CN114733514A - Monolithic catalyst containing cryptomelane type potassium-manganese composite oxides with different morphologies as well as preparation method and application of monolithic catalyst - Google Patents
Monolithic catalyst containing cryptomelane type potassium-manganese composite oxides with different morphologies as well as preparation method and application of monolithic catalyst Download PDFInfo
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/32—Manganese, technetium or rhenium
- B01J23/34—Manganese
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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
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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
- B01J37/10—Heat treatment in the presence of water, e.g. steam
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F23—COMBUSTION APPARATUS; COMBUSTION PROCESSES
- F23R—GENERATING COMBUSTION PRODUCTS OF HIGH PRESSURE OR HIGH VELOCITY, e.g. GAS-TURBINE COMBUSTION CHAMBERS
- F23R3/00—Continuous combustion chambers using liquid or gaseous fuel
- F23R3/40—Continuous combustion chambers using liquid or gaseous fuel characterised by the use of catalytic means
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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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Abstract
The invention discloses a preparation method of an integral catalyst containing cryptomelane type potassium-manganese composite oxides with different shapes, which comprises the following steps: in a potassium permanganate aqueous solution, growing cryptomelane type potassium manganese composite oxide on DPF in situ by adopting a hydrothermal method to obtain the monolithic catalyst, and recording the monolithic catalyst as K-OMS-2/DPF, wherein in potassium permanganate aqueous solutions with different concentrations and pH values, catalysts with different shapes can be obtained; according to the method, potassium permanganate and glucose are used as raw materials, cryptomelane type potassium-manganese composite oxides with different shapes are grown in situ on the DPF by a hydrothermal method, and the activity of the catalyst can be improved by regulating and controlling different shapes to enhance effective contact with soot particles; the preparation method provided by the invention has the advantages of simple process, strong controllability, strong practicability, no need of special equipment and harsh conditions and the like.
Description
Technical Field
The invention relates to the technical field of catalyst preparation and application, in particular to an integral catalyst containing cryptomelane type potassium-manganese composite oxides with different shapes, and a preparation method and application thereof.
Background
Compared with a gasoline engine, a diesel engine has the characteristics of high thermal efficiency, good economy, low CO emission, durability, stable performance and the like, so that the application of the diesel engine to automobiles is widely concerned. However, diesel vehicles emit many pollutants due to operating conditions such as: particulate Matter (PM), NOx, HC, CO, polycyclic aromatic hydrocarbons, and a small amount of metal ions. Among them, Particulate Matter (PM) is the most serious pollutant (mainly composed of dry carbon, soluble organic matter (SOF) and a small amount of sulfuric acid and sulfate) and is the most difficult to eliminate, and it is a great hazard to the atmospheric environment and human health, and has attracted people's attention.
Currently, the focus on diesel soot particulate removal is on developing various techniques to control the emissions of these pollutants, and to enforce more stringent soot emission regulations to drive the development of a variety of strategies that can be divided into three categories: the cleaning of diesel oil, the improvement of an engine and an exhaust emission post-treatment technology. The diesel oil cleaning technology and the engine improving technology are internal purification, and the tail gas post-treatment technology belongs to external purification. The diesel vehicle catalytic post-treatment technology is a necessary means for efficiently purifying the PM2.5 discharged by the tail gas of a motor vehicle, and the research of the technology faces the challenge of designing and preparing a high-performance catalyst coated on the surface of an exhaust post-treatment filter and efficiently coating a high-activity catalyst on the surface of the filter. In the aspect of catalysts, manganese-based oxides, particularly cryptomelane type potassium manganese composite oxides, have the characteristics of rich resources, low raw material cost, environmental friendliness and the like, and show excellent performance on catalytic combustion of carbon smoke. Therefore, the cryptomelane type potassium-manganese composite oxide has strong application potential when being coated on the surface of the tail gas post-treatment filter. In the aspect of catalyst coating, the conventional industrial coating method mainly comprises the steps of preparing a powder catalyst, mixing the powder catalyst with silica sol, alumina sol, an adhesive and the like to form a coating slurry, coating the slurry on the wall of a Diesel Particulate Filter (DPF) by using a special coating machine, and drying and calcining to obtain the DPF (CDPF) containing the catalyst. CDPF prepared by coating means, wherein the DPF carrier only acts as an indirect support, the active coating is the actual carrier for the catalytically active components, which may be referred to as "second carrier" of the DPF carrier catalyst. This type of coating often has long-standing problems, such as uncontrolled exposure of the active sites of the catalyst, low catalyst utilization, poor adhesion of the coating, and complex processes and equipment.
It is therefore an urgent problem to provide a method to achieve in situ growth of active components on DPF carriers.
Disclosure of Invention
In view of the above, the invention discloses an integral catalyst containing cryptomelane type potassium-manganese composite oxides with different morphologies, and a preparation method and application thereof.
The technical scheme provided by the invention is specifically that a preparation method of an integral catalyst containing cryptomelane type potassium-manganese composite oxides with different shapes comprises the following steps: in a potassium permanganate aqueous solution, cryptomelane type potassium manganese composite oxide is grown on DPF in situ by adopting a hydrothermal method to obtain the monolithic catalyst which is marked as K-OMS-2/DPF, wherein in potassium permanganate aqueous solutions with different concentrations and pH values, catalysts with different morphologies can be obtained and marked as K-OMS-2/DPF-mx-pHyM represents the content of potassium permanganate, and pH represents acidity or alkalinity.
Preferably, the method specifically comprises the following steps:
1) pre-treating the DPF;
2) putting the pretreated DPF into a glucose solution for full immersion, and taking out; drying to remove excessive liquid; carbonizing the dried sample to obtain a DPF @ C material;
3) respectively putting the DPF @ C material and potassium permanganate aqueous solutions with different concentrations and pH values into a reaction kettle, sealing the reaction kettle, and transferring the reaction kettle to a constant temperature condition of 100-160 ℃ for reaction for 6-18 h; after the reaction is finished, cooling to room temperature, taking out the reacted material, washing and removing redundant liquid on the material; and (3) placing the sample at a constant temperature of 60-100 ℃ for drying for 8-10h, and finally calcining at 350-750 ℃ for 3-5h to obtain the monolithic catalyst K-OMS-2/DPF.
Preferably, the method for pretreating a DPF in step 1) sequentially comprises: cutting, calcining and soaking in dilute nitric acid; wherein the calcination temperature is 550-1000 ℃, and the time is 2-8 h; the concentration of the dilute nitric acid is 0.1-2.4 mol/L.
Preferably, the glucose concentration in the step 2) is 0.2-1.2mol/L, and nitrogen is introduced for carbonization when in carbonization, wherein the carbonization temperature is 300-550 ℃ in a nitrogen atmosphere, and the nitrogen flow rate is 80-100 mL/min.
Preferably, the mass range of the potassium permanganate in the step 3) is 0-2.5 g; the pH value of the potassium permanganate aqueous solution is 1-13; the heating rate during calcination is 1-5 ℃/min.
Preferably, the catalysts of different morphologies are in particular: the manganese-based oxides synthesized under the condition of different potassium permanganate concentrations are all K2-xMn8O16When the pH value of the potassium permanganate solution is 1, the synthesized manganese-based oxide is Mn2O3And K2-xMn8O16When the pH value is 3-13, the synthesized manganese-based oxides are all K2-xMn8O16。
Preferably, the temperature is programmed to 350-750 ℃ at a temperature rising rate of 1-5 ℃/min during the calcination in the step 3).
In a second aspect, the invention provides an integral catalyst containing cryptomelane type potassium manganese composite oxides with different shapes, the catalyst is prepared by the method, the catalyst consists of DPF carriers and cryptomelane type potassium manganese composite oxides with different shapes, and the catalyst has rod-shaped, net-shaped and sheet-shaped shapes under different potassium permanganate concentrations and acid-base conditions.
Preferably, the cryptomelane-type potassium-manganese composite oxide having a rod shape has a diameter of 10nm to 100nm and a length of 200nm to 3 μm.
In a third aspect, the application of the monolithic catalyst containing cryptomelane type potassium-manganese composite oxides with different shapes can be used in catalytic combustion reaction of carbon smoke particles.
The invention provides a preparation method of an integral catalyst containing cryptomelane type potassium-manganese composite oxides with different shapes. The catalytic combustion of the soot particles is a gas (reaction gas) -solid (soot particles) -solid (catalyst) three-phase deep oxidation reaction. The contact between the catalyst and the soot particles is a very critical factor. Compared with the method of coating the powder catalyst with the same weight, the method of the invention can expose more contact area of the soot and the catalyst by constructing some special-shaped nano structures on the DPF in situ, thereby further improving the combustion efficiency of the soot particles. Meanwhile, the consumption of the catalyst can be greatly reduced under the condition of the coating with the same thickness by an in-situ growth mode, so that the cost is saved.
According to the method, potassium permanganate and glucose are used as raw materials, cryptomelane type potassium-manganese composite oxides with different morphologies are grown in situ on the DPF by a hydrothermal method, and the activity of the catalyst can be improved by regulating different morphologies to enhance effective contact with soot particles. The preparation method has the advantages of simple process, strong controllability, strong practicability, no need of special equipment and harsh conditions and the like.
It is to be understood that both the foregoing general description and the following detailed description are exemplary and explanatory only and are not restrictive of the disclosure.
Drawings
The accompanying drawings, which are incorporated in and constitute a part of this specification, illustrate embodiments consistent with the invention and together with the description, serve to explain the principles of the invention.
In order to more clearly illustrate the embodiments or technical solutions in the prior art of the present invention, the drawings used in the description of the embodiments or prior art will be briefly described below, and it is obvious for those skilled in the art that other drawings can be obtained based on these drawings without creative efforts.
FIG. 1 is a scanning electron micrograph of a DPF carrier provided in example 1 of the disclosure;
FIG. 2 is a scanning electron micrograph of a DPF @ C material provided in example 1 of the present disclosure;
FIG. 3 is a K-OMS-2/DPF-m according to example 1 of the present disclosurex-pH7Scanning electron micrographs of the materials;
FIG. 4 shows K-OMS-2/DPF-m provided in example 1 of the present disclosurex-pH7XRD pattern of the material;
FIG. 5 shows K-OMS-2/DPF-m according to the disclosure of the invention7-pHy SEM images of the material.
Detailed Description
Reference will now be made in detail to the exemplary embodiments, examples of which are illustrated in the accompanying drawings. When the following description refers to the accompanying drawings, like numbers in different drawings represent the same or similar elements unless otherwise indicated. The implementations described in the following exemplary examples do not represent all implementations consistent with the present invention. Rather, they are merely examples of systems consistent with certain aspects of the invention, as detailed in the appended claims.
Aiming at solving the problems of uncontrollable exposure of active sites of the diesel soot particulate catalyst, low utilization rate of the catalyst, poor adhesion of a coating, complex process and equipment and the like in the prior art. The embodiment provides a preparation method of an integral catalyst containing cryptomelane type potassium-manganese composite oxides with different shapes, which comprises the following steps: in a potassium permanganate aqueous solution, cryptomelane type potassium manganese composite oxide is grown on DPF in situ by adopting a hydrothermal method to obtain the monolithic catalyst which is recorded as K-OMS-2/DPF, wherein in potassium permanganate aqueous solutions with different concentrations and pH values, different shapes and appearances can be obtainedCatalyst (D) denoted as K-OMS-2/DPF-mx-pHyM represents the content of potassium permanganate and pH represents acidity or alkalinity.
The method specifically comprises the following steps:
1) pre-treating the DPF;
the method of pre-treating a DPF comprises, in order: cutting, calcining and soaking in dilute nitric acid; wherein the calcination temperature is 550-1000 ℃, and the time is 2-8 h; the concentration of the dilute nitric acid is 0.1-2.4 mol/L.
When the method is specifically implemented, the DPF can be cut into small cubes with uniform size, and edge burrs are polished to be flat and smooth. And then placing the small cubes into a muffle furnace for temperature programming and controlled roasting, cooling to room temperature, taking out the small cubes from the muffle furnace, and soaking the small cubes in a dilute nitric acid solution for 12-48 h.
Washing the DPF small cube soaked by the dilute nitric acid by using distilled water until the washing liquid is neutral;
finally, the residual liquid was blown off with an ear-washing ball, dried overnight in an oven and stored in a storage box.
The impurities on the inner surface and the outer surface of the carrier can be removed conveniently after the treatment in the steps, and the in-situ growth of the cryptomelane type potassium-manganese composite oxide on the surface and in the pore canal can be facilitated.
2) Putting the pretreated DPF into a glucose solution for full immersion, and taking out; drying to remove excessive liquid; carbonizing the dried sample to obtain the DPF @ C material;
wherein, the concentration of the glucose in the step 2) is 0.2-1.2mol/L, nitrogen is needed to be introduced for carbonization during carbonization, wherein the carbonization temperature is 300-550 ℃ in the nitrogen atmosphere, and the flow rate of the nitrogen is 80-100 mL/min.
In the specific operation, the following steps can be adopted: firstly, a certain amount of dextrose monohydrate is weighed, dissolved in deionized water and fully stirred to form a uniform dextrose solution. And (3) putting the pretreated DPF microcubes into the glucose solution, fully soaking, taking out, drying redundant liquid by using an ear washing ball, and putting the pretreated DPF microcubes into an oven at 80-120 ℃ for drying overnight. Finally, the dried sample was placed in a tube furnace and N was passed through2And carrying out carbonization operation to obtain the DPF @ C material.
The preparation steps have simple process and low cost, have no pollution to the environment and meet the requirement of green chemistry; and 2) carbonizing the DPF adsorbed with glucose, forming a carbon film with uniform coverage on the DPF carrier through carbonization, ensuring that glucose solution is uniformly distributed in rich pore channels of the DPF because a carbon source is glucose solution, and forming a uniform carbon film on the inner surface and the outer surface of the whole DPF carrier after carbonization, wherein the carbon film is the key of subsequent K-OMS-2 loading on the inner surface and the outer surface of the DPF.
3) Respectively putting the DPF @ C material and potassium permanganate aqueous solutions with different concentrations and pH values into a reaction kettle, sealing the reaction kettle, and transferring the reaction kettle to a constant temperature of 100 ℃ and 160 ℃ for reaction for 6-18 h; after the reaction is finished, cooling to room temperature, taking out the reacted material, washing and removing redundant liquid on the material; and (3) placing the sample at a constant temperature of 60-100 ℃ for drying for 8-10h, and finally calcining at 350-750 ℃ for 3-5h to obtain the monolithic catalyst K-OMS-2/DPF.
The specific operation method of the step 3) comprises the following steps: firstly, weighing potassium permanganate with different amounts, dissolving the potassium permanganate in deionized water with different pH values to form a homogeneous solution, transferring the homogeneous solution to a hydrothermal reaction kettle, and enabling the pH value of the solution to pass through HNO3And the amount of KOH was controlled. And then, putting the DPF @ C material into a reaction kettle, sealing the reaction kettle, and transferring the reaction kettle to an oven 100 and keeping the temperature at 160 ℃ for 6-18 h. After the reaction is finished, cooling to room temperature, taking out the reacted catalyst, washing with a large amount of deionized water, and drying the redundant liquid by using an ear washing ball. The sample is placed in an oven at 60-100 ℃ for drying for 8-10h, and finally calcined at 350-750 ℃ for 3-5 h.
The mass range of the potassium permanganate in the step 3) is 0-2.5 g; the pH value of the potassium permanganate aqueous solution is 1-13; the heating rate during calcination is 1-5 ℃/min.
The catalysts with different morphologies are specifically as follows: the manganese-based oxides synthesized under the condition of different potassium permanganate concentrations are all K2-xMn8O16When the pH value of the potassium permanganate solution is 1, the synthesized manganese-based oxide is Mn2O3And K2-xMn8O16When the pH value is 3-13, the synthesized manganese-based oxides are allK2-xMn8O16。
In the step 3), the temperature is programmed to 350-750 ℃ at a temperature rising rate of 1-5 ℃/min.
The preparation method has simple preparation process and realizes large-scale production; the key point of the invention is the regulation and control of the concentration and the pH value of the potassium permanganate solution in the step 3), wherein the concentration of the potassium permanganate solution can determine the reaction degree of potassium permanganate and a carbon film on a DPF carrier and the length-diameter ratio of a K-OMS-2 nanorod; the change of the pH value has great influence on the appearance and the crystal form of the K-OMS-2, the appearance of the manganese-based oxide is changed into a rod-shaped structure from a layered structure along with the increase of the pH value, then the manganese-based oxide is changed into a spherical and rod-shaped mixed structure, and the crystal form is changed from Mn2O3And K2-xMn8O16Is gradually changed into a single K2-xMn8O16(K-OMS-2) crystal structure;
the embodiment also provides an integral catalyst containing cryptomelane type potassium manganese composite oxides with different shapes, the catalyst is prepared by the method, the catalyst is composed of DPF carriers and cryptomelane type potassium manganese composite oxides with different shapes, and the shapes of the catalyst under different potassium permanganate concentrations and acid-base conditions comprise a rod shape, a net shape and a sheet shape.
The diameter of the cryptomelane-type potassium-manganese composite oxide with a rod shape is 10nm-100nm, and the length is 200nm-3 mu m.
The catalyst can be used in catalytic combustion reaction of carbon smoke particles, and all the catalysts can completely remove the carbon smoke particles below 450 ℃.
The invention will now be further illustrated with reference to specific examples, which are not intended to limit the scope of the invention.
Example 1
Pre-treating DPF carriers
Firstly, cutting the DPF into small cubes with the length multiplied by the width multiplied by the height multiplied by 1cm, polishing edge burrs by using sand paper to enable the small cubes to be flat and smooth, then putting the small cubes into a muffle furnace, raising the temperature by program, controlling the roasting, wherein the roasting temperature is 550-1000 ℃, and the roasting time is 2-8 h. Cooling to room temperature, taking out from the muffle furnace, and soaking in 0.1-2.4mol/L dilute nitric acid solution for 12-48 h. And (4) washing the DPF small cubes soaked in the dilute nitric acid by using distilled water until the washing liquid is neutral. Finally, the residual liquid is blown off by an ear washing ball, and the ear washing ball is put into an oven at 80-120 ℃ for drying overnight and is stored in a storage box.
Preparation of DPF @ C Material
First, 0.2-4.5g of dextrose monohydrate is weighed and dissolved in 20-60mL of deionized water and stirred well to form a homogeneous glucose solution. And (3) putting the pretreated DPF microcubes into the glucose solution, taking out after full immersion, drying redundant liquid by using an aurilave, and putting the DPF microcubes into an oven at 80-120 ℃ for drying overnight. Finally, the dried sample was placed in a tube furnace and N was passed through2Carbonizing at the temperature of 300 ℃ and 550 ℃ and operating at the nitrogen flow rate of 80-100mL/min to obtain the DPF @ C material.
Preparation of K-OMS-2/DPF-mx-pH7Material
0-2.5g of potassium permanganate is weighed according to the stoichiometric ratio and placed in a 250mL beaker, 80-120mL of deionized water is added, and the mixture is stirred for 0.5h under magnetic stirring to obtain a uniform potassium permanganate solution. The solution was transferred to a 150mL hydrothermal reaction kettle and the DPF @ C material was placed in solution upright. It is worth noting that before the DPF @ C material is put in, a cushion should be put in first, so that the material is always in a suspended state in the hydrothermal reaction process. Then, the reaction kettle is sealed and transferred to an oven 100 and the constant temperature of 160 ℃ for reaction for 6 to 18 hours. After the reaction is finished, cooling to room temperature, taking out the reacted DPF catalyst, washing with a large amount of deionized water, and blowing the excessive liquid by using an aurilave. The sample is placed in a drying oven at 60-100 ℃ for drying for 8-10h, and finally calcined at 350-750 ℃ for 3-5h to obtain K-OMS-2/DPF-mx-pH7A catalyst. FIG. 3 shows K-OMS-2/DPF-mx-pH7Scanning electron microscope photograph of the material, and it can be seen from FIG. 3 that K-OMS-2/DPF-m is prepared under different potassium permanganate content conditionsx-pH7The catalyst forms uniform and dense nanorod structures on the surface of the DPF and in the pore channel. With the increase of the content of potassium permanganate, the diameter of the nano rod is gradually increasedIncreasing, while the length of the nanorods decreases gradually. The diameter of the nano rod is in the range of 10nm-100nm, and the length is in the range of 200nm-3 μm. FIG. 4 shows the preparation of K-OMS-2/DPF-m under different potassium permanganate content conditionsx-pH7XRD patterns of catalyst and pure carrier DPF, and K-OMS-2/DPF-m prepared under different potassium permanganate content conditions can be seen from the XRD patternsx-pH7The catalysts all have obvious cryptomelane K2- xMn8O16Characteristic diffraction peaks of the material. Table 1 shows the preparation of K-OMS-2/DPF-m under different potassium permanganate content conditionsx-pH7The catalyst has good activity to the combustion of soot particles.
TABLE 1 preparation of K-OMS-2/DPF-m under different potassium permanganate content conditionsx-pH7Performance of catalyst for catalytic combustion of soot particles
Example 2
K-OMS-2/DPF-m7-PHyMethod for producing materials
Weighing 0-2.5g of potassium permanganate according to the stoichiometric ratio, placing the potassium permanganate in a 250mL beaker, adding 80-120mL of deionized water with different pH values, and stirring for 0.5h under magnetic stirring to obtain a uniform solution. The pH of the solution (pH 1,3,5,9,11,13) was measured by HNO3And the amount of KOH is regulated. The solution was transferred to a 150mL hydrothermal reaction kettle and the DPF @ C material was placed upright in the solution using the same principle as in embodiment 1. Then, the reaction kettle is sealed and transferred to an oven 100 and the constant temperature of 160 ℃ for reaction for 6 to 18 hours. After the reaction is finished, cooling to room temperature, taking out the reacted DPF catalyst, washing with a large amount of deionized water, and blowing the excessive liquid by using an aurilave. The sample is placed in a drying oven at 60-100 ℃ for drying for 8-10h, and then is calcined in a muffle furnace at 350-750 ℃ for 3-5h, wherein the heating rate is 5 ℃/min. FIG. 5 shows the preparation of K-OMS-2/DPF-m under different pH conditions7-pHyThe scanning electron micrograph of the catalyst shows from FIG. 5 that under the strong acidic condition, the catalyst is in a net structure, and is uniform and dense along with the weakening of acidityShort rod-like structures occur. Under weakly acidic conditions, the short rod-like structure grows longer. However, the morphology change of the catalyst is clearly opposite under alkaline conditions. Under weakly alkaline conditions, the catalyst takes on a long rod structure, with an alkaline short rod structure. Whereas under strongly alkaline conditions a partly lamellar structure occurs. K-OMS-2/DPF-m prepared under different pH value conditions7-pHyThe catalysts are verified to have obvious cryptomelane type potassium-manganese composite oxide characteristic diffraction peaks. Table 2 shows the preparation of K-OMS-2/DPF-m at different pH values7-pHyThe combustion performance of the catalyst on soot particles can be seen, and the prepared catalyst has good activity.
TABLE 2 preparation of K-OMS-2/DPF-m at different pH values7-pHyPerformance of catalyst for catalytic combustion of soot particles
Example 3
Method for evaluating catalyst activity: a gas chromatography detection system is utilized, and a catalyst adopts a fixed bed mode;
the method comprises the following specific steps: firstly, weighing the charcoal smoke according to the weight ratio of the active components to the charcoal smoke of 10:1, adding 4-10ml of absolute ethyl alcohol, and carrying out ultrasonic oscillation for 10-20min at 60-100Hz, so that the charcoal smoke can be uniformly dispersed. The prepared K-OMS-2/DPF-m4-pHy catalyst was then placed in a well-soaked and excess liquid was blown dry with an ear-washing bulb. Finally, the sample is placed in an oven at 40-90 ℃ to be dried for 6-10 h. K-OMS-2/DPF-m4-pHy mixed with soot was coated with quartz wool and charged into a 36mm quartz reaction tube. Controlling the gas flow to be 50mL/min, the volume content of NO in the gas to be 2000ppm, and O2The volume content of (A) is 10%, and the balance is Ar; the heating rate is controlled to be about 2 ℃/min.
Evaluation method: the oxidation capability of the catalyst is strongWeakly expressed as the combustion temperature of the soot particles, wherein the ignition temperature (T10), the temperature corresponding to the maximum combustion rate (T50) and the burnout temperature (T90) of the soot particles respectively represent the temperature points corresponding to 10%, 50% and 90% of the soot combustion, and are calculated by subjecting CO generated by the combustion of carbon black in the temperature programmed oxidation reaction to2Integration of the curve with CO, CO2The temperature points corresponding to the values of 10%, 50%, 90% of the sum of the integrated areas of CO are T10, T50, and T90. Wherein SCO2 mIndicates the CO corresponding to the catalyst at the time of maximum soot burning rate2And (4) selectivity. The results of catalytic combustion of soot particles on pure DPF support are shown in Table 3, which shows that the combustion temperature of pure soot is higher in the absence of catalyst, indicating that the K-OMS-2/DPF-m prepared by the present invention is7-pHyThe catalyst has high catalytic activity for catalytic combustion of soot particles.
TABLE 3 catalytic Combustion Activity of pure soot particles
Other embodiments of the invention will be apparent to those skilled in the art from consideration of the specification and practice of the invention disclosed herein. This application is intended to cover any variations, uses, or adaptations of the invention following, in general, the principles of the invention and including such departures from the present disclosure as come within known or customary practice within the art to which the invention pertains. It is intended that the specification and examples be considered as exemplary only, with a true scope and spirit of the invention being indicated by the following claims.
It will be understood that the invention is not limited to the precise arrangements described above and shown in the drawings and that various modifications and changes may be made without departing from the scope thereof. The scope of the invention is limited only by the appended claims.
Claims (10)
1. Cryptomelane type potassium-manganese composite material containing different morphologiesA method for preparing an oxide monolith catalyst, comprising: in a potassium permanganate aqueous solution, cryptomelane type potassium manganese composite oxide is grown on DPF in situ by adopting a hydrothermal method to obtain the monolithic catalyst which is marked as K-OMS-2/DPF, wherein in potassium permanganate aqueous solutions with different concentrations and pH values, catalysts with different morphologies can be obtained and marked as K-OMS-2/DPF-mx-pHyM represents the content of potassium permanganate, and pH represents acidity or alkalinity.
2. The preparation method of the monolithic catalyst containing cryptomelane type potassium-manganese composite oxides with different morphologies as claimed in claim 1, which is characterized by comprising the following steps:
1) pre-treating the DPF;
2) putting the pretreated DPF into a glucose solution for full immersion, and taking out; drying to remove excessive liquid; carbonizing the dried sample to obtain the DPF @ C material;
3) respectively putting the DPF @ C material and potassium permanganate aqueous solutions with different concentrations and pH values into a reaction kettle, sealing the reaction kettle, and transferring the reaction kettle to a constant temperature of 100 ℃ and 160 ℃ for reaction for 6-18 h; after the reaction is finished, cooling to room temperature, taking out the reacted material, washing and removing redundant liquid on the material; and (3) placing the sample at a constant temperature of 60-100 ℃ for drying for 8-10h, and finally calcining at 350-750 ℃ for 3-5h to obtain the monolithic catalyst K-OMS-2/DPF.
3. The preparation method of the monolithic catalyst containing cryptomelane type potassium-manganese composite oxides with different morphologies as claimed in claim 2, wherein the method for pretreating the DPF in the step 1) sequentially comprises the following steps: cutting, calcining and soaking in dilute nitric acid; wherein the calcination temperature is 550-1000 ℃, and the time is 2-8 h; the concentration of the dilute nitric acid is 0.1-2.4 mol/L.
4. The preparation method of the monolithic catalyst containing cryptomelane-type potassium-manganese composite oxides with different morphologies as claimed in claim 2, wherein the glucose concentration in the step 2) is 0.2-1.2mol/L, nitrogen is required to be introduced for carbonization during carbonization, wherein the carbonization temperature is 300-550 ℃ and the nitrogen flow rate is 80-100mL/min in the nitrogen atmosphere.
5. The preparation method of the monolithic catalyst containing cryptomelane type potassium-manganese composite oxides with different morphologies as claimed in claim 2, wherein the mass range of the potassium permanganate in the step 3) is 0-2.5 g; the pH value of the potassium permanganate aqueous solution is 1-13; the heating rate during calcination is 1-5 ℃/min.
6. The preparation method of the monolithic catalyst containing cryptomelane type potassium-manganese composite oxides with different morphologies according to claim 5, wherein the catalyst with different morphologies is specifically: the manganese-based oxides synthesized under the condition of different potassium permanganate concentrations are all K2-xMn8O16When the pH value of the potassium permanganate solution is 1, the synthesized manganese-based oxide is Mn2O3And K2- xMn8O16When the pH value is 3-13, the synthesized manganese-based oxides are all K2-xMn8O16。
7. The method for preparing the monolithic catalyst containing the cryptomelane type potassium-manganese composite oxides with different morphologies as claimed in claim 2, wherein the temperature is programmed to 350-750 ℃ at a temperature rise rate of 1-5 ℃/min during the calcination in the step 3).
8. The monolithic catalyst containing cryptomelane type potassium-manganese composite oxides with different shapes is characterized by being prepared by the method of claims 1-7, the catalyst consists of DPF carriers and cryptomelane type potassium-manganese composite oxides with different shapes, and the catalyst has shapes including rods, nets and sheets under the conditions of different potassium permanganate concentrations and acid-base conditions.
9. The monolithic catalyst containing cryptomelane-type potassium-manganese composite oxides with different morphologies as claimed in claim 8, wherein the rod-shaped cryptomelane-type potassium-manganese composite oxide has a diameter of 10nm to 100nm and a length of 200nm to 3 μm.
10. The application of the monolithic catalyst containing cryptomelane type potassium-manganese composite oxides with different morphologies is characterized in that the catalyst can be used in catalytic combustion reaction of soot particles.
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