CN107497417B - A kind of mesoporous denitrating catalyst and the preparation method and application thereof - Google Patents
A kind of mesoporous denitrating catalyst and the preparation method and application thereof Download PDFInfo
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- CN107497417B CN107497417B CN201710696186.2A CN201710696186A CN107497417B CN 107497417 B CN107497417 B CN 107497417B CN 201710696186 A CN201710696186 A CN 201710696186A CN 107497417 B CN107497417 B CN 107497417B
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- oxide
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- 239000003054 catalyst Substances 0.000 title claims abstract description 58
- 238000002360 preparation method Methods 0.000 title claims abstract description 39
- 229910044991 metal oxide Inorganic materials 0.000 claims abstract description 32
- 150000004706 metal oxides Chemical class 0.000 claims abstract description 32
- JMTJYLISOWJQAT-UHFFFAOYSA-N [Zr].[V].[Ti] Chemical compound [Zr].[V].[Ti] JMTJYLISOWJQAT-UHFFFAOYSA-N 0.000 claims abstract description 28
- 239000002131 composite material Substances 0.000 claims abstract description 27
- QVQLCTNNEUAWMS-UHFFFAOYSA-N barium oxide Chemical compound [Ba]=O QVQLCTNNEUAWMS-UHFFFAOYSA-N 0.000 claims abstract description 16
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 11
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229910001928 zirconium oxide Inorganic materials 0.000 claims abstract description 10
- 239000011230 binding agent Substances 0.000 claims abstract description 9
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000000203 mixture Substances 0.000 claims abstract description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 24
- 239000008367 deionised water Substances 0.000 claims description 23
- 229910021641 deionized water Inorganic materials 0.000 claims description 23
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 21
- 238000003756 stirring Methods 0.000 claims description 19
- 229910052720 vanadium Inorganic materials 0.000 claims description 18
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims description 18
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 15
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 13
- 229910052726 zirconium Inorganic materials 0.000 claims description 13
- 239000010936 titanium Substances 0.000 claims description 12
- 229910052719 titanium Inorganic materials 0.000 claims description 12
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims description 10
- 239000002253 acid Substances 0.000 claims description 10
- 238000001035 drying Methods 0.000 claims description 10
- 238000013019 agitation Methods 0.000 claims description 7
- 239000003513 alkali Substances 0.000 claims description 7
- UNTBPXHCXVWYOI-UHFFFAOYSA-O azanium;oxido(dioxo)vanadium Chemical compound [NH4+].[O-][V](=O)=O UNTBPXHCXVWYOI-UHFFFAOYSA-O 0.000 claims description 7
- 238000002425 crystallisation Methods 0.000 claims description 7
- 230000008025 crystallization Effects 0.000 claims description 7
- 238000001125 extrusion Methods 0.000 claims description 7
- 235000006408 oxalic acid Nutrition 0.000 claims description 7
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims description 6
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 6
- 239000003546 flue gas Substances 0.000 claims description 6
- JMXKSZRRTHPKDL-UHFFFAOYSA-N titanium ethoxide Chemical compound [Ti+4].CC[O-].CC[O-].CC[O-].CC[O-] JMXKSZRRTHPKDL-UHFFFAOYSA-N 0.000 claims description 6
- 150000001875 compounds Chemical class 0.000 claims description 5
- 239000012456 homogeneous solution Substances 0.000 claims description 4
- 239000011148 porous material Substances 0.000 claims description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 3
- CXRFDZFCGOPDTD-UHFFFAOYSA-M Cetrimide Chemical compound [Br-].CCCCCCCCCCCCCC[N+](C)(C)C CXRFDZFCGOPDTD-UHFFFAOYSA-M 0.000 claims description 3
- 229910052782 aluminium Inorganic materials 0.000 claims description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 3
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 claims description 3
- 229910021502 aluminium hydroxide Inorganic materials 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 2
- 239000000908 ammonium hydroxide Substances 0.000 claims description 2
- 239000003795 chemical substances by application Substances 0.000 claims description 2
- 238000000748 compression moulding Methods 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- CMZUMMUJMWNLFH-UHFFFAOYSA-N sodium metavanadate Chemical compound [Na+].[O-][V](=O)=O CMZUMMUJMWNLFH-UHFFFAOYSA-N 0.000 claims description 2
- 239000004575 stone Substances 0.000 claims description 2
- 238000005406 washing Methods 0.000 claims description 2
- 229910000166 zirconium phosphate Inorganic materials 0.000 claims description 2
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims 3
- QOSMNYMQXIVWKY-UHFFFAOYSA-N Propyl levulinate Chemical compound CCCOC(=O)CCC(C)=O QOSMNYMQXIVWKY-UHFFFAOYSA-N 0.000 claims 2
- BKEOXUSOEGMVTL-UHFFFAOYSA-N trimethyl-$l^{3}-bromane Chemical compound CBr(C)C BKEOXUSOEGMVTL-UHFFFAOYSA-N 0.000 claims 2
- 239000004411 aluminium Substances 0.000 claims 1
- -1 isopropyl ester Chemical class 0.000 claims 1
- 239000006185 dispersion Substances 0.000 abstract description 3
- 230000003993 interaction Effects 0.000 abstract description 2
- 230000009257 reactivity Effects 0.000 abstract description 2
- CSSYLTMKCUORDA-UHFFFAOYSA-N barium(2+);oxygen(2-) Chemical class [O-2].[Ba+2] CSSYLTMKCUORDA-UHFFFAOYSA-N 0.000 abstract 1
- 239000000047 product Substances 0.000 abstract 1
- 239000000376 reactant Substances 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 36
- 239000007788 liquid Substances 0.000 description 16
- 239000000843 powder Substances 0.000 description 13
- 238000010438 heat treatment Methods 0.000 description 11
- PMTRSEDNJGMXLN-UHFFFAOYSA-N titanium zirconium Chemical compound [Ti].[Zr] PMTRSEDNJGMXLN-UHFFFAOYSA-N 0.000 description 11
- 239000002243 precursor Substances 0.000 description 10
- 238000010792 warming Methods 0.000 description 10
- 235000011114 ammonium hydroxide Nutrition 0.000 description 6
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 6
- 229910001593 boehmite Inorganic materials 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 5
- 239000007789 gas Substances 0.000 description 5
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 description 5
- 238000010907 mechanical stirring Methods 0.000 description 5
- 229910052751 metal Inorganic materials 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- 238000000465 moulding Methods 0.000 description 5
- 239000003643 water by type Substances 0.000 description 5
- 238000000034 method Methods 0.000 description 4
- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical compound CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 description 4
- 241000416536 Euproctis pseudoconspersa Species 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 230000007613 environmental effect Effects 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 description 2
- SNRUBQQJIBEYMU-UHFFFAOYSA-N dodecane Chemical compound CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 2
- 229910000069 nitrogen hydride Inorganic materials 0.000 description 2
- DCKVNWZUADLDEH-UHFFFAOYSA-N sec-butyl acetate Chemical compound CCC(C)OC(C)=O DCKVNWZUADLDEH-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- GQPLMRYTRLFLPF-UHFFFAOYSA-N Nitrous Oxide Chemical class [O-][N+]#N GQPLMRYTRLFLPF-UHFFFAOYSA-N 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 1
- 238000003916 acid precipitation Methods 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- POJOORKDYOPQLS-UHFFFAOYSA-L barium(2+) 5-chloro-2-[(2-hydroxynaphthalen-1-yl)diazenyl]-4-methylbenzenesulfonate Chemical compound [Ba+2].C1=C(Cl)C(C)=CC(N=NC=2C3=CC=CC=C3C=CC=2O)=C1S([O-])(=O)=O.C1=C(Cl)C(C)=CC(N=NC=2C3=CC=CC=C3C=CC=2O)=C1S([O-])(=O)=O POJOORKDYOPQLS-UHFFFAOYSA-L 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000031709 bromination Effects 0.000 description 1
- 238000005893 bromination reaction Methods 0.000 description 1
- 238000010531 catalytic reduction reaction Methods 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000008246 gaseous mixture Substances 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 238000001802 infusion Methods 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 230000035800 maturation Effects 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000006722 reduction reaction Methods 0.000 description 1
- 239000000779 smoke Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 230000005619 thermoelectricity Effects 0.000 description 1
- AISMNBXOJRHCIA-UHFFFAOYSA-N trimethylazanium;bromide Chemical compound Br.CN(C)C AISMNBXOJRHCIA-UHFFFAOYSA-N 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
- B01J23/16—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
- B01J23/20—Vanadium, niobium or tantalum
- B01J23/22—Vanadium
-
- 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
-
- B01J35/615—
-
- B01J35/635—
-
- B01J35/638—
-
- B01J35/647—
-
- 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
Abstract
The present invention provides a kind of mesoporous denitrating catalysts and the preparation method and application thereof, are 100% calculating with the total weight of the mesoporous denitrating catalyst, it includes the vanadium titanium zirconium composite mesopore metal oxides and binder surplus of 85-95wt%；Wherein, the vanadium titanium zirconium composite mesopore metal oxide has regular hexagonal mesoporous structure, in the vanadium titanium zirconium composite mesopore metal oxide, titanium oxide, Zirconium oxide are spaced apart composition mesoporous wall, and barium oxide is evenly distributed on the inner surface of mesopore orbit；It is in terms of 100% by the total weight of the vanadium titanium zirconium composite mesopore metal oxide, it includes the barium oxides of the titanium oxide of 30-80%, the Zirconium oxide of 25-75% and 1-10%.The catalyst that the present invention is prepared has the characteristics that large specific surface area, active component high degree of dispersion, reactant and product diffusional resistance are small, reactivity is high, the interaction of resistance to high-speed, active component and carrier is strong and thermal stability is good.
Description
Technical field
The present invention relates to a kind of mesoporous denitrating catalysts and the preparation method and application thereof, belong to gas denitrifying technology field.
Background technique
Nitrogen oxides be acid rain, photochemical fog, atmosphere pollution main reason, also have to ozone layer certain broken
Bad effect.With the development of economy with increasingly serious Environmental Protection Situation, environmental protection administration to the emission reduction requirement of every profession and trade and dynamics not
Disconnected to increase, therefore, adjoint nitrogen oxides formula also results in the concern of people during flue gas and exhaust emissions.The hair in China
Electric form is mainly based on thermoelectricity, while motor vehicle possesses that total amount is larger, therefore the discharged nitrous oxides in China are mainly derived from
Coal steam-electric plant smoke and automotive emission.Selective catalytic reduction (SCR) technology is with its denitrification rate height, technology maturation, product
The reasons such as environmental protection are one of current most widely used gas denitrifying technologies.
The performance of catalyst is the key that gas denitrifying technology, and generally requiring the active component of catalyst is variable valency gold
Belong to, carrier specific surface area with higher and good high temperature resistance.The catalyst for denitrating flue gas used at this stage mainly with
TiO2、V2O5、WO3、CeO2Based on equal composite oxide catalysts, need to adjust WO in actual application3、CeO2Deng ratio
To prevent the TiO of Anatase2Crystal transfer occurs and then generates brilliant red stone.In addition, the ratio of composite oxide catalysts carrier
Surface area is smaller, is unfavorable for the dispersion of active component, and the V loaded by infusion process2O5Active component is easy under the high temperature conditions
In being sintered and falling off, have a certain impact to the denitration performance of regenerated catalyst.
Therefore develop that a kind of high temperature resistant, stability is good, specific surface area is higher, low-cost mesoporous denitrating catalyst seems
It is particularly necessary.
Summary of the invention
In order to solve the above shortcomings and deficiencies, the purpose of the present invention is to provide a kind of vanadium titanium zirconium composite mesopore metal oxygens
Compound.
The object of the invention is also to provide the preparation methods of above-mentioned vanadium titanium zirconium composite mesopore metal oxide.
The object of the invention is also to provide a kind of mesoporous denitrations containing above-mentioned vanadium titanium zirconium composite mesopore metal oxide
Catalyst.
The object of the invention is also to provide the preparation methods of above-mentioned mesoporous denitrating catalyst.
The object of the invention is also to provide application of the above-mentioned mesoporous denitrating catalyst in denitrating flue gas.
In order to achieve the above objectives, the present invention provides a kind of vanadium titanium zirconium composite mesopore metal oxide, with regular six
Square meso-hole structure, in the vanadium titanium zirconium composite mesopore metal oxide, titanium oxide, Zirconium oxide, which are spaced apart, constitutes mesoporous hole
Wall, barium oxide are evenly distributed on the inner surface of mesopore orbit；
It is in terms of 100% by the total weight of the vanadium titanium zirconium composite mesopore metal oxide, it includes the titanyls of 30-80wt%
The barium oxide of object, the Zirconium oxide of 25-75wt% and 1-10wt%；And the titanium oxide, Zirconium oxide and barium oxide
The sum of weight fraction be 100%.
Specific embodiment according to the present invention, it is preferable that the specific surface area of the vanadium titanium zirconium composite mesopore metal oxide
Greater than 100m2/ g, mesopore volume 0.5-1.2mL/g, average pore size 2-6nm.
The present invention also provides the preparation methods of above-mentioned vanadium titanium zirconium composite mesopore metal oxide comprising following steps:
(1) titanium source, zirconium source are mixed, stirring forms homogeneous solution；
(2) prehydrolysis is carried out after mixing in vanadium source rapidly with homogeneous solution obtained by step (1)；
(3) under agitation, the solution obtained after prehydrolysis is added dropwise to the deionized water of template and alkali source dropwise
In solution, continue stirring to forming uniform sol solutions；
(4) sol solutions are subjected to crystallization under hydrothermal conditions, after filter, washing, drying, roasting, obtain vanadium
Titanium zirconium composite mesopore metal oxide.
Specific embodiment according to the present invention, in the preparation method, it is preferable that the titanium source include metatitanic acid four just
One of butyl ester, tetraisopropyl titanate, tetraethyl titanate, tetra-tert titanate esters or titanium colloidal sol.
Specific embodiment according to the present invention, in the preparation method, it is preferable that the zirconium source include zirconic acid four just
One of butyl ester, zirconium-n-propylate or zirconium colloidal sol.
Specific embodiment according to the present invention, in the preparation method, it is preferable that the vanadium source includes ammonium metavanadate
And/or sodium vanadate and oxalic acid are the aqueous solution that 1:2 is made into molar ratio.
Specific embodiment according to the present invention, in the preparation method, it is preferable that step (2) the prehydrolysis temperature
Degree is 50-90 DEG C.
Specific embodiment according to the present invention, in the preparation method, it is preferable that the alkali source includes hydroxide
The combination of one or more of sodium, potassium hydroxide and ammonium hydroxide.
Specific embodiment according to the present invention, in the preparation method, it is preferable that the template includes dodecane
Base trimethylammonium bromide, tetradecyltrimethylammonium bromide, cetyl trimethylammonium bromide and octadecyl trimethyl bromination
The combination of one or more of ammonium.
Specific embodiment according to the present invention, in the preparation method, it is preferable that the titanium source, zirconium source, vanadium source,
The molar ratio of template, alkali source and deionized water is (2.0-10.0): (1.0-10.0): 1.0:(0.5-1.5): (5.0-
20.0):(100.0-500.0)。
Specific embodiment according to the present invention, in the preparation method, it is preferable that step (4) described hydrothermal condition
Temperature be 120-180 DEG C, reaction time 12-72h.
Specific embodiment according to the present invention, in the preparation method, it is preferable that the temperature of step (4) described drying
Degree is 80-120 DEG C, time 8-24h.
Specific embodiment according to the present invention, in the preparation method, it is preferable that the temperature of step (4) described roasting
Degree is 500-650 DEG C, time 4-12h.It is described to be roasted to the liter less than 5 DEG C/min in the specific embodiment of the invention
System temperature is risen to 500-650 DEG C of roasting 4-12h from the temperature after drying by warm rate.
The present invention also provides a kind of mesoporous denitrating catalyst, containing above-mentioned vanadium titanium zirconium composite mesopore metal oxide,
It is 100% calculating with the total weight of the mesoporous denitrating catalyst, it includes the oxidations of the vanadium titanium zirconium composite mesopore metal of 85-95wt%
Object and binder surplus.
Specific embodiment according to the present invention, it is preferable that the specific surface area of the mesoporous denitrating catalyst is greater than 150m2/
G, mesopore volume 0.69-1.2mL/g, average pore size 2-10nm；
It is highly preferred that the mesopore volume is 0.8-1.2mL/g.
Specific embodiment according to the present invention, in the mesoporous denitrating catalyst, it is preferable that the binder includes
The combination of one or more of boehmite (SB powder), aluminium hydroxide and Aluminum sol.
The present invention also provides the preparation methods of above-mentioned mesoporous denitrating catalyst comprising following steps:
Extrusion or compression molding are carried out after vanadium titanium zirconium composite mesopore metal oxide is mixed with deionized water, binder,
Again after drying, roasting, the mesoporous denitrating catalyst is obtained.
Specific embodiment according to the present invention, in the preparation method of the catalyst, it is preferable that the vanadium titanium zirconium is compound
The mass ratio of mesopore metal oxide, binder and deionized water is 10:(1.0-3.0): (1.5-4.0).
Specific embodiment according to the present invention, in the preparation method of the catalyst, it is preferable that the temperature of the drying
It is 80-120 DEG C, time 8-24h.
Specific embodiment according to the present invention, in the preparation method of the catalyst, it is preferable that the temperature of the roasting
It is 500-650 DEG C, time 4-12h.It is described to be roasted to the heating less than 5 DEG C/min in the specific embodiment of the invention
System temperature is risen to 500-650 DEG C of roasting 4-12h from the temperature after drying by rate.
The present invention also provides application of the mesoporous denitrating catalyst in denitrating flue gas.
The preparation method of mesoporous denitrating catalyst provided by the present invention is pre- using titanium source, zirconium source mixed liquor and vanadium source solution
The method of hydrolysis uniformly mixes in vanadium source with titanium source, zirconium source, molten after mixed uniformly prehydrolysis during forming sol solutions
Liquid can form micella with template fast reaction under the action of alkali source, then after hydrothermal aging, drying, roasting process
To the metal oxide powder with regular hexagonal mesoporous structure；Obtain this there is the metal oxygen of regular hexagonal mesoporous structure
In compound powder, barium oxide active component will be slow the inner surface for migrating and being evenly distributed on mesopore orbit, titanium, Zirconium oxide
It is spaced apart composition mesoporous wall.Since titanium zirconium uniformly mixes, and zirconium oxide has good high temperature resistance, therefore, energy
It is enough effectively to prevent titanium oxide that crystal transfer occurs under the high temperature conditions.
There is large specific surface area, active component high degree of dispersion, reaction by the mesoporous denitrating catalyst that the present invention is prepared
Object and product diffusional resistance are small, reactivity is high, the interaction of resistance to high-speed, active component and carrier is strong and thermal stability is good etc.
Feature is suitable for industrial application.
Detailed description of the invention
Fig. 1 is the TEM figure for the mesoporous denitrating catalyst that the embodiment of the present invention 1 is prepared；
Fig. 2 is the XRD diagram for the mesoporous out of stock catalyst that the embodiment of the present invention 5 is prepared；
Fig. 3 is the TEM figure for the mesoporous out of stock catalyst that the embodiment of the present invention 5 is prepared.
Specific embodiment
In order to which technical characteristic of the invention, purpose and beneficial effect are more clearly understood, now to skill of the invention
Art scheme carries out described further below, but should not be understood as that limiting the scope of the invention.
Embodiment 1
A kind of mesoporous denitrating catalyst is present embodiments provided, through the following steps that be prepared:
It is stirred evenly after 68.1g tetra-n-butyl titanate, four N-butyl of 76.7g zirconic acid are mixed, obtains titanium zirconium mixed liquor；
7.3g ammonium metavanadate, 11.3g oxalic acid are dissolved in 100mL deionized water, 80 DEG C are heated under stirring condition, is kept
10min obtains vanadium source solution；
Titanium zirconium mixed liquor is mixed rapidly with vanadium source solution, it is uniformly molten to being formed that prehydrolysis is stirred in 60 DEG C of waters bath with thermostatic control
Liquid obtains precursor liquid；
It takes 90g concentrated ammonia liquor (25wt%), 18.2g cetyl trimethylammonium bromide to be dissolved in 450mL deionized water, stirs
To formation clear solution；
Precursor liquid after prehydrolysis is added dropwise in resulting clear solution dropwise under agitation, is added dropwise to complete subsequent
Continuous stirring is to forming uniform sol solutions；
By above-mentioned sol solutions move into hydrothermal crystallizing kettle, 120 DEG C crystallization 72 hours, after being filtered, washed under the conditions of 80 DEG C
It is 12 hours dry, then, 550 DEG C being warming up to according to 2 DEG C/min heating rate and is roasted, roasting obtained mesoporous gold after 4 hours
Belong to oxide powder；
20g mesopore metal oxide powder is mixed with 6.0g boehmite, 8g deionized water and is put after mechanical stirring
Enter extrusion in banded extruder, it is 20 hours dry under the conditions of 100 DEG C after molding, then, it is warming up to according to 2 DEG C/min heating rate
550 DEG C are roasted, and roasting can obtain mesoporous denitrating catalyst after 4 hours, are denoted as A1, transmission electron microscope picture (shows as shown in Figure 1
It anticipates vertical mesopore orbit direction meso-hole structure)；From figure 1 it appears that the catalyst is with apparent regular arranged in parallel
Straight hole road, aperture are about 2.6nm, show that catalyst manufactured in the present embodiment has apparent meso-hole structure.
Embodiment 2
The present embodiment provides a kind of mesoporous denitrating catalysts, through the following steps that be prepared:
It is stirred evenly after 53.2g tetraisopropyl titanate, 40.9g zirconium-n-propylate are mixed, obtains titanium zirconium mixed liquor；
7.3g ammonium metavanadate, 11.3g oxalic acid are dissolved in 100mL deionized water, 80 DEG C are heated under stirring condition, is kept
10min obtains vanadium source solution；
Titanium zirconium mixed liquor is mixed rapidly with vanadium source solution, it is uniformly molten to being formed that prehydrolysis is stirred in 60 DEG C of waters bath with thermostatic control
Liquid obtains precursor liquid；
87g concentrated ammonia liquor (25wt%), 21.0g cetyl trimethylammonium bromide is taken to be dissolved in 450mL deionized water, stirring is extremely
Form clear solution；
Precursor liquid after prehydrolysis is added dropwise to dropwise under agitation in the resulting clear solution of previous step, is dripped
Continue stirring after to forming uniform sol solutions；
By above-mentioned sol solutions move into hydrothermal crystallizing kettle, 140 DEG C crystallization 48 hours, after being filtered, washed under the conditions of 100 DEG C
It is 10 hours dry, then, 500 DEG C being warming up to according to 2 DEG C/min heating rate and is roasted, roasting obtained mesoporous gold after 4 hours
Belong to oxide powder；
20g mesopore metal oxide powder is mixed with 4.5g aluminium hydroxide, 7.0g deionized water and is put after mechanical stirring
Enter extrusion in banded extruder, it is 12 hours dry under the conditions of 100 DEG C after molding, then, it is warming up to according to 2 DEG C/min heating rate
500 DEG C are roasted, and mesoporous denitrating catalyst can be obtained after 16 hours in roasting, are denoted as A2.
Embodiment 3
The present embodiment provides a kind of mesoporous denitrating catalysts, through the following steps that be prepared:
It is stirred evenly after 128.0g tetraethyl titanate, four N-butyl of 143.6g zirconic acid are mixed, obtains titanium zirconium mixed liquor；
7.3g ammonium metavanadate, 11.3g oxalic acid are dissolved in 100mL deionized water, 90 DEG C are heated under stirring condition, is kept
10min obtains vanadium source solution；
Titanium zirconium mixed liquor is mixed rapidly with vanadium source solution, it is uniformly molten to being formed that prehydrolysis is stirred in 70 DEG C of waters bath with thermostatic control
Liquid obtains precursor liquid；
It takes 52.4g concentrated ammonia liquor (25wt%), 12.1g cetyl trimethylammonium bromide to be dissolved in 450mL deionized water, stirs
To formation clear solution；
Precursor liquid after prehydrolysis is added dropwise to dropwise under agitation in the resulting clear solution of previous step, is dripped
Continue stirring after to forming uniform sol solutions；
By above-mentioned sol solutions move into hydrothermal crystallizing kettle, 160 DEG C crystallization 40 hours, after being filtered, washed under the conditions of 120 DEG C
It is 8 hours dry, then, 600 DEG C being warming up to according to 2 DEG C/min heating rate and is roasted, roasting obtained mesoporous metal after 6 hours
Oxide powder；
After 20g mesopore metal oxide powder is mixed simultaneously mechanical stirring with 5.0g boehmite, 6.0g deionized water
It is put into extrusion in banded extruder, it is 14 hours dry under the conditions of 100 DEG C after molding, then, it is warming up to according to 2 DEG C/min heating rate
500 DEG C are roasted, and roasting can obtain mesoporous denitrating catalyst after 8 hours, are denoted as A3.
Embodiment 4
The present embodiment provides a kind of mesoporous denitrating catalysts, through the following steps that be prepared:
130.0g titanium colloidal sol (is contained into TiO225.1wt%), 76.7g zirconium colloidal sol (contains ZrO2It is stirred after 27.2wt%) mixing
Uniformly, titanium zirconium mixed liquor is obtained；
7.3g ammonium metavanadate, 11.3g oxalic acid are dissolved in 100mL deionized water, 80 DEG C are heated under stirring condition, is kept
10min obtains vanadium source solution；
Titanium zirconium mixed liquor is mixed rapidly with vanadium source solution, it is uniformly molten to being formed that prehydrolysis is stirred in 65 DEG C of waters bath with thermostatic control
Liquid obtains precursor liquid；
It takes 39.5g concentrated ammonia liquor (25wt%), 24.5g cetyl trimethylammonium bromide to be dissolved in 450mL deionized water, stirs
To formation clear solution；
Precursor liquid after prehydrolysis is added dropwise to dropwise under agitation in the resulting clear solution of previous step, is dripped
Continue stirring after to forming uniform sol solutions；
By above-mentioned sol solutions move into hydrothermal crystallizing kettle, 180 DEG C crystallization 12 hours, after being filtered, washed under the conditions of 100 DEG C
It is 6 hours dry, then, 550 DEG C being warming up to according to 2 DEG C/min heating rate and is roasted, roasting obtained mesoporous metal after 6 hours
Oxide powder；
After 20g mesopore metal oxide powder is mixed simultaneously mechanical stirring with 3.0g boehmite, 5.0g deionized water
It is put into extrusion in banded extruder, it is 12 hours dry under the conditions of 120 DEG C after molding, then, it is warming up to according to 2 DEG C/min heating rate
550 DEG C are roasted, and mesoporous denitrating catalyst can be obtained after 10 hours in roasting, are denoted as A4.
Embodiment 5
The present embodiment provides a kind of mesoporous denitrating catalysts, through the following steps that be prepared:
It is stirred evenly after 89.6g tetra-tert titanate esters, four N-butyl of 81.7g zirconic acid are mixed, obtains titanium zirconium mixed liquor；
7.3g ammonium metavanadate, 11.3g oxalic acid are dissolved in 100mL deionized water, 80 DEG C are heated under stirring condition, is kept
10min obtains vanadium source solution；
Titanium zirconium mixed liquor is mixed rapidly with vanadium source solution, it is uniformly molten to being formed that prehydrolysis is stirred in 60 DEG C of waters bath with thermostatic control
Liquid obtains precursor liquid；
90g concentrated ammonia liquor (25wt%), 18.2g cetyl trimethylammonium bromide is taken to be dissolved in 450mL deionized water, stirring is extremely
Form clear solution；
Precursor liquid after prehydrolysis is added dropwise to dropwise under agitation in the resulting clear solution of previous step, is dripped
Continue stirring after to forming uniform sol solutions；
By above-mentioned sol solutions move into hydrothermal crystallizing kettle, 120 DEG C crystallization 72 hours, after being filtered, washed under the conditions of 80 DEG C
It is 12 hours dry, then, 550 DEG C being warming up to according to 2 DEG C/min heating rate and is roasted, roasting obtained mesoporous gold after 4 hours
Belong to oxide powder；
After 20g mesopore metal oxide powder is mixed simultaneously mechanical stirring with 2.0g boehmite, 6.0g deionized water
It is put into extrusion in banded extruder, it is 8 hours dry under the conditions of 100 DEG C after molding, then, it is warming up to according to 2 DEG C/min heating rate
550 DEG C are roasted, roasting 4 hours after mesoporous denitrating catalyst can be obtained, be denoted as A5, XRD spectra as shown in Fig. 2, its
Transmission electron microscope picture is as shown in Figure 3 (the hexagonal mesoporous arrangement in schematic vertical aperture direction)；
From figure 2 it can be seen that XRD spectra has apparent diffraction maximum at 2 °, at 4-6 ° there are two faint diffraction maximum, this
100,110 and 200 crystal faces with hexagonal mesoporous structural material are respectively corresponded, which further demonstrates prepared by the present invention
Catalyst has regular hexagonal mesoporous structure；
It can obviously observe that the catalyst has the aperture in the regular arrangement of " honeycomb " shape from Fig. 3.
Application examples
The application example evaluates the performance for the mesoporous denitrating catalyst being prepared in embodiment 1-5, reacts item
Part are as follows: normal pressure, 300 DEG C, the loadings of mesoporous denitrating catalyst are 2.0g；Unstripped gas is NO, NH3、N2And O2Gaseous mixture,
Middle NO, NH3Volume fraction be 0.08%, O2Volume fraction is 2.5%, total gas volume air speed GHSV=12000h-1.Respectively urge
The results are shown in Table 1 for agent respective performances parameter and determination of activity:
Table 1
From table 1 it follows that the mesoporous denitrating catalyst that the application is prepared is used for denitrating flue gas reaction, tool
There is higher conversion rate of NOx, this shows catalyst reaction activity height and resistance to high-speed.
Claims (24)
1. a kind of vanadium titanium zirconium composite mesopore metal oxide, with regular hexagonal mesoporous structure, in compound Jie of the vanadium titanium zirconium
In mesoporous metal oxide, titanium oxide, Zirconium oxide are spaced apart composition mesoporous wall, and barium oxide is evenly distributed on mesoporous hole
The inner surface in road；
By the total weight of the vanadium titanium zirconium composite mesopore metal oxide be 100% in terms of, it includes the titanium oxide of 30-80wt%,
The Zirconium oxide of 25-75wt% and the barium oxide of 1-10wt%；And the weight of the titanium oxide, Zirconium oxide and barium oxide
Measuring the sum of score is 100%.
2. vanadium titanium zirconium composite mesopore metal oxide according to claim 1, which is characterized in that compound Jie of vanadium titanium zirconium
The specific surface area of mesoporous metal oxide is greater than 100m2/ g, mesopore volume 0.5-1.2mL/g, average pore size 2-6nm.
3. the preparation method of vanadium titanium zirconium composite mesopore metal oxide of any of claims 1 or 2 comprising following steps:
(1) titanium source, zirconium source are mixed, stirring forms homogeneous solution；
(2) prehydrolysis is carried out after mixing in vanadium source rapidly with homogeneous solution obtained by step (1)；
(3) under agitation, the solution obtained after prehydrolysis is added dropwise to the deionized water solution of template and alkali source dropwise
In, continue stirring to forming uniform sol solutions；
(4) sol solutions are subjected to crystallization under hydrothermal conditions, after filter, washing, drying, roasting, obtain vanadium titanium zirconium
Composite mesopore metal oxide.
4. preparation method according to claim 3, which is characterized in that the titanium source includes tetra-n-butyl titanate, metatitanic acid four
One of isopropyl ester, tetraethyl titanate, tetra-tert titanate esters or titanium colloidal sol.
5. preparation method according to claim 3, which is characterized in that the zirconium source include four N-butyl of zirconic acid, zirconic acid just
One of propyl ester or zirconium colloidal sol.
6. the preparation method according to claim 4, which is characterized in that the zirconium source include four N-butyl of zirconic acid, zirconic acid just
One of propyl ester or zirconium colloidal sol.
7. preparation method according to claim 3, which is characterized in that the vanadium source includes ammonium metavanadate and/or sodium vanadate
It is in molar ratio the solution that 1:2 is made into oxalic acid.
8. preparation method according to claim 3, which is characterized in that the prehydrolysis temperature is 50-90 DEG C.
9. preparation method according to claim 3, which is characterized in that the alkali source include sodium hydroxide, potassium hydroxide and
The combination of one or more of ammonium hydroxide.
10. preparation method according to claim 3, which is characterized in that the template includes trimethyl bromine
Change one of ammonium, tetradecyltrimethylammonium bromide, cetyl trimethylammonium bromide and Cetyltrimethylammonium bromide
Or several combination.
11. preparation method according to claim 9, which is characterized in that the template includes trimethyl bromine
Change one of ammonium, tetradecyltrimethylammonium bromide, cetyl trimethylammonium bromide and Cetyltrimethylammonium bromide
Or several combination.
12. preparation method according to claim 3, which is characterized in that the temperature of the hydrothermal condition is 120-180 DEG C,
Reaction time is 12-72h.
13. preparation method according to claim 3, which is characterized in that the temperature of step (4) described drying is 80-120
DEG C, time 8-24h.
14. preparation method according to claim 3, which is characterized in that the temperature of step (4) described roasting is 500-650
DEG C, time 4-12h.
15. according to the described in any item preparation methods of claim 3-14, which is characterized in that the titanium source, zirconium source, vanadium source, mould
The molar ratio of plate agent, alkali source and deionized water is (2.0-10.0): (1.0-10.0): 1.0:(0.5-1.5): (5.0-20.0):
(100.0-500.0)。
16. a kind of mesoporous denitrating catalyst, containing vanadium titanium zirconium composite mesopore metal oxide of any of claims 1 or 2, with
The total weight of the mesoporous denitrating catalyst is 100% calculating, and it includes the vanadium titanium zirconium composite mesopore metal oxides of 85-95wt%
And binder surplus.
17. mesoporous denitrating catalyst according to claim 16, which is characterized in that the ratio table of the mesoporous denitrating catalyst
Area is greater than 150m2/ g, mesopore volume 0.69-1.2mL/g, average pore size 2-10nm.
18. mesoporous denitrating catalyst according to claim 17, which is characterized in that the mesopore volume is 0.8-1.2mL/
g。
19. mesoporous denitrating catalyst according to claim 16, which is characterized in that the binder includes intending thin water aluminium
The combination of one or more of stone, aluminium hydroxide and Aluminum sol.
20. the preparation method of the described in any item mesoporous denitrating catalysts of claim 16-19 comprising following steps:
Extrusion or compression molding are carried out after vanadium titanium zirconium composite mesopore metal oxide is mixed with deionized water, binder, then are passed through
After dry, roasting, the mesoporous denitrating catalyst is obtained.
21. preparation method according to claim 20, which is characterized in that the vanadium titanium zirconium composite mesopore metal oxide,
Binder and the mass ratio of deionized water are 10:(1.0-3.0): (1.5-4.0).
22. preparation method according to claim 20, which is characterized in that the temperature of the drying is 80-120 DEG C, the time
For 8-24h.
23. according to the described in any item preparation methods of claim 20-22, which is characterized in that the temperature of the roasting is 500-
650 DEG C, time 4-12h.
24. application of the described in any item mesoporous denitrating catalysts of claim 16-19 in denitrating flue gas.
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