CN113198524A - Copper molecular sieve catalyst and preparation method and application thereof - Google Patents
Copper molecular sieve catalyst and preparation method and application thereof Download PDFInfo
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- CN113198524A CN113198524A CN202110437096.8A CN202110437096A CN113198524A CN 113198524 A CN113198524 A CN 113198524A CN 202110437096 A CN202110437096 A CN 202110437096A CN 113198524 A CN113198524 A CN 113198524A
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- molecular sieve
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- membered ring
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- 239000002808 molecular sieve Substances 0.000 title claims abstract description 149
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 title claims abstract description 145
- 239000010949 copper Substances 0.000 title claims abstract description 137
- 229910052802 copper Inorganic materials 0.000 title claims abstract description 95
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 93
- 239000003054 catalyst Substances 0.000 title claims abstract description 34
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- 238000000034 method Methods 0.000 claims abstract description 47
- 239000011148 porous material Substances 0.000 claims abstract description 22
- 230000008569 process Effects 0.000 claims abstract description 15
- 150000001413 amino acids Chemical class 0.000 claims abstract description 14
- CSDREXVUYHZDNP-UHFFFAOYSA-N alumanylidynesilicon Chemical compound [Al].[Si] CSDREXVUYHZDNP-UHFFFAOYSA-N 0.000 claims abstract description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 16
- 235000001014 amino acid Nutrition 0.000 claims description 13
- 239000000758 substrate Substances 0.000 claims description 10
- 238000001035 drying Methods 0.000 claims description 8
- OPQARKPSCNTWTJ-UHFFFAOYSA-L copper(ii) acetate Chemical group [Cu+2].CC([O-])=O.CC([O-])=O OPQARKPSCNTWTJ-UHFFFAOYSA-L 0.000 claims description 7
- 229910001868 water Inorganic materials 0.000 claims description 7
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 6
- QNAYBMKLOCPYGJ-REOHCLBHSA-N L-alanine Chemical compound C[C@H](N)C(O)=O QNAYBMKLOCPYGJ-REOHCLBHSA-N 0.000 claims description 6
- 235000004279 alanine Nutrition 0.000 claims description 6
- 238000001354 calcination Methods 0.000 claims description 6
- 229910052782 aluminium Inorganic materials 0.000 claims description 5
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 5
- 239000003638 chemical reducing agent Substances 0.000 claims description 4
- 238000005342 ion exchange Methods 0.000 claims description 4
- WHUUTDBJXJRKMK-UHFFFAOYSA-N Glutamic acid Natural products OC(=O)C(N)CCC(O)=O WHUUTDBJXJRKMK-UHFFFAOYSA-N 0.000 claims description 3
- AYFVYJQAPQTCCC-UHFFFAOYSA-N Threonine Natural products CC(O)C(N)C(O)=O AYFVYJQAPQTCCC-UHFFFAOYSA-N 0.000 claims description 3
- 239000004473 Threonine Substances 0.000 claims description 3
- 229910021529 ammonia Inorganic materials 0.000 claims description 3
- 238000001914 filtration Methods 0.000 claims description 3
- 235000013922 glutamic acid Nutrition 0.000 claims description 3
- 239000004220 glutamic acid Substances 0.000 claims description 3
- 239000007791 liquid phase Substances 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- 229910052710 silicon Inorganic materials 0.000 claims description 3
- 239000010703 silicon Substances 0.000 claims description 3
- MTCFGRXMJLQNBG-REOHCLBHSA-N (2S)-2-Amino-3-hydroxypropansäure Chemical compound OC[C@H](N)C(O)=O MTCFGRXMJLQNBG-REOHCLBHSA-N 0.000 claims description 2
- WHUUTDBJXJRKMK-VKHMYHEASA-N L-glutamic acid Chemical compound OC(=O)[C@@H](N)CCC(O)=O WHUUTDBJXJRKMK-VKHMYHEASA-N 0.000 claims description 2
- AYFVYJQAPQTCCC-GBXIJSLDSA-N L-threonine Chemical compound C[C@@H](O)[C@H](N)C(O)=O AYFVYJQAPQTCCC-GBXIJSLDSA-N 0.000 claims description 2
- MTCFGRXMJLQNBG-UHFFFAOYSA-N Serine Natural products OCC(N)C(O)=O MTCFGRXMJLQNBG-UHFFFAOYSA-N 0.000 claims description 2
- 239000007864 aqueous solution Substances 0.000 claims description 2
- 238000010531 catalytic reduction reaction Methods 0.000 claims description 2
- 238000002485 combustion reaction Methods 0.000 claims description 2
- 150000001875 compounds Chemical class 0.000 claims description 2
- 229910000365 copper sulfate Inorganic materials 0.000 claims description 2
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 claims description 2
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 claims description 2
- 235000004400 serine Nutrition 0.000 claims description 2
- 235000008521 threonine Nutrition 0.000 claims description 2
- 230000003197 catalytic effect Effects 0.000 abstract description 11
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 22
- 238000006243 chemical reaction Methods 0.000 description 20
- 239000000203 mixture Substances 0.000 description 20
- 229910052593 corundum Inorganic materials 0.000 description 15
- 229910001845 yogo sapphire Inorganic materials 0.000 description 15
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 13
- 230000000052 comparative effect Effects 0.000 description 12
- 239000007789 gas Substances 0.000 description 10
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 8
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 8
- 239000000843 powder Substances 0.000 description 8
- 238000003756 stirring Methods 0.000 description 8
- 229910021536 Zeolite Inorganic materials 0.000 description 7
- 239000008367 deionised water Substances 0.000 description 7
- 229910021641 deionized water Inorganic materials 0.000 description 7
- 238000002474 experimental method Methods 0.000 description 7
- 238000012360 testing method Methods 0.000 description 7
- 239000010457 zeolite Substances 0.000 description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 239000000499 gel Substances 0.000 description 6
- 229910000069 nitrogen hydride Inorganic materials 0.000 description 6
- 239000000377 silicon dioxide Substances 0.000 description 6
- 230000032683 aging Effects 0.000 description 5
- 230000001588 bifunctional effect Effects 0.000 description 5
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- 238000004435 EPR spectroscopy Methods 0.000 description 4
- 235000019270 ammonium chloride Nutrition 0.000 description 4
- 238000001362 electron spin resonance spectrum Methods 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 3
- 230000006872 improvement Effects 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 239000000741 silica gel Substances 0.000 description 3
- 229910002027 silica gel Inorganic materials 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- 238000005303 weighing Methods 0.000 description 3
- RKMGAJGJIURJSJ-UHFFFAOYSA-N 2,2,6,6-Tetramethylpiperidine Substances CC1(C)CCCC(C)(C)N1 RKMGAJGJIURJSJ-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 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 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- DKNWSYNQZKUICI-UHFFFAOYSA-N amantadine Chemical compound C1C(C2)CC3CC2CC1(N)C3 DKNWSYNQZKUICI-UHFFFAOYSA-N 0.000 description 2
- 229960003805 amantadine Drugs 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 229910052681 coesite Inorganic materials 0.000 description 2
- 229910052906 cristobalite Inorganic materials 0.000 description 2
- 230000018044 dehydration Effects 0.000 description 2
- 238000006297 dehydration reaction Methods 0.000 description 2
- 230000036571 hydration Effects 0.000 description 2
- 238000006703 hydration reaction Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- -1 polytetrafluoroethylene Polymers 0.000 description 2
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 2
- 239000004810 polytetrafluoroethylene Substances 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- 238000010791 quenching Methods 0.000 description 2
- 230000000171 quenching effect Effects 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- 239000010935 stainless steel Substances 0.000 description 2
- 229910052682 stishovite Inorganic materials 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 229910052723 transition metal Inorganic materials 0.000 description 2
- 150000003624 transition metals Chemical class 0.000 description 2
- 229910052905 tridymite Inorganic materials 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 229910000323 aluminium silicate Inorganic materials 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000001311 chemical methods and process Methods 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 238000006356 dehydrogenation reaction Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 229910001387 inorganic aluminate Inorganic materials 0.000 description 1
- 229910052909 inorganic silicate Inorganic materials 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000005504 petroleum refining Methods 0.000 description 1
- 231100000572 poisoning Toxicity 0.000 description 1
- 230000000607 poisoning effect Effects 0.000 description 1
- 238000010926 purge Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000002407 reforming Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000007873 sieving Methods 0.000 description 1
- 238000003980 solgel method Methods 0.000 description 1
- 239000011973 solid acid Substances 0.000 description 1
- 238000000967 suction filtration Methods 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000004876 x-ray fluorescence Methods 0.000 description 1
Images
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- 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
- B01J29/50—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the erionite or offretite type, e.g. zeolite T, as exemplified by patent document US2950952
- B01J29/52—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the erionite or offretite type, e.g. zeolite T, as exemplified by patent document US2950952 containing iron group metals, noble metals or copper
- B01J29/56—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
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/86—Catalytic processes
- B01D53/90—Injecting reactants
-
- 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
- B01J37/30—Ion-exchange
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2251/00—Reactants
- B01D2251/20—Reductants
- B01D2251/206—Ammonium compounds
- B01D2251/2062—Ammonia
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2257/00—Components to be removed
- B01D2257/40—Nitrogen compounds
- B01D2257/404—Nitrogen oxides other than dinitrogen oxide
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2258/00—Sources of waste gases
- B01D2258/01—Engine exhaust gases
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- 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
- B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
- B01J2229/10—After treatment, characterised by the effect to be obtained
- B01J2229/18—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself
- B01J2229/186—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself not in framework positions
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- 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
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- Chemical & Material Sciences (AREA)
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- Organic Chemistry (AREA)
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- Environmental & Geological Engineering (AREA)
- General Chemical & Material Sciences (AREA)
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- Analytical Chemistry (AREA)
- Crystallography & Structural Chemistry (AREA)
- Biomedical Technology (AREA)
- Health & Medical Sciences (AREA)
- Combustion & Propulsion (AREA)
- Catalysts (AREA)
- Silicates, Zeolites, And Molecular Sieves (AREA)
Abstract
The invention relates to a copper molecular sieve catalyst, a preparation method and application thereof, in particular to an eight-membered ring small pore molecular sieve loaded with copper and application thereof in a mobile source tail gas treatment process. A copper molecular sieve which is an eight-membered ring small pore molecular sieve loaded with copper, wherein isolated Cu is contained in the copper molecular sieve2+Has a relative mass content of x, Cu (OH)+The relative content by mass of (A) is 1-x,x is 70-90%; and the silicon-aluminum ratio in the copper molecular sieve is 8-21. The invention obtains two different copper species, namely Cu (OH), by introducing amino acid in the copper-carrying process of the copper-type molecular sieve+And isolated Cu2+The relative proportion of the copper molecular sieve is controlled in an optimized range, so that the catalytic performance is obviously improved, and the practicability is improved.
Description
The application is a divisional application of an invention patent application with the invention name of 'copper molecular sieve catalyst and a preparation method and application thereof' on application date 2021.01.29 and application number 202110122611.3.
Technical Field
The invention relates to a copper molecular sieve catalyst, a preparation method and application thereof, in particular to an eight-membered ring small pore molecular sieve loaded with copper and application thereof in a mobile source tail gas treatment process.
Background
Molecular sieves have been widely used as solid acid catalysts with excellent properties in petroleum refining and chemical processes. The regular and uniform pore structure, pore size close to that of reactant molecules and proper acidity are the basis for the wide application of molecular sieve catalysts. The metal component is introduced into the molecular sieve to form the bifunctional catalyst, and the catalyst shows excellent catalytic performance in a plurality of reaction processes such as hydrogenation, dehydrogenation, reforming and the like by virtue of the synergistic effect of the acid center and the metal center. Common metal components in the bifunctional catalyst include transition metals such as nickel, cobalt, iron, and copper.
In recent years, transition metal supported eight-membered ring small pore molecular sieves are one of the most interesting bifunctional catalysts, and have been successfully commercially applied in the process of denitration of mobile source tail gas at present. Due to the obvious stability, excellent catalytic activity and hydrocarbon poisoning resistance, the bifunctional catalyst has a wider application prospect.
CN110721736A discloses a preparation method of a copper-containing molecular sieve-metal oxide composite catalyst, which comprises preparing a precursor of a metal oxide by a sol-gel process, and then compounding the precursor with a copper-containing molecular sieve according to a specific ratio by means of an impregnation process. Compared with the technical scheme of preparing the copper type molecular sieve by the conventional liquid phase ion exchange method, the method has a complex preparation process and is not beneficial to industrial production.
The catalytic performance of the above bifunctional catalysts still needs to be improved.
Disclosure of Invention
The inventors have found that for copper molecular sieve catalysts, the chemical state of the copper species in the molecular sieve has a crucial influence on the catalytic performance, and the catalytic performance of the copper species is significantly improved when the copper species is present in a specific chemical state.
The invention provides a copper molecular sieve, which is an eight-membered ring small pore molecular sieve loaded with copper, wherein isolated Cu in the copper molecular sieve2+Has a relative mass content of x, Cu (OH)+The relative mass content of the compound is 1-x, and x is 70-90 percent; and the silicon-aluminum ratio in the copper molecular sieve is 8-21.
Through a great deal of research, the inventor discovers that the isolated Cu in the copper molecular sieve obtained by the conventional preparation method2+The content is low, which causes the copper molecular sieve to be in NH3NO conversion in SCR reactions is difficult to increase. The invention controls two different copper species in the copper molecular sieve, namely Cu (OH)+And isolated Cu2+Within the above-mentioned range of the relative content or relative proportion by mass, the catalytic performance can be remarkably improved, thereby achieving an improvement in the practicality.
According to an embodiment of the present invention, in the copper molecular sieve, isolated Cu2+The relative mass content of (a), x, is 70% to 90%, optionally 71% to 87%, specifically 70%, 71%, 72%, 74%, 77%, 80%, 81%, 83%, 87%, 90%, for example.
According to an embodiment of the present invention, in the copper molecular sieve, Cu (OH)+The relative content by mass of (A) can be selected from 10% -30%, can be selected from 13% -28%, and specifically is 10%, 13%, 17% for example％、19％、20％、23％、26％、28％、29％、30％。
According to an embodiment of the present invention, in the copper molecular sieve, the silica-alumina ratio may be 8 to 21, optionally 8.3 to 20.4, specifically, 8, 8.24, 8.30, 13.73, 13.89, 14.28, 18.10, 20.32, 20.40, 20.41, 21.
According to an embodiment of the invention, the eight-membered ring small pore molecular sieve may be selected from CHA, AEI, LTA and AFX, wherein CHA, AEI are preferred.
According to an embodiment of the present invention, the copper content in the copper molecular sieve is 2.5 wt% to 3.5 wt%, optionally 2.7 wt% to 3.2 wt%, specifically, for example, 2.5 wt%, 2.56 wt%, 2.64 wt%, 2.75 wt%, 2.86 wt%, 2.92 wt%, 2.94 wt%, 3.02 wt%, 3.37 wt%, 3.5 wt%.
In another aspect, the invention also provides a preparation method of the copper molecular sieve.
The inventors surprisingly found that the introduction of amino acid into the copper-negative process of a copper-type molecular sieve can well control two different copper species, namely Cu (OH)+And isolated Cu2+In a certain amount or relative proportion, thereby significantly improving the catalytic performance thereof.
A process for preparing copper molecular sieve includes mixing eight-membered small-pore molecular sieve, copper source and amino acid, and calcining.
It will be understood by those skilled in the art that, in the method for preparing the copper molecular sieve of the present invention, the eight-membered ring small pore molecular sieve includes a hydrogen type eight-membered ring small pore molecular sieve and an ammonia type eight-membered ring small pore molecular sieve.
According to the embodiment of the invention, the eight-membered ring small pore molecular sieve, the copper source and the amino acid are mixed in the aqueous solution for liquid phase ion exchange, and then the mixture is filtered, dried and roasted.
According to the embodiment of the invention, the mass ratio of the eight-membered ring small pore molecular sieve, the copper source and the amino acid is 1 (0.1-1.0) to (0.05-0.5).
Research finds that the introduction of amino acid in the copper-negative process can well control two different copper species, namely Cu (OH)+And isolated Cu2+In the relative amounts or relative proportions by mass ofWithin the desired range.
According to an embodiment of the invention, the copper source may be selected from copper acetate, copper nitrate, copper sulfate.
According to an embodiment of the present invention, the amino acid may be selected from one or more of alanine, glutamic acid, threonine, and serine.
According to an embodiment of the invention, the eight-membered ring small pore molecular sieve, the copper source and the amino acid may be mixed in water, treated at 30-90 ℃ for 1-24h (in some embodiments, at 65-75 ℃ for 3h), dried and then calcined. Thus, isolated Cu in the copper type molecular sieve can be promoted2+The content of (a).
According to the embodiment of the invention, the roasting can be carried out in an air atmosphere, and can be generally carried out for 4-8 h.
The invention also provides a catalyst, which comprises the copper molecular sieve and a honeycomb substrate.
According to an embodiment of the invention, the copper molecular sieves of the catalyst are deposited on a honeycomb substrate.
According to embodiments of the invention, the honeycomb substrate may be selected from a wall-flow substrate or a flow-through substrate.
According to an embodiment of the invention, the catalyst further comprises a binder, which is an alumina or zirconia based binder.
The invention also provides the application of the catalyst in selective catalytic reduction of ammonia.
The present invention also provides a method for treating exhaust gas, comprising bringing a NOx-containing combustion exhaust gas into contact with the above-mentioned catalyst.
The present invention also provides an exhaust gas treatment device comprising the above catalyst, wherein exhaust gas is delivered from a diesel engine to a location downstream of an exhaust gas device, where a reducing agent is added, and an exhaust gas stream comprising the added reducing agent is delivered to the catalyst.
Definition of terms
As used herein, the mass relative content refers to Cu (OH) in the copper molecular sieve+Or isolated Cu2+Mass ofCu(OH)+And isolated Cu2+Percentage of the sum of the masses of (a).
As used herein, the eight-membered ring small pore molecular sieve refers to a molecular sieve having 8T atoms constituting the pore opening as defined by the Structure Commission of the International Zeolite Association.
Herein, the silica to alumina ratio refers to the molar ratio of silica to alumina in the copper molecular sieve.
Herein, "CHA" refers to a zeolite having a framework structure code CHA as identified by the International Zeolite Association (IZA) structure committee.
Herein, "AEI" refers to a zeolite having a framework structure code AEI as identified by the International Zeolite Association (IZA) structure committee.
Herein, "calcining" or "calcining" refers to heating a material in air, oxygen, or an inert atmosphere. Calcination is performed to decompose the metal salt and promote metal ion exchange within the catalyst.
Herein, "zeolite" refers to aluminosilicate molecular sieves comprising a framework of alumina and silica configurations (i.e., repeating SiO4 and AlO4 tetrahedral units), and also includes doping of other elements in the framework structure. Under certain synthesis conditions, the zeolite may be "siliceous", meaning that aluminum is present only as an impurity.
The invention obtains two different copper species, namely Cu (OH), by introducing amino acid in the copper-carrying process of the copper-type molecular sieve+And isolated Cu2+The relative proportion of the copper molecular sieve is controlled in an optimized range, so that the catalytic performance is obviously improved, and the practicability is improved. Experimental results show that the NH of the copper type molecular sieve obtained in the embodiment of the invention3The SCR performance is obviously improved, the NO conversion rate of a fresh sample at 200 ℃ reaches 99%, the NO conversion rate of a fresh sample at 550 ℃ reaches 85%, the NO conversion rate of the aged sample at 200 ℃ reaches 95%, and the NO conversion rate of the aged sample at 550 ℃ reaches 75%, and the SCR performance is superior to that of a comparative sample. The copper molecular sieve prepared by the invention is in NH3The catalyst has excellent catalytic performance in SCR reaction and has wide application prospect in the process of treating tail gas of a mobile source.
Drawings
FIG. 1 is an EPR spectrum measured in a dehydrated and hydrated state in a fresh state for Cu-CHA molecular sieve 2A prepared in example 2 and molecular sieve 2A-1 prepared in comparative example 1.
Detailed Description
The present application will be described in detail with reference to examples, but the present application is not limited to these examples.
The raw materials in the examples of the present application were all purchased commercially, unless otherwise specified.
The analysis method in the examples of the present application is as follows:
the silicon to aluminum ratio of the sample was determined using a Japanese ZSX Primus II X-ray fluorescence spectrometer.
The copper to aluminum ratio of the samples was determined using an Agilent Varian715-ES type plasma emission spectrometer.
And determining the type and relative content of copper species in the copper molecular sieve by using a quantum EPR100 type continuous wave electron paramagnetic resonance spectrometer.
The calculation of the NO conversion in the examples of the present application is performed according to the following formula:
NO conversion rate (reactor inlet NO concentration-reactor outlet NO concentration)/(reactor inlet NO concentration) × 100%
In the examples of the present application, the NO conversion was calculated based on the nitrogen mole number.
Example 1 preparation of H-CHA molecular sieves 1A, 1B and 1C
372.0 g of 25 wt% N, N, N-trimethyl amantadine hydroxide as a template agent is added into 319.5 g of deionized water, the mixture is uniformly mixed, 12.9 g of sodium hydroxide is added into the mixture, the mixture is fully stirred, 53.2 g of sodium metaaluminate (the content of alumina is 51 wt%) is added into the mixture, the mixture is fully stirred, and finally 150.0 g of solid silica gel (SiO is added2Content 98 wt%), stirring for 2h gave the starting gel. Al in the starting gel2O3、SiO2N, N, N-trimethyl amantadine hydroxide, OH-And H2The molar ratio of O is 1: 10.00: 1.67: 2.86: 124.92. transferring the initial gel into a stainless steel reaction kettle with a polytetrafluoroethylene lining, crystallizing at 165 ℃ for 36 hours, taking out, quenching, carrying out solid-liquid separation on a crystallized product, washing, drying,obtaining Na-CHA molecular sieve raw powder. Roasting the obtained molecular sieve raw powder at 550 ℃ for 6 hours, then exchanging the molecular sieve raw powder at 65 ℃ for 3 hours by using an ammonium chloride solution according to the proportion that 10ml of the ammonium chloride solution (the concentration is 1mol/L) is added into each gram of the molecular sieve, washing and drying the molecular sieve raw powder, roasting the molecular sieve raw powder at 520 ℃ for 6 hours to obtain the H-CHA molecular sieve, and measuring the SiO of the molecular sieve raw powder by an XRF method2/Al2O3Sample 1A was taken as sample 8.12.
According to the above experimental method, the amount of sodium metaaluminate added was adjusted to 32.7 g and 22.3 g, respectively, and other experimental steps and conditions were kept unchanged to prepare H-CHA molecular sieves 1B and 1C, SiO of the two samples2/Al2O313.76 and 20.25 respectively.
Example 2 preparation of Cu-CHA molecular sieves 2A, 2B and 2C
3.6g alanine was added to 350mL deionized water, stirred well to dissolve, then 10.5g copper acetate (Cu (CH)3COO)2·H2O), fully stirring, weighing 50g of H-CHA molecular sieve 1A prepared according to the method and conditions in the embodiment 1, adding the mixture, heating to 65 ℃, stirring for 3H, filtering, drying, and finally roasting in an air atmosphere at 550 ℃ for 4H to obtain Cu-CHA molecular sieve 2A. The SiO of the obtained Cu-CHA molecular sieve 2A is determined by an XRF method2/Al2O3The Cu content was measured by ICP method to be 3.02 wt% as 8.30.
According to the experimental method, the H-CHA molecular sieves 1B and 1C are respectively subjected to copper exchange, the experimental steps and conditions are kept unchanged, Cu-CHA molecular sieves 2B and 2C are prepared, and SiO of the obtained samples is measured by an XRF method2/Al2O313.89 and 20.41, respectively, and Cu contents of 2.75 wt% and 2.56 wt% as measured by the ICP method.
EXAMPLE 3 preparation of Cu-CHA molecular sieves 3A, 3B and 3C
4.2g glutamic acid was added to 350mL deionized water, stirred well to dissolve, and then 13.5g copper acetate (Cu (CH)3COO)2·H2O), fully stirring, weighing 50g of the H-CHA molecular sieve 1A obtained in the example 1, adding the mixture, heating to 65 ℃, stirring for 3H, filtering, drying, finally roasting in an air atmosphere at 550 ℃ for 4H,obtaining the Cu-CHA molecular sieve 3A. The SiO of the obtained Cu-CHA molecular sieve 3A is determined by an XRF method2/Al2O3Cu content was measured by ICP method to 8.24 and was 3.37 wt%.
According to the experimental method, the H-CHA molecular sieves 1B and 1C are respectively subjected to copper exchange, the experimental steps and conditions are kept unchanged, Cu-CHA molecular sieves 2B and 2C are prepared, and SiO of the obtained samples is measured by an XRF method2/Al2O313.73 and 20.32, respectively, and Cu contents of 2.92 wt% and 2.86 wt% as measured by ICP method.
Example 4 preparation of H-AEI molecular sieves 4A and 4B
285.8 g of 25 wt% hydroxide-1, 1,3, 5-tetramethylpiperidine solution as a template agent is added into 383.3 g of deionized water, the mixture is uniformly mixed, 48.3 g of sodium hydroxide is added into the mixture, the mixture is fully stirred, and 60.0 g of ultrastable Y molecular sieve (USY, SiO is the ratio of silicon to aluminum)2/Al2O312, silica content 88.8 wt%, alumina content 11.2 wt%) was added thereto, stirred well, and finally 96.0 g of solid silica gel (SiO) was added2Content 98 wt%), stirring for 2h gave the starting gel. Al in the starting gel2O3、 SiO 21,1,3, 5-tetramethylpiperidine hydroxide, OH-and H2The molar ratio of O is 1: 22.00: 4.10: 14.70: 297.15. and transferring the initial gel to a stainless steel reaction kettle with a polytetrafluoroethylene lining, crystallizing at 150 ℃ for 48 hours, taking out, quenching, carrying out solid-liquid separation on a crystallized product, washing and drying to obtain the Na-AEI molecular sieve raw powder. Roasting the obtained molecular sieve raw powder at 550 deg.C for 6 hr, then exchanging with ammonium chloride solution at 65 deg.C for 3 hr according to the proportion of adding 10ml ammonium chloride solution (concentration is 1mol/L) into each gram of molecular sieve, roasting at 520 deg.C for 6 hr to obtain H-AEI molecular sieve, measuring its SiO by XRF method2/Al2O3Sample 4A was taken as sample 18.97.
According to the experimental method, the adding amounts of the ultrastable Y molecular sieve and the solid silica gel are respectively adjusted to 76.57 g and 70.1 g, other experimental steps and conditions are kept unchanged, the H-AEI molecular sieve 4B is prepared, and the SiO of the obtained sample is2/Al2O3It was 14.15.
EXAMPLE 5 preparation of Cu-AEI molecular sieves 5A and 5B
6.1g threonine was added to 350mL deionized water, stirred well to dissolve, and then 15.0g copper acetate (Cu (CH)3COO)2·H2O), fully stirring, weighing 50g of H-AEI molecular sieve 4A prepared according to the method and conditions in the embodiment 4, adding the mixture, then heating to 75 ℃, stirring for 3H, carrying out suction filtration, drying, and finally roasting in an air atmosphere at 550 ℃ for 4H to obtain the Cu-AEI molecular sieve 5A. The SiO of the obtained Cu-AEI molecular sieve 5A is measured by an XRF method2/Al2O3The Cu content was measured by ICP as 18.10 and was 2.64 wt%.
According to the experimental method, the Cu-AEI molecular sieve 5B is prepared by carrying out copper exchange on the H-AEI molecular sieve 4B and keeping the experimental steps and conditions unchanged, and the SiO of the obtained sample is measured by an XRF method2/Al2O3Each 14.28, and a Cu content of 2.94 wt% by ICP method.
Comparative example 1 preparation of Cu-CHA molecular sieves 2A-1, 2B-1 and 2C-1
10.5g of copper acetate (Cu (CH)3COO)2·H2O) is added into 350mL of deionized water, fully stirred until the mixture is dissolved, then the mixture is added and fully stirred, 50g of the H-CHA molecular sieve 1A prepared according to the method and the conditions in the embodiment 1 is weighed and added into the mixture, then the mixture is heated to 65 ℃ and stirred for 3H, filtered, dried and finally roasted for 4H in an air atmosphere at 550 ℃ to obtain the Cu-CHA molecular sieve 2A-1. The SiO of the obtained Cu-CHA molecular sieve 2A is determined by an XRF method2/Al2O3Cu content was measured by ICP method to 8.36 and was 3.14 wt%.
According to the above experimental method, the Cu-CHA molecular sieves 2B-1 and 2C-1 are prepared by respectively performing copper exchange on the H-CHA molecular sieves 1B and 1C, keeping the experimental steps and conditions unchanged, and measuring the SiO of the obtained samples by an XRF method2/Al2O313.94 and 20.37, respectively, and Cu contents of 2.62 wt% and 2.43 wt% as measured by the ICP method.
Comparative example 2 preparation of Cu-AEI molecular sieves 5A-1 and 5B-1
15.0g of copper acetate (Cu (CH)3COO)2·H2O) is added into 350mL of deionized water, fully stirred until the mixture is dissolved, then the mixture is added and fully stirred, 50g of H-AEI molecular sieve 4A prepared according to the method and the conditions in the embodiment 4 is weighed and added into the mixture, then the mixture is heated to 75 ℃ and stirred for 3H, filtered, dried and finally roasted for 4H in an air atmosphere at 550 ℃ to obtain the Cu-AEI molecular sieve 5A-1. The SiO of the obtained Cu-AEI molecular sieve 4A is measured by an XRF method2/Al2O3The Cu content was 2.78 wt% by ICP measurement 18.28.
According to the experimental method, the Cu-AEI molecular sieve 5B-1 is prepared by carrying out copper exchange on the H-AEI molecular sieve 4B and keeping the experimental steps and conditions unchanged, and the SiO of the obtained sample is measured by an XRF method2/Al2O3Each 14.11, and the Cu content was 3.05 wt% by ICP method.
Example 6 EPR testing of Cu-CHA molecular sieves 2A, 2B, 2C, 3A, 3B, 3C, 2A-1, 2B-1, 2C-1 and Cu-AEI molecular sieves 5A, 5B, 5A-1 and 5B-1
Cu-CHA and Cu-AEI molecular sieves obtained in example 2, example 3, example 5, comparative example 1 and comparative example 2 were characterized for copper species in the fresh and aged states, respectively, using EPR. The aging conditions were: 10 percent (volume fraction) of water vapor at 800 ℃, and the aging time is 10 hours; the test conditions were that the sample mass was 50mg, the scanning time was 240 seconds, the microwave power was 0.2mW, the modulation frequency was 100kHz, and the modulation amplitude was 2 Gauss. And respectively testing EPR spectrograms of the sample in hydration and dehydration states, wherein the dehydration condition is 300 ℃ purging for 4h, and the untreated sample is in the hydration state. EPR spectra of the Cu-CHA molecular sieve 2A prepared in example 2 and the molecular sieve 2A-1 prepared in comparative example 1 in dehydrated and hydrated state are shown in FIG. 1, in which a peak at 3400G on the EPR spectrum in the hydrated state represents Cu (OH)+And isolated Cu2+Sum of (1), peak at 3400G in dehydrated state represents Cu2+. Cu (OH) was determined by twice integrating the peak area of the sample tested at two different states+And isolated Cu2+The relative contents by mass of (A) are shown in Table 1.
TABLE 1 Cu (OH) in copper molecular sieves+And isolated Cu2+Relative mass content of
In Table 1, Cu (OH)+Relative content by mass, isolated Cu2+The mass relative content refers to Cu (OH) in the copper molecular sieve+Isolated Cu2+Account for Cu (OH)+And isolated Cu2+Percentage of the sum of the masses of (a).
Example 7 catalytic Performance testing of Cu-CHA molecular sieves 2A, 2B, 2C, 3A, 3B, 3C, 2A-1, 2B-1, 2C-1 and Cu-AEI molecular sieves 5A, 5B, 5A-1 and 5B-1
The Cu-CHA and Cu-AEI molecular sieves obtained in example 2, example 3, example 5, comparative example 1 and comparative example 2 were aged under the following conditions: at 800 deg.C, 10% (volume fraction) of water vapor, and aging for 10 h. Tabletting and sieving fresh and aged copper molecular sieve catalyst, and taking 20-40 mesh molecular sieve particles as NH3Evaluation of the performance of the SCR catalytic reaction. The test is carried out on a small-sized fixed bed reactor, the test temperature is 100-550 ℃, the normal pressure is realized, and the reaction space velocity is 100000h-1，NH3The concentration is 500ppm, the NO concentration is 500ppm, 5% (volume fraction) O2，N2As a balance gas. Fresh and aged Cu-CHA molecular sieve catalysts 2A, 2B, 2C, 3A, 3B, 3C, 2A-1, 2B-1, 2C-1 and Cu-AEI molecular sieve catalysts 5A, 5B, 5A-1 and 5B-1 at NH3Results of the conversion test at different temperatures of NO in the SCR reaction are shown in table 2.
In which EPR spectra measured in a dehydrated and hydrated state in a fresh state of the Cu-CHA molecular sieve 2A prepared in example 2 and the molecular sieve 2A-1 prepared in comparative example 1 are shown in FIG. 1.
Table 2 fresh and aged copper molecular sieve catalyst in NH3NO conversion in SCR reactions
Respectively prepared in comparative example 2 and comparative example 1The prepared series of copper-type molecular sieves Cu-CHA molecular sieves 2A-2C and Cu-CHA molecular sieves 2A-1-2C-1 can be seen from Table 1 that the fresh state of a sample obtained by introducing alanine in the copper-negative process is isolated bivalent copper Cu2+The relative mass content of the Cu is 72-83%, and the Cu is an aging isolated divalent copper2+The mass relative content is 85-93%; fresh state isolated bivalent copper Cu of sample obtained without introducing amino acid in copper-negative process2+The relative mass content of the Cu is 49-65%, and the Cu is an aging isolated divalent copper2+The mass relative content is 73-82%; namely, the introduction of alanine in the copper-negative process remarkably improves the isolation of bivalent copper Cu in the Cu-CHA molecular sieve2+Mass relative content. As can be seen from Table 2, for the samples with the same Si/Al ratio and copper content, the introduction of alanine by the negative copper process significantly improved the NH content3NO conversion in SCR reaction at 200 ℃ and 550 ℃.
Although the invention has been described in detail hereinabove with respect to specific embodiments thereof, it will be apparent to those skilled in the art that modifications and improvements can be made thereto without departing from the scope of the invention. Accordingly, such modifications and improvements are intended to be within the scope of the invention as claimed.
Claims (12)
1. A copper molecular sieve is characterized in that the copper molecular sieve is an eight-membered ring small pore molecular sieve loaded with copper, and isolated Cu in the copper molecular sieve2+Has a relative mass content of x, Cu (OH)+The relative mass content of the compound is 1-x, and x is 70-90 percent; and the silicon-aluminum ratio in the copper molecular sieve is 8-21.
2. The copper molecular sieve of claim 1, wherein x is 71% to 87%; optionally, x is 70%, 71%, 72%, 74%, 77%, 80%, 81%, 83%, 87%, or 90%.
3. The copper molecular sieve of claim 1 or 2, wherein the ratio of silicon to aluminum in the copper molecular sieve is 8.3 to 20.4; preferably 8.3 to 13.89; and may be selected from 8, 8.24, 8.30, 13.73, 13.89, 14.28, 18.10, 20.32, 20.40, 20.41 or 21.
4. The copper molecular sieve of any of claims 1 to 3, wherein the eight-member ring small pore molecular sieve is selected from CHA, AEI, LTA and AFX.
5. The copper molecular sieve of any one of claims 1 to 4, wherein the copper content of the copper molecular sieve is from 2.5 wt% to 3.5 wt%; preferably 2.7 wt% to 3.2 wt%; and may be selected to be 2.5 wt%, 2.56 wt%, 2.64 wt%, 2.75 wt%, 2.86 wt%, 2.92 wt%, 2.94 wt%, 3.02 wt%, 3.37 wt% or 3.5 wt%.
6. The process of any one of claims 1 to 5, wherein the process comprises mixing the eight-membered ring small pore molecular sieve, the copper source and the amino acid in an aqueous solution, performing liquid phase ion exchange, filtering, drying and calcining.
7. The preparation method according to claim 6, wherein the mass ratio of the eight-membered ring small pore molecular sieve, the copper source and the amino acid is 1 (0.1-1.0) to (0.05-0.5); and/or the presence of a gas in the gas,
the copper source is selected from copper acetate, copper nitrate and copper sulfate; and/or the presence of a gas in the gas,
the amino acid is selected from one or more of alanine, glutamic acid, threonine and serine.
8. The method of claim 6 or 7, comprising mixing the eight-membered ring small pore molecular sieve, the copper source and the amino acid in water, treating at 30-90 ℃ for 1-24h, drying and calcining; alternatively, the treatment is carried out for 3h at the temperature of 65-75 ℃.
9. A catalyst comprising the copper molecular sieve of any one of claims 1 to 5; the catalyst further comprises a honeycomb substrate; optionally, the copper molecular sieves are deposited on the honeycomb substrate; alternatively, the honeycomb substrate may be selected from a wall flow substrate or a flow-through substrate.
10. Use of a copper molecular sieve according to any one of claims 1 to 5 or a copper molecular sieve prepared by a process according to any one of claims 6 to 8 or a catalyst according to claim 9 in ammonia selective catalytic reduction; optionally, the temperature at the time of application is 200 ℃.
11. A method for treating exhaust gas, comprising contacting a NOx-containing combustion exhaust gas with the copper molecular sieve of any one of claims 1 to 5 or the copper molecular sieve produced by the method of any one of claims 6 to 8 or the catalyst of claim 9.
12. An exhaust gas treatment device comprising the catalyst of claim 9, wherein exhaust gas is delivered from a diesel engine to a location downstream of an exhaust gas device where a reducing agent is added, and an exhaust gas stream comprising the added reducing agent is delivered to the catalyst.
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| US20050133053A1 (en) * | 2003-12-22 | 2005-06-23 | Philip Morris Usa Inc. | Smoking articles comprising copper-exchanged molecular sieves |
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| CN110523432A (en) * | 2019-10-29 | 2019-12-03 | 山东国瓷功能材料股份有限公司 | Cu-CHA containing copper zeolite and its catalyst, application |
| CN110681414A (en) * | 2019-12-09 | 2020-01-14 | 山东国瓷功能材料股份有限公司 | Copper-containing loaded molecular sieve with high hydrothermal stability, and preparation method and application thereof |
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| US20050133053A1 (en) * | 2003-12-22 | 2005-06-23 | Philip Morris Usa Inc. | Smoking articles comprising copper-exchanged molecular sieves |
| CN104707648A (en) * | 2013-12-16 | 2015-06-17 | 中国科学院大连化学物理研究所 | Ionothermal post-synthesis for synthesis of functional heteroatomic molecular sieve |
| CN110523432A (en) * | 2019-10-29 | 2019-12-03 | 山东国瓷功能材料股份有限公司 | Cu-CHA containing copper zeolite and its catalyst, application |
| CN110681414A (en) * | 2019-12-09 | 2020-01-14 | 山东国瓷功能材料股份有限公司 | Copper-containing loaded molecular sieve with high hydrothermal stability, and preparation method and application thereof |
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