CN109201052A - A kind of diesel soot particle oxidation catalyst and preparation method thereof - Google Patents
A kind of diesel soot particle oxidation catalyst and preparation method thereof Download PDFInfo
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- CN109201052A CN109201052A CN201811160971.7A CN201811160971A CN109201052A CN 109201052 A CN109201052 A CN 109201052A CN 201811160971 A CN201811160971 A CN 201811160971A CN 109201052 A CN109201052 A CN 109201052A
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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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- 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
- B01J23/66—Silver or gold
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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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0215—Coating
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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
- F01N3/08—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for rendering innocuous
- F01N3/10—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for rendering innocuous by thermal or catalytic conversion of noxious components of exhaust
- F01N3/105—General auxiliary catalysts, e.g. upstream or downstream of the main catalyst
- F01N3/106—Auxiliary oxidation catalysts
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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
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Abstract
The invention discloses a kind of diesel soot particle oxidation catalysts and preparation method thereof.It is made of coating material and the active component being immersed on coating material；Active component is made of the precious metal salt containing Pt and Pd；Noble metal total content is 0.5~3g/ft3 in catalyst, and the weight ratio of precious metals pt and Pd are 2:1~10:1；Coating material is the metal composite oxide of high cerium content, wherein cerium oxide weight percent content is greater than or equal to 80%.Preparation method includes: directly to mix coating material and the precious metal salt solution of active component；By stirring, ball milling, pH1.5~5.5 are controlled to adjust, partial size D50 is 2 μm~7 μm, solid content≤20%；Coated on carrier, roasting is obtained.Catalyst carrier grout distribution of the present invention is uniform, and no plug-hole phenomenon, back pressure is low in the tail gas clean-up processing system of practical application, has high oxygen storage power, can be realized at a lower temperature the quickly purpose of oxidation PM.
Description
Technical field
The invention belongs to catalyst research preparation technical fields, especially belong to the preparation of motor-driven vehicle gas disposal catalyst research
Technical field, in particular to a kind of oxidation catalyst and its system with good low temperature catalysis oxidation diesel soot particle (PM)
Standby technology.
Background technique
The diesel engine thermal efficiency is high, and fuel oil after high-temperature oxydation, discharges a large amount of heat, but lack due to being laid out in cylinder
Oxygen or high temperature, part fuel oil form the solid granule based on carbon, i.e. PM by deterioration dehydrogenation；Or burning is not
Adequacy merges dissolved organic matter together with machine oil, generates a large amount of carbon soot particles, i.e. SOF；In addition to this, also
The inorganic matters such as part of sulfuric acid salt particle, mix, and form a large amount of black smoke, are discharged among atmosphere by tail gas, PM
Particle is smaller, and harm to the human body is bigger, and usual PM particle size integrated distribution, can be to the respiratory system of human body in 0.1-1.0um
Cause serious damage.Therefore, stringent emission limit regulation has all been done in emission regulation to PM by various countries.
In recent years, with the continuous development of car industry, as emission regulation is more and more harsh, after motor vehicle exhaust gases
Reason system reinforces the catharsis to PM in exhaust gas, it appears more and more important.By using honeycomb ceramic filter filter,
PM trapping is got up, then under the catalysed oxidn of coated catalysts, being oxidized removing to fall is current numerous studies
Direction.Temperature, which is arranged, according to diesel engine original more concentrates on 300 DEG C hereinafter, this causes to trap usually between 200~400 DEG C
To PM be difficult in O2Under the conditions of existing, active oxidation is carried out, on the contrary, in NO2In the presence of, then oxygen can occur to PM
Change, has huge booster action, PM is oxidized to CO2, this requires have a large amount of NO in air-flow2In the presence of in other words, it is desirable that
Catalysis material must have good NO oxidability.Actual PM trapping during, when PM is trapped it is a certain amount of when, largely
PM is covered on the surface of catalyst, causes Catalytic Layer and airflow layer to completely cut off, can not provide a large amount of active oxygen, makes its PM that oxygen occur
Change, accumulated as PM is trapped, then the back pressure that will lead to entire after-treatment system sharply increases, and causes to engine operation serious bad
Changing influences, and then requires catalysis material to have good oxygen storage capacity at this time, to generate a large amount of active oxygen, promotes NO that oxygen occurs
Change, finally promote PM at a lower temperature, oxidation ignition quickly occurs, promotes after temperature accumulates gradually, and in turn
Catalysis oxidation occurs for NO, while providing more active oxygens, and further PM is promoted to aoxidize.
Honeycomb ceramic filter filter coated catalysts mainly include noble metal (PGM) with catalytic activity and its urge
Change material, in particular for the oxidation of PM, with greater need for the effect between concern catalysis material and PM, cerium oxide is as a kind of
Good hydrogen-storing material has been widely used for purifying vehicle exhaust field, but its high-temperature stability is poor, by high-temperature water
After heat ageing, specific surface and its hole hold deterioration and collapse than more serious, this has seriously affected the oxygen storage capacity of this material, also greatly
Abundant application of the limit value to its performance.Performance improvement is carried out by certain mode, while carrying out certain pretreatment to material,
Its high-temperature stability and its catalytic oxidation performance to PM can then be greatlyd improve.It realizes in NO2Auxiliary under, in lower temperature
Under the conditions of degree, the catalysis oxidation of PM is fast implemented.This not only improves only the safety of engine operation, post-processes it entirely
System temperature is quickly oxidized removing and falls less than 600 DEG C, while while trapping PM, can improve significantly engine
Operational efficiency, reduce because post-processing purifying system generate back pressure to engine cause deterioration influence.
Summary of the invention
Deficiency discloses one kind with good low temperature catalysis oxidation diesel soot particle to the present invention according to prior art
(PM) oxidation catalyst and its technology of preparing.Catalyst cost is being reduced the problem to be solved in the present invention is to provide a kind of
Meanwhile preparation method and its catalyst with good low temperature catalysis oxidation diesel soot beaded catalyst.
The invention is realized by the following technical scheme:
A kind of diesel soot particle oxidation catalyst, it is characterised in that: the catalyst is by coating material and is immersed in
Active component on coating material is made；
Active component is made of the precious metal salt containing Pt and Pd；Noble metal total content is 0.5~3g/ft in catalyst3, expensive
The weight ratio of Pt metal and Pd are 2:1~10:1；
Coating material is the metal composite oxide of high cerium content, wherein cerium oxide weight percent content is greater than or waits
In 80%.
It also include at least one of single-phase oxide or/and composite oxides in the metal composite oxide；It is single-phase
Oxide includes: zirconium oxide, lanthana, praseodymium oxide, titanium oxide；Composite oxides include: aluminium oxide-zirconium oxide, aluminium oxide-oxygen
Change titanium, Ceria-zirconia, cerium oxide-praseodymium oxide, alumina-thoria.
The cerium oxide through rare earth element, transition metal or/and alkali metals modified, rare earth modified element include: La, Ce,
One or more of Pr, Sm, Er, Nd, Y, Re, transition metal, alkali metals modified include: K, Sr, Cr, Ag, Mn, Fe, Cu,
One or more of Zr, Mo, W, Ni, Hf are doped.
Coating material partial size≤10 μm, specific surface area >=100m2/g。
The noble metal precursor body is the inorganic salts containing Pt and Pd, and inorganic salts include but is not limited to nitrate, sulfate, vinegar
Hydrochlorate and amine close coordination salt, the mass percentage concentration 0.1%~1.0% in catalyst coatings material.
The invention also discloses above-mentioned catalyst and its carrier to coat preparation method.
A kind of diesel soot particle oxidation catalyst preparation method, comprising the following steps:
(1) coating material and active component are weighed by above-mentioned catalyst components dosage；
(2) coating material and the precious metal salt solution of active component are directly mixed；By stirring, ball milling, control to adjust
PH1.5~5.5, partial size D50 are 2 μm~7 μm, solid content≤20%；
(3) it being coated on carrier, the catalyst slurry of step (2) preparation is coated on carrier, upper loading capacity is 10~
30g/L；
(4) it roasts, maturing temperature: 550 DEG C~850 DEG C, calcining time: 5~50 hours.
Slurry is coated to above honeycomb ceramic filter filter-carrier by the catalyst slurry using lower grouting way,
Detailed process includes: to constrain flow direction and its flow rate of slurry by being in the milk from the bottom to top, when Starch Level reaches design
Height when, stop grouting.
Catalyst coat of the present invention constitutes signal layer coating structure in carrier surface.Catalysis material disclosed by the invention composition,
Catalysis material coated weight, precious metal ratios and its coating can be realized in the distribution of honeycomb ceramic filter filter with inner surface
The purpose of PM is quickly aoxidized at a lower temperature.
Cerium-oxide contents are more than or equal to 80% in coating material of the present invention, while by rare earth, transition metal or/and alkali gold
Belong to and being modified, then in conjunction with a certain amount of precious metal salt solution, forms catalyst material after roasting, the present invention is contained using high cerium
Material is measured, has higher oxygen storage capacity, after PM trapping accumulation arrives a certain amount of, tail gas and catalyst coatings is completely cut off, caused
A large amount of oxygen cannot come into full contact with catalyst coatings, need a large amount of active oxygen at this time, go that NO is promoted to aoxidize, promote simultaneously
Contact active oxygen with PM.In addition a certain amount of noble metal is added, it is good to be on the one hand that noble metal has the NO in air-flow
Oxidability provides enough NO for the oxidation of PM2, on the other hand add a small amount of Pd, by Pt and Pd collocation use, be in order to
The high-temperature aging resisting ability for improving Pt, finally in NO2It is that soot is fast at a lower temperature and under the common booster action of active oxygen
Speed aoxidizes.
The present invention controls the total dosage of catalyst, this mainly take into account after-treatment system to the trapping ability of PM with it is right
The catalysis oxidation efficiency of PM obviously increases the back pressure for directly affecting entire after-treatment system when catalyst material coated weight is excessive
Add, even if also influencing the service ability of engine in the case where no trapping PM；When catalyst material coated weight is too low
, then will lead to that PM oxidation efficiency is too low, to influence the removing of PM, also further influence the operational efficiency of engine；
The present invention provides optimal paint-on techniques.
The present invention optimizes precious metal ratios, optimizes the composition of catalyst by adjusting the coated weight of catalyst, in your total gold
Belong in the lower situation of usage amount, realizes the purpose of quickly oxidation PM.
In method for preparing catalyst of the present invention: coating material and precious metal salt solution directly being mixed, by stirring, ball milling
After process, pH:2.5~4.5, D50:2 μm of partial size~7 μm, solid content :≤20% are controlled.By slurry by way of lower grouting
It is coated among honeycomb ceramic filter filter inner wall.Lower grouting way is in the milk from the bottom to top, and slurry is circulated into and has been carried out
In the carrier of bottom coating, when Starch Level reaches the height of design, stop grouting；Slurry pours into the height of carrier, passes through liquid
Face sensor is identified, i.e., when Starch Level reaches the height of setting, is prompted by sensor alarm, at this point, can stop
Slurries pour into.
The present invention, using the reasonable control of slurries partial size D50 and solid content, realizes coating uniformity when carrier is coated
Requirement, while meeting the design requirement of coated weight, the catalyst carrier grout distribution that the present invention coats is uniform, no plug-hole
Phenomenon, back pressure is low in the tail gas clean-up processing system of practical application, and the present invention is suitable by the pH in accurately control preparation
Carrying capacity and its selection of coating catalysis material and catalysis material size controlling, are realized to noble metal in coating material in coating
Be uniformly distributed, improve dispersion degree of the noble metal in catalysis material, and then influence catalyst coat to the oxidability of NO,
Coating catalysis material being uniformly distributed in DPF wall surface is improved simultaneously, and then increases the exposure level of catalysis material and PM, is improved and is lived
Property oxygen, NO2 and PM contact the frequency, to improve the ability of catalysis oxidation PM.
Detailed description of the invention
Increase of the Fig. 1 for catalyst unit of embodiment of the present invention inlet temperature, the extension of testing time, catalyst unit back pressure
Changing rule, in figure, abscissa is the testing time, and unit: the second (S), the left ordinate of attached drawing is catalyst unit inlet temperature, single
Position: DEG C, right ordinate is catalyst unit back pressure, unit: kPa.
Increase of the Fig. 2 for catalyst unit of embodiment of the present invention inlet temperature, the extension of testing time, catalyst unit back pressure
Changing rule, in figure, abscissa is the testing time, and unit: the second (S), the left ordinate of attached drawing is catalyst unit inlet temperature, single
Position: DEG C, right ordinate is catalyst unit back pressure, unit: kPa.
Increase of the Fig. 3 for catalyst unit of embodiment of the present invention inlet temperature, the extension of testing time, catalyst unit back pressure
Changing rule, in figure, abscissa is the testing time, and unit: the second (S), the left ordinate of attached drawing is catalyst unit inlet temperature, single
Position: DEG C, right ordinate is catalyst unit back pressure, unit: kPa.
Specific embodiment
The present invention is specifically described below by example, the present embodiment is served only for carrying out the present invention further
Illustrate, but should not be understood as limiting the scope of the invention, those skilled in the art is according to the content of aforementioned present invention
The some nonessential modifications and adaptations made also belong to the scope of protection of the invention.
White carrier used in following embodiment is honeycomb ceramic filter filtration supports (300 mesh/in of cordierite material2),
Embodiment 1
Catalyst preparation one, includes the following steps:
1) configuration of slurries: by by preferred coating material cerium oxide-praseodymium oxide-lanthana, oxide weight is formed
Percentage: 90:5:5 selects platinum nitrate and palladium nitrate salting liquid, pH:3.0, D90=7.0 μm, solid content is stirred for 13%, ball
Mill.
2) coating coats: being coated according to carrying capacity on 20g/L coating, carrying capacity 3.0g/ft on noble metal3。
3) it dries: the catalyst for having completed coating being dried by 105 DEG C, time 2.0h.
4) it roasts: the catalyst after drying being put in meshbeltfurnace and is roasted, atmosphere is air, roasts 4 at 650 DEG C
Hour, calcining process is completed, catalysis material butt coated weight is 18g/L.
Embodiment 2
Catalyst preparation two, includes the following steps:
1) configuration of slurries: by by preferred coating material cerium oxide-praseodymium oxide-zirconium oxide, oxide weight is formed
Percentage: 80:5:15 selects platinum nitrate and palladium nitrate salting liquid, pH:3.5, D90=7.3 μm, solid content is stirred for 13%,
Ball milling.
2) coating coats: being coated according to carrying capacity on 20g/L coating, carrying capacity 1.0g/ft on noble metal3。
3) it dries: the catalyst for having completed coating being dried by 105 DEG C, time 2.5h.
4) it roasts: the catalyst after drying being put in meshbeltfurnace and is roasted, atmosphere is air, roasts 4 at 650 DEG C
Hour, calcining process is completed, catalysis material butt coated weight is 22g/L.
Embodiment 3
Catalyst preparation three, includes the following steps:
1) configuration of slurries: by by preferred coating material cerium oxide-praseodymium oxide-silver oxide, oxide weight is formed
Percentage: 95:4:1 selects platinum nitrate and palladium nitrate salting liquid, pH:4.0, D90=6.2 μm, solid content is stirred for 12.3%,
Ball milling.
2) coating coats: being coated according to carrying capacity on 20g/L coating, carrying capacity 1.0g/ft on noble metal3。
3) it dries: the catalyst for having completed coating being dried by 105 DEG C, time 3h.
4) it roasts: the catalyst after drying being put in meshbeltfurnace and is roasted, atmosphere is air, roasts 4 at 650 DEG C
Hour, calcining process is completed, catalysis material butt coated weight is 19.0g/L.
Detect example
Attached 1: detection method description, specific as follows:
After simply encapsulating, it is connected to the outlet end of engine according to by the catalyst unit prepared, first completion PM
Load, design flow are 3.0g ± 0.5g/L, are then tested for the property in accordance with the following steps.
Constant engine by adjusting load control system catalyst unit inlet temperature, and is stablized 250 in speed at maximum torque
± 10 DEG C, 20 ± 5min is run, with 20 DEG C of interval elevated inlet temperature, until 330 ± 10 DEG C.
When detecting that the exhaust drop off pressure of sample is decreased obviously during stable conditions, corresponding temperature at this time, as
Oxidation initiation temperature occurs for PM.
Catalyst unit inlet temperature is recorded, reaches after back pressure starts reduction, continues growing 20 DEG C of sample inlet temperature, with
Just PM oxidation initiation temperature is confirmed.
The result shows that three embodiments can fast implement PM oxidation ignition at 290 DEG C, i.e. back pressure takes place obviously
Downward trend.Illustrate to form in catalyst material of the present invention, the coated weight of design, bullion content and its preparation process control ginseng
In number range, it is able to achieve the purpose of fast eliminating PM, and to accelerate the rate of back pressure reduction, is selecting main material ceria
And its other than content, then the submember adulterated to it is needed to carry out crucial selection, and according to invention, then it is able to achieve
State requirement.
Claims (7)
1. a kind of diesel soot particle oxidation catalyst, it is characterised in that:
The catalyst is made of coating material and the active component being immersed on coating material；
Active component is made of the precious metal salt containing Pt and Pd；Noble metal total content is 0.5~3g/ft in catalyst3, noble metal
The weight ratio of Pt and Pd is 2:1~10:1；
Coating material is the metal composite oxide of high cerium content, wherein cerium oxide weight percent content is greater than or equal to
80%.
2. diesel soot particle oxidation catalyst according to claim 1, it is characterised in that: the composition metal oxidation
It also include at least one of single-phase oxide or/and composite oxides in object；Single-phase oxide include: zirconium oxide, lanthana,
Praseodymium oxide, titanium oxide；Composite oxides include: aluminium oxide-zirconium oxide, aluminium oxide-titanium oxide, Ceria-zirconia, oxidation
Cerium-praseodymium oxide, alumina-thoria.
3. diesel soot particle oxidation catalyst according to claim 1, it is characterised in that: the cerium oxide is through rare earth
Element, transition metal or/and alkali metals modified, rare earth modified element include: one of La, Ce, Pr, Sm, Er, Nd, Y, Re
Or it is several, transition metal, alkali metals modified include: one of K, Sr, Cr, Ag, Mn, Fe, Cu, Zr, Mo, W, Ni, Hf or several
Kind is doped.
4. diesel soot particle oxidation catalyst according to claim 1, it is characterised in that: the coating material partial size
≤ 10 μm, specific surface area >=100m2/g。
5. diesel soot particle oxidation catalyst according to claim 1, it is characterised in that: the noble metal precursor body
For the inorganic salts containing Pt and Pd, inorganic salts include but is not limited to that nitrate, sulfate, acetate and amine close coordination salt, are being urged
Change the mass percentage concentration 0.1%~1.0% in coating material.
6. a kind of diesel soot particle oxidation catalyst preparation method, it is characterised in that:
(1) coating material and active component are weighed according to any one of claim 1 to the 5 catalyst components dosage；
(2) coating material and the precious metal salt solution of active component are directly mixed；By stirring, ball milling, pH1.5 is controlled to adjust
~5.5, partial size D50 are 2 μm~7 μm, solid content≤20%；
(3) it is coated on carrier, the catalyst slurry of step (2) preparation is coated on carrier, upper loading capacity is 10~30g/
L；
(4) it roasts, maturing temperature: 550 DEG C~850 DEG C, calcining time: 5~50 hours.
7. the preparation method of diesel soot particle oxidation catalyst according to claim 6, it is characterised in that: described to urge
Slurry is coated to above honeycomb ceramic filter filter-carrier by agent slurries using lower grouting way, and detailed process includes:
By being in the milk from the bottom to top, flow direction and its flow rate of slurry are constrained, when Starch Level reaches the height of design, is stopped
Grouting.
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| CN109999803A (en) * | 2019-04-16 | 2019-07-12 | 中自环保科技股份有限公司 | A kind of the cerium base catalyst and preparation process of low-temperature catalytic oxidation soot |
| CN110193366A (en) * | 2019-06-06 | 2019-09-03 | 无锡威孚环保催化剂有限公司 | Catalyst and preparation method thereof with good soot ignition performance |
| CN111821971A (en) * | 2020-07-30 | 2020-10-27 | 中自环保科技股份有限公司 | Integral catalyst for catalytic regeneration of soot and preparation method thereof |
| CN112221511A (en) * | 2020-10-13 | 2021-01-15 | 天津大学 | Ternary metal oxide based diesel particulate oxidation catalyst and preparation method thereof |
| CN114483257A (en) * | 2022-01-26 | 2022-05-13 | 中自环保科技股份有限公司 | Catalytic filter with coating of net structure and preparation method thereof |
| CN114534776A (en) * | 2022-01-19 | 2022-05-27 | 中自环保科技股份有限公司 | Sulfur-resistant diesel vehicle oxidation type catalyst and preparation method thereof |
| CN116212866A (en) * | 2023-03-09 | 2023-06-06 | 同济大学 | A kind of high anti-sulfur CDPF catalyst of low-temperature catalytic soot and preparation method |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN109999803A (en) * | 2019-04-16 | 2019-07-12 | 中自环保科技股份有限公司 | A kind of the cerium base catalyst and preparation process of low-temperature catalytic oxidation soot |
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| CN112221511A (en) * | 2020-10-13 | 2021-01-15 | 天津大学 | Ternary metal oxide based diesel particulate oxidation catalyst and preparation method thereof |
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Application publication date: 20190115 |