CN116116419A - Cerium-based perovskite catalyst for catalytic oxidation of diesel particulate matters, and preparation method and application thereof - Google Patents

Cerium-based perovskite catalyst for catalytic oxidation of diesel particulate matters, and preparation method and application thereof Download PDF

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CN116116419A
CN116116419A CN202211567414.3A CN202211567414A CN116116419A CN 116116419 A CN116116419 A CN 116116419A CN 202211567414 A CN202211567414 A CN 202211567414A CN 116116419 A CN116116419 A CN 116116419A
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catalyst
perovskite
nitrate
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韩志涛
王梦婷
刘雨斌
胡宇晴
潘新祥
陈玄
陆诗建
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Dalian Maritime University
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Abstract

The invention relates to a cerium-based perovskite catalyst for catalytic oxidation of diesel particulate matters, and a preparation method and application thereof, and belongs to the technical field of catalysts. The composition general formula of the catalyst is A 1‑x K x MO 3 Wherein x is more than or equal to 0 and less than or equal to 0.4, A is Ce, sr, pr or Ca, and M is Fe, co, mn, ni or Cu. Metal nitrate of A, metal nitrate of B and KNO 3 Adding the mixture into a solvent, and stirring until the mixture is completely dissolved; adding citric acid into the solution, heating, stirring and evaporating to obtain gel; grinding the obtained solid into powder after drying; roasting to obtain the catalyst powder. The catalyst prepared by the method has excellent catalytic oxidation activity. The combustion temperature of the catalytic oxidation PM is reduced under different conversion rates, and Ce is used 0.8 K 0.2 CoO 3 The catalyst has the best performance, T 10 、T 50 、T 90 326 ℃, 383 ℃ and 426 ℃, respectively. Therefore, the catalyst prepared by the method has higher catalytic activity and low cost, and is more suitable for large-scale industrial application.

Description

Cerium-based perovskite catalyst for catalytic oxidation of diesel particulate matters, and preparation method and application thereof
Technical Field
The invention belongs to the technical field of catalysts, and particularly relates to a cerium-based perovskite catalyst for catalyzing and oxidizing diesel particulate matters, and a preparation method and application thereof.
Background
Soot Particulate Matter (PM) has the broadest potential environmental impact, including mainly on health, climate change and ecological environmental impact. PM in the tail gas of the diesel engine can seriously harm the health of a human body after being inhaled by the human body. The off-board trapping and filtering (DPF) technology is one of the main technologies for purifying PM in diesel vehicles, and the particulate trap can cause gradual increase of exhaust back pressure after capturing soot, thereby affecting the dynamic performance of a diesel engine, so that efficient regeneration of the particulate trap is a key point for ensuring reliable operation of the particulate trap. Currently, DPF regeneration techniques fall into two broad categories, active regeneration and passive regeneration. The active regeneration method is characterized in that when the back pressure of the exhaust gas of the diesel engine rises to reach a certain threshold value, fuel and air are injected into the exhaust pipe, and the fuel and the air are combusted, so that the temperature of the bed layer of the particle catcher can be quickly increased to the soot oxidation combustion temperature (more than 650 ℃), and soot is removed, and the nano channel of the particle catcher is regenerated. Although active regeneration methods are effective in regenerating particulate traps, soot particulate removal is not complete and requires a relatively complex combustion system. The passive regeneration method is to reduce the activation energy of the soot oxidation combustion reaction by using the catalyst, so that the temperature of the soot oxidation combustion reaction is obviously reduced to the exhaust temperature of the diesel engine (< 380 ℃). The method does not need additional energy supplementing, only needs to supplement and spray a certain amount of air into the exhaust pipe, and has relatively simple control technology. The core of the passive regeneration technology is that a low-temperature efficient oxidation combustion catalyst of soot is needed, so that the development of the low-temperature type soot oxidation combustion catalyst is always the direction of scientific research and technological development.
Noble metal catalysts (Ag, au, pd, pt and the like) have strong catalytic activity and are applied to the field of catalytic combustion. A catalyst for purifying exhaust gas pollutants of diesel locomotives such as soot is disclosed in US 2003/0104932, and comprises noble metals such as Pt and Pd attached to Zr-W oxides. In chinese patent CN 1554859a method for removing soot particles using a filter and a clean-up catalyst is disclosed, using Pt-V 2 O 5 /Al 2 O 3 Noble metal catalysts. These noble metal catalysts can oxidize or decompose soluble organic compounds (SOF), HC and CO at the same time, however, because Pt-based catalysts are expensive and resource-inefficient, these methods currently employed to support noble metal catalysts such as Pt, pd, etc. on particulate traps (DPFs) to remove soot particles suffer from a number of limitations. The non-noble metal has low price and rich reserves, and the non-noble metal-based catalyst is increasingly becoming a research hotspot in the field of domestic and foreign catalytic combustion. Perovskite type metal oxide (ABO) 3 ) Has excellent heat stability, poisoning resistance and good catalytic activity, and has received attention from a plurality of researchers. The A-site element of the traditional perovskite type oxide is mainly alkali metal, alkaline earth metal or rare earth metal, such as K, ca, sr, la, ce, pr and the like; and the B-site element is mainly transition metal, such as Fe, mn, co, ni and Cu.
In Chinese patent CN 103861610A, a preparation and application of a hollow perovskite catalyst with high activity is disclosed, the catalyst has a nano hollow particle structure and La 1-x Sr x Fe 1-y Mn y O 3 The molar ratio of the sum of lanthanum and strontium cations to the sum of iron and manganese cations of the perovskite characteristic composite oxide is 0.6-2, and the content of the strontium and manganese cations can be modulated, namely the value range of x is 0-0.1, and the value range of y is 0-0.3. However, the preparation method of the catalyst is complex, and the requirements on the required raw materials and reaction conditions are high, so that the catalyst is not beneficial to large-scale popularization.
Therefore, the invention provides the K-substituted Ce-based perovskite type catalyst which can obviously reduce the catalytic combustion temperature of diesel engine soot and has low price on the basis of the catalytic combustion of the diesel engine soot particles which are researched at present.
Disclosure of Invention
The invention solves the main technical problems of providing a Ce 1-x K x CoO 3 The perovskite catalyst has high catalytic activity on the combustion of soot particles in diesel engine emission, so that the combustion temperature of the soot particles is greatly reduced, the catalyst does not contain noble metals, and the catalyst cost is reduced while the catalytic activity is improved.
The invention provides a K-substituted perovskite catalyst, which is characterized in that the A-site element in the perovskite catalyst is partially substituted by K element, so that the catalytic combustion activity of the perovskite catalyst is further improved.
A perovskite catalyst for catalytic oxidation of diesel particulate matter is characterized in that the catalyst has a composition general formula A 1-x K x MO 3 Wherein x is more than or equal to 0 and less than or equal to 0.4, A is Ce, sr, pr or Ca, and M is Fe, co, mn, ni or Cu.
The invention also provides a preparation method of the perovskite catalyst, which mainly comprises the following steps:
(1) Respectively weighing a certain amount of metal nitrate of A, metal nitrate of M and KNO 3 Adding the mixture into deionized water, and stirring until the mixture is completely dissolved;
(2) A certain amount of citric acid (C 6 H 8 O 7 ·H 2 O), adding the mixture into the step (1), and stirring the mixture, wherein the molar ratio of the citric acid to the metal ions is 1:1;
(3) Placing the precursor solution obtained in the step (2) into a constant-temperature water bath kettle, and continuously stirring and evaporating until the precursor solution is thick honey-like gel;
(4) Placing the gel obtained in the step (3) in a constant-temperature air-blast drying oven, and drying;
(5) Grinding the solid obtained in the step (4) into powder;
(6) And (5) roasting the solid obtained in the step (5) in an air atmosphere to obtain the catalyst powder.
Further, in the above technical scheme, the metal nitrate of a is cerium nitrate hydrate, strontium nitrate hydrate, praseodymium nitrate hydrate, calcium nitrate hydrate; the metal nitrate of M is hydrated ferric nitrate, hydrated cobalt nitrate, hydrated manganese nitrate, hydrated nickel nitrate or hydrated copper nitrate.
Further, based on the technical scheme, the stirring time in the step (2) is 10-20 min; the constant-temperature water bath temperature in the step (3) is 75-85 ℃, the stirring speed is 400-600 rpm, and the stirring time is 2.5-3.5 h; the drying temperature in the step (4) is 100-120 ℃ and the drying time is 20-26 h; the heating rate in the step (6) is 3 ℃/min, the roasting temperature is 650-750 ℃, and the heat preservation time is 2.5-3.5 h.
Further, in the above technical scheme, in the step (6), the mesh number of the catalyst powder is 40 to 60 mesh.
The invention also provides application of the catalyst in DPF catalyst development.
Further, in the technical scheme, the perovskite catalyst and the soot are fully mixed according to the mass ratio of 10:1, 1000ppm of NO and 5% of O 2 The balance being N 2 The gas flow rate is 200mL/min, and the reaction operation temperature is 150-650 ℃.
Possible reaction mechanisms of soot combustion:
(1) Reactive oxygen species O 2- And O - Directly on the surface of the catalystThe soot particles are catalytically combusted;
(2) NO generates NO under the action of active oxygen 2 ，NO 2 Adsorption on the catalyst surface followed by migration and soot particle action and oxidation;
(3) The NO in the gas phase adsorbs on the catalyst surface and combines with the active oxygen to form an intermediate species of nitrite or nitrate, and the soot particles oxidize under the action of the intermediate species.
CeO 2 Has stronger oxygen storage and release capacity, and the reason is that Ce has two valence states of +3 and +4. When the oxygen content in the tail gas is large, cerium oxide is formed by Ce 2 O 3 To CeO 2 Conversion, oxidation reaction occurs: ce (Ce) 2 O 3 +1/2O 2 →CeO 2 Storing oxygen in the tail gas; when the oxygen in the tail gas is insufficient, ceO is used for 2 →Ce 2 O 3 +1/2O 2 Oxygen can be released again, so that the catalytic performance of the catalyst is improved.
The invention has the beneficial effects that
The invention provides a preparation method of a perovskite catalyst for catalytic oxidation of diesel particulate matters. The method utilizes K to replace and modify the A-site element of the perovskite catalyst, thereby providing the catalyst with better PM catalytic oxidation performance.
The catalyst prepared by the method has excellent catalytic oxidation activity as shown by the experimental result of catalyst performance evaluation. The combustion temperature of the catalytic oxidation PM is reduced under different conversion rates, and Ce is used 0.8 K 0.2 CoO 3 The catalyst has the best performance, T 10 、T 50 、T 90 326 ℃, 383 ℃ and 426 ℃, respectively. Therefore, the catalyst prepared by the method has higher catalytic activity and low cost, and is more suitable for large-scale industrial application.
Drawings
FIG. 1 shows CeMO of comparative examples 1, 2, 3, 4, 5 3 (m= Co, fe, cu, mn, ni) catalyst XRD results pattern.
FIG. 2 shows comparative example 5, example 1, example 2, example 3, and examplesCe of example 4 1-x K x CoO 3 (x= 0,0.1,0.2,0.3,0.4) catalyst XRD results pattern.
FIG. 3 is CO of comparative examples 1, 2, 3, 4, 5 2 Concentration as a function of reaction temperature.
Fig. 4 shows the change of the soot conversion rate with the reaction temperature in comparative examples 1, 2, 3, 4 and 5.
FIG. 5 is CO of comparative example 5, example 1, example 2, example 3, example 4 2 Concentration as a function of reaction temperature.
Fig. 6 shows the change in the soot conversion rate with the reaction temperature in comparative example 5, example 1, example 2, example 3, and example 4.
FIG. 7 is CO of examples 2, 5, 6, 7 and 8 2 Concentration as a function of reaction temperature.
Fig. 8 shows the change in the soot conversion rate with the reaction temperature in examples 2, 5, 6, 7 and 8.
As can be seen from FIG. 1, all catalyst samples synthesized perovskite structures, but stronger CeO appeared 2 Characteristic peaks, therefore the catalyst is perovskite and CeO 2 Is a mixture of (a) and (b).
As can be seen from fig. 2, all catalysts have characteristic peaks of perovskite, but their peak intensities are relatively weak. All catalysts have two attributes to CeO 2 When x is more than or equal to 0.3, the peak intensity is stronger. All catalysts have a composition of Co 3 O 4 The characteristic peaks (36.8 °, 65.4 °) of (a) are probably due to CeO formation due to partial Ce ions not forming perovskite structure 2 Resulting in a portion of the Co ions also forming their oxides. When x is more than or equal to 0.4, the attribution of K appears 2 CoO 3 New characteristic peak (31.2 °) appears at the same time as a Co-attribute 3 O 4 Possibly due to the increased doping level of K, too many K ions cannot be accommodated in the lattice, resulting in partial K ions and Co ions being detached from the perovskite unit cellInto an independent crystalline phase.
As can be seen from fig. 3 and 4, ceMO 3 (m= Mn, fe, co, cu, ni) perovskite catalyst-produced CO 2 The concentration range is 1000-1600ppm. CeMO (Cemo) 3 T of perovskite catalyst m Lowest, 420 ℃; ceMO (Cemo) 3 (m= Mn, fe, co, cu, ni) the order of the catalytic soot combustion performance of the perovskite catalyst is: ceCoO (CeCoO) 3 ＞CeMnO 3 ＞CeNiO 3 ＞CeCuO 3 ＞CeFeO 3 By CeCoO 3 The perovskite type catalyst has the best catalytic soot combustion performance.
As can be seen from fig. 5 and 6, ce 0.8 K 0.2 CoO 3 CO produced by perovskite catalyst 2 The highest concentration can reach 1824ppm peak value, T m At 391 ℃, it is demonstrated that the catalyst is capable of rapidly burning soot to burn-out in this temperature range. CO produced by other catalysts 2 The highest concentration is about 1600ppm, compared with Ce 0.8 K 0.2 CoO 3 Perovskite catalysts are relatively poor; after substitution of the K moiety, when x > 0.2, CO 2 The peak concentration gradually decreases; ce (Ce) 1-x K x CoO 3 The order of the catalytic soot combustion performance of the perovskite catalysts (x=0.1, 0.2,0.3, 0.4) is: ce (Ce) 0.8 K 0.2 CoO 3 ＞Ce 0.7 K 0.3 CoO 3 ＞Ce 0.9 K 0.1 CoO 3 ＞Ce 0.6 K 0.4 CoO 3 ＞CeCoO 3 By Ce 0.8 K 0.2 CoO 3 The perovskite type catalyst has the best catalytic soot combustion performance.
As can be seen from fig. 7 and 8, ce 0.8 K 0.2 CoO 3 CO produced by perovskite catalyst 2 The concentration is highest. Ce (Ce) 0.8 K 0.2 MO 3 (m= Mn, fe, co, cu, ni) perovskite catalyst catalytic soot combustion performance order is: ce (Ce) 0.8 K 0.2 CoO 3 ＞Ce 0.8 K 0.2 MnO 3 ＞Ce 0.8 K 0.2 FeO 3 ＞Ce 0.8 K 0.2 NiO 3 ＞Ce 0.8 K 0.2 CuO 3 。Ce 0.8 K 0.2 CoO 3 Perovskite catalysts exhibit the best catalytic soot combustion activity, T 10 、T 50 、T 90 326 ℃, 383 ℃ and 426 ℃ respectively.
Detailed Description
The following examples further illustrate the invention, but the invention is not limited to the following examples. Any insubstantial changes and substitutions made by one of ordinary skill in the art in light of the disclosure herein are intended to be encompassed by the invention as claimed.
The test reagents used in the following examples, unless otherwise specified, are all conventional biochemical reagents; the experimental methods are conventional methods unless otherwise specified.
CeMO used in the following comparative examples 3 (m= Mn, fe, co, cu, ni) the preparation method of the perovskite catalyst is as follows:
(1) 3.472g Ce (NO) was weighed out separately 3 ) 3 ·6H 2 O, different contents of Mn (NO) 3 ) 2 ·4H 2 O or Fe (NO) 3 ) 3 ·9H 2 O or Co (NO) 3 ) 2 ·6H 2 O or Cu (NO) 3 ) 2 ·3H 2 O or Ni (NO) 3 ) 2 ·6H 2 Adding O into 50mL of deionized water, and stirring until the O is completely dissolved;
(2) 3.072gC was weighed in a ratio of citric acid to total metal ion mass=1:1 (molar ratio) 6 H 8 O 7 ·H 2 Adding O into the step (1) and stirring for 10min;
(3) Placing the precursor solution obtained in the step (2) in a constant-temperature water bath kettle with the temperature of 80 ℃, and continuously stirring and evaporating at the rotating speed of 400rpm to obtain thick honey-like gel;
(4) Drying the gel obtained in the step (3) in a 110 ℃ constant temperature blast drying oven for 24 hours;
(5) Grinding the solid obtained in the step (4) into powder;
(6) And (3) placing the solid obtained in the step (5) in an air atmosphere, heating to 700 ℃ at a speed of 3 ℃/min, roasting, and then preserving heat for 3 hours to obtain the catalyst powder.
The experimental conditions for evaluating the catalytic combustion activity of the catalyst are as follows: NO concentration: 1000ppm, O 2 Concentration: 5%, balance gas: n (N) 2 Catalyst dosage: 0.1g, quartz sand dosage: 0.3g, carbon black: 0.01g.
CeMO used in comparative examples 1 to 5 below 3 Specific preparation parameters of the perovskite catalyst are as follows:
comparative example 1
2.008g Mn (NO) was weighed out 3 ) 2 ·4H 2 O, according to CeMO described above 3 Preparation of catalyst comparative example 1 catalyst was obtained, comparative example 1 being CeMnO 3 The method comprises the steps of carrying out a first treatment on the surface of the The comparative example 1 catalyst was subjected to a soot activity evaluation experimental test.
Comparative example 2
3.232g of Fe (NO) 3 ) 3 ·9H 2 O, according to CeMO described above 3 Preparation of catalyst comparative example 2 catalyst was obtained, comparative example 2 being CeFeO 3 The method comprises the steps of carrying out a first treatment on the surface of the The comparative example 2 catalyst was subjected to a soot activity evaluation experimental test.
Comparative example 3
1.936g Cu (NO) was weighed out 3 ) 2 ·3H 2 O, according to CeMO described above 3 Preparation method of catalyst comparative example 3 catalyst was obtained, comparative example 3 being CeCuO 3 The method comprises the steps of carrying out a first treatment on the surface of the The comparative example 3 catalyst was subjected to a soot activity evaluation experimental test.
Comparative example 4
2.328g Ni (NO) 3 ) 2 ·6H 2 O, according to CeMO described above 3 Preparation of catalyst comparative example 4 catalyst was obtained, comparative example 4 was CeNiO 3 The method comprises the steps of carrying out a first treatment on the surface of the The comparative example 4 catalyst was subjected to a soot activity evaluation experimental test.
Comparative example 5
2.328g of Co (NO) 3 ) 2 ·6H 2 O, according to CeMO described above 3 Preparation of catalyst comparative example 5 was obtained, comparative example 5 being CeCoO 3 The method comprises the steps of carrying out a first treatment on the surface of the The comparative example 5 was subjected to a soot activity evaluation experimental test.
Ce used in examples 1 to 4 below 1-x K x CoO 3 The preparation method of the perovskite catalyst comprises the following steps:
(1) Respectively weighing Ce (NO) with different contents 3 ) 3 ·6H 2 O, co (NO) with different contents 3 ) 2 ·6H 2 KNO with different O content 3 Adding the mixture into 50mL of deionized water, and stirring until the mixture is completely dissolved;
(2) 3.072gC was weighed in a ratio of citric acid to total metal ion mass=1:1 (molar ratio) 6 H 8 O 7 ·H 2 Adding O into the step (1) and stirring for 10min;
(3) Placing the precursor solution obtained in the step (2) in a constant-temperature water bath kettle with the temperature of 80 ℃, and continuously stirring and evaporating at the rotating speed of 400rpm to obtain thick honey-like gel;
(4) Drying the gel obtained in the step (3) in a 110 ℃ constant temperature blast drying oven for 24 hours;
(5) Grinding the solid obtained in the step (4) into powder;
(6) And (3) placing the solid obtained in the step (5) in an air atmosphere, heating to 700 ℃ at a speed of 3 ℃/min, roasting, and then preserving heat for 3 hours to obtain the catalyst powder.
The experimental conditions for evaluating the catalytic combustion activity of the catalyst are as follows: NO concentration: 1000ppm, O 2 Concentration: 5%, balance gas: n (N) 2 Catalyst dosage: 0.1g, quartz sand dosage: 0.3g, carbon black: 0.01g.
Ce used in examples 1 to 4 below 1-x K x CoO 3 Specific preparation parameters of the perovskite-type catalysts (x=0.1, 0.2,0.3, 0.4) are as follows:
example 1
4.122g Ce (NO) was weighed out separately 3 ) 3 ·6H 2 O、3.071g Co(NO 3 ) 2 ·6H 2 O、0.107g KNO 3 、4.052g C 6 H 8 O 7 ·H 2 O, according to Ce 1-x K x CoO 3 Catalyst 1 is obtained by a preparation method of the catalyst, and the catalyst 1 is Ce 0.9 K 0.1 CoO 3 The method comprises the steps of carrying out a first treatment on the surface of the The mesh number of the catalyst 1 powder is 40-60 mesh; the catalyst 1 was subjected to a soot activity evaluation experimental test.
Example 2
3.827g Ce (NO) was weighed out separately 3 ) 3 ·6H 2 O、3.208g Co(NO 3 ) 2 ·6H 2 O、0.223g KNO 3 、4.233g C 6 H 8 O 7 ·H 2 O, according to Ce 1-x K x CoO 3 Catalyst 2 is obtained by the preparation method of the catalyst, and the catalyst 2 is Ce 0.8 K 0.2 CoO 3 The method comprises the steps of carrying out a first treatment on the surface of the The mesh number of the catalyst 2 powder is 40-60 mesh; the catalyst 2 was subjected to a soot activity evaluation experimental test.
Example 3
3.505g Ce (NO) was weighed out separately 3 ) 3 ·6H 2 O、3.357g Co(NO 3 ) 2 ·6H 2 O、0.350g KNO 3 、4.430g C 6 H 8 O 7 ·H 2 O, according to Ce 1-x K x CoO 3 Catalyst 3 is obtained by the preparation method of the catalyst, and the catalyst 3 is Ce 0.7 K 0.3 CoO 3 The method comprises the steps of carrying out a first treatment on the surface of the The mesh number of the catalyst 3 powder is 40-60 mesh; the catalyst 3 was subjected to a soot activity evaluation experimental test.
Example 4
3.151g Ce (NO) was weighed out separately 3 ) 3 ·6H 2 O、3.521g Co(NO 3 ) 2 ·6H 2 O、0.489g KNO 3 、4.647g C 6 H 8 O 7 ·H 2 O, according to Ce 1-x K x CoO 3 Catalyst 4 is obtained by the preparation method of the catalyst, and the catalyst 4 is Ce 0.6 K 0.4 CoO 3 The method comprises the steps of carrying out a first treatment on the surface of the The mesh number of the catalyst 4 powder is 40-60 mesh; the catalyst 4 was subjected to a soot activity evaluation experimental test.
Ce used in examples 5 to 8 below 0.8 K 0.2 MO 3 (m= Mn, fe, cu, ni) the preparation method of the perovskite catalyst is as follows:
(1) Respectively weighing Ce (NO) with different contents 3 ) 3 ·6H 2 O, different contents of Mn (NO) 3 ) 2 ·4H 2 O or Fe (NO) 3 ) 3 ·9H 2 O or Cu (NO) 3 ) 2 ·3H 2 O or Ni (NO) 3 ) 2 ·6H 2 O and 0.222g KNO 3 Adding the mixture into 50mL of deionized water, and stirring until the mixture is completely dissolved;
(2) 0.222g KNO was weighed out in a ratio of citric acid to total metal ion mass=1:1 (molar ratio) 3 Adding the mixture into the step (1) and stirring for 10min;
(3) Placing the precursor solution obtained in the step (2) in a constant-temperature water bath kettle with the temperature of 80 ℃, and continuously stirring and evaporating at the rotating speed of 400rpm to obtain thick honey-like gel;
(4) Drying the gel obtained in the step (3) in a 110 ℃ constant temperature blast drying oven for 24 hours;
(5) Grinding the solid obtained in the step (4) into powder;
(6) And (3) placing the solid obtained in the step (5) in an air atmosphere, heating to 700 ℃ at a speed of 3 ℃/min, roasting, and then preserving heat for 3 hours to obtain the catalyst powder.
The experimental conditions for evaluating the catalytic combustion activity of the catalyst are as follows: NO concentration: 1000ppm, O 2 Concentration: 5%, balance gas: n (N) 2 Catalyst dosage: 0.1g, quartz sand dosage: 0.3g, carbon black: 0.01g.
Ce used in examples 5 to 8 below 0.8 K 0.2 MO 3 (m= Mn, fe, cu, ni) specific preparation parameters of the perovskite catalyst are as follows:
example 5
3.906g Ce (NO) was weighed out separately 3 ) 3 ·6H 2 O、2.761g Mn(NO 3 ) 2 ·4H 2 O、4.224gC 6 H 8 O 7 ·H 2 O, according to Ce 0.8 K 0.2 MO 3 Catalyst 5 is obtained by the preparation method of the catalyst, and the catalyst 5 is Ce 0.8 K 0.2 MnO 3 The method comprises the steps of carrying out a first treatment on the surface of the The mesh number of the catalyst 5 powder is 40-60 mesh; the experimental test for evaluating soot activity was performed on the example 5.
Example 6
3.863g Ce (NO) was weighed out separately 3 ) 3 ·6H 2 O、4.444g Fe(NO 3 ) 3 ·9H 2 O、4.224g C 6 H 8 O 7 ·H 2 O, according to Ce 0.8 K 0.2 MO 3 Catalyst 6 is obtained by the preparation method of the catalyst, and the catalyst 6 is Ce 0.8 K 0.2 FeO 3 The method comprises the steps of carrying out a first treatment on the surface of the The mesh number of the catalyst 6 powder is 40-60 mesh; the catalyst 6 was subjected to a soot activity evaluation experimental test.
Example 7
3.732g Ce (NO) was weighed out separately 3 ) 3 ·6H 2 O、2.614g Fe(NO 3 ) 3 ·9H 2 O、4.147g C 6 H 8 O 7 ·H 2 O, according to Ce 0.8 K 0.2 MO 3 Preparation method of catalyst to obtain catalyst 7, catalyst 7 is Ce 0.8 K 0.2 CuO 3 The method comprises the steps of carrying out a first treatment on the surface of the The mesh number of the catalyst 7 powder is 40-60 mesh; the catalyst 7 was subjected to a soot activity evaluation experimental test.
Example 8
3.819g Ce (NO) was weighed out separately 3 ) 3 ·6H 2 O、3.201g Ni(NO 3 ) 2 ·6H 2 O、4.224g C 6 H 8 O 7 ·H 2 O, according to Ce 0.8 K 0.2 MO 3 Catalyst 8 is obtained by the preparation method of the catalyst, and the catalyst 8 is Ce 0.8 K 0.2 NiO 3 The method comprises the steps of carrying out a first treatment on the surface of the The mesh number of the catalyst 8 powder is 40-60 mesh; the catalyst 8 was subjected to a soot activity evaluation experimental test.

Claims (10)

1. A perovskite catalyst for catalytic oxidation of diesel particulate matter is characterized in that the catalyst has a composition general formula A 1-x K x MO 3 Wherein x is more than or equal to 0 and less than or equal to 0.4, A is Ce, sr, pr or Ca, and M is Fe, co, mn, ni or Cu.
2. The method for producing a perovskite-type catalyst according to claim 1, comprising the steps of:
(1) Metal nitrate of A, metal nitrate of M and KNO 3 Adding the mixture into a solvent, and stirring until the mixture is completely dissolved;
(2) Adding citric acid into the step (1), and stirring; the molar ratio of the citric acid to the metal ions is 1:1;
(3) Heating, stirring and evaporating the precursor solution obtained in the step (2) to convert into gel;
(4) Drying the gel obtained in the step (3);
(5) Grinding the solid obtained in the step (4) into powder;
(6) And (5) roasting the solid obtained in the step (5) in an air atmosphere to obtain the catalyst powder.
3. The method for producing a perovskite catalyst according to claim 2, wherein in the step (1), the metal nitrate of a is cerium nitrate hydrate, strontium nitrate hydrate, praseodymium nitrate hydrate, calcium nitrate hydrate; the metal nitrate of the M is hydrated ferric nitrate, hydrated cobalt nitrate, hydrated manganese nitrate, hydrated nickel nitrate or hydrated copper nitrate; the solvent is deionized water.
4. The method for producing a perovskite catalyst according to claim 2, wherein in the step (2), the stirring time is 10 to 20 minutes.
5. The method for preparing a perovskite catalyst according to claim 2, wherein in the step (3), the heating is performed by using a constant temperature water bath, the heating temperature is 75-85 ℃, the stirring speed is 400-600 rpm, and the heating time is 2.5-3.5 h.
6. The method for preparing a perovskite catalyst according to claim 2, wherein in the step (4), a blast drying oven is used for drying, the drying temperature is 100-120 ℃, and the drying time is 20-26 hours.
7. The method for producing a perovskite catalyst according to claim 2, wherein in the step (6), the temperature rise rate is 3 ℃/min, the calcination temperature is 650 to 750 ℃, and the heat preservation time is 2.5 to 3.5 hours.
8. The method for producing a perovskite catalyst according to claim 2, wherein in the step (6), the mesh number of the catalyst powder is 40 to 60 mesh.
9. The use of a perovskite-type catalyst according to claim 1, characterized in that the catalyst is used in DPF catalyst development.
10. Use of a perovskite catalyst according to claim 9, characterized in that the perovskite catalyst is thoroughly mixed with soot in a mass ratio of 10:1, 1000ppm no,5% o 2 The balance being N 2 The gas flow rate is 200mL/min, and the reaction operation temperature is 150-650 ℃.
CN202211567414.3A 2022-12-07 2022-12-07 Cerium-based perovskite catalyst for catalytic oxidation of diesel particulate matters, and preparation method and application thereof Pending CN116116419A (en)

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