CN113385188A - Integral cDPF composite material for diesel vehicle and preparation method thereof - Google Patents
Integral cDPF composite material for diesel vehicle and preparation method thereof Download PDFInfo
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- CN113385188A CN113385188A CN202110940493.7A CN202110940493A CN113385188A CN 113385188 A CN113385188 A CN 113385188A CN 202110940493 A CN202110940493 A CN 202110940493A CN 113385188 A CN113385188 A CN 113385188A
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- cordierite
- cdpf
- composite material
- whisker
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- 239000002131 composite material Substances 0.000 title claims abstract description 31
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- 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 claims abstract description 31
- 229910052878 cordierite Inorganic materials 0.000 claims abstract description 26
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims abstract description 24
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims abstract description 16
- 229910001981 cobalt nitrate Inorganic materials 0.000 claims abstract description 16
- FYDKNKUEBJQCCN-UHFFFAOYSA-N lanthanum(3+);trinitrate Chemical compound [La+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O FYDKNKUEBJQCCN-UHFFFAOYSA-N 0.000 claims abstract description 16
- 229940071125 manganese acetate Drugs 0.000 claims abstract description 16
- UOGMEBQRZBEZQT-UHFFFAOYSA-L manganese(2+);diacetate Chemical compound [Mn+2].CC([O-])=O.CC([O-])=O UOGMEBQRZBEZQT-UHFFFAOYSA-L 0.000 claims abstract description 16
- 239000011259 mixed solution Substances 0.000 claims abstract description 12
- 238000001035 drying Methods 0.000 claims abstract description 8
- 238000002156 mixing Methods 0.000 claims abstract description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000013078 crystal Substances 0.000 claims abstract description 5
- 239000008367 deionised water Substances 0.000 claims abstract description 5
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 5
- 238000000034 method Methods 0.000 claims description 13
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical class [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 claims description 8
- 238000010438 heat treatment Methods 0.000 claims description 8
- 239000000243 solution Substances 0.000 claims description 7
- 239000000126 substance Substances 0.000 claims description 7
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 5
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 5
- 238000012986 modification Methods 0.000 claims description 5
- 230000004048 modification Effects 0.000 claims description 5
- 229910052938 sodium sulfate Inorganic materials 0.000 claims description 5
- 235000011152 sodium sulphate Nutrition 0.000 claims description 5
- 238000003756 stirring Methods 0.000 claims description 4
- AMVQGJHFDJVOOB-UHFFFAOYSA-H aluminium sulfate octadecahydrate Chemical compound O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.[Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O AMVQGJHFDJVOOB-UHFFFAOYSA-H 0.000 claims description 3
- 238000000227 grinding Methods 0.000 claims description 3
- 239000003054 catalyst Substances 0.000 abstract description 12
- 230000008929 regeneration Effects 0.000 abstract description 11
- 238000011069 regeneration method Methods 0.000 abstract description 11
- 238000001914 filtration Methods 0.000 abstract description 5
- KZHJGOXRZJKJNY-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Si]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O KZHJGOXRZJKJNY-UHFFFAOYSA-N 0.000 abstract description 3
- 238000011068 loading method Methods 0.000 abstract description 3
- 229910052863 mullite Inorganic materials 0.000 abstract description 3
- 229910002254 LaCoO3 Inorganic materials 0.000 abstract description 2
- 239000000758 substrate Substances 0.000 abstract description 2
- 238000002791 soaking Methods 0.000 abstract 1
- 239000004071 soot Substances 0.000 description 10
- 239000002245 particle Substances 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 8
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 6
- 239000007789 gas Substances 0.000 description 6
- 229910052760 oxygen Inorganic materials 0.000 description 6
- 239000001301 oxygen Substances 0.000 description 6
- 230000003197 catalytic effect Effects 0.000 description 5
- 239000011572 manganese Substances 0.000 description 4
- 239000000919 ceramic Substances 0.000 description 3
- 238000013461 design Methods 0.000 description 3
- 239000013618 particulate matter Substances 0.000 description 3
- 238000000746 purification Methods 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 229910002451 CoOx Inorganic materials 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 238000002485 combustion reaction Methods 0.000 description 2
- 239000000779 smoke Substances 0.000 description 2
- 230000010718 Oxidation Activity Effects 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 210000004081 cilia Anatomy 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 229910052593 corundum Inorganic materials 0.000 description 1
- 235000013399 edible fruits Nutrition 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 239000004570 mortar (masonry) Substances 0.000 description 1
- 239000011664 nicotinic acid Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 230000007847 structural defect Effects 0.000 description 1
- 238000012876 topography Methods 0.000 description 1
- 239000011882 ultra-fine particle Substances 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
- 229910001845 yogo sapphire Inorganic materials 0.000 description 1
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/889—Manganese, technetium or rhenium
- B01J23/8892—Manganese
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/92—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
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- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/14—Silica and magnesia
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Abstract
The invention provides an integral cDPF composite material for a diesel vehicle and a preparation method thereof, wherein the integral cDPF composite material comprises the following steps: preparing cordierite modified by the crystal whisker; mixing lanthanum nitrate, cobalt nitrate, manganese acetate, deionized water and citric acid to prepare a mixed solution; and (4) soaking cordierite into the mixed solution, taking out, drying, and roasting in a muffle furnace to obtain the product. The composite material of the invention uses cordierite modified by mullite whisker surface as a substrate, has higher specific surface area, can load more catalysts, greatly improves the filtering efficiency of DPF, can realize the passive regeneration of DPF by loading perovskite LaCoO3 catalyst on the whisker surface, and the prepared monolithic cDPF composite material has high-efficiency filtering performance and passive regeneration performance.
Description
Technical Field
The invention belongs to the technical field of diesel vehicle tail gas treatment, and particularly relates to an integral cDPF composite material for a diesel vehicle and a preparation method thereof.
Background
Diesel Particulate Filters (DPF) have a high Particulate matter purification efficiency and are recognized as the most effective way to treat soot particles in Diesel engines. The DPF usually adopts the wall-flow design, and such design can make tail gas get into adjacent outlet port passageway after passing porous ceramic's wall from open-ended one end, and the particulate matter in the tail gas can be detained on the porous ceramic wall at this moment, has realized the entrapment of particulate matter in the tail gas. Cordierite-based honeycomb ceramics are excellent DPF materials with a chemical composition of: 2 MgO: 5SiO2：2Al2O3And has high mechanical strength, low thermal expansion coefficient and good high-temperature structural stability. However, cordierite has a relatively low specific surface area (0.7 m)2/g) results in a reduction in the amount of its surface-coated catalytically active component, thereby impairing the catalytic activity of the monolithic cDPF.
The coating ɤ -Al is commonly used in industry2O3To increase the specific surface area of cordierite matrix, ɤ -Al2O3The capture efficiency of the ultrafine particles is very limited, so the cordierite carrier is structurally modified and synthesized on the surface thereof to prepare IThe reticular whisker structure with large specific surface area and high trapping amount is characterized in that the bionic design concept of animal skin cilia is adopted, the surface microstructure of a cordierite carrier is optimized, the specific surface area of the cordierite carrier is improved, and the trapping and purifying efficiency of the DPF on carbon smoke particles is improved. Meanwhile, with the prolonged trapping time of the DPF on the soot particles, the soot particles are accumulated on the surface of the DPF, which can cause the back pressure of the DPF to increase, and the normal operation of the engine is affected. In order to solve this problem, the DPF needs to be subjected to regeneration purification treatment. At present, two methods of active regeneration and passive regeneration are generally adopted to remove soot particles trapped by the DPF to achieve regeneration of the filter, and the active regeneration is to use an active heating method to enable the exhaust temperature or the temperature of the DPF to reach about 550-650 ℃ of soot combustion when the soot particle accumulation reaches a certain degree; and passive regeneration is to load a catalytic coating on the DPF to form an integral cDPF catalyst, so that the combustion temperature of soot particles in the DPF is reduced. The efficient reaction activity of the catalyst is an important link for ensuring the motor vehicle exhaust emission to reach the standard, so how to improve the purification capacity of the DPF catalyst and the stable surface loading of the DPF catalyst are important research points and breakthrough points in the future.
Disclosure of Invention
In view of this, the present invention is directed to an integrated cDPF composite material for a diesel vehicle and a preparation method thereof, so as to increase the loading amount of a catalyst, improve the filtering performance, and realize the passive regeneration of a DPF.
In order to achieve the purpose, the technical scheme of the invention is realized as follows:
a preparation method of an integral cDPF composite material for a diesel vehicle comprises the following steps:
(1) preparing cordierite modified by the crystal whisker;
(2) mixing lanthanum nitrate, cobalt nitrate, manganese acetate and deionized water, stirring to form a solution, and mixing the solution and citric acid to prepare a mixed solution;
(3) immersing the cordierite modified by the crystal whisker into the mixed solution, taking out the cordierite after a period of time, and drying to obtain a sample;
(4) and (3) putting the sample into a muffle furnace for roasting to obtain the integrated cDPF composite material.
Preferably, the step (1) is embodied as follows:
roasting aluminum sulfate octadecahydrate to obtain dehydrated aluminum sulfate, grinding and uniformly mixing diatomite, aluminum sulfate and sodium sulfate, pouring the mixture onto cordierite in a crucible to completely cover the cordierite, and placing the crucible into a muffle furnace to roast to obtain the whisker modified cordierite.
Preferably, the ratio of the amounts of the substances of kieselguhr, aluminum sulfate and sodium sulfate is 1:3: 40.
Preferably, the crucible is roasted in a muffle furnace at 900-1100 ℃ for 2-4h, such as 900 ℃ for 4h, 950 ℃ for 3.5h, 1000 ℃ for 3h, 1050 ℃ for 2.5h, and 1100 ℃ for 2 h; preferably, the temperature is 995-.
Preferably, the amount ratio of lanthanum nitrate, cobalt nitrate and manganese acetate in the step (2) is 1:0.6-0.9:0.1-0.4, and may be, for example, 1:0.6:0.4, 1:0.65:0.35, 1:0.7:0.3, 1:0.75:0.25, 1:0.8:0.2, 1:0.85:0.15, 1:0.9:0.1, etc.; preferably, the mass ratio of lanthanum nitrate, cobalt nitrate and manganese acetate is 1:0.9:0.1, 1:0.8:0.2, 1:0.7:0.3 or 1:0.6: 0.4; further preferably, the amount ratio of the lanthanum nitrate, the cobalt nitrate and the manganese acetate is 1:0.9: 0.1.
Preferably, the amount of the substance of citric acid added in step (2) is equal to the sum of the amounts of the substances of lanthanum nitrate, cobalt nitrate and manganese acetate.
Preferably, step (3) is embodied as follows:
and immersing the cordierite subjected to whisker modification into the mixed solution, vacuumizing in a vacuum drier, standing for a period of time, heating in a water bath for a period of time, taking out, and drying in an oven to obtain a sample.
Preferably, the standing time is 0.5-2h, such as 0.5h, 0.6h, 0.8h, 1.0h, 1.2h, 1.4h, 1.6h, 1.8h, 2.0h, etc., the heating time is 2-4h, such as 2h, 2.2h, 2.4h, 2.6h, 2.8h, 3.0h, 3.2h, 3.4h, 3.6h, 3.8h, 4.0h, etc., the drying temperature is 90-120 deg.C, such as 90 deg.C, 95 deg.C, 100 deg.C, 105 deg.C, 110 deg.C, 115 deg.C, 120 deg.C, etc.; preferably, the standing time is 1h, the heating time is 3h, and the drying temperature is 95-105 ℃.
Preferably, the step (4) is embodied as follows:
the sample is put into a muffle furnace and heated to 395 ℃ and 405 ℃ at the speed of 3-5 ℃/min and kept for 2h, for example, the sample can be heated to 395 ℃ at the speed of 3 ℃/min, heated to 400 ℃ at the speed of 4 ℃/min, heated to 405 ℃ at the speed of 5 ℃ and the like, and then heated to 645 ℃ and 655 ℃ and kept for 6h, for example, 645 ℃, 647 ℃, 650 ℃, 653 ℃, 655 ℃ and the like, so as to obtain the monolithic cDPF composite material.
An integrated cDPF composite for diesel vehicles, prepared by any of the above-described methods of preparation.
Compared with the prior art, the integral cDPF composite material for the diesel vehicle and the preparation method thereof have the following advantages:
(1) the monolithic cDPF composite material disclosed by the invention uses cordierite subjected to mullite whisker surface modification as a substrate, has a higher specific surface area, can be loaded with more catalysts, and greatly improves the filtering efficiency of the DPF;
(2) the monolithic cDPF composite material is prepared by impregnating mullite whisker surface modified cordierite, and perovskite LaCoO is loaded on the surface of the whisker3The catalyst can realize the passive regeneration of the DPF, and the prepared integral cDPF composite material has high-efficiency filtering performance and passive regeneration performance.
Drawings
The accompanying drawings, which are incorporated in and constitute a part of this specification, illustrate an embodiment of the invention and, together with the description, serve to explain the invention and not to limit the invention. In the drawings:
FIG. 1 is a schematic SEM microtopography of a monolithic cDPF composite according to an embodiment of the invention;
FIG. 2 is a graphical representation of the results of testing the soot catalytic ability of an integrated cDPF composite according to an embodiment of the invention;
FIG. 3 shows H for a monolithic cDPF composite catalyst according to an embodiment of the present invention2-TPR test junctionSchematic representation of the fruit.
Detailed Description
Unless defined otherwise, technical terms used in the following examples have the same meanings as commonly understood by one of ordinary skill in the art to which the present invention belongs. The test reagents used in the following examples, unless otherwise specified, are all conventional biochemical reagents; the experimental methods are conventional methods unless otherwise specified.
The monolithic cDPF composite material for the diesel vehicle prepared by the invention is cordierite-mullite-LaCoO3A composite oxide. The integral catalyst has certain catalytic performance on carbon smoke particles in the tail gas of a diesel vehicle, and also has good application in the trapping work of the particles in the tail gas of the vehicle. The present invention will be described in detail with reference to the following examples and accompanying drawings.
Example 1
The method comprises the following steps: roasting the aluminum sulfate octadecahydrate at a certain temperature for a certain time to obtain dehydrated aluminum sulfate.
Step two: according to the following steps: 3:40, grinding and uniformly mixing the diatomite, the aluminum sulfate and the sodium sulfate by using a mortar, covering the mixture on a small cordierite sample in a crucible to enable the cordierite to be completely covered, and then putting the crucible into a muffle furnace to be roasted for 3 hours at 1000 ℃ to obtain the whisker modified cordierite.
Step three: according to the following steps: 0.9: weighing lanthanum nitrate, cobalt nitrate and manganese acetate according to the mass ratio of 0.1, adding the lanthanum nitrate, the cobalt nitrate and the manganese acetate into deionized water, stirring the mixture for a period of time to prepare a solution, and adding citric acid into the solution after a solute is completely dissolved to prepare a mixed solution with a certain concentration. The amount of the substance added to the citric acid is the sum of the amounts of the substances of lanthanum nitrate, cobalt nitrate and manganese acetate.
Step four: and (3) placing the mixed solution into a beaker with a proper size, immersing the whisker modified cordierite obtained in the step two into the beaker, transferring the beaker into a vacuum drier, vacuumizing, standing for 1h, placing the beaker into a water bath kettle, keeping the temperature for 3h, and taking out a sample to an oven to dry at 100 ℃.
Step five: and putting the sample obtained in the fourth step into a muffle furnace, raising the temperature to 400 +/-5 ℃ at the speed of 3-5 ℃/min, keeping the temperature for 2h, raising the temperature to 650 +/-5 ℃ and keeping the temperature for 6h to obtain the integrated cDPF composite material, wherein the SEM micro-topography is shown in figure 1.
Example 2
The embodiment provides a preparation method of an integral cDPF composite material for a diesel vehicle, and the difference between the embodiment and the embodiment 1 is that the proportion of lanthanum nitrate, cobalt nitrate and manganese acetate is 1:0.8: 0.2.
example 3
The embodiment provides a preparation method of an integral cDPF composite material for a diesel vehicle, and the difference between the embodiment and the embodiment 1 is that the proportion of lanthanum nitrate, cobalt nitrate and manganese acetate is 1:0.7: 0.3.
example 4
The embodiment provides a preparation method of an integral cDPF composite material for a diesel vehicle, and the difference between the embodiment and the embodiment 1 is that the proportion of lanthanum nitrate, cobalt nitrate and manganese acetate is 1:0.6: 0.4.
comparative example 1
The difference from example 1 is that the cordierite after whisker modification was not immersed in the mixed solution, and the other operation steps were the same as example 1.
Comparative example 2
The difference from the example 1 is that the ratio of 1: 1:0, adding lanthanum nitrate, cobalt nitrate and manganese acetate into deionized water, stirring for a period of time to prepare a solution, adding citric acid after solute is completely dissolved to prepare a mixed solution with a certain concentration, and the other operation steps are the same as those in the embodiment 1.
Comparative example 3
The difference from example 1 is that the cordierite used in comparative example 3 is not whisker-modified, and the other operation steps are the same as those of example 1.
The soot catalytic ability of the monolithic cPDF composites prepared in example 1 and comparative examples 1-3 was tested and the results are shown in fig. 2, wherein the monolithic cPDF composite prepared in example 1 has higher conversion rate under the same temperature conditions.
As shown in FIG. 3, H2 is given for the samples of example 1 and comparative example 2TPR spectrum to evaluate the reduction performance of the catalyst, three reduction peaks were present for the monolithic cDPF in comparative example 2, the weak reduction peak at 242 ℃ corresponding to the physical adsorption of oxygen on the sample surface and the reduction of CoOx clusters, which was not detectable by XRD, and the reduction peak at 382 ℃ attributed to Co clusters3+Reduction to Co2+And the removal of surface adsorbed oxygen Oads, and the reduction peak at 552 ℃ is attributed to Co2+Reduction to Co0 and lattice oxygen orlat. The sample after Mn doping in example 1 showed more reduction peaks than the sample of comparative example 2, and it can be seen that CoOx cluster (215 ℃), Co cluster3+Reduction to Co2+And the reduction peak (346- & 387 ℃) removed by the surface adsorbed oxygen Oads are moved forward to a certain extent because the B-site Mn partially replaces Co to cause structural defects of the perovskite, more adsorbed oxygen is generated on the surface, and the reduction peak in the high-temperature region is slightly moved backwards (623 ℃), but the peak area is greatly increased, which indicates that LaCoO is doped after Mn3The mobility of surface lattice oxygen increases. H2The TPR results are consistent with the performance test results, indicating that Mn doping on the monolithic cDPF can improve the oxidation activity of the monolithic cDPF on soot.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like that fall within the spirit and principle of the present invention are intended to be included therein.
Claims (10)
1. The preparation method of the integrated cDPF composite material for the diesel vehicle is characterized by comprising the following steps of:
(1) preparing cordierite modified by the crystal whisker;
(2) mixing lanthanum nitrate, cobalt nitrate, manganese acetate and deionized water, stirring to form a solution, and mixing the solution and citric acid to prepare a mixed solution;
(3) immersing the cordierite modified by the crystal whisker into the mixed solution, taking out the cordierite after a period of time, and drying to obtain a sample;
(4) and (3) putting the sample into a muffle furnace for roasting to obtain the integrated cDPF composite material.
2. The method according to claim 1, wherein the step (1) is embodied as follows:
roasting aluminum sulfate octadecahydrate to obtain dehydrated aluminum sulfate, grinding and uniformly mixing diatomite, aluminum sulfate and sodium sulfate, pouring the mixture onto cordierite in a crucible to completely cover the cordierite, and placing the crucible into a muffle furnace to roast to obtain the whisker modified cordierite.
3. The method of claim 2, wherein: the mass ratio of the diatomite, the aluminum sulfate and the sodium sulfate is 1:3: 40.
4. The method of claim 2, wherein: the roasting temperature of the crucible in a muffle furnace is 900-1100 ℃, and the roasting time is 2-4 h.
5. The method of claim 1, wherein: in the step (2), the mass ratio of the lanthanum nitrate to the cobalt nitrate to the manganese acetate is 1:0.6-0.9: 0.1-0.4.
6. The method of claim 1, wherein: the amount of the citric acid substance added in the step (2) is equal to the sum of the amounts of the lanthanum nitrate, the cobalt nitrate and the manganese acetate.
7. The method according to claim 1, wherein the step (3) is embodied as follows:
and immersing the cordierite subjected to whisker modification into the mixed solution, vacuumizing in a vacuum drier, standing for a period of time, heating in a water bath for a period of time, taking out, and drying in an oven to obtain a sample.
8. The method of claim 7, wherein: standing for 0.5-2h, heating for 2-4h, and drying at 90-120 deg.C.
9. The method according to claim 1, wherein the step (4) is embodied as follows:
and (3) putting the sample into a muffle furnace, heating to 395-405 ℃ at the speed of 3-5 ℃/min, and keeping for 2h, and then heating to 645-655 ℃ and keeping for 6h to obtain the integrated cDPF composite material.
10. A monolithic cDPF composite for diesel vehicles, characterized in that it is prepared by the process of any one of claims 1 to 9.
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| PCT/CN2022/112807 WO2023020495A1 (en) | 2021-08-17 | 2022-08-16 | Monolithic cdpf composite material for diesel vehicle and preparation method therefor |
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| CN115069231A (en) * | 2022-07-22 | 2022-09-20 | 中国矿业大学(北京) | Integral SCR catalyst for back corona catalytic component and preparation method thereof |
| WO2023020495A1 (en) * | 2021-08-17 | 2023-02-23 | 中汽研汽车检验中心（天津）有限公司 | Monolithic cdpf composite material for diesel vehicle and preparation method therefor |
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| CN109364915B (en) * | 2018-11-23 | 2021-05-14 | 江苏中创清源科技有限公司 | Perovskite type composite metal oxide catalyst and preparation method thereof |
| CN111151257A (en) * | 2019-12-30 | 2020-05-15 | 山东科技大学 | Integral perovskite catalyst, preparation method and application thereof |
| CN113385188B (en) * | 2021-08-17 | 2021-11-02 | 中汽研（天津）汽车工程研究院有限公司 | Integral cDPF composite material for diesel vehicle and preparation method thereof |
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| CN107206356A (en) * | 2014-12-19 | 2017-09-26 | 庄信万丰股份有限公司 | Catalyst manufacture method |
| CN105642297A (en) * | 2015-12-29 | 2016-06-08 | 中国石油大学(北京) | Method for coating surface of iolite with macro-porous perovskite oxide catalyst |
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