CN114433123A - Monolithic honeycomb catalyst for low-temperature SCR denitration and preparation method and application thereof - Google Patents
Monolithic honeycomb catalyst for low-temperature SCR denitration and preparation method and application thereof Download PDFInfo
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- CN114433123A CN114433123A CN202011221405.XA CN202011221405A CN114433123A CN 114433123 A CN114433123 A CN 114433123A CN 202011221405 A CN202011221405 A CN 202011221405A CN 114433123 A CN114433123 A CN 114433123A
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- catalyst
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- 239000003054 catalyst Substances 0.000 title claims abstract description 140
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 93
- 238000001035 drying Methods 0.000 claims abstract description 43
- 239000004408 titanium dioxide Substances 0.000 claims abstract description 43
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 42
- 239000002243 precursor Substances 0.000 claims abstract description 36
- 229910044991 metal oxide Inorganic materials 0.000 claims abstract description 23
- 150000004706 metal oxides Chemical class 0.000 claims abstract description 23
- 239000002071 nanotube Substances 0.000 claims abstract description 23
- 230000032683 aging Effects 0.000 claims abstract description 18
- 238000002156 mixing Methods 0.000 claims abstract description 18
- 238000001125 extrusion Methods 0.000 claims abstract description 12
- 238000007580 dry-mixing Methods 0.000 claims abstract description 11
- 238000004898 kneading Methods 0.000 claims abstract description 11
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 10
- 229910016978 MnOx Inorganic materials 0.000 claims abstract description 3
- 239000000843 powder Substances 0.000 claims description 47
- 238000000034 method Methods 0.000 claims description 34
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 28
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 27
- 239000000047 product Substances 0.000 claims description 21
- 239000007864 aqueous solution Substances 0.000 claims description 19
- 239000011230 binding agent Substances 0.000 claims description 19
- 238000006243 chemical reaction Methods 0.000 claims description 19
- 239000003546 flue gas Substances 0.000 claims description 17
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 16
- 239000000243 solution Substances 0.000 claims description 16
- 238000003756 stirring Methods 0.000 claims description 16
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims description 15
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 14
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 14
- 150000003839 salts Chemical class 0.000 claims description 14
- 239000003365 glass fiber Substances 0.000 claims description 13
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 13
- 239000002244 precipitate Substances 0.000 claims description 13
- 239000000725 suspension Substances 0.000 claims description 12
- 238000005406 washing Methods 0.000 claims description 12
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 claims description 11
- 238000000465 moulding Methods 0.000 claims description 11
- 239000012266 salt solution Substances 0.000 claims description 11
- 235000011187 glycerol Nutrition 0.000 claims description 10
- 239000011572 manganese Substances 0.000 claims description 10
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 10
- 239000002202 Polyethylene glycol Substances 0.000 claims description 9
- 238000000975 co-precipitation Methods 0.000 claims description 9
- 150000002696 manganese Chemical class 0.000 claims description 9
- 229920001223 polyethylene glycol Polymers 0.000 claims description 9
- 239000003513 alkali Substances 0.000 claims description 8
- 239000003795 chemical substances by application Substances 0.000 claims description 8
- 229920000609 methyl cellulose Polymers 0.000 claims description 8
- 239000001923 methylcellulose Substances 0.000 claims description 8
- 235000010981 methylcellulose Nutrition 0.000 claims description 8
- 235000011121 sodium hydroxide Nutrition 0.000 claims description 8
- 239000000126 substance Substances 0.000 claims description 8
- 239000012670 alkaline solution Substances 0.000 claims description 7
- 238000001556 precipitation Methods 0.000 claims description 7
- 235000017550 sodium carbonate Nutrition 0.000 claims description 7
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 7
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 claims description 6
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 6
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 6
- VXAUWWUXCIMFIM-UHFFFAOYSA-M aluminum;oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Al+3] VXAUWWUXCIMFIM-UHFFFAOYSA-M 0.000 claims description 6
- 239000001099 ammonium carbonate Substances 0.000 claims description 6
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 6
- 239000004202 carbamide Substances 0.000 claims description 6
- 235000013877 carbamide Nutrition 0.000 claims description 6
- 229910052720 vanadium Inorganic materials 0.000 claims description 6
- 229910052782 aluminium Inorganic materials 0.000 claims description 5
- 239000003345 natural gas Substances 0.000 claims description 5
- 239000002994 raw material Substances 0.000 claims description 5
- 239000000853 adhesive Substances 0.000 claims description 4
- 230000001070 adhesive effect Effects 0.000 claims description 4
- 229910052804 chromium Inorganic materials 0.000 claims description 4
- 238000001914 filtration Methods 0.000 claims description 4
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 claims description 4
- 229910052750 molybdenum Inorganic materials 0.000 claims description 4
- 229910052759 nickel Inorganic materials 0.000 claims description 4
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 claims description 4
- 229910052718 tin Inorganic materials 0.000 claims description 4
- 229910052721 tungsten Inorganic materials 0.000 claims description 4
- 229910052725 zinc Inorganic materials 0.000 claims description 4
- 229910052726 zirconium Inorganic materials 0.000 claims description 4
- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 claims description 3
- 229910019142 PO4 Inorganic materials 0.000 claims description 3
- DPXJVFZANSGRMM-UHFFFAOYSA-N acetic acid;2,3,4,5,6-pentahydroxyhexanal;sodium Chemical compound [Na].CC(O)=O.OCC(O)C(O)C(O)C(O)C=O DPXJVFZANSGRMM-UHFFFAOYSA-N 0.000 claims description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 3
- 235000012538 ammonium bicarbonate Nutrition 0.000 claims description 3
- 235000012501 ammonium carbonate Nutrition 0.000 claims description 3
- 239000001768 carboxy methyl cellulose Substances 0.000 claims description 3
- 229920002678 cellulose Polymers 0.000 claims description 3
- 239000001913 cellulose Substances 0.000 claims description 3
- 150000002505 iron Chemical class 0.000 claims description 3
- 235000019353 potassium silicate Nutrition 0.000 claims description 3
- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 claims description 3
- 229920001027 sodium carboxymethylcellulose Polymers 0.000 claims description 3
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims description 3
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 2
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 2
- 239000004568 cement Substances 0.000 claims description 2
- 239000004927 clay Substances 0.000 claims description 2
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 2
- PVFSDGKDKFSOTB-UHFFFAOYSA-K iron(3+);triacetate Chemical compound [Fe+3].CC([O-])=O.CC([O-])=O.CC([O-])=O PVFSDGKDKFSOTB-UHFFFAOYSA-K 0.000 claims description 2
- 229940071125 manganese acetate Drugs 0.000 claims description 2
- 229940099596 manganese sulfate Drugs 0.000 claims description 2
- 239000011702 manganese sulphate Substances 0.000 claims description 2
- 235000007079 manganese sulphate Nutrition 0.000 claims description 2
- UOGMEBQRZBEZQT-UHFFFAOYSA-L manganese(2+);diacetate Chemical compound [Mn+2].CC([O-])=O.CC([O-])=O UOGMEBQRZBEZQT-UHFFFAOYSA-L 0.000 claims description 2
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 claims description 2
- 229910052751 metal Inorganic materials 0.000 claims description 2
- 239000002184 metal Substances 0.000 claims description 2
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical compound [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 claims description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 2
- 239000010452 phosphate Substances 0.000 claims description 2
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 2
- 244000275012 Sesbania cannabina Species 0.000 claims 1
- 239000008279 sol Substances 0.000 claims 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 abstract description 8
- 229910052717 sulfur Inorganic materials 0.000 abstract description 8
- 239000011593 sulfur Substances 0.000 abstract description 8
- 230000009467 reduction Effects 0.000 abstract description 4
- 239000000203 mixture Substances 0.000 description 24
- 238000000227 grinding Methods 0.000 description 11
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 10
- 238000005516 engineering process Methods 0.000 description 10
- 241000219782 Sesbania Species 0.000 description 9
- SZQUEWJRBJDHSM-UHFFFAOYSA-N iron(3+);trinitrate;nonahydrate Chemical compound O.O.O.O.O.O.O.O.O.[Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O SZQUEWJRBJDHSM-UHFFFAOYSA-N 0.000 description 9
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 8
- 239000011259 mixed solution Substances 0.000 description 8
- 229910017604 nitric acid Inorganic materials 0.000 description 8
- 238000007670 refining Methods 0.000 description 7
- 239000002245 particle Substances 0.000 description 6
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 5
- 229910052748 manganese Inorganic materials 0.000 description 5
- 238000002485 combustion reaction Methods 0.000 description 4
- 239000012065 filter cake Substances 0.000 description 4
- 229910052742 iron Inorganic materials 0.000 description 4
- 230000001376 precipitating effect Effects 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 238000006722 reduction reaction Methods 0.000 description 4
- 238000000967 suction filtration Methods 0.000 description 4
- 239000006228 supernatant Substances 0.000 description 4
- 238000009210 therapy by ultrasound Methods 0.000 description 4
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 3
- 238000010531 catalytic reduction reaction Methods 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- 238000005303 weighing Methods 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 2
- 239000004480 active ingredient Substances 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 229910000069 nitrogen hydride Inorganic materials 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 235000021317 phosphate Nutrition 0.000 description 2
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 2
- 239000002912 waste gas Substances 0.000 description 2
- 241000196324 Embryophyta Species 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- BIGPRXCJEDHCLP-UHFFFAOYSA-N ammonium bisulfate Chemical compound [NH4+].OS([O-])(=O)=O BIGPRXCJEDHCLP-UHFFFAOYSA-N 0.000 description 1
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 1
- 229910052921 ammonium sulfate Inorganic materials 0.000 description 1
- 235000011130 ammonium sulphate Nutrition 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000001311 chemical methods and process Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000006477 desulfuration reaction Methods 0.000 description 1
- 230000023556 desulfurization Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 238000010894 electron beam technology Methods 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum oxide Inorganic materials [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Inorganic materials O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- 238000005554 pickling Methods 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000002000 scavenging effect Effects 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000000779 smoke Substances 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 231100000167 toxic agent Toxicity 0.000 description 1
- 239000003440 toxic substance Substances 0.000 description 1
- 210000002268 wool Anatomy 0.000 description 1
Classifications
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- 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
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/889—Manganese, technetium or rhenium
- B01J23/8892—Manganese
-
- 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
- B01D53/8603—Removing sulfur compounds
- B01D53/8609—Sulfur oxides
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- 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
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
- B01J21/063—Titanium; Oxides or hydroxides thereof
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
- B01J21/066—Zirconium or hafnium; Oxides or hydroxides thereof
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- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
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- B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
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- B01J37/082—Decomposition and pyrolysis
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- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/10—Heat treatment in the presence of water, e.g. steam
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01D2257/00—Components to be removed
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- B01D2257/302—Sulfur oxides
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
Abstract
The invention relates to an integral honeycomb catalyst for low-temperature SCR denitration, and a preparation method and application thereof. The integral honeycomb low-temperature SCR denitration catalyst comprises a carrier and an active component; the carrier is a doped titanium dioxide nanotube doped with metal oxide; the active component is MnOxAnd FeOyWherein x is 1 to 2 and y is 1 to 1.5; the molar ratio of the element Mn to the element Fe in the active component is (10-0.1): 1; the catalyst is a monolithic honeycomb catalyst. The carrier, the active component precursor and the forming auxiliary agent are subjected to dry mixing, kneading, mixing, aging, extrusion, drying and roasting to obtain the integral honeycomb denitration catalyst. The integral honeycomb-shaped low-temperature SCR denitration catalyst prepared by the invention has excellent water resistance, sulfur resistance and stability, and has low strength and high pressure reduction, thereby having wide industrial application prospect.
Description
Technical Field
The invention relates to the field of catalysts, and in particular relates to an integral honeycomb catalyst for low-temperature SCR denitration, and a preparation method and application thereof.
Background
In recent years, with the increasing awareness of environmental protection and the increasing strictness of national environmental protection requirements, boiler NO is used in various regionsxThe emission limit of the boiler is more and more strict, and NO of the newly built boiler in the heavy point areas of Beijing, Zhengzhou, Shanghai and the likexThe index is 50mg/m3Even 30mg/m3. Reduction of NO produced during fuel combustion by altering combustion conditionsxLow NOxCombustion technology, at best only with a reduction in NOxThe emission is about 50 percent, so that tail flue gas denitration technology is needed to further reduce NOxAnd (4) discharging.
The denitration technique of flue gas after combustion refers to that NO in the flue gas is enabled to be generated through various physical and chemical processesxReduction or decomposition to N2Or NO removal by scavenging N-containing speciesx. Flue gas denitration techniques can be roughly classified into dry methods (catalytic methods) and wet methods (absorption methods) according to the state of a reaction system. The wet flue gas denitration means that water or aqueous solution of acid, alkali, salt and other substances is used for absorbing NO in the waste gasxThe process for purifying waste gas is also disclosed. However, the technology has some problems which are difficult to overcome, so that the application value is limited. The dry flue gas denitration technology mainly comprises a selective catalytic reduction method (SCR), a selective non-catalytic reduction method (SNCR), an electron beam method (EB), a pulse corona low-temperature plasma method (PCIPCP) and an SNRB (SO)x-NOx-ROx-BOx) Combined control process and combined denitration and desulfurization technology (SNO)x) Processes, solid absorption/regeneration methods, and the like. Compared with the wet denitration technology, the dry denitration technology has higher efficiency, smaller floor area, no or little harmful by-products and no need of a flue gas heating system, so that most power plant boilers adopt the dry denitration technology, wherein a selective catalytic reduction method (NH) of a vanadium-based catalyst is used3SCR) are the most widely used, but some problems still remain: first, the effective active temperature range of the vanadium-based catalyst is broad, for commercial V2O5-WO3/TiO2And V2O5-MoO3/TiO2In NH3The optimal reaction temperature range is 380-420 ℃ under the condition that the NO is 1:1 in stoichiometric ratio, and NH is generated when the temperature exceeds the upper limit of the range3Side reactions of oxidation take place to form N2O and NO, thereby reducing the conversion rate of NO, which requires that a denitration device must be installed at a suitable position in the flue; secondly, as an active groupPartial V2O5Is a highly toxic substance and is easy to cause secondary pollution to human bodies and the environment; third, V2O5Is easy to remove SO in the flue gas2By oxidation to SO3Thereby reacting with NH3The reaction generates ammonium sulfate and ammonium bisulfate, thereby causing the activity of the catalyst to be reduced and causing potential safety hazard due to the blockage of a reactor. In conclusion, the space and technical problems of the reconstruction of the existing industrial device cause great economic loss and complexity of engineering reconstruction, so that the rapid development of the low-temperature SCR denitration technology is necessary.
At present, the low-temperature SCR denitration catalyst mainly comprises carbon-based catalysts, molecular sieves and manganese-based catalysts. In literature reports, it can be seen that the denitration reaction temperature of various low-temperature SCR denitration catalysts is mostly between 80 and 250 ℃, and the denitration performance and N are2The selectivity is not poor, but the general problem is that the water resistance and sulfur resistance of the catalyst are poor, and when the water content in the flue gas reaches 10%, the performance of the catalyst is greatly reduced. In the face of industrially high water content (15% to 30%) flue gases, such as those fed with natural gas, the catalyst has been substantially deactivated. Therefore, the lower water resistance and sulfur resistance of the existing catalyst become the bottleneck of the catalyst life and the industrial application, and further research and improvement are needed.
Disclosure of Invention
In order to solve the problems in the prior art, the invention provides a monolithic honeycomb catalyst for low-temperature SCR denitration. In particular to a monolithic honeycomb catalyst for low-temperature SCR denitration and a preparation method and application thereof. The monolithic honeycomb catalyst for low-temperature SCR denitration and the preparation method thereof have the advantages of simple and easy production, excellent water resistance, sulfur resistance and stability, suitability for low-temperature denitration of high-water-content flue gas with natural gas as a raw material and wide industrial application prospect.
One of the purposes of the invention is to provide a monolithic honeycomb catalyst for low-temperature SCR denitration, which comprises the following components in percentage by total weight of the catalyst:
the weight content of the carrier is 39-97 percent; preferably 45-90%;
the weight content of the active component is 3-61%; preferably 10-55%;
the specific surface area of the carrier is 50-300 m2/g；
The active component is selected from MnOxAnd FeOyWherein x is 1 to 2 and y is 1 to 1.5;
preferably, the carrier is a doped titanium dioxide nanotube doped with a metal oxide; wherein, the metal can be one or more selected from Zr, Pr, La, Ce, Cu, Zn, Mo, Al, Sn, Ni, W, V and Cr.
The catalyst is a monolithic honeycomb catalyst.
Wherein the content of the first and second substances,
based on the total weight of the catalyst as percentage,
the carrier may be present in an amount selected from 40%, 45%, 50%, 55%, 60%, 65%, 70%, 75%, 80%, 85%, 90% by weight or any value therebetween;
the active ingredient may be present in an amount selected from 60%, 55%, 50%, 45%, 40%, 35%, 30%, 25%, 20%, 15%, 10% by weight or any value therebetween.
The molar ratio of the element Mn to the element Fe in the active component can be (10-0.1): 1, preferably (0.2-5): 1, more preferably (1 to 4): 1.
the carrier can be a doped titanium dioxide nanotube doped with metal oxide; the support may comprise a metal oxide and titania, wherein the molar ratio of metal oxide to titania may be 1: (1 to 100), preferably 1: (30-95), more preferably 1: (50-90).
Another object of the present invention is to provide a method for preparing the monolithic honeycomb catalyst for low-temperature SCR denitration, which comprises the following steps:
mixing the precursor of the active component with a carrier, and adding the components including a forming aid to prepare the integral honeycomb catalyst for low-temperature SCR denitration; wherein, a coprecipitation method is adopted to prepare a precursor of the active component; the carrier is prepared by a hydrothermal method.
Specifically, the following steps may be included:
1) dissolving soluble salt corresponding to the active component in water to form salt solution;
2) preparing the salt solution into a precursor of the active component of the catalyst by adopting a coprecipitation method;
3) preparing the components including metal oxide and nano titanium dioxide powder into a nano tube by a hydrothermal method, and taking the nano tube as a carrier;
4) dry-mixing the precursor of the catalyst active component, the carrier and the components including the forming auxiliary agent, kneading, mixing and aging to obtain a forming blank;
5) and extruding and molding the molded blank to obtain the integral honeycomb catalyst, and drying and roasting to obtain the integral honeycomb catalyst for low-temperature SCR denitration.
Wherein the content of the first and second substances,
in the step 1) described above, the step of,
the soluble salt corresponding to the active component comprises soluble manganese salt and soluble ferric salt;
the soluble manganese salt is selected from at least one of manganese nitrate, manganese acetate and manganese sulfate; the soluble ferric salt is selected from at least one of ferric trichloride, ferric nitrate and ferric acetate;
the molar ratio of the element Mn in the soluble manganese salt to the element Fe in the soluble iron salt is (10-0.1): 1; preferably (0.2-5): 1, more preferably (1 to 4): 1.
the concentration of the soluble salt corresponding to the active component in the salt solution is 0.1-3.0 mol/L. (total mol concentration of soluble salts of active ingredients).
And/or, in the step 2),
adding the salt solution into an alkali solution, stirring to form a precipitate, aging, washing, filtering and drying to obtain a precursor of the active component of the catalyst;
wherein the content of the first and second substances,
the alkali solution can be at least one of aqueous solutions of sodium carbonate, ammonia water, ammonium carbonate, ammonium bicarbonate, urea and sodium hydroxide;
the concentration of the alkali solution can be 0.1-3 mol/L;
the pH value of the precipitate can be 7-11;
the precipitation temperature can be 30-90 ℃, and the drying temperature can be 30-120 ℃; preferably, the water content of the precursor of the catalyst active component obtained after drying may be 1 to 10%.
And/or, in the step 3),
adding components including metal oxide and titanium dioxide powder into an alkaline solution to obtain a suspension; carrying out hydrothermal reaction on the suspension to obtain a hydrothermal product containing metal oxide and titanium dioxide; washing and drying the hydrothermal product to obtain a doped titanium dioxide nanotube which is a carrier;
wherein the content of the first and second substances,
the metal oxide can be at least one of oxides of Zr, Pr, La, Ce, Cu, Zn, Mo, Al, Sn, Ni, W, V and Cr; and/or the presence of a gas in the gas,
the molar ratio of the metal oxide to the amount of titanium dioxide may be 1: (1 to 100), preferably 1: (30-95), more preferably 1: (50-90).
The reaction conditions of the hydrothermal reaction may be: reacting for 24-72 h at 100-160 ℃;
the drying temperature can be 60-120 ℃.
The specific surface area of the titanium dioxide powder is 100-300 m2(ii)/g; specifically, the specific surface area is 100 to 300m2Per gram of nano-sized anatase titanium dioxide.
The alkaline solution can be a strong alkaline solution, and is preferably a sodium hydroxide or potassium hydroxide solution with the concentration of 5-15 mol/L;
and/or, in the step 4),
the forming aid may comprise the following components: water, a binder, an extrusion aid, a pore-forming agent and a structural assistant;
the amount of the water can be 10-50 g/100g of powder; the powder is the sum of the precursor of the active component in the step 4) and the carrier;
the binder may comprise an organic binder and an inorganic binder;
the organic binder can be selected from cellulose, preferably at least one of sodium carboxymethyl cellulose and methyl cellulose; the dosage of the organic binder can be 1-5 g/100g of powder;
the inorganic adhesive can be at least one of pseudo-boehmite powder, silica sol, alumina sol, phosphates, water glass and clay cement; the dosage of the inorganic adhesive can be 1-40 g/100g of powder;
the extrusion aid can be at least one of sesbania powder, glycerol, polyethylene glycol and polyvinyl alcohol; the amount of the extrusion aid can be 1-15 g/100g of powder;
the pore-forming agent can be at least one of activated carbon, ammonia water and urea, and the dosage of the pore-forming agent can be 1-5 g/100g of powder;
the structural auxiliary agent can be rod-shaped glass fiber, the length of the structural auxiliary agent is 0.1-10 mm, and the dosage of the structural auxiliary agent is 1-20 g/100g of powder.
And/or, in the step 5),
the extrusion molding is to obtain the integral honeycomb catalyst, which means that the conventional honeycomb catalyst mold in the field is adopted for extrusion molding, and the opening structure of the catalyst mold is not limited to triangular, quadrangular, hexagonal, circular and other special-shaped structures.
The drying step may include: the drying temperature is 30-120 ℃, and the drying humidity is 5-90%; the water content of the dried product is 1-10%;
the firing step may include: the roasting temperature is 300-800 ℃, and the roasting time can be 4-12 h.
More specifically, the preparation method may comprise the steps of:
1. adding one or more of metal oxides (oxides of Zr/Pr/La/Ce/Cu/Zn// Mo/Al/Sn/Ni/W/V/Cr) and titanium dioxide powder into 5-15 mol/L sodium hydroxide solution, stirring at normal temperature for 1-12 h, and carrying out ultrasonic treatment for 1-12 h to obtain a mixed suspension, wherein the molar ratio of the metal oxides to the titanium dioxide is 1: (1-100); pouring the obtained mixed suspension into a hydrothermal reaction kettle, and reacting for 24-72 hours at 100-160 ℃; when the reaction kettle is cooled to room temperature, pouring out the supernatant, wherein the lower precipitate is the hydrothermal product of the metal oxide and the titanium dioxide; and (3) pickling the hydrothermal product with hydrochloric acid, washing the product with distilled water to be neutral, and drying the product in an oven at the temperature of 60-120 ℃ to obtain the doped titanium dioxide nanotube carrier.
2. According to the molar ratio of the element Mn in the soluble manganese salt to the element Fe in the soluble iron salt being (10-0.1): 1, weighing soluble manganese salt and soluble ferric salt, dissolving the soluble manganese salt and the soluble ferric salt in water, and stirring to form a mixed salt solution with the concentration of 0.1-3.0 mol/L; adding the mixed salt solution into an alkaline solution (or adding the mixed salt solution in a sequential manner or in a concurrent manner) formed by one or more of common alkalis such as sodium carbonate, ammonia water, ammonium carbonate, ammonium bicarbonate, urea, sodium hydroxide and the like at a certain dropping speed, wherein the concentration of the alkaline solution can be 0.1-3 mol/L, continuously stirring to form a precipitate, the key pH value of the precipitate can be 7-11, and then aging, washing, filtering and drying to obtain the precursor of the active component of the catalyst. The preferable precipitation temperature is 30-90 ℃, the preferable drying temperature is 30-120 ℃, and the water content of the dried product can be 1-10%.
3. The prepared doped titanium dioxide nanotube carrier, the precursor of the catalyst active component prepared by coprecipitation and a forming aid, including at least one of a binder, a structural aid, an extrusion aid, a pore-forming agent and the like, are subjected to dry mixing, kneading, filtering, blank making and ageing, and finally, the wool material is extruded into a catalyst blank body through extrusion equipment.
Wherein the binder can be at least one selected from inorganic binder and organic binder, the inorganic binder can be one or more selected from aluminum sol, silica sol, phosphate, etc., and the organic binder can be cellulose. The extrusion aid can be sesbania powder, glycerin and the like; the pore-forming agent is active carbon and the like; the structural auxiliary agent is rod-shaped glass fiber with the length of 0.1-10 mm.
4. And drying the extruded catalyst blank until the water content is 1-10% in an environment with the temperature of 30-120 ℃ and the humidity of 5-90%. And then roasting in a muffle furnace to obtain a finished product catalyst, wherein the roasting temperature is 300-800 ℃, and the roasting time can be 4-12 h.
The equipment used in the preparation method of the invention is common equipment in the prior art.
The invention also aims to provide the application of the monolithic honeycomb catalyst for low-temperature SCR denitration or the catalyst prepared by the preparation method, in particular the application of the monolithic honeycomb catalyst for low-temperature SCR denitration in low-temperature denitration of high-water-content flue gas, preferably the application in low-temperature denitration of high-water-content flue gas taking natural gas as a raw material.
The substantial difference between the present invention and the prior art is: the doped titanium dioxide nanotube is used, and the catalyst auxiliary agent is highly dispersed on the titanium dioxide nanotube, so that the water resistance, the sulfur resistance and the stability of the catalyst are greatly improved. The honeycomb monolithic catalyst is formed by adopting inorganic and organic binders, so that the finished product rate in the catalyst forming process is ensured, and the finished catalyst has good mechanical strength.
The invention has the beneficial effects that: the invention provides a monolithic honeycomb catalyst for low-temperature SCR denitration and a preparation method thereof, the method is simple and easy to produce, and the prepared monolithic honeycomb catalyst has excellent water resistance, sulfur resistance and stability, can be suitable for low-temperature denitration of high-water-content flue gas taking natural gas as a raw material, and has wide industrial application prospect.
Detailed Description
While the present invention will be described in detail with reference to the following examples, it should be understood that the following examples are illustrative of the present invention and are not to be construed as limiting the scope of the present invention.
The endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and such ranges or values should be understood to encompass values close to those ranges or values. For ranges of values, between the endpoints of each of the ranges and the individual points, and between the individual points may be combined with each other to give one or more new ranges of values, and these ranges of values should be considered as specifically disclosed herein.
Source of raw materials
Titanium dioxide: xuancheng Jingrui New Material Co., Ltd, model VK-TA15, specific surface area 118m2/g；
Analytically pure zirconium dioxide, west longa science ltd;
50% manganese nitrate aqueous solution, available from west longa science corporation;
ferric nitrate nonahydrate, manufactured by west longa science ltd;
65% nitric acid, manufactured by Shirong scientific corporation;
glass fiber, 3mm in length, Shanghai Michelin Biochemical technology, Inc.;
hydrochloric acid, Beijing chemical plant.
Other starting materials or reagents are commercially available.
Example 1:
preparing a titanium dioxide nanotube carrier: weighing 50g of titanium dioxide particles, slowly pouring the titanium dioxide particles into a beaker containing 1000mL of 10mol/L sodium hydroxide solution, stirring the titanium dioxide particles at normal temperature for 1 hour, and then carrying out ultrasonic treatment for 1 hour to obtain a titanium dioxide mixed suspension; then moving the mixed suspension into 4 300mL hydrothermal reaction kettles, reacting for 48h at 130 ℃, opening the reaction kettles after the reaction kettles are cooled to room temperature, pouring out the supernatant, washing the lower-layer precipitate with hydrochloric acid, and then washing with water until the pH value is 7; and finally, drying the washed precipitate in an oven at the temperature of 80 ℃ to obtain the titanium dioxide nanotube carrier.
Preparation of the precursor of the catalyst active component: by adopting forward coprecipitation, 50 mass percent of manganese nitrate aqueous solution is used as a manganese source, ferric nitrate nonahydrate is used as an iron source, and a precursor mixed solution with the concentration of 1mol/L is prepared according to the mass ratio of 50 mass percent of manganese nitrate aqueous solution to the ferric nitrate nonahydrate of 120/55 and is fully stirred and mixed. And then adding the prepared 1.5mol/L sodium carbonate solution into the precursor mixed solution at a dropping speed of 80-120 drops/min, continuously stirring and precipitating the primary product until the pH is 9.0, keeping the precipitation reaction temperature at 60 ℃, then aging the precipitated product for 1h under stirring at 60 ℃, then carrying out suction filtration and water washing to obtain a filter cake, drying at 110 ℃ until the water content is 5%, and then grinding for later use.
Preparation of the honeycomb catalyst: and (3) mixing the prepared carrier and the precursor of the active component according to the mass ratio of 5: 1, mixing and mechanically grinding to obtain catalyst molding powder, adding 10g/100g of pseudo-boehmite powder, 1.5g/100g of sesbania powder, 1g/100g of glass fiber, 2g/100g of methylcellulose, 2g/100g of activated carbon, 5g/100g of glycerol and polyethylene glycol mixture, placing the mixture in a kneader for dry mixing, kneading the mixture by using 5 wt% of nitric acid aqueous solution, refining mud and aging to obtain a catalyst blank, extruding the catalyst blank by using a universal die device with 100mm and 40 holes, drying the catalyst blank at 110 ℃, drying the catalyst blank to obtain the catalyst blank with 5% of water content, and roasting the catalyst blank in a muffle furnace at 600 ℃ for 8 hours to obtain the low-temperature SCR honeycomb monolithic catalyst S1A.
Examples 2 to 5:
preparing a Zr-doped titanium dioxide nanotube carrier: weighing 1.0g of ZrO2And 50g of titanium dioxide particles, slowly pouring the mixture into a beaker containing 1000mL of 10mol/L sodium hydroxide solution, stirring the mixture for 1 hour at normal temperature, and then carrying out ultrasonic treatment for 1 hour to obtain ZrO2Mixed suspension with titanium dioxide; then, the mixed suspension is moved into 4 hydrothermal reaction kettles with the volume of 300mL, the hydrothermal reaction kettle is reacted for 48 hours at the temperature of 130 ℃, the reaction kettle is opened after being cooled to the room temperature, the supernatant is poured off, and the lower-layer precipitate is washed by hydrochloric acid and then washed by water until the pH value is 7; and finally, drying the washed precipitate in an oven at the temperature of 80 ℃ to obtain the Zr-doped titanium dioxide nanotube carrier.
Preparation of the precursor of the catalyst active component: by adopting forward coprecipitation, 50 mass percent of manganese nitrate aqueous solution is used as a manganese source, ferric nitrate nonahydrate is used as an iron source, and a precursor mixed solution with the concentration of 1mol/L is prepared according to the mass ratio of 50 mass percent of manganese nitrate aqueous solution to the ferric nitrate nonahydrate of 120/55 and is fully stirred and mixed. And then adding the prepared 1.5mol/L sodium carbonate solution into the precursor mixed solution at a dropping speed of 80-120 drops/min, continuously stirring and precipitating the primary product until the pH is 9.0, keeping the precipitation reaction temperature at 60 ℃, then aging the precipitated product for 1h under stirring at 60 ℃, then carrying out suction filtration and water washing to obtain a filter cake, drying at 110 ℃ until the water content is 5%, and then grinding for later use.
Catalyst A: and (3) mixing the prepared carrier and the active component precursor according to the mass ratio of 5: 1, mixing and mechanically grinding to obtain catalyst molding powder, adding 10g/100g of pseudo-boehmite powder, 1.5g/100g of sesbania powder, 1g/100g of glass fiber, 2g/100g of methylcellulose, 2g/100g of activated carbon, 5g/100g of glycerol and polyethylene glycol mixture, placing the mixture in a kneader for dry mixing, kneading the mixture by using 5 wt% of nitric acid aqueous solution, refining mud and aging to obtain a catalyst blank, extruding the catalyst blank by using a universal die device with 100mm and 40 holes, drying the catalyst blank at 110 ℃, drying the catalyst blank to obtain the catalyst blank with 5% of water content, and roasting the catalyst blank in a muffle furnace at 600 ℃ for 8 hours to obtain the low-temperature SCR honeycomb monolithic catalyst S2A.
And (2) preparing the carrier and the active component precursor in a mass ratio of 4: 1, mixing and mechanically grinding to obtain catalyst molding powder, adding 10g/100g of silica sol, 2g/100g of sesbania powder, 1g/100g of glass fiber, 3g/100g of methylcellulose, 2g/100g of activated carbon and 10g/100g of glycerol and polyethylene glycol mixture into the catalyst molding powder, placing the mixture into a kneader for dry mixing, kneading the mixture by using 5 wt% nitric acid aqueous solution, refining mud and aging to obtain a catalyst blank, extruding the catalyst blank by using a 100 mm-100 mm 40-hole universal die device, drying the catalyst blank at 110 ℃, drying the catalyst blank to obtain a water content of 5%, and roasting the catalyst blank in a muffle furnace at 600 ℃ for 8 hours to obtain the low-temperature SCR honeycomb monolithic catalyst S2B.
Catalyst C: and (3) mixing the prepared carrier and the active component precursor according to the mass ratio of 3: 1, mixing and mechanically grinding to obtain catalyst molding powder, adding 5g/100g of powdered water glass, 1.5g/100g of powdered sesbania powder, 1g/100g of powdered glass fiber, 2g/100g of powdered sodium carboxymethyl cellulose, 5g/100g of powdered urea, 5g/100g of powdered glycerin and polyethylene glycol mixture, putting the mixture in a kneader for dry mixing, kneading the mixture by using 5 wt% of nitric acid aqueous solution, refining mud and aging to obtain a catalyst blank, extruding the catalyst blank by using a 100 mm-100 mm 40-hole universal die device, drying the catalyst blank at 110 ℃, drying the catalyst blank to obtain the low-temperature SCR honeycomb monolithic catalyst S2C, and roasting the catalyst blank in a muffle furnace at 600 ℃ for 8 hours.
Catalyst D: and (2) mixing the prepared carrier and the active component precursor according to the mass ratio of 2: 1, mixing and mechanically grinding to obtain catalyst molding powder, adding 15g/100g of alumina sol, 1.5g/100g of sesbania powder, 1g/100g of glass fiber, 2g/100g of methylcellulose, 5g/100g of ammonia water and 5g/100g of glycerol and polyethylene glycol mixture into the catalyst molding powder, placing the mixture into a kneader for dry mixing, kneading the mixture by using 5 wt% nitric acid aqueous solution, refining mud and aging to obtain a catalyst blank, extruding the catalyst blank by using a 100 mm-100 mm 40-hole universal die device, drying the catalyst blank at 110 ℃, drying the catalyst blank to obtain the low-temperature SCR honeycomb monolithic catalyst S2D, and roasting the catalyst blank in a muffle furnace at 600 ℃ for 8 hours to obtain the low-temperature SCR honeycomb monolithic catalyst.
Example 6:
preparing a La-doped titanium dioxide nanotube carrier: weigh 4.0gLa2O3And 50g of titanium dioxide particles, slowly pouring the titanium dioxide particles into a beaker containing 1000mL of 10mol/L sodium hydroxide solution, stirring the mixture for 1 hour at normal temperature, and then carrying out ultrasonic treatment for 1 hour to obtain La2O3Mixed suspension with titanium dioxide; then, the mixed suspension is moved into 4 hydrothermal reaction kettles with the volume of 300mL, the hydrothermal reaction kettle is reacted for 48 hours at the temperature of 130 ℃, the reaction kettle is opened after being cooled to the room temperature, the supernatant is poured off, and the lower-layer precipitate is washed by hydrochloric acid and then washed by water until the pH value is 7; and finally, drying the washed precipitate in an oven at 80 ℃ to obtain the La-doped titanium dioxide nanotube carrier.
Preparation of the precursor of the catalyst active component: by adopting forward coprecipitation, 50 mass percent of manganese nitrate aqueous solution is used as a manganese source, ferric nitrate nonahydrate is used as an iron source, and a precursor mixed solution with the concentration of 1mol/L is prepared according to the mass ratio of 50 mass percent of manganese nitrate aqueous solution to the ferric nitrate nonahydrate of 120/55 and is fully stirred and mixed. And then adding the prepared 1.5mol/L sodium carbonate solution into the precursor mixed solution at a dropping speed of 80-120 drops/min, continuously stirring and precipitating the primary product until the pH is 9.0, keeping the precipitation reaction temperature at 60 ℃, then aging the precipitated product for 1h under stirring at 60 ℃, then carrying out suction filtration and water washing to obtain a filter cake, drying at 110 ℃ until the water content is 5%, and then grinding for later use.
Preparation of the honeycomb catalyst: and (3) mixing the prepared carrier and the active component precursor according to the mass ratio of 5: 1, mixing and mechanically grinding to obtain catalyst molding powder, adding 10g/100g of pseudo-boehmite powder, 1.5g/100g of sesbania powder, 1g/100g of glass fiber, 2g/100g of methylcellulose, 2g/100g of activated carbon, 5g/100g of glycerol and polyethylene glycol mixture, placing the mixture in a kneader for dry mixing, kneading the mixture by using 5 wt% of nitric acid aqueous solution, refining mud and aging to obtain a catalyst blank, extruding the catalyst blank by using a universal die device with 100mm and 40 holes, drying the catalyst blank at 110 ℃, drying the catalyst blank to obtain the catalyst blank with 5% of water content, and roasting the catalyst blank in a muffle furnace at 600 ℃ for 8 hours to obtain the low-temperature SCR honeycomb monolithic catalyst S3A.
Comparative example 1:
titanium dioxide with the model of VK-TA15 is used as a carrier.
Preparation of the precursor of the catalyst active component: by adopting forward coprecipitation, 50 mass percent of manganese nitrate aqueous solution is used as a manganese source, ferric nitrate nonahydrate is used as an iron source, and a precursor mixed solution with the concentration of 1mol/L is prepared according to the mass ratio of 50 mass percent of manganese nitrate aqueous solution to the ferric nitrate nonahydrate of 120/55 and is fully stirred and mixed. And then adding the prepared 1.5mol/L sodium carbonate solution into the precursor mixed solution at a dropping speed of 80-120 drops/min, continuously stirring and precipitating the primary product until the pH is 9.0, keeping the precipitation reaction temperature at 60 ℃, then aging the precipitated product for 1h under stirring at 60 ℃, then carrying out suction filtration and water washing to obtain a filter cake, drying at 110 ℃ until the water content is 5%, and then grinding for later use.
Preparation of the honeycomb catalyst: and (3) mixing the prepared carrier and the active component precursor according to the mass ratio of 5: 1, mixing and mechanically grinding to obtain catalyst molding powder, adding 10g/100g of pseudo-boehmite powder, 1.5g/100g of sesbania powder, 1g/100g of glass fiber, 2g/100g of methylcellulose, 2g/100g of activated carbon, 5g/100g of glycerol and polyethylene glycol mixture, placing the mixture in a kneader for dry mixing, kneading the mixture by using 5 wt% of nitric acid aqueous solution, refining mud and aging to obtain a catalyst blank, extruding the catalyst blank by using a universal die device with 100mm and 40 holes, drying the catalyst blank at 110 ℃, drying the catalyst blank to obtain a water content of 5%, and roasting the catalyst blank in a muffle furnace at 600 ℃ for 8 hours to obtain the low-temperature SCR honeycomb monolithic catalyst D1A.
Evaluation of denitration activity of catalyst: the simulated smoke comprises the following components: 120ppmNO, 120ppmNH3，5％O2，20％H2O，40ppmSO2The balance being N2. The evaluation temperature is 160-320 ℃, and the airspeed is 3000h-1Specific NO conversions are shown in table 1.
TABLE 1 NO conversion at different temperatures%
| Catalyst and process for preparing same | 160℃ | 200℃ | 220℃ | 250℃ | 300℃ | 320℃ |
| S1A | 25.3％ | 36.5％ | 70.3％ | 75.1％ | 73.6％ | 60.2％ |
| S2A | 30.5％ | 41.2％ | 76.5％ | 80.2％ | 78.2％ | 67.0％ |
| S2B | 56.3％ | 81.1％ | 90.2％ | 91.0％ | 88.2％ | 71％ |
| S2C | 59.3％ | 84.4％ | 90.5％ | 91.2％ | 89.9％ | 71.8％ |
| S2D | 59.7％ | 83.5％ | 90.7％ | 91.6％ | 90.2％ | 72.0％ |
| S3A | 30.4％ | 41.6％ | 76.1％ | 80.0％ | 77.6％ | 66.4％ |
| D1A | 1.2％ | 2.7％ | 10.5％ | 23.2％ | 20.5％ | 10.3％ |
As can be seen from the evaluation results in Table 1, although the water content in the flue gas was as high as 20% and the sulfur content was 40ppm SO2Under the condition of (1), the catalyst adopting the titanium dioxide nanotube as the carrier, in particular the catalyst adopting the metal oxide doped titanium dioxide nanotube as the carrier still keeps higher NO conversion rate and has good water resistance and sulfur resistance. The integral honeycomb catalyst prepared by the method has high strength, and the pressure reduction is more beneficial to industrial application.
The preferred embodiments of the present invention have been described in detail, however, the present invention is not limited to the specific details of the above embodiments, and various simple modifications may be made to the technical solution of the present invention within the technical idea of the present invention, and these simple modifications are within the protective scope of the present invention.
It should be noted that the various technical features described in the above embodiments can be combined in any suitable manner without contradiction, and the invention is not described in any way for the possible combinations in order to avoid unnecessary repetition.
Claims (11)
1. A monolithic honeycomb catalyst for low temperature SCR denitration, the catalyst comprising the following components in an amount of 100% by total weight of the catalyst:
the weight content of the carrier is 39-97 percent; preferably 45-90%;
the weight content of the active component is 3-61%; preferably 10-55%;
the active component is selected from MnOxAnd FeOyWherein x is 1 to 2 and y is 1 to 1.5;
preferably, the carrier is a doped titanium dioxide nanotube doped with a metal oxide; wherein the metal is selected from one or more of Zr, Pr, La, Ce, Cu, Zn, Mo, Al, Sn, Ni, W, V and Cr;
the catalyst is a monolithic honeycomb catalyst.
2. The monolithic honeycomb catalyst for low-temperature SCR denitration according to claim 1, characterized in that: the molar ratio of the element Mn to the element Fe in the active component is (10-0.1): 1.
3. the monolithic honeycomb catalyst for low-temperature SCR denitration according to claim 1 or 2, characterized in that:
the carrier is a doped titanium dioxide nanotube doped with metal oxide; the carrier comprises a metal oxide and titanium dioxide, wherein the molar ratio of the metal oxide to the titanium dioxide is 1: (1-100);
preferably, the specific surface area of the carrier is 50-300 m2/g。
4. The preparation method of the monolithic honeycomb catalyst for low-temperature SCR denitration according to any one of claims 1 to 3, characterized by comprising the steps of:
mixing the precursor of the active component with a carrier, and adding the components including a forming aid to prepare the integral honeycomb catalyst for low-temperature SCR denitration; wherein, a coprecipitation method is adopted to prepare a precursor of the active component; the carrier is prepared by a hydrothermal method.
5. The method of preparing the monolithic honeycomb catalyst for low-temperature SCR denitration according to claim 4, characterized by comprising the steps of:
1) dissolving soluble salt corresponding to the active component in water to form salt solution;
2) preparing the salt solution into a precursor of the active component by adopting a coprecipitation method;
3) preparing the components including metal oxide and nano titanium dioxide powder into a nano tube by a hydrothermal method, and taking the nano tube as a carrier;
4) dry-mixing the precursor of the active component, the carrier and the components including the forming auxiliary agent, kneading, mixing and aging to obtain a forming blank;
5) and extruding and molding the molded blank to obtain the integral honeycomb catalyst, and drying and roasting to obtain the integral honeycomb catalyst for low-temperature SCR denitration.
6. The method of claim 5, wherein the method comprises the steps of:
in the step 1) described above, the step of,
the soluble salt corresponding to the active component comprises soluble manganese salt and soluble ferric salt; the soluble manganese salt is selected from at least one of manganese nitrate, manganese acetate and manganese sulfate; the soluble ferric salt is selected from at least one of ferric trichloride, ferric nitrate and ferric acetate;
the molar ratio of the element Mn in the soluble manganese salt to the element Fe in the soluble iron salt is (10-0.1): 1;
the concentration of the soluble salt corresponding to the active component in the salt solution is 0.1-3.0 mol/L.
7. The method of claim 5, wherein the method comprises the steps of:
in the step 2) of the said step,
adding the salt solution into an alkali solution, stirring to form a precipitate, aging, washing, filtering and drying to obtain a precursor of the active component;
wherein the content of the first and second substances,
the alkali solution is at least one of aqueous solutions of sodium carbonate, ammonia water, ammonium carbonate, ammonium bicarbonate, urea and sodium hydroxide;
the concentration of the alkali solution is 0.1-3 mol/L;
the pH value of the precipitate is 7-11; the precipitation temperature is 30-90 ℃;
the drying temperature is 30-120 ℃; preferably, the water content of the precursor of the active component obtained after drying is 1-10%.
8. The method according to claim 5, wherein the method comprises the following steps:
in the step 3), the step of the method comprises the following steps,
adding components including metal oxide and titanium dioxide powder into an alkaline solution to obtain a suspension; carrying out hydrothermal reaction on the suspension to obtain a hydrothermal product containing metal oxide and titanium dioxide; washing and drying the hydrothermal product to obtain a doped titanium dioxide nanotube which is a carrier;
wherein the content of the first and second substances,
the metal oxide is selected from at least one of oxides of Zr, Pr, La, Ce, Cu, Zn, Mo, Al, Sn, Ni, W, V and Cr;
the molar ratio of the metal oxide to the titanium dioxide powder is 1: (1-100);
the specific surface area of the titanium dioxide powder is 100-300 m2/g；
The alkaline solution is a strong alkali solution, and is preferably a sodium hydroxide or potassium hydroxide solution with the concentration of 5-15 mol/L;
the reaction conditions of the hydrothermal reaction are as follows: reacting for 24-72 h at 100-160 ℃;
the drying temperature is 60-120 ℃.
9. The method of claim 5, wherein the method comprises the steps of:
the forming auxiliary agent comprises the following components: water, a binder, an extrusion aid, a pore-forming agent and a structural assistant;
the using amount of the water is 10-50 g/100g of powder;
the powder is the sum of the precursor of the active component in the step 4) and the carrier;
the binder comprises an organic binder and an inorganic binder;
the organic binder is selected from cellulose, preferably at least one of sodium carboxymethyl cellulose and methyl cellulose; the dosage of the organic binder is 1-5 g/100g of powder;
the inorganic adhesive is selected from at least one of pseudo-boehmite powder, silica sol, alumina sol, phosphate, water glass and clay cement; the dosage of the inorganic adhesive is 1-40 g/100g of powder;
the extrusion aid is at least one of sesbania powder, glycerol, polyethylene glycol and polyvinyl alcohol, and the amount of the extrusion aid is 1-15 g/100g of powder;
the pore-forming agent is at least one of activated carbon, ammonia water and urea, and the dosage of the pore-forming agent is 1-5 g/100g of powder;
the structural auxiliary agent is rod-shaped glass fiber, the length of the rod-shaped glass fiber is 0.1-10 mm, and the dosage of the rod-shaped glass fiber is 1-20 g/100g of powder.
10. The method of claim 5, wherein the method comprises the steps of:
in the step 5), the step (c) is carried out,
the drying step comprises: the drying temperature is 30-120 ℃, and the water content of the dried product is 1-10%;
the roasting step comprises: the roasting temperature is 300-800 ℃, and the roasting time is 4-12 h.
11. Use of the monolithic honeycomb catalyst according to any one of claims 1 to 3 or the catalyst prepared by the preparation method according to any one of claims 4 to 10 in low-temperature denitration of high-water-content flue gas, more preferably in low-temperature denitration of high-water-content flue gas using natural gas as a raw material.
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Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101733101A (en) * | 2009-12-03 | 2010-06-16 | 浙江大学 | Denitrifying catalyst using titanium dioxide nano tubes as carrier and process for preparing same |
| CN105727985A (en) * | 2016-01-27 | 2016-07-06 | 中国建筑材料科学研究总院 | Honeycomb integral type low temperature denitrifying catalyst and preparation method thereof |
| CN105800680A (en) * | 2016-03-14 | 2016-07-27 | 武汉理工大学 | Preparation method of titanium dioxide nanotube doped with transition metal |
| CN106423193A (en) * | 2016-09-21 | 2017-02-22 | 中国建筑材料科学研究总院 | Honeycomb manganese denitration catalyst and preparation method thereof |
| CN106621807A (en) * | 2017-02-15 | 2017-05-10 | 中南大学 | Flue gas treatment method for realizing desulphurization and denitrification simultaneously by using lanthanum-cerium oxide-loaded titanium dioxide nanotube array for catalytic reduction |
| CN107899567A (en) * | 2017-12-01 | 2018-04-13 | 延海港 | A kind of mesoporous Zr, Ce codope SCR catalyst |
| CN109092323A (en) * | 2017-06-20 | 2018-12-28 | 中国石油化工股份有限公司 | Low-temperature SCR catalyst for denitrating flue gas and its preparation method and application |
| CN110354843A (en) * | 2019-08-28 | 2019-10-22 | 华北电力大学 | A kind of thin-walled honeycomb formula low temperature sulfur resistive SCR denitration and preparation method thereof |
| WO2020103848A1 (en) * | 2018-11-21 | 2020-05-28 | 南京工业大学 | Environmentally-friendly high-temperature denitration catalyst and preparation method therefor |
| CN111450876A (en) * | 2020-04-26 | 2020-07-28 | 合肥工业大学 | Low-temperature SCR denitration catalyst using carriers with different particle sizes to load Mn and preparation method thereof |
-
2020
- 2020-11-05 CN CN202011221405.XA patent/CN114433123B/en active Active
Patent Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101733101A (en) * | 2009-12-03 | 2010-06-16 | 浙江大学 | Denitrifying catalyst using titanium dioxide nano tubes as carrier and process for preparing same |
| CN105727985A (en) * | 2016-01-27 | 2016-07-06 | 中国建筑材料科学研究总院 | Honeycomb integral type low temperature denitrifying catalyst and preparation method thereof |
| CN105800680A (en) * | 2016-03-14 | 2016-07-27 | 武汉理工大学 | Preparation method of titanium dioxide nanotube doped with transition metal |
| CN106423193A (en) * | 2016-09-21 | 2017-02-22 | 中国建筑材料科学研究总院 | Honeycomb manganese denitration catalyst and preparation method thereof |
| CN106621807A (en) * | 2017-02-15 | 2017-05-10 | 中南大学 | Flue gas treatment method for realizing desulphurization and denitrification simultaneously by using lanthanum-cerium oxide-loaded titanium dioxide nanotube array for catalytic reduction |
| CN109092323A (en) * | 2017-06-20 | 2018-12-28 | 中国石油化工股份有限公司 | Low-temperature SCR catalyst for denitrating flue gas and its preparation method and application |
| CN107899567A (en) * | 2017-12-01 | 2018-04-13 | 延海港 | A kind of mesoporous Zr, Ce codope SCR catalyst |
| WO2020103848A1 (en) * | 2018-11-21 | 2020-05-28 | 南京工业大学 | Environmentally-friendly high-temperature denitration catalyst and preparation method therefor |
| CN110354843A (en) * | 2019-08-28 | 2019-10-22 | 华北电力大学 | A kind of thin-walled honeycomb formula low temperature sulfur resistive SCR denitration and preparation method thereof |
| CN111450876A (en) * | 2020-04-26 | 2020-07-28 | 合肥工业大学 | Low-temperature SCR denitration catalyst using carriers with different particle sizes to load Mn and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| 齐雪: "改性TiO2负载Fe-Mn脱硝催化剂的研究", 《中国优秀硕士学位论文全文数据库 工程科技I辑》 * |
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