CN104588036A - Universal small gasoline engine tail gas purification metal wire pie catalyst and preparation method thereof - Google Patents
Universal small gasoline engine tail gas purification metal wire pie catalyst and preparation method thereof Download PDFInfo
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- CN104588036A CN104588036A CN201510047688.3A CN201510047688A CN104588036A CN 104588036 A CN104588036 A CN 104588036A CN 201510047688 A CN201510047688 A CN 201510047688A CN 104588036 A CN104588036 A CN 104588036A
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Abstract
The invention relates to a universal small gasoline engine tail gas purification metal wire pie catalyst, and belongs to the technical field of preparation of a universal small gasoline engine tail gas catalyst. The universal small gasoline engine tail gas purification metal wire pie catalyst comprises a metal wire pie carrier and a catalyst coating; with metal wires as framework, the metal wire pie carrier is prepared by netting, winding, extruding to be pie, solder coating and high-temperature soldering; the catalyst coating is prepared from active Al2O3 and cerium-enriched rare earth composite oxide oxygen storage material; the active Al2O3 is of composite oxide of gamma-Al2O3 carried noble metal palladium, platinum and palladium, palladium and rhodium or platinum, palladium and rhodium; the mass percentage of cerium oxide in the cerium-enriched rare earth composite oxide oxygen storage material is 50-100%. The preparation method disclosed by the invention is simple; the metal wire pie carrier has high supporting strength and is not likely to shrink and deform, so the activity of the catalyst is better, and the endurance is longer.
Description
Technical field
The present invention relates to a kind of catalyst for purifying exhaust of petrol engine and preparation method thereof, belong to the preparing technical field of general small-size gasoline engine tail-gas catalyst.
Background technology
The dynamic power machine of general small-size gasoline engine to be gasoline be fuel, CO, HC and NOx are the main exhaust pollutants of general small-size gasoline engine.External purification for general small-size gasoline engine mainly refers to and install tai-gas clean-up catalyst additional in silencer.Due to self Drainage feature of general small-size gasoline engine, the requirement of the following several respects of tai-gas clean-up catalyst demand fulfillment: 1) HC+NOx is the emphasis of general small-size gasoline engine emission control, but because NOx emission is lower, proportion is less, therefore HC is the key needing to administer; 2) muffler space of general small-size gasoline engine is less, and therefore catalyst should have smaller volume and high transformation efficiency; 3) general small-size gasoline engine delivery temperature is at 350 ~ 600 DEG C, exceed the initiation temperature of catalyst, the normal use of catalyst can be guaranteed, but HC and CO oxidation reaction can discharge a large amount of heats simultaneously, therefore reaction bed temperature is close to even more than 1000 DEG C, therefore requires that catalyst possesses good resistance to elevated temperatures; 4) catalyst of general small-size gasoline engine must possess low cost, high-performance and have the feature of good durability.
Wire pie carried catalyst can meet several respects requirement of above-mentioned tail gas purification of general small-size gasoline engine catalyst, is therefore one of tai-gas clean-up catalyst that general small-size gasoline engine is conventional.But metal spinning cake carrier is very easily contraction distortion under the impact of high-speed high temperature gas flow, and then cause friction fracture of wire, waste gas gas leakage and coating abrasion to come off, cause catalyst failure, therefore overcoming or reducing the contraction distortion of metal spinning cake carrier under high-speed high temperature gas flow is problem in the urgent need to address.
Summary of the invention
The object of the invention is to solve the easy contraction distortion of wire pie carrier traditional in prior art, the shortcoming of the catalyst failure causing coating shedding that carrier adheres to and exhaust gas leakage to cause, provide a kind of preparation method simple, catalyst activity is better, the tail gas purification of general small-size gasoline engine wire pie Catalysts and its preparation method that persistence is longer.
The present invention adopts following technical scheme: a kind of tail gas purification of general small-size gasoline engine wire pie catalyst, comprise wire pie carrier and catalyst coat, described wire pie carrier take metal wire material as skeleton, by knotting, rolling, be squeezed into, pie, coated with solder and high temperature brazing are prepared from, and described catalyst coat comprises active A l
2o
3with rich cerium type complex rare-earth oxidate containing valuable metal hydrogen-storing material, active A l in described catalyst coat
2o
3mass percent be 60 ~ 90%, the mass percent of rich cerium type rare earth oxygen storage material is 10 ~ 40%.
Further, described active A l
2o
3γ-Al
2o
3the composite oxides of supported precious metal palladium, platinum and palladium, palladium and rhodium or platinum, palladium and rhodium.
Further, the cerium oxide mass percent in described rich cerium type complex rare-earth oxidate containing valuable metal hydrogen-storing material is 50 ~ 100%.
The preparation method of tail gas purification of general small-size gasoline engine wire pie catalyst, comprises the steps:
(1) preparation of metal spinning cake carrier: metal wire material is knotted, rolls and be squeezed into pie, then put into nickel-based brazing cream and stop 1 ~ 5s, propose with the speed of 10 ~ 50mm/s, 0.5 ~ 1h is dried at 100 ~ 200 DEG C, put into the weldering of high temperature brazing slice, be prepared into wire pie carrier;
(2) pretreatment of carrier: wire pie carrier step (1) prepared 700 ~ 1100 DEG C of roasting pretreatment 1 ~ 4h in air atmosphere, to remove residual oil stain and to form metal-oxide film;
(3) active Al
2o
3preparation: adopt equi-volume process, according to the γ-Al of per unit mass
2o
3the water yield of powder adsorption, dipping precious metal palladium, platinum and palladium, palladium and rhodium or platinum, palladium and rhodium solution are in γ-Al
2o
3on powder, the total load amount of precious metal palladium, platinum and palladium, palladium and rhodium or platinum, palladium and rhodium is γ-Al
2o
30.5 ~ 30% of powder weight;
(4) preparation of coating slurry: by active A l
2o
3, the mixing of rich cerium type rare earth oxygen storage material, wherein active A l
2o
3mass percentage concentration be 60 ~ 90%, the mass percentage concentration of rich cerium type rare earth oxygen storage material is 10 ~ 40%, and add deionized water and stirring, the solid content in coating slurry is 10% ~ 35%, adopt ball mill to carry out ball milling to coating slurry, serous granule degree D90 is 5 ~ 30 μm;
(5) apply: propose after 1 ~ 3min in coating slurry metal spinning cake carrier impregnation prepared in step (4), put into centrifuge and dry, centrifuge speed is 800 ~ 1200r/min;
(6) dry: the metal spinning cake carrier after coating in step (5) is dried 1 ~ 4h at 100 ~ 200 DEG C, after oven dry under 400 ~ 600 DEG C of conditions roasting 2 ~ 4h;
(7) repeat step (4) and step (5), until the coating amount on metal spinning cake carrier reaches 10g/L ~ 50g/L, obtain tail gas purification of general small-size gasoline engine catalyst.
Further, the quality of described wire pie catalyst carrier is 3 ~ 15g/.
Further, described metal spinning cake is cuboid cake or cylinder cake.
Further, the metal wire material diameter of metal spinning cake carrier is 0.3 ~ 0.5mm, and material is FeCrAl alloy.
Preparation method of the present invention is simple, the catalyst prepared is not easily contraction distortion under high-speed hot conditions, avoid the distortion of conventional metals spinning cake carrier shrinks and the catalyst failure that catalyst layer comes off and exhaust gas leakage causes that causes, improve activity and the durability of catalyst, catalyst extends service life.
Detailed description of the invention
Below in conjunction with specific embodiment, the invention will be further described
Metal spinning cake carrier S 1 makes: knotted by metal wire material, roll and be squeezed into pie, then put into nickel-based brazing cream and stop 3s, propose with the speed of 30mm/s, 0.5h is dried at 120 DEG C, put into the weldering of high temperature brazing slice, be prepared into the rectangular-shaped carrier of metal spinning cake of coated catalysts coating; The string diameter of metal wire material is 0.35mm, the FeCrAl alloy material of material to be the trade mark be 0Cr20Al5, and wire pie appearance and size is the cuboid of 30*18*18, and the length of cuboid end face is 30mm, and wide is 18mm, is highly 18mm; Vehicle weight is 7.5g.
Metal spinning cake carrier S 2 makes: knotted by metal wire material, then through rolling, be squeezed into cuboid finished product, not coated with solder and do not carry out high temperature brazing measure; The string diameter of metal wire material is 0.35mm, the FeCrAl alloy material of material to be the trade mark be 0Cr20Al5, and wire pie appearance and size is the cuboid of 30*18*18, and the length of cuboid end face is 30mm, and wide is 18mm, is highly 18mm; Vehicle weight is 7.5g.
Embodiment one:
Prepare tail gas purification of general small-size gasoline engine wire pie catalyst M1: the preparation of wire pie carrier is identical with the method for S1.By wire pie carrier high-temperature process 5h at 950 DEG C; Get the γ-Al of 100g
2o
3, progressively drip deionized water, until infiltrate all powders, the total amount that record drips water is 143g; Get the palladium nitrate solution containing 15g palladium, be diluted to 443.3g, adopt equi-volume impregnating load palladium nitrate to the γ-Al of 310g
2o
3on; Weigh the cerium zirconium sosoloid hydrogen-storing material that 175g cerium-oxide contents is 55%; Weigh 1923g deionized water, by the γ-Al of deionized water, cerium zirconium sosoloid hydrogen-storing material and supported palladium
2o
3be mixed together and stir 2h, to slurries ball milling, controlling serous granule degree D90 is 16 μm.
Coating: metal spinning cake carrier is immersed in 3min in slurries, puts into centrifuge 1200r/min and dry, then by load, the carrier of slurries dries 4h, then in 600 DEG C of roasting 2h in 120 DEG C.Repeat the step of above-mentioned coating, until the coating amount on metal spinning cake carrier reaches 40g/L, obtain tail gas purification of general small-size gasoline engine wire pie catalyst.
Embodiment two:
Prepare tail gas purification of general small-size gasoline engine wire pie catalyst M2: the preparation method of wire pie carrier is identical with S2 preparation method, residue preparation process is identical with embodiment one.
Embodiment three:
Prepare tail gas purification of general small-size gasoline engine wire pie catalyst M3: the preparation method of wire pie carrier is identical with S1 preparation method, residue preparation process is identical with embodiment one, but the content of cerium oxide in the cerium zirconium sosoloid hydrogen-storing material selected is 30%.
Embodiment four:
Prepare tail gas purification of general small-size gasoline engine wire pie catalyst M4:
Metal wire material is knotted, rolls and be squeezed into pie, then put into nickel-based brazing cream and stop 1s, propose with the speed of 10mm/s, 0.5h is dried at 100 DEG C, put into the weldering of high temperature brazing slice, be prepared into the wire pie carrier of cylindrical shape, vehicle weight is 3g; The metal wire material diameter of metal spinning cake carrier is 0.3mm, and material is FeCrAl alloy.By the wire pie carrier 700 DEG C of roasting pretreatment 1h in air atmosphere prepared, to remove residual oil stain and to form metal-oxide film; According to the water yield of the γ-Al2O3 powder adsorption of per unit mass, dipping precious metal palladium, platinum and palladium, palladium and rhodium or platinum, palladium and rhodium solution are in γ-Al
2o
3on powder, the total load amount of noble metal platinum, palladium and rhodium is γ-Al
2o
30.5% of powder weight; By active A l
2o
3, the mixing of rich cerium type rare earth oxygen storage material, wherein active A l
2o
3mass percentage concentration be 60%, rich cerium type rare earth oxygen storage material mass percentage concentration is 40%, and adding deionized water to the solid content of slurries is 10%, and adopt ball mill to carry out ball milling to coating slurry, serous granule degree D90 is 5 μm; Metal spinning cake carrier impregnation proposed after 1min in coating slurry, put into centrifuge and dry, centrifuge speed is 800r/min; By coating after metal spinning cake carrier at 100 DEG C, dry 1h, after oven dry under 400 DEG C of conditions roasting 2h; Repetitive coatings step, until the coating amount on metal spinning cake carrier reaches 10g/L, obtains tail gas purification of general small-size gasoline engine catalyst.
Embodiment five:
Prepare tail gas purification of general small-size gasoline engine wire pie catalyst M5:
Knotted by metal wire material, roll and be squeezed into pie, then put into nickel-based brazing cream and stop 5s, propose with the speed of 50mm/s, at 200 DEG C, dry 1h, put into the weldering of high temperature brazing slice, be prepared into rectangle wire pie carrier, vehicle weight is 15g; By the wire pie carrier 1100 DEG C of roasting pretreatment 4h in air atmosphere prepared, to remove residual oil stain and to form metal-oxide film; According to the γ-Al of per unit mass
2o
3the water yield of powder adsorption, dipping precious metal palladium, platinum and palladium, palladium and rhodium or platinum, palladium and rhodium solution are in γ-Al
2o
3on powder, the total load amount of noble metal platinum and palladium is γ-Al
2o
330% of powder weight; By active A l
2o
3, the mixing of rich cerium type rare earth oxygen storage material, wherein active A l
2o
3mass percentage concentration be 90%, rich cerium type rare earth oxygen storage material mass percentage concentration is 10%, and adding deionized water to the solid content of slurries is 35%, and adopt ball mill to carry out ball milling to coating slurry, serous granule degree D90 is 30 μm; Metal spinning cake carrier impregnation proposed after 3min in coating slurry, put into centrifuge and dry, centrifuge speed is 1200r/min; By coating after metal spinning cake carrier at 200 DEG C, dry 4h, after oven dry under 600 DEG C of conditions roasting 4h; Repetitive coatings step, until the coating amount on metal spinning cake carrier reaches 50g/L, obtains tail gas purification of general small-size gasoline engine catalyst.
Wire pie carrier crush test:
Adopt micro-control electronic universal tester with the speed of 1mm/min, vertical S1 or S2 carrier end face, exerts pressure to wire pie carrier, and test silk screen is out of shape the maximum pressure that can bear.Concrete test result is in table 1
Table 1
Complete machine emission test
Choose the 26cc general small-size gasoline engine of certain factory production as test engine, sample M1, M2, M3, M4 and M5 of preparing according to embodiment one embodiment two and embodiment three are encapsulated in the silencer of 26cc general small-size gasoline engine respectively, carry out durable test according to the Abgasgesetz of U.S. EPA III, the resistance to emission result long afterwards of 50h is in table 2.
Table 2
| Sample | HC(g/kw.h) | NOx(g/kw.h) | CO(g/kw.h) | HC+NOx(g/kw.h) |
| M1 | 27.7 | 0.01 | 20.54 | 27.71 |
| M2 | 80.5 | 0.35 | 500.07 | 80.85 |
| M3 | 38.01 | 0.21 | 177.41 | 38.22 |
| M4 | 28.3 | 0.01 | 21.67 | 28.31 |
| M5 | 27.8 | 0.01 | 20.58 | 27.81 |
As can be seen from table 2 data, the complete machine HC+NOx of equipped sample M2 discharges much larger than M1, M3, M4 and M5, also far above the HC+NOx limit value 50g/kw.h of rules and regulations.Cut silencer open and observe catalyst structure change, find that sample M2 contraction distortion fracture of wire phenomenon is serious, and significant change does not occur sample M1 structural integrity, therefore the contraction distortion of M2 causes the complete machine HC+NOx of equipped sample M2 to discharge far more than the main cause of M1 and M3.
From table 2 data, the complete machine HC+NOx of equipped sample M1, M4 and M5 discharges all lower than M3, and wherein in M3, the cerium-oxide contents of cerium zirconium hydrogen-storing material is less than 50%.
In sum by metal spinning cake coated with solder and after soldering, improve the support strength of metal spinning cake carrier, decrease carrier contraction distortion in actual use, be thus conducive to the durability keeping tail gas purification of general small-size gasoline engine wire pie catalyst; Activity and the durability of catalyst is further increased by the hydrogen-storing material using cerium-oxide contents to be greater than 50%; By installing catalyst prepared by preparation method of the present invention additional, the requirement of EPA III pair of general small-size gasoline engine exhaust emissions durability can be met.
Claims (7)
1. a tail gas purification of general small-size gasoline engine wire pie catalyst, comprise wire pie carrier and catalyst coat, it is characterized in that: described wire pie carrier take metal wire material as skeleton, by knotting, rolling, be squeezed into, pie, coated with solder and high temperature brazing are prepared from, and described catalyst coat comprises active A l
2o
3with rich cerium type complex rare-earth oxidate containing valuable metal hydrogen-storing material, active A l in described catalyst coat
2o
3mass percent be 60 ~ 90%, the mass percent of rich cerium type rare earth oxygen storage material is 10 ~ 40%.
2. tail gas purification of general small-size gasoline engine wire pie catalyst as claimed in claim 1, is characterized in that: described active A l
2o
3γ-Al
2o
3the composite oxides of supported precious metal palladium, platinum and palladium, palladium and rhodium or platinum, palladium and rhodium.
3. tail gas purification of general small-size gasoline engine wire pie catalyst as claimed in claim 1, is characterized in that: the cerium oxide mass percent in described rich cerium type complex rare-earth oxidate containing valuable metal hydrogen-storing material is 50 ~ 100%.
4. the preparation method of tail gas purification of general small-size gasoline engine wire pie catalyst as claimed in claim 1, is characterized in that: comprise the steps:
(1) preparation of metal spinning cake carrier: metal wire material is knotted, rolls and be squeezed into pie, then put into nickel-based brazing cream and stop 1 ~ 5s, propose with the speed of 10 ~ 50mm/s, at 100 ~ 200 DEG C, dry 0.5 ~ 1h, put into the weldering of high temperature brazing slice, be prepared into wire pie carrier;
(2) pretreatment of carrier: wire pie carrier step (1) prepared 700 ~ 1100 DEG C of roasting pretreatment 1 ~ 4h in air atmosphere, to remove residual oil stain and to form metal-oxide film;
(3) active Al
2o
3preparation: adopt equi-volume process, according to the γ-Al of per unit mass
2o
3the water yield of powder adsorption, dipping precious metal palladium, platinum and palladium, palladium and rhodium or platinum, palladium and rhodium solution are in γ-Al
2o
3on powder, the total load amount of precious metal palladium, platinum and palladium, palladium and rhodium or platinum, palladium and rhodium is γ-Al
2o
30.5 ~ 30% of powder weight;
(4) preparation of coating slurry: by active A l
2o
3, the mixing of rich cerium type rare earth oxygen storage material, wherein active A l
2o
3mass percentage concentration be 60 ~ 90%, the mass percentage concentration of rich cerium type rare earth oxygen storage material is 10 ~ 40%, and add deionized water and stirring, the solid content in coating slurry is 10% ~ 35%, adopt ball mill to carry out ball milling to coating slurry, serous granule degree D90 is 5 ~ 30 μm;
(5) apply: propose after 1 ~ 3min in coating slurry metal spinning cake carrier impregnation prepared in step (4), put into centrifuge and dry, centrifuge speed is 800 ~ 1200r/min;
(6) dry: the metal spinning cake carrier after coating in step (5) is dried 1 ~ 4h at 100 ~ 200 DEG C, after oven dry under 400 ~ 600 DEG C of conditions roasting 2 ~ 4h;
(7) repeat step (4) and step (5), until the coating amount on metal spinning cake carrier reaches 10g/L ~ 50g/L, obtain tail gas purification of general small-size gasoline engine catalyst.
5. tail gas purification of general small-size gasoline engine wire pie catalyst as claimed in claim 1, is characterized in that: the quality of described wire pie catalyst carrier is 3 ~ 15g/.
6. tail gas purification of general small-size gasoline engine wire pie catalyst as claimed in claim 1, is characterized in that: described metal spinning cake is cuboid cake or cylinder cake.
7. tail gas purification of general small-size gasoline engine wire pie catalyst as claimed in claim 1, is characterized in that: the metal wire material diameter of metal spinning cake carrier is 0.3 ~ 0.5mm, and material is FeCrAl alloy.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105107500A (en) * | 2015-07-23 | 2015-12-02 | 无锡威孚环保催化剂有限公司 | Preparation method and applications of catalyst used for water heater waste gas treatment |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105107500A (en) * | 2015-07-23 | 2015-12-02 | 无锡威孚环保催化剂有限公司 | Preparation method and applications of catalyst used for water heater waste gas treatment |
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