CN107321343A - One kind is without vanadium denitration catalyst and preparation method thereof - Google Patents
One kind is without vanadium denitration catalyst and preparation method thereof Download PDFInfo
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- CN107321343A CN107321343A CN201710432875.2A CN201710432875A CN107321343A CN 107321343 A CN107321343 A CN 107321343A CN 201710432875 A CN201710432875 A CN 201710432875A CN 107321343 A CN107321343 A CN 107321343A
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- 239000003054 catalyst Substances 0.000 title claims abstract description 110
- 238000002360 preparation method Methods 0.000 title claims abstract description 33
- 229910052720 vanadium Inorganic materials 0.000 title claims abstract description 32
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 title claims abstract description 32
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 27
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 27
- 239000000463 material Substances 0.000 claims abstract description 26
- 239000010936 titanium Substances 0.000 claims abstract description 25
- 239000000843 powder Substances 0.000 claims abstract description 24
- 238000002156 mixing Methods 0.000 claims abstract description 20
- 239000002243 precursor Substances 0.000 claims abstract description 19
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims abstract description 18
- 229910052721 tungsten Inorganic materials 0.000 claims abstract description 16
- 239000010937 tungsten Substances 0.000 claims abstract description 16
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims abstract description 15
- 229910052750 molybdenum Inorganic materials 0.000 claims abstract description 15
- 239000011733 molybdenum Substances 0.000 claims abstract description 15
- 229910052761 rare earth metal Inorganic materials 0.000 claims abstract description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 13
- 150000002910 rare earth metals Chemical class 0.000 claims abstract description 11
- 238000006555 catalytic reaction Methods 0.000 claims abstract description 10
- 239000011148 porous material Substances 0.000 claims abstract description 9
- 239000012065 filter cake Substances 0.000 claims abstract description 3
- 230000001105 regulatory effect Effects 0.000 claims abstract description 3
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 33
- 238000000034 method Methods 0.000 claims description 23
- 239000002253 acid Substances 0.000 claims description 15
- 239000003795 chemical substances by application Substances 0.000 claims description 10
- 239000002202 Polyethylene glycol Substances 0.000 claims description 9
- 229920001223 polyethylene glycol Polymers 0.000 claims description 9
- 229910001404 rare earth metal oxide Inorganic materials 0.000 claims description 4
- 238000005245 sintering Methods 0.000 claims description 3
- 244000275012 Sesbania cannabina Species 0.000 claims description 2
- 239000008367 deionised water Substances 0.000 claims description 2
- 229910021641 deionized water Inorganic materials 0.000 claims description 2
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 2
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims 1
- 238000003756 stirring Methods 0.000 abstract description 28
- 239000003546 flue gas Substances 0.000 abstract description 10
- 230000000694 effects Effects 0.000 abstract description 9
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 abstract description 7
- 230000007547 defect Effects 0.000 abstract description 4
- 230000015572 biosynthetic process Effects 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 35
- 239000002002 slurry Substances 0.000 description 20
- 238000004523 catalytic cracking Methods 0.000 description 15
- 238000001035 drying Methods 0.000 description 15
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 14
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 14
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 14
- 238000005406 washing Methods 0.000 description 13
- 238000006243 chemical reaction Methods 0.000 description 12
- RAHZWNYVWXNFOC-UHFFFAOYSA-N sulfur dioxide Inorganic materials O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 description 12
- 235000018660 ammonium molybdate Nutrition 0.000 description 9
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Inorganic materials O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 description 9
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 description 8
- 229940010552 ammonium molybdate Drugs 0.000 description 8
- 239000011609 ammonium molybdate Substances 0.000 description 8
- ODPUKHWKHYKMRK-UHFFFAOYSA-N cerium;nitric acid Chemical compound [Ce].O[N+]([O-])=O ODPUKHWKHYKMRK-UHFFFAOYSA-N 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 8
- 239000002245 particle Substances 0.000 description 8
- AKEJUJNQAAGONA-UHFFFAOYSA-N sulfur trioxide Inorganic materials O=S(=O)=O AKEJUJNQAAGONA-UHFFFAOYSA-N 0.000 description 8
- 235000011114 ammonium hydroxide Nutrition 0.000 description 7
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 description 7
- 239000011259 mixed solution Substances 0.000 description 7
- 238000001556 precipitation Methods 0.000 description 7
- 238000007789 sealing Methods 0.000 description 7
- 229910000349 titanium oxysulfate Inorganic materials 0.000 description 7
- 150000002500 ions Chemical class 0.000 description 6
- 239000013078 crystal Substances 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 5
- 238000001914 filtration Methods 0.000 description 5
- 229910001385 heavy metal Inorganic materials 0.000 description 5
- 238000012545 processing Methods 0.000 description 5
- 150000003863 ammonium salts Chemical class 0.000 description 4
- 230000009286 beneficial effect Effects 0.000 description 4
- 230000003197 catalytic effect Effects 0.000 description 4
- 238000000975 co-precipitation Methods 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- 238000005336 cracking Methods 0.000 description 3
- 238000000151 deposition Methods 0.000 description 3
- 230000008021 deposition Effects 0.000 description 3
- 238000011065 in-situ storage Methods 0.000 description 3
- 238000005360 mashing Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- MSOUIOOSDCFNQJ-UHFFFAOYSA-N [Mo].[W].[Ti] Chemical compound [Mo].[W].[Ti] MSOUIOOSDCFNQJ-UHFFFAOYSA-N 0.000 description 2
- 239000011149 active material Substances 0.000 description 2
- XKMRRTOUMJRJIA-UHFFFAOYSA-N ammonia nh3 Chemical compound N.N XKMRRTOUMJRJIA-UHFFFAOYSA-N 0.000 description 2
- 239000012752 auxiliary agent Substances 0.000 description 2
- UNTBPXHCXVWYOI-UHFFFAOYSA-O azanium;oxido(dioxo)vanadium Chemical compound [NH4+].[O-][V](=O)=O UNTBPXHCXVWYOI-UHFFFAOYSA-O 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 239000003344 environmental pollutant Substances 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 238000001027 hydrothermal synthesis Methods 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 229910003455 mixed metal oxide Inorganic materials 0.000 description 2
- -1 nitric acid rare earth Chemical class 0.000 description 2
- 239000012466 permeate Substances 0.000 description 2
- 231100000719 pollutant Toxicity 0.000 description 2
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 2
- 239000012266 salt solution Substances 0.000 description 2
- 238000012216 screening Methods 0.000 description 2
- 239000004408 titanium dioxide Substances 0.000 description 2
- MAKDTFFYCIMFQP-UHFFFAOYSA-N titanium tungsten Chemical compound [Ti].[W] MAKDTFFYCIMFQP-UHFFFAOYSA-N 0.000 description 2
- 229910052684 Cerium Inorganic materials 0.000 description 1
- 229910052692 Dysprosium Inorganic materials 0.000 description 1
- 229910052691 Erbium Inorganic materials 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 229910052693 Europium Inorganic materials 0.000 description 1
- 229910052688 Gadolinium Inorganic materials 0.000 description 1
- 229910052689 Holmium Inorganic materials 0.000 description 1
- 229910052765 Lutetium Inorganic materials 0.000 description 1
- 229910052779 Neodymium Inorganic materials 0.000 description 1
- GQPLMRYTRLFLPF-UHFFFAOYSA-N Nitrous Oxide Chemical class [O-][N+]#N GQPLMRYTRLFLPF-UHFFFAOYSA-N 0.000 description 1
- 229910052777 Praseodymium Inorganic materials 0.000 description 1
- 229910052773 Promethium Inorganic materials 0.000 description 1
- 229910052772 Samarium Inorganic materials 0.000 description 1
- 229910052771 Terbium Inorganic materials 0.000 description 1
- 229910052775 Thulium Inorganic materials 0.000 description 1
- 229910052769 Ytterbium Inorganic materials 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- QGAVSDVURUSLQK-UHFFFAOYSA-N ammonium heptamolybdate Chemical compound N.N.N.N.N.N.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.[Mo].[Mo].[Mo].[Mo].[Mo].[Mo].[Mo] QGAVSDVURUSLQK-UHFFFAOYSA-N 0.000 description 1
- 230000003321 amplification Effects 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 238000003556 assay Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- XUFUCDNVOXXQQC-UHFFFAOYSA-L azane;hydroxy-(hydroxy(dioxo)molybdenio)oxy-dioxomolybdenum Chemical compound N.N.O[Mo](=O)(=O)O[Mo](O)(=O)=O XUFUCDNVOXXQQC-UHFFFAOYSA-L 0.000 description 1
- 238000010531 catalytic reduction reaction Methods 0.000 description 1
- 230000001413 cellular effect Effects 0.000 description 1
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 description 1
- 239000003426 co-catalyst Substances 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 238000002242 deionisation method Methods 0.000 description 1
- 238000006477 desulfuration reaction Methods 0.000 description 1
- 230000023556 desulfurization Effects 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- KBQHZAAAGSGFKK-UHFFFAOYSA-N dysprosium atom Chemical compound [Dy] KBQHZAAAGSGFKK-UHFFFAOYSA-N 0.000 description 1
- UYAHIZSMUZPPFV-UHFFFAOYSA-N erbium Chemical compound [Er] UYAHIZSMUZPPFV-UHFFFAOYSA-N 0.000 description 1
- OGPBJKLSAFTDLK-UHFFFAOYSA-N europium atom Chemical compound [Eu] OGPBJKLSAFTDLK-UHFFFAOYSA-N 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- UIWYJDYFSGRHKR-UHFFFAOYSA-N gadolinium atom Chemical compound [Gd] UIWYJDYFSGRHKR-UHFFFAOYSA-N 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 229910052602 gypsum Inorganic materials 0.000 description 1
- 239000010440 gypsum Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- KJZYNXUDTRRSPN-UHFFFAOYSA-N holmium atom Chemical compound [Ho] KJZYNXUDTRRSPN-UHFFFAOYSA-N 0.000 description 1
- 238000010237 hybrid technique Methods 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 229910052746 lanthanum Inorganic materials 0.000 description 1
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical group [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- OHSVLFRHMCKCQY-UHFFFAOYSA-N lutetium atom Chemical compound [Lu] OHSVLFRHMCKCQY-UHFFFAOYSA-N 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000001465 metallisation Methods 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- QEFYFXOXNSNQGX-UHFFFAOYSA-N neodymium atom Chemical compound [Nd] QEFYFXOXNSNQGX-UHFFFAOYSA-N 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 238000003199 nucleic acid amplification method Methods 0.000 description 1
- ZYPJORZNHDXKSD-UHFFFAOYSA-N oxotitanium;sulfuric acid Chemical compound [Ti]=O.OS(O)(=O)=O ZYPJORZNHDXKSD-UHFFFAOYSA-N 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 238000005504 petroleum refining Methods 0.000 description 1
- 239000004926 polymethyl methacrylate Substances 0.000 description 1
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 1
- PUDIUYLPXJFUGB-UHFFFAOYSA-N praseodymium atom Chemical compound [Pr] PUDIUYLPXJFUGB-UHFFFAOYSA-N 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- VQMWBBYLQSCNPO-UHFFFAOYSA-N promethium atom Chemical compound [Pm] VQMWBBYLQSCNPO-UHFFFAOYSA-N 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000006722 reduction reaction Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- KZUNJOHGWZRPMI-UHFFFAOYSA-N samarium atom Chemical compound [Sm] KZUNJOHGWZRPMI-UHFFFAOYSA-N 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- GZCRRIHWUXGPOV-UHFFFAOYSA-N terbium atom Chemical compound [Tb] GZCRRIHWUXGPOV-UHFFFAOYSA-N 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- FRNOGLGSGLTDKL-UHFFFAOYSA-N thulium atom Chemical compound [Tm] FRNOGLGSGLTDKL-UHFFFAOYSA-N 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- NAWDYIZEMPQZHO-UHFFFAOYSA-N ytterbium Chemical compound [Yb] NAWDYIZEMPQZHO-UHFFFAOYSA-N 0.000 description 1
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/24—Chromium, molybdenum or tungsten
- B01J23/30—Tungsten
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/86—Catalytic processes
- B01D53/8621—Removing nitrogen compounds
- B01D53/8625—Nitrogen oxides
- B01D53/8628—Processes characterised by a specific catalyst
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/24—Chromium, molybdenum or tungsten
- B01J23/28—Molybdenum
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/64—Pore diameter
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2258/00—Sources of waste gases
- B01D2258/02—Other waste gases
- B01D2258/0283—Flue gases
-
- 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
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Environmental & Geological Engineering (AREA)
- Health & Medical Sciences (AREA)
- Biomedical Technology (AREA)
- Analytical Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Catalysts (AREA)
- Exhaust Gas Treatment By Means Of Catalyst (AREA)
Abstract
The invention discloses one kind without vanadium denitration catalyst and preparation method thereof, step is as follows：(1) by titanium source presoma formation solution；(2) the co-catalysis component precursor being made up of one or both of tungsten source precursor, molybdenum source precursor is formed into solution, and be successively well mixed with the solution of (1)；(3) regulation solution ph is precipitated, filtered to 7~12 after regulating step (2) resulting material is well mixed；(4) filter cake obtained by step (3) is added into water, is tuned into pulpous state, add rare earth source precursor solution, dried, be calcined after mixing, grind to form powder；(5) powder of step (4) is mixed into pulp with one kind in tungsten source precursor solution or molybdenum source precursor solution, after stirring, plus pore creating material, dry, be calcined after mixing, form denitrating catalyst.Denitrating catalyst prepared by the present invention can overcome in the prior art denitrating catalyst activated centre in flue gas it is unbalanced, the unstable defect of activity.
Description
Technical field
The present invention relates to one kind without vanadium denitration catalyst and preparation method thereof, especially a kind of resistance heavy metals of flue gases
The denitrating catalyst preparation method of deposition, the invention belongs to New Inorganic Materials technical field.
Background technology
Nitrogen oxides (NOx) it is one of main atmosphere pollution, emission request is increasingly strict.China《" 12 " are saved
Can the comprehensive programme of work of emission reduction》Middle regulation：By 2015, national discharged nitrous oxides total amount declined 10% than 2010.
The GB13223-2001 that the national environmental protection of in September, 2011 portion is promulgated《Fossil-fuel power plant atmospheric pollutant emission standard》Thermal power plant NOx is arranged
Put concentration and make more strict requirements：Newly-built the 3rd period, enlarging, the coal-burning boiler of reconstruction are provided, NOx highests allow discharge
Concentration is 100mg/m3.What national environmental protection portion was promulgated《Petroleum refining industry pollutant emission standard》It is required that：On July 1st, 2015
Rise, nitrogen oxides requirement is less than 200mg/m in newly-built catalytic cracking unit discharge regenerated flue gas3, special emission limit requires small
In 100mg/m3, on July 1st, 2017, existing enterprise also performed the standard.In numerous gas denitrifying technologies, selective catalysis is also
The technology that it is still international mainstream that former method (Selective Catalytic Reduction, SCR), which is, its NOxRemoval efficiency is reachable
To 80%~90%.Wherein, denitrating catalyst is the core of SCR technology, and developed country just have developed in the eighties in last century
For a series of denitrating catalysts of coal characteristics, boiler type etc., many R＆D institutions of China are coal-fired for China with enterprise
Boiler and catalytic cracking flue gas situation have also carried out a series of research, and develop some denitrating catalysts.
CN201010537130 proposes the method that denitrating catalyst is prepared using hydrothermal method, first by titanium source presoma
With the mixing of tungsten source presoma, it is placed in autoclave and carries out hydro-thermal reaction, be filtered, washed and dried and obtain titanium tungsten powder denitration catalyst
Agent, while can also introduce the elements such as vanadium and molybdenum, prepares multi-metal-oxide catalyst.Catalyst activity component prepared by this method
Crystal grain is small, specific surface area is larger, but by being sufficiently mixed process material aggregation extent of the same race may be caused higher due to no
Phenomenon occurs, and certain influence is had on catalyst activity.
CN201110345605 proposes a kind of preparation method of denitrating catalyst, and tungsten is sequentially added into metatitanic acid slurry
Sour ammonium, ammonium molybdate and ammonium metavanadate, ultrasonic wave mashing, then pH value is adjusted to 4.0~6.5, stand, separate, drying is catalyzed
Agent powder.This method technique is simple, cost is low, but ammonium metavanadate is added with solid, and the dissolubility of vanadium is still to be tested, and vanadium disperses
Although activity very high, SO when uneven2/SO3Conversion ratio can be higher, influences catalyst performance.
CN201210400949 proposes a kind of preparation method of titanium dioxide-tungstic acid composite granule, by para-tungstic acid
Ammonium salt solution is added in metatitanic acid slurries, and directly vacuum drying obtains finished product after stirring.This method technique is simple, but titanium-tungsten
Mixing intensity is relatively low, and the performance to material can have a certain impact.
In summary, the preparation of denitrating catalyst is directed to the mixing of Multimetal oxide, hybrid mode and technique
Difference can not distinguish the denitration performance of catalyst, NO completelyxConversion ratio can reach more than 90%, illustrate special metal oxygen
The catalytic activity of compound is higher, and scattered inequality can still obtain higher NOxConversion ratio.The quality of catalyst overall performance is also
Need to be verified from otherwise sign, while the preparation of catalyst will also take into account the operability of industry amplification.
The content of the invention
It is a primary object of the present invention to provide one kind without vanadium denitration catalyst and preparation method thereof, to overcome prior art
Middle denitrating catalyst activated centre in flue gas is unbalanced, the unstable defect of activity.
The object of the present invention is achieved like this, and a kind of preparation method this method without vanadium denitration catalyst includes following step
Suddenly：
(1) titanium source presoma is dissolved in acid and forms solution；
(2) the co-catalysis component precursor being made up of one or both of tungsten source precursor, molybdenum source precursor is dissolved
Solution is formed, and is successively well mixed with the solution of (1)；
(3) well mixed rear solution ph, to 7~12, is precipitated, filtered obtained by regulating step (2)；
(4) deionized water is added in filter cake obtained by step (3), is tuned into pulpous state, add rare earth source precursor solution, mixing
After uniform, directly it is dried, is calcined, grind to form powder；
(5) one kind in the powder of step (4) and tungsten source precursor solution or molybdenum source precursor solution is mixed into slurry
Shape, after stirring, plus pore creating material, after being well mixed, dry, be calcined, form denitrating catalyst.
Titanium source presoma, tungsten source presoma, molybdenum source presoma, rare earth source presoma, pore creating material are used in the present invention
It is that denitrating catalyst prepares conventional material in the prior art, consumption selects appropriate amount, the present invention also according to process characteristic
It is not any limitation as especially.The present invention has done following preferred.
The preparation method of denitrating catalyst of the present invention, the titanium source presoma is preferably titanyl sulfate or inclined titanium
Acid, the acid is inorganic acid, and the step (1) forms solution with TiO2Meter, content is preferably 15~40g/L.
Tungsten source presoma is preferably secondary in preparation method of the present invention without vanadium denitration catalyst, the step (2)
Ammonium tungstate or ammonium metatungstate, tungsten source presoma is with WO3Meter, titanium source presoma is with TiO2Meter, tungsten source presoma and titanium source forerunner
Body mass ratio is 1.0~10.0:100.
Molybdenum source presoma in preparation method of the present invention without vanadium denitration catalyst, the step (2) is preferably
Ammonium dimolybdate, three ammonium molybdates, ammonium tetramolybdate, the one or more of ammonium heptamolybdate and ammonium octamolybdate, the molybdenum source presoma with
MoO3Meter, titanium source presoma is with TiO2The mass ratio of meter, molybdenum source presoma and titanium source presoma is preferably 1.0~10.0:100.
Preparation method of the present invention without vanadium denitration catalyst, step (4) middle rare earth source presoma is preferably
One or more in nitric acid rare earth, rare earth oxalate, rare earth oxide, rare earth element is lanthanum (La), cerium (Ce), praseodymium (Pr), neodymium
(Nd), promethium (Pm), samarium (Sm), europium (Eu), gadolinium (Gd), terbium (Tb), dysprosium (Dy), holmium (Ho), erbium (Er), thulium (Tm), ytterbium (Yb), lutetium
(Lu) one or more in, rare earth source presoma is with Re2O3Meter, titanium source presoma is with TiO2Meter, step (2) gained is mixed
The mass ratio for closing uniform rear solution middle rare earth source presoma and titanium source presoma is 0.1~10:100；
In preparation method of the present invention without vanadium denitration catalyst, the step (5) mixing time be preferably 10~
60min。
Slurry water contains in preparation method of the present invention without vanadium denitration catalyst, the step (4) and step (5)
Amount preferably 25~55%.
Co-catalysis component presoma in preparation method of the present invention without vanadium denitration catalyst, the step (5)
Consumption is in terms of trioxide, and the titanium source presoma consumption is with TiO2Meter, trioxide and TiO2Mass ratio is preferably 0.5~
2.0:100。
The preparation method of denitrating catalyst of the present invention, the titanium source presoma consumption is with TiO2Meter, the step
(5) pore creating material is the one or more in polyethylene glycol oxide, polymethyl methacrylate, sesbania powder, addition and TiO in2's
Mass ratio is preferably 0.1~1.0:100.
Sintering temperature is best in the preparation method of denitrating catalyst of the present invention, the step (4) and step (5)
For 400~650 DEG C, roasting time is preferably 4~10h.
Pore creating material of the present invention, leaves in catalyst matrix micro- by the use of its own molecular structure as template, after roasting
Hole, increases the microcellular structure of catalyst.
Present invention also offers a kind of denitrating catalyst, it is prepared by the preparation method of above-mentioned denitrating catalyst.
Beneficial effects of the present invention：
(1) using the method for mixing in situ, titanium atom and cocatalyst component is mixed in atomic level, cause follow-up
The crystal produced in coprecipitation process, lattice defect is more, and mixed-metal oxides particle diameter is small and homogeneous, bigger than surface, simultaneously
Improve titanium dioxide crystal turns brilliant temperature, beneficial to the performance of catalytic activity；
(2) rare earth source is added when catalyst co-precipitation material is not calcined, permeates deeper in titanium-tungsten (molybdenum) particle surface,
Connection is closer, disperses evenly, fired rear catalyst activity is more stable；
(3) powder material prepared entered after once roasting, and covered one layer of cocatalyst component on its surface, while plus
Enter polyethylene glycol oxide, also possessed nanometer level microporous while making catalyst particle surface that there are more co-catalysis components to adhere to,
Both heavy metals of flue gases oxide can have been resisted in its surface nonuniform deposition, high catalyst performance can be ensured again.
Embodiment
Embodiments of the invention are elaborated below：The present embodiment is carried out lower premised on technical solution of the present invention
Implement, give detailed embodiment and process, but protection scope of the present invention is not limited to following embodiments, following implementation
The experimental method of unreceipted actual conditions in example, generally according to normal condition.
Catalyst sample and catalytic cracking spent catalyst hybrid technique：Screening takes 20 after the fresh catalyst of preparation is crushed
~40 mesh powders；Vanadium in 40~60 mesh powders, catalytic cracking spent catalyst (LDO) is taken to aoxidize after catalytic cracking spent catalyst screening
Thing content about 1%.Two kinds of powders in mass ratio 1:1 mixing, in air atmosphere, at 350 DEG C, mixes 24h, screens out urge afterwards
Agent powder is evaluated.Fresh catalyst is contacted in mixed process with waste acetic acid, can be urged useless catalytic cracking
Active material vanadium in agent is uneven to be transferred on fresh catalyst, causes fresh catalyst surface reactive material vanadium to aoxidize
Thing concentrates accumulation, causes catalyst Topically active to strengthen, and then can increase the SO of catalyst2/SO3Conversion ratio, reduces denitration catalyst
Agent overall performance.
NOxConversion ratio appreciation condition：Air speed 4000h-1, 350 DEG C of reaction temperature, air inlet NOxFor 600mg/Nm3、SO2For
1000mg/Nm3, ammonia nitrogen ratio be that 1, water content is 10%.
NOx、SO2Method for measurement of concentration：Flue gas continuous on-line analysis instrument, Siemens ULTRAMAT23.
SO2/SO3Conversion ratio assay method：Wet desulfurization of flue gas by limestone-gypsum method device performance acceptance test specification (DL/
T998-2006)。
Following examples are that the present invention is illustrated, and " % " described in embodiment and comparative example refers to quality percentage and contained
Amount.
Embodiment 1：
It will contain with TiO2Meter 500g titanyl sulfate is dissolved in sulfuric acid solution, is added and is contained with WO3Count 22.5g metatungstic acid
Ammonium salt solution, forms and contains TiO2For 35g/L mixed solutions, stir and ammoniacal liquor regulation pH value is gradually added after 2h to 9.5, precipitation is complete
Afterwards, filter, wash；Material after washing is spent into ion water making into the slurry that moisture content is 50% again, added with CeO2Count 40g's
Cerous nitrate solution, stirs after 1.5h, convection drying, 8h is calcined at 620 DEG C；After roasting powder again with WO3Count 7.5g inclined tungsten
Aqueous 30% slurry is made in acid ammonium solution, after stirring add 4g polyethylene glycol oxides, stirring 40min, sealing and standing 24h, drying,
Denitrating catalyst is obtained after 620 DEG C of roasting 8h.Above-mentioned gained fresh catalyst and mixed with catalytic cracking vanadium-containing wasting catalyst high temperature
Close rear catalyst to evaluate respectively, the results are shown in Table 1 data.
Comparative example 1：
Ammonium metatungstate does not use two step addition methods, and remaining is same as Example 1, will contain with TiO2Count 500g sulfuric acid
Oxygen titanium is dissolved in sulfuric acid solution, is added and is contained with WO330g ammonium metatungstate solution is counted, is formed and contains TiO2For 35g/L mixed solutions,
Ammoniacal liquor is gradually added after stirring 2h and adjusts pH value to 9.5, after precipitation is complete, filtering, washing；Again by material deionization after washing
The slurry that moisture content is 50% is made in water, adds with CeO240g cerous nitrate solution is counted, is stirred after 1.5h, convection drying, 620
Denitrating catalyst is obtained after being calcined 8h at DEG C；Aqueous 30% slurry is made in powder again after roasting, and 4g polyoxygenateds are added after stirring
Denitrating catalyst is obtained after ethene, stirring 40min, sealing and standing 24h, drying, 620 DEG C of roasting 8h.Above-mentioned gained fresh catalyst
Agent and evaluated respectively with catalytic cracking vanadium-containing wasting catalyst high temperature mixing rear catalyst, the results are shown in Table 1 data.
Embodiment 2
It will contain with TiO2Meter 500g titanyl sulfate is dissolved in sulfuric acid solution, is added and is contained with MoO3The ammonium molybdate for counting 20g is molten
Liquid, forms and contains TiO2For 35g/L mixed solutions, stir and ammoniacal liquor regulation pH value is gradually added after 2h to 8.5, after precipitation is complete, mistake
Filter, washing；Material after washing is spent into ion water making into the slurry that moisture content is 50% again, added with CeO2Count 30g nitric acid
Cerium solution, stirs after 1.5h, convection drying, 8h is calcined at 600 DEG C；After roasting powder again with MoO3Count 6g ammonium molybdate solution
Aqueous 30% slurry is made, 4g polyethylene glycol oxides, stirring 40min, sealing and standing 24h, drying, 600 DEG C of roastings are added after stirring
Denitrating catalyst is obtained after burning 8h.Above-mentioned gained fresh catalyst and it is catalyzed after being mixed with catalytic cracking vanadium-containing wasting catalyst high temperature
Agent is evaluated respectively, the results are shown in Table 1 data.
Comparative example 2
Added without pore creating material polyethylene glycol oxide, remaining is same as Example 2, will contain with TiO2Count 500g titanyl sulfate
It is dissolved in sulfuric acid solution, adds and contain with MoO320g ammonium molybdate solution is counted, is formed and contains TiO2For 35g/L mixed solutions, stirring
Ammoniacal liquor is gradually added after 2h and adjusts pH value to 8.5, after precipitation is complete, filtering, washing；Material after washing is spent into ion water making again
Into the slurry that moisture content is 50%, add with CeO230g cerous nitrate solution is counted, is stirred after 1.5h, convection drying, at 600 DEG C
It is calcined 8h；After roasting powder again with MoO3Aqueous 30% slurry, stirring 40min, sealing is made in meter 6g ammonium molybdate solution
Denitrating catalyst is obtained after standing 24h, drying, 600 DEG C of roasting 8h.Above-mentioned gained fresh catalyst and useless containing vanadium with catalytic cracking
Catalyst high temperature mixing rear catalyst is evaluated respectively, the results are shown in Table 1 data.
Embodiment 3
It will contain with TiO2Meter 500g titanyl sulfate is dissolved in sulfuric acid solution, is added and is contained with MoO3Meter 20g ammonium molybdate,
With WO320g ammonium metatungstate solution is counted, is formed and contains TiO2For 35g/L mixed solutions, stir and ammoniacal liquor regulation pH is gradually added after 2h
Value is to 8.5, after precipitation is complete, filtering, washing；Material after washing is spent into ion water making into the slurry that moisture content is 50% again,
Add with CeO225g cerous nitrate solution is counted, stirs after 1.5h, convection drying, 8h is calcined at 600 DEG C；After roasting powder again with
With MoO3Aqueous 30% slurry is made in meter 6g ammonium metatungstate solution, and 3.5g polyethylene glycol oxides, stirring are added after stirring
Denitrating catalyst is obtained after 40min, sealing and standing 24h, drying, 600 DEG C of roasting 8h.Above-mentioned gained fresh catalyst and with catalysis
Cracking vanadium-containing wasting catalyst high temperature mixing rear catalyst is evaluated respectively, the results are shown in Table 1 data.
Comparative example 3
Technique used presses CN201110345605 embodiments 1, by the metatitanic acid scattered mashing of dust technology, filters to neutrality,
Add water metatitanic acid mashing is scattered, obtained metatitanic acid slurry.Ammonium tungstate, cerous nitrate and molybdenum are sequentially added in metatitanic acid slurry
Sour ammonium, makes the mass ratio of three kinds of ammonium salts and metatitanic acid reach the ratio of embodiment 3, makes its composition identical, then by mixed material
Allow the ammonium salt of addition to dissolve with stirring to pulp, disperse, ammonium salt is fully adsorbed to metatitanic acid surface, with nitre acid for adjusting pH value extremely
5.0.Stand, dry, 300 DEG C of heat treatment 4h are to obtain catalyst.Above-mentioned gained fresh catalyst and useless containing vanadium with catalytic cracking
Catalyst high temperature mixing rear catalyst is evaluated respectively, the results are shown in Table 1 data.
Embodiment 4
It will contain with TiO2Meter 500g titanyl sulfate is dissolved in sulfuric acid solution, is added and is contained with MoO3Meter 15g ammonium molybdate,
With WO315g ammonium metatungstate solution is counted, is formed and contains TiO2For 35g/L mixed solutions, stir and ammoniacal liquor regulation pH is gradually added after 2h
Value is to 8.5, after precipitation is complete, filtering, washing；Material after washing is spent into ion water making into the slurry that moisture content is 50% again,
Add with CeO220g cerous nitrate solution is counted, stirs after 1.5h, convection drying, 8h is calcined at 600 DEG C；After roasting powder again with
With WO3Aqueous 30% slurry is made in meter 5g ammonium metatungstate solution, addition 3.5g polyethylene glycol oxides after stirring, stirring 40min,
Denitrating catalyst is obtained after sealing and standing 24h, drying, 600 DEG C of roasting 8h.Above-mentioned gained fresh catalyst and contain with catalytic cracking
Vanadium dead catalyst high temperature mixing rear catalyst is evaluated respectively, the results are shown in Table 1 data.
Comparative example 4
Technique used presses CN103143396 embodiments 1, a kind of honeycomb type flue gas denitration catalyst, with the raw material of parts by weight
Extruded shaping, sintering are formed, and the final active formulation ratio reached is consistent with embodiment 4, makes its composition identical.It is cellular to urge
Agent is size-reduced to be evaluated to 20~40 mesh.Above-mentioned gained fresh catalyst and mixed with catalytic cracking vanadium-containing wasting catalyst high temperature
Close rear catalyst to evaluate respectively, the results are shown in Table 1 data.
Embodiment 5
It will contain with TiO2Meter 500g titanyl sulfate is dissolved in sulfuric acid solution, is added and is contained with MoO3Meter 25g ammonium molybdate,
With WO325g ammonium metatungstate solution is counted, is formed and contains TiO2For 35g/L mixed solutions, stir and ammoniacal liquor regulation pH is gradually added after 2h
Value is to 8.5, after precipitation is complete, filtering, washing；Material after washing is spent into ion water making into the slurry that moisture content is 50% again,
Add with CeO250g cerous nitrate solution is counted, stirs after 1.5h, convection drying, 8h is calcined at 600 DEG C；After roasting powder again with
With WO3Aqueous 30% slurry is made in meter 10g ammonium metatungstate solution, and 3.5g polymethyl methacrylates are added after stirring, are stirred
Denitrating catalyst is obtained after mixing 40min, sealing and standing 24h, drying, 600 DEG C of roasting 8h.Above-mentioned gained fresh catalyst and with urging
Change cracking vanadium-containing wasting catalyst high temperature mixing rear catalyst to evaluate respectively, the results are shown in Table 1 data.
The embodiment of table 1 and comparative example evaluating data contrast table
Found by embodiment and comparative example：The denitrating catalyst of the resistance heavy metal deposition of embodiment has good effect
Really, it is preliminary the mixing rank of active material is reached molecule rank by mixing in situ, through being co-precipitated the nanometer slightly evacuated
Particle, then rare earth oxide is introduced in particle surface and shallow-layer, catalyst intermediate is obtained after roasting, is ground to form after powder,
Strengthen again in the presence of pore-creating auxiliary agent in the co-catalyst for being introduced into and hindering that heavy metallic oxide is deposited in gas phase, evaluating catalyst
NOxConversion ratio when ammonia nitrogen ratio is 1, up to more than 95%, and catalyst sulfur dioxide/sulphur trioxide conversion rate is relatively low, warp
After catalytic cracking mixed processing containing heavy metal dusts, catalyst activity does not almost weaken, and illustrates that catalyst performance is excellent；It is de-
In denox catalyst preparation method, if being handled without (4) step, only retain first time calcined catalyst sample, contain through catalytic cracking
After vanadium dead catalyst mixed processing, SO2/SO3Conversion ratio has increased slightly；If pore-creating auxiliary agent is not added with the processing of (4) step, through catalysis
After cracking vanadium-containing wasting catalyst mixed processing, SO2/SO3Conversion ratio also has increased slightly.In a word, the fresh denitration that prepared by the present invention is urged
Catalyst after agent and processing with the conditions of when evaluating, SO2/SO3Conversion ratio is lower than other comparative examples, with good
Catalytic activity.
Beneficial effects of the present invention：
(1) using the method for mixing in situ, titanium atom and cocatalyst component is mixed in atomic level, cause follow-up
The crystal produced in coprecipitation process, lattice defect is more, and mixed-metal oxides particle diameter is small and homogeneous, bigger than surface, simultaneously
Improve titanium dioxide crystal turns brilliant temperature, beneficial to the performance of catalytic activity；
(2) rare earth source is added when catalyst co-precipitation material is not calcined, permeates deeper in titanium-tungsten (molybdenum) particle surface,
Connection is closer, disperses evenly, and fired rear catalyst activity is more preferably；
(3) powder material prepared entered after once roasting, and covered one layer of cocatalyst component on its surface, while plus
Enter polyethylene glycol oxide, also possessed nanometer level microporous while making catalyst particle surface that there are more co-catalysis components to adhere to,
Both heavy metals of flue gases oxide can have been resisted in its surface nonuniform deposition, high catalyst performance can be ensured again.
Certainly, the present invention can also have other various embodiments, ripe in the case of without departing substantially from spirit of the invention and its essence
Various corresponding changes and deformation, but these corresponding changes and deformation can be made according to the present invention by knowing those skilled in the art
The protection domain of the claims in the present invention should all be belonged to.
Claims (10)
1. a kind of preparation method without vanadium denitration catalyst, it is characterised in that this method comprises the following steps：
(1) titanium source presoma is dissolved in acid and forms solution；
(2) the co-catalysis component precursor being made up of one or both of tungsten source precursor, molybdenum source precursor is dissolved and formed
Solution, and be successively well mixed with the solution of (1)；
(3) well mixed rear solution ph, to 7~12, is precipitated, filtered obtained by regulating step (2)；
(4) deionized water is added in filter cake obtained by step (3), is tuned into pulpous state, added rare earth source precursor solution, be well mixed
Afterwards, directly it is dried, is calcined, grinds to form powder；
(5) powder of step (4) is mixed into pulp with one kind in tungsten source precursor solution or molybdenum source precursor solution, stirred
After mixing, plus pore creating material, after being well mixed, dry, be calcined, form denitrating catalyst.
2. preparation method according to claim 1, it is characterised in that tungsten source presoma is with WO in the step (2)3Meter, titanium
Source presoma is with TiO2The mass ratio of meter, tungsten source presoma and titanium source presoma is 1.0~10.0:100.
3. preparation method according to claim 1, it is characterised in that molybdenum source presoma is with MoO in the step (2)3Meter,
Titanium source presoma is with TiO2The mass ratio of meter, molybdenum source presoma and titanium source presoma is 1.0~10.0:100.
4. preparation method according to claim 1, it is characterised in that step (4) middle rare earth source presoma is with Re2O3
Meter, titanium source presoma is with TiO2Meter, the matter of well mixed rear solution middle rare earth source presoma and titanium source presoma obtained by step (2)
Amount is than being 0.1~10:100.
5. preparation method according to claim 1, it is characterised in that one kind in the step (5) in tungsten source or molybdenum source
Precursor consumption is in terms of trioxide, and the titanium source presoma consumption is with TiO2Meter, trioxide and TiO2Mass ratio is preferably
0.5~2.0:100.
6. preparation method according to claim 1, it is characterised in that co-catalysis component presoma in the step (2)
Consumption is in terms of trioxide form, and the titanium source presoma consumption is with TiO2Meter, trioxide and TiO2Mass ratio be 0.5~
2.0:100。
7. preparation method according to claim 1, it is characterised in that the titanium source presoma consumption is with TiO2Meter, the step
Suddenly pore creating material addition and TiO in (5)2Mass ratio be 0.1~1.0:100.
8. preparation method according to claim 1, it is characterised in that the pore creating material in step (5) is polyethylene glycol oxide, gathered
One or more in methyl methacrylate, sesbania powder.
9. preparation method according to claim 1, it is characterised in that sintering temperature is equal in the step (4) and step (5)
For 400~650 DEG C, roasting time is 4~10h.
10. one kind is without vanadium denitration catalyst, it is characterised in that it is without vanadium denitration catalyst described in any one of claim 1 to 9
Prepared by the preparation method of agent.
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| CN111841526A (en) * | 2020-07-06 | 2020-10-30 | 中国科学院兰州化学物理研究所 | Modified Ce-Ti medium-low temperature flue gas denitration catalyst powder and preparation method thereof |
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