JP5837088B2 - 窒素酸化物の触媒的改善への金属ドープゼオライトおよびゼオタイプの使用 - Google Patents
窒素酸化物の触媒的改善への金属ドープゼオライトおよびゼオタイプの使用 Download PDFInfo
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- JP5837088B2 JP5837088B2 JP2013542542A JP2013542542A JP5837088B2 JP 5837088 B2 JP5837088 B2 JP 5837088B2 JP 2013542542 A JP2013542542 A JP 2013542542A JP 2013542542 A JP2013542542 A JP 2013542542A JP 5837088 B2 JP5837088 B2 JP 5837088B2
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- 150000003254 radicals Chemical class 0.000 description 1
- 239000012495 reaction gas Substances 0.000 description 1
- 230000002468 redox effect Effects 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 230000011514 reflex Effects 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 230000027756 respiratory electron transport chain Effects 0.000 description 1
- 239000006254 rheological additive Substances 0.000 description 1
- 238000001175 rotational moulding Methods 0.000 description 1
- 238000005464 sample preparation method Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000013341 scale-up Methods 0.000 description 1
- 238000007873 sieving Methods 0.000 description 1
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 1
- 229910010271 silicon carbide Inorganic materials 0.000 description 1
- 231100001055 skeletal defect Toxicity 0.000 description 1
- 238000010561 standard procedure Methods 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 238000012619 stoichiometric conversion Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-L sulfite Chemical class [O-]S([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-L 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 230000008685 targeting Effects 0.000 description 1
- 238000003419 tautomerization reaction Methods 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 238000006257 total synthesis reaction Methods 0.000 description 1
- 239000010891 toxic waste Substances 0.000 description 1
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 description 1
- 229910052902 vermiculite Inorganic materials 0.000 description 1
- 239000010455 vermiculite Substances 0.000 description 1
- 235000019354 vermiculite Nutrition 0.000 description 1
- 239000002912 waste gas Substances 0.000 description 1
- 229910052727 yttrium Inorganic materials 0.000 description 1
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 description 1
Classifications
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- B01J29/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively
- B01J29/42—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively containing iron group metals, noble metals or copper
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Description
i)a)ゼオライトと
b)触媒活性金属の化合物と
の乾燥混合物の提供
ii)この混合物の均質すり潰し
iii)規定温度への反応器中での混合物の加熱
iv)規定温度での混合物の維持、および
v)室温へ冷却および金属ドープゼオライトの取得
を含むイオン交換ゼオライトの製造方法を開示している、米国特許出願公開第2010075834号明細書に特許請求されている。
i)ゼオライトもしくはゼオタイプと、V、Cr、Mn、Fe、Co、Ni、Cu、Nb、Mo、Ru、Rh、Pd、Ag、およびCeからなる群から選択される遷移金属および配位子から形成される錯体であって、100℃〜500℃の温度で分解して金属または金属イオンを生成する錯体を含む前駆体化合物との乾燥均質混合物を提供するステップと;
ii)この混合物を、金属または金属イオンの固体状態昇華を開始させるのに十分な温度および時間でか焼するステップと;
iii)金属ドープゼオライトもしくはゼオタイプを取得するステップと
を含む金属ドープゼオライトもしくはゼオタイプの製造方法を適用することによって達成される。この発明が行われた日に、本材料の耐久性およびその触媒特性が、先行技術のそれらと比べて、より少ない本発明による材料が匹敵する効果をもたらすか、同じの量の材料が優れた結果に役立つかのどちらかであり、それは、順繰りに商業規模で製造されるときにコストの低下をもたらすような程度まで高められることは当業者によって予見され得なかった。
の構造を有してもよい。
の配位子のようなこの同族系の関連メンバーを包含する。
A:十分に混合されるSAPO34スラリーへのCu(NO3)2溶液添加からの3%Cu−SAPO34
B:不十分に混合されるSAPO34スラリーへのCu(NO3)2結晶添加からの3%Cu−SAPO34
C:物理的混合からの3%Cu−SAPO34
D:か焼物理的混合からの3%Cu−SAPO34
E:水性イオン交換からの3%Cu−SAPO34
F:Cuアセチルアセトネートの昇華からの3%Cu−SAPO34
G:シュウ酸Cu(CuC2O4)の昇華からの3%Cu−SAPO34
H:酢酸Cu(Cu(CH3COO)2)の昇華からの3%Cu−SAPO34
I:ペイント振盪機(本文を参照されたい)を用いて混合しながらの昇華からの2%Cu−SAPO34
J:コーヒーミル(本文を参照されたい)を用いて混合しながらの昇華からの2%Cu−SAPO34
K:オーバーヘッド攪拌機(本文を参照されたい)を用いて混合しながらの昇華からの2%Cu−SAPO34
a)簡単さ:本方法は、2つの乾燥粉末の混合、それに続く高温処理を含む。複雑な混合装置またはスラリー取り扱いシステムの必要はまったくない。乾式プロセスは、スラリー濾過、洗浄または乾燥のいかなる必要性をもなくす。さらに、本方法は、か焼中に使用される雰囲気または反応器圧力に関して鈍感である。これは、保護ガスも還元ガスもどちらも適用される必要がないという点において先行技術に勝る利点である。
b)費用:材料節約は、a)に記載される装置およびプロセスに頼らずに合成の簡単さから生じる。スラリーpHおよび温度などの監視装置の排除からさらに節約できる。
c)時間:完成粉末の製造は、従来の湿式交換の複数日要件またはスラリー含浸/か焼の数時間要件(均一性を確実にするための、スラリー化学などに基づくゼオライト/ゼオタイプの湿潤の発熱の関与を制限するための混合時間)とは違って2時間ほどの短時間で完了することができる。
d)環境影響の低減:先行技術の方法とは違って本方法は、副生物発生を前駆体配位子の分解からの化学量論量のCO2に限定する。イオン交換でのような、甚だしい水性廃棄物流れの発生も、SSIEについて見られるような潜在的な毒性の排出物、たとえばHFもしくはHClガス、またはスラリー含浸/か焼法で知られているような含N化合物(有機アミンもしくは窒素酸化物)(NH3もしくはスラリーpH調整/金属沈澱に使用された有機窒素塩基の燃焼からの)の発生もない。さらに調製の化学量論性を考えると、触媒を製造するために必要とされる過剰の材料または追加の化学薬品はまったくなく、環境影響を最小限に低減する。
e)ドーパント導入のためのより強固な、柔軟性のある方法:ドーパント・ターゲティングは、前駆体材料の強熱減量についての簡単な計算を必要とする。任意の追加の化学種またはプロセスの不在は、絶対最小値に対するあらゆる累積公差を減らす。
f)性能利益:従来のスラリー含浸/か焼法とは違って本昇華法は、ゼオライト/ゼオタイプの特有の活性交換中心に金属を直接導入する。したがって誘導期はまったく観察されない。さらに、昇華法による金属ドーピングの効率の増加を考えると、最適性能のために必要とされる「完全な」金属ドーピングを得るためにゼオライト/ゼオタイプを「オーバーロードする」必要はまったくない。これは、触媒活性相、たとえば、別個のまたは従来型のX線回折法によって検出可能な、CuO(黒銅鉱)の形成から生じる可能性があるような、触媒選択性の向上、すなわち寄生性NH3酸化の減少を提供する。第二に、金属ロードの減少が、ドーパントと骨組との間の高温(>750℃)固体状態反応、熟成中/熟成後の相崩壊および触媒不活性な新相の形成の主原因を制限するので、金属含有骨組材料の耐久性/熟成安定性の向上が実現される。最後に、乾式昇華法は、スラリーpH調整剤またはレオロジー調整剤、たとえばHNO3またはTEAHの必要性を排除する。酸性または塩基性の、両クラスのこれらの調整剤の使用は、両化学種がゼオライトもしくはゼオタイプと反応し、そして骨組原子を抽出し、それによって構造を不安定化させる可能性があるので、問題がある。そのような損傷は、フレッシュ粉末では検出できないが、高温耐久性にとって悪影響を有することが知られている。
用語「第一」、「第二」などは本明細書では、重要さのいかなる順番も意味せず、むしろ一要素を別の要素から区別するために使用され、用語「a」および「an」は本明細書では、量の限定を意味せず、むしろ被参照項目の少なくとも1つの存在を意味することがさらに指摘されるべきである。さらに、本明細書に開示されるすべての範囲は包含的で、合体でき、たとえば、「約5重量%〜約20重量%が望ましく、約10重量%〜約15重量%がより望ましい状態で、約25重量パーセント(重量%)以下」の範囲は、終点およびその範囲のすべての中間の値、たとえば「約5重量%〜約25重量%、約5重量%〜約15重量%」などを含む。
Claims (11)
- i)ゼオライトもしくはゼオタイプと、式I:
L1は、カルボニル、アミン、アルキル、アルコキシ、アルケン、アレーン、ホスフィンまたは他の中性配位子であり;
mは、0〜6の範囲の数であり;
nは、Mの原子価に等しい数であり;
L2は、ジケトネート、ケトイミネートまたは式II:
の配位子である]
の構造を有する、遷移金属と配位子とから形成される錯体を含む1つ以上の前駆体化合物との乾燥均質混合物を提供するステップと;
ii)前記混合物を、前記前駆体化合物を動員し、そして分解させるのに十分な温度および時間で減圧せずにか焼するステップと;
iii)金属ドープゼオライトもしくはゼオタイプを取得するステップと
を含む金属ドープゼオライトもしくはゼオタイプの製造方法に従って製造された材料または材料の混合物を含む触媒であって、フロースルー式セラミックモノリス、金属基材発泡体上にまたは壁流フィルタ基材上にコートされたアルミナ、チタニア、非ゼオライト系シリカ−アルミナ、シリカ、ジルコニアおよびそれら混合物からなる群から選択される不活性の耐熱性バインダーを含む触媒の、窒素の酸化物の選択的接触還元のための使用。 - 前記材料または材料の混合物と前記バインダーとが、フロースルー式セラミックモノリス、金属基材発泡体上にまたは壁流フィルタ基材上に個別域にコートされる、請求項1に記載の触媒の使用。
- i)ゼオライトもしくはゼオタイプと、式I:
L1は、カルボニル、アミン、アルキル、アルコキシ、アルケン、アレーン、ホスフィンまたは他の中性配位子であり;
mは、0〜6の範囲の数であり;
nは、Mの原子価に等しい数であり;
L2は、ジケトネート、ケトイミネートまたは式II:
の配位子である]
の構造を有する、遷移金属と配位子とから形成される錯体を含む1つ以上の前駆体化合物との乾燥均質混合物を提供するステップと;
ii)前記混合物を、前記前駆体化合物を動員し、そして分解させるのに十分な温度および時間で減圧せずにか焼するステップと;
iii)金属ドープゼオライトもしくはゼオタイプを取得するステップと
を含む金属ドープゼオライトもしくはゼオタイプの製造方法に従って製造された材料または材料の混合物の押出によって形成されたモノリス触媒の、窒素の酸化物の選択的接触還元のための使用。 - 前記ゼオライトもしくはゼオタイプが、フォージャサイト型、ペンタシル型、菱沸石ゼオライトもしくはゼオタイプ、または構造型CHAおよび関連構造型の他の「8−員環」構造体の1つまたは混合物からなる群から選択される、請求項1〜3のいずれか一項に記載の触媒またはモノリス触媒の使用。
- 前記金属が、Fe、Cu、Co、Ag、およびCeの群から選択される、請求項1〜4のいずれか一項に記載の触媒またはモノリス触媒の使用。
- 前記錯体配位子が、ジケトネート構造種およびカルボニル種を含む群の1つまたは混合物から選択される、請求項1〜5のいずれか一項に記載の触媒またはモノリス触媒の使用。
- 前記混合物が200℃以上〜650℃の温度でか焼される、請求項1〜6のいずれか一項に記載の触媒またはモノリス触媒の使用。
- 前記混合物が、350〜450℃の温度で1〜5時間か焼される、請求項1〜7のいずれか一項に記載の触媒またはモノリス触媒の使用。
- 前記混合物が、ゼオライトもしくはゼオタイプ材料と0.01重量%金属〜10重量%金属のその後の金属ドーパント・ローディングを提供するため前記前駆体化合物とを含む、請求項1〜8のいずれか一項に記載の触媒またはモノリス触媒の使用。
- 窒素含有還元剤源が、0.5〜2の触媒入口で有効なNH3:NOx比(α比)を与えるように導入される、請求項1〜9のいずれか一項に記載の触媒またはモノリス触媒の使用。
- 前記触媒の入口で記録されるNO:NO2比が容積で1:0〜1:3である、請求項1〜10のいずれか一項に記載の触媒またはモノリス触媒の使用。
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EP10015547A EP2463028A1 (en) | 2010-12-11 | 2010-12-11 | Process for the production of metal doped zeolites and zeotypes and application of same to the catalytic removal of nitrogen oxides |
EP10015547.2 | 2010-12-11 | ||
PCT/EP2011/072190 WO2012076648A1 (en) | 2010-12-11 | 2011-12-08 | Process for the production of metal doped zeolites and zeotypes and application of same to the catalytic remediation of nitrogen oxides |
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JP2014507361A JP2014507361A (ja) | 2014-03-27 |
JP5837088B2 true JP5837088B2 (ja) | 2015-12-24 |
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US (1) | US8865120B2 (ja) |
EP (2) | EP2463028A1 (ja) |
JP (1) | JP5837088B2 (ja) |
KR (1) | KR101950670B1 (ja) |
CN (1) | CN103260757B (ja) |
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-
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- 2010-12-11 EP EP10015547A patent/EP2463028A1/en not_active Withdrawn
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2011
- 2011-12-08 EP EP11802884.4A patent/EP2648845B1/en active Active
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- 2011-12-08 CN CN201180059452.1A patent/CN103260757B/zh active Active
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US8865120B2 (en) | 2014-10-21 |
RU2013131779A (ru) | 2015-01-20 |
EP2648845A1 (en) | 2013-10-16 |
KR101950670B1 (ko) | 2019-02-21 |
CN103260757A (zh) | 2013-08-21 |
US20130251611A1 (en) | 2013-09-26 |
RU2595336C2 (ru) | 2016-08-27 |
JP2014507361A (ja) | 2014-03-27 |
BR112013014529A2 (pt) | 2016-09-20 |
CN103260757B (zh) | 2016-06-15 |
KR20140035323A (ko) | 2014-03-21 |
EP2463028A1 (en) | 2012-06-13 |
BR112013014529B1 (pt) | 2019-05-14 |
WO2012076648A1 (en) | 2012-06-14 |
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