JP4776869B2 - Exhaust gas purification catalyst, exhaust gas purification material using the same, and method for producing the same - Google Patents

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（表１）から明らかなように、同じ種類の触媒組成を用いた場合でも、排ガス浄化触媒として比較例１で得られる排ガス浄化触媒よりも実施例１で得られる排ガス浄化触媒の方が、より低温でパティキュレートを燃焼できることがわかった。
【０１２６】
（実施例２）
触媒担体としてチタニアの代わりにＴａ₂Ｏ₅を用いた他は、実施例１と同様にして粉体触媒を得た。
【０１２７】
（実施例３）
触媒担体としてチタニアの代わりにＮｂ₂Ｏ₅を用いた他は、実施例１と同様にして粉体触媒を得た。
【０１２８】
（実施例４）
触媒担体としてチタニアの代わりにＷＯ₃を用いた他は、実施例１と同様にして粉体触媒を得た。
【０１２９】
（実施例５）
触媒担体としてチタニアの代わりにＳｎＯ₂を用いた他は、実施例１と同様にして粉体触媒を得た。
【０１３０】
（実施例６）
触媒担体としてチタニアの代わりにＳｉＯ₂を用いた他は、実施例１と同様にして粉体触媒を得た。
【０１３１】
（実施例７）
触媒担体としてチタニアの代わりにＡｌ₂Ｏ₃を用いた他は、実施例１と同様にして粉体触媒を得た。
【０１３２】
（実施例８）
触媒担体としてチタニアの代わりにＺｒＯ₂を用いた他は、実施例１と同様にして粉体触媒を得た。
【０１３３】
（実施例９）
触媒担体としてチタニアの代わりにＣｅＯ₂を用いた他は、実施例１と同様にして粉体触媒を得た。
【０１３４】
（実施例１０）
触媒担体としてチタニアの代わりにＬａ₂Ｏ₃を用いた他は、実施例１と同様にして粉体触媒を得た。
【０１３５】
（比較例２）
触媒担体としてチタニアの代わりにＦｅ₂Ｏ₃を用いた他は、実施例１と同様にして粉体触媒を得た。
【０１３６】
（評価例２）
実施例２〜実施例１０および比較例２において、評価例１と同様にしてパティキュレートの燃焼実験を行った。上記燃焼試験における各排ガス浄化触媒の５％燃焼温度を実施例１とともに（表２）に示した。
【０１３７】
【表２】

（表２）から明らかなように、同じ構造の排ガス浄化触媒を用いた場合、用いる担体として、比較例２に示した担体を用いた排ガス浄化触媒よりも実施例２〜実施例１０および実施例１に示した担体を用いた排ガス浄化触媒が、低温でパティキュレートを燃焼できることがわかった。
【０１３８】
（実施例１１）
触媒担体として１μｍチタニアの代わりに０．０１μｍのチタニアを用いた他は、実施例１と同様にして粉体触媒を得た。
【０１３９】
（実施例１２）
触媒担体として１μｍチタニアの代わりに０．１μｍのチタニアを用いた他は、実施例１と同様にして粉体触媒を得た。
【０１４０】
（実施例１３）
触媒担体として１μｍチタニアの代わりに１０μｍのチタニアを用いた他は、実施例１と同様にして粉体触媒を得た。
【０１４１】
（実施例１４）
触媒担体として１μｍチタニアの代わりに５０μｍのチタニアを用いた他は、実施例１と同様にして粉体触媒を得た。
【０１４２】
（実施例１５）
触媒担体として１μｍチタニアの代わりに１０００μｍのチタニアを用いた他は、実施例１と同様にして粉体触媒を得た。
【０１４３】
（比較例３）
触媒担体として１μｍチタニアの代わりに０．００１μｍのチタニアを用いた他は、実施例１と同様にして粉体触媒を得た。
【０１４４】
（比較例４）
触媒担体として１μｍチタニアの代わりに１００００μｍのチタニアを用いた他は、実施例１と同様にして粉体触媒を得た。
【０１４５】
（評価例３）
実施例１１〜実施例１５および比較例３〜４において、評価例１と同様にしてパティキュレートの燃焼実験を行った。上記燃焼試験における各排ガス浄化触媒の５％燃焼温度を実施例１とともに（表３）に示した。
【０１４６】
【表３】

（表３）から明らかなように、同じ構造の排ガス浄化触媒を用いた場合、用いる触媒担体として、比較例３〜４で得られる排ガス浄化触媒よりも実施例１１〜実施例１５および実施例１に示した担体を用いた排ガス浄化触媒、好ましくは実施例１２〜実施例１４および実施例１に示した担体を用いた排ガス浄化触媒が、低温でパティキュレートを燃焼できることがわかった。
【０１４７】
（実施例１６）
アルカリ硫酸塩として硫酸セシウムの代わりに硫酸カリウムと硫酸セシウムを重量比で１：１で混合したものを用いた他は、実施例１と同様にして粉体触媒を得た。
【０１４８】
（実施例１７）
アルカリ硫酸塩として硫酸セシウムの代わりに硫酸リチウムを用いた他は、実施例１と同様にして粉体触媒を得た。
【０１４９】
（実施例１８）
アルカリ硫酸塩として硫酸セシウムの代わりに硫酸ナトリウムを用いた他は、実施例１と同様にして粉体触媒を得た。
【０１５０】
（実施例１９）
アルカリ硫酸塩として硫酸セシウムの代わりに硫酸カリウムを用いた他は、実施例１と同様にして粉体触媒を得た。
【０１５１】
（実施例２０）
アルカリ硫酸塩として硫酸セシウムの代わりに硫酸ルビジウムを用いた他は、実施例１と同様にして粉体触媒を得た。
【０１５２】
（比較例５）
硫酸セシウムの代わりに硫酸カルシウムを用いた他は、実施例１と同様にして粉体触媒を得た。
【０１５３】
（評価例４）
実施例１６〜実施例２０及び比較例５において、評価例１と同様にしてパティキュレートの燃焼実験を行った。上記燃焼試験における各排ガス浄化触媒の５％燃焼温度を実施例１とともに（表４）に示した。
【０１５４】
【表４】

（表４）から明らかなように、同じ構造の排ガス浄化触媒を用いた場合、比較例５で得られる排ガス浄化触媒よりも実施例１６〜実施例２０および実施例１に示したアルカリ硫酸塩を用いた排ガス浄化触媒、好ましくは実施例１６および実施例１に示したアルカリ硫酸塩を用いた排ガス浄化触媒が、低温でパティキュレートを燃焼できることがわかった。
【０１５５】
（参考例１）
遷移金属の酸化物として銅−バナジウム複合酸化物（Ｃｕ₅Ｖ₂Ｏ₁₀）とマンガン酸化物の代わりにＣｕＯを用いた他は、実施例１と同様にして粉体触媒を得た。
【０１５６】
（参考例２）
遷移金属の酸化物として銅−バナジウム複合酸化物（Ｃｕ₅Ｖ₂Ｏ₁₀）とマンガン酸化物の代わりにＭｎＯ₂を用いた他は、実施例１と同様にして粉体触媒を得た。
【０１５７】
（参考例３）
遷移金属の酸化物として銅−バナジウム複合酸化物（Ｃｕ₅Ｖ₂Ｏ₁₀）とマンガン酸化物の代わりにＣｏＯ₃を用いた他は、実施例１と同様にして粉体触媒を得た。
【０１５８】
（参考例４）
遷移金属の酸化物として銅−バナジウム複合酸化物（Ｃｕ₅Ｖ₂Ｏ₁₀）とマンガン酸化物の代わりにＶ₂Ｏ₅を用いた他は、実施例１と同様にして粉体触媒を得た。
【０１５９】
（参考例５）
遷移金属の酸化物として銅−バナジウム複合酸化物（Ｃｕ₅Ｖ₂Ｏ₁₀）とマンガン酸化物の代わりにＭｏＯ₃を用いた他は、実施例１と同様にして粉体触媒を得た。
【０１６０】
（参考例６）
遷移金属の酸化物として銅−バナジウム複合酸化物（Ｃｕ₅Ｖ₂Ｏ₁₀）とマンガン酸化物の代わりにＷＯ₃を用いた他は、実施例１と同様にして粉体触媒を得た。
【０１６１】
（参考例７）
遷移金属の酸化物として銅−バナジウム複合酸化物（Ｃｕ₅Ｖ₂Ｏ₁₀）とマンガン酸化物の代わりにＣｕ₂Ｏを用いた他は、実施例１と同様にして粉体触媒を得た。
【０１６２】
（参考例８）
遷移金属の酸化物として銅−バナジウム複合酸化物（Ｃｕ₅Ｖ₂Ｏ₁₀）とマンガン酸化物の代わりにＣｕ₂Ｏ₃を用いた他は、実施例１と同様にして粉体触媒を得た。
【０１６３】
（参考例９）
遷移金属の酸化物として銅−バナジウム複合酸化物（Ｃｕ₅Ｖ₂Ｏ₁₀）の代わりに銅−バナジウム複合酸化物（ＣｕＶ₂Ｏ₆）を用いた他は、実施例１と同様にして粉体触媒を得た。
【０１６４】
（参考例１０）
遷移金属の酸化物として銅−バナジウム複合酸化物（Ｃｕ₅Ｖ₂Ｏ₁₀）の代わりに銅−バナジウム複合酸化物（Ｃｕ₃Ｖ₂Ｏ₈）を用いた他は、実施例１と同様にして粉体触媒を得た。
【０１６５】
（比較例６）
遷移金属の酸化物として銅−バナジウム複合酸化物（Ｃｕ₅Ｖ₂Ｏ₁₀）とマンガン酸化物の代わりにＬａＭｎＣｏＯ₃を用いた他は、実施例１と同様にして粉体触媒を得た。
【０１６６】
（評価例５）
参考例１〜参考例１０及び比較例６において、評価例１と同様にしてパティキュレートの燃焼実験を行った。上記燃焼試験における各排ガス浄化材の５％燃焼温度を実施例１とともに（表５）に示した。
【０１６７】
【表５】

（表５）から明らかなように、同じ構造の排ガス浄化触媒を用いた場合、担持させる遷移金属の金属酸化物として、比較例６で得られる排ガス浄化触媒よりも参考例１〜参考例１０および実施例１に示した化合物を担持させた排ガス浄化触媒が、より低温でパティキュレートを燃焼できることがわかった。
【０１６８】
（実施例２１）
実施例１で得られた粉体７５ｇと、分散剤としてフローレン（Ｇ−７０００共栄社化学製）３ｇと、無水エタノール４３０ｇと、２ｍｍのジルコニアボール１０００ｇを１０００ｍｌ密閉容器に入れ、スラリー分散器（レッドデビル製）にて２時間分散させてスラリーを得た。
【０１６９】
得られたスラリーに分散剤としてフローレン５ｇと、無水エタノール８５０ｇを混合したものを加えて希釈されたスラリーを得た。
【０１７０】
次に、耐熱性の３次元構造体としてウォールフロータイプのコージェライトフィルター（ＮＧＫ製 ５．６６インチ、１００セル／インチ²）を、２セル×５セル×１５ｍｍに切り出し、これを上記で得られたスラリー溶液に含浸させ、余分なスラリーをエアーガンにて取り除いた後、乾燥器にて６０℃で乾燥後、電気炉にて６００℃で５時間熱処理することにより、排ガス浄化材を製造した。
【０１７１】
（比較例７）
銅の塩として硫酸銅五水和物（和光純薬製）５００ｇと、バナジウムの塩として酸化硫酸バナジウム（和光純薬製）７００ｇと、アルカリ硫酸塩のとして硫酸セシウム（添川理化学製）１０００ｇと、マンガン塩として酢酸マンガン四水和物（和光純薬製）３ｇと、を精製水３０００ｇに加え十分に攪拌して触媒の水溶液を得た。
【０１７２】
得られた水溶液に、耐熱性の３次元構造体としてウォールフロータイプのコージェライトフィルター（ＮＧＫ製、５．６６インチ、１００セル／インチ²）を、２セル×５セル×１５ｍｍに切り出し、これを上記で得られ水溶液に含浸させ、余分な溶液をエアーガンにて取り除いた後、乾燥器にて６０℃で乾燥後、電気炉にて７００℃、５時間熱処理することにより、排ガス浄化材を製造した。
【０１７３】
（評価例６）
実施例２１、比較例７で得られた排ガス浄化材について、以下のようなパティキュレートの燃焼実験を行った。
【０１７４】
実施例２１、比較例７でで得られた排ガス浄化材の１つに模擬パティキュレート（ナカライ製のカーボン）の粉末をフィルタ表面に担持させて、内径１２ｍｍの石英ガラス製反応管内に充填した。
【０１７５】
反応管内に４ｖｏｌ％の酸素と、７０ｐｐｍのＳＯ₂と、ＮＯガス１００ｐｐｍとを含む窒素ガスからなる試験ガスを流量５００ｃｃ／分で通気しながら、反応管の外周部に配設した管状電気炉にて反応管内を定速で昇温し、この時のガス流出側の位置に配設された炭酸ガスセンサーにより試験ガス中の炭酸ガス濃度を検出し、５％のパティキュレートが燃焼した際の温度（以下、５％燃焼温度と略称する。）を決定した。充填させたパティキュレートのカーボン量（既知量）と発生したＣＯ＋ＣＯ₂量（測定値）から燃焼率を計算した。上記燃焼試験における各排ガス浄化材の５％燃焼温度を（表６）に示した。
【０１７６】
【表６】

（表６）から明らかなように、同じ種類の触媒組成を用いた場合でも、実施例２１で得られる排ガス浄化材の方が、比較例７で得られる排ガス浄化材よりも低温でパティキュレートを燃焼することができることがわかった。
【０１７７】
（実施例２２）
触媒担体としてチタニアの代わりにＴａ₂Ｏ₅を用いた他は、実施例２１と同様にして排ガス浄化材を得た。
【０１７８】
（実施例２３）
触媒担体としてチタニアの代わりにＮｂ₂Ｏ₅を用いた他は、実施例２１と同様にして排ガス浄化材を得た。
【０１７９】
（実施例２４）
触媒担体としてチタニアの代わりにＷＯ₃を用いた他は、実施例２１と同様にして排ガス浄化材を得た。
【０１８０】
（実施例２５）
触媒担体としてチタニアの代わりにＳｎＯ₂を用いた他は、実施例２１と同様にして排ガス浄化材を得た。
【０１８１】
（実施例２６）
触媒担体としてチタニアの代わりにＳｉＯ₂を用いた他は、実施例２１と同様にして排ガス浄化材を得た。
【０１８２】
（実施例２７）
触媒担体としてチタニアの代わりにＡｌ₂Ｏ₃を用いた他は、実施例２１と同様にして排ガス浄化材を得た。
【０１８３】
（実施例２８）
触媒担体としてチタニアの代わりにＺｒＯ₂を用いた他は、実施例２１と同様にして排ガス浄化材を得た。
【０１８４】
（実施例２９）
触媒担体としてチタニアの代わりにＣｅＯ₂を用いた他は、実施例２１と同様にして排ガス浄化材を得た。
【０１８５】
（実施例３０）
触媒担体としてチタニアの代わりにＬａ₂Ｏ₃を用いた他は、実施例２１と同様にして排ガス浄化材を得た。
【０１８６】
（比較例８）
触媒担体としてチタニアの代わりにＦｅ₂Ｏ₃を用いた他は、実施例２１と同様にして排ガス浄化材を得た。
【０１８７】
（評価例７）
実施例２２〜実施例３０および比較例８において、評価例６と同様にしてパティキュレートの燃焼実験を行った。上記燃焼試験における各排ガス浄化材の５％燃焼温度を実施例１とともに（表７）に示した。
【０１８８】
【表７】

（表７）から明らかなように、同じ構造の排ガス浄化触媒を用いた場合、用いる触媒担体として、比較例８で示した担体を用いた排ガス浄化材よりも実施例２１〜実施例３０に示した担体を用いた排ガス浄化材が、より低温でパティキュレートを燃焼できることがわかった。
【０１８９】
（実施例３１）
触媒担体として１μｍチタニアの代わりに０．０１μｍのチタニアを用いた他は、実施例２１と同様にして排ガス浄化材を得た。
【０１９０】
（実施例３２）
触媒担体として１μｍチタニアの代わりに０．１μｍのチタニアを用いた他は、実施例２１と同様にして排ガス浄化材を得た。
【０１９１】
（実施例３３）
触媒担体として１μｍチタニアの代わりに１０μｍのチタニアを用いた他は、実施例２１と同様にして排ガス浄化材を得た。
【０１９２】
（実施例３４）
触媒担体として１μｍチタニアの代わりに５０μｍのチタニアを用いた他は、実施例２１と同様にして排ガス浄化材を得た。
【０１９３】
（実施例３５）
触媒担体として１μｍチタニアの代わりに１０００μｍのチタニアを用いた他は、実施例２１と同様にして排ガス浄化材を得た。
【０１９４】
（比較例９）
触媒担体として１μｍチタニアの代わりに０．００１μｍのチタニアを用いた他は、実施例２１と同様にして排ガス浄化材を得た。
【０１９５】
（比較例１０）
触媒担体として１μｍチタニアの代わりに１００００μｍのチタニアを用いた他は、実施例２１と同様にして排ガス浄化材を得た。
【０１９６】
（評価例８）
実施例３１〜実施例３５および比較例９〜１０において、評価例６と同様にしてパティキュレートの燃焼実験を行った。上記燃焼試験における各排ガス浄化材の５％燃焼温度を実施例１とともに（表８）に示した。
【０１９７】
【表８】

（表８）から明らかなように、同じ構造の排ガス浄化触媒を用いた場合、用いる触媒担体として、比較例９〜１０で得られる排ガス浄化材よりも実施例３１〜実施例３５および実施例２１に示した担体を用いた排ガス浄化材、好ましくは実施例３２〜実施例３４および実施例２１に示した担体を用いた排ガス浄化材が、低温でパティキュレートを燃焼できることがわかった。
【０１９８】
（実施例３６）
アルカリ硫酸塩として硫酸セシウムの代わりに硫酸カリウムと硫酸セシウムを重量比で１：１で混合したものを用いた他は、実施例２１と同様にして排ガス浄化材を得た。
【０１９９】
（実施例３７）
アルカリ硫酸塩として硫酸セシウムの代わりに硫酸リチウムを用いた他は、実施例２１と同様にして排ガス浄化材を得た。
【０２００】
（実施例３８）
アルカリ硫酸塩として硫酸セシウムの代わりに硫酸ナトリウムを用いた他は、実施例２１と同様にして排ガス浄化材を得た。
【０２０１】
（実施例３９）
アルカリ硫酸塩として硫酸セシウムの代わりに硫酸カリウムを用いた他は、実施例２１と同様にして排ガス浄化材を得た。
【０２０２】
（実施例４０）
アルカリ硫酸塩として硫酸セシウムの代わりに硫酸ルビジウムを用いた他は、実施例２１と同様にして排ガス浄化材を得た。
【０２０３】
（比較例１１）
硫酸セシウムの代わりに硫酸カルシウムを用いた他は、実施例２１と同様にして排ガス浄化材を得た。
【０２０４】
（評価例９）
実施例３６〜実施例４０及び比較例１１において、評価例６と同様にしてパティキュレートの燃焼実験を行った。上記燃焼試験における各排ガス浄化材の５％燃焼温度を実施例２１とともに（表９）に示した。
【０２０５】
【表９】

（表９）から明らかなように、同じ構造の排ガス浄化触媒を用いた場合、比較例１１で得られる排ガス浄化材よりも実施例３６〜実施例４０および実施例２１に示したアルカリ硫酸塩を用いた排ガス浄化材、好ましくは実施例３６および実施例２１に示したアルカリ硫酸塩を用いた排ガス浄化材が、低温でパティキュレートを燃焼できることがわかった。
【０２０６】
（参考例１１）
遷移金属の酸化物として銅−バナジウム複合酸化物（Ｃｕ₅Ｖ₂Ｏ₁₀）とマンガン酸化物の代わりにＣｕＯを用いた他は、実施例２１と同様にして排ガス浄化材を得た。
【０２０７】
（参考例１２）
遷移金属の酸化物として銅−バナジウム複合酸化物（Ｃｕ₅Ｖ₂Ｏ₁₀）とマンガン酸化物の代わりにＭｎＯ₂を用いた他は、実施例２１と同様にして排ガス浄化材を得た。
【０２０８】
（参考例１３）
遷移金属の酸化物として銅−バナジウム複合酸化物（Ｃｕ₅Ｖ₂Ｏ₁₀）とマンガン酸化物の代わりにＣｏＯ₃を用いた他は、実施例２１と同様にして排ガス浄化材を得た。
【０２０９】
（参考例１４）
遷移金属の酸化物として銅−バナジウム複合酸化物（Ｃｕ₅Ｖ₂Ｏ₁₀）とマンガン酸化物の代わりにＶ₂Ｏ₅を用いた他は、実施例２１と同様にして排ガス浄化材を得た。
【０２１０】
（参考例１５）
遷移金属の酸化物として銅−バナジウム複合酸化物（Ｃｕ₅Ｖ₂Ｏ₁₀）とマンガン酸化物の代わりにＭｏＯ₃を用いた他は、実施例２１と同様にして排ガス浄化材を得た。
【０２１１】
（参考例１６）
遷移金属の酸化物として銅−バナジウム複合酸化物（Ｃｕ₅Ｖ₂Ｏ₁₀）とマンガン酸化物の代わりにＷＯ₃を用いた他は、実施例２１と同様にして排ガス浄化材を得た。
【０２１２】
（参考例１７）
遷移金属の酸化物として銅−バナジウム複合酸化物（Ｃｕ₅Ｖ₂Ｏ₁₀）とマンガン酸化物の代わりにＣｕ₂Ｏを用いた他は、実施例２１と同様にして排ガス浄化材を得た。
【０２１３】
（参考例１８）
遷移金属の酸化物として銅−バナジウム複合酸化物（Ｃｕ₅Ｖ₂Ｏ₁₀）とマンガン酸化物の代わりにＣｕ₂Ｏ₃を用いた他は、実施例２１と同様にして排ガス浄化材を得た。
【０２１４】
（参考例１９）
遷移金属の酸化物として銅−バナジウム複合酸化物（Ｃｕ₅Ｖ₂Ｏ₁₀）の代わりに銅−バナジウム複合酸化物（ＣｕＶ₂Ｏ₆）を用いた他は、実施例２１と同様にして排ガス浄化材を得た。
【０２１５】
（参考例２０）
遷移金属の酸化物として銅−バナジウム複合酸化物（Ｃｕ₅Ｖ₂Ｏ₁₀）の代わりに銅−バナジウム複合酸化物（Ｃｕ₃Ｖ₂Ｏ₈）を用いた他は、実施例２１と同様にして排ガス浄化材を得た。
【０２１６】
（比較例１２）
遷移金属の酸化物として銅−バナジウム複合酸化物（Ｃｕ₅Ｖ₂Ｏ₁₀）とマンガン酸化物の代わりにＬａＭｎＣｏＯ₃を用いた他は、実施例２１と同様にして排ガス浄化材を得た。
【０２１７】
（評価例１０）
参考例１１〜参考例２０及び比較例１２において、評価例６と同様にしてパティキュレートの燃焼実験を行った。上記燃焼試験における各排ガス浄化材の５％燃焼温度を実施例２１とともに（表１０）に示した。
【０２１８】
【表１０】

（表１０）から明らかなように、同じ構造の排ガス浄化触媒を用いた場合、担持させる遷移金属の金属酸化物として、比較例１２で得られる排ガス浄化材よりも参考例１１〜参考例２０および実施例２１示した化合物を担持させた排ガス浄化材が、より低温でパティキュレートを燃焼できることがわかった。
【０２１９】
（実施例４１）
触媒スラリーの溶媒として無水エタノールの代わりに１０％の水分を含有するエタノールを用いた他は、実施例２１と同様にして排ガス浄化材を得た。
【０２２０】
（比較例１３）
触媒スラリーの溶媒として無水エタノールの代わりに精製水を用いた他は、実施例２１と同様にして排ガス浄化材を得た。
【０２２１】
（評価例１１）
実施例４１及び比較例１３において、評価例６と同様にしてパティキュレートの燃焼実験を行った。上記燃焼試験における各排ガス浄化材の５％燃焼温度を実施例２１とともに（表１１）に示した。
【０２２２】
【表１１】

（表１１）から明らかなように、同じ構造の排ガス浄化触媒を用いた場合、担持させる遷移金属の金属酸化物として、比較例１３で得られる排ガス浄化材よりも実施例４１に示した化合物を担持させた排ガス浄化材が、より低温でパティキュレートを燃焼でき、さらに実施例２１に示した化合物を担持させた排ガス浄化材が、より低温でパティキュレートを燃焼できることがわかった。
【０２２３】
【発明の効果】
以上のように本発明の排ガス浄化触媒及びそれを用いた排ガス浄化材およびその製造方法によれば、パティキュレートの燃焼に高い触媒活性を有する排ガス浄化触媒および排ガス浄化材を提供できることから、排ガス温度に近い低温で排ガス中のパティキュレートを燃焼除去できるという優れた効果が得られる。[0001]
BACKGROUND OF THE INVENTION
The present invention uses an exhaust gas purification catalyst for purifying exhaust gas by burning particulates (solid carbon fine particles, liquid or solid high molecular weight hydrocarbon fine particles) contained in exhaust gas discharged from a diesel engine, and the same. The present invention relates to an exhaust gas purification material and a method for producing the same.
[0002]
[Prior art]
In recent years, particulates discharged from diesel engines have a particle size of almost 1 μm (microns) or less, easily float in the atmosphere and easily taken into the human body by breathing, and the particulates are carcinogenic such as benzpyrene. It has become clear that it contains sexual substances, and its impact on the human body has become a major problem. For this reason, the regulation of particulate emission from diesel engines is further strengthened, and accordingly, an exhaust gas purification catalyst and an exhaust gas purification material capable of efficiently removing particulates are desired.
[0003]
Conventionally, as one method of removing particulates from exhaust gas, particulates in exhaust gas are collected using an exhaust gas purification material consisting of a heat-resistant three-dimensional structure, and after the back pressure rises, There is a method in which the exhaust gas purifying body is heated by a heating means such as an electric heater, the accumulated particulates are burned, and converted into carbon dioxide gas and discharged to the outside.
[0004]
However, the above method has a problem that the combustion temperature of the particulates is high, and a large amount of energy is required to burn and remove the collected particulates and regenerate the filter. In addition, there is a problem that the filter is melted and cracked due to combustion in a high temperature region and its reaction heat. Furthermore, since a special apparatus is required, there has been a problem that the purification apparatus is increased in size and cost.
[0005]
On the other hand, there is a method in which fine particles are subjected to a combustion reaction by catalytic action using a catalyst, and combustion regeneration is performed at the temperature of the exhaust gas in the exhaust gas without using a heating means such as a heater.
[0006]
The catalyst-supported exhaust gas purification material includes a heat-resistant three-dimensional structure supporting an exhaust gas purification catalyst made of metal oxide or the like. It can be burned at a lower temperature by catalytic action.
[0007]
If the particulates can be combusted at the exhaust gas temperature using the exhaust gas purification material carrying such an exhaust gas purification catalyst, it is not necessary to arrange the heating means in the exhaust gas purification device, and the configuration of the exhaust gas purification device can be reduced. Can be simple.
[0008]
However, at present, it is difficult for the exhaust gas purifying material carrying the exhaust gas purifying catalyst to sufficiently burn the particulates at the exhaust gas temperature, and the combined use with the heating means is indispensable. Therefore, development of an exhaust gas purification catalyst and an exhaust gas purification material carrying an exhaust gas purification catalyst having a high catalytic activity capable of burning particulates at a lower temperature is desired.
[0009]
As exhaust gas purification catalysts, it has been known that catalysts using metal oxides such as copper and vanadium have a relatively high activity.
[0010]
For example, (Patent Document 1) states that “a particulate purification catalyst comprising a combination of at least one selected from copper and a compound thereof and at least one selected from a metal capable of taking a plurality of oxidation states and a compound thereof. Is disclosed.
[0011]
(Patent Document 2) discloses “a catalyst for purifying particulates in exhaust gas comprising at least one selected from vanadium and vanadium compounds”.
[0012]
(Patent Document 3) discloses “a catalyst for exhaust gas purification in which an alkali metal oxide and a noble metal are added to a metal oxide such as copper, manganese, molybdenum, etc. and a method for producing the same”.
[0013]
[Patent Document 1]
JP 58-143840 A
[Patent Document 2]
JP 58-174236 A
[Patent Document 3]
Japanese Examined Patent Publication No. 4-42063
[0014]
[Problems to be solved by the invention]
However, the conventional exhaust gas purification catalyst and exhaust gas purification material have the following problems.
[0015]
(1) First, since the exhaust gas purification catalyst described in (Patent Document 1) and (Patent Document 2) is not high enough that the catalytic activity of the exhaust gas purification catalyst can sufficiently burn the particulates at a low temperature of the exhaust gas, The particulates collected by the exhaust gas purification material cannot be burned at the exhaust gas temperature, and there is a problem that the combined use with the heating means is indispensable.
[0016]
(2) Further, the exhaust gas purifying catalyst described in (Patent Document 3) uses an alkali metal oxide in the configuration of the exhaust gas purifying catalyst. There was a problem that scattering or reaction with other catalyst components occurred due to heat.
[0017]
(3) Furthermore, the exhaust gas purifying catalyst described in (Patent Document 3) has a problem in that it is poisoned by sulfur oxides contained in the exhaust gas and the catalytic activity is lowered.
[0018]
The present invention solves the above-mentioned conventional problems, has high catalytic activity in particulate combustion, can fully exhibit the respective catalytic characteristics, and can sufficiently burn and remove particulates at a temperature close to the exhaust gas temperature. An object of the present invention is to provide an exhaust gas purification catalyst having a high exhaust gas purification rate, and to provide an exhaust gas purification material that can burn and remove particulates with extremely high efficiency, and is excellent in durability and economy, and a method for producing the same To do.
[0019]
[Means for Solving the Problems]
  In order to solve the above problems, the exhaust gas purification catalyst of the present invention isA titania powder having a particle size of 0.01 μm to 1000 μm, a copper salt, a vanadium salt,An alkali metal sulfate,It was obtained by adding water to a manganese salt, stirring, drying, and firing.Thereby, a catalyst contact area increases, As a result, a contact point with the particulate in diesel exhaust gas increases, and a highly active exhaust gas purification catalyst can be obtained. Moreover, the use of an alkali metal sulfate increases the heat resistance of the alkali metal and improves the durability. Moreover, the durability with respect to the sulfur oxide contained in exhaust gas increases by using an alkali metal sulfate. In addition, the required amount of catalyst can be reduced and the cost can be reduced.
[0020]
  The exhaust gas purifying material of the present invention includes a heat-resistant three-dimensional structure and a three-dimensional structure.Using ethanol as solventAnd a layer of the formed exhaust gas purification catalyst. Thereby, it is possible to prevent deterioration of the catalyst performance due to the suppression of the reaction between the catalyst component and the filter component.
[0021]
  The method for producing an exhaust gas purifying material of the present invention comprises a component containing an alkali metal sulfate and a transition metal oxide.Using ethanol as solventIt has a step of supporting a catalyst on a heat-resistant three-dimensional structure after forming a powdery catalyst by supporting it on the surface of an inorganic oxide having heat resistance. Compared with the solution impregnation method, the loading amount can be easily controlled. Moreover, compared with the conventional catalyst solution impregnation method, a catalyst component can be uniformly supported on a filter. Moreover, the drying method of a manufacturing process becomes easy compared with the conventional catalyst solution impregnation method.
[0022]
Further, the method for producing an exhaust gas purifying material of the present invention includes a process characterized by using alcohol as a solvent when a powdered catalyst is supported on a heat-resistant three-dimensional structure. Thus, elution of the catalyst component into the catalyst-containing solvent can be prevented, the ideal catalyst composition can be maintained, and the catalyst component can be uniformly supported on the filter.
[0023]
DETAILED DESCRIPTION OF THE INVENTION
  The exhaust gas purifying catalyst according to claim 1 of the present invention isA titania powder having a particle size of 0.01 μm to 1000 μm, a copper salt, a vanadium salt,An alkali metal sulfate,It was obtained by adding water to manganese salt, stirring, drying, and firing.is doing. With this configuration, the following effects can be obtained.
[0024]
(1) By forming a catalyst component on the surface of an inorganic oxide having heat resistance, the surface area of the catalyst is increased. As a result, the contact point with particulates in diesel exhaust gas is increased, and a highly active exhaust gas purification catalyst is obtained. Obtainable.
[0025]
(2) By forming the catalyst component on the surface of the inorganic oxide having heat resistance, the required amount of catalyst can be reduced, an exhaust gas purification catalyst can be obtained at low cost, and the economy is excellent.
[0026]
The method for supporting the alkali metal sulfate and the transition metal oxide on the surface of the inorganic oxide having heat resistance is not particularly limited, and any method can be used. preferable.
[0027]
  The exhaust gas purifying catalyst according to claim 2 of the present invention is as follows.Instead of titania,Ta, Nb, W, Sn, Si, AlAn inorganic oxide containing at least one element selected from Zr, Ce, and LaFeatures usedIt is said. This configuration,The following effects are obtained.
[0028]
(1) The catalyst deterioration due to the reaction between the inorganic oxide and the catalyst component can be prevented, and the oxidation performance of the particulates can be exhibited most efficiently and stably.
[0029]
  The present inventionExcretionGas purification catalystTiO ₂ Depending on the configuration of,The following effects are obtained.
[0030]
(1) The catalyst deterioration due to the reaction between the inorganic oxide and the catalyst component can be best prevented, and the particulate oxidation performance can be exhibited most efficiently and stably.
[0031]
  The present inventionExcretionGas purification catalyst, ResistantThermally conductive inorganic oxide has a particle size of 0.01 μm to 1000 μmmDepending on configuration,The following effects are obtained.
[0032]
(1) Since the inorganic oxide having heat resistance is a powder having a particle size of 0.01 μm to 1000 μm, preferably 0.1 μm to 50 μm, the particulates can be efficiently burned and removed, and the catalytic activity Can be increased.
[0033]
  Claims of the invention3The exhaust gas purifying catalyst according to claim 1, whereinOr 2The alkali metal sulfate contains at least one alkali metal sulfate selected from cesium sulfate and potassium sulfate. With this configuration, the claim1 or 2In addition to the above action, the following action is obtained.
[0034]
(1) Since the alkali metal sulfate contains at least one alkali metal sulfate selected from cesium sulfate and potassium sulfate, the particulates can be efficiently burned and removed, and the catalytic activity can be enhanced. it can.
[0035]
  Claims of the invention4The exhaust gas purification catalyst according to claim 1,Any one of 1 to 3The alkali metal sulfate has a structure containing cesium sulfate. With this configuration, claims 1 to3In addition to the above action, the following action is obtained.
[0036]
(1) Since the alkali metal sulfate contains cesium sulfate, the particulates can be burned and removed efficiently, and the catalytic activity can be enhanced.
[0047]
  Claims of the invention5The exhaust gas purifying material described in 1 is a heat-resistant three-dimensional structure and a three-dimensional structure on the three-dimensional structure.Using ethanol as solventClaims formed1 to 4The following actions are obtained by the configuration including the exhaust gas purification catalyst layer according to any one of the above.
[0048]
(1) By forming a catalyst component on the surface of the inorganic oxide having heat resistance, the surface area of the catalyst is increased. As a result, the contact point with the particulates in the diesel exhaust gas is increased. An exhaust gas purification material having a layer can be obtained.
[0049]
(2) By forming a catalyst component on the surface of the heat-resistant inorganic oxide, the required amount of catalyst can be reduced, and an exhaust gas purification material equipped with an exhaust gas purification catalyst can be obtained at a low cost. Excellent economy.
[0050]
(3) Since the catalyst component is formed on the inorganic oxide in advance and then supported on the heat-resistant three-dimensional structure, the reaction between the three-dimensional structure and the catalyst component is compared with the conventional catalyst solution impregnation method. And a highly active exhaust gas purification material can be obtained.
[0051]
(4) Since the catalyst component is generated on an inorganic oxide in advance and then supported on a heat-resistant three-dimensional structure, the amount of catalyst supported can be easily controlled compared to the conventional catalyst solution impregnation method. Thus, it is possible to obtain an exhaust gas purifying material having a loading amount according to the application.
[0052]
(5) Since the catalyst component is generated on the inorganic oxide in advance and then supported on the heat-resistant three-dimensional structure, the catalyst is uniformly supported on the three-dimensional structure compared to the conventional catalyst solution impregnation method. And a highly active exhaust gas purification material can be obtained.
[0053]
(6) Since the catalyst component is generated on the inorganic oxide in advance and then supported on the heat-resistant three-dimensional structure, the drying method in the manufacturing process is simplified compared to the conventional catalyst solution impregnation method. .
[0054]
The method for forming the exhaust gas purification catalyst on the heat-resistant three-dimensional structure is not particularly limited, and any method can be used, and examples thereof include an impregnation method and a wash coat method.
[0055]
  The present inventionExcretionGas purificationMaterialIs, ResistantThe inorganic oxide having heat has a configuration containing an inorganic oxide containing at least one element selected from Ta, Nb, W, Sn, Si, Ti, Al, Zr, Ce, and La. This configuration,The following effects are obtained.
[0056]
(1) The catalyst deterioration due to the reaction between the inorganic oxide and the catalyst component can be prevented, and the oxidation performance of the particulates can be exhibited most efficiently and stably.
[0057]
  The present inventionExcretionGas purificationMaterialIs, ResistantInorganic oxide with thermal properties is TiO₂It has the structure containing. This configuration,The following effects are obtained.
[0058]
(1) The catalyst deterioration due to the reaction between the inorganic oxide and the catalyst component can be best prevented, and the particulate oxidation performance can be exhibited most efficiently and stably.
[0059]
  The present inventionExcretionGas purificationMaterialIs, ResistantThermally conductive inorganic oxide has a particle size of 0.01 μm to 1000 μmmIt has the characteristics of being a powder in the range. This configuration,The following effects are obtained.
[0060]
(1) Since the inorganic oxide having heat resistance is a powder having a particle size of 0.01 μm to 1000 μm, preferably 0.1 μm to 50 μm, the particulates can be efficiently burned and removed, and the catalytic activity Can be increased.
[0061]
  The present inventionExcretionGas purificationMaterialIsAThe Lucari metal sulfate has at least one alkali metal sulfate selected from cesium sulfate and potassium sulfate. This configuration,The following effects are obtained.
[0062]
(1) Since the alkali metal sulfate contains at least one alkali metal sulfate selected from cesium sulfate and potassium sulfate, the particulates can be efficiently burned and removed, and the catalytic activity can be enhanced. it can.
[0063]
  The present inventionExcretionGas purificationMaterialIsALucari metal sulfate has a structure containing cesium sulfate. This configuration,The following effects are obtained.
[0064]
(1) Since the alkali metal sulfate contains cesium sulfate, the particulates can be burned and removed efficiently, and the catalytic activity can be enhanced.
[0075]
  The exhaust gas purifying material according to claim 6 of the present invention is the claim5The heat-resistant three-dimensional structure is a wall flow type honeycomb filter, or a flow through type honeycomb filter, foam, or metal filter. With this configuration, the claim5In addition to the actions described in (1), the following actions are obtained.
[0076]
(1) Since the tertiary structure having heat resistance is formed of a wall flow type honeycomb filter, a flow-through type honeycomb filter, a foam or a metal filter, about 100% of the particulate component is filtered. And the collection efficiency can be maximized.
[0077]
(2) Since the three-dimensional structure is formed of a wall flow type honeycomb filter, a flow-through type honeycomb filter, a foam or a metal filter, the contact area between the exhaust gas purification catalyst and the particulate increases. Thus, it is possible to efficiently burn and remove the particulates, and to obtain an exhaust gas purification material that is extremely excellent in exhaust gas purification ability.
[0078]
  Claim7The method for producing an exhaust gas purifying material described in 1 is applied to a heat-resistant three-dimensional structure.Using ethanol as solventClaim1 to 4The exhaust gas purification catalyst according to any one of the above is supported. With this configuration, the following effects can be obtained.
[0079]
(1) By forming a catalyst component on the surface of an inorganic oxide having heat resistance, the surface area of the catalyst is increased. As a result, the contact point with particulates in diesel exhaust gas is increased, and a highly active exhaust gas purification catalyst is obtained. The manufacturing method of the exhaust gas purification material provided can be provided.
[0080]
(2) By forming a catalyst component on the surface of a heat-resistant inorganic oxide, the required amount of catalyst can be reduced, and a method for producing an exhaust gas purification material equipped with an exhaust gas purification catalyst can be obtained at low cost. And is economical.
[0081]
(3) Since the catalyst component is formed on the inorganic oxide in advance and then supported on the heat-resistant three-dimensional structure, the reaction between the three-dimensional structure and the catalyst component is compared with the conventional catalyst solution impregnation method. And a method for producing a highly active exhaust gas purification material can be provided.
[0082]
(4) Since the catalyst component is generated on an inorganic oxide in advance and then supported on a heat-resistant three-dimensional structure, the amount of catalyst supported can be easily controlled compared to the conventional catalyst solution impregnation method. Thus, it is possible to obtain an exhaust gas purifying material having a loading amount according to the application.
[0083]
(5) Since the catalyst component is generated on the inorganic oxide in advance and then supported on the heat-resistant three-dimensional structure, the catalyst is uniformly supported on the three-dimensional structure compared to the conventional catalyst solution impregnation method. And a highly active exhaust gas purification material can be obtained.
[0084]
(6) Since the catalyst component is generated on the inorganic oxide in advance and then supported on the heat-resistant three-dimensional structure, the drying method in the manufacturing process is simplified compared to the conventional catalyst solution impregnation method. .
[0087]
  Claim8The method for producing an exhaust gas purifying material according to claim 11 to 4When the exhaust gas purifying catalyst described in any of the above is supported on a heat-resistant three-dimensional structure, ethanol is used as a solvent. With this configuration, the following effects can be obtained.
[0088]
(1) The solvent is inexpensive and the particulates can be burned at a lower temperature.
[0089]
  Claim9The method for producing an exhaust gas purifying material according to claim 18In, it has the structure that ethanol is absolute ethanol. With this configuration, the following effects can be obtained.
[0090]
(1) The particulates can be burned at a lower temperature without containing water.
[0091]
Each structure of the exhaust gas purification catalyst and the exhaust gas purification material in one embodiment of the present invention will be described.
[0092]
First, an inorganic oxide having heat resistance as a carrier for supporting a catalyst component will be described. Examples of the heat-resistant inorganic oxide supporting a catalyst component containing at least an alkali metal sulfate and a transition metal oxide include Ta, Nb, W, Sn, Si, Ti, Al, Zr, Ce, and La. An inorganic oxide containing at least one element selected from can be used.
[0093]
Specific examples of these inorganic oxides include Ta₂O_Five, Nb₂O_Five, WO_Three, SnO₂, SiO₂, TiO₂, Al₂O_Three, ZrO₂, CeO₂, La₂O_ThreeOf these, one or more of these oxides can be used.
[0094]
The catalyst component containing at least the alkali metal sulfate and the transition metal oxide is supported on the surface of the inorganic oxide, thereby increasing the surface area of the catalyst component and increasing the chance of contact with the particulate. Purification efficiency is improved. Furthermore, the required amount of catalyst can be reduced, and the cost can be reduced. Furthermore, by using these inorganic oxides as a support, deterioration of the catalyst component due to the reaction between the support and the catalyst component can be prevented, and the particulate oxidation performance by the catalyst component can be exhibited efficiently and stably. It becomes possible.
[0095]
Among these inorganic oxides, TiO₂(Titania) is particularly preferred because it can best prevent deterioration of the catalyst component due to reaction with the catalyst component.
[0096]
Further, these heat-resistant inorganic oxides are powders having a particle size in the range of 0.01 μm to 1000 μm, preferably 0.1 μm to 50 μm, so that the particulates can be burned and removed efficiently. And the catalytic activity can be increased.
[0097]
Next, the alkali metal sulfate will be described. Examples of the alkali metal include lithium (Li), sodium (Na), potassium (K), rubidium (Rb), and cesium (Cs), and one or more sulfates of these alkali metals can be used. .
[0098]
Specific examples of the alkali metal sulfate include lithium sulfate, sodium sulfate, potassium sulfate, rubidium sulfate, and cesium sulfate, and it is particularly preferable to contain cesium sulfate alone or a mixture of cesium sulfate and potassium sulfate. .
Use of alkali metal sulfate improves durability against sulfur oxides in exhaust gas, prevents catalyst components from being deteriorated by sulfur oxides, and maximizes catalytic activity against particulates. be able to.
[0104]
Here, the alkali metal sulfate and the transition metal oxide are preferably supported uniformly on the inorganic oxide. Further, the alkali metal sulfate and transition metal oxide supported on the surface of the inorganic oxide may be in a continuous layer state or a discontinuous stripe state on the surface of the inorganic oxide. Also good. Furthermore, a state in which an alkali metal sulfate or a transition metal oxide is dispersed may be used. That is, in the present invention, the exhaust gas purification catalyst layer includes a discontinuous striped state and a dispersed state.
[0105]
In addition, as the heat-resistant three-dimensional structure that supports the above-described exhaust gas purification catalyst, a material such as metal or ceramic is used.
[0106]
As the metal, an alloy such as iron, copper, nickel, chromium, etc., alone or in combination of two or more kinds can be used.
[0107]
As the ceramic material, cordierite, aluminum titanate, mullite, α-alumina, zirconia, titania, silicon carbide, silica, silica / alumina, alumina / zirconia, or the like can be used.
[0108]
As the heat-resistant three-dimensional structure on which the exhaust gas purification catalyst layer is formed, a wall flow type ceramic honeycomb, a flow through type ceramic honeycomb, a metal honeycomb, a metal foam, a metal mesh, a ceramic foam, or the like is used. A wall flow type ceramic honeycomb is preferably used.
[0109]
A wall-through type honeycomb filter, or a flow-through type foam or metal filter is preferable.
[0110]
Here, the material of the honeycomb-shaped filter is not particularly limited, but metal, ceramic, or the like is used. Cordierite is preferably used as the material for the honeycomb filter.
[0111]
The shape of the foam may be any foam type filter having pores continuous in the three-dimensional direction.
[0112]
Although the material of a foam is not specifically limited, such as a metal and a ceramic, the cordierite ceramic foam is used suitably.
[0113]
The number of cells of the honeycomb filter is preferably 50 cells to 500 cells / square inch, and more preferably 100 cells to 400 cells / square inch. The foaming ratio of the foam is preferably 5 to 50 / square inch, and more preferably 10 to 30 / square inch.
[0114]
Further, the method for supporting the alkali metal sulfate and the transition metal oxide on the surface of the inorganic oxide having heat resistance is not particularly limited, and any method can be used. Etc. are preferred.
[0115]
Furthermore, the method for forming the exhaust gas purification catalyst on the heat-resistant three-dimensional structure is not particularly limited, and any method can be used. Examples thereof include an impregnation method and a wash coating method.
[0116]
In addition, when the powdery catalyst is supported on a heat-resistant three-dimensional structure, alcohol can be used as a solvent so that particulates can be combusted at a lower temperature than when water is used as the solvent. Can do. In particular, the alcohol is preferably ethanol, and more preferably absolute ethanol. By using absolute ethanol, the particulates can be burned at a lower temperature without containing water. Although the detailed mechanism is not clear, when water is used as the solvent, it is considered that the catalyst component is dissolved in water, and as a result, the amount supported on the three-dimensional structure is reduced. On the other hand, when alcohol is used, it is considered that the catalyst component does not dissolve in the solvent, the supported amount can be maintained and high activity can be obtained.
[0117]
INDUSTRIAL APPLICABILITY The present invention can be used not only for exhaust gas from automobile engines, but also for removing particulates from engines such as cultivators, ships and trains, industrial engines, combustion furnaces and boilers.
[0118]
Note that the present invention is not limited to the above-described embodiment, and various modifications can be made without departing from the spirit of the present invention.
[0119]
【Example】
Hereinafter, more specific embodiments will be described.
[0120]
  Example 1
  1000 g of titania powder (Ishihara Sangyo, MC-90, particle size 1 μm), 100 g of copper sulfate pentahydrate (made by Wako Pure Chemical) as a copper salt, and vanadium oxide sulfate (made by Wako Pure Chemical) as a vanadium salt 120 g, 850 g of cesium sulfate (manufactured by Soekawa Rikagaku) as an alkali sulfate, 0.53 g of manganese acetate tetrahydrate (manufactured by Wako Pure Chemical Industries) as a manganese salt, and 3300 g of purified water were added to the cold evaporator. And dried under reduced pressure, and the obtained powder was baked in an electric furnace at 700 ° C for 5 hours,powderA body catalyst was obtained.
[0121]
  (Comparative Example 1)
  1000 g of titania powder (Ishihara Sangyo, MC-90, particle size 1 μm), 100 g of copper sulfate pentahydrate (made by Wako Pure Chemical) as a copper salt, and vanadium oxide sulfate (made by Wako Pure Chemical) as a vanadium salt After adding 3300 g of purified water to 120 g and 0.5 g of manganese acetate tetrahydrate (manufactured by Wako Pure Chemical Industries, Ltd.) as a manganese salt, the mixture was sufficiently stirred and dried under reduced pressure with a cold evaporator. Firing at 700 ° C for 5 hours in an electric furnace, TouchA medium powder was obtained.
[0122]
10 g of the powder obtained above and 10 g of cesium sulfate were mixed in a powder state in an agate mortar to obtain a powder catalyst.
[0123]
(Evaluation example 1)
The following particulate combustion experiments were conducted on the powder catalysts obtained in Example 1 and Comparative Example 1.
[0124]
Each powder catalyst and simulated particulate (carbon made by Nacalai) were mixed at a weight ratio of 1: 1 in a mortar, and this mixture was filled into a reaction tube made of quartz glass having an inner diameter of 12 mm. 4 vol% oxygen and 70 ppm SO in the reaction tube₂Then, the inside of the reaction tube was heated at a constant speed in a tubular electric furnace disposed on the outer periphery of the reaction tube while a test gas composed of nitrogen gas containing 100 ppm of NO gas was vented at a flow rate of 500 cc / min. At this time, the carbon dioxide concentration in the test gas is detected by a carbon dioxide sensor disposed at the position on the exhaust gas side, and the temperature at which 5% particulate burns (hereinafter abbreviated as 5% combustion temperature). It was determined. Filled particulate carbon (known amount) and generated CO + CO₂The combustion rate was calculated from the quantity (measured value). The 5% combustion temperature of each exhaust gas purification catalyst in the combustion test is shown in Table 1.
[0125]
[Table 1]

As is clear from (Table 1), the exhaust gas purification catalyst obtained in Example 1 is more preferable than the exhaust gas purification catalyst obtained in Comparative Example 1 as an exhaust gas purification catalyst even when the same type of catalyst composition is used. It was found that particulates can be burned at low temperatures.
[0126]
(Example 2)
Ta instead of titania as catalyst support₂O_FiveA powder catalyst was obtained in the same manner as in Example 1 except that was used.
[0127]
(Example 3)
Nb instead of titania as catalyst support₂O_FiveA powder catalyst was obtained in the same manner as in Example 1 except that was used.
[0128]
Example 4
WO instead of titania as catalyst support_ThreeA powder catalyst was obtained in the same manner as in Example 1 except that was used.
[0129]
(Example 5)
SnO instead of titania as catalyst support₂A powder catalyst was obtained in the same manner as in Example 1 except that was used.
[0130]
(Example 6)
SiO instead of titania as catalyst support₂A powder catalyst was obtained in the same manner as in Example 1 except that was used.
[0131]
(Example 7)
Al instead of titania as catalyst support₂O_ThreeA powder catalyst was obtained in the same manner as in Example 1 except that was used.
[0132]
(Example 8)
ZrO instead of titania as catalyst support₂A powder catalyst was obtained in the same manner as in Example 1 except that was used.
[0133]
Example 9
CeO instead of titania as catalyst support₂A powder catalyst was obtained in the same manner as in Example 1 except that was used.
[0134]
(Example 10)
La instead of titania as catalyst support₂O_ThreeA powder catalyst was obtained in the same manner as in Example 1 except that was used.
[0135]
(Comparative Example 2)
Fe instead of titania as catalyst support₂O_ThreeA powder catalyst was obtained in the same manner as in Example 1 except that was used.
[0136]
(Evaluation example 2)
In Examples 2 to 10 and Comparative Example 2, a particulate combustion experiment was conducted in the same manner as in Evaluation Example 1. The 5% combustion temperature of each exhaust gas purification catalyst in the combustion test is shown in Table 2 together with Example 1.
[0137]
[Table 2]

As is clear from Table 2, when the exhaust gas purification catalyst having the same structure is used, Examples 2 to 10 and Examples are more effective than the exhaust gas purification catalyst using the carrier shown in Comparative Example 2 as the carrier to be used. It was found that the exhaust gas purification catalyst using the carrier shown in 1 can burn particulates at a low temperature.
[0138]
(Example 11)
A powder catalyst was obtained in the same manner as in Example 1 except that 0.01 μm titania was used instead of 1 μm titania as the catalyst support.
[0139]
Example 12
A powder catalyst was obtained in the same manner as in Example 1 except that 0.1 μm titania was used instead of 1 μm titania as the catalyst support.
[0140]
(Example 13)
A powder catalyst was obtained in the same manner as in Example 1 except that 10 μm titania was used instead of 1 μm titania as the catalyst support.
[0141]
(Example 14)
A powder catalyst was obtained in the same manner as in Example 1 except that 50 μm titania was used instead of 1 μm titania as the catalyst support.
[0142]
(Example 15)
A powder catalyst was obtained in the same manner as in Example 1 except that 1000 μm titania was used instead of 1 μm titania as the catalyst support.
[0143]
(Comparative Example 3)
A powder catalyst was obtained in the same manner as in Example 1 except that 0.001 μm titania was used instead of 1 μm titania as the catalyst support.
[0144]
(Comparative Example 4)
A powder catalyst was obtained in the same manner as in Example 1 except that 10000 μm titania was used instead of 1 μm titania as the catalyst support.
[0145]
(Evaluation example 3)
In Examples 11 to 15 and Comparative Examples 3 to 4, particulate combustion experiments were performed in the same manner as in Evaluation Example 1. The 5% combustion temperature of each exhaust gas purification catalyst in the combustion test is shown in Table 3 together with Example 1.
[0146]
[Table 3]

As is clear from Table 3, when the exhaust gas purification catalyst having the same structure is used, Examples 11 to 15 and Example 1 are used as catalyst carriers to be used rather than the exhaust gas purification catalysts obtained in Comparative Examples 3 to 4. It has been found that the exhaust gas purification catalyst using the carrier shown in FIG. 1, preferably the exhaust gas purification catalyst using the carrier shown in Examples 12 to 14 and Example 1, can burn particulates at a low temperature.
[0147]
(Example 16)
A powder catalyst was obtained in the same manner as in Example 1, except that potassium sulfate and cesium sulfate were mixed at a weight ratio of 1: 1 instead of cesium sulfate as the alkali sulfate.
[0148]
(Example 17)
A powder catalyst was obtained in the same manner as in Example 1 except that lithium sulfate was used in place of cesium sulfate as the alkali sulfate.
[0149]
(Example 18)
A powder catalyst was obtained in the same manner as in Example 1 except that sodium sulfate was used in place of cesium sulfate as the alkali sulfate.
[0150]
(Example 19)
A powder catalyst was obtained in the same manner as in Example 1 except that potassium sulfate was used as the alkali sulfate instead of cesium sulfate.
[0151]
(Example 20)
A powder catalyst was obtained in the same manner as in Example 1 except that rubidium sulfate was used as the alkali sulfate instead of cesium sulfate.
[0152]
(Comparative Example 5)
A powder catalyst was obtained in the same manner as in Example 1 except that calcium sulfate was used instead of cesium sulfate.
[0153]
(Evaluation example 4)
In Examples 16 to 20 and Comparative Example 5, a particulate combustion experiment was performed in the same manner as in Evaluation Example 1. The 5% combustion temperature of each exhaust gas purification catalyst in the combustion test is shown in Table 4 together with Example 1.
[0154]
[Table 4]

As is clear from (Table 4), when the exhaust gas purification catalyst having the same structure was used, the alkali sulfates shown in Examples 16 to 20 and Example 1 were used rather than the exhaust gas purification catalyst obtained in Comparative Example 5. It was found that the exhaust gas purification catalyst used, preferably the exhaust gas purification catalyst using the alkali sulfate shown in Example 16 and Example 1, can burn particulates at a low temperature.
[0155]
  (referenceExample1)
  Copper-vanadium complex oxide (Cu_FiveV₂O_Ten) And manganese oxide instead of manganese oxide were used in the same manner as in Example 1 to obtain a powder catalyst.
[0156]
  (referenceExample2)
  Copper-vanadium complex oxide (Cu_FiveV₂O_Ten) And manganese oxide instead of MnO₂A powder catalyst was obtained in the same manner as in Example 1 except that was used.
[0157]
  (referenceExample3)
  Copper-vanadium complex oxide (Cu_FiveV₂O_Ten) And CoO instead of manganese oxide_ThreeA powder catalyst was obtained in the same manner as in Example 1 except that was used.
[0158]
  (referenceExample4)
  Copper-vanadium complex oxide (Cu_FiveV₂O_Ten) And V instead of manganese oxide₂O_FiveA powder catalyst was obtained in the same manner as in Example 1 except that was used.
[0159]
  (referenceExample5)
  Copper-vanadium complex oxide (Cu_FiveV₂O_Ten) And MoO instead of manganese oxide_ThreeA powder catalyst was obtained in the same manner as in Example 1 except that was used.
[0160]
  (referenceExample6)
  Copper-vanadium complex oxide (Cu_FiveV₂O_Ten) And manganese oxide instead of WO_ThreeA powder catalyst was obtained in the same manner as in Example 1 except that was used.
[0161]
  (referenceExample7)
  Copper-vanadium complex oxide (Cu_FiveV₂O_Ten) And Cu instead of manganese oxide₂A powder catalyst was obtained in the same manner as in Example 1 except that O was used.
[0162]
  (referenceExample8)
  Copper-vanadium complex oxide (Cu_FiveV₂O_Ten) And Cu instead of manganese oxide₂O_ThreeA powder catalyst was obtained in the same manner as in Example 1 except that was used.
[0163]
  (referenceExample9)
  Copper-vanadium complex oxide (Cu_FiveV₂O_TenCopper-vanadium complex oxide (CuV)₂O₆) Was used in the same manner as in Example 1 to obtain a powder catalyst.
[0164]
  (referenceExample10)
  Copper-vanadium complex oxide (Cu_FiveV₂O_Ten) Copper-vanadium complex oxide (Cu_ThreeV₂O₈) Was used in the same manner as in Example 1 to obtain a powder catalyst.
[0165]
(Comparative Example 6)
Copper-vanadium complex oxide (Cu_FiveV₂O_Ten) And LaMnCoO instead of manganese oxide_ThreeA powder catalyst was obtained in the same manner as in Example 1 except that was used.
[0166]
  (Evaluation example 5)
  referenceExample1~referenceExample10In Comparative Example 6, a particulate combustion experiment was performed in the same manner as in Evaluation Example 1. The 5% combustion temperature of each exhaust gas purifying material in the combustion test is shown in Table 5 together with Example 1.
[0167]
[Table 5]

As is clear from (Table 5), when the exhaust gas purification catalyst having the same structure is used, the metal oxide of the transition metal to be supported is more than the exhaust gas purification catalyst obtained in Comparative Example 6.referenceExample1~referenceExample10It was also found that the exhaust gas purification catalyst carrying the compound shown in Example 1 can burn particulates at a lower temperature.
[0168]
  (Example21)
  75 g of the powder obtained in Example 1, 3 g of fluorene (manufactured by G-7000 Kyoeisha Chemical Co., Ltd.), 430 g of absolute ethanol, and 1000 g of 2 mm zirconia balls as a dispersant are placed in a 1000 ml sealed container, and a slurry disperser (Red Devil) For 2 hours to obtain a slurry.
[0169]
A slurry obtained by adding 5 g of fluorene and 850 g of absolute ethanol as a dispersant to the obtained slurry to obtain a diluted slurry was obtained.
[0170]
Next, a wall flow type cordierite filter (NGK 5.66 inches, 100 cells / inch) as a heat-resistant three-dimensional structure.²) Is cut into 2 cells × 5 cells × 15 mm, impregnated with the slurry solution obtained above, excess slurry is removed with an air gun, dried at 60 ° C. with a dryer, and then placed in an electric furnace. The exhaust gas purification material was manufactured by heat-treating at 600 ° C. for 5 hours.
[0171]
(Comparative Example 7)
500 g of copper sulfate pentahydrate (manufactured by Wako Pure Chemical Industries) as a copper salt, 700 g of vanadium oxide sulfate (manufactured by Wako Pure Chemical Industries) as a salt of vanadium, and 1000 g of cesium sulfate (manufactured by Soekawa Riken) as an alkali sulfate 3 g of manganese acetate tetrahydrate (manufactured by Wako Pure Chemical Industries, Ltd.) as a manganese salt was added to 3000 g of purified water and sufficiently stirred to obtain an aqueous catalyst solution.
[0172]
A wall flow type cordierite filter (manufactured by NGK, 5.66 inch, 100 cells / inch) as a heat-resistant three-dimensional structure is added to the obtained aqueous solution²) Was cut into 2 cells × 5 cells × 15 mm, impregnated with the aqueous solution obtained above, and the excess solution was removed with an air gun, dried at 60 ° C. with a drier, and then 700 with an electric furnace. An exhaust gas purification material was produced by heat treatment at 5 ° C. for 5 hours.
[0173]
  (Evaluation example 6)
  Example21The exhaust gas purification material obtained in Comparative Example 7 was subjected to the following particulate combustion experiment.
[0174]
  Example21One of the exhaust gas purifying materials obtained in Comparative Example 7 was loaded with a simulated particulate (carbon made by Nacalai) on the filter surface and filled into a quartz glass reaction tube having an inner diameter of 12 mm.
[0175]
4 vol% oxygen and 70 ppm SO in the reaction tube₂Then, the inside of the reaction tube was heated at a constant speed in a tubular electric furnace disposed on the outer periphery of the reaction tube while venting a test gas composed of nitrogen gas containing 100 ppm NO gas at a flow rate of 500 cc / min. The carbon dioxide concentration in the test gas is detected by a carbon dioxide sensor disposed at a position on the gas outflow side, and the temperature at which 5% particulate burns (hereinafter abbreviated as 5% combustion temperature) is used. Were determined. Filled particulate carbon (known amount) and generated CO + CO₂The combustion rate was calculated from the quantity (measured value). Table 5 shows the 5% combustion temperature of each exhaust gas purifying material in the combustion test.
[0176]
[Table 6]

As is clear from Table 6, even when the same type of catalyst composition was used, the examples21It was found that the exhaust gas purification material obtained in the above can burn particulates at a lower temperature than the exhaust gas purification material obtained in Comparative Example 7.
[0177]
  (Example22)
  Ta instead of titania as catalyst support₂O_FiveOther than using21In the same manner, an exhaust gas purifying material was obtained.
[0178]
  (Example23)
  Nb instead of titania as catalyst support₂O_FiveOther than using21In the same manner, an exhaust gas purifying material was obtained.
[0179]
  (Example24)
  WO instead of titania as catalyst support_ThreeOther than using21In the same manner, an exhaust gas purifying material was obtained.
[0180]
  (Example25)
  SnO instead of titania as catalyst support₂Other than using21In the same manner, an exhaust gas purifying material was obtained.
[0181]
  (Example26)
  SiO instead of titania as catalyst support₂Other than using21In the same manner, an exhaust gas purifying material was obtained.
[0182]
  (Example27)
  Al instead of titania as catalyst support₂O_ThreeOther than using21In the same manner, an exhaust gas purifying material was obtained.
[0183]
  (Example28)
  ZrO instead of titania as catalyst support₂Other than using21In the same manner, an exhaust gas purifying material was obtained.
[0184]
  (Example29)
  CeO instead of titania as catalyst support₂Other than using21In the same manner, an exhaust gas purifying material was obtained.
[0185]
  (Example30)
  La instead of titania as catalyst support₂O_ThreeOther than using21In the same manner, an exhaust gas purifying material was obtained.
[0186]
  (Comparative Example 8)
  Fe instead of titania as catalyst support₂O_ThreeOther than using21In the same manner, an exhaust gas purifying material was obtained.
[0187]
  (Evaluation example 7)
  Example22~Example30In Comparative Example 8, a particulate combustion experiment was conducted in the same manner as in Evaluation Example 6. The 5% combustion temperature of each exhaust gas purifying material in the combustion test is shown in Table 7 together with Example 1.
[0188]
[Table 7]

As is clear from Table 7, when the exhaust gas purification catalyst having the same structure is used, the catalyst carrier to be used is more practical than the exhaust gas purification material using the carrier shown in Comparative Example 8.21~Example30It was found that the exhaust gas purifying material using the carrier shown in 1 can burn particulates at a lower temperature.
[0189]
  (Example31)
  Example 1 except that 0.01 μm titania was used instead of 1 μm titania as the catalyst support21In the same manner, an exhaust gas purifying material was obtained.
[0190]
  (Example32)
  Example 1 except that 0.1 μm titania was used instead of 1 μm titania as the catalyst support21In the same manner, an exhaust gas purifying material was obtained.
[0191]
  (Example33)
  Example 1 except that 10 μm titania was used instead of 1 μm titania as the catalyst support21In the same manner, an exhaust gas purifying material was obtained.
[0192]
  (Example34)
  Example 1 except that 50 μm titania was used instead of 1 μm titania as the catalyst support21In the same manner, an exhaust gas purifying material was obtained.
[0193]
  (Example35)
  Example 1 except that 1000 μm titania was used instead of 1 μm titania as the catalyst support21In the same manner, an exhaust gas purifying material was obtained.
[0194]
  (Comparative Example 9)
  Example 1 except that 0.001 μm titania was used instead of 1 μm titania as the catalyst support21In the same manner, an exhaust gas purifying material was obtained.
[0195]
  (Comparative Example 10)
  Example 1 except that 10000 μm titania was used instead of 1 μm titania as the catalyst support21In the same manner, an exhaust gas purifying material was obtained.
[0196]
  (Evaluation example 8)
  Example31~Example35In Comparative Examples 9 to 10, the particulate combustion experiment was performed in the same manner as in Evaluation Example 6. The 5% combustion temperature of each exhaust gas purifying material in the combustion test is shown in Table 8 together with Example 1.
[0197]
[Table 8]

As is clear from (Table 8), when the exhaust gas purification catalyst having the same structure is used, the catalyst carrier to be used is more practical than the exhaust gas purification material obtained in Comparative Examples 9 to 10.31~Example35And examples21Exhaust gas purification material using the carrier shown in FIG.32~Example34And examples21It was found that the exhaust gas purifying material using the carrier shown in 2 can burn particulates at low temperatures.
[0198]
  (Example36)
  Except for using alkaline sulfate as a mixture of potassium sulfate and cesium sulfate at a weight ratio of 1: 1 instead of cesium sulfate,21In the same manner, an exhaust gas purifying material was obtained.
[0199]
  (Example37)
  Except for using lithium sulfate instead of cesium sulfate as the alkali sulfate,21In the same manner, an exhaust gas purifying material was obtained.
[0200]
  (Example38)
  Except for using sodium sulfate instead of cesium sulfate as the alkali sulfate,21In the same manner, an exhaust gas purifying material was obtained.
[0201]
  (Example39)
  Example 1 except that potassium sulfate was used instead of cesium sulfate as the alkali sulfate.21In the same manner, an exhaust gas purifying material was obtained.
[0202]
  (Example40)
  Except for using rubidium sulfate instead of cesium sulfate as alkali sulfate,21In the same manner, an exhaust gas purifying material was obtained.
[0203]
  (Comparative Example 11)
  Except for using calcium sulfate instead of cesium sulfate,21In the same manner, an exhaust gas purifying material was obtained.
[0204]
  (Evaluation example 9)
  Example36~Example40In Comparative Example 11, a particulate combustion experiment was conducted in the same manner as in Evaluation Example 6. Example of 5% combustion temperature of each exhaust gas purifying material in the above combustion test21(Table 9).
[0205]
[Table 9]

As is clear from (Table 9), when the exhaust gas purification catalyst having the same structure was used, the embodiment was more effective than the exhaust gas purification material obtained in Comparative Example 11.36~Example40And examples21Exhaust gas purification material using the alkali sulfate shown in FIG.36And examples21It was found that the exhaust gas purification material using the alkali sulfate shown in Fig. 1 can burn particulates at a low temperature.
[0206]
  (referenceExample11)
  Copper-vanadium complex oxide (Cu_FiveV₂O_TenAnd CuO instead of manganese oxide,21In the same manner, an exhaust gas purifying material was obtained.
[0207]
  (referenceExample12)
  Copper-vanadium complex oxide (Cu_FiveV₂O_Ten) And manganese oxide instead of MnO₂Other than using21In the same manner, an exhaust gas purifying material was obtained.
[0208]
  (referenceExample13)
  Copper-vanadium complex oxide (Cu_FiveV₂O_Ten) And CoO instead of manganese oxide_ThreeOther than using21In the same manner, an exhaust gas purifying material was obtained.
[0209]
  (referenceExample14)
  Copper-vanadium complex oxide (Cu_FiveV₂O_Ten) And V instead of manganese oxide₂O_FiveOther than using21In the same manner, an exhaust gas purifying material was obtained.
[0210]
  (referenceExample15)
  Copper-vanadium complex oxide (Cu_FiveV₂O_Ten) And MoO instead of manganese oxide_ThreeOther than using21In the same manner, an exhaust gas purifying material was obtained.
[0211]
  (referenceExample16)
  Copper-vanadium complex oxide (Cu_FiveV₂O_Ten) And manganese oxide instead of WO_ThreeOther than using21In the same manner, an exhaust gas purifying material was obtained.
[0212]
  (referenceExample17)
  Copper-vanadium complex oxide (Cu_FiveV₂O_Ten) And Cu instead of manganese oxide₂Other than using O, Examples21In the same manner, an exhaust gas purifying material was obtained.
[0213]
  (referenceExample18)
  Copper-vanadium complex oxide (Cu_FiveV₂O_Ten) And Cu instead of manganese oxide₂O_ThreeOther than using21In the same manner, an exhaust gas purifying material was obtained.
[0214]
  (referenceExample19)
  Copper-vanadium complex oxide (Cu_FiveV₂O_TenCopper-vanadium complex oxide (CuV)₂O₆) Except that21In the same manner, an exhaust gas purifying material was obtained.
[0215]
  (referenceExample20)
  Copper-vanadium complex oxide (Cu_FiveV₂O_Ten) Copper-vanadium complex oxide (Cu_ThreeV₂O₈) Except that21In the same manner, an exhaust gas purifying material was obtained.
[0216]
  (Comparative Example 12)
  Copper-vanadium complex oxide (Cu_FiveV₂O_Ten) And LaMnCoO instead of manganese oxide_ThreeOther than using21In the same manner, an exhaust gas purifying material was obtained.
[0217]
  (Evaluation example 10)
  referenceExample11~referenceExample20In Comparative Example 12, a particulate combustion experiment was performed in the same manner as in Evaluation Example 6. Example of 5% combustion temperature of each exhaust gas purifying material in the above combustion test21(Table 10).
[0218]
[Table 10]

As is clear from (Table 10), when the exhaust gas purification catalyst having the same structure is used, the metal oxide of the transition metal to be supported is more than the exhaust gas purification material obtained in Comparative Example 12.referenceExample11~referenceExample20And examples21It was found that the exhaust gas purifying material carrying the indicated compound can burn particulates at a lower temperature.
[0219]
  (Example41)
  Example 1 except that ethanol containing 10% water was used instead of absolute ethanol as the solvent for the catalyst slurry.21In the same manner, an exhaust gas purifying material was obtained.
[0220]
  (Comparative Example 13)
  Except that purified water was used instead of absolute ethanol as a solvent for the catalyst slurry,21In the same manner, an exhaust gas purifying material was obtained.
[0221]
  (Evaluation example 11)
  Example41In Comparative Example 13, a particulate combustion experiment was performed in the same manner as in Evaluation Example 6. Example of 5% combustion temperature of each exhaust gas purifying material in the above combustion test21(Table 11).
[0222]
[Table 11]

As is clear from (Table 11), when the exhaust gas purifying catalyst having the same structure is used, the metal oxide of the transition metal to be supported is more practical than the exhaust gas purifying material obtained in Comparative Example 13.41The exhaust gas purifying material carrying the compound shown in 1 can burn particulates at a lower temperature.21It was found that the exhaust gas purifying material carrying the compound shown in (1) can burn particulates at a lower temperature.
[0223]
【The invention's effect】
As described above, according to the exhaust gas purification catalyst of the present invention, the exhaust gas purification material using the same, and the method for producing the same, it is possible to provide an exhaust gas purification catalyst and an exhaust gas purification material having high catalytic activity for burning particulates. An excellent effect is obtained that the particulates in the exhaust gas can be burned and removed at a low temperature close to.

Claims (9)

  It was obtained by adding water to a titania powder having a particle size of 0.01 μm to 1000 μm, a copper salt, a vanadium salt, an alkali metal sulfate, and a manganese salt, stirring, drying, and firing. An exhaust gas purification catalyst characterized by that.   The inorganic oxide containing at least one element selected from Ta, Nb, W, Sn, Si, Al, Zr, Ce, and La is used instead of titania. Exhaust gas purification catalyst.   The exhaust gas purification catalyst according to claim 1 or 2, wherein the alkali metal sulfate contains at least one alkali metal sulfate selected from cesium sulfate and potassium sulfate.   The exhaust gas purification catalyst according to any one of claims 1 to 3, wherein the alkali metal sulfate contains cesium sulfate. A three-dimensional structure having heat resistance, and an exhaust gas purification catalyst layer according to any one of claims 1 to 4 formed using ethanol as a solvent on the three-dimensional structure. Exhaust gas purification material. 6. The exhaust gas purifying material according to claim 5 , wherein the heat-resistant three-dimensional structure is a wall flow type honeycomb filter, or a flow through type honeycomb filter, foam or metal filter. The method of manufacturing the exhaust gas purifying material characterized by carrying the exhaust gas purifying catalyst according to any one using ethanol of claims 1 to 4 as a solvent in a three-dimensional structure having a heat resistance. A method for producing an exhaust gas purification material, wherein ethanol is used as a solvent when the exhaust gas purification catalyst according to any one of claims 1 to 4 is supported on a three-dimensional structure having heat resistance. The method for producing an exhaust gas purifying material according to claim 8 , wherein the ethanol is absolute ethanol.