CN109499607A - A kind of copper and iron composite honeycomb coating type denitrating catalyst and its preparation method and application - Google Patents
A kind of copper and iron composite honeycomb coating type denitrating catalyst and its preparation method and application Download PDFInfo
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- CN109499607A CN109499607A CN201811344553.3A CN201811344553A CN109499607A CN 109499607 A CN109499607 A CN 109499607A CN 201811344553 A CN201811344553 A CN 201811344553A CN 109499607 A CN109499607 A CN 109499607A
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- copper
- molecular sieve
- iron composite
- catalyst
- denitrating catalyst
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- 239000003054 catalyst Substances 0.000 title claims abstract description 86
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 title claims abstract description 82
- 239000010949 copper Substances 0.000 title claims abstract description 61
- 238000000576 coating method Methods 0.000 title claims abstract description 60
- 239000011248 coating agent Substances 0.000 title claims abstract description 59
- 229910052802 copper Inorganic materials 0.000 title claims abstract description 52
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 49
- 229910052742 iron Inorganic materials 0.000 title claims abstract description 40
- 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 54
- 239000002808 molecular sieve Substances 0.000 claims abstract description 48
- 229910052878 cordierite Inorganic materials 0.000 claims abstract description 44
- 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 claims abstract description 44
- 238000000034 method Methods 0.000 claims abstract description 29
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 claims abstract description 20
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims abstract description 20
- 239000011230 binding agent Substances 0.000 claims abstract description 19
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 18
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000000919 ceramic Substances 0.000 claims abstract description 13
- 230000008569 process Effects 0.000 claims abstract description 13
- 238000006555 catalytic reaction Methods 0.000 claims abstract description 10
- 238000001802 infusion Methods 0.000 claims abstract description 5
- 238000005342 ion exchange Methods 0.000 claims abstract description 3
- 241000365446 Cordierites Species 0.000 claims description 46
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 41
- 239000008367 deionised water Substances 0.000 claims description 30
- 229910021641 deionized water Inorganic materials 0.000 claims description 30
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 26
- 229910017604 nitric acid Inorganic materials 0.000 claims description 26
- 239000002002 slurry Substances 0.000 claims description 22
- 239000000243 solution Substances 0.000 claims description 19
- 238000003756 stirring Methods 0.000 claims description 19
- 229920002565 Polyethylene Glycol 400 Polymers 0.000 claims description 14
- 238000006243 chemical reaction Methods 0.000 claims description 11
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 9
- 238000000498 ball milling Methods 0.000 claims description 9
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 8
- 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
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 claims description 8
- 229910052593 corundum Inorganic materials 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
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical group O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 6
- 229920001030 Polyethylene Glycol 4000 Polymers 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
- OPQARKPSCNTWTJ-UHFFFAOYSA-L copper(ii) acetate Chemical compound [Cu+2].CC([O-])=O.CC([O-])=O OPQARKPSCNTWTJ-UHFFFAOYSA-L 0.000 claims description 6
- 239000007789 gas Substances 0.000 claims description 6
- 239000002253 acid Substances 0.000 claims description 5
- 230000004048 modification Effects 0.000 claims description 5
- 238000012986 modification Methods 0.000 claims description 5
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 claims description 5
- 229960004029 silicic acid Drugs 0.000 claims description 5
- 235000012239 silicon dioxide Nutrition 0.000 claims description 5
- 239000004094 surface-active agent Substances 0.000 claims description 5
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 claims description 4
- 229910000323 aluminium silicate Inorganic materials 0.000 claims description 4
- 150000001879 copper Chemical class 0.000 claims description 4
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 claims description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 3
- 238000002485 combustion reaction Methods 0.000 claims description 3
- 235000006408 oxalic acid Nutrition 0.000 claims description 3
- 150000003839 salts Chemical class 0.000 claims description 3
- 229910052710 silicon Inorganic materials 0.000 claims description 3
- 239000010703 silicon Substances 0.000 claims description 3
- 238000001914 filtration Methods 0.000 claims description 2
- 238000007654 immersion Methods 0.000 claims description 2
- 229940068918 polyethylene glycol 400 Drugs 0.000 claims description 2
- 229940057838 polyethylene glycol 4000 Drugs 0.000 claims description 2
- 230000003252 repetitive effect Effects 0.000 claims description 2
- 239000012266 salt solution Substances 0.000 claims description 2
- 239000013598 vector Substances 0.000 claims description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims 1
- 238000006116 polymerization reaction Methods 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 13
- 230000002153 concerted effect Effects 0.000 abstract description 3
- 238000011031 large-scale manufacturing process Methods 0.000 abstract 1
- 241000264877 Hippospongia communis Species 0.000 description 29
- 238000000643 oven drying Methods 0.000 description 16
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 13
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 13
- 238000010438 heat treatment Methods 0.000 description 12
- 229910001593 boehmite Inorganic materials 0.000 description 11
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 description 11
- 239000004411 aluminium Substances 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 9
- 238000001935 peptisation Methods 0.000 description 8
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 7
- 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
- 229910052717 sulfur Inorganic materials 0.000 description 7
- 239000011593 sulfur Substances 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
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- 239000000853 adhesive Substances 0.000 description 6
- 230000001070 adhesive effect Effects 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 6
- 150000002431 hydrogen Chemical class 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- RAHZWNYVWXNFOC-UHFFFAOYSA-N sulfur dioxide Inorganic materials O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 description 5
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 5
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- 238000009413 insulation Methods 0.000 description 4
- 231100000572 poisoning Toxicity 0.000 description 4
- 230000000607 poisoning effect Effects 0.000 description 4
- 239000004575 stone Substances 0.000 description 4
- 229910021536 Zeolite Inorganic materials 0.000 description 3
- 229910021529 ammonia Inorganic materials 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 231100000614 poison Toxicity 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
- 239000010457 zeolite Substances 0.000 description 3
- 239000005864 Sulphur Substances 0.000 description 2
- BYFGZMCJNACEKR-UHFFFAOYSA-N aluminium(i) oxide Chemical compound [Al]O[Al] BYFGZMCJNACEKR-UHFFFAOYSA-N 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 229910001648 diaspore Inorganic materials 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical compound O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 230000007096 poisonous effect Effects 0.000 description 2
- 230000002195 synergetic effect Effects 0.000 description 2
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 229910008332 Si-Ti Inorganic materials 0.000 description 1
- 229910006749 Si—Ti Inorganic materials 0.000 description 1
- 238000003916 acid precipitation Methods 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 239000000809 air pollutant Substances 0.000 description 1
- 231100001243 air pollutant Toxicity 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000005253 cladding Methods 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000000701 coagulant Substances 0.000 description 1
- 230000007547 defect Effects 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
- 239000003599 detergent Substances 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000012851 eutrophication Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 229910052635 ferrosilite Inorganic materials 0.000 description 1
- 244000144992 flock Species 0.000 description 1
- 239000003546 flue gas Substances 0.000 description 1
- 239000000295 fuel oil Substances 0.000 description 1
- 239000003292 glue Substances 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
- 239000003595 mist Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 229910000069 nitrogen hydride Inorganic materials 0.000 description 1
- RJIWZDNTCBHXAL-UHFFFAOYSA-N nitroxoline Chemical compound C1=CN=C2C(O)=CC=C([N+]([O-])=O)C2=C1 RJIWZDNTCBHXAL-UHFFFAOYSA-N 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 230000020477 pH reduction Effects 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 239000002245 particle Substances 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
- 229920000642 polymer Polymers 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- -1 silicate sulfates Chemical class 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- GOLXNESZZPUPJE-UHFFFAOYSA-N spiromesifen Chemical compound CC1=CC(C)=CC(C)=C1C(C(O1)=O)=C(OC(=O)CC(C)(C)C)C11CCCC1 GOLXNESZZPUPJE-UHFFFAOYSA-N 0.000 description 1
- 239000000758 substrate 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
- 239000004408 titanium dioxide Substances 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
- 238000010792 warming Methods 0.000 description 1
- 239000003643 water by type Substances 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
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/50—Catalysts, in general, characterised by their form or physical properties characterised by their shape or configuration
- B01J35/56—Foraminous structures having flow-through passages or channels, e.g. grids or three-dimensional monoliths
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/0009—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)
- Crystallography & Structural Chemistry (AREA)
- Environmental & Geological Engineering (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 honeycomb coating type denitrating catalyst and its preparation method and application.The present invention is using ion-exchange or copper-based molecular sieve prepared by infusion process as active component, and addition polyferric silicate sulfate is co-catalysis component, using honeycomb cordierite ceramic block as carrier, using Aluminum sol as binder.Gained catalyst of the invention is prepared with vacuum coat method, and easy to operate, coating procedure is not easy plug-hole, is easy to large-scale production；Coating load amount is big, and the firmness of active component coating is high；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 220 ~ 510 DEG C has a good application prospect 90% or more in moving source and stationary source denitration direction.
Description
Technical field
The present invention relates to new material technology field more particularly to a kind of copper and iron composite honeycomb coating type denitrating catalyst and its
Preparation method and application.
Background technique
Nitrogen oxides (NOx) it is a kind of important atmosphere pollution.NOxDischarge to human production life and natural environment
Bring great harm.NOxAcid 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, China's car ownership sustainable growth, motor vehicle exhaust emission
Pollution on the environment is on the rise, and has become one of primary source of big and medium-sized cities air pollutants.Wherein, diesel vehicle
Have become China motor vehicle NOxWith the main partaker of PM2.5 discharge.NOxDischarge amount increase sharply, seriously polluted life
State environment becomes one of an important factor for restricting social development.Therefore, how NO is effectively eliminatedxHave become environmental protection neck at present
An important topic to attract people's attention in domain.
In numerous NOxIn 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 applicable not only to the stationary sources flue gas such as coal-burning power plant, Industrial Boiler
Nitre can equally be well applied to the moving sources fuel oil tail gas denitration such as gasoline car and diesel vehicle.The technology has denitration efficiency height, selection
The advantages that property is good, reliable for operation, easy to maintain.Catalyst is NH3The most crucial part of SCR system, performance, which directly affects, is
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 is generally 300
~400 DEG C, denitration efficiency is 90% or more.Although catalytic component based on vanadium application technology mature, there is also obvious for its application
Defect is mainly manifested in following three aspects: first, V2O5Belong to high toxic material, be easy to happen during the reaction distillation or
It falls off, not only reduces the denitration activity of catalyst, and threatened human health and destroyed ecological environment, the U.S. and Japan
Forbid purifying using vanadium-based catalyst systems for exhaust gas from diesel vehicle NOx.Second, navajoite reserves are relatively fewer, vanadium oxidation
The price of object presoma is higher.Third, catalyst carrier TiO2Take place sintering at 400 DEG C, catalyst at 450 DEG C or more
Service life will be greatly reduced.Due to TiO2Crystal form is gradated by Detitanium-ore-type as rutile-type, and crystal particle diameter increases at multiple
Greatly, micropore quantity falls sharply, so that the effective ratio area of catalyst is reduced, catalyst activity is reduced.Therefore, the wide activity temperature of exploitation
Spend window, the novel environment friendly denitrating catalyst of high hydrothermal stability is a 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
N2Selectivity, has a good application prospect.Currently, copper-based molecular sieve is as denitrating catalyst active component in movement
Source denitration field realizes commercialization and promotes.This moving source denitrating catalyst is that the molecular sieve of Metal Supported is coated on to violet blueness
Stone surface is prepared.Cordierite has many advantages, such as that thermal expansion coefficient is low, light-weight, economical strong, after being widely used as motor vehicle
The catalyst carrier of processing unit.Molecular sieve slurry can be coated uniformly on cordierite surface, molecules of active components by cladding process
The dosage of sieve is relatively fewer, and effective rate of utilization is high.Molecular sieve integral extruding type honeycomb catalyst is by molecular sieve and carrier one
Mixing extrusion is played, so that high-cost molecular sieve effective rate of utilization is low.In addition, the hole of molecular sieve integral extruding type honeycomb catalyst
Density is relatively small, and specific surface area is small, so that denitration activity is relatively low.
It is domestic at present it has been reported that some SCR honeycomb coating type denitrating catalysts, and it is most of all show it is excellent
NOx detergent power.CN104353485A discloses a kind of preparation method of honeycomb substrate catalyst of molecular sieve denitration, the catalysis
Using Cu/ZSM-5 as active component, infusion process coating has 90% or more denitration efficiency at 170~500 DEG C for agent.The active component
Hydrothermal stability and anti-SO2Poisoning performance is poor, and infusion process single application rate is low, and application is limited.
CN104117381A discloses a kind of diesel vehicle oxidative catalyst containing Al-Si-Ti composite oxides, the catalyst with
Precious metals pt and Pd are active component, although the activity of catalyst is higher, noble metal catalyst higher cost and be easy because
Sulfur poisoning and inactivate, reduce the service life of catalyst.
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 that slow sulfation occur, so that the activity of catalyst reduces.
Polyferric silicate sulfate (PSF) is a kind of polymer with branch or reticular structure.Usually as a kind of coagulant, it is used for
Organic matter in flocks water there is no application 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 honeycomb coating type denitrating catalyst that denitration efficiency is high and water resistant anti-sulfur poisonous performance is strong, the catalyst is with cordierite
Ceramic honey comb is carrier, and carrier surface coats active coating, and the active component of the active coating is the modified molecular sieve of mantoquita,
Co-catalysis group is divided into polyferric silicate sulfate；Its component include: in parts by weight the modified molecular sieve of 7.5~15 parts of mantoquitas, 0.5~
2.5 parts of polyferric silicate sulfates, 7.5~15 parts of boehmites, 5~10 parts of nitric acid, 70~80 parts of cordierites, 1.5~3.5 parts of surfaces
Activating agent.
One aspect of the present invention utilizes the special stereochemical structure of PSF, can be improved the high-temperature hydrothermal stability of copper-based molecular sieve；
On the other hand it is acted on using the concerted catalysis between transition metal iron and copper, has widened the active temperature windows of catalyst, and
Improve the sulfur poisoning resistance of catalyst.Therefore, it in conjunction with the synergistic effect between copper-based molecular sieve and polyferric silicate sulfate, improves
High-temperature hydrothermal stability, denitration activity and the anti-sulfur poisonous performance of molecular sieve, exploitation performance are stable, cheap, environmental-friendly
Denitrating catalyst all there is critically important realistic meaning for moving source and stationary source denitration.
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 hole density of the cordierite is 200~800 mesh.
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 surfactant is one of polyethylene glycol-4000 and polyethylene glycol-400 or any ratio
Two kinds of example.Invention additionally discloses the preparation methods of this copper and iron composite honeycomb coating type denitrating catalyst, include the following steps:
(1) prepared by active component: 7.5~15 parts of quasi- molecular sieves being modified being added in copper salt solution, are protected at 60~100 DEG C
Temperature 1~4h of reaction, filtering, 100~120 DEG C of dry 3~6h, 500~600 DEG C of 3~5h of roasting；Or molecular sieve is added to mantoquita
In solution, 2~12h is impregnated at 15~40 DEG C, 100~120 DEG C of dry 3~6h, 500~600 DEG C of 3~5h of roasting obtain copper
The modified molecular sieve of salt, i.e., copper-based molecular sieve；
(2) Vehicle element: cordierite is put into 2~8h of immersion in 3~10wt.% acid solution, is eluted with deionized water into
Property, 100~120 DEG C of dry 3~6h；
(3) prepared by binder: 7.5~15 parts of boehmites and 1.5~3.5 parts of surfactants are added to polyferric silicate sulfate
In solution, the concentration of the polymeric silicicacid ferrous solution is calculated as 0.2~2.5wt.% with Fe, after stirring 0.5~2h at 10~80 DEG C, then
5~10 parts of nitric acid are added, 0.5~2h of stirring is prepared into Aluminum sol at 10~80 DEG C；
(4) prepared by active component slurry: after active component ball milling obtained by step (1), Aluminum sol slurry obtained by step (3) is added
In, 1~2h is stirred at 10~80 DEG C；
(5) active component coats: cordierite block obtained by step (2) is put into ceramic cavity, it will be obtained by step (4) with vacuumizing method
Aluminum sol slurry sucks in cordierite duct, blows duct raffinate after taking-up, 100~120 DEG C of dry 3~6h, and 500~600 DEG C
Roast 3~5h；Repetitive coatings 1~3 time as needed.
The coating rate of the copper and iron composite honeycomb coating type denitrating catalyst is calculated as follows:
Wherein ω is catalyst coating rate, m0For empty vectors quality, m1For the sample gross mass for being coated with catalyst after roasting.
Further, acid solution described in step (2) is one of sulfuric acid, acetic acid, oxalic acid and nitric acid.
This copper and iron composite honeycomb coating type denitrating catalyst is also claimed in moving source denitration or stationary source in the present invention
Application in denitration, the moving source denitration include the motor-driven diesel exhaust denitrification process of motor vehicle, ship；The stationary source is de-
Nitre includes power plant, boiler and factory's combustion tail gas denitrification process.
The beneficial effects of the present invention are: the present invention is using copper-based molecular sieve as active component, using polyferric silicate sulfate as co-catalysis
Component.Concerted catalysis effect occurs for Fe and Cu, not only increases the denitration activity of catalyst, and improve the water resistant of catalyst
Sulfur resistance.The preparation method of catalyst of the present invention is vacuum coat method, and easy to operate, coating procedure is not easy plug-hole, is easy to advise
Modelling production；Module single application rate high (> 13%) and firmness height (single application expulsion rate < 2.0%).Gained of the invention
Denitration efficiency of the honeycomb catalyst within the scope of 220~510 DEG C is equal in moving source and stationary source denitration direction 90% or more
There is good application prospect.
Detailed description of the invention
Fig. 1 is the test result line chart of the denitration efficiency of embodiment 6 and 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 honeycomb coating type denitrating catalyst, component include: 28.8g SSZ-39 molecular sieve in parts by weight
(Hydrogen, SiO2/Al2O3Molar ratio is 17:1), 3.77g copper acetate, 1.65g polyferric silicate sulfate, 29.25g boehmite,
16.09g nitric acid, cordierite, the 4.64g PEG-400 that hole density is 600 mesh, deionized water 245.12g.
The preparation method of above-mentioned copper and iron composite honeycomb coating type denitrating catalyst, steps are as follows:
(1) prepared by active component: 3.77g copper acetate being dissolved into 100.0 deionized waters, 28.8g SSZ-39 is added thereto
Dipping 8h is sufficiently stirred at 30 DEG C, 100 DEG C of oven drying 6h, 500 DEG C of roasting 5h of Muffle furnace are put into after dehydration, rises for molecular sieve
Warm 2 DEG C/min of rate.
(2) Vehicle element: cordierite block being put into 5% sulfuric acid solution and impregnates 8h, is eluted with deionized water to neutrality,
100 DEG C of oven drying 6h.
(3) prepared by binder: by 1.65g polyferric silicate sulfate (Fe content in terms of 20%, similarly hereinafter) be dissolved into 145.12g go from
In sub- water, 29.25g boehmite and 4.64g PEG-400 is added, stirs 0.5h at 60 DEG C, adds 16.09g nitric acid, 60
1h peptization is stirred at DEG C, prepares aluminium sol adhesive.
(4) prepared by active component slurry: after Cu/SSZ-39 ball milling obtained by (1), being added in binder obtained by (3), 60 DEG C
Lower stirring 2h.
(5) active component coats: ceramic cavity will be put by cordierite block obtained by (2), with vacuumizing method by (4) gained slurry
It sucks in cordierite duct, duct raffinate, 100 DEG C of oven drying 6h, 500 DEG C of roasting 5h of Muffle furnace is blown after taking-up.
Its active testing condition is (similarly hereinafter), the nitric oxide of 500ppm, the ammonia of 500ppm, the titanium dioxide of 450ppm
Sulphur, 10% vapor, 5% oxygen, reaction Balance Air be nitrogen, loaded catalyst 90mL, reaction velocity 6,
000h-1, catalyst size is 30mm × 30mm × 100mm.
Embodiment 2
A kind of copper and iron composite honeycomb coating type denitrating catalyst, component include: 33.0g SSZ-13 molecular sieve in parts by weight
(Hydrogen, SiO2/Al2O molar ratio is 27:1), 3.53g copper nitrate, 3.00g polyferric silicate sulfate, 36.0g boehmite, 21.6g
Nitric acid, cordierite, 6.21g PEG-4000, the deionized water 164.4g that hole density is 300 mesh.
The preparation method of above-mentioned copper and iron composite honeycomb coating type denitrating catalyst, steps are as follows:
(1) prepared by active component: 3.53g copper nitrate being dissolved into 26.4g deionized water, 33.0g SSZ-13 is added thereto
Molecular sieve impregnates 4h, 110 DEG C of oven drying 5h, 550 DEG C of roasting 4h of Muffle furnace, heating rate 2 after being sufficiently stirred at 40 DEG C
℃/min。
(2) Vehicle element: cordierite block being put into 6% acetum and impregnates 8h, is eluted with deionized water to neutrality,
110 DEG C of dry 5h.
(3) prepared by binder: 3.00g polyferric silicate sulfate being dissolved into 138.0g deionized water, 36.0g is added and intends thin water
Aluminium stone and 6.21g PEG-4000 stir 1h at 40 DEG C, add 21.6g nitric acid, stir 2h peptization at 40 DEG C, prepare Aluminum sol
Binder.
(4) prepared by active component slurry: after Cu/SSZ-13 ball milling obtained by (1), being added in binder obtained by (3), 40 DEG C
Lower stirring 1.5h.
(5) active component coats: ceramic cavity will be put by cordierite block obtained by (2), with vacuumizing method by (4) gained slurry
It sucks in cordierite duct, duct raffinate, 110 DEG C of oven drying 5h, 550 DEG C of roasting 4h of Muffle furnace is blown after taking-up.
(6) it secondary coating: repeats step (5)
Embodiment 3
A kind of copper and iron composite honeycomb coating type denitrating catalyst, component include: 60.0g SAPO-34 molecular sieve in parts by weight
(Hydrogen, P2O5Content is 45.7%, Al2O3Content is 44.00%, SiO2Content be 10.3%), 5.48g copper nitrate, 6.00g it is poly-
Close ferrosilite, 52.0g boehmite, 33.8g nitric acid, hole density be the cordierites of 200 mesh, 12.32g PEG-4000, go from
Sub- water 216.0g.
The preparation method of above-mentioned copper and iron composite honeycomb coating type denitrating catalyst, steps are as follows:
(1) prepared by active component: 5.48g copper nitrate being dissolved into 48.0g deionized water, 60.0g SAPO- is added thereto
34 molecular sieves impregnate 12h, 120 DEG C of oven drying 4h, 600 DEG C of roasting 3h of Muffle furnace, heating rate after being sufficiently stirred at 20 DEG C
2℃/min。
(2) Vehicle element: cordierite block being put into 8% oxalic acid solution and impregnates 6h, is eluted with deionized water to neutrality,
120 DEG C of dry 4h.
(3) prepared by binder: 6.00g polyferric silicate sulfate being dissolved into 168.0g deionized water, 52.0g is added and intends thin water
Aluminium stone and 12.32g PEG-4000 stir 1h at 20 DEG C, add 33.8g nitric acid, stir 2h peptization at 20 DEG C, it is molten to prepare aluminium
Glue caking agent.
(4) prepared by active component slurry: after Cu/SAPO-34 ball milling obtained by (1), being added in binder obtained by (3), 20
2h is stirred at DEG C.
(5) active component coats: ceramic cavity will be put by cordierite block obtained by (2), with vacuumizing method by (4) gained slurry
It sucks in cordierite duct, duct raffinate, 120 DEG C of oven drying 4h, 600 DEG C of roasting 3h of Muffle furnace, heating speed is blown after taking-up
2 DEG C/min of rate.
(6) it secondary coating: repeats step (5)
(7) it coats: repeating step (6) three times
Embodiment 4
A kind of copper and iron composite honeycomb coating type denitrating catalyst, component include: 70.0g ZSM-5 molecular sieve in parts by weight
(Hydrogen, SiO2/Al2O3Molar ratio is 30:1), 5.64g copper acetate, 10.00g polyferric silicate sulfate, 62.5g boehmite,
37.5g nitric acid, cordierite, 14.58g PEG-400, the deionized water 615.0g that hole density is 300 mesh.
The preparation method of above-mentioned copper and iron composite honeycomb coating type denitrating catalyst, steps are as follows:
(1) prepared by active component: 5.64g copper acetate being dissolved into 350.0g deionized water, 70.0g ZSM-5 is added thereto
Molecular sieve, the insulation reaction 2h at 90 DEG C, 120 DEG C of oven drying 4h, Muffle furnace 600 DEG C of roastings 3h, 2 DEG C/min of heating rate.
(2) Vehicle element: cordierite block is put into 10% nitric acid solution and impregnates 4h, is eluted with deionized water into
Property, 120 DEG C of dry 4h.
(3) prepared by binder: 10.00g polyferric silicate sulfate being dissolved into 265.0g deionized water, addition 62.5g intends thin
Diaspore and 14.58g PEG-400 stir 1.5h at 35 DEG C, add 37.5g nitric acid, 1.5h peptization, preparation are stirred at 75 DEG C
Aluminium sol adhesive.
(4) prepared by active component slurry: after Cu/ZSM-5 ball milling obtained by (1), being added in binder obtained by (3), 75 DEG C
Lower stirring 2h.
(5) active component coats: ceramic cavity will be put by cordierite block obtained by (2), with vacuumizing method by (4) gained slurry
It sucks in cordierite duct, duct raffinate, 120 DEG C of oven drying 4h, 600 DEG C of roasting 3h of Muffle furnace, heating speed is blown after taking-up
2 DEG C/min of rate.
(6) it secondary coating: repeats step (5)
(7) it coats: repeating step (6) three times
Embodiment 5
A kind of copper and iron composite honeycomb coating type denitrating catalyst, component include: 39.0g SSZ-13 molecular sieve in parts by weight
(ammonium type, SiO2/Al2O3Molar ratio is 25:1), 4.74g copper sulphate, 4.80g polyferric silicate sulfate, 45.0g boehmite,
24.75g nitric acid, cordierite, 10.08g PEG-400, the deionized water 405.0g that hole density is 500 mesh.
The preparation method of above-mentioned copper and iron composite honeycomb coating type denitrating catalyst, steps are as follows:
(1) prepared by active component: 4.74g copper sulphate being dissolved into 195.0g deionized water, 39.0g SSZ- is added thereto
13 molecular sieves, the insulation reaction 3h at 80 DEG C, 110 DEG C of oven drying 5h, 550 DEG C of roasting 4h of Muffle furnace, 2 DEG C of heating rate/
min。
(2) Vehicle element: cordierite block being put into 8% sulfuric acid solution and impregnates 5h, is eluted with deionized water to neutrality,
110 DEG C of dry 5h.
(3) prepared by binder: 4.80g polymeric silicicacid ferrous solution being dissolved into 210.0g deionized water, it is quasi- that 45.0g is added
Boehmite and 10.08g PEG-400 stir 2h at 15 DEG C, add 37.5g nitric acid, stir 2h peptization at 15 DEG C, prepare aluminium
Sol adhesive.
(4) prepared by active component slurry: after Cu/SSZ-13 ball milling obtained by (1), being added in binder obtained by (3), 15 DEG C
Lower stirring 2h.
(5) active component coats: ceramic cavity will be put by cordierite block obtained by (2), with vacuumizing method by (4) gained slurry
It sucks in cordierite duct, duct raffinate, 110 DEG C of oven drying 5h, 550 DEG C of roasting 4h of Muffle furnace, heating speed is blown after taking-up
2 DEG C/min of rate.
(6) it secondary coating: repeats step (5)
Embodiment 6
A kind of copper and iron composite honeycomb coating type denitrating catalyst, component include: 48.0g Zeolite Beta in parts by weight
Molecular sieve (Hydrogen, SiO2/Al2O3Molar ratio is 40:1), 6.84g copper sulphate, 10.20g polyferric silicate sulfate, 48.0g intend thin water aluminium
Stone, 31.2g nitric acid, cordierite, 8.64g PEG-400, the deionized water 480.0g that hole density is 400 mesh.
The preparation method of above-mentioned copper and iron composite honeycomb coating type denitrating catalyst, steps are as follows:
(1) prepared by active component: 6.84g copper sulphate being dissolved into 240.0g deionized water, 48.0g SSZ- is added thereto
13 molecular sieves, the insulation reaction 4h at 80 DEG C, 100 DEG C of oven drying 6h, 500 DEG C of roasting 5h of Muffle furnace, 2 DEG C of heating rate/
min。
(2) Vehicle element: cordierite block being put into 8% nitric acid solution and impregnates 6h, is eluted with deionized water to neutrality,
100 DEG C of dry 6h.
(3) prepared by binder: 10.20g polyferric silicate sulfate being dissolved into 240.0g deionized water, addition 48.0g intends thin
Diaspore and 8.64g PEG-400 stir 1.5h at 25 DEG C, add 31.0g nitric acid, 1.5h peptization, preparation are stirred at 25 DEG C
Aluminium sol adhesive.
(4) prepared by active component slurry: after Cu/Beta ball milling obtained by (1), being added in binder obtained by (3), at 25 DEG C
Stir 2h.
(5) active component coats: ceramic cavity will be put by cordierite block obtained by (2), with vacuumizing method by (4) gained slurry
It sucks in cordierite duct, duct raffinate, 100 DEG C of oven drying 6h, 500 DEG C of roasting 5h of Muffle furnace, heating speed is blown after taking-up
2 DEG C/min of rate.
(6) it secondary coating: repeats step (5)
(7) it coats: repeating step (6) three times
Comparative example 1
A kind of copper and iron composite honeycomb coating type denitrating catalyst, component include: 48.0g Zeolite Beta in parts by weight
Molecular sieve (Hydrogen, SiO2/Al2O3Molar ratio is 40:1), 6.84g copper sulphate, 48.0g boehmite, 31.2g nitric acid, Kong Mi
Degree is cordierite, 8.64g PEG-400, the deionized water 240.0g of 400 mesh.
The preparation method of above-mentioned copper and iron composite honeycomb coating type denitrating catalyst, steps are as follows:
(1) prepared by active component: 6.84g copper sulphate being dissolved into 240.0g deionized water, 48.0g SSZ- is added thereto
13 molecular sieves, the insulation reaction 4h at 80 DEG C, 100 DEG C of oven drying 6h, 500 DEG C of roasting 5h of Muffle furnace, 2 DEG C of heating rate/
min。
(2) Vehicle element: cordierite block being put into 8% nitric acid solution and impregnates 6h, is eluted with deionized water to neutrality,
100 DEG C of dry 6h.
(3) prepared by binder: 48.0g boehmite and 8.64g PEG-400 are added in 240.0g deionized water,
1.5h is stirred at 25 DEG C, 31.0g nitric acid is added, stirs 1.5h peptization at 25 DEG C, prepare aluminium sol adhesive.
(4) prepared by active component slurry: after Cu/Beta ball milling obtained by (1), being added in binder obtained by (3), at 25 DEG C
Stir 2h.
(5) active component coats: ceramic cavity will be put by cordierite block obtained by (2), with vacuumizing method by (4) gained slurry
It sucks in cordierite duct, duct raffinate, 100 DEG C of oven drying 6h, 500 DEG C of roasting 5h of Muffle furnace, heating speed is blown after taking-up
2 DEG C/min of rate.
(6) it secondary coating: repeats step (5)
(7) it coats: repeating step (6) three times
Comparative example 2
A kind of copper and iron composite honeycomb coating type denitrating catalyst, component include: in parts by weight
10.20g polyferric silicate sulfate, 48.0g boehmite, 31.2g nitric acid, cordierite, the 8.64g that hole density is 400 mesh
PEG-400, deionized water 240.0g.
The preparation method of above-mentioned copper and iron composite honeycomb coating type denitrating catalyst, steps are as follows:
(1) Vehicle element: cordierite block being put into 8% nitric acid solution and impregnates 6h, is eluted with deionized water to neutrality, 100
DEG C dry 6h.
(2) prepared by binder: 9.71g polymeric silicicacid ferrous solution being dissolved into 240.0g deionized water, it is quasi- that 48.0g is added
Boehmite and 8.64g PEG-400 stir 1.5h at 25 DEG C, add 31.0g nitric acid, 1.5h peptization, system are stirred at 25 DEG C
Standby aluminium sol adhesive.
(3) active component coats: ceramic cavity will be put by cordierite block obtained by (1), with vacuumizing method by (2) gained slurry
It sucks in cordierite duct, duct raffinate, 100 DEG C of oven drying 6h, 500 DEG C of roasting 5h of Muffle furnace, heating speed is blown after taking-up
2 DEG C/min of rate.
(4) it secondary coating: repeats step (3)
(5) it coats: repeating step (4) three times
Carry out the active testing of coating rate, expulsion rate and denitration efficiency respectively to each embodiment and comparative example 1,2.
Active testing condition is as follows: the nitric oxide of 500ppm, the ammonia of 500ppm, the sulfur dioxide of 500ppm, and 10%
Vapor, 5% oxygen, reaction Balance Air be nitrogen, loaded catalyst 90mL, reaction velocity 8,000h-1, catalysis
Agent is having a size of 30mm × 30mm × 100mm.
The expulsion rate of catalyst carries out ultrasonic vibration experimental check by numerical control supersonic cleaning machine, by the catalysis after coating
Agent is put into ultrasonic machine, ultrasonic vibration 10min.The coating shedding rate of catalyst is calculated according to following formula:
Wherein η is catalyst expulsion rate, m2For the quality of coated catalysts after ultrasonic vibration.
Test result is as follows table 1:
The coating of 1 honeycomb denitrating catalyst of table and reactivity parameter table
| Experiment numbers | Coating rate ω/% | Expulsion rate η/% | T80% | T90% |
| Embodiment 1 | 21.5 | 1.83 | 210-520 | 230-500 |
| Embodiment 2 | 26.5 | 2.39 | 210-520 | 230-500 |
| Embodiment 3 | 34.7 | 3.64 | 200-530 | 220-510 |
| Embodiment 4 | 41.5 | 4.48 | 200-540 | 220-520 |
| Embodiment 5 | 39.8 | 4.06 | 200-530 | 220-510 |
| Embodiment 6 | 46.6 | 5.13 | 190-540 | 210-510 |
| Comparative example 1 | 43.7 | 5.05 | 190-460 | 210-430 |
| Comparative example 2 | 22.5 | 3.58 | 330-530 | 360-500 |
The test result of one of embodiment (embodiment 6) and comparative example 1,2 is depicted as shown in FIG. 1 with data markers
Line chart, it can be seen that:, under the conditions of logical sulphur water flowing, present invention gained copper and iron composite catalyst (embodiment 6) it is de-
Denitration efficiency of the nitre efficiency within the scope of 210~510 DEG C is 90% or more, and copper-based molecular sieve catalyst (comparative example 1) is de-
Denitration efficiency of the nitre efficiency within the scope of 210~430 DEG C is 90% or more, the denitration of polymeric silicicacid iron catalyst (comparative example 2)
Denitration efficiency of the efficiency within the scope of 360~510 DEG C is 90% or more.It is good to illustrate that copper-based molecular sieve and polyferric silicate sulfate have
Synergic catalytic effect, 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 honeycomb coating type denitrating catalyst, it is characterised in that: using cordierite honeycomb ceramic as carrier, carrier
Surface coats active coating, and the active component of the active coating is the modified molecular sieve of mantoquita, and co-catalysis group is divided into polymerization silicon
Sour iron；Its component includes: the modified molecular sieve of 7.5~15 parts of mantoquitas, 0.5~2.5 part of polyferric silicate sulfate, 7.5 in parts by weight
~15 parts of boehmites, 5~10 parts of nitric acid, 70~80 parts of cordierites, 1.5~3.5 parts of surfactants.
2. copper and iron composite honeycomb coating type denitrating 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.
3. copper and iron composite honeycomb coating type denitrating catalyst according to claim 1, which is characterized in that the cordierite
Hole density is 200~800 mesh.
4. copper and iron composite honeycomb coating type denitrating 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 honeycomb coating type denitrating catalyst according to claim 1, which is characterized in that the surface-active
Agent is two kinds of one of polyethylene glycol-4000 and polyethylene glycol-400 or arbitrary proportion.
7. the preparation method of copper and iron composite honeycomb coating type denitrating catalyst described in claim 1, which is characterized in that including such as
Lower step:
(1) prepared by active component: 7.5~15 parts of quasi- molecular sieves being modified being added in copper salt solution, are protected at 60~100 DEG C
Temperature 1~4h of reaction, filtering, 100~120 DEG C of dry 3~6h, 500~600 DEG C of 3~5h of roasting；Or molecular sieve is added to mantoquita
In solution, 2~12h is impregnated at 15~40 DEG C, 100~120 DEG C of dry 3~6h, 500~600 DEG C of 3~5h of roasting obtain copper
The modified molecular sieve of salt, i.e., copper-based molecular sieve；
(2) Vehicle element: cordierite is put into 2~8h of immersion in 3~10wt.% acid solution, is eluted with deionized water into
Property, 100~120 DEG C of dry 3~6h；
(3) prepared by binder: 7.5~15 parts of boehmites and 1.5~3.5 parts of surfactants are added to polyferric silicate sulfate
In solution, the concentration of the polymeric silicicacid ferrous solution is calculated as 0.2~2.5wt.% with Fe, after stirring 0.5~2h at 10~80 DEG C, then
5~10 parts of nitric acid are added, 0.5~2h of stirring is prepared into Aluminum sol at 10~80 DEG C；
(4) prepared by active component slurry: after active component ball milling obtained by step (1), Aluminum sol slurry obtained by step (3) is added
In, 1~2h is stirred at 10~80 DEG C；
(5) active component coats: cordierite block obtained by step (2) is put into ceramic cavity, it will be obtained by step (4) with vacuumizing method
Aluminum sol slurry sucks in cordierite duct, blows duct raffinate after taking-up, 100~120 DEG C of dry 3~6h, and 500~600 DEG C
Roast 3~5h；Repetitive coatings 1~3 time as needed；
Coating rate is calculated as follows:
Wherein ω is catalyst coating rate, m0For empty vectors quality, m1For the sample gross mass for being coated with catalyst after roasting.
8. the preparation method of copper and iron composite honeycomb coating type denitrating catalyst according to claim 7, which is characterized in that step
Suddenly acid solution described in (2) is one of sulfuric acid, acetic acid, oxalic acid and nitric acid.
9. any copper and iron composite honeycomb coating type denitrating catalyst of claim 1-8 is de- in moving source denitration or stationary source
Application in nitre, the moving source denitration include the motor-driven diesel exhaust denitrification process of motor vehicle, ship；The stationary source denitration
Including power plant, boiler and factory's combustion tail gas denitrification process.
10. the obtained product of preparation method of copper and iron composite honeycomb coating type denitrating catalyst described in claim 8 or 9 exists
Application in moving source denitration or stationary source denitration, the moving source denitration include that motor vehicle, the motor-driven diesel exhaust of ship are de-
Nitre process；The stationary source denitration includes power plant, boiler and factory's combustion tail gas denitrification process.
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