CN107715875A - A kind of GPF four-way catalysts and preparation method thereof - Google Patents
A kind of GPF four-way catalysts and preparation method thereof Download PDFInfo
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- CN107715875A CN107715875A CN201711057455.7A CN201711057455A CN107715875A CN 107715875 A CN107715875 A CN 107715875A CN 201711057455 A CN201711057455 A CN 201711057455A CN 107715875 A CN107715875 A CN 107715875A
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/56—Platinum group metals
- B01J23/63—Platinum group metals with rare earths or actinides
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F01—MACHINES OR ENGINES IN GENERAL; ENGINE PLANTS IN GENERAL; STEAM ENGINES
- F01N—GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR MACHINES OR ENGINES IN GENERAL; GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR INTERNAL COMBUSTION ENGINES
- F01N3/00—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust
- F01N3/02—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for cooling, or for removing solid constituents of, exhaust
- F01N3/021—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for cooling, or for removing solid constituents of, exhaust by means of filters
- F01N3/033—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for cooling, or for removing solid constituents of, exhaust by means of filters in combination with other devices
- F01N3/035—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for cooling, or for removing solid constituents of, exhaust by means of filters in combination with other devices with catalytic reactors, e.g. catalysed diesel particulate filters
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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
- B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
Abstract
The invention discloses a kind of GPF four-way catalysts and preparation method thereof, including GPF carriers and catalyst coat.The catalyst coat is coated on GPF carrier inlet end port walls, in terms of oxide gross mass, including following component and content：Co-catalysis metal oxide 0 13%, activated alumina 30 60%, rare-earth transition metal composite oxides 30 60%, active component 0 3%, remaining is binding agent；Active component includes the first noble metal, Rh oxide, and the first noble metal is selected from Pd or Pt；Catalyst coat be activated alumina is supported on by the first noble metal, Rh, the slurry coating that the first noble metal, the Rh catalyst powders that are formed on rare-earth transition metal composite oxides are mixed to get forms, the 70g/L of coated weight 30；Active component mass ratio is the first noble metal：Rh=1‑1.5：1, the first bullion content is 4 20g/ft3, and Rh contents are 3 15g/ft3.The present invention can not block GPF ceramic channel walls, and high-efficient purification CO, HC, NOx, particulate matter, realize quaternary catalytic while reducing catalyst back pressure.
Description
Technical field
The present invention relates to motor vehicle exhaust emission field, more particularly to a kind of GPF catalyst and preparation method.
Background technology
Recently as the fast development of auto industry, also to ecological environment while the life to people brings convenient
Cause serious destruction.Motor vehicle emission pollutant mainly includes carbon monoxide (CO), hydrocarbon (HC), nitrogen oxides
(NOx), particulate matter etc..To limit vehicle exhaust pollution on the environment, country has put into effect a series of regulation and it has been discharged
Limit value is provided.
With《GB18352.6-2016 light-duty vehicles pollutant emission limit and measuring method》(Chinese 6th stage)
Issue, from the year two thousand twenty July 1, the standard of state six will be implemented in full.Relative to《GB18352.5-2013 light-duty vehicle pollutants
Emission limit and measuring method》For the standard of state five, state six requires more harsh, and not only CO and HC is on the basis of the limit value of state five
Add tight 30% or so, added sternly the control requirement to NOx, at the same require directly jetting gasoline engine each operating mode will keep it is stable and
Relatively low particulate matter quality (PM) and particulate matter quantity (PN).Its Chinese 6a discharge standard, PM limit values are 4.5mg/km, and PN is limited
It is worth for 6.0 × 1011Individual/km；State's 6b discharge standards, PM limit values are 3mg/km, and PN limit values are 6.0 × 1011Individual/km.
In order to adapt to the requirement of the emission limit of state six, GPF becomes gasoline engine post processing as surface type grain catcher
Standard configuration in system.Its importance will be equivalent to the diesel particulate trap (DPF) on diesel engine.GPF filtering
Mechanism is essentially identical with DPF, that is, is vented and passes through porous wall, abbreviation " wall stream " with certain flow velocity.GPF wall-flow types trap
The filtration body of device is made up of multiple square ducts, by the ceramic phase that thin-walled is breathed freely every when one between adjacent duct
When the import in individual duct is plugged, outlet is necessarily unlimited, and the outlet in the adjacent duct of surrounding can be plugged.It is such
Structure result in tail gas enter from unlimited duct it is fashionable could must be opened wide by ventilative thin wall ceramic from outlet it is adjacent
Duct is discharged, and therefore the particulate matter in tail gas is attached on the wall of intake channel, reached the purpose of particle collection.
Research of the international renowned company such as Japanese NGK, U.S. CORNING and BASF to GPF achieves larger progress,
Through there are some commercialized products；The U of CN 203702290 are to inspire confidence in a kind of disclosed cordierite by domestic Wuxi prestige
Wall-flow type GPF, it can effectively trap the particulate matter in vehicle exhaust.Although they gradually walk in the research to GPF carriers
Enter the stage of ripeness, but the research done for GPF catalyst this aspect is still very few.
The content of the invention
The technical problems to be solved by the invention are to overcome above mentioned problem, and propose a kind of GPF four-way catalysts and
Its method prepared, by GPF supported on carriers palladium rhodium catalysis coatings, composition quaternary catalytic.Do not blocking GPF ceramic holes
Road, carbon monoxide, hydrocarbon, oxynitrides and particulate matter can be effectively intercepted while reducing catalyst back pressure.
The technical scheme is that：A kind of GPF four-way catalysts of the present invention, including GPF carriers and catalyst
Coating, it is characterised in that：The catalyst coat is coated on GPF carrier inlet end port walls, in terms of oxide gross mass,
Including following component and content：Co-catalysis metal oxide 0-13%, activated alumina 30-60%, rare earth-transition metal are compound
Oxide 30-60%, active component 0-3%, remaining is binding agent；Active component includes the oxide and your gold of the first noble metal
Belong to Rh oxide, first noble metal is selected from Pd or Pt；The catalyst coat is in activity by the first noble-metal-supported
The the first noble metal catalyst powder and Rh formed on aluminum oxide, rare earth-transition metal composite oxides is supported on active oxidation
The slurry coating that the Rh catalyst powders formed on aluminium, rare earth-transition metal composite oxides are sufficiently mixed to obtain is formed, and it is applied
The amount of covering is 30-70g/L；The active component mass ratio is the first noble metal：Rh=1-1.5：1, the first bullion content is 4-
20g/ft3, Rh contents are 3-15g/ft3。
Wherein, the first noble metal selects Pd or Pt, is mainly used in converting CO and HC, and with price is relatively low, aboundresources,
The advantages that heat resistance is preferable；Rh is the main component for controlling amount of nitrogen oxides, can effectively handle NOx, and durability it is good,
It is not easy to be poisoned.
Further, in GPF four-way catalysts of the present invention, the GPF carriers are wall-flow filter, are had
50-70% porosity.This cause tail gas enter from the duct that GPF carriers open wide it is fashionable must be by ventilative thin wall ceramic
Therefore it can be attached to from the particulate matter in the unlimited adjoining cell channels discharge in outlet, tail gas on the wall of intake channel, can be efficient
Ground reaches the purpose of particle collection and catalyzed conversion.
Further, in GPF four-way catalysts of the present invention, the co-catalysis metal oxide be selected from La, Ce,
One or more in Zr, Fe, Mn, Ni, Ba oxide, it is the heat endurance that can improve carrier/active coating that it, which is acted on,
And mechanical strength, and sintering of catalyst can be suppressed, promote being uniformly distributed for catalyst.
Further, in GPF four-way catalysts of the present invention, the activated alumina is to contain 1-20% dopants
Composite alumina, the dopant is selected from La2O3、ZrO2、CeO2、Y2O3In one of which or several, the active oxidation
The specific surface area of aluminium is in 120-200 ㎡/g, pore volume 0.4-0.8cc/g.Above-mentioned dopant selects rare earth-transition metal, can
It is effectively increased the stability of Structure of activated aluminas and the catalytic activity of base metal.
Further, in GPF four-way catalysts of the present invention, the rare earth-transition metal composite oxides include
Following component and content：40-60%ZrO2, 20-50%CeO2, 10-20%La2O3, 0-10%Y2O3, 0-10%Pr6O11、0-
10% Nd2O3, 0-10%MnO2, 0-10%Sr2O3, 0-10%Co2O3.Rare earth-transition metal composite oxides are as storage oxygen material
Material, preferably storage oxygen effect can be reached, can be supplied oxygen in time when air-fuel ratio changes；In addition certain urge is also acted
Change acts on, and can reduce CO, HC, NOx discharge capacity.
The invention also discloses a kind of preparation method of GPF four-way catalysts, it is characterised in that：Comprise the following steps：
(1) raw material and pretreatment are weighed：According to each component content in catalyst coat (in terms of oxide gross mass)：Co-catalysis gold
Belong to oxide 0-13%, activated alumina 30-60%, rare earth-transition metal composite oxides 30-60%, active component 0-
3%, remaining is binding agent, and active component mass ratio is the first noble metal：Rh=1-1.5：1, the first bullion content is 4-
20g/ft3, Rh contents are 3-15g/ft3, calculate and weigh co-catalysis metal oxide soluble salt, be activated alumina powder, dilute
Soil-compound transition metal oxide powder, the nitrate solution of the first noble metal, Rh nitrate solution, binding agent, ice vinegar
Acid, wherein the first noble metal is selected from Pd or Pt；Activated alumina powder, rare earth-transition metal composite oxide powder are passed through
Muffle furnace passes through 1-5 hour high-temperature process at 800-1050 DEG C, makes the basic pore-free of the material after processing；
(2) the first noble metal catalyst powder is prepared：Take co-catalysis metal oxide soluble salt in a certain amount of step (1), work
Property alumina powder, rare earth-transition metal composite oxide powder, the nitrate solution of the first noble metal, by co-catalysis metal
Oxide soluble salt is dissolved in appropriate pure water, by activated alumina powder, rare earth-transition metal composite oxide power, is helped
Catalytic metal oxide soluble salt solution adds ball grinder ball milling 3-8min and stands 20-60min, adds the first noble metal
Nitrate solution continues ball milling 1-5min, stands 30-90min, forms slurry；Slurry is poured out and is placed in 100-150 DEG C of drying, powder
Through 500-850 DEG C of roasting 1-3h after broken, the first noble metal catalyst powder is obtained；
(3) Rh catalyst powders are prepared：Take co-catalysis metal oxide soluble salt, the activated alumina in a certain amount of step (1)
Powder, rare earth-transition metal composite oxide powder, Rh nitrate solution, co-catalysis metal oxide soluble salt is dissolved
, can by activated alumina powder, rare earth-transition metal composite oxide power, co-catalysis metal oxide in appropriate pure water
Salt solution adds ball grinder ball milling 3-8min and stands 20-60min, and the nitrate solution for adding Rh continues ball milling 1-
5min, 30-90min is stood, form slurry；Slurry is poured out and is placed in 100-150 DEG C of drying, through 500-850 DEG C of roasting after crushing
1-3h, obtain Rh catalyst powders；
(4) slurry is prepared：According to the first noble metal catalyst powder：Rh catalyst powder=1-1.5:1, take a certain amount of bonding
Agent, the first noble metal catalyst powder, Rh catalyst powders are added in ball grinder, add oxide gross mass 2-5% ice
Acetic acid and appropriate pure water, ball milling 5-20min, adding pure water and adjusting solid content makes its equal to 25-36%, abundant ball milling 1-5min
Even mixing, is filtrated to get slurry；
(5) applying coating：By coating coated weight 30-70g/L, slurry is quantitatively uploaded with coating machine in the inlet end of GPF carriers, is adopted
Most water in slurry is taken out of from outlet side with coating machine, uniformly coating is stored in GPF carrier inlet end port walls to slurry
On；
(6) coating is dried：Coated GPF carriers are dried into 0.3-1h using hot-air seasoning line, then through 500-850 DEG C of roasting 1-
5h, obtain described GPF four-way catalysts.
Above-mentioned preparation process is coated using negative pressure or pressure difference mode, and coating is adsorbed from inlet end or the mode of pressure difference applies
Be layed onto on the thin-walled of GPF carriers, enable to coating uniform to be distributed on the ceramic thin-walled of GPF carriers, strengthen to CO, HC,
NOx catalytic effect.Meanwhile high-temperature roasting is carried out to the GPF carriers after coating and more effectively can be consolidated catalyst coat
It is scheduled on the ceramic thin-walled of GPF carriers.
Further, in the preparation method of GPF four-way catalysts of the present invention, the GPF carriers are wall-flow type mistake
Filter, there is 50-70% porosity.
Further, in the preparation method of GPF four-way catalysts of the present invention, the co-catalysis metal oxide can
One or more in nitrate or acetate of the dissolved salt selected from La, Ce, Zr, Fe, Mn, Ni, Ba.
Further, in the preparation method of GPF four-way catalysts of the present invention, the activated alumina powder be containing
There is the composite alumina of 1-20% dopants, the dopant is selected from La2O3、ZrO2、CeO2、Y2O3In one of which or several
Kind, the specific surface area of the activated alumina powder is in 120-200 ㎡/g, pore volume 0.4-0.8cc/g.
Further, in the preparation method of GPF four-way catalysts of the present invention, the rare earth-transition metal is compound
Oxide powder includes following component and content：40-60%ZrO2, 20-50%CeO2, 10-20%La2O3, 0-10%Y2O3、0-
10% Pr6O11, 0-10%Nd2O3, 0-10%MnO2, 0-10%Sr2O3, 0-10%Co2O3。
The beneficial effects of the invention are as follows：
1st, the present invention, compared to traditional GPF, is not only protected by coating palladium rhodium or platinum rhodium catalysis coating in GPF carriers inlet end
Card Pd, Pt, Rh, co-catalysis metal etc. will not block GPF ceramic channel walls, can reduce catalyst back pressure, keep its good
Grain thing interception result, and quaternary height can also be realized in the effective purified treatment carbon monoxide of inlet end, hydrocarbon, oxynitrides
Effect catalysis, is particularly suitable for use under high-speed state, can show more preferable particulate matter interception result.
2nd, preparation method of the present invention is simple, by the way that the first noble metal, Rh is oxide carried in difference from different co-catalysis
Activated alumina, the first noble metal, Rh catalyst powders are formed on rare earth-transition metal composite oxides, bonding is mixed into
Slurry coating forms, and single application mode, simplifies production technology, reduces production cost；And coating uniform is fine and close, tack
Can be good, the amount of PM, PN in exhaust will not be increased because of the presence of coating, noble metal and co-catalysis metal oxide uniformly divide
Dissipate, its catalytic action to CO, HC, NOx can be obviously improved.
3rd, preparation process of the present invention is pre- to the high temperature of activated alumina powder, rare earth-transition metal composite oxide powder
Processing can make the basic pore-free of material, improve the durability of catalyst, and it can be made preferably to carry active component and help and urged
Change metal, and noble metal that can be after proof load is not easy to be buried.
Brief description of the drawings
PM concentration of emissions and rotation speed relation curve under difference catalytic treatment state when Fig. 1 is engine 1.5L engine bench tests.
PN concentration of emissions and rotation speed relation curve under difference catalytic treatment state when Fig. 2 is engine 1.5L engine bench tests.
Back pressure and rotation speed relation curve under difference catalytic treatment state when Fig. 3 is engine 1.5L engine bench tests.
Embodiment
In conjunction with accompanying drawing, the present invention is further illustrated.
Embodiment 1
The present embodiment is Φ 118.4*127 (mm) from specification, and hole mesh number is the wall-flow type of 300cpsi cordierites
GPF carriers；The soluble salt solution of co-catalysis metal oxide is from cerous nitrate (mass fraction 39%), lanthanum nitrate (quality point
Number for 37.00%), zirconium acetate solution (mass fraction 25%)；Activated alumina powder selects 2.5%La2O3With 97.5%
Al2O3, specific surface area is 197.494 ㎡/g, pore volume 0.7624cc/g；Rare earth-transition metal composite oxide powder selects cerium
Zirconium lanthanum yttrium and cerium zirconium lanthanum neodymium, the main component of wherein cerium zirconium lanthanum yttrium is 40%CeO2, 50%ZrO2, 5%La2O3, 5%Y2O3, cerium
The main component of zirconium lanthanum neodymium is 25%CeO2, 68%ZrO2, 3%La2O3, 4%Nd2O3；Binding agent is 10% from mass fraction
Alumina gel, glacial acetic acid from chemistry it is pure, the first noble metal selects Pd, and its nitrate solution is that mass fraction is 15.03%
Palladium nitrate, Rh nitrate solution are the rhodium nitrate that mass fraction is 9.77%, active component Pd:Rh=1:1.
(1) raw material and pretreatment are weighed：According to each component content in catalyst coat (in terms of oxide gross mass):Help and urge
Change metal oxide 3.298% (including cerium oxide 1.358%, lanthana 0.97%, zirconium oxide 0.97%), activated alumina
46.621%th, rare earth-transition metal composite oxides 46.233% (including cerium zirconium lanthanum yttrium 22.795%, cerium zirconium lanthanum neodymium
23.438%), active component 0.848% (including palladium oxide 0.424%, rhodium oxide 0.424%), binding agent 3%, and activearm
It is Pd to divide mass ratio：Rh=1:1, noble metal total content is 12g/ft3, calculate and weigh co-catalysis metal oxide soluble salt,
Activated alumina powder, rare earth-transition metal composite oxide powder, palladium nitrate solution, rhodium nitrate solution, binding agent, and will
Activated alumina powder, rare earth-transition metal composite oxide powder are passed through at 5 hours high temperature by Muffle furnace at 1000 DEG C
Reason, makes the basic pore-free of the material after processing.
(2) Pd catalyst powders 205g is prepared：By oxide mass in Pd catalyst powders than respectively 2%, 1%,
2%th, 47.126%, 47%, 0.874%, take out cerous nitrate, lanthanum nitrate, acetic acid zirconium, active oxidation aluminium powder powder in step (1)
End, cerium zirconium lanthanum yttrium, palladium nitrate solution；Cerous nitrate, lanthanum nitrate, acetic acid zirconium are dissolved in appropriate pure water, by active oxidation aluminium powder
Body, cerium zirconium lanthanum yttrium, cerous nitrate, lanthanum nitrate, zirconium acetate solution add ball grinder ball milling 5min and stand 30min, add nitric acid
Palladium solution continues ball milling 3min, stands 1h, forms slurry；Slurry is poured out and is placed in 120 DEG C of drying, through 600 DEG C of roastings after crushing
2h, obtain Pd catalyst powders.
(3) Rh catalyst powders 205g is prepared：By oxide mass in Rh catalyst powders than respectively 0.8%, 1%,
49%th, 48.326%, 0.874%, take out lanthanum nitrate in step (1), acetic acid zirconium, active oxidation aluminium powder powder, cerium zirconium lanthanum neodymium,
Rhodium nitrate solution；Lanthanum nitrate, acetic acid zirconium are dissolved in appropriate pure water, by activated alumina powder, cerium zirconium lanthanum neodymium, lanthanum nitrate,
Zirconium acetate solution adds ball grinder ball milling 5min and stands 30min, adds rhodium nitrate solution and continues ball milling 3min, stands 1h,
Form slurry；Slurry is poured out and is placed in 120 DEG C of drying, through 600 DEG C of roasting 2h after crushing, obtains Rh catalyst powders.
(4) slurry 400g is prepared：According to Pd catalyst powders：Rh catalyst powder=1:1, oxide mass ratio in slurry
Respectively 3%, 48.5%, 48.5%, take binding agent, Pd catalyst powder, Rh catalyst powder to add ball grinder, and add oxygen
The glacial acetic acid of compound total amount 3% and appropriate water, ball milling 10min, add pure water and adjust solid content to 33% ball milling 2min, mistake
Filter obtains slurry.
(5) applying coating：Be 50g/L by coating coated weight, slurry is quantitatively uploaded with coating machine 211.76g slurries in
The inlet end of GPF carriers, most water in slurry is taken out of from outlet side using coating machine, uniformly coating is stored in GPF to slurry
On the ceramic wall of inlet end through hole, GPF coatings are completed.
(6) coating is dried：Coated GPF catalyst is dried into 0.5h using hot-air seasoning line, then through 550 DEG C of roastings
3h, obtain GPF four-way catalysts.
Catalyst obtained by above is GPF catalyst A.
Embodiment 2
In the case where other are constant, the GPF catalyst B that coated weight is 30g/L is similarly made.
Embodiment 3
In the case where other are constant, the GPF catalyst C that coated weight is 70g/L is similarly made.
Embodiment 4
Other are identical with GPF catalyst A, and it is Pd to change active component mass ratio：Rh=4：3, and Pd, Rh total content are
14g/ft3, coating coated weight is 50g/L, obtains GPF catalyst D.
Embodiment 5
Other are identical with GPF catalyst A, and the first noble metal selects Pt, and it is Pt to change active component mass ratio：Rh=1：
1, and Pt, Rh noble metal total content are 12g/ft3, coating coated weight is 50g/L, obtains GPF catalyst E.
Embodiment 6
The present embodiment is Φ 118.4*127 (mm) from specification, and hole mesh number is 300cpsi, the wall-flow type of cordierite
GPF carriers；Active alumina powder selects 1%La2O3, 3%CeO2And 96%Al2O3, specific surface area 187.24m2/ g, pore volume
For 0.6954cc/g；The soluble salt solution of co-catalysis metal oxide is from cerous nitrate (mass fraction 39%), lanthanum nitrate (matter
Measure fraction for 37.00%), zirconium acetate solution (mass fraction 25%)；Binding agent is from the Alumina gel that mass fraction is 10%；
Glacial acetic acid is pure from chemistry, and the first noble metal selects Pd, its nitrate solution be mass fraction be 15.03% palladium nitrate, Rh
Nitrate solution be rhodium nitrate that mass fraction is 9.77%.
In the present embodiment, active component mass ratio is Pd：Rh=1:1, noble-metal coated amount is 12g/ft3, coating coating
Measure as 50g/L, ball milling is carried out using planetary ball mill, noble-metal coated machine is coated.Active alumina powder and cerium zirconium lanthanum
Yttrium, cerium zirconium lanthanum neodymium pass through 5h high-temperature process using Muffle furnace at 1000 DEG C.
GPF catalyst F is made with GPF catalyst A in other manufacturing process.
Test case 1
For blank pipe, TWC+GPF carriers, TWC+GPF catalyst A, TWC+GPF catalyst B, TWC+GPF catalyst C,
TWC+GPF catalyst D, TWC+GPF catalyst seven kinds of catalytic treatment states of E, emission test, pollutant are carried out using vehicle 1.5L
Detection project is CO, THC, NOx, PM, PN five.In test, TWC catalysis assemblies are using same, a dismounting GPF part.
Table 1 shows the concentration of emission by every pollutant after above-mentioned each catalytic treatment state.
As shown in Table 1, GPF catalyst A, B, C, D, E, F that prepared by above-described embodiment 1-6 has preferably to CO, HC, NOx
Catalytic action, there is excellent treatment effect to PM, PN.
Test case 2
For blank pipe, TWC+GPF carriers, TWC+GPF catalyst A, TWC+GPF catalyst B, TWC+GPF catalyst C five
Kind state, engine bench test is carried out using engine 1.5L.
With reference to Fig. 1-Fig. 3 understand, the GPF four-way catalysts prepared by embodiment 1-3 shown in PM, PN processing compared with
Good treatment effect；And back pressure increase is smaller.Compared with GPF four-way catalysts, PM, PN treatment effect and back pressure exist GPF carriers
It is essentially identical in slow-speed of revolution test, although a little higher than GPF carriers of GPF four-way catalysts back pressure at high speed, increasing degree
It is smaller, and PM, PN treatment effect are obviously improved.
The principle and its effect of the specific embodiment described herein only illustrative present invention, not for limitation
The present invention.Any person skilled in the art can all be carried out under the spirit and scope without prejudice to the present invention to above-described embodiment
Modifications and changes.Therefore, as long as those of ordinary skill in the art without departing from disclosed spirit with
All equivalent modifications completed under technological thought or change, it should be covered by the claim of the present invention.
Claims (10)
1. a kind of GPF four-way catalysts, including GPF carriers and catalyst coat, it is characterised in that：The catalyst coat coating
On GPF carrier inlet end port walls, in terms of oxide gross mass, including following component and content：Co-catalysis metal aoxidizes
Thing 0-13%, activated alumina 30-60%, rare earth-transition metal composite oxides 30-60%, active component 0-3%, remaining
For binding agent；Active component includes the oxide of the first noble metal and noble metal Rh oxide, and first noble metal is selected from
Pd or Pt；The catalyst coat be by the first noble-metal-supported on activated alumina, rare earth-transition metal composite oxides
The first noble metal catalyst powder and the Rh formed is supported on activated alumina, formed on rare earth-transition metal composite oxides
The slurry coating that is sufficiently mixed to obtain of Rh catalyst powders form, its coated weight is 30-70g/L；The active component quality
Than for the first noble metal：Rh=1-1.5：1, the first bullion content is 4-20g/ft3, Rh contents are 3-15g/ft3。
2. GPF four-way catalysts according to claim 1, it is characterised in that：The GPF carriers are wall-flow filter,
Porosity with 50-70%.
3. GPF four-way catalysts according to claim 1, it is characterised in that：The co-catalysis metal oxide be selected from La,
One or more in Ce, Zr, Fe, Mn, Ni, Ba oxide.
4. GPF four-way catalysts according to claim 1, it is characterised in that：The activated alumina is to contain 1-20%
The composite alumina of dopant, the dopant are selected from La2O3、ZrO2、CeO2、Y2O3In one of which or several, the work
The specific surface area of property aluminum oxide is in 120-200 ㎡/g, pore volume 0.4-0.8cc/g.
5. GPF four-way catalysts according to claim 1, it is characterised in that：The rare earth-transition metal composite oxides
Including following component and content：40-60%ZrO2, 20-50%CeO2, 10-20%La2O3, 0-10%Y2O3, 0-10%Pr6O11、
0-10%Nd2O3, 0-10%MnO2, 0-10%Sr2O3, 0-10%Co2O3。
A kind of 6. preparation method of GPF four-way catalysts, it is characterised in that：Comprise the following steps：
(1) raw material and pretreatment are weighed：According to each component content in catalyst coat (in terms of oxide gross mass)：Co-catalysis gold
Belong to oxide 0-13%, activated alumina 30-60%, rare earth-transition metal composite oxides 30-60%, active component 0-
3%, remaining is binding agent, and active component mass ratio is the first noble metal：Rh=1-1.5：1, the first bullion content is 4-
20g/ft3, Rh contents are 3-15g/ft3, calculate and weigh co-catalysis metal oxide soluble salt, be activated alumina powder, dilute
Soil-compound transition metal oxide powder, the nitrate solution of the first noble metal, Rh nitrate solution, binding agent, ice vinegar
Acid, wherein the first noble metal is selected from Pd or Pt；Activated alumina powder, rare earth-transition metal composite oxide powder are passed through
Muffle furnace passes through 1-5 hour high-temperature process at 800-1050 DEG C, makes the basic pore-free of the material after processing；
(2) the first noble metal catalyst powder is prepared：Take co-catalysis metal oxide soluble salt in a certain amount of step (1), work
Property alumina powder, rare earth-transition metal composite oxide powder, the nitrate solution of the first noble metal, by co-catalysis metal
Oxide soluble salt is dissolved in appropriate pure water, by activated alumina powder, rare earth-transition metal composite oxide power, is helped
Catalytic metal oxide soluble salt solution adds ball grinder ball milling 3-8min and stands 20-60min, adds the first noble metal
Nitrate solution continues ball milling 1-5min, stands 30-90min, forms slurry；Slurry is poured out and is placed in 100-150 DEG C of drying, powder
Through 500-850 DEG C of roasting 1-3h after broken, the first noble metal and catalyst powder are obtained；
(3) Rh catalyst powders are prepared：Take co-catalysis metal oxide soluble salt, the activated alumina in a certain amount of step (1)
Powder, rare earth-transition metal composite oxide powder, Rh nitrate solution, co-catalysis metal oxide soluble salt is dissolved
, can by activated alumina powder, rare earth-transition metal composite oxide power, co-catalysis metal oxide in appropriate pure water
Salt solution adds ball grinder ball milling 3-8min and stands 20-60min, and the nitrate solution for adding Rh continues ball milling 1-
5min, 30-90min is stood, form slurry；Slurry is poured out and is placed in 100-150 DEG C of drying, through 500-850 DEG C of roasting after crushing
1-3h, obtain Rh catalyst powders；
(4) slurry is prepared：According to the first noble metal catalyst powder：Rh catalyst powder=1-1.5:1, take a certain amount of bonding
Agent, the first noble metal catalyst powder, Rh catalyst powders are added in ball grinder, add oxide gross mass 2-5% ice
Acetic acid and appropriate pure water, ball milling 5-20min, adding pure water and adjusting solid content makes its equal to 25-36%, abundant ball milling 1-5min
Even mixing, is filtrated to get slurry；
(5) applying coating：By coating coated weight 30-70g/L, slurry is quantitatively uploaded with coating machine in the inlet end of GPF carriers, is adopted
Most water in slurry is taken out of from outlet side with coating machine, uniformly coating is stored in GPF carrier inlet end port walls to slurry
On；
(6) coating is dried：Coated GPF carriers are dried into 0.3-1h using hot-air seasoning line, then through 500-850 DEG C of roasting 1-
5h, obtain described GPF four-way catalysts.
7. the preparation method of GPF four-way catalysts according to claim 6, it is characterised in that：The GPF carriers are wall stream
Formula filter, there is 50-70% porosity.
8. the preparation method of GPF four-way catalysts according to claim 6, it is characterised in that：The co-catalysis metal oxygen
One or more in nitrate or acetate of the compound soluble salt selected from La, Ce, Zr, Fe, Mn, Ni, Ba.
9. the preparation method of GPF four-way catalysts according to claim 6, it is characterised in that：The active oxidation aluminium powder
Body is the composite alumina containing 1~20% dopant, and the dopant is selected from La2O3、ZrO2、CeO2、Y2O3In wherein one
Kind is several, and the specific surface area of the activated alumina powder is in 120-200 ㎡/g, pore volume 0.4-0.8cc/g.
10. the preparation method of GPF four-way catalysts according to claim 6, it is characterised in that：The rare earth-transition gold
Category composite oxide powder includes following component and content：40-60%ZrO2, 20-50%CeO2, 10-20%La2O3, 0-10%
Y2O3, 0-10%Pr6O11, 0-10%Nd2O3, 0-10%MnO2, 0-10%Sr2O3, 0-10%Co2O3。
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