CN111558372B - Medium-low temperature supported nano copper oxide particle catalyst and preparation method and application thereof - Google Patents
Medium-low temperature supported nano copper oxide particle catalyst and preparation method and application thereof Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 143
- 239000002245 particle Substances 0.000 title claims abstract description 103
- 239000005751 Copper oxide Substances 0.000 title claims abstract description 77
- 229910000431 copper oxide Inorganic materials 0.000 title claims abstract description 77
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 title claims abstract description 76
- 238000002360 preparation method Methods 0.000 title claims abstract description 27
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims abstract description 46
- 238000000034 method Methods 0.000 claims abstract description 31
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 28
- 238000003756 stirring Methods 0.000 claims abstract description 26
- 239000007788 liquid Substances 0.000 claims abstract description 25
- 239000011259 mixed solution Substances 0.000 claims abstract description 25
- 238000001035 drying Methods 0.000 claims abstract description 19
- 239000002243 precursor Substances 0.000 claims abstract description 13
- 238000001914 filtration Methods 0.000 claims abstract description 9
- 239000012716 precipitator Substances 0.000 claims abstract description 7
- 238000000746 purification Methods 0.000 claims abstract description 5
- 238000002156 mixing Methods 0.000 claims abstract description 3
- 239000000243 solution Substances 0.000 claims description 48
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 23
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 21
- 239000004408 titanium dioxide Substances 0.000 claims description 10
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 claims description 8
- 235000006408 oxalic acid Nutrition 0.000 claims description 7
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 claims description 6
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 6
- 239000001099 ammonium carbonate Substances 0.000 claims description 6
- 235000012501 ammonium carbonate Nutrition 0.000 claims description 6
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 6
- 230000003197 catalytic effect Effects 0.000 claims description 6
- 229910000365 copper sulfate Inorganic materials 0.000 claims description 2
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 claims description 2
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 claims description 2
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 2
- 230000000694 effects Effects 0.000 abstract description 33
- 239000002244 precipitate Substances 0.000 abstract description 26
- 206010027439 Metal poisoning Diseases 0.000 abstract description 18
- 229910052783 alkali metal Inorganic materials 0.000 abstract description 18
- 150000001340 alkali metals Chemical class 0.000 abstract description 18
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 abstract description 7
- 229910052717 sulfur Inorganic materials 0.000 abstract description 7
- 239000011593 sulfur Substances 0.000 abstract description 7
- 238000003915 air pollution Methods 0.000 abstract description 2
- 238000006243 chemical reaction Methods 0.000 description 126
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 113
- 238000012360 testing method Methods 0.000 description 48
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 description 26
- 229910000069 nitrogen hydride Inorganic materials 0.000 description 24
- 239000000203 mixture Substances 0.000 description 19
- 239000012159 carrier gas Substances 0.000 description 12
- 239000000779 smoke Substances 0.000 description 12
- 238000000975 co-precipitation Methods 0.000 description 10
- 125000001967 indiganyl group Chemical group [H][In]([H])[*] 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 9
- 239000010949 copper Substances 0.000 description 8
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 6
- 229910052802 copper Inorganic materials 0.000 description 6
- 239000006185 dispersion Substances 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 5
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 4
- SXTLQDJHRPXDSB-UHFFFAOYSA-N copper;dinitrate;trihydrate Chemical compound O.O.O.[Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O SXTLQDJHRPXDSB-UHFFFAOYSA-N 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 230000002776 aggregation Effects 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 230000006872 improvement Effects 0.000 description 3
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 2
- 238000005054 agglomeration Methods 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 description 2
- 230000001276 controlling effect Effects 0.000 description 2
- FTXJFNVGIDRLEM-UHFFFAOYSA-N copper;dinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O FTXJFNVGIDRLEM-UHFFFAOYSA-N 0.000 description 2
- QYCVHILLJSYYBD-UHFFFAOYSA-L copper;oxalate Chemical compound [Cu+2].[O-]C(=O)C([O-])=O QYCVHILLJSYYBD-UHFFFAOYSA-L 0.000 description 2
- 238000006477 desulfuration reaction Methods 0.000 description 2
- 230000023556 desulfurization Effects 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 239000000428 dust Substances 0.000 description 2
- 239000003344 environmental pollutant Substances 0.000 description 2
- 239000003546 flue gas Substances 0.000 description 2
- 238000011068 loading method Methods 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 230000001737 promoting effect Effects 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- 229910052720 vanadium Inorganic materials 0.000 description 2
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 2
- 239000010457 zeolite Substances 0.000 description 2
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 239000000809 air pollutant Substances 0.000 description 1
- 231100001243 air pollutant Toxicity 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000012876 carrier material Substances 0.000 description 1
- 238000010531 catalytic reduction reaction Methods 0.000 description 1
- 239000004568 cement Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 239000008358 core component Substances 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000008014 freezing Effects 0.000 description 1
- 238000007710 freezing Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000002957 persistent organic pollutant Substances 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
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- 238000007670 refining Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
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Classifications
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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
- B01J37/02—Impregnation, coating or precipitation
- B01J37/03—Precipitation; Co-precipitation
- B01J37/031—Precipitation
- B01J37/035—Precipitation on carriers
-
- 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
- B01J23/72—Copper
-
- B01J35/393—
-
- B01J35/394—
Abstract
The invention belongs to the technical field of air pollution control, and discloses a medium-low temperature supported nano copper oxide particle catalyst, and a preparation method and application thereof. The method comprises the following steps: (1) dissolving a copper oxide precursor in a mixed solution formed by hydrogen peroxide and water to prepare ice blocks; (2) mixing a catalyst carrier and a precipitator to prepare a turbid liquid; (3) putting the ice blocks prepared in the step (1) into the turbid liquid in the step (2), and stirring and dissolving at low temperature; (4) after the ice blocks are dissolved, filtering, drying the obtained precipitate, and roasting to obtain the final catalyst. The copper oxide particles prepared by the method have high dispersibility on a carrier, the average size of the copper oxide is 1-5 nm, and the obtained medium-low temperature loaded nano copper oxide particle catalyst has excellent medium-low temperature activity and N when used for NOx purification2Selectivity, sulfur resistance, water resistance and alkali metal poisoning resistance.
Description
Technical Field
The invention belongs to the technical field of air pollution control, and particularly relates to a medium-low temperature supported nano copper oxide particle catalyst, and a preparation method and application thereof.
Background
As fossil fuelsThe main energy source providing world economic power inevitably causes the generation of various air pollutants, such as sulfur dioxide, nitrogen oxides (NOx), particulate matters, volatile organic pollutants and the like in the combustion process. Since 2011, the total amount of NOx emission far exceeds that of SO in terms of emission of various atmospheric pollutants2The method becomes a key object for controlling pollutants in China. The Selective Catalytic Reduction (SCR) denitration technology is the flue gas denitration technology which is widely applied, has the highest market share and is most stable and reliable in operation in the world at present due to mature technology and high efficiency, and is successfully applied to flue gas treatment of power station boilers, glass kilns, cement kilns and the like.
The denitration catalyst is used as a core component of the SCR technology, and plays a decisive role in development, popularization and application of the SCR technology. V2O5-WO3(MO3)/TiO2The catalyst, as the most common commercial catalyst, has the advantages of high activity, strong selectivity, good sulfur resistance and the like, but has certain economic feasibility only when being arranged in a dust removal and desulfurization device. However, when the catalyst is arranged after the dust removal and desulfurization device, the reaction temperature is greatly reduced, and the low-temperature denitration performance of the catalyst is more strictly required. Meanwhile, the vanadium-based catalyst faces practical problems of poor stability, high biotoxicity, easy corrosion of sulfate-induced equipment and the like, so that the development of a novel non-vanadium-based catalyst with good medium-low temperature activity is significant and urgent in demand.
In recent years, the denitration performance of copper-based catalysts has been studied, and the copper-based catalysts are candidates for metal oxide SCR catalysts due to good low-temperature catalytic activity. Copper-based catalysts in the form of copper ion-exchanged zeolites, such as Cu/SAPO-34, have relatively high low temperature catalytic activity, but are mainly confronted with the problem of relatively high cost of copper ion-exchanged zeolites. According to the report of Lilu et al (Applied Catalysis B: Environmental,2017,207:366-2/CeO2The activity of the catalyst is unsupported TiO2/CeO2Three times the catalyst activity, but at different Cu loadings, is facing N2Poor selectivity and the likeA problem; according to the report of West-Jong et al (Acs Applied Materials)&2014,6(11) 8134-8145), the NOx conversion rate of the CuCeTi catalyst is over 100% under the low temperature condition of 200 ℃, and the dispersion degree of particles on the carrier is far higher than the single active particle loading condition, so that the improvement of the dispersion degree of the active particles on the catalyst is beneficial to promoting the catalytic reaction under the low temperature condition, and is an important link in the catalyst preparation process.
At present, a large number of patents at home and abroad disclose various types of denitration catalysts and preparation processes, but the preparation has excellent medium-low temperature activity and N2Selective and resistant copper-based denitration catalyst processes have been reported only rarely, and the present invention will provide a way and a specific method to overcome the above problems.
Disclosure of Invention
In order to overcome the defects of the prior art, the invention mainly aims to provide a preparation method of a medium-low temperature supported nano copper oxide particle catalyst;
the invention also aims to provide the medium-low temperature supported nano copper oxide particle catalyst prepared by the method, and in the catalyst prepared by the preparation method, copper oxide particles have higher particle dispersion degree and smaller particle size on a carrier;
the invention further aims to provide the application of the medium-low temperature supported nano copper oxide particle catalyst in the catalytic purification of NOx.
The purpose of the invention is realized by the following scheme:
a preparation method of a medium-low temperature supported nano copper oxide particle catalyst comprises the following steps:
(1) dissolving a copper oxide precursor in a mixed solution formed by hydrogen peroxide and water, and making into ice blocks;
(2) mixing a catalyst carrier with a precipitator to form a turbid liquid;
(3) adding the ice blocks prepared in the step (1) into the turbid liquid obtained in the step (2), and stirring to completely dissolve the ice blocks;
(4) and (4) after the ice blocks in the step (3) are dissolved, filtering, drying and roasting the obtained solution to finally obtain the medium-low temperature loaded nano copper oxide particle catalyst.
The copper oxide precursor in the step (1) can be at least one of copper nitrate, copper chloride and copper sulfate;
the total amount of the hydrogen peroxide and the water in the step (1) meets the condition that the concentration of a copper oxide precursor in the mixed solution is 0.01-1 g/mL; preferably 0.1 to 0.5 g/mL.
The volume ratio of the hydrogen peroxide to the water in the step (1) is 0.2-1; preferably 0.2 to 0.8.
The catalyst carrier in the step (2) can be one of titanium dioxide particles or aluminum oxide particles; preferably, the particle size of the catalyst carrier is 10-500 nm.
The precipitant in the step (2) can be one of oxalic acid solution, ammonium carbonate solution or ammonia water; preferably, the concentration of the precipitant is 1 to 3 mol/L.
The ratio of the catalyst carrier to the precipitator in the step (2) is 0.01-1 g/mL; preferably 0.1 to 0.5 g/mL.
The dosage of the ice blocks and the turbid liquid in the step (3) meets the requirement that the mass fraction of copper oxide in the product after roasting in the step (4) is 1-15 percent, and the balance is a catalyst carrier;
the stirring temperature in the step (3) is that the mixture is stirred and dissolved at the temperature of-5 to 25 ℃, and the stirring speed is preferably 500 to 1000 r/min;
the drying in the step (4) is drying at 80-120 ℃, and the roasting is roasting at 300-500 ℃ for 3-5 hours;
the medium-low temperature supported nano copper oxide particle catalyst prepared by the method is characterized in that copper oxide particles have high dispersibility on a carrier, and the average particle size of the nano copper oxide particles is 1-5 nm;
the medium-low temperature loaded nano copper oxide particle catalyst is applied to the catalytic purification of NOx.
The principle of successful preparation of the medium-low temperature loaded nano copper oxide particle catalyst provided by the invention is as follows: in the process of forming the copper oxide precursor solution, a mixed solution formed by hydrogen peroxide and water is usedThe liquid is used as a solvent, and provides conditions for refining the aperture of the catalyst and amplifying the specific surface area under certain oxidation action; under the condition of low temperature, ice blocks made of the copper oxide precursor solution are slowly dissolved in turbid liquid formed by a solution formed by a precipitator and a catalyst carrier, so that the reaction rate of liquid phase synthesis is controlled; in the process of slowly releasing the copper oxide precursor, copper oxalate precipitates generated by reaction with an oxalic acid solution are uniformly dispersed on the surface of the carrier, so that agglomeration and growth of particles are avoided; in the roasting process, the cupric oxalate is decomposed to generate nano-copper oxide particles which interact with the carrier to have medium-low temperature activity and N on the catalyst2The selectivity, sulfur resistance, water resistance and alkali metal poisoning resistance have positive promoting effects.
The medium-low temperature supported nano copper oxide particle catalyst provided by the invention has excellent medium-low temperature denitration activity and high N2The principle of selectivity, sulfur resistance, water resistance and alkali metal poisoning resistance is as follows: compared with the traditional method, in the aspect of structure optimization, under the low-temperature condition, the copper oxide precursor solution slowly releases reactants in the form of ice blocks, and by controlling the reaction rate, on one hand, the agglomeration of particles is avoided, the higher particle dispersion degree is achieved, on the other hand, the growth of the particles is inhibited, the smaller particle size is obtained, and meanwhile, under the existence condition of hydrogen peroxide, the particle size is further reduced and the specific surface area is enlarged; in the aspect of performance improvement, the ice-melting preparation process enables more chemisorption oxygen and active sites to be generated on the surface of the catalyst, NOx adsorbing species tend to be converted from bidentate nitrate species to generate more surface acid sites, and the NOx adsorbing species have low-temperature denitration activity and N in the catalyst2The improvement of selectivity, sulfur resistance, water resistance and alkali metal poisoning resistance has important significance.
Compared with the prior art, the invention has the following advantages and beneficial effects:
(1) the preparation method is simple and effective. The method is improved on the basis of the traditional coprecipitation method, the precursor solution is slowly released into the carrier solution of the catalyst in the form of ice blocks, and the dispersion degree and the size of particles are regulated and controlled by reducing the reaction rate.
(2) Higher particle dispersion and smaller particle size. The copper oxide particles prepared by the method are highly dispersed on the surface of the carrier, the size of the prepared catalyst is smaller than that of the copper oxide particles obtained by the traditional method, the average size is 1-5 nm, and the aggregation and growth of the copper oxide particles are effectively controlled in the preparation process of the catalyst;
(3) excellent medium and low temperature denitration performance, N2Selectivity and resistance. Compared with the catalyst prepared by the traditional method, the copper oxide particles prepared by the method are uniformly distributed on the carrier material, and meanwhile, the catalyst generates more surface active species and chemisorbed oxygen, and has excellent medium-low temperature denitration performance and N when being used for catalytic purification of NOx2Selectivity; in the experiments of sulfur resistance, water resistance and alkali metal poisoning resistance, the denitration performance of the copper oxide particle catalyst prepared by the method is superior to that of the traditional preparation method, the high denitration efficiency can be maintained at a certain temperature, and the copper oxide particle catalyst has excellent characteristics of sulfur resistance, water resistance and alkali metal poisoning resistance.
Drawings
FIG. 1 is a crystal structure diagram of a medium-low temperature supported nano copper oxide particle catalyst, wherein CuTi-Ice is used in example 1 and a coprecipitation method is used in CuTi-Con is used in comparative example 1.
Fig. 2 is a morphology distribution diagram of a medium-low temperature supported nano copper oxide particle catalyst, wherein (a) an ice-melting method is used in example 1, and (b) a coprecipitation method is used in comparative example 1.
Fig. 3 is a morphology distribution diagram of a medium-low temperature supported nano copper oxide particle catalyst, wherein (a) and (c) are the example 1 by using a freezing method, and (b) and (d) are the comparative example 1 by using a coprecipitation method.
Detailed Description
The present invention will be described in further detail with reference to examples and drawings, but the embodiments of the present invention are not limited thereto.
The reagents used in the examples are commercially available without specific reference.
Example 1
A preparation method of a supported nano copper oxide particle catalyst comprises the following steps:
(1) 3.25g of copper nitrate hexahydrate was dissolved in a mixed solution of 2mL of hydrogen peroxide and 8mL of water, and then made into ice cubes.
(2) 50mL of oxalic acid solution with the concentration of 1mol/L is taken, then 8.63g of titanium dioxide with the particle size of 100nm is added, and the mixture is stirred to prepare turbid liquid.
(3) Putting the ice blocks obtained in the step (1) into the turbid liquid, and stirring and dissolving at the temperature of 0 ℃ at the speed of 1000 r/min.
(4) After the ice pieces have dissolved, the precipitate is filtered off.
(5) And drying the precipitate at 80 ℃, and then roasting at 400 ℃ for 3h to finally prepare a catalyst sample.
In the catalyst sample obtained, the copper oxide particles were highly dispersed on the support and had an average size of 5 nm. Activity and selectivity testing of the catalyst: 0.5g of the prepared catalyst is put into a fixed bed reactor for activity and selectivity tests, the test reaction temperature is 100-450 ℃, and the space velocity is about 50,000h-1Simulating the smoke from N2、O2、NO、NH3And SO2Composition of NO 700ppm, NH3700ppm, O25% (volume percent), SO2200ppm (when used), N2Is a carrier gas. When the reaction temperature is 200 ℃, the NOx conversion rate is stabilized at 90 percent; at a reaction temperature of less than 300 ℃, N2The amount of O produced is less than 12 ppm; SO (SO)2Under the existing condition, when the reaction temperature is 250 ℃, the NOx conversion rate is stabilized at 85 percent; 4.5 vol.% H2In the presence of O, when the reaction temperature is 250 ℃, the NOx conversion rate is stabilized at 80 percent; when KNO is selected3When the above catalyst sample was immersed in a solution (0.02g/mL) to perform an alkali metal poisoning resistance test, the NOx conversion was stabilized at 75% at a reaction temperature of 250 ℃.
Example 2
A preparation method of a supported nano copper oxide particle catalyst comprises the following steps:
(1) 2.5g of copper chloride was dissolved in a mixed solution of 3mL of hydrogen peroxide and 7mL of water, and then made into ice cubes.
(2) 50mL of 2mol/L ammonium carbonate solution was taken, 8.63g of alumina particles having a particle size of 150nm were added, and the mixture was stirred to prepare a turbid solution.
(3) Putting the ice blocks obtained in the step (1) into the turbid liquid, and stirring and dissolving at the temperature of minus 5 ℃ at the speed of 500 r/min.
(4) After the ice pieces have dissolved, the precipitate is filtered off.
(5) And drying the precipitate at 120 ℃, and then roasting at 500 ℃ for 3h to finally prepare a catalyst sample.
In the catalyst sample obtained, the copper oxide particles were highly dispersed on the support and had an average size of 4 nm. Activity and selectivity testing of the catalyst: 0.5g of the prepared catalyst is put into a fixed bed reactor for activity and selectivity tests, the test reaction temperature is 100-450 ℃, and the space velocity is about 50,000h-1Simulating the smoke from N2、O2、NO、NH3And SO2Composition of NO 700ppm, NH3700ppm, O25% (volume percent), SO2200ppm (when used), N2Is a carrier gas. When the reaction temperature is 250 ℃, the NOx conversion rate is stabilized at 95 percent, and when the reaction temperature is lower than 300 ℃, N2The amount of O produced is less than 10 ppm; SO (SO)2Under the existing condition, when the reaction temperature is 250 ℃, the NOx conversion rate is stabilized at 80 percent; 4.5 vol.% H2In the presence of O, when the reaction temperature is 250 ℃, the NOx conversion rate is stabilized at 75 percent; when KNO is selected3When the above catalyst sample was immersed in a solution (0.02g/mL) to perform an alkali metal poisoning resistance test, the NOx conversion was stabilized at 75% at a reaction temperature of 250 ℃.
Example 3
A preparation method of a supported nano copper oxide particle catalyst comprises the following steps:
(1) 2.35g of copper nitrate trihydrate was dissolved in a mixed solution of 4mL of hydrogen peroxide and 6mL of water, and then made into ice cubes.
(2) 50mL of 2mol/L ammonia water is taken, 15g of titanium dioxide with the particle size of 100nm is added, and the mixture is stirred to prepare turbid liquid.
(3) Putting the ice blocks obtained in the step (1) into the turbid liquid, and stirring and dissolving at the speed of 800r/min at the temperature of 20 ℃.
(4) After the ice pieces have dissolved, the precipitate is filtered off.
(5) And drying the precipitate at 90 ℃, and then roasting at 450 ℃ for 3h to finally prepare a catalyst sample.
In the catalyst sample obtained, the average size of the copper oxide particles was 4 nm. Activity and selectivity testing of the catalyst: 0.5g of the prepared catalyst is put into a fixed bed reactor for activity and selectivity tests, the test reaction temperature is 100-450 ℃, and the space velocity is about 50,000h-1Simulating the smoke from N2、O2、NO、NH3And SO2Composition of NO 700ppm, NH3700ppm, O25% (volume percent), SO2200ppm (when used), N2Is a carrier gas. When the reaction temperature is 450 ℃, the NOx conversion rate is stabilized at 100 percent; at a reaction temperature of less than 300 ℃, N2The amount of O produced is less than 8 ppm; SO (SO)2Under the existing condition, when the reaction temperature is 250 ℃, the NOx conversion rate is stabilized at 85 percent; 4.5 vol.% H2In the presence of O, when the reaction temperature is 250 ℃, the NOx conversion rate is stabilized at 83 percent; when KNO is selected3When the above catalyst sample was impregnated with a solution (0.02g/mL) to perform an alkali metal poisoning resistance test, the NOx conversion was stabilized at 78% at a reaction temperature of 250 ℃.
Example 4
A preparation method of a supported nano copper oxide particle catalyst comprises the following steps:
(1) 1.44g of copper nitrate trihydrate was dissolved in a mixed solution of 2.5mL of hydrogen peroxide and 7.5mL of water, and then made into ice cubes.
(2) 50mL of oxalic acid solution with the concentration of 3mol/L is taken, 10g of alumina particles with the particle size of 150nm are added, and the mixture is stirred to prepare turbid liquid.
(3) Putting the ice blocks obtained in the step (1) into the turbid liquid, and stirring and dissolving at the speed of 1000r/min at the temperature of 25 ℃.
(4) After the ice pieces have dissolved, the precipitate is filtered off.
(5) And drying the precipitate at 80 ℃, and then roasting at 400 ℃ for 5 hours to finally prepare a catalyst sample.
Prepared byIn the catalyst sample, the average size of the copper oxide particles was 4 nm. Activity and selectivity testing of the catalyst: 0.5g of the prepared catalyst is put into a fixed bed reactor for activity and selectivity tests, the test reaction temperature is 100-450 ℃, and the space velocity is about 50,000h-1Simulating the smoke from N2、O2、NO、NH3And SO2Composition of NO 700ppm, NH3700ppm, O25% (volume percent), SO2200ppm (when used), N2Is a carrier gas. When the reaction temperature is 300 ℃, the NOx conversion rate is stabilized at 100 percent; at a reaction temperature of less than 300 ℃, N2The amount of O produced is less than 14 ppm; SO (SO)2Under the existing condition, when the reaction temperature is 250 ℃, the NOx conversion rate is stabilized at 80 percent; 4.5 vol.% H2In the presence of O, when the reaction temperature is 250 ℃, the NOx conversion rate is stabilized at 88 percent; when KNO is selected3When the above catalyst sample was immersed in a solution (0.02g/mL) to perform an alkali metal poisoning resistance test, the NOx conversion was stabilized at 80% at a reaction temperature of 250 ℃.
Example 5
A preparation method of a supported nano copper oxide particle catalyst comprises the following steps:
(1) 2.18g of copper chloride was dissolved in a mixed solution of 3.5mL of hydrogen peroxide and 6.5mL of water, and then made into ice cubes.
(2) 50mL of 1mol/L ammonia water is taken, 10g of titanium dioxide particles with the particle size of 100nm are added, and the mixture is stirred to prepare turbid liquid.
(3) Putting the ice blocks obtained in the step (1) into the turbid liquid, and stirring and dissolving at the temperature of 10 ℃ at the speed of 600 r/min.
(4) After the ice pieces have dissolved, the precipitate is filtered off.
(5) And drying the precipitate at 110 ℃, and then roasting at 450 ℃ for 4h to finally prepare a catalyst sample.
In the catalyst sample obtained, the average size of the copper oxide particles was 3 nm. Activity and selectivity testing of the catalyst: 0.5g of the prepared catalyst is put into a fixed bed reactor for activity and selectivity tests, the test reaction temperature is 100-450 ℃, and the space velocity is about 50,000h-1Simulating the smoke from N2、O2、NO、NH3And SO2Composition of NO 700ppm, NH3700ppm, O25% (volume percent), SO2200ppm (when used), N2Is a carrier gas. When the reaction temperature is 350 ℃, the NOx conversion rate is stabilized at 100 percent; at a reaction temperature of less than 300 ℃, N2The amount of O produced is less than 15 ppm; SO (SO)2Under the existing condition, when the reaction temperature is 250 ℃, the NOx conversion rate is stabilized at 83 percent; 4.5 vol.% H2In the presence of O, when the reaction temperature is 250 ℃, the NOx conversion rate is stabilized at 80 percent; when KNO is selected3When the above catalyst sample was immersed in a solution (0.02g/mL) to perform an alkali metal poisoning resistance test, the NOx conversion was stabilized at 75% at a reaction temperature of 250 ℃.
Example 6
A preparation method of a supported nano copper oxide particle catalyst comprises the following steps:
(1) 1.5g of copper chloride was dissolved in a mixed solution of 4.5mL of hydrogen peroxide and 5.5mL of water, and then made into ice cubes.
(2) 50mL of 1mol/L ammonium carbonate solution was taken, 10g of titanium dioxide particles having a particle size of 100nm were added, and the mixture was stirred to prepare a turbid solution.
(3) Putting the ice blocks obtained in the step (1) into the turbid liquid, and stirring and dissolving at the temperature of 10 ℃ at the speed of 1000 r/min.
(4) After the ice pieces have dissolved, the precipitate is filtered off.
(5) And drying the precipitate at 100 ℃, and then roasting at 300 ℃ for 3h to finally prepare a catalyst sample.
In the catalyst sample obtained, the average size of the copper oxide particles was 4 nm. Activity and selectivity testing of the catalyst: 0.5g of the prepared catalyst is put into a fixed bed reactor for activity and selectivity tests, the test reaction temperature is 100-450 ℃, and the space velocity is about 50,000h-1Simulating the smoke from N2、O2、NO、NH3And SO2Composition of NO 700ppm, NH3700ppm, O25% (volume percent), SO2200ppm (when used), N2Is a carrier gas. When the reaction temperature is 100 ℃, the NOx conversion rate is stabilized at 70 percent; at a reaction temperature of less than 300 ℃, N2The amount of O produced is less than 10 ppm; SO (SO)2Under the existing condition, when the reaction temperature is 250 ℃, the NOx conversion rate is stabilized at 88 percent; 4.5 vol.% H2In the presence of O, when the reaction temperature is 250 ℃, the NOx conversion rate is stabilized at 85 percent; when KNO is selected3When the above catalyst sample was immersed in a solution (0.02g/mL) to perform an alkali metal poisoning resistance test, the NOx conversion was stabilized at 80% at a reaction temperature of 250 ℃.
Comparative example 1
The coprecipitation method for preparing the copper oxide particle catalyst comprises the following steps:
(1) dissolving 3.25g of copper nitrate hexahydrate in a mixed solution of 2mL of hydrogen peroxide and 8mL of water;
(2) taking 50mL of oxalic acid solution with the concentration of 1mol/L, then adding 8.63g of titanium dioxide with the particle size of 100nm, and stirring to prepare turbid liquid;
(3) dripping the mixed solution in the step (1) into the turbid solution in the step (2), and stirring and dissolving at the speed of 1000r/min at the temperature of 0 ℃;
(4) after the solution is fully mixed, filtering out precipitate;
(5) and drying the precipitate at 80 ℃, and then roasting at 400 ℃ for 3h to finally prepare a catalyst sample.
In the catalyst sample obtained, the average size of the copper oxide particles was 30 nm. Activity and selectivity testing of the catalyst: 0.5g of the prepared catalyst is put into a fixed bed reactor for activity and selectivity tests, the test reaction temperature is 100-450 ℃, and the space velocity is about 50,000h-1Simulating the smoke from N2、O2、NO、NH3And SO2Composition of NO 700ppm, NH3700ppm, O25% (volume percent), SO2200ppm (when used), N2Is a carrier gas. When the reaction temperature is 200 ℃, the NOx conversion rate is stabilized at 65%; at a reaction temperature of less than 300 ℃, N2The amount of O produced is less than 40 ppm; SO (SO)2Under the existing condition, when the reaction temperature is 250 ℃, the NOx conversion rate is stabilized at 55 percent; 4.5 vol.% H2Under the condition of O existence, when the reaction temperature is 250 ℃, the NOx conversion rate is stabilized at 45 percent; when KNO is selected3When the above catalyst sample was immersed in a solution (0.02g/mL) to perform an alkali metal poisoning resistance test, the NOx conversion was stabilized at 40% at a reaction temperature of 250 ℃.
Comparative example 2
The coprecipitation method for preparing the copper oxide particle catalyst comprises the following steps:
(1) 2.5g of copper chloride is dissolved in a mixed solution of 3mL of hydrogen peroxide and 7mL of water;
(2) taking 50mL of 2mol/L ammonium carbonate solution, adding 8.63g of alumina particles with the particle size of 150nm, and stirring to prepare turbid liquid;
(3) dropping the mixed solution in the step (1) into the turbid solution in the step (2), and stirring and dissolving at the temperature of minus 5 ℃ at the speed of 500 r/min;
(4) after the solution is fully mixed, filtering out precipitate;
(5) and drying the precipitate at 120 ℃, and then roasting at 500 ℃ for 3h to finally prepare a catalyst sample.
In the catalyst sample obtained, the average size of the copper oxide particles was 28 nm. Activity and selectivity testing of the catalyst: 0.5g of the prepared catalyst is put into a fixed bed reactor for activity and selectivity tests, the test reaction temperature is 100-450 ℃, and the space velocity is about 50,000h-1Simulating the smoke from N2、O2、NO、NH3And SO2Composition of NO 700ppm, NH3700ppm, O25% (volume percent), SO2200ppm (when used), N2Is a carrier gas. When the reaction temperature is 350 ℃, the NOx conversion rate is stabilized at 70 percent; at a reaction temperature of less than 300 ℃, N2The generation amount of O is less than 60 ppm; SO (SO)2Under the existing condition, when the reaction temperature is 200 ℃, the NOx conversion rate is stabilized at 60 percent; 4.5 vol.% H2In the presence of O, when the reaction temperature is 250 ℃, the NOx conversion rate is stabilized at 50 percent; when KNO is selected3When the above catalyst sample was immersed in a solution (0.02g/mL) to perform an alkali metal poisoning resistance test, the NOx conversion was stabilized at 40% at a reaction temperature of 250 ℃.
Comparative example 3
The coprecipitation method for preparing the copper oxide particle catalyst comprises the following steps:
(1) dissolving 2.35g of copper nitrate trihydrate in a mixed solution of 4mL of hydrogen peroxide and 6mL of water;
(2) taking 50mL of 2mol/L ammonia water, adding 15g of titanium dioxide with the particle size of 100nm, and stirring to prepare a turbid solution;
(3) dripping the mixed solution in the step (1) into the turbid solution in the step (2), and stirring and dissolving at the speed of 800r/min at the temperature of 20 ℃;
(4) after the solution is fully mixed, filtering out precipitate;
(5) and drying the precipitate at 90 ℃, and then roasting at 450 ℃ for 3h to finally prepare a catalyst sample.
In the catalyst sample obtained, the average size of the copper oxide particles was 30 nm. Activity and selectivity testing of the catalyst: 0.5g of the prepared catalyst is put into a fixed bed reactor for activity and selectivity tests, the test reaction temperature is 100-450 ℃, and the space velocity is about 50,000h-1Simulating the smoke from N2、O2、NO、NH3And SO2Composition of NO 700ppm, NH3700ppm, O25% (volume percent), SO2200ppm (when used), N2Is a carrier gas. When the reaction temperature is 450 ℃, the NOx conversion rate is stabilized at 60 percent; at a reaction temperature of less than 300 ℃, N2The amount of O produced is less than 65 ppm; SO (SO)2Under the existing condition, when the reaction temperature is 250 ℃, the NOx conversion rate is stabilized at 55 percent; 4.5 vol.% H2Under the condition of O existence, when the reaction temperature is 250 ℃, the NOx conversion rate is stabilized at 45 percent; when KNO is selected3When the above catalyst sample was immersed in a solution (0.02g/mL) to perform an alkali metal poisoning resistance test, the NOx conversion was stabilized at 45% at a reaction temperature of 250 ℃.
Comparative example 4
The coprecipitation method for preparing the copper oxide particle catalyst comprises the following steps:
(1) 1.44g of copper nitrate trihydrate was dissolved in a mixed solution of 2.5mL of hydrogen peroxide and 7.5mL of water;
(2) taking 50mL of oxalic acid solution with the concentration of 3mol/L, then adding 10g of alumina particles with the particle size of 150nm, and stirring to prepare turbid liquid;
(3) dripping the mixed solution in the step (1) into the turbid solution in the step (2), and stirring and dissolving at the speed of 1000r/min at the temperature of 25 ℃;
(4) after the solution is fully mixed, filtering out precipitate;
(5) and drying the precipitate at 80 ℃, and then roasting at 400 ℃ for 5 hours to finally prepare a catalyst sample. The average size of the copper oxide particles in the prepared catalyst sample was 25 nm. Activity and selectivity testing of the catalyst: 0.5g of the prepared catalyst is put into a fixed bed reactor for activity and selectivity tests, the test reaction temperature is 100-450 ℃, and the space velocity is about 50,000h-1Simulating the smoke from N2、O2、NO、NH3And SO2Composition of NO 700ppm, NH3700ppm, O25% (volume percent), SO2200ppm (when used), N2Is a carrier gas. When the reaction temperature is 300 ℃, the NOx conversion rate is stabilized at 75 percent; at a reaction temperature of less than 300 ℃, N2The amount of O produced is less than 50 ppm; SO (SO)2Under the existing condition, when the reaction temperature is 250 ℃, the NOx conversion rate is stabilized at 60 percent; 4.5 vol.% H2In the presence of O, when the reaction temperature is 250 ℃, the NOx conversion rate is stabilized at 50 percent; when KNO is selected3When the above catalyst sample was immersed in a solution (0.02g/mL) to perform an alkali metal poisoning resistance test, the NOx conversion was stabilized at 45% at a reaction temperature of 250 ℃.
Comparative example 5
The coprecipitation method for preparing the copper oxide particle catalyst comprises the following steps:
(1) 2.18g of copper chloride was dissolved in a mixed solution of 3.5mL of hydrogen peroxide and 6.5mL of water;
(2) taking 50mL of 1mol/L ammonia water, then adding 10g of titanium dioxide particles with the particle size of 100nm, and stirring to prepare turbid liquid;
(3) dripping the mixed solution in the step (1) into the turbid solution in the step (2), and stirring and dissolving at the speed of 600r/min at the temperature of 10 ℃;
(4) after the solution is fully mixed, filtering out precipitate;
(5) and drying the precipitate at 110 ℃, and then roasting at 450 ℃ for 4h to finally prepare a catalyst sample.
In the catalyst sample obtained, the average size of the copper oxide particles was 32 nm. Activity and selectivity testing of the catalyst: 0.5g of the prepared catalyst is put into a fixed bed reactor for activity and selectivity tests, the test reaction temperature is 100-450 ℃, and the space velocity is about 50,000h-1Simulating the smoke from N2、O2、NO、NH3And SO2Composition of NO 700ppm, NH3700ppm, O25% (volume percent), SO2200ppm (when used), N2Is a carrier gas. When the reaction temperature is 350 ℃, the NOx conversion rate is stabilized at 80 percent; at a reaction temperature of less than 300 ℃, N2The amount of O produced is less than 50 ppm; SO (SO)2Under the existing condition, when the reaction temperature is 250 ℃, the NOx conversion rate is stabilized at 55 percent; 4.5 vol.% H2In the presence of O, when the reaction temperature is 250 ℃, the NOx conversion rate is stabilized at 40 percent; when KNO is selected3When the above catalyst sample was immersed in a solution (0.02g/mL) to perform an alkali metal poisoning resistance test, the NOx conversion was stabilized at 30% at a reaction temperature of 250 ℃.
Comparative example 6
The coprecipitation method for preparing the copper oxide particle catalyst comprises the following steps:
(1) dissolving 1.5g of copper chloride in a mixed solution of 4.5mL of hydrogen peroxide and 5.5mL of water;
(2) taking 50mL of 1mol/L ammonium carbonate solution, adding 10g of titanium dioxide particles with the particle size of 100nm, and stirring to prepare turbid liquid;
(3) dripping the mixed solution in the step (1) into the turbid solution in the step (2), and stirring and dissolving at the temperature of 10 ℃ at the speed of 1000 r/min;
(4) after the solution is fully mixed, filtering out precipitate;
(5) and drying the precipitate at 100 ℃, and then roasting at 300 ℃ for 3h to finally prepare a catalyst sample.
To obtainThe average size of the copper oxide particles in the catalyst sample of (2) was 30 nm. Activity and selectivity testing of the catalyst: 0.5g of the prepared catalyst is put into a fixed bed reactor for activity and selectivity tests, the test reaction temperature is 100-450 ℃, and the space velocity is about 50,000h-1Simulating the smoke from N2、O2、NO、NH3And SO2Composition of NO 700ppm, NH3700ppm, O25% (volume percent), SO2200ppm (when used), N2Is a carrier gas. When the reaction temperature is 100 ℃, the NOx conversion rate is stabilized at 30 percent; at a reaction temperature of less than 300 ℃, N2The generation amount of O is less than 20 ppm; SO (SO)2Under the existing condition, when the reaction temperature is 250 ℃, the NOx conversion rate is stabilized at 50 percent; 4.5 vol.% H2In the presence of O, when the reaction temperature is 250 ℃, the NOx conversion rate is stabilized at 40 percent; when KNO is selected3When the above catalyst sample was immersed in a solution (0.02g/mL) to perform an alkali metal poisoning resistance test, the NOx conversion was stabilized at 35% at a reaction temperature of 250 ℃.
The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and all such changes, modifications, substitutions, combinations, and simplifications are intended to be included in the scope of the present invention.
Claims (9)
1. A preparation method of a medium-low temperature loaded nano copper oxide particle catalyst is characterized by comprising the following steps:
(1) dissolving a copper oxide precursor in a mixed solution formed by hydrogen peroxide and water, and making into ice blocks;
(2) mixing a catalyst carrier with a precipitator to form a turbid liquid;
(3) adding the ice blocks prepared in the step (1) into the turbid liquid obtained in the step (2), and stirring to completely dissolve the ice blocks;
(4) after the ice blocks in the step (3) are dissolved, filtering, drying and roasting the obtained solution to finally obtain the supported nano copper oxide particle catalyst;
the total amount of the hydrogen peroxide and the water in the step (1) meets the condition that the concentration of a copper oxide precursor in the mixed solution is 0.01-1 g/mL; the volume ratio of the hydrogen peroxide to the water is 0.2-1;
the precipitant in the step (2) is one of oxalic acid solution, ammonium carbonate solution or ammonia water.
2. The preparation method of the medium-low temperature supported nano copper oxide particle catalyst according to claim 1, characterized in that:
the copper oxide precursor in the step (1) is at least one of copper chloride, copper nitrate and copper sulfate.
3. The preparation method of the medium-low temperature supported nano copper oxide particle catalyst according to claim 1, characterized in that:
the catalyst carrier in the step (2) is one of titanium dioxide particles or aluminum oxide particles.
4. The preparation method of the medium-low temperature supported nano copper oxide particle catalyst according to claim 1, characterized in that:
the particle size of the catalyst carrier in the step (2) is 10-500 nm;
the concentration of the precipitant in the step (2) is 1-3 mol/L;
the ratio of the catalyst carrier to the precipitator in the step (2) is 0.01-1 g/mL.
5. The method for preparing the supported nano copper oxide particle catalyst according to claim 1, wherein:
the total amount of the hydrogen peroxide and the water in the step (1) meets the condition that the concentration of a copper oxide precursor in the mixed solution is 0.1-0.5 g/mL;
the ratio of the hydrogen peroxide to the water in the step (1) is 0.2-0.8;
the ratio of the catalyst carrier to the precipitator in the step (2) is 0.1-0.5 g/mL.
6. The preparation method of the medium-low temperature supported nano copper oxide particle catalyst according to any one of claims 1 to 5, characterized by comprising the following steps:
the dosage of the ice blocks and the turbid liquid in the step (3) meets the requirement that the mass fraction of the copper oxide in the product after roasting in the step (4) is 1-15 percent, and the balance is a catalyst carrier.
7. The preparation method of the medium-low temperature supported nano copper oxide particle catalyst according to claim 1, characterized in that:
stirring and dissolving at the stirring temperature of-5-25 ℃, wherein the stirring speed is 500-1000 r/min;
the drying in the step (4) is drying at 80-120 ℃, and the roasting is roasting at 300-500 ℃ for 3-5 hours.
8. The medium-low temperature supported nano copper oxide particle catalyst prepared by the method according to any one of claims 1 to 7.
9. The use of the medium-low temperature supported nano copper oxide particle catalyst according to claim 8 in catalytic purification of NOx.
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