CN103987662B - 稳定化的微孔结晶材料、其制备方法以及选择性催化还原NOx的用途 - Google Patents
稳定化的微孔结晶材料、其制备方法以及选择性催化还原NOx的用途 Download PDFInfo
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- CN103987662B CN103987662B CN201280058960.2A CN201280058960A CN103987662B CN 103987662 B CN103987662 B CN 103987662B CN 201280058960 A CN201280058960 A CN 201280058960A CN 103987662 B CN103987662 B CN 103987662B
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- crystalline material
- metal
- microporous crystalline
- mixtures
- copper
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- 239000002178 crystalline material Substances 0.000 title claims abstract description 37
- 238000010531 catalytic reduction reaction Methods 0.000 title claims abstract description 9
- 238000002360 preparation method Methods 0.000 title description 2
- 239000000463 material Substances 0.000 claims abstract description 63
- 229910052751 metal Inorganic materials 0.000 claims abstract description 41
- 239000002184 metal Substances 0.000 claims abstract description 41
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 37
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 34
- 238000000034 method Methods 0.000 claims abstract description 31
- 239000000203 mixture Substances 0.000 claims abstract description 25
- 239000010457 zeolite Substances 0.000 claims abstract description 22
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 claims abstract description 21
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 20
- 239000010949 copper Substances 0.000 claims abstract description 20
- 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 20
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 19
- 229910052802 copper Inorganic materials 0.000 claims abstract description 19
- 229910021536 Zeolite Inorganic materials 0.000 claims abstract description 18
- 239000007789 gas Substances 0.000 claims abstract description 18
- 229910052742 iron Inorganic materials 0.000 claims abstract description 18
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 16
- 229910052783 alkali metal Inorganic materials 0.000 claims abstract description 10
- 150000001340 alkali metals Chemical class 0.000 claims abstract description 10
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims abstract description 9
- 150000001342 alkaline earth metals Chemical class 0.000 claims abstract description 9
- 239000013078 crystal Substances 0.000 claims abstract description 8
- 229910052761 rare earth metal Inorganic materials 0.000 claims abstract description 8
- 239000011575 calcium Substances 0.000 claims description 34
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 31
- 229910001868 water Inorganic materials 0.000 claims description 27
- 229910052791 calcium Inorganic materials 0.000 claims description 22
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 18
- 229910052700 potassium Inorganic materials 0.000 claims description 15
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 14
- QGZKDVFQNNGYKY-UHFFFAOYSA-O ammonium group Chemical group [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 14
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 13
- 239000011591 potassium Substances 0.000 claims description 13
- 239000011148 porous material Substances 0.000 claims description 11
- 229910052782 aluminium Inorganic materials 0.000 claims description 9
- 239000004411 aluminium Substances 0.000 claims description 9
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 9
- 230000015572 biosynthetic process Effects 0.000 claims description 9
- 238000003786 synthesis reaction Methods 0.000 claims description 9
- 238000007598 dipping method Methods 0.000 claims description 7
- 229910052712 strontium Inorganic materials 0.000 claims description 7
- 229910021529 ammonia Inorganic materials 0.000 claims description 6
- 239000007791 liquid phase Substances 0.000 claims description 6
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 claims description 6
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 5
- 229910052788 barium Inorganic materials 0.000 claims description 5
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 claims description 5
- 229910052792 caesium Inorganic materials 0.000 claims description 5
- TVFDJXOCXUVLDH-UHFFFAOYSA-N caesium atom Chemical compound [Cs] TVFDJXOCXUVLDH-UHFFFAOYSA-N 0.000 claims description 5
- 238000005342 ion exchange Methods 0.000 claims description 5
- 229910052746 lanthanum Inorganic materials 0.000 claims description 5
- 229910052749 magnesium Inorganic materials 0.000 claims description 5
- 239000011777 magnesium Substances 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 5
- 229910052701 rubidium Inorganic materials 0.000 claims description 5
- IGLNJRXAVVLDKE-UHFFFAOYSA-N rubidium atom Chemical compound [Rb] IGLNJRXAVVLDKE-UHFFFAOYSA-N 0.000 claims description 5
- 229910052684 Cerium Inorganic materials 0.000 claims description 4
- 229910052779 Neodymium Inorganic materials 0.000 claims description 4
- 229910052777 Praseodymium Inorganic materials 0.000 claims description 4
- ZMIGMASIKSOYAM-UHFFFAOYSA-N cerium Chemical compound [Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce] ZMIGMASIKSOYAM-UHFFFAOYSA-N 0.000 claims description 4
- 229910052681 coesite Inorganic materials 0.000 claims description 4
- 150000001875 compounds Chemical class 0.000 claims description 4
- 229910052906 cristobalite Inorganic materials 0.000 claims description 4
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 claims description 4
- QEFYFXOXNSNQGX-UHFFFAOYSA-N neodymium atom Chemical compound [Nd] QEFYFXOXNSNQGX-UHFFFAOYSA-N 0.000 claims description 4
- PUDIUYLPXJFUGB-UHFFFAOYSA-N praseodymium atom Chemical compound [Pr] PUDIUYLPXJFUGB-UHFFFAOYSA-N 0.000 claims description 4
- 229910001404 rare earth metal oxide Inorganic materials 0.000 claims description 4
- 239000007787 solid Substances 0.000 claims description 4
- 229910052682 stishovite Inorganic materials 0.000 claims description 4
- 229910052905 tridymite Inorganic materials 0.000 claims description 4
- 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 2
- 239000004111 Potassium silicate Substances 0.000 claims description 2
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 2
- 239000004202 carbamide Substances 0.000 claims description 2
- 150000002430 hydrocarbons Chemical class 0.000 claims description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 2
- NNHHDJVEYQHLHG-UHFFFAOYSA-N potassium silicate Chemical compound [K+].[K+].[O-][Si]([O-])=O NNHHDJVEYQHLHG-UHFFFAOYSA-N 0.000 claims description 2
- 235000019353 potassium silicate Nutrition 0.000 claims description 2
- 229910052913 potassium silicate Inorganic materials 0.000 claims description 2
- 229910052708 sodium Inorganic materials 0.000 claims description 2
- 239000011734 sodium Substances 0.000 claims description 2
- 229930195733 hydrocarbon Natural products 0.000 claims 1
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims 1
- 238000011282 treatment Methods 0.000 description 19
- 238000006243 chemical reaction Methods 0.000 description 18
- 238000001035 drying Methods 0.000 description 13
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 11
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 10
- 238000001914 filtration Methods 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 9
- YNAVUWVOSKDBBP-UHFFFAOYSA-N Morpholine Chemical compound C1COCCN1 YNAVUWVOSKDBBP-UHFFFAOYSA-N 0.000 description 8
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 8
- 238000012423 maintenance Methods 0.000 description 7
- 241000264877 Hippospongia communis Species 0.000 description 6
- 230000032683 aging Effects 0.000 description 6
- 229910000069 nitrogen hydride Inorganic materials 0.000 description 6
- 238000005406 washing Methods 0.000 description 6
- 235000003283 Pachira macrocarpa Nutrition 0.000 description 5
- 241001083492 Trapa Species 0.000 description 5
- 235000014364 Trapa natans Nutrition 0.000 description 5
- 238000002425 crystallisation Methods 0.000 description 5
- 230000008025 crystallization Effects 0.000 description 5
- 150000002739 metals Chemical class 0.000 description 5
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- 239000005416 organic matter Substances 0.000 description 5
- 235000009165 saligot Nutrition 0.000 description 5
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 4
- ZCCIPPOKBCJFDN-UHFFFAOYSA-N calcium nitrate Chemical compound [Ca+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ZCCIPPOKBCJFDN-UHFFFAOYSA-N 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- 239000008367 deionised water Substances 0.000 description 4
- 229910021641 deionized water Inorganic materials 0.000 description 4
- 150000002500 ions Chemical class 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- 235000012239 silicon dioxide Nutrition 0.000 description 4
- 230000000694 effects Effects 0.000 description 3
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 229940073455 tetraethylammonium hydroxide Drugs 0.000 description 3
- LRGJRHZIDJQFCL-UHFFFAOYSA-M tetraethylazanium;hydroxide Chemical compound [OH-].CC[N+](CC)(CC)CC LRGJRHZIDJQFCL-UHFFFAOYSA-M 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
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 2
- 229910000323 aluminium silicate Inorganic materials 0.000 description 2
- 239000011324 bead Substances 0.000 description 2
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 2
- 239000000920 calcium hydroxide Substances 0.000 description 2
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 2
- 239000003638 chemical reducing agent Substances 0.000 description 2
- 239000002872 contrast media Substances 0.000 description 2
- OPQARKPSCNTWTJ-UHFFFAOYSA-L copper(ii) acetate Chemical compound [Cu+2].CC([O-])=O.CC([O-])=O OPQARKPSCNTWTJ-UHFFFAOYSA-L 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000005470 impregnation Methods 0.000 description 2
- 230000002779 inactivation Effects 0.000 description 2
- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical compound [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 description 2
- 229910000360 iron(III) sulfate Inorganic materials 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 239000013081 microcrystal Substances 0.000 description 2
- 239000002808 molecular sieve Substances 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 230000000737 periodic effect Effects 0.000 description 2
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 2
- 239000010453 quartz Substances 0.000 description 2
- 238000004088 simulation Methods 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [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
- 238000004438 BET method Methods 0.000 description 1
- 229910014454 Ca-Cu Inorganic materials 0.000 description 1
- 229910014460 Ca-Fe Inorganic materials 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 244000131316 Panax pseudoginseng Species 0.000 description 1
- 235000005035 Panax pseudoginseng ssp. pseudoginseng Nutrition 0.000 description 1
- 235000003140 Panax quinquefolius Nutrition 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- HFNUUHLSQPLBQI-UHFFFAOYSA-N acetic acid;calcium Chemical compound [Ca].CC(O)=O HFNUUHLSQPLBQI-UHFFFAOYSA-N 0.000 description 1
- 238000003916 acid precipitation Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 238000005056 compaction Methods 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 235000008434 ginseng Nutrition 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- 238000001802 infusion Methods 0.000 description 1
- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum oxide Inorganic materials [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 description 1
- FYDKNKUEBJQCCN-UHFFFAOYSA-N lanthanum(3+);trinitrate Chemical compound [La+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O FYDKNKUEBJQCCN-UHFFFAOYSA-N 0.000 description 1
- GJKFIJKSBFYMQK-UHFFFAOYSA-N lanthanum(3+);trinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[La+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O GJKFIJKSBFYMQK-UHFFFAOYSA-N 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- DOTMOQHOJINYBL-UHFFFAOYSA-N molecular nitrogen;molecular oxygen Chemical compound N#N.O=O DOTMOQHOJINYBL-UHFFFAOYSA-N 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- VDGJOQCBCPGFFD-UHFFFAOYSA-N oxygen(2-) silicon(4+) titanium(4+) Chemical compound [Si+4].[O-2].[O-2].[Ti+4] VDGJOQCBCPGFFD-UHFFFAOYSA-N 0.000 description 1
- 239000004323 potassium nitrate Substances 0.000 description 1
- 235000010333 potassium nitrate Nutrition 0.000 description 1
- 238000013112 stability test Methods 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- RXSHXLOMRZJCLB-UHFFFAOYSA-L strontium;diacetate Chemical compound [Sr+2].CC([O-])=O.CC([O-])=O RXSHXLOMRZJCLB-UHFFFAOYSA-L 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- HWCKGOZZJDHMNC-UHFFFAOYSA-M tetraethylammonium bromide Chemical compound [Br-].CC[N+](CC)(CC)CC HWCKGOZZJDHMNC-UHFFFAOYSA-M 0.000 description 1
Classifications
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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
- B01J29/88—Ferrosilicates; Ferroaluminosilicates
-
- 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
- B01J29/03—Catalysts comprising molecular sieves not having base-exchange properties
- B01J29/035—Microporous crystalline materials not having base exchange properties, such as silica polymorphs, e.g. silicalites
- B01J29/0352—Microporous crystalline materials not having base exchange properties, such as silica polymorphs, e.g. silicalites containing iron group metals, noble metals or copper
- B01J29/0356—Iron group metals or copper
-
- 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
- B01J29/064—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof containing iron group metals, noble metals or copper
- B01J29/072—Iron group metals or copper
-
- 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
- B01J29/7049—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
- B01J29/7065—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
- 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
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/82—Phosphates
- B01J29/83—Aluminophosphates [APO compounds]
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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
- B01J29/82—Phosphates
- B01J29/84—Aluminophosphates containing other elements, e.g. metals, boron
- B01J29/85—Silicoaluminophosphates [SAPO compounds]
-
- 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
- B01J35/40—Catalysts, in general, characterised by their form or physical properties characterised by dimensions, e.g. grain size
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B37/00—Compounds having molecular sieve properties but not having base-exchange properties
- C01B37/06—Aluminophosphates containing other elements, e.g. metals, boron
- C01B37/08—Silicoaluminophosphates [SAPO compounds], e.g. CoSAPO
-
- 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
-
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Abstract
本发明公开了开孔为3至5埃的微孔结晶材料,其中材料包含选自碱土金属、稀土元素、碱金属或其混合物的第一金属以及选自铁、铜或其混合物的第二金属,并且所述材料具有3至10的二氧化硅与氧化铝的摩尔比(SAR)。本发明公开的微孔结晶材料可以包含具有双6环(d6r)构造单元和8环开孔的晶体结构,如国际沸石协会结构委员会定义的结构代码为CHA、LEV、AEI、AFT、AFX、EAB、ERI、KFI、SAT、TSC和SAV的骨架类型所示例的。本发明还公开了选择性催化还原废气中的氮氧化物的方法,其包括使废气至少部分接触包含本发明的微孔结晶材料的物体。
Description
本申请要求2011年12月2日提交的第61/566,106号美国临时申请的优先权,将其全部内容引入本文作为参考。
总体来说,本发明提供了开孔为3至5埃的微孔结晶材料,其中所述材料包含选自碱土金属、稀土元素、碱金属或其混合物的第一金属,以及选自铁和/或铜的第二金属。本发明还涉及制备和使用该微孔结晶材料的方法,其包括选择性催化还原(SCR)废气中的氮氧化物 (NOx)。
氮氧化物(NOx)长久以来被认为是污染气体,主要原因在于其腐蚀作用。实际上,它们是造成酸雨的主要原因。NOx污染的主要源头是柴油汽车和固定污染源(如燃煤电厂和汽轮机)的废气中排放的 NOx。为了避免这些有害的排放,使用SCR并且SCR涉及采用沸石催化剂将NOx转化为氮和水。
因此,一直存在对这样的改进的微孔结晶材料的需求:所述材料具有强化性能和水热稳定性以使得能够用于选择性催化还原废气中的 NOx。
发明概述
为了满足该需求,本发明人发现了包含选自碱土金属、稀土元素、碱金属或其混合物的第一金属以及选自铁、铜或其混合物的第二金属的材料,其开孔为3至5埃,并且具有3至10的二氧化硅与氧化铝的摩尔比(SAR)。在一个实施方案中,所述材料通过不使用有机结构导向剂(OSDA)(directing agent)的方法合成。在一个实施方案中,所述材料包含国际沸石协会结构委员会定义的CHA结构。在一个实施方案中,所述材料可以包含具有双6环(d6r)构造单元和8环开孔的晶体结构,如国际沸石协会结构委员会定义的结构代码为LEV、 AEI、AFT、AFX、EAB、ERI、KFI、SAT、TSC和SAV的骨架类型所示例的。
本文描述的材料表现出优异的水热稳定性。例如,本发明公开的材料通常在高达10vol%的水蒸气存在下暴露于700-900℃的温度下 1-16小时后保持其至少70%的表面积和微孔体积。
本发明还公开了采用所公开的微晶材料选择性催化还原废气中的氮氧化物的方法。在一个实施方案中,该方法包括:
使废气至少部分接触包含开孔为3至5埃的微孔结晶材料的物体,其中所述材料包含选自碱土金属、稀土元素、碱金属或其混合物的第一金属以及选自铁、铜或其混合物的第二金属。
理解的是,本发明所述的材料可以用在物体中,如具有沟槽的或蜂巢状的物体;填充床,如球、卵形物、小球、片、挤出物、其它颗粒或其组合;微球;或构件,如板或管的形式。
如本领域技术人员会理解的,具有沟槽的或蜂巢状的物体或构件是通过将所述结晶材料洗覆到预成型的蜂巢状物体上或通过挤出包含所述结晶材料的混合物来形成的。
除了上文讨论的主题以外,本发明还包括许多其它示例性特征,如下文阐明的那些。要理解的是,上下文的描述都仅是示例性的。
附图的简要说明
附图结合到说明书中并构成该说明书的一部分。所有的NH3-SCR 数据都是在以下条件下采集的:500ppm NO;NH3/NO=1.0;5vol%O2;余量的N2;空速=50,000h-1。
图1对比了含和不含Ca的Fe-菱沸石在700℃下10%水/空气中蒸汽处理16小时后的SCR数据。
图2对比了含和不含Ca的Cu-菱沸石在700℃下10%水/空气中蒸汽处理16小时后的SCR数据。
图3对比了含和不含Ca的Cu-SAPO-34在900℃下10%水/空气中蒸汽处理1小时后的SCR数据。
发明详述
定义
“水热稳定的”是指具有在暴露于高温和/或高湿条件(相比室温) 一定时间段后保留一定百分比的初始表面积和/或微孔体积的能力。例如,在一个实施方案中,其意在表示在暴露于模拟汽车废气的条件下,如高达900℃的温度,包括范围在700至900℃的温度,存在体积百分比(vol%)高达为10%的水蒸气,时间范围从长达1小时,或者甚至长达16小时,如在1至16小时的时间范围内保持其至少70%,如至少80%、至少90%或甚至至少95%的表面积和微孔体积。
“初始表面积”是指在将其暴露于任何老化条件之前新近制备的结晶材料的表面积。
“初始微孔体积”是指在将其暴露于任何老化条件之前新近制备的结晶材料的微孔体积。
“直接合成”(或其任何说法)是指在沸石已经形成后无需掺杂金属的过程的方法,如之后的离子交换或浸渍法。
“国际沸石协会结构委员会定义的”意指包括但不限于Baerlocher 等编辑的第六修订版的“Atlas of Zeolite Framework Types”(Elsevier 2007)中描述的结构的那些结构,将其全部内容引入本文作为参考。
“双6环(d6r)”是Baerlocher等编辑的第六修订版的“Atlas of ZeoliteFramework Types”(Elsevier2007)中描述的结构构造单元,将其全部内容引入本文作为参考。
“选择性催化还原”或“SCR”是指在氧存在下还原NOx(通常用氨) 以形成氮和H2O。
“废气”是指任何在工业过程或操作中以及通过内燃机(如来自任何形式的机动车辆)形成的废气。
本文使用的词语“选自(chosen from)”或“选自(selected from)”是指选择单一的组分或两个(或更多)组分的组合。例如,本文描述的大结晶、不含有机物的菱沸石的金属部分可以选自铜和铁,其意味着金属可以包含铜或铁,或者铜和铁的组合。
本发明公开了包含选自碱土金属、稀土元素、碱金属或其混合物的第一金属以及选自铁、铜或其混合物的第二金属的材料。碱土金属是位于元素周期表第2主族的6种元素。可以包含在本发明中作为第一金属使用的碱土金属的非限制性实例包括镁、钙、锶或钡、或其混合物。碱金属是位于元素周期表第1主族的6种元素,不包括氢。可以包含在本发明中作为第一金属使用的碱金属的非限制性实例包括钾、铷、铯或其混合物。
在一个实施方案中,所述材料可以包含具有双6环(d6r)构造单元和8环开孔的晶体结构,如国际沸石协会结构委员会定义的结构代码为CHA、LEV、AEI、AFT、AFX、EAB、ERI、KFI、SAT、TSC 和SAV的骨架类型所示例的(Ch.Baerlocher,L.B.McCusker and D.H.Olson,Atlas of Zeolite Framework Types,6th revised edition, Elsevier,Amsterdam,2007)。
例如,微孔结晶材料可以包含微孔硅铝酸盐沸石,如硅铝酸盐菱沸石。
本发明所述的材料通常具有3至10,如5至7的二氧化硅与氧化铝的摩尔比(SAR)。
所述材料可以通过不使用有机结构导向剂(OSDA)的方法来合成。
理解的是,包括例如镁、钙、锶、钡、镧、铈、镨、钕、混合的稀土氧化物、钾、铷、铯或其混合物的第一金属以及例如铜或铁或其混合物的第二金属可以通过液相或固体离子交换、浸渍或直接合成结合来引入。
如本领域技术人员会理解的是,第一和第二金属可以通过液相或固体离子交换、浸渍或直接合成结合引入到材料中。
在一个实施方案中,第一金属的量为材料总重量的至少0.2重量%,在一个实施方案中,第一金属的量为材料总重量的为0.2重量%至5.0重量%。在一个实施方案中,第一金属包含钙,其量为结晶材料总重量的0.2重量%至5.0重量%。
第一金属与铝的原子比可以介于0.05和0.80之间。在一个实施方案中,材料的第一金属为钙,且钙与铝的原子比介于0.05和0.50之间。
如本文所述,第二金属(如铜)的量可以为结晶材料总重量的0.5 重量%至10.0重量%。在一个实施方案中,材料的第二金属为铜,且铜与铝的原子比介于0.05和0.20之间。
微孔结晶材料还可以包含其量为结晶材料总重量的0.5重量%至 10.0重量%的铁。在一个实施方案中,材料的第二金属为铁,铁与铝的原子比介于0.05和0.30之间。
材料通常包含平均尺寸范围为0.3微米至小于10微米,如0.3微米至5.0微米的晶体。
本文描述的材料显现出优异的水热稳定性。例如,在高达10vol%的水蒸气存在下暴露在700-800℃的温度1-16小时后,本文公开的材料通常保持其至少70%的表面积和微孔体积。
本文公开的材料可以通过以下方法合成,该方法包括:
将钠源、钾源、氧化铝源、二氧化硅源、水和任选的晶种材料混合以形成凝胶,其中所述凝胶具有低于0.5的钾与二氧化硅(K/SiO2) 的摩尔比,和低于0.35的氢氧根与二氧化硅(OH/SiO2)的摩尔比;
在范围为80℃至200℃的温度下在容器中加热所述凝胶形成结晶产物;
将所述产物进行铵交换;以及
通过液相或固体离子交换、浸渍或通过直接合成结合来将第一和第二金属引入所述结晶材料中。
在一个实施方案中,本发明的氧化铝源和二氧化硅源包含钾交换的、质子交换的、铵交换的Y型沸石,硅酸钾或其混合物。
本发明还公开了采用本发明的微晶材料选择性催化还原废气中的氮氧化物的方法。在一个实施方案中,该方法包括:
使废气至少部分接触包含开孔为3至5埃的微孔结晶材料的物体,
其中,所述材料包含选自碱土金属、稀土元素、碱金属或其混合物的第一金属,以及选自铁、铜或其混合物的第二金属。
在一个实施方案中,接触步骤可以在氨、脲或产生氨的化合物的存在下进行。
在另一个实施方案中,接触步骤可以在烃类化合物的存在下进行。
如所提及的,所述方法中使用的材料可以包含具有双6环(d6r) 构造单元和8环开孔的晶体结构,如国际沸石协会结构委员会定义的结构代码为CHA、LEV、AEI、AFT、AFX、EAB、ERI、KFI、SAT、 TSC和SAV的骨架类型所示例的。
在一个实施方案中,本发明的方法中使用的材料包含硅铝磷酸盐 (SAPO)分子筛,如具有CHA骨架类型的SAPO-34。本发明的方法中使用的结晶SAPO分子筛的SiO2的量为结晶材料总重量的1重量%至20重量%。
理解的是,包括例如镁、钙、锶、钡、镧、铈、镨、钕、混合的稀土氧化物、钾、铷、铯或其混合物的第一金属,以及例如铜的第二金属可以通过液相或固体离子交换、浸渍或直接合成结合来引入。
在一个实施方案中,第一金属的重为结晶材料总重量的至少0.2 重量%。当第一金属包含钙时,其通常的量为结晶材料总重量的0.2 重量%至5.0重量%。
当第二金属包含铜时,其通常的量为结晶材料总重量的0.5重量%至10.0重量%。
当第二金属包含铁时,其通常的量也为结晶材料总重量的0.5重量%至10.0重量%。
在一个实施方案中,本发明的方法使用的材料包含尺寸范围为0.3 至5微米的晶体。
理解的是,本文所描述的材料可以用在物体中,如具有沟槽的或蜂巢状的物体;填充床,如球、卵形物、小球、片、挤出物、其它颗粒或其组合;微球;或构件,如板或管的形式。
本领域技术人员将理解的是,具有沟槽的或蜂巢状的物体或构件是通过将所述结晶材料洗覆到预成型的蜂巢状物体上或通过挤出包含所述结晶材料的混合物来形成的。
实施例
将通过以下非限制性的实施例进一步阐明本发明,所述实施例意在纯粹示例本发明。
实施例1(大结晶不含有机物的菱沸石的合成)
将去离子水、氢氧化钾溶液(45wt%KOH)和钾交换的Y型沸石粉末混合在一起以形成具有以下组成的凝胶:5.5SiO2:1.0Al2O3: 1.09K2O:66H2O。该凝胶组合物的OH/SiO2比为0.05。将凝胶在室温下搅拌约30分钟,然后加入1.5wt%的菱沸石种子并再搅拌30分钟。然后将凝胶装入高压反应釜。将高压反应釜加热至120℃并维持温度达60小时,同时在300rpm下搅拌。冷却后,通过过滤回收产物,并用去离子水洗涤。得到的产物具有菱沸石的XRD图形,SAR为5.5,包含16.5wt%的K2O。将产物用硝酸铵交换四次从而将钾含量降低至0.27wt%K2O。
实施例2(铵交换的菱沸石的Ca-交换)
随后将实施例1得到的样品在80℃下与硝酸钙交换2小时。交换后,过滤材料,用去离子水洗涤,然后干燥。
实施例3(Ca-菱沸石的Fe-交换)
将实施例2得到的钙交换的菱沸石样品在环境温度下与硫酸铁交换3小时。过滤、洗涤并干燥后,样品包含2.5wt%CaO和 5.2wt%Fe2O3。
对比实施例4(铵交换的菱沸石的Fe-交换)
将实施例1得到的铵交换的菱沸石在环境温度下与硫酸铁交换3 小时。过滤、洗涤并干燥后,样品包含3.2wt%Fe2O3。
实施例5(Ca-菱沸石的Cu-交换)
将来自实施例2的钙交换的菱沸石样品在60℃下与硝酸铜交换2 小时。过滤、洗涤并干燥后,样品包含2.7wt%CaO和5.5wt%CuO。
对比实施例6(铵交换的菱沸石的Cu-交换)
将实施例1得到的铵交换的菱沸石样品在60℃下与硝酸铜交换 2小时。过滤、洗涤并干燥后,样品包含5.0wt%CuO。
实施例7(大结晶不含有机物的菱沸石的合成)
将去离子水、氢氧化钾溶液(45wt%KOH)和钾交换的Y型沸石粉末混合在一起形成具有以下组成的凝胶:5.5SiO2:1.0Al2O3:1.02 K2O:66H2O。该凝胶组合物的OH/SiO2比为0.025。将凝胶在室温下搅拌约30分钟,然后加入0.5wt%的菱沸石种子并再搅拌30分钟。然后将凝胶装入高压反应釜。将高压反应釜加热至140℃并维持温度达36小时,同时在300rpm下搅拌。冷却后,通过过滤回收产物,并用去离子水洗涤。得到的产物具有菱沸石的XRD图形,SAR为5.6,包含16.7wt%的K2O。将产物与硝酸铵交换两次从而将钾含量降低至2.0wt%K2O。
实施例8(铵交换的菱沸石的Ca-交换)
随后将实施例7得到的样品在80℃下与硝酸钙交换2小时。交换后,过滤材料,用去离子水洗涤,然后干燥。
实施例9(Ca-菱沸石的Cu-交换)
将实施例8得到的钙交换的菱沸石样品在60℃下与硝酸铜交换2 小时。过滤、洗涤并干燥后,样品包含2.9wt%CaO和5.4wt%CuO。
实施例10(Ca-菱沸石的Cu-交换)
将实施例8得到的钙交换的菱沸石样品在60℃下与硝酸铜交换2 小时。过滤、洗涤并干燥后,样品包含3.1wt%CaO和3.2wt%CuO。
实施例11(乙酸铜对钙交换的菱沸石的始润浸渍)
将实施例8得到的钙交换的菱沸石样品在环境温度下用乙酸铜浸渍。浸渍后,将材料在550℃下煅烧2小时。样品包含4.2wt%CaO 和2.1wt%CuO。
实施例12(铵交换的菱沸石的Sr-交换)
随后将实施例1得到的样品在80℃下与乙酸锶交换2小时。交换后,过滤材料,用去离子水洗涤,然后干燥。
实施例13(Sr-菱沸石的Cu-交换)
将实施例12得到的锶交换的菱沸石样品在60℃下与硝酸铜交换 2小时。过滤、洗涤并干燥后,样品包含8.9wt%SrO和5.0wt%CuO。
实施例14(硝酸镧对铵交换的菱沸石的始润浸渍)
将实施例7得到的样品在环境温度下用硝酸镧溶液浸渍。浸渍后,将材料在550℃下煅烧2小时。
实施例15(La-菱沸石的Cu-交换)
随后将实施例14得到的镧-菱沸石样品在60℃下与硝酸铜交换2 小时。过滤、洗涤并干燥后,样品包含8.7wt%La2O3和3.0wt%CuO。
样品性能评价
在700、750和/或800℃和10vol%水蒸气存在下持续16小时,对来自实施例3-6和9-15的样品进行蒸汽处理以模拟汽车废气老化条件。
老化前后的材料的表面积按照BET法采用氮吸收来测定。采用 QuantachromeAutosorb装置进行这些测定,且在液氮温度下相对压力(P/P0)在0.01和0.05之间收集数据。
采用t-曲线法将同时作为表面积测量值的氮吸收数据也用于计算材料的微孔体积。
采用NH3作为还原剂以流通式反应器测试水热老化的材料在NOx转化方面的活性。挤压粉末沸石样品并筛分至35/70目并装入石英管反应器。用于NH3-SCR的气体组成为500ppm NO、500ppm NH3、 5vol%O2、0.6%H2O和余量的N2。空速为50,000h-1。反应器的温度渐变并采用MKS MultiGas2030红外分析仪确定每个温度间隔的 NO转化率。
表1对比了在700℃下10%水/空气中蒸汽处理16小时后,采用含和不含Ca的Fe-菱沸石的NH3-SCR期间,表面积的保持率和NO 的转化率。
表1
实施例 | 实施例3 | 对比实施例4 | |
Fe2O3 | wt% | 5.2 | 3.2 |
CaO | wt% | 2.5 | 0 |
Fe/Al原子比 | 0.15 | 0.09 | |
Ca/Al原子比 | 0.10 | 0.00 | |
初始表面积 | m2/g | 640 | 677 |
700℃下蒸汽处理后的表面积 | m2/g | 564 | 328 |
表面积保持率 | % | 88 | 49 |
初始微孔体积 | cc/g | 0.24 | 0.26 |
700℃下蒸汽处理后的微孔体积 | cc/g | 0.21 | 0.11 |
300℃下的NO转化率 | % | 90.7 | 14.9 |
500℃下的NO转化率 | % | 93.4 | 56.6 |
表1显示Ca-Fe菱沸石的表面积保持率超过了不含Ca的对比材料的表面积保持率。在该失活模拟暴露之后,本发明的材料的表面积和微孔体积保持率应为至少70%,优选为至少80%。
参考图1中显示的SCR数据,清楚地看到当对在700℃下10%水/空气中进行蒸汽处理16小时的样品进行测试时,额外包含Ca的 Fe-菱沸石的NOx转化率超过了不含Ca的Fe-菱沸石的NOx转化率。
表2对比了在700℃下10%水/空气中蒸汽处理16小时后,采用含和不含Ca的Cu-菱沸石的NH3-SCR期间,表面积的保持率和NO 的转化率。
表2
实施例 | 实施例5 | 对比实施例6 | |
CuO | wt% | 5.5 | 5.0 |
CaO | wt% | 2.7 | 0.0 |
Cu/Al原子比 | 0.16 | 0.15 | |
Ca/Al原子比 | 0.11 | 0.00 | |
初始表面积 | m2/g | 642 | 638 |
700℃下蒸汽处理后的表面积 | m2/g | 583 | 512 |
表面积保持率 | % | 91 | 80 |
初始微孔体积 | cc/g | 0.25 | 0.24 |
700℃下蒸汽处理后的微孔体积 | cc/g | 0.22 | 0.18 |
175℃下的NO转化率 | % | 99.7 | 86.1 |
450℃下的NO转化率 | % | 92.2 | 87.9 |
表3对比了在750℃下10%水/空气中蒸汽处理16小时后,采用含和不含Ca、Sr或La的Cu-菱沸石的NH3-SCR期间表面积保持率和NO转化率。
表3
表4对比了在800℃下10%水/空气中蒸汽处理16小时后,采用含和不含Ca的Cu-菱沸石的NH3-SCR期间,表面积的保持率和NO 的转化率。
表4
表2-4显示Ca-Cu菱沸石的表面积保持率超过了不含Ca的对比材料的表面积保持率。在这些失活模拟暴露,例如在700-800℃下10%水/空气中暴露16小时之后,本发明的材料的表面积和微孔体积保持率应为至少70%,优选为至少80%。
图2对比了在700℃下10%水/空气中蒸汽处理16小时后,采用含和不含Ca的Cu-菱沸石得到的SCR数据。图2的数据显示在200℃至高于400℃的温度范围内改善的NOx活性。
实施例16(SAPO-34的合成)
将拟薄水铝石-氧化铝、磷酸、铵稳定化的二氧化硅溶胶(Nyacol 2040NH4)、氢氧化四乙铵(TEAOH)溶液、吗啉和去离子水混合在一起以形成具有以下摩尔组成的凝胶:
0.6SiO2:1.0Al2O3:1.0P2O5:0.85吗啉:0.4TEAOH:32.5H2O
将凝胶在室温下搅拌约30分钟并加入凝胶总无机固体的约1%的量的SAPO-34种子,然后装入高压反应釜。将高压反应釜加热至180℃并保持该温度达24小时。冷却后,通过过滤回收产物并用去离子水洗涤。然后将产物干燥并煅烧以除去有机物。SAPO-34产物包含约12%的SiO2。
对比实施例17(SAPO-34的Cu-交换)
将实施例16得到的SAPO-34样品在60℃下与硝酸铜交换3小时。过滤后,洗涤并干燥包含3.0wt%CuO的样品。
实施例18(SAPO-34的Ca-交换)
将实施例16得到的SAPO-34样品在环境温度下与氢氧化钙交换 2小时。过滤、洗涤并干燥后,样品包含0.9wt%CaO。
实施例19(Ca-SAPO-34的Cu-交换)
将实施例18得到的Ca-SAPO-34样品在环境温度下与硝酸铜交换 4小时。过滤、洗涤并干燥后,样品包含1.9wt%CuO和0.8wt%CaO。
实施例20(SAPO-34的K-交换)
将实施例16得到的SAPO-34样品在80℃下与硝酸钾交换2小时。过滤、洗涤并干燥后,样品包含1.5wt%K2O。
实施例21(K-SAPO-34的Cu-交换)
将实施例20得到的K-SAPO-34样品在环境温度下与硝酸铜交换 4小时。过滤、洗涤并干燥后,样品包含3.0wt%CuO和1.5wt%K2O。
实施例22(Ca-SAPO-34的直接合成)
将拟薄水铝石-氧化铝、磷酸、铵稳定化的二氧化硅溶胶(Nyacol 2040NH4)、乙酸钙、氢氧化四乙铵(TEAOH)溶液、吗啉和去离子水混合在一起以形成具有以下摩尔组成的凝胶:
0.5SiO2:1.0Al2O3:1.0P2O5:0.1CaO:0.85吗啉:0.4TEAOH: 31.5H2O
将凝胶在室温下搅拌约30分钟并加入凝胶总无机固体的约1%的量的SAPO-34种子,然后装入高压反应釜。将高压反应釜加热至180℃并保持该温度达24小时。冷却后,通过过滤回收产物并用去离子水洗涤。然后将产物干燥并煅烧以除去有机物。Ca-SAPO-34产物包含约 11%的SiO2和1.7%CaO。
实施例23(直接合成的Ca-SAPO-34的Cu-交换)
将实施例22得到的Ca-SAPO-34样品在60℃下与硝酸铜交换3 小时。过滤、洗涤并干燥后,样品包含3.0wt%CuO。
实施例24(SAPO-34的Ca-和Cu-交换)
将实施例16得到的Ca-SAPO-34样品在40℃下与氢氧化钙和硝酸铜交换3小时。过滤、洗涤并干燥后,样品包含3.5wt%CuO和0.60 wt%CaO。
热水稳定性测试
通过将4g材料在12g水中制浆来进行水稳定性测试。将浆料置于 23mL高压釜(Parr bomb)中,将高压釜置于105℃的烘箱中达24 小时。随后,过滤、洗涤并干燥浆料。在水处理前后分析表面积。
蒸汽稳定性测试
还将样品在900℃、10vol%水蒸气存在下进行蒸汽处理1小时以模拟汽车废气老化条件。采用NH3作为还原剂以流通式反应器测试水热老化的材料在NOx转化方面的活性。挤压粉末沸石样品并筛分至 35/70目,装入石英管反应器。反应器的温度渐变并采用红外分析仪确定每个温度间隔的NO转化率。
表5对比了在105℃下水处理24小时后各种SAPO-34样品的表面积保持率。
表5
表5显示了将Ca或K加至SAPO-34,如实施例18、19、20、21、 23和24那样,使材料对热水处理稳定,而不含Ca或K的材料(实施例16获得的SAPO-34和对比实施例17获得的Cu-SAPO-34)经过水处理基本完全被破坏。经过热水处理后,本发明的SAPO-34材料保持其至少40%和优选至少60%的表面积和微孔体积,这是理想的。
表6对比了在900℃下10%水/空气中蒸汽处理1小时后,实施例 17、23和24的NH3-SCR期间的NO转化率。
表6
实施例 | 对比实施例17 | 实施例23 | 实施例24 | |
175℃下的NO转化率 | % | 81.7 | 97.6 | 96.1 |
450℃下的NO转化率 | % | 77.0 | 82.0 | 77.5 |
表6显示在900℃下蒸汽处理1小时后,本发明的包含Ca的实施例23和24的NH3-SCR活性比不使用Ca的对比实施例17更强,特别是在低温(如175℃)下。
图3对比了对比实施例17和本发明实施例23在900℃下10%水 /空气中蒸汽处理1小时后的SCR数据。数据显示包含两种金属(此处为钙)的SAPO-34样品表现出相对于不含Ca的样品改善的NOx转化效率。
除非另外指明,说明书和权利要求中使用的所有表示成分、反应条件等的数量的数字应被理解为在各种情况下均由术语“约”进行修饰。相应地,除非相反地指明,以下说明书和所附的权利要求书中提出的数值参数都是可以根据本发明力图获得的理想性质来变化的近似值。
考虑到说明书和本申请公开的发明的实施,其它的本发明的实施方案对于本领域技术人员是显而易见的。说明书和实施例意在被认为仅是示例性的,本发明真正的范围是由以下的权利要求所示的。
Claims (15)
1.一种微孔结晶材料,其具有3至5埃的开孔,具有3至10的二氧化硅与氧化铝的摩尔比(SAR)且包含选自镁、钙、锶、钡、镧、铈、镨、钕、混合的稀土氧化物、铷、铯或其混合物的碱土金属、稀土元素或碱金属的第一金属,以及选自铜、铁或其混合物的第二金属;其中所述第一金属与铝的原子比介于0.05和0.80之间。
2.根据权利要求1所述的微孔结晶材料,其中所述材料包含具有双6环构造单元和8环开孔的晶体结构。
3.根据权利要求1所述的微孔结晶材料,其中所述材料包含CHA结构。
4.根据权利要求2所述的微孔结晶材料,其中所述晶体结构包含LEV、AEI、AFT、AFX、EAB、ERI、KFI、SAT、TSC和SAV的结构代码。
5.根据权利要求1所述的微孔结晶材料,其中所述第一和第二金属通过液相或固体离子交换、浸渍或直接合成结合来引入到所述材料中。
6.根据权利要求1所述的微孔结晶材料,其中所述材料包含钙,且钙与铝的原子比介于0.05和0.50之间。
7.根据权利要求1所述的微孔结晶材料,其中所述材料包含铜,且铜与铝的原子比介于0.05和0.20之间。
8.根据权利要求1所述的微孔结晶材料,其中所述材料包含铁,且铁与铝的原子比介于0.05和0.30之间。
9.根据权利要求1所述的微孔结晶材料,其中所述材料包含的晶体的平均晶体尺寸为0.3至5微米。
10.根据权利要求1所述的微孔结晶材料,其中所述材料在高达10vol%的水蒸气存在下暴露在700-800℃的温度1-16小时后保持其至少70%的表面积和微孔体积。
11.一种选择性催化还原废气中的氮氧化物的方法,所述方法包括:
使所述废气至少部分地接触包含权利要求1至10任一项所述的微孔结晶材料的物品。
12.根据权利要求11所述的方法,其中所述接触步骤是在氨、产生氨的化合物或烃类化合物存在下进行的。
13.根据权利要求12所述的方法,其中所述产生氨的化合物是脲。
14.一种制备根据权利要求1至10任一项所述的微孔结晶材料的方法,所述方法包括:
将钠源、钾源、氧化铝源、二氧化硅源、水及任选的晶种材料混合以形成凝胶,其中所述凝胶具有低于0.5的钾与二氧化硅K/SiO2的摩尔比,和低于0.35的氢氧根与二氧化硅OH/SiO2的摩尔比;
在容器中将所述凝胶加热至80至200℃的温度以形成结晶产物;
将所述产物进行铵交换;以及
通过液相或固体离子交换、浸渍或直接合成结合将含有选自镁、钙、锶、钡、镧、铈、镨、钕、混合的稀土氧化物、铷、铯或其混合物的碱土金属、稀土元素或碱金属的第一金属,以及选自铜、铁或其混合物的第二金属引入到所述结晶材料中,
其中所述第一金属与铝的原子比介于0.05和0.80之间。
15.根据权利要求14所述的方法,其中所述氧化铝源和二氧化硅源包含钾交换的、质子交换的、铵交换的Y型沸石,硅酸钾或其混合物。
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