CN110114135B - 一种挤出蜂窝催化剂 - Google Patents
一种挤出蜂窝催化剂 Download PDFInfo
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- CN110114135B CN110114135B CN201780080930.4A CN201780080930A CN110114135B CN 110114135 B CN110114135 B CN 110114135B CN 201780080930 A CN201780080930 A CN 201780080930A CN 110114135 B CN110114135 B CN 110114135B
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- catalyst
- vanadium
- oxide
- antimony
- calculated
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- 239000003054 catalyst Substances 0.000 title claims abstract description 177
- 238000000034 method Methods 0.000 claims abstract description 53
- 238000002485 combustion reaction Methods 0.000 claims abstract description 10
- XHCLAFWTIXFWPH-UHFFFAOYSA-N [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] XHCLAFWTIXFWPH-UHFFFAOYSA-N 0.000 claims description 45
- 229910000410 antimony oxide Inorganic materials 0.000 claims description 45
- VTRUBDSFZJNXHI-UHFFFAOYSA-N oxoantimony Chemical compound [Sb]=O VTRUBDSFZJNXHI-UHFFFAOYSA-N 0.000 claims description 45
- 229910001935 vanadium oxide Inorganic materials 0.000 claims description 45
- 239000000203 mixture Substances 0.000 claims description 41
- 239000002243 precursor Substances 0.000 claims description 32
- 229910052720 vanadium Inorganic materials 0.000 claims description 32
- 229910010413 TiO 2 Inorganic materials 0.000 claims description 31
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims description 30
- 239000011230 binding agent Substances 0.000 claims description 24
- 239000011159 matrix material Substances 0.000 claims description 24
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 23
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 21
- 229910052787 antimony Inorganic materials 0.000 claims description 19
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 claims description 17
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 14
- 230000008569 process Effects 0.000 claims description 11
- 238000001354 calcination Methods 0.000 claims description 10
- 239000000463 material Substances 0.000 claims description 10
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 9
- 239000003638 chemical reducing agent Substances 0.000 claims description 9
- 239000011148 porous material Substances 0.000 claims description 9
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 8
- GNTDGMZSJNCJKK-UHFFFAOYSA-N divanadium pentaoxide Chemical compound O=[V](=O)O[V](=O)=O GNTDGMZSJNCJKK-UHFFFAOYSA-N 0.000 claims description 8
- 238000001035 drying Methods 0.000 claims description 8
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims description 6
- 229910021536 Zeolite Inorganic materials 0.000 claims description 5
- 239000000654 additive Substances 0.000 claims description 5
- 229910052878 cordierite Inorganic materials 0.000 claims description 5
- JSKIRARMQDRGJZ-UHFFFAOYSA-N dimagnesium dioxido-bis[(1-oxido-3-oxo-2,4,6,8,9-pentaoxa-1,3-disila-5,7-dialuminabicyclo[3.3.1]nonan-7-yl)oxy]silane Chemical compound [Mg++].[Mg++].[O-][Si]([O-])(O[Al]1O[Al]2O[Si](=O)O[Si]([O-])(O1)O2)O[Al]1O[Al]2O[Si](=O)O[Si]([O-])(O1)O2 JSKIRARMQDRGJZ-UHFFFAOYSA-N 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 5
- 239000004014 plasticizer Substances 0.000 claims description 5
- 239000010457 zeolite Substances 0.000 claims description 5
- 229910021550 Vanadium Chloride Inorganic materials 0.000 claims description 4
- NNTGNYIMRIVRSJ-UHFFFAOYSA-N [V].C(O)CN Chemical compound [V].C(O)CN NNTGNYIMRIVRSJ-UHFFFAOYSA-N 0.000 claims description 4
- 229910000323 aluminium silicate Inorganic materials 0.000 claims description 4
- 239000003125 aqueous solvent Substances 0.000 claims description 4
- UNTBPXHCXVWYOI-UHFFFAOYSA-O azanium;oxido(dioxo)vanadium Chemical compound [NH4+].[O-][V](=O)=O UNTBPXHCXVWYOI-UHFFFAOYSA-O 0.000 claims description 4
- 239000003795 chemical substances by application Substances 0.000 claims description 4
- 239000002270 dispersing agent Substances 0.000 claims description 4
- 239000011888 foil Substances 0.000 claims description 4
- 150000004767 nitrides Chemical class 0.000 claims description 4
- OGUCKKLSDGRKSH-UHFFFAOYSA-N oxalic acid oxovanadium Chemical compound [V].[O].C(C(=O)O)(=O)O OGUCKKLSDGRKSH-UHFFFAOYSA-N 0.000 claims description 4
- RPESBQCJGHJMTK-UHFFFAOYSA-I pentachlorovanadium Chemical compound [Cl-].[Cl-].[Cl-].[Cl-].[Cl-].[V+5] RPESBQCJGHJMTK-UHFFFAOYSA-I 0.000 claims description 4
- 239000000377 silicon dioxide Substances 0.000 claims description 4
- LSGOVYNHVSXFFJ-UHFFFAOYSA-N vanadate(3-) Chemical compound [O-][V]([O-])([O-])=O LSGOVYNHVSXFFJ-UHFFFAOYSA-N 0.000 claims description 4
- UUUGYDOQQLOJQA-UHFFFAOYSA-L vanadyl sulfate Chemical compound [V+2]=O.[O-]S([O-])(=O)=O UUUGYDOQQLOJQA-UHFFFAOYSA-L 0.000 claims description 4
- 229910000352 vanadyl sulfate Inorganic materials 0.000 claims description 4
- 229940041260 vanadyl sulfate Drugs 0.000 claims description 4
- FAPDDOBMIUGHIN-UHFFFAOYSA-K antimony trichloride Chemical compound Cl[Sb](Cl)Cl FAPDDOBMIUGHIN-UHFFFAOYSA-K 0.000 claims description 3
- JRLDUDBQNVFTCA-UHFFFAOYSA-N antimony(3+);trinitrate Chemical compound [Sb+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O JRLDUDBQNVFTCA-UHFFFAOYSA-N 0.000 claims description 3
- MVMLTMBYNXHXFI-UHFFFAOYSA-H antimony(3+);trisulfate Chemical compound [Sb+3].[Sb+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O MVMLTMBYNXHXFI-UHFFFAOYSA-H 0.000 claims description 3
- WSXIMVDZMNWNRF-UHFFFAOYSA-N antimony;ethane-1,2-diol Chemical compound [Sb].OCCO WSXIMVDZMNWNRF-UHFFFAOYSA-N 0.000 claims description 3
- JVLRYPRBKSMEBF-UHFFFAOYSA-K diacetyloxystibanyl acetate Chemical compound [Sb+3].CC([O-])=O.CC([O-])=O.CC([O-])=O JVLRYPRBKSMEBF-UHFFFAOYSA-K 0.000 claims description 3
- 239000011949 solid catalyst Substances 0.000 claims description 3
- YPMOSINXXHVZIL-UHFFFAOYSA-N sulfanylideneantimony Chemical compound [Sb]=S YPMOSINXXHVZIL-UHFFFAOYSA-N 0.000 claims description 3
- 238000004108 freeze drying Methods 0.000 claims description 2
- 239000003365 glass fiber Substances 0.000 claims description 2
- 229910052596 spinel Inorganic materials 0.000 claims description 2
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- 230000000996 additive effect Effects 0.000 claims 1
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- 239000007789 gas Substances 0.000 description 32
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 17
- 229910052742 iron Inorganic materials 0.000 description 8
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 6
- 150000001720 carbohydrates Chemical class 0.000 description 5
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- 238000002360 preparation method Methods 0.000 description 5
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- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- 238000010531 catalytic reduction reaction Methods 0.000 description 3
- 229910000765 intermetallic Inorganic materials 0.000 description 3
- 238000011068 loading method Methods 0.000 description 3
- 150000007524 organic acids Chemical class 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
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- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
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- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical class [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 1
- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 description 1
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- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 description 1
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- 229920001732 Lignosulfonate Polymers 0.000 description 1
- 239000004117 Lignosulphonate Substances 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 229920003091 Methocel™ Polymers 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 235000021355 Stearic acid Nutrition 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 description 1
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Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/92—Chemical or biological purification of waste gases of engine exhaust gases
- B01D53/94—Chemical or biological purification of waste gases of engine exhaust gases by catalytic processes
- B01D53/9404—Removing only nitrogen compounds
- B01D53/9409—Nitrogen oxides
- B01D53/9413—Processes characterised by a specific catalyst
- B01D53/9418—Processes characterised by a specific catalyst for removing nitrogen oxides by selective catalytic reduction [SCR] using a reducing agent in a lean exhaust gas
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/847—Vanadium, niobium or tantalum or polonium
- B01J23/8472—Vanadium
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61B—DIAGNOSIS; SURGERY; IDENTIFICATION
- A61B17/00—Surgical instruments, devices or methods, e.g. tourniquets
- A61B17/16—Bone cutting, breaking or removal means other than saws, e.g. Osteoclasts; Drills or chisels for bones; Trepans
- A61B17/1642—Bone cutting, breaking or removal means other than saws, e.g. Osteoclasts; Drills or chisels for bones; Trepans for producing a curved bore
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61B—DIAGNOSIS; SURGERY; IDENTIFICATION
- A61B17/00—Surgical instruments, devices or methods, e.g. tourniquets
- A61B17/16—Bone cutting, breaking or removal means other than saws, e.g. Osteoclasts; Drills or chisels for bones; Trepans
- A61B17/1662—Bone cutting, breaking or removal means other than saws, e.g. Osteoclasts; Drills or chisels for bones; Trepans for particular parts of the body
- A61B17/1671—Bone cutting, breaking or removal means other than saws, e.g. Osteoclasts; Drills or chisels for bones; Trepans for particular parts of the body for the spine
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61B—DIAGNOSIS; SURGERY; IDENTIFICATION
- A61B17/00—Surgical instruments, devices or methods, e.g. tourniquets
- A61B17/34—Trocars; Puncturing needles
- A61B17/3403—Needle locating or guiding means
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61B—DIAGNOSIS; SURGERY; IDENTIFICATION
- A61B17/00—Surgical instruments, devices or methods, e.g. tourniquets
- A61B17/34—Trocars; Puncturing needles
- A61B17/3417—Details of tips or shafts, e.g. grooves, expandable, bendable; Multiple coaxial sliding cannulas, e.g. for dilating
- A61B17/3421—Cannulas
-
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Abstract
公开了一种挤出蜂窝催化剂，一种制备所述催化剂的方法，一种通过使用所述催化剂还原内燃机废气中的NOx的方法，和一种处理由发电厂产生的排放气体的方法，包括将排放气体暴露于所述催化剂。
Description
技术领域
本发明通常涉及一种挤出蜂窝催化剂，一种制备所述催化剂的方法，一种通过使用所述催化剂还原内燃机废气中的NOx的方法，和一种处理由发电厂产生的排放气体的方法，所述方法包括将排放气体暴露于所述催化剂。
背景
NOx是对环境和人类有害的移动源和静止源的主要废气之一。为了从废气中除去NOx，迄今为止已开发了催化还原方法。催化还原方法适于处理大量废气，在这些中，据报告包括加入氨作为还原剂以将NOx选择性催化还原为N2的方法是出众的。该选择性催化还原(SCR)中使用的催化剂需要宽温度范围如200-600℃内还原NOx。此外，这些催化剂的SCR活性在长期水热和硫老化之后不应急剧降低。V2O5/WO3/TiO2催化剂由于与Cu-沸石SCR相比，其具有更好的S耐受性而在工业上是公知的。如Applied CatalysisA：General，80(1992)，第135-148页所述，在V2O5/TiO2上掺杂WO3 1)提高了活性并拓宽了SCR的温度窗口；2)提高了对碱金属氧化物和砷氧化物的毒物抗性；3)减少了NH3氧化以及SO2氧化。
随着近年来对静止和移动应用实施更严格的NOx排放标准，极其需要高性能和低成本的NOx去除催化剂。作为高性能和低成本的解决方案，已开发了挤出蜂窝V2O5/WO3/TiO2来减少NOx。挤出蜂窝催化剂是整体式的整料型物体，其具有多个通道，在操作期间气体流过所述通道。
在先的公开文本US7507684B2、US2014/0157763A1、WO2010/099395揭示了挤出蜂窝V2O5/WO3/TiO2催化剂的制备及其在除去NOx应用中的用途。另一公开文献WO2013/179129试图要求保护由(Ax)(Ty)(Rz)VO4组成的挤出型壁流催化剂，其中A为至少一种碱土金属，T为至少一种过渡金属，R为至少一种稀土金属，x、y、z为各金属与钒酸根(VO4)的摩尔比，其中1≥x，y，z≥0，x+y+z＝1。然而，WO2013/179129没有公开含V和Sb的催化剂的任何实例。
WO2013/017873A1进一步公开了一种用具有另一层Cu-SAPO或SSZ-13或WOx/CeO2-ZrO2的Fe-β沸石或V2O5/WO3/TiO2或Fe-ZSM-5(MFI)制成的涂覆的挤出型基材或催化剂，以进一步改善在不同应用(例如对气体组成较不敏感的SCR催化剂)中的功能性。
SABIC提交了专利申请US2003/0144539A1，并且要求保护VSbaMbOx结构及其在烷烃和烯烃的氨氧化中的应用，其中M为至少一种选自镁、铝、锆、硅、铪、钛和铌的元素，a为0.5-20，b为2-50，x由存在的元素的价态要求决定。重要的是，V和Sb在基体材料M中是分离的，并且不形成混合氧化物。
KR专利号101065242和US专利号2009143225公开了一种在低温下具有改善的NOx转化率的SCR催化剂组合物及其合成，其中所述催化剂具有式V2O5/Sb2O3/TiO2，其中V/Sb二元体系负载在载体材料上。然而，US2009143225中提到的式子和制备方法不能制得挤出蜂窝催化剂。
在US8975206B2中，公开了一种负载的XVO4结构(XVO4/S)，其中X表示Bi、Sb、Ga或Al等，S为包含TiO2的载体材料，并且在实施例中仅使用TiO2/WO3/SiO2作为载体。
尽管进行了上述工作，但从未研究或公开使用钒氧化物作为活性组分且使用锑氧化物或铁氧化物作为助催化剂的挤出蜂窝V-SCR催化剂。
发明概述
本发明的目的是提供一种新型挤出蜂窝V-SCR催化剂。与传统的挤出蜂窝V2O5/WO3/TiO2SCR催化剂相比，该新设计的催化剂显示出在宽温度范围内更好的性能和优异的热稳定性。
所述目的可通过一种挤出蜂窝催化剂、一种制备所述催化剂的方法、一种通过使用所述催化剂还原内燃机废气中的NOx的方法和一种通过使用所述催化剂处理由发电厂产生的排放气体的方法来实现。
在本发明的第一方面中，提供了一种挤出蜂窝催化剂，其包含作为活性组分的钒氧化物和作为助催化剂的锑氧化物或铁氧化物。
在本发明的第二方面中，提供了一种制备本发明催化剂的方法，包括以下步骤：
i)将钒氧化物和/或其前体、锑氧化物和/或其前体、锑和钒的混合氧化物、铁和钒的混合氧化物、载体和/或其前体以及任选的粘合剂和/或基体和/
或其前体混合成可成型的混合物；
ii)将可成型的混合物挤出成通流式蜂窝催化剂体；
iii)干燥催化剂体；和
iv)煅烧催化剂体。
在本发明的第三方面中，提供了一种还原内燃机废气中的NOx的方法，包括在还原剂，优选NH3存在下，使废气与本发明的催化剂接触。
在本发明的第四方面中，提供了一种处理由发电厂产生的排放气体的方法，包括将排放气体暴露于所述催化剂。
与传统的挤出蜂窝V2O5/WO3/TiO2SCR催化剂相比，本发明的催化剂显示出在宽温度范围内更好的性能和优异的热稳定性。
附图简介
图1显示了本发明的挤出蜂窝催化剂。
发明详述
<挤出蜂窝催化剂>
在本发明的第一方面中，提供了一种挤出蜂窝催化剂，其包含作为活性组分的钒氧化物和作为助催化剂的锑氧化物或铁氧化物。
相对于催化剂的总重量，钒氧化物的负载量(以V2O5计算)为0.5-5重量％，优选为1-5重量％，更优选为1-3重量％。
催化剂中的Sb是助催化剂，用于改善活性物种钒氧化物的热稳定性。相对于催化剂的总重量，锑氧化物的负载量(以Sb2O3计算)为0.75-30重量％，优选为1.5-15重量％，更优选为3-15重量％。
V/Sb摩尔比可为8:1-1:8，更优选为6:1-1:3，最优选为5:1-1:2。
本发明的挤出催化剂包含活性载体材料。用于活性物质钒氧化物和助催化剂锑氧化物的活性载体材料包括但不限于：氧化铝、氧化锆、二氧化钛、二氧化硅、二氧化硅-氧化铝、二氧化硅-二氧化钛、钨-二氧化钛、二氧化硅-钨-二氧化钛、沸石、氧化铈-氧化锆混合氧化物，以及任意两种或更多种上述材料的混合物。优选地，载体材料包含或者更优选由纯TiO2，TiO2和SiO2二者，或者TiO2和WO3二者，或者TiO2、SiO2和WO3组成。
此外，可加入至少一种粘合剂和/或基体组分以改善最终挤出产物的机械强度。粘合剂和/或基体材料可选自堇青石、氮化物、碳化物、硼化物、金属间化合物、硅铝酸盐、尖晶石、氧化铝和/或掺杂氧化铝、二氧化硅、二氧化钛、氧化锆、二氧化钛-氧化锆、玻璃纤维及其任意两种或更多种的混合物。
就钒氧化物(以V2O5形式计算)、锑氧化物(以Sb2O3形式计算)、锑和钒的混合氧化物、铁和钒的混合氧化物以及活性载体材料的总重量而言的活性物质以挤出催化剂总重量的百分比计可在10-100％之间，优选在50-95％之间，更优选在70-90％之间，最优选在75-90％之间变化。挤出催化剂中的额外粘合剂和/或基体材料含量的重量可在0-50％之间，优选在5-30％之间，最优选在10-25％之间变化，基于催化剂的总重量，从而使得最终产物兼具良好的脱硝性能和同时足够的机械强度的优点。
所述催化剂可进一步包含其他活性组分，例如选自锑和钒的混合氧化物如SbVO4，以及铁和钒的混合氧化物如FeVO4中的至少一种。
本发明的催化剂可呈通流式蜂窝催化剂体的形式，即具有连续的流动通道。蜂窝催化剂体的流动通道为薄壁通道，其可具有任何合适的横截面形状和尺寸，例如梯形、矩形、正方形、正弦形、六边形、椭圆形或圆形。该结构可包含每平方英寸横截面至多900个气体入口(即，孔)(在下文中缩写为cpsi)，其中根据本发明，结构优选具有50-600cpsi，更优选200-600cpsi，甚至更优选300-600cpsi。
本发明的挤出蜂窝催化剂是具有多个通道的整体式的整料型物体，在操作过程中气体流过所述通道。由于省略了陶瓷基材和负载比涂覆催化剂更高量的催化活性组分，挤出蜂窝催化剂具有更低的总成本，并且在相同的催化剂体积下提供了更大的活性质量，因此在宽温度范围内提供了更好的性能。
另一个优点是，通过仅使用一个团块进行挤出，消除了陶瓷基材和活性涂层之间的临界界面。即使蜂窝具有一定量的脆性，活性材料也不会损失。
<制备挤出催化剂的方法>
本发明的第二方面涉及一种制备本发明催化剂的方法。
所述挤出催化剂可通过包括以下步骤的方法制备：
i)将钒氧化物和/或其前体、锑氧化物和/或其前体、锑和钒的混合氧化物、铁和钒的混合氧化物、载体和/或其前体以及任选的粘合剂和/或基体和/或其前体混合成可成型的混合物；
ii)将可成型的混合物挤出成通流式蜂窝催化剂体；
iii)干燥催化剂体；和
iv)煅烧催化剂体。
在步骤i)中，可将至少一种粘合剂和/或基体组分加入到混合物中以改善最终挤出产物的机械强度。这些材料可选自堇青石、氮化物、碳化物、硼化物、金属间化合物、硅铝酸盐、尖晶石、氧化铝和/或掺杂氧化铝、二氧化硅、二氧化钛、氧化锆、二氧化钛-氧化锆、玻璃纤维及其任意两种或更多种的混合物。
在所述方法的步骤i)中，可任选地加入任何常规添加剂，例如增塑剂和/或分散剂等。合适的增塑剂是本领域技术人员所已知的，例如聚氧化乙烯或各种淀粉(例如获自德国Dow Wolff Cellulosics GmbH的WALOCEL，获自德国Dow Wolff Cellulosics GmbH的METHOCEL)，纤维素醚，羧甲基纤维素等，或其他官能化的碳水化合物(例如通过乙氧基化或丙氧基化改性的淀粉、糊精、乳糖、葡萄糖、糖或糖醇，烷氧基化的碳水化合物，氢化或部分氢化的碳水化合物和/或烷氧基化的、氢化或部分氢化的碳水化合物)。合适的分散剂是本领域技术人员所已知的，例如石墨和相当的润滑剂(例如聚乙二醇、聚氧化乙烯、甲基纤维素、石蜡、硬脂酸或硬脂酸盐、羧酸、聚硅氧烷、石油、蜡乳液、木素磺酸盐等)。可调节任选的添加剂的重量以适应挤出操作，例如为0.5-5％，优选为1-3％，基于催化剂的总重量。
在步骤i)中，为了使粉末混合物胶溶，可任选地加入沉淀剂如有机酸。合适的有机酸选自甲酸、乙酸或双官能酸如草酸、酒石酸等。有机酸的量可为1-20重量％，基于催化剂的总重量。所述酸可稀释或浓缩。
此外，在步骤i)中，可任选地加入造孔剂。造孔剂在催化剂煅烧期间分解，并在催化剂体中产生细孔。通过选择造孔剂的类型、粒度和用量，可控制孔的数量和孔径。合适的造孔剂选自无机造孔剂如碳酸铵、碳酸氢铵、氯化铵盐等，或其他可热分解的无机碳如石墨、煤灰等)和/或由具有或不具有官能团如羧基、羟基的碳水化合物组成的有机造孔剂如纤维、聚合物、聚苯乙烯(PS)、聚甲基丙烯酸甲酯等。
步骤i)可在溶剂存在下进行。溶剂可为本领域已知的任何合适的溶剂，优选为含水溶剂，优选溶剂为去离子水。
步骤ii)可借助任何市售的合适挤出设备进行。
挤出物可呈通流式蜂窝催化剂体的形式，即具有连续的流动通道。蜂窝催化剂体的流动通道为薄壁通道，其可具有任何合适的横截面形状和尺寸，例如梯形、矩形、正方形、正弦形、六边形、椭圆形或圆形。该结构可具有至多900cpsi，其中根据本发明，结构优选具有50-600cpsi，更优选300-600cpsi，甚至更优选350-600cpsi。
在挤出后，可将挤出物包裹在箔中并在空气中干燥或在-10℃至-30℃下低压(例如0.3-10毫巴)冷冻干燥。干燥时间可为1小时至6个月。
在干燥后，将所得挤出物煅烧。煅烧温度可为250-700℃，优选为450-650℃。煅烧时间可为10分钟至10小时。
在本发明的上下文中，钒氧化物的前体和锑氧化物的前体旨在表示随后在该方法中通过在氧化条件下煅烧或以其他方式可分别转化为钒氧化物和锑氧化物的化合物。
钒氧化物的前体可选自钒酸铵、草酸氧钒、五氧化二钒、钒单乙醇胺、氯化钒、三氯代氧化钒、硫酸氧钒和锑酸钒。
锑氧化物的前体可选自乙酸锑、乙二醇锑、硫酸锑、硝酸锑、氯化锑、硫化锑、氧化锑和钒酸锑。
<还原废气中的NOx的方法>
本发明的第三方面涉及一种还原内燃机废气中的NOx的方法，包括在还原剂，优选NH3存在下，使废气与本发明的催化剂接触。
在本发明的实施方案中，使废气与催化剂在150-650℃或180-600℃或200-550℃的温度下接触。
废气与挤出催化剂的接触在还原剂存在下进行。可用于本发明的还原剂可为本领域本身已知的用于还原NOx的任何还原剂，例如NH3。NH3可来自于尿素。
相对于废气的流动方向，本发明的上游或下游可存在其他催化剂。
在本发明的优选实施方案中，内燃机为柴油机。
<还原废气中的NOx的方法>
本发明的第四方面涉及一种处理由发电厂产生的排放气体的方法，包括将排放气体暴露于所述催化剂。
因此，本发明涉及以下实施方案。
1.一种挤出蜂窝催化剂，包含：
a)作为活性组分的钒氧化物，和作为助催化剂的锑氧化物；或
b)锑和钒的混合氧化物；或
c)铁和钒的混合氧化物。
2.根据第1项的催化剂，其中其进一步包含粘合剂和/或基体材料。
3.根据第1或2项的催化剂，其中所述催化剂进一步包含至少一种选自氧化铝、氧化锆、二氧化钛、二氧化硅、二氧化硅-氧化铝、二氧化硅-二氧化钛、钨-二氧化钛、二氧化硅-钨-二氧化钛、沸石、二氧化铈、二氧化铈-氧化锆混合氧化物和任意两种或更多种上述材料的混合物的活性载体。
4.根据第3项的催化剂，其中活性载体为TiO2基材料，优选包含或更优选由TiO2，TiO2和SiO2的混合物，TiO2和WO3的混合物，或TiO2、SiO2和WO3的混合物组成。
5.根据第1-4项中任一项的催化剂，其中基于催化剂的总重量，钒氧化物(以V2O5形式计算)的量为0.5-5重量％，优选为1-5重量％，更优选为1-3重量％。
6.根据第1-5项中任一项的催化剂，其中基于催化剂的总重量，锑氧化物(以Sb2O3形式计算)的量为0.75-30重量％，优选为1.5-15重量％，更优选为3-15重量％。
7.根据第1-6项中任一项的催化剂，其中所述催化剂包含钒氧化物和锑氧化物，并且Sb/V摩尔比为8:1-1:8，更优选为6:1-1:3，最优选为5:1-1:2。
8.根据第1-7项中任一项的催化剂，其中所述催化剂包含至多900孔/平方英寸横截面(以下称为cpsi)，优选50-600cpsi，更优选200-600cpsi，甚至更优选300-600cpsi。
9.根据第1-8项中任一项的催化剂，其中基于催化剂的总重量，钒氧化物(以V2O5形式计算)、锑氧化物(以Sb2O3形式计算)、锑和钒的混合氧化物、铁和钒的混合氧化物以及活性载体的总重量为50-95％，优选为70-90％，更优选为75-90％。
10.根据第1-9项中任一项的催化剂，其中粘合剂和/或基体材料选自堇青石、玻璃纤维、氮化物、碳化物、硼化物、金属间化合物、硅铝酸盐、尖晶石、氧化铝和/或掺杂氧化铝、二氧化硅、二氧化钛、氧化锆、二氧化钛-氧化锆及其任意两种或更多种的混合物中的至少一种。
11.根据第1-10项中任一项的催化剂，其中粘合剂和/或基体材料的重量比为0-50％，优选为5-30％，最优选为10-25％，基于催化剂的总重量。
12.根据第1-11项中任一项的催化剂，其中钒氧化物(以V2O5形式计算)的量为1-5重量％，锑氧化物(以Sb2O3形式计算)的量为1.5-15重量％，钒氧化物(以V2O5形式计算)、锑氧化物(以Sb2O3形式计算)和活性载体的总重量为70-90％，粘合剂和/或基体材料的重量比为5-30％。
13.根据第1-11中任一项的催化剂，其中钒氧化物(以V2O5形式计算)的量为1-3重量％，锑氧化物(以Sb2O3形式计算)的量为3-15重量％，钒氧化物(以V2O5形式计算)、锑氧化物(以Sb2O3形式计算)和活性载体的总重量为75-90％，粘合剂和/或基体材料的重量比为10-25％。
14.一种制备第1-13项中任一项的催化剂的方法，包括以下步骤：
i)将钒氧化物和/或其前体、锑氧化物和/或其前体、锑和钒的混合氧化物、铁和钒的混合氧化物、载体和/或其前体以及任选的粘合剂和/或基体和/或其前体混合成可成型的混合物；
ii)将可成型的混合物挤出成通流式蜂窝催化剂体；
iii)干燥催化剂体；和
iv)煅烧催化剂体。
15.根据第14项的方法，包括以下步骤：
-提供包含钒氧化物和/或其前体、锑氧化物和/或其前体、锑和钒的混合氧化物、铁和钒的混合氧化物、载体和/或其前体，和任选的粘合剂和/或基体及其前体的溶液或混合物，并将所述溶液或混合物混合以获得可成型的混合物；
-将可成型的混合物挤出成具有连续通道和具有孔密度为200cpsi的六边形横截面的通流式蜂窝催化剂体；
-将催化剂体包裹在箔中并将其在空气中干燥6周或在-10℃至-30℃下低压冷冻干燥；
-在600℃的温度下煅烧1-6小时以形成固体催化剂体。
16.根据第14或15项的方法，其中钒氧化物的前体选自钒酸铵、草酸氧钒、五氧化二钒、钒单乙醇胺、氯化钒、三氯代氧化钒、硫酸氧钒和锑酸钒。
17.根据第14-16项中任一项的方法，其中锑氧化物的前体选自乙酸锑、乙二醇锑、硫酸锑、硝酸锑、氯化锑、硫化锑、氧化锑和钒酸锑。
18.根据第14-17项中任一项的方法，其中在步骤i)中加入含水溶剂和/或加入造孔剂。
19.根据第14-18项中任一项的方法，其中在步骤i)中加入一种或多种常规添加剂如增塑剂和/或分散剂和/或沉淀剂。
20.一种催化剂，其可通过第14-19项中任一项的方法获得。
21.一种还原内燃机废气中的NOx的方法，包括在还原剂，优选NH3的存在下使废气与第1-13和20项中任一项的催化剂接触。
22.根据第21项的方法，其中使废气在150-650℃、180-600℃或200-550℃的温度下与所述催化剂接触。
23.根据第21或22项的方法，其中内燃机为柴油机。
24.一种处理由发电厂产生的排放气体的方法，包括将排放气体暴露于第1-13和20项中任一项的催化剂。
实施例
提供以下实施例来阐述本发明，但决不限制本发明。
对于实施例使用相同的氧化物起始物质和相同的粘合剂以研究不同活性组分和组合物的性能，当然，对Sb和/或V化合物存在其他起始物质的各种组合。
<制备催化剂的一般程序>
实施例中使用的混合V/Sb氧化物VSbO4如下制备：将40.0g V2O5和64.1g Sb2O3混合在300g DI水中，并搅拌以形成悬浮液。将该悬浮液在200℃下喷雾干燥以形成氧化物的混合物。
混合V/Fe氧化物VFeO4获自Treibacher。
将市售的粉状锑氧化物(获自Campine的Sb2O3)、钒氧化物(V2O5)、VSbO4和VFeO4与作为粘合剂和/或基体材料的TiO2基载体TiO2(获自Crystal的DT51)或WO3/TiO2(获自Crystal的DT52)和堇青石808M/27，以及增塑剂聚氧化乙烯PEO Alkox E160(2％)和Walcell MW15000GB(1％)混合，并用甲酸水溶液处理成可成型和可流动的滑泥。
在获自的挤出设备中，将可成型的混合物挤出成通流式蜂窝催化剂体，即具有连续通道且具有孔密度为100cpsi的圆形横截面。随后，将催化剂体包裹在箔中并在空气中干燥6周，然后将其展开干燥直到其不显示出进一步的重量损失。
然后，将催化剂体在600℃的温度下煅烧3小时以形成固体催化剂体。
表1
将所得催化剂在550℃下陈化100小时，并在反应器上评价。将所有催化剂切成1英寸直径和3英寸长的芯材，并置于固定实验室模拟器中进行测试。在性能评价期间，测量催化剂在200℃和500℃下的催化活性以了解低温和高温下的脱硝性能。进料气体由以下组成：500ppm NH3、500ppm NO、10％H2O、5％O2，余量为N2。空速为60,000h-1。催化剂入口温度首先在进料气体中升至200℃。监测并记录催化剂出口处的NH3、NOx浓度，直至二者的浓度变得稳定。然后，将催化剂入口温度进一步升至500℃，再次监测并记录催化剂出口的NOx和NH3浓度，直至它们都变得稳定。在评价中，催化剂入口的NOx和NH3浓度均为500ppm且不改变。脱硝％效率通过以下公式计算：
脱硝％＝100×(500ppm-出口稳定的NOx)/500ppm
实施例和对比实施例中的催化剂的配方以及在低温和高温下各自的脱硝性能列于表1中。钒氧化物的重量百分比以V2O5形式计算。锑氧化物的重量百分比以Sb2O3形式计算。
尽管已结合目前被视为实际的示例性实施方案描述了本发明，然而应理解的是，本发明不限于所公开的实施方案，而是相反，本发明旨在涵盖包括在所附权利要求的主旨和范围内的各种修改和等同设置。
Claims (41)
1.一种挤出蜂窝催化剂，包含：
a)作为活性组分的钒氧化物，和作为助催化剂的锑氧化物；或
b)锑和钒的混合氧化物；
其中所述催化剂包含300-600孔/平方英寸横截面，其中所述催化剂不含凹凸棒土，
其中该催化剂进一步包含粘合剂和/或基体材料，
其中基于催化剂的总重量，以V2O5形式计算的钒氧化物的量为0.5-5重量％，和
其中基于催化剂的总重量，以Sb2O3形式计算的锑氧化物的量为0.75-30重量％。
2.根据权利要求1的催化剂，其中所述催化剂进一步包含至少一种选自氧化铝、氧化锆、二氧化钛、二氧化硅、二氧化硅-氧化铝、二氧化硅-二氧化钛、钨-二氧化钛、二氧化硅-钨-二氧化钛、沸石、二氧化铈、二氧化铈-氧化锆混合氧化物和任意两种或更多种上述材料的混合物的活性载体。
3.根据权利要求2的催化剂，其中活性载体为TiO2基材料。
4.根据权利要求3的催化剂，其中活性载体为TiO2基材料，且包含TiO2，TiO2和SiO2的混合物，TiO2和WO3的混合物，或TiO2、SiO2和WO3的混合物。
5.根据权利要求3的催化剂，其中活性载体为TiO2基材料，且由TiO2，TiO2和SiO2的混合物，TiO2和WO3的混合物，或TiO2、SiO2和WO3的混合物组成。
6.根据权利要求1-5中任一项的催化剂，其中基于催化剂的总重量，以V2O5形式计算的钒氧化物的量为1-5重量％。
7.根据权利要求6的催化剂，其中基于催化剂的总重量，以V2O5形式计算的钒氧化物的量为1-3重量％。
8.根据权利要求1-5中任一项的催化剂，其中基于催化剂的总重量，以Sb2O3形式计算的锑氧化物的量为1.5-15重量％。
9.根据权利要求6的催化剂，其中基于催化剂的总重量，以Sb2O3形式计算的锑氧化物的量为1.5-15重量％。
10.根据权利要求8的催化剂，其中基于催化剂的总重量，以Sb2O3形式计算的锑氧化物的量为3-15重量％。
11.根据权利要求1-5中任一项的催化剂，其中所述催化剂包含钒氧化物和锑氧化物，并且Sb/V摩尔比为8:1-1:8。
12.根据权利要求6的催化剂，其中所述催化剂包含钒氧化物和锑氧化物，并且Sb/V摩尔比为8:1-1:8。
13.根据权利要求8的催化剂，其中所述催化剂包含钒氧化物和锑氧化物，并且Sb/V摩尔比为8:1-1:8。
14.根据权利要求11的催化剂，其中所述催化剂包含钒氧化物和锑氧化物，并且Sb/V摩尔比为6:1-1:3。
15.根据权利要求11的催化剂，其中所述催化剂包含钒氧化物和锑氧化物，并且Sb/V摩尔比为5:1-1:2。
16.根据权利要求1-5中任一项的催化剂，其中基于催化剂的总重量，以V2O5形式计算的钒氧化物、以Sb2O3形式计算的锑氧化物、锑和钒的混合氧化物以及活性载体的总重量为50-95％。
17.根据权利要求16的催化剂，其中基于催化剂的总重量，以V2O5形式计算的钒氧化物、以Sb2O3形式计算的锑氧化物、锑和钒的混合氧化物以及活性载体的总重量为70-90％。
18.根据权利要求16的催化剂，其中基于催化剂的总重量，以V2O5形式计算的钒氧化物、以Sb2O3形式计算的锑氧化物、锑和钒的混合氧化物以及活性载体的总重量为75-90％。
19.根据权利要求1-5中任一项的催化剂，其中粘合剂和/或基体材料选自堇青石、玻璃纤维、氮化物、碳化物、硼化物、金属间化合物、硅铝酸盐、尖晶石、氧化铝和/或掺杂氧化铝、二氧化硅、二氧化钛、氧化锆、二氧化钛-氧化锆及其任意两种或更多种的混合物中的至少一种。
20.根据权利要求1-5中任一项的催化剂，其中粘合剂和/或基体材料的重量比为0-50％，基于催化剂的总重量。
21.根据权利要求20的催化剂，其中粘合剂和/或基体材料的重量比为5-30％，基于催化剂的总重量。
22.根据权利要求20的催化剂，其中粘合剂和/或基体材料的重量比为10-25％，基于催化剂的总重量。
23.根据权利要求1-5中任一项的催化剂，其中基于催化剂的总重量，以V2O5形式计算的钒氧化物的量为1-5重量％，以Sb2O3形式计算的锑氧化物的量为1.5-15重量％，以V2O5形式计算的钒氧化物、以Sb2O3形式计算的锑氧化物和活性载体的总重量为70-90％，粘合剂和/或基体材料的重量比为5-30％。
24.根据权利要求1-5中任一项的催化剂，其中基于催化剂的总重量，以V2O5形式计算的钒氧化物的量为1-3重量％，以Sb2O3形式计算的锑氧化物的量为3-15重量％，以V2O5形式计算的钒氧化物、以Sb2O3形式计算的锑氧化物和活性载体的总重量为75-90％，粘合剂和/或基体材料的重量比为10-25％。
25.一种制备权利要求1-24中任一项的催化剂的方法，包括以下步骤：
i)将钒氧化物和/或其前体、锑氧化物和/或其前体、锑和钒的混合氧化物、载体和/或其前体以及任选的粘合剂和/或基体和/或其前体混合成可成型的混合物；
ii)将可成型的混合物挤出成通流式蜂窝催化剂体；
iii)干燥催化剂体；和
iv)煅烧催化剂体。
26.根据权利要求25的方法，包括以下步骤：
-提供包含钒氧化物和/或其前体、锑氧化物和/或其前体、锑和钒的混合氧化物、载体和/或其前体，和任选的粘合剂和/或基体及其前体的溶液或混合物，并将所述溶液或混合物混合以获得可成型的混合物；
-将可成型的混合物挤出成具有连续通道和具有孔密度为200cpsi的六边形横截面的通流式蜂窝催化剂体；
-将催化剂体包裹在箔中并将其在空气中干燥6周或在-10℃至-30℃下低压冷冻干燥；
-在600℃的温度下煅烧1-6小时以形成固体催化剂体。
27.根据权利要求25的方法，其中钒氧化物的前体选自钒酸铵、草酸氧钒、五氧化二钒、钒单乙醇胺、氯化钒、三氯代氧化钒、硫酸氧钒和锑酸钒。
28.根据权利要求26的方法，其中钒氧化物的前体选自钒酸铵、草酸氧钒、五氧化二钒、钒单乙醇胺、氯化钒、三氯代氧化钒、硫酸氧钒和锑酸钒。
29.根据权利要求25-28中任一项的方法，其中锑氧化物的前体选自乙酸锑、乙二醇锑、硫酸锑、硝酸锑、氯化锑、硫化亚锑、氧化锑和钒酸锑。
30.根据权利要求25-28中任一项的方法，其中在步骤i)中加入含水溶剂和/或加入造孔剂。
31.根据权利要求29的方法，其中在步骤i)中加入含水溶剂和/或加入造孔剂。
32.根据权利要求25-28中任一项的方法，其中在步骤i)中加入一种或多种常规添加剂。
33.根据权利要求32的方法，其中所述添加剂为增塑剂和/或分散剂和/或沉淀剂。
34.一种催化剂，其可通过权利要求25-33中任一项的方法获得。
35.一种还原内燃机废气中的NOx的方法，包括在还原剂的存在下使废气与权利要求1-24和34中任一项的催化剂接触。
36.根据权利要求35的方法，其中所述还原剂为NH3。
37.根据权利要求35的方法，其中使废气在150-650℃的温度下与所述催化剂接触。
38.根据权利要求37的方法，其中使废气在180-600℃的温度下与所述催化剂接触。
39.根据权利要求37的方法，其中使废气在200-550℃的温度下与所述催化剂接触。
40.根据权利要求35-39中任一项的方法，其中内燃机为柴油机。
41.一种处理由发电厂产生的排放气体的方法，包括将排放气体暴露于权利要求1-24和34中任一项的催化剂。
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| CN106170612A (zh) * | 2014-02-06 | 2016-11-30 | 庄信万丰催化剂(德国)有限公司 | 用于500至4500kw内燃机的富氧排气中的氮氧化物还原的紧凑型选择性催化还原系统 |
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| JP5110954B2 (ja) * | 2007-05-09 | 2012-12-26 | エヌ・イーケムキャット株式会社 | 選択還元型触媒を用いた排気ガス浄化触媒装置並びに排気ガス浄化方法 |
| GB2493449B (en) | 2011-08-03 | 2014-01-15 | Johnson Matthey Plc | Extruded honeycomb catalyst |
| GB2522547B (en) | 2012-06-01 | 2018-12-12 | Johnson Matthey Plc | Selective catalytic reduction wall flow filter incorporating a vanadate |
| CN103157480B (zh) * | 2013-02-04 | 2015-02-18 | 合肥工业大学 | 一种氧化钒/铁氧化物脱硝催化剂及其制备方法和应用 |
| KR101631487B1 (ko) * | 2015-12-17 | 2016-06-17 | 허승주 | 촉매폐기물을 이용한 선택적 환원반응의 저온 탈질촉매 및 그 제조방법 |
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2017
- 2017-12-28 US US16/474,830 patent/US20190344247A1/en not_active Abandoned
- 2017-12-28 WO PCT/CN2017/119423 patent/WO2018121676A1/en unknown
- 2017-12-28 EP EP17888606.5A patent/EP3562580A4/en active Pending
- 2017-12-28 CN CN201780080930.4A patent/CN110114135B/zh active Active
- 2017-12-28 JP JP2019536098A patent/JP7218991B2/ja active Active
- 2017-12-28 KR KR1020197022043A patent/KR20190098762A/ko not_active IP Right Cessation
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2022
- 2022-10-25 US US18/049,347 patent/US20240082827A9/en active Pending
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| WO2016024126A1 (en) * | 2014-08-15 | 2016-02-18 | Johnson Matthey Public Limited Company | Zoned catalyst for treating exhaust gas |
| CN106111118A (zh) * | 2016-06-20 | 2016-11-16 | 浙江三龙催化剂有限公司 | 一种脱硝催化剂的制备方法及其应用 |
Also Published As
| Publication number | Publication date |
|---|---|
| JP7218991B2 (ja) | 2023-02-07 |
| US20190344247A1 (en) | 2019-11-14 |
| KR20190098762A (ko) | 2019-08-22 |
| WO2018121676A1 (en) | 2018-07-05 |
| JP2020514027A (ja) | 2020-05-21 |
| EP3562580A4 (en) | 2020-08-26 |
| EP3562580A1 (en) | 2019-11-06 |
| US20240082827A9 (en) | 2024-03-14 |
| US20230077366A1 (en) | 2023-03-16 |
| CN110114135A (zh) | 2019-08-09 |
| BR112019013487A2 (pt) | 2020-01-07 |
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