CN109499606A - A kind of copper and iron composite SCR honeycomb type denitrification catalyst and its preparation method and application - Google Patents
A kind of copper and iron composite SCR honeycomb type denitrification catalyst and its preparation method and application Download PDFInfo
- Publication number
- CN109499606A CN109499606A CN201811344526.6A CN201811344526A CN109499606A CN 109499606 A CN109499606 A CN 109499606A CN 201811344526 A CN201811344526 A CN 201811344526A CN 109499606 A CN109499606 A CN 109499606A
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- Prior art keywords
- copper
- molecular sieve
- honeycomb type
- catalyst
- type denitrification
- Prior art date
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- 239000003054 catalyst Substances 0.000 title claims abstract description 100
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 title claims abstract description 92
- 239000010949 copper Substances 0.000 title claims abstract description 78
- 229910052802 copper Inorganic materials 0.000 title claims abstract description 62
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 60
- 229910052742 iron Inorganic materials 0.000 title claims abstract description 45
- 239000002131 composite material Substances 0.000 title claims abstract description 36
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims abstract description 61
- 239000002808 molecular sieve Substances 0.000 claims abstract description 55
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 50
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 claims abstract description 34
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 claims abstract description 25
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims abstract description 24
- 239000003365 glass fiber Substances 0.000 claims abstract description 21
- 239000004408 titanium dioxide Substances 0.000 claims abstract description 21
- 235000014655 lactic acid Nutrition 0.000 claims abstract description 17
- 239000004310 lactic acid Substances 0.000 claims abstract description 17
- 229920001131 Pulp (paper) Polymers 0.000 claims abstract description 13
- 230000032683 aging Effects 0.000 claims abstract description 11
- 238000000034 method Methods 0.000 claims abstract description 10
- 230000008569 process Effects 0.000 claims abstract description 8
- 239000011230 binding agent Substances 0.000 claims abstract description 6
- 238000001802 infusion Methods 0.000 claims abstract description 3
- 238000005342 ion exchange Methods 0.000 claims abstract description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 33
- 239000008367 deionised water Substances 0.000 claims description 24
- 229910021641 deionized water Inorganic materials 0.000 claims description 24
- 235000010215 titanium dioxide Nutrition 0.000 claims description 24
- 235000021355 Stearic acid Nutrition 0.000 claims description 20
- 238000001035 drying Methods 0.000 claims description 20
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 claims description 20
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 claims description 20
- 239000008117 stearic acid Substances 0.000 claims description 20
- 239000000843 powder Substances 0.000 claims description 15
- 229920002134 Carboxymethyl cellulose Polymers 0.000 claims description 14
- 239000001768 carboxy methyl cellulose Substances 0.000 claims description 13
- 235000010948 carboxy methyl cellulose Nutrition 0.000 claims description 13
- 239000008112 carboxymethyl-cellulose Substances 0.000 claims description 13
- 241000219782 Sesbania Species 0.000 claims description 12
- 239000011094 fiberboard Substances 0.000 claims description 10
- 238000010438 heat treatment Methods 0.000 claims description 10
- 238000000643 oven drying Methods 0.000 claims description 10
- 238000003756 stirring Methods 0.000 claims description 10
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 8
- OPQARKPSCNTWTJ-UHFFFAOYSA-L copper(ii) acetate Chemical compound [Cu+2].CC([O-])=O.CC([O-])=O OPQARKPSCNTWTJ-UHFFFAOYSA-L 0.000 claims description 8
- 229910052593 corundum Inorganic materials 0.000 claims description 8
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical group O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims description 8
- 239000001257 hydrogen Substances 0.000 claims description 8
- 229910052739 hydrogen Inorganic materials 0.000 claims description 8
- 229910001845 yogo sapphire Inorganic materials 0.000 claims description 8
- 239000001866 hydroxypropyl methyl cellulose Substances 0.000 claims description 7
- 229920003088 hydroxypropyl methyl cellulose Polymers 0.000 claims description 7
- 235000010979 hydroxypropyl methyl cellulose Nutrition 0.000 claims description 7
- UFVKGYZPFZQRLF-UHFFFAOYSA-N hydroxypropyl methyl cellulose Chemical compound OC1C(O)C(OC)OC(CO)C1OC1C(O)C(O)C(OC2C(C(O)C(OC3C(C(O)C(O)C(CO)O3)O)C(CO)O2)O)C(CO)O1 UFVKGYZPFZQRLF-UHFFFAOYSA-N 0.000 claims description 7
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical class [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 claims description 7
- 150000001879 copper Chemical class 0.000 claims description 6
- 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 6
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 claims description 6
- 238000001914 filtration Methods 0.000 claims description 6
- 239000007789 gas Substances 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 6
- 230000004048 modification Effects 0.000 claims description 5
- 238000012986 modification Methods 0.000 claims description 5
- 229910000323 aluminium silicate Inorganic materials 0.000 claims description 4
- 239000012266 salt solution Substances 0.000 claims description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 3
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 claims description 3
- 238000002485 combustion reaction Methods 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims description 3
- 150000003608 titanium Chemical class 0.000 claims description 3
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 claims description 2
- 229960004029 silicic acid Drugs 0.000 claims description 2
- 229910052710 silicon Inorganic materials 0.000 claims description 2
- 239000010703 silicon Substances 0.000 claims description 2
- 235000012239 silicon dioxide Nutrition 0.000 claims description 2
- 239000000243 solution Substances 0.000 claims description 2
- 150000003839 salts Chemical class 0.000 claims 2
- 239000002202 Polyethylene glycol Substances 0.000 claims 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims 1
- 229920001223 polyethylene glycol Polymers 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 12
- 238000006555 catalytic reaction Methods 0.000 abstract description 3
- 230000002153 concerted effect Effects 0.000 abstract description 3
- 239000000463 material Substances 0.000 abstract description 3
- 238000007598 dipping method Methods 0.000 abstract description 2
- 238000011031 large-scale manufacturing process Methods 0.000 abstract description 2
- 238000007493 shaping process Methods 0.000 abstract description 2
- 238000000465 moulding Methods 0.000 abstract 1
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 31
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 22
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 13
- 238000012360 testing method Methods 0.000 description 13
- 229910052757 nitrogen Inorganic materials 0.000 description 11
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 10
- 238000010792 warming Methods 0.000 description 10
- 239000011593 sulfur Substances 0.000 description 8
- 229910052717 sulfur Inorganic materials 0.000 description 8
- RAHZWNYVWXNFOC-UHFFFAOYSA-N sulfur dioxide Inorganic materials O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 description 8
- 230000009466 transformation Effects 0.000 description 8
- 229910052681 coesite Inorganic materials 0.000 description 7
- 229910052906 cristobalite Inorganic materials 0.000 description 7
- 239000000377 silicon dioxide Substances 0.000 description 7
- 229910052682 stishovite Inorganic materials 0.000 description 7
- 229910052905 tridymite Inorganic materials 0.000 description 7
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 150000002431 hydrogen Chemical class 0.000 description 6
- 239000002253 acid Substances 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 5
- 231100000572 poisoning Toxicity 0.000 description 5
- 230000000607 poisoning effect Effects 0.000 description 5
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 4
- 229910021536 Zeolite Inorganic materials 0.000 description 4
- 239000006071 cream Substances 0.000 description 4
- 239000003546 flue gas Substances 0.000 description 4
- 239000010457 zeolite Substances 0.000 description 4
- 239000005864 Sulphur Substances 0.000 description 3
- 229910021529 ammonia Inorganic materials 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical compound O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 description 3
- 238000006213 oxygenation reaction Methods 0.000 description 3
- 229910052720 vanadium Inorganic materials 0.000 description 3
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 3
- BYFGZMCJNACEKR-UHFFFAOYSA-N aluminium(i) oxide Chemical compound [Al]O[Al] BYFGZMCJNACEKR-UHFFFAOYSA-N 0.000 description 2
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 2
- 229910052921 ammonium sulfate Inorganic materials 0.000 description 2
- 235000011130 ammonium sulphate Nutrition 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- QVQLCTNNEUAWMS-UHFFFAOYSA-N barium oxide Chemical compound [Ba]=O QVQLCTNNEUAWMS-UHFFFAOYSA-N 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000018109 developmental process Effects 0.000 description 2
- 235000003891 ferrous sulphate Nutrition 0.000 description 2
- 239000011790 ferrous sulphate Substances 0.000 description 2
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 description 2
- 229910000359 iron(II) sulfate Inorganic materials 0.000 description 2
- 229940071125 manganese acetate Drugs 0.000 description 2
- UOGMEBQRZBEZQT-UHFFFAOYSA-L manganese(2+);diacetate Chemical compound [Mn+2].CC([O-])=O.CC([O-])=O UOGMEBQRZBEZQT-UHFFFAOYSA-L 0.000 description 2
- 229910000069 nitrogen hydride Inorganic materials 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 231100000614 poison Toxicity 0.000 description 2
- 229910001404 rare earth metal oxide Inorganic materials 0.000 description 2
- 230000002195 synergetic effect Effects 0.000 description 2
- WWILHZQYNPQALT-UHFFFAOYSA-N 2-methyl-2-morpholin-4-ylpropanal Chemical compound O=CC(C)(C)N1CCOCC1 WWILHZQYNPQALT-UHFFFAOYSA-N 0.000 description 1
- 229910017827 Cu—Fe Inorganic materials 0.000 description 1
- 241000790917 Dioxys <bee> Species 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 239000002841 Lewis acid Substances 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- CZSABVBCTRZESY-UHFFFAOYSA-N [O-2].[O-2].[Ti+4].OS(O)(=O)=O Chemical compound [O-2].[O-2].[Ti+4].OS(O)(=O)=O CZSABVBCTRZESY-UHFFFAOYSA-N 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 238000003916 acid precipitation Methods 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 230000001413 cellular effect Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000005253 cladding Methods 0.000 description 1
- 239000000701 coagulant Substances 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 229910052878 cordierite Inorganic materials 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 230000001627 detrimental effect Effects 0.000 description 1
- JSKIRARMQDRGJZ-UHFFFAOYSA-N dimagnesium dioxido-bis[(1-oxido-3-oxo-2,4,6,8,9-pentaoxa-1,3-disila-5,7-dialuminabicyclo[3.3.1]nonan-7-yl)oxy]silane Chemical compound [Mg++].[Mg++].[O-][Si]([O-])(O[Al]1O[Al]2O[Si](=O)O[Si]([O-])(O1)O2)O[Al]1O[Al]2O[Si](=O)O[Si]([O-])(O1)O2 JSKIRARMQDRGJZ-UHFFFAOYSA-N 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000012851 eutrophication Methods 0.000 description 1
- 229910052635 ferrosilite Inorganic materials 0.000 description 1
- 244000144992 flock Species 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000002779 inactivation Effects 0.000 description 1
- 150000007517 lewis acids Chemical group 0.000 description 1
- 239000003595 mist Substances 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 230000020477 pH reduction Effects 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 239000002574 poison Substances 0.000 description 1
- 230000007096 poisonous effect Effects 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 1
- -1 silicate sulfates Chemical class 0.000 description 1
- 239000000779 smoke Substances 0.000 description 1
- 230000019635 sulfation Effects 0.000 description 1
- 238000005670 sulfation reaction Methods 0.000 description 1
- 239000002352 surface water Substances 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
- B01J29/72—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65 containing iron group metals, noble metals or copper
- B01J29/76—Iron group metals or copper
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/86—Catalytic processes
- B01D53/8621—Removing nitrogen compounds
- B01D53/8625—Nitrogen oxides
- B01D53/8628—Processes characterised by a specific catalyst
-
- 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
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
-
- 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
- B01J29/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively
- B01J29/42—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively containing iron group metals, noble metals or copper
- B01J29/46—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
- B01J29/72—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
- B01J29/7615—Zeolite Beta
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- 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)
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0215—Coating
- B01J37/0217—Pretreatment of the substrate before coating
-
- 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
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Environmental & Geological Engineering (AREA)
- Crystallography & Structural Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Biomedical Technology (AREA)
- Analytical Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Exhaust Gas Treatment By Means Of Catalyst (AREA)
- Catalysts (AREA)
Abstract
The present invention discloses a kind of copper and iron composite SCR honeycomb type denitrification catalyst and its preparation method and application.Gained catalyst of the invention is using ion-exchange or copper-based molecular sieve prepared by infusion process as active component, and using the titanium dioxide of polyferric silicate sulfate dipping preparation as carrier, shaping assistant includes glass fibre, binder, wood pulp and lactic acid etc..Pug through molding, it is aging, dry, roast and etc. be prepared into honeycomb type denitrification catalyst.The preparation method of gained catalyst of the invention is simple, and cost of material is low, is easy to large-scale production；Good concerted catalysis effect is formed between copper and iron bimetallic, not only increases the denitration activity of catalyst, and improve the anti-H of catalyst2O and anti-SO2Performance.Denitration efficiency of the gained catalyst of the invention within the scope of 250 ~ 450 DEG C has a good application prospect 80% or more in stationary source denitration direction.
Description
Technical field
The present invention relates to new materials, and in particular to a kind of copper and iron composite SCR honeycomb type denitrification catalyst and preparation method thereof
And application.
Background technique
Nitrogen oxides (NO x ) it is a kind of important atmosphere pollution.NO x Discharge to human production life and natural environment
Bring great harm.NO x Acid rain, acid mist and photochemical fog can not only be caused, promote global warming.In addition, nitrogen deposition amount
Increase, will lead to surface water eutrophication and land, wetland, lithic drainage acidification and poison, further to land
It is damaged with aquatic system.With the rapid development of domestic economy, the energy resource structure based on coal leads to NO x Discharge amount it is fast
Speed increases, and seriously polluted ecological environment, becomes one of an important factor for restricting social development.Therefore, how effectively to eliminate
NO x Have become an important topic to attract people's attention in current environment protection field.
In numerous NO x In emission control technique, ammonia SCR technology (NH3- SCR) it is to answer in the world at present
With one of the gas denitrifying technology that most, technology is most mature, it is de- to be widely used in the stationary sources flue gas such as coal-burning power plant, Industrial Boiler
Nitre, the technology have many advantages, such as that denitration efficiency is high, selectivity is good, reliable for operation, easy to maintain.Catalyst is NH3SCR system
Most crucial part, performance directly affect the whole denitration efficiency and stability of system, are the key that denitration Project Success.
V2O5-WO3(MoO3)-TiO2It is the NH industrially generally used3SCR catalyst, operating temperature generally 300 ~
400 DEG C, by V2O5It is carried on anatase structured type titanium dioxide (titanium dioxide), adulterates WO3Or MoO3It is modified.Detitanium-ore-type TiO2
There is Lewis acid abundant site on surface, and not with SO2Reaction, is exposed in sulfur-containing smoke gas for a long time and is also able to maintain its microcosmic knot
Structure is constant, has preferable resistance to SO_2.Although catalytic component based on vanadium application technology mature, its application is lacked there is also obvious
It falls into, is mainly manifested in: V2O5Belong to high toxic material, large-scale use may be detrimental to health and generate secondary environmental pollution
Problem；SO2To SO3Oxygenation efficiency it is high, SO3With NH3It is reacted with vapor and generates ammonium sulfate and ammonium hydrogen sulfate, easily condense in downstream
On pipeline, the blocking and corrosion of pipeline are caused；Navajoite reserves are relatively fewer, and the price of barium oxide presoma is higher；Low temperature is living
Property it is poor, in the underrun stage, flue-gas temperature is lower (generally at 250 ~ 310 DEG C) for power plant, and common catalytic component based on vanadium is difficult
To meet requirement.Therefore, wide active temperature windows, low SO are developed2The non-vanadium base environment-friendly type denitrating catalyst of oxygenation efficiency is
One hot subject of domestic and international academia and industrial circle.
Metal Supported molecular sieve denitrating catalyst not only has relatively wide active temperature windows, but also has higher
N2Selective and lower SO2Oxidability has a good application prospect.Currently, copper zeolite is living as denitrating catalyst
Property component moving source denitration field realize commercialization promote.Moving source denitrating catalyst is by the molecule of Metal Supported
Sieve is coated on cordierite surface.Since the catalyst activity component of cladding process preparation and the adhesive force of carrier are limited, active component
Continuous loss can be washed away with high ash content, stationary source denitration application is restricted.Therefore, stationary source denitrating catalyst is usually whole
Body squeezes out honeycomb fashion, i.e., active component, carrier and shaping assistant is directly fabricated to honeycomb, is uniformly distributed in active component
In carrier.In this case, even if catalyst has abrasion in high ash content flue gas, higher denitration activity can still be kept.
It is domestic at present it has been reported that some SCR denitrations, and most of all show excellent NOxPurify energy
Power.Publication number CN104971780A and CN105126922A propose using rare earth oxide as main active component, with molecular sieve and
Titanium dioxide etc. is that carrier prepares cellular catalyst, due to the higher cost of rare earth oxide and molecular sieve, causes to push away on a large scale
Wide and application difficult.CN102698810A discloses a kind of preparation method of honeycomb type denitrification catalyst, and the catalyst is with sulphur
Sour ferrous and manganese acetate is main active component, on the one hand the addition of ferrous sulfate makes catalyst high temperature with higher living
Property；On the other hand, it will become ferriferous oxide after ferrous sulfate calcining, excessive ferriferous oxide improves SO2Oxygenation efficiency increases
The production rate of ammonium sulfate.Although the addition of manganese acetate improves the low-temperature denitration activity of catalyst, while but also catalyst
Sulfur poisoning resistance have a greatly reduced quality.
Copper-based molecular sieve has preferable denitration activity at 300 DEG C or so, but its water resistant and sulfur poisoning resistance need
It improves.Vapor can make the structure collapses dealuminzation of molecular sieve, while active component being caused to migrate, and cause catalyst inactivation.SO2
It can make active metal Cu sulfation, so that the activity of catalyst reduces.Polyferric silicate sulfate (PSF) is a kind of band branch or netted
The polymer of structure.Usually as a kind of coagulant, for the organic matter in flocks water, application there is no in denitration direction.
Summary of the invention
The purpose of the present invention is overcome the deficiencies of the prior art and provide a kind of at low cost, simple process, temperature window mouth width,
The copper and iron composite SCR honeycomb type denitrification catalyst that denitration efficiency is high and water resistant anti-sulfur poisonous performance is strong, the active group of the catalyst
It is divided into the modified molecular sieve of mantoquita, carrier is the modified titanium dioxide of polyferric silicate sulfate.
One aspect of the present invention utilizes the special stereochemical structure of polyferric silicate sulfate (PSF), improves copper-based molecular sieve high-temperature water
Thermal stability；On the other hand it is acted on using the concerted catalysis between transition metal iron and copper, has not only widened the activity of catalyst
Temperature window (250 ~ 450 DEG C), and improve the sulfur poisoning resistance of catalyst.Copper-based molecular sieve and polyferric silicate sulfate and titanium
Synergistic effect between white powder carrier improves the high-temperature hydrothermal stability of molecular sieve, the denitration performance of catalyst and sulfur poisoning-resistant
Performance, stable, cheap, the environmental-friendly denitrating catalyst of exploitation performance have stationary source denitrating flue gas critically important
Realistic meaning.
Further, this kind of copper and iron composite SCR honeycomb type denitrification catalyst, component includes: 5 ~ 15 in parts by weight
The modified titanium dioxide of the modified molecular sieve of part mantoquita, 70 ~ 85 parts of polyferric silicate sulfates, 4 ~ 8 parts of glass fibres, 2 ~ 3 parts of bondings
Agent, 0.5 ~ 1 part of wood pulp or sesbania powder, 0.2 ~ 0.5 part of stearic acid and 2 ~ 3 parts of lactic acid.
Further, the molecular sieve of the mantoquita modification is obtained by ion-exchange or infusion process modification, used in modification
Mantoquita includes: one of copper acetate, copper nitrate or copper sulphate, and wherein copper is 1 ~ 10wt.% in modified molecular screen.
Further, the molecular sieve being modified by mantoquita is aluminosilicate molecular sieves or silicoaluminophosphamolecular molecular sieve, type
For Hydrogen or ammonium type, topology molecular sieve structure is AFX, CHA, BEA or MFI, preferably SSZ-39, SSZ-13, SAPO-34,
Zeolite Beta or ZSM-5.
Further, SiO in the aluminosilicate molecular sieves2/Al2O3Molar ratio be 10 ~ 40:1；The sial phosphorus
The mass fraction of silicon is 5 ~ 12% in hydrochlorate molecular sieve.
Further, the titanium dioxide be polyferric silicate sulfate impregnate to obtain, wherein in modified titanium ferro element be 0.5 ~
2wt.%。
Further, the binder is carboxymethyl cellulose (CMC), hydroxypropyl methyl cellulose (HPMC) or polyoxygenated
The mixing of one or both of ethylene (PEO).
Invention additionally discloses the preparation methods of this copper and iron composite SCR honeycomb type denitrification catalyst, and steps are as follows:
(1) the quasi- molecular sieve being modified is added in copper salt solution, keeps the temperature 2 ~ 4h at 60 ~ 100 DEG C (at preferably 80 ~ 90 DEG C),
The modified molecular sieve of the mantoquita, also referred to as copper-based molecular sieve is obtained by filtration；Or molecular sieve is added in copper salt solution, 10 ~
4 ~ 12h is impregnated at 40 DEG C (preferably at 25 ~ 40 DEG C) to get copper-based molecular sieve.
(2) polymeric silicicacid ferrous solution is added into 70 ~ 85 parts of titanium dioxides, 0.5 ~ 1h is sufficiently stirred to being uniformly mixed, stirs
It is warming up to pug temperature in batch mixer and reaches 80 ~ 90 DEG C, be stirred 0.5 ~ 1h at this temperature, it is modified to obtain polyferric silicate sulfate
Titanium dioxide；
(3) 5 ~ 15 parts of copper-based molecular sieves obtained by step (1) are added into step (2) pug, it is stirred 0.5 at 80 ~ 90 DEG C ~
1h；
(4) 4 ~ 8 parts of glass fibres of addition, 2 ~ 3 parts of binders, 0.5 ~ 1 part of wood pulp or sesbania powder into step (3), 0.2 ~ 0.5 part
Stearic acid, 2 ~ 3 parts of lactic acid and deionized water are kneaded 0.5 ~ 1h at 80 ~ 90 DEG C, are drained after mixing, control pug
Moisture content is 30 ~ 33%；
(5) pug obtained by step (4) is sealed aging 18 ~ 36h；
(6) by pug obtained by step (5) through vacuum extruding form, the wet base of honeycomb type denitrification catalyst is obtained, and with liner sponge
Fiberboard carton packed.
(7) by wet base obtained by step (6) in climatic chamber drying, drying process are as follows: temperature is increased to 70 by 30 ~ 40 DEG C
~ 80 DEG C, humidity is reduced to 30% ~ 40% by 70% ~ 80%, then is transferred to 100 ~ 120 DEG C of 4 ~ 6h of oven drying and obtains dry body；
(8) by step (7) resulting dry body in 500 ~ 600 DEG C of 4 ~ 6h of roasting of Muffle furnace, heating rate is 2 DEG C/min.
Application of this copper and iron composite SCR honeycomb type denitrification catalyst in stationary source denitration is also claimed in the present invention,
Application including but not limited in power plant, boiler and factory's combustion tail gas denitrification process.
The beneficial effects of the present invention are: the present invention is main active component using copper-based molecular sieve, catalyst has preferable
Middle low-temperature denitration activity.Using the modified titanium dioxide of polyferric silicate sulfate as carrier, concerted catalysis on the one hand occurs with copper-based molecular sieve
Effect, improves the high temperature denitration activity of catalyst；On the other hand the water resistant sulfur resistance of catalyst is improved.It is of the invention high
The molecular sieve dosage of cost is less, keeps the cost of catalyst controllable.The preparation method of catalyst is simple, is easy to large-scale production.
Denitration efficiency of the gained honeycomb catalyst of the invention within the scope of 250 ~ 450 DEG C has 80% or more in stationary source denitration direction
There is good application prospect.
Detailed description of the invention
Fig. 1 is the denitration efficiency test result line chart of embodiment 4 Yu comparative example 1,2.
Specific embodiment
The principles and features of the present invention are described below, and the given examples are served only to explain the present invention, is not intended to limit
Determine the scope of the present invention.
Embodiment 1
A kind of copper and iron composite SCR honeycomb type denitrification catalyst, component include: 29.45g copper acetate, 225g in parts by weight
SSZ-39 molecular sieve (Hydrogen, SiO2/Al2O3Molar ratio is 17:1), 2445g titanium dioxide, 73.35g polyferric silicate sulfate (Fe content
In terms of 20%, similarly hereinafter), 180g glass fibre, 36g CMC, 30g PEO, 15g wood pulp, 9g stearic acid and 60g lactic acid.
The preparation method of above-mentioned copper and iron composite SCR honeycomb type denitrification catalyst, steps are as follows:
(1) 29.45g copper acetate is dissolved into 800g deionized water, 225g SSZ-39 molecular sieve is added thereto, at 30 DEG C
Under be sufficiently stirred dipping 8h, obtain Cu/SSZ-39 after dehydration.
(2) 73.35g polyferric silicate sulfate is dissolved into 1026.9g deionized water, 2445g titanium dioxide is added thereto, stirs
After mixing 0.5h, it is warming up to pug temperature and reaches 80 ~ 90 DEG C, continue to be stirred 1h.
(3) Cu/SSZ-39 molecular sieve obtained by (1) is added into (2) pug, is stirred 1h at 80 ~ 90 DEG C.
(4) to be added in (3) 180g glass fibre, 36g CMC, 30g PEO, 15g wood pulp, 9g stearic acid, 60g lactic acid and
398.1g deionized water.It after being kneaded 0.5h at 80 ~ 90 DEG C, is drained, test pug moisture content is 30.5%.
(5) by pug obtained by step be sealed it is aging for 24 hours.
(6) pug obtained by step (5) is obtained into the wet base of honeycomb type denitrification catalyst through vacuum extruding form, and uses liner
The fiberboard carton of sponge is packed.
(7) by wet base obtained by step (6) in climatic chamber drying, drying condition are as follows: 30 DEG C-humidity of temperature 70% is dry
6h, the dry 6h of 40 DEG C-humidity of temperature 60%, the dry 6h of temperature 50 C-humidity 50%, the dry 6h of temperature 60 C-humidity 40% are transferred to
100 DEG C of oven drying 6h.
(8) by step (7) products obtained therefrom in 500 DEG C of roasting 6h of Muffle furnace, heating rate is 2 DEG C/min, and it is multiple to obtain copper and iron
Close SCR honeycomb type denitrification catalyst.
Gained catalyst is greater than 80% in 250 ~ 450 DEG C of transformation efficiency of the oxides of nitrogen, turns in 280 ~ 440 DEG C of nitrogen oxides
Rate is greater than 90%.Its active testing condition is (similarly hereinafter), the nitric oxide of 500ppm, the ammonia of 500ppm, the dioxy of 500ppm
Change sulphur, 10% vapor, 5% oxygen, reaction Balance Air be nitrogen, loaded catalyst 90mL, reaction velocity 8,
000h-1, catalyst size is 30mm × 30mm × 100mm.
Embodiment 2
A kind of copper and iron composite SCR honeycomb type denitrification catalyst, component include: 24.09g copper nitrate, 225g in parts by weight
SSZ-13 molecular sieve (Hydrogen, SiO2/Al2O molar ratio is 27:1), 2415g titanium dioxide, 72.45g polyferric silicate sulfate, 174g glass
Fiber, 45g HPMC, 24g PEO, 30g wood pulp, 12g stearic acid and 75g lactic acid.
The preparation method of above-mentioned copper and iron composite SCR honeycomb type denitrification catalyst, steps are as follows:
(1) 24.09g copper nitrate is dissolved into 180g deionized water, 225g SSZ-13 molecular sieve is added thereto, at 40 DEG C
4h is impregnated after being sufficiently stirred, and obtains Cu/SSZ-13.
(2) 72.45g polyferric silicate sulfate is dissolved into 1304.1g deionized water, 2415g titanium dioxide is added thereto, stirs
After mixing 1h, it is warming up to pug temperature and reaches 80 ~ 90 DEG C, continue to be stirred 1h.
(3) Cu/SSZ-13 molecular sieve obtained by (1) is added into (2) pug, is stirred 1h at 80 ~ 90 DEG C.
(4) 174g glass fibre, 45g HPMC, 24g PEO, 30g wood pulp, 12g stearic acid, 75g lactic acid are added in (3)
With 215.5g deionized water.It after being kneaded 0.5h at 80 ~ 90 DEG C, is drained, test pug moisture content is 32%.
(5) pug obtained by step is sealed aging 18h.
(6) pug obtained by step (5) is obtained into the wet base of honeycomb type denitrification catalyst through vacuum extruding form, and uses liner
The fiberboard carton of sponge is packed.
(7) by wet base obtained by step (6) in climatic chamber drying, drying condition are as follows: 30 DEG C-humidity of temperature 70% is dry
6h, the dry 6h of 40 DEG C-humidity of temperature 60%, the dry 6h of temperature 50 C-humidity 50%, the dry 6h of temperature 60 C-humidity 40% are transferred to
120 DEG C of oven drying 4h.
(8) by step (7) products obtained therefrom in 550 DEG C of roasting 5h of Muffle furnace, heating rate is 2 DEG C/min, and it is multiple to obtain copper and iron
Close SCR honeycomb type denitrification catalyst.
Gained catalyst is greater than 80% in 250 ~ 450 DEG C of transformation efficiency of the oxides of nitrogen, turns in 270 ~ 450 DEG C of nitrogen oxides
Rate is greater than 90%.
Embodiment 3
A kind of copper and iron composite SCR honeycomb type denitrification catalyst, component include: 41.08g copper nitrate, 450g in parts by weight
SAPO-34 molecular sieve (Hydrogen, P2O5Content is 45.7%, Al2O3Content is 44.00%, SiO2Content be 10.3%), 2100g titanium white
Powder, 63.0g polyferric silicate sulfate, 240g glass fibre, 45g CMC, 30g PEO, 30g sesbania powder, 15g stearic acid and 90g lactic acid.
The preparation method of above-mentioned copper and iron composite SCR honeycomb type denitrification catalyst, steps are as follows:
(1) 41.08g copper nitrate is dissolved into 325g deionized water, 450g SAPO-34 molecular sieve is added thereto, at 20 DEG C
12h is impregnated after being sufficiently stirred, and obtains Cu/SAPO-34.
(2) 63.0g polyferric silicate sulfate is dissolved into 1008g deionized water, 2100g titanium dioxide, stirring is added thereto
After 0.5h, it is warming up to pug temperature and reaches 80 ~ 90 DEG C, continue to be stirred 1h.
(3) Cu/SAPO-34 molecular sieve obtained by (1) is added into (2) pug, is stirred 1h at 80 ~ 90 DEG C.
(4) 240g glass fibre, 45g CMC, 30g PEO, 30g sesbania powder, 15g stearic acid, 90g cream are added in (3)
Acid and 470.7g deionized water.It after being kneaded 1h at 80 ~ 90 DEG C, is drained, test pug moisture content is 31.5%.
(5) pug obtained by step is sealed aging 30h.
(6) pug obtained by step (5) is obtained into the wet base of honeycomb type denitrification catalyst through vacuum extruding form, and uses liner
The fiberboard carton of sponge is packed.
(7) by wet base obtained by step (6) in climatic chamber drying, drying condition are as follows: 30 DEG C-humidity of temperature 70% is dry
6h, the dry 6h of 40 DEG C-humidity of temperature 60%, the dry 6h of temperature 50 C-humidity 50%, the dry 6h of temperature 60 C-humidity 40% are transferred to
110 DEG C of oven drying 5h.
(8) by step (7) products obtained therefrom in 600 DEG C of roasting 4h of Muffle furnace, heating rate is 2 DEG C/min, and it is multiple to obtain copper and iron
Close SCR honeycomb type denitrification catalyst.
Gained catalyst is greater than 80% in 250 ~ 450 DEG C of transformation efficiency of the oxides of nitrogen, turns in 280 ~ 440 DEG C of nitrogen oxides
Rate is greater than 90%.
Embodiment 4
A kind of copper and iron composite SCR honeycomb type denitrification catalyst, component include: 36.25g copper acetate, 450g in parts by weight
ZSM-5 molecular sieve (Hydrogen, SiO2/Al2O3Molar ratio is 30:1), 2160g titanium dioxide, 64.8g polyferric silicate sulfate, 210g glass
Fiber, 36g CMC, 24g PEO, 18g sesbania powder, 12g stearic acid and 90g lactic acid.
The preparation method of above-mentioned copper and iron composite SCR honeycomb type denitrification catalyst, steps are as follows:
(1) 36.25g copper acetate is dissolved into 2250g deionized water, 450g ZSM-5 molecular sieve is added thereto, at 90 DEG C
2h is reacted, obtains Cu/ZSM-5 after filtering.
(2) 64.8g polyferric silicate sulfate is dissolved into 1188g deionized water, 2160g titanium dioxide, stirring is added thereto
After 1h, it is warming up to pug temperature and reaches 80 ~ 90 DEG C, continue to be stirred 1h.
(3) Cu/ZSM-5 molecular sieve obtained by (1) is added into (2) pug, is stirred 0.5h at 80 ~ 90 DEG C.
(4) 210g glass fibre, 36g CMC, 24g PEO, 18g sesbania powder, 12g stearic acid, 90g cream are added in (3)
Acid and 250.2g deionized water.It after being kneaded 1h at 80 ~ 90 DEG C, is drained, test pug moisture content is 32%.
(5) by pug obtained by step be sealed it is aging for 24 hours.
(6) pug obtained by step (5) is obtained into the wet base of honeycomb type denitrification catalyst through vacuum extruding form, and uses liner
The fiberboard carton of sponge is packed.
(7) by wet base obtained by step (6) in climatic chamber drying, drying condition are as follows: 30 DEG C-humidity of temperature 70% is dry
6h, the dry 6h of 40 DEG C-humidity of temperature 60%, the dry 6h of temperature 50 C-humidity 50%, the dry 6h of temperature 60 C-humidity 40% are transferred to
120 DEG C of oven drying 4h.
(8) by step (7) products obtained therefrom in 500 DEG C of roasting 6h of Muffle furnace, heating rate is 2 DEG C/min, and it is multiple to obtain copper and iron
Close SCR honeycomb type denitrification catalyst.
Gained catalyst is greater than 80% in 250 ~ 450 DEG C of transformation efficiency of the oxides of nitrogen, turns in 280 ~ 450 DEG C of nitrogen oxides
Rate is greater than 90%.
Embodiment 5
A kind of copper and iron composite SCR honeycomb type denitrification catalyst, component include: 18.23g copper sulphate, 150g in parts by weight
SSZ-13 molecular sieve (ammonium type, SiO2/Al2O3Molar ratio is 25:1), 2550g titanium dioxide, 76.5g polyferric silicate sulfate, 135g glass
Fiber, 45g HPMC, 30g PEO, 18g wood pulp, 6g stearic acid and 66g lactic acid.
The preparation method of above-mentioned copper and iron composite SCR honeycomb type denitrification catalyst, steps are as follows:
(1) 18.23g copper sulphate is dissolved into 450g deionized water, 150g SSZ-13 molecular sieve is added thereto, at 80 DEG C
3h is reacted, obtains Cu/SSZ-13 after filtering.
(2) 76.5g polyferric silicate sulfate is dissolved into 1275g deionized water, 2550g titanium dioxide, stirring is added thereto
After 1h, it is warming up to pug temperature and reaches 80 ~ 90 DEG C, continue to be stirred 0.5h.
(3) Cu/SSZ-13 molecular sieve obtained by (1) is added into (2) pug, is stirred 0.5h at 80 ~ 90 DEG C.
(4) 135g glass fibre, 45g HPMC, 30g PEO, 18g wood pulp, 6g stearic acid, 66g lactic acid are added in (3)
With 255.9g deionized water.It after being kneaded 1h at 80 ~ 90 DEG C, is drained, test pug moisture content is 31%.
(5) pug obtained by step is sealed aging 36h.
(6) pug obtained by step (5) is obtained into the wet base of honeycomb type denitrification catalyst through vacuum extruding form, and uses liner
The fiberboard carton of sponge is packed.
(7) by wet base obtained by step (6) in climatic chamber drying, drying condition are as follows: 30 DEG C-humidity of temperature 70% is dry
6h, the dry 6h of 40 DEG C-humidity of temperature 60%, the dry 6h of temperature 50 C-humidity 50%, the dry 6h of temperature 60 C-humidity 40% are transferred to
110 DEG C of oven drying 5h.
(8) by step (7) products obtained therefrom in 550 DEG C of roasting 5h of Muffle furnace, heating rate is 2 DEG C/min, and it is multiple to obtain copper and iron
Close SCR honeycomb type denitrification catalyst.
Gained catalyst is greater than 80% in 250 ~ 450 DEG C of transformation efficiency of the oxides of nitrogen, turns in 280 ~ 440 DEG C of nitrogen oxides
Rate is greater than 90%.
Embodiment 6
A kind of copper and iron composite SCR honeycomb type denitrification catalyst, component include: 42.75g copper sulphate, 300g in parts by weight
Zeolite Beta molecular sieve (Hydrogen, SiO2/Al2O3Molar ratio is 40:1), 2400g titanium dioxide, 72.0g polyferric silicate sulfate,
159g glass fibre, 60g CMC, 15g wood pulp, 6g stearic acid and 60g lactic acid.
The preparation method of above-mentioned copper and iron composite SCR honeycomb type denitrification catalyst, steps are as follows:
(1) 42.75g copper sulphate is dissolved into 1500g deionized water, and 300g Zeolite Beta molecular sieve is added thereto,
4h is reacted at 80 DEG C, obtains Cu/beta after filtering.
(2) 72.0g polyferric silicate sulfate is dissolved into 864g deionized water, 2400g titanium dioxide is added thereto, stir 1h
Afterwards, it is warming up to pug temperature and reaches 80 ~ 90 DEG C, continue to be stirred 0.5h.
(3) Cu/beta molecular sieve obtained by (1) is added into (2) pug, is stirred 1h at 80 ~ 90 DEG C.
(4) 159g glass fibre, 60g CMC, 15g wood pulp, 6g stearic acid, 60g lactic acid and 622.7g are added in (3) to go
Ionized water.It after being kneaded 1h at 80 ~ 90 DEG C, is drained, test pug moisture content is 32.5%.
(5) pug obtained by step is sealed aging 20h.
(6) pug obtained by step (5) is obtained into the wet base of honeycomb type denitrification catalyst through vacuum extruding form, and uses liner
The fiberboard carton of sponge is packed.
(7) by wet base obtained by step (6) in climatic chamber drying, drying condition are as follows: 30 DEG C-humidity of temperature 70% is dry
6h, the dry 6h of 40 DEG C-humidity of temperature 60%, the dry 6h of temperature 50 C-humidity 50%, the dry 6h of temperature 60 C-humidity 40% are transferred to
100 DEG C of oven drying 6h.
(8) by step (7) products obtained therefrom in 600 DEG C of roasting 4h of Muffle furnace, heating rate is 2 DEG C/min, and it is multiple to obtain copper and iron
Close SCR honeycomb type denitrification catalyst.
Gained catalyst is greater than 80% in 250 ~ 450 DEG C of transformation efficiency of the oxides of nitrogen, turns in 270 ~ 450 DEG C of nitrogen oxides
Rate is greater than 90%.
Comparative example 1
A kind of copper and iron composite SCR honeycomb type denitrification catalyst, component include: 36.25g copper acetate, 450g in parts by weight
ZSM-5 molecular sieve (Hydrogen, SiO2/Al2O3Molar ratio is 30:1), 2160g titanium dioxide, 210g glass fibre, 36g CMC, 24g
PEO, 18g sesbania powder, 12g stearic acid and 90g lactic acid.
The preparation method of above-mentioned copper and iron composite SCR honeycomb type denitrification catalyst, steps are as follows:
(1) 36.25g copper acetate is dissolved into 2250g deionized water, 450g ZSM-5 molecular sieve is added thereto, at 90 DEG C
2h is reacted, obtains Cu/ZSM-5 after filtering.
(2) 1188g deionized water is added into 2160g titanium dioxide, after stirring 1h, is warming up to pug temperature and reaches 80 ~ 90
DEG C, continue to be stirred 1h.
(3) Cu/ZSM-5 molecular sieve obtained by (1) is added into (2) pug, is stirred 0.5h at 80 ~ 90 DEG C.
(4) 210g glass fibre, 36g CMC, 24g PEO, 18g sesbania powder, 12g stearic acid, 90g cream are added in (3)
Acid and 250.2g deionized water.It after being kneaded 1h at 80 ~ 90 DEG C, is drained, test pug moisture content is 32%.
(5) by pug obtained by step be sealed it is aging for 24 hours.
(6) pug obtained by step (5) is obtained into the wet base of honeycomb type denitrification catalyst through vacuum extruding form, and uses liner
The fiberboard carton of sponge is packed.
(7) by wet base obtained by step (6) in climatic chamber drying, drying condition are as follows: 30 DEG C-humidity of temperature 70% is dry
6h, the dry 6h of 40 DEG C-humidity of temperature 60%, the dry 6h of temperature 50 C-humidity 50%, the dry 6h of temperature 60 C-humidity 40% are transferred to
120 DEG C of oven drying 4h.
(8) by step (7) products obtained therefrom in 500 DEG C of roasting 6h of Muffle furnace, heating rate is 2 DEG C/min, and it is multiple to obtain copper and iron
Close SCR honeycomb type denitrification catalyst.
Gained catalyst is greater than 80% in 280 ~ 450 DEG C of transformation efficiency of the oxides of nitrogen, turns in 310 ~ 450 DEG C of nitrogen oxides
Rate is greater than 90%.
Comparative example 2
A kind of copper and iron composite SCR honeycomb type denitrification catalyst, component include: 2160g titanium dioxide, 64.8g poly- in parts by weight
Close ferrosilite, 210g glass fibre, 36g CMC, 24g PEO, 18g sesbania powder, 12g stearic acid and 90g lactic acid.
The preparation method of above-mentioned copper and iron composite SCR honeycomb type denitrification catalyst, steps are as follows:
(1) 64.8g polyferric silicate sulfate is dissolved into 1188g deionized water, 2160g titanium dioxide is added thereto, after stirring 1h,
It is warming up to pug temperature and reaches 80 ~ 90 DEG C, continue to be stirred 1h.
(2) 210g glass fibre, 36g CMC, 24g PEO, 18g sesbania powder, 12g stearic acid, 90g cream are added in (1)
Acid and 250.2g deionized water.It after being kneaded 1h at 80 ~ 90 DEG C, is drained, test pug moisture content is 32%.
(3) by pug obtained by step be sealed it is aging for 24 hours.
(4) pug obtained by step (3) is obtained into the wet base of honeycomb type denitrification catalyst through vacuum extruding form, and uses liner
The fiberboard carton of sponge is packed.
(5) by wet base obtained by step (4) in climatic chamber drying, drying condition are as follows: 30 DEG C-humidity of temperature 70% is dry
6h, the dry 6h of 40 DEG C-humidity of temperature 60%, the dry 6h of temperature 50 C-humidity 50%, the dry 6h of temperature 60 C-humidity 40% are transferred to
120 DEG C of oven drying 4h.
(6) by step (5) products obtained therefrom in 500 DEG C of roasting 6h of Muffle furnace, heating rate is 2 DEG C/min, and it is multiple to obtain copper and iron
Close SCR honeycomb type denitrification catalyst.
Gained catalyst is greater than 80% in 320 ~ 450 DEG C of transformation efficiency of the oxides of nitrogen, turns in 340 ~ 450 DEG C of nitrogen oxides
Rate is greater than 90%.
One of embodiment (embodiment 4) and comparative example 1,2 are carried out respectively respectively according to following active testing condition
The active testing of denitration efficiency: the nitric oxide of 500ppm, the ammonia of 500ppm, the sulfur dioxide of 500ppm, 10% water steam
Gas, 5% oxygen, reaction Balance Air are nitrogen, loaded catalyst 90mL, reaction velocity 8,000h-1, catalyst size
For 30mm × 30mm × 100mm.
Test result is depicted as the line chart shown in FIG. 1 with data markers, it can be seen that:
Under the conditions of logical sulphur water flowing, at 250 DEG C, embodiment 4(Cu-Fe composite sample), comparative example 1(Cu sample) and comparative example 2
The denitration efficiency of (Fe sample) is respectively 82.4%, 69.3% and 29.8%.Gained copper and iron composite catalyst of the invention is 250 ~ 450
Denitration efficiency within the scope of DEG C illustrates that copper-based molecular sieve and polyferric silicate sulfate have good synergic catalytic effect 80% or more,
Improve the denitration activity and sulfur resistive water resistant poisoning performance of catalyst.
The foregoing is merely presently preferred embodiments of the present invention, is not intended to limit the invention, it is all in spirit of the invention and
Within principle, any modification, equivalent replacement, improvement and so on be should all be included in the protection scope of the present invention.
Claims (10)
1. a kind of copper and iron composite SCR honeycomb type denitrification catalyst, it is characterised in that: active component is the modified molecular sieve of mantoquita,
Carrier is the modified titanium dioxide of polyferric silicate sulfate.
2. copper and iron composite SCR honeycomb type denitrification catalyst according to claim 1, which is characterized in that its component is by weight
Number includes: 5 ~ 15 parts of molecular sieves, 70 ~ 85 parts of titanium dioxides, 4 ~ 8 parts of glass fibres, 2 ~ 3 parts of binders, 0.5 ~ 1 part
Wood pulp or sesbania powder, 0.2 ~ 0.5 part of stearic acid and 2 ~ 3 parts of lactic acid.
3. copper and iron composite SCR honeycomb type denitrification catalyst according to claim 1, which is characterized in that the mantoquita is modified
Molecular sieve obtained by ion-exchange or infusion process modification, modified used mantoquita includes copper acetate, copper nitrate or copper sulphate
One of, wherein copper is 1 ~ 10wt.% in modified molecular screen.
4. copper and iron composite SCR honeycomb type denitrification catalyst according to claim 1, which is characterized in that be modified by mantoquita
Molecular sieve is aluminosilicate molecular sieves or silicoaluminophosphamolecular molecular sieve, and type is Hydrogen or ammonium type, and topology molecular sieve structure is
AFX, CHA, BEA or MFI.
5. copper and iron composite SCR honeycomb type denitrification catalyst according to claim 4, which is characterized in that the aluminosilicate
SiO in molecules of salt sieve2/Al2O3Molar ratio be 10 ~ 40:1；In the silicoaluminophosphamolecular molecular sieve mass fraction of silicon be 5 ~
12%。
6. copper and iron composite SCR honeycomb type denitrification catalyst according to claim 1, which is characterized in that the titanium dioxide is
Polyferric silicate sulfate impregnates to obtain, and wherein ferro element is 0.5 ~ 2 wt.% in modified titanium.
7. copper and iron composite SCR honeycomb type denitrification catalyst according to claim 2, which is characterized in that the binder is
The mixing of one or both of carboxymethyl cellulose, hydroxypropyl methyl cellulose or polyethylene glycol oxide.
8. a kind of preparation method of copper and iron composite SCR honeycomb type denitrification catalyst as claimed in claim 2, which is characterized in that packet
Include following steps:
(1) 5 ~ 15 parts of quasi- molecular sieves being modified are added in copper salt solution, 1 ~ 4h is kept the temperature at 60 ~ 100 DEG C, copper is obtained by filtration
The modified molecular sieve of salt, also referred to as copper-based molecular sieve, or molecular sieve is added in copper salt solution, impregnate 2 at 10 ~ 40 DEG C ~
12h obtains the modified molecular sieve of mantoquita, i.e., copper-based molecular sieve；
(2) 70 ~ 85 parts of titanium dioxides are added in polymeric silicicacid ferrous solution, 0.5 ~ 1h are sufficiently stirred to being uniformly mixed, stirring heats up
Into batch mixer, pug temperature reaches 80 ~ 90 DEG C, is stirred 0.5 ~ 1h at this temperature, obtains the modified titanium of polyferric silicate sulfate
White powder；
(3) copper-based molecular sieve obtained by step (1) is added into the pug of step (2), is stirred 0.5 ~ 1h at 80 ~ 90 DEG C；
(4) 4 ~ 8 parts of glass fibres of addition, 2 ~ 3 parts of binders, 0.5 ~ 1 part of wood pulp or sesbania powder into step (3), 0.2 ~ 0.5 part
Stearic acid, 2 ~ 3 parts of lactic acid and deionized water are kneaded 0.5 ~ 1h at 80 ~ 90 DEG C, are drained after mixing, control pug
Moisture content is 30 ~ 33%；
(5) pug obtained by step (4) is sealed aging 18 ~ 36h；
(6) by pug obtained by step (5) through vacuum extruding form, the wet base of honeycomb type denitrification catalyst is obtained, and with liner sponge
Fiberboard carton packed；
(7) by wet base obtained by step (6) in climatic chamber drying, drying process are as follows: temperature is increased to 70 ~ 80 by 30 ~ 40 DEG C
DEG C, humidity is reduced to 30% ~ 40% by 70% ~ 80%, then is transferred to 100 ~ 120 DEG C of 4 ~ 6h of oven drying and obtains dry body；
(8) by dry body obtained by step (7) in 500 ~ 600 DEG C of 4 ~ 6h of roasting of Muffle furnace, heating rate is 2 DEG C/min.
9. a kind of -8 any copper and iron composite SCR honeycomb type denitrification catalysts are in power plant, boiler or work according to claim 1
Application in factory's combustion tail gas denitrification process.
10. a kind of obtained production of preparation method of copper and iron composite SCR honeycomb type denitrification catalyst according to claim 9
Application of the product in power plant, boiler or factory's combustion tail gas denitrification process.
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