CN116920850A - Multifunctional catalyst applied to medium-low temperature flue gas purification and preparation method thereof - Google Patents
Multifunctional catalyst applied to medium-low temperature flue gas purification and preparation method thereof Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 85
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 title claims abstract description 57
- 239000003546 flue gas Substances 0.000 title claims abstract description 57
- 238000000746 purification Methods 0.000 title claims abstract description 19
- 238000002360 preparation method Methods 0.000 title abstract description 16
- 238000006243 chemical reaction Methods 0.000 claims abstract description 44
- 239000002131 composite material Substances 0.000 claims abstract description 33
- 230000003197 catalytic effect Effects 0.000 claims abstract description 31
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 28
- 239000000203 mixture Substances 0.000 claims abstract description 26
- 229910052751 metal Inorganic materials 0.000 claims abstract description 25
- 230000009467 reduction Effects 0.000 claims abstract description 25
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 22
- 230000003647 oxidation Effects 0.000 claims abstract description 20
- 229910020634 Co Mg Inorganic materials 0.000 claims abstract description 13
- 230000008859 change Effects 0.000 claims abstract description 4
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 81
- 239000000243 solution Substances 0.000 claims description 81
- 239000008367 deionised water Substances 0.000 claims description 24
- 229910021641 deionized water Inorganic materials 0.000 claims description 24
- 238000006722 reduction reaction Methods 0.000 claims description 24
- 238000003756 stirring Methods 0.000 claims description 22
- 238000000034 method Methods 0.000 claims description 20
- 102000020897 Formins Human genes 0.000 claims description 19
- 108091022623 Formins Proteins 0.000 claims description 19
- 229910002091 carbon monoxide Inorganic materials 0.000 claims description 19
- 238000001354 calcination Methods 0.000 claims description 18
- 229910052760 oxygen Inorganic materials 0.000 claims description 12
- 230000008569 process Effects 0.000 claims description 11
- 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 10
- 239000011777 magnesium Substances 0.000 claims description 10
- 238000010438 heat treatment Methods 0.000 claims description 9
- 239000011259 mixed solution Substances 0.000 claims description 9
- 239000007790 solid phase Substances 0.000 claims description 9
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 8
- 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 claims description 8
- 238000005187 foaming Methods 0.000 claims description 8
- 239000002184 metal Substances 0.000 claims description 8
- 229910017604 nitric acid Inorganic materials 0.000 claims description 8
- 239000000843 powder Substances 0.000 claims description 8
- 238000012360 testing method Methods 0.000 claims description 8
- 229940011182 cobalt acetate Drugs 0.000 claims description 7
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 claims description 7
- UEGPKNKPLBYCNK-UHFFFAOYSA-L magnesium acetate Chemical compound [Mg+2].CC([O-])=O.CC([O-])=O UEGPKNKPLBYCNK-UHFFFAOYSA-L 0.000 claims description 6
- 229940069446 magnesium acetate Drugs 0.000 claims description 6
- 235000011285 magnesium acetate Nutrition 0.000 claims description 6
- 239000011654 magnesium acetate Substances 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 4
- 229910020599 Co 3 O 4 Inorganic materials 0.000 claims description 2
- 238000010531 catalytic reduction reaction Methods 0.000 claims description 2
- 238000001035 drying Methods 0.000 claims description 2
- 239000006260 foam Substances 0.000 claims description 2
- 238000000227 grinding Methods 0.000 claims description 2
- 239000003344 environmental pollutant Substances 0.000 abstract description 14
- 231100000719 pollutant Toxicity 0.000 abstract description 14
- 230000007613 environmental effect Effects 0.000 abstract description 3
- 239000008204 material by function Substances 0.000 abstract description 2
- 239000007789 gas Substances 0.000 description 23
- 238000011056 performance test Methods 0.000 description 14
- 229910021645 metal ion Inorganic materials 0.000 description 11
- 238000000354 decomposition reaction Methods 0.000 description 6
- 238000011068 loading method Methods 0.000 description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 238000013112 stability test Methods 0.000 description 3
- 239000002253 acid Substances 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000007774 longterm Effects 0.000 description 2
- 230000002195 synergetic effect Effects 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 235000005979 Citrus limon Nutrition 0.000 description 1
- 244000131522 Citrus pyriformis Species 0.000 description 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- 206010021143 Hypoxia Diseases 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000010668 complexation reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 229910001882 dioxygen Inorganic materials 0.000 description 1
- 230000008030 elimination Effects 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000033116 oxidation-reduction process Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000000779 smoke Substances 0.000 description 1
- BHZOKUMUHVTPBX-UHFFFAOYSA-M sodium acetic acid acetate Chemical class [Na+].CC(O)=O.CC([O-])=O BHZOKUMUHVTPBX-UHFFFAOYSA-M 0.000 description 1
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/86—Catalytic processes
- B01D53/864—Removing carbon monoxide or hydrocarbons
-
- 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
- B01D53/46—Removing components of defined structure
- B01D53/62—Carbon oxides
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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
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
-
- 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
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/78—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with alkali- or alkaline earth metals
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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
- B01J37/08—Heat treatment
- B01J37/082—Decomposition and pyrolysis
- B01J37/088—Decomposition of a metal salt
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2257/00—Components to be removed
- B01D2257/50—Carbon oxides
- B01D2257/504—Carbon dioxide
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2258/00—Sources of waste gases
- B01D2258/02—Other waste gases
- B01D2258/0283—Flue gases
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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
- B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A50/00—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
- Y02A50/20—Air quality improvement or preservation, e.g. vehicle emission control or emission reduction by using catalytic converters
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- Catalysts (AREA)
Abstract
The invention discloses a multifunctional catalyst applied to medium-low temperature flue gas purification and a preparation method thereof, and belongs to the technical field of environmental functional materials and atmospheric pollutant control. A multifunctional catalyst applied to medium-low temperature flue gas purification consists of the following components: cuO, co 3 O 4 And MgO, wherein the mass of CuO accounts for 0.5-10% of the mass of the CoMgO composite oxide carrier, the mol ratio x of Mg element to the total amount of Co-Mg metal elements in the CoMgO composite oxide carrier is 0.05-0.25, the invention also specifically discloses a preparation method of the multifunctional catalyst applied to medium-low temperature flue gas purification, the multifunctional catalyst is simultaneously applied to CO catalytic oxidation and CO reduction NO reaction, andthe catalyst has better middle-low temperature catalytic activity, long-time running stability and water resistance, and can be applied to industrial flue gas treatment under different working conditions or with larger flue gas composition change.
Description
Technical Field
The invention belongs to the technical field of environmental functional materials and atmospheric pollutant control, and particularly relates to a multifunctional catalyst applied to medium-low temperature flue gas purification and a preparation method thereof.
Background
In recent years, in the background of ultra-low emission and synergistic pollution reduction and carbon reduction in the industrial industry, higher requirements are put on atmospheric pollutant control. CO and NO, as two typical atmospheric pollutants, pose serious threats to ecological safety and human health. Therefore, how to efficiently eliminate CO and NO in flue gas is an important research topic in the environmental field. The CO catalytic oxidation can oxidize CO into CO under the oxygen-enriched condition by the action of a catalyst 2 And the CO reduction NO reaction can realize the synergistic elimination of two pollutants under the condition of oxygen deficiency. The catalyst is used as the core of catalytic reaction and is important to the reaction performance. In the prior art, different catalysts are usually required to be used for medium-low temperature flue gas under different conditions, so that the application scenes of large variation of different working conditions and flue gas compositions in the operation process can not be met. Therefore, there is an urgent need to develop a catalyst having multiple functions to adapt to its application under different working conditions.
Disclosure of Invention
Based on the defects of the existing catalyst, the invention provides a multifunctional catalyst applied to medium-low temperature flue gas purification and a preparation method thereof, and the multifunctional catalyst can be simultaneously applied to CO catalytic oxidation and CO reduction NO reaction, has better medium-low temperature catalytic activity, long-time running stability and water resistance, and can be applied to industrial flue gas treatment with larger change of flue gas composition under different working conditions.
The invention adopts the following technical proposal to solve the technical problems, and is a multifunctional catalyst applied to medium-low temperature flue gas purification, which is characterized in that the multifunctional catalyst comprises the following components in percentage by weightThe composition of the following components: cuO, co 3 O 4 And MgO, wherein the mass of CuO is Co 3 O 4 The molar ratio x of Mg element to Co-Mg metal element in the composite oxide carrier is 0.05-0.25, and the multifunctional catalyst is applied to CO catalytic oxidation and CO reduction NO reaction simultaneously, has good middle-low temperature catalytic activity, long-time running stability and water resistance, and can be applied to industrial flue gas treatment with large change of different working conditions or flue gas composition.
Further limited, the multifunctional catalyst is applied to low-temperature CO catalytic oxidation or medium-low temperature CO reduction NO reaction, and comprises the following specific processes: will contain CO and O 2 Or the flue gas of CO and NO is introduced into a fixed bed reactor loaded with a multifunctional catalyst, so that the gas-solid phase full contact and reaction are realized.
Further defined, the test temperature ranges of the low-temperature CO catalytic oxidation and the medium-low temperature CO catalytic reduction NO are 30-150 ℃ and 75-400 ℃ respectively.
The invention relates to a preparation method of a multifunctional catalyst applied to medium-low temperature flue gas purification, which is characterized by comprising the following specific steps:
step S1, adding magnesium acetate and cobalt acetate into deionized water, and uniformly stirring and mixing to obtain a clear and transparent purple solution, wherein the molar ratio x of Mg element to the total amount of Co-Mg metal elements is 0.05-0.25;
step S2, dissolving citric acid in deionized water to obtain a clear and transparent colorless solution;
step S3, adding the colorless solution obtained in the step S2 into the purple solution obtained in the step S1, continuously stirring to uniformly mix the colorless solution, adding the nitric acid solution, and fully stirring and uniformly mixing to obtain a mixed solution;
step S4, heating, stirring and concentrating the mixed solution obtained in the step S3 at 80-100 ℃ to gel, and then transferring the gel into an oven to foam at 120-150 ℃;
s5, grinding the foaming product obtained in the step S4, pre-decomposing at 160-200 ℃, and calcining the pre-decomposed powder to obtain a CoMgO composite oxide carrier;
and S6, dissolving copper nitrate trihydrate corresponding to 0.5-10wt% of CuO load mass fraction into deionized water to obtain copper nitrate solution, adding the CoMgO composite oxide carrier obtained in the step S5 with the corresponding weight into the obtained copper nitrate solution, stirring to uniformly mix, drying the mixture, and calcining to obtain the multifunctional catalyst.
Further defined is a molar ratio of the total amount of Co-Mg metal elements in the purple solution to citric acid in the colorless solution of 1:1-1:3 in step S3.
Further defined, the calcination process in step S5 is performed at 5 ℃ for min -1 The temperature rise rate of (2) is raised from room temperature to 250 ℃ for 1 hour, and then 10 ℃ for min -1 Is heated to 500-700 ℃ for 3 hours.
Further defined, the calcination process in step S5 is specifically carried out by first heating at 5℃for min -1 The temperature rise rate of (2) is raised from room temperature to 250 ℃ for 1 hour, and then 10 ℃ for min -1 Is heated to 550 ℃ for 3 hours.
Further defined, the calcination process in step S6 is to raise the temperature to 400-600 ℃ for 1-5 hours.
Further defined, the calcination process in step S6 is to raise the temperature to 500 ℃ for 3 hours.
Because the existing catalyst generally needs to use different catalysts for different flue gas conditions, the efficient removal of pollutants in the flue gas under different working conditions and application scenes with large changes of flue gas composition cannot be met. The CuO/CoMgO multifunctional catalyst has better molecular oxygen activation and oxidation-reduction performance, and can eliminate CO and NO under the medium-low temperature condition. The high-efficiency multifunctional catalyst is prepared by adopting a citric acid complexation method and wet impregnation, can eliminate pollutants contained in smoke through CO catalytic oxidation and CO reduction NO reaction under oxygen-enriched and oxygen-deficient conditions respectively, and has good removal efficiency and long-time operation stability under medium-low temperature conditions.
Compared with the prior art, the invention has the following advantages and beneficial effects:
1. the preparation method of the multifunctional catalyst is simple, has low cost, and is beneficial to mass production and practical application in medium-low temperature flue gas purification.
2. The multifunctional catalyst has the CO content of 4000 ppm and the volume fraction of 10 percent O 2 And a gas space velocity of 30000 h -1 1000 ppm CO,1000 ppm NO and gas space velocity of 50000 h -1 Under the simulated flue gas condition, better medium-low temperature conversion efficiency can be realized, and even the catalyst with lower CuO load ratio still can show better catalytic performance. In addition, the catalyst has better long-time operation stability, and can meet the medium-low temperature flue gas purification requirements under different working conditions.
Drawings
FIG. 1 shows the catalytic efficiency (b) of a CuO/CoMgO catalyst in CO reduction NO (a) and CO catalytic oxidation reactions with different Mg-Co ratios;
FIG. 2 shows the catalytic efficiency (b) of CuO/CoMgO catalysts with different CuO loading ratios in CO reduction NO (a) and CO catalytic oxidation reactions;
FIG. 3 is a graph showing the results of long-term running stability test of a CuO/CoMgO catalyst supporting 5wt% of CuO in CO catalytic oxidation and CO reduction NO reactions.
Detailed Description
The above-described matters of the present invention will be described in further detail by way of examples, but it should not be construed that the scope of the above-described subject matter of the present invention is limited to the following examples, and all techniques realized based on the above-described matters of the present invention are within the scope of the present invention.
Examples
Preparation of the catalyst: the total amount of metal elements is 15 mmol, and the molar ratio of the metal elements is 0.75:14.25%x=0.05) was added to 50 mL deionized water and vigorously stirred for 1 hour to give a clear, transparent purple solution. 22.5 mmol of citric acid was dissolved in 50 mL deionized water to give a clear and transparent citric acid solution. Adding citric acid solution into the purple metal ion solution, and continuously stirring to uniformly mix the citric acid solution and the metal ion solution. To the obtained mixed solution, a 10 mL nitric acid solution was added and stirred well, and then the solution was concentrated to a gel state with heating and stirring at 90 ℃.The gel was transferred to an oven for foaming at 140 ℃ for 10 hours, followed by pre-decomposition at 180 ℃ for 10 hours. The pre-decomposed powder is first treated in a box furnace at 5 deg.c for min -1 The temperature rise rate of (2) is raised from room temperature to 250 ℃ for 1 hour, and then 10 ℃ for min -1 The temperature rise rate of (2) is raised to 550 ℃ and kept for 3 hours, and the CoMgO composite oxide carrier is obtained by calcination. Copper nitrate trihydrate 0.46 to g corresponding to a CuO loading mass fraction of 5wt% was dissolved in deionized water to obtain a copper nitrate solution 10 to mL, 3 g of a coop composite oxide carrier was added to the solution, and the mixture was stirred for 12 hours to mix it uniformly. The mixture was then dried and calcined at 500 ℃ for 3 hours to obtain a multifunctional catalyst for use in medium and low temperature flue gas purification. Wherein the mass of CuO accounts for 5% of the total mass of the CoMgO composite oxide carrier, and the molar ratio of the Mg element to the total Co-Mg metal element in the CoMgO composite oxide carrierx0.05.
Performance test of the catalyst: and (3) introducing the simulated flue gas containing pollutants into a fixed bed reactor loaded with the prepared multifunctional catalyst, so as to realize full contact and reaction of gas and solid phases. At 4000 ppm CO, volume fraction 10% O 2 And a gas space velocity of 30000 h -1 1000 ppm CO,1000 ppm NO and gas space velocity of 50000 h -1 Under the simulated flue gas condition, the performance test of CO catalytic oxidation and CO reduction NO reaction is respectively carried out at the test temperature range of 30-150 ℃ and 75-400 ℃. As shown in FIG. 1, the catalyst shows better CO reduction NO performance, and reaches 100 percent of NO and CO conversion rate (in (a) in FIG. 1) in the range of 125-400 ℃ and 200-400 ℃; the CO conversion rate of 100% or more is achieved in the temperature range of 110 to 150 ℃ (fig. 1 (b)).
Examples
Preparation of the catalyst: the total amount of metal elements is 15 mmol, and the molar ratio of the metal elements is 2.25:12.75%x=0.15) the corresponding magnesium acetate and cobalt acetate were added to 50 mL deionized water and vigorously stirred for 1 hour to give a clear, transparent purple solution. 22.5 mmol of citric acid was dissolved in 50 mL deionized water to give a clear and transparent citric acid solution. Adding citric acid solution into the purple metal ion solution, and continuously stirring to uniformly mix the citric acid solution and the metal ion solution. To the obtained mixed solutionAfter adding 10 mL nitric acid solution to the solution and stirring the solution thoroughly, the solution was concentrated to gel state with heating and stirring at 90 ℃. The gel was transferred to an oven for foaming at 140 ℃ for 10 hours, followed by pre-decomposition at 180 ℃ for 10 hours. The pre-decomposed powder is first treated in a box furnace at 5 deg.c for min -1 The temperature rise rate of (2) is raised from room temperature to 250 ℃ for 1 hour, and then 10 ℃ for min -1 The temperature rise rate of (2) is raised to 550 ℃ and kept for 3 hours, and the CoMgO composite oxide carrier is obtained by calcination. Copper nitrate trihydrate 0.46 to g corresponding to a CuO loading mass fraction of 5wt% was dissolved in deionized water to obtain a copper nitrate solution of 10 mL, 3 g of coop composite oxide carrier was added to the solution, and stirred for 12 hours to mix uniformly. The mixture is then dried and calcined at 500 ℃ for 3 hours to obtain the high-efficiency multifunctional catalyst applied to medium-low temperature flue gas purification. Wherein the mass of CuO accounts for 5% of the total mass of the CoMgO composite oxide carrier, and the molar ratio of the Mg element to the total Co-Mg metal element in the CoMgO composite oxide carrierx0.15.
Performance test of the catalyst: and (3) introducing the simulated flue gas containing pollutants into a fixed bed reactor loaded with the prepared multifunctional catalyst, so as to realize full contact and reaction of gas and solid phases. At 4000 ppm CO, volume fraction 10% O 2 And a gas space velocity of 30000 h -1 1000 ppm CO,1000 ppm NO and gas space velocity of 50000 h -1 Under the simulated flue gas condition, the performance test of CO catalytic oxidation and CO reduction NO reaction is respectively carried out at the test temperature range of 30-150 ℃ and 75-400 ℃. As shown in FIG. 1, the catalyst shows better CO reduction NO performance, and reaches 100 percent of NO and CO conversion rate (in (a) in FIG. 1) in the range of 125-400 ℃ and 200-400 ℃; a CO conversion of 100% is achieved in the temperature range of 100-150 c (fig. 1 (b)).
Examples
Preparation of the catalyst: the total amount of metal elements is 15 mmol, and the molar ratio of the metal elements is 3.75:11.25%x=0.25) of the corresponding magnesium acetate and cobalt acetate were added to 50 mL deionized water and vigorously stirred for 1 hour to give a clear, transparent purple solution. 22.5 mmol of citric acid was dissolved in 50 mL deionized water to give a clear and transparent citric acid solution. Lemon is addedThe acid solution is added into the purple metal ion solution, and the solution is continuously stirred to be uniformly mixed. To the obtained mixed solution, a 10 mL nitric acid solution was added and stirred well, and then the solution was concentrated to a gel state with heating and stirring at 90 ℃. The gel was transferred to an oven for foaming at 140 ℃ for 10 hours, followed by pre-decomposition at 180 ℃ for 10 hours. The pre-decomposed powder is first treated in a box furnace at 5 deg.c for min -1 The temperature rise rate of (2) is raised from room temperature to 250 ℃ for 1 hour, and then 10 ℃ for min -1 The temperature rise rate of (2) is raised to 550 ℃ and kept for 3 hours, and the CoMgO composite oxide carrier is obtained by calcination. Copper nitrate trihydrate 0.46 to g corresponding to a CuO loading mass fraction of 5wt% was dissolved in deionized water to obtain a copper nitrate solution of 10 mL, 3 g of coop composite oxide carrier was added to the solution, and stirred for 12 hours to mix uniformly. The mixture is then dried and calcined at 500 ℃ for 3 hours to obtain the high-efficiency multifunctional catalyst applied to medium-low temperature flue gas purification. Wherein the mass of CuO accounts for 5% of the total mass of the CoMgO composite oxide carrier, and the molar ratio of the Mg element to the total Co-Mg metal element in the CoMgO composite oxide carrierx0.25.
Performance test of the catalyst: and (3) introducing the simulated flue gas containing pollutants into a fixed bed reactor loaded with the prepared multifunctional catalyst, so as to realize full contact and reaction of gas and solid phases. At 4000 ppm CO, volume fraction 10% O 2 And a gas space velocity of 30000 h -1 1000 ppm CO,1000 ppm NO and gas space velocity of 50000 h -1 Under the simulated flue gas condition, the performance test of CO catalytic oxidation and CO reduction NO reaction is respectively carried out at the test temperature range of 30-150 ℃ and 75-400 ℃. As shown in FIG. 1, the catalyst shows better CO reduction NO performance, and reaches 100 percent of NO and CO conversion rate (in (a) in FIG. 1) in the range of 150-400 ℃ and 200-400 ℃; 100% CO conversion is achieved in the temperature range 110-150 ℃ (FIG. 1 (b)).
Examples
Preparation of the catalyst: the total amount of metal elements is 15 mmol, and the molar ratio of the metal elements is 2.25:12.75%x=0.15) the corresponding magnesium acetate and cobalt acetate were added to 50 mL deionized water and vigorously stirred for 1 hour to give a clear, transparent purple solution.22.5 mmol of citric acid was dissolved in 50 mL deionized water to give a clear and transparent citric acid solution. Adding citric acid solution into the purple metal ion solution, and continuously stirring to uniformly mix the citric acid solution and the metal ion solution. To the obtained mixed solution, a 10 mL nitric acid solution was added and stirred well, and then the solution was concentrated to a gel state with heating and stirring at 90 ℃. The gel was transferred to an oven for foaming at 140 ℃ for 10 hours, followed by pre-decomposition at 180 ℃ for 10 hours. The pre-decomposed powder is first treated in a box furnace at 5 deg.c for min -1 The temperature rise rate of (2) is raised from room temperature to 250 ℃ for 1 hour, and then 10 ℃ for min -1 The temperature rise rate of (2) is raised to 550 ℃ and kept for 3 hours, and the CoMgO composite oxide carrier is obtained by calcination. Copper nitrate trihydrate 0.046, 0.046 g corresponding to a CuO loading mass fraction of 0.5wt% was dissolved in deionized water to obtain a copper nitrate 10 mL solution, 3 g of a coop composite oxide carrier was added to the solution, and stirred for 12 hours to mix uniformly. The mixture is then dried and calcined at 500 ℃ for 3 hours to obtain the high-efficiency multifunctional catalyst applied to medium-low temperature flue gas purification. Wherein the mass of CuO accounts for 0.5 percent of the total mass of the CoMgO composite oxide carrier, and the mol ratio of the Mg element and the total Co-Mg metal element in the CoMgO composite oxide carrierx0.15.
Performance test of the catalyst: and (3) introducing the simulated flue gas containing pollutants into a fixed bed reactor loaded with the prepared multifunctional catalyst, so as to realize full contact and reaction of gas and solid phases. At 4000 ppm CO, volume fraction 10% O 2 And a gas space velocity of 30000 h -1 1000 ppm CO,1000 ppm NO and gas space velocity of 50000 h -1 Under the simulated flue gas condition, the performance test of CO catalytic oxidation and CO reduction NO reaction is respectively carried out at the test temperature range of 30-150 ℃ and 75-400 ℃. As shown in fig. 2, the catalyst shows better performance of reducing NO by CO, and reaches 100% conversion rate of NO and CO in the range of 125-400 ℃ and 200-400 ℃ (fig. 2 (a)); 100% CO conversion is achieved in the temperature range of 90-150 ℃ (FIG. 2 (b)).
Examples
Preparation of the catalyst: the total amount of metal elements is 15 mmol, and the molar ratio of the metal elements is 2.25:12.75%x=0.15) corresponding to bMagnesium acid and cobalt acetate were added to 50 mL deionized water and vigorously stirred for 1 hour to give a clear, transparent purple solution. 22.5 mmol of citric acid was dissolved in 50 mL deionized water to give a clear and transparent citric acid solution. Adding citric acid solution into the purple metal ion solution, and continuously stirring to uniformly mix the citric acid solution and the metal ion solution. To the obtained mixed solution, a 10 mL nitric acid solution was added and stirred well, and then the solution was concentrated to a gel state with heating and stirring at 90 ℃. The gel was transferred to an oven for foaming at 140 ℃ for 10 hours, followed by pre-decomposition at 180 ℃ for 10 hours. The pre-decomposed powder is first treated in a box furnace at 5 deg.c for min -1 The temperature rise rate of (2) is raised from room temperature to 250 ℃ for 1 hour, and then 10 ℃ for min -1 The temperature rise rate of (2) is raised to 550 ℃ and kept for 3 hours, and the CoMgO composite oxide carrier is obtained by calcination. Copper nitrate trihydrate 0.28, 0.28 g corresponding to a CuO loading mass fraction of 3wt% was dissolved in deionized water to obtain a copper nitrate solution of 10, 10 mL, 3 g of coop composite oxide carrier was added to the solution, and stirred for 12 hours to mix uniformly. The mixture is then dried and calcined at 500 ℃ for 3 hours to obtain the high-efficiency multifunctional catalyst applied to medium-low temperature flue gas purification. Wherein the mass of CuO accounts for 3% of the total mass of the CoMgO composite oxide carrier, and the molar ratio of the Mg element to the total Co-Mg metal element in the CoMgO composite oxide carrierx0.15.
Performance test of the catalyst: and (3) introducing the simulated flue gas containing pollutants into a fixed bed reactor loaded with the prepared multifunctional catalyst, so as to realize full contact and reaction of gas and solid phases. At 4000 ppm CO, volume fraction 10% O 2 And a gas space velocity of 30000 h -1 1000 ppm CO,1000 ppm NO and gas space velocity of 50000 h -1 Under the simulated flue gas condition, the performance test of CO catalytic oxidation and CO reduction NO reaction is respectively carried out at the test temperature range of 30-150 ℃ and 75-400 ℃. As shown in fig. 2, the catalyst shows better performance of reducing NO by CO, and reaches 100% conversion rate of NO and CO in the range of 150-400 ℃ and 200-400 ℃ (fig. 2 (a)); 100% CO conversion is achieved in the temperature range 110-150 ℃ (FIG. 2 (b)).
Examples
Preparation of the catalyst: will beThe total amount of the metal elements is 15 mmol, and the molar ratio of the metal elements is 2.25:12.75%x=0.15) the corresponding magnesium acetate and cobalt acetate were added to 50 mL deionized water and vigorously stirred for 1 hour to give a clear, transparent purple solution. 22.5 mmol of citric acid was dissolved in 50 mL deionized water to give a clear and transparent citric acid solution. Adding citric acid solution into the purple metal ion solution, and continuously stirring to uniformly mix the citric acid solution and the metal ion solution. To the obtained mixed solution, a 10 mL nitric acid solution was added and stirred well, and then the solution was concentrated to a gel state with heating and stirring at 90 ℃. The gel was transferred to an oven for foaming at 140 ℃ for 10 hours, followed by pre-decomposition at 180 ℃ for 10 hours. The pre-decomposed powder is first treated in a box furnace at 5 deg.c for min -1 The temperature rise rate of (2) is raised from room temperature to 250 ℃ for 1 hour, and then 10 ℃ for min -1 The temperature rise rate of (2) is raised to 550 ℃ and kept for 3 hours, and the CoMgO composite oxide carrier is obtained by calcination. Copper nitrate trihydrate 0.92 and g corresponding to a CuO load mass fraction of 10wt% was dissolved in deionized water to obtain a copper nitrate solution of 10 mL, 3 g of a coop composite oxide carrier was added to the solution, and the mixture was stirred for 12 hours to mix it uniformly. The mixture is then dried and calcined at 500 ℃ for 3 hours to obtain the high-efficiency multifunctional catalyst applied to medium-low temperature flue gas purification. Wherein the mass of CuO accounts for 10% of the total mass of the CoMgO composite oxide carrier, and the molar ratio of the Mg element to the total Co-Mg metal element in the CoMgO composite oxide carrierx0.15.
Performance test of the catalyst: and (3) introducing the simulated flue gas containing pollutants into a fixed bed reactor loaded with the prepared multifunctional catalyst, so as to realize full contact and reaction of gas and solid phases. At 4000 ppm CO, volume fraction 10% O 2 And a gas space velocity of 30000 h -1 1000 ppm CO,1000 ppm NO and gas space velocity of 50000 h -1 Under the simulated flue gas condition, the performance test of CO catalytic oxidation and CO reduction NO reaction is respectively carried out at the test temperature range of 30-150 ℃ and 75-400 ℃. As shown in fig. 2, the catalyst shows better performance of reducing NO by CO, and reaches 100% conversion rate of NO and CO in the range of 150-400 ℃ and 200-400 ℃ (fig. 2 (a)); 100% CO conversion is achieved in the temperature range 110-150 ℃ (FIG. 2 (b)).
Examples
Preparation of the catalyst: the procedure for the preparation of the catalyst in this example was identical to that in example 2.
Performance test of the catalyst: and (3) introducing the simulated flue gas containing pollutants into a fixed bed reactor loaded with the prepared multifunctional catalyst, so as to realize full contact and reaction of gas and solid phases. At 4000 ppm CO, volume fraction 10% O 2 And a gas space velocity of 30000 h -1 1000 ppm CO,1000 ppm NO and gas space velocity of 50000 h -1 And (3) carrying out long-time operation performance test of the catalyst in CO catalytic oxidation and CO reduction NO reaction under the simulated flue gas condition. As shown in fig. 3, the CO conversion of the catalyst was maintained above 79% (initial CO conversion 83.6%) by conducting a long-term running stability test of CO catalytic oxidation at 80 ℃ for 15 hours; in addition, a long run stability test of catalytic CO reduction NO was performed at 100 ℃ for 15 hours, with NO and CO conversions of the catalyst maintained above 85% and 59%, respectively (initial NO and CO conversions of 86.5% and 60.8%). The results show that the catalyst can show better long-time operation stability in CO catalytic oxidation and CO reduction NO reaction.
While the basic principles, principal features and advantages of the present invention have been described in the foregoing examples, it will be appreciated by those skilled in the art that the present invention is not limited by the foregoing examples, but is merely illustrative of the principles of the invention, and various changes and modifications can be made without departing from the scope of the invention, which is defined by the appended claims.
Claims (9)
1. The multifunctional catalyst for purifying medium-low temperature flue gas is characterized by comprising the following components: cuO, co 3 O 4 And MgO, wherein the mass of CuO is Co 3 O 4 0.5% -10% of the mass of MgO (CoMgO) composite oxide carrier, wherein the molar ratio x of Mg element to Co-Mg metal element in the composite oxide carrier is 0.05-0.25, and the multifunctional catalyst is simultaneously applied to CO catalytic oxidation and CO catalytic oxidationIn the CO reduction NO reaction, the catalyst has better middle-low temperature catalytic activity, long-time running stability and water resistance, and can be applied to industrial flue gas treatment under different working conditions or with larger flue gas composition change.
2. The multifunctional catalyst for medium and low temperature flue gas purification according to claim 1, wherein: the multifunctional catalyst is applied to low-temperature CO catalytic oxidation or medium-low-temperature CO reduction NO reaction, and comprises the following specific processes: will contain CO and O 2 Or the flue gas of CO and NO is introduced into a fixed bed reactor loaded with a multifunctional catalyst, so that the gas-solid phase full contact and reaction are realized.
3. The multifunctional catalyst for medium and low temperature flue gas purification according to claim 2, wherein: the test temperature ranges of the low-temperature CO catalytic oxidation and the medium-low temperature CO catalytic reduction NO are 30-150 ℃ and 75-400 ℃ respectively.
4. A method for preparing the multifunctional catalyst for purifying medium and low temperature flue gas according to claim 1, which is characterized by comprising the following specific steps:
step S1, adding magnesium acetate and cobalt acetate into deionized water, and uniformly stirring and mixing to obtain a clear and transparent purple solution, wherein the molar ratio x of Mg element to the total amount of Co-Mg metal elements is 0.05-0.25;
step S2, dissolving citric acid in deionized water to obtain a clear and transparent colorless solution;
step S3, adding the colorless solution obtained in the step S2 into the purple solution obtained in the step S1, continuously stirring to uniformly mix the colorless solution, adding the nitric acid solution, and fully stirring and uniformly mixing to obtain a mixed solution;
step S4, heating, stirring and concentrating the mixed solution obtained in the step S3 at 80-100 ℃ to gel, and then transferring the gel into an oven to foam at 120-150 ℃;
s5, grinding the foaming product obtained in the step S4, pre-decomposing at 160-200 ℃, and calcining the pre-decomposed powder to obtain a CoMgO composite oxide carrier;
and S6, dissolving copper nitrate trihydrate corresponding to 0.5-10wt% of CuO load mass fraction into deionized water to obtain copper nitrate solution, adding the CoMgO composite oxide carrier obtained in the step S5 with the corresponding weight into the obtained copper nitrate solution, stirring to uniformly mix, drying the mixture, and calcining to obtain the multifunctional catalyst.
5. The method for preparing the multifunctional catalyst for purifying medium and low temperature flue gas according to claim 4, which is characterized in that: and in the step S3, the molar ratio of the total amount of Co-Mg metal elements in the purple solution to the citric acid in the colorless solution is 1:1-1:3.
6. The method for preparing the multifunctional catalyst for purifying medium and low temperature flue gas according to claim 4, which is characterized in that: the calcination process in the step S5 is that 5 ℃ for min is adopted firstly -1 The temperature rise rate of (2) is raised from room temperature to 250 ℃ for 1 hour, and then 10 ℃ for min -1 Is heated to 500-700 ℃ for 3 hours.
7. The method for preparing the multifunctional catalyst for purifying medium and low temperature flue gas according to claim 4, which is characterized in that: the calcination process in the step S5 is specifically that the temperature is 5 ℃ for min -1 The temperature rise rate of (2) is raised from room temperature to 250 ℃ for 1 hour, and then 10 ℃ for min -1 Is heated to 550 ℃ for 3 hours.
8. The method for preparing the multifunctional catalyst for purifying medium and low temperature flue gas according to claim 4, which is characterized in that: the calcination process in the step S6 is to raise the temperature to 400-600 ℃ and keep the temperature for 1-5 hours.
9. The method for preparing the multifunctional catalyst for purifying medium and low temperature flue gas according to claim 4, which is characterized in that: the calcination process in step S6 is to raise the temperature to 500 ℃ and keep for 3 hours.
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