JP4419440B2 - New proton type beta zeolite - Google Patents

Description

【００２１】
（式中のＡは、３３０℃を中心とする主ピーク、Ｂは、５００℃以上の脱離ピークを表す。図１参照。）
【００２２】
また、本発明のプロトン型βゼオライトは、そのＦＴ−ＩＲスペクトルを未処理のものと比較した場合、３７８２ｃｍ^−１の吸収が検出限界以下である特徴を有する。（図３参照）
【００２３】
本発明のプロトン型βゼオライトは、ケトンの存在下、一価フェノール類を過酸化物で酸化する二価フェノール類の製造において好適に使用される。
【００２４】
ここで使用される一価フェノールとしては、例えば、フェノール、一価モノアルキルフェノール、一価ハロゲン化フェノール、一価ポリアルキルフェノールが挙げられる。
【００２５】
一価モノアルキルフェノールが有するアルキル基としては、直鎖又は分岐状の炭素原子数１〜６個のアルキル基が挙げられる。アルキル基の位置は、反応に関与しなければ特に限定されない。これら化合物としては、例えば、ｏ−，ｍ−又はｐ−クレゾール、ｏ−，ｍ−又はｐ−エチルフェノール、ｏ−プロピルフェノール、ｐ−イソプロピルフェノール、ｍ−ブチルフェノール、ｐ−イソブチルフェノール、ｐ−ｔ−ブチルフェノール、ｍ−イソブチルフェノール、ｐ−ペンチルフェノール、ｐ−ヘキシルフェノールが挙げられる。
【００２６】
一価ハロゲン化フェノールが有するハロゲン原子としては、フッ素、塩素、臭素、ヨウ素が挙げられる。ハロゲン原子の数及び位置は、反応に関与しなければ特に限定されない。これら化合物としては、例えば、ｏ−，ｍ−又はｐ−フルオロフェノール、ｏ−，ｍ−又はｐ−クロロフェノール、ｏ−，ｍ−又はｐ−ブロモフェノール、ｏ−，ｍ−又はｐ−ヨウ化フェノール、２，３−、２，４−、２，５−、２，６−、３，４−又は３，５−ジクロロフェノール、２，３−、２，４−、２，５−、２，６−、３，４−又は３，５−ジブロモロフェノール、２，３，４−、２，３，５−、２，３，６−、２，４，５−、２，４，６−又は３，４，５−トリクロロフェノールが挙げられる。
【００２７】
一価ポリアルキルフェノールが有するアルキル基としては、直鎖又は分岐状の炭素原子数１〜６個のアルキル基が挙げられる。アルキル基の数及び位置は、反応に関与しなければ特に限定されない。これら化合物としては、例えば、２，３−、２，４−、２，５−、２，６−、３，５−又は３，４−ジメチルフェノール、２，３，４−、２，３，５−、２，３，６−又は３，４，５−トリメチルフェノール、２，４，５−トリメチルフェノール、２，３，４，５−又は２，３，５，６−テトラメチルフェノール、２−エチル−３−メチルフェノール、３−ｔ−ブチル−４−メチルフェノール、２−イソプロピル−５−メチルフェノール、２−ペンチル−６−メチルフェノール、３−ヘキシル−５−メチルフェノールが挙げられる。
【００２８】
本発明のプロトン型βゼオライトを用いた二価フェノールの製法において使用されるケトンとしては、例えば、モノケトン、ジケトンが挙げられる。モノケトンとしては、非環式又は環式モノケトンが挙げられる。非環式モノケトンとしては、例えば、炭素原子数３〜２０個、好ましくは３〜１０個の直鎖状又は分岐状脂肪族モノケトンや芳香族モノケトンを挙げることができる。これら化合物の水素原子はハロゲン原子（フッ素原子、塩素原子、臭素原子又はヨウ素原子）で置換されてもよい。ハロゲン原子の数及び位置は、反応に関与しなければ特に限定されない。
【００２９】
直鎖状脂肪族モノケトンとしては、例えば、アセトン、メチルエチルケトン、２−ペンタノン、３−ペンタノン、２−ヘキサノン、２−ヘプタノン、３−ヘプタノン、４−ヘプタノン、２−オクタノン、２−ノナノン、３−デカンノン、６−ウンデカノン、２−トリデカノン、７−トリデカノン、２−テトラデカノン、２−ペンタデカノン、２−ヘキサデカノン、２−ヘプタデカノン、３−オクタデカノン、４−ノナデカノン、１−クロロ−２−プロパノン、１−クロロ−３−ヘプタノン、１−ブロモ−３−ヘプタノンが挙げられる。
【００３０】
分岐状脂肪族モノケトンとしては、例えば、３−メチル−２−ブタノン、３−メチル−２−ペンタノン、４−メチル−２−ペンタノン、３，３−ジメチル−２−ブタノン、２，４−ジメチル−３−ペンタノン、６−メチル−２−ヘプタノン、２，６−ジメチル−４−ヘプタノン、２，２，４，４−テトラメチル−３−ヘプタノンが挙げられる。芳香族モノケトンとしては、例えば、アセトフェノン、ベンゾフェノン、１−フェニル−３−プロパノン、１−フェニル−１−ブタノン、１−フェニル−３−ブタノン、１−フェニル−３−ペンタノン、１，３−ジフェニル−２−プロパノンが挙げられる。
【００３１】
環式モノケトンとしては、例えば、炭素原子数５〜１２個のシクロアルキルモノケトンを挙げることができる。これら化合物の水素原子はハロゲン原子（フッ素原子、塩素原子、臭素原子又はヨウ素原子）、或いは炭素原子数１〜６個の直鎖状又は分岐状のアルキル基などの置換基で置換されてもよい。置換基の数及び位置は、反応に関与しなければ特に限定されない。これら化合物としては、例えば、シクロペンタノン、シクロヘキサノン、シクロドデカノン、２−クロロシクロヘキサノン、２−エチル−１−シクロペンタノン、２−メチル−１−シクロヘキサノンを挙げることができる。
【００３２】
ジケトンとしては、非環式又は環式ジケトンが挙げられる。非環式ジケトンとしては、例えば、炭素原子数５〜２１個、好ましくは５〜１２個の直鎖状又は分岐状脂肪族ジケトンや芳香族ジケトンを挙げることができる。これら化合物の水素原子はハロゲン原子（フッ素原子、塩素原子、臭素原子又はヨウ素原子）で置換されてもよい。ハロゲン原子の数及び位置は、反応に関与しなければ特に限定されない。直鎖状脂肪族ジケトンとしては、例えば、２，３−ブタンジオン、２，４−ペンタンジオン、２，５−ヘキサンジオンが挙げられる。分岐状脂肪族ジケトンとしては、例えば、２，５−ジメチル−３，４−ヘキサンジオンが挙げられる。芳香族ジケトンとしては、例えば、１，２−ジフェニルエタン−１，２−ジオンが挙げられる。
【００３３】
環式ジケトンとしては、例えば、炭素原子数５〜１２個の環式ジケトンを挙げることができる。これら化合物の水素原子はハロゲン原子（フッ素原子、塩素原子、臭素原子又はヨウ素原子）、又は炭素原子数１〜６個の直鎖状又は分岐状のアルキル基などの置換基で置換されてもよい。置換基の数及び位置は、反応に関与しなければ特に限定されない。環式ジケトンとしては、例えば、１，４−シクロヘキサンジオンが挙げられる。
【００３４】
本発明のプロトン型βゼオライトを用いた二価フェノールの製法において使用されるケトンとして好ましいものは、直鎖状又は分岐状脂肪族モノケトン、或いは環式モノケトンであり、更に好ましいものは、直鎖状又は分岐状脂肪族モノケトンであり、その中でも４−メチル−２−ペンタノン、３−ペンタノンが特に好ましい。
【００３５】
ケトンの使用量は、過酸化物に対するケトンのモル比（ケトン：過酸化物）が０．２：１〜５：１になるような割合であることが好ましい。
【００３６】
本発明のプロトン型βゼオライトを用いた二価フェノールの製法では、必ずしも必須ではないが、微量の鉄イオン等の溶存金属イオンが反応に及ぼす悪影響を避けるため、少量の燐酸を添加しても構わない。燐酸としては、オルト燐酸、ピロ燐酸、メタ燐酸、三燐酸、四燐酸、ポリ燐酸、無水燐酸、燐酸性水溶液が挙げられるが、燐酸性水溶液が好ましい。燐酸性水溶液の濃度としては、０．００１〜１００重量％が好ましい。
【００３７】
燐酸の使用量は、一価フェノールに対する燐酸の重量比（燐酸：一価フェノール）が０．０００１：１〜０．０５：１になるような割合であることが好ましい。
【００３８】
本発明のプロトン型βゼオライトを用いた二価フェノールの製法において使用される過酸化物は、過酸化水素などの無機過酸化物、又は、ケトンパーオキサイド、脂肪族過カルボン酸などの有機過酸化物が挙げられる。
【００３９】
ケトンパーオキサイドとしては、例えば、炭素原子数が３〜２０個、好ましくは３〜１０個であるジアルキルケトンパーオキサイドが挙げられる。これら化合物としては、例えば、ジメチルケトンパーオキサイド、ジエチルケトンパーオキサイド、メチルエチルケトンパーオキサイド、メチル−ｎ−プロピルケトンパーオキサイド、メチルイソプロピルケトンパーオキサイド、及びメチルイソブチルケトンパーオキサイドなどを挙げられる。
【００４０】
脂肪族過カルボン酸としては、過酢酸、過プロピオン酸などを挙げられる。
【００４１】
過酸化水素としては、０．１重量％以上、好ましくは０．１〜９０重量％の過酸化水素水を使用することができるが、３０〜８０重量％のものが更に好ましい。
【００４２】
本発明のプロトン型βゼオライトを用いた二価フェノールの製法において使用される過酸化物としては、過酸化水素またはケトンパーオキサイドか好ましい。このケトンパーオキサイドはケトンと過酸化水素の接触により合成可能であり、ここで使用されるケトンは前記と同様のものである。
【００４３】
過酸化物の使用量は、一価フェノールに対する過酸化物のモル比（過酸化物：一価フェノール）が１：１〜１：１００、更には１：５〜１：２０になるような範囲であることが好ましい。
【００４４】
過酸化物の反応系内への添加方法としては、一括して反応開始時に添加しても構わないが、副反応の併発を抑制して、高収率で反応を進行させるために、数回に分割して添加するか、または送液ポンプを用いて微量ずつ連続的に添加するのが好ましい。分割添加の場合は、一回あたりの過酸化物の一価フェノールに対する添加量は、モル比（過酸化物：一価フェノール）で０．０５：１００〜２：１００、更に好ましくは０．１：１００〜２：１００である。また、分割添加、連続添加いずれの場合においても、反応系内における過酸化物の一価フェノールに対する量はモル比で０．０５：１００〜２：１００の範囲が好ましく、更には０．１：１００〜１：１００の範囲が好ましい。
【００４５】
前記の二価フェノールの製造において使用される本発明のプロトン型βゼオライトの形状としては、粉体、粒体、ペレット、ハニカム状成形体などを挙げることができる。
【００４６】
前記の二価フェノールの製造に応じた形状としては、例えば、液相バッチ式反応器を用いて製造する時には、粉体、粒体などを使用するのが好ましく、液相流通式反応器を用いた時には、ペレット、ハニカム状成形体などが好ましい。
【００４７】
前記の二価フェノールの製造において、プロトン型βゼオライトの使用量は、一価フェノールに対するプロトン型βゼオライトの重量比（βゼオライト：一価フェノール）が１：１〜１：５００、更には１：５〜１：１００になるような範囲であることが好ましい。
【００４８】
前記の二価フェノールの製造における反応温度は、２０〜３００℃、更には４０〜２００℃であることが好ましい。反応時間は、例えば、プロトン型βゼオライトのＡｌ：Ｓｉ（原子比）の違いや反応温度によって異なるが、特に制限は無い。また、反応は大気圧で行えるが減圧又は加圧下で行ってもよい。反応は、液相で、バッチ式、流通式、トリクルベッド方式などで行うことができる。
【００４９】
前記の二価フェノールの製造の方法としては、例えば、一価フェノール、過酸化水素、ケトン及び燐酸を、βゼオライトをあらかじめ充填した反応器に供給して、一価フェノールを酸化してニ価フェノールを生成させ、反応器から反応混合物を排出させる反応などが挙げられる。
【００５０】
前記の二価フェノールの製造で得られる二価フェノールは、原料の一価フェノールの構造に対応して、１種類あるいは数種類のものの混合物として得られる。また、これらの二価フェノールは、常法にて分離、精製して得ることができる。
【００５１】
【実施例】
以下、本発明を実施例及び比較例によって具体的に説明する。なお、本発明はこれら実施例で制限されるものではない。
【００５２】
二価フェノールの収率は、次式に従って求めたものである。なお、分析はガスクロマトグラフィーにより行った。
【００５３】
【数２】

【００５４】
実施例１．（Ｈ／βＨＮＯ_３（３８）の調製）
Ａｌ：Ｓｉ＝１：３８であるゼオリスト製のプロトン型βゼオライト粉体（以下Ｈ／β（３８）と記載）５．０ｇを、硝酸性水溶液（ｐＨ＝１．３５）が４０ｍｌ入ったナスフラスコに入れ、これをオイルバスで８０℃に加熱して、攪拌を行った。２時間後、ゼオライトを濾過して、イオン交換水で洗浄した後、１１０℃で乾燥し、５５０℃で２．５時間空気焼成した。得られたプロトン型βゼオライト（以下Ｈ／βＨＮＯ_３（３８）と記載）のＩＣＰ発光分析を行ったところ、同βゼオライト中のＡｌ：Ｓｉ（原子比）は、Ａｌ：Ｓｉ＝１：７８であった。また、ＮＨ_３−ＴＰＤ測定（昇温速度２０℃／分、測定範囲１００℃〜７００℃）を行ったところ、未処理を行わなかったのものと比べ５００℃以上の強い酸点に帰属される脱離ピークが著しく減少していた(図２参照)。この図に示したＮＨ_３−ＴＰＤスペクトルから、５００℃以上の温度領域に存在する強い酸点の量を、前記式１から計算したところ、０．５５μｍｏｌ／ｇであったのに対し、硝酸未処理のもの（Ｈ／β（３８））では３．０μｍｏｌ／ｇと顕著な差が認められた。またＦＴ−ＩＲスペクトルを比較したところ、Ｈ／β（３８）で検出された３７８２cm^{- １}の吸収は検出されなかった（図３参照）。
【００５５】
実施例２．（Ｈ／βＨＮＯ_３（１３）の調製）
Ａｌ：Ｓｉ＝１：１３であるゼオリスト製のプロトン型βゼオライト粉体（以下Ｈ／β（１３）と記載）５．０ｇを、硝酸性水溶液（ｐＨ＝１．３０）が４０ｍｌ入ったナスフラスコに入れ、これをオイルバスで８０℃に加熱して、攪拌を行った。２時間後、ゼオライトを濾過して、イオン交換水で洗浄した後、１１０℃で乾燥し、５５０℃で２．５時間空気焼成した。得られたプロトン型βゼオライト（以下Ｈ／βＨＮＯ_３（１３）と記載）のＩＣＰ発光分析を行ったところ、βゼオライト中のＡｌ：Ｓｉ（原子比）は、Ａｌ：Ｓｉ＝１：６９であった。また、ＮＨ_３−ＴＰＤ測定（昇温速度２０℃／分、測定範囲１００℃〜７００℃）を行ったところ、未処理のもの（Ｈ／β（１３））と比べ５００℃以上の強い酸点に帰属される脱離ピークが著しく減少していた。実施例１と同様にして算出した強い酸点の量は、Ｈ／βＨＮＯ_３（１３）では１．８μｍｏｌ／ｇであったのに対し、Ｈ／β（１３）では４．２μｍｏｌ／ｇと顕著な差が認められた。
また、ＦＴ−ＩＲスペクトルを比較したところ、Ｈ／β（１３）で検出された３７８２cm^{- １}の吸収は検出されなかった。
【００５６】
実施例３．
実施例１で調製されたＨ／βＨＮＯ_３（３８）０．２０ｇ、フェノール１０．０ｇ、３−ペンタノン０．２７ｇ、８５重量％燐酸性水溶液０．０２ｇを３００ｍｌのフラスコに入れて、窒素雰囲気に置換した後、攪拌しながら６０℃まで昇温した。次いで、この温度において、６０％重量過酸化水素水を０．１０ｇ滴下し、１．５分後更に０．１０ｇ、３分後更に０．１０ｇ滴下して、最初の滴下から５分になるまで反応させた。
その結果、ニ価フェノールの収率は、カテコールが５２．８％、ハイドロキノンが４１．５％で、カテコールとハイドロキノンの合計収率は９４．３％であった。
【００５７】
実施例４．
反応温度を１００℃とした以外は実施例３と同様に反応させた。
その結果、ニ価フェノールの収率は、カテコールが５４．９％、ハイドロキノンが４１．１％で、カテコールとハイドロキノンの合計収率は９６．０％であった。
【００５８】
比較例１．
Ｈ／βＨＮＯ_３（３８）をＨ／β（３８）とした以外は実施例３と同様に反応させた。
その結果、ニ価フェノールの収率は、カテコールが５０．０％、ハイドロキノンが３４．７％で、カテコールとハイドロキノンの合計収率は８４．７％であった。
【００５９】
比較例２．
反応温度を１００℃とした以外は比較例４と同様に反応させた。
その結果、ニ価フェノールの収率は、カテコールが５１．４％、ハイドロキノンが３３．６％で、カテコールとハイドロキノンの合計収率は８５．０％であった。
【００６０】
実施例５
Ｈ／βＨＮＯ_３（３８）をＨ／βＨＮＯ_３（１３）とした以外は実施例４と同様に反応させた。
その結果、ニ価フェノールの収率は、カテコールが５２．６％、ハイドロキノンが３９．１％で、カテコールとハイドロキノンの合計収率は９１．７％であった。
【００６１】
比較例３
Ｈ／βＨＮＯ_３（３８）をＨ／β（１３）とした以外は実施例４と同様に反応させた。
その結果、ニ価フェノールの収率は、カテコールが４９．３％、ハイドロキノンが３３．８％で、カテコールとハイドロキノンの合計収率は８３．１％であった。
【００６２】
【表１】

【００６３】
実施例６．
実施例１で調製したＨ／βＨＮＯ_３（３８）０．２０ｇ、フェノール１０．０ｇ、３−ペンタノン０．２７ｇを３００ｍｌのフラスコに入れ、窒素雰囲気に置換した後、攪拌しながら１００℃まで昇温した。次いで、この温度において、６０％重量過酸化水素水を０．１０ｇ滴下し、１．５分後更に０．１０ｇ、３分後更に０．１０ｇ、４．５分後に０．１ｇ、６分後に０．１ｇ、７．５分後に０．１ｇ滴下して、最初の滴下から１０分になるまで反応させた。
その結果、ニ価フェノールの収率は、カテコールが４８．４％、ハイドロキノンが４３．７％で、カテコールとハイドロキノンの合計収率は９２．１％であった。
【００６４】
実施例７．
反応前原料に８５％燐酸性水溶液０．０２ｇを加えた以外は実施例６と同様に反応させた。
その結果、ニ価フェノールの収率は、カテコールが５０．４％、ハイドロキノンが４０．４％で、カテコールとハイドロキノンの合計収率は９０．８％であった。
【００６５】
比較例３．
Ｈ／βＨＮＯ_３（３８）をＨ／β（３８）とした以外は実施例６と同様に反応させた。
その結果、ニ価フェノールの収率は、カテコールが４５．１％、ハイドロキノンが３７．９％で、カテコールとハイドロキノンの合計収率は８３．１％であった。
【００６６】
比較例４．
Ｈ／βＨＮＯ_３（３８）をＨ／β（３８）とした以外は実施例７と同様に反応させた。
その結果、ニ価フェノールの収率は、カテコールが４７．７％、ハイドロキノンが３３．０％で、カテコールとハイドロキノンの合計収率は８０．７％であった。
【００６７】
【表２】

【００６８】
【発明の効果】
本発明のプロトン型βゼオライトは、βゼオライトを酸性水溶液に浸漬する簡便な調製方法で得られるものである。本プロトン型βゼオライトは、一価フェノール類を過酸化物で酸化する二価フェノール類の製造において、低温側でも高い反応性を示し、高収率で二価フェノール類を製造することができる。
【図面の簡単な説明】
【図１】プロトン型βゼオライトのアンモニア昇温脱離法（ＮＨ_３−ＴＰＤ）のスペクトル（模式図）
【図２】Ｈ／β（３８）及びＨ／βＨＮＯ_３（３８）のアンモニア昇温脱離法（ＮＨ_３−ＴＰＤ）のスペクトル
【図３】Ｈ／β（３８）及びＨ／βＨＮＯ_３（３８）のＦＴ−ＩＲスペクトル[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a novel proton type β zeolite and a method for preparing the same, and a method for producing a dihydric phenol by oxidizing a monohydric phenol with a peroxide in the presence of the zeolite and a ketone.
[0002]
[Prior art]
As a technique for producing dihydric phenols by oxidizing monohydric phenols using zeolite as a catalyst, for example, Patent Document 1 includes an example using faujasite or mordenite containing a rare earth metal. Examples using proton type ZSM-5 are respectively described. Patent Document 3 reports a natural zeolite such as shabazite or a synthetic zeolite such as US-Y and ZSM-5. However, the yield of the desired product is not sufficient in these techniques. Moreover, there is no mention of the correlation between the strength of acid sites present on these zeolites and the catalytic activity in the production of dihydric phenols.
[0003]
Non-Patent Document 1 describes an example using TS-1 (one containing titanium in a lattice of ZSM-5). However, as shown in Non-Patent Document 2, TS-1 has problems in that the reproducibility of its preparation is often a problem and the yield of the target product is not sufficient.
[0004]
Non-Patent Document 3 describes a comparison of β-zeolite containing TS-1 and titanium in the lattice. The TS-1 yield of hydrogen peroxide is 71.5% and β-containing titanium. The yield of zeolite is 62.8%, which is not sufficient.
[0005]
Patent Document 4 and Patent Document 5 describe examples using β zeolite, and further describe that the yield of dihydric phenols is improved by using β zeolite into which alkali metal ions are introduced. However, the β zeolite described in these documents has a high temperature dependency of the reaction yield, and the yield on the low temperature side of 90 ° C. or lower was not sufficient. Accordingly, since the temperature range is limited in carrying out the reaction, further improvements have been demanded.
[0006]
[Patent Document 1]
US Pat. No. 3,580,956
[Patent Document 2]
US Pat. No. 4,578,521
[Patent Document 3]
French Patent Application Publication No. 2693457
[Patent Document 4]
US Pat. No. 6,441,250
[Patent Document 5]
Japanese Patent Laid-Open No. 2003-26623
[Non-Patent Document 1]
Advances in Catalysis, 41 (1996),
p. 253-334
[Non-Patent Document 2]
Accounts of Chemical Research, 31 (8), (1998) p. 485-493
[Non-Patent Document 3]
Journal of Physical Chemistry, 203,
(2001) p. 201-212
[Non-Patent Document 4]
Journal of Physical Chemistry, 104
(2000), p. 2853-2859
[Non-Patent Document 5]
Catalyst Preparation Chemistry, Kodansha (1980) p. 61-73
[Non-Patent Document 6]
Microporous and Mesoporous Materials, 40 (2000) p. 271-281
[Non-Patent Document 7]
Keulemans, “Gas Chromatography”, Reinhold, New York, 1957, p. 39
[0007]
[Problems to be solved by the invention]
An object of the present invention is to produce a novel proton type β zeolite that is easy to prepare and exhibits high reactivity even at low temperatures, and monohydric phenols using the same, to produce dihydric phenols in high yield It is to provide an industrial manufacturing method.
[0008]
[Means for Solving the Problems]
As a result of investigations to solve the above-mentioned problems, the present inventors have found a novel proton-type β zeolite, and oxidized the monohydric phenols using the zeolite to produce the dihydric phenols in a high yield. The present invention was completed by finding an industrial process for producing dihydric phenols.
That is, the present invention is as follows.
[0009]
The first invention is an ammonia temperature programmed desorption method (NH₃-TPD) spectrum, there is an acid point showing a desorption peak in the range of plus or minus 100 ° C. around 330 ° C., and the amount of strong acid points showing a desorption peak of 500 ° C. or higher is 2.5 μmol / The present invention relates to a proton type β zeolite controlled to g or less.
[0010]
In the second invention, β zeolite having Al: Si (atomic ratio) of 1:25 to 1: 10000 is immersed in an acidic aqueous solution having a pH of 0 to 6, washed with water, dried, and further baked. The present invention relates to a method for preparing the proton type β zeolite of the first invention.
[0011]
The third invention relates to a process for producing dihydric phenols characterized in that monohydric phenols are oxidized with peroxides in the presence of proton type β zeolite and ketone of the first invention.
[0012]
DETAILED DESCRIPTION OF THE INVENTION
The present invention is described in detail below.
The proton type β zeolite of the present invention can be obtained by immersing β zeolite in an acidic aqueous solution, taking it out, washing it with water, drying it, and firing it.
Here, as β zeolite, β zeolite having Al: Si (atomic ratio) of 1:25 to 1: 10000 is preferably used. This ratio can be controlled by the composition of Si compound and Al compound, which are raw materials for β zeolite, such as sodium silicate and sodium aluminate.
[0013]
As this β zeolite, proton type β zeolite, ammonium ion exchange type β zeolite, alkali metal ion exchange type β zeolite, or the like that has not been treated with the acidic aqueous solution of the present invention can be used.
As the proton type β zeolite not treated with the acidic aqueous solution of the present invention, a commercially available product or a proton type β zeolite newly prepared by the method described in Non-Patent Document 4 can be used.
A commercially available thing can be used for an ammonium ion exchange type beta zeolite. The alkali metal ion exchange type β zeolite can be prepared by the method described in Non-Patent Document 5 in which proton type β zeolite is immersed in the metal ion-containing aqueous solution such as alkali metal nitrate, hydrochloride or sulfate. .
Among these β zeolites, proton type β zeolite that has not been treated with the acidic aqueous solution of the present invention is preferably used.
[0014]
The acid used in the acidic aqueous solution of the present invention is not particularly limited, but aliphatic carboxylic acids (formic acid, acetic acid, propionic acid, citric acid, etc.), aromatic carboxylic acids (benzoic acid, etc.), amino acids (aspartic acid, Organic acids such as glutamic acid) or sulfonic acids (such as trifluoromethylsulfonic acid), or inorganic acids (such as nitric acid, phosphoric acid, hydrofluoric acid, hydrochloric acid, sulfuric acid, etc.), but inorganic acids are preferred, and nitric acid is also preferred. Is preferred.
[0015]
As said acidic aqueous solution, what was adjusted to pH 0-6 is used. Further, the amount used is not particularly limited as long as the β zeolite is sufficiently immersed.
[0016]
The immersion temperature of the β zeolite of the present invention in an acidic aqueous solution is in the range of room temperature to 120 ° C, preferably 40 to 90 ° C.
The immersion time is 1 to 12 hours.
This dipping operation is preferably performed with stirring, but a sufficiently similar effect can be obtained even when left standing.
[0017]
Next, the β zeolite immersed in the acidic aqueous solution is taken out and washed with water. Although the extraction method is not specifically limited here, For example, it is performed by methods, such as filtration. Moreover, as water used for water washing, ion-exchange water is preferable.
[0018]
The washed β zeolite is dried.
The temperature range for drying is 90 to 150 ° C. The drying time is 1 hour to 2 days depending on the amount of β zeolite.
After this drying, the β zeolite is calcined. Although the temperature range of baking is 350-950 degreeC, 450-850 degreeC is preferable.
The firing time is 1 to 24 hours.
[0019]
The proton type β zeolite of the present invention obtained by performing the above acidic aqueous solution treatment is an ammonia temperature-programmed desorption method (NH₃-TPD, temperature increase rate 20 ° C./min, measurement range 100 ° C. to 700 ° C.) When compared with an untreated spectrum, an acid point showing a desorption peak in the range of plus or minus 100 ° C. centering on 330 ° C. And the amount of strong acid sites showing a desorption peak at 500 ° C. or higher is 2.5 μmol / g or less, and further 0.0005 μmol / g (calculated from the detection limit of the desorption peak) or more and 2.5 μmol. / G or less. The untreated peak near 200 ° C. is derived from physically adsorbed ammonia based on the dispersion force and the like existing on the β zeolite structure, and is remarkably reduced by the acidic aqueous solution. (See Figure 2)
Here, the amount of strong acid sites is determined by the ammonia temperature programmed desorption method (NH₃-TPD), calculated from the amount of desorbed ammonia (see Non-Patent Document 6).
In addition, the amount of desorbed ammonia is calculated according to the quantification method described in Non-Patent Document 7, with the desorption peak at 500 ° C. or higher at the bottom of the main peak centered at 330 ° C. being calculated from the previous main peak. The area was divided by an extension line and quantified from the area. (See Figure 1 and Formula 1 below)
[0020]
[Expression 1]

[0021]
(A in the formula represents a main peak centered at 330 ° C., and B represents a desorption peak at 500 ° C. or higher. See FIG. 1.)
[0022]
In addition, the proton type β zeolite of the present invention has 3782 cm when its FT-IR spectrum is compared with an untreated one.^-1The absorption is below the detection limit. (See Figure 3)
[0023]
The proton-type β zeolite of the present invention is suitably used in the production of dihydric phenols that oxidize monohydric phenols with peroxides in the presence of ketones.
[0024]
Examples of the monohydric phenol used here include phenol, monovalent monoalkylphenol, monovalent halogenated phenol, and monovalent polyalkylphenol.
[0025]
Examples of the alkyl group possessed by the monovalent monoalkylphenol include linear or branched alkyl groups having 1 to 6 carbon atoms. The position of the alkyl group is not particularly limited as long as it does not participate in the reaction. These compounds include, for example, o-, m- or p-cresol, o-, m- or p-ethylphenol, o-propylphenol, p-isopropylphenol, m-butylphenol, p-isobutylphenol, pt -Butylphenol, m-isobutylphenol, p-pentylphenol, p-hexylphenol.
[0026]
Examples of the halogen atom possessed by the monovalent halogenated phenol include fluorine, chlorine, bromine and iodine. The number and position of halogen atoms are not particularly limited as long as they are not involved in the reaction. These compounds include, for example, o-, m- or p-fluorophenol, o-, m- or p-chlorophenol, o-, m- or p-bromophenol, o-, m- or p-iodination. Phenol, 2,3-, 2,4-, 2,5-, 2,6-, 3,4- or 3,5-dichlorophenol, 2,3-, 2,4-, 2,5-, 2 , 6-, 3,4- or 3,5-dibromophenol, 2,3,4-, 2,3,5-, 2,3,6-, 2,4,5-, 2,4,6 -Or 3,4,5-trichlorophenol.
[0027]
Examples of the alkyl group that the monovalent polyalkylphenol has include a linear or branched alkyl group having 1 to 6 carbon atoms. The number and position of alkyl groups are not particularly limited as long as they do not participate in the reaction. Examples of these compounds include 2,3-, 2,4-, 2,5-, 2,6-, 3,5- or 3,4-dimethylphenol, 2,3,4-, 2,3, 5-, 2,3,6- or 3,4,5-trimethylphenol, 2,4,5-trimethylphenol, 2,3,4,5- or 2,3,5,6-tetramethylphenol, 2 -Ethyl-3-methylphenol, 3-t-butyl-4-methylphenol, 2-isopropyl-5-methylphenol, 2-pentyl-6-methylphenol, 3-hexyl-5-methylphenol.
[0028]
Examples of the ketone used in the method for producing a dihydric phenol using the proton type β zeolite of the present invention include monoketones and diketones. Monoketones include acyclic or cyclic monoketones. Examples of the acyclic monoketone include linear or branched aliphatic monoketone and aromatic monoketone having 3 to 20 carbon atoms, preferably 3 to 10 carbon atoms. The hydrogen atom of these compounds may be substituted with a halogen atom (fluorine atom, chlorine atom, bromine atom or iodine atom). The number and position of halogen atoms are not particularly limited as long as they are not involved in the reaction.
[0029]
Examples of the linear aliphatic monoketone include acetone, methyl ethyl ketone, 2-pentanone, 3-pentanone, 2-hexanone, 2-heptanone, 3-heptanone, 4-heptanone, 2-octanone, 2-nonanone, and 3-decanone. 6-undecanone, 2-tridecanone, 7-tridecanone, 2-tetradecanone, 2-pentadecanone, 2-hexadecanone, 2-heptadecanone, 3-octadecanone, 4-nonadecanone, 1-chloro-2-propanone, 1-chloro-3 -Heptanone, 1-bromo-3-heptanone.
[0030]
Examples of the branched aliphatic monoketone include 3-methyl-2-butanone, 3-methyl-2-pentanone, 4-methyl-2-pentanone, 3,3-dimethyl-2-butanone, 2,4-dimethyl- Examples include 3-pentanone, 6-methyl-2-heptanone, 2,6-dimethyl-4-heptanone, and 2,2,4,4-tetramethyl-3-heptanone. Examples of the aromatic monoketone include acetophenone, benzophenone, 1-phenyl-3-propanone, 1-phenyl-1-butanone, 1-phenyl-3-butanone, 1-phenyl-3-pentanone, 1,3-diphenyl- 2-propanone is mentioned.
[0031]
Examples of cyclic monoketones include cycloalkyl monoketones having 5 to 12 carbon atoms. The hydrogen atom of these compounds may be substituted with a halogen atom (a fluorine atom, a chlorine atom, a bromine atom or an iodine atom), or a substituent such as a linear or branched alkyl group having 1 to 6 carbon atoms. . The number and position of the substituents are not particularly limited as long as they do not participate in the reaction. Examples of these compounds include cyclopentanone, cyclohexanone, cyclododecanone, 2-chlorocyclohexanone, 2-ethyl-1-cyclopentanone, and 2-methyl-1-cyclohexanone.
[0032]
Diketones include acyclic or cyclic diketones. Examples of the acyclic diketone include linear or branched aliphatic diketones and aromatic diketones having 5 to 21 carbon atoms, preferably 5 to 12 carbon atoms. The hydrogen atom of these compounds may be substituted with a halogen atom (fluorine atom, chlorine atom, bromine atom or iodine atom). The number and position of halogen atoms are not particularly limited as long as they are not involved in the reaction. Examples of the linear aliphatic diketone include 2,3-butanedione, 2,4-pentanedione, and 2,5-hexanedione. Examples of the branched aliphatic diketone include 2,5-dimethyl-3,4-hexanedione. Examples of the aromatic diketone include 1,2-diphenylethane-1,2-dione.
[0033]
Examples of the cyclic diketone include cyclic diketones having 5 to 12 carbon atoms. The hydrogen atom of these compounds may be substituted with a halogen atom (a fluorine atom, a chlorine atom, a bromine atom or an iodine atom), or a substituent such as a linear or branched alkyl group having 1 to 6 carbon atoms. . The number and position of the substituents are not particularly limited as long as they do not participate in the reaction. Examples of the cyclic diketone include 1,4-cyclohexanedione.
[0034]
Preferred as the ketone used in the process for producing a dihydric phenol using the proton type β zeolite of the present invention is a linear or branched aliphatic monoketone, or a cyclic monoketone, and more preferred is a straight chain. Or it is a branched aliphatic monoketone, and 4-methyl-2-pentanone and 3-pentanone are particularly preferable among them.
[0035]
The amount of ketone used is preferably such that the molar ratio of ketone to peroxide (ketone: peroxide) is 0.2: 1 to 5: 1.
[0036]
In the process for producing a dihydric phenol using the proton type β zeolite of the present invention, a small amount of phosphoric acid may be added in order to avoid the adverse effect of dissolved metal ions such as iron ions on the reaction. Absent. Examples of phosphoric acid include orthophosphoric acid, pyrophosphoric acid, metaphosphoric acid, triphosphoric acid, tetraphosphoric acid, polyphosphoric acid, phosphoric anhydride, and phosphoric acid aqueous solution, and a phosphoric acid aqueous solution is preferable. The concentration of the phosphoric acid aqueous solution is preferably 0.001 to 100% by weight.
[0037]
The amount of phosphoric acid used is preferably such that the weight ratio of phosphoric acid to monohydric phenol (phosphoric acid: monohydric phenol) is 0.0001: 1 to 0.05: 1.
[0038]
The peroxide used in the method for producing a dihydric phenol using the proton type β zeolite of the present invention is an inorganic peroxide such as hydrogen peroxide, or an organic peroxide such as a ketone peroxide or an aliphatic percarboxylic acid. Things.
[0039]
Examples of the ketone peroxide include dialkyl ketone peroxide having 3 to 20 carbon atoms, preferably 3 to 10 carbon atoms. Examples of these compounds include dimethyl ketone peroxide, diethyl ketone peroxide, methyl ethyl ketone peroxide, methyl-n-propyl ketone peroxide, methyl isopropyl ketone peroxide, and methyl isobutyl ketone peroxide.
[0040]
Examples of the aliphatic percarboxylic acid include peracetic acid and perpropionic acid.
[0041]
As hydrogen peroxide, 0.1% by weight or more, preferably 0.1 to 90% by weight of hydrogen peroxide water can be used, but 30 to 80% by weight is more preferable.
[0042]
As the peroxide used in the process for producing a dihydric phenol using the proton type β zeolite of the present invention, hydrogen peroxide or ketone peroxide is preferable. This ketone peroxide can be synthesized by contacting a ketone with hydrogen peroxide, and the ketone used here is the same as described above.
[0043]
The amount of peroxide used is such that the molar ratio of peroxide to monohydric phenol (peroxide: monohydric phenol) is 1: 1 to 1: 100, more preferably 1: 5 to 1:20. It is preferable that
[0044]
As a method for adding peroxide into the reaction system, it may be added all at once at the start of the reaction, but in order to prevent the side reactions from occurring and to advance the reaction in a high yield, several times. It is preferable to add in portions or to add continuously in small amounts using a liquid feed pump. In the case of divided addition, the addition amount of peroxide to monohydric phenol per time is 0.05: 100 to 2: 100, more preferably 0.1 in terms of molar ratio (peroxide: monohydric phenol). : 100-2: 100. In addition, in any case of divided addition and continuous addition, the amount of peroxide to monohydric phenol in the reaction system is preferably in the range of 0.05: 100 to 2: 100, more preferably 0.1: A range of 100 to 1: 100 is preferred.
[0045]
Examples of the shape of the proton-type β zeolite of the present invention used in the production of the dihydric phenol include powders, granules, pellets, and honeycomb-shaped formed bodies.
[0046]
As the shape according to the production of the dihydric phenol, for example, when producing using a liquid phase batch reactor, it is preferable to use powder, granules, etc., and a liquid phase flow reactor is used. Pellets and honeycomb shaped bodies are preferable.
[0047]
In the production of the dihydric phenol, the amount of the proton type β zeolite used is such that the weight ratio of the proton type β zeolite to the monohydric phenol (β zeolite: monohydric phenol) is 1: 1 to 1: 500, and further 1: The range is preferably 5 to 1: 100.
[0048]
The reaction temperature in the production of the dihydric phenol is preferably 20 to 300 ° C, more preferably 40 to 200 ° C. The reaction time varies depending on, for example, the difference in Al: Si (atomic ratio) of the proton type β zeolite and the reaction temperature, but is not particularly limited. The reaction can be performed at atmospheric pressure, but may be performed under reduced pressure or increased pressure. The reaction can be carried out in a liquid phase by a batch system, a flow system, a trickle bed system, or the like.
[0049]
As a method for producing the dihydric phenol, for example, monohydric phenol, hydrogen peroxide, ketone and phosphoric acid are supplied to a reactor pre-filled with β zeolite, and the monohydric phenol is oxidized to dihydric phenol. And a reaction for discharging the reaction mixture from the reactor.
[0050]
The dihydric phenol obtained by the production of the dihydric phenol can be obtained as one kind or a mixture of several kinds corresponding to the structure of the monohydric phenol of the raw material. These dihydric phenols can be obtained by separation and purification by a conventional method.
[0051]
【Example】
Hereinafter, the present invention will be specifically described with reference to Examples and Comparative Examples. In addition, this invention is not restrict | limited by these Examples.
[0052]
The yield of dihydric phenol is determined according to the following formula. The analysis was performed by gas chromatography.
[0053]
[Expression 2]

[0054]
Example 1. (H / βHNO₃(Preparation of (38))
Eggplant flask in which 5.0 g of proton type β zeolite powder (hereinafter referred to as H / β (38)) manufactured by Zeolis with Al: Si = 1: 38 and 40 ml of aqueous nitric acid solution (pH = 1.35) are contained. The mixture was heated to 80 ° C. in an oil bath and stirred. After 2 hours, the zeolite was filtered, washed with ion-exchanged water, dried at 110 ° C., and calcined at 550 ° C. for 2.5 hours. Proton type β zeolite obtained (hereinafter referred to as H / βHNO)₃As a result of the ICP emission analysis of (38), the Al: Si (atomic ratio) in the β zeolite was Al: Si = 1: 78. NH₃-TPD measurement (temperature increase rate 20 ° C./min, measurement range 100 ° C. to 700 ° C.) showed a marked desorption peak attributed to a strong acid point of 500 ° C. or higher compared to the untreated sample. It decreased (see FIG. 2). NH shown in this figure₃From the -TPD spectrum, the amount of strong acid sites present in the temperature region of 500 ° C. or higher was calculated from the above formula 1, and was 0.55 μmol / g, whereas that of nitric acid untreated (H / β In (38)), a remarkable difference of 3.0 μmol / g was recognized. Further, when the FT-IR spectrum was compared, it was found to be 3782 cm detected by H / β (38).^{- 1}No absorption was detected (see FIG. 3).
[0055]
Example 2 (H / βHNO₃(13) Preparation)
Eggplant flask containing 5.0 g of Zeolist proton type β zeolite powder (hereinafter referred to as H / β (13)) having Al: Si = 1: 13 and 40 ml of aqueous nitrate solution (pH = 1.30) The mixture was heated to 80 ° C. in an oil bath and stirred. After 2 hours, the zeolite was filtered, washed with ion-exchanged water, dried at 110 ° C., and calcined at 550 ° C. for 2.5 hours. Proton type β zeolite obtained (hereinafter referred to as H / βHNO)₃When the ICP emission analysis of (described as (13)) was performed, the Al: Si (atomic ratio) in the β zeolite was Al: Si = 1: 69. NH₃-TPD measurement (temperature increase rate 20 ° C./min, measurement range 100 ° C. to 700 ° C.) is attributed to a strong acid point of 500 ° C. or higher compared to the untreated one (H / β (13)). The desorption peak was significantly reduced. The amount of strong acid sites calculated in the same manner as in Example 1 is H / βHNO.₃In (13), it was 1.8 μmol / g, whereas in H / β (13), a significant difference was observed with 4.2 μmol / g.
Moreover, when the FT-IR spectrum was compared, it was detected by H / β (13) at 3782 cm.^{- 1}No absorption was detected.
[0056]
Example 3
H / βHNO prepared in Example 1₃(38) 0.20 g, 10.0 g phenol, 0.27 g 3-pentanone, 0.02 g 85% by weight phosphoric acid aqueous solution were placed in a 300 ml flask and replaced with a nitrogen atmosphere. Warm up. Next, at this temperature, 0.10 g of 60% by weight hydrogen peroxide solution was dropped, and after 1.5 minutes, further 0.10 g, and after 3 minutes, another 0.10 g was dropped, until 5 minutes from the first drop. Reacted.
As a result, the yield of divalent phenol was 52.8% for catechol and 41.5% for hydroquinone, and the total yield of catechol and hydroquinone was 94.3%.
[0057]
Example 4
The reaction was conducted in the same manner as in Example 3 except that the reaction temperature was 100 ° C.
As a result, the yield of dihydric phenol was 54.9% for catechol and 41.1% for hydroquinone, and the total yield of catechol and hydroquinone was 96.0%.
[0058]
Comparative Example 1
H / βHNO₃The reaction was conducted in the same manner as in Example 3 except that (38) was changed to H / β (38).
As a result, the yield of dihydric phenol was 50.0% for catechol and 34.7% for hydroquinone, and the total yield of catechol and hydroquinone was 84.7%.
[0059]
Comparative Example 2
The reaction was conducted in the same manner as in Comparative Example 4 except that the reaction temperature was 100 ° C.
As a result, the yield of dihydric phenol was 51.4% for catechol and 33.6% for hydroquinone, and the total yield of catechol and hydroquinone was 85.0%.
[0060]
Example 5
H / βHNO₃(38) H / βHNO₃The reaction was conducted in the same manner as in Example 4 except that (13) was used.
As a result, the yield of dihydric phenol was 52.6% for catechol and 39.1% for hydroquinone, and the total yield of catechol and hydroquinone was 91.7%.
[0061]
Comparative Example 3
H / βHNO₃The reaction was conducted in the same manner as in Example 4 except that (38) was changed to H / β (13).
As a result, the yield of dihydric phenol was 49.3% for catechol and 33.8% for hydroquinone, and the total yield of catechol and hydroquinone was 83.1%.
[0062]
[Table 1]

[0063]
Example 6
H / βHNO prepared in Example 1₃(38) 0.20 g, 10.0 g of phenol, and 0.27 g of 3-pentanone were placed in a 300 ml flask and replaced with a nitrogen atmosphere, and then heated to 100 ° C. with stirring. Next, at this temperature, 0.10 g of 60% by weight hydrogen peroxide solution was added dropwise, 1.5 minutes later 0.10 g, 3 minutes further 0.10 g, 4.5 minutes 0.1 g, 6 minutes later 0.1 g, 0.1 g was added dropwise after 7.5 minutes, and the reaction was continued until 10 minutes from the first addition.
As a result, the yield of dihydric phenol was 48.4% for catechol and 43.7% for hydroquinone, and the total yield of catechol and hydroquinone was 92.1%.
[0064]
Example 7
The reaction was conducted in the same manner as in Example 6 except that 0.02 g of 85% phosphoric acid aqueous solution was added to the raw material before the reaction.
As a result, the yield of divalent phenol was 50.4% for catechol and 40.4% for hydroquinone, and the total yield of catechol and hydroquinone was 90.8%.
[0065]
Comparative Example 3
H / βHNO₃The reaction was conducted in the same manner as in Example 6 except that (38) was changed to H / β (38).
As a result, the yield of dihydric phenol was 45.1% for catechol and 37.9% for hydroquinone, and the total yield of catechol and hydroquinone was 83.1%.
[0066]
Comparative Example 4
H / βHNO₃The reaction was conducted in the same manner as in Example 7 except that (38) was changed to H / β (38).
As a result, the yield of dihydric phenol was 47.7% for catechol and 33.0% for hydroquinone, and the total yield of catechol and hydroquinone was 80.7%.
[0067]
[Table 2]

[0068]
【The invention's effect】
The proton type β zeolite of the present invention is obtained by a simple preparation method in which β zeolite is immersed in an acidic aqueous solution. This proton type β zeolite exhibits high reactivity even at low temperatures in the production of dihydric phenols that oxidize monohydric phenols with peroxides, and can produce dihydric phenols in a high yield.
[Brief description of the drawings]
FIG. 1 Ammonia temperature programmed desorption method (NH₃-TPD) spectrum (schematic diagram)
FIG. 2: H / β (38) and H / βHNO₃(38) Ammonia temperature programmed desorption method (NH₃-TPD) spectrum
FIG. 3. H / β (38) and H / βHNO₃FT-IR spectrum of (38)

Claims (2)

Ammonia temperature programmed desorption (NH ₃ -TPD) spectrum, there is an acid point showing a desorption peak in the range of plus or minus 100 ° C. around 330 ° C., and the amount of strong acid points showing a desorption peak of 500 ° C. or higher is 2.5 μmol / A method for producing a dihydric phenol, which comprises oxidizing a monohydric phenol with a peroxide in the presence of a proton type β zeolite and a ketone which are not more than g. The method for producing a dihydric phenol according to claim 1, wherein the peroxide is hydrogen peroxide or ketone peroxide.

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