CN111514886A - Medium-low temperature SCR denitration catalyst with composite microsphere structure and application thereof - Google Patents
Medium-low temperature SCR denitration catalyst with composite microsphere structure and application thereof Download PDFInfo
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- 229910052742 iron Inorganic materials 0.000 claims abstract description 10
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 10
- 229910052684 Cerium Inorganic materials 0.000 claims abstract description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 5
- 229910052718 tin Inorganic materials 0.000 claims abstract description 5
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- 239000011572 manganese Substances 0.000 description 37
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- 238000002360 preparation method Methods 0.000 description 15
- 238000001354 calcination Methods 0.000 description 12
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- 239000002994 raw material Substances 0.000 description 9
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- 238000000975 co-precipitation Methods 0.000 description 7
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- 238000005516 engineering process Methods 0.000 description 4
- 238000011056 performance test Methods 0.000 description 4
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 3
- NGCDGPPKVSZGRR-UHFFFAOYSA-J 1,4,6,9-tetraoxa-5-stannaspiro[4.4]nonane-2,3,7,8-tetrone Chemical compound [Sn+4].[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O NGCDGPPKVSZGRR-UHFFFAOYSA-J 0.000 description 2
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- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium(3+);trinitrate Chemical compound [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 description 2
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- 229910001873 dinitrogen Inorganic materials 0.000 description 2
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- 230000002195 synergetic effect Effects 0.000 description 2
- DUNKXUFBGCUVQW-UHFFFAOYSA-J zirconium tetrachloride Chemical compound Cl[Zr](Cl)(Cl)Cl DUNKXUFBGCUVQW-UHFFFAOYSA-J 0.000 description 2
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonium chloride Substances [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
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- MVFCKEFYUDZOCX-UHFFFAOYSA-N iron(2+);dinitrate Chemical compound [Fe+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MVFCKEFYUDZOCX-UHFFFAOYSA-N 0.000 description 1
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- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
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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
- 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
- B01J23/70—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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- B01J35/40—
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- B01J35/50—
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/082—Decomposition and pyrolysis
- B01J37/088—Decomposition of a metal salt
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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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/34—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation
- B01J37/341—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation
- B01J37/343—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation of ultrasonic wave energy
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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 invention discloses a medium-low temperature SCR denitration catalyst with a composite microsphere structure and medium-low temperature NH thereof3The application of the catalyst in SCR denitration is characterized in that the catalyst is prepared by an ultrasonic atomization pyrolysis method, and the method comprises the following specific steps: (1) adding an active metal source and titanium tetrachloride into deionized water or absolute ethyl alcohol, and uniformly stirring to obtain a precursor liquid;the active metal source contains at least one element of Mn, Fe, Zr, Sn and Ce; (2) pouring the precursor liquid into an ultrasonic atomizer for atomization, flowing into a quartz tube reactor along with carrier gas for pyrolysis, collecting particles formed after pyrolysis, washing with deionized water, drying, rolling and screening, and finally roasting at 350-500 ℃ to obtain the medium-low temperature SCR denitration catalyst with a composite microsphere structure; the composite microsphere structure is a spherical carrier surface loaded with active component spheres.
Description
Technical Field
The invention relates to the technical field of catalysis, in particular to a medium-low temperature SCR denitration catalyst with a composite microsphere structure and application thereof.
Background
NH3Selective catalytic reduction technique (NH)3Selective Catalytic Reduction，NH3SCR) is currently removing NOxOne of the main techniques of (1), NH3SCR denitration catalysts are the core of this technology. Conventional NH3SCR denitration catalyst (mainly V)2O5Based catalysts, e.g. V2O5/WO3-TiO2、V2O5/MoO3-TiO2Etc.) the temperature is required to be 300-400 ℃ to achieve higher denitration efficiency, and in recent years, a large amount of tail gas discharged by non-electric industries is mainly at medium-low temperature<300 ℃) is mainly flue gas, if the traditional NH is needed3The SCR denitration catalyst exerts a good denitration effect, and the flue gas needs to be heated to more than 300 ℃, which undoubtedly increases the denitration cost greatly.
Therefore, it is urgently needed to develop a catalyst having a good SCR denitration activity at medium and low temperatures, and the catalyst should have a special structure with a large specific surface area, so that the dispersibility of active components is improved, and the catalyst can exert a good denitration performance at medium and low temperatures. At present, common methods for preparing the SCR catalyst comprise a sol-gel method, an impregnation method, a coprecipitation method and the like, but the methods generally have the defects of long preparation time, high precursor price, low-temperature activity of the catalyst, unstable activity and the like.
The ultrasonic atomization pyrolysis method is characterized in that a metal salt solution is sprayed into a high-temperature atmosphere in a mist shape, at the moment, the evaporation of a solvent and the thermal decomposition of the metal salt are immediately caused, and then a solid phase is separated out due to supersaturation, so that the nano powder is directly obtained; or spraying the solution into high-temperature atmosphere for drying, and then performing heat treatment to form powder.
At present, the ultrasonic atomization pyrolysis method has been used for preparing an electrocatalyst (e.g., the patent technology with publication number CN 107744817A), a photocatalyst (e.g., the patent technology with publication number CN 103007968A), a thin film material (e.g., the patent technology with publication number CN 1776013A), and the like, but there is no report on the preparation of an SCR denitration catalyst.
Disclosure of Invention
Aiming at the defects in the field, the invention provides a medium-low temperature SCR denitration catalyst with a composite microsphere structure, which is prepared by an ultrasonic atomization pyrolysis method, and titanium dioxide is used as a carrier, and a specific metal oxide is used as an active component. Compared with the traditional impregnation method and coprecipitation method, the catalyst prepared by the preparation method disclosed by the invention has a composite microsphere structure, so that the hollow structure of the catalyst is obviously increased, the specific surface area of the catalyst is larger, the dispersion degree of active components is higher and the distribution is more uniform, the action of active metal is fully exerted, and the medium-low temperature denitration activity is higher.
A medium-low temperature SCR denitration catalyst with a composite microsphere structure is prepared by an ultrasonic atomization pyrolysis method, and comprises the following specific steps:
(1) adding an active metal source and titanium tetrachloride into deionized water or absolute ethyl alcohol, and uniformly stirring to obtain a precursor solution; the active metal source contains at least one element of Mn, Fe, Zr, Sn and Ce;
(2) pouring the precursor solution into an ultrasonic atomizer for atomization, flowing into a quartz tube reactor along with carrier gas for pyrolysis, collecting particles formed after pyrolysis, washing with deionized water, drying, rolling, screening, and finally roasting to obtain the medium-low temperature SCR denitration catalyst with the composite microsphere structure;
the composite microsphere structure is a spherical carrier surface loaded with active component spheres.
The carrier is TiO2The active component is an active metal oxide, and the active metal comprises at least one of Mn, Fe, Zr, Sn and Ce.
The method has the advantages of simple and easily-controlled reaction operation, short catalyst preparation period and simple and convenient collection method, and the prepared catalyst shows excellent denitration performance in a medium-low temperature range.
According to research, the active metal source preferably contains both Mn and Fe. Obtained by the preparation method of the invention and made of TiO2In a catalytic system using the catalyst as a carrier, Mn and Fe, Zr, Sn and Ce respectively form double active components, and the result shows that the Mn and Fe have a synergistic effect, so that the particle size of the catalyst can be further reduced, and the redox performance and the low-temperature (120-180 ℃) denitration performance of the catalyst are remarkably improved. Still more preferably, the molar ratio of Fe to Mn in the medium-low temperature SCR denitration catalyst with the composite microsphere structure is 1: 10.
In step (2), the carrier gas may be nitrogen, air or oxygen, preferably nitrogen. It has been found that the oxygen concentration in the carrier gas affects the dispersibility of the catalyst, and the lower the oxygen concentration, the higher the catalyst dispersibility and the better the denitration activity, and therefore, it is preferable to use nitrogen gas as the carrier gas.
In the step (2), the pyrolysis temperature is 300-500 ℃.
In the step (2), the drying temperature is 60-100 ℃, and the drying time is 10-12 h.
In the step (2), roasting is carried out after rolling and screening to 60-100 meshes, wherein the roasting temperature is 350-600 ℃, the roasting time is 1.5-2 h, and the preferred roasting temperature is 350-500 ℃. Research shows that when the roasting temperature exceeds 500 ℃, the composite microsphere structure of the catalyst is broken, so that the denitration activity is reduced, and the roasting temperature is preferably 350-500 ℃.
In the step (2), the particles formed after pyrolysis are collected in a collecting device with 3 gas washing bottles connected in series continuously, and a filter screen for collecting and blocking the particles from escaping is arranged at the outlet of the last gas washing bottle.
The invention also provides the medium-low temperature NH of the SCR denitration catalyst with the composite microsphere structure3The application of the composite microsphere structure in SCR denitration is that the SCR denitration catalyst with the composite microsphere structure has good denitration efficiency under the condition that the denitration temperature is 120-240 ℃.
Preferably, theApplication of SCR denitration catalyst with composite microsphere structure to medium-low-temperature NH3And in SCR denitration, the active metal source contains both Mn and Fe.
Compared with the prior art, the invention has the main advantages that: compared with the traditional method (an impregnation method and a coprecipitation method) under the medium-low temperature condition of 120-240 ℃, the medium-low temperature SCR denitration catalyst with the composite microsphere structure prepared by the ultrasonic atomization pyrolysis method has more excellent denitration efficiency, and has the advantages of small aggregation degree, low crystallinity, good dispersibility and the like. Meanwhile, the catalyst prepared by the method has the advantages of low price of raw materials, short preparation time and low production cost.
Drawings
FIG. 1 is an SEM photograph of a medium-low temperature SCR denitration catalyst with a composite microsphere structure prepared in example 1;
FIG. 2 is an SEM photograph of the medium-low temperature SCR denitration catalyst with a composite microsphere structure prepared in example 2;
FIG. 3 is a denitration performance test chart of the medium-low temperature SCR denitration catalysts with composite microsphere structures respectively prepared in examples 1 to 5;
FIG. 4 is an SEM photograph of the medium-low temperature SCR denitration catalyst with a composite microsphere structure prepared in example 6;
FIG. 5 is an SEM photograph of the medium-low temperature SCR denitration catalyst with a composite microsphere structure prepared in example 7;
FIG. 6 is an SEM photograph of the medium-low temperature SCR denitration catalyst with a composite microsphere structure prepared in example 8;
FIG. 7 is an SEM photograph of the medium-low temperature SCR denitration catalyst with a composite microsphere structure prepared in example 9;
fig. 8 is a denitration performance test chart of the catalysts prepared in example 1 and comparative example 1, respectively.
Detailed Description
The invention is further described with reference to the following drawings and specific examples. It should be understood that these examples are for illustrative purposes only and are not intended to limit the scope of the present invention. The following examples are conducted under conditions not specified, usually according to conventional conditions, or according to conditions recommended by the manufacturer.
Example 1
(1) Preparation of precursor solution
Manganese nitrate (Mn (NO) was weighed in a molar ratio of n (Mn) to n (Ti) of 0.5:1 in the final sample3)2) And titanium tetrachloride (TiCl)4) Adding the mixture into deionized water, and stirring the mixture in a stirring device for 30min to fully dissolve the raw materials to obtain a precursor solution.
(2) Ultrasonic atomization pyrolysis
The prepared precursor solution is poured into an ultrasonic atomizer for atomizing, nitrogen is used as carrier gas, atomized liquid drops are carried into a quartz tube reactor for pyrolysis at 500 ℃. The particles formed by pyrolysis are collected in a collecting device with 3 gas washing bottles connected in series, and a filter screen is arranged at an outlet to further prevent the particles from escaping.
(3) Particle treatment
And drying the collected particles at 60 ℃ for 12 hours, and rolling and screening the particles to 60-100 meshes. The stability was improved by further calcining the granules in a tube furnace at 500 ℃ for 2 h. The finally obtained medium-low temperature SCR denitration catalyst with a composite microsphere structure is represented as Mn (0.5)/TiO2As shown in the SEM photograph, the overall size of the microspheres is less than 3.2 μm, and it can be observed that the active component beads are loaded on the surface of the spherical carrier.
(4) Test of denitration Performance
The resulting catalyst was placed in a fixed bed quartz tube reactor under simulated atmosphere (NO: 1000ppmv, NH)3：1000ppmv，O2: 5 vol%, and the balance N2) The denitration performance of a sample is tested at 120-240 ℃, and the total gas flow is 1000mL/min (space velocity GHSV of 30000 h)-1)。
Example 2
(1) Preparation of precursor solution
Iron nitrate (Fe (NO) was weighed in a molar ratio of n (Fe), n (Mn), n (Ti) 0.05:0.5:1 in the final sample3)3) Manganese nitrate (Mn (NO)3)2) And titanium tetrachloride (TiCl)4) Adding into anhydrous ethanol, stirring in stirring device for 30min to dissolve the raw materialsAnd obtaining a precursor solution through solution.
(2) Ultrasonic atomization pyrolysis
The prepared precursor solution is poured into an ultrasonic atomizer for atomizing, nitrogen is used as carrier gas, atomized liquid drops are carried into a quartz tube reactor for pyrolysis at 450 ℃. The particles formed by pyrolysis are collected in a collecting device with 3 gas washing bottles connected in series, and a filter screen is arranged at an outlet to further prevent the particles from escaping.
(3) Particle treatment
And drying the collected particles at 90 ℃ for 10 hours, and rolling and screening the particles to 60-100 meshes. The stability was improved by further calcining the granules in a tube furnace at 500 ℃ for 2 h. The finally obtained medium-low temperature SCR denitration catalyst with a composite microsphere structure is expressed as Fe (0.05) -Mn (0.5)/TiO2SEM pictures are shown in FIG. 2, and the microsphere size is less than 2.6 μm.
(4) Test of denitration Performance
The resulting catalyst was placed in a fixed bed quartz tube reactor under simulated atmosphere (NO: 1000ppmv, NH)3：1000ppmv，O2: 5 vol%, and the balance N2) The denitration performance of a sample is tested at 120-240 ℃, and the total gas flow is 1000mL/min (GHSV is 30000 h)-1)。
Example 3
(1) Preparation of precursor solution
Cerium nitrate (Ce (NO) was weighed in a molar ratio of n (Ce), n (Mn), n (Ti) 0.05:0.5:1 in the final sample3)3) Manganese nitrate (Mn (NO)3)2) And titanium tetrachloride (TiCl)4) Adding into deionized water, stirring in a stirring device for 30min to fully dissolve the raw materials to obtain a precursor solution.
(2) Ultrasonic atomization pyrolysis
The prepared precursor solution is poured into an ultrasonic atomizer for atomizing, nitrogen is used as carrier gas, atomized liquid drops are carried into a quartz tube reactor for pyrolysis at 350 ℃. The particles formed by pyrolysis are collected in a collecting device with 3 gas washing bottles connected in series, and a filter screen is arranged at an outlet to further prevent the particles from escaping.
(3) Particle treatment
Drying the collected particles at 80 ℃ for 11 hours, and rolling and screening the particles to 60-100 meshes. The stability was improved by further calcining the pellets in a tube furnace at 475 ℃ for 1.5 h. The finally obtained medium-low temperature SCR denitration catalyst with a composite microsphere structure is represented as Ce (0.05) -Mn (0.5)/TiO2.。
(4) Test of denitration Performance
The resulting catalyst was placed in a fixed bed quartz tube reactor under simulated atmosphere (NO: 1000ppmv, NH)3：1000ppmv，O2: 5 vol%, and the balance N2) The denitration performance of a sample is tested at 120-240 ℃, and the total gas flow is 1000mL/min (GHSV is 30000 h)-1)。
Example 4
(1) Preparation of precursor solution
Zirconium tetrachloride (ZrCl) was weighed in a molar ratio of n (Zr), n (Mn), n (Ti) 0.05:0.5:1 in the final sample4) Manganese nitrate (Mn (NO)3)2) And titanium tetrachloride (TiCl)4) Adding the mixture into deionized water, and stirring the mixture in a stirring device for 30min to fully dissolve the raw materials to obtain a precursor solution.
(2) Ultrasonic atomization pyrolysis
The prepared precursor solution is poured into an ultrasonic atomizer for atomizing, nitrogen is used as carrier gas, atomized liquid drops are carried into a quartz tube reactor for pyrolysis at 300 ℃. The particles formed by pyrolysis are collected in a collecting device with 3 gas washing bottles connected in series, and a filter screen is arranged at an outlet to further prevent the particles from escaping.
(3) Particle treatment
And drying the collected particles at 70 ℃ for 10 hours, and rolling and screening the particles to 60-100 meshes. The stability was improved by further calcining the granules in a tube furnace at 350 c for 2 h. The finally obtained medium-low temperature SCR denitration catalyst with a composite microsphere structure is expressed as Zr (0.05) -Mn (0.5)/TiO2。
(4) Test of denitration Performance
The resulting catalyst was placed in a fixed bed quartz tube reactor under simulated atmosphere (NO: 1000ppmv, NH)3：1000ppmv，O2: 5 vol%, and the balance N2) The denitration performance of a sample is tested at 120-240 ℃, and the total gas flow is 1000mL/min (GHSV is 30000 h)-1)。
Example 5
(1) Preparation of precursor solution
Tin oxalate (SnC) was weighed in a molar ratio of n (Sn), n (Mn), n (Ti) 0.05:0.5:1 in the final sample2O4) Manganese nitrate (Mn (NO)3)2) And titanium tetrachloride (TiCl)4) Adding into anhydrous ethanol, and stirring in a stirring device for 30min to fully dissolve the raw materials to obtain precursor solution.
(2) Ultrasonic atomization pyrolysis
The prepared precursor solution is poured into an ultrasonic atomizer for atomizing, nitrogen is used as carrier gas, atomized liquid drops are carried into a quartz tube reactor for pyrolysis at 500 ℃. The particles formed by pyrolysis are collected in a collecting device with 3 gas washing bottles connected in series, and a filter screen is arranged at an outlet to further prevent the particles from escaping.
(3) Particle treatment
And drying the collected particles at 100 ℃ for 10 hours, and rolling and screening the particles to 60-100 meshes. The stability was improved by further calcining the granules in a tube furnace at 400 ℃ for 2 h. The finally obtained medium-low temperature SCR denitration catalyst with a composite microsphere structure is expressed as Sn (0.05) -Mn (0.5)/TiO2。
(4) Test of denitration Performance
The resulting catalyst was placed in a fixed bed quartz tube reactor under simulated atmosphere (NO: 1000ppmv, NH)3：1000ppmv，O2: 5 vol%, and the balance N2) The denitration performance of a sample is tested at 120-240 ℃, and the total gas flow is 1000mL/min (GHSV is 30000 h)-1)。
The denitration performance test results of the catalysts respectively prepared in the embodiments 1 to 5 are shown in fig. 3, and it can be seen that the catalyst prepared by the invention shows good denitration efficiency in a medium-low temperature range (120 to 240 ℃), and the denitration efficiency at 240 ℃ exceeds 95%. Wherein, the denitration activity of the catalyst in the embodiment 2 is 120-180 ℃ compared with that of the catalyst in other embodimentsCompared with the prior art, the method is obviously more excellent and embodies that the TiO prepared by the ultrasonic atomization pyrolysis method2In the catalytic system which is a carrier, Mn and Fe have synergistic action.
Example 6
(1) Preparation of precursor solution
Manganese nitrate (Mn (NO) was weighed in a molar ratio of n (Mn) to n (Ti) of 0.5:1 in the final sample3)2) And titanium tetrachloride (TiCl)4) Adding the mixture into deionized water, and stirring the mixture in a stirring device for 30min to fully dissolve the raw materials to obtain a precursor solution.
(2) Ultrasonic atomization pyrolysis
The prepared precursor solution is poured into an ultrasonic atomizer for atomizing, nitrogen is used as carrier gas, atomized liquid drops are carried into a quartz tube reactor for pyrolysis at 500 ℃. The particles formed by pyrolysis are collected in a collecting device with 3 gas washing bottles connected in series, and a filter screen is arranged at an outlet to further prevent the particles from escaping.
(3) Particle treatment
And drying the collected particles at 60 ℃ for 12 hours, and rolling and screening the particles to 60-100 meshes. The stability was improved by further calcining the granules in a tube furnace at 600 ℃ for 2 h. The finally obtained medium-low temperature SCR denitration catalyst with a composite microsphere structure is represented as Mn (0.5)/TiO2In the SEM photograph shown in FIG. 4, it can be observed that the composite microspheres of some samples are cracked due to the over-high calcination temperature.
Example 7
(1) Preparation of precursor solution
Manganese nitrate (Mn (NO) was weighed in a molar ratio of n (Mn) to n (Ti) of 0.4:1 in the final sample3)2) And titanium tetrachloride (TiCl)4) Adding the mixture into deionized water, and stirring the mixture in a stirring device for 30min to fully dissolve the raw materials to obtain a precursor solution.
(2) Ultrasonic atomization pyrolysis
The prepared precursor solution is poured into an ultrasonic atomizer for atomizing, and the atomized liquid drops are carried into a quartz tube reactor to be pyrolyzed at 450 ℃ by taking air as carrier gas. The particles formed by pyrolysis are collected in a collecting device with 3 gas washing bottles connected in series, and a filter screen is arranged at an outlet to further prevent the particles from escaping.
(3) Particle treatment
And drying the collected particles at 60 ℃ for 12 hours, and rolling and screening the particles to 60-100 meshes. The stability was improved by further calcining the pellets in a tube furnace at 500 ℃ for 1.5 h. The finally obtained medium-low temperature SCR denitration catalyst with a composite microsphere structure is represented as Mn (0.4)/TiO2Air, SEM photograph as shown in FIG. 5.
Example 8
(1) Preparation of precursor solution
Manganese nitrate (Mn (NO) was weighed in a molar ratio of n (Mn) to n (Ti) of 0.4:1 in the final sample3)2) And titanium tetrachloride (TiCl)4) Adding the mixture into deionized water, and stirring the mixture in a stirring device for 30min to fully dissolve the raw materials to obtain a precursor solution.
(2) Ultrasonic atomization pyrolysis
The prepared precursor solution is poured into an ultrasonic atomizer for atomizing, nitrogen is used as carrier gas, atomized liquid drops are carried into a quartz tube reactor for pyrolysis at 500 ℃. The particles formed by pyrolysis are collected in a collecting device with 3 gas washing bottles connected in series, and a filter screen is arranged at an outlet to further prevent the particles from escaping.
(3) Particle treatment
And drying the collected particles at 60 ℃ for 12 hours, and rolling and screening the particles to 60-100 meshes. The stability was improved by further calcining the granules in a tube furnace at 500 ℃ for 2 h. The finally obtained medium-low temperature SCR denitration catalyst with a composite microsphere structure is represented as Mn (0.4)/TiO2-N2The SEM photograph is shown in FIG. 6.
Example 9
(1) Preparation of precursor solution
Manganese nitrate (Mn (NO) was weighed in a molar ratio of n (Mn) to n (Ti) of 0.4:1 in the final sample3)2) And titanium tetrachloride (TiCl)4) Adding the mixture into deionized water, and stirring the mixture in a stirring device for 30min to fully dissolve the raw materials to obtain a precursor solution.
(2) Ultrasonic atomization pyrolysis
The prepared precursor solution is poured into an ultrasonic atomizer for atomizing, oxygen is used as carrier gas, atomized liquid drops are carried into a quartz tube reactor for pyrolysis at 475 ℃. The particles formed by pyrolysis are collected in a collecting device with 3 gas washing bottles connected in series, and a filter screen is arranged at an outlet to further prevent the particles from escaping.
(3) Particle treatment
And drying the collected particles at 90 ℃ for 10 hours, and rolling and screening the particles to 60-100 meshes. The stability was improved by further calcining the granules in a tube furnace at 500 ℃ for 2 h. The finally obtained medium-low temperature SCR denitration catalyst with a composite microsphere structure is represented as Mn (0.4)/TiO2-O2The SEM photograph is shown in FIG. 7.
From fig. 5 to 7, it can be observed that the composite microsphere structure can be obtained in air, oxygen and nitrogen atmosphere, and the active component loading can be observed on the microsphere surface. As can be seen from comparison of fig. 5 to 7, the higher the oxygen content in the carrier gas is, the more significant the agglomeration phenomenon of the catalyst is, and therefore, in order to increase the dispersion degree of the catalyst and reduce the particle size of the catalyst, the nitrogen gas is preferably used as the carrier gas to obtain the better denitration performance.
Comparative example 1
Preparing a precursor solution according to the catalyst proportion and the method of the embodiment 1, and preparing Mn (0.5)/TiO by adopting an impregnation method and a coprecipitation method respectively2。
The dipping method comprises the following steps: and continuously stirring the precursor solution in an oil bath at 110 ℃ for 10h to evaporate the solvent, drying the obtained sample at 110 ℃ overnight, calcining at 500 ℃ for 5h, and rolling and screening to 60-100 meshes to obtain the final sample.
A coprecipitation method: under ice-water bath conditions, excess ammonia solution was added to the precursor solution with continuous stirring until pH 10, stirring was continued for 3h and aging was carried out for 24 h. After which it was filtered and the filter cake was washed to neutrality and dried overnight at 110 ℃. And finally, calcining the sample at 500 ℃ for 5 hours, and rolling and screening to 60-100 meshes to obtain the final sample.
The samples obtained by the immersion method and the coprecipitation method were removed as in example 1Nitrate Performance test method denitration Activity test was performed, and compared with Mn (0.5)/TiO prepared in example 12As a comparison of the denitration performance, the results are shown in fig. 8, and it can be seen that the catalyst prepared by the method of the present invention exhibits superior denitration performance compared to the conventional impregnation method and co-precipitation method.
Furthermore, it should be understood that various changes and modifications can be made by one skilled in the art after reading the above description of the present invention, and equivalents also fall within the scope of the invention as defined by the appended claims.
Claims (9)
1. The medium-low temperature SCR denitration catalyst with a composite microsphere structure is characterized by being prepared by an ultrasonic atomization pyrolysis method, and comprises the following specific steps:
(1) adding an active metal source and titanium tetrachloride into deionized water or absolute ethyl alcohol, and uniformly stirring to obtain a precursor solution; the active metal source contains at least one element of Mn, Fe, Zr, Sn and Ce;
(2) pouring the precursor solution into an ultrasonic atomizer for atomization, flowing into a quartz tube reactor along with carrier gas for pyrolysis, collecting particles formed after pyrolysis, cleaning with deionized water, drying, rolling and screening, and finally roasting at 350-500 ℃ to obtain the medium-low temperature SCR denitration catalyst with the composite microsphere structure;
the composite microsphere structure is a spherical carrier surface loaded with active component spheres.
2. The medium-low temperature SCR denitration catalyst with a composite microsphere structure according to claim 1, wherein in the step (2), the carrier gas is nitrogen, air or oxygen.
3. The medium-low temperature SCR denitration catalyst with the composite microsphere structure according to claim 1, wherein in the step (2), the pyrolysis temperature is 300-500 ℃.
4. The medium-low temperature SCR denitration catalyst with the composite microsphere structure according to claim 1, wherein in the step (2), the drying temperature is 60-100 ℃ and the drying time is 10-12 h.
5. The medium-low temperature SCR denitration catalyst with the composite microsphere structure according to claim 1, wherein in the step (2), the medium-low temperature SCR denitration catalyst is burnt after being rolled and sieved to 60-100 meshes.
6. The medium-low temperature SCR denitration catalyst with the composite microsphere structure according to claim 1, wherein in the step (2), the roasting time is 1.5-2 h.
7. The medium-low temperature SCR denitration catalyst with a composite microsphere structure according to claim 1, wherein in the step (2), the particles formed after pyrolysis are collected in a collecting device formed by continuously connecting 3 gas washing cylinders in series, and a filter screen for collecting and blocking the particles from escaping is arranged at the outlet of the last gas washing cylinder.
8. The medium-low temperature SCR denitration catalyst with the composite microsphere structure according to any one of claims 1 to 7, wherein the medium-low temperature NH is generated in the medium-low temperature SCR denitration catalyst3The application of the denitration catalyst in SCR denitration is characterized in that the denitration temperature is 120-240 ℃.
9. The use according to claim 8, wherein the active metal source contains both Mn and Fe.
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