible ionization method described above, and then extracted into the aqueous layer, and the catalyst contained in the aqueous layer is further decontaminated by the reversible deionization method described above. Provided is a hydroformylation process characterized by extracting an ionized, non-ionized catalyst into a water-insoluble organic medium.
[0024]
The present invention also provides a hydroformylation method in which a water-soluble ethylenically unsaturated compound is reacted with carbon monoxide and hydrogen in the presence of a hydroformylation catalyst ionized by the above-described reversible ionization method. In order to separate the catalyst from the water-soluble hydroformylation product after the reaction, the ionized catalyst in the obtained reaction mixture is deionized by the above-mentioned reversible deionization method, and the nonionized catalyst is removed. Provided is a hydroformylation process for the production of aldehydes characterized by extraction into a water-insoluble organic medium.
[0025]
Hereinafter, the reversible ionization method and the reversible nonionization method of the hydroformylation catalyst of the present invention will be described in detail.
[0026]
The rhodium compound used in the reversible ionization method and the reversible nonionization method of the hydroformylation catalyst of the present invention has a catalytic ability to promote the hydroformylation reaction of the ethylenically unsaturated compound from the beginning, or the hydroformylation reaction conditions The rhodium compound which is a compound which acquires such catalytic ability below and is conventionally used in the catalyst for hydroformylation can be used. Such rhodium compounds include RhO, Rh₂O, Rh₂O₃, RhO₂Rhodium oxides such as rhodium oxide, rhodium nitrate, rhodium sulfate, rhodium chloride, rhodium iodide, rhodium acetate, etc., Rh₄(CO)₁₂, Rh₆(CO)₁₆, Rh (acac) (CO)₂And rhodium complex compounds such as rhodium acetylacetonate.
[0027]
In the present invention, an organophosphorus compound having at least one tertiary amine residue and tertiary phosphorous residue each having a coordination ability to the rhodium compound is used as a ligand of the rhodium compound.
[0028]
This organophosphorus compound becomes ammonium carbonate and ionizes when its tertiary amine residue reacts with water and carbon dioxide. Therefore, the catalyst itself coordinated with the organophosphorus compound is also ionized and becomes water-soluble. For this reason, it becomes possible to extract a catalyst with water or to perform a hydroformylation reaction in an aqueous phase.
[0029]
On the other hand, the ammonium carbonate residue in the ionized catalyst releases carbon dioxide by heating or the like to be nonionized and returns to the original tertiary amine residue. Therefore, the catalyst itself is also deionized and becomes water-insoluble. For this reason, it becomes possible to extract a catalyst to a non-aqueous organic medium or to perform a hydroformylation reaction in a non-aqueous organic phase.
[0030]
Thus, by using an organic phosphorus compound having at least one tertiary amine residue and tertiary phosphorus residue as a ligand for the rhodium compound, the catalyst is reversibly ionized or non-ionized. can do. Thus, the catalyst can be present in the same phase as the raw material and the product during the hydroformylation reaction, and can be separated into a different phase from the raw material and the product after completion of the reaction.
[0031]
The organophosphorus compound having at least one tertiary amine residue and at least one tertiary phosphorus residue is not particularly limited as long as it has the above-described action. Examples of the group include those in which three alkyl groups or aryl groups are bonded to the N atom, and the tertiary phosphorus residue can have a structure such as phosphine or phosphite. As such an organic phosphorus compound, a compound represented by any of the following formulas (1) to (4) can be preferably used:
[0032]
[Chemical 6]

{In Formula (1), R¹Is a linear, branched or cyclic alkyl group or a phenyl group or naphthyl group (these are optionally substituted with other substituents such as hydroxyl group, halogen, etc.)BaseAnd may be substituted with a hydrocarbon group having 1 to 10 carbon atoms, such as R²Is a hydrogen atom, an alkyl group having 1 to 5 carbon atoms such as methyl, ethyl, isopropyl or cyclopentyl, a nitro group or a halogen atom such as chloro or bromo, m is 1, 2 or 3, and n is 0 or 1 And x is 0, 1 or 2, y and z are independently 0, 1, 2 or 3, provided that the sum of x, y and z is 3 and X¹And X²Is independently a hydrogen atom or —NR³R⁴(Where R³And R⁴Is independently an alkyl group having 1 to 4 carbon atoms such as methyl, ethyl, propyl, isopropyl and butyl, provided that X and y are not 0.¹And X²Are not hydrogen atoms at the same time, and if y is 0, X²Is -NR³R⁴And if z is 0, X¹Is -NR³R⁴Is};
[0033]
[Chemical 7]

{In Formula (2), R⁵And R⁶Is independently a hydrogen atom, an alkyl group having 1 to 5 carbon atoms such as methyl, ethyl, isopropyl or cyclopentyl, a nitro group or a halogen atom such as chloro or bromo, and m and n are as defined in formula (1) And p is 1, 2 or 3, q is 0 or 1, and a, b, c and d are independently 0, 1 or 2, provided thatThe sum of a and b is 2, and the sum of c and d is 2.Z is a cyclic or non-cyclic divalent hydrocarbon group having 1 to 10 carbon atoms such as methylene, ethylene or cyclohexylene, and X³, X⁴, X⁵And X⁶Is independently a hydrogen atom or —NR³R⁴(Where R³And R⁴Is as defined in formula (1)), provided that a, b, c and d are all 1³, X⁴, X⁵And X⁶Are not hydrogen atoms at the same time and X is 0⁴, X⁵And X⁶At least one of -NR³R⁴And when b is 0, X³, X⁵And X⁶At least one of -NR³R⁴And when c is 0, X³, X⁴And X⁶At least one of -NR³R⁴And when d is 0, X³, X⁴And X⁵At least one of -NR³R⁴Is};
[0034]
[Chemical 8]

{In Formula (3), R⁷And R⁹Is independently a hydrogen atom, an alkyl group having 1 to 6 carbon atoms such as methyl, ethyl, isopropyl, or a phenyl group, and R⁸And R¹⁰Is independently a hydrogen atom, an alkyl group having 1 to 6 carbon atoms such as methyl, ethyl or isopropyl, a nitro group or a halogen atom such as chloro or bromo, and r and s are independently 0, 1, 2 or 3 E is 1, 2 or 3, f is 0, 1 or 2, provided that the sum of e and f is 3, and X⁷Is -NR³R⁴(Where R³And R⁴Is as defined in formula (1)); and
[0035]
[Chemical 9]

{In Formula (4), R⁵, R⁶, M, n, p, q, a, b, c, d, X³, X⁴, X⁵, X⁶And Z are as defined in Formula (2)}.
[0036]
Among these formulas (1) to (4), more preferred specific organophosphorus compounds include those of the following formulas (5) to (22).
[0037]
[Chemical Formula 10]
P [CH₂N (C₂H₅)₂]₃                               (5)
(C₄H₉)₂PCH₂N (CH₃)₂                         (6)
(C₄H₉)₂PCH₂CH₂N (CH₃)₂                   (7)
P [CH₂CH₂CH₂N (CH₃)₂]₃                     (8)
P [CH₂CH₂CH₂N (C₂H₅)₂]₃                   (9)
P [CH₂CH₂N (t-C₄H₉)₂]₃                   (10)
(C₈H₁₇) P [CH₂N (CH₃)₂]₂                 (11)
(C₆H₁₃)₂PCH₂CH₂CH₂N (CH₃)₂         (12)
(C₆H₅)₂PCH₂N (CH₃)₂                       (13)
(C₆H₅)₂PCH₂CH₂N (CH₃)₂                 (14)
P [CH₂CH₂C₆H₄N (CH₃)₂]₃                 (15)
P [C₆H₄N (CH₃)₂]₃                             (16)
P [C₆H₄CH₂N (CH₃)₂]₃                       (17)
C₆H₅P [C₆H₄N (CH₃)₂]₂                     (18)
C₆H₅P [C₆H₄CH₂N (CH₃)₂]₂               (19)
C₆H₅P [CH₂CH₂CH₂N (CH₃)₂]₂           (20)
(C₆H₅)₂P [C₆H₄N (CH₃)₂] (21)
(C₆H₅)₂P [C₆H₄CH₂N (i-C₃H₇)₂] (22)
[0038]
In the hydroformylation catalyst used in the reversible ionization method and non-ionization method of the present invention, if the amount of the organophosphorus compound used is too small, the stability of the catalyst is impaired, and if it is too large, the reaction rate decreases. The organophosphorus compound of the component (b) is preferably used in an amount of 1 to 10000 gram atoms, more preferably 10 to 1000 gram atoms, with respect to 1 gram atom of the rhodium compound of the component (a) in terms of rhodium atoms. .
[0039]
In the present invention, when the organophosphorus compound of component (b) is used in excess relative to the rhodium compound of component (a), an organophosphorus compound that is not coordinated to the rhodium compound also exists. However, in order to keep the hydroformylation reaction conditions at the time of recycling the catalyst as constant as possible, it is preferable that an organophosphorus compound not coordinated with the rhodium compound is present in the same phase as the hydroformylation catalyst. For this purpose, it is preferable to reversibly ionize or non-ionize the organophosphorus compound that is not coordinated to the rhodium compound in the same manner as the organophosphorus compound coordinated to the rhodium compound.
[0040]
In the reversible ionization method of the present invention, the catalyst comprising such components is reacted with water and carbon dioxide to convert the tertiary amine residue of the organophosphorus compound ligand to ammonium carbonate. In this case, if the reaction temperature is too high, the liberation rate of carbon dioxide gas is faster than the ionization rate, and if the reaction temperature is too low, the ionization rate is too slow. It is preferable. Moreover, there is no restriction | limiting in particular in the pressure of a carbon dioxide gas, but it is preferable from the point of operativity to carry out in the range of 1-50 atmospheres.
[0041]
In the reversible deionization method of the present invention, the ionized catalyst thus releases carbon dioxide gas from the tertiary amine residue converted to ammonium carbonate of the organophosphorus compound ligand by a known method. Is reversibly deionized. For example, the ionized catalyst can be heated to 70 to 100 ° C. in an aqueous phase, or the catalyst can be placed under reduced pressure.
[0042]
Next, in the presence of a hydroformylation catalyst that can be reversibly ionized or non-ionized in this manner, an ethylenically unsaturated compound is reacted with carbon monoxide and hydrogen to produce the corresponding aldehyde. The hydroformylation process consists of 1) the case where the ethylenically unsaturated compound and the corresponding product are water-insoluble (nonpolar) and 2) the case where the ethylenically unsaturated compound and the corresponding product are water-soluble (polar) This will be described in detail separately for each case.
[0043]
1) When the ethylenically unsaturated compound and the corresponding product are water-insoluble (non-polar).
[0044]
1-a) First, in the presence of a hydroformylation catalyst comprising a non-ionized rhodium compound of component (a) and an organophosphorus compound of component (b) which are not ionized. Then, carbon monoxide and hydrogen are hydroformylated to convert to the corresponding aldehyde. Specifically, a water-insoluble ethylenically unsaturated compound and a hydroformylation catalyst are charged into a stirring reaction vessel or a bubble reaction vessel, and a mixed reaction gas of hydrogen and carbon monoxide is placed in this vessel. [H ₂ / CO(Preferably molar ratio = about 0.5 to 5)] is generally introduced at a pressure of 1 to 300 atmospheres, preferably 5 to 100 atmospheres, and generally heated to a temperature of 20 to 160 ° C., preferably 50 to 140 ° C. Stir. In this case, the hydroformylation catalyst is preferably prepared by separately introducing components (a) and (b) into the hydroformylation reaction system and reacting them in the system to form a complex. Moreover, such a reaction can be performed by a continuous system or a batch system.
[0045]
In addition, if the amount of the hydroformylation catalyst used in the hydroformylation reaction is too small, the reaction rate is too slow, and if it is too large, the reaction rate cannot be effectively increased, and the catalyst cost is excessively increased. Therefore, the concentration range is preferably 0.001 to 10 milligram atoms, more preferably 0.005 to 5 milligram atoms in terms of rhodium atoms per liter of the reaction solution.
[0046]
The concentration of the organophosphorus compound in the reaction solution depends on the type of rhodium compound, but in the case of monodentate, the concentration range is 0.1 to 500 milligram atoms in terms of phosphorus atoms per liter of reaction solution. Is preferable, and a concentration range of 0.5 to 200 milligram atoms is more preferable. Moreover, in the case of an organophosphorus compound having two or more dents, it is preferably used in a range of 0.1 to 5 moles relative to the rhodium atom.
[0047]
In this hydroformylation reaction, an inert water-insoluble organic solvent can be used. For example, aromatic compounds such as benzene, toluene and xylene, aliphatic hydrocarbons such as hexane, octane and cyclohexane, ethers such as diethyl ether and diphenyl ether, ketones such as cyclohexanone and methyl isobutyl ketone, dioctyl phthalate, ethyl acetate Esters such as, and ketones such as cyclohexanone can be appropriately selected and used.
[0048]
1-b) Next, the hydroformylation catalyst in the hydroformylation reaction mixture is ionized (polarized) by the action of carbon dioxide in the presence of water by the reversible ionization method of the present invention, and the ionized catalyst. Is extracted into an aqueous medium as an extractant. As a result, the water-insoluble product and the catalyst can be easily separated, and the product can be easily separated and the catalyst can be recovered. In addition, by collecting the catalyst by means of extraction, the catalyst is not heated in the presence of the product when the product is separated. Therefore, the catalyst is deteriorated by heating, or the product and its decomposition are decomposed by heating. It is possible to avoid poisoning of the catalyst with an object, and to extend the catalyst life.
[0049]
As such an aqueous medium, water is preferably used, and the amount used is 1/10 to 10/1 volume times, preferably 1/5 to 5/1 volume times that of the reaction mixture.
[0050]
Furthermore, aromatic hydrocarbons such as benzene and toluene, and aliphatic hydrocarbons such as hexane and cyclohexane can be added to promote layer separation.
[0051]
In order to prevent the catalyst from being deteriorated, it is preferable to perform the extraction operation with an aqueous medium at a temperature of 10 to 50 ° C. under a carbon dioxide pressure (preferably 1 to 50 atm).
[0052]
1-c) Next, by the reversible deionization method of the present invention described above, carbon dioxide gas is liberated from the catalyst contained in the aqueous layer to be deionized (depolarized), and the catalyst is converted into a water-insoluble organic medium. To extract. At this time, by using the raw material water-insoluble ethylenically unsaturated compound as the water-insoluble organic medium, the hydroformylation reaction can be easily performed again, and the catalyst can be easily recycled.
[0053]
The amount of the water-insoluble organic medium used is generally 1/10 to 10/1 volume times, preferably 1/5 to 5/1 volume times that of the reaction mixture. Moreover, in order to promote carbon dioxide release, it is preferable to perform non-ionization of the catalyst and extraction with a water-insoluble organic medium at a temperature of 70 to 110 ° C. Alternatively, it can be performed under reduced pressure.
[0054]
The separated hydroformylation product (aldehyde) can be isolated by ordinary means such as crystallization and distillation.
[0055]
2) When the ethylenically unsaturated compound and the corresponding product are water-soluble (nonpolar).
[0056]
2-a) First, hydroformyl comprising a rhodium compound of component (a) and an organophosphorus compound of component (b) obtained by ionizing a water-soluble ethylenically unsaturated compound by the above-described reversible ionization method of the present invention. In the presence of a catalyst for conversion, carbon monoxide and hydrogen are subjected to a hydroformylation reaction to convert to the corresponding aldehyde. Specifically, a water-soluble ethylenically unsaturated compound, a non-ionized hydroformylation catalyst and water are charged into a stirred reaction vessel or a bubble reaction vessel, and carbon dioxide gas is introduced into the vessel. This can be done by ionizing the catalyst and then introducing a mixed reaction gas of hydrogen and carbon monoxide. In this case, the conditions for the hydroformylation reaction are as described in the hydroformylation reaction of the water-insoluble ethylenically unsaturated compound. However, the solvent to be used is not a water-insoluble solvent, and a water-soluble organic solvent such as dimethyl sulfoxide, sulfolane, lower alcohol, and acetone can be used.
[0057]
Further, it is desirable to keep the partial pressure of carbon dioxide in the gas phase at 0.1 to 100 atm in order to prevent the catalyst from being deionized during the hydroformylation reaction.
[0058]
2-b) Next, by the reversible deionization method of the present invention described above, carbon dioxide is liberated from the catalyst in the hydroformylation reaction mixture to be nonionized, and the catalyst is extracted into a water-insoluble organic medium. The catalyst deionization operation and the extraction operation can be performed in parallel at the same time.
[0059]
By such extraction, the water-soluble hydroformylation product and the catalyst can be easily separated, and the product can be easily separated and the catalyst can be recovered. In addition, by collecting the catalyst by means of extraction, the catalyst is not heated in the presence of the product when the product is separated. Therefore, the catalyst is deteriorated by heating, or the product and its decomposition are decomposed by heating. It is possible to avoid poisoning of the catalyst with an object, and to extend the catalyst life.
[0060]
Examples of such a water-insoluble organic medium include aromatic hydrocarbons such as benzene, toluene, xylene and cumene, and aliphatic hydrocarbons such as hexane, octane, cyclohexane and methylcyclohexane. The amount is 1/10 to 10/1 volume times of the reaction mixture, preferably 1/5 to 5/1 volume times.
[0061]
In addition, water can be added to promote layer separation.
[0062]
In order to promote the liberation of carbon dioxide gas, it is preferable to perform non-ionization of the catalyst and extraction with a water-insoluble organic medium at a temperature of 70 to 110 ° C. Alternatively, it can be performed under reduced pressure.
[0063]
2-c) Next, the catalyst extracted into the water-insoluble organic medium is ionized by the above-described reversible ionization method of the present invention, and the ionized catalyst is extracted into the aqueous medium. At this time, by dissolving the water-soluble ethylenically unsaturated compound in the aqueous medium, the hydroformylation reaction can be easily performed again, and the catalyst can be easily recycled.
[0064]
The amount of the aqueous medium used is generally 1/10 to 10/1 volume times of the reaction mixture, preferably 1/5 to 5/1 volume times.
[0065]
The hydroformylation product (aldehyde) separated by extraction can be further purified by ordinary means such as crystallization and distillation.
[0066]
In the present invention, the ethylenically unsaturated compound to be subjected to the hydroformylation reaction may be a linear, branched or cyclic terminal or internal olefin having 2 or more carbon atoms such as ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 2-butene, isobutene, 2-octene, 1,7-octadiene, vinylcyclohexene, dicyclopentadiene, cyclooctadiene, butadiene polymer, isoprene polymer Unsaturated aliphatic hydrocarbons such as styrene, α-methylstyrene, β-methylstyrene, alkyl group nucleus-substituted styrene, styrenes such as divinylbenzene, allyl alcohol, methallyl alcohol, crotyl alcohol, 2-butene- 1,4-diol, 3-methyl-3-butene-1-o Contains functional groups such as vinyl alcohol, allyl acetate, methyl acrylate, methyl methacrylate, 7-octen-1-al, unsaturated alcohols such as alcohol, 7-octen-1-ol, 2,7-octadienol And a wide range of ethylenically unsaturated compounds such as olefins having inorganic salt residues such as sodium allyl sulfonate and sodium styrene sulfonate.
[0067]
In the hydroformylation reaction of the two embodiments of the present invention, the catalyst can be selectively extracted by ionizing or deionizing the catalyst, and the hydroformylation reaction mixture is divided into a product-containing layer and a catalyst component-containing layer. Although it isolate | separates, it can also carry out in presence of inert gas, such as nitrogen gas, and carbon monoxide / hydrogen mixed gas at the time of this isolation | separation. Further, when the catalyst is extracted, if the layers are not sufficiently separated, it is preferable to use a centrifugal separation operation together in order to promote the layer separation.
[0068]
While the hydroformylation reaction and the catalyst recovery are repeated, the amount of catalyst loss may reach a level that cannot be ignored, but the reaction rate can be easily maintained by adding a catalyst component.
[0069]
[Action]
In the hydroformylation method of the present invention, an organophosphorus compound having at least one tertiary amine residue and at least one tertiary phosphorus residue is coordinated to a rhodium compound having catalytic ability to promote the hydroformylation reaction. Is used as a catalyst for hydroformylation.
[0070]
On the other hand, by the reversible ionization method of the present invention, the tertiary amine residue of this organophosphorus compound is ionized by reacting it with water and carbon dioxide to convert it to ammonium carbonate. Further, by the reversible deionization method of the present invention, carbon dioxide gas is liberated from the ammonium carbonate residue of the ionized catalyst, thereby converting to a tertiary amine and deionization. Thus, the hydroformylation catalyst can be reversibly ionized or non-ionized. Accordingly, the hydroformylation catalyst can be freely dissolved or extracted in a water-insoluble organic medium, or dissolved or extracted in an aqueous medium.
[0071]
Therefore, in the hydroformylation method of the present invention, the reversible ionization method or non-ionization method of the hydroformylation catalyst is used, regardless of whether the ethylenically unsaturated compound is water-soluble or water-insoluble. Depending on the nature of the ethylenically unsaturated compound, the catalyst can be ionized or non-ionized to allow the catalyst to contact the ethylenically unsaturated compound in a homogeneous solution.
[0072]
In addition, after completion of the reaction, the catalyst is brought into an ionic state opposite to that during the hydroformylation reaction, so that the catalyst can be selectively extracted, separated and recovered from the hydroformylation reaction mixture, and the product can be separated at the same time. Become.
[0073]
Furthermore, by reversing the ionic state of the catalyst in the extract, that is, by extracting the catalyst into a medium containing an ethylenically unsaturated compound in the same ionic state as in the hydroformylation reaction, the extract is kept as it is. It is possible to cause a hydroformylation reaction between carbon oxide and hydrogen. Thus, the catalyst can be easily recycled. Therefore, it is possible to industrially advantageously produce the corresponding aldehyde from the ethylenically unsaturated compound by a hydroformylation reaction at a low production cost.
[0074]
【Example】
The present invention will be described more specifically with reference to the following examples, but the present invention is not limited to these examples.
[0075]
Example 1
A 300 ml electromagnetic stirring autoclave equipped with a gas inlet and a sampling port was charged with 2.58 mg (0.01 mmol) of dicarbonylacetylacetonatodium, 433 mg (1 mmol) of tri (p-N, N-dimethylaminomethylphenyl) phosphine. ), 20 g (0.139 mol) of sodium allyl sulfonate and 90 g of water were charged so as not to touch the air, and carbon dioxide gas was introduced into the autoclave at 10 kg / cm.²The solution was supplied until the pressure reached G to obtain a uniform solution.
[0076]
Next, a mixed gas of hydrogen / carbon monoxide = 1/1 was continuously supplied into the autoclave, and the total pressure was 60 kg / cm.²G. While maintaining the pressure, the reaction mixture was stirred, and the internal temperature was raised to 80 ° C. over 20 minutes. In this state, hydroformylation reaction was performed for 5 hours. As a result, the yield of hydroformylation product (a mixture of 4-sulfobutanal sodium salt and 3-sulfo-2-methylpropanal sodium salt) was 38%.
[0077]
Next, the reaction mixture in the autoclave was pumped into a 1-liter three-necked flask equipped with a reflux apparatus so as not to touch air, and 100 g of toluene was added so as not to touch air. While maintaining the internal temperature at 90 ° C., nitrogen gas was flowed at 1 liter / hr, and stirring was performed for 2 hours while releasing carbon dioxide gas. Stirring was stopped, the reaction mixture was separated into two layers, and the lower aqueous layer was extracted.
[0078]
20 g (0.139 mol) of sodium allylsulfonate and 90 g of water were added to the remaining toluene layer containing the upper catalyst. The obtained mixed solution was charged into an autoclave without touching air, the inside of the autoclave was replaced with carbon dioxide, and further 10 kg / cm with carbon dioxide.²While maintaining the pressure of G, the mixture was stirred at 20 ° C. for 1 hour. Stop stirring, pump into a 1 liter separatory funnel previously replaced with a mixed gas of hydrogen / carbon monoxide = 1/1, leave it to separate into two layers, and touch the lower layer aqueous solution to the air Then, the mixture was transferred to an autoclave and a hydroformylation reaction was performed under the same reaction conditions as in the first round. As a result, the yield of hydroformylation product was 43%.
[0079]
Example 2
A 300 ml electromagnetically stirred autoclave equipped with a gas inlet and a sampling port was charged with 2.58 mg (0.01 mmol) of dicarbonylacetylacetonatodium and 1.08 g of tri (p-N, N-dimethylaminomethylphenyl) phosphine. (2.5 mmol) and 70 g of 1-octene were charged so as not to be exposed to air, and the pressure in the autoclave was 20 kg / cm with a mixed gas of hydrogen / carbon monoxide = 2/1.²G pressure was used. While maintaining the pressure, an off gas was flowed at 15 liter / hr, and the internal temperature was raised to 90 ° C. over 20 minutes with stirring. In this state, hydroformylation reaction was performed for 5 hours. The conversion rate of 1-octene as a raw material was 92%, and the hydroformylation selectivity was 95%. Moreover, the linear ratio of the produced aldehyde was 80%.
[0080]
Subsequently, the hydrogen / carbon monoxide mixed gas in the autoclave was released until the internal pressure became equal to the atmospheric pressure. Thereafter, 200 ml of water was charged into the autoclave so as not to touch the air, and the inside was replaced with carbon dioxide, and further 10 kg / cm with carbon dioxide.²While maintaining the pressure of G, the mixture was stirred at 25 ° C. for 3 hours. After the stirring was stopped, the mixed solution was transferred to the separation tank so as not to come into contact with air and separated into two layers.
[0081]
The lower layer aqueous solution was transferred to a 1-liter three-necked flask equipped with a reflux apparatus so as not to be exposed to air, and 70 g of 1-octene was further added. The internal temperature of this three-necked flask was kept at 80 ° C., nitrogen gas was allowed to flow at 2 liter / h, and the mixture was stirred for 2 hours while releasing carbon dioxide gas. Stirring was stopped and the reaction mixture was separated into two layers. And 1-octene containing the catalyst component of an upper layer was moved to the autoclave so that it might not touch air, and hydroformylation reaction was performed on the same reaction conditions as the 1st time. As a result, the conversion rate of 1-octene as a raw material was 86%, and the hydroformylation selectivity was 95%. Moreover, the linear ratio of the produced aldehyde was 80%.
[0082]
Example 3
A 300 ml electromagnetic stirring autoclave equipped with a gas inlet and a sampling port was charged with 1.935 mg (0.0075 mmol) of dicarbonylacetylacetonatodium and 162.4 mg of tri (p-N, N-dimethylaminomethylphenyl) phosphine. (0.375 mmol) and 64 g of 7-octen-1-al (containing 10 wt% of n-octanal) so as not to come into contact with air, and the pressure of the autoclave is a mixed gas of hydrogen / carbon monoxide = 1/1 90kg / cm²G pressure was used. While maintaining the pressure, the internal temperature was raised to 100 ° C. over 20 minutes. In this state, hydroformylation reaction was performed for 30 minutes. As a result, the conversion rate of the starting material 7-octen-1-al was 79%.
[0083]
Subsequently, the hydrogen / carbon monoxide mixed gas in the autoclave was released until the internal pressure became equal to the atmospheric pressure. Thereafter, 100 ml of water was charged into the autoclave so as not to come into contact with air, and the inside was replaced with carbon dioxide, and further 12 kg / cm 2 with carbon dioxide.²While maintaining the pressure of G, the mixture was stirred at 20 ° C. for 3 hours. After stopping the stirring, the mixed solution was transferred to a separation tank maintained in a hydrogen / carbon monoxide atmosphere so as not to be exposed to air, and subjected to a centrifugal separation process (10000 G, 10 minutes) to separate into two layers.
[0084]
The lower layer aqueous solution was transferred to a 1-liter three-necked flask equipped with a reflux apparatus so as not to come in contact with air, and further 7-octen-1-al (64 g, containing 10 wt% of n-octanal) was added. The internal temperature of this three-necked flask was kept at 90 ° C., nitrogen gas was flowed at 1 liter / hr, and the mixture was stirred for 2 hours while releasing carbon dioxide gas. Stirring was stopped and the reaction mixture was separated into two layers. And 7-octen-1-al containing the catalyst component of the upper layer was moved to the autoclave so that it might not touch air, and hydroformylation reaction was performed on the same reaction conditions as the 1st time. The conversion rate of 7-octen-1-al as a raw material was 66%.
[0085]
Example 4
To a 300 ml electromagnetic stirring autoclave having a gas inlet and a sampling port, 1.548 mg (0.006 mmol) of dicarbonylacetylacetonatodium, 260 mg of tri (p-N, N-dimethylaminomethylphenyl) phosphine (0 .6 mmol), 102 g of 7-octen-1-al (containing 10 wt% of n-octanal) so as not to come into contact with air, and the pressure in the autoclave is 30 kg with a mixed gas of hydrogen / carbon monoxide = 1/1 / Cm²G pressure was used. While maintaining the pressure, the internal temperature was raised to 90 ° C. over 30 minutes with stirring. In this state, hydroformylation reaction was performed for 6 hours. The conversion rate of the raw material 7-octen-1-al was 96%.
[0086]
Subsequently, the hydrogen / carbon monoxide mixed gas in the autoclave was released until the internal pressure became equal to the atmospheric pressure. Then, 120 ml of water was charged into an autoclave so as not to be exposed to air, and the inside thereof was replaced with carbon dioxide, and further 6 kg / cm with carbon dioxide.²While maintaining the pressure of G, the mixture was stirred at 30 ° C. for 2 hours. After the stirring was stopped, the mixed solution was transferred to a separation tank maintained in a hydrogen / carbon monoxide atmosphere so as not to be exposed to air, and subjected to centrifugal separation (10000 G, 10 minutes) to separate into two layers.
[0087]
The lower layer aqueous solution was transferred to a 1-liter three-necked flask equipped with a reflux apparatus so as not to be exposed to air, and 102 g of 7-octen-1-al (containing 10 wt% of n-octanal) was further added. The internal temperature of this three-necked flask was kept at 100 ° C., nitrogen gas was allowed to flow at 1 liter / hr, and stirring was performed for 1 hour while liberating carbon dioxide gas. Stirring was stopped and the reaction mixture was separated into two layers. The raw material 7-octen-1-al containing the catalyst component in the upper layer was transferred to an autoclave so as not to be exposed to air, and hydroformylation reaction was performed under the same reaction conditions as the first time. The conversion rate of the starting material 7-octen-1-al was 81%.
[0088]
Example 5
A 300 ml electromagnetic stirring autoclave equipped with a gas inlet and a sampling port was charged with 1.29 mg (0.005 mmol) of dicarbonylacetylacetonatodium and 43.3 mg of tri (p-N, N-dimethylaminomethylphenyl) phosphine. (0.1 mmol) and 85 g of 7-octen-1-al (containing 10 wt% of n-octanal) so as not to come into contact with air, and the pressure in the autoclave is a mixed gas of hydrogen / carbon monoxide = 1/1 30kg / cm²G pressure was used. The internal temperature was raised to 100 ° C. over 30 minutes with stirring. In this state, a hydroformylation reaction was performed for 3 hours. The conversion rate of 7-octen-1-al as a raw material was 89%.
[0089]
Subsequently, the hydrogen / carbon monoxide mixed gas in the autoclave was released until the internal pressure became equal to the atmospheric pressure. Thereafter, 50 ml of water is charged into an autoclave so as not to be exposed to air, and the inside thereof is replaced with carbon dioxide, and further with carbon dioxide, 10 kg / cm 2 is added.²While maintaining the pressure of G, the mixture was stirred at 40 ° C. for 5 hours. After the stirring was stopped, the mixed solution was transferred to a separation tank maintained in a hydrogen / carbon monoxide atmosphere so as not to be exposed to air, and subjected to centrifugal separation (10000 G, 10 minutes) to separate into two layers.
[0090]
The lower layer aqueous solution was transferred to a 1 liter three-necked flask equipped with a reflux apparatus so as not to be exposed to air, and 85 g of 7-octen-1-al (containing 10 wt% of n-octanal) was further added. The internal temperature of this three-necked flask was kept at 80 ° C., nitrogen gas was flowed at 1 liter / hr, and the mixture was stirred for 1 hour while releasing carbon dioxide gas. Stirring was stopped and the reaction mixture was separated into two layers. And the raw material (7-octen-1-al) containing the catalyst component of the upper layer was moved to the autoclave so that it might not touch air, and hydroformylation reaction was performed on the same reaction conditions as the 1st time. The conversion rate of 7-octen-1-al as a raw material was 61%.
[0091]
Example 6
A 300 ml electromagnetic stirring autoclave equipped with a gas inlet and a sampling port was charged with 1.29 mg (0.005 mmol) of dicarbonylacetylacetonatodium and 1.08 g of tri (p-N, N-dimethylaminomethylphenyl) phosphine. (2.5 mmol) and 85 g of 2,7-octadienol were charged so as not to come into contact with air, and the pressure in the autoclave was 15 kg / cm with a mixed gas of hydrogen / carbon monoxide = 3/1.²G pressure was used. While maintaining the pressure, an off gas was flowed at 15 liter / hr, and the internal temperature was raised to 85 ° C. over 20 minutes while stirring. In this state, a hydroformylation reaction was performed for 4.5 hours. The conversion rate of 2,7-octadienol as a raw material was 62%, and the yield of 9-hydroxy-7-nonen-1-al was 43%.
[0092]
Subsequently, the hydrogen / carbon monoxide mixed gas in the autoclave was released until the internal pressure became equal to the atmospheric pressure. Thereafter, 100 ml of water was charged into an autoclave so as not to be exposed to air, and the inside thereof was replaced with carbon dioxide, and further 15 kg / cm with carbon dioxide.²While maintaining the pressure of G, the mixture was stirred at 20 ° C. for 3 hours. After the stirring was stopped, the mixed solution was transferred to a separation tank maintained in a hydrogen / carbon monoxide atmosphere so as not to come in contact with air, and subjected to centrifugal separation (10000 G, 30 minutes) to separate into two layers.
[0093]
The lower layer aqueous solution was transferred to a 1-liter three-necked flask equipped with a reflux apparatus without touching the air, and 85 g of 2,7-octadienol was further added. The internal temperature of this three-necked flask was kept at 80 ° C., nitrogen gas was allowed to flow at 1 liter / hr, and the mixture was stirred for 2 hours while releasing carbon dioxide gas. Stirring was stopped and the reaction mixture was separated into two layers. Then, the raw material 2,7-octadienol containing the upper catalyst component was transferred to an autoclave so as not to be exposed to air, and a hydroformylation reaction was performed under the same reaction conditions as in the first time. The conversion rate of the raw material 2,7-octadienol was 58%, and the yield of 9-hydroxy-7-nonen-1-al was 40%.
[0094]
Example 7
To a 300 ml electromagnetic stirring autoclave having a gas inlet and a sampling port, 1.548 mg (0.006 mmol) of dicarbonylacetylacetonatodium, 260 mg of tri (p-N, N-dimethylaminomethylphenyl) phosphine (0 .6 mmol) and 2,7-octadienol 102 g so as not to come into contact with air, and the pressure in the autoclave is 30 kg / cm with a mixed gas of hydrogen / carbon monoxide = 3/1.²G pressure was used. While maintaining the pressure, an off-gas was flowed at 15 liter / hr, and the internal temperature was raised to 100 ° C. over 20 minutes with stirring. In this state, hydroformylation reaction was performed for 4 hours. The conversion rate of the raw material 2,7-octadienol was 70%, and the yield of 9-hydroxy-7-nonen-1-al was 44%.
[0095]
Subsequently, the hydrogen / carbon monoxide mixed gas in the autoclave was released until the internal pressure became equal to the atmospheric pressure. Then, 60 ml of water is charged into an autoclave so as not to be exposed to air, and the inside is replaced with carbon dioxide, and further 10 kg / cm with carbon dioxide.²While maintaining the pressure of G, the mixture was stirred for 1 hour while maintaining the internal temperature at 35 ° C. After the stirring was stopped, the mixed solution was transferred to a separation tank kept in a hydrogen / carbon monoxide atmosphere so as not to be exposed to air, and subjected to a centrifugal separation process (10000 G, 30 minutes) to separate into two layers.
[0096]
The lower layer aqueous solution was transferred to a 1-liter three-necked flask equipped with a reflux apparatus so as not to be exposed to air, and 102 g of 2,7-octadienol was further added. The internal temperature of this three-necked flask was kept at 90 ° C., helium gas was flowed at 1 liter / hr, and the mixture was stirred for 1 hour while releasing carbon dioxide gas. Stirring was stopped and the reaction mixture was separated into two layers. Then, the raw material 2,7-octadienol containing the upper catalyst component was transferred to an autoclave so as not to be exposed to air, and a hydroformylation reaction was performed under the same reaction conditions as in the first time. The conversion rate of the raw material 2,7-octadienol was 65%. The yield of 9-hydroxy-7-nonen-1-al was 41%.
[0097]
Example 8
A 300 ml electromagnetic stirring autoclave equipped with a gas inlet and a sampling port was charged with 1.29 mg (0.005 mmol) of dicarbonylacetylacetonatodium and 43.3 mg of tri (p-N, N-dimethylaminomethylphenyl) phosphine. (0.1 mmol) and 91 g of styrene were charged so as not to touch the air, and the pressure in the autoclave was 90 kg / cm with a mixed gas of hydrogen / carbon monoxide = 1/1.²G pressure was used. While maintaining the pressure, the internal temperature was raised to 110 ° C. over 20 minutes with stirring. In this state, hydroformylation reaction was performed for 6 hours. The conversion rate of the raw material styrene was 72%, and the hydroformylation selectivity was 98%. Moreover, the linear ratio of the produced aldehyde was 20%.
[0098]
Subsequently, the hydrogen / carbon monoxide mixed gas in the autoclave was released until the internal pressure became equal to the atmospheric pressure. Then, 25 ml of water and 50 ml of n-hexane were charged into an autoclave so as not to be exposed to air, and the inside thereof was replaced with carbon dioxide, and further, 6 kg / cm 3 with carbon dioxide.²The pressure was maintained at G and the mixture was stirred at 25 ° C. for 1 hour. After stopping the stirring, the mixed solution was transferred to a separation tank maintained in a carbon dioxide gas atmosphere so as not to be exposed to air, and separated into two layers.
[0099]
The lower layer aqueous solution was transferred to a 1-liter three-necked flask equipped with a reflux apparatus so as not to come in contact with air, and 91 g of styrene was further added. The internal temperature of this three-necked flask was kept at 90 ° C., nitrogen gas was allowed to flow at 1 liter / hr, and stirring was performed for 1 hour while releasing carbon dioxide gas. Stirring was stopped and the reaction mixture was separated into two layers. The raw material styrene containing the catalyst component in the upper layer was transferred to an autoclave so as not to be exposed to air, and a hydroformylation reaction was performed under the same reaction conditions as in the first time. The conversion rate of the raw material styrene was 55%, and the hydroformylation selectivity was 98%. Moreover, the linear ratio of the produced aldehyde was 20%.
[0100]
Example 9
A 300 ml electromagnetic stirring autoclave equipped with a gas inlet and a sampling port was charged with 2.58 mg (0.01 mmol) of dicarbonylacetylacetonatodium and 217 mg of tri (pN, N-dimethylaminomethylphenyl) phosphine (0. 5 mmol), 2-butene-1,4-diol 44 g (0.5 mol) and water 59 g were charged so as not to come in contact with air, and carbon dioxide gas was introduced into the autoclave at 10 kg / cm.²The solution was supplied until the pressure reached G to obtain a uniform solution.
[0101]
Subsequently, a mixed gas of hydrogen / carbon monoxide = 1/1 is continuously supplied into the autoclave, and the total pressure is 80 kg / cm.²G pressure was used. While maintaining the pressure, the internal temperature was raised to 60 ° C. over 30 minutes. In this state, hydroformylation reaction was performed for 10 hours. As a result, 2-formyl-1,4-butanediol was obtained as a hydroformylation product in a yield of 30%.
[0102]
Next, the reaction solution in the autoclave is immediately cooled and pumped into a 1-liter three-necked flask equipped with a reflux device so as not to come in contact with air, and 200 ml of toluene and 100 ml of water are kept out of contact with air. The temperature of the three-necked flask was raised at a rate of 30 ° C./hour from the room temperature to 90 ° C. while flowing nitrogen gas at a rate of 1 liter / hr, and carbon dioxide gas was supplied for another hour after reaching 90 ° C. Stir while liberating. Stirring was stopped, the reaction mixture was separated into two layers, and the lower aqueous solution was extracted.
[0103]
To the toluene layer containing the remaining upper catalyst, 44 g (0.5 mol) of 2-butene-1,4-diol and 59 g of water were added. The obtained mixed solution was charged into an autoclave so as not to come into contact with air, the inside of the autoclave was replaced with carbon dioxide, and further, 12 kg / cm 2 with carbon dioxide.²While maintaining the pressure of G, the mixture was stirred at 25 ° C. for 2 hours. Stirring was stopped, and the mixture was pumped to a 1-liter separatory funnel previously substituted with a mixed gas of hydrogen / carbon monoxide = 1/1, and allowed to stand to separate into two layers. The lower layer aqueous solution was transferred to an autoclave so as not to be exposed to air, and a hydroformylation reaction was performed under the same reaction conditions as in the first time. As a result, 2-formyl-1,4-butanediol was obtained in a yield of 24%.
[0104]
Example 10
A 300 ml electromagnetic stirring autoclave equipped with a gas inlet and a sampling port was charged with 1.29 mg (0.005 mmol) of dicarbonylacetylacetonatodium and 217 mg of tri (pN, N-dimethylaminomethylphenyl) phosphine (0. 5 mmol), 2-butene-1,4-diol 44 g (0.5 mol) and water 59 g were charged so as not to come in contact with air, and carbon dioxide gas was introduced into the autoclave at 10 kg / cm.²The solution was supplied until the pressure reached G to obtain a uniform solution.
[0105]
Next, a mixed gas of hydrogen / carbon monoxide = 1/1 was continuously supplied into the autoclave, and the total pressure was 120 kg / cm.²G pressure was applied. While maintaining the pressure and stirring, the internal temperature was raised to 60 ° C. over 30 minutes. In this state, hydroformylation reaction was performed for 6 hours. As a result, 2-formyl-1,4-butanediol was obtained in a yield of 10% as a hydroformylation product.
[0106]
Next, the reaction solution in the autoclave is immediately cooled, and pumped into a 1-liter three-necked flask equipped with a reflux apparatus so as not to come in contact with air. While flowing nitrogen gas at a rate of 1 liter / hr, the temperature inside the three-necked flask was increased from room temperature to 90 ° C at a rate of 30 ° C per hour, and carbon dioxide was released for another hour after reaching 90 ° C. And stirred. Stirring was stopped, the reaction mixture was separated into two layers, and the lower aqueous solution was extracted.
[0107]
The remaining 1-octene containing the upper catalyst was charged into a 500 ml electromagnetic stirring autoclave equipped with a gas inlet and a sampling port so as not to be exposed to air, and the atmosphere was hydrogen / carbon monoxide = 1/1. With a mixed gas of 120 kg / cm²While maintaining the pressure of G, the internal temperature was raised to 110 ° C. over 20 minutes with stirring. In this state, hydroformylation reaction was performed for 4 hours. The raw material 1-octene conversion was 91%, and hydroformylation selectivity was 98%. Moreover, the linear ratio of the produced aldehyde was 60%.
[0108]
【The invention's effect】
According to the present invention, regardless of whether the ethylenically unsaturated compound is water-soluble or water-insoluble, the ethylenically unsaturated compound can be reacted at an industrially sufficient reaction rate without using a large amount of non-aqueous polar solvent. The compound can be hydroformylated to produce an aldehyde, and the catalyst can be easily recovered in high yield, and the recovered catalyst can be recycled.

Claims (9)

A hydroformylation catalyst comprising the following components (a) and (b) for use in a hydroformylation reaction in which an ethylenically unsaturated compound is reacted with carbon monoxide and hydrogen to convert it to the corresponding aldehyde:
(A) a rhodium compound; and (b) a method for reversibly ionizing an organophosphorus compound having at least one tertiary amine residue and tertiary phosphorus residue each having a coordination ability to the rhodium compound. Wherein the catalyst is ionized by bringing the catalyst into contact with water and carbon dioxide gas and reacting with the tertiary amine residue of the organophosphorus compound as ammonium carbonate. Catalyst reversible ionization method. The reversible ionization method for a hydroformylation catalyst according to claim 1, wherein the organophosphorus compound of component (b) is represented by any one of formulas (1) to (4):

{In Formula (1), R ¹ is a hydrocarbon group having 1 to 10 carbon atoms, R ² is a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, a nitro group, or a halogen atom; Or 3, n is 0 or 1, x is 0, 1 or 2, and y and z are independently 0, 1, 2 or 3, provided that the sum of x, y and z 3 and X ¹ and X ² are independently a hydrogen atom or —NR ³ R ⁴ (wherein R ³ and R ⁴ are independently an alkyl group having 1 to 4 carbon atoms), However, when both y and z are not 0, X ¹ and X ² are not simultaneously hydrogen atoms, when y is 0, X ² is —NR ³ R ⁴ , and when z is 0, X ¹ is —NR ³ R ⁴ };

{In Formula (2), R ⁵ and R ⁶ are independently a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, a nitro group, or a halogen atom, and m and n are as defined in Formula (1). , P is 1, 2 or 3, q is 0 or 1, a, b, c and d are independently 0, 1 or 2, provided that the sum of a and b is 2 and the sum of c and d is 2, Z is a divalent hydrocarbon group having 1 to 10 carbon atoms, and X ³ , X ⁴ , X ⁵ and X ⁶ are independently a hydrogen atom or —NR ³ R ⁴ (wherein R ³ and R ⁴ are as defined in Formula (1)), provided that a, b, c and d are all 1, X ³ , X ⁴ , X ⁵ and X ⁶ is not a hydrogen atom at the same time, and when a is 0, at least one of X ⁴ , X ⁵ and X ⁶ is —NR ³ R ⁴ , and when b is 0, X ³ , X ⁵ and X 6 ^At least one of ⁶ is —NR ³ R ⁴ , and when c is 0, at least one of X ³ , X ⁴ and X ⁶ is —NR ³ R ⁴ , and when d is 0, X ³ , X ⁴ And at least one of X ⁵ is —NR ³ R ⁴ };

{In Formula (3), R ⁷ and R ⁹ are independently a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or a phenyl group, and R ⁸ and R ¹⁰ are independently a hydrogen atom, having 1 to 6 carbon atoms. An alkyl group, a nitro group or a halogen atom, wherein r and s are independently 0, 1, 2 or 3, e is 1, 2 or 3, and f is 0, 1 or 2. , The sum of e and f is 3, and X ⁷ is —NR ³ R ^4, where R ³ and R ⁴ are as defined in formula (1)}; and

{In the formula ^{(4), R 5, R} 6, m, n, p, q, a, b, c, d, X 3, X 4, X 5, X 6 and Z are as defined in formula (2) It ’s the street}. The organophosphorus compound of component (b) is represented by formulas (5) to (22).

The reversible ionization method of the catalyst for hydroformylation of Claim 2 represented by either formula. The organic phosphorus compound of a component (b) is mix | blended by 1-10000 gram atom with respect to 1 gram atom of rhodium compounds of a component (a) in conversion of a rhodium atom in any one of Claims 1-3. Of reversible ionization of hydroformylation catalyst. A method for reversibly deionizing a hydroformylation catalyst reversibly ionized by the method according to any one of claims 1 to 4, wherein the ionization is performed by liberating carbon dioxide from the ionized catalyst. A method for reversibly deionizing a hydroformylation catalyst, comprising deionizing the formed catalyst. In a hydroformylation method for producing an aldehyde by reacting a water-insoluble ethylenically unsaturated compound with carbon monoxide and hydrogen in the presence of a hydroformylation catalyst, the water-insoluble ethylenically unsaturated compound, carbon monoxide, In order to separate the catalyst from the water-insoluble hydroformylation product after reacting with hydrogen, the catalyst in the reaction mixture is ionized by the process of any one of claims 1 to 4 and then extracted into an aqueous layer Further, the hydroformylation method is characterized in that the ionized catalyst contained in the aqueous layer is deionized by the method according to claim 5 and the non-ionized catalyst is extracted into a water-insoluble organic medium. The hydroformylation method according to claim 6, wherein the water-insoluble organic medium contains a water-insoluble ethylenically unsaturated compound, carbon monoxide and hydrogen are introduced into the medium, and the hydroformylation reaction is performed again. In the hydroformylation method which manufactures an aldehyde by reacting a water-soluble ethylenically unsaturated compound with carbon monoxide and hydrogen in the presence of an ionized hydroformylation catalyst, the hydroformylation catalyst according to any one of claims 1 to 4. The ionized catalyst in the resulting reaction mixture is deionized by the process of claim 5 using a catalyst ionized by the process and separating the catalyst from the water-soluble hydroformylation product after the reaction. A hydroformylation process, characterized in that the non-ionized catalyst is extracted into a water-insoluble organic medium. A water-insoluble organic medium containing a catalyst deionized by the method according to claim 5 is contacted with water containing a water-soluble ethylenically unsaturated compound and carbon dioxide to ionize the catalyst, thereby ionizing the catalyst. The hydroformylation method according to claim 8, wherein the catalyst is extracted into an aqueous layer, carbon monoxide and hydrogen are introduced into the extract, and the hydroformylation reaction is performed again.