CN113262798A - Manganese-based wire mesh monolithic catalyst for catalytic combustion and preparation method thereof - Google Patents
Manganese-based wire mesh monolithic catalyst for catalytic combustion and preparation method thereof Download PDFInfo
- Publication number
- CN113262798A CN113262798A CN202110392710.3A CN202110392710A CN113262798A CN 113262798 A CN113262798 A CN 113262798A CN 202110392710 A CN202110392710 A CN 202110392710A CN 113262798 A CN113262798 A CN 113262798A
- Authority
- CN
- China
- Prior art keywords
- wire mesh
- catalyst
- manganese
- mno
- alpha
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Withdrawn
Links
- 239000003054 catalyst Substances 0.000 title claims abstract description 62
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 title claims abstract description 30
- 229910052748 manganese Inorganic materials 0.000 title claims abstract description 30
- 239000011572 manganese Substances 0.000 title claims abstract description 30
- 238000007084 catalytic combustion reaction Methods 0.000 title claims abstract description 13
- 238000002360 preparation method Methods 0.000 title claims abstract description 8
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 22
- 238000000034 method Methods 0.000 claims abstract description 18
- 238000011065 in-situ storage Methods 0.000 claims abstract description 9
- 229910000314 transition metal oxide Inorganic materials 0.000 claims abstract description 5
- 229910052751 metal Inorganic materials 0.000 claims description 34
- 239000002184 metal Substances 0.000 claims description 34
- 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 claims description 23
- 238000004140 cleaning Methods 0.000 claims description 21
- 238000001035 drying Methods 0.000 claims description 21
- 229910003144 α-MnO2 Inorganic materials 0.000 claims description 19
- 239000000203 mixture Substances 0.000 claims description 16
- 239000012286 potassium permanganate Substances 0.000 claims description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 15
- DDFHBQSCUXNBSA-UHFFFAOYSA-N 5-(5-carboxythiophen-2-yl)thiophene-2-carboxylic acid Chemical compound S1C(C(=O)O)=CC=C1C1=CC=C(C(O)=O)S1 DDFHBQSCUXNBSA-UHFFFAOYSA-N 0.000 claims description 14
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 14
- 239000004202 carbamide Substances 0.000 claims description 14
- 238000001816 cooling Methods 0.000 claims description 14
- 239000008367 deionised water Substances 0.000 claims description 14
- 229910021641 deionized water Inorganic materials 0.000 claims description 14
- 229910052723 transition metal Inorganic materials 0.000 claims description 13
- -1 transition metal salt Chemical class 0.000 claims description 13
- 239000011259 mixed solution Substances 0.000 claims description 9
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 claims description 8
- 239000002073 nanorod Substances 0.000 claims description 7
- 239000000243 solution Substances 0.000 claims description 7
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 claims description 5
- 229940011182 cobalt acetate Drugs 0.000 claims description 4
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 claims description 4
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims description 4
- 229910001981 cobalt nitrate Inorganic materials 0.000 claims description 4
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 claims description 4
- 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 4
- 239000007864 aqueous solution Substances 0.000 claims description 2
- 239000002245 particle Substances 0.000 abstract description 9
- 230000003197 catalytic effect Effects 0.000 abstract description 7
- 238000006243 chemical reaction Methods 0.000 abstract description 7
- 238000000576 coating method Methods 0.000 abstract description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract 2
- 229910052799 carbon Inorganic materials 0.000 abstract 2
- 239000000779 smoke Substances 0.000 abstract 2
- 230000003647 oxidation Effects 0.000 abstract 1
- 238000007254 oxidation reaction Methods 0.000 abstract 1
- 238000011068 loading method Methods 0.000 description 14
- 239000004071 soot Substances 0.000 description 14
- 239000010963 304 stainless steel Substances 0.000 description 4
- 229910000619 316 stainless steel Inorganic materials 0.000 description 4
- 229910000589 SAE 304 stainless steel Inorganic materials 0.000 description 4
- 238000011156 evaluation Methods 0.000 description 4
- 230000007613 environmental effect Effects 0.000 description 3
- 239000000835 fiber Substances 0.000 description 3
- 238000001000 micrograph Methods 0.000 description 3
- 239000011148 porous material Substances 0.000 description 3
- 238000001878 scanning electron micrograph Methods 0.000 description 3
- 238000009210 therapy by ultrasound Methods 0.000 description 3
- 238000002485 combustion reaction Methods 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000000227 grinding Methods 0.000 description 2
- 230000008929 regeneration Effects 0.000 description 2
- 238000011069 regeneration method Methods 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- 239000000725 suspension Substances 0.000 description 2
- 206010007269 Carcinogenicity Diseases 0.000 description 1
- 229910021281 Co3O4In Inorganic materials 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 238000003915 air pollution Methods 0.000 description 1
- 238000003491 array Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000007670 carcinogenicity Effects 0.000 description 1
- 231100000260 carcinogenicity Toxicity 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 229910052878 cordierite Inorganic materials 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 239000002283 diesel fuel Substances 0.000 description 1
- JSKIRARMQDRGJZ-UHFFFAOYSA-N dimagnesium dioxido-bis[(1-oxido-3-oxo-2,4,6,8,9-pentaoxa-1,3-disila-5,7-dialuminabicyclo[3.3.1]nonan-7-yl)oxy]silane Chemical compound [Mg++].[Mg++].[O-][Si]([O-])(O[Al]1O[Al]2O[Si](=O)O[Si]([O-])(O1)O2)O[Al]1O[Al]2O[Si](=O)O[Si]([O-])(O1)O2 JSKIRARMQDRGJZ-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000002121 nanofiber Substances 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Substances [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000011112 process operation Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000002604 ultrasonography Methods 0.000 description 1
- 229910001868 water Inorganic materials 0.000 description 1
- 229910003145 α-Fe2O3 Inorganic materials 0.000 description 1
Images
Classifications
-
- 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
- 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
-
- B01J35/40—
-
- B01J35/60—
-
- 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
- B01J37/10—Heat treatment in the presence of water, e.g. steam
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F01—MACHINES OR ENGINES IN GENERAL; ENGINE PLANTS IN GENERAL; STEAM ENGINES
- F01N—GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR MACHINES OR ENGINES IN GENERAL; GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR INTERNAL COMBUSTION ENGINES
- F01N3/00—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust
- F01N3/02—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for cooling, or for removing solid constituents of, exhaust
- F01N3/021—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for cooling, or for removing solid constituents of, exhaust by means of filters
- F01N3/033—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for cooling, or for removing solid constituents of, exhaust by means of filters in combination with other devices
- F01N3/035—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for cooling, or for removing solid constituents of, exhaust by means of filters in combination with other devices with catalytic reactors, e.g. catalysed diesel particulate filters
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F23—COMBUSTION APPARATUS; COMBUSTION PROCESSES
- F23G—CREMATION FURNACES; CONSUMING WASTE PRODUCTS BY COMBUSTION
- F23G7/00—Incinerators or other apparatus for consuming industrial waste, e.g. chemicals
- F23G7/06—Incinerators or other apparatus for consuming industrial waste, e.g. chemicals of waste gases or noxious gases, e.g. exhaust gases
- F23G7/07—Incinerators or other apparatus for consuming industrial waste, e.g. chemicals of waste gases or noxious gases, e.g. exhaust gases in which combustion takes place in the presence of catalytic material
Abstract
The invention discloses a manganese-based wire mesh monolithic catalyst for catalytic combustion and a preparation method thereof, and is characterized in that the catalyst is prepared by growing an active component alpha-MnO on the surface of a wire mesh carrier through an in-situ hydrothermal synthesis method2The active component is loaded by 0.5-5% of the mass of the wire mesh carrier, wherein MO and alpha-MnO are2The mol ratio is 1 (0.1-0.5), and MO is transition metal oxide. The invention has simple process and easy implementation, the active component of the catalyst is firmly combined with the carrier and is not easy to crack and fall off, and the active component hasA large number of available reaction sites. Under the loose contact mode, the integral catalyst can reduce the carbon smoke oxidation temperature to be within the exhaust temperature range (below 400 ℃) of a diesel engine, is an effective integral catalyst for eliminating the carbon smoke particles in the tail gas of the diesel engine, solves the problems of low bonding strength, few reaction sites and poor catalytic performance of the catalyst prepared by the existing coating method, and has remarkable economic benefit and social benefit.
Description
Technical Field
The invention belongs to the fields of environmental engineering materials, environmental catalysis and environmental protection, and particularly relates to a manganese-based wire mesh monolithic catalyst for catalytic combustion and a preparation method thereof.
Background
The diesel engine has high fuel efficiency, large torque output and CO2Low discharge and the like, and is widely applied in the transportation industry. However, the soot particles generated by the combustion of diesel oil not only cause serious air pollution, but also have strong carcinogenicity. The national six standards stipulate that the mass emission of the particulate matters in the diesel engine tail gas in China must be lower than 10 mg/kWh. To achieve this, a Diesel Particulate Filter (DPF) must be installed behind the Diesel engine, and the DPF can trap soot particles efficiently. However, the accumulation of soot particulates results in increased pressure drop losses and reduced diesel engine performance, requiring regeneration of the DPF. The catalyst is loaded on the surface of the DPF, so that the residual heat in the tail gas of the diesel engine can be effectively utilized to enable soot particles to burn at a lower temperature. The existing catalyst is loaded on DPF by adopting a coating method, the process operation is complex, and the prepared catalyst has the defects of low bonding strength, few active sites, large pressure drop loss, poor regeneration effect and the like. In addition, in order to enhance the binding ability between the catalyst and the DPF and prevent the catalyst from cracking or falling off, the catalyst particles need to be finely ground, and the structure of the catalyst is damaged by the severe grinding process (C.Agrafiotis et al.J.Mater.Sci.Lett.18(1999) 1421-1424). And the porous powder catalyst with multiple active sites is not suitable for being prepared into an integral catalyst by a coating method, and the porous structure of the catalyst is damaged in the grinding process.
By in-situ hydrothermal growthThe above-mentioned disadvantages of the coating method can be overcome by growing the catalyst active component directly onto the surface of the support. Chinese patent CN109499593A discloses growing ZnO nano-array on cordierite filter surface in situ, then loading K2CO3A method of making a monolithic catalyst. The method focuses on the problem of low bonding strength of the active component and the carrier, but the method does not solve the problem of reduction of reaction sites after loading, and the catalytic performance is still higher about 440 ℃. And the influence of the secondary hydrothermal method on the reaction sites and the catalytic activity of the integral catalyst is not reported.
Disclosure of Invention
The invention aims to provide a manganese-based wire mesh monolithic catalyst for catalytic combustion aiming at the defects of low bonding strength of active components, few reaction sites, low catalytic activity and the like of monolithic catalysts prepared by the prior art, and the invention also aims to provide a preparation method of the catalyst.
The technical scheme of the invention is as follows: a manganese-based wire mesh monolithic catalyst for catalytic combustion is characterized in that the catalyst is prepared by growing an active component alpha-MnO on the surface of a wire mesh carrier through an in-situ hydrothermal synthesis method2The active component is loaded by 0.5-5% of the mass of the wire mesh carrier, wherein MO and alpha-MnO are2The mol ratio is 1 (0.1-0.5), and MO is transition metal oxide.
Preferably, the wire mesh carrier is any one of a 304 stainless wire mesh, a 316 stainless wire mesh or a 201 stainless wire mesh; the mesh number of the wire mesh carrier is 50-500 meshes; the transition metal oxide being Co3O4、Fe2O3Or CuO.
The invention also provides a method for preparing the manganese-based wire mesh monolithic catalyst for catalytic combustion,
the method comprises the following specific steps:
(1) pretreatment of the wire mesh carrier: cleaning the metal wire mesh, and drying for later use;
(2) in-situ hydrothermal synthesis method for growing MO nano array: dissolving transition metal salt, ammonium fluoride and urea in deionized water to prepare a mixed solution; placing the mixture into a wire mesh, transferring the mixture into a high-pressure hydrothermal reaction kettle, and reacting for 2-12 hours at the temperature of 80-140 ℃; after cooling, taking out the wire mesh, cleaning and drying; preserving heat for 1-2 h at 400-700 ℃ to obtain a metal wire mesh with an MO nano array;
(3) in-situ hydrothermal synthesis method for growing alpha-MnO2And (3) nano-rods: immersing the metal wire mesh with the MO nano array in a deionized water solution of potassium permanganate, transferring the metal wire mesh into a high-pressure hydrothermal reaction kettle, and reacting for 3-36 h at 100-180 ℃; after cooling, taking out the wire mesh, cleaning and drying; and preserving the heat for 4-6 hours at 400-700 ℃ to finally obtain the manganese-based wire mesh monolithic catalyst.
Preferably, the transition metal salt in the step (2) is any one of cobalt nitrate, ferric nitrate, cobalt chloride, copper nitrate or cobalt acetate; the concentration of the transition metal salt in the mixed solution is 0.01-0.05 mol/L, the concentration of the ammonium fluoride is 0.02-0.10 mol/L, and the concentration of the urea is 0.03-0.20 mol/L.
Preferably, the mass ratio of the metal wire mesh to the transition metal salt in the step (2) is 1 (0.03-0.15).
Preferably, the concentration of the potassium permanganate aqueous solution in the step (3) is 0.03-0.1 mol/L. Preferably, the mass ratio of the potassium permanganate to the metal wire mesh in the step (3) is (0.04-0.5): 1.
Has the advantages that:
(1) the manganese-based wire mesh monolithic catalyst provided by the invention has rich pore structures and can provide a large number of effective reaction sites; the active components of the catalyst are firmly combined with the metal wire mesh carrier and are not easy to fall off.
(2) The manganese-based wire mesh monolithic catalyst provided by the invention has excellent catalytic activity on soot combustion, and can meet the requirement of eliminating soot particles within the exhaust temperature range (below 400 ℃) of a diesel engine.
(3) Compared with the traditional coating method, the preparation method of the manganese-based wire mesh monolithic catalyst provided by the invention has the advantages of simple operation flow, wide raw material source, low price and the like.
Drawings
FIG. 1 shows grown Co prepared in example 1 of the present invention3O4Scanning electron micrographs of metal screens in nanoarrays.
FIG. 2 shows the grown α -MnO prepared in example 1 of the present invention2/Co3O4Scanning electron micrographs of manganese-based wire mesh monolithic catalysts in nanoarrays.
FIG. 3 shows the grown α -MnO prepared in example 1 of the present invention2/Co3O4Scanning electron microscope images of the manganese-based wire mesh monolithic catalyst of the nano array after 30min ultrasonic treatment.
FIG. 4 shows the grown α -MnO prepared in example 1 of the present invention2/Co3O4A performance curve diagram of the manganese-based wire mesh monolithic catalyst for catalytic combustion of soot particulate under a simulated diesel engine tail gas condition is provided.
Detailed Description
The present invention is illustrated in detail by the following specific examples, which are to be construed as merely illustrative and explanatory of the present invention and not limitative of the scope thereof.
Example 1
(1) Cleaning and drying 3.91g of a 500-mesh 304 stainless steel wire net for later use;
(2) dissolving 0.59g of cobalt nitrate, 0.24g of ammonium fluoride and 0.96g of urea in deionized water to prepare a mixed solution of 0.02mol/L of cobalt nitrate, 0.04mol/L of ammonium fluoride and 0.1mol/L of urea; putting the mixture into a 304 stainless steel wire mesh (the mass ratio of the metal wire mesh to the transition metal salt is 1:0.15), transferring the mixture into a high-pressure hydrothermal reaction kettle, and reacting for 5 hours at 120 ℃; after cooling, taking out the wire mesh, cleaning and drying; keeping the temperature at 500 ℃ for 2h to obtain the product with Co3O4A metal wire mesh of nano-arrays.
FIG. 1 shows the prepared grown Co3O4The scanning electron microscope image of the metal wire mesh with the nano array shows that uniform Co grows on the surface of the metal wire mesh3O4Nanoarrays, the average diameter of the nanofibers was 70nm, and the thickness of the fiber layer was 11 μm. The developed pore structure between the fibers provides more effective reaction sites, which is beneficial to the penetration of soot particles into the fiber layer.
(3) Will grow with Co3O4The metal wire mesh of the nano array is immersed into a solution (0.05mol/L) of 1.95g of potassium permanganate dissolved in deionized water (the mass ratio of potassium permanganate to metal wire mesh is 0.50:1), and transferred into a high-pressure hydrothermal reaction kettle to react for 24 hours at 160 ℃; after cooling, taking out the wire mesh, cleaning and drying; keeping the temperature at 550 ℃ for 5h to finally obtain Co3O4Growth of alpha-MnO on the surface of nano array2Manganese-based wire mesh monolithic catalyst of nanorod and active component alpha-MnO2/Co3O4Is 5 wt.%, Co3O4Loading of 4.23 wt.%, alpha-MnO2Loading was 0.77 wt.% (Co)3O4And alpha-MnO2The molar ratio was 1: 0.5).
FIG. 2 shows growth of alpha-MnO2/Co3O4Scanning electron micrographs of nano-arrayed manganese-based wire mesh monolithic catalysts with a "brush-like" open structure can provide more contact sites for soot to penetrate deep into the catalyst through the pores of the surface. FIG. 3 is the prepared grown alpha-MnO2/Co3O4The scanning electron microscope image of the manganese-based wire mesh monolithic catalyst of the nano array after 30min ultrasonic treatment shows that the brush-shaped active components of the sample after ultrasonic treatment do not fall off, which indicates that the carrier and the active components of the preparation method provided by the invention have higher bonding strength.
(4) Performance evaluation of manganese-based wire mesh monolithic catalyst: 50mg of soot particles are added to 10mL of absolute ethanol and dispersed to a suspension by ultrasound. The suspension is added dropwise to the prepared catalyst surface, wherein the mass ratio of soot particles to catalyst coating is 1:2.5, with a deviation of less than 15%. The soot-added sample was dried in an oven at 110 ℃ for 30 min. The catalytic performance was evaluated on a fixed bed reactor with a gas feed composition of 500ppm NO, 6 vol.% H2O，10vol.％O2The balance being N2The gas flow rate was 100 mL/min. Raising the temperature from 150 ℃ to 700 ℃ at a speed of 6 ℃/min, and detecting CO in the tail gas by using a non-spectroscopic infrared spectrometerxComposition and calculating the temperature value of the soot catalytic combustion.
FIG. 4 shows the growth of alpha-MnO2/Co3O4A performance curve diagram of the manganese-based wire mesh monolithic catalyst for catalytic combustion of soot particulate under a simulated diesel engine tail gas condition is provided. As can be seen from the figure, the prepared catalyst simulates T in the exhaust gas atmosphere of a diesel engine50(temperature corresponding to 50% soot removal) 358 ℃.
Example 2
(1) And cleaning 13.00g of 200-mesh 201 stainless steel wire mesh, and drying for later use.
(2) Dissolving 0.78g of cobalt chloride, 0.09g of ammonium fluoride and 0.22g of urea in deionized water to prepare a mixed solution of 0.05mol/L of cobalt chloride, 0.02mol/L of ammonium fluoride and 0.03mol/L of urea; putting the mixture into a 201 stainless steel wire mesh (the mass ratio of the metal wire mesh to the transition metal salt is 1:0.06), transferring the mixture into a high-pressure hydrothermal reaction kettle, and reacting for 2 hours at 80 ℃; after cooling, taking out the wire mesh, cleaning and drying; keeping the temperature at 400 ℃ for 1h to obtain the product with Co3O4A metal wire mesh of a nano-array;
(3) will grow with Co3O4The metal wire mesh of the nano array is immersed into 0.52g of solution (0.03mol/L) of potassium permanganate dissolved in deionized water (the mass ratio of potassium permanganate to metal wire mesh is 0.04:1), and transferred into a high-pressure hydrothermal reaction kettle to react for 3 hours at 100 ℃; after cooling, taking out the wire mesh, cleaning and drying; keeping the temperature at 400 ℃ for 4h to finally obtain Co3O4Growth of alpha-MnO on the surface of nano array2Manganese-based wire mesh monolithic catalyst of nanorod, in which the active component is alpha-MnO2/Co3O4Loading of 2 wt.%, Co3O4In an amount of 1.93 wt.%, alpha-MnO2Loading was 0.07 wt.% (Co)3O4And alpha-MnO2The molar ratio was 1: 0.1).
(4) Performance evaluation of manganese-based wire mesh monolithic catalyst: test conditions such asAs shown in example 1, T of the prepared catalyst in an atmosphere simulating exhaust gas of a diesel engine was measured50The temperature was 375 ℃.
Example 3
(1) Cleaning 13.70g of a 50-mesh 316 stainless steel wire net, and drying for later use;
(2) dissolving 0.41g of ferric nitrate, 0.63g of ammonium fluoride and 2.04g of urea in deionized water to prepare a mixed solution of 0.01mol/L of ferric nitrate, 0.10mol/L of ammonium fluoride and 0.20mol/L of urea; putting the mixture into a 316 stainless steel wire mesh (the mass ratio of the metal wire mesh to the transition metal salt is 1:0.03), transferring the mixture into a high-pressure hydrothermal reaction kettle, and reacting for 12 hours at 140 ℃; after cooling, taking out the wire mesh, cleaning and drying; keeping the temperature at 700 ℃ for 1h to obtain the Fe growing on2O3A metal wire mesh of a nano-array;
(3) will grow Fe2O3The metal wire mesh of the nano array is immersed into a solution (0.10mol/L) of 2.74g potassium permanganate dissolved in deionized water (the mass ratio of the potassium permanganate to the metal wire mesh is 0.20:1), and is transferred into a high-pressure hydrothermal reaction kettle to react for 36 hours at 180 ℃; after cooling, taking out the wire mesh, cleaning and drying; keeping the temperature at 700 ℃ for 6h to finally obtain Fe2O3Growth of alpha-MnO on the surface of nano array2Manganese-based wire mesh monolithic catalyst of nanorod, in which the active component is alpha-MnO2/Fe2O3Loading of 0.5 wt.%, Fe2O3In an amount of 0.44 wt.%, alpha-MnO2Loading was 0.06 wt.% (Fe)2O3And alpha-MnO2The molar ratio was 1: 0.25).
(4) Performance evaluation of manganese-based wire mesh monolithic catalyst: test conditions were as in example 1, and T of the prepared catalyst in an atmosphere simulating exhaust gas of diesel engine was measured50It was 395 ℃.
Example 4
(1) Cleaning 8.18g of 300-mesh 304 stainless steel wire mesh, and drying for later use;
(2) dissolving 0.90g of copper nitrate, 0.30g of ammonium fluoride and 1.44g of urea in deionized water to prepare a mixed solution of 0.03mol/L of copper nitrate, 0.05mol/L of ammonium fluoride and 0.15mol/L of urea; putting the mixture into a 304 stainless steel wire mesh (the mass ratio of the metal wire mesh to the transition metal salt is 1:0.11), transferring the mixture into a high-pressure hydrothermal reaction kettle, and reacting for 5 hours at 120 ℃; after cooling, taking out the wire mesh, cleaning and drying; preserving the heat for 2 hours at 500 ℃ to obtain a wire mesh on which a CuO nano array grows;
(3) immersing the metal wire mesh on which the CuO nano array grows into a solution (0.08mol/L) of 0.82g of potassium permanganate dissolved in deionized water (the mass ratio of the potassium permanganate to the metal wire mesh is 0.10:1), transferring the metal wire mesh into a high-pressure hydrothermal reaction kettle, and reacting for 24 hours at 160 ℃; after cooling, taking out the wire mesh, cleaning and drying; keeping the temperature at 600 ℃ for 5h to finally obtain the alpha-MnO grown on the surface of the CuO nano array2Manganese-based wire mesh monolithic catalyst of nanorod, in which the active component is alpha-MnO2The loading of CuO was 3.8 wt.%, the loading of CuO was 3.43 wt.%, alpha-MnO2Loading was 0.37 wt.% (CuO vs. alpha-MnO)2The molar ratio was 1: 0.1).
(4) The catalysts described above were tested for catalytic activity: test conditions were as in example 1, and T of the prepared catalyst in an atmosphere simulating exhaust gas of diesel engine was measured50Is 372 ℃.
Example 5
(1) Cleaning 5.72g of a 400-mesh 316 stainless steel wire net, and drying for later use;
(2) dissolving 0.78g of cobalt acetate, 0.26g of ammonium fluoride and 0.84g of urea in deionized water to prepare a mixed solution of 0.03mol/L of cobalt acetate, 0.05mol/L of ammonium fluoride and 0.20mol/L of urea; putting the mixture into a 316 stainless steel wire mesh (the mass ratio of the metal wire mesh to the transition metal salt is 1:0.13), transferring the mixture into a high-pressure hydrothermal reaction kettle, and reacting for 12 hours at 100 ℃; after cooling, taking out the wire mesh, cleaning and drying; keeping the temperature at 500 ℃ for 2h to obtain the product with Co3O4A metal wire mesh of a nano-array;
(3) will grow with Co3O4The metal wire mesh of the nano array is immersed into a solution (0.05mol/L) of 1.43g of potassium permanganate dissolved in deionized water (the mass ratio of potassium permanganate to metal wire mesh is 0.25:1), and transferred into a high-pressure hydrothermal reaction kettle to react for 36 hours at 140 ℃; taking out the wire mesh after cooling, cleaning and drying; keeping the temperature at 550 ℃ for 6h,finally obtaining the product in Co3O4Growth of alpha-MnO on the surface of nano array2Manganese-based wire mesh monolithic catalyst of nanorod, in which the active component is alpha-MnO2/Co3O4Loading of 4.5 wt.%, Co3O4Loading of 4.13 wt.%, alpha-MnO2Loading was 0.37 wt.% (Co)3O4And alpha-MnO2The molar ratio was 1: 0.25).
(4) Performance evaluation of manganese-based wire mesh monolithic catalyst: test conditions were as in example 1, and T of the prepared catalyst in an atmosphere simulating exhaust gas of diesel engine was measured50The temperature was 365 ℃.
Claims (7)
1. A manganese-based wire mesh monolithic catalyst for catalytic combustion is characterized in that the catalyst is prepared by growing an active component alpha-MnO on the surface of a wire mesh carrier through an in-situ hydrothermal synthesis method2The active component is loaded by 0.5-5% of the mass of the wire mesh carrier, wherein MO and alpha-MnO are2The mol ratio is 1 (0.1-0.5), and MO is transition metal oxide.
2. The manganese-based wire mesh monolithic catalyst for catalytic combustion as claimed in claim 1, wherein the wire mesh carrier is any one of 304 stainless wire mesh, 316 stainless wire mesh or 201 stainless wire mesh; the mesh number of the wire mesh carrier is 50-500 meshes; the transition metal oxide being Co3O4、Fe2O3Or CuO.
3. A method for preparing the manganese-based wire mesh monolithic catalyst for catalytic combustion according to claim 1, comprising the following specific steps:
(1) pretreatment of the wire mesh carrier: cleaning the metal wire mesh, and drying for later use;
(2) in-situ hydrothermal synthesis method for growing MO nano array: dissolving transition metal salt, ammonium fluoride and urea in deionized water to prepare a mixed solution; placing the mixture into a wire mesh, transferring the mixture into a high-pressure hydrothermal reaction kettle, and reacting for 2-12 hours at the temperature of 80-140 ℃; after cooling, taking out the wire mesh, cleaning and drying; preserving heat for 1-2 h at 400-700 ℃ to obtain a metal wire mesh with an MO nano array;
(3) in-situ hydrothermal synthesis method for growing alpha-MnO2And (3) nano-rods: immersing the metal wire mesh with the MO nano array in a deionized water solution of potassium permanganate, transferring the metal wire mesh into a high-pressure hydrothermal reaction kettle, and reacting for 3-36 h at 100-180 ℃; after cooling, taking out the wire mesh, cleaning and drying; and preserving the heat for 4-6 hours at 400-700 ℃ to finally obtain the manganese-based wire mesh monolithic catalyst.
4. The method according to claim 3, wherein the transition metal salt in the step (2) is any one of cobalt nitrate, ferric nitrate, cobalt chloride, copper nitrate or cobalt acetate; the concentration of the transition metal salt in the mixed solution is 0.01-0.05 mol/L, the concentration of the ammonium fluoride is 0.02-0.10 mol/L, and the concentration of the urea is 0.03-0.20 mol/L.
5. The method according to claim 3, wherein the mass ratio of the wire mesh to the transition metal salt in the step (2) is 1 (0.03-0.15).
6. The method according to claim 3, wherein the concentration of the aqueous solution of potassium permanganate in step (3) is 0.03 to 0.1 mol/L.
7. The preparation method according to claim 3, characterized in that the mass ratio of potassium permanganate to wire mesh in step (3) is (0.04-0.5): 1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110392710.3A CN113262798A (en) | 2021-04-13 | 2021-04-13 | Manganese-based wire mesh monolithic catalyst for catalytic combustion and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110392710.3A CN113262798A (en) | 2021-04-13 | 2021-04-13 | Manganese-based wire mesh monolithic catalyst for catalytic combustion and preparation method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN113262798A true CN113262798A (en) | 2021-08-17 |
Family
ID=77228750
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202110392710.3A Withdrawn CN113262798A (en) | 2021-04-13 | 2021-04-13 | Manganese-based wire mesh monolithic catalyst for catalytic combustion and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN113262798A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113649008A (en) * | 2021-08-19 | 2021-11-16 | 郑州大学 | High-activity integral catalyst for eliminating soot particles in tail gas of diesel vehicle and preparation method thereof |
| CN114832832A (en) * | 2022-06-06 | 2022-08-02 | 武汉理工大学 | Copper doped alpha-MnO 2 -110 catalyst, preparation method and application thereof |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20140256534A1 (en) * | 2011-09-28 | 2014-09-11 | University Of Connecticut | Metal oxide nanorod arrays on monolithic substrates |
| CN104841450A (en) * | 2015-04-14 | 2015-08-19 | 上海大学 | Preparation method of composite oxide entire denitration catalyst with three-dimensional graded core-shell structure |
| CN106475111A (en) * | 2016-09-21 | 2017-03-08 | 浙江大学 | A kind of Co3O4@MnO2Nucleocapsid structure porous nano column material and preparation method thereof |
| CN109364938A (en) * | 2018-10-10 | 2019-02-22 | 河北科技大学 | A kind of cobalt-manganese catalyst and preparation method thereof eliminated for volatile organic matter oxidation |
| CN110142046A (en) * | 2019-05-26 | 2019-08-20 | 天津大学 | A kind of nickel foam integral catalyzer synthetic method with 3D structure, application |
| CN110586125A (en) * | 2019-09-18 | 2019-12-20 | 天津大学 | High-activity foam copper monolithic catalyst and synthesis method and application thereof |
-
2021
- 2021-04-13 CN CN202110392710.3A patent/CN113262798A/en not_active Withdrawn
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20140256534A1 (en) * | 2011-09-28 | 2014-09-11 | University Of Connecticut | Metal oxide nanorod arrays on monolithic substrates |
| CN104841450A (en) * | 2015-04-14 | 2015-08-19 | 上海大学 | Preparation method of composite oxide entire denitration catalyst with three-dimensional graded core-shell structure |
| CN106475111A (en) * | 2016-09-21 | 2017-03-08 | 浙江大学 | A kind of Co3O4@MnO2Nucleocapsid structure porous nano column material and preparation method thereof |
| CN109364938A (en) * | 2018-10-10 | 2019-02-22 | 河北科技大学 | A kind of cobalt-manganese catalyst and preparation method thereof eliminated for volatile organic matter oxidation |
| CN110142046A (en) * | 2019-05-26 | 2019-08-20 | 天津大学 | A kind of nickel foam integral catalyzer synthetic method with 3D structure, application |
| CN110586125A (en) * | 2019-09-18 | 2019-12-20 | 天津大学 | High-activity foam copper monolithic catalyst and synthesis method and application thereof |
Non-Patent Citations (1)
| Title |
|---|
| GENG LIU ET AL.: "Promoting Diesel Soot Combustion Efficiency over Hierarchical Brushlike alpha-MnO2 and Co3O4 Nanoarrays by Improving Reaction Sites", 《INDUSTRIAL & ENGINEERING CHEMISTRY RESEARCH》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113649008A (en) * | 2021-08-19 | 2021-11-16 | 郑州大学 | High-activity integral catalyst for eliminating soot particles in tail gas of diesel vehicle and preparation method thereof |
| CN114832832A (en) * | 2022-06-06 | 2022-08-02 | 武汉理工大学 | Copper doped alpha-MnO 2 -110 catalyst, preparation method and application thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN113262798A (en) | Manganese-based wire mesh monolithic catalyst for catalytic combustion and preparation method thereof | |
| CN110013849B (en) | Ag-silver-doped modified manganese-based mullite oxidation catalyst and preparation and application thereof | |
| CN102941088B (en) | Catalyst for concurrently removing CO, CH, NOx and PM, and preparation method thereof | |
| CN107837826B (en) | Regeneration process method of inactivated flue gas denitration catalyst | |
| CN107282101B (en) | In-situ load modification method of SAPO-34 molecular sieve catalyst for diesel vehicle tail gas purification | |
| CN105618077B (en) | A kind of preparation method of denitration honeycomb ceramic catalyst and its catalyst of preparation | |
| CN114247448A (en) | Oxidation type catalyst for diesel engine exhaust aftertreatment and manufacturing method thereof | |
| CN113198529A (en) | Metal carrier loaded copper-based SCR catalyst and preparation method thereof | |
| CN110721674A (en) | Manganese-based montmorillonite low-temperature SCR catalyst and preparation method thereof | |
| CN113385188B (en) | Integral cDPF composite material for diesel vehicle and preparation method thereof | |
| CN105903478B (en) | Medium-low temperature SCR catalyst with wider use temperature and preparation method thereof | |
| CN114251158B (en) | Diesel exhaust particulate matter catalytic filter and method for manufacturing same | |
| CN209569054U (en) | The after-treatment system of diesel engine vent gas | |
| CN1139428C (en) | Purifying catalyst for diesel engine exhaust gas and its preparing method | |
| CN106799225A (en) | A kind of potassium support type soot combustion catalyst and its preparation method and application | |
| CN103861612A (en) | Catalyst used for diesel engine tail gas soot collection catalysis | |
| CN101444743B (en) | Catalyst for processing particles in diesel engine emissions, and preparation method thereof | |
| CN109012647A (en) | A kind of diesel engine vent gas soot removing metal composite oxide catalyst and preparation method thereof | |
| CN112473683B (en) | Powder sintering filtering catalytic material based on gradient pore structure and preparation method thereof | |
| CN115178292A (en) | High-sulfur-resistance molecular sieve-based monolithic SCR catalyst and preparation method thereof | |
| CN111379613B (en) | Diesel particulate trap loaded with macroporous perovskite oxide and application thereof | |
| CN111085217A (en) | Three-dimensional porous Mn-Co microspheres grown on cordierite, and preparation and application thereof | |
| JPH01142208A (en) | Filter for collecting diesel particulate | |
| CN114471537B (en) | Preparation method of lanthanum-manganese composite oxide catalyst | |
| CN101773832A (en) | Method for preparing BaFeO3 perovskite catalyst with excellent sulfur resistance for storing nitrogen oxide |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| WW01 | Invention patent application withdrawn after publication | ||
| WW01 | Invention patent application withdrawn after publication |
Application publication date: 20210817 |