CN113244926A - Perovskite catalyst for synergistically catalyzing and oxidizing nitric oxide and mercury and preparation method thereof - Google Patents
Perovskite catalyst for synergistically catalyzing and oxidizing nitric oxide and mercury and preparation method thereof Download PDFInfo
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- CN113244926A CN113244926A CN202010963519.5A CN202010963519A CN113244926A CN 113244926 A CN113244926 A CN 113244926A CN 202010963519 A CN202010963519 A CN 202010963519A CN 113244926 A CN113244926 A CN 113244926A
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- MWUXSHHQAYIFBG-UHFFFAOYSA-N Nitric oxide Chemical compound O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 title claims abstract description 53
- 239000003054 catalyst Substances 0.000 title claims abstract description 45
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 title claims abstract description 35
- 229910052753 mercury Inorganic materials 0.000 title claims abstract description 18
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- 230000001590 oxidative effect Effects 0.000 title claims abstract description 9
- 230000003647 oxidation Effects 0.000 claims abstract description 19
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 19
- 230000003197 catalytic effect Effects 0.000 claims abstract description 13
- 229910021645 metal ion Inorganic materials 0.000 claims abstract description 8
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 54
- 239000012266 salt solution Substances 0.000 claims description 30
- 238000010438 heat treatment Methods 0.000 claims description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 17
- 238000001816 cooling Methods 0.000 claims description 14
- 229910052751 metal Inorganic materials 0.000 claims description 12
- 239000002184 metal Substances 0.000 claims description 12
- 238000001035 drying Methods 0.000 claims description 10
- 238000000034 method Methods 0.000 claims description 10
- 229910002651 NO3 Inorganic materials 0.000 claims description 8
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 8
- 238000000227 grinding Methods 0.000 claims description 8
- 239000002243 precursor Substances 0.000 claims description 8
- 239000000243 solution Substances 0.000 claims description 8
- 238000004506 ultrasonic cleaning Methods 0.000 claims description 8
- 238000002156 mixing Methods 0.000 claims description 7
- 239000008139 complexing agent Substances 0.000 claims description 6
- FYDKNKUEBJQCCN-UHFFFAOYSA-N lanthanum(3+);trinitrate Chemical compound [La+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O FYDKNKUEBJQCCN-UHFFFAOYSA-N 0.000 claims description 6
- 150000003839 salts Chemical class 0.000 claims description 6
- 238000009210 therapy by ultrasound Methods 0.000 claims description 6
- 229910021642 ultra pure water Inorganic materials 0.000 claims description 6
- 239000012498 ultrapure water Substances 0.000 claims description 6
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical group [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims description 5
- 229910001981 cobalt nitrate Chemical group 0.000 claims description 5
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical group [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 claims description 4
- 238000003756 stirring Methods 0.000 claims description 2
- 230000002153 concerted effect Effects 0.000 claims 5
- 238000004519 manufacturing process Methods 0.000 claims 1
- 229910052723 transition metal Inorganic materials 0.000 abstract description 5
- 229910052748 manganese Inorganic materials 0.000 abstract description 4
- 150000003624 transition metals Chemical group 0.000 abstract description 4
- 230000000694 effects Effects 0.000 abstract description 3
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 abstract description 2
- 230000002349 favourable effect Effects 0.000 abstract description 2
- 239000003546 flue gas Substances 0.000 abstract description 2
- 229910052761 rare earth metal Inorganic materials 0.000 abstract description 2
- 150000002910 rare earth metals Chemical class 0.000 abstract description 2
- 238000003980 solgel method Methods 0.000 abstract description 2
- 238000001179 sorption measurement Methods 0.000 abstract 2
- 238000006243 chemical reaction Methods 0.000 description 5
- 229910002254 LaCoO3 Inorganic materials 0.000 description 4
- 238000002441 X-ray diffraction Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 239000011572 manganese Substances 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 229910002328 LaMnO3 Inorganic materials 0.000 description 2
- 239000012159 carrier gas Substances 0.000 description 2
- 150000001768 cations Chemical class 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- -1 oxygen ions Chemical class 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- 239000011865 Pt-based catalyst Substances 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 238000003916 acid precipitation Methods 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000010531 catalytic reduction reaction Methods 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000002440 industrial waste Substances 0.000 description 1
- 229910052747 lanthanoid Inorganic materials 0.000 description 1
- 150000002602 lanthanoids Chemical class 0.000 description 1
- 238000003760 magnetic stirring Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000006722 reduction reaction Methods 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 238000004056 waste incineration Methods 0.000 description 1
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- 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
- B01J23/83—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 rare earths or actinides
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- 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
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- 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
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- 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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- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
- B01J37/0027—Powdering
- B01J37/0036—Grinding
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- 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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- C01B21/00—Nitrogen; Compounds thereof
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Abstract
Hair brushThe invention discloses a perovskite catalyst capable of synergistically catalyzing and oxidizing nitric oxide and elemental mercury and a preparation method thereof, mainly aims at the research of the catalytic oxidation of nitric oxide and gaseous elemental mercury in coal-fired flue gas, and belongs to the field of atmospheric pollution control3And AB0.5B’0.5O3Wherein, the metal ion of A is rare earth metal element La, the B site is transition metal Mn and Co, the B 'site is transition metal Mn and Co, and B is not equal to B'. The invention adds ultrasonic assistance on the basis of a sol-gel method, is favorable for forming a perovskite catalyst with regular morphology, and the adsorption catalyst has good activity of catalyzing and oxidizing nitric oxide, higher mercury adsorption effect, low price and high economic feasibility.
Description
Technical Field
The invention relates to a perovskite catalyst for synergistically catalyzing and oxidizing nitric oxide and mercury and a preparation method thereof, belonging to the technical field of atmospheric pollution control.
Background
The fire coal flue gas of a thermal power plant is a main emission source of nitrogen oxides and gaseous elemental mercury in the atmosphere, and the nitrogen oxides can cause a series of environmental problems such as photochemical smog, acid rain, ozone cavities, greenhouse effect and the like. The elementary mercury is difficult to dissolve in water, has strong toxicity, volatility and biological accumulation, and the like, so that the elementary mercury attracts wide attention of countries and international organizations in the world. At present, the Selective Catalytic Reduction (SCR) technology, which is a mature technology for removing nitrogen oxides, is a Lean-burn NOX Trap (LNT) technology in the aspect of automobile exhaust purification treatment. In both of these technical approaches, the oxidation of NO to NO2 is a critical step in the reaction. When the ratio of NO to NO2 is 1, NOX reduction is most effective in the SCR reaction; in the LNT reaction, NO is more easily stored after oxidation to NO 2. And NO2 has higher water solubility than NO, which is more favorable for later removal. The emission limit of elemental mercury in the newly established standard of atmospheric pollutants of thermal power plants in China at the present stage is specified to be 30 mu g/m 3. When the elemental mercury is oxidized, the elemental mercury is more easily subjected to subsequent absorption treatment. It is therefore necessary to select a catalyst that is effective in synergistically catalyzing the oxidation of nitric oxide and gaseous elemental mercury. The catalyst for catalytic oxidation of nitric oxide is a Pt-based catalyst, but the catalyst is often expensive to use due to the precious metal Pt. The currently available method is to prepare a catalyst that can synergistically catalyze the oxidation of nitric oxide and elemental mercury.
The perovskite catalyst is a general name of a general class of compounds with the same structure as natural perovskite (CaTiO3), and the general formula of the perovskite catalyst can be ABO 3. In the ABO3 structure, the A site is a cation with a large ionic radius (typically > 0.09nm) such as the alkali metals, alkaline earth metals, and lanthanides, which is located in the body core and can coordinate with 12 oxygen ions. The B site is usually a cation with a small ionic radius (usually > 0.05nm), generally a transition metal element, Al, Sn, etc., and is located in the center of the octahedron and coordinated with 6 oxygen ions. Meanwhile, compared with a noble metal catalyst, the perovskite catalyst has the characteristics of low price, stable structure, good catalytic activity, stable thermodynamic performance at high temperature and the like, and has a higher application prospect in the field of atmospheric pollution control.
Disclosure of Invention
The invention aims to solve the technical problem of providing a perovskite catalyst for synergistically catalyzing and oxidizing nitric oxide and mercury and a preparation method thereof, and the perovskite catalyst has good catalytic oxidation performance of nitric oxide and elemental mercury, low price and high economic feasibility.
The invention is realized by the following scheme: the preparation method of the perovskite catalyst for synergistically catalyzing and oxidizing nitric oxide and mercury comprises the following steps:
step one, adding salt A and salt B into ultrapure water according to the molar mass of the total ratio of 1:1, and magnetically stirring to form a metal salt solution;
step two, uniformly mixing the metal salt solution obtained in the step one with a citric acid complexing agent;
thirdly, putting the mixed salt solution obtained in the second step into an ultrasonic cleaning instrument for ultrasonic treatment, then heating the mixed salt solution in a water bath until the nitrate solution forms sol gel, and then drying the sol gel in a drying oven;
and step four, roasting the perovskite precursor obtained in the step three in a muffle furnace for 4-5h, then cooling to room temperature at a constant speed, and finally grinding and tabletting the sample to obtain the finished perovskite catalyst with the granularity of 40-60 meshes.
In the first step, the salt A is lanthanum nitrate, and the site B is manganese nitrate and cobalt nitrate.
The general chemical formula of the perovskite catalyst is ABO3And AB0.5B’0.5O3Wherein, the metal ion of A is rare earth metal element La, the B site is transition metal Mn and Co, the B 'site is transition metal Mn and Co, and B is not equal to B'.
And in the second step, the addition proportion of the citric acid is that the molar ratio of the total metal ions to the citric acid is 1: 2.
And ultrasonically treating the mixed salt solution obtained in the second step in an ultrasonic cleaning instrument for 0-60min, then heating the mixed salt solution in a water bath at the water bath temperature of 80 ℃ until the nitrate solution forms sol gel, and then drying the mixed salt solution in an oven at the temperature of 110-120 ℃ for 12 h.
And placing the perovskite precursor obtained in the step three in a muffle furnace, uniformly heating to 700-800 ℃ at a heating rate of 5-10 ℃/min, roasting for 4-5h, and then uniformly cooling to room temperature at a cooling rate of 2-3 ℃/min. And finally, grinding and tabletting the sample to obtain the finished perovskite catalyst with the granularity of 40-60 meshes.
A perovskite catalyst for synergistically catalyzing and oxidizing nitric oxide and mercury is prepared based on the preparation method.
The perovskite catalyst prepared by the preparation method is applied to catalytic oxidation of nitric oxide and elemental mercury.
The invention has the beneficial effects that:
(1) the method adopts ultrasonic auxiliary treatment and utilizes a sol-gel method to prepare the perovskite catalyst, and the preparation method is simple, easy to operate and suitable for large-scale industrial application;
(2) the perovskite catalyst has the advantages of stable structure, excellent thermal stability, long service life and capability of keeping higher catalytic activity for a long time;
(3) the perovskite catalyst prepared by the method is low in use price, and is suitable for denitration and mercury removal in coal-fired power plants and other industrial waste gases, such as waste incineration boilers, automobile exhaust treatment and some chemical plants.
Drawings
FIG. 1 is an XRD pattern of a doped LaCoO3 double perovskite catalyst of example 1;
FIG. 2 is an XRD pattern of a doped LaMnO3 double perovskite catalyst of example 3;
FIG. 3 is a plot of nitric oxide conversion versus temperature for examples 1-4.
Fig. 4 is a plot of elemental mercury conversion versus temperature for examples 1-4.
Detailed Description
The invention is further described below with reference to fig. 1-4, without limiting the scope of the invention.
In the following description, for purposes of clarity, not all features of an actual implementation are described, well-known functions or constructions are not described in detail since they would obscure the invention with unnecessary detail, it being understood that in the development of any actual embodiment, numerous implementation details must be set forth in order to achieve the developer's specific goals, such as compliance with system-related and business-related constraints, changing from one implementation to another, and it being recognized that such development effort might be complex and time consuming, but would nevertheless be a routine undertaking for those of ordinary skill in the art.
Example 1: the perovskite catalyst of the embodiment is LaCoO3；
(1) Lanthanum nitrate and cobalt nitrate are added into ultrapure water according to the molar mass ratio of 1:1, and are magnetically stirred to form a metal salt solution;
(2) uniformly mixing the metal salt solution obtained in the step (1) with a citric acid complexing agent, wherein the addition ratio of citric acid is that the molar ratio of total metal ions to citric acid is 1: 2;
(3) and (3) carrying out ultrasonic treatment on the mixed salt solution obtained in the step (2) in an ultrasonic cleaning instrument for 60min, and then heating the mixed salt solution in a water bath at the water bath temperature of 80 ℃ until the nitrate solution forms sol gel. Then drying in an oven at 110 ℃ for 12 h;
(4) and (4) placing the perovskite precursor obtained in the step (3) in a muffle furnace, uniformly heating to 700 ℃ at a heating rate of 5 ℃/min, roasting for 5h, and then uniformly cooling to room temperature at a cooling rate of 2 ℃/min. And then grinding and tabletting the sample to obtain the finished perovskite catalyst with the granularity of 40-60 meshes.
The XRD pattern of the perovskite catalyst LaCoO3 of the embodiment is shown in figure 1, and compared with LaCoO3 standard cards, the method can obtain a pure-phase perovskite structure without occurrence of a miscellaneous peak.
The total flow of gas distribution is 600mL/min, the concentration of NO is 500ppm, the oxygen content is 10 percent, the carrier gas is nitrogen, the temperature of the gas mixing tank is 200 ℃, and the airspeed is 50000/h. When the combined removal experiment is carried out, the temperature of a water bath kettle is maintained at 70 ℃, the flow of mercury vapor carrier gas N2 is controlled at 100mL/min, the blank concentration of mercury at an inlet is 47.8 mu g/m3, and the experimental temperature condition is 100-400 ℃. The highest NO oxidation efficiency is 81.3% under the condition of 285 ℃; the maximum removal efficiency of the elemental mercury at 150 ℃ is 86.3 percent, and the elemental mercury is stabilized to be more than 80 percent between 150 ℃ and 285 ℃.
Example 2: the perovskite catalyst of this example was LaCoO 3;
(1) lanthanum nitrate and cobalt nitrate are added into ultrapure water according to the molar mass ratio of 1:1 in the total proportion and are magnetically stirred to form a metal salt solution;
(2) uniformly mixing the metal salt solution obtained in the step (1) with a citric acid complexing agent, wherein the addition ratio of citric acid is that the molar ratio of total metal ions to citric acid is 1: 2;
(3) and (3) carrying out ultrasonic treatment on the mixed salt solution obtained in the step (2) in an ultrasonic cleaning instrument for 0min, and then heating the mixed salt solution in a water bath at the water bath temperature of 80 ℃ until the nitrate solution forms sol gel. Then drying in an oven at 110 ℃ for 12 h;
(4) and (4) placing the perovskite precursor obtained in the step (3) in a muffle furnace, uniformly heating to 700 ℃ at a heating rate of 5 ℃/min, roasting for 5h, and then uniformly cooling to room temperature at a cooling rate of 2 ℃/min. And then grinding and tabletting the sample to obtain the finished perovskite catalyst with the granularity of 40-60 meshes. The example is based on the example 1, ultrasonic assistance is not added, the efficiency of the synergistic catalytic oxidation is obviously lower than that of the example 1, and the highest oxidation efficiency of NO at 350 ℃ is 59%; the maximum removal efficiency of elemental mercury at 200 ℃ was 83.96%.
Example 3: the perovskite catalyst of the present example is LaMnO3；
(1) Lanthanum nitrate and manganese nitrate are added into ultrapure water according to the molar mass ratio of 1:1 in the total proportion and are magnetically stirred to form a metal salt solution;
(2) uniformly mixing the metal salt solution obtained in the step (1) with a citric acid complexing agent, wherein the addition ratio of citric acid is that the molar ratio of total metal ions to citric acid is 1: 2;
(3) and (3) carrying out ultrasonic treatment on the mixed salt solution obtained in the step (2) in an ultrasonic cleaning instrument for 30min, and then heating the mixed salt solution in a water bath at the water bath temperature of 80 ℃ until the nitrate solution forms sol gel. Then drying in an oven at 120 ℃ for 12 h;
(4) and (4) placing the perovskite precursor obtained in the step (3) in a muffle furnace, uniformly heating to 800 ℃ at a heating rate of 10 ℃/min, roasting for 4h, and then uniformly cooling to room temperature at a cooling rate of 2.5 ℃/min. And then grinding and tabletting the sample to obtain the finished perovskite catalyst with the granularity of 40-60 meshes. This example has a maximum NO oxidation efficiency of 63% at 350 ℃ under the test conditions of example 1; the maximum removal efficiency of elemental mercury at 150 ℃ was 93.97%.
Example 4: the perovskite catalyst of the embodiment is LaMn0.5Co0.5O3；
(1) Lanthanum nitrate, manganese nitrate and cobalt nitrate are added into ultrapure water according to the molar mass ratio of 1:1(La: Mn: Co is 1:0.5:0.5) to form a metal salt solution through magnetic stirring;
(2) uniformly mixing the metal salt solution obtained in the step (1) with a citric acid complexing agent, wherein the addition ratio of citric acid is that the molar ratio of total metal ions to citric acid is 1: 2;
(3) and (3) carrying out ultrasonic treatment on the mixed salt solution obtained in the step (2) in an ultrasonic cleaning instrument for 10min, and then heating the mixed salt solution in a water bath at the water bath temperature of 80 ℃ until the nitrate solution forms sol gel. Then drying in an oven at 110 ℃ for 12 h;
(4) and (4) placing the perovskite precursor obtained in the step (3) in a muffle furnace, uniformly heating to 700 ℃ at a heating rate of 10 ℃/min, roasting for 5h, and then uniformly cooling to room temperature at a cooling rate of 3 ℃/min. And then grinding and tabletting the sample to obtain the finished perovskite catalyst with the granularity of 40-60 meshes. This example has a maximum NO oxidation efficiency of 65% at 350 ℃ under the test conditions of example 1; the maximum elemental mercury removal efficiency was 86.02% at 150 ℃.
Although the invention has been described and illustrated in some detail, it should be understood that various modifications may be made to the described embodiments or equivalents may be substituted, as will be apparent to those skilled in the art, without departing from the spirit of the invention.
Claims (7)
1. The preparation method of the perovskite catalyst for synergistically catalyzing and oxidizing nitric oxide and mercury is characterized by comprising the following steps of: the method comprises the following steps:
step one, adding salt A and salt B into ultrapure water according to the molar mass of the total ratio of 1:1, and magnetically stirring to form a metal salt solution;
step two, uniformly mixing the metal salt solution obtained in the step one with a citric acid complexing agent;
thirdly, putting the mixed salt solution obtained in the second step into an ultrasonic cleaning instrument for ultrasonic treatment, then heating the mixed salt solution in a water bath until the nitrate solution forms sol gel, and then drying the sol gel in a drying oven;
and step four, roasting the perovskite precursor obtained in the step three in a muffle furnace for 4-5h, then cooling to room temperature at a constant speed, and finally grinding and tabletting the sample to obtain the finished perovskite catalyst with the granularity of 40-60 meshes.
2. The method of preparing a perovskite catalyst for the concerted catalytic oxidation of nitric oxide and mercury according to claim 1 wherein: in the first step, the salt A is lanthanum nitrate, and the site B is manganese nitrate and cobalt nitrate.
3. The method of preparing a perovskite catalyst for the concerted catalytic oxidation of nitric oxide and mercury according to claim 1 wherein: and in the second step, the addition proportion of the citric acid is that the molar ratio of the total metal ions to the citric acid is 1: 2.
4. The method of preparing a perovskite catalyst for the concerted catalytic oxidation of nitric oxide and mercury according to claim 1 wherein: and ultrasonically treating the mixed salt solution obtained in the second step in an ultrasonic cleaning instrument for 0-60min, then heating the mixed salt solution in a water bath at the water bath temperature of 80 ℃ until the nitrate solution forms sol gel, and then drying the mixed salt solution in an oven at the temperature of 110-120 ℃ for 12 h.
5. The method of preparing a perovskite catalyst for the concerted catalytic oxidation of nitric oxide and mercury according to claim 1 wherein: and placing the perovskite precursor obtained in the step three in a muffle furnace, uniformly heating to 700-800 ℃ at a heating rate of 5-10 ℃/min, roasting for 4-5h, and then uniformly cooling to room temperature at a cooling rate of 2-3 ℃/min. And finally, grinding and tabletting the sample to obtain the finished perovskite catalyst with the granularity of 40-60 meshes.
6. A perovskite catalyst for the concerted catalytic oxidation of nitric oxide and mercury made by the process of manufacture according to claims 1-5.
7. Use of a perovskite catalyst prepared on the basis of the preparation method according to claims 1 to 5 for the catalytic oxidation of nitric oxide and elementary mercury.
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