JP6804835B2 - 窒素酸化物(NOx)還元触媒および窒素酸化物(NOx)を還元するプロセス - Google Patents
窒素酸化物(NOx)還元触媒および窒素酸化物(NOx)を還元するプロセス Download PDFInfo
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- JP6804835B2 JP6804835B2 JP2015214200A JP2015214200A JP6804835B2 JP 6804835 B2 JP6804835 B2 JP 6804835B2 JP 2015214200 A JP2015214200 A JP 2015214200A JP 2015214200 A JP2015214200 A JP 2015214200A JP 6804835 B2 JP6804835 B2 JP 6804835B2
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- MWUXSHHQAYIFBG-UHFFFAOYSA-N Nitric oxide Chemical compound O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 title claims description 305
- 239000003054 catalyst Substances 0.000 title claims description 71
- 230000009467 reduction Effects 0.000 title claims description 40
- 238000000034 method Methods 0.000 title claims description 24
- 230000008569 process Effects 0.000 title claims description 23
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 63
- 239000001301 oxygen Substances 0.000 claims description 63
- 229910052760 oxygen Inorganic materials 0.000 claims description 63
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 22
- 229910052723 transition metal Inorganic materials 0.000 claims description 22
- 230000002950 deficient Effects 0.000 claims description 21
- 238000006243 chemical reaction Methods 0.000 claims description 20
- -1 transition metal tungstate Chemical class 0.000 claims description 20
- 239000007789 gas Substances 0.000 claims description 17
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 16
- 229930195733 hydrocarbon Natural products 0.000 claims description 15
- 239000000203 mixture Substances 0.000 claims description 15
- 239000004215 Carbon black (E152) Substances 0.000 claims description 14
- 150000002430 hydrocarbons Chemical class 0.000 claims description 14
- 229910052802 copper Inorganic materials 0.000 claims description 13
- 229910052742 iron Inorganic materials 0.000 claims description 13
- 229910052748 manganese Inorganic materials 0.000 claims description 13
- 229910052759 nickel Inorganic materials 0.000 claims description 13
- 239000000446 fuel Substances 0.000 claims description 11
- 239000002245 particle Substances 0.000 claims description 10
- 229910052757 nitrogen Inorganic materials 0.000 claims description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 9
- 239000001569 carbon dioxide Substances 0.000 claims description 8
- 229910002092 carbon dioxide Inorganic materials 0.000 claims description 8
- 229910001868 water Inorganic materials 0.000 claims description 8
- 239000013078 crystal Substances 0.000 claims description 3
- 238000006722 reduction reaction Methods 0.000 description 31
- 239000002105 nanoparticle Substances 0.000 description 7
- JCXJVPUVTGWSNB-UHFFFAOYSA-N nitrogen dioxide Inorganic materials O=[N]=O JCXJVPUVTGWSNB-UHFFFAOYSA-N 0.000 description 7
- 238000012360 testing method Methods 0.000 description 7
- 230000003197 catalytic effect Effects 0.000 description 6
- 230000000694 effects Effects 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 5
- MGWGWNFMUOTEHG-UHFFFAOYSA-N 4-(3,5-dimethylphenyl)-1,3-thiazol-2-amine Chemical compound CC1=CC(C)=CC(C=2N=C(N)SC=2)=C1 MGWGWNFMUOTEHG-UHFFFAOYSA-N 0.000 description 3
- 230000007246 mechanism Effects 0.000 description 3
- 230000009834 selective interaction Effects 0.000 description 3
- 150000003624 transition metals Chemical class 0.000 description 3
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000001027 hydrothermal synthesis Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 238000006213 oxygenation reaction Methods 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 239000010970 precious metal Substances 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 206010021143 Hypoxia Diseases 0.000 description 1
- 239000006004 Quartz sand Substances 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000004061 bleaching Methods 0.000 description 1
- 229910021386 carbon form Inorganic materials 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- VUZPPFZMUPKLLV-UHFFFAOYSA-N methane;hydrate Chemical compound C.O VUZPPFZMUPKLLV-UHFFFAOYSA-N 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 239000010948 rhodium Substances 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- CMPGARWFYBADJI-UHFFFAOYSA-L tungstic acid Chemical compound O[W](O)(=O)=O CMPGARWFYBADJI-UHFFFAOYSA-L 0.000 description 1
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Description
本発明は、窒素酸化物(NOx)を還元するための触媒および窒素酸化物(NOx)を還元するためのプロセスに関する。
燃焼機関からの排ガスは、スモッグおよび他の形態の環境公害の一因となる窒素酸化物(NOx)を作り出す。環境を保護して政府規制を満たすために、これらの機関の排気流からNOxを除去すべきである。現在の三元触媒コンバータ技術は、一定の制約条件下で自動車の排ガス中のNOxを除去するために使用され得る。たとえば、三元触媒は、摂氏300度よりも高い高温で作用する。また、現在の排出基準を満たすために、三元触媒は、白金、ロジウムおよびパラジウムなどの大量の貴金属を含有している。さらに、先行技術の触媒は、酸素の存在下でNOxと反応するのが困難であり得る。
一局面では、式:MWO4を有する遷移金属タングステン酸塩を含み、MはMn、Fe、Co、NiおよびCuからなるグループから選択される、窒素酸化物(NOx)還元触媒が開示される。
本開示は、窒素酸化物(NOx)を還元する形成方法、プロセスおよび/または窒素、水および二酸化炭素を発生するための窒素酸化物(NOx)の還元のための触媒組成物を提供する。触媒は、式:MWO4を有する遷移金属タングステン酸塩を含んでもよく、MはMn、Fe、Co、NiおよびCuからなるグループから選択される。触媒は、酸素豊富環境および酸素欠乏環境で利用されてもよい。この触媒は、狭く規定された条件でしか作用しない多くの三元触媒とは異なり、さまざまな条件での反応を可能にする貴金属フリー触媒を提供する。当該触媒は、現在の先行技術の触媒とは対照的に、酸素豊富環境および酸素欠乏環境における窒素酸化物(NOx)と触媒の表面との選択的な相互作用を可能にする。
MWO4の調製
Co(NO3)2、MnCl2、Fecl2、Ni(NO3)2またはCu(SO4)4およびNa2WO4×2H2Oの出発材料をシグマアルドリッチ社から購入し、さらなる精製なしに直接使用した。典型的な合成においては、(0.2M)Na2WO4溶液を強い攪拌下で化学量論的に(0.2M)遷移金属溶液と組合わせた。次に、溶液混合物をマイクロ波ガラス管に入れた。マイクロ波反応器(アントンパール社のMicrowave 300)でマイクロ波補助水熱合成を行った。マイクロ波管を、最大電力(800W)でさまざまな温度まで加熱した。以下により詳細に説明されるように、マイクロ波に晒すことをさまざま時間にわたって維持した。マイクロ波に晒した後、強制的な空気流によって管を冷却した。結果として得られた生成物を遠心分離機で複数回DI水で洗った後、摂氏60度で1晩真空乾燥した。乾燥ステップの後、触媒材料を摂氏550度で60分間空気中でか焼した。
MWO4の活性試験
活性試験は、実験室規模の充填床反応器(PID Eng&Tech社のMicroactivity-Reference)において行なった。炭化水素プロピレン(C3H6)によって、NO還元に対する活性を判定した。活性試験は、酸素欠乏条件および酸素豊富条件の両方において化学量論的条件下で行なった。図3に示されるように、酸素欠乏条件下では、NO:C3H6の化学量論比は9:1であり、酸素豊富条件下では、NO:C3H6:O2の化学量論比は3:1:3である。さらに図3に示されるように、100mgの触媒材料を400mgの石英砂と組合せ、100ml/分の全流量(気体時空間速度GHSV〜15,000逆時間)を酸素豊富条件および酸素欠乏条件の両方における試験に使用した。前処理段階は、反応器および触媒混合物を摂氏500度まで加熱し、当該温度を酸化条件下で15分間維持する(30ml/分のHeバランスにおける10%O2)ことを含む。その後、反応器を冷却し、一定の試験において一酸化窒素(NO、x=1)の形態の窒素酸化物(NOx)、炭化水素(C3H6)および酸素の気体混合物を導入して所定時間にわたって摂氏50度で維持した。その後、反応器を摂氏600度まで加熱した。さまざまなデータに反映されているようにさまざまな温度で測定を行なった。これは以下により詳細に説明される。
Claims (11)
- 窒素酸化物(NOx)を還元するプロセスであって、
窒素酸化物(NOx)および炭化水素燃料を含む排ガス混合物を提供するステップと、
式:MWO4を有する遷移金属タングステン酸塩を含む窒素酸化物(NOx)還元触媒を提供するステップとを備え、MはMn、Fe、Co、NiおよびCuからなるグループから選択され、前記プロセスはさらに、
前記排ガス混合物を前記窒素酸化物(NOx)還元触媒の表面と接触させて窒素、水および二酸化炭素を形成するステップを備え、
前記遷移金属タングステン酸塩は、4.9〜28.2m 2 /gの比表面積を有する分散粒子を含む、プロセス。 - 前記排ガス混合物は酸素をさらに含む、請求項1に記載のプロセス。
- 前記窒素酸化物(NOx)還元触媒は式:MWO4を有する遷移金属タングステン酸塩を含み、MはMn、Fe、CoおよびCuからなるグループから選択される、請求項2に記載のプロセス。
- 前記窒素酸化物(NOx)還元触媒は式:MWO4を有する遷移金属タングステン酸塩を含み、MはNiおよびCoからなるグループから選択され、前記触媒は酸素欠乏環境において窒素酸化物(NOx)を還元する、請求項1に記載のプロセス。
- 前記遷移金属タングステン酸塩は結晶構造を含む、請求項1に記載のプロセス。
- 前記遷移金属タングステン酸塩は、10〜60ナノメートルの粒径を有する、請求項1に記載のプロセス。
- 前記触媒は式:MnWO4を有し、前記触媒は酸素の存在下で窒素酸化物(NOx)を還元する、請求項1に記載のプロセス。
- 前記触媒は、前記窒素酸化物(NOx)変換および酸素変換が互いにほぼ等しいように、酸素の存在下でNOx変換に対して高い選択性を有する、請求項7に記載のプロセス。
- 前記触媒は、90パーセントよりも高い窒素酸化物(NOx)変換を有する、請求項7に記載のプロセス。
- 窒素酸化物(NOx)を還元するプロセスであって、
窒素酸化物(NOx)および炭化水素燃料を含む排ガス混合物を提供するステップと、
式:MWO4を有する遷移金属タングステン酸塩を含む窒素酸化物(NOx)還元触媒を提供するステップとを備え、MはMn、Fe、CoおよびCuからなるグループから選択され、前記プロセスはさらに、
酸素の存在下で前記排ガス混合物を前記窒素酸化物(NOx)還元触媒の表面と接触させて窒素、水および二酸化炭素を形成するステップを備え、
前記遷移金属タングステン酸塩は、4.9〜28.2m 2 /gの比表面積を有する分散粒子を含む、プロセス。 - 窒素酸化物(NOx)を還元するプロセスであって、
窒素酸化物(NOx)および炭化水素燃料を含む排ガス混合物を提供するステップと、
式:MWO4を有する遷移金属タングステン酸塩を含む窒素酸化物(NOx)還元触媒を提供するステップとを備え、MはNiおよびCoからなるグループから選択され、前記プロセスはさらに、
酸素欠乏環境において前記排ガス混合物を前記窒素酸化物(NOx)還元触媒の表面と接触させて窒素、水および二酸化炭素を形成するステップを備え、
前記遷移金属タングステン酸塩は、4.9〜28.2m 2 /gの比表面積を有する分散粒子を含む、プロセス。
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