CN108295865A - A kind of integral honeycomb low temperature SCR denitration catalyst and preparation method thereof - Google Patents
A kind of integral honeycomb low temperature SCR denitration catalyst and preparation method thereof Download PDFInfo
- Publication number
- CN108295865A CN108295865A CN201810172992.4A CN201810172992A CN108295865A CN 108295865 A CN108295865 A CN 108295865A CN 201810172992 A CN201810172992 A CN 201810172992A CN 108295865 A CN108295865 A CN 108295865A
- Authority
- CN
- China
- Prior art keywords
- duct
- metal oxide
- catalyst
- low temperature
- nano mineral
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000003054 catalyst Substances 0.000 title claims abstract description 106
- 238000002360 preparation method Methods 0.000 title claims abstract description 33
- 229910052500 inorganic mineral Inorganic materials 0.000 claims abstract description 70
- 239000011707 mineral Substances 0.000 claims abstract description 70
- 229910044991 metal oxide Inorganic materials 0.000 claims abstract description 56
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 37
- 230000001413 cellular effect Effects 0.000 claims abstract description 31
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Inorganic materials O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 claims abstract description 27
- 150000004706 metal oxides Chemical class 0.000 claims abstract description 16
- 239000000203 mixture Substances 0.000 claims abstract description 15
- 239000000919 ceramic Substances 0.000 claims description 49
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 27
- 238000000034 method Methods 0.000 claims description 25
- 239000000725 suspension Substances 0.000 claims description 17
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 16
- 230000008569 process Effects 0.000 claims description 14
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 12
- 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 12
- 229910017604 nitric acid Inorganic materials 0.000 claims description 12
- 239000002994 raw material Substances 0.000 claims description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 10
- 229910052878 cordierite Inorganic materials 0.000 claims description 10
- 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 description 10
- 238000010348 incorporation Methods 0.000 claims description 10
- 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 10
- 239000002557 mineral fiber Substances 0.000 claims description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- 239000003945 anionic surfactant Substances 0.000 claims description 9
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 8
- 238000007598 dipping method Methods 0.000 claims description 8
- 238000003756 stirring Methods 0.000 claims description 8
- 239000000470 constituent Substances 0.000 claims description 7
- 239000010936 titanium Substances 0.000 claims description 7
- 239000002253 acid Substances 0.000 claims description 6
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims description 6
- 229910001981 cobalt nitrate Inorganic materials 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
- 238000010438 heat treatment Methods 0.000 claims description 6
- 229910052719 titanium Inorganic materials 0.000 claims description 6
- 239000005995 Aluminium silicate Substances 0.000 claims description 5
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 5
- 235000012211 aluminium silicate Nutrition 0.000 claims description 5
- FPCJKVGGYOAWIZ-UHFFFAOYSA-N butan-1-ol;titanium Chemical compound [Ti].CCCCO.CCCCO.CCCCO.CCCCO FPCJKVGGYOAWIZ-UHFFFAOYSA-N 0.000 claims description 5
- 239000008367 deionised water Substances 0.000 claims description 5
- 229910021641 deionized water Inorganic materials 0.000 claims description 5
- 239000006185 dispersion Substances 0.000 claims description 5
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 claims description 5
- 238000012545 processing Methods 0.000 claims description 5
- 238000007670 refining Methods 0.000 claims description 5
- 238000000967 suction filtration Methods 0.000 claims description 5
- 229910002651 NO3 Inorganic materials 0.000 claims description 4
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 4
- 238000000137 annealing Methods 0.000 claims description 4
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 claims description 4
- 239000000292 calcium oxide Substances 0.000 claims description 4
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 claims description 4
- 239000004927 clay Substances 0.000 claims description 4
- 229910052742 iron Inorganic materials 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 4
- RCEAADKTGXTDOA-UHFFFAOYSA-N OS(O)(=O)=O.CCCCCCCCCCCC[Na] Chemical compound OS(O)(=O)=O.CCCCCCCCCCCC[Na] RCEAADKTGXTDOA-UHFFFAOYSA-N 0.000 claims description 3
- 235000012222 talc Nutrition 0.000 claims description 3
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical group [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 claims description 2
- 229910052570 clay Inorganic materials 0.000 claims description 2
- 238000012986 modification Methods 0.000 claims description 2
- 230000004048 modification Effects 0.000 claims description 2
- 239000000454 talc Substances 0.000 claims description 2
- 229910052623 talc Inorganic materials 0.000 claims description 2
- 239000002131 composite material Substances 0.000 abstract description 7
- 239000000843 powder Substances 0.000 abstract description 5
- 230000007547 defect Effects 0.000 abstract description 3
- 239000002121 nanofiber Substances 0.000 abstract description 2
- 239000007789 gas Substances 0.000 description 18
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 10
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 10
- 230000003197 catalytic effect Effects 0.000 description 10
- 238000007254 oxidation reaction Methods 0.000 description 10
- 238000006555 catalytic reaction Methods 0.000 description 8
- 238000005516 engineering process Methods 0.000 description 8
- 239000011572 manganese Substances 0.000 description 8
- 230000003647 oxidation Effects 0.000 description 8
- 238000012360 testing method Methods 0.000 description 8
- 229910002089 NOx Inorganic materials 0.000 description 7
- 238000006243 chemical reaction Methods 0.000 description 7
- 230000000694 effects Effects 0.000 description 7
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 6
- 239000000571 coke Substances 0.000 description 6
- JCXJVPUVTGWSNB-UHFFFAOYSA-N nitrogen dioxide Inorganic materials O=[N]=O JCXJVPUVTGWSNB-UHFFFAOYSA-N 0.000 description 6
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 5
- 229910016978 MnOx Inorganic materials 0.000 description 5
- 239000003795 chemical substances by application Substances 0.000 description 5
- 239000003546 flue gas Substances 0.000 description 5
- 239000010949 copper Substances 0.000 description 4
- 239000008187 granular material Substances 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- 229910052717 sulfur Inorganic materials 0.000 description 4
- 239000011593 sulfur Substances 0.000 description 4
- 229910052684 Cerium Inorganic materials 0.000 description 3
- 238000005054 agglomeration Methods 0.000 description 3
- 230000002776 aggregation Effects 0.000 description 3
- 238000013459 approach Methods 0.000 description 3
- 238000010531 catalytic reduction reaction Methods 0.000 description 3
- 229910052802 copper Inorganic materials 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- AMWRITDGCCNYAT-UHFFFAOYSA-L manganese oxide Inorganic materials [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 229910002551 Fe-Mn Inorganic materials 0.000 description 2
- MWUXSHHQAYIFBG-UHFFFAOYSA-N Nitric oxide Chemical compound O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 2
- 239000005864 Sulphur Substances 0.000 description 2
- 239000006096 absorbing agent Substances 0.000 description 2
- 238000001354 calcination Methods 0.000 description 2
- 239000012159 carrier gas Substances 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 238000002485 combustion reaction Methods 0.000 description 2
- 239000000945 filler Substances 0.000 description 2
- 239000003365 glass fiber Substances 0.000 description 2
- 239000004615 ingredient Substances 0.000 description 2
- 238000002386 leaching Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 229910052748 manganese Inorganic materials 0.000 description 2
- 230000001846 repelling effect Effects 0.000 description 2
- 235000019355 sepiolite Nutrition 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 2
- 230000009466 transformation Effects 0.000 description 2
- 229910052723 transition metal Inorganic materials 0.000 description 2
- 229910052726 zirconium Inorganic materials 0.000 description 2
- MGWGWNFMUOTEHG-UHFFFAOYSA-N 4-(3,5-dimethylphenyl)-1,3-thiazol-2-amine Chemical compound CC1=CC(C)=CC(C=2N=C(N)SC=2)=C1 MGWGWNFMUOTEHG-UHFFFAOYSA-N 0.000 description 1
- 229910015189 FeOx Inorganic materials 0.000 description 1
- 239000005909 Kieselgur Substances 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- 239000004113 Sepiolite Substances 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- -1 Sodium alkyl sulfonate Chemical class 0.000 description 1
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 1
- WYCDUUBJSAUXFS-UHFFFAOYSA-N [Mn].[Ce] Chemical compound [Mn].[Ce] WYCDUUBJSAUXFS-UHFFFAOYSA-N 0.000 description 1
- LXASOGUHMSNFCR-UHFFFAOYSA-D [V+5].[V+5].[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O Chemical compound [V+5].[V+5].[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O LXASOGUHMSNFCR-UHFFFAOYSA-D 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 238000003916 acid precipitation Methods 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- RCFVMJKOEJFGTM-UHFFFAOYSA-N cerium zirconium Chemical compound [Zr].[Ce] RCFVMJKOEJFGTM-UHFFFAOYSA-N 0.000 description 1
- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium(3+);trinitrate Chemical compound [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 229910052593 corundum Inorganic materials 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000001802 infusion Methods 0.000 description 1
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 1
- 210000001161 mammalian embryo Anatomy 0.000 description 1
- PPNAOCWZXJOHFK-UHFFFAOYSA-N manganese(2+);oxygen(2-) Chemical class [O-2].[Mn+2] PPNAOCWZXJOHFK-UHFFFAOYSA-N 0.000 description 1
- 239000000320 mechanical mixture Substances 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 238000011017 operating method Methods 0.000 description 1
- 125000001477 organic nitrogen group Chemical group 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 239000002574 poison Substances 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 231100000572 poisoning Toxicity 0.000 description 1
- 230000000607 poisoning effect Effects 0.000 description 1
- 229910052573 porcelain Inorganic materials 0.000 description 1
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000006722 reduction reaction Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229910052624 sepiolite Inorganic materials 0.000 description 1
- 238000007873 sieving Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000003685 thermal hair damage Effects 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 239000000052 vinegar Substances 0.000 description 1
- 235000021419 vinegar Nutrition 0.000 description 1
- 229910001845 yogo sapphire Inorganic materials 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
- 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
- B01D53/8621—Removing nitrogen compounds
- B01D53/8625—Nitrogen oxides
- B01D53/8628—Processes characterised by a specific catalyst
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/86—Catalytic processes
- B01D53/90—Injecting reactants
-
- B01J35/56—
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2255/00—Catalysts
- B01D2255/20—Metals or compounds thereof
- B01D2255/206—Rare earth metals
- B01D2255/2065—Cerium
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2255/00—Catalysts
- B01D2255/20—Metals or compounds thereof
- B01D2255/207—Transition metals
- B01D2255/20707—Titanium
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2255/00—Catalysts
- B01D2255/20—Metals or compounds thereof
- B01D2255/207—Transition metals
- B01D2255/2073—Manganese
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2255/00—Catalysts
- B01D2255/20—Metals or compounds thereof
- B01D2255/207—Transition metals
- B01D2255/20738—Iron
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2255/00—Catalysts
- B01D2255/20—Metals or compounds thereof
- B01D2255/207—Transition metals
- B01D2255/20746—Cobalt
Abstract
A kind of integral honeycomb low temperature SCR denitration catalyst of the present invention and preparation method thereof, is related to including the catalyst of metal oxide, by 1~10% modified Nano mineral fibres by percentage to the quality, 80~98% TiO2With 1~10% metal oxide Fe2O3‑MnO2、CuO‑MnO2Or CeO2‑MnO2Composition, the aperture in each cellular through-hole duct is the length of side 1~2cm squares, duct 0.3~0.5cm of wall thickness, 10~15cm of orifice throat length, through-hole number 1200, cellular through-hole duct interpenetrating are inserted into gas passage, and low temperature range is 200 DEG C~100 DEG C, it is composite modified to the progress of Mn base catalyst using anion-modified nanofiber miberal powder, overcome the defect for the low temperature SCR denitration catalyst for still not reaching higher denitration efficiency at 200 DEG C or less in the prior art.
Description
Technical field
Technical scheme of the present invention is related to including the catalyst of metal oxide, and specifically a kind of integral honeycomb is low
Warm SCR denitration and preparation method thereof.
Background technology
In recent years, oxynitrides NOx(i.e. nitric oxide NO and nitrogen dioxide NO2General name) discharge capacity present always
Go out the trend of rising, can all there is tens million of tons of NO every yearxIt is discharged into air.NOxIt can cause very serious atmospheric environment
Pollution problem, such as：Acid rain, photochemical fog, ozone hole and greenhouse effects.NOxGeneration and air high-temp combustion
Closely related, air high-temp combustion can make nitrogen react generation NO with oxygen, and NO can be further by O2Oxidation generates NO2；In addition,
Organic nitrogen, the NO3-N and NO2-N contained in fuel or raw material can also decompose at 500 DEG C and generate NO and NO2。
In currently used denitration technology, SCR denitration system be economical and the technology of efficient technology relative maturity it
One, still, SCR denitration just has higher transformation efficiency at 300 DEG C~1200 DEG C.In order to meet this temperature condition,
Catalysis reaction is merely able to setting before particle absorber and desulfurizer, so if this measure is taken, SCR denitration catalysis
Agent surface will necessarily form particle accumulation and can be by the SO in exhaust gas2Corrosion, to cause SCR denitration to inactivate.It solves
There are two types of the methods of this problem, when after SCR catalytic device is installed on particle absorber and desulfurizer, but this is needed
One heating device is installed to heat up to tail gas；Second is that research and development are a kind of reaching the low of high conversion efficiency at 200 DEG C or less
Warm SCR denitration.Compare by practice, later approach is more economical, easy and feasible.
The prior art of the preparation method of low temperature SCR denitration catalyst has following report：Document [Pt-free, non-
thermal plasma-assisted NOx,storage and reduction over M/Ba/Al2O3, (M=Mn, Fe,
Co, Ni, Cu) catalysts, Z.Zhang, et al.] in report and use infusion process using aluminium oxide as catalyst main carriers
A series of method for preparing transition-metal catalysts, these methods are obviously also deposited with the temperature of industrial low-temperature denitration and efficiency requirements
In gap；Secondly Al is used2O3As carrier, the sulfur resistive water repelling property of catalyst cannot be obviously improved.Document [Low
temperature selective catalytic reduction of NOx with NH3over amorphous MnOx
Catalysts prepared by three methods, X.Tang, et al.] it reports item is prepared using different hydro-thermals
MnO of the part synthesis with diverse microcosmic appearancexThe method of catalyst, although experiment obtains tubular nanometer MnOxCatalyst low temperature is de-
Nitre efficiency is best, but itself the result shows that, the pattern modification experiment of single oxide is not sufficient to MnOxCatalytic activity reach
To the level of industrial low-temperature denitration, especially single MnOxThe sulfur resistive characteristic of catalyst is very poor, needs to introduce other transition elements
It is modified, this disadvantage MnO prepared in CN106166493AxCatalyst equally exists.Document [Low-
temperature selective catalytic reduction of NO with NH3over iron and
Manganese oxides supported on titania, T.R.Yang, et al.] in report use coprecipitation with
Fe elements are as doped chemical to Mn-TiO2Low-temperature SCR catalyst is modified, although experiment conclusion obtains Fe-Mn charges
Transfer can promote MnOxCatalytic efficiency, but be co-precipitated the Fe-Mn oxides prepared of hair and be clearly present agglomeration, and
And anatase TiO2Generating process and Mn2+Oxidation process exist conflict, as anatase TiO2When generation, in catalyst still
There are a large amount of Mn2+.A kind of method that CN106582642A discloses novel compositions catalyst and its Selective Catalytic Reduction of NO is
By activated carbon, Cu- sepiolites and metal oxide uniform, tabletting and sieving combination catalysis obtained according to proportioning mechanical mixture
Agent, but the catalyst uses Cu for major catalytic component, suitable low-temperature denitration commercial Application is not achieved in low-temperature denitration performance
Integral catalyzer level, distance actual use there is also prodigious gaps.CN102407073A discloses two sections a kind of
Microwave catalysis reaction bed method of denitration, the wherein catalyst of first segment microwave catalysis reaction bed are Cu-HZSM-5 or Mn/MgFe2O4
Catalyst；The catalyst of second segment microwave catalysis reaction bed is activated carbon or activated carbon supported MnO, CuO or CeO-CuO, MgO-
FeOx、CeO-ZrO2Catalyst, which is divided into former and later two workshop sections, and wherein rear portion uses
Activated carbon with volatilization oxidisability is carrier and sorbing material, this is just that the stability of the catalyst has buried hidden danger；In addition,
The catalyst system and catalyzing has also used two step micro ware auxiliary catalysis technologies, hence it is evident that improves the cost of catalytic process.In addition to this
CN106582642A and CN103433034B discloses activated carbon or activated coke load manganese-cerium composite oxide low-temperature SCR catalyst
And preparation method thereof, such method is composite oxide supported in the activated coke particle compared with high-ratio surface and mechanical strength by Mn, Ce
On, drawbacks described above is equally existed, first, can not ensure the oxidation process of the coke at 200 DEG C, second is that the coke in preparation process
Oxidation and Mn2+Oxidation equally exist conflict, can not ensure to generate enough Mn in the case that coke is not oxidized3+And Mn4 +, and due to the reproducibility of coke, Mn2+Oxidation process can be more difficult.CN102614890B is disclosed for nitric acid, nitre
The honeycomb monolith SCR catalyst of salt tail gas denitration, it has the carrier of netted honeycomb hole, coated in honeycomb hole surface by internal
Aluminium oxide active layer and the active constituent composition that is immersed on aluminum oxide activating layer, carrier is made of cordierite powder and auxiliary material,
The System Catalyst has used the cordierite of better stability as carrier component, can reduce catalytic process gas flow temperature wave
The dynamic thermal damage caused by catalyst, but its catalyst uses aluminium oxide as load ingredient so that its water resistant and sulfur resistive
Ability be not so good as TiO2Catalyst as load ingredient；Secondly preparation process uses traditional dipping means, can not avoid
The defect of active component agglomeration.CN101444727A discloses V-W-Ti system SCR catalysts for SCR denitrating flue gas
Integral honeycombed catalyst and preparation method thereof, CN103785407B disclose a kind of preparation method of cellular SCR catalyst,
Raw material is ammonium tungstate, vanadium oxalate, cerous nitrate, ferric nitrate, cerium zirconium sosoloid, and honeycomb substrate is cordierite, from above-mentioned two pieces patent
In technology involved raw material can be seen that this be it is a kind of be doped using W-V systems as activated centre and to it is modified
Technology, it is well known that the catalyst optimal use range of V-W systems is at 300 DEG C or more, this is not one kind in a strict sense
Low temperature SCR denitration catalyst, it is extremely limited in the catalytic activity of low-temperature space；In addition under these conditions catalyst by water and sulphur
Poisoning Phenomenon it is extremely serious, generally use V-W systems as catalyst be not appropriate for low-temperature SCR technology require.
CN106179301A, CN101721993A, CN104785246A and CN103816919B, which are disclosed, a kind of to be adulterated with Ce
TiO2For the low-temperature SCR catalyst and preparation method thereof of carrier, MnO is loadedXFor catalyst activity component it may first have to specific
It is that, though the catalyst that above-mentioned file is reported has certain low temperature active and anti-poisoning ability, it develops range only
It is only limited to the preparation level of powder catalyst, secondly can't avoid TiO2Powder and active component are in preparation process
Agglomeration can have TiO2Phase transformation and Mn2+Temperature contradiction between oxidation.CN102114424A discloses a kind of low-temperature flue gas
Denitration SCR catalyst and preparation method, by the one or more member in carrier and manganese oxide and Ce, Zr, Ti, Co, Fe, Cu
The composite oxides composition of element, carrier is glass fibre and/or diatomite, although silicon involved in the catalyst and preparation method
The content of diatomaceous earth load, but active component Ce, Zr, Co, Fe, Cu that the catalyst of the system is chosen are not low temperature SCR denitrations
The higher element of efficiency；Additionally due to TiO2Carrier appearance is should be used as, because of single TiO2Its low temperature SCR denitration efficiency is no more than
20%, therefore TiO therein2It is introduced as just the carrier with sulfur resistive water repelling property；Last the prior art is by diatomite
The substitute for merely serving as glass fibre is included in, and is not directed to the effect of diatomaceous porous structure.In short, above-mentioned monoblock type
In SCR denitration, cordierite, diatomite or/and sepiolite are also utilized as just carrier filler, not to catalyst
The performance of active component plays castering action.
In conclusion still changing in the prior art without a kind of mineral that can reach higher denitration efficiency at 200 DEG C or less
Property integrated low temperature SCR denitration.
Invention content
The technical problem to be solved by the present invention is to：A kind of integral honeycomb low temperature SCR denitration catalyst and its system are provided
Preparation Method, the low temperature range which uses are 200 DEG C~100 DEG C, by by percentage to the quality 1~
10% modified Nano mineral fibres, 80~98% TiO2With 1~10% metal oxide Fe2O3-MnO2、CuO-MnO2Or
CeO2-MnO2It is composite modified to have carried out joint using the nanofiber miberal powder after anion-modified to Mn bases catalyst for composition,
Surface can adsorb catalyst granules, and intert form gas passage mutually, overcome in the prior art still without a kind of energy
The defect of enough mineral modified integrated low temperature SCR denitrations for reaching higher denitration efficiency at 200 DEG C or less.
Technical solution is used by the present invention solves the technical problem：A kind of integral honeycomb low temperature SCR denitration catalysis
Agent, wherein the active constituent of SCR denitration by by percentage to the quality be 1~10% modified Nano mineral fibres, 80~
98% TiO2With 1~10% metal oxide Fe2O3-MnO2、CuO-MnO2Or CeO2-MnO2Composition, honeycomb ceramic carrier
Overall dimensions be 26.3~50.5cm × 26.3~50.5cm × 10~15cm, the aperture in each cellular through-hole duct is side
The wall thickness of the square of long 1~2cm, duct is 0.3~0.5cm, and the length in duct is 10~15cm, and through-hole number is 1200,
Cellular through-hole duct is interspersed mutually to form gas passage, and the low temperature range is 200 DEG C~100 DEG C.
A kind of preparation method of above-mentioned integral honeycomb low temperature SCR denitration catalyst, is as follows：
The first step prepares titanium-metal oxide sol：
It uses four fourth fat of metatitanic acid for titanium source, is mixed with absolute ethyl alcohol, the volume ratio of butyl titanate and absolute ethyl alcohol is 1:
4, be added any one nitrate in manganese nitrate and ferric nitrate, copper nitrate or cobalt nitrate in mixed process, manganese nitrate with
The molal weight ratio of any one nitrate in ferric nitrate, copper nitrate or cobalt nitrate is 1:1, sol system is formed, and at this
Mass percent concentration is added in sol system is for 95% concentrated nitric acid and pure acetic acid, the volume ratio of the concentrated nitric acid and pure acetic acid
1:10, the pH value of the sol system is adjusted to 0.9~1, titanium-metal oxide sol is thus made；
Second step prepares modified Nano mineral fibres：
Processing is modified to nano mineral fiber using anion surfactant, raw material nano mineral fibres is added
In the deionized water of 10 times of its quality, and the anion surfactant that mass ratio is 1~5% is added, 1h is stirred, after suction filtration
It is dry, modified Nano mineral fibres is made；
Third walks, and prepares the colloidal sol suspension of titanium-metal oxide and modified Nano mineral fibres：
Modified Nano mineral fibres made from above-mentioned second step is added to titanium-metal oxide made from the above-mentioned first step
In colloidal sol, the addition of the modified Nano mineral fibres is the 5~10% of titanium-metal oxide sol quality, in dispersion machine
It is persistently stirred 12~24 hours with 150~300 revs/min of rotating speeds, it is fine with modified Nano mineral that titanium-metal oxide is consequently formed
The colloidal sol suspension of dimension；
4th step prepares ceramic honeycomb idiosome：
Based on cordierite or kaolin, in mass ratio 10: 1 incorporation calcium oxide, talcum, clay, diatomite or expansion
Arbitrary three kinds in soil, the incorporation of these three mineral is respectively the one third for mixing total amount, and liquid is used after carrying out vacuum mud refining
It extrudes out, machine is pressed into ceramic honeycomb idiosome, is then dried under the conditions of temperature is controlled at 80~120 DEG C, is thus made whole
Body size is 26.3~50.5cm × 26.3~50.5cm × 10~15cm, and the aperture in each cellular through-hole duct is the length of side 1
The wall thickness of the square of~2cm, duct is 0.3~0.5cm, and the length in duct is 10~15cm, and through-hole number is 1200, honeycomb
Intert the ceramic honeycomb idiosome for forming gas passage mutually in shape through-hole duct；
5th step impregnates ceramic honeycomb idiosome：
By ceramic honeycomb idiosome made from above-mentioned 4th step be immersed in above-mentioned third step titanium-metal oxide obtained with
In the colloidal sol suspension of modified Nano mineral fibres, temperature control is 1~2 hour in 25 DEG C of room temperature, dip time, is thus completed
Impregnate ceramic honeycomb idiosome；
6th step prepares integral honeycomb low temperature SCR denitration catalyst：
Above-mentioned 5th step is completed into dipping titanium-metal oxide and the bee after the colloidal sol suspension of modified Nano mineral fibres
Nest shape ceramic idiosome is taken out, and is roasted under the conditions of 450~500 DEG C and the 5~7h that anneals, heating rate are 5~10 DEG C/min, moved back
5~10 DEG C/min of rate at top speed form Detitanium-ore-type TiO2, Mn2+It is converted to Mn3+And Mn4+, integral honeycomb low temperature is thus made
SCR denitration, wherein SCR denitration by 1~10% modified Nano mineral fibres by percentage to the quality, 80~
98% TiO2With 1~10% metal oxide Fe2O3-MnO2、CuO-MnO2Or CeO2-MnO2Composition, honeycomb ceramic carrier
Overall dimensions be 26.3~50.5cm × 26.3~50.5cm × 10~15cm, the aperture in each cellular through-hole duct is side
The wall thickness of the square of long 1~2cm, duct is 0.3~0.5cm, and the length in duct is 10~15cm, and through-hole number is 1200,
After tested, the low temperature range is 200 DEG C~100 DEG C.
A kind of preparation method of above-mentioned integral honeycomb low-temperature SCR catalyst, the anion surfactant are 12
Sodium alkyl sulfonate, lauryl sodium sulfate or neopelex.
A kind of preparation method of above-mentioned integral honeycomb low-temperature SCR catalyst, involved raw material, reagent and equipment are logical
It crosses known approach to obtain, raw material nano mineral fibres source is operative employee obtained by method disclosed in ZL200910070297.8
Skill is that those skilled in the art will appreciate that.
Compared with prior art, the present invention has following substantive distinguishing features outstanding：
(1) the nano mineral fiber surface in a kind of integral honeycomb low temperature SCR denitration catalyst of the present invention can be adsorbed
A certain amount of catalyst granules, and intert form gas passage mutually, NO in flue gas can be promotedxDiffusion in the catalyst
And absorption.In addition SiO possessed by nano mineral fiber itself2It is formed firmly with ceramic idiosome in roasting process at branch
Chemical bond improves catalyst in the intensity of load on ceramic idiosome surface, and then can improve integrated low temperature denitrating catalyst
Service life.
(2) the metal oxide Fe in a kind of integral honeycomb low temperature SCR denitration catalyst of the present invention2O3-MnO2、CuO-
MnO2Or Co2O3-MnO2With good low-temperature denitration performance, wherein above-mentioned three kinds of transition metal elements can be formed with Mn atoms
Share electron pair form, contributes to NOxOxidation and NH3Certain embodiments.
(3) a kind of preparation method of integral honeycomb low temperature SCR denitration catalyst of the present invention uses anion-modified for the first time
Nano mineral fiber afterwards has carried out Mn bases catalyst that joint is composite modified, loaded modified nano mineral fiber rear catalyst
Significant change can occur for pattern, and the porosity of catalyst can also be promoted because of the addition of modified Nano mineral fibres, and then be catalyzed
The low-temperature denitration performance of agent has been significantly improved.
(4) present invention and the essential distinction of prior art CN106166493A are, a kind of integral honeycomb of the present invention
Low temperature SCR denitration catalyst is a kind of supported modified catalyst of multielement.
(5) present invention and the essential distinction of prior art CN106582642A are, a kind of integral honeycomb of the present invention
The low-temperature SCR catalytic effect of the active component used in low temperature SCR denitration catalyst is apparent.
(6) present invention and the essential distinction of prior art CN102407073A are, a kind of integral honeycomb of the present invention
The preparation method of low temperature SCR denitration catalyst is catalyzed for a step, has no the supplementary means such as additional microwave.
(7) present invention and the essential distinction of the prior art CN106582642A and CN103433034B are, the present invention
A kind of integral honeycomb low temperature SCR denitration catalyst avoids using the carbon-based material conduct that oxygenolysis can occur at 200 DEG C
Carrier.
(8) present invention and the essential distinction of prior art CN102614890B are, a kind of integral honeycomb of the present invention
TiO in low temperature SCR denitration catalyst2Water resistant and sulphur poison performance higher.
(9) present invention and the essential distinction of the prior art CN101444727A and CN103785407B are, the present invention
A kind of integral honeycomb low temperature SCR denitration catalyst is the low temperature SCR denitration catalyst being suitable within the scope of 200 DEG C~100 DEG C.
(10) present invention with the prior art CN106179301A, CN101721993A, CN104785246A and
The essential distinction of CN103816919B is, a kind of preparation method of integral honeycomb low temperature SCR denitration catalyst of the present invention
The modified Nano mineral fibres with nanostructure is used to be modified the reuniting effect of catalyst granules.
(11) present invention and the essential distinction of prior art CN102114424A are, a kind of integral honeycomb of the present invention
Modified Nano mineral fibres not only as filler or is loaded substitute by the preparation method of low temperature SCR denitration catalyst, and
Modified Nano mineral fibres as promotion catalyst dispersity and is promoted into Mn2+Oxidation one is indispensable to be modified to separate
Enter, the utilization and analysis to modified Nano mineral fibres are more deep and thorough.
Compared with prior art, the present invention has following marked improvement
(1) a kind of preparation method of integral honeycomb low temperature SCR denitration catalyst of the present invention uses a step impregnation-calcination method
Integrated low temperature denitrating catalyst is prepared, reduces the roasting number of carrier cordierite ceramic, reduces being prepared into for catalyst
This.Simultaneously as carrier inside touches NOxThe probability of gas is extremely low, and a kind of integral honeycomb low temperature SCR denitration of the present invention is urged
Catalyst component is not added in the preparation process of ceramic idiosome in the preparation method of agent, only with dipping means by mine
For object composite catalyzing material load on ceramic monolith surface, high degree reduces the dosage of catalyst, further saves monoblock type
The manufacturing cost of low-temperature denitration catalyst.
(2) modified Nano mineral are introduced in a kind of preparation method of integral honeycomb low temperature SCR denitration catalyst of the present invention
The purpose of fiber is to ensure the constant situation of calcination temperature in preparation process, promote the dispersibility of catalyst granules
Under, that is, ensure Detitanium-ore-type TiO2Under conditions of generation, Mn is promoted as far as possible2+With the contact probability of air, significantly promote
Mn2+Oxidation process.
(3) NO of a kind of integral honeycomb low temperature SCR denitration catalyst of the inventionxHigh conversion rate, can be at 150 DEG C
Reach 90% denitration efficiency, actual test proves as follows：
Test equipment is：The KM940 type flue gas analyzers of Kane companies of Britain production；
Test condition is：
1) NO=NH3=800ppm；
2)O2=8%, N2For carrier gas；
3) total flow=1L/min；
4) air speed GHSV=50,000h-1。
Test result is：
Catalytic efficiency can reach 80% at 100 DEG C, and catalytic efficiency can reach 90% at 150 DEG C, catalyst at 200 DEG C
Efficiency reaches 99%.
Specific implementation mode
Embodiment 1
A kind of integral honeycomb low temperature SCR denitration catalyst of the present embodiment, wherein SCR denitration activity at
Point by be by percentage to the quality 5% modified Nano mineral fibres, 85% TiO2With 10% metal oxide Fe2O3-MnO2
The overall dimensions of composition, honeycomb ceramic carrier are 38.4cm × 38.4cm × 12.5cm, the aperture in each cellular through-hole duct
Wall thickness for the square of length of side 1.5cm, duct is 0.4cm, and the length in duct is 12.5cm, and through-hole number is 1200, honeycomb
Shape through-hole duct is interspersed mutually to form gas passage, and the low temperature range is 200 DEG C~100 DEG C.
A kind of preparation method of above-mentioned integral honeycomb low temperature SCR denitration catalyst, is as follows：
The first step prepares titanium-metal oxide sol：
It uses four fourth fat of metatitanic acid for titanium source, is mixed with absolute ethyl alcohol, the volume ratio of butyl titanate and absolute ethyl alcohol is 1:
4, manganese nitrate and ferric nitrate are added in mixed process, manganese nitrate is 1 with ferric nitrate molal weight ratio:1, form sol body
System, and concentrated nitric acid and the pure acetic acid that mass percent concentration is 95%, the concentrated nitric acid and pure acetic acid are added in the sol system
Volume ratio be 1:10, the pH value of the sol system is adjusted to 0.95, titanium-metal oxide sol is thus made；
Second step prepares modified Nano mineral fibres：
Processing is modified to nano mineral fiber using anion surfactant, raw material nano mineral fibres is added
In the deionized water of 10 times of its quality, and the dodecyl sodium sulfate that mass ratio is 2.5% is added, stirs 1h, done after suction filtration
It is dry, modified Nano mineral fibres is made；
Third walks, and prepares the colloidal sol suspension of titanium-metal oxide and modified Nano mineral fibres：
Modified Nano mineral fibres made from above-mentioned second step is added to titanium-metal oxide made from the above-mentioned first step
In colloidal sol, the addition of the modified Nano mineral fibres is the 7.5% of titanium-metal oxide sol quality, in dispersion machine with
175 revs/min of rotating speeds persistently stir 18 hours, and titanium-metal oxide is consequently formed and the colloidal sol of modified Nano mineral fibres is outstanding
Turbid；
4th step prepares ceramic honeycomb idiosome：
Based on cordierite or kaolin, in mass ratio 10: 1 incorporation calcium oxide, diatomite and swelled ground, these three mines
The incorporation of object is respectively the one third for mixing total amount, is squeezed out with hydraulic pressure after carrying out vacuum mud refining, machine is pressed into cellular pottery
Porcelain idiosome, then temperature control at 100 DEG C under the conditions of dry, thus be made overall dimensions be 38.4cm × 38.4cm ×
The aperture of 12.5cm, each cellular through-hole duct are the square of length of side 1.5cm, and the wall thickness in duct is 0.4cm, the length in duct
Degree is 12.5cm, and through-hole number is 1200, and the ceramic honeycomb idiosome for forming gas passage is interted mutually in cellular through-hole duct；
5th step impregnates ceramic honeycomb idiosome：
By ceramic honeycomb idiosome made from above-mentioned 4th step be immersed in above-mentioned third step titanium-metal oxide obtained with
In the colloidal sol suspension of modified Nano mineral fibres, temperature control is 1.5 hours in 25 DEG C of room temperature, dip time, is thus completed
Impregnate ceramic honeycomb idiosome；
6th step prepares integral honeycomb low temperature SCR denitration catalyst：
Above-mentioned 5th step is completed into dipping titanium-metal oxide and the bee after the colloidal sol suspension of modified Nano mineral fibres
Nest shape ceramic idiosome is taken out, and is roasted under the conditions of 475 DEG C and the 6h that anneals, heating rate are 8 DEG C/min, 8 DEG C/minute of annealing rate
Clock forms Detitanium-ore-type TiO2, Mn2+It is converted to Mn3+And Mn4+, integral honeycomb low temperature SCR denitration catalyst is thus made,
In, the active constituent of SCR denitration by be by percentage to the quality 5% modified Nano mineral fibres, 85% TiO2With
10% metal oxide Fe2O3-MnO2The overall dimensions of composition, honeycomb ceramic carrier are 38.4cm × 38.4cm × 12.5cm,
The wall thickness of the square that the aperture in each cellular through-hole duct is length of side 1.5cm, duct is 0.4cm, and the length in duct is
12.5cm, through-hole number are 1200, and cellular through-hole duct is interspersed mutually to form gas passage, after tested, low temperature range 200
DEG C~100 DEG C.
Embodiment 2
A kind of integral honeycomb low temperature SCR denitration catalyst of the present embodiment, wherein SCR denitration activity at
Point by be by percentage to the quality 1% modified Nano mineral fibres, 98% TiO2With 1% metal oxide CuO-MnO2Group
At the overall dimensions of honeycomb ceramic carrier are 26.3cm × 26.3cm × 10cm, and the aperture in each cellular through-hole duct is side
The wall thickness of the square of long 1cm, duct is 0.3cm, and the length in duct is 10cm, and through-hole number is 1200, cellular through-hole hole
Road is interspersed mutually to form gas passage, and the low temperature range is 200 DEG C~100 DEG C.
A kind of preparation method of above-mentioned integral honeycomb low temperature SCR denitration catalyst, is as follows：
The first step prepares titanium-metal oxide sol：
It uses four fourth fat of metatitanic acid for titanium source, is mixed with absolute ethyl alcohol, the volume ratio of butyl titanate and absolute ethyl alcohol is 1:
4, it is added manganese nitrate and copper nitrate in mixed process, the molal weight ratio of manganese nitrate and copper nitrate is 1:1, form sol body
System, and concentrated nitric acid and the pure acetic acid that mass percent concentration is 95%, the concentrated nitric acid and pure acetic acid are added in the sol system
Volume ratio be 1:10, the pH value of the sol system is adjusted to 0.9, titanium-metal oxide sol is thus made；
Second step prepares modified Nano mineral fibres：
Processing is modified to nano mineral fiber using anion surfactant, raw material nano mineral fibres is added
In the deionized water of 10 times of its quality, and the lauryl sodium sulfate that mass ratio is 1% is added, stirs 1h, dried after suction filtration,
Modified Nano mineral fibres is made；
Third walks, and prepares the colloidal sol suspension of titanium-metal oxide and modified Nano mineral fibres：
Modified Nano mineral fibres made from above-mentioned second step is added to titanium-metal oxide made from the above-mentioned first step
In colloidal sol, the addition of the modified Nano mineral fibres is the 5% of titanium-metal oxide sol quality, with 150 in dispersion machine
Rev/min rotating speed persistently stirs 12 hours, and titanium-metal oxide is consequently formed and the colloidal sol of modified Nano mineral fibres is suspended
Liquid；
4th step prepares ceramic honeycomb idiosome：
Based on cordierite or kaolin, in mass ratio 10: 1 incorporation talcums, clay and diatomite, these three mineral
Incorporation is respectively the one third for mixing total amount, is squeezed out with hydraulic pressure after carrying out vacuum mud refining, machine is pressed into ceramic honeycomb embryo
Then body is dried under the conditions of temperature is controlled at 80 DEG C, it is 26.3cm × 26.3cm × 10cm that overall dimensions, which are thus made, each
The aperture in cellular through-hole duct is the square of length of side 1cm, and the wall thickness in duct is 0.3cm, and the length in duct is 10cm, through-hole
Number is 1200, and the ceramic honeycomb idiosome for forming gas passage is interted mutually in cellular through-hole duct；
5th step impregnates ceramic honeycomb idiosome：
By ceramic honeycomb idiosome made from above-mentioned 4th step be immersed in above-mentioned third step titanium-metal oxide obtained with
In the colloidal sol suspension of modified Nano mineral fibres, in 25 DEG C of room temperature, dip time is 1 hour, thus completes leaching for temperature control
Stain ceramic honeycomb idiosome；
6th step prepares integral honeycomb low temperature SCR denitration catalyst：
Above-mentioned 5th step is completed into dipping titanium-metal oxide and the bee after the colloidal sol suspension of modified Nano mineral fibres
Nest shape ceramic idiosome is taken out, and is roasted under the conditions of 450 DEG C and the 5h that anneals, heating rate are 5 DEG C/min, 5 DEG C/minute of annealing rate
Clock forms Detitanium-ore-type TiO2, Mn2+It is converted to Mn3+And Mn4+, integral honeycomb low temperature SCR denitration catalyst is thus made,
In, the active constituent of SCR denitration by be by percentage to the quality 1% modified Nano mineral fibres, 98% TiO2With
1% metal oxide CuO-MnO2The overall dimensions of composition, honeycomb ceramic carrier are 26.3cm × 26.3cm × 10cm, each
The aperture in cellular through-hole duct is the square of length of side 1cm, and the wall thickness in duct is 0.3cm, and the length in duct is 10cm, through-hole
Number is 1200, and cellular through-hole duct is interspersed mutually to form gas passage, and after tested, low temperature range is 200 DEG C~100 DEG C.
Embodiment 3
A kind of integral honeycomb low temperature SCR denitration catalyst, wherein the active constituent of SCR denitration is by with quality
Percentages be 10% modified Nano mineral fibres, 80% TiO2With 10% metal oxide CeO2-MnO2Composition, honeycomb
The overall dimensions of ceramic monolith are 50.5cm × 50.5cm × 15cm, and the aperture in each cellular through-hole duct is length of side 2cm's
The wall thickness of square, duct is 0.5cm, and the length in duct is 15cm, and through-hole number is 1200, and cellular through-hole duct is worn mutually
It inserts and forms gas passage, the low temperature range is 200 DEG C~100 DEG C.
A kind of preparation method of above-mentioned integral honeycomb low temperature SCR denitration catalyst, is as follows：
The first step prepares titanium-metal oxide sol：
It uses four fourth fat of metatitanic acid for titanium source, is mixed with absolute ethyl alcohol, the volume ratio of butyl titanate and absolute ethyl alcohol is 1:
4, it is added in manganese nitrate and cobalt nitrate in mixed process, the molal weight ratio of manganese nitrate and cobalt nitrate is 1:1, form colloidal sol
System, and concentrated nitric acid and the pure acetic acid that mass percent concentration is 95%, the concentrated nitric acid and pure vinegar are added in the sol system
The volume ratio of acid is 1:10, the pH value of the sol system is adjusted to 1, titanium-metal oxide sol is thus made；
Second step prepares modified Nano mineral fibres：
Processing is modified to nano mineral fiber using anion surfactant, raw material nano mineral fibres is added
In the deionized water of 10 times of its quality, and the neopelex that mass ratio is 5% is added, stirs 1h, done after suction filtration
It is dry, modified Nano mineral fibres is made；
Third walks, and prepares the colloidal sol suspension of titanium-metal oxide and modified Nano mineral fibres：
Modified Nano mineral fibres made from above-mentioned second step is added to titanium-metal oxide made from the above-mentioned first step
In colloidal sol, the addition of the modified Nano mineral fibres is the 10% of titanium-metal oxide sol quality, in dispersion machine with
300 revs/min of rotating speeds persistently stir 24 hours, and titanium-metal oxide is consequently formed and the colloidal sol of modified Nano mineral fibres is outstanding
Turbid；
4th step prepares ceramic honeycomb idiosome：
Based on cordierite or kaolin, in mass ratio 10: 1 incorporation calcium oxide, clay and swelled ground, these three mineral
Incorporation be respectively mix total amount one third, carry out vacuum mud refining after squeezed out with hydraulic pressure, machine is pressed into ceramic honeycomb
Then idiosome is dried under the conditions of temperature is controlled at 120 DEG C, it is 50.5cm × 50.5cm × 15cm that overall dimensions, which are thus made,
The wall thickness of the square that the aperture in each cellular through-hole duct is length of side 2cm, duct is 0.5cm, and the length in duct is 15cm,
Through-hole number is 1200, and the ceramic honeycomb idiosome for forming gas passage is interted mutually in cellular through-hole duct；
5th step impregnates ceramic honeycomb idiosome：
By ceramic honeycomb idiosome made from above-mentioned 4th step be immersed in above-mentioned third step titanium-metal oxide obtained with
In the colloidal sol suspension of modified Nano mineral fibres, in 25 DEG C of room temperature, dip time is 2 hours, thus completes leaching for temperature control
Stain ceramic honeycomb idiosome；
6th step prepares integral honeycomb low temperature SCR denitration catalyst：
Above-mentioned 5th step is completed into dipping titanium-metal oxide and the bee after the colloidal sol suspension of modified Nano mineral fibres
Nest shape ceramic idiosome is taken out, and is roasted under the conditions of 500 DEG C and the 7h that anneals, heating rate are 10 DEG C/min, and 10 DEG C of annealing rate/
Minute, form Detitanium-ore-type TiO2, Mn2+It is converted to Mn3+And Mn4+, integral honeycomb low temperature SCR denitration catalyst is thus made,
Wherein, the active constituent of SCR denitration by be by percentage to the quality 10% modified Nano mineral fibres, 80% TiO2
With 10% metal oxide CeO2-MnO2The overall dimensions of composition, honeycomb ceramic carrier are 50.5cm × 50.5cm × 15cm,
The wall thickness of the square that the aperture in each cellular through-hole duct is length of side 2cm, duct is 0.5cm, and the length in duct is 15cm,
Through-hole number is 1200, and cellular through-hole duct is interspersed mutually to form gas passage, and after tested, the low temperature range is 200 DEG C
~100 DEG C.
A kind of NO of integral honeycomb low temperature SCR denitration catalyst made from above three embodimentsxConversion ratio is practical to be surveyed
Under test result：
Test equipment is：The KM940 type flue gas analyzers of Kane companies of Britain production；
Test condition is：
1) NO=NH3=800ppm；
2)O2=8%, N2For carrier gas；
3) total flow=1L/min；
4) air speed GHSV=50,000h-1。
Test result is：
Catalytic efficiency can reach 80% at 100 DEG C, and catalytic efficiency can reach 90% at 150 DEG C, catalyst at 200 DEG C
Efficiency reaches 99%.
In above-described embodiment, involved raw material, reagent and equipment are obtained by known approach, and raw material nano mineral are fine
It is obtained by method disclosed in ZL200910070297.8 to tie up source, and operating procedure is that those skilled in the art will appreciate that.
Claims (3)
1. a kind of integral honeycomb low temperature SCR denitration catalyst, it is characterised in that：Wherein, the active constituent of SCR denitration
By be by percentage to the quality 1~10% modified Nano mineral fibres, 80~98% TiO2With 1~10% metal oxide
Fe2O3-MnO2、CuO-MnO2Or CeO2-MnO2Composition, the overall dimensions of honeycomb ceramic carrier be 26.3~50.5cm × 26.3~
The aperture of 50.5cm × 10~15cm, each cellular through-hole duct is the square of 1~2cm of the length of side, and the wall thickness in duct is 0.3
The length of~0.5cm, duct are 10~15cm, and through-hole number is 1200, and the interspersed gas that formed leads to mutually in cellular through-hole duct
Road, the low temperature range are 200 DEG C~100 DEG C.
2. a kind of preparation method of integral honeycomb low temperature SCR denitration catalyst, it is characterised in that be as follows：
The first step prepares titanium-metal oxide sol：
It uses four fourth fat of metatitanic acid for titanium source, is mixed with absolute ethyl alcohol, the volume ratio of butyl titanate and absolute ethyl alcohol is 1:4,
Any one nitrate in manganese nitrate and ferric nitrate, copper nitrate or cobalt nitrate, manganese nitrate and nitric acid are added in mixed process
The molal weight ratio of any one nitrate in iron, copper nitrate or cobalt nitrate is 1:1, sol system is formed, and in the colloidal sol
The volume ratio of the concentrated nitric acid and pure acetic acid that addition mass percent concentration is 95% in system, the concentrated nitric acid and pure acetic acid is 1:10,
The pH value of the sol system is adjusted to 0.9~1, titanium-metal oxide sol is thus made；
Second step prepares modified Nano mineral fibres：
Processing is modified to nano mineral fiber using anion surfactant, raw material nano mineral fibres is added 10 times
In the deionized water of its quality, and the anion surfactant that mass ratio is 1~5% is added, stirs 1h, dried after suction filtration,
Modified Nano mineral fibres is made；
Third walks, and prepares the colloidal sol suspension of titanium-metal oxide and modified Nano mineral fibres：
Modified Nano mineral fibres made from above-mentioned second step is added to titanium-metal oxide sol made from the above-mentioned first step
In, the addition of the modified Nano mineral fibres is the 5~10% of titanium-metal oxide sol quality, with 150 in dispersion machine
~300 revs/min of rotating speeds persistently stir 12~24 hours, and titanium-metal oxide and modified Nano mineral fibres is consequently formed
Colloidal sol suspension；
4th step prepares ceramic honeycomb idiosome：
Based on cordierite or kaolin, in mass ratio 10: 1 incorporation calcium oxide, talcum, clay, diatomite or swelled ground
Arbitrary three kinds, the incorporations of these three mineral is respectively the one third for mixing total amount, is squeezed with hydraulic pressure after carrying out vacuum mud refining
Go out, machine is pressed into ceramic honeycomb idiosome, is then dried under the conditions of temperature is controlled at 80~120 DEG C, and whole ruler is thus made
Very little is 26.3~50.5cm × 26.3~50.5cm × 10~15cm, and the aperture in each cellular through-hole duct is 1~2cm of the length of side
Square, the wall thickness in duct is 0.3~0.5cm, and the length in duct is 10~15cm, and through-hole number is 1200, cellular logical
Intert the ceramic honeycomb idiosome for forming gas passage mutually in hole duct；
5th step impregnates ceramic honeycomb idiosome：
Ceramic honeycomb idiosome made from above-mentioned 4th step is immersed in above-mentioned third step titanium-metal oxide obtained and modification
In the colloidal sol suspension of nano mineral fiber, in 25 DEG C of room temperature, dip time is 1~2 hour, thus completes dipping for temperature control
Ceramic honeycomb idiosome；
6th step prepares integral honeycomb low temperature SCR denitration catalyst：
By above-mentioned 5th step complete dipping titanium-metal oxide with it is cellular after the colloidal sol suspension of modified Nano mineral fibres
Ceramic idiosome is taken out, and is roasted under the conditions of 450~500 DEG C and the 5~7h that anneals, heating rate are 5~10 DEG C/min, annealing speed
5~10 DEG C/min of rate forms Detitanium-ore-type TiO2, Mn2+It is converted to Mn3+And Mn4+, integral honeycomb low-temperature SCR is thus made
Denitrating catalyst, wherein SCR denitration is by 1~10% modified Nano mineral fibres by percentage to the quality, 80~98%
TiO2With 1~10% metal oxide Fe2O3-MnO2、CuO-MnO2Or CeO2-MnO2Composition, the whole ruler of honeycomb ceramic carrier
Very little is 26.3~50.5cm × 26.3~50.5cm × 10~15cm, and the aperture in each cellular through-hole duct is 1~2cm of the length of side
Square, the wall thickness in duct is 0.3~0.5cm, and the length in duct is 10~15cm, and through-hole number is 1200, after tested, institute
It is 200 DEG C~100 DEG C to state low temperature range.
3. a kind of preparation method of integral honeycomb low-temperature SCR catalyst according to claim 2, it is characterised in that：It is described
Anion surfactant is dodecyl sodium sulfate, lauryl sodium sulfate or neopelex.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810172992.4A CN108295865B (en) | 2018-03-02 | 2018-03-02 | Integral honeycomb low-temperature SCR denitration catalyst and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810172992.4A CN108295865B (en) | 2018-03-02 | 2018-03-02 | Integral honeycomb low-temperature SCR denitration catalyst and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN108295865A true CN108295865A (en) | 2018-07-20 |
| CN108295865B CN108295865B (en) | 2024-03-22 |
Family
ID=62848967
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201810172992.4A Active CN108295865B (en) | 2018-03-02 | 2018-03-02 | Integral honeycomb low-temperature SCR denitration catalyst and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN108295865B (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110841653A (en) * | 2019-08-28 | 2020-02-28 | 南京晓庄学院 | Preparation method of low-temperature denitration catalyst |
| CN110937881A (en) * | 2018-09-25 | 2020-03-31 | 中国石油化工股份有限公司 | Integral titanium oxide-aluminum oxide material and preparation method thereof |
| CN111375375A (en) * | 2018-12-29 | 2020-07-07 | 中国石油化工股份有限公司 | Desulfurization adsorbent and preparation method thereof |
| CN113912411A (en) * | 2021-09-22 | 2022-01-11 | 云南菲尔特环保科技股份有限公司 | Cordierite thermal shock-resistant thin-wall catalyst carrier and preparation method thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102614890A (en) * | 2012-04-01 | 2012-08-01 | 江西中科凯瑞环保催化有限公司 | Honeycomb integrated selective catalytic reduction (SCR) catalyst for nitric acid and nitrate tail gas denitration |
| CN102755887A (en) * | 2012-08-07 | 2012-10-31 | 江苏龙源催化剂有限公司 | Preparation method of semiconductor control rectifier (SCR) denitration catalytic agent applicable to high temperature smoke condition |
| CN105289676A (en) * | 2015-10-27 | 2016-02-03 | 展宗城 | Foam-like low-temperature SCR catalyst and preparation method thereof |
| JP2017170308A (en) * | 2016-03-22 | 2017-09-28 | 株式会社日本触媒 | Method for producing honeycomb type denitration catalyst |
-
2018
- 2018-03-02 CN CN201810172992.4A patent/CN108295865B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102614890A (en) * | 2012-04-01 | 2012-08-01 | 江西中科凯瑞环保催化有限公司 | Honeycomb integrated selective catalytic reduction (SCR) catalyst for nitric acid and nitrate tail gas denitration |
| CN102755887A (en) * | 2012-08-07 | 2012-10-31 | 江苏龙源催化剂有限公司 | Preparation method of semiconductor control rectifier (SCR) denitration catalytic agent applicable to high temperature smoke condition |
| CN105289676A (en) * | 2015-10-27 | 2016-02-03 | 展宗城 | Foam-like low-temperature SCR catalyst and preparation method thereof |
| JP2017170308A (en) * | 2016-03-22 | 2017-09-28 | 株式会社日本触媒 | Method for producing honeycomb type denitration catalyst |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110937881A (en) * | 2018-09-25 | 2020-03-31 | 中国石油化工股份有限公司 | Integral titanium oxide-aluminum oxide material and preparation method thereof |
| CN111375375A (en) * | 2018-12-29 | 2020-07-07 | 中国石油化工股份有限公司 | Desulfurization adsorbent and preparation method thereof |
| CN110841653A (en) * | 2019-08-28 | 2020-02-28 | 南京晓庄学院 | Preparation method of low-temperature denitration catalyst |
| CN110841653B (en) * | 2019-08-28 | 2023-03-03 | 南京晓庄学院 | Preparation method of low-temperature denitration catalyst |
| CN113912411A (en) * | 2021-09-22 | 2022-01-11 | 云南菲尔特环保科技股份有限公司 | Cordierite thermal shock-resistant thin-wall catalyst carrier and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN108295865B (en) | 2024-03-22 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN108295865A (en) | A kind of integral honeycomb low temperature SCR denitration catalyst and preparation method thereof | |
| CN107570163B (en) | A kind of support type VOCs catalyst for catalytic combustion and preparation method thereof | |
| JP6595088B2 (en) | SCR catalyst for removing nitrogen oxides and method for producing the same | |
| CN104056658B (en) | Low-temperature sulfur-resistant denitration catalyst and preparing method thereof | |
| CN102698810B (en) | Honeycomb type denitration catalyst and preparation method thereof | |
| CN109569587A (en) | A kind of manganese-based low-temperature catalyst for denitrating flue gas and preparation method thereof | |
| KR101629483B1 (en) | Vanadium-based denitration catalyst and preparing method of the same | |
| CN108067296A (en) | A kind of preparation method of cellular Mn based low-temperature denitration catalysts | |
| CN108067291B (en) | A kind of preparation method of honeycomb rare earth based denitration catalyst | |
| CN106076318A (en) | A kind of preparation method of integral catalyzer | |
| CN106944093B (en) | A kind of Ca-Ti ore type honeycomb monolith methane catalytic combustion catalyst and preparation method thereof | |
| CN112657552B (en) | Vanadium phosphorus oxygen low-temperature denitration catalyst and molding preparation method thereof | |
| CN106268786A (en) | A kind of low-temperature denitration catalyst and preparation method thereof | |
| CN111530471A (en) | Ferromanganese composite oxide based monolithic denitration catalyst and preparation method thereof | |
| CN104923213B (en) | A kind of nontoxic rare-earth type denitrating catalyst and its preparation method and application | |
| CN105727934B (en) | A kind of foramen magnum-mesoporous TiO2Denitrating catalyst of containing transition metal and preparation method thereof | |
| CN106824174A (en) | A kind of coccoid catalyst of high-efficient purification nitrogen oxides and preparation method thereof | |
| JPH02502445A (en) | Catalyst and its manufacturing method | |
| CN109603808B (en) | Preparation method and application of zirconium pillared montmorillonite-loaded Ce-Nb composite catalyst | |
| CN104415763A (en) | Modified diatomite and preparation method thereof | |
| CN104415766A (en) | Coal-fired power station flue gas denitration composite catalyst and preparation method thereof | |
| CN112717967A (en) | Rare earth-based medium-low temperature SCR catalyst and preparation method thereof | |
| KR20190104707A (en) | Catalyst for selectively reducing nitric oxide and nitric oxide reduction system using the same | |
| CN112642450A (en) | Preparation method of phosphorus-doped carbon aerogel supported manganese cerium catalyst | |
| JP3765942B2 (en) | Exhaust gas purification catalyst compound, catalyst containing the compound, and process for producing the same |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |