JP2010527877A - 金属ドープゼオライト及びその製造プロセス - Google Patents
金属ドープゼオライト及びその製造プロセス Download PDFInfo
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Abstract
【選択図】 なし
Description
Mn+ n[ (AlO2)x(SiO2)y]itH2O
これは、通常三次元ネットワークを形成する共通の酸素原子によって結びつけられた四面体のSiO4/2及びAlO4/2を有する。Si/Al=y/x比は、いわゆる“Lowenstein Rule(ここで、「o」の文字はウムラウト)”に従っていつも1以上であり、それは、2つの近くにある負電荷の四面体のAlO4 -は互いに隣り合わないであろうことを示す。従って、より多くの交換スペースは、低いSi/Al比を有する金属に対して利用できるが、一方で、前記ゼオライトは、ますます熱的に不安定になる。
a) 8〜10の範囲の値に前記懸濁液のpHを増加させ、好ましくはNH4OH(アンモニア水)を用いて該pHを増加させ、且つ前記反応容器の酸素レベルを10%未満、好ましくは5%未満の値にセットするステップと、
b)1.5〜6の範囲の値に前記pHを減少させるステップと、
c)金属塩を加え、そして1〜15時間にわたって反応させるステップと、
d)前記金属交換(ドープ)ゼオライトを濾過し洗浄するステップと
を含んでいる、前記金属交換ドープゼオライトの生成のためのプロセスによって達成される。
UV/VIS MIR拡散反射測定は、拡散反射を有するPerkin Elmer UV/VISスペクトロメータと、参照としてのBaSO4とを用いて、本発明に従って得られたゼオライトにおいて実施された。吸収強度は、Schuster-Kubelka-Munk式(しばしば、Kubelka Munk理論とも呼ばれる。)に従って求められた。
鉄交換(若しくはドープ)ゼオライトの生成
2 gのNH4-ZSM5(代わりにH-ZSM5若しくはNa-ZSM5も用いられた。)は、水溶液に該水溶液に対して10〜15重量%の量で懸濁され、室温下でかき混ぜられた。そして、アンモニア水の形態でのアンモニアが、ゼオライトに対するNH3の比0.04で加えられ、その結果、9よりも大きいpHがセットされた。該pHはほとんど10であった。
このようにして得られた鉄交換ゼオライトは、SCR反応中に仮にあったとしてもほんのわずかしか活性がない多核の鉄クラスター(即ち、3よりも多い鉄原子)に割り当てられた10 - 25,000 cm-1の範囲の波長でのバンドを示さなかった。
コバルト交換ゼオライトの生成
硫酸鉄(FeSO4・7 H2O)の代わりに、対応する量のCo(NO3)2若しくは代わりのCo(acac)2((acac)=アセチルアセトネート)が用いられたこと以外は、例1と同様に反応が実施された。硫酸の代わりに、対応する量の0.01 MのHNO3が用いられた。
銅交換ゼオライトの生成
対応する量の銅−アセチルアセトネート溶液が金属塩として用いられ、さらに0.01 MのHNO3が酸として用いられたこと以外は、例1と同様に合成が行われた。
銀交換ゼオライトの生成
AgNO3が金属塩として用いられ、且つ0.01 MのHNO3が酸として用いられたこと以外は、例1と同様に合成が行われた。
ニッケル交換ゼオライトの生成
Ni(NO3)2が金属塩として用いられ、且つ0.01 MのHNO3が酸として用いられたこと以外は、例1と同様に合成が行われた。
例1で得られた触媒は、NOのN2への還元中にテストされた。
この比較触媒は、固体イオン交換により得られた。
NO: 500 ppm
NH3: 500 ppm
H2O: 50体積%
SV (空間速度): 80,000
残り: N2
Claims (22)
- 交換金属が単量体として、及び/または二量体の種としてゼオライト中に存在する金属交換ゼオライト。
- 前記ゼオライトが、構造様式AEL、BEA、CHA、EUO、FAO、FER、KFI、LTA、LTL、MAZ、MOR、MEL、MTW、LEV、OFF、TON及びMFIのゼオライトから選ばれることを特徴とする請求項1記載のゼオライト。
- 前記ゼオライトが、構造様式BEA、MFI、FER、MOR、MTW、ERIを有するゼオライトから選ばれることを特徴とする請求項2記載のゼオライト。
- 前記ゼオライトの細孔サイズが、0.4〜1.5nmであることを特徴とする請求項2又は3記載のゼオライト。
- 前記交換金属が触媒活性であることを特徴とする請求項4記載のゼオライト。
- 前記交換金属が、Fe、Co、Ni、Ag、Cu、V、Rh、Pd、Pt、Irからなる群から選ばれることを特徴とする請求項5記載のゼオライト。
- 前記交換金属が、Fe、Co、Ni、Cuからなる群から選ばれることを特徴とする請求項6記載のゼオライト。
- 前記交換金属が、前記ゼオライトの全重量に対して金属酸化物として計算される1〜5重量%の量で存在することを特徴とする請求項6又は7記載のゼオライト。
- ゼオライト骨格の交換し得る場所の50%よりも多くが、前記交換金属で占められていることを特徴とする請求項8記載のゼオライト。
- まずゼオライトの懸濁水溶液が密閉可能な反応容器内で準備され、さらに、
a)前記懸濁液のpHを8〜10の範囲の値に増加させ、且つ前記反応容器の酸素レベルを10%未満の値にセットするステップと、
b)前記pHを1.5〜6の範囲の値に減少させるステップと、
c)金属塩を加え、そして1〜15時間にわたって反応させるステップと、
d)前記金属交換ゼオライトを濾過し且つ洗浄するステップと
を備える先の請求項の何れか一項に記載の金属交換ゼオライトの生成のためのプロセス。 - 前記懸濁液が、5〜25重量%のゼオライトを含有することを特徴とする請求項10記載のプロセス。
- アンモニア水の形態でのアンモニアを加えることにより、ステップa)でのpHの増加が行われることを特徴とする請求項11記載のプロセス。
- ゼオライトに対するアンモニアのモル比が、0.01〜0.1の値を有することを特徴とする請求項12記載のプロセス。
- 鉱酸を加えることにより、前記pHがステップb)で減少されることを特徴とする請求項13記載のプロセス。
- 前記pHが1.5〜3の範囲の値でセットされることを特徴とする請求項14記載のプロセス。
- 前記pHを減少させた後に、前記懸濁液が、80〜100℃の範囲の温度で加熱されることを特徴とする請求項14又は15記載のプロセス。
- ステップc)での交換反応中に、前記反応容器での酸素レベルが5%未満にセットされることを特徴とする請求項16記載のプロセス。
- 工程d)の後に得られるゼオライトが、100℃よりも高い温度で乾燥されることを特徴とする請求項17記載のプロセス。
- 前記プロセスが、数回実施されることを特徴とする請求項17又は18記載のプロセス。
- 前記乾燥されたゼオライトが、400〜600℃の温度で焼成されることを特徴とする請求項18又は19記載のプロセス。
- 前記焼成が不活性ガスのもとで行われることを特徴とする請求項20記載のプロセス。
- 前記金属が、単量体として及び/又は二量体の種として存在し、請求項10〜21の何れか1項に記載のプロセスで得られる金属交換ゼオライト。
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DE102007063604A DE102007063604A1 (de) | 2007-05-24 | 2007-05-24 | Metalldotierter Zeolith und Verfahren zu dessen Herstellung |
DE102007063604.2 | 2007-05-24 | ||
PCT/EP2008/004089 WO2008141823A2 (de) | 2007-05-24 | 2008-05-21 | Metalldotierter zeolith und verfahren zu dessen herstellung |
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JP7516560B2 (ja) | 2020-06-25 | 2024-07-16 | ビーエーエスエフ コーポレーション | 銅促進ゼオライトを調製する方法 |
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KR20160033688A (ko) | 2013-06-14 | 2016-03-28 | 유니제오 가부시키가이샤 | Mn+ 치환 베타형 제올라이트, 그를 포함하는 가스 흡착제 및 그의 제조 방법, 및 일산화질소의 제거 방법 |
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JP7516560B2 (ja) | 2020-06-25 | 2024-07-16 | ビーエーエスエフ コーポレーション | 銅促進ゼオライトを調製する方法 |
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US20100172828A1 (en) | 2010-07-08 |
US20140322127A1 (en) | 2014-10-30 |
EP2158038A2 (de) | 2010-03-03 |
DE102007063604A1 (de) | 2008-12-04 |
US9669397B2 (en) | 2017-06-06 |
PL2158038T3 (pl) | 2019-09-30 |
DK2158038T3 (da) | 2019-05-13 |
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