WO2023013359A1 - 排ガス浄化触媒 - Google Patents
排ガス浄化触媒 Download PDFInfo
- Publication number
- WO2023013359A1 WO2023013359A1 PCT/JP2022/026992 JP2022026992W WO2023013359A1 WO 2023013359 A1 WO2023013359 A1 WO 2023013359A1 JP 2022026992 W JP2022026992 W JP 2022026992W WO 2023013359 A1 WO2023013359 A1 WO 2023013359A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- mol
- exhaust gas
- cha
- type zeolite
- alkaline earth
- Prior art date
Links
- 239000003054 catalyst Substances 0.000 title claims abstract description 120
- 238000000746 purification Methods 0.000 title claims abstract description 77
- 239000010457 zeolite Substances 0.000 claims abstract description 116
- 229910021536 Zeolite Inorganic materials 0.000 claims abstract description 115
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims abstract description 110
- 150000001342 alkaline earth metals Chemical class 0.000 claims abstract description 56
- 229910052783 alkali metal Inorganic materials 0.000 claims abstract description 54
- 150000001340 alkali metals Chemical class 0.000 claims abstract description 54
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims abstract description 54
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000000203 mixture Substances 0.000 claims description 17
- 239000007848 Bronsted acid Substances 0.000 claims description 16
- 238000004519 manufacturing process Methods 0.000 claims description 12
- 238000002156 mixing Methods 0.000 claims description 12
- 239000000758 substrate Substances 0.000 claims description 12
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 7
- 239000011575 calcium Substances 0.000 claims description 7
- 229910052791 calcium Inorganic materials 0.000 claims description 7
- 238000000034 method Methods 0.000 claims description 7
- 230000003197 catalytic effect Effects 0.000 claims description 6
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 5
- 150000001242 acetic acid derivatives Chemical class 0.000 claims description 5
- 150000004649 carbonic acid derivatives Chemical class 0.000 claims description 5
- 150000004679 hydroxides Chemical class 0.000 claims description 5
- 229910052700 potassium Inorganic materials 0.000 claims description 5
- 239000011591 potassium Substances 0.000 claims description 5
- 229920006395 saturated elastomer Polymers 0.000 claims description 5
- 239000011734 sodium Substances 0.000 claims description 5
- 150000003467 sulfuric acid derivatives Chemical class 0.000 claims description 5
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 4
- 229910052788 barium Inorganic materials 0.000 claims description 4
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 claims description 4
- 229910052708 sodium Inorganic materials 0.000 claims description 4
- 229910001963 alkali metal nitrate Inorganic materials 0.000 claims description 3
- 229910001964 alkaline earth metal nitrate Inorganic materials 0.000 claims description 3
- 238000001354 calcination Methods 0.000 claims description 3
- 239000007789 gas Substances 0.000 description 105
- 230000000052 comparative effect Effects 0.000 description 26
- 239000010949 copper Substances 0.000 description 25
- 239000010410 layer Substances 0.000 description 18
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 10
- 239000000463 material Substances 0.000 description 9
- 239000011248 coating agent Substances 0.000 description 8
- 238000000576 coating method Methods 0.000 description 8
- 150000002500 ions Chemical class 0.000 description 8
- 229910052751 metal Inorganic materials 0.000 description 8
- 239000011230 binding agent Substances 0.000 description 7
- 238000005342 ion exchange Methods 0.000 description 7
- 239000002184 metal Substances 0.000 description 7
- 239000002585 base Substances 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 5
- 238000011156 evaluation Methods 0.000 description 5
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- 229910052782 aluminium Inorganic materials 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 229910052878 cordierite Inorganic materials 0.000 description 4
- 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 description 4
- 238000007580 dry-mixing Methods 0.000 description 4
- 229910052809 inorganic oxide Inorganic materials 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical group [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 4
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 4
- 238000007086 side reaction Methods 0.000 description 4
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 description 4
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 3
- ITHZDDVSAWDQPZ-UHFFFAOYSA-L barium acetate Chemical compound [Ba+2].CC([O-])=O.CC([O-])=O ITHZDDVSAWDQPZ-UHFFFAOYSA-L 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 229910000069 nitrogen hydride Inorganic materials 0.000 description 3
- 229910000510 noble metal Inorganic materials 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 2
- ZCCIPPOKBCJFDN-UHFFFAOYSA-N calcium nitrate Chemical compound [Ca+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ZCCIPPOKBCJFDN-UHFFFAOYSA-N 0.000 description 2
- 239000006255 coating slurry Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 239000000470 constituent Substances 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000010304 firing Methods 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 239000004570 mortar (masonry) Substances 0.000 description 2
- 235000010333 potassium nitrate Nutrition 0.000 description 2
- 239000004323 potassium nitrate Substances 0.000 description 2
- 239000010948 rhodium Substances 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 235000010344 sodium nitrate Nutrition 0.000 description 2
- 239000004317 sodium nitrate Substances 0.000 description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- 229910001413 alkali metal ion Inorganic materials 0.000 description 1
- 229910001420 alkaline earth metal ion Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 229910052792 caesium Inorganic materials 0.000 description 1
- TVFDJXOCXUVLDH-UHFFFAOYSA-N caesium atom Chemical compound [Cs] TVFDJXOCXUVLDH-UHFFFAOYSA-N 0.000 description 1
- UNYSKUBLZGJSLV-UHFFFAOYSA-L calcium;1,3,5,2,4,6$l^{2}-trioxadisilaluminane 2,4-dioxide;dihydroxide;hexahydrate Chemical compound O.O.O.O.O.O.[OH-].[OH-].[Ca+2].O=[Si]1O[Al]O[Si](=O)O1.O=[Si]1O[Al]O[Si](=O)O1 UNYSKUBLZGJSLV-UHFFFAOYSA-L 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 238000010531 catalytic reduction reaction Methods 0.000 description 1
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 description 1
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 description 1
- 229910052676 chabazite Inorganic materials 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 239000011247 coating layer Substances 0.000 description 1
- 229910000365 copper sulfate Inorganic materials 0.000 description 1
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 1
- OPQARKPSCNTWTJ-UHFFFAOYSA-L copper(ii) acetate Chemical compound [Cu+2].CC([O-])=O.CC([O-])=O OPQARKPSCNTWTJ-UHFFFAOYSA-L 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 239000005431 greenhouse gas Substances 0.000 description 1
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 150000002823 nitrates Chemical class 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 229910052701 rubidium Inorganic materials 0.000 description 1
- IGLNJRXAVVLDKE-UHFFFAOYSA-N rubidium atom Chemical compound [Rb] IGLNJRXAVVLDKE-UHFFFAOYSA-N 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 229910052712 strontium Inorganic materials 0.000 description 1
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Classifications
-
- 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
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
- B01J29/72—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65 containing iron group metals, noble metals or copper
- B01J29/76—Iron group metals or copper
-
- 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
-
- 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
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
- B01J29/72—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65 containing iron group metals, noble metals or copper
- B01J29/76—Iron group metals or copper
- B01J29/763—CHA-type, e.g. Chabazite, LZ-218
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/50—Catalysts, in general, characterised by their form or physical properties characterised by their shape or configuration
- B01J35/56—Foraminous structures having flow-through passages or channels, e.g. grids or three-dimensional monoliths
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/024—Multiple impregnation or coating
- B01J37/0246—Coatings comprising a zeolite
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/04—Mixing
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02T—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO TRANSPORTATION
- Y02T10/00—Road transport of goods or passengers
- Y02T10/10—Internal combustion engine [ICE] based vehicles
- Y02T10/12—Improving ICE efficiencies
Definitions
- the present invention relates to an exhaust gas purification catalyst.
- a selective catalytic reduction (SCR) system is known as a technology for reducing and purifying NOx in exhaust gas emitted from a diesel engine before it is released into the atmosphere.
- An SCR system is a technology that uses a reducing agent, such as ammonia (or an ammonia source such as urea), to reduce NOx in the exhaust gas to N2 .
- Cu-zeolite which is zeolite ion-exchanged with copper (Cu)
- Cu copper
- Patent Document 1 explains that an exhaust gas purification catalyst using Cu-CHA-type zeolite, which is obtained by ion-exchanging chabazite-type zeolite represented by the structure code "CHA" with copper (Cu), has excellent NOx purification performance. It is
- N 2 O is produced as a by-product in NOx purification by the SCR system. Since N 2 O is a greenhouse gas that contributes to global warming, its emissions should be controlled.
- the present invention has been made in view of the above circumstances. Accordingly, it is an object of the present invention to provide an exhaust gas purifying catalyst that has a sufficiently high NOx purification efficiency and produces a small amount of N 2 O.
- the present invention for solving the above problems is as follows.
- An exhaust gas purification catalyst containing a Cu—CHA type zeolite The Cu-CHA-type zeolite has a silica-alumina ratio (SAR) of 20.0 or less and contains an alkali metal and an alkaline earth metal.
- ⁇ Mode 2>> The amount of Cu in the Cu-CHA-type zeolite is 0.10 mol/mol-Al or more and 0.40 mol/mol-Al or less with respect to 1 mol of Al atoms in the Cu-CHA-type zeolite.
- the Bronsted acid content of the Cu—CHA-type zeolite is 0.200 mmol/g or less, and the Bronsted acid amount of the Cu—CHA-type zeolite is measured as follows: NH 3 Defined as a value obtained by assigning the integrated value (mmol) of the amount to the mass (g) of the Cu-CHA type zeolite: (i) the Cu-CHA - type zeolite is saturated with NH3 at 100°C, and The temperature is raised to 600°C at a rate of °C/min, and the amount of NH3 contained in the discharged N2 gas is integrated at temperatures from 350°C to 600°C.
- the exhaust gas purifying catalyst according to any one of aspects 1 to 5.
- an exhaust gas purifying catalytic device that has sufficiently high NOx purification efficiency and produces a small amount of N 2 O.
- the exhaust gas purification catalyst of the present invention is An exhaust gas purifying catalyst containing a Cu—CHA type zeolite,
- the Cu-CHA-type zeolite has a silica-alumina ratio (SAR) of 20.0 or less and contains an alkali metal and an alkaline earth metal.
- SAR silica-alumina ratio
- the exhaust gas purification catalyst of the present invention uses a Cu-CHA-type zeolite with an SAR of 20.0 or less.
- a Cu-zeolite with a low SAR that is, a Cu-zeolite with a relatively large proportion of alumina has excellent NOx purification performance.
- the NOx purification performance is particularly enhanced.
- the low SAR Cu-CHA type zeolite as described above further contains an alkali metal and an alkaline earth metal.
- the exhaust gas purifying catalyst of the present invention has reduced N 2 O emissions.
- the alkali metal and alkaline earth metal coat the Bronsted acid to limit the progress of the side reaction (3), thereby suppressing the generation of N 2 O. Conceivable.
- the present inventors focused on the fact that the Bronsted acid of zeolite has a "1Al site” represented by (A) below and a "2Al site” represented by (B) below.
- M AM Monovalent alkali metal ions
- M AEM divalent alkaline earth metal ions
- the exhaust gas purifying catalyst of the present invention has a sufficiently high NOx purifying efficiency and a small amount of N 2 O generated due to the mechanism described above.
- the invention is not bound by any particular theory.
- the exhaust gas purifying catalyst of the present invention contains a Cu—CHA type zeolite.
- the “Cu—CHA type zeolite” is obtained by ion-exchanging a chabazite type zeolite indicated by the structure code “CHA” with Cu.
- the Cu—CHA type zeolite has a silica-alumina ratio (SAR) of 20.0 or less.
- SAR silica-alumina ratio
- the SAR of the Cu-CHA type zeolite in the exhaust gas purification catalyst of the present invention may be 18 or less, 16 or less, 15 or less, 12 or less, 10 or less, 8 or less, or 6 or less from the viewpoint of increasing the NOx purification rate. .
- the SAR of the Cu—CHA type zeolite may be 4 or more, 6 or more, 8 or more, or 10 or more.
- the amount of Cu in the Cu-CHA-type zeolite is 0.10 mol/mol-Al or more and 0 with respect to 1 mol of Al atoms in the Cu-CHA-type zeolite. 0.15 mol/mol-Al or more, 0.20 mol/mol-Al or more, 0.25 mol/mol-Al or more, or 0.30 mol/mol-Al or more.
- the amount of Cu in the Cu-CHA type zeolite is 0.50 mol/mol-Al or less per 1 mol of Al atoms in the Cu-CHA-type zeolite. It may be 0.45 mol/mol-Al or less, 0.40 mol/mol-Al or less, 0.35 mol/mol-Al or less, 0.30 mol/mol-Al or less, or 0.25 mol/mol-Al or less.
- the CHA-type zeolite may be ion-exchanged with ions other than Cu together with Cu.
- the ratio of Cu in the ions taken into the CHA-type zeolite by ion exchange be high.
- the proportion of Cu in all ions taken into the CHA-type zeolite by ion exchange is 80% by mass or more, 85% by mass or more, 90% by mass or more, 95% by mass or more, and 98% by mass. or more, or 99% by mass or more, or 100% by mass.
- the Cu-CHA type zeolite as described above further contains an alkali metal and an alkaline earth metal.
- the Cu—CHA type zeolite “containing alkali metals and alkaline earth metals” means that the Cu—CHA type zeolite contains these metal elements such as oxides, compounds, salts, metals, ions, etc. or any combination thereof.
- the chemical forms of the alkali metal and the alkaline earth metal are mutually variable depending on the situation in which the exhaust gas purifying catalyst is placed.
- the exhaust gas purifying catalyst of the present invention can exhibit desired performance as long as it contains an alkali metal and an alkaline earth metal.
- the alkali metal may be, for example, lithium, sodium, potassium, rubidium, cesium, etc., and in particular, may be one or two selected from sodium and potassium.
- the alkaline earth metal may be, for example, calcium, strontium, barium, etc., and in particular, may be one or two selected from barium and calcium.
- the amount of the alkali metal in the Cu-CHA-type zeolite is 0.005 mol/mol-Al or more with respect to 1 mol of Al atoms in the Cu-CHA-type zeolite. It may be 0.010 mol/mol-Al or more, 0.020 mol/mol-Al or more, 0.030 mol/mol-Al or more, 0.040 mol/mol-Al or more, or 0.050 mol/mol-Al or more.
- the amount of alkali metal in the Cu-CHA-type zeolite is 0.800 mol/mol-Al or less, 0.800 mol/mol-Al or less per 1 mol of Al atoms in the Cu-CHA-type zeolite. 600 mol/mol-Al or less, 0.400 mol/mol-Al or less, 0.300 mol/mol-Al or less, 0.200 mol/mol-Al or less, 0.100 mol/mol-Al or less, or 0.080 mol/mol- It may be Al or less.
- the amount of the alkaline earth metal in the Cu-CHA-type zeolite is 0.005 mol/mol-Al per 1 mol of Al atoms in the Cu-CHA-type zeolite. 0.010 mol/mol-Al or more, 0.050 mol/mol-Al or more, 0.100 mol/mol-Al or more, 0.150 mol/mol-Al or more, or 0.200 mol/mol-Al or more good.
- the amount of alkaline earth metal in the Cu-CHA-type zeolite is 0.300 mol/mol-Al or less per 1 mol of Al atoms in the Cu-CHA-type zeolite. It may be 0.250 mol/mol-Al or less, 0.200 mol/mol-Al or less, 0.150 mol/mol-Al or less, 0.100 mol/mol-Al or less, or 0.050 mol/mol-Al or less.
- the total valence of Cu, alkali metals, and alkaline earth metals (2 ⁇ Cu (mol) + 1 ⁇ Alkali metal (mol) + 2 ⁇ alkaline earth metal (mol)) is 0.5 mol/mol-Al or more, 0.6 mol/mol-Al or more, 0.7 mol/mol-Al or more, or 0.8 mol /mol-Al or more.
- the ratio of the total valences of Cu, alkali metals and alkaline earth metals to 1 mol of Al atoms in the Cu—CHA zeolite is 1.0 or less, 0.00. It may be 9 or less, or 0.8 or less.
- the exhaust gas purifying catalyst of the present invention is an exhaust gas purifying catalyst containing a Cu-CHA zeolite, the Cu-CHA zeolite having an SAR of 20.0 or less, and an alkali metal and alkaline earth Contains metal.
- the exhaust gas purifying catalyst of the present invention may contain precious metals in addition to such Cu-CHA type zeolite. This noble metal may be carried on the exhaust gas purifying catalyst of the present invention.
- the noble metal contained in the exhaust gas purification catalyst of the present invention may be selected from platinum group elements, particularly palladium (Pd), platinum (Pt), and rhodium (Rh).
- the Cu—CHA-type zeolite contained in the exhaust gas purification catalyst of the present invention is effectively coated with Bronsted acid (1Al site and 2Al site) by the contained alkali metal and alkaline earth metal, and the amount of Bronsted acid is is decreasing.
- the Bronsted acid amount of the Cu—CHA type zeolite contained in the exhaust gas purifying catalyst of the present invention is 0.200 mmol/g or less, 0.190 mmol/g as the millimole amount of Bronsted acid points per 1 g of Cu—CHA type zeolite. 0.180 mmol/g or less, or 0.170 mmol/g or less.
- the Bronsted acid content of the Cu—CHA-type zeolite may be 0.100 mmol/g or more, 0.120 mmol/g or more, or 0.150 mmol/g or more.
- the Bronsted acid content of the Cu-CHA-type zeolite is defined as a value obtained by assigning the integrated value (mmol) of the amount of NH 3 measured as follows by the mass (g) of the Cu-CHA-type zeolite.
- Ru (i) NH 3 was saturated at 100° C. to the Cu—CHA zeolite, and ( ii) the Cu—CHA zeolite with NH 3 was saturated at 35° C./ The temperature is raised to 600°C at a rate of 1 min, and the amount of NH3 contained in the discharged N2 gas is integrated at temperatures from 350°C to 600°C.
- the exhaust gas purification catalyst of the present invention as described above is suitable as an SCR catalyst.
- the exhaust gas purifying catalyst of the present invention is, for example, A Cu-CHA-type zeolite having an SAR of 20.0 or less, and an alkali metal source and an alkaline earth metal source are mixed to obtain a mixture, and calcining the obtained mixture. .
- a Cu-CHA zeolite with an SAR of 20.0 or less may be produced by ion-exchanging a CHA zeolite with an SAR of 20.0 or less with Cu ions. This ion exchange may be carried out by bringing a CHA-type zeolite having an SAR of 20.0 or less into contact with a Cu ion source.
- the Cu ion source may be, for example, a salt such as copper acetate or copper sulfate.
- the CHA-type zeolite with an SAR of 20.0 or less and the Cu ion source may be mixed by either dry mixing or wet mixing. Dry mixing may be done by mixing the two together in a suitable mixer. Wet mixing may be performed by mixing the two together in a suitable solvent (eg, water).
- a suitable solvent eg, water
- the alkali metal source may be an alkali metal nitrate, acetate, carbonate, sulfate, hydroxide, or the like, and one or more selected from these may be used.
- the alkaline earth metal source may be nitrates, acetates, carbonates, sulfates, hydroxides, etc. of alkaline earth metals, and one or more selected from these may be used. .
- the Cu-CHA-type zeolite having an SAR of 20.0 or less and the alkali metal source and alkaline earth metal source may be mixed by either dry mixing or wet mixing.
- Wet blending may be performed by blending both in a suitable blender.
- Wet mixing may be performed by mixing the two together in a suitable solvent (eg, water).
- a mixture obtained by dry-mixing or wet-mixing a Cu—CHA-type zeolite having an SAR of 20.0 or less and an alkali metal source and an alkaline earth metal source is then calcined to obtain the material of the present invention.
- An exhaust gas purifying catalyst is obtained.
- Firing of the mixture may be performed by a known method.
- an exhaust gas purification catalyst device is provided.
- the exhaust gas purifying catalyst device of the present invention is An exhaust gas purifying catalytic device comprising a substrate and a catalyst layer on the substrate, The catalyst layer contains the exhaust gas purification catalyst of the present invention described above, It is an exhaust gas purification catalyst device.
- the base material may be appropriately selected according to the base material in the desired exhaust gas purification catalyst device.
- the constituent material of the base material may be, for example, cordierite, metal, or the like.
- the substrate may be straight-flow or wall-flow.
- the substrate in the exhaust gas purifying catalyst device of the present invention may typically be, for example, a cordierite straight-flow or wall-flow monolith honeycomb substrate.
- the catalyst layer in the exhaust gas purification catalyst device of the present invention contains the exhaust gas purification catalyst of the present invention.
- This catalyst layer may contain optional components other than the exhaust gas purifying catalyst of the present invention.
- Optional components of the catalyst layer may be, for example, inorganic oxides other than the Cu—CHA-type zeolite, binders, and the like.
- Inorganic oxides other than Cu-CHA-type zeolite contained in the catalyst layer may be oxides of one or more elements selected from, for example, aluminum, silicon, titanium, zirconium, rare earth elements, and the like. Specific examples of inorganic oxides include alumina, zirconia, and ceria. A noble metal may be supported on one or more of these inorganic oxides.
- binders contained in the catalyst layer include alumina-based binders, zirconia-based binders, silica-based binders, and titania-based binders.
- the exhaust gas purification catalyst device of the present invention may be manufactured by any method.
- the exhaust gas purifying catalytic device of the present invention may be manufactured, for example, by a method including forming a catalyst layer on a substrate.
- the base material may be appropriately selected according to the base material in the desired exhaust gas purification catalyst device.
- it may be a cordierite straight-flow monolithic honeycomb substrate.
- a coating liquid containing the exhaust gas purifying catalyst of the present invention is coated on this base material to form a coat layer, and the obtained coat layer is baked to form a catalyst layer on the base material. After coating and before baking, the coating layer may be dried, if necessary.
- the coating liquid may contain the exhaust gas purifying catalyst of the present invention and, if necessary, optional components or precursors thereof.
- the solvent of the coating liquid may be water, or an aqueous organic solvent, or a mixture thereof, typically water.
- the coating of the coating liquid, and the drying and baking after coating may be carried out according to known methods.
- a straight-flow type cordierite honeycomb substrate having an apparent volume of about 1 L was coated with the catalyst layer coating slurry so that the coating amount after drying was 120 g/L.
- An exhaust gas purifying catalyst device was manufactured by firing for a period of time.
- the concentration unit "ppm" in the above is parts per million based on mass.
- Table 1 shows the composition of the model gas.
- the present invention aims at reducing the amount of N 2 O produced while maintaining a high NOx purification rate in a Cu—CHA type zeolite having an SAR of about 20.0 or less. was confirmed.
- Manufacture of exhaust gas purifying catalyst device The same Cu-CHA-type zeolite with SAR 7.5 and Cu content per Al atom of 0.22 mol/mol-Al as used in Comparative Example 3, as well as an alkali metal source and alkaline earth Metallic sources were dry mixed in a mortar for 30 minutes. The resulting mixture is calcined in air at 500° C. for 3 hours to produce a Cu—CHA-type zeolite (AM-AEM-containing Cu—CHA) containing alkali metal (AM) and alkaline earth metal (AEM). Obtained.
- An exhaust gas purification catalyst device was manufactured in the same manner as in Comparative Example 1, except that the AM-AEM-containing Cu-CHA obtained above was used instead of the Cu-CHA-type zeolite, and hydrothermal durability was performed. , the N 2 O emission amount and the NOx purification rate were evaluated.
- alkali metal source and alkaline earth metal source the following compounds were used, respectively, depending on the type of metal. "-" in Table 3 indicates that the corresponding alkali metal or alkaline earth metal was not added.
- K potassium nitrate Na: sodium nitrate Ba: barium acetate
- N 2 gas containing 750 ppm of NH 3 was applied to the exhaust gas purifying catalyst device manufactured using the Cu—CHA type zeolite of each comparative example and example at a catalyst layer temperature of 100 ° C. at a space velocity of 600 h ⁇ 1 .
- the mixture was allowed to flow for 30 minutes, and NH 3 was saturated and adsorbed on the exhaust gas purifying catalyst device.
- the circulation gas was switched to N 2 gas, and the temperature of the catalyst layer was raised to 600° C. at a rate of 35° C./min while circulating at a space velocity of 600 h ⁇ 1 .
- the integrated value (mmol) of the amount of NH 3 contained in the exhaust gas at temperatures from 350°C to 600°C is assigned by the mass (g) of the Cu—CHA type zeolite in the exhaust gas purification catalyst device. was taken as the amount of B acid per 1 g of Cu—CHA type zeolite.
- the obtained B acid amount is also shown in Table 3.
- the Cu—CHA-type zeolite contains both alkali metals and alkaline earth metals more than the case where only alkali metals are contained (Comparative Example 5). In Examples 2 and 3, which contained , the decrease in the amount of B acid sites was greater.
- Example 5 calcium was used as the alkaline earth metal, and calcium nitrate was used as the alkaline earth metal source.
- Example 6 when the Cu—CHA-type zeolite contains only calcium as an alkaline earth metal (Comparative Example 12), the N 2 O emission amount and the NOx purification rate at an inlet gas temperature of 300° C. are substantially reduced.
- Example 5 containing potassium as an alkali metal together with calcium as an alkaline earth metal, the NOx purification rate at the inlet gas temperature of 300 ° C. was maintained, while the N 2 O emission amount was reduced. effectively reduced.
- Example 6>> The same Cu-CHA-type zeolite with an SAR of 15.0 and an amount of Cu per Al atom of 0.30 mol/mol-Al as used in Comparative Example 2, and an alkali metal source and an alkaline earth metal source were added in a mortar for 30 minutes. Dry mixed for 1 minute. The resulting mixture was calcined in air at 500° C. for 3 hours to obtain a Cu—CHA type zeolite containing an alkali metal source and an alkaline earth metal (Cu—CHA containing AM-AEM).
- An exhaust gas purification catalyst device was manufactured in the same manner as in Comparative Example 1, except that the AM-AEM-containing Cu-CHA obtained above was used instead of the Cu-CHA-type zeolite, and hydrothermal durability was performed. , the N 2 O emission amount and the NOx purification rate were evaluated.
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Abstract
Description
前記Cu-CHA型ゼオライトは、シリカアルミナ比(SAR)が20.0以下であり、かつ、アルカリ金属及びアルカリ土類金属を含んでいる、
排ガス浄化触媒。
《態様2》前記Cu-CHA型ゼオライトにおけるCu量が、前記Cu-CHA型ゼオライト中のAl原子1モルに対して、0.10mol/mol-Al以上0.40mol/mol-Al以下である、態様1に記載の排ガス浄化触媒。
《態様3》前記アルカリ金属の量が、前記Cu-CHA型ゼオライト中のAl原子1モルに対して、0.005mol/mol-Al以上であり、かつ、
前記アルカリ土類金属の量が、前記Cu-CHA型ゼオライト中のAl原子1モルに対して、0.01mol/mol-Al以上である、
態様1又は2に記載の排ガス浄化触媒。
《態様4》前記アルカリ金属の量が、前記Cu-CHA型ゼオライト中のAl原子1モルに対して、0.10mol/mol-Al以下である、態様1~3のいずれか一項に記載の排ガス浄化触媒。
《態様5》前記アルカリ土類金属の量が、前記Cu-CHA型ゼオライト中のAl原子1モルに対して、0.20mol/mol-Al以下である、態様1~4のいずれか一項に記載の排ガス浄化触媒。
《態様6》前記Cu-CHA型ゼオライトのブレンステッド酸量が、0.200mmol/g以下であり、かつ
前記Cu-CHA型ゼオライトのブレンステッド酸量が、下記のようにして測定されるNH3量の積算値(mmol)を、前記Cu-CHA型ゼオライトの質量(g)で割り付けた値として定義される:
(i)前記Cu-CHA型ゼオライトに対して、100℃にてNH3を飽和吸着させ、そして
(ii)NH3を飽和吸着させた前記Cu-CHA型ゼオライトを、N2ガス流通下に35℃/分の速度で600℃まで昇温させて、排出されるN2ガス中に含まれるNH3量を、350℃以上600℃までの温度で積算する、
態様1~5のいずれか一項に記載の排ガス浄化触媒。
《態様7》前記アルカリ金属が、ナトリウム及びカリウムから選択される、1種又は2種である、態様1~6のいずれか一項に記載の排ガス浄化触媒。
《態様8》前記アルカリ土類金属が、バリウム及びカルシウムから選択される、1種又は2種である、態様1~7のいずれか一項に記載の排ガス浄化触媒。
《態様9》SCR触媒である、態様1~8のいずれか一項に記載の排ガス浄化触媒。
《態様10》基材、及び前記基材上の触媒層を含む、排ガス浄化触媒装置であって、
前記触媒層が、態様1~9のいずれか一項に記載の排ガス浄化触媒を含む、
排ガス浄化触媒装置。
《態様11》SARが20.0以下のCu-CHA型ゼオライト、並びにアルカリ金属源及びアルカリ土類金属源を混合して混合物を得ること、並びに
得られた混合物を焼成すること
を含む、態様1~9のいずれか一項に記載の排ガス浄化触媒の製造方法。
《態様12》前記アルカリ金属源が、アルカリ金属の硝酸塩、炭酸塩、水酸化物、硫酸塩、及び酢酸塩から選択される1種又は2種以上である、態様11に記載の排ガス浄化触媒の製造方法。
《態様13》前記アルカリ土類金属源が、アルカリ土類金属の硝酸塩、炭酸塩、水酸化物、硫酸塩、及び酢酸塩から選択される1種又は2種以上である、態様11又は12に記載の排ガス浄化触媒の製造方法。
本発明の排ガス浄化触媒は、
Cu-CHA型ゼオライトを含む排ガス浄化触媒であって、
Cu-CHA型ゼオライトは、シリカアルミナ比(SAR)が20.0以下であり、かつ、アルカリ金属及びアルカリ土類金属を含んでいる、
排ガス浄化触媒である。
2NO+4NH3+2O2→3N2+6H2O (1)
2NO2+2NO+2NH3→3N2+3H2O (2)
2NO2+2NH3→NH4NO3+N2+H2O (3)
NH4NO3→N2O+2H2O (4)
本発明の排ガス浄化触媒は、Cu-CHA型ゼオライトを含む。「Cu-CHA型ゼオライト」とは、構造コード「CHA」で示されるチャバサイト型のゼオライトを、Cuでイオン交換したものである。
(i)Cu-CHA型ゼオライトに対して、100℃にてNH3を飽和吸着させ、そして
(ii)NH3を飽和吸着させたCu-CHA型ゼオライトを、N2ガス流通下に35℃/分の速度で600℃まで昇温させて、排出されるN2ガス中に含まれるNH3量を、350℃以上600℃までの温度で積算する。
本発明の排ガス浄化触媒は、例えば、
SARが20.0以下のCu-CHA型ゼオライト、並びにアルカリ金属源及びアルカリ土類金属源を混合して混合物を得ること、並びに
得られた混合物を焼成すること
を含む、方法によって製造されてよい。
本発明の別の観点によると、排ガス浄化触媒装置が提供される。
基材、及び基材上の触媒層を含む、排ガス浄化触媒装置であって、
触媒層が、上記に説明した本発明の排ガス浄化触媒を含む、
排ガス浄化触媒装置である。
基材の構成材料は、例えば、コージェライト、金属等であってよい。基材は、ストレートフロー型であっても、ウォールフロー型であってもよい。
本発明の排ガス浄化触媒装置は、任意の方法で製造されてよい。
(1)排ガス浄化触媒装置の製造
シリカアルミナ比(SAR)26.0、Al原子当たりのCu量0.08mol/mol-AlのCu-CHA型ゼオライト、シリコーン系バインダー、及び水を混合して、固形分濃度30質量%の触媒層塗工用スラリーを得た。
得られた排ガス浄化触媒装置に、水蒸気10質量%を含む空気を流通させながら、触媒層温度650℃にて50時間の水熱耐久を行った。
水熱耐久後の排ガス浄化触媒装置に、下記組成のモデルガスを、空間速度80,000h-1にて供給して、流通させながら、入りガス温度300℃におけるN2O排出量及びNOx浄化率、並びに入りガス温度600℃におけるNOx浄化率を評価した。これらの量の評価は、組成が安定した後の排出ガスの組成に基づいて、以下の基準により行った。
N2O排出量:組成が安定した後の排出ガス中のN2O濃度(ppm)
NOx浄化率(%):{1-(排出ガス中のNOx濃度(ppm)/供給ガス中のNOx濃度(ppm)}×100
Cu-CHA型ゼオライトとして、SAR及びCu量が、それぞれ、表2に記載の値のCu-CHA型ゼオライトを用いた他は、比較例1と同様にして、排ガス浄化触媒装置を製造し、水熱耐久を行ったうえで、N2O排出量及びNOx浄化率の評価を行った。
(1)排ガス浄化触媒装置の製造
比較例3で用いたのと同じ、SAR7.5、Al原子当たりのCu量0.22mol/mol-AlのCu-CHA型ゼオライト、並びにアルカリ金属源及びアルカリ土類金属源を、乳鉢中で30分間、乾式混合した。得られた混合物を、空気中、500℃にて3時間焼成して、アルカリ金属(AM)及びアルカリ土類金属(AEM)を含む、Cu-CHA型ゼオライト(AM-AEM含有Cu-CHA)を得た。
アルカリ金属の種類及び量、並びにアルカリ土類金属の量を、それぞれ、表3に記載のとおりとなるように変更した他は、実施例1と同様にして、排ガス浄化触媒装置を製造し、水熱耐久を行ったうえで、N2O排出量及びNOx浄化率の評価を行った。表3において、アルカリ金属及びアルカリ土類金属の量は、それぞれ、ゼオライト中のAl原子1モルに対する金属原子量として示す。
K:硝酸カリウム
Na:硝酸ナトリウム
Ba:酢酸バリウム
比較例3及び50、並びに実施例2及び3で得られたCu-CHA型ゼオライトについては、以下の方法によって、ブレンステッド酸量(B酸量)を測定した。
アルカリ金属及びアルカリ土類金属の種類及び量を、それぞれ、表4に記載のとおりとなるように変更した他は、実施例1と同様にして、排ガス浄化触媒装置を製造し、水熱耐久を行ったうえで、入りガス温度300℃におけるN2O排出量及びNOx浄化率の評価を行った。表4において、アルカリ金属及びアルカリ土類金属の量は、それぞれ、ゼオライト中のAl原子1モルに対する金属原子量として示す。
比較例2で用いたのと同じ、SAR15.0、Al原子当たりのCu量0.30mol/mol-AlのCu-CHA型ゼオライト、並びにアルカリ金属源及びアルカリ土類金属源を、乳鉢中で30分間、乾式混合した。得られた混合物を、空気中、500℃にて3時間焼成して、アルカリ金属源及びアルカリ土類金属を含むCu-CHA型ゼオライト(AM-AEM含有Cu-CHA)を得た。
Claims (13)
- Cu-CHA型ゼオライトを含む排ガス浄化触媒であって、
前記Cu-CHA型ゼオライトは、シリカアルミナ比(SAR)が20.0以下であり、かつ、アルカリ金属及びアルカリ土類金属を含んでいる、
排ガス浄化触媒。 - 前記Cu-CHA型ゼオライトにおけるCu量が、前記Cu-CHA型ゼオライト中のAl原子1モルに対して、0.10mol/mol-Al以上0.40mol/mol-Al以下である、請求項1に記載の排ガス浄化触媒。
- 前記アルカリ金属の量が、前記Cu-CHA型ゼオライト中のAl原子1モルに対して、0.005mol/mol-Al以上であり、かつ、
前記アルカリ土類金属の量が、前記Cu-CHA型ゼオライト中のAl原子1モルに対して、0.01mol/mol-Al以上である、
請求項1又は2に記載の排ガス浄化触媒。 - 前記アルカリ金属の量が、前記Cu-CHA型ゼオライト中のAl原子1モルに対して、0.10mol/mol-Al以下である、請求項1~3のいずれか一項に記載の排ガス浄化触媒。
- 前記アルカリ土類金属の量が、前記Cu-CHA型ゼオライト中のAl原子1モルに対して、0.20mol/mol-Al以下である、請求項1~4のいずれか一項に記載の排ガス浄化触媒。
- 前記Cu-CHA型ゼオライトのブレンステッド酸量が、0.200mmol/g以下であり、かつ
前記Cu-CHA型ゼオライトのブレンステッド酸量が、下記のようにして測定されるNH3量の積算値(mmol)を、前記Cu-CHA型ゼオライトの質量(g)で割り付けた値として定義される:
(i)前記Cu-CHA型ゼオライトに対して、100℃にてNH3を飽和吸着させ、そして
(ii)NH3を飽和吸着させた前記Cu-CHA型ゼオライトを、N2ガス流通下に35℃/分の速度で600℃まで昇温させて、排出されるN2ガス中に含まれるNH3量を、350℃以上600℃までの温度で積算する、
請求項1~5のいずれか一項に記載の排ガス浄化触媒。 - 前記アルカリ金属が、ナトリウム及びカリウムから選択される、1種又は2種である、請求項1~6のいずれか一項に記載の排ガス浄化触媒。
- 前記アルカリ土類金属が、バリウム及びカルシウムから選択される、1種又は2種である、請求項1~7のいずれか一項に記載の排ガス浄化触媒。
- SCR触媒である、請求項1~8のいずれか一項に記載の排ガス浄化触媒。
- 基材、及び前記基材上の触媒層を含む、排ガス浄化触媒装置であって、
前記触媒層が、請求項1~9のいずれか一項に記載の排ガス浄化触媒を含む、
排ガス浄化触媒装置。 - SARが20.0以下のCu-CHA型ゼオライト、並びにアルカリ金属源及びアルカリ土類金属源を混合して混合物を得ること、並びに
得られた混合物を焼成すること
を含む、請求項1~9のいずれか一項に記載の排ガス浄化触媒の製造方法。 - 前記アルカリ金属源が、アルカリ金属の硝酸塩、炭酸塩、水酸化物、硫酸塩、及び酢酸塩から選択される1種又は2種以上である、請求項11に記載の排ガス浄化触媒の製造方法。
- 前記アルカリ土類金属源が、アルカリ土類金属の硝酸塩、炭酸塩、水酸化物、硫酸塩、及び酢酸塩から選択される1種又は2種以上である、請求項11又は12に記載の排ガス浄化触媒の製造方法。
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US20160107119A1 (en) * | 2014-10-16 | 2016-04-21 | Battelle Memorial Institute | CATALYSTS FOR ENHANCED REDUCTION OF NOx GASES AND PROCESSES FOR MAKING AND USING SAME |
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