CN113828307A - Carbon smoke combustion reaction catalyst and preparation method and application thereof - Google Patents
Carbon smoke combustion reaction catalyst and preparation method and application thereof Download PDFInfo
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- 239000007809 chemical reaction catalyst Substances 0.000 title claims abstract description 70
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- 238000002360 preparation method Methods 0.000 title description 4
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- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 4
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- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium(3+);trinitrate Chemical compound [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 description 1
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- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
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Images
Classifications
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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
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/56—Platinum group metals
- B01J23/63—Platinum group metals with rare earths or actinides
-
- 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
- B01D53/92—Chemical or biological purification of waste gases of engine exhaust gases
- B01D53/94—Chemical or biological purification of waste gases of engine exhaust gases by catalytic processes
-
- 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
- B01J23/10—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of rare earths
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- B01J35/40—
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- B01J35/51—
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- B01J35/613—
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- B01J35/633—
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- B01J35/647—
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- 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
- F01N3/08—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for rendering innocuous
- F01N3/10—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for rendering innocuous by thermal or catalytic conversion of noxious components of exhaust
- F01N3/18—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for rendering innocuous by thermal or catalytic conversion of noxious components of exhaust characterised by methods of operation; Control
- F01N3/20—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for rendering innocuous by thermal or catalytic conversion of noxious components of exhaust characterised by methods of operation; Control specially adapted for catalytic conversion ; Methods of operation or control of catalytic converters
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- 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
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01D2258/01—Engine exhaust gases
Abstract
The invention relates to the technical field of catalysts, and discloses a carbon smoke combustion reaction catalyst. The catalyst comprises a carrier and metallic ruthenium loaded on the carrier, wherein the content of the metallic ruthenium is 0.5-6 mass based on the total mass of the carrierPercent; the carrier is flower-shaped CeO2Nano-microsphere, said flower-like CeO2The average diameter of the nano-microspheres is 1-5 mu m, and the flower-shaped CeO2The average thickness of petal-shaped nanosheet layer of the nanosphere is 10-20nm, and the specific surface area is 40-60m2Per g, average pore volume of 0.1-0.5cm3(iv) g, the average pore diameter is 5-15nm, and the average grain size is 10-15 nm. The carbon smoke combustion reaction catalyst provided by the invention has excellent catalytic performance and stability.
Description
Technical Field
The invention relates to the technical field of catalysts, in particular to a soot combustion reaction catalyst and a preparation method and application thereof.
Background
The diesel vehicle has efficient and durable power source, good economic benefit and CO2The discharge amount is low, and the method is widely used. The carbon smoke particles discharged from the tail gas of the diesel vehicle are the main source of PM2.5 in the atmosphere, which not only causes serious pollution problem to the atmosphere, but also causes harm to the production, life and physical and mental health of people.
Therefore, the reduction of the emission of the motor vehicle exhaust pollutants, especially the purification of the diesel exhaust emission is a great research requirement for serving the blue sky defense war and the atmospheric pollution prevention and control combat, and the development of the research on the aspect has important environmental protection significance.
Catalytic post-treatment technology is the most effective control method at present, and soot catalytic combustion is a deep oxidation reaction which occurs in a three-phase interface. In the process of the catalytic combustion reaction of the soot, the effective contact of the catalyst and reactants is crucial to the reaction performance, and the oxidation-reduction performance of the catalyst is closely related to the catalytic performance.
In past studies, numerous materials have been used to catalyze soot combustion reactions, and many have demonstrated excellent catalytic performance for catalyzing soot combustion, e.g., Pt, Pd in noble metals show excellent catalytic performance for soot oxidation.
However, in the process of burning the soot, the noble metal is easy to sinter and agglomerate, so that the catalytic activity is obviously reduced, and secondly, the noble metal is expensive, so that the wide application of the noble metal is severely limited.
Therefore, it is of great significance to develop a soot combustion reaction catalyst with low cost and high catalytic activity, and to improve the utilization rate of noble metals.
Disclosure of Invention
The invention aims to solve the problem that the catalytic activity of the soot combustion reaction catalyst is reduced due to easy sintering and agglomeration in the prior art.
In order to achieve the above object, a first aspect of the present invention provides a soot combustion reaction catalyst comprising a carrier and metallic ruthenium supported on the carrier, the metallic ruthenium being contained in an amount of 0.5 to 6 mass% based on the total mass of the carrier; the carrier is flower-shaped CeO2Nano-microsphere, said flower-like CeO2The average diameter of the nano-microspheres is 1-5 mu m, and the flower-shaped CeO2The average thickness of petal-shaped nanosheet layer of the nanosphere is 10-20nm, and the specific surface area is 40-60m2Per g, average pore volume of 0.1-0.5cm3(iv) g, the average pore diameter is 5-15nm, and the average grain size is 10-15 nm.
In a second aspect the present invention provides a method of preparing a soot combustion reaction catalyst, the method comprising the steps of:
(1) in the presence of a solvent I, carrying out a first contact reaction on a carrier, a ruthenium source and a polyvinylpyrrolidone aqueous solution to obtain a first mixed solution; wherein the carrier is the flower-shaped CeO2Nano-microsphere, said flower-like CeO2The average diameter of the nano-microspheres is 1-5 mu m, and the flower-shaped CeO2The average thickness of petal-shaped nanosheet layer of the nanosphere is 10-20nm, and the specific surface area is 40-60m2Per g, average pore volume of 0.1-0.5cm3Per g, average pore diameter of 5-15nm, flat crystal grainThe average size is 10-15 nm;
(2) in the presence of a solvent II, carrying out a second contact reaction on the first mixed solution and sodium borohydride, and sequentially carrying out first drying and first roasting on a product obtained after the second contact reaction;
the amount of the ruthenium source is controlled so that the content of the metallic ruthenium in the catalyst is 0.5 to 6 mass% based on the total mass of the support.
In a third aspect, the present invention provides a soot combustion reaction catalyst prepared by the method of the second aspect.
A fourth aspect of the invention provides the use of a soot combustion reaction catalyst as described in the first or third aspect for catalysing a soot combustion reaction.
The invention uses flower-shaped CeO2The nano-microsphere is used as a carrier, and the metal ruthenium is loaded on the carrier to be used as an active component, so that the problems of high-temperature sintering and agglomeration of the noble metal can be solved, the utilization rate of the noble metal can be improved, and the formed soot combustion reaction catalyst has excellent catalytic performance and stability.
Drawings
FIG. 1 shows flower-like CeO in the present invention2Scanning electron microscope image of the nanosphere-1;
FIG. 2 shows flower-like CeO in the present invention2Transmission electron micrographs of nanosphere-1 and the soot combustion catalyst prepared in example 1;
FIG. 3 shows flower-like CeO in the present invention2A transmission electron microscope image corrected by spherical aberration of the nano microsphere-1 and the soot combustion reaction catalyst prepared in example 1;
FIG. 4 is a surface elemental composition analysis chart of the soot combustion reaction catalyst prepared in example 1 of the present invention;
FIG. 5 shows flower-like CeO in the present invention2X-ray diffraction spectra of the nano-microsphere-1 and the soot combustion reaction catalyst prepared in example 1;
FIG. 6 shows flower-like CeO in the present invention2The catalytic activity evaluation chart of the carbon smoke combustion reaction catalyst prepared by the nano microsphere-1 and the embodiment 1 is shown;
FIG. 7 is a graph showing the stability evaluation of the soot combustion reaction catalyst prepared in example 1 of the present invention.
Detailed Description
The endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and such ranges or values should be understood to encompass values close to those ranges or values. For ranges of values, between the endpoints of each of the ranges and the individual points, and between the individual points may be combined with each other to give one or more new ranges of values, and these ranges of values should be considered as specifically disclosed herein.
In the present invention, the flower-like CeO2The nano-microsphere is formed by mutually interpenetrating and stacking petal-shaped nano-sheet layers, is in a standard spherical shape and has a mesoporous structure.
The flower-like CeO2The average diameter of the nano microsphere refers to a plurality of standard spherical flower-shaped CeO2Average value of diameter of the nanospheres.
The flower-like CeO2The average thickness of petal-shaped nanosheet layers of the nano microspheres refers to the spherical flower-shaped CeO2Average thickness value of nanosheet layer of the nanospheres.
The average size of the crystal grains refers to single nanometer CeO2The size of the single crystal grains can be obtained by XRD test and calculation through the Sherrer formula.
In the present invention, unless otherwise specified, the room temperature or room temperature is 25. + -. 2 ℃.
As described above, the first aspect of the present invention provides a soot combustion reaction catalyst comprising a carrier and metallic ruthenium supported on the carrier, the metallic ruthenium being contained in an amount of 0.5 to 6 mass% based on the total mass of the carrier; the carrier is flower-shaped CeO2Nano-microsphere, said flower-like CeO2The average diameter of the nano-microspheres is 1-5 mu m, and the flower-shaped CeO2The average thickness of petal-shaped nanosheet layer of the nanosphere is 10-20nm, and the specific surface area is 40-60m2Per g, average pore volume of 0.1-0.5cm3In g, average pore diameter of5-15nm, and the average grain size is 10-15 nm.
Preferably, the content of the metallic ruthenium is 2 to 6 mass% based on the total mass of the support. The inventors have found that with this embodiment in the preferred case, a soot combustion reaction catalyst having more excellent catalytic performance and stability can be obtained.
Preferably, the flower-like CeO2The average diameter of the nano-microspheres is 1-3 mu m, and the flower-shaped CeO2The average thickness of petal-shaped nanosheet layer of the nanosphere is 15-20nm, and the specific surface area is 49-56m2Per g, average pore volume of 0.1-0.3cm3(iv) g, the average pore diameter is 9-11nm, and the average grain size is 12-14 nm. The inventors found that the soot combustion reaction catalyst obtained in this preferable case has more excellent catalytic performance.
As previously mentioned, a second aspect of the present invention provides a method of preparing a soot combustion reaction catalyst, the method comprising the steps of:
(1) in the presence of a solvent I, carrying out a first contact reaction on a carrier, a ruthenium source and a polyvinylpyrrolidone aqueous solution to obtain a first mixed solution; wherein the carrier is flower-shaped CeO2Nano-microsphere, said flower-like CeO2The average diameter of the nano-microspheres is 1-5 mu m, and the flower-shaped CeO2The average thickness of petal-shaped nanosheet layer of the nanosphere is 10-20nm, and the specific surface area is 40-60m2Per g, average pore volume of 0.1-0.5cm3Per g, the average pore diameter is 5-15nm, and the average grain size is 10-15 nm;
(2) in the presence of a solvent II, carrying out a second contact reaction on the first mixed solution and sodium borohydride, and sequentially carrying out first drying and first roasting on a product obtained after the second contact reaction;
the amount of the ruthenium source is controlled so that the content of the metallic ruthenium in the catalyst is 0.5 to 6 mass% based on the total mass of the support.
Preferably, in the step (1), the method further comprises preparing the flower-shaped CeO by a method comprising the following operations2Nano-microspheres:
(a) in the presence of a first solvent, carrying out contact mixing I on a cerium source, glucose and acrylamide to obtain a mixed solution I;
(b) contacting and mixing the mixed solution I with an alkaline solvent to obtain a mixed solution II;
(c) and heating the mixed solution III, filtering to obtain a solid material, and sequentially drying I and roasting I the solid material.
The invention has no special requirements on the operation method of the filtration, and only needs to obtain solid materials, and exemplarily, the invention adopts a centrifugal mode for filtration.
Preferably, in step (a), the cerium source is cerium nitrate hexahydrate.
Preferably, in step (a), the cerium source, the glucose and the acrylamide are used in a mass ratio of 1: 0.8-1.0: 0.3-0.5.
Preferably, in step (a), the conditions of contacting mixing I include at least: the stirring speed is 200-400rpm, the temperature is 20-40 ℃, and the time is 4-6 h.
Preferably, in step (b), the basic solvent is ammonia.
The amount and concentration of the aqueous ammonia are not particularly limited in the present invention, and the aqueous ammonia is, for example, 25 to 28 wt%.
Preferably, in step (b), the conditions of contacting mixing II include at least: the stirring speed is 200-400rpm, the temperature is 20-40 ℃, and the time is 4-6 h.
Preferably, in step (c), the conditions of the heat treatment include at least: the temperature is 160 ℃ and 180 ℃, and the time is 48-72 h.
Preferably, in step (c), the conditions of drying I comprise at least: the temperature is 60-80 ℃ and the time is 10-12 h.
Preferably, in step (c), the conditions of calcination I include at least: the temperature is 500 ℃ and 600 ℃, the time is 3-6h, and the heating rate is 1-3 ℃/min.
Preferably, in step (1), the ruthenium source is an aqueous solution of ruthenium trichloride. The concentration of the aqueous ruthenium trichloride solution is not particularly required in the present invention, and illustratively, the concentration of the aqueous ruthenium trichloride solution is 8 to 10 g/L.
Preferably, in the step (1), the amount of the ruthenium source is 5 to 10mL and the amount of the polyvinylpyrrolidone aqueous solution is 30 to 35mL, relative to 1g of the support.
The concentration of the polyvinylpyrrolidone aqueous solution is not particularly required in the present invention, and the concentration of the polyvinylpyrrolidone aqueous solution is, for example, 1 to 3 mol/L.
Preferably, in step (1), the conditions of the first contact reaction include at least: the stirring speed is 200-400rpm, the temperature is 20-40 ℃, and the time is 1-5 h.
Preferably, in step (2), the method further comprises: before the second contact reaction, dissolving the sodium borohydride in the solvent II to obtain a sodium borohydride solution, and dropwise adding the sodium borohydride solution into the first mixed solution.
Preferably, in the step (2), the dropping speed of the sodium borohydride solution is 0.3-0.5 mL/min.
Preferably, in the step (2), the molar ratio of the sodium borohydride to the ruthenium source calculated by the ruthenium element is 4-10: 1.
Preferably, in step (2), the conditions of the second contact reaction at least include: the stirring speed is 300-600rpm, the temperature is 20-40 ℃, and the time is 60-180 min.
Preferably, in step (2), the conditions of the first drying include at least: the temperature is 60-80 ℃ and the time is 10-12 h.
Preferably, in the step (2), the conditions of the first firing at least include: the temperature is 500 ℃ and 600 ℃, the time is 3-6h, and the heating rate is 1-3 ℃/min.
The present invention does not require any particular kind of solvent I, solvent II, and first solvent, and only needs to be capable of performing a dissolving function, and exemplarily, the solvent I, the solvent II, and the first solvent are all water.
As previously mentioned, a third aspect of the present invention provides a soot combustion reaction catalyst prepared by the method of the second aspect.
As previously mentioned, a fourth aspect of the invention provides the use of a soot combustion reaction catalyst as described in the first or third aspect for catalysing a soot combustion reaction.
The present invention will be described in detail below by way of examples. In the following examples, various raw materials used unless otherwise specified are commercially available.
Carrier: flower-like CeO2Nanometer microsphere-1 with average diameter of 2 μm and flower-like CeO2The average thickness of the petal-shaped nanosheet layer of the nanosphere-1 is 18nm, and the specific surface area is 56m2Per g, average pore volume 0.21cm3(ii)/g, average pore diameter is 10.8nm, and average grain size is 13.1 nm;
the flower-like CeO2The nano microsphere-1 is prepared by adopting a method comprising the following operations:
(a) dissolving 2.17g of cerous nitrate hexahydrate in 80mL of deionized water at room temperature to obtain a cerous nitrate solution, adding 1.98g of glucose and 1.05g of acrylamide, and stirring at 400rpm for 5 hours to obtain a mixed solution I;
(b) adding 3.2mL of ammonia water into the mixed solution I at room temperature, and stirring at 400rpm for 5 hours to obtain a mixed solution II;
(c) transferring the mixed solution II into a reaction kettle, keeping the temperature at 180 ℃ for 72h, naturally cooling to room temperature, centrifuging to obtain a solid material, respectively washing the solid material for 4 times by using deionized water and absolute ethyl alcohol, placing the washed solid material into a drying oven at 80 ℃ for drying for 12h, roasting the obtained powder sample in the air, wherein the roasting temperature is 500 ℃, the roasting time is 4h, and the heating rate is 2 ℃/min;
carrier: flower-like CeO2Nanosphere-2, with flower-like CeO2The preparation method of the nano microsphere-1 is similar, except that the temperature of the heating treatment is 170 ℃; wherein, the CeO is flower-shaped2The average diameter of the nano microsphere-2 is 4 mu m, and the nano microsphere-2 is flower-shaped CeO2The average thickness of the petal-shaped nanosheet layer of the nanosphere-2 is 10nm, and the specific surface area is 60m2In g, average pore volume of 0.18cm3(ii)/g, average pore diameter is 10.5nm, and average grain size is 12.7 nm;
cerium oxide: from Annaiji corporation;
a cerium source: cerous nitrate hexahydrate, available from Shanghai Allantin Biotechnology Ltd;
glucose: from Annaiji corporation;
acrylamide: from Annaiji corporation;
ammonia water: the concentration is 25 wt%;
ruthenium source: ruthenium trichloride, available from beijing waweritaceae chemical company;
polyvinylpyrrolidone: the weight average molecular weight is 30000, and is available from Shanghai Aladdin Biotechnology Ltd;
sodium borohydride: purchased from Shanghai Aladdin Biotechnology Ltd;
in the following examples, the contents of ruthenium metal and the carrier in the catalyst were measured by inductively coupled plasma emission spectroscopy (ICP-OES);
in the following examples, the concentrations of the aqueous solutions of ruthenium trichloride and polyvinylpyrrolidone were each 10g/L and 1.212mol/L, respectively.
Example 1
The present embodiment provides a method for preparing a soot combustion reaction catalyst, comprising the steps of:
(1) 0.5g of flower-like CeO was added at room temperature2Dispersing the nano microspheres-1 in 500mL of deionized water, adding 4.104mL of ruthenium trichloride aqueous solution, then adding 16.32mL of polyvinylpyrrolidone solution, and stirring at 300rpm for 2h to obtain a first mixed solution;
(2) dissolving 0.02g of sodium borohydride in 30mL of deionized water to obtain a sodium borohydride solution, slowly dropwise adding the sodium borohydride solution into the first mixed solution at a dropwise adding speed of 0.5mL/min at room temperature, wherein the stirring speed is 400rpm until all the sodium borohydride solution is completely dropwise added, continuously stirring for 30min, filtering to obtain a solid precipitate, drying the solid precipitate in a 60 ℃ drying box for 12h, roasting the obtained powder sample in air at a roasting temperature of 500 ℃ for 4h at a heating rate of 2 ℃/min to obtain a carbon smoke combustion reaction catalyst S1;
in the soot combustion reaction catalyst S1, in the form of flower-like CeO2The total mass of the nanoparticle carrier was taken as a reference, and the content of ruthenium metal was 4 mass%.
Example 2
The present embodiment provides a method for preparing a soot combustion reaction catalyst, comprising the steps of:
(1) 0.5g of flower-like CeO was added at room temperature2Dispersing the nano microspheres-1 in 400mL of deionized water, adding 6.156mL of ruthenium trichloride aqueous solution, then adding 25.48mL of polyvinylpyrrolidone solution, and stirring at 300rpm for 2h to obtain a first mixed solution;
(2) dissolving 0.04g of sodium borohydride in 30mL of deionized water to obtain a sodium borohydride solution, slowly dropwise adding the sodium borohydride solution into the first mixed solution at a dropwise adding speed of 0.3mL/min at room temperature, stirring at 400rpm until all the sodium borohydride solution is completely dropwise added, continuously stirring for 30min, filtering to obtain a solid precipitate, drying the solid precipitate in a drying box at 80 ℃ for 10h, roasting the obtained powder sample in air at a roasting temperature of 600 ℃, a roasting time of 3h and a heating rate of 3 ℃/min to obtain the carbon smoke combustion reaction catalyst S2.
In the soot combustion reaction catalyst S2, in the form of flower-like CeO2The total mass of the nanoparticle carrier was taken as a reference, and the content of ruthenium metal was 6 mass%.
Example 3
The present embodiment provides a method for preparing a soot combustion reaction catalyst, comprising the steps of:
(1) 0.5g of flower-like CeO was added at room temperature2Dispersing the nano microsphere-1 in 400mL of deionized water, adding 2.052mL of ruthenium trichloride aqueous solution, then adding 8.372mL of polyvinylpyrrolidone solution, and stirring at 300rpm for 2 hours to obtain a first mixed solution;
(2) dissolving 0.03g of sodium borohydride in 30mL of deionized water to obtain a sodium borohydride solution, slowly dropwise adding the sodium borohydride solution into the first mixed solution at a dropwise adding speed of 0.4mL/min at room temperature, wherein the stirring speed is 400rpm until all the sodium borohydride solution is completely dropwise added, continuously stirring for 30min, filtering to obtain a solid precipitate, drying the solid precipitate in a 70 ℃ drying box for 12h, roasting the obtained powder sample in air at a roasting temperature of 550 ℃, a roasting time of 5h and a heating rate of 2 ℃/min to obtain the carbon smoke combustion reaction catalyst S3.
In the soot combustion reaction catalyst S3, in the form of flower-like CeO2The total mass of the nano microsphere carrier is taken as a reference, and the content of the metal ruthenium is 2 mass percent.
Example 4
This example prepares a soot combustion reaction catalyst in a similar manner to example 1, except that, in step (1), equal mass of flower-like CeO is used2Nano microsphere-2 substituted flower-shaped CeO2Nano microsphere-1.
The soot combustion reaction catalyst S4 was obtained.
In the soot combustion reaction catalyst S4, in the form of flower-like CeO2The total mass of the nanoparticle carrier was taken as a reference, and the content of ruthenium metal was 4 mass%.
Example 5
This example prepares a soot combustion reaction catalyst in a similar manner to example 1, except that in step (1), 0.513mL of an aqueous solution of ruthenium trichloride was used.
The soot combustion reaction catalyst S5 was obtained.
In the soot combustion reaction catalyst S5, in the form of flower-like CeO2The total mass of the nano microsphere carrier is taken as a reference, and the content of the metal ruthenium is 1 mass percent.
Comparative example 1
This comparative example A soot combustion catalyst was prepared in a similar manner to example 1, except that in step (1), 7.182mL of an aqueous solution of ruthenium trichloride was used.
The soot combustion reaction catalyst DS1 was obtained.
In the soot combustion reaction catalyst DS1, in the form of flower-shaped CeO2The total mass of the nanoparticle carrier was taken as a reference, and the content of ruthenium metal was 7 mass%.
Comparative example 2
This comparative example A soot combustion reaction catalyst was prepared in a similar manner to example 1, except that in step (1), flower-like CeO was replaced with equal mass of cerium oxide2Nano microsphere-1.
The soot combustion reaction catalyst DS2 was obtained.
In the soot combustion reaction catalyst DS2, the content of metallic ruthenium was 4 mass% based on the total mass of the ceria carrier.
Comparative example 3
This comparative example a soot combustion reaction catalyst was prepared in a similar manner to example 1, except that in step (1), an equal mass of chloroplatinic acid solution was used in place of the aqueous ruthenium trichloride solution.
The soot combustion reaction catalyst DS3 was obtained.
In the soot combustion reaction catalyst DS3, in the form of flower-shaped CeO2The total mass of the nano microsphere carrier is taken as a reference, and the content of the metal platinum is 4 mass percent.
Test example 1
The soot combustion reaction catalysts prepared in the examples and the comparative examples are applied to catalyzing the combustion of soot particles, and flower-shaped CeO is adopted2The activity of the catalyst is evaluated by using a fixed bed microreactor-gas chromatography detection system by using the nano microsphere-1 as a control group, and the ignition temperature (T) of the soot particles is calculated10) Temperature (T) at which the conversion reaches 50%50) Temperature (T) at which the conversion reaches 90%90) And CO2The specific results are shown in Table 1.
The specific method comprises the following steps: weighing the above flower-shaped CeO2Mixing nanometer microsphere-1 or soot combustion reaction catalyst 0.1g and soot particles 0.01g with spoon to simulate real conditions, loading the obtained mixture into quartz tube reactor, and introducing reaction gas (its component is 5 vol.)% of O22000ppm NO, the balance argon), the total flow rate is 50mL/min, the temperature is heated to 650 ℃ from room temperature, the heating rate is 2 ℃/min, sampling is carried out at intervals of 5min, and the corresponding CO and CO at the temperature point are recorded2And (4) concentration.
Wherein, T10、T50、T90The calculation method comprises the following steps: CO and CO produced by the combustion of soot2Integration of concentration, CO2The temperature points corresponding to the values of 10%, 50% and 90% of the sum of the areas of CO are T10、T50And T90；
CO2Selectivity (S)CO2 m) The calculation formula of (2) is as follows: (export CO)2Concentration/outlet CO of2And total concentration of CO) × 100%.
TABLE 1
| Example numbering | T10/℃ | T50/℃ | T90/℃ | SCO2 m/％ |
| Example 1 | 282 | 333 | 387 | 99.3 |
| Example 2 | 285 | 342 | 396 | 99.3 |
| Example 3 | 283 | 338 | 389 | 99.4 |
| Example 4 | 286 | 343 | 405 | 99.5 |
| Example 5 | 310 | 348 | 390 | 99.1 |
| Comparative example 1 | 300 | 368 | 410 | 99.1 |
| Comparative example 2 | 303 | 376 | 420 | 98.3 |
| Comparative example 3 | 300 | 378 | 421 | 99.3 |
| Flower-like CeO2Nano microsphere-1 | 302 | 375 | 420 | 95.9 |
As can be seen from the results in Table 1, the present invention is represented by flower-like CeO2The nano-microsphere is used as a carrier, and the metal ruthenium is loaded on the carrier to be used as an active component, so that the catalytic performance and selectivity of the catalyst for catalyzing the combustion of the soot can be remarkably improved.
Test example 2
The stability of the soot combustion catalyst prepared in example 1 was evaluated, and the activity of the catalyst was evaluated using a fixed bed microreactor-gas chromatography detection system, and the specific results are shown in table 2.
The specific method comprises the following steps: weighing 0.1g of soot combustion reaction catalyst and 0.01g of soot particles, mixing the two with a spoon to simulate real conditions, placing the obtained mixture into a quartz tube reactor, and introducing reaction gas (the component is 5 vol% of O)22000ppm NO, the balance being argon), the total flow rate being 50mL/min, heating from room temperature to 650 ℃, the rate of temperature rise being 2 ℃/min;
collecting a catalyst sample in the quartz tube reactor, and mixing the catalyst sample with fresh carbon smoke particles according to a mass ratio of 10:1 mixing both sufficiently to simulate real conditions, the remaining operations being the same as the previous ones, circulating 5 times, calculating T according to the same method as in test example 110、T50、T90And SCO2 m。
TABLE 2
| Example numbering | T10/℃ | T50/℃ | T90/℃ | SCO2 m/％ |
| Cycle 1 | 282 | 333 | 387 | 99.3 |
| 2 nd cycle | 283 | 335 | 386 | 99.4 |
| |
282 | 334 | 387 | 99.3 |
| Cycle 4 | 284 | 335 | 386 | 99.4 |
| Cycle 5 | 285 | 335 | 385 | 99.3 |
As can be seen from Table 2, the soot combustion reaction catalyst provided by the invention has excellent stability, and after 5-cycle activity tests, the selectivity of the catalyst can reach 99.5% of the initial state.
The present invention exemplarily provides flower-shaped CeO2Scanning Electron microscopy of nanosphere-1, flower-like CeO2Transmission electron microscopy images of nanosphere-1 and soot combustion catalyst prepared in example 1, flower-like CeO2Spherical aberration correction transmission electron microscope images of the nanoparticle-1 and the soot combustion reaction catalyst prepared in example 1, surface elemental composition analysis image of the soot combustion reaction catalyst prepared in example 1, flower-like CeO2X-ray diffraction patterns of the soot combustion reaction catalyst prepared from the nanosphere-1 and the catalyst prepared in example 1, flower-shaped CeO2The evaluation graphs of the catalytic activity of the nano microsphere-1 and the soot combustion reaction catalyst prepared in example 1 and the stability of the soot combustion reaction catalyst prepared in example 1 are shown in fig. 1-7, respectively.
FIG. 1 flower-like CeO according to the present invention2Scanning electron microscope image of nanosphere-1.
As can be seen from FIG. 1, the flower-like CeO provided by the present invention2The nano-microspheres are spherical and are formed by mutually interpenetrating and stacking petal-shaped nano-sheet layers.
FIG. 2 shows flower-like CeO2Transmission electron microscopy images of nanosphere-1 and the soot combustion catalyst prepared in example 1, wherein (2a) is flower-like CeO2The transmission electron microscope picture of the nano microsphere-1, and the picture (2b) is the transmission electron microscope picture of the soot combustion reaction catalyst prepared in example 1.
As can be seen from FIG. 2, flower-like CeO2Nano microsphere-1 and charcoal smoke combustionThe reaction catalyst is in a flower-shaped nano microsphere structure, and ruthenium-loaded metal does not damage flower-shaped CeO2The microsphere structure of the nano microsphere.
FIG. 3 is flower-like CeO2The spherical aberration of the soot combustion reaction catalyst prepared from the nanosphere-1 and the catalyst prepared in example 1 was corrected by transmission electron microscopy, wherein the image (3a) is flower-like CeO2The spherical aberration of the nanosphere-1 was corrected by transmission electron microscopy, and the graph (3b) was corrected by transmission electron microscopy of the soot combustion reaction catalyst prepared in example 1.
As can be seen from FIG. 3, flower-like CeO2The nanometer microsphere-1 and the carbon smoke combustion reaction catalyst both keep the flower-shaped nanometer microsphere shape, the average inner diameter is 1.4 mu m, and the average outer diameter is 2.0 mu m.
FIG. 4 is a surface elemental composition analysis chart of the soot combustion reaction catalyst prepared in example 1, wherein chart (4a) is flower-like CeO2Scanning electron micrograph of nanosphere-1, wherein FIG (4b) shows flower-like CeO2The distribution of Ru, Ce and O on the surface of the nanosphere-1 is shown in FIG. 4c, which is flower-shaped CeO with background2The distribution of Ru element on the surface of the nanosphere-1 is shown in FIG. 4d2The distribution of Ru element on the surface of the nanosphere-1 is shown in FIG. 4e, which is the flower-like CeO without background2The distribution of Ce on the surface of the nanosphere-1 is shown in FIG. 4f, which is flower-shaped CeO without background2The distribution of O element contained on the surface of the nano microsphere-1.
As can be seen from FIG. 4, flower-like CeO2The metal ruthenium loaded on the nano-microspheres is uniformly dispersed in the flower-shaped CeO2The surface of the nanospheres.
FIG. 5 is flower-like CeO2X-ray diffraction spectra of the nano-microsphere-1 and the soot combustion reaction catalyst prepared in example 1.
As can be seen from FIG. 5, flower-like CeO2The nanometer microsphere and the carbon smoke combustion reaction catalyst have the same diffraction characteristic peak, and the characteristic peak of metallic ruthenium does not appear in the figure, which shows that the loaded metallic ruthenium has smaller size and high dispersion.
FIG. 6 is flower-like CeO2Nanosphere-1 andthe evaluation chart of the catalytic activity of the soot combustion reaction catalyst prepared in example 1.
As can be seen from fig. 6, the catalyst provided by the present invention has more excellent catalytic performance and selectivity.
FIG. 7 is a graph showing the stability evaluation of the soot combustion reaction catalyst prepared in example 1.
As can be seen from FIG. 7, the soot combustion reaction catalyst provided by the present invention catalyzes the T of soot combustion activity after 5 cycles of activity test10、T50And T90The selectivity of the catalyst is basically kept unchanged, the variation range is within 5 ℃, the initial state of the selectivity of the catalyst is basically kept, and 99.5 percent of the selectivity of the catalyst can be achieved after five times of circulation, which shows that the catalyst for the soot combustion reaction has excellent stability.
The preferred embodiments of the present invention have been described above in detail, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, many simple modifications can be made to the technical solution of the invention, including combinations of various technical features in any other suitable way, and these simple modifications and combinations should also be regarded as the disclosure of the invention, and all fall within the scope of the invention.
Claims (10)
1. A soot combustion reaction catalyst is characterized by comprising a carrier and metallic ruthenium loaded on the carrier, wherein the content of the metallic ruthenium is 0.5-6 mass percent based on the total mass of the carrier; the carrier is flower-shaped CeO2Nano-microsphere, said flower-like CeO2The average diameter of the nano-microspheres is 1-5 mu m, and the flower-shaped CeO2The average thickness of petal-shaped nanosheet layer of the nanosphere is 10-20nm, and the specific surface area is 40-60m2Per g, average pore volume of 0.1-0.5cm3(iv) g, the average pore diameter is 5-15nm, and the average grain size is 10-15 nm.
2. The catalyst according to claim 1, wherein the content of the metallic ruthenium is 2 to 6 mass% based on the total mass of the support.
3. The catalyst according to claim 1, wherein the flower-like CeO2The average diameter of the nano-microspheres is 1-3 mu m, and the flower-shaped CeO2The average thickness of petal-shaped nanosheet layer of the nanosphere is 15-20nm, and the specific surface area is 49-56m2Per g, average pore volume of 0.1-0.3cm3(iv) g, the average pore diameter is 9-11nm, and the average grain size is 12-14 nm.
4. A method of preparing a soot combustion reaction catalyst, comprising the steps of:
(1) in the presence of a solvent I, carrying out a first contact reaction on a carrier, a ruthenium source and a polyvinylpyrrolidone aqueous solution to obtain a first mixed solution; wherein the carrier is flower-shaped CeO2Nano-microsphere, said flower-like CeO2The average diameter of the nano-microspheres is 1-5 mu m, and the flower-shaped CeO2The average thickness of petal-shaped nanosheet layer of the nanosphere is 10-20nm, and the specific surface area is 40-60m2Per g, average pore volume of 0.1-0.5cm3Per g, the average pore diameter is 5-15nm, and the average grain size is 10-15 nm;
(2) in the presence of a solvent II, carrying out a second contact reaction on the first mixed solution and sodium borohydride, and sequentially carrying out first drying and first roasting on a product obtained after the second contact reaction;
the amount of the ruthenium source is controlled so that the content of the metallic ruthenium in the catalyst is 0.5 to 6 mass% based on the total mass of the support.
5. The process according to claim 4, wherein, in the step (1), the ruthenium source is an aqueous solution of ruthenium trichloride.
6. The process according to claim 4 or 5, wherein in step (1), the conditions of the first contact reaction comprise at least: the stirring speed is 200-400rpm, the temperature is 20-40 ℃, and the time is 1-5 h.
7. The process according to any one of claims 4 to 6, wherein, in the step (2), the molar ratio of the sodium borohydride to the ruthenium source in terms of ruthenium element is 4-10: 1.
8. The method according to any one of claims 4 to 7, wherein in step (2), the conditions of the second contact reaction comprise at least: the stirring speed is 300-600rpm, the temperature is 20-40 ℃, and the time is 60-180 min;
preferably, in step (2), the conditions of the first drying include at least: the temperature is 60-80 ℃, and the time is 10-12 h;
preferably, in the step (2), the conditions of the first firing at least include: the temperature is 500 ℃ and 600 ℃, the time is 3-6h, and the heating rate is 1-3 ℃/min.
9. A soot combustion reaction catalyst prepared by the method of any one of claims 4 to 8.
10. Use of a soot combustion reaction catalyst as claimed in any one of claims 1-3, 9 for catalysing a soot combustion reaction.
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104815635A (en) * | 2015-04-30 | 2015-08-05 | 中国石油大学(北京) | Catalyst for combustion of carbon smoke particles, preparation method and application thereof |
| CN108940384A (en) * | 2018-08-24 | 2018-12-07 | 中国石油大学(北京) | A kind of catalyst and its preparation method and application of soot combustion reaction |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104815635A (en) * | 2015-04-30 | 2015-08-05 | 中国石油大学(北京) | Catalyst for combustion of carbon smoke particles, preparation method and application thereof |
| CN108940384A (en) * | 2018-08-24 | 2018-12-07 | 中国石油大学(北京) | A kind of catalyst and its preparation method and application of soot combustion reaction |
Non-Patent Citations (2)
| Title |
|---|
| S. AOUAD等: ""Study of the Ru/Ce System in the Oxidation of Carbon Black and Volatile Organic Compounds"", 《KINETICS AND CATALYSIS》 * |
| 王伟: ""电催化剂的表界面调控及其用于碱性析氢/析氧/氧还原反应的研究"", 《南京大学博士学位论文》 * |
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