CN116212944B - Lean-burn methanol fuel automobile exhaust purification catalyst and preparation method thereof - Google Patents
Lean-burn methanol fuel automobile exhaust purification catalyst and preparation method thereof Download PDFInfo
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
- B01J29/72—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65 containing iron group metals, noble metals or copper
- B01J29/74—Noble metals
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- 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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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2258/00—Sources of waste gases
- B01D2258/01—Engine exhaust gases
- B01D2258/016—Methanol engines
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A50/00—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
- Y02A50/20—Air quality improvement or preservation, e.g. vehicle emission control or emission reduction by using catalytic converters
Abstract
The application discloses a lean-burn methanol fuel automobile exhaust purification catalyst and a preparation method thereof, belonging to the environmental protection field related to the atmospheric pollution control of catalytic technology application. The catalyst comprises a catalyst carrier and a catalyst coating; the catalyst coating comprises a GOC catalyst coating and an SCR catalyst coating, wherein the GOC catalyst coating takes noble metal as an active ingredient, and the SCR catalyst coating takes a rare earth modified small molecular sieve as an active ingredient. The catalyst has the advantages of low noble metal content, low ignition temperature and high highest conversion efficiency, and realizes the efficient purification of tail gas of conventional pollutants and unconventional pollutants in the tail gas of the lean-burn methanol fuel automobile.
Description
Technical Field
The application belongs to the field of environmental protection related to atmospheric pollution control by catalytic technology application, and particularly relates to a lean-burn methanol fuel automobile exhaust purification catalyst and a preparation method thereof.
Background
The methanol fuel automobile is an automobile using methanol as fuel. The methanol is rich in resources and renewable, belongs to biomass energy, and the moderate development of the methanol automobile is a way for relieving the energy problem. However, methanol belongs to secondary energy and also brings about certain environmental pollution. Lean burn (lean burn) refers to combustion of an engine under the condition that the actual air-fuel ratio is greater than the theoretical air-fuel ratio, and the lean burn can enable the combustion of fuel to be more complete and is an effective measure for reducing the total exhaust emission, but lean-burn methanol fuel automobiles still generate CH 3 OH, CO and NO x Such conventional contaminants, also include intermediate CH of methanol 2 Unconventional contamination of O and the likeTail gas from the object, and how to purify the pollutants emitted by methanol-fuelled automobiles, is a concern.
Disclosure of Invention
Aiming at the problems in the prior art, the application provides a lean-burn methanol fuel automobile exhaust gas purifying catalyst and a preparation method thereof, and the catalyst has the advantages of low noble metal content, low ignition temperature and high highest conversion efficiency, and realizes the efficient purification of the exhaust gas of conventional pollutants and unconventional pollutants in the lean-burn methanol fuel automobile exhaust gas.
In order to achieve the above purpose, the present application proposes the following technical scheme:
a lean-burn methanol fuel automobile exhaust gas purifying catalyst, which comprises a catalyst carrier and a catalyst coating;
the catalyst coating comprises a GOC catalyst coating and an SCR catalyst coating;
the load of the GOC catalyst coating is 100-150g/L, and the load of the SCR catalyst coating is 170-180g/L.
Further, the catalyst carrier is cordierite honeycomb ceramic, the porosity is 34+/-3%, and the pore diameter is 3-6 mu m.
Further, the preparation method of the GOC catalyst comprises the following steps:
1) Preparing a colloid binder by a sol method: mixing soluble salt, pseudo-boehmite and deionized water, and adjusting the pH value to 3-5 by using an acid solution to prepare a colloid binder;
2) Preparation of an impregnating stock solution: ceO is added with 2 And ZrO(s) 2 Mixing with deionized water, adding into colloid binder after fully stirring, and stirring uniformly to obtain soaking stock solution; ceO (CeO) 2 The mol percentage of ZrO is 10-35 percent 2 5-20% by mole;
3) Preparation of GOC catalyst: and adding the noble metal salt solution into the dipping stock solution to obtain the GOC catalyst with the solid content of 20-40%.
Further, in the step 1), the mass ratio of the soluble salt, the pseudo-boehmite and the deionized water is 0.1:1:5; in step 2), the CeO 2 、ZrO 2 The mass ratio of the deionized water to the water is (1-2) to 1.5:10; in the step 3), the noble metal salt solution comprises one or more of palladium nitrate, tetraamine palladium nitrate, palladium chloride, palladium acetate, platinum nitrate, tetraamine platinum nitrate, platinum chloride or platinum acetate.
Still further, the soluble salt is one or more of praseodymium nitrate, lanthanum nitrate, gadolinium nitrate, magnesium nitrate, ammonium paratungstate, ammonium molybdate, zirconium nitrate, chromium nitrate, zinc nitrate, and barium acetate.
Further, gamma-Al in the pseudo-boehmite 2 O 3 The mole percentage of (2) is 5-20%.
Further, in step 1), the acidic solution includes one or more of nitric acid, hydrochloric acid, sulfuric acid, or oxalic acid.
Further, the preparation method of the SCR catalyst comprises the following steps:
s1, preparing a colloid binder by a sol method: mixing soluble salt, pseudo-boehmite and deionized water, and adjusting the pH value to 3-5 by using an acid solution to prepare a colloid binder;
s2, preparing a rare earth modified small molecular sieve: mixing rare earth nitrate, a small molecular sieve and deionized water, volatilizing water through heating and stirring, roasting at 500-700 ℃, and grinding to obtain rare earth modified small molecular sieve powder; the rare earth nitrate is praseodymium nitrate, neodymium nitrate, gadolinium nitrate or lanthanum nitrate;
s3, preparation of an SCR catalyst: mixing and stirring rare earth modified small molecular sieve powder, rare earth catalyst, alumina, soluble salt, deionized water and colloid binder, controlling pH to 3-5, viscosity to 1000-3000 mpa.s and solid content to 30-40%, thus obtaining the SCR catalyst.
Further, in S1, the mass ratio of the soluble salt, the pseudo-boehmite and the deionized water is 0.1:1:5; in S2, the mass ratio of the rare earth nitrate to the small molecular sieve to the deionized water is 0.05:1:3; in S3, the mass ratio of the rare earth modified small molecular sieve powder, the rare earth catalyst, the alumina, the soluble salt and the deionized water is 3:1:3:0.35:20.
Further, in S1, the soluble salt is one or more of lanthanum nitrate, praseodymium nitrate, gadolinium nitrate, magnesium nitrate, ammonium paratungstate, ammonium molybdate, zirconium nitrate, chromium nitrate, zinc nitrate and barium acetate; the acidic solution includes one or more of nitric acid, hydrochloric acid, sulfuric acid, or oxalic acid.
Further, in S1, gamma-Al in the pseudo-boehmite 2 O 3 The mole percentage of (2) is 5-20%.
Further, in S3, the rare earth nitrate is praseodymium nitrate, neodymium nitrate, gadolinium nitrate or lanthanum nitrate.
The application also provides a preparation method of the lean-burn methanol fuel automobile exhaust purification catalyst, which comprises the following steps:
A. coating GOC catalyst coating at 1/2 of the front part of a carrier by negative pressure, drying for 5-20min at 60-120 ℃ hot air, then coating at 1/2 of the rear part of the carrier by negative pressure, drying for 5-20min at 60-120 ℃ hot air, and then placing the coated sample in 450-600 ℃ environment for roasting for 1-5h to obtain GOC catalyst coating;
B. the preparation method comprises the steps of coating an SCR catalyst coating on a carrier coated with a GOC catalyst coating at 1/2 under negative pressure, drying for 5-20min at 60-120 ℃ under hot air, coating on the carrier coated with the GOC catalyst coating at 1/2 under negative pressure, drying for 5-20min at 60-120 ℃ under hot air, and roasting the coated sample in an environment of 450-600 ℃ for 1-5h to obtain the SCR catalyst coating.
The application also provides application of the lean-burn methanol fuel automobile exhaust purification catalyst in lean-burn methanol fuel automobile exhaust purification treatment.
Compared with the prior art, the application has the beneficial effects that:
the application provides a lean-burn methanol fuel automobile exhaust purification catalyst, which comprises a catalyst carrier and a catalyst coating, wherein the catalyst coating comprises a GOC catalyst coating and an SCR catalyst coating, the GOC catalyst coating takes sol with high specific surface area prepared by pseudo-boehmite, soluble salt and acid as a binder, and takes Al with high specific surface area 2 O 3 As a base for dispersing noble metals, with oxygen storage materials CeO 2 And ZrO(s) 2 Directly participate in catalytic reaction to treat CO and NO x And precious metal is used as an active material, and finally the lean-burn methanol fuel automobile exhaust purification GOC catalyst with high specific surface area and large pore volume is obtained. Because the lean combustion technology of the engine can reduce CO and H 2 、CH 3 Emission of pollutants such as OH and the like, but the traditional methanol engine aftertreatment catalyst is used for NO x Will drastically decrease the catalytic ability of (c) resulting in lean NO combustion x Emissions are increased and GOC catalysts cannot be treated, so that the addition of SCR catalysts to achieve NO x The conversion mechanism equation is: NO+NO 2 +2NH 3 →2N 2 +3H 2 O。
The catalyst has the advantages of low ignition temperature, high highest conversion efficiency and low cost on the premise of low noble metal consumption, and realizes the simultaneous high-efficiency purification of conventional pollutants and unconventional pollutants in the tail gas of the methanol fuel automobile. Meanwhile, the tail gas purifying catalyst with different noble metal active components comprises two types of Pt/Pd and Pt, and the lean-burn methanol fuel automobile tail gas purifying catalyst loaded with different noble metals can be selected according to different automobile types and tail gas treatment requirements, so that the cost control is realized.
Drawings
In order to more clearly illustrate the embodiments of the present application or the technical solutions in the prior art, the drawings that are needed in the embodiments will be briefly described below, and it is obvious that the drawings in the following description are only some embodiments of the present application, and other drawings may be obtained according to these drawings without inventive effort for a person skilled in the art.
FIG. 1 is a graph showing the performance test of the lean-burn methanol fuel automobile exhaust gas purifying catalyst prepared in example 4;
FIG. 2 is a graph showing the performance test of the lean-burn methanol fuel automobile exhaust gas purifying catalyst prepared in comparative example 1;
FIG. 3 is a graph showing the performance test of the lean-burn methanol fuel automobile exhaust gas purifying catalyst prepared in comparative example 2;
fig. 4 is a graph showing performance test of the lean-burn methanol fuel automobile exhaust gas purifying catalyst prepared in comparative example 3.
Detailed Description
Various exemplary embodiments of the application will now be described in detail, which should not be considered as limiting the application, but rather as more detailed descriptions of certain aspects, features and embodiments of the application.
It is to be understood that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the application. In addition, for numerical ranges in this disclosure, it is understood that each intermediate value between the upper and lower limits of the ranges is also specifically disclosed. Every smaller range between any stated value or stated range, and any other stated value or intermediate value within the stated range, is also encompassed within the application. The upper and lower limits of these smaller ranges may independently be included or excluded in the range.
Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this application belongs. Although only preferred methods and materials are described herein, any methods and materials similar or equivalent to those described herein can be used in the practice or testing of the present application. All documents mentioned in this specification are incorporated by reference for the purpose of disclosing and describing the methods and/or materials associated with the documents. In case of conflict with any incorporated document, the present specification will control.
It will be apparent to those skilled in the art that various modifications and variations can be made in the specific embodiments of the application described herein without departing from the scope or spirit of the application. Other embodiments will be apparent to those skilled in the art from consideration of the specification of the present application. The specification and examples of the present application are exemplary only.
As used herein, the terms "comprising," "including," "having," "containing," and the like are intended to be inclusive and mean an inclusion, but not limited to.
The raw materials used in the following examples of the present application are commercially available unless otherwise specified.
The application aims at generating CH aiming at a lean-burn methanol fuel automobile 3 OH, CO and NO x Iso-conventional contaminants and intermediate products CH of methanol 2 The catalyst comprises a catalyst carrier, a GOC catalyst coating and an SCR catalyst coating, wherein the GOC catalyst coating takes noble metal as an active ingredient, and the SCR catalyst coating takes a rare earth modified small molecular sieve as an active ingredient. A colloid binder is prepared by a sol method and is mixed with CeO 2 And ZrO(s) 2 Mixing in a certain proportion, selectively loading different noble metal active ingredients on the composite oxide by an impregnation method, preparing the tail gas purification GOC catalyst, preparing the rare earth modified small molecular sieve by the impregnation method, mixing the rare earth modified small molecular sieve with nitrate, and preparing the tail gas purification SCR catalyst. The catalyst has the advantages of low noble metal content, low ignition temperature and high highest conversion efficiency, and realizes the efficient purification of tail gas of conventional pollutants and unconventional pollutants in the tail gas of the lean-burn methanol fuel automobile.
The preparation method of the lean-burn methanol fuel automobile exhaust purification catalyst comprises the following steps:
(1) Preparing a colloid binder by a sol method: mixing soluble salt, pseudo-boehmite and deionized water, and adjusting the pH value to 3-5 by using an acid solution to prepare a colloid binder; the mole percentage of the alumina is 5-20%;
(2) Preparation of GOC catalyst coating:
a. preparation of an impregnating stock solution: ceO is added with 2 、ZrO 2 Mixing with deionized water, adding the prepared colloid binder after fully stirring, and uniformly stirring to obtain an impregnating stock solution; wherein CeO is 2 The mol percentage of ZrO is 10-35 percent 2 5-20% by mole;
preparation of GOC catalyst coating: adding a noble metal (mainly Pt and Pd) salt solution into the dipping stock solution, loading the solution into ZrO by a dipping method 2 -Al 2 O 3 ，CeO 2 -Al 2 O 3 Obtaining GOC catalyst coating; the particle size of the paint is 2-10 mu m; the wet load of the GOC catalyst coating is 300-650g/L, and the dry load is 100-150g/L;
c. coating GOC catalyst coating at 1/2 place in front of honeycomb ceramic carrier with negative pressure, drying at 60-120deg.C hot air for 5-20min, coating at 1/2 place behind honeycomb ceramic carrier with negative pressure, drying at 60-120deg.C hot air for 5-20min, and calcining the coated honeycomb ceramic carrier in 450-600deg.C environment for 1-5h to obtain GOC catalyst coating;
the coating connection position can be overcoated by 0.5-2cm, and the difference of coating thickness is formed in the middle of the honeycomb ceramic carrier, so that the air flow is changed in the process of making tail gas pass through the catalyst, and the catalyst function is fully exerted, wherein ZrO 2 : gamma-Al in pseudo-boehmite 2 O 3 ：CeO 2 : pt: pd mass ratio is = (5-17.5): (20-55): (2.5-10): (0.02-0.2): (0.01-0.1).
(3) Preparation of SCR catalyst coating:
(1) rare earth modified small molecular sieve preparation: mixing rare earth nitrate, a small molecular sieve and deionized water, volatilizing water through heating and stirring (the temperature is 100 ℃ for 1-3 h), roasting for 4h at 500-700 ℃ and grinding to obtain rare earth modified small molecular sieve powder (the particle size is 2-5 mu m);
(2) preparation of SCR catalyst coating: mixing and stirring rare earth modified small molecular sieve powder, rare earth catalyst, alumina, soluble salt, deionized water and a colloid binder, and performing viscosity adjustment on self-made sol (the colloid binder prepared in the step (1)) and organic matters, controlling pH to be 3-5, and controlling viscosity to be 1000-3000 mpa.s and solid content to be 30-40%, thus obtaining the SCR catalyst coating; the particle size of the paint is 2-10 mu m; wet loading of 425-600g/L and dry loading of 160-200g/L;
(3) the prepared SCR catalyst coating is coated at the front 1/2 of the honeycomb ceramic carrier at negative pressure, dried for 5-20min at the hot air of 60-120 ℃, then the coating is coated at the rear 1/2 of the honeycomb ceramic carrier at negative pressure, dried for 5-20min at the hot air of 60-120 ℃, and then the coated honeycomb ceramic carrier is put into the environment of 450-600 ℃ for roasting for 1-5h, thus obtaining the SCR catalyst coating.
In some preferred embodiments, step (1), the soluble salt is one or more of lanthanum nitrate, praseodymium nitrate, gadolinium nitrate, magnesium nitrate, ammonium paratungstate, ammonium molybdate, zirconium nitrate, chromium nitrate, zinc nitrate, and barium acetate; the acidic solution includes one or more of nitric acid, hydrochloric acid, sulfuric acid, or oxalic acid.
In some preferred embodiments, step (1), the mass ratio of the soluble salt, pseudo-boehmite, and deionized water is 0.1:1:5.
In some preferred embodiments, step (2), the CeO 2 、ZrO 2 And deionized water in the mass ratio of (1-2) to 1.5 to 10.
In some preferred embodiments, step (2), the noble metal salt solution comprises one or more of palladium nitrate, tetraamine palladium nitrate, palladium chloride, palladium acetate, platinum nitrate, tetraamine platinum nitrate, platinum chloride, or platinum acetate. More preferred are platinum nitrate and palladium nitrate. In the application, if the palladium-containing salt solution and the platinum-containing salt solution are required to be loaded on GOC catalyst slurry, the palladium-containing salt solution and the platinum-containing salt solution are uniformly mixed, and then the mixed solution is loaded on the GOC catalyst slurry by adopting an impregnation method.
In some preferred embodiments, step (3), the rare earth nitrate is praseodymium nitrate, neodymium nitrate, gadolinium nitrate or lanthanum nitrate; the small molecular sieve is a small-pore SSZ-13 molecular sieve; the rare earth catalyst is cerium-zirconium storage and culture powder; the soluble salt is one or more of praseodymium nitrate, gadolinium nitrate, magnesium nitrate, ammonium paratungstate, ammonium molybdate, zirconium nitrate, chromium nitrate, zinc nitrate and barium acetate; the acidic solution includes one or more of nitric acid, hydrochloric acid, sulfuric acid, or oxalic acid.
In some preferred embodiments, step (3), the mass ratio of rare earth nitrate, small molecular sieve and deionized water is 0.05:1:3; the mass ratio of the rare earth modified small molecular sieve powder to the rare earth catalyst to the alumina to the soluble salt to the deionized water is 3:1:3:0.35:20.
The total content of noble metal in the catalyst finished product is 60-100g/ft 3 。
The following examples serve as further illustrations of the technical solutions of the application.
Example 1
The preparation method of the lean-burn methanol fuel automobile exhaust purification catalyst comprises the following steps:
(1) Preparing a colloid binder by a sol method: weighing 3g of pseudo-boehmite, adding the pseudo-boehmite into 15g of deionized water, standing for 2 hours, stirring, adding 0.3g of lanthanum nitrate, and adding nitric acid to adjust the pH value to 5 to obtain a colloid binder; standby for use
(2) Preparation of GOC catalyst coating:
preparation of an impregnating stock solution: 15g CeO 2 And 15g ZrO 2 Mixing with 110g of deionized water, fully stirring, adding the prepared colloid binder, and uniformly stirring to obtain an impregnating stock solution;
preparation of GOC catalyst coating: adding 0.36g of platinum nitrate solution with solid content and 0.8g of palladium nitrate solution with solid content into the dipping stock solution, uniformly stirring to obtain GOC catalyst coating, coating the GOC catalyst coating on a honeycomb ceramic carrier with the volume of 0.2L, and roasting for 4 hours at 550 ℃ to obtain GOC catalyst coating, thus obtaining the lean-burn methanol fuel automobile exhaust purification catalyst;
the coating method comprises the following steps: coating GOC catalyst coating at 1/2 of the front of the honeycomb ceramic carrier with negative pressure, drying at 120deg.C hot air for 5-20min, coating at 1/2 of the rear of the honeycomb ceramic carrier with negative pressure, and drying at 120deg.C hot air for 5-20min.
Example 2
As in example 1, the difference is that CeO in step (2) 2 Is 10g by mass of ZrO 2 The mass of (2) was 15g.
Example 3
As in example 1, the difference is that CeO in step (2) 2 Is 20g, zrO 2 The mass of (2) was 15g.
Example 4
The preparation method of the lean-burn methanol fuel automobile exhaust purification catalyst comprises the following steps:
(1) Preparing a colloid binder by a sol method: weighing 3g of pseudo-boehmite, adding the pseudo-boehmite into 15g of deionized water, standing for 2 hours, stirring, adding 0.3g of lanthanum nitrate, and adding nitric acid to adjust the pH value to 5 to obtain a colloid binder; standby for use
(2) Preparation of GOC catalyst coating:
preparation of an impregnating stock solution: 15g CeO 2 And 15g ZrO 2 Mixing with 110g of deionized water, fully stirring, adding the prepared colloid binder, and uniformly stirring to obtain an impregnating stock solution;
preparation of GOC catalyst coating: adding 0.36g of platinum nitrate solution with solid content and 0.8g of palladium nitrate solution with solid content into the dipping stock solution, uniformly stirring to obtain GOC catalyst coating, coating the GOC catalyst coating on a honeycomb ceramic carrier with the volume of 0.2L, and roasting for 4 hours at 550 ℃ to obtain GOC catalyst coating;
(3) Preparation of SCR catalyst coating:
rare earth modified small molecular sieve preparation: mixing 10g of rare earth nitrate, 200g of small molecular sieve and 600g of deionized water, volatilizing water through heating and stirring (the temperature is 100 ℃ for 1 h), roasting for 4h at 550 ℃ and grinding to obtain rare earth modified small molecular sieve powder (the particle size range is 2-5 mu m);
preparation of SCR catalyst coating: mixing and stirring 30g of rare earth modified small molecular sieve powder, 10g of rare earth catalyst (particularly cerium-zirconium storage powder), 30g of alumina, 3.5g of soluble salt (particularly praseodymium nitrate), 200g of deionized water and 20g of colloid binder prepared in the step (1), and controlling the pH to be 5, the viscosity to 2500 mpa.s and the solid content to be 35%, thus obtaining the SCR catalyst coating;
and (3) coating the prepared SCR catalyst coating on the GOC catalyst coating in the step (2), and roasting for 4 hours at 550 ℃ to obtain the SCR catalyst coating, namely the lean-burn methanol fuel automobile exhaust purification catalyst.
The coating methods of the GOC catalyst coating and the SCR catalyst coating are as follows: coating GOC catalyst coating at 1/2 of the front of the honeycomb ceramic carrier with negative pressure, drying at 120deg.C hot air for 5-20min, coating at 1/2 of the rear of the honeycomb ceramic carrier with negative pressure, and drying at 120deg.C hot air for 5-20min.
Example 5
As in example 1, the difference is that CeO in step (2) 2 Is 10g by mass of ZrO 2 The mass of (2) was 15g.
Example 6
As in example 1, the difference is that CeO in step (2) 2 Is 20g, zrO 2 The mass of (2) was 15g.
Comparative example 1
The difference is that palladium nitrate in step (2) is removed as in example 4.
Comparative example 2
As in example 4, except that ZrO in step (2) was removed 2 I.e. 30g CeO was added 2 。
Comparative example 3
The difference is that the same mass as that of the platinum nitrate solution and the palladium nitrate solution in the step (2) is replaced with rhodium nitrate solution as in example 4.
Test example 1
The performance of the lean-burn methanol fuel automobile exhaust purification catalyst prepared in the embodiment 1-3 is tested by a small sample evaluation analyzer, the test conditions are shown in the table 1, and the detection results are shown in the table 2.
TABLE 1
| Airspeed of (space velocity) | CO | C 3 H 6 | NO | CO 2 | O 2 | H 2 O |
| 40000 | 6000ppm | 300ppm | 1000ppm | 10％ | 0.5％ | 10％ |
TABLE 2
As can be seen from Table 2, ceO 2 The proportion is within the range of 40-60%, the oxygen storage performance of the sample is high, and the conversion rate of CO and NO is high at 200-700 ℃.
Test example 2
The performance of the lean-burn methanol fuel automobile exhaust gas purifying catalyst prepared in example 4 and the comparative example thereof was tested by using a small sample evaluation analyzer under the test conditions shown in tables 3 to 4, and the test results of example 4 are shown in fig. 1.
TABLE 3 Table 3
| NO | NH 3 | H 2 O | O 2 | CO 2 | N 2 | SV |
| 500ppm | 500ppm | 10％ | 10％ | 8％ | balance | 50000h -1 |
TABLE 4 Table 4
As can be seen from fig. 1, the fresh state and the aging table performance of the SCR catalyst finished product meet the requirements of the national six law.
The test result of comparative example 1 is shown in fig. 2, and the fresh performance of the product is slightly different from that of example 4, but the aging performance of the product is poor, so that the sample lacking palladium metal is poor in aging performance and unsatisfactory.
The test result of comparative example 2 is shown in fig. 3, and the fresh state and aging state performances of the product are reduced, so that the stability of the product is poor.
Comparative example 3 the test results are shown in FIG. 4, which shows similar performance to example 4, in NO x The transformation performance is better, but the toxin resistance is poorer, and the cost is higher.
The foregoing description of the preferred embodiments of the application is not intended to limit the application to the particular embodiments disclosed, but on the contrary, the intention is to cover all modifications, equivalents, and alternatives falling within the spirit and scope of the application.
Claims (6)
1. The lean-burn methanol fuel automobile exhaust purification catalyst is characterized by comprising a catalyst carrier and a catalyst coating;
the catalyst coating comprises a GOC catalyst coating and an SCR catalyst coating;
the load of the GOC catalyst coating is 100-150g/L, and the load of the SCR catalyst coating is 170-180g/L;
the preparation method of the GOC catalyst comprises the following steps:
1) Preparing a colloid binder by a sol method: mixing soluble salt, pseudo-boehmite and deionized water, and adjusting the pH value to 3-5 by using an acid solution to prepare a colloid binder;
2) Preparation of an impregnating stock solution: ceO is added with 2 And ZrO(s) 2 Mixing with deionized water, adding into colloid binder after fully stirring, and stirring uniformly to obtain soaking stock solution;
3) Preparation of GOC catalyst: adding the noble metal salt solution into the dipping stock solution to obtain GOC catalyst with the solid content of 20-40%;
in the step 3), the noble metal salt solution is platinum nitrate and palladium nitrate;
the preparation method of the SCR catalyst comprises the following steps:
s1, preparing a colloid binder by a sol method: mixing soluble salt, pseudo-boehmite and deionized water, and adjusting the pH value to 3-5 by using an acid solution to prepare a colloid binder;
s2, preparing a rare earth modified small molecular sieve: mixing rare earth nitrate, a small molecular sieve and deionized water, volatilizing water through heating and stirring, roasting at 500-700 ℃, and grinding to obtain rare earth modified small molecular sieve powder;
s3, preparation of an SCR catalyst: mixing and stirring rare earth modified small molecular sieve powder, rare earth catalyst, alumina, soluble salt, deionized water and colloid binder, controlling pH to 3-5, viscosity to 1000-3000 mpa.s and solid content to 30-40%, thus obtaining the SCR catalyst.
2. The lean-burn methanol fuel automobile exhaust gas purifying catalyst according to claim 1, wherein the catalyst carrier is cordierite honeycomb ceramic, the porosity is 34±3%, and the pore diameter is 3-6 μm.
3. The lean burn methanol fuel automobile exhaust gas purifying catalyst of claim 1, wherein in step 1), the mass ratio of the soluble salt, pseudo-boehmite and deionized water is 0.1:1:5; in step 2), the CeO 2 、ZrO 2 And deionized water in the mass ratio of (1-2) to 1.5 to 10.
4. The lean burn methanol fuel automobile exhaust gas purifying catalyst of claim 1, wherein in S1, the mass ratio of the soluble salt, pseudo-boehmite and deionized water is 0.1:1:5; in S2, the mass ratio of the rare earth nitrate to the small molecular sieve to the deionized water is 0.05:1:3; in S3, the mass ratio of the rare earth modified small molecular sieve powder, the rare earth catalyst, the alumina, the soluble salt and the deionized water is 3:1:3:0.35:20.
5. A method for preparing the lean-burn methanol fuel automobile exhaust gas purifying catalyst according to any one of claims 1 to 4, comprising the steps of:
A. coating GOC catalyst coating at 1/2 of the front part of a carrier by negative pressure, drying for 5-20min at 60-120 ℃ hot air, then coating at 1/2 of the rear part of the carrier by negative pressure, drying for 5-20min at 60-120 ℃ hot air, and then placing the coated sample in 450-600 ℃ environment for roasting for 1-5h to obtain GOC catalyst coating;
B. the preparation method comprises the steps of coating an SCR catalyst coating on a carrier coated with a GOC catalyst coating at 1/2 under negative pressure, drying for 5-20min at 60-120 ℃ under hot air, coating on the carrier coated with the GOC catalyst coating at 1/2 under negative pressure, drying for 5-20min at 60-120 ℃ under hot air, and roasting the coated sample in an environment of 450-600 ℃ for 1-5h to obtain the SCR catalyst coating.
6. Use of the lean-burn methanol fuel automobile exhaust gas purifying catalyst according to any one of claims 1 to 4 in lean-burn methanol fuel automobile exhaust gas purifying treatment.
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| DE10340653B4 (en) * | 2003-09-03 | 2006-04-27 | Hte Ag The High Throughput Experimentation Company | Catalyst for the removal of pollutants from exhaust gases of lean-burn engines with ruthenium as active metal |
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