CN112337482B - Preparation method of composite material and catalyst - Google Patents
Preparation method of composite material and catalyst Download PDFInfo
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- CN112337482B CN112337482B CN202011277697.9A CN202011277697A CN112337482B CN 112337482 B CN112337482 B CN 112337482B CN 202011277697 A CN202011277697 A CN 202011277697A CN 112337482 B CN112337482 B CN 112337482B
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- 239000003054 catalyst Substances 0.000 title claims abstract description 78
- 239000002131 composite material Substances 0.000 title claims abstract description 52
- 238000002360 preparation method Methods 0.000 title claims abstract description 25
- 239000000463 material Substances 0.000 claims abstract description 47
- 238000000034 method Methods 0.000 claims abstract description 15
- 239000000126 substance Substances 0.000 claims abstract description 14
- 150000001875 compounds Chemical class 0.000 claims abstract description 10
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 105
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 46
- 238000003756 stirring Methods 0.000 claims description 41
- 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 claims description 36
- 239000002952 polymeric resin Substances 0.000 claims description 34
- 229920003002 synthetic resin Polymers 0.000 claims description 34
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 claims description 30
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 22
- 229910001868 water Inorganic materials 0.000 claims description 20
- 239000002202 Polyethylene glycol Substances 0.000 claims description 18
- IWOUKMZUPDVPGQ-UHFFFAOYSA-N barium nitrate Chemical compound [Ba+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O IWOUKMZUPDVPGQ-UHFFFAOYSA-N 0.000 claims description 18
- 229920001223 polyethylene glycol Polymers 0.000 claims description 18
- GPNDARIEYHPYAY-UHFFFAOYSA-N palladium(ii) nitrate Chemical compound [Pd+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O GPNDARIEYHPYAY-UHFFFAOYSA-N 0.000 claims description 15
- 238000010438 heat treatment Methods 0.000 claims description 13
- 229910052751 metal Inorganic materials 0.000 claims description 11
- 239000000843 powder Substances 0.000 claims description 11
- 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 description 9
- 238000001035 drying Methods 0.000 claims description 8
- 238000002156 mixing Methods 0.000 claims description 6
- 238000004519 manufacturing process Methods 0.000 claims description 4
- 239000002184 metal Substances 0.000 claims description 4
- 150000001768 cations Chemical class 0.000 claims description 3
- 239000007789 gas Substances 0.000 abstract description 24
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 abstract description 24
- 238000006243 chemical reaction Methods 0.000 abstract description 17
- 238000000746 purification Methods 0.000 abstract description 12
- 230000000694 effects Effects 0.000 abstract description 11
- 229930195733 hydrocarbon Natural products 0.000 abstract description 8
- 150000002430 hydrocarbons Chemical class 0.000 abstract description 8
- 230000008569 process Effects 0.000 abstract description 8
- 238000011069 regeneration method Methods 0.000 abstract description 8
- 239000004215 Carbon black (E152) Substances 0.000 abstract description 6
- 239000000243 solution Substances 0.000 description 95
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 41
- 229910000510 noble metal Inorganic materials 0.000 description 23
- 230000002045 lasting effect Effects 0.000 description 13
- 238000005303 weighing Methods 0.000 description 12
- 230000003197 catalytic effect Effects 0.000 description 8
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- 238000011282 treatment Methods 0.000 description 7
- 150000002500 ions Chemical class 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 229910002091 carbon monoxide Inorganic materials 0.000 description 5
- 238000001816 cooling Methods 0.000 description 5
- 238000000227 grinding Methods 0.000 description 5
- 238000007873 sieving Methods 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- 229910052684 Cerium Inorganic materials 0.000 description 4
- 238000002441 X-ray diffraction Methods 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 239000011259 mixed solution Substances 0.000 description 4
- 229940068918 polyethylene glycol 400 Drugs 0.000 description 4
- 238000006479 redox reaction Methods 0.000 description 4
- 230000009467 reduction Effects 0.000 description 4
- 238000006722 reduction reaction Methods 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 3
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 description 3
- 230000000536 complexating effect Effects 0.000 description 3
- 239000006185 dispersion Substances 0.000 description 3
- 239000000835 fiber Substances 0.000 description 3
- 230000006872 improvement Effects 0.000 description 3
- MVFCKEFYUDZOCX-UHFFFAOYSA-N iron(2+);dinitrate Chemical compound [Fe+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MVFCKEFYUDZOCX-UHFFFAOYSA-N 0.000 description 3
- 239000002923 metal particle Substances 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 239000012495 reaction gas Substances 0.000 description 3
- 238000005245 sintering Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- 229910052788 barium Inorganic materials 0.000 description 2
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
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- 239000012153 distilled water Substances 0.000 description 2
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- 230000033116 oxidation-reduction process Effects 0.000 description 2
- 229910052763 palladium Inorganic materials 0.000 description 2
- 230000002441 reversible effect Effects 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 239000011593 sulfur Substances 0.000 description 2
- 230000032683 aging Effects 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 229910001422 barium ion Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
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- 230000000977 initiatory effect Effects 0.000 description 1
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- 229910052742 iron Inorganic materials 0.000 description 1
- 229910052746 lanthanum Inorganic materials 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
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- 238000001179 sorption measurement Methods 0.000 description 1
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- 239000002912 waste gas Substances 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
- B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
- B01J23/8933—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals also combined with metals, or metal oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/8946—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals also combined with metals, or metal oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with alkali or alkaline earth metals
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- 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
- B01D53/922—Mixtures of carbon monoxide or hydrocarbons and nitrogen oxides
- B01D53/925—Simultaneous elimination of carbon monoxide or hydrocarbons and nitrogen oxides
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- 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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- 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
- B01D53/944—Simultaneously removing carbon monoxide, hydrocarbons or carbon making use of oxidation catalysts
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- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/391—Physical properties of the active metal ingredient
- B01J35/394—Metal dispersion value, e.g. percentage or fraction
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- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
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Abstract
The invention relates to the technical field of materials, and discloses a composite material, a preparation method thereof and a catalyst. The composite material is a perovskite structure intelligent catalyst material which can be used for purifying motor vehicle tail gas, and comprises a compound with a chemical formula of La 1‑x Ba x Fe 1‑y‑z Ce y Pd z O 3 Therefore, the self-regeneration characteristic of LaFePd series materials is maintained, and the conversion performance of nitrogen oxides and unburned hydrocarbon is greatly improved, so that the LaFePd series materials have better purification effect when being used as a motor vehicle tail gas purification catalyst. The preparation method of the composite material has the advantages of simple process, low cost and good material performance. Therefore, the composite material has better practicability in serving as a tail gas catalyst and is easy to popularize and apply. The catalyst provided by the application comprises the composite material.
Description
Technical Field
The invention relates to the technical field of materials, in particular to a composite material, a preparation method thereof and a catalyst.
Background
Noble metal catalysts are widely used to purify nitrogen oxides, carbon monoxide and unburned hydrocarbons emitted by motor vehicles. However, conventional noble metal catalysts are subject to sintering and noble metal particle growth during use, and the surface area is reduced, resulting in deterioration of the catalyst, so that an excessive amount of noble metal must be used to ensure that the durability of the catalyst meets the requirements. This results in a higher material cost for the catalyst. The existing material of a part of catalysts has higher preparation cost, and more harsh experimental conditions are needed to obtain more ideal synthesis effect. Therefore, the existing catalyst material has the problems of high manufacturing cost and poor performance. Therefore, improvements in the materials of the catalyst and the preparation process thereof are necessary.
In view of this, the present invention has been made.
Disclosure of Invention
The invention aims to provide a composite material, a preparation method of the composite material and a catalyst.
The invention is realized in the following way:
in a first aspect, embodiments of the present invention provide a composite material,comprises a chemical formula La 1-x Ba x Fe 1-y-z Ce y Pd z O 3 Wherein x=0.1 to 0.5, y=0.1 to 0.5, and z=0.05 to 0.1.
In an alternative embodiment, x=0.1, y=0.1, and z=0.05 in the formula;
alternatively, in the formula, x=0.3, y=0.3, and z=0.05;
alternatively, in the formula, x=0.5, y=0.5, and z=0.05.
In a second aspect, an embodiment of the present invention provides a method for preparing a composite material according to the foregoing embodiment, including:
preparing a first solution containing ferric nitrate, cerium nitrate and palladium nitrate according to the metering proportion of metal elements in a chemical formula;
mixing the first solution with a citric acid solution to obtain a second solution;
mixing the second solution with a solution containing lanthanum nitrate and barium nitrate according to the metering proportion of metal elements in the chemical formula to obtain a third solution;
preparing a polymer resin using polyethylene glycol and a third solution;
and drying and roasting the polymer resin to obtain the composite material.
In an alternative embodiment, the step of preparing a first solution comprising ferric nitrate, cerium nitrate, palladium nitrate, comprises:
preparing a solution containing ferric nitrate and cerium nitrate;
the solution containing iron nitrate and cerium nitrate was mixed with a palladium nitrate solution and stirred to obtain a first solution.
In an alternative embodiment, the total molar amount of citric acid in the citric acid solution is the same as the total molar amount of metal cations in the compound in the composite material to be finally prepared, the concentration of the citric acid solution is 0.3-0.5 mol/L, and the first solution and the citric acid solution are mixed and stirred for 20-30 min.
In an alternative embodiment, the step of preparing the polymer resin using polyethylene glycol and the third solution comprises:
and (3) dripping polyethylene glycol into the third solution, stirring for 20-30 min, and heating in a water bath while stirring until the polymer resin is formed.
In an alternative embodiment, the polyethylene glycol is a polyethylene glycol having a molecular weight of 350-450, and the polyethylene glycol is added in an amount of 60-70% of the mass of citric acid in the citric acid solution.
In an alternative embodiment, the step of drying and firing the polymer resin comprises:
drying the polymer resin, grinding and sieving;
the powder of the polymer resin is baked, and in the baking process, heat preservation is respectively carried out in a plurality of temperature sections which are sequentially increased.
In an alternative embodiment, the step of baking the powder of the polymer resin, during which the respective insulation is carried out in a plurality of temperature segments that rise in sequence, comprises:
the powder of the polymer resin is subjected to heat preservation at 100-120 ℃ for 0.5-1.5 h, 180-220 ℃ for 0.5-1.5 h, 350-450 ℃ for 1-2 h and 500-600 ℃ for 2-4 h.
In a third aspect, the present examples provide a catalyst comprising the composite of the preceding embodiments, or comprising the composite made by the method of any of the preceding embodiments.
The invention has the following beneficial effects:
the composite material provided by the application comprises a compound material with a chemical formula of La 1-x Ba x Fe 1-y-z Ce y Pd z O 3 The composite material maintains the self-regeneration characteristic of LaFePd series materials, and greatly improves the conversion performance of nitrogen oxides and unburned hydrocarbon, so that the composite material is a perovskite structure intelligent catalyst material which can be used for purifying motor vehicle tail gas, and has a good purifying effect after being used as a motor vehicle tail gas purifying catalyst. The preparation method of the composite material provided by the application is simple in process and low in cost, can realize stable output of the composite material, and ensures that the performance of the material is better. On the premise of ensuring the same catalytic conversion performance, the composite materialThe material can directly reduce the noble metal consumption by 60-70%, and has better durability. Therefore, the composite material has good practicability when used as a tail gas catalyst, is easy to popularize and apply, and has high practical value.
The catalyst provided by the application comprises the composite material, so that the catalyst has the advantages of good catalytic effect and low manufacturing cost.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings that are needed in the embodiments will be briefly described below, it being understood that the following drawings only illustrate some embodiments of the present invention and therefore should not be considered as limiting the scope, and other related drawings may be obtained according to these drawings without inventive effort for a person skilled in the art.
FIG. 1 shows La prepared in various examples of the present application 1-x Ba x Fe 1-y-z Ce y Pd z O 3 XRD patterns of the series of materials;
FIGS. 2 (a) - (c) are La prepared according to various embodiments of the present application 1-x Ba x Fe 1-y-z Ce y Pd z O 3 Scanning electron microscope images of materials;
FIG. 3 shows La prepared in various examples of the present application 1-x Ba x Fe 1-y-z Ce y Pd z O 3 The series of materials are applied to the light-off characteristic curves of the automobile exhaust purification catalysts;
FIG. 4 shows La prepared in example 1 of the present application 0.9 Ba 0.1 Fe 0.85 Ce 0.1 Pd 0.05 O 3 XRD patterns of fresh, reduced and oxidized states;
FIG. 5 shows La prepared in example 1 of the present application 0.9 Ba 0.1 Fe 0.85 Ce 0.1 Pd 0.05 O 3 A characteristic curve applied to the self-regeneration performance of the automobile exhaust purification catalyst;
FIG. 6 shows La prepared in example 1 of the present application 0.9 Ba 0.1 Fe 0.85 Ce 0.1 Pd 0.05 O 3 A comparison chart of the emission performance of the whole vehicle (a fresh-state whole vehicle I-type test) applied to an automobile exhaust purification catalyst;
FIG. 7 shows La prepared in example 1 of the present application 0.9 Ba 0.1 Fe 0.85 Ce 0.1 Pd 0.05 O 3 The comparative graph of the emission performance of the whole automobile (I type test of the whole automobile after the durability of the 16 ten thousand kilometers of real automobile) is applied to the automobile exhaust purification catalyst.
Detailed Description
Noble metal catalysts are widely used to purify nitrogen oxides, carbon monoxide and unburned hydrocarbons emitted by motor vehicles. However, conventional noble metal catalysts are subject to sintering and noble metal particle growth during use, and the surface area is reduced, resulting in deterioration of the catalyst, so that an excessive amount of noble metal must be used to ensure that the durability of the catalyst meets the requirements. The inventor finds that the LaFe perovskite structure is favorable for stable dispersion and existence of doped ions, after doped with high-activity noble metal Pd ions, the LaFePd material can inhibit noble metal particles from growing up by reversibly overflowing and entering perovskite lattices in the waste gas environment of redox circulation, so that the catalytic activity of the LaFePd material is still higher after long-term use and aging, and the LaFePd material is obviously superior to the conventional noble metal catalyst material in activity and stability. In the aspect of sulfur resistance, laFePd series materials are loaded on a bottom layer with a double-coating structure and applied to a close-coupled catalyst, and the catalyst has better sulfur resistance. Pd in the LaFePd material can overflow or enter a perovskite structure along with the change of an external redox environment, so that the self-regeneration of the catalyst material is realized, and the LaFePd material becomes an intelligent catalyst composite material. The composite material can reduce the consumption of noble metal and ensure the durability of the catalyst.
The LaFePd series material has a plurality of preparation methods, the synthesis temperature is generally 700-900 ℃, the reaction process is relatively severe, explosion and fire are easy to be initiated, even the ideal synthesis effect can be obtained by vacuum drying, the experimental condition is severe, and the cost is relatively high. The high-temperature synthesis can lead to the reduction of the initial activity of noble metal Pd, in addition, the conversion performance of LaFePd series materials on nitrogen oxides and unburned hydrocarbon is slightly poorer than that of the traditional noble metal catalyst, and the factors lead to the fact that the LaFePd series materials are difficult to be widely applied to the motor vehicle exhaust gas purification catalyst as an intelligent catalyst material. Therefore, the improvement of the formula and the preparation process of the LaFePd series material is necessary.
Therefore, the application provides a composite material and a preparation method thereof, so as to solve at least one of the problems of poor performance, high manufacturing cost and the like of the existing catalyst material when treating tail gas.
In order to make the objects, technical solutions and advantages of the embodiments of the present invention more clear, the technical solutions of the embodiments of the present invention will be clearly and completely described below. The specific conditions are not noted in the examples and are carried out according to conventional conditions or conditions recommended by the manufacturer. The reagents or apparatus used were conventional products commercially available without the manufacturer's attention.
The composite material provided by the embodiment of the application comprises a compound material with a chemical formula of La 1-x Ba x Fe 1-y-z Ce y Pd z O 3 Wherein x=0.1 to 0.5, y=0.1 to 0.5, and z=0.05 to 0.1.x, y, z may be selected as desired within the above ranges. For example, x=0.1, y=0.1, z=0.05; alternatively, x=0.3, y=0.3, z=0.05; still alternatively, in the formula, x=0.5, y=0.5, and z=0.05.
According to the composite material provided by the embodiment of the application, the barium (Ba) and the cerium (Ce) are doped in the LaFePd series material in a certain proportion, the adsorption and conversion capability of the catalyst material to nitrogen oxides can be improved by introducing the barium, the catalyst is promoted by doping the cerium, and particularly, the conversion performance of hydrocarbon can be obviously improved by doping the cerium to the catalyst containing noble metal Pd. The composite material is a perovskite structure intelligent catalyst material which can be used for purifying tail gas of motor vehicles.
The preparation method of the composite material provided by the embodiment of the application comprises the following steps:
(1) According to the chemical formula (La 1-x Ba x Fe 1-y-z Ce y Pd z O 3 ) The first solution containing ferric nitrate, cerium nitrate and palladium nitrate is prepared according to the metering proportion of metal elements.
Optionally, the step includes: preparing a solution containing ferric nitrate and cerium nitrate; the solution containing iron nitrate and cerium nitrate was mixed with a palladium nitrate solution and stirred to obtain a first solution. Specifically, the required ferric nitrate (optionally Fe (NO) 3 ) 3 ·9H 2 O) and cerium nitrate (optionally Ce (NO) 3 ) 4 ·6H 4 O) is added into a proper amount of distilled water, and optionally, the total concentration of Fe and Ce ions is 0.3-0.5 mol/L. And then stirring at room temperature until the ferric nitrate and the cerium nitrate are completely dissolved (stirring for 5-10 min, and specifically, stirring can be performed by using a mechanical stirrer).
And then adding a palladium nitrate solution into the solution in which the ferric nitrate and the cerium nitrate are dissolved according to the metal element metering proportion in the chemical formula, and continuously stirring uniformly at room temperature (stirring for 20-30 min) to obtain a first solution.
(2) The first solution is mixed with a citric acid solution to obtain a second solution.
Optionally, in the step, the total molar quantity of the citric acid in the citric acid solution is the same as the total molar quantity of the metal cations in the compound in the composite material to be finally prepared, the concentration of the citric acid solution is 0.3-0.5 mol/L, and the first solution and the citric acid solution are mixed and stirred for 20-30 min to obtain the second solution. Similarly, this agitation may be achieved by a mechanical stirrer.
Optionally, the citric acid solution is slowly added (for 20-30 min) to the first solution, and stirring is performed for 20-30 min after all the citric acid solution is added. In this embodiment, the citric acid solution is slowly added, because if the citric acid solution is added quickly, the concentration of the citric acid solution in the mixed solution is easily too high, the complexing reaction of local metal ions and citric acid in the mixed solution is aggravated, the noble metal Pd ions are quickly aggregated, atomic-level dispersion cannot be realized, and the dispersity of the noble metal Pd ions is reduced, thereby influencing the catalytic performance. The slowly added citric acid solution has the function of ensuring that continuously added citric acid is continuously consumed by reaction in the complexing reaction process of metal ions and citric acid in the mixed solution, the concentration of the citric acid in the mixed solution is kept at a lower level until the complete reaction is completed, the complexing reaction is uniform, and the noble metal Pd ions realize atomic-level dispersion.
(3) And mixing the second solution with a solution containing lanthanum nitrate and barium nitrate according to the metering proportion of the metal elements in the chemical formula to obtain a third solution.
In this step, a solution containing lanthanum nitrate and barium nitrate can be prepared by: according to the metering proportion of metal elements in the chemical formula, the required lanthanum nitrate (selected as La (NO 3 ) 4 ·6H 2 O) and barium nitrate (Ba (NO) 3 ) 2 ) Dissolving a proper amount of distilled water (optionally, enabling the total concentration of La and Ba ions to be 0.3-0.5 mol/L), and stirring for 10-15 min. And then slowly (lasting for 20-25 min) adding the obtained solution into the second solution, and continuously stirring at room temperature for 20-30 min to obtain a third solution.
(4) The polymer resin is prepared using polyethylene glycol and the third solution.
Optionally, the method specifically includes: and (3) dripping polyethylene glycol into the third solution, stirring for 20-30 min, and heating in a water bath while stirring until the polymer resin is formed. Alternatively, the polyethylene glycol in embodiments of the present application may be a polyethylene glycol having a molecular weight of 350-450, such as polyethylene glycol 400. The addition amount of polyethylene glycol is 60-70% of the mass of citric acid in the citric acid solution. Optionally, the polyethylene glycol is slowly added dropwise during the process of adding the third solution for 1-2 min, and the reason of the slow addition is similar to the addition of the citric acid solution. The water bath temperature can be selected to be 60-80 ℃, and the stirring time is about 60-100 min.
(5) And drying and roasting the polymer resin to obtain the composite material.
The method specifically comprises the following steps: drying the polymer resin, grinding and sieving; the powder of the polymer resin is baked, and in the baking process, heat preservation is respectively carried out in a plurality of temperature sections which are sequentially increased. Specifically, the polymer resin can be baked in an oven with a set temperature of 60-80 ℃ for 12-24 hours to realize drying. And then ground and sieved, such as by a 40 mesh sieve, to form a powder (or granule) material of a particle size that meets the catalyst use requirements. Then, the temperature is increased at a heating rate of 3-5 ℃/min, then the powder of the polymer resin is sequentially subjected to heat preservation at 100-120 ℃ for 0.5-1.5 h, at 180-220 ℃ for 0.5-1.5 h, at 350-450 ℃ for 1-2 h and at 500-600 ℃ for 2-4 h. And then optionally cooling to room temperature along with the furnace to obtain the required composite material.
In the embodiment of the application, the preparation temperature of the composite material can be not more than 600 ℃, so that the preparation method has smaller difficulty and risk compared with the existing LaFePd series material preparation, the reaction process is relatively mild, and explosion and fire are relatively difficult to initiate. And the composite material prepared by the method comprises La 1-x Ba x Fe 1-y-z Ce y Pd z O 3 The self-regeneration characteristic of LaFePd series materials is maintained, the conversion performance of nitrogen oxides and unburned hydrocarbon is greatly improved, and the composite material is a perovskite structure intelligent catalyst material which can be used for purifying motor vehicle tail gas. The preparation method has simple process and low cost. On the premise of ensuring the same catalytic conversion performance, the composite material can directly reduce the noble metal consumption by 60-70%, and has better durability. Therefore, when the catalyst is applied to the tail gas catalyst, the catalyst has better practicability, is easy to popularize and apply and has higher practical value.
The features and capabilities of the present invention are described in further detail below in connection with the examples.
Example 1 (La) 0.9 Ba 0.1 Fe 0.85 Ce 0.1 Pd 0.05 O 3 Preparation
Weighing 0.85mol of ferric nitrate (Fe (NO) 3 ) 3 ·9H 2 O) and 0.1mol of cerium nitrate (Ce (NO) 3 ) 3 ·6H 2 O) was placed in a 10L beaker, 2000g of water was added and dissolved at room temperature with stirring using a mechanical stirrer for 10min.
And (3) weighing 0.05mol of palladium nitrate solution (wherein palladium accounts for 15wt.% of the palladium nitrate solution), uniformly and slowly (lasting for 5 min) adding the palladium nitrate solution into the solution of the step (A), and continuously stirring for 30min to obtain a first solution for later use.
Weighing 2mol of citric acid, putting into a 5L beaker, adding 4000g of water, stirring and dissolving for 5min by using a mechanical stirrer under the temperature condition, uniformly and slowly (lasting for 30 min) adding the solution into the first solution obtained in the step, and continuously stirring for 30min at room temperature to obtain a second solution for later use.
0.9mol of lanthanum nitrate (La (NO) 3 ) 3 ·6H 2 O) and 0.1mol of barium nitrate (Ba (NO) 3 ) 2 ) Put into a 5L beaker, 2000g of water was added, and the mixture was dissolved by stirring with a mechanical stirrer at room temperature for 15 minutes. Then slowly adding the solution into the second solution obtained in the step (lasting for 20 min), and continuously stirring at room temperature for 30min to obtain a third solution for later use.
And fifthly, weighing 250g of polyethylene glycol 400, uniformly and slowly dropwise adding (lasting 2 min) into the third solution obtained in the step IV, and continuously stirring at room temperature for 30min for later use.
The solution obtained in step five is heated in a water bath (water bath temperature: 80 ℃ C.) while continuing to stir until the polymer resin is formed (for about 80 minutes).
The polymer resin of step I is dried in an oven (80 ℃ C.) for about 24 hours.
Grinding the polymer resin obtained in the step (II), and sieving with a 40-mesh sieve for later use.
Roasting: roasting the polymer resin powder obtained in the step by using a fiber resistance furnace, heating at a heating rate of 5 ℃/min, sequentially carrying out heat preservation at 120 ℃ for 1h,200 ℃ for 1h,350 ℃ for 1h and 550 ℃ for 2h, and cooling to room temperature along with the furnace to obtain the composite material.
Example 2 (La) 0.7 Ba 0.3 Fe 0.65 Ce 0.3 Pd 0.05 O 3 Preparation
Weighing 0.65mol of ferric nitrate (Fe (NO) 3 ) 3 ·9H 2 O) and 0.3mol of cerium nitrate (Ce (NO) 3 ) 3 ·6H 2 O) put into a 10L beaker, add2000g of water was added thereto, and the mixture was dissolved by stirring with a mechanical stirrer at room temperature for 10 minutes.
Weighing 0.05mol of palladium nitrate solution (15 wt.%) and uniformly and slowly (lasting for 5 min) adding the solution into the solution obtained in the step (A), and continuously stirring for 30min to obtain a first solution for later use.
Weighing 2mol of citric acid, putting into a 5L beaker, adding 4000g of water, stirring and dissolving for 5min by using a mechanical stirrer under the temperature condition, uniformly and slowly (lasting for 30 min) adding the solution into the first solution obtained in the step, and continuously stirring for 30min at room temperature to obtain a second solution for later use.
0.7mol of lanthanum nitrate (La (NO) 3 ) 3 ·6H 2 O) and 0.3mol of barium nitrate (Ba (NO) 3 ) 2 ) Put into a 5L beaker, 2000g of water was added, and the mixture was dissolved by stirring with a mechanical stirrer at room temperature for 15 minutes. Then slowly adding the solution into the second solution obtained in the step (lasting for 20 min), and continuously stirring at room temperature for 30min to obtain a third solution for later use.
And fifthly, weighing 250g of polyethylene glycol 400, uniformly and slowly dropwise adding (lasting 2 min) into the third solution obtained in the step IV, and continuously stirring at room temperature for 30min for later use.
Heating the solution obtained in step (II) in a water bath (water bath temperature: 80 ℃) while continuing to stir until the polymer resin is formed (for about 80 minutes).
The polymer resin of step I is dried in an oven (80 ℃ C.) for about 24 hours.
Grinding the polymer resin obtained in the step (II), and sieving with a 40-mesh sieve for later use.
Roasting: roasting the polymer resin powder obtained in the step by using a fiber resistance furnace, heating at a heating rate of 5 ℃/min, sequentially carrying out heat preservation at 120 ℃ for 1h,200 ℃ for 1h,350 ℃ for 1h and 550 ℃ for 2h, and cooling to room temperature along with the furnace to obtain the composite material.
Example 3 (La) 0.5 Ba 0.5 Fe 0.45 Ce 0.5 Pd 0.05 O 3 Preparation
Weighing 0.45mol of ferric nitrate (Fe (NO) 3 ) 3 ·9H 2 O) and 0.5mol of cerium nitrate (Ce (NO) 3 ) 3 ·6H 2 O) was placed in a 10L beaker, 2000g of water was added and dissolved at room temperature with stirring using a mechanical stirrer for 10min.
Weighing 0.05mol of palladium nitrate solution (15 wt.%) and uniformly and slowly (lasting for 5 min) adding the solution into the solution obtained in the step (A), and continuously stirring for 30min to obtain a first solution for later use.
Weighing 2mol of citric acid, putting into a 5L beaker, adding 4000g of water, stirring and dissolving for 5min by using a mechanical stirrer under the temperature condition, uniformly and slowly (lasting for 30 min) adding the solution into the first solution obtained in the step, and continuously stirring for 30min at room temperature to obtain a second solution for later use.
0.5mol of lanthanum nitrate (La (NO) 3 ) 3 ·6H 2 O) and 0.5mol of barium nitrate (Ba (NO) 3 ) 2 ) Put into a 5L beaker, 2000g of water was added, and the mixture was dissolved by stirring with a mechanical stirrer at room temperature for 15 minutes. Then slowly adding the solution into the second solution obtained in the step (lasting for 20 min), and continuously stirring at room temperature for 30min to obtain a third solution for later use.
And fifthly, weighing 250g of polyethylene glycol 400, uniformly and slowly dropwise adding (lasting 2 min) into the third solution obtained in the step IV, and continuously stirring at room temperature for 30min for later use.
The solution of step II is heated with a water bath (water bath temperature: 80 ℃ C.) while continuing to stir until a polymer resin is formed (for about 80 minutes).
The polymer resin of step I is dried in an oven (80 ℃ C.) for about 24 hours.
Grinding the polymer resin obtained in the step (II), and sieving with a 40-mesh sieve for later use.
Roasting: roasting the polymer resin powder obtained in the step by using a fiber resistance furnace, heating at a heating rate of 5 ℃/min, sequentially carrying out heat preservation at 120 ℃ for 1h,200 ℃ for 1h,350 ℃ for 1h and 550 ℃ for 2h, and cooling to room temperature along with the furnace to obtain the composite material.
The above examples are respectively carried out on the compound La 0.9 Ba 0.1 Fe 0.85 Ce 0.1 Pd 0.05 O 3 、La 0.7 Ba 0.3 Fe 0.65 Ce 0.3 Pd 0.05 O 3 、La 0.5 Ba 0.5 Fe 0.45 Ce 0.5 Pd 0.05 O 3 While the preparation of the composite material of the above is described, it should be understood that the parameters of the above examples may be adjusted within suitable ranges (as described in the detailed description of the embodiment of the invention before example 1) according to practical needs, such as adjusting the stirring duration, the duration of component addition, and the holding time, holding temperature, heating rate, etc. In addition, the addition amount of each component can be adjusted according to the chemical formula of the compound to be obtained, for example, in the preparation of La 0.7 Ba 0.3 Fe 0.6 Ce 0.3 Pd 0.1 O 3 When the composition is used, the usage amount of each component can be as follows: iron nitrate 0.6mol, cerium nitrate 0.3mol, palladium nitrate 0.1mol, lanthanum nitrate 0.7mol, and barium nitrate 0.3mol.
FIG. 1 shows La prepared in various examples of the present application 1-x Ba x Fe 1-y-z Ce y Pd z O 3 XRD pattern of the series of materials. As can be seen from FIG. 1, the prepared materials are of a typical perovskite structure, the crystal forms are complete, and no other oxide phases are found. FIGS. 2 (a) - (c) are La prepared according to various embodiments of the present application 1-x Ba x Fe 1-y-z Ce y Pd z O 3 A scanning electron microscope image of a material, wherein fig. 2 (a) corresponds to example 1, fig. 2 (b) corresponds to example 2, and fig. 2 (c) corresponds to example 3. It can be seen that the microstructure of the ceramic powder is porous, particles are uniformly dispersed, the particle size is nano-scale, and no obvious sintering phenomenon exists. La (La) 1-x Ba x Fe 1-y-z Ce y Pd z O 3 These characteristics of the series of materials determine that it can exert better and durable catalytic activity.
La prepared in the above 3 examples 1-x Ba x Fe 1-y-z Ce y Pd z O 3 Application of series materials in purifying automobile tail gasEvaluation of the activity of the catalyst.
The activity evaluation of the catalyst was carried out on a catalyst sample evaluation tester (Tianjin Li Yuan, science and technology Co., ltd.) using a monolithic catalyst of phi 20X 30X 400cpsi, pre-treated at 450℃for 1 hour in a reaction gas atmosphere, and then N was introduced 2 Purging and cooling to room temperature, and performing ignition characteristic test, wherein the temperature is required to be increased from room temperature to 450 ℃ at a heating rate of 20 ℃/min, and the airspeed is 55000h -1 And (3) measuring under the condition. The reaction gas is simulated gas distribution of automobile exhaust, and the composition of the reaction gas is 0.60 percent of CO and 0.15 percent of THC (C 3 H 8 :C 3 H 6 =1:2)，0.08%NO，0.6%O 2 ，10% CO 2 Balance gas N 2 . The contents of the respective components in the exhaust gas before and after the reaction were analyzed by using an automobile exhaust gas analyzer (HORIBA 7400H type, japan) to calculate the conversion of the respective components.
FIG. 3 shows La prepared in various examples of the present application 1-x Ba x Fe 1-y-z Ce y Pd z O 3 The series of materials are applied to the light-off characteristic curves of the automobile exhaust purification catalysts. The results of evaluating the activity of the catalyst can be seen in fig. 3, in which curve a represents example 1, curve b represents example 2, and curve c represents example 3. As can be seen from the analysis results, the composite material prepared in each example has better performance, wherein La prepared in example 1 0.9 Ba 0.1 Fe 0.85 Ce 0.1 Pd 0.05 O 3 The light-off properties, i.e. the activity, are best.
The self-regeneration performance of the composite material prepared in the embodiment of the present application applied to an automobile exhaust gas purifying catalyst is verified by taking the example 1 as an example:
the technical scheme includes that the operating principle of the automobile tail gas purifying catalyst is that carbon monoxide, nitrogen oxides and unburned hydrocarbon in tail gas are converted into non-toxic and harmless carbon dioxide, nitrogen and water through oxidation-reduction reaction. Examination of La prepared in example 1 0.9 Ba 0.1 Fe 0.85 Ce 0.1 Pd 0.05 O 3 The phase structure and grain size during the oxidation-reduction reaction can be verifiedI regenerate performance. FIG. 4 shows La prepared in example 1 of the present application 0.9 Ba 0.1 Fe 0.85 Ce 0.1 Pd 0.05 O 3 XRD patterns of fresh, reduced and oxidized states. As can be seen from fig. 4, the phase structures of the fresh state, the reduced state and the oxidized state are all typical perovskite structures, the crystal forms are complete, and no other oxide phases are found; after redox treatment, the structure and grain size were not significantly changed, indicating La prepared in example 1 0.9 Ba 0.1 Fe 0.85 Ce 0.1 Pd 0.05 O 3 Can regenerate itself during the oxidation-reduction reaction, and is characterized by the stability of phase structure and grain size.
Fig. 5 shows La prepared in example 1 of the present application 0.9 Ba 0.1 Fe 0.85 Ce 0.1 Pd 0.05 O 3 The characteristic curve applied to the self-regeneration performance of the automobile exhaust purification catalyst, wherein a curve a represents a fresh state, a curve b represents a first reduction treatment, a curve c represents a first oxidation treatment, a curve d represents a second reduction treatment, and a curve e represents a second oxidation treatment. It can be seen that the light-off performance of the catalyst is distributed in two states relative to the fresh state after repeated oxidation-reduction treatment, the light-off performance of the reduced state is improved, the light-off performance of the oxidized state is reduced, and the light-off performance of the catalyst can realize reversible change after two oxidation-reduction treatments. Description of La prepared in example 1 0.9 Ba 0.1 Fe 0.85 Ce 0.1 Pd 0.05 O 3 The catalyst can be applied to an automobile exhaust purification catalyst, and can realize reversible self-regeneration under the condition of oxidation-reduction reaction. In the use process of the automobile exhaust gas purifying catalyst in a real automobile, the air-fuel ratio always fluctuates near the theoretical air-fuel ratio (14.7:1), namely the automobile exhaust gas purifying catalyst is used in the exhaust gas environment of redox circulation. Therefore, la prepared in example 1 0.9 Ba 0.1 Fe 0.85 Ce 0.1 Pd 0.05 O 3 As an intelligent catalyst, the catalyst can always keep better catalytic activity in the actual use process.
Taking example 1 as an example, the emission performance of the composite material prepared in the embodiment of the present application applied to the automobile exhaust gas purifying catalyst is verified as follows:
the standard of the emission performance of the whole vehicle is developed in a certain 1.5T state VI vehicle type, and the traditional noble metal catalyst (comparative example) and the catalyst containing La are respectively selected 0.9 Ba 0.1 Fe 0.85 Ce 0.1 Pd 0.05 O 3 The catalysts (example 1) of the whole vehicle type I test standard was carried out using La 0.9 Ba 0.1 Fe 0.85 Ce 0.1 Pd 0.05 O 3 The noble metal dosage is reduced by 70% compared with the traditional noble metal catalyst. FIGS. 6 and 7 show La prepared in example 1 0.9 Ba 0.1 Fe 0.85 Ce 0.1 Pd 0.05 O 3 The whole vehicle emission performance comparison chart applied to the automobile exhaust purification catalyst corresponds to the whole vehicle emission in a fresh state and the whole vehicle emission after the durability of the 16 ten thousand kilometers of real vehicles respectively. From the I-type test emission result of the whole car, the two types of catalysts can meet the discharge requirement of VIa tail gas of the automobile country and La is used 0.9 Ba 0.1 Fe 0.85 Ce 0.1 Pd 0.05 O 3 The catalyst has better performance and has room for further cost reduction.
The above partial verification is only explained by taking example 1 as an example. Similarly, la of the compound in the above composite material 1-x Ba x Fe 1-y-z Ce y Pd z O 3 The x, y and z have similar performances after being changed within the scope disclosed in the embodiment of the application. Not described here one by one.
The embodiment of the application also discloses a catalyst, which comprises the composite material provided by the embodiment of the application. Therefore, the catalyst has the characteristics of low cost and good catalytic purification effect on motor vehicle tail gas.
The above is only a preferred embodiment of the present invention, and is not intended to limit the present invention, but various modifications and variations can be made to the present invention by those skilled in the art. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (5)
1. A preparation method of a composite material is characterized in that the composite material comprises a compound material with a chemical formula of La 1-x Ba x Fe 1-y- z Ce y Pd z O 3 Wherein x=0.1 to 0.5, y=0.1 to 0.5, and z=0.05 to 0.1, the preparation method comprising:
preparing a first solution containing ferric nitrate, cerium nitrate and palladium nitrate according to the metering proportion of metal elements in the chemical formula;
mixing the first solution with a citric acid solution to obtain a second solution;
mixing the second solution with a solution containing lanthanum nitrate and barium nitrate according to the metering proportion of the metal elements in the chemical formula to obtain a third solution;
preparing polymer resin by using polyethylene glycol and the third solution, wherein the polyethylene glycol is polyethylene glycol with the molecular weight of 350-450, and the adding amount of the polyethylene glycol is 60-70% of the mass of citric acid in the citric acid solution;
drying and roasting the polymer resin to obtain the composite material;
the step of drying and roasting the polymer resin comprises the following steps:
and (3) insulating the powder of the polymer resin at 100-120 ℃ for 0.5-1.5 h, at 180-220 ℃ for 0.5-1.5 h, at 350-450 ℃ for 1-2 h and at 500-600 ℃ for 2-4 h.
2. The method of preparing according to claim 1, wherein the step of preparing the first solution containing ferric nitrate, cerium nitrate, palladium nitrate comprises:
preparing a solution containing ferric nitrate and cerium nitrate;
mixing and stirring the solution containing ferric nitrate and cerium nitrate with a palladium nitrate solution to obtain the first solution.
3. The preparation method according to claim 1, wherein the total molar amount of citric acid in the citric acid solution is the same as the total molar amount of metal cations in the compound in the composite material to be finally prepared, and the concentration of the citric acid solution is 0.3 to 0.5 mol/L, and the first solution is stirred for 20 to 30 minutes after being mixed with the citric acid solution.
4. The method of claim 1, wherein the step of preparing the polymer resin using polyethylene glycol and the third solution comprises:
and (3) dripping polyethylene glycol into the third solution, stirring for 20-30 min, heating in a water bath, and stirring at the same time until the polymer resin is formed.
5. A catalyst comprising a composite material produced by the production method according to any one of claims 1 to 4.
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