CN104797337A - 在选择性催化还原中用作催化剂的氧化铝硅酸盐沸石-型材料及其制造方法 - Google Patents
在选择性催化还原中用作催化剂的氧化铝硅酸盐沸石-型材料及其制造方法 Download PDFInfo
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- CN104797337A CN104797337A CN201380058685.9A CN201380058685A CN104797337A CN 104797337 A CN104797337 A CN 104797337A CN 201380058685 A CN201380058685 A CN 201380058685A CN 104797337 A CN104797337 A CN 104797337A
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- zeolite
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- 239000003054 catalyst Substances 0.000 title claims abstract description 44
- 238000000034 method Methods 0.000 title claims abstract description 41
- 239000000463 material Substances 0.000 title claims description 73
- 238000010531 catalytic reduction reaction Methods 0.000 title abstract description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 title description 9
- 230000008569 process Effects 0.000 title description 5
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 title description 3
- 239000010457 zeolite Substances 0.000 claims abstract description 110
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims description 100
- 229910021536 Zeolite Inorganic materials 0.000 claims description 98
- WGYKZJWCGVVSQN-UHFFFAOYSA-N propylamine Chemical compound CCCN WGYKZJWCGVVSQN-UHFFFAOYSA-N 0.000 claims description 44
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 40
- 230000004048 modification Effects 0.000 claims description 39
- 238000012986 modification Methods 0.000 claims description 39
- 239000000203 mixture Substances 0.000 claims description 22
- 238000006243 chemical reaction Methods 0.000 claims description 21
- 229910021529 ammonia Inorganic materials 0.000 claims description 20
- 229910052751 metal Inorganic materials 0.000 claims description 20
- 239000002184 metal Substances 0.000 claims description 20
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 18
- 239000013078 crystal Substances 0.000 claims description 15
- 238000002441 X-ray diffraction Methods 0.000 claims description 14
- 230000032683 aging Effects 0.000 claims description 13
- -1 alkali metal cation Chemical class 0.000 claims description 12
- 239000000758 substrate Substances 0.000 claims description 12
- 239000003795 chemical substances by application Substances 0.000 claims description 11
- 229910052757 nitrogen Inorganic materials 0.000 claims description 11
- 239000010949 copper Substances 0.000 claims description 10
- 238000002425 crystallisation Methods 0.000 claims description 10
- 230000008025 crystallization Effects 0.000 claims description 10
- 238000005342 ion exchange Methods 0.000 claims description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 8
- 239000011541 reaction mixture Substances 0.000 claims description 8
- 229910052802 copper Inorganic materials 0.000 claims description 7
- 239000007848 Bronsted acid Substances 0.000 claims description 6
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 6
- 229910052783 alkali metal Inorganic materials 0.000 claims description 6
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 claims description 6
- 229910021502 aluminium hydroxide Inorganic materials 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims description 6
- 229910052742 iron Inorganic materials 0.000 claims description 6
- 239000010936 titanium Substances 0.000 claims description 6
- 229910052719 titanium Inorganic materials 0.000 claims description 6
- 229910052726 zirconium Inorganic materials 0.000 claims description 6
- 208000035126 Facies Diseases 0.000 claims description 5
- 238000010438 heat treatment Methods 0.000 claims description 5
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 3
- 150000001340 alkali metals Chemical class 0.000 claims description 3
- 229910017052 cobalt Inorganic materials 0.000 claims description 3
- 239000010941 cobalt Substances 0.000 claims description 3
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 3
- 239000008119 colloidal silica Substances 0.000 claims description 3
- 239000003517 fume Substances 0.000 claims description 3
- 229910017604 nitric acid Inorganic materials 0.000 claims description 3
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 2
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 2
- 239000003863 metallic catalyst Substances 0.000 claims description 2
- 150000003839 salts Chemical class 0.000 claims description 2
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims 2
- 239000002912 waste gas Substances 0.000 claims 2
- 238000000151 deposition Methods 0.000 claims 1
- 238000007598 dipping method Methods 0.000 claims 1
- 238000007493 shaping process Methods 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 abstract description 3
- 239000000523 sample Substances 0.000 description 26
- 238000003795 desorption Methods 0.000 description 15
- 230000015572 biosynthetic process Effects 0.000 description 13
- 238000002360 preparation method Methods 0.000 description 13
- 238000003786 synthesis reaction Methods 0.000 description 13
- 238000010586 diagram Methods 0.000 description 11
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- 150000001768 cations Chemical class 0.000 description 10
- 239000002253 acid Substances 0.000 description 8
- 238000004458 analytical method Methods 0.000 description 8
- MWUXSHHQAYIFBG-UHFFFAOYSA-N Nitric oxide Chemical compound O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 6
- 229910052782 aluminium Inorganic materials 0.000 description 6
- 230000003197 catalytic effect Effects 0.000 description 6
- 239000001307 helium Substances 0.000 description 6
- 229910052734 helium Inorganic materials 0.000 description 6
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 6
- 229910052739 hydrogen Inorganic materials 0.000 description 6
- 238000000634 powder X-ray diffraction Methods 0.000 description 6
- 239000000377 silicon dioxide Substances 0.000 description 6
- 239000004411 aluminium Substances 0.000 description 5
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 5
- 239000007789 gas Substances 0.000 description 5
- 239000001301 oxygen Substances 0.000 description 5
- 229910052760 oxygen Inorganic materials 0.000 description 5
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 5
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 5
- 238000010521 absorption reaction Methods 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- 239000012153 distilled water Substances 0.000 description 4
- 239000008187 granular material Substances 0.000 description 4
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 4
- 238000012544 monitoring process Methods 0.000 description 4
- 230000003647 oxidation Effects 0.000 description 4
- 238000007254 oxidation reaction Methods 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- 229910052710 silicon Inorganic materials 0.000 description 4
- 239000010703 silicon Substances 0.000 description 4
- 229910002016 Aerosil® 200 Inorganic materials 0.000 description 3
- 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 3
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 229910000831 Steel Inorganic materials 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 239000008367 deionised water Substances 0.000 description 3
- 229910021641 deionized water Inorganic materials 0.000 description 3
- 238000002389 environmental scanning electron microscopy Methods 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 3
- 239000002002 slurry Substances 0.000 description 3
- 229910052708 sodium Inorganic materials 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- 239000010959 steel Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- PAWQVTBBRAZDMG-UHFFFAOYSA-N 2-(3-bromo-2-fluorophenyl)acetic acid Chemical compound OC(=O)CC1=CC=CC(Br)=C1F PAWQVTBBRAZDMG-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- 229910000323 aluminium silicate Inorganic materials 0.000 description 2
- 238000001354 calcination Methods 0.000 description 2
- 238000010790 dilution Methods 0.000 description 2
- 239000012895 dilution Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005470 impregnation Methods 0.000 description 2
- 239000002808 molecular sieve Substances 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 238000006722 reduction reaction Methods 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical class [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- 241001580017 Jana Species 0.000 description 1
- 239000002841 Lewis acid Substances 0.000 description 1
- OBNDGIHQAIXEAO-UHFFFAOYSA-N [O].[Si] Chemical compound [O].[Si] OBNDGIHQAIXEAO-UHFFFAOYSA-N 0.000 description 1
- 239000002250 absorbent Substances 0.000 description 1
- 230000002745 absorbent Effects 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 1
- 229910000272 alkali metal oxide Inorganic materials 0.000 description 1
- 229910000287 alkaline earth metal oxide Inorganic materials 0.000 description 1
- DKNWSYNQZKUICI-UHFFFAOYSA-N amantadine Chemical compound C1C(C2)CC3CC2CC1(N)C3 DKNWSYNQZKUICI-UHFFFAOYSA-N 0.000 description 1
- 239000000908 ammonium hydroxide Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 238000006757 chemical reactions by type Methods 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000002149 energy-dispersive X-ray emission spectroscopy Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000005496 eutectics Effects 0.000 description 1
- 235000021050 feed intake Nutrition 0.000 description 1
- 238000009415 formwork Methods 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- CYPPCCJJKNISFK-UHFFFAOYSA-J kaolinite Chemical compound [OH-].[OH-].[OH-].[OH-].[Al+3].[Al+3].[O-][Si](=O)O[Si]([O-])=O CYPPCCJJKNISFK-UHFFFAOYSA-J 0.000 description 1
- 229910052622 kaolinite Inorganic materials 0.000 description 1
- 150000007517 lewis acids Chemical class 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 239000003550 marker Substances 0.000 description 1
- 238000004949 mass spectrometry Methods 0.000 description 1
- 239000013335 mesoporous material Substances 0.000 description 1
- 239000012229 microporous material Substances 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 238000012797 qualification Methods 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 125000005372 silanol group Chemical group 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
Classifications
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- B01D53/34—Chemical or biological purification of waste gases
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
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- B01D53/8625—Nitrogen oxides
- B01D53/8628—Processes characterised by a specific catalyst
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- 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
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- B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
- B01J29/7049—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65 containing rare earth elements, titanium, zirconium, hafnium, zinc, cadmium, mercury, gallium, indium, thallium, tin or lead
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- 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
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
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- 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
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
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- 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
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- B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
- B01J37/0018—Addition of a binding agent or of material, later completely removed among others as result of heat treatment, leaching or washing,(e.g. forming of pores; protective layer, desintegrating by heat)
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- B01J37/02—Impregnation, coating or precipitation
- B01J37/0201—Impregnation
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- B01J37/08—Heat treatment
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B39/00—Compounds having molecular sieve and base-exchange properties, e.g. crystalline zeolites; Their preparation; After-treatment, e.g. ion-exchange or dealumination
- C01B39/02—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof; Direct preparation thereof; Preparation thereof starting from a reaction mixture containing a crystalline zeolite of another type, or from preformed reactants; After-treatment thereof
- C01B39/06—Preparation of isomorphous zeolites characterised by measures to replace the aluminium or silicon atoms in the lattice framework by atoms of other elements, i.e. by direct or secondary synthesis
- C01B39/08—Preparation of isomorphous zeolites characterised by measures to replace the aluminium or silicon atoms in the lattice framework by atoms of other elements, i.e. by direct or secondary synthesis the aluminium atoms being wholly replaced
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B39/00—Compounds having molecular sieve and base-exchange properties, e.g. crystalline zeolites; Their preparation; After-treatment, e.g. ion-exchange or dealumination
- C01B39/02—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof; Direct preparation thereof; Preparation thereof starting from a reaction mixture containing a crystalline zeolite of another type, or from preformed reactants; After-treatment thereof
- C01B39/06—Preparation of isomorphous zeolites characterised by measures to replace the aluminium or silicon atoms in the lattice framework by atoms of other elements, i.e. by direct or secondary synthesis
- C01B39/08—Preparation of isomorphous zeolites characterised by measures to replace the aluminium or silicon atoms in the lattice framework by atoms of other elements, i.e. by direct or secondary synthesis the aluminium atoms being wholly replaced
- C01B39/085—Group IVB- metallosilicates
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B39/00—Compounds having molecular sieve and base-exchange properties, e.g. crystalline zeolites; Their preparation; After-treatment, e.g. ion-exchange or dealumination
- C01B39/02—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof; Direct preparation thereof; Preparation thereof starting from a reaction mixture containing a crystalline zeolite of another type, or from preformed reactants; After-treatment thereof
- C01B39/06—Preparation of isomorphous zeolites characterised by measures to replace the aluminium or silicon atoms in the lattice framework by atoms of other elements, i.e. by direct or secondary synthesis
- C01B39/08—Preparation of isomorphous zeolites characterised by measures to replace the aluminium or silicon atoms in the lattice framework by atoms of other elements, i.e. by direct or secondary synthesis the aluminium atoms being wholly replaced
- C01B39/087—Ferrosilicates
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- C—CHEMISTRY; METALLURGY
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Abstract
本发明的公开内容一般地提供称为PIDC-MM-0501,PIDC-MM-0502和PIDC-MM-0805/0806或PIDC-型沸石的新型STT-型沸石材料,和这些沸石的制造方法。本发明的公开内容还提供这些沸石材料作为催化剂的用途和制备所述催化剂的方法。PIDC-MM-型沸石或STT-型沸石材料可用作催化剂,例如在选择性催化还原(SCR)应用中用作催化剂。
Description
发明领域
本发明的公开内容涉及在选择性催化还原(SCR)反应中用作催化剂的氧化铝硅酸盐或硅铝酸盐沸石-型材料和形成所述催化剂的方法。
发明背景
在这一部分中的说明仅仅提供关于本发明公开内容的背景信息且不可能构成现有技术。
沸石是一种具有基于氧离子的延伸的三维网络框架的结晶硅铝酸盐。所有沸石的基本结构单元是包围小的硅或铝离子的四个氧阴离子的四面体。排列这些四面体,使得这四个氧阴离子中每一个本身又与另一氧化硅或氧化铝四面体共享。晶体晶格在三维上延伸,且计算出每一氧阴离子的电荷,即氧化态为-2。每一硅离子具有它的+4电荷,这通过四个四面体氧阴离子平衡,和因此氧化硅四面体是电中性的。每一铝四面体具有-1的残留电荷,因为三价铝键合到四个氧阴离子上。这一残留的电荷通过占据非-框架位置且充当供给强酸的布朗斯台德位点的阳离子平衡,这将在以下的示意图中并在R.Szostak为作者的Molecular Sieves:Principles of Synthesis and Identification,第2版,Blackie Academic and Professional,London,1998中进一步描述。
典型地由含有碱金属或碱土金属氧化物源;硅的氧化物源;任选地氧化铝源;和由1-金刚烷胺,其衍生物,N,N,N-三甲基-1-金刚烷铵氢氧化物,及其混合物衍生的阳离子的含水反应混合物,制备含高氧化硅的沸石或分子筛。气相法白炭黑用作硅氧化物的典型来源,而氢氧化铝用作氧化铝的典型来源。通过结晶形成的“原样合成的”结晶沸石然后可进行进一步处理。例如,可通过热处理(即煅烧),除去结构导向剂(SDA)。这种进一步的处理包括使用已知方法,例如使用稀的酸溶液或硝酸铵溶液,通过离子交换除去金属阳离子。
Y.Nakagawa等人在Microporous and Mesoporous Materials,22(1998),第69-85页中通过计算确定了可使用Ν,Ν,Ν-三甲基-1-金刚烷铵阳离子制造的五种不同的沸石。它们的分子模型计算与它们的实验数据一致。他们报道了这一模板使SSZ-13,SSZ-23,SSZ-24,SSZ-25和SSZ-31类型的沸石结晶。他们示出了共同地通过两个SDA制造的五种沸石的结晶场边界。Ν,Ν,Ν-三甲基-1-金刚烷铵SDA分子使菱沸石相在SAR 10-40处结晶,而STT相在SAR 50-70处结晶。很少有有机模板会产生SSZ-23的结构。
发明概述
本发明的公开内容一般地涉及称为PIDC-MM-0501,PIDC-MM-0502和PIDC-MM-0805/0806或PIDC-MM-型沸石的新型STT-型沸石材料,和制造这些沸石的方法。本发明的公开内容还提供这些沸石材料作为催化剂的用途和制备所述催化剂的方法。令人惊奇的是,这些新型材料结构作为在本文描述的反应类型和特定组的合成条件下的产品形式出现。STT-型沸石材料包括大于约19:1-约250:1的四价元素的氧化物与三价元素的氧化物的摩尔比,且特征可在于在x-射线衍射图案内存在的特定峰。
PIDC-MM-型沸石或改性的STT-型沸石材料可用作催化剂,例如在SCR应用中作为催化剂。针对氨和正丙胺二者,在新的PIDC-MM-型材料上的温度编程的解吸(TPD)研究的比较表明,与已知的SSZ-13沸石相比,它们含有更加强酸性的位点。在TPD测量中,通过使用具有碱性特征的探针分子,例如氨和正丙胺,和测量它们被解吸时的温度,监控所合成的沸石的酸强度。
制备沸石-型材料的方法通常包括形成含水反应混合物,所述含水反应混合物包括四价元素的氧化物源;三价元素的氧化物源;碱金属源;和有机结构导向剂,所述有机结构导向剂的至少一部分包括N,N,N-三甲基-1-金刚烷胺氢氧化物;维持该含水混合物在足以使沸石型材料晶体的结晶条件下,从而显示出特定的x-射线衍射图案;和回收该沸石晶体。
由沸石-型材料制备催化剂的方法包括下述步骤:用硝酸使沸石-型材料脱铝,形成脱铝的沸石;用金属盐的水溶液浸渍或离子交换该脱铝的沸石;和将选自Cu,Fe,Co,Zr,Ti或其混合物中的一种金属掺入到脱铝沸石的框架位点内。
根据本文提供的说明,进一步的应用领域是显而易见的。应当理解,说明书和具体实施例意欲仅仅为了阐述的目的,且并不意欲限制本发明公开内容的范围。
附图简述
本文描述的附图仅仅为了阐述的目的,且绝对并不意欲限制本发明公开内容的范围。
图1是根据本发明公开内容的教导制备改性的STT沸石的示意图;
图2是根据实施例1制备的沸石的x-射线粉末衍射分析谱图;
图3是根据实施例1制备的煅烧过的沸石的x-射线粉末衍射分析谱图;
图4是根据实施例2制备的沸石的x-射线粉末衍射分析谱图;
图5是根据实施例2制备的煅烧过的沸石的x-射线粉末衍射分析谱图;
图6是根据实施例3制备的沸石的x-射线粉末衍射分析谱图;
图7是根据实施例3制备的煅烧过的沸石的x-射线粉末衍射分析谱图;
图8提供在合成(a)现有的SSZ-13(PIDC-801),(b)PIDC-MM-0501沸石-型材料,和c)PIDC-MM-0502沸石-型材料中获得的产品的扫描电镜(SEM)图像;
图9是TPD仪器的示意图;
图10是由根据本发明公开内容的教导制备的新鲜沸石样品显示出的氨解吸曲线的图示;
图11是由通过水热老化(750℃24小时,10%H2O)的沸石样品显示出的氨解吸曲线的图示;
图12是由根据本发明公开内容的教导制备的新鲜沸石样品显示出的正丙胺解吸曲线的图示;
图13是由通过水热老化(750℃24小时,具有10%水蒸气)的沸石样品显示出的正丙胺解吸曲线的图示;
图14提供根据本发明公开内容的教导制备的沸石样品显示出的正丙胺和丙烯解吸曲线的图示;
图15是由来自图14所示的图表的样品显示出的正丙胺解吸曲线的展开图;
图16是由来自图14所示的图表的样品显示出的丙烯解吸曲线的展开图;
图17是对于根据本发明公开内容的教导制备的新鲜Cu-PIDC-MM-型沸石和对于在750℃,10%H2O下水热老化24小时的沸石样品在200℃下的NOx转化率的图示;和
图18是对于根据本发明公开内容的教导制备的新鲜Cu-PIDC-MM-型沸石和对于在750℃,10%H2O下水热老化24小时的沸石样品在500℃下的NOx转化率的图示
详细说明
下述说明性质上仅仅是例举,且绝不意欲限制本发明的公开内容或其应用或用途。应当理解,在说明书当中,相应的参考标记是指相同或相应的部件和特征。
本发明的公开内容一般地提供改性的STT沸石-型材料,它显示出对选择性催化还原(SCR)反应的催化活性。根据本文描述的合成条件制备的这种沸石-型材料显示出优于现有的SSZ-13型沸石的高催化活性,这通过氨和正丙胺温度解吸研究证明。采用“原样合成”的材料的XRD反射,在d=1.08(7.8%);0.837(4.0);0.845(3.6);0.480(4.5);0.456(3.8);0.445(1.6);0.416(4.0);和0.364(2.6)nm处,观察到存在STT-型沸石。原样制备的沸石的经验凝胶组成用下式表示:
5.577 NaOH:4.428 RNOH:Al2O3:28 SiO2:1219.7 H2O
给出下述具体实施方案,阐述根据本发明公开内容的教导制备的改性的STT沸石-型材料的制备,鉴定和用途,且不应当解释为限制本发明公开内容的范围。鉴于本发明的公开内容,本领域技术人员会理解,可在本文公开的具体实施方案中作出许多变化,且在没有脱离或者超出本发明公开内容的精神或范围的情况下,仍然获得相同或类似的结果。本领域技术人员将进一步理解,本文报道的任何性能代表常规地测量且可通过多种不同方法获得的性能。本文描述的方法代表在没有超出本发明公开内容的范围情况下,可利用的一种这样的方法和其他方法。
参考图1,一般地通过搅拌反应物,直到获得均匀的乳状溶液,制备本发明公开内容的改性的STT沸石-型材料。在2.0L Parr高压釜中,在150℃-160℃下进行沸石晶体的合成4-7天。一旦冷却,则将反应器容器的内容物倾倒在过滤器内,并用蒸馏水洗涤该晶体,和在120℃下干燥过夜。在合成之后,在离子交换之前,煅烧沸石,以便除去沸石框架结构导向剂。
通过结晶形成的“原样合成的”结晶沸石可进行进一步处理。例如,可通过热处理(即,煅烧),除去模板或结构导向剂(SDA)。这种进一步处理也可包括借助本领域技术人员已知的任何方法,其中包括,但不限于,使用稀酸或硝酸铵溶液的方法,通过离子交换,除去金属阳离子。
可借助标准的离子交换技术,例如在美国专利No.3,140,249,美国专利No.3,140,251,和美国专利No.3,140,253中描述的那些,通过用金属阳离子取代一些现有的阳离子,将金属引入到沸石内。典型的阳离子取代可包括使用选自周期表中第1-12族及其混合物中的金属阳离子,优选周期表中第1,2和8族的元素。
具有掺入到框架内的过渡金属的沸石显示出不同且非常有价值的催化活性。例如,过去多年来,含钴的沸石已经是很感兴趣的主题,这主要是因为它们在用甲烷选择性催化还原(SCR)氮氧化物中具有催化性能。这一反应是重要的,因为预期甲烷替代氨作为从静态源中释放的NOx的还原剂。美国公布No.2008/0226545A1公开了在宽的温度范围内,使用通过氨的选择性催化还原氮氧化物,铜交换的沸石在控制从气态介质中释放NOx的用途。
影响沸石催化剂的催化活性的重要因素是针对该催化剂选择的制备路线。例如,Janas等人在Applied Catalysis B:Environmental,91,(2009),第217页中描述了在选择性催化还原(SCR)NOx中,铜含量对铜β沸石(CuSiBEA)的催化活性的影响。通过两步后合成方法,可控制铜掺入到β沸石的框架内,获得CuSIBEA催化剂。
所得产物通过XRD表征。使用0.02°2θ的步长,从5到35°的2θ,获得图案。使用Carl-Zeiss显微镜,获得扫描电镜(SEM)图像和能量分散X-射线光谱法(EDAX)化学分析。在与MKS Cirrus质谱仪耦联的2920Micromeritics仪器上进行温度解吸研究。所有合成的材料是白色粉末。
本发明公开内容的方法提供含金属的改性STT-型沸石的合成方法,其具有28:1的原样制备的氧化硅与氧化铝摩尔比,且掺入金属,例如铜,铁,钴,锆,钛或其混合物到该脱铝氧化硅的框架位点内。该方法包括下述步骤:(1)用硝酸使沸石脱铝,接着(2)用金属盐的水溶液,例如Cu(NO3)2·H2O溶液浸渍所得脱铝的沸石。来自该金属盐溶液的金属阳离子占据沸石框架内事先被铝(Al)阳离子占据的位点。该方法可任选地包括下述步骤:在用金属盐水溶液浸渍之后,加热改性的STT-型沸石到至少150℃,或约160℃的温度。在含金属的改性的STT-型沸石内存在的金属量范围为约0.3-约10.0%,或者约0.3-约3.3%,基于含金属的改性的STT-型沸石的总重量。该沸石框架的孔度典型地小于约6纳米。
根据本发明公开内容的另一方面,提供在含金属的改性的STT-型沸石催化剂的制备中使用的改性的STT-型沸石的制备方法。该方法一般地提供(A):(B)的摩尔比大于约19:1的改性STT-型沸石,其中(A)是四价元素氧化物的氧化物,和(B)是三价元素的氧化物。该方法包括形成含水反应混合物,所述含水反应混合物包括(A)源;(B)源;碱金属阳离子源;和有机结构导向剂(SDA),其中至少一部分SDA包括Ν,Ν,Ν-三甲基-1-金刚烷胺氢氧化物;维持该含水反应混合物在足以形成STT-型沸石晶体的结晶条件下,和回收改性的STT-型沸石晶体。
碱金属阳离子源优选是碱金属氢氧化物,且碱金属阳离子是原样合成的结晶氧化物材料的一部分,进而平衡在其内的价电子电荷。例如,四价元素可以是硅,且(A)源是水含量为约2wt%的气相法白炭黑,而三价元素可以是铝,且(B)源是水含量小于或等于约63%的干燥的氢氧化铝。所得沸石的孔度典型地小于约6nm。
仍然参考图1,根据本发明公开内容的教导制备的沸石-型材料可用作催化剂,例如在SCR应用中用作催化剂。通过具有碱性特征的探针分子,例如氨和正丙胺,通过测量它们被解吸时的温度(温度编程的解吸测量方法),监控所合成的沸石样品的酸强度。通过氨温度编程的解吸和正丙胺-TPD技术,测量样品的酸度。任选地,可在蜂窝结构,其中包括壁流式基底(wall flow substrate),金属基底,或挤出基底或挤出物上沉积含金属的催化剂。
用Cu,Fe,Co,Zr,Ti或其混合物替代沸石结构内部的铝会增加沸石催化剂的SCR活性。在框架晶格内具有金属的改性STT-型沸石能储存较少的氨。这一金属取代过程会降低在催化剂内存在的布朗斯台德酸位点量,且用路易斯酸位点替代这些位点。总体上金属替代会降低在氨SCR催化剂内出现的NOx漏失(slip)。
实施例1-合成PIDC-MM-0501改性的STT-型沸石材料。
结合氢氧化钠溶液和N,N,N-三甲基-1-金刚烷胺氢氧化物。调节氢氧化铝,接着氧化硅Aerosil 200。向所获得的混合物中添加去离子水。搅拌反应物,直到获得均匀的乳状溶液。将所得浆液转移到2.0L Parr不锈钢容器内并密封该容器。在160℃下加热该反应器容器6天以供制备PIDC-0501沸石材料。一旦冷却,则倾倒反应器容器的内容物到过滤器内,并用蒸馏水洗涤晶体,和在120℃下干燥过夜。在合成之后,在离子交换之前煅烧沸石粉末,以便除去沸石的框架结构导向剂。
在下表1中概述了,以及在图2和3中示出了由这一工序获得的PIDC-MM-0501沸石产品的X-射线衍射图案。所制备的沸石包括SSZ-13和SSZ-23相的混合物。在x-射线衍射图案中,在下述2θ:8.22,9.68,14.51,15.55,17.9,18.58,19.3,19.66,21.5,和27.4处的每一峰归因于存在SSZ-23相,而其他峰归因于存在SSZ-13相。
表1.PIDC-MM-0501的x-射线数据(实施例1)
实施例2-合成PIDC-MM-0502和PIDC-MM-0805/0806改性的STT沸石-型材料
结合氢氧化钠溶液和N,N,N-三甲基-1-金刚烷胺氢氧化物。添加氢氧化铝,接着氧化硅Aerosil 200。向所得混合物中添加去离子水。搅拌该反应物,直到获得均匀的乳状溶液。将所得浆液转移到2.0L Parr不锈钢容器内并密封该容器。在160℃下加热该反应器容器7天。一旦冷却,则倾倒反应器容器的内容物到过滤器内,并用蒸馏水洗涤晶体,和在120℃下干燥过夜。加热温度,温度猛增和结晶过程的轻微差别导致形貌轻微的变化,从而导致PIDC-MM-0502和PIDC-MM-0805/0806沸石材料。在合成之后,在离子交换之前煅烧沸石粉末,以便除去沸石的框架结构导向剂。
在图4和5中提供了由这一工序获得的PIDC-MM-0502沸石产品的X-射线衍射(XRD)图案。XRD分析表明这一沸石由SSZ-13和SSZ-23这两个相组成,其中在下述2θ处的峰归因于SSZ-23相:8.22,9.68,14.51,15.55,17.9,18.58,19.3,19.66,21.5,和27.4,而其他的每一个峰归因于SSZ-13相。发现在这一实施例中PIDC-MM-0502材料的X-射线衍射(XRD)图案类似于PIDC-MM-0501材料(参见实施例1),所不同的是归因于SSZ-23相的峰的相对强度增加。这一峰强度的增加是较长的反应时间导致的,较长的反应时间有利于SSZ-23沸石相结晶。
实施例3-合成常规的纯SSZ-13(PIDC-0801)
结合氢氧化钠溶液和N,N,N-三甲基-1-金刚烷胺氢氧化物。添加氢氧化铝,接着氧化硅Aerosil 200。向所得混合物中添加去离子水。搅拌该反应物,直到获得均匀的乳状溶液。将所得浆液转移到2.0L Parr不锈钢容器内并密封该容器。在150℃下加热该反应器容器4天。一旦冷却,则倾倒反应器容器的内容物到过滤器内,并用蒸馏水洗涤晶体,和在120℃下干燥过夜。在合成之后,在离子交换之前煅烧沸石粉末,以便除去沸石的框架结构导向剂。
在图6和7中提供了由这一工序获得的常规沸石产品的X-射线衍射团。在实施例中制备的常规沸石和本发明公开内容的沸石之间观察到的差别是在下述2θ度处存在峰:8.22,9.68,14.51,15.55,17.9,18.58,19.3,19.66,21.5,和27.4,这归因于出现SSZ-23相。这些峰不存在于在这一实施例中制备的常规SSZ-13沸石的XRD图案内。
现参考图8,比较在合成(A)实施例3-现有的SSZ-13(CHA),(B)实施例1-PIDC-0501沸石-型材料,和(C)实施例2-PIDC-MM-0502沸石-型材料中获得的产品的扫描电镜(SEM)图像。在图8A中,现有的SSZ-13沸石显示出平均粒度为2-10μm的典型的菱沸石的立方形状。然而,在图8B中,PIDC-MM-0501材料显示出立方和球形颗粒的混合物,例如棒状物。在图8C中,PIDC-MM-0502材料也显示出立方和球形颗粒的混合物。在这一附图中,球形颗粒的表面聚集有立方晶体。因此,根据本发明公开内容制备的材料(图8B和8C)显示出与预示SSZ-23沸石结构的球形颗粒共晶的预示SSZ-13沸石结构的立方颗粒。改性的STT-型沸石材料具有D50为约0.1-50微米的粒度。
实施例4-温度编程的解吸
采用碱性分子NH3和正丙胺的温度编程的解吸,研究在现有的SSZ-13,和本文中制备的PIDC-MM沸石-型材料上酸性位点的总体性质与分布。在与MKS Cirrus Mass Spec设备内的导热率检测仪(TCD)相连的2920Micromeritic仪器上,记录TPD光谱。在图9中示出了示意图。
典型地,对于NH3-TPD来说,在500℃下,在20℃/min的速率下,在25mL min-1的氦气流中,预处理0.1g催化剂30分钟,然后冷却到100℃的解吸温度。在100℃下用稀释的氨(10%氨/90%氩气)饱和该催化剂30分钟。在饱和之后,在25mL min-1下,用氦气净化样品20分钟,以除去在沸石表面上的微弱吸附的氨。然后在20℃/min的加热速率下,采用在25mL min-1下维持的流动氦气,从100℃升高样品温度到650℃,最终在650℃下保持40分钟。使用质谱仪,监控解吸的NH3。
典型地,对于正丙基-TPD来说,在500℃下,在25mL min-1的氦气流中,预处理0.1g催化剂30分钟,然后冷却到100℃的解吸温度。在60℃下加热含有正丙胺的烧瓶,生成正丙胺蒸汽。用稀释的正丙胺给催化剂投料(dose)。反复投料,直到样品饱和,这通过存在5个等高峰佐证。在饱和之后,在25mL min-1下,用氦气净化样品20分钟,以除去在沸石表面上的微弱吸附的氨。然后在20℃/min的加热速率下,从100℃升高样品温度到650℃,同时流动的氦气为25mLmin-1。使用质谱仪,监控解吸的正丙胺。
由它们的TPD峰面积,评价从这三个样品中解吸的氨量(图10)。存在两个NH3解吸峰。在约160℃下的NH3解吸峰与弱酸位点有关,和在高于480℃处的另一峰与强酸位点有关。这三种沸石PIDC-MM-0501,PIDC-MM-0502和PIDC-0801(常规)显示出不同的酸度。在图11中示出了水热老化的沸石样品的氨解吸曲线。对于新鲜和老化的样品二者来说,与纯SSZ-13相比,新的PIDC沸石-型材料的解吸性能显著较高。如表2所示,在这些样品上氨的解吸能力以下述顺序增加:PIDC-0801(常规)<PIDC-MM-0501<PIDC-MM-0502。
表2
Lot#PIDC-MM | 酸度(mmol/g) | 解吸温度 |
0501 | 0.77 | 493.3 |
0502 | 1.065 | 512 |
0801(常规) | 0.768 | 474 |
图12和14中针对新鲜样品,和图13中针对老化样品分别示出了正丙胺TPD曲线的结果。所有样品在160℃和380℃处显示出两个解吸峰,这暗示在这些样品上存在两个能量活性类型的正丙胺吸收位点,代表正丙胺的酸度和丙烯酸度)。较高温度的解吸峰可归因于正丙胺与在沸石样品的表面处存在的硅烷醇基较强的相互作用。本发明公开内容的PIDC-MM沸石-型材料的吸收性能显著高于现有或常规的SSZ-13。
对于与正丙胺酸度对应的曲线部分来说,在图15中提供了来自图14的解吸曲线的展开图,和对于与丙烯酸度对应的曲线部分来说,在图16中提供了来自图14的解吸曲线的展开图。在这两个曲线中,本发明公开内容的PIDC-MM沸石-型材料的吸收显著高于现有或常规的SSZ-13的吸收。事实上,由解吸获得的丙烯量(在图16中的曲线下的面积)对应于1.61mmol/g SSZ-13材料),而PIDC-MM-0805,PIDC-MM-0502,和PIDC-MM-0806沸石-型材料显示出2.86,3.48,和4.27mmol/g沸石材料。因此,PIDC-MM沸石-型材料显示出更大数量的布朗斯台德酸位点,以及布朗斯台德酸位点比SSZ-13沸石材料内存在的位点显著更强。事实上,这些布朗斯台德酸位点导致显示出与SSZ-13沸石相比,正丙胺温度解吸的增加大于50%的沸石-型材料。
使用充当微流反应器的Micromeritics 2920和在穿过样品之后,进行气体浓度分析的MKS残留气体分析仪,测试NOx转化率。采用下述气体浓度,测试样品:NO=175ppm;NO2=175ppm;NH3=350ppm;和O2=175ppm。在50,000-1/hr的空间速率下,测试样品。由在恒定压力下通过MKS残留气体分析仪45分钟之后的稳态条件计算NOx转化值。分别在图17中针对新鲜样品和在图18中针对老化样品示出了NOx转化率的结果。在200℃和550℃这两个温度下老化之后,NOx转化率下降。在约200℃下新鲜催化剂的NOx转化率性能为75%,和在约500℃下为约70%。对于水热老化的催化剂来说,在约200℃下催化剂的NOx转化率性能为30%。对于水热老化的催化剂来说,在约500℃下催化剂的NOx转化率性能为35%。NOx转化率的这一下降证明活性损失,这种损失是在暴露于水热老化条件之后样品酸度降低导致的。
为了阐述和描述的目的列出了本发明的前述说明和各种形式。并不意欲穷举或限制本发明到所公开的精确形式上。鉴于上述教导,许多改性或变化是可能的。选择并描述所讨论的形式,以提供本发明原理及其实际应用的最好阐述,从而使得本领域普通技术人员能以各种形式且在各种修饰下利用本发明,因为它们适合于所考虑的特定用途。所有这种改性和变化在所附权利要求确定的本发明范围内,当根据它们公平,合法和公正授权的宽度解释时。
Claims (28)
1.一种用作催化剂的结晶的改性STT-型沸石材料,该改性STT-型沸石材料包括摩尔比大于约19:1到约250:1的四价元素的氧化物与三价元素的氧化物,且具有如图3所示的x-射线衍射图案内的峰。
2.权利要求1的改性STT-型沸石材料,其中在X-射线衍射图案内,在下述2θ度处的峰归因于存在SSZ-23沸石相:8.22,9.68,14.51,15.55,17.9,18.58,19.3,19.66,21.5,和27.4。
3.权利要求1和2的改性STT-型沸石材料,其中四价元素的氧化物与三价元素的氧化物的摩尔比为约19:1到50:1。
4.权利要求1-3的改性STT-型沸石材料,其中经验凝胶组成用下式表示:
5.577 OH:4.428 RNOH:Al2O3:28 SiO2:1219.7 H2O。
5.权利要求1-4的改性STT-型沸石材料,其中该沸石-型材料进一步包括选自铜、铁、钴、锆、钛及其混合物中的一种金属。
6.权利要求5的改性STT-型沸石材料,其中含金属的沸石-型材料在选择性催化还原(SCR)反应中充当催化剂。
7.权利要求5-6的改性STT-型沸石材料,其中在该催化剂中存在的金属范围为0.3-10.0%,基于该沸石催化剂的总重量。
8.权利要求1-7的改性STT-型沸石材料,其中该沸石-型材料的特征在于氨温度解吸和正丙胺温度解吸分别比相应的SSZ-13沸石的解吸大至少1.4和2.0倍。
9.权利要求1-8的改性STT-型沸石材料,其中水热老化的沸石-型材料的特征在于氨温度解吸和正丙胺温度解吸分别比相应的SSZ-13沸石的解吸大至少1.5和6.5倍。
10.权利要求5的改性STT-型沸石材料,其中该催化剂含有离子交换的金属Cu,Fe,Co,Zr,Ti,其足以维持含氮氧化物的废气流内的NOx转化率性能。
11.权利要求10的改性STT-型沸石材料,其中在约200℃下新鲜催化剂的NOx转化率性能为75%。
12.权利要求11的改性STT-型沸石材料,其中在约500℃下新鲜催化剂的NOx转化率性能为约70%。
13.权利要求10的改性STT-型沸石材料,其中在约200℃下,对于水热老化的催化剂来说,该催化剂的NOx转化率性能为30%。
14.权利要求13的改性STT-型沸石材料,其中在约500℃下,对于水热老化的催化剂来说,该催化剂的NOx转化率性能为35%。
15.权利要求5-14的改性STT-型沸石材料,其中含金属的沸石沉积在蜂窝结构、金属基底或成形的挤出物上。
16.权利要求15的改性STT-型沸石材料,其中蜂窝状基底包括壁流式基底。
17.权利要求1-16的改性STT-型沸石材料,其中该沸石-型材料具有D50为约0.1-50微米的粒度。
18.一种制备含金属的催化剂的方法,该方法包括下述步骤:
用硝酸使沸石脱铝;
用金属盐水溶液浸渍或离子交换该脱铝的沸石;和
将选自Cu,Fe,Co,Zr,Ti中的一种或其混合物中的金属掺入到脱铝的沸石的框架位点内。
19.权利要求18的方法,其中催化剂在框架内掺入到金属中,其含量足以维持在含氮氧化物的废气流内的NOx转化率性能。
20.权利要求18-19的方法,其中该方法进一步包括在蜂窝状基底、金属基底或挤出的基底上沉积该催化剂。
21.权利要求20的方法,其中该蜂窝状基底包括壁流式基底。
22.权利要求18-21的方法,该方法进一步包括制备沸石,使得它具有四价元素的氧化物与三价元素的氧化物的摩尔比大于约19:1,所述沸石通过下述步骤制备:
形成含水反应混合物,所述含水反应混合物包括四价元素的氧化物源;三价元素的氧化物源;碱金属源;和有机结构导向剂,所述有机结构导向剂的至少一部分是N,N,N-三甲基-1-金刚烷胺氢氧化物;
在足以使沸石型材料晶体结晶的条件下维持该含水混合物,所述晶体具有图2中提供的x-射线衍射图;和
回收该沸石晶体。
23.权利要求22的方法,其中四价元素的氧化物源是水含量为约2wt%的气相法白炭黑。
24.权利要求22的方法,其中三价元素的氧化物源是氢氧化铝。
25.权利要求22-24的方法,其中碱金属阳离子平衡在结晶沸石-型材料内的价电子电荷。
26.权利要求18-25的方法,其中该方法进一步包括加热沸石到至少150℃的温度。
27.权利要求26的方法,其中加热沸石到约160℃的温度。
28.权利要求1-7的改性STT-型沸石材料,其中该沸石-型材料的特征在于布朗斯台德酸位点强于SSZ-13沸石中的这种位点且存的数量大于在SSZ-13沸石中的这种位点;
其中布朗斯台德酸位点导致显示出与SSZ-13沸石相比,正丙胺温度解吸增加大于50%的沸石-型材料。
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US201361791709P | 2013-03-15 | 2013-03-15 | |
US61/791,709 | 2013-03-15 | ||
PCT/US2013/062083 WO2014052698A1 (en) | 2012-09-28 | 2013-09-27 | An alumina silicate zeolite-type material for use as a catalyst in selective catalytic reduction and process of making thereof |
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CN107511179A (zh) * | 2016-06-16 | 2017-12-26 | 太平洋工业发展公司 | 具有储氧能力(osc)的掺杂催化剂载体材料及其制造方法 |
CN111629828A (zh) * | 2017-12-28 | 2020-09-04 | 环球油品有限责任公司 | 硅铝酸盐沸石uzm-50 |
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US9187334B2 (en) * | 2013-10-11 | 2015-11-17 | Chevron U.S.A. Inc. | Molecular sieve SSZ-96 |
US9192924B1 (en) * | 2014-06-04 | 2015-11-24 | Chevron U.S.A. Inc. | Molecular sieve SSZ-99 |
US9193600B1 (en) * | 2014-06-04 | 2015-11-24 | Chevron U. S. A. Inc. | Method for making molecular sieve SSZ-99 |
WO2018067214A1 (en) * | 2016-10-05 | 2018-04-12 | Chevron U.S.A. Inc. | Molecular sieve ssz-107, its synthesis and use |
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- 2013-09-27 CN CN201380058685.9A patent/CN104797337B/zh active Active
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CN111629828B (zh) * | 2017-12-28 | 2023-07-21 | 环球油品有限责任公司 | 硅铝酸盐沸石uzm-50 |
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JP6267712B2 (ja) | 2018-01-24 |
EP2900372A1 (en) | 2015-08-05 |
WO2014052698A1 (en) | 2014-04-03 |
EP2900372B1 (en) | 2018-01-10 |
US10328421B2 (en) | 2019-06-25 |
CN104797337B (zh) | 2018-04-20 |
US20150266007A1 (en) | 2015-09-24 |
JP2015536889A (ja) | 2015-12-24 |
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