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 PDF

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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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core
catalyst
shell structure
cofe
structure copolymer
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曲振平
朱婷
王辉
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Dalian University of Technology
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    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D53/00Separation 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
    • B01D53/34Chemical or biological purification of waste gases
    • B01D53/74General processes for purification of waste gases; Apparatus or devices specially adapted therefor
    • B01D53/86Catalytic processes
    • B01D53/8621Removing nitrogen compounds
    • B01D53/8625Nitrogen oxides
    • B01D53/8628Processes characterised by a specific catalyst
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/002Mixed oxides other than spinels, e.g. perovskite
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/74Iron group metals
    • B01J23/75Cobalt
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00Catalysts, in general, characterised by their form or physical properties
    • B01J35/30Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
    • B01J35/396Distribution of the active metal ingredient
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00Catalysts, in general, characterised by their form or physical properties
    • B01J35/40Catalysts, in general, characterised by their form or physical properties characterised by dimensions, e.g. grain size
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00Catalysts, in general, characterised by their form or physical properties
    • B01J35/60Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/61Surface area
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D2251/00Reactants
    • B01D2251/20Reductants
    • B01D2251/206Ammonium compounds
    • B01D2251/2062Ammonia

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  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
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  • Environmental & Geological Engineering (AREA)
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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

A kind of core-shell structure copolymer ball CoFe2O4Catalyst and the preparation method and application thereof
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
CN201910797909.7A 2019-08-27 2019-08-27 A kind of core-shell structure copolymer ball CoFe2O4Catalyst and the preparation method and application thereof Withdrawn CN110404542A (en)

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CN111992211A (en) * 2020-09-27 2020-11-27 宁夏共宣环保科技有限责任公司 Denitration catalyst with core-shell structure and preparation method thereof
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

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Publication number Priority date Publication date Assignee Title
CN111229035A (en) * 2020-01-21 2020-06-05 鞍钢股份有限公司 Denitration method suitable for sintering flue gas
CN111992211A (en) * 2020-09-27 2020-11-27 宁夏共宣环保科技有限责任公司 Denitration catalyst with core-shell structure and preparation method thereof
CN111992211B (en) * 2020-09-27 2023-04-28 宁夏共宣环保科技有限责任公司 Denitration catalyst with core-shell structure, and preparation method and application thereof
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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