CN113578303A - Preparation method of SCR denitration catalyst with ultralow vanadium load by taking perovskite type composite oxide as carrier and prepared catalyst - Google Patents
Preparation method of SCR denitration catalyst with ultralow vanadium load by taking perovskite type composite oxide as carrier and prepared catalyst Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 57
- 239000002131 composite material Substances 0.000 title claims abstract description 37
- 229910052720 vanadium Inorganic materials 0.000 title claims abstract description 21
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 title claims abstract description 21
- 238000002360 preparation method Methods 0.000 title claims abstract description 9
- UNTBPXHCXVWYOI-UHFFFAOYSA-O azanium;oxido(dioxo)vanadium Chemical compound [NH4+].[O-][V](=O)=O UNTBPXHCXVWYOI-UHFFFAOYSA-O 0.000 claims abstract description 37
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims abstract description 27
- 238000010438 heat treatment Methods 0.000 claims abstract description 21
- 238000001035 drying Methods 0.000 claims abstract description 17
- 238000002156 mixing Methods 0.000 claims abstract description 16
- 238000003756 stirring Methods 0.000 claims abstract description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 13
- 238000011068 loading method Methods 0.000 claims abstract description 11
- 235000006408 oxalic acid Nutrition 0.000 claims abstract description 9
- 238000007873 sieving Methods 0.000 claims abstract description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 3
- 238000000227 grinding Methods 0.000 claims abstract description 3
- 239000004570 mortar (masonry) Substances 0.000 claims abstract description 3
- 238000000034 method Methods 0.000 claims description 18
- 239000000203 mixture Substances 0.000 claims description 10
- 229910002971 CaTiO3 Inorganic materials 0.000 claims description 8
- 229910002254 LaCoO3 Inorganic materials 0.000 claims description 5
- 229910002321 LaFeO3 Inorganic materials 0.000 claims description 5
- 229910002113 barium titanate Inorganic materials 0.000 claims description 5
- 229910002340 LaNiO3 Inorganic materials 0.000 claims description 2
- 229910002370 SrTiO3 Inorganic materials 0.000 claims description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims 1
- 239000011575 calcium Substances 0.000 claims 1
- 229910052791 calcium Inorganic materials 0.000 claims 1
- 229910052500 inorganic mineral Inorganic materials 0.000 claims 1
- 239000011707 mineral Substances 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 13
- 230000009286 beneficial effect Effects 0.000 abstract 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 42
- GNTDGMZSJNCJKK-UHFFFAOYSA-N divanadium pentaoxide Chemical compound O=[V](=O)O[V](=O)=O GNTDGMZSJNCJKK-UHFFFAOYSA-N 0.000 description 24
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 19
- 230000000052 comparative effect Effects 0.000 description 15
- 239000004408 titanium dioxide Substances 0.000 description 7
- 238000006243 chemical reaction Methods 0.000 description 6
- 238000007605 air drying Methods 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- 239000003546 flue gas Substances 0.000 description 4
- 238000006467 substitution reaction Methods 0.000 description 4
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 3
- YOSLGHBNHHKHST-UHFFFAOYSA-N cerium manganese Chemical compound [Mn].[Mn].[Mn].[Mn].[Mn].[Ce] YOSLGHBNHHKHST-UHFFFAOYSA-N 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- 239000000969 carrier Substances 0.000 description 2
- 238000010531 catalytic reduction reaction Methods 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 229910000069 nitrogen hydride Inorganic materials 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 229910052719 titanium Inorganic materials 0.000 description 2
- 239000010936 titanium Substances 0.000 description 2
- WKXHZKXPFJNBIY-UHFFFAOYSA-N titanium tungsten vanadium Chemical compound [Ti][W][V] WKXHZKXPFJNBIY-UHFFFAOYSA-N 0.000 description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- 229910017771 LaFeO Inorganic materials 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 238000003421 catalytic decomposition reaction Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000000779 smoke Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 238000013112 stability test Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000003887 surface segregation Methods 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
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- 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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- B01J23/16—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
- B01J23/20—Vanadium, niobium or tantalum
- B01J23/22—Vanadium
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Abstract
The invention discloses a preparation method of an SCR denitration catalyst with ultralow vanadium loading by taking perovskite type composite oxide as a carrier, relating to the technical field of denitration catalysts and comprising the following steps: (1) dissolving ammonium metavanadate in an oxalic acid solution, and fully stirring to completely dissolve the ammonium metavanadate to obtain an ammonium metavanadate solution; the concentration of ammonium metavanadate in the ammonium metavanadate solution is 2-6 g/L; (2) grinding the perovskite type composite oxide by using an agate mortar and then sieving; (3) mixing an ammonium metavanadate solution and a perovskite type composite oxide, and stirring to be viscous under the water bath heating condition, wherein the mixing ratio of the ammonium metavanadate solution to the perovskite type oxide is 100mL:100 g; (4) and drying the viscous product, and roasting at 550-650 ℃ for 2-5 h. The invention has the beneficial effects that: not only ensures the denitration activity and stability of the catalyst, but also reduces the usage amount of vanadium.
Description
Technical Field
The invention relates to the technical field of denitration catalysts, in particular to a preparation method of an SCR denitration catalyst with ultralow vanadium loading by taking perovskite type composite oxide as a carrier and a prepared catalyst.
Background
Nitrogen Oxides (NO) produced in flue gas of industrial kilnx) There are three types of (1): thermal, rapid and fuel types. For reducing NO in flue gasxConcentration, typically by spraying ammonia water inside the kiln to make NOxUnder the action of high temperature and NH3Conversion by reaction to N2I.e. the selective non-catalytic reduction technique (SNCR). However, the technology can only reduce about 50-70% of NO in the smokexThe emission requirement cannot be met for a common industrial kiln, so that the NO in the flue gas can be further reduced by using a Selective Catalytic Reduction (SCR) technology at the rear end of treatmentxThe concentration of (c).
The core of the SCR denitration technology is a denitration catalyst, and the existing commercial SCR denitration catalyst is mainly a vanadium-tungsten-titanium catalyst, and can meet the requirements of flue gas denitration in different temperature ranges of high, medium and low temperatures. The medium-low temperature denitration has higher requirement on the activity of the catalyst, and the high-temperature denitration has higher thermal stability on the catalyst. Titanium dioxide (TiO) can be generated in the vanadium-tungsten-titanium SCR denitration catalyst at high temperature2) Crystal phase transition of the carrier and agglomeration of the active components.
Perovskite-type oxide (ABO)3) The substance has direct catalytic decomposition effect on NO and the like, for example, a patent with the publication number of CN106492791A discloses a medium-low temperature denitration catalyst and a preparation method thereof, wherein the catalyst takes strontium-doped cerium-manganese perovskite type composite oxide and superfine titanium dioxide as carriers, and the prepared catalyst has the characteristics of low temperatureThe high activity is mainly attributed to Mn (having low-temperature denitration activity) in the strontium-doped cerium-manganese perovskite type composite oxide. But due to anatase type TiO2Starting at 610 ℃ towards rutile TiO2The conversion (Fuchunlin, Wei stannum, titanium dioxide crystal form conversion research, coating industry, 1999, 2: 28-30) is achieved, so that the catalyst which takes the strontium-doped cerium-manganese perovskite type composite oxide and the superfine titanium dioxide as the carriers and vanadium pentoxide as the main active components is only suitable for medium and low temperature denitration, but cannot keep higher thermal stability and denitration activity at high temperature (600-650 ℃).
Disclosure of Invention
The technical problem to be solved by the invention is to lack an SCR denitration catalyst with thermal stability and denitration activity at high temperature.
The invention solves the technical problems through the following technical means:
a preparation method of an SCR denitration catalyst with ultralow vanadium load by taking a perovskite type composite oxide as a carrier comprises the following steps:
(1) dissolving ammonium metavanadate in an oxalic acid solution, and fully stirring to obtain an ammonium metavanadate solution; the concentration of ammonium metavanadate in the ammonium metavanadate solution is 2-6 g/L;
(2) mixing perovskite type composite oxide (ABO)3) Grinding the mixture by using an agate mortar and sieving the mixture to prepare a catalyst carrier;
(3) mixing the ammonium metavanadate solution obtained in the step (1) with the catalyst carrier obtained in the step (2), and stirring the mixture under the water bath heating condition until the mixture is viscous, wherein the mixing ratio of the ammonium metavanadate solution to the perovskite type oxide is 100mL:100 g;
(4) and (4) drying the viscous product obtained in the step (3), and roasting at 600-650 ℃ for 2-5 h.
Has the advantages that: the present invention uses perovskite type composite oxide (ABO)3) The catalyst is a carrier, on one hand, the good thermal stability of the carrier is utilized to adjust the concentration of ammonium metavanadate and the proportion of the ammonium metavanadate and the perovskite type oxide, so that the thermal stability of the SCR denitration catalyst under the working condition of high temperature (600-650 ℃) is improved, and on the other hand, the titanium ore type is utilizedComposite oxide (ABO)3) The characteristic of directly catalyzing and decomposing NO at high temperature reduces the active component V2O5Amount of (2) and amount of (2)<0.5 percent. The method not only ensures the denitration activity and stability of the catalyst, but also reduces the use amount of vanadium.
Compared with the method adopting anatase type titanium dioxide as a carrier, the method can obviously improve the denitration activity of the catalyst.
Preferably, the concentration of the oxalic acid solution in the step (1) is 10-100 g/L.
Preferably, the perovskite-type composite oxide (ABO) in the step (2)3) Comprising CaTiO3、BaTiO3、SrTiO3、LaCoO3、LaFeO3、LaNiO3。
Preferably, the step (2) is performed by sieving with a 200-mesh sieve.
Preferably, the perovskite-type composite oxide is CaTiO3。
Preferably, the temperature of the water bath heating in the step (3) is 65-90 ℃.
Preferably, the drying in step (4) adopts a temperature-programmed drying method, and the drying procedure is as follows: heating from room temperature to 90 deg.C at 5 deg.C/min and holding for 2h, and then heating to 10 deg.C at 5 deg.C/min and holding for 2 h.
Has the advantages that: the purpose of low-speed temperature rise and stage heat preservation at the speed of 5 ℃/min is to prevent the active components from generating surface segregation in the drying process, so that the active components are not uniformly distributed on the carrier.
The invention also provides the SCR denitration catalyst prepared by the method.
Has the advantages that: the catalyst prepared by the invention has good thermal stability and denitration activity.
The invention has the advantages that: the present invention uses perovskite type composite oxide (ABO)3) The carrier is used, on one hand, the good thermal stability of the carrier is utilized to improve the thermal stability of the SCR denitration catalyst under the working condition of high temperature (600-650 ℃), on the other hand, the titanium ore type composite oxide (ABO) is utilized3) The characteristic of directly catalyzing and decomposing NO at high temperature reduces the active component V2O5Amount of (2) and amount of (2)<0.5 percent. The method not only ensures the denitration activity and stability of the catalyst, but also reduces the use amount of vanadium.
Compared with the method adopting anatase type titanium dioxide as a carrier, the method can obviously improve the denitration activity of the catalyst.
Drawings
FIG. 1 is a graph showing the results of the stability test of the catalysts of example 1 of the present invention and comparative example 1.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention, and it is obvious that the described embodiments are some embodiments of the present invention, but not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Test materials, reagents and the like used in the following examples are commercially available unless otherwise specified.
The specific techniques or conditions not specified in the examples can be performed according to the techniques or conditions described in the literature in the field or according to the product specification.
Example 1
The preparation method of the SCR denitration catalyst with ultralow vanadium load by taking the perovskite type composite oxide as the carrier specifically comprises the following steps:
(1) dissolving 0.6g of ammonium metavanadate in 100mL of oxalic acid solution with the concentration of 100g/L, and fully stirring to completely dissolve the ammonium metavanadate to obtain the ammonium metavanadate solution.
(2) Mixing the ammonium metavanadate solution obtained in the step (1) with 100g of CaTiO sieved by a 200-mesh sieve3And (4) uniformly mixing.
(3) And (3) stirring the mixture obtained in the step (2) under the heating condition of a water bath at 85 ℃ to evaporate water to be viscous.
(4) Drying the viscous product obtained in the step (3) in a forced air drying oven, wherein the drying procedure is as follows: heating from room temperature to 90 deg.C at 5 deg.C/min and holding for 2h, and then heating to 10 deg.C at 5 deg.C/min and holding for 2 h.
(5) Roasting the dried product obtained in the step (4) in a muffle furnace at 650 ℃, wherein the roasting time is 3h, and naturally cooling to obtain the perovskite type composite oxide CaTiO3Supported ultra low vanadium loaded SCR denitration catalyst wherein V2O5The loading of (b) was 0.46%.
Example 2
(1) Dissolving 0.5g of ammonium metavanadate in 100mL of oxalic acid solution with the concentration of 70g/L, and fully stirring to completely dissolve the ammonium metavanadate to obtain the ammonium metavanadate solution.
(2) Mixing the ammonium metavanadate solution obtained in the step (1) with 100g of BaTiO sieved by a 200-mesh sieve3And (4) uniformly mixing.
(3) And (3) stirring the mixture obtained in the step (2) under the heating condition of a water bath at 90 ℃ to evaporate water to be viscous.
(4) Drying the viscous product obtained in the step (3) in a forced air drying oven, wherein the drying procedure is as follows: heating from room temperature to 90 deg.C at 5 deg.C/min and holding for 2h, and then heating to 10 deg.C at 5 deg.C/min and holding for 2 h.
(5) Roasting the dried product obtained in the step (4) in a muffle furnace at 650 ℃, wherein the roasting time is 5h, and naturally cooling to obtain the perovskite type composite oxide BaTiO3Supported ultra low vanadium loaded SCR denitration catalyst wherein V2O5The loading capacity of the catalyst is 0.39 percent
Example 3
(1) Dissolving 0.3g of ammonium metavanadate in 100mL of oxalic acid solution with the concentration of 80g/L, and fully stirring to completely dissolve the ammonium metavanadate to obtain the ammonium metavanadate solution.
(2) Mixing the ammonium metavanadate solution obtained in the step (1) with 100g of LaFeO sieved by a 200-mesh sieve3And (4) uniformly mixing.
(3) And (3) stirring the mixture obtained in the step (2) under the water bath heating condition of 65 ℃ to evaporate water to be viscous.
(4) Drying the viscous product obtained in the step (3) in a forced air drying oven, wherein the drying procedure is as follows: heating from room temperature to 90 deg.C at 5 deg.C/min and holding for 2h, and then heating to 10 deg.C at 5 deg.C/min and holding for 2 h.
(5) Roasting the dried product obtained in the step (4) in a muffle furnace at 625 ℃, wherein the roasting time is 2h, and naturally cooling to obtain the perovskite type composite oxide LaFeO3Supported ultra low vanadium loaded SCR denitration catalyst wherein V2O5The loading of (b) was 0.23%.
Example 4
(1) Dissolving 0.4g of ammonium metavanadate in 100mL of oxalic acid solution with the concentration of 30g/L, and fully stirring to completely dissolve the ammonium metavanadate to obtain the ammonium metavanadate solution.
(2) Mixing the ammonium metavanadate solution obtained in the step (1) with 100g of LaCoO sieved by a 200-mesh sieve3And (4) uniformly mixing.
(3) And (3) stirring the mixture obtained in the step (2) under the water bath heating condition of 70 ℃ to evaporate water to be viscous.
(4) Drying the viscous product obtained in the step (3) in a forced air drying oven, wherein the drying procedure is as follows: heating from room temperature to 90 deg.C at 5 deg.C/min and holding for 2h, and then heating to 10 deg.C at 5 deg.C/min and holding for 2 h.
(5) Roasting the dried product obtained in the step (4) in a muffle furnace at 630 ℃ for 4h, and naturally cooling to obtain the perovskite type composite oxide LaCoO3Supported ultra low vanadium loaded SCR denitration catalyst wherein V2O5The amount of (B) was 0.31%.
Comparative example 1
This comparative example differs from example 1 in that: perovskite type composite oxide CaTiO3By substitution of anatase type TiO2。
Comparative example 2
This comparative example differs from example 2 in that: mixing perovskite type composite oxide BaTiO3By substitution of anatase type TiO2。
Comparative example 3
This comparative example differs from example 3 in that: the perovskite type composite oxide LaFeO3By replacement withAnatase type TiO2。
Comparative example 4
This comparative example differs from example 4 in that: the perovskite type composite oxide LaCoO3By substitution of anatase type TiO2。
Experimental data and analysis:
the denitration performance evaluation of the denitration catalysts in examples 1 to 4 and comparative examples 1 to 4 was performed under the following reaction conditions: NO concentration 2000ppm, NH3Concentration 2000ppm, 10 vol.% O2The others are Ar, and the space velocity is 20000h-1The reaction temperature was 650 ℃. The denitration performance is shown in Table 1. The results of the catalyst stability experiments for example 1 and comparative example 1 are shown in fig. 1.
TABLE 1 measurement results of denitration performance of catalyst
| Item | Catalyst and process for preparing same | Denitration efficiency/%) |
| Example 1 | V2O5/CaTiO3 | 89.43 |
| Comparative example 1 | V2O5/TiO2 | 70.23 |
| Example 2 | V2O5/BaTiO3 | 75.93 |
| Comparative example 2 | V2O5/TiO2 | 63.29 |
| Example 3 | V2O5/LaFeO3 | 47.24 |
| Comparative example 3 | V2O5/TiO2 | 35.27 |
| Example 4 | V2O5/LaCoO3 | 52.36 |
| Comparative example 4 | V2O5/TiO2 | 45.56 |
The test results showed that perovskite-type composite oxides (ABO) obtained in examples 1, 2, 3 and 4 of the present invention3) SCR denitration catalyst with ultralow vanadium load as carrier and anatase type TiO2Is a V of a carrier2O5/TiO2Compared with the denitration catalyst, the denitration catalyst has higher denitration activity at 650 ℃, and when the carrier is CaTiO3In this case, the denitration efficiency is the best. This shows that the denitration catalyst of the present invention has better adaptability to high temperature conditions.
The above examples are only intended to illustrate the technical solution of the present invention, but not to limit it; although the present invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some technical features may be equivalently replaced; and such modifications or substitutions do not depart from the spirit and scope of the corresponding technical solutions of the embodiments of the present invention.
Claims (8)
1. A preparation method of an SCR denitration catalyst with ultralow vanadium load by taking perovskite type composite oxide as a carrier is characterized by comprising the following steps: the method comprises the following steps:
(1) dissolving ammonium metavanadate in an oxalic acid solution, and fully stirring to obtain an ammonium metavanadate solution; the concentration of ammonium metavanadate in the ammonium metavanadate solution is 2-6 g/L;
(2) grinding the perovskite type composite oxide by using an agate mortar, and sieving to prepare a catalyst carrier;
(3) mixing the ammonium metavanadate solution obtained in the step (1) with the perovskite type composite oxide obtained in the step (2), and stirring the mixture under the water bath heating condition until the mixture is sticky, wherein the mixing ratio of the ammonium metavanadate solution to the perovskite type oxide is 100mL:100 g;
(4) and (4) drying the viscous product obtained in the step (3), and roasting at 600-650 ℃ for 2-5 h.
2. The method for preparing the SCR denitration catalyst with the ultralow vanadium loading by using the perovskite type composite oxide as the carrier according to claim 1, is characterized in that: the concentration of the oxalic acid solution in the step (1) is 10-100 g/L.
3. The method for preparing the SCR denitration catalyst with the ultralow vanadium loading by using the perovskite type composite oxide as the carrier according to claim 1, is characterized in that: the perovskite type composite oxide in the step (2) comprises CaTiO3、BaTiO3、SrTiO3、LaCoO3、LaFeO3、LaNiO3。
4. The method of claim 3, wherein said step is performed in the presence of calcium and titaniumThe preparation method of the SCR denitration catalyst with ultralow vanadium loading and with the mineral composite oxide as the carrier is characterized by comprising the following steps of: the perovskite type composite oxide is CaTiO3。
5. The method for preparing the SCR denitration catalyst with the ultralow vanadium loading by using the perovskite type composite oxide as the carrier according to claim 1, is characterized in that: and (3) sieving with a 200-mesh sieve in the step (2).
6. The method for preparing the SCR denitration catalyst with the ultralow vanadium loading by using the perovskite type composite oxide as the carrier according to claim 1, is characterized in that: the temperature of the water bath heating in the step (3) is 65-90 ℃.
7. The method for preparing the SCR denitration catalyst with the ultralow vanadium loading by using the perovskite type composite oxide as the carrier according to claim 1, is characterized in that: in the step (4), the drying adopts a temperature programming drying mode, and the drying program is as follows: heating from room temperature to 90 deg.C at 5 deg.C/min and holding for 2h, and then heating to 10 deg.C at 5 deg.C/min and holding for 2 h.
8. An SCR denitration catalyst produced by the method of any one of claims 1 to 7.
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Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS63305938A (en) * | 1987-06-08 | 1988-12-13 | Toyota Central Res & Dev Lab Inc | Catalyst for purifying exhaust gas |
| JPH0780310A (en) * | 1993-06-29 | 1995-03-28 | Idemitsu Kosan Co Ltd | Production of perovskite or perovskite-like structure oxide carrying catalyst |
| JPH11151440A (en) * | 1997-07-18 | 1999-06-08 | Tokyo Gas Co Ltd | Catalyst for decomposing and removing nitrogen oxides and decomposing and removing method of nitrogen oxides |
| JPH11342336A (en) * | 1998-06-01 | 1999-12-14 | Tokyo Gas Co Ltd | Catalyst a for removal of nitrogen oxides by decomposition and method |
| CN1714931A (en) * | 2004-06-14 | 2006-01-04 | 中国科学院生态环境研究中心 | The perovskite type rare earth complex oxide catalyst of catalytic decomposition NOx under the excess oxygen |
| CN101934227A (en) * | 2010-09-09 | 2011-01-05 | 复旦大学 | Catalyst for selective reduction of NOx with NH3 and preparation method thereof |
| CN104415745A (en) * | 2013-08-22 | 2015-03-18 | 上海郎特汽车净化器有限公司 | Perovskite structure substance and preparation method thereof |
| CN105214670A (en) * | 2015-10-14 | 2016-01-06 | 东南大学 | The preparation being low temperature support type denitrating catalyst in carrier with former iron ore and method of testing |
| CN106423143A (en) * | 2016-05-30 | 2017-02-22 | 南京大学扬州化学化工研究院 | Catalyst for removing nitric oxide in exhaust gas at low temperature and preparation method and application of catalyst |
| CN109331801A (en) * | 2018-11-16 | 2019-02-15 | 内蒙古工业大学 | A kind of nanoporous TiO prepared with triethanolamine2For the preparation method of the vanadium based denitration catalyst of carrier |
-
2021
- 2021-08-03 CN CN202110886537.2A patent/CN113578303A/en active Pending
Patent Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS63305938A (en) * | 1987-06-08 | 1988-12-13 | Toyota Central Res & Dev Lab Inc | Catalyst for purifying exhaust gas |
| JPH0780310A (en) * | 1993-06-29 | 1995-03-28 | Idemitsu Kosan Co Ltd | Production of perovskite or perovskite-like structure oxide carrying catalyst |
| JPH11151440A (en) * | 1997-07-18 | 1999-06-08 | Tokyo Gas Co Ltd | Catalyst for decomposing and removing nitrogen oxides and decomposing and removing method of nitrogen oxides |
| JPH11342336A (en) * | 1998-06-01 | 1999-12-14 | Tokyo Gas Co Ltd | Catalyst a for removal of nitrogen oxides by decomposition and method |
| CN1714931A (en) * | 2004-06-14 | 2006-01-04 | 中国科学院生态环境研究中心 | The perovskite type rare earth complex oxide catalyst of catalytic decomposition NOx under the excess oxygen |
| CN101934227A (en) * | 2010-09-09 | 2011-01-05 | 复旦大学 | Catalyst for selective reduction of NOx with NH3 and preparation method thereof |
| CN104415745A (en) * | 2013-08-22 | 2015-03-18 | 上海郎特汽车净化器有限公司 | Perovskite structure substance and preparation method thereof |
| CN105214670A (en) * | 2015-10-14 | 2016-01-06 | 东南大学 | The preparation being low temperature support type denitrating catalyst in carrier with former iron ore and method of testing |
| CN106423143A (en) * | 2016-05-30 | 2017-02-22 | 南京大学扬州化学化工研究院 | Catalyst for removing nitric oxide in exhaust gas at low temperature and preparation method and application of catalyst |
| CN109331801A (en) * | 2018-11-16 | 2019-02-15 | 内蒙古工业大学 | A kind of nanoporous TiO prepared with triethanolamine2For the preparation method of the vanadium based denitration catalyst of carrier |
Non-Patent Citations (2)
| Title |
|---|
| CHILUKOTI SRILAKSHMI ET AL.: "An Efficient Vanadia Supported SrTiO3 Nanocatalyst for the Selective Oxidation of Benzylalcohol to Benzaldehyde", vol. 5, pages 4500 - 4508 * |
| 夏海涛等: "催化剂设计与制备工艺", 化学工业出版社, pages: 248 * |
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