CN107790116A - The preparation of spinel catalyst and the elimination applied to nitrogen oxides - Google Patents
The preparation of spinel catalyst and the elimination applied to nitrogen oxides Download PDFInfo
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- CN107790116A CN107790116A CN201610806395.3A CN201610806395A CN107790116A CN 107790116 A CN107790116 A CN 107790116A CN 201610806395 A CN201610806395 A CN 201610806395A CN 107790116 A CN107790116 A CN 107790116A
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- spinel
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- electrostatic spinning
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- 239000003054 catalyst Substances 0.000 title claims abstract description 54
- 229910052596 spinel Inorganic materials 0.000 title claims abstract description 16
- 239000011029 spinel Substances 0.000 title claims abstract description 15
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 title claims description 20
- 238000003379 elimination reaction Methods 0.000 title abstract description 7
- 230000008030 elimination Effects 0.000 title abstract description 4
- 238000010041 electrostatic spinning Methods 0.000 claims abstract description 14
- 238000000034 method Methods 0.000 claims abstract description 11
- 239000007787 solid Substances 0.000 claims abstract description 6
- 238000010438 heat treatment Methods 0.000 claims abstract description 4
- 239000000203 mixture Substances 0.000 claims abstract description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 17
- 238000001035 drying Methods 0.000 claims description 7
- 229910052742 iron Inorganic materials 0.000 claims description 6
- 229910052748 manganese Inorganic materials 0.000 claims description 6
- 239000008139 complexing agent Substances 0.000 claims description 5
- 239000002904 solvent Substances 0.000 claims description 5
- 238000003756 stirring Methods 0.000 claims description 5
- 238000000746 purification Methods 0.000 claims description 4
- 150000003839 salts Chemical class 0.000 claims description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 4
- 229910052802 copper Inorganic materials 0.000 claims description 3
- 229910052759 nickel Inorganic materials 0.000 claims description 3
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 3
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 3
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical class CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 2
- 229910052796 boron Inorganic materials 0.000 claims description 2
- -1 polypropylene cyanogen Polymers 0.000 claims description 2
- 238000005245 sintering Methods 0.000 claims description 2
- 229910052723 transition metal Inorganic materials 0.000 claims description 2
- 150000003624 transition metals Chemical class 0.000 claims description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims 3
- 229910002651 NO3 Inorganic materials 0.000 claims 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims 2
- 238000009987 spinning Methods 0.000 claims 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims 1
- 230000000877 morphologic effect Effects 0.000 claims 1
- 239000002994 raw material Substances 0.000 claims 1
- 239000000126 substance Substances 0.000 claims 1
- 229910016506 CuCo2O4 Inorganic materials 0.000 abstract description 13
- 238000006243 chemical reaction Methods 0.000 abstract description 12
- 230000000694 effects Effects 0.000 abstract description 4
- 239000003546 flue gas Substances 0.000 abstract description 4
- 230000008569 process Effects 0.000 abstract description 4
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 abstract description 3
- 229910002518 CoFe2O4 Inorganic materials 0.000 abstract description 2
- 239000013078 crystal Substances 0.000 abstract description 2
- 239000002073 nanorod Substances 0.000 abstract description 2
- 229910005949 NiCo2O4 Inorganic materials 0.000 abstract 1
- 239000000446 fuel Substances 0.000 abstract 1
- 230000001105 regulatory effect Effects 0.000 abstract 1
- 239000002121 nanofiber Substances 0.000 description 10
- 239000000243 solution Substances 0.000 description 10
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- 239000007789 gas Substances 0.000 description 6
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 5
- 239000002086 nanomaterial Substances 0.000 description 5
- PXRKCOCTEMYUEG-UHFFFAOYSA-N 5-aminoisoindole-1,3-dione Chemical compound NC1=CC=C2C(=O)NC(=O)C2=C1 PXRKCOCTEMYUEG-UHFFFAOYSA-N 0.000 description 4
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical compound O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 description 4
- 239000002070 nanowire Substances 0.000 description 4
- 229910000069 nitrogen hydride Inorganic materials 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 229910000510 noble metal Inorganic materials 0.000 description 3
- 230000009467 reduction Effects 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- 229910016507 CuCo Inorganic materials 0.000 description 2
- 239000003708 ampul Substances 0.000 description 2
- 239000003638 chemical reducing agent Substances 0.000 description 2
- 235000019504 cigarettes Nutrition 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 238000002347 injection Methods 0.000 description 2
- 239000007924 injection Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000010453 quartz Substances 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 230000009466 transformation Effects 0.000 description 2
- 241000196324 Embryophyta Species 0.000 description 1
- 229910026161 MgAl2O4 Inorganic materials 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 239000012876 carrier material Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000005518 electrochemistry Effects 0.000 description 1
- 230000005686 electrostatic field Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- DOTMOQHOJINYBL-UHFFFAOYSA-N molecular nitrogen;molecular oxygen Chemical compound N#N.O=O DOTMOQHOJINYBL-UHFFFAOYSA-N 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- RJIWZDNTCBHXAL-UHFFFAOYSA-N nitroxoline Chemical compound C1=CN=C2C(O)=CC=C([N+]([O-])=O)C2=C1 RJIWZDNTCBHXAL-UHFFFAOYSA-N 0.000 description 1
- 230000001473 noxious effect Effects 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 231100000572 poisoning Toxicity 0.000 description 1
- 230000000607 poisoning effect Effects 0.000 description 1
- 230000007096 poisonous effect Effects 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000011946 reduction process Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 239000011010 synthetic spinel Substances 0.000 description 1
- 239000002351 wastewater Substances 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
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/74—Iron group metals
- B01J23/75—Cobalt
-
- 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
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/005—Spinels
-
- 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
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/10—Magnesium; Oxides or hydroxides thereof
-
- 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
- B01J23/005—Spinels
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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
- B01J23/32—Manganese, technetium or rhenium
- B01J23/34—Manganese
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/72—Copper
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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
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/74—Iron group metals
- B01J23/745—Iron
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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
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/74—Iron group metals
- B01J23/755—Nickel
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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
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/78—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with alkali- or alkaline earth metals
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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
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/889—Manganese, technetium or rhenium
- B01J23/8892—Manganese
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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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
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- B01J35/30—
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- B01J35/40—
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- 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
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- 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
Abstract
The present invention provides the NO_x elimination that a kind of spinel-type catalyst of high activity is used for the discharge of the coal-fired flue-gas such as thermal power plant and nitric plant.The catalyst shows high NO in wider air-fuel ratio rangexConversion ratio, and show excellent low temperature active.Prepared catalyst is prepared by high-voltage electrostatic spinning method, and spinel compositions mainly include CuCo2O4,NiCo2O4,FeCo2O4,CoMn2O4,CoFe2O4Pattern Deng, the catalyst of preparation includes crystal face and size and can regulated and controled by method of electrostatic spinning combination heat treatment process, and wherein hollow pipe type spinelle is in NOxPerformance in elimination will be much better than solid nano rod.The denitration effect that the present invention provides catalyst is better than traditional NOxEliminate catalyst.Easy to operate and preparation technology is simple, cost is low, NOxHigh conversion rate, there is obvious industrial application value.
Description
Technical field
The invention belongs to nano-catalytic application, and in particular to the preparation side of high-efficiency denitration catalyst under a kind of low temperature
Method.
Background technology
In recent years, problem of environmental pollution is increasingly by global extensive concern and attention.Particularly in China, haze
Problem has turned into the Social Events of relation national economy sustainable development and people's life health.Nitrogen oxides (NOx) be
One of main predecessor of photochemical fog is produced, and exhaust gas from diesel vehicle, coal-burning power plant discharge flue gas and coal-burned industrial boiler cigarette
Gas is to produce NOxMain source.China is by development for many years, various NOxAlthough removing sulfuldioxide obtains relatively broad answer
With, but because of NOxPollution causes the overall state of haze still to cannot get the containment of essence.
In numerous removing NOxIn technology, SCR (SCR) is most effective removing NOxOne of technology.SCR skills
Art is to contain NOxFlue gas in spray into ammonia, urea or other reducing agents, in the presence of catalyst optionally with cigarette
NO in gasxReaction generation N2And water, the core of the technology is catalyst.SCR catalyst mainly includes three classes at present：(1) transition
Metal-based catalyst.Wherein, V2O5-WO3(MoO3)/TiO2It is the catalyst of current large-scale commercial application, but its activity is warm
Area is at 300-400 DEG C, and V2O5For noxious material.(2) Pt, Pd and Rh etc. are the noble metal-based catalysts of active component.Though they
So there is excellent NO under cryogenicxReducing activity, but easy SO2It is poisoned and by reducing agent NH3It is oxidized to N2O, and noble metal
The factor such as expensive limits the extensive use of noble metal-based catalysts.(3) molecular sieve is the catalyst of carrier.ZSM-5 and
MFI equimoleculars sieve for carrier catalyst because active warm area it is wider, and catalyst it is discarded after be easily recycled and cause concern, but this
The easy SO of type catalyst2Poisoning, and the more hydroxyl in surface causes hydrothermal stability poor simultaneously.Therefore, active warm area is researched and developed
Wide, good hydrothermal stability and resistance to SO2Advanced the SCR carrier materials and catalyst of poisoning are that the above-mentioned catalyst of solution is of problems
It is crucial.
In recent years, numerous researchs show, can realize that pattern and the size of nano material etc. are micro- by electrostatic spinning technique
See the synchronization modulation of structure.Method of electrostatic spinning refers to that polymer solution overcomes surface tension and viscosity under high voltage electrostatic field
Power forms injection thread, and thread, due to the quick volatilization of solvent, is finally formed by curing fibre in course of injection on collection device
Dimension.The technology can synthesize the different-shape nano material with surface multilevel hierarchy and internal multilayered structure on a large scale, strictly according to the facts
The heart/hollow nano fiber, hetero-junctions, nucleocapsid structure, meso-porous nano pipe and spiral nano-fibre etc..The nano material prepared
Not only size uniform, adjustable length, and morphology controllable, while there is very big specific surface area.These nano materials compared to
Traditional nano material has the performance such as more excellent electrochemistry and sensing, but not yet reports that preparing various 1D using this method receives
Rice material is simultaneously applied to NOxElimination reaction.
However, there is presently no Patents and document for electrostatic spinning to NOxThe microstructure for eliminating catalyst is entered
The relevant report of row regulation and control.
The content of the invention
Present disclosure is specific as follows：
A kind of spinel based catalysts for purification of nitrogen oxides, it is characterized in that：The molecule of the spinel-type catalyst
Formula is AB2O4, wherein A positions are mainly Mg, Cu, Co, Fe, Mn and Ni, and B is predominantly Al, Co, Mn, Fe, such as MgAl2O4,
CuCo2O4,CoMn2O4,FeCo2O4,CoFe2O4Deng.
Due to conventional method prepare spinel based catalysts, it is necessary to temperature>700 DEG C, cause the specific surface area of spinelle
It is smaller, it is unfavorable for the raising of catalytic performance.Therefore, patent of the present invention passes through Gao Jufen by using high-voltage electrostatic spinning device
Son is template, and addition complexing agent, and the presoma of synthetic spinel under different voltages and flow velocity, the presoma is fired
Afterwards, after high dimeric molecule and complexing agent decompose, spinel structure is formed, required temperature is 400 DEG C, and specific surface area is much big
In conventional method synthesis.
Above-mentioned described high dimeric molecule, can be polypropylene cyanogen (PAN), its corresponding solvent is N-N dimethylformamides
(DMF)；High dimeric molecule can also be polyvinylpyrrolidone (PVP), and its corresponding solvent is water or DMF.Described height gathers
The quality of molecule and the total mass ratio of inorganic salts are 2:1.Described complexing agent is mainly citric acid (CA), and its corresponding quality is pre-
For the 1/4 of high dimeric molecule.
The high-voltage electrostatic spinning of theory described above, the high pressure used is 18-22kV, flow velocity 0.6-1.0mL/h.
The electrostatic spinning sample of collection, by 100 DEG C of drying, sintering temperature is 400-450 DEG C, time 2-4h, is risen
Warm speed is 0.5-10 DEG C/min, wherein be calcined by 0.5-1 DEG C/min, obtain for hollow pipe type spinelle, and pass through>1
DEG C/min roasting, the obtained spinel catalyst for either solid nanorods shape.
Catalyst described above, specific surface area 80-110m2/ g, its specific surface area are greater than traditional coprecipitation
Preparation spinelle (<50m2/g)。
The catalyst of above-mentioned preparation, it is mainly used in applied to the nitrogen oxygen discharged in the coal-fired flue-gas such as thermal power plant and nitric plant
Compound eliminates.
The spinel catalyst of synthesis, such as CuCo2O4, the catalyst preparation process is simple, no contaminated wastewater, and traditional
V2O5-WO3(MoO3)/TiO2Catalyst, which is compared, has higher low temperature NOxConversion ratio, anti-sulfur poisonous performance and higher water resistant
Performance.
The present invention uses following scheme：For NOxEliminate the CuCo of catalyst2O4Prepare, its feature is as follows：By mol ratio
For 1:2 Cu (NO3)2·3H2O and Co (NO3)2·6H2O is dissolved in 19mL DMF, states 0.30g is added in solution then up
CA and 1.2g PAN, are stirred at room temperature 24h.The solution to stir is by electrostatic spinning apparatus, in 22kV, 1mL/h conditions
Under, form 1-dimention nano fiber.The nanofiber of collection obtains CuCo by drying roasting2O4。
The present invention has following advantage：
(1) the catalyst pattern prepared is homogeneous, and crystal face and size are controllable.
(2) there is high specific surface area.
(3) compared with traditional V bases catalyst, there is higher NO at low temperaturexConversion ratio and anti-SO2Poisoning performance；Prepare
Process is simple, no sewage discharge, and substantially reduces the synthesis cost of catalyst, has extensive prospects for commercial application.
Brief description of the drawings
Fig. 1：CuCo2O4Hollow pipe and CuCo2O4The scanning figure of nano wire.
Fig. 2：CuCo2O4Hollow pipe and CuCo2O4The NO of nano wirexEliminate performance.
Fig. 3：CuCo2O4Hollow pipe and CuCo2O4The anti-SO of nano wire2Poisoning performance.
Fig. 4：CuCo2O4Hollow pipe and CuCo2O4The heat endurance of nano wire.
Embodiment
Cu (NO of the invention by by mol ratio for 0.4mmol3)2·3H2O and 0.8mmol Co (NO3)2·6H2O is dissolved in
In 19mL DMF, 1.44mmol grams of CA and 1.2 gram of PAN of addition in solution is stated then up, 24h is stirred at room temperature.Stirring is equal
Even solution under the conditions of 22kV, 1mL/h, forms 1-dimention nano fiber by electrostatic spinning apparatus.The nanofiber warp of collection
Cross drying roasting and obtain CuCo2O4。
The present invention is applied to NOxSCR technology, NOxReduction process is as follows：In continuous stream actuating miniature reactor
Upper carry out NOxConversion ratio determines, amount of samples 0.5mL, air speed 150,000h-1, sample, constant temperature reduction NO at 50-400 DEG Cx, gas
Body volume composition is 294ppm NO, 350ppm NH3, 3vol%O2(Ar Balance Airs), NOxConversion ratio passes through chemiluminescence NO-
NO2-NOxAnalyzer detects (Thermo, 42i-HL).N2Selectivity is detected (Nicolet Nexus 6700) by infrared facility.
It is several embodiments of the present invention below, further illustrates the present invention, but the present invention is not limited only to this.Embodiment
1
Cu (NO of the invention by by mol ratio for 0.4mmol3)2·3H2O and 0.8mmolCo (NO3)2·6H2O is dissolved in
In 19mL DMF, addition 1.44mmolCA and 1.2g PAN in solution are stated then up, 24h is stirred at room temperature.Stir
Solution pass through electrostatic spinning apparatus, under the conditions of 22kV, 1mL/h, formed 1-dimention nano fiber.The nanofiber of collection passes through
100 DEG C of drying, 400 are calcined, and heating rate is 0.5 DEG C/min in roasting process, and the catalyst of preparation is labeled as CuCo2O4。
NOxElimination process:0.5ml samples are taken to be placed in u-shaped (i.d=8mm) quartz ampoule, in continuous stream actuating miniature reactor
Upper carry out NOxReducing property determines, air speed 150,000h-1, sample, constant temperature reduction NO at 50-400 DEG Cx, gas volume, which forms, is
294ppm NO,350ppm NH3, 3vol%O2(Ar Balance Airs), NOxConversion ratio passes through chemiluminescence NO-NO2-NOxAnalyzer is examined
Survey (Thermo, 42i-HL).N2Selectivity is detected (Nicolet Nexus 6700) by infrared facility.And temperature be 250
DEG C it is passed through 100ppm SO2And 10vol%H2O。
Described catalyst is at above-mentioned appreciation condition, 200 DEG C, NOxIt is converted into N2Conversion ratio be 99%.Catalyst 400
DEG C keep 30h, find nitrogen oxidation conversion ratio keep 99% (Fig. 3).250 DEG C by 100ppm SO2Afterwards, CuCo2O4-
Solid transformation efficiency of the oxides of nitrogen is reduced to 61% (Fig. 4) by 99%.Embodiment 2
Cu (NO of the invention by by mol ratio for 0.4mmol3)2·3H2O and 0.8mmol Co (NO3)2·6H2O is dissolved in
In 19mL DMF, addition 1.44mmol CA and 1.2g PAN in solution are stated then up, 24h is stirred at room temperature.Stir
Solution pass through electrostatic spinning apparatus, under the conditions of 22kV, 1mL/h, formed 1-dimention nano fiber.The nanofiber of collection passes through
100 DEG C of drying, 400 are calcined, and heating rate is 10 DEG C/min in roasting process, and the catalyst of preparation is labeled as CuCo2O4-solid
(as shown in Figure 1).NOxElimination process:0.5ml samples are taken to be placed in u-shaped (i.d=8mm) quartz ampoule, it is anti-in continuous stream actuating miniature
Answer and NO is carried out on devicexReducing property determines, air speed 150,000h-1, sample, constant temperature reduction NO at 50-400 DEG Cx, gas volume group
As 294ppm NO, 350ppm NH3, 3vol%O2(Ar Balance Airs), NOxConversion ratio passes through chemiluminescence NO-NO2-NOxAnalysis
Instrument detects (Thermo, 42i-HL).N2Selectivity is detected (Nicolet Nexus 6700) by infrared facility.And it is in temperature
250 DEG C are passed through 100ppm SO2And 10vol%H2O。
Described catalyst is at above-mentioned appreciation condition, 200 DEG C, NOxIt is converted into N2Conversion ratio be 54%, such as Fig. 2 institutes
Show.At 250 DEG C by 100ppm SO2Afterwards, CuCo2O4- solid transformation efficiency of the oxides of nitrogen is reduced to 53% by 99%.
Claims (8)
1. a kind of spinel based catalysts for purification of nitrogen oxides, it is characterized in that：The catalyst is by two kinds of transition metal members
Element composition, the chemical formula of its main component is AB2O4, wherein A positions are Mg, Cu, Co, Fe, Mn and Ni, and B positions are Al, Co, Mn, Fe.
2. the spinel based catalysts of purification of nitrogen oxides according to claim 1, it is characterised in that：The catalyst leads to
Cross high pressure method of electrostatic spinning regulation and control pattern.The preparing raw material of the catalyst mainly includes high dimeric molecule, complexing agent and inorganic salts
And have solvent.
3. spinel based catalysts preparation method according to claim 2, wherein high dimeric molecule refer mainly to polypropylene cyanogen and
Polyvinylpyrrolidone, described complexing agent are mainly citric acid, and described inorganic salts are mainly nitrate or acetate；Made
Solvent is mainly water and N-N dimethylformamides.
4. the spinel based catalysts according to right 1 or 3, its pattern can realize regulation and control, including solid bar, hollow pipe,
Tube-in-tube.
5. the spinel based catalysts according to right 1 or 3, it is characterised in that：The specific surface area of the catalyst is 80-
110m2/g。
6. requiring the preparation method of spinel based catalysts according to power 1 or 3, comprise the following steps：
(1) by a certain amount of Mg, Cu, Co, a kind of nitrate or acetic acid in one kind and Ni, Al, Co, Mn, Fe in Fe, Mn
Salt, it is dissolved in a certain amount of N-N dimethyl formamide solutions.
(2) 0.1-0.4g citric acid and the high dimeric molecules of 1.2g is added, stirs 24h.
(3) by high-voltage electrostatic spinning device, in 18-22kV voltages, flow velocity is to carry out spinning under 0.6-1.0mL/h.
(4) product of spinning is collected, is dried and is calcined.
(5) by adjusting the speed of roasting, the Morphological control of spinel catalyst is realized.
7. according to the spinelle base preparation method of the 6 desired catalyst, it is characterised in that：Described drying temperature is 100
DEG C, drying time 12-24h, sintering temperature is 400-450 DEG C, time 2-4h, and heating rate is 0.5-10 DEG C/min.
8. the purification of nitrogen oxides in the stationary sources such as thermal power plant and nitric plant is applied to according to claim 1 catalyst.
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