CN110947394A - ZIF-67-Mn/Co-based low-temperature NO oxidation catalyst, and preparation method and application thereof - Google Patents
ZIF-67-Mn/Co-based low-temperature NO oxidation catalyst, and preparation method and application thereof Download PDFInfo
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- 238000007254 oxidation reaction Methods 0.000 title claims abstract description 32
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- 239000011572 manganese Substances 0.000 claims abstract description 40
- 239000013078 crystal Substances 0.000 claims abstract description 29
- 239000000243 solution Substances 0.000 claims abstract description 28
- 229910052751 metal Inorganic materials 0.000 claims abstract description 17
- 239000002184 metal Substances 0.000 claims abstract description 17
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- 238000000034 method Methods 0.000 claims abstract description 10
- 239000002904 solvent Substances 0.000 claims abstract description 10
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 claims abstract description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000013110 organic ligand Substances 0.000 claims abstract description 9
- 238000002156 mixing Methods 0.000 claims abstract description 8
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical class [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims abstract description 7
- 229910017052 cobalt Inorganic materials 0.000 claims abstract description 7
- 239000010941 cobalt Substances 0.000 claims abstract description 7
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims abstract description 7
- 238000001914 filtration Methods 0.000 claims abstract description 7
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- 150000003839 salts Chemical class 0.000 claims abstract description 7
- 238000005406 washing Methods 0.000 claims abstract description 7
- 239000013384 organic framework Substances 0.000 claims abstract description 6
- 239000012266 salt solution Substances 0.000 claims abstract description 6
- 230000004913 activation Effects 0.000 claims abstract description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 78
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 claims description 9
- 239000011259 mixed solution Substances 0.000 claims description 7
- 230000008569 process Effects 0.000 claims description 3
- 229940011182 cobalt acetate Drugs 0.000 claims description 2
- 229910021446 cobalt carbonate Inorganic materials 0.000 claims description 2
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims description 2
- 229910001981 cobalt nitrate Inorganic materials 0.000 claims description 2
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- 229910000361 cobalt sulfate Inorganic materials 0.000 claims description 2
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 claims description 2
- ZOTKGJBKKKVBJZ-UHFFFAOYSA-L cobalt(2+);carbonate Chemical compound [Co+2].[O-]C([O-])=O ZOTKGJBKKKVBJZ-UHFFFAOYSA-L 0.000 claims description 2
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 claims description 2
- 229940071125 manganese acetate Drugs 0.000 claims description 2
- 235000006748 manganese carbonate Nutrition 0.000 claims description 2
- 239000011656 manganese carbonate Substances 0.000 claims description 2
- 229940093474 manganese carbonate Drugs 0.000 claims description 2
- 229940099596 manganese sulfate Drugs 0.000 claims description 2
- 235000007079 manganese sulphate Nutrition 0.000 claims description 2
- 239000011702 manganese sulphate Substances 0.000 claims description 2
- UOGMEBQRZBEZQT-UHFFFAOYSA-L manganese(2+);diacetate Chemical compound [Mn+2].CC([O-])=O.CC([O-])=O UOGMEBQRZBEZQT-UHFFFAOYSA-L 0.000 claims description 2
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 claims description 2
- 229910000016 manganese(II) carbonate Inorganic materials 0.000 claims description 2
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 claims description 2
- XMWCXZJXESXBBY-UHFFFAOYSA-L manganese(ii) carbonate Chemical compound [Mn+2].[O-]C([O-])=O XMWCXZJXESXBBY-UHFFFAOYSA-L 0.000 claims description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 2
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- 239000013291 MIL-100 Substances 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
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- 229910052757 nitrogen Inorganic materials 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
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- 239000012159 carrier gas Substances 0.000 description 1
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- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 description 1
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- UBEWDCMIDFGDOO-UHFFFAOYSA-N cobalt(II,III) oxide Inorganic materials [O-2].[O-2].[O-2].[O-2].[Co+2].[Co+3].[Co+3] UBEWDCMIDFGDOO-UHFFFAOYSA-N 0.000 description 1
- UPWOEMHINGJHOB-UHFFFAOYSA-N cobalt(III) oxide Inorganic materials O=[Co]O[Co]=O UPWOEMHINGJHOB-UHFFFAOYSA-N 0.000 description 1
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- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 1
- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum oxide Inorganic materials [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 description 1
- PPNAOCWZXJOHFK-UHFFFAOYSA-N manganese(2+);oxygen(2-) Chemical class [O-2].[Mn+2] PPNAOCWZXJOHFK-UHFFFAOYSA-N 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 239000012621 metal-organic framework Substances 0.000 description 1
- 229910052758 niobium Inorganic materials 0.000 description 1
- 239000010955 niobium Substances 0.000 description 1
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 description 1
- 229910000484 niobium oxide Inorganic materials 0.000 description 1
- URLJKFSTXLNXLG-UHFFFAOYSA-N niobium(5+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Nb+5].[Nb+5] URLJKFSTXLNXLG-UHFFFAOYSA-N 0.000 description 1
- 231100000252 nontoxic Toxicity 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
- B01J23/70—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
- B01J23/84—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 arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/889—Manganese, technetium or rhenium
- B01J23/8892—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
- 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
- B01J23/74—Iron group metals
- B01J23/75—Cobalt
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- B01J35/394—
-
- B01J35/61—
Abstract
The invention discloses a ZIF-67-Mn/Co-based low-temperature NO oxidation catalyst, a preparation method and application thereof, wherein the method comprises the following steps: (1) dissolving manganese metal salt and cobalt metal salt in a solvent to obtain metal salt solution; (2) dissolving 2-methylimidazole in a solvent to obtain an organic ligand solution; (3) carrying out ultrasonic treatment on the metal salt solution and the organic ligand solution, mixing, and carrying out hydrothermal reaction to obtain a ZIF-67-Mn/Co bimetal organic framework crystal; (4) soaking the ZIF-67-Mn/Co bimetallic organic framework crystal into an alcohol solution for activation to obtain an activated crystal; (5) and washing, filtering and roasting the activated crystal to obtain the low-temperature NO oxidation catalyst. The low-temperature NO oxidation catalyst has good low-temperature denitration activity and can meet the current industrial requirements. Therefore, the catalyst has great potential application prospect in the aspect of low-temperature catalytic oxidation of NOx.
Description
Technical Field
The invention relates to the technical field of NOx removal, in particular to a ZIF-67-Mn/Co-based low-temperature NO oxidation catalyst, and a preparation method and application thereof.
Background
Atmospheric pollutants NOx (NO, N)2O3，NO2，N2O4) The annual increase of the content in the air brings a series of environmental problems, such as haze, acid rain, photochemical smog and the like, so that the balance of an ecosystem and the health of human beings are greatly challenged. At present, the source of NOx generation mainly comes from flue gas of various chemical enterprises which provide energy power with fossil fuels such as coal and the like, including thermal power plants, ceramic plants, cement plants and the like. Therefore, NOx emission reduction and treatment become the primary means for treating atmospheric pollution.
The most widely used control technology for atmospheric nitrogen oxides is the Selective Catalytic Reduction (SCR) technology, which utilizes NH3Reducing NOx to non-toxic N2And H2O, because it has the advantages of wide high-temperature operation temperature range (more than 300 ℃), strong adaptability, high denitration efficiency and the like, the O is widely used for denitration of coal-fired power plants. However, the prior SCR denitration technology has the bottleneck problems in the use process that: the optimal use temperature of the SCR denitration catalyst in the power plant is 300-400 ℃, and the flue temperature of non-electric industries such as cement plants, ceramic plants and the like is low<At the stage of 200 ℃, the SCR denitration efficiency is low at low temperature, if the existing SCR denitration technology is applied, a heating device needs to be additionally arranged to reheat the flue gas to 400 ℃ of 300-. Such as Wang et al [ Wang P, Chen S, Gao S, et al, Niobium oxide defined by a novel SCR catalyst with a novel cellulose resistance to a lotus, phosphor, and lead [ J].Applied Catalysis B:Environmental,2018,231:299-309.]A CeNT denitration catalyst is synthesized by a hydrothermal synthesis method, and the NOx conversion rate is enabled to be wide at 275 ℃ and 450 ℃ by loading niobium oxideThe temperature range exceeds 90%, but when the temperature is lowered to about 200 ℃, the conversion effect of the catalyst rapidly decreases to about 20%, and it is difficult to act in the low temperature range. The same problems are also present in the currently developed metal-organic framework materials, such as Zhang et al [ ZHANG W, SHI Y, LI C, et al. Synthesis of bimetallic MOFs MIL-100(Fe-Mn) as an effective Catalyst for selective catalytic Reduction of NOxwith NH3[J].2016,146(10):1956-64.]The synthesized MIL-100(Fe-Mn) shows over 90 percent of NOx conversion rate in the temperature range of 260-330 ℃, but the conversion rate is reduced to below 50 percent along with the temperature reduction to 180 ℃, so that the industrial application requirement is difficult to achieve. Therefore, how to effectively improve the denitration activity of the SCR denitration catalyst in the low temperature region has become a focus of research.
Research shows that NH3The most important reactions of SCR are the following three:
4NH3+4NH3+4NO+O2→4N2+6H2O (1)
4NH3+2NO+2NO2→4N2+6H2O (2)
2NO+O2→2NO2(3)
the fast SCR reaction (2)) has the lowest activation barrier, the temperature of the highest reaction rate is lower than 200 ℃, the reaction rate is more than 10 times faster than that of the common SCR reaction (1)), and the fast SCR reaction is the core reaction of the SCR low-temperature reaction. However, in the flue gas discharged by actual combustion, NO accounts for 90% -95% of the total NOx, so that the NO in the tail gas needs to be partially oxidized into NO2The NO oxidation rate (NO/NOx) reaches 50% -60%, and the efficiency of the whole SCR reaction system can reach the highest. Therefore, NO oxidation (reaction (3)) becomes a step of controlling the SCR conversion rate and the reaction rate, and improvement of the low-temperature oxidation performance of the catalyst becomes a key to improvement of the low-temperature SCR denitration performance.
In addition, the NO in the low-temperature interval of the SCR system is improvedXOne of the main methods for conversion efficiency is to add an Oxidation Catalyst (DOC) to the front end of the SCR system. DOC uses O in flue gas under the action of NO catalytic oxidation catalyst2Directly oxidize NO in the flue gas into NO2And then introducing the pretreated tail gas into an SCR catalytic system, thereby realizing rapid SCR reaction. For the DOC process, selecting a DOC catalyst with low temperature high catalytic oxidation activity will greatly improve the conversion of NOx at low temperature for the SCR reaction. However, most of the current research on catalytic oxidation of NO has been focused on high temperature regions, such as Zhang et al [ Zhang M, Li C, Qu L, et al2,over FeMnOx/TiO2:Effect of iron and manganese oxides loading sequences andthe catalytic mechanism study[J].Applied Surface Science,2014,300(3):58-65.]The Fe (0.15)/Mn (0.3)/TiO2 catalyst is prepared, the NO conversion rate is up to 70% at 300 ℃, but the catalyst has low catalytic activity at low temperature, and the NO conversion rate is only about 38% at 200 ℃. Zhao et al [ ZhaoB, Ran R, Wu X, et al2,and Mn/ZrO2,catalysts for NOoxidation[J].Catalysis Communications,2014,56(41):36-40.]Preparing MnOx/ZrO2The conversion rate of NO of the catalyst is as high as 78% at 270 ℃, but the conversion rate of NO is sharply reduced along with the reduction of temperature, and the conversion rate of NO is only about 25% at 170 ℃, which is far lower than the technical requirement. Patent CN 105188919B prepared a platinum and palladium supported ceria-alumina composite for pre-oxidation of NO, exhibiting an oxidation rate of 54% at 250 ℃, three times higher than that of the reference sample of silica-alumina prepared without ceria, and thus the lower SCR efficiency was also greatly improved. Patent CN 105688920A adopts a dipping method to apply ZrO on2Surface loaded with Co3O4、La2O3And the NO conversion rate reaches 56% at 200 ℃, so that the denitration efficiency at 180 ℃ is improved from 53% to 63%. Therefore, the research of a catalytic material with high NO conversion rate at low temperature is a necessary requirement for the effective industrial application of SCR technology in the low temperature region.
Disclosure of Invention
In order to overcome the defects of the prior art, the invention provides a low-temperature NO oxidation catalyst based on ZIF-67-Mn/Co, and a preparation method and application thereof. Mn-Co bimetal and 2-methylimidazole rich in C, N are coordinated to form a ZIF-67 material with a high specific surface area, and then pyrolysis is carried out to generate a porous carbon nitrogen catalyst material with uniformly dispersed active sites and good stability, so that excellent NO low-temperature oxidation activity is reflected. Can be used for removing NOx discharged by enterprises such as power plants, cement plants, ceramic plants and the like.
The purpose of the invention is realized by the following technical scheme.
A preparation method of a ZIF-67-Mn/Co-based low-temperature NO oxidation catalyst comprises the following steps:
(1) dissolving manganese metal salt and cobalt metal salt in a solvent to obtain metal salt solution;
(2) dissolving 2-methylimidazole in a solvent to obtain an organic ligand solution;
(3) carrying out ultrasonic treatment on the metal salt solution and the organic ligand solution, then mixing, putting the mixed solution into a reactor, and carrying out hydrothermal reaction to obtain a ZIF-67-Mn/Co bimetal organic framework crystal;
(4) soaking the ZIF-67-Mn/Co bimetallic organic framework crystal into an alcohol solution for activation to obtain an activated crystal;
(5) and washing, filtering and roasting the activated crystal to obtain the low-temperature NO oxidation catalyst.
Preferably, the manganese metal salt in the step (1) is one or more of manganese nitrate, manganese sulfate, manganese carbonate and manganese acetate; the cobalt metal salt is one or more of cobalt nitrate, cobalt sulfate, cobalt carbonate and cobalt acetate.
Preferably, the molar ratio of the manganese metal salt to the cobalt metal salt in the step (1) is 1: 1-1: 4; further preferred is Mn (NO)3)2With Co (NO)3)3·6H2O, the molar ratio is 1: 2.
Preferably, the solvent in step (1) or step (2) is any one of water and methanol.
Further preferably, the solvent in step (1) is methanol; the solvent in the step (2) is methanol.
Preferably, the concentration of the organic ligand solution in the step (2) is 50-300 g/L.
Further preferably, the concentration of the organic ligand solution is 150 g/L.
Preferably, the time of the ultrasound in the step (3) is 10min-50 min; the temperature of the hydrothermal reaction is 20-50 ℃, and the time is 12-30 h.
More preferably, the hydrothermal reaction temperature is 25 ℃ and the reaction time is 24 h.
Further preferably, the ultrasonic time is 15 min.
Preferably, the alcohol solution in the step (4) is any one of methanol and ethanol; the soaking time is 12-24 hours.
Further preferably, the soaking time is 12 hours.
Preferably, the roasting temperature in the step (5) is 300-400 ℃, the roasting time is 2-3 h, and the roasting atmosphere is air.
Further preferably, the roasting temperature is 350 ℃, the time is 2.5h, and the roasting atmosphere is air.
The ZIF-67-Mn/Co-based low-temperature NO oxidation catalyst prepared by the preparation method.
The ZIF-67-Mn/Co-based low-temperature NO oxidation catalyst is applied to removal of nitrogen oxides.
Compared with the prior art, the invention has the following advantages and beneficial effects:
(1) compared with the traditional supported catalyst, the catalyst provided by the invention has the advantages of high dispersion of metal active components, good crystal form and the like, and can effectively avoid agglomeration of the metal active components, so that the catalyst has high catalytic oxidation activity on NO.
(2) Compared with the existing low-temperature denitration catalyst, the catalyst disclosed by the invention has the advantages that the NO oxidation rate can reach more than 50% within 125-250 ℃, and the industrial requirements are met.
(3) The preparation method has the advantages of cheap and easily-obtained raw materials, simple preparation method and low production cost, and is beneficial to industrial large-scale application.
Drawings
FIG. 1 is an XRD pattern of the crystalline materials obtained in examples 1 to 5 of the present invention.
FIG. 2 is an XRD pattern of the catalysts obtained in examples 1 to 5 of the present invention.
FIG. 3 is a graph of NO conversion at different temperatures for catalysts obtained in examples 1-5 of the present invention.
Detailed Description
The invention is further described below with reference to the drawings and examples, but the scope of the invention as claimed is not limited to the scope of the examples.
Example 1
(1) 600ul of Mn (NO) with a mass concentration of 50%3)2Solution and 0.750g Co (NO)3)3·6H2Adding O into 20ml of methanol, and carrying out ultrasonic treatment for 15 min;
(2) adding 1.000g of 2-methylimidazole into 20ml of methanol, and carrying out ultrasonic treatment for 15 min;
(3) mixing the solutions, placing the mixed solution in a drying oven at 25 ℃, reacting for 24h, cooling the solution, removing supernatant, adding fresh methanol, soaking and activating at room temperature for 12h to obtain an activated crystal material (marked as ZIF-67-Mn: Co ═ 1: 1);
(4) washing the activated crystal material with methanol, filtering, and vacuum drying at 50 ℃;
(5) and (3) roasting the dried crystal material in a muffle furnace at 350 ℃ for 2.5h to obtain the ZIF-67(Mn/Co) based low-temperature oxidation catalyst (marked as MnCo-C1).
Example 2
(1) 400ul of Mn (NO) with a mass concentration of 50%3)2Solution and 1.000g Co (NO)3)3·6H2Adding O into 20ml of methanol, and carrying out ultrasonic treatment for 15 min;
(2) adding 3.000g of 2-methylimidazole into 20ml of methanol, and carrying out ultrasonic treatment for 15 min;
(3) mixing the solutions, placing the mixed solution in a drying oven at 25 ℃, reacting for 24h, cooling the solution, removing supernatant, adding fresh methanol, soaking and activating at room temperature for 12h to obtain an activated crystal material (marked as ZIF-67-Mn: Co ═ 1: 2);
(4) washing the activated crystal material with methanol, filtering, and vacuum drying at 50 ℃;
(5) and (3) roasting the dried crystal material in a muffle furnace at 350 ℃ for 2.5h to obtain the ZIF-67(Mn/Co) based low-temperature oxidation catalyst (marked as MnCo-C2).
Example 3
(1) 300ul of Mn (NO) with a mass concentration of 50%3)2Solution and 1.125g Co (NO)3)3·6H2Adding O into 20ml of methanol, and carrying out ultrasonic treatment for 30 min;
(2) adding 3.000g of 2-methylimidazole into 20ml of methanol, and carrying out ultrasonic treatment for 30 min;
(3) mixing the solutions, placing the mixed solution in a drying oven at 35 ℃, reacting for 21h, cooling the solution, removing supernatant, adding fresh methanol, soaking and activating at room temperature for 12h to obtain an activated crystal material (marked as ZIF-67-Mn: Co ═ 1: 3);
(4) the activated crystalline material was washed with methanol and filtered. Drying the filtered material in a vacuum drying oven at 50 ℃;
(5) and (3) roasting the dried crystal material in a muffle furnace at 350 ℃ for 2.5h to obtain the ZIF-67(Mn/Co) based low-temperature oxidation catalyst (marked as MnCo-C3).
Example 4
(1) Adding 240ul of Mn (NO) with a mass concentration of 50%3)2Solution and 1.200g Co (NO)3)3·6H2Adding O into 20ml of methanol, and carrying out ultrasonic treatment for 50 min;
(2) adding 3.000g of 2-methylimidazole into 20ml of methanol, and carrying out ultrasonic treatment for 50 min;
(3) mixing the solutions, placing the mixed solution in a drying oven at 20 ℃, reacting for 30h, cooling the solution, removing supernatant, adding fresh methanol, soaking and activating at room temperature for 18h to obtain an activated crystal material (marked as ZIF-67-Mn: Co ═ 1: 4);
(4) washing the activated crystal material with methanol, filtering, and vacuum drying at 50 ℃;
(5) and (3) roasting the dried crystal material in a muffle furnace at 300 ℃ for 3.0h to obtain the ZIF-67(Mn/Co) based low-temperature oxidation catalyst (marked as MnCo-C4).
Example 5
(1) 1.500g of Co (NO)3)3·6H2Adding O into 20ml of methanol, and carrying out ultrasonic treatment for 10 min;
(2) 2.000g of 2-methylimidazole is added into 20ml of methanol, and ultrasonic treatment is carried out for 10 min;
(3) mixing the solutions, placing the mixed solution in a drying oven at 50 ℃, reacting for 12h, cooling the solution, removing supernatant, adding fresh methanol, soaking and activating at room temperature for 24h to obtain an activated crystal material (marked as ZIF-67-Co);
(4) washing the activated crystal material with methanol, filtering, and vacuum drying at 50 ℃;
(5) and (3) roasting the dried crystal material in a muffle furnace at 400 ℃ for 2.0h to obtain the ZIF-67-Co-based low-temperature oxidation catalyst (marked as Co-C).
X-ray diffraction analysis
An X-ray diffractometer model D8-ADVANCE of Bruker company, Germany is adopted, the operation conditions are copper target, 40KV, 40mA, step length is 0.02 degree, and scanning speed is 17.7 seconds per step. The metal skeleton crystals prepared in examples 1 to 5 were characterized by ZIF-67-Mn: Co ═ 1:1, ZIF-67-Mn: Co ═ 1:2, ZIF-67-Mn: Co ═ 1:3, ZIF-67-Mn: Co ═ 1:4, ZIF-67-Co, and ZIF-67(Mn/Co) -based low-temperature oxidation catalysts MnCo-C1, MnCo-C2, MnCo-C3, MnCo-C4, and Co-C, respectively.
Fig. 1 shows XRD patterns of ZIF-67-Mn: Co ═ 1:1, ZIF-67-Mn: Co ═ 1:2, ZIF-67-Mn: Co ═ 1:3, ZIF-67-Mn: Co ═ 1:4, and ZIF-67-Co prepared in examples 1 to 5 of the present invention, and it can be seen from fig. 1 that five materials all have distinct characteristic peaks, all belonging to the characteristic peaks of ZIF-67.
FIG. 2 shows XRD patterns of MnCo-C1, MnCo-C2, MnCo-C3, MnCo-C4, and Co-C prepared in examples 1 to 5 of the present invention, and it can be seen from FIG. 2 that the five catalysts each have distinct characteristic peaks, all assigned to the ZIF-67-derived Co2O3And Mn3O4The intensity of the main peak (2 theta is 37 degrees) of MnCo-C2 is the highest, which shows that the crystal form of the derivative oxide is better, the metal is uniformly dispersed, and the activity is the highest.
Catalytic Oxidation Performance test
The catalysts prepared in examples 1 to 5 were loaded in a fixed bed reactor and tested for catalytic oxidation activity of NO. The activity test conditions were as follows: the temperature of the reaction system is 75-250 ℃, and the space velocity of simulated flue gas is 25000h-1The content is as follows: NO 500ppm, O210.0 percent of carrier gas N2. The total flow rate of gas was 210 mL/min. The fixed catalytic reaction bed is a quartz tube, the inner diameter is 8.0mm, and the filling height is 9.7 mm. NO and NO2The concentration was measured on-line by a Testo 350 smoke analyser. The conversion calculation formula is as follows:
in the formula NO2 outIs quartz tube outlet NO2Concentration; NOinIs the quartz tube inlet NO concentration.
FIG. 3 shows MnCo-C1, MnCo-C2, MnCo-C3, MnCo-C4, Co-C in O prepared in examples 1 to 52The concentration is 10%, and the NO conversion rate under the condition of the temperature of 75-250 ℃ is shown in figure 3, compared with other catalysts, the MnCo-C2 catalyst shows excellent NO catalytic performance under the same temperature, and the NO conversion rate reaches 50.7% at the temperature of 125 ℃.
Claims (10)
1. A preparation method of a ZIF-67-Mn/Co-based low-temperature NO oxidation catalyst is characterized by comprising the following steps:
(1) dissolving manganese metal salt and cobalt metal salt in a solvent to obtain metal salt solution;
(2) dissolving 2-methylimidazole in a solvent to obtain an organic ligand solution;
(3) carrying out ultrasonic treatment on the metal salt solution and the organic ligand solution, then mixing, putting the mixed solution into a reactor, and carrying out hydrothermal reaction to obtain a ZIF-67-Mn/Co bimetal organic framework crystal;
(4) soaking the ZIF-67-Mn/Co bimetallic organic framework crystal into an alcohol solution for activation to obtain an activated crystal;
(5) and washing, filtering and roasting the activated crystal to obtain the low-temperature NO oxidation catalyst.
2. The method according to claim 1, wherein the manganese metal salt of step (1) is one or more of manganese nitrate, manganese sulfate, manganese carbonate and manganese acetate; the cobalt metal salt is one or more of cobalt nitrate, cobalt sulfate, cobalt carbonate and cobalt acetate.
3. The preparation method according to claim 1, wherein the molar ratio of the manganese metal salt to the cobalt metal salt in the step (1) is 1: 1-1: 4.
4. The method according to claim 1, wherein the solvent used in step (1) or step (2) is any one of water and methanol.
5. The preparation method according to claim 1, wherein the concentration of the organic ligand solution in the step (2) is 50-300 g/L.
6. The method for preparing the compound of claim 1, wherein the time for the ultrasonic treatment in the step (3) is 10min to 50 min; the temperature of the hydrothermal reaction is 20-50 ℃, and the time is 12-30 h.
7. The method according to claim 1, wherein the alcohol solution in step (4) is any one of methanol and ethanol; the soaking time is 12-24 hours.
8. The preparation method of claim 1, wherein the roasting temperature in the step (5) is 300-400 ℃, the roasting time is 2-3 h, and the roasting atmosphere is air.
9. A ZIF-67-Mn/Co based low temperature NO oxidation catalyst made by the process of any one of claims 1-8.
10. The use of a ZIF-67-Mn/Co based low temperature NO oxidation catalyst as claimed in claim 9 for removal of nitrogen oxides.
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