CN114130400A - Doped perovskite catalyst, preparation method and application thereof - Google Patents
Doped perovskite catalyst, preparation method and application thereof Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 57
- 238000002360 preparation method Methods 0.000 title claims description 8
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 claims abstract description 16
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 14
- 238000000034 method Methods 0.000 claims abstract description 10
- 230000003197 catalytic effect Effects 0.000 claims abstract description 8
- 239000000126 substance Substances 0.000 claims abstract description 8
- 229910052709 silver Inorganic materials 0.000 claims abstract description 5
- 229910052712 strontium Inorganic materials 0.000 claims abstract description 5
- MWUXSHHQAYIFBG-UHFFFAOYSA-N Nitric oxide Chemical compound O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 claims description 43
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 39
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims description 15
- 229910001981 cobalt nitrate Inorganic materials 0.000 claims description 15
- 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 15
- 238000010438 heat treatment Methods 0.000 claims description 14
- 229910052751 metal Inorganic materials 0.000 claims description 14
- 239000002184 metal Substances 0.000 claims description 13
- 239000011259 mixed solution Substances 0.000 claims description 13
- 230000003647 oxidation Effects 0.000 claims description 13
- 239000000243 solution Substances 0.000 claims description 12
- 239000012266 salt solution Substances 0.000 claims description 10
- 238000001816 cooling Methods 0.000 claims description 9
- 238000001035 drying Methods 0.000 claims description 8
- 238000002156 mixing Methods 0.000 claims description 6
- 239000002243 precursor Substances 0.000 claims description 6
- 238000009210 therapy by ultrasound Methods 0.000 claims description 6
- 229910002651 NO3 Inorganic materials 0.000 claims description 5
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 5
- 238000000227 grinding Methods 0.000 claims description 4
- 238000004506 ultrasonic cleaning Methods 0.000 claims description 4
- 239000007864 aqueous solution Substances 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 3
- 238000003756 stirring Methods 0.000 claims description 3
- 238000003760 magnetic stirring Methods 0.000 claims description 2
- 229910001960 metal nitrate Inorganic materials 0.000 claims description 2
- 239000007789 gas Substances 0.000 abstract description 11
- 229910052753 mercury Inorganic materials 0.000 abstract description 9
- 239000003344 environmental pollutant Substances 0.000 abstract description 6
- 231100000719 pollutant Toxicity 0.000 abstract description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 4
- 229910052746 lanthanum Inorganic materials 0.000 abstract description 4
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 abstract description 4
- 239000001301 oxygen Substances 0.000 abstract description 4
- 229910052760 oxygen Inorganic materials 0.000 abstract description 4
- 230000000694 effects Effects 0.000 abstract description 3
- 230000002265 prevention Effects 0.000 abstract description 3
- 238000010521 absorption reaction Methods 0.000 abstract description 2
- 230000009286 beneficial effect Effects 0.000 abstract description 2
- 238000004064 recycling Methods 0.000 abstract description 2
- 238000004056 waste incineration Methods 0.000 abstract description 2
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 10
- DHEQXMRUPNDRPG-UHFFFAOYSA-N strontium nitrate Chemical compound [Sr+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O DHEQXMRUPNDRPG-UHFFFAOYSA-N 0.000 description 10
- 239000000463 material Substances 0.000 description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- 239000000047 product Substances 0.000 description 6
- 229910002273 La1–xSrxCoO3 Inorganic materials 0.000 description 5
- 229910001961 silver nitrate Inorganic materials 0.000 description 5
- 230000007613 environmental effect Effects 0.000 description 4
- 239000012467 final product Substances 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 238000002441 X-ray diffraction Methods 0.000 description 3
- 239000012159 carrier gas Substances 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 229910021642 ultra pure water Inorganic materials 0.000 description 3
- 239000012498 ultrapure water Substances 0.000 description 3
- MGWGWNFMUOTEHG-UHFFFAOYSA-N 4-(3,5-dimethylphenyl)-1,3-thiazol-2-amine Chemical compound CC1=CC(C)=CC(C=2N=C(N)SC=2)=C1 MGWGWNFMUOTEHG-UHFFFAOYSA-N 0.000 description 2
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 2
- 229910002254 LaCoO3 Inorganic materials 0.000 description 2
- 238000002485 combustion reaction Methods 0.000 description 2
- 230000018109 developmental process Effects 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 239000003546 flue gas Substances 0.000 description 2
- 229910000474 mercury oxide Inorganic materials 0.000 description 2
- UKWHYYKOEPRTIC-UHFFFAOYSA-N mercury(ii) oxide Chemical compound [Hg]=O UKWHYYKOEPRTIC-UHFFFAOYSA-N 0.000 description 2
- JCXJVPUVTGWSNB-UHFFFAOYSA-N nitrogen dioxide Inorganic materials O=[N]=O JCXJVPUVTGWSNB-UHFFFAOYSA-N 0.000 description 2
- 239000010453 quartz Substances 0.000 description 2
- 238000005070 sampling Methods 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 229910019606 La0.5Sr0.5CoO3 Inorganic materials 0.000 description 1
- 229910002138 La0.6Sr0.4CoO3 Inorganic materials 0.000 description 1
- 229910019828 La0.7Sr0.3CoO3 Inorganic materials 0.000 description 1
- 229910002187 La0.8Sr0.2CoO3 Inorganic materials 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- 229910003508 Sr0.3CoO3 Inorganic materials 0.000 description 1
- 238000003916 acid precipitation Methods 0.000 description 1
- 238000003915 air pollution Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 239000008139 complexing agent Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000010926 purge Methods 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
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- 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
- B01J23/83—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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Abstract
The invention discloses a doped perovskite catalyst which is characterized in that: the chemical general formula is La1‑xAxCoO3Wherein X is 0.1-0.5, A is Sr or Ag. The invention has the beneficial effects that: still has stronger thermal stability at 1000 ℃; the intractable NO and Hg are mixed0Oxidation to NO with high water solubility2And Hg2+Then, the treatment, prevention and control of the pollutants and the recycling of the pollutants can be realized by combining methods such as water absorption and the like; the prepared lanthanum cobaltate with different Sr or Ag contents is more than the traditional ABO3Lanthanum cobaltate with the structure contains more oxygen vacancies, more active sites, enhanced thermal stability and higher low-temperature activity; the structure is stable, the thermal stability is excellent, the service life is long, and the high catalytic activity can be maintained for a long time; the method is low in use price, and is suitable for denitration and mercury removal of tail gas of coal-fired power plants, tail gas treatment of waste incineration boilers, automobile tail gas treatment and some chemical plants.
Description
Technical Field
The invention relates to a doped perovskite catalyst, a preparation method and application thereof, and belongs to the technical field of air pollution control.
Background
Nitric Oxide (NO) and elemental mercury (Hg0) are common atmospheric pollutants found in the tail gas from the combustion of fossil fuels. NO causes a series of environmental problems such as photochemical smog, acid rain, ozone holes, greenhouse effect and the like. Meanwhile, the united nations environmental planning agency (UNEP) has pointed out that mercury pollution has become an important factor threatening the environment and human health, and data shows that the total amount of mercury emitted into the atmosphere every year worldwide is up to 5000 tons, with the mercury released from coal combustion accounting for about 45% of the total amount. Therefore, how to economically and effectively control the emission of NO and Hg0 in the coal-fired flue gas is an environmental problem which is urgently needed to be solved in China and the world environmental protection field.
Disclosure of Invention
The invention aims to solve the technical problem of providing a nitric oxide and elemental mercury oxidation catalyst which has good nitric oxide and elemental mercury catalytic oxidation performance, low price and high economic feasibility and a preparation method thereof.
The invention is realized by the following scheme: a doped perovskite catalyst characterized by: the chemical general formula is La1-xAxCoO3Wherein X is 0.1-0.5, A is Sr or Ag.
A preparation method of a doped perovskite catalyst comprises the following steps:
step one, forming an aqueous solution system by nitrate of lanthanum nitrate and A metal and cobalt nitrate;
step two, preparing a citric acid solution;
step three, mixing the metal salt solution obtained in the step one with the citric acid solution obtained in the step two;
step four, magnetically stirring the mixed solution obtained in the step three to obtain a uniformly mixed solution;
placing the mixed solution obtained in the step four in an ultrasonic cleaning machine for ultrasonic treatment to further uniformly mix the metal elements;
putting the mixed solution obtained in the fifth step into a water bath kettle, and heating in a water bath;
seventhly, putting the gel-state substance obtained in the sixth step into a constant-temperature drying box, and drying overnight;
step eight, placing the fluffy perovskite precursor obtained in the step seven in a muffle furnace for roasting for 4-5 hours, and then cooling to room temperature;
step nine, grinding and tabletting the sample obtained in the step eight to obtain the finished perovskite catalyst with the granularity of 40-60 meshes.
And the concentration of the citric acid solution in the second step is 1 mol/L.
And in the third step, the metal salt solution and the citric acid solution are mixed according to the mass ratio of 1: 2.
The magnetic stirring time in the fourth step is 60min, and the ultrasonic treatment time in the fifth step is 60-120 min.
And in the sixth step, the temperature of water bath heating is 80 ℃, and the time is 5 hours.
And step eight, uniformly heating the fluffy perovskite precursor to 700-800 ℃ at a heating rate of 5-10 ℃/min in a muffle furnace, roasting for 4-5 h, and then cooling to room temperature at a cooling rate of 2-5 ℃/min.
In the first step, the molar mass ratio of the lanthanum nitrate to the nitrate of the metal A to the cobalt nitrate is 0.9:0.1:1 or 0.8:0.2:1 or 0.7:0.3:1 or 0.6:0.4:1 or 0.5:0.5: 1.
La1-xSrxCoO3catalyst in catalyzing oxygenNitric oxide and elemental mercury.
La1-xAgxCoO3Use of a catalyst for the catalytic oxidation of nitric oxide.
The invention has the beneficial effects that:
1. the doped perovskite catalyst still has strong thermal stability at 1000 ℃;
2. the invention relates to a doped perovskite catalyst La1-xSrxCoO3The intractable NO and Hg are mixed0Oxidation to NO with high water solubility2And Hg2+Then, the treatment, prevention and control of the pollutants and the recycling of the pollutants can be realized by combining methods such as water absorption and the like;
3. compared with the traditional ABO, the lanthanum cobaltate with different Sr or Ag contents prepared by the preparation method of the doped perovskite catalyst3Lanthanum cobaltate with the structure contains more oxygen vacancies, more active sites, enhanced thermal stability and higher low-temperature activity;
4. the doped 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;
5. the catalyst prepared by the preparation method of the doped perovskite catalyst is low in use price, and is suitable for denitration and mercury removal of tail gas of a coal-fired power plant, treatment of tail gas of a waste incineration boiler, treatment of automobile tail gas and chemical plants;
6. the doped perovskite catalyst is mainly used for prevention, control and treatment of nitrogen oxides and elemental mercury in coal-fired flue gas, nitric oxide and the elemental mercury are oxidized into nitrogen dioxide and mercury oxide, and then the nitrogen dioxide and the mercury oxide are removed by combining a wet dust removal system or are absorbed by solution, so that the regeneration and the utilization of pollutants are achieved.
Drawings
FIG. 1 is La1-xSrxCoO3(X ═ 0.1 to 0.5) XRD pattern of perovskite catalyst.
FIG. 2 is La1-xAgxCoO3(X-0.1-0.5) perovskite catalysisXRD pattern of the agent.
Detailed Description
The invention is further described below with reference to fig. 1-2, 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.
La1-xSrxCoO3The application of the catalyst in the reaction of catalytic oxidation of nitric oxide and elemental mercury is characterized in that the specific reaction conditions are as follows: 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 space velocity is 50000h-1Mercury vapor carrier gas N2The flow rate is controlled at 100mL/min, and the inlet mercury blank concentration is 47.8 mu g/m3The experimental temperature condition is 100-400 ℃.
Comparative example: the perovskite catalyst of the embodiment is LaCoO3；
Step one, 1.6246g and 1.455g of lanthanum nitrate and cobalt nitrate are weighed and dissolved in ultrapure water to prepare an aqueous solution system;
step two, preparing 1mol/L citric acid solution;
step three, mixing the metal salt solution obtained in the step one and the citric acid solution obtained in the step two according to the mass ratio of 1: 2;
step four, magnetically stirring the mixed solution obtained in the step three for 60min to obtain a uniformly mixed solution;
placing the mixed solution obtained in the step four in an ultrasonic cleaning machine for ultrasonic treatment for 60min to further uniformly mix the metal elements;
putting the mixed solution obtained in the fifth step into a water bath kettle, and heating the mixed solution in the water bath kettle for 5 hours at the temperature of 80 ℃;
seventhly, putting the gel-state substance obtained in the sixth step into a constant-temperature drying box, and drying overnight;
step eight, placing the fluffy perovskite precursor obtained in the step seven into a muffle furnace, uniformly heating to 700 ℃ at a heating rate of 5 ℃/min, roasting for 5h, and then cooling to room temperature at a cooling rate of 5 ℃/min;
step nine, grinding and tabletting the sample obtained in the step eight to obtain the finished perovskite catalyst with the granularity of 40-60 meshes.
Example 1: the perovskite catalyst of the present example was La0.9Sr0.1CoO3；
Firstly, 1.4621g of lanthanum nitrate, 0.1058g of strontium nitrate and 1.455g of cobalt nitrate are weighed according to the amount of 0.005mol, and are added into ultrapure water to be magnetically stirred 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, wherein the addition ratio of citric acid is that the molar ratio of total metal ions to citric acid is 1: 2;
carrying out ultrasonic treatment on the mixed salt solution obtained in the step two in an ultrasonic cleaning instrument for 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 sol gel in a drying oven at the temperature of 110 ℃ overnight;
and step four, placing the perovskite precursor obtained in the step three in a muffle furnace, uniformly heating to 700 ℃ at a heating rate of 5 ℃/min, roasting for 5 hours, and then naturally cooling to room temperature. Finally grinding and tabletting the sample to obtain a finished product La with the granularity of 40-60 meshes0.9Sr0.1CoO3A perovskite catalyst.
Example 2: the perovskite catalyst of the present example was La0.8Sr0.2CoO3；
Example 2 compared with example 1, except that the mass of lanthanum nitrate, strontium nitrate and cobalt nitrate were 1.2997g, 0.2116g and 1.455g, and other operating conditions and material amounts were the same as in example 1, the final product La was obtained0.8Sr0.2CoO3A perovskite catalyst.
Example 3: the perovskite catalyst of the present example was La0.7Sr0.3CoO3；
Example 3 was compared to example 1 except that the masses of lanthanum nitrate, strontium nitrate and cobalt nitrate were 1.1372g, 0.3174g and 1.455 g. Other operating conditions and material consumption are the same as those in example 1, and finally the finished product La is obtained0.7Sr0.3CoO3A perovskite catalyst.
Example 4: the perovskite catalyst of the present example was La0.6Sr0.4CoO3；
Example 4 was compared to example 1 except that the masses of lanthanum nitrate, strontium nitrate and cobalt nitrate were 0.9738g, 0.4233g and 1.455 g. Other operating conditions and material consumption are the same as those in example 1, and finally the finished product La is obtained0.6Sr0.4CoO3A perovskite catalyst.
Example 5: the perovskite catalyst of the present example was La0.5Sr0.5CoO3；
Example 5 was compared to example 1 except that the masses of lanthanum nitrate, strontium nitrate and cobalt nitrate were 0.8123g, 0.5291g and 1.455 g. Other operating conditions and material consumption are the same as those in example 1, and finally the finished product La is obtained0.5Sr0.5CoO3A perovskite catalyst.
The XRD patterns of the Sr-substituted perovskite catalysts prepared in examples 1-5 are shown in legend 1, and it can be seen that all the examples show distinct perovskite characteristic peaks.
Test example:
filling a fresh catalyst into a quartz tube, firstly purging with nitrogen for 1h at 100 ℃, then raising the temperature to 400 ℃ from 100 ℃, and controlling the sampling point time to be 10min during the period of time of NO and Hg0The oxidation rate of (a) is shown in Table 1.
TABLE 1 La1-xSrxCoO3(X ═ 0-0.5) perovskite catalyzed oxidation of NO and Hg0The oxidation rate of (c).
La1-xAgxCoO3The application of the catalyst in the catalytic oxidation of nitric oxide comprises the following specific reaction conditions: 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 space velocity is 50000h-1The experimental temperature condition is 100-400 ℃.
Example 6: the perovskite catalyst of the present example was La0.9Ag0.1CoO3；
Lanthanum nitrate, silver nitrate and cobalt nitrate are added into ultrapure water according to the molar mass ratio of 0.9:0.1:1, and are magnetically stirred to form a metal salt solution; other operating conditions and material consumption are the same as those in example 1, and finally the finished product La is obtained0.9Ag0.1CoO33A perovskite catalyst.
Example 7: the perovskite catalyst of the present example was La0.8Ag0.2CoO3；
Example 7 compares with example 1, except that lanthanum nitrate, silver nitrate and cobalt nitrate are weighed according to the molar mass ratio of 0.8:0.2:1, other operating conditions and material consumption are the same as example 1, and finally the finished La product is obtained0.8Ag0.2CoO3A perovskite catalyst.
Example 8: the perovskite catalyst of the present example was La0.7Ag0.3CoO3；
Example 8 compared with example 1, except that lanthanum nitrate, silver nitrate and cobalt nitrate were weighed according to a molar mass ratio of 0.7:0.3:1, other operating conditions and material amounts were the same as in example 1, and finally the final product La was obtained0.7Ag0.3CoO3A perovskite catalyst.
Example 9: the perovskite catalyst of the present example was La0.6Ag0.4CoO3；
Example 9 compared with example 1, except that lanthanum nitrate, silver nitrate and cobalt nitrate were weighed according to a molar mass ratio of 0.6:0.4:1, other operating conditions and material amounts were the same as in example 1, and finally the final product La was obtained0.6Ag0.4CoO3A perovskite catalyst.
Example 10: the perovskite catalyst of the present example was La0.5Ag0.5CoO3；
Example 10 compared with example 1, except that lanthanum nitrate, silver nitrate and cobalt nitrate were weighed according to a molar mass ratio of 0.5:0.5:1, other operating conditions and material amounts were the same as in example 1, and finally the final product La was obtained0.5Ag0.5CoO3A perovskite catalyst.
The XRD patterns of the doped perovskite catalysts prepared in examples 6-10 are shown in a legend 2, and it can be seen from the graphs that all the examples show obvious perovskite characteristic peaks, but the characteristic peaks of Ag are gradually obvious along with the increase of the substitution amount of doped metal Ag, which proves that Ag is well doped into perovskite LaCoO3In the structure of (1).
Test example:
the fresh catalyst was packed in a quartz tube, and first purged with nitrogen at 100 ℃ for 1 hour, and then heated from 100 ℃ to 400 ℃ with the sampling point time controlled at 10min, and the nitrogen monoxide oxidation rate was as shown in table 2.
TABLE 2 La1-xAgxCoO3(X ═ 0-0.5) perovskite catalyzed oxidation nitrogen monoxide oxidation rate (%).
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 (10)
1. A doped perovskite catalyst characterized by: the chemical general formula is La1-xAxCoO3Wherein X is 0.1-0.5, A is Sr or Ag.
2. A preparation method of a doped perovskite catalyst is characterized by comprising the following steps: the method comprises the following steps:
step one, forming an aqueous solution system by nitrate of lanthanum nitrate and A metal and cobalt nitrate;
step two, preparing a citric acid solution;
step three, mixing the metal salt solution obtained in the step one with the citric acid solution obtained in the step two;
step four, magnetically stirring the mixed solution obtained in the step three to obtain a uniformly mixed solution;
placing the mixed solution obtained in the step four in an ultrasonic cleaning machine for ultrasonic treatment to further uniformly mix the metal elements;
putting the mixed solution obtained in the fifth step into a water bath kettle, and heating in a water bath;
seventhly, putting the gel-state substance obtained in the sixth step into a constant-temperature drying box, and drying overnight;
step eight, placing the fluffy perovskite precursor obtained in the step seven in a muffle furnace for roasting for 4-5 hours, and then cooling to room temperature;
step nine, grinding and tabletting the sample obtained in the step eight to obtain the finished perovskite catalyst with the granularity of 40-60 meshes.
3. The process according to claim 2, wherein the step of preparing a doped perovskite catalyst comprises: and the concentration of the citric acid solution in the second step is 1 mol/L.
4. The process according to claim 2, wherein the step of preparing a doped perovskite catalyst comprises: and in the third step, the metal salt solution and the citric acid solution are mixed according to the mass ratio of 1: 2.
5. The process according to claim 2, wherein the step of preparing a doped perovskite catalyst comprises: the magnetic stirring time in the fourth step is 60min, and the ultrasonic treatment time in the fifth step is 60-120 min.
6. The process according to claim 2, wherein the step of preparing a doped perovskite catalyst comprises: and in the sixth step, the temperature of water bath heating is 80 ℃, and the time is 5 hours.
7. The process according to claim 2, wherein the step of preparing a doped perovskite catalyst comprises: and step eight, uniformly heating the fluffy perovskite precursor to 700-800 ℃ at a heating rate of 5-10 ℃/min in a muffle furnace, roasting for 4-5 h, and then cooling to room temperature at a cooling rate of 2-5 ℃/min.
8. The process according to claim 2, wherein the step of preparing a doped perovskite catalyst comprises: in the first step, the molar mass ratio of the lanthanum nitrate to the nitrate of the metal A to the cobalt nitrate is 0.9:0.1:1 or 0.8:0.2:1 or 0.7:0.3:1 or 0.6:0.4:1 or 0.5:0.5: 1.
9. la prepared based on claim 21-xSrxCoO3The application of the catalyst in catalytic oxidation of nitric oxide and elemental mercury.
10. La prepared based on claim 21-xAgxCoO3Use of a catalyst for the catalytic oxidation of nitric oxide.
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