CN116726909A - Ce-Mn bimetallic oxide with high water resistance as well as preparation method and application thereof - Google Patents
Ce-Mn bimetallic oxide with high water resistance as well as preparation method and application thereof Download PDFInfo
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 57
- 238000002360 preparation method Methods 0.000 title abstract description 11
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims abstract description 61
- 239000003054 catalyst Substances 0.000 claims abstract description 46
- 239000011572 manganese Substances 0.000 claims abstract description 42
- 238000005530 etching Methods 0.000 claims abstract description 38
- 239000002253 acid Substances 0.000 claims abstract description 14
- 125000000896 monocarboxylic acid group Chemical group 0.000 claims abstract description 6
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 3
- 239000000243 solution Substances 0.000 claims description 39
- 238000001354 calcination Methods 0.000 claims description 29
- 238000001035 drying Methods 0.000 claims description 27
- 238000006243 chemical reaction Methods 0.000 claims description 26
- 239000002244 precipitate Substances 0.000 claims description 24
- 239000008367 deionised water Substances 0.000 claims description 14
- 229910021641 deionized water Inorganic materials 0.000 claims description 14
- 239000000725 suspension Substances 0.000 claims description 11
- 238000001914 filtration Methods 0.000 claims description 9
- -1 cerium ions Chemical class 0.000 claims description 8
- 238000000034 method Methods 0.000 claims description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 7
- 229910052684 Cerium Inorganic materials 0.000 claims description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 6
- 229910001437 manganese ion Inorganic materials 0.000 claims description 6
- 239000000047 product Substances 0.000 claims description 6
- 239000007790 solid phase Substances 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 6
- 150000000703 Cerium Chemical class 0.000 claims description 4
- 239000003513 alkali Substances 0.000 claims description 4
- 150000002696 manganese Chemical class 0.000 claims description 4
- 239000000843 powder Substances 0.000 claims description 4
- 238000005406 washing Methods 0.000 claims description 4
- 230000008569 process Effects 0.000 claims description 3
- GPRLSGONYQIRFK-UHFFFAOYSA-N hydron Chemical compound [H+] GPRLSGONYQIRFK-UHFFFAOYSA-N 0.000 claims description 2
- 239000011259 mixed solution Substances 0.000 claims description 2
- 229910001415 sodium ion Inorganic materials 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 4
- 230000003197 catalytic effect Effects 0.000 abstract description 5
- 230000009286 beneficial effect Effects 0.000 abstract description 4
- 230000007613 environmental effect Effects 0.000 abstract description 4
- 239000000463 material Substances 0.000 abstract description 4
- 230000004048 modification Effects 0.000 abstract description 4
- 238000012986 modification Methods 0.000 abstract description 4
- 238000001179 sorption measurement Methods 0.000 abstract description 4
- 239000002131 composite material Substances 0.000 abstract description 3
- 229910052751 metal Inorganic materials 0.000 abstract description 3
- 239000002184 metal Substances 0.000 abstract description 3
- 239000011148 porous material Substances 0.000 abstract description 3
- 238000004090 dissolution Methods 0.000 abstract description 2
- 238000003915 air pollution Methods 0.000 abstract 1
- QQZMWMKOWKGPQY-UHFFFAOYSA-N cerium(3+);trinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O QQZMWMKOWKGPQY-UHFFFAOYSA-N 0.000 abstract 1
- ALIMWUQMDCBYFM-UHFFFAOYSA-N manganese(2+);dinitrate;tetrahydrate Chemical compound O.O.O.O.[Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ALIMWUQMDCBYFM-UHFFFAOYSA-N 0.000 abstract 1
- 239000002994 raw material Substances 0.000 abstract 1
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 38
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 description 20
- 230000000694 effects Effects 0.000 description 6
- 229910052739 hydrogen Inorganic materials 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 238000005303 weighing Methods 0.000 description 5
- 239000007848 Bronsted acid Substances 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 238000010531 catalytic reduction reaction Methods 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 230000007547 defect Effects 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- 230000033116 oxidation-reduction process Effects 0.000 description 2
- 239000000779 smoke Substances 0.000 description 2
- 239000002841 Lewis acid Substances 0.000 description 1
- 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
- 238000003917 TEM image Methods 0.000 description 1
- 229910010413 TiO 2 Inorganic materials 0.000 description 1
- 238000003916 acid precipitation Methods 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 230000009849 deactivation Effects 0.000 description 1
- 230000002939 deleterious effect Effects 0.000 description 1
- 238000006477 desulfuration reaction Methods 0.000 description 1
- 230000023556 desulfurization Effects 0.000 description 1
- 230000003009 desulfurizing effect Effects 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000002715 modification method Methods 0.000 description 1
- 239000012716 precipitator Substances 0.000 description 1
- 230000002468 redox effect Effects 0.000 description 1
- 239000006104 solid solution Substances 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 238000011144 upstream manufacturing Methods 0.000 description 1
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/32—Manganese, technetium or rhenium
- B01J23/34—Manganese
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/86—Catalytic processes
- B01D53/8621—Removing nitrogen compounds
- B01D53/8625—Nitrogen oxides
- B01D53/8628—Processes characterised by a specific catalyst
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- 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
- B01D53/90—Injecting reactants
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2251/00—Reactants
- B01D2251/20—Reductants
- B01D2251/206—Ammonium compounds
- B01D2251/2062—Ammonia
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- Chemical & Material Sciences (AREA)
- Environmental & Geological Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Biomedical Technology (AREA)
- Analytical Chemistry (AREA)
- Oil, Petroleum & Natural Gas (AREA)
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Abstract
The invention discloses a Ce-Mn bimetallic oxide modified by high water resistance acetic acid etching, a preparation method and application thereof. The catalyst is prepared by taking manganese nitrate tetrahydrate and cerium nitrate hexahydrate as raw materials, preparing a CeMnOx bimetallic composite oxide through a hydrothermal method and high-temperature roasting, and then performing acetic acid etching modification to obtain the CeMnOx-CH 3 COOH high water-resistant low-temperature denitration catalyst (' metal Ce doped ' and ' weak acid CH) 3 COOH etching "composite modification means"). The Ce-Mn bimetallic catalyst surface provided by the invention has rich internal pore canal structure after being subjected to acetic acid etching and excellent dissolution, has higher specific surface area and is more beneficial to NH 3 Is adsorbed by the adsorption column; high denitration rate is achieved at low temperatureA NOx removal rate of approximately 100% can be achieved at only 80 ℃; the high water resistance of nearly 100% is stable at 200 ℃, and the catalyst has application prospect in the fields of environmental catalytic materials and air pollution control.
Description
Technical Field
The invention belongs to a low-temperature denitration catalyst and a preparation method thereof, and particularly relates to a preparation and acid etching modification method and application of a Ce-Mn bimetallic oxide with high water resistance; the catalyst can be used for catalytic reduction (NH) of ammonia serving as a reducing agent at low temperature (less than 240 ℃) of smoke temperature 3 -SCR) denitration, the removal rate of nitrogen oxides (NOx) is close to 100% at 80-240 ℃, and the catalyst has ultra-high water resistance, and belongs to the field of environmental catalytic materials and atmospheric pollution control.
Background
The deleterious nature of nitrogen oxides (NOx) has become a serious environmental concern for the public, and they are emitted primarily from stationary sources (e.g., coal-fired power plants) and from mobile sources (e.g., motor vehicles). These emissions can cause problems with acid rain, photochemical smog, etc., thereby compromising human health. In the currently available technology, NH 3 Selective catalytic reduction of NOx (NH) 3 SCR) has proven to be an effective, reliable and economical method of controlling NOx emissions. However, conventional V 2 O 5 -WO 3 (MoO 3 )/TiO 2 The catalyst is usually arranged at the upstream of the electric dust collector and the desulfurizing device, and has the defects of high and narrow operating temperature window (300-420 ℃); if it is placed downstream of the electric precipitator and the desulfurization device, the smoke temperature is generally lower than 250 ℃, and part of water is adhered to the surface of the catalyst in a liquid state at a low temperature to cause the deactivation phenomenon of the catalyst. Therefore, how to increase the low temperature Gao Tuo nitrate rate and high water resistance of the catalyst is a hot spot of current research.
MnOx-based catalyst pair NH at low temperature 3 The SCR reaction has excellent catalytic activity, which has the advantages of being eco-friendly, earth-resource rich and inexpensive. However, pure MnOx catalysts also have some challenges to overcome, including low specific surface area, narrow operating temperature window, poor thermal stability and poor H resistance 2 O-property. CeO (CeO) 2 Due to its good redox properties and oxygen vacancies in the materialBit and Ce 4+ /Ce 3+ Redox pair-related high oxygen storage/release capability is widely used to eliminate NOx, and at the same time, can promote the adsorption of NOx, provide stronger acid sites and enhance NO to NO 2 And improves the water resistance of the catalyst, this for NH 3 The SCR reaction is particularly advantageous. Thus, manganese oxide (MnOx) and CeO 2 Combining to form a Ce-Mn bimetallic catalyst may improve NH of the material to NOx 3 Denitration activity and water resistance of SCR.
In addition, the denitration activity and the water resistance of the catalyst can be obviously improved by carrying out acetic acid etching modification on the catalyst. According to the related research, the activity of the catalyst is proved to be subjected to NH in the SCR reaction 3 The adsorption capacity of the MnOx-based catalyst is mainly influenced by Lewis and Bronsted acid sites, and the Bronsted acid sites have little effect on the SCR reaction, because after supporting MnOx, the strength of the Bronsted acid sites is greatly reduced or even eliminated, and NH adsorbed on Mn ions or Lewis weak acid sites of MnOx 3 Can effectively participate in the low-temperature SCR reaction. As acetic acid is weak acid, in the process of etching Ce-Mn bimetallic acid, lewis weak acid sites on the surface of a catalyst carrier are effectively increased, and meanwhile, elements on the surface of the catalyst are optimally dissolved, and the internal pore structure and the specific surface area are increased, so that the promotion of the catalytic reduction capability of the catalyst is promoted, and the catalyst is more beneficial to NH 3 The denitration activity and the water resistance of the catalyst are obviously improved by the adsorption of the catalyst.
Because the MnOx-based catalyst is easily covered by partial steam to be deactivated by exposing the MnOx-based catalyst to a low-temperature environment in a tail end arrangement mode, the efficiency of removing NOx by using only a single technology is low and the water resistance is poor, so the invention aims to research and develop a method for preparing a high water resistance low-temperature denitration catalyst by using a double-site (oxidation-reduction and acid-base site) regulation and control coupling technology.
Disclosure of Invention
The invention aims to provide a metal Ce doped and weak acid CH aiming at the defects in the prior art 3 The MnOx-based high water resistance low temperature denitration catalyst prepared by the composite modification means of COOH etching. Wherein, the metal Ce is doped to form Mn-Ce solid solution structure after Ce is introduced, and can haveEffectively increase oxygen vacancy and other defects, improve oxidation-reduction capacity, and improve low-temperature denitration rate and H resistance 2 Toxicity in O; while "weak acid CH 3 The COOH etching effectively improves the specific surface area, and meanwhile, lewis weak acid sites are added, so that the water resistance and the catalytic activity are obviously improved.
The specific steps of the invention are as follows:
in a first aspect, the invention provides a Ce-Mn bimetallic oxide modified by highly water-resistant acetic acid etching, which is obtained by adding a solution containing manganese ions and cerium ions into an alkali solution to perform heating reaction to obtain a solid-phase product, and then sequentially performing first calcination, acid etching and second calcination on the solid-phase product.
Preferably, the solution containing manganese ions and cerium ions is added into the mixed solution obtained after the alkali solution is added, the concentration of manganese ions is 0.2-0.8 mol/L, the concentration of cerium ions is 0.2-0.8 mol/L, and the concentration of hydroxide ions is 1.0-2.0 mol/L. The temperature of the heating reaction is 120-150 ℃ and the duration is 24-48 hours.
Preferably, the acid etching process is as follows: adding the solid phase product into hydrogen ion with the molar concentration of 0.6-2.4 mol.L -1 CH of (2) 3 Etching in COOH solution for 0.2-0.6 hr.
Preferably, the calcination temperature of the first calcination is 300-500 ℃ and the calcination time is 3-5 h. The calcination temperature of the second calcination is 300-500 ℃ and the calcination time is 3-5 h.
In a second aspect, the invention provides a preparation method of the Ce-Mn bimetallic oxide modified by high water resistance acetic acid etching, comprising the following steps:
1. the Ce-Mn bimetallic oxide is obtained by a hydrothermal method:
step (1) a NaOH solution was prepared as a reaction solution A.
And (2) dissolving manganese salt and cerium salt in deionized water and fully stirring to obtain a solution B.
Step (3) the reaction solution A is added dropwise to the solution B and stirred well to obtain a suspension C.
And (4) transferring the suspension C into a high-pressure reaction kettle, heating for 24-48 h, and filtering to obtain a precipitate D.
And (5) washing the precipitate D with deionized water and absolute ethyl alcohol alternately for a plurality of times to wash Na+ ions from the precipitate D until the pH value of the solution is unchanged, thereby obtaining the precipitate E.
And (6) drying the precipitate E, and calcining in air to obtain the modified Ce-Mn bimetallic oxide F.
2. Acetic acid is selected for etching and modifying Ce-Mn bimetallic oxide F:
and (7) preparing a CH3COOH solution serving as an etching solution G.
And (8) immersing the modified Ce-Mn bimetallic oxide F in an etching solution G for etching to obtain a precipitate H.
And (9) filtering and drying the precipitate H, and calcining in air to obtain the Ce-Mn bimetallic oxide with high water resistance.
Preferably, the manganese salt is formed by Mn (NO 3 ) 2 ·4H 2 O powder configuration, cerium salt was prepared by Ce (NO 3 ) 3 ·6H 2 And (3) O powder configuration.
Preferably, in the step (2), the stirring time of the solution B is controlled within 1 to 2 hours. In the step (3), the stirring time of the suspension C is controlled within 3-6 h.
Preferably, in the step (6), the drying temperature is 60 to 80 ℃ and the drying time is controlled within 6 to 12 hours. In the step (9), the drying temperature is 60-80 ℃, the drying time is controlled within 3-6 h, the calcining temperature is 300-500 ℃, and the calcining time is controlled within 3-5 h.
In a third aspect, the invention provides an application of a Ce-Mn bimetallic oxide modified by high water resistance acetic acid etching as a catalyst in SCR denitration.
Preferably, the SCR denitration is performed at a temperature of 80 to 240 ℃.
For the prior art, the invention has the following beneficial effects:
1. the Ce-Mn bimetallic catalyst surface provided by the invention has rich internal pore canal structure after being subjected to acetic acid etching and excellent dissolution, has higher specific surface area and is more beneficial to NH 3 Exhibits a superior low temperatureDenitration activity and water resistance;
2. compared with the prior art [ for example: the conversion rate of NOx reaches 100% in the invention patent (application number: 202011333961.6) at 150-200 ℃; the invention (application number: 202010583208.6) maintains the denitration efficiency of more than 80% at 160-300 ℃, and maintains the water-resistant performance of more than 80% at 180 ℃ in the presence of water content (14 vol%), compared with the invention, the invention achieves high denitration rate at low temperature, and can achieve the NOx removal rate of nearly 100% only at 80 ℃ (the temperature is advanced by nearly 70 ℃); the high water resistance (without a descending trend) which is stable and is close to 100 percent at 200 ℃, and the method has potential application prospect in the fields of environmental catalytic materials and atmospheric pollution control.
Drawings
FIG. 1 is a graph showing the NOx conversion of the acetic acid etching modified Ce-Mn bimetallic oxide low temperature denitration catalyst prepared in example 1 of the present invention at 50-240 ℃.
FIG. 2 shows that the acetic acid etching modified Ce-Mn bimetallic oxide low temperature denitration catalyst prepared in example 1 of the present invention is subjected to a temperature of 200 ℃ and a volume percentage of H of 10% 2 Graph of water resistance under O.
Fig. 3 is a high resolution Transmission Electron Microscope (TEM) image of the acetic acid etching modified ce—mn bimetallic oxide low temperature denitration catalyst prepared in example 1 of the present invention.
Detailed Description
The invention will be further illustrated with reference to specific examples, but the scope of the invention is not limited thereto.
Example 1
The preparation method of the high water resistance acetic acid etching modified Ce-Mn bimetallic low-temperature SCR denitration catalyst comprises the following steps: take 2.51gMn (NO) 3 ) 2 ·4H 2 O and 4.34g Ce (NO) 3 ) 3 ·6H 2 O was dissolved in 20ml of deionized water and stirred together for 1 hour, then 60ml of 4mol.L was added -1 The solution was stirred for another 3 hours to obtain a suspension, and transferred to a reaction vessel, and the mixture was heated to 120 ℃ and maintained at that temperature for 24 hours. Then washing the obtained precipitate with deionized water for several times, washing with absolute ethyl alcohol for one time,until the pH of the solution is unchanged. After drying in an oven at 60 ℃ for 12 hours, the sample was finally calcined in 500 ℃ air for 5 hours. Weighing 1g of prepared Ce-Mn bimetallic oxide and immersing in 0.6mol.L -1 Etching for 0.4h, filtering the obtained precipitate, fully drying in a drying oven at 60 ℃ for 3h, and finally calcining in air at 500 ℃ for 5h.
The catalyst prepared in this example has a NOx conversion of approximately 100% at 80-240℃as shown in FIG. 1, and 10vol% H at 200 ℃ 2 The water resistance at O was nearly 100% (as shown in figure 2). The TEM image of the catalyst prepared in this example is shown in FIG. 3, and FIG. 3 shows CeO exposing a high proportion of {111} crystal face 2 Mn of {222} and {400} crystal planes 2 O 3 And Mn of {112} crystal face 3 O 4 。
Example 2
The preparation method of the high water resistance acetic acid etching modified Ce-Mn bimetallic low-temperature SCR denitration catalyst comprises the following steps: take 8.03gMn (NO) 3 ) 2 ·4H 2 O and 3.47g Ce (NO) 3 ) 3 ·6H 2 O was dissolved in 20ml of deionized water and stirred together for 1.5 hours, then 45ml of 4mol.L was added -1 The solution was stirred for another 3 hours to obtain a suspension, and transferred to a reaction vessel, and the mixture was heated to 120 ℃ and maintained at that temperature for 24 hours. The resulting precipitate was then washed several times with deionized water and once with absolute ethanol until the solution pH was unchanged. After drying in an oven at 60 ℃ for 12 hours, the sample was finally calcined in 500 ℃ air for 4 hours. Weighing 1g of prepared Ce-Mn bimetallic oxide and immersing in 0.8mol.L -1 Etching for 0.4h, filtering the obtained precipitate, fully drying in a drying oven at 60 ℃ for 3h, and finally calcining in air at 500 ℃ for 4h.
The catalyst has a NOx conversion of 97% or more at 80-240 ℃ and 10vol% H at 200 DEG C 2 The water resistance under O is above 98%.
Example 3
The preparation method of the high water resistance acetic acid etching modified Ce-Mn bimetallic low-temperature SCR denitration catalyst comprises the following steps: take 7.03gMn (NO) 3 ) 2 ·4H 2 O and 5.21g Ce (NO) 3)3 ·6H 2 O was dissolved in 20ml of deionized water and stirred together for 2 hours, then 50ml of 4mol.L was added -1 The solution was stirred for another 3 hours to obtain a suspension, and transferred to a reaction vessel, and the mixture was heated to 130 ℃ and maintained at that temperature for 24 hours. The resulting precipitate was then washed several times with deionized water and once with absolute ethanol until the solution pH was unchanged. After drying in an oven at 60 ℃ for 8 hours, the sample was finally calcined in 500 ℃ air for 3 hours. Weighing 1g of prepared Ce-Mn bimetallic oxide and immersing in 1.0mol.L -1 Etching for 0.6h, filtering the obtained precipitate, fully drying in a drying oven at 60 ℃ for 4h, and finally calcining in air at 500 ℃ for 3h.
The catalyst has NOx conversion rate of 96% or more at 80-240 ℃ and 10vol% H at 200 DEG C 2 The water resistance under O is more than 97%.
Example 4
The preparation method of the high water resistance acetic acid etching modified Ce-Mn bimetallic low-temperature SCR denitration catalyst comprises the following steps: take 3.01gMn (NO) 3 ) 2 ·4H 2 O and 12.15g Ce (NO) 3 ) 3 ·6H 2 O was dissolved in 20ml of deionized water and stirred together for 2 hours, then 50ml of 4mol.L was added -1 The solution was stirred for another 3 hours to obtain a suspension, and transferred to a reaction vessel, and the mixture was heated to 150 ℃ and maintained at that temperature for 24 hours. The resulting precipitate was then washed several times with deionized water and once with absolute ethanol until the solution pH was unchanged. After drying in an oven at 60 ℃ for 10 hours, the sample was finally calcined in 500 ℃ air for 3 hours. Weighing 1g of prepared Ce-Mn bimetallic oxide and immersing in 0.5 mol.L -1 Etching for 0.5h, filtering the obtained precipitate, fully drying in a drying oven at 60 ℃ for 4h, and finally calcining in air at 500 ℃ for 3h.
The catalyst has a NOx conversion of 98% or more at 80-240 ℃ and 10vol% H at 200 DEG C 2 The water resistance under O is over 99 percent.
Example 5
The high water resistance acetic acid etchingThe preparation method of the corrosion modified Ce-Mn bimetallic low-temperature SCR denitration catalyst comprises the following steps: take 9.04gMn (NO) 3 ) 2 ·4H 2 O and 1.74g Ce (NO) 3 ) 3 ·6H 2 O was dissolved in 20ml of deionized water and stirred together for 2 hours, and then 55ml of 4mol.L was added -1 The solution was stirred for another 3 hours to obtain a suspension, and transferred to a reaction vessel, and the mixture was heated to 120 ℃ and maintained at that temperature for 24 hours. The resulting precipitate was then washed several times with deionized water and once with absolute ethanol until the solution pH was unchanged. After drying in an oven at 60 ℃ for 12 hours, the sample was finally calcined in 500 ℃ air for 5 hours. Weighing 1g of prepared Ce-Mn bimetallic oxide and immersing in 2.0mol.L -1 Etching for 0.4h, filtering the obtained precipitate, fully drying in a drying oven at 60 ℃ for 5h, and finally calcining in air at 500 ℃ for 5h.
The catalyst has NOx conversion rate of 96% or more at 80-240 ℃ and 10vol% H at 200 DEG C 2 The water resistance under O is over 96 percent.
Claims (10)
1. A Ce-Mn bimetallic oxide with high water resistance is characterized in that: the method comprises the steps of adding a solution containing manganese ions and cerium ions into an alkali solution, heating and reacting to obtain a solid-phase product, and then sequentially carrying out first calcination, acid etching and second calcination on the solid-phase product.
2. A highly water resistant Ce-Mn bimetallic oxide as claimed in claim 1, wherein: adding a solution containing manganese ions and cerium ions into the mixed solution obtained after the alkali solution is added, wherein the concentration of the manganese ions is 0.2-0.8 mol/L, the concentration of the cerium ions is 0.2-0.8 mol/L, and the concentration of the hydroxide ions is 1.0-2.0 mol/L; the temperature of the heating reaction is 120-150 ℃ and the duration is 24-48 hours.
3. A highly water resistant Ce-Mn bimetallic oxide as claimed in claim 1, wherein: the acid etching process comprises the following steps: adding the solid phase product into hydrogen ion with the molar concentration of 0.6-2.4 mol.L -1 CH of (2) 3 COOH solutionEtching for 0.2-0.6 h.
4. A highly water resistant Ce-Mn bimetallic oxide as claimed in claim 1, wherein: the calcination temperature of the first calcination is 300-500 ℃ and the calcination time is 3-5 h. The calcination temperature of the second calcination is 300-500 ℃ and the calcination time is 3-5 h.
5. A process for preparing a Ce-Mn bimetallic oxide having high water resistance according to any one of claims 1 to 4, wherein: the method comprises the following steps:
1. the Ce-Mn bimetallic oxide is obtained by a hydrothermal method:
step (1) a NaOH solution was prepared as a reaction solution A.
And (2) dissolving manganese salt and cerium salt in deionized water and fully stirring to obtain a solution B.
Step (3) the reaction solution A is added dropwise to the solution B and stirred well to obtain a suspension C.
And (4) transferring the suspension C into a high-pressure reaction kettle, heating for 24-48 h, and filtering to obtain a precipitate D.
And (5) washing the precipitate D with deionized water and absolute ethyl alcohol alternately for a plurality of times to wash Na+ ions from the precipitate D until the pH value of the solution is unchanged, thereby obtaining the precipitate E.
And (6) drying the precipitate E, and calcining in air to obtain the modified Ce-Mn bimetallic oxide F.
2. Acetic acid is selected for etching and modifying Ce-Mn bimetallic oxide F:
and (7) preparing a CH3COOH solution serving as an etching solution G.
And (8) immersing the modified Ce-Mn bimetallic oxide F in an etching solution G for etching to obtain a precipitate H.
And (9) filtering and drying the precipitate H, and calcining in air to obtain the Ce-Mn bimetallic oxide with high water resistance.
6. The method of manufacturing according to claim 5, wherein: the manganese salt passes throughMn(NO 3 ) 2 ·4H 2 O powder configuration, cerium salt was prepared by Ce (NO 3 ) 3 ·6H 2 And (3) O powder configuration.
7. The method of manufacturing according to claim 5, wherein: in the step (2), the stirring time of the solution B is controlled within 1-2 h. In the step (3), the stirring time of the suspension C is controlled within 3-6 h.
8. The method of manufacturing according to claim 5, wherein: in the step (6), the drying temperature is 60-80 ℃ and the drying time is controlled within 6-12 h. In the step (9), the drying temperature is 60-80 ℃, the drying time is controlled within 3-6 h, the calcining temperature is 300-500 ℃, and the calcining time is controlled within 3-5 h.
9. The Ce-Mn bimetallic oxide with high water resistance is applied to SCR denitration as a catalyst.
10. The use according to claim 9, characterized in that: the SCR denitration is carried out at the temperature of 80-240 ℃.
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