CN110404542A - A kind of core-shell structure copolymer ball CoFe2O4Catalyst and the preparation method and application thereof - Google Patents
A kind of core-shell structure copolymer ball CoFe2O4Catalyst and the preparation method and application thereof Download PDFInfo
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- CN110404542A CN110404542A CN201910797909.7A CN201910797909A CN110404542A CN 110404542 A CN110404542 A CN 110404542A CN 201910797909 A CN201910797909 A CN 201910797909A CN 110404542 A CN110404542 A CN 110404542A
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- 239000011258 core-shell material Substances 0.000 title claims abstract description 44
- 229920001577 copolymer Polymers 0.000 title claims abstract description 41
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- 239000003054 catalyst Substances 0.000 claims abstract description 69
- 229910002518 CoFe2O4 Inorganic materials 0.000 claims abstract description 24
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 24
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 15
- 238000010531 catalytic reduction reaction Methods 0.000 claims abstract description 13
- 229910052742 iron Inorganic materials 0.000 claims abstract description 10
- 239000002131 composite material Substances 0.000 claims abstract description 3
- 238000006243 chemical reaction Methods 0.000 claims description 20
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical group OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 12
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 12
- 238000002604 ultrasonography Methods 0.000 claims description 12
- 239000003960 organic solvent Substances 0.000 claims description 11
- 229910017052 cobalt Inorganic materials 0.000 claims description 9
- 239000010941 cobalt Substances 0.000 claims description 9
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 9
- 238000003756 stirring Methods 0.000 claims description 8
- 238000001035 drying Methods 0.000 claims description 7
- 239000002245 particle Substances 0.000 claims description 7
- 239000002243 precursor Substances 0.000 claims description 7
- 235000011187 glycerol Nutrition 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 6
- 238000001354 calcination Methods 0.000 claims description 5
- GQPLMRYTRLFLPF-UHFFFAOYSA-N Nitrous Oxide Chemical class [O-][N+]#N GQPLMRYTRLFLPF-UHFFFAOYSA-N 0.000 claims description 4
- 239000013078 crystal Substances 0.000 claims description 4
- 229910003321 CoFe Inorganic materials 0.000 claims description 3
- 239000003795 chemical substances by application Substances 0.000 claims description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 3
- 238000005119 centrifugation Methods 0.000 claims description 2
- QGUAJWGNOXCYJF-UHFFFAOYSA-N cobalt dinitrate hexahydrate Chemical group O.O.O.O.O.O.[Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O QGUAJWGNOXCYJF-UHFFFAOYSA-N 0.000 claims description 2
- 239000002077 nanosphere Substances 0.000 claims description 2
- 150000002823 nitrates Chemical class 0.000 claims description 2
- 238000001338 self-assembly Methods 0.000 claims description 2
- 238000005406 washing Methods 0.000 claims description 2
- 230000007613 environmental effect Effects 0.000 abstract description 4
- 238000000746 purification Methods 0.000 abstract description 3
- 238000006555 catalytic reaction Methods 0.000 abstract description 2
- 239000002994 raw material Substances 0.000 abstract 2
- RIVZIMVWRDTIOQ-UHFFFAOYSA-N cobalt iron Chemical group [Fe].[Co].[Co].[Co] RIVZIMVWRDTIOQ-UHFFFAOYSA-N 0.000 abstract 1
- 238000010276 construction Methods 0.000 abstract 1
- 239000000203 mixture Substances 0.000 abstract 1
- 229910052723 transition metal Inorganic materials 0.000 abstract 1
- 150000003624 transition metals Chemical class 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 11
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 10
- 238000000034 method Methods 0.000 description 8
- 239000003546 flue gas Substances 0.000 description 7
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 6
- 230000000694 effects Effects 0.000 description 5
- 239000007789 gas Substances 0.000 description 5
- 239000011259 mixed solution Substances 0.000 description 4
- 230000001376 precipitating effect Effects 0.000 description 4
- 239000012495 reaction gas Substances 0.000 description 4
- 230000002776 aggregation Effects 0.000 description 3
- 238000004220 aggregation Methods 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 238000005245 sintering Methods 0.000 description 3
- 241001012508 Carpiodes cyprinus Species 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 230000006378 damage Effects 0.000 description 2
- 239000003344 environmental pollutant Substances 0.000 description 2
- 239000002082 metal nanoparticle Substances 0.000 description 2
- DOTMOQHOJINYBL-UHFFFAOYSA-N molecular nitrogen;molecular oxygen Chemical compound N#N.O=O DOTMOQHOJINYBL-UHFFFAOYSA-N 0.000 description 2
- 239000002808 molecular sieve Substances 0.000 description 2
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical compound O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 description 2
- RJIWZDNTCBHXAL-UHFFFAOYSA-N nitroxoline Chemical compound C1=CN=C2C(O)=CC=C([N+]([O-])=O)C2=C1 RJIWZDNTCBHXAL-UHFFFAOYSA-N 0.000 description 2
- 231100000719 pollutant Toxicity 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 238000006722 reduction reaction Methods 0.000 description 2
- 238000005070 sampling Methods 0.000 description 2
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 2
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- 230000010757 Reduction Activity Effects 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 238000003916 acid precipitation Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 150000001875 compounds Chemical group 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000011978 dissolution method Methods 0.000 description 1
- 239000005431 greenhouse gas Substances 0.000 description 1
- 210000004209 hair Anatomy 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 230000002779 inactivation Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 230000001473 noxious effect Effects 0.000 description 1
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 230000008439 repair process Effects 0.000 description 1
- 230000029058 respiratory gaseous exchange Effects 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 210000002268 wool Anatomy 0.000 description 1
Classifications
-
- 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
- B01J23/70—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
-
- B01J35/396—
-
- B01J35/40—
-
- B01J35/61—
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2251/00—Reactants
- B01D2251/20—Reductants
- B01D2251/206—Ammonium compounds
- B01D2251/2062—Ammonia
Abstract
The invention belongs to environmental catalysis purification techniques fields, disclose a kind of core-shell structure copolymer ball CoFe2O4Catalyst and the preparation method and application thereof.The present invention uses raw material iron from a wealth of sources, cheap, and the ferro-cobalt core-shell structure copolymer composite oxide catalysts with special construction are prepared by simple and easy hydro-thermal method.The catalyst has unique structure composition, shows excellent ammine selectivity catalytic reduction NOxActive and anti-air speed performance.The preparation method of catalyst is simple and efficient reliably, and raw material is easy to get, and has versatility, and controllable degree is high, can be used for the preparation of a variety of transition metal nucleocapsid catalysts, obtained catalyst is uniform, porous.
Description
Technical field
The invention belongs to environmental catalysis purification techniques fields, and in particular to one kind is applied to ammine selectivity catalytic reduction nitrogen oxygen
The CoFe with core-shell structure copolymer spherical structure of compound2O4Catalyst and preparation method thereof.
Background technique
With the development of science and technology, the pollutant in atmosphere is also to increase year by year, although country has formulated Atmosphere control standard,
But due to the needs of industrial development, atmosphere pollution is still a global pollution problem.Wherein nitrogen oxides (NOx) make
For one of the major pollutants in atmosphere, the secondary pollutions such as photochemical fog problem, acid rain, formation ozone hole etc. can be caused
Great environmental problem, while to human health, biology breathing all causes certain toxic action.NOxSource can be divided into nature
Source and artificial source, in NOxIn artificial source emission, using coal-fired plant flue gas as the stationary source NO of representativexWith using exhaust gas from diesel vehicle as generation
The moving source NO of tablexAbout 60% and 40% NO is occupied respectivelyxDischarge share.How NO is effectively removedxAs current environment
The important topic administered and protected.In numerous NOxIn administering method, with NH3For reducing agent Selective Catalytic Reduction of NOx(NH3-
SCR) method is maximally efficient and is most hopeful to carry out the NO of large-scale practical applicationxRemoval technology.Since the 1970s
It is widely used in stationary source denitrating flue gas.SCR catalyst system is the core of SCR technology.At present, the NH3- of industrial applications
SCR catalyst is mainly V2O5-WO3(MoO3)/TiO2Catalyst.The catalyst is mainly used in the de- of stationary source coal-fired flue-gas
Nitre, and have been incorporated into the NO of exhaust gas from diesel vehiclexControl field.But the catalyst system is limited due to self shortcoming
Further using for it is made.Such as contain noxious material V in the catalyst2O5If V occurs in use process2O5Fall off or
The a large amount of catalyst inactivated after person's use, entering has bio-toxicity in environment, can all cause to environment and biology serious
Harm；The catalyst system generates a large amount of greenhouse gases N when also having relatively narrow operation temperature window, high temperature2O, simultaneously in height
Temperature is to SO2Oxidability it is strong, the disadvantages of high high-temp stability is poor.Therefore, many researchers are dedicated to developing novel environmental
Friendly has high NH3SCR activity, wide operation temperature window, the catalyst system for adapting to high-speed environment, hydrothermally stable, with
Phase is applied to stationary source and moving source flue gas NOxCatalytic purification.Studying more catalyst type at present has molecular sieve or expensive
The loaded catalysts such as metal have special appearance catalyst etc..But the loaded catalysts such as molecular sieve or noble metal exist
Expensive, the disadvantages of Precious Metals Resources are rare, there are easy-sinterings, aggregation inactivation, anti-high-speed energy for special appearance catalyst
The disadvantages of power is poor.Numerous for NO in stationary source and moving source flue gasxThe NH of control3SCR catalyst.The catalyst purport of design
Solving NH3The key problems such as relatively low, anti-air speed ability of catalyst system of low temperature active in-SCR.
Summary of the invention
The technology of the present invention solves the problems, such as: overcoming the deficiencies of the prior art and provide a kind of applied to ammine selectivity catalytic reduction
The catalyst and preparation method thereof with core-shell structure copolymer spherical structure of nitrogen oxides.The catalyst is in ammine selectivity catalytic reduction nitrogen oxygen
The sintering and loss of metal nanoparticle can be prevented in the reaction of compound, and its nucleocapsid structure is also possible to prevent in flue gas
Polluter lead to active reduction in catalyst activity position surface aggregation, core-shell structure not only substantially increases surface
Product, to increase contact area and the contact point of reaction gas.And then greatly improve the reactivity of catalyst.
Technical solution of the present invention:
A kind of core-shell structure copolymer ball CoFe2O4Catalyst, core-shell structure copolymer ball CoFe2O4The core of catalyst is CoFe2O4, shell CoFe2O4；
Core-shell structure copolymer ball CoFe2O4The group of catalyst becomes the cobalt of 1:2 molar ratio: the core-shell structure copolymer spherical structure for the composite oxides building that iron is formed
Catalyst；That is core-shell structure copolymer ball CoFe2O4The core of catalyst is single crystal phase CoFe2O4Particle, shell are single crystal phase CoFe2O4Particle,
The particle is self-assembly of core-shell structure copolymer nanosphere.
The core-shell structure copolymer ball CoFe2O4The partial size of catalyst is 0.58-0.83um, and the partial size of core is 0.45-0.76um, shell
With a thickness of 0.13-0.16um.
A kind of core-shell structure copolymer ball CoFe2O4The preparation method of catalyst, includes the following steps:
(1) organic solvent A and organic solvent B are mixed, stirs 30-60min at 30-50 DEG C, organic solvent A and organic
The volume ratio of solvent B is 5:1；
(2) cobalt precursor ultrasound 5-20min at 30-50 DEG C in Ultrasound Instrument is added in the solution obtained to step (1), then
Iron presoma is added and stirs 30-60min at 30-50 DEG C；Cobalt precursor and the molar ratio of iron presoma are 1:2；
(3) solution for obtaining step (2) is after the completion of 160-200 DEG C, hydro-thermal reaction 6-12h, hydro-thermal, centrifugation, washing,
Drying；
(4) sample after step (3) drying is calcined in 400-600 DEG C, calcination time 1-3h obtains the core-shell structure copolymer
Sphere catalyst.
The cobalt precursor is cobalt nitrate hexahydrate；The iron presoma is nine water ferric nitrates；The organic solvent A
For isopropanol；The organic solvent B is glycerine.
In step (3), hydrothermal temperature is 180 DEG C, and the hydro-thermal time is 8h.
In step (4), maturing temperature is 500 DEG C, and heating rate is 1 DEG C/min, calcining time 2h.
The mode of the dissolution cobalt precursor is ultrasonic dissolution method；The mode of dissolved iron presoma is stirring and dissolving method.
Core-shell structure copolymer ball CoFe2O4The catalyst that catalyst is reacted as ammine selectivity catalytic reduction nitrous oxides, in reaction,
NH3=500ppm, NO=500ppm, O2=3vol.%, Ar are as Balance Air, GHSV=40000h-1And 120000h-1。
Beneficial effects of the present invention:
(1) catalyst of the invention has nucleocapsid structure, therefore can in ammine selectivity catalytic reduction nitrous oxides reaction
To prevent the sintering and loss of metal nanoparticle, and its nucleocapsid structure is also possible to prevent the polluter in flue gas and is urging
Agent active sites surface aggregation and lead to active reduction, core-shell structure substantially increases the specific surface area of catalyst, effectively mentions
The contact area of high reaction gas and contact point, and then significant the reactivity for improving catalyst.
(2) preparation process of the invention is simple, and operation is easy and easy to control, can be mass-produced.
(3) present invention can regulate and control the pattern and particle size of catalyst, in turn by control hydro-thermal time and hydrothermal temperature
Influence the performance of catalyst.
(4) catalyst of the present invention shows very high ammine selectivity catalytic reduction activity at 250 DEG C, even if being in air speed
120000h-1High-speed reaction condition under still do not inactivate, show very high middle low temperature active and high-speed stability.
Detailed description of the invention
Fig. 1 is that the Electronic Speculum of 1 sample of embodiment characterizes (TEM) figure；
Fig. 2 is that the Electronic Speculum of 2 sample of embodiment characterizes (TEM) figure；
Fig. 3 is that the Electronic Speculum of 3 sample of embodiment characterizes (TEM) figure；
Fig. 4 is X-ray diffraction (XRD) figure of 2 sample of embodiment；
Fig. 5 is that the sample that embodiment 1-3 is prepared removes NO for ammine selectivity catalytic reductionxHigh-speed
(120000h-1) under the conditions of activity figure；
Fig. 6 is 2 sample of embodiment for ammine selectivity catalytic reduction removal NOxDifferent air speed activity figures.
Specific embodiment
The present invention is described in detail below by embodiment, but scope of the presently claimed invention is not by these
The limitation of embodiment.Meanwhile embodiment has been merely given as reaching the partial condition of this purpose, is not meant to must satisfy these
This purpose just may be implemented in condition.
Embodiment 1
Hydro-thermal method prepares core-shell structure copolymer spherical structure catalyst, specific preparation step are as follows:
(1) 50mL isopropanol and 10mL glycerine are added to 100mL to be placed in the beaker of magnetic stir bar, are stirred in magnetic force
It mixes and 30min is stirred at room temperature on device；
(2) the load weighted Co (NO of 0.25mmol is added in the mixed solution obtained to step (1)3)3·6H2O sample is placed in
Ultrasound 10min adds load weighted 0.5mmol Fe (NO to being completely dissolved under the conditions of 30 DEG C in Ultrasound Instrument3)3·9H2O is in room
30min is stirred under the conditions of temperature；
(3) solution that step (2) obtains is poured into 100mL reaction kettle, is started to warm up in an oven in room temperature to 180
DEG C, hydro-thermal reaction 6h；
(4) after hydro-thermal reaction is complete, solution 6000rad/s is taken out after reaction kettle is cooled to room temperature and is centrifuged 5min, it will be yellow
Color precipitating be placed in 80 DEG C of drying 12h in baking oven, later in Muffle furnace with the heating rate of 1 DEG C/min to 500 DEG C, holding 2h.
Finally obtained core-shell structure copolymer sphere catalyst.
Fig. 1 is that the Electronic Speculum of 1 sample of embodiment characterizes (TEM) figure, as shown, be formed by oxide assembles shape well
Glomeration, and be complete core-shell structure copolymer spherical structure.The partial size (diameter) of core-shell structure copolymer ball is in 0.48um between 0.68um at this time.Core
Partial size (diameter) is 0.4-0.68um；Part shell with a thickness of 0.08um.
Embodiment 2
Hydro-thermal method prepares core-shell structure copolymer spherical structure catalyst, specific preparation step are as follows:
(1) 50mL isopropanol and 10mL glycerine are added to 100mL to be placed in the beaker of magnetic stir bar, are stirred in magnetic force
It mixes and 30min is stirred at room temperature on device；
(2) the load weighted Co (NO of 0.25mmol is added in the mixed solution obtained to step (1)3)3·6H2O sample is placed in
Ultrasound 10min adds load weighted 0.5mmol Fe (NO to being completely dissolved under the conditions of 30 DEG C in Ultrasound Instrument3)3·9H2O is in room
30min is stirred under the conditions of temperature；
(3) solution that step (2) obtains is poured into 100mL reaction kettle, is started to warm up in an oven in room temperature to 180
DEG C, hydro-thermal reaction 8h；
(4) after hydro-thermal reaction is complete, solution 6000rad/s is taken out after reaction kettle is cooled to room temperature and is centrifuged 5min, it will be yellow
Color precipitating be placed in 80 DEG C of drying 12h in baking oven, later in Muffle furnace with the heating rate of 1 DEG C/min to 500 DEG C, holding 2h.
Finally obtained core-shell structure copolymer sphere catalyst.
Fig. 2 is that the Electronic Speculum of 2 sample of embodiment characterizes (TEM) figure, as shown, be formed by oxide assembles shape well
It is spherical at solid core-shell structure copolymer, structural integrity.The partial size of core-shell structure copolymer ball is in 0.58um between 0.83um at this time.The partial size of core is
0.45-0.76um；The shell with a thickness of 0.13-0.16um.
Embodiment 3
Hydro-thermal method prepares core-shell structure copolymer spherical structure catalyst, specific preparation step are as follows:
(1) 50mL isopropanol and 10mL glycerine are added to 100mL to be placed in the beaker of magnetic stir bar, are stirred in magnetic force
It mixes and 30min is stirred at room temperature on device；
(2) the load weighted Co (NO of 0.25mmol is added in the mixed solution obtained to step (1)3)3·6H2O sample is placed in
Ultrasound 10min adds load weighted 0.5mmol Fe (NO to being completely dissolved under the conditions of 30 DEG C in Ultrasound Instrument3)3·9H2O is in room
30min is stirred under the conditions of temperature；
(3) solution that step (2) obtains is poured into 100mL reaction kettle, is started to warm up in an oven in room temperature to 180
DEG C, hydro-thermal reaction 12h；
(4) after hydro-thermal reaction is complete, solution 6000rad/s is taken out after reaction kettle is cooled to room temperature and is centrifuged 5min, it will be yellow
Color precipitating be placed in 80 DEG C of drying 12h in baking oven, later in Muffle furnace with the heating rate of 1 DEG C/min to 500 DEG C, holding 2h.
Finally obtained core-shell structure copolymer sphere catalyst.
Fig. 3 is that the Electronic Speculum of 3 sample of embodiment characterizes (TEM) figure, as shown, the oxide formed forms apparent core-
Shell structure.The partial size of core-shell structure copolymer ball is in 0.24um between 0.5um at this time.The partial size of core is 0.2-0.54um；The thickness of part shell
For 0.04um.
Comparative example 1
Hydro-thermal method prepares core-shell structure copolymer spherical structure catalyst, specific preparation step are as follows:
(1) 50mL isopropanol and 10mL glycerine are added to 100mL to be placed in the beaker of magnetic stir bar, are stirred in magnetic force
It mixes and 30min is stirred at room temperature on device；
(2) the load weighted Co (NO of 0.25mmol is added in the mixed solution obtained to step (1)3)3·6H2O sample is placed in
Ultrasound 10min adds load weighted 0.5mmol Fe (NO to being completely dissolved under the conditions of 30 DEG C in Ultrasound Instrument3)3·9H2O is in room
30min is stirred under the conditions of temperature；
(3) solution that step (2) obtains is poured into 100mL reaction kettle, is started to warm up in an oven in room temperature to 180
DEG C, hydro-thermal reaction is for 24 hours；
(4) after hydro-thermal reaction is complete, solution 6000rad/s is taken out after reaction kettle is cooled to room temperature and is centrifuged 5min, it will be yellow
Color precipitating be placed in 80 DEG C of drying 12h in baking oven, later in Muffle furnace with the heating rate of 1 DEG C/min to 500 DEG C, holding 2h.
Finally obtained core-shell structure copolymer sphere catalyst.
It in air speed is 120000h that Fig. 5, which is embodiment 1-3 sample and 1 sample of comparative example,-1High-speed reaction condition under work
Property figure due to hydro-thermal overlong time lead to be formed by nucleocapsid structure destruction, activity is decreased obviously.
Embodiment 4
Weigh 0.2g CoFe2O4For catalyst in U-shaped reaction tube, catalyst low side uses silica wool, is passed through reaction gas NH3
=500ppm, NO=500ppm, O2=3vol.%, Ar are as Balance Air, GHSV=120000h-1, total gas couette is
300mL/min.25 DEG C of temperature spots carry out ammine selectivity catalytic reduction NO since 100 DEG CxActive testing.Reaction gas and production
Object gas NO, NO2, NOxIt is monitored on-line using Thermo Hi-42.It counts from 100 DEG C of constant temperature 30min post-sampling measuring points, it
Afterwards respectively at 125 DEG C, 150 DEG C, 175 DEG C, 200 DEG C, 225 DEG C, 250 DEG C, 275 DEG C, 300 DEG C, 325 DEG C of each thermostatics
The numeration of 30min post-sampling.
In order to detect the anti-air speed ability of catalyst, under reaction atmosphere, guarantee total gas couette is 300mL/min, is passed through
Change the quality of catalyst to change air speed.It is 40000h in air speed GHSV such as Fig. 6-1When, catalyst n OxConversion ratio is in 200-
80% or more conversion ratio is kept in 325 DEG C of temperature ranges；It is 120000h in air speed GHSV-1When, catalyst n OxConversion ratio exists
80% or more conversion ratio is kept in 225-300 DEG C of temperature range.
It should be noted that those skilled in the art are that this hair may be implemented completely according to the various embodiments described above of the present invention
Bright independent claims and the full scope of appurtenance, realize process and the same the various embodiments described above of method；And the present invention is not
It elaborates and partly belongs to techniques well known.
Above embodiments are provided just for the sake of the description purpose of the present invention, and are not intended to limit the scope of the invention.This
The range of invention is defined by the following claims.It does not depart from spirit and principles of the present invention and the various equivalent replacements made and repairs
Change, should all cover within the scope of the present invention.
Claims (9)
1. a kind of core-shell structure copolymer ball CoFe2O4Catalyst, which is characterized in that core-shell structure copolymer ball CoFe2O4The core of catalyst is CoFe2O4,
Shell is CoFe2O4；Core-shell structure copolymer ball CoFe2O4The group of catalyst becomes the cobalt of 1:2 molar ratio: the composite oxides building that iron is formed
Core-shell structure copolymer spherical structure catalyst；That is core-shell structure copolymer ball CoFe2O4The core of catalyst is single crystal phase CoFe2O4Particle, shell are single crystal phase
CoFe2O4Particle, the particle are self-assembly of core-shell structure copolymer nanosphere.
2. core-shell structure copolymer ball CoFe according to claim 12O4Catalyst, which is characterized in that the core-shell structure copolymer ball CoFe2O4It urges
The partial size of agent is 0.58-0.83um, and the partial size of core is 0.45-0.76um, shell with a thickness of 0.13-0.16um.
3. a kind of core-shell structure copolymer ball CoFe2O4The preparation method of catalyst, which comprises the steps of:
(1) organic solvent A and organic solvent B are mixed, 30-60min, organic solvent A and organic solvent is stirred at 30-50 DEG C
The volume ratio of B is 5:1；
(2) cobalt precursor ultrasound 5-20min at 30-50 DEG C in Ultrasound Instrument is added in the solution obtained to step (1), adds
Iron presoma stirs 30-60min at 30-50 DEG C；Cobalt precursor and the molar ratio of iron presoma are 1:2；
(3) solution for obtaining step (2) after the completion of 160-200 DEG C, hydro-thermal reaction 6-12h, hydro-thermal, washing, dry by centrifugation
It is dry；
(4) sample after step (3) drying is calcined in 400-600 DEG C, calcination time 1-3h obtains the core-shell structure copolymer ball and urges
Agent.
4. preparation method according to claim 3, which is characterized in that the cobalt precursor is cobalt nitrate hexahydrate；It is described
Iron presoma be nine water ferric nitrates；The organic solvent A is isopropanol；The organic solvent B is glycerine.
5. preparation method according to claim 3 or 4, which is characterized in that in step (3), hydrothermal temperature is 180 DEG C, water
The hot time is 8h.
6. preparation method according to claim 3 or 4, which is characterized in that in step (4), maturing temperature is 500 DEG C, is risen
Warm rate is 1 DEG C/min, calcining time 2h.
7. preparation method according to claim 5, which is characterized in that in step (4), maturing temperature is 500 DEG C, heating speed
Rate is 1 DEG C/min, calcining time 2h.
8. a kind of core-shell structure copolymer ball CoFe2O4The catalyst that catalyst is reacted as ammine selectivity catalytic reduction nitrous oxides.
9. core-shell structure copolymer ball CoFe according to claim 82O4Catalyst is reacted as ammine selectivity catalytic reduction nitrous oxides
Catalyst, which is characterized in that in reaction, NH3=500ppm, NO=500ppm, O2=3vol.%, Ar as Balance Air,
GHSV=40000h-1And 120000h-1。
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| CN113257579A (en) * | 2021-04-15 | 2021-08-13 | 安徽大学 | Cobalt ferrite/cobalt iron alloy nano composite counter electrode material and preparation method thereof |
| CN113257579B (en) * | 2021-04-15 | 2022-07-19 | 安徽大学 | Cobalt ferrite/cobalt iron alloy nano composite counter electrode material and preparation method thereof |
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Application publication date: 20191105 |