CN107233912A - A kind of two-part catalyst handled for exhaust gas from diesel vehicle and preparation method thereof - Google Patents

A kind of two-part catalyst handled for exhaust gas from diesel vehicle and preparation method thereof Download PDF

Info

Publication number
CN107233912A
CN107233912A CN201710485488.5A CN201710485488A CN107233912A CN 107233912 A CN107233912 A CN 107233912A CN 201710485488 A CN201710485488 A CN 201710485488A CN 107233912 A CN107233912 A CN 107233912A
Authority
CN
China
Prior art keywords
catalyst
ceo
formula
molecular sieve
prepared
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
CN201710485488.5A
Other languages
Chinese (zh)
Other versions
CN107233912B (en
Inventor
杨向光
易婷
张波
张一波
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Changchun Institute of Applied Chemistry of CAS
Original Assignee
Changchun Institute of Applied Chemistry of CAS
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Changchun Institute of Applied Chemistry of CAS filed Critical Changchun Institute of Applied Chemistry of CAS
Priority to CN201710485488.5A priority Critical patent/CN107233912B/en
Publication of CN107233912A publication Critical patent/CN107233912A/en
Application granted granted Critical
Publication of CN107233912B publication Critical patent/CN107233912B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • B01J29/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively
    • B01J29/42—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively containing iron group metals, noble metals or copper
    • B01J29/46—Iron group metals or copper
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/34—Chemical or biological purification of waste gases
    • B01D53/92—Chemical or biological purification of waste gases of engine exhaust gases
    • B01D53/94—Chemical or biological purification of waste gases of engine exhaust gases by catalytic processes
    • B01D53/9404—Removing only nitrogen compounds
    • B01D53/9409—Nitrogen oxides
    • B01D53/9413—Processes characterised by a specific catalyst
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • B01J29/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively
    • B01J29/42—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively containing iron group metals, noble metals or copper
    • B01J29/44—Noble metals
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • B01J29/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively
    • B01J29/48—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively containing arsenic, antimony, bismuth, vanadium, niobium tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
    • B01J29/72—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65 containing iron group metals, noble metals or copper
    • B01J29/74—Noble metals
    • B01J29/7415—Zeolite Beta
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
    • B01J29/72—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65 containing iron group metals, noble metals or copper
    • B01J29/74—Noble metals
    • B01J29/7476—MWW-type, e.g. MCM-22, ERB-1, ITQ-1, PSH-3 or SSZ-25
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
    • B01J29/72—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65 containing iron group metals, noble metals or copper
    • B01J29/76—Iron group metals or copper
    • B01J29/7615—Zeolite Beta
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
    • B01J29/72—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65 containing iron group metals, noble metals or copper
    • B01J29/76—Iron group metals or copper
    • B01J29/7676—MWW-type, e.g. MCM-22, ERB-1, ITQ-1, PSH-3 or SSZ-25
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
    • B01J29/78—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65 containing arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J29/7815—Zeolite Beta
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
    • B01J29/78—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65 containing arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J29/7876—MWW-type, e.g. MCM-22, ERB-1, ITQ-1, PSH-3 or SSZ-25
    • 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
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
    • B01J35/396—Distribution of the active metal ingredient
    • 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
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/40—Catalysts, in general, characterised by their form or physical properties characterised by dimensions, e.g. grain size
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2258/00—Sources of waste gases
    • B01D2258/01—Engine exhaust gases
    • B01D2258/012—Diesel engines and lean burn gasoline engines

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Combustion & Propulsion (AREA)
  • Health & Medical Sciences (AREA)
  • Biomedical Technology (AREA)
  • Environmental & Geological Engineering (AREA)
  • Analytical Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Catalysts (AREA)

Abstract

The invention provides a kind of two-part catalyst handled for exhaust gas from diesel vehicle, including：The catalyst A of the inlet end and catalyst B of outlet side；The catalyst A has formula：CeO2X/ molecular sieves；Wherein, X is selected from CuO, Fe2O3Or MnO2；The catalyst B has formula：M@CeO2/ molecular sieve；Wherein, M is selected from Rh, Pt or Pd.Compared with prior art, the two-part catalyst that the present invention is provided has high eradicating efficacy and selectivity in wide temperature range for exhaust gas from diesel vehicle processing to nitrogen oxides, and can eliminate particulate matter to a certain extent, while having escape ammonia to eliminate function.Wherein, catalyst B in outlet side also has DOC catalyst functions simultaneously.Test result indicates that, the two-part catalyst that the present invention is provided is in 150 550 DEG C, high-speed 240000h‑1Under the conditions of, with active, the good stability of the conversion of nitrogen oxides higher than 80% and the N excellent in high temperature2Selectivity；And the soot particulate matter during tail gas can be eliminated at 450 DEG C or so.

Description

A kind of two-part catalyst handled for exhaust gas from diesel vehicle and preparation method thereof
Technical field
The present invention relates to have catalyst technical field, more particularly to a kind of two-part catalysis handled for exhaust gas from diesel vehicle Agent and preparation method thereof.
Background technology
Nitrogen oxides (NOx) it is primarily referred to as NO and NO2, wherein NO accounts for 95%.Nitrogen oxides be main atmosphere pollution it One, it is directly contacted with air and water can bring many harm, such as acid rain, photochemical fog, stratospheric ozone loss, the whole world Climate change etc..Nitrogen oxides in air mostly come from moving source (motor vehicle) and stationary source (predominantly thermal power plant, Industrial burning device) two aspects, wherein, the nitrogen oxides in the whole world 95% derives from vehicular emission (49%) and power plant emission (46%).And increasing sharply for the growth and vehicles number with energy resource consumption, it is discharged into after a large amount of Fossil fuel consumptions big The acidic materials such as the nitrogen oxides in gas are more and more, and atmosphere pollution is also increasingly serious.Therefore, as the whole world is to nitrogen oxides Discharge limitation is more and more stricter, and how efficiently to eliminate nitrogen oxides becomes worldwide problem.
At present, the method for eliminating nitrogen oxides is a lot, wherein ammine selectivity catalytic reduction nitrous oxides (NH3- SCR), because Its efficiency high, relative cost performance are high, have become one of maximally efficient method of elimination nitrogen oxides.And selective catalysis One of key of nitrogen oxides reduction technology is exactly catalyst, traditional, the commercialized catalyst for being used for eliminating nitrogen oxides Mainly V2O5-WO3/TiO2Catalyst, high NO can be shown at 300 DEG C~400 DEG CxRemoval efficiency.
But, use it for exhaust gas from diesel vehicle processing and there is also some problems, such as：Temperature window is narrow, high temperature N2Selectivity Difference, there is N2O generation and NH3Oxidation, and TiO2Crystal structure change can occur at high temperature, catalytic activity is reduced, together When vanadium exist to environment and poison and can to bear air speed low.The catalyst for vehicle maintenance service has Bath in the prior art The SSZ-13 molecular sieve catalysts of husband, although temperature window is relatively wide, resistance to high-speed, but its, low temperature active is not high, it is impossible to eliminate Particulate matter；And granular material discharged in exhaust gas from diesel vehicle has very big harm into air to people.Therefore, exploitation one kind can be There is high eradicating efficacy and selectivity to nitrogen oxides in more wide temperature range, and particulate matter can be eliminated to a certain extent Catalyst turns into those skilled in the art's technical problem urgently to be resolved hurrily.
The content of the invention
In view of this, it is an object of the invention to provide it is a kind of for exhaust gas from diesel vehicle handle two-part catalyst and its Preparation method, the two-part catalyst that the present invention is provided is for exhaust gas from diesel vehicle processing, to nitrogen oxidation in wide temperature range Thing has high eradicating efficacy and selectivity, and can eliminate particulate matter to a certain extent.
The invention provides a kind of two-part catalyst handled for exhaust gas from diesel vehicle, including：The catalyst A of inlet end With the catalyst B of outlet side；
The catalyst A has formula shown in formula (I)：
CeO2- X/ molecular sieve formula (I)s；
Wherein, X is selected from CuO, Fe2O3Or MnO2；
The catalyst B has formula shown in formula (II)：
M@CeO2/ molecular sieve formula (II)；
Wherein, M is selected from Rh, Pt or Pd.
It is preferred that, in the formula (I), CeO2Mol ratio with X is (3~19)：1.
It is preferred that, in the formula (I), the molecular sieve is selected from ZSM-5, MCM-56 or BEA；
The CeO2- X and the mass ratio of molecular sieve are 1：(1~10).
It is preferred that, in the formula (II), M and CeO2 mol ratio are 1：(8~32).
It is preferred that, in the formula (II), the molecular sieve is selected from ZSM-5, MCM-56 or BEA；
The M@CeO2 and the mass ratio of molecular sieve are 1：(1~10).
It is preferred that, the mass ratio of the catalyst A and catalyst B are (0.5~3)：1.
Present invention also offers a kind of preparation method of the two-part catalyst described in above-mentioned technical proposal, including following step Suddenly：
A) cerium source, X ' sources and triethylamine are subjected to hydro-thermal reaction in the first solvent, obtain CeO2- X nano particle；It is described X ' sources are selected from copper source, source of iron or manganese source；
B) M ' sources, cerium source and ammoniacal liquor are subjected to coprecipitation reaction in the second solvent, obtain M@CeO2Nuclear shell structure nano Particle；M ' the sources are selected from rhodium source, platinum source or palladium source；
C) CeO for obtaining step a)2The M@CeO that-X nano particle and step b) are obtained2Core-shell structure nanometer particle is distinguished Loaded with molecular sieve, respectively obtain catalyst A and catalyst B；
D) catalyst A is arranged on inlet end, catalyst B is arranged on outlet side, obtained for exhaust gas from diesel vehicle processing Two-part catalyst；
The step a) and b) no order limitation.
It is preferred that, the temperature of hydro-thermal reaction described in step a) is 160 DEG C~200 DEG C, and the time is 20h~30h.
It is preferred that, temperature 50 C~70 DEG C of coprecipitation reaction described in step b), the time is 0.5h~1.5h.
It is preferred that, CeO described in step c)2The average grain diameter of-X nano particle is 3nm~5nm；The M@CeO2Nucleocapsid knot The average grain diameter of structure nano-particle is 45nm~55nm.
The invention provides a kind of two-part catalyst handled for exhaust gas from diesel vehicle, include the catalyst A of inlet end With the catalyst B of outlet side；The catalyst A has formula：CeO2- X/ molecular sieves；Wherein, X is selected from CuO, Fe2O3Or MnO2； The catalyst B has formula：M@CeO2/ molecular sieve；Wherein, M is selected from Rh, Pt or Pd.Compared with prior art, the present invention is carried The two-part catalyst of confession for exhaust gas from diesel vehicle processing, have in wide temperature range to nitrogen oxides high eradicating efficacy and Selectivity, and particulate matter can be eliminated to a certain extent.Test result indicates that, the two-part catalyst that the present invention is provided exists 150-550 DEG C, high-speed 240000h-1Under the conditions of, with active, the good stability of the conversion of nitrogen oxides higher than 80% with And in high temperature excellent N2Selectivity；And the soot particulate matter during tail gas can be eliminated at 450 DEG C or so.
In addition, the two-part catalyst preparation process that provides of the present invention is simple, mild condition, cost are low, and not only to ring Border is not polluted, and is also had urea concurrently and is decomposed and eliminate escape NH3Effect.
Brief description of the drawings
Fig. 1 is the CeO that embodiment 1 is prepared2-Fe2O3The TEM photos of nano-particle；
Fig. 2 is the Rh@CeO that embodiment 1 is prepared2The TEM photos of core-shell structure nanometer particle；
Fig. 3 is the CeO that embodiment 5 is prepared2-Fe2O3/ MCM-56 TEM photos；
Fig. 4 is the Rh@CeO that embodiment 5 is prepared2/ MCM-56 TEM photos；
Fig. 5 is embodiment 10, the activity contrast of the two-part catalyst nitrogen oxides reduction of the offer of comparative example 3~4 Figure.
Embodiment
The technical scheme in the embodiment of the present invention will be clearly and completely described below, it is clear that described implementation Example only a part of embodiment of the invention, rather than whole embodiments.Based on the embodiment in the present invention, this area is common The every other embodiment that technical staff is obtained under the premise of creative work is not made, belongs to the model that the present invention is protected Enclose.
The invention provides a kind of two-part catalyst handled for exhaust gas from diesel vehicle, including：The catalyst A of inlet end With the catalyst B of outlet side；
The catalyst A has formula shown in formula (I)：
CeO2- X/ molecular sieve formula (I)s；
Wherein, X is selected from CuO, Fe2O3Or MnO2；
The catalyst B has formula shown in formula (II)：
M@CeO2/ molecular sieve formula (II)；
Wherein, M is selected from Rh, Pt or Pd.
In the present invention, the two-part catalyst is known for exhaust gas from diesel vehicle processing using those skilled in the art Reactor such as tubular fixed-bed reactor.According to as well known to those skilled in the art, two sections for carrying out catalytic reaction Formula catalyst has inlet end and outlet side according to gas flow direction in course of reaction, and the first haptoreaction gas of the inlet end goes out Reaction gas is contacted behind gas end, it is not specifically limited to this by the present invention.
In the present invention, the two-part catalyst includes the catalyst A of inlet end and the catalyst B of outlet side.At this In invention, the catalyst A has formula shown in formula (I)：
CeO2- X/ molecular sieve formula (I)s；
Wherein, X is selected from CuO, Fe2O3Or MnO2, preferably CuO.In the present invention, the CeO2- X is catalyst A work Property component, molecular sieve be catalyst A carrier.In the preferred embodiment of the invention, the X is CuO, and the catalyst A is For CeO2- CuO/ molecular sieves；The X is Fe2O3, the catalyst A is CeO2-Fe2O3/ molecular sieve；The X is MnO2, institute State catalyst A as CeO2-MnO2/ molecular sieve.In the present invention, in the formula (I), CeO2Mol ratio with X be preferably (3~ 19)：1, more preferably (4~17)：1, yet more preferably (6~13)：1, be most preferably (6.7~9.3)：1.
In the present invention, in the formula (I), the molecular sieve is preferably selected from ZSM-5, MCM-56 or BEA, more preferably MCM-56.The present invention is not particularly limited to the source of the molecular sieve, using above-mentioned ZSM- well known to those skilled in the art 5th, MCM-56 and BEA commercial goods or laboratory own product.In the preferred embodiment of the invention, the molecular sieve is ZSM-5, the ZSM-5 silica alumina ratio are preferably (5~20)：1, more preferably 12：1.In the preferred embodiment of the invention, institute Molecular sieve is stated for MCM-56, the silica alumina ratio of the MCM-56 is preferably (15~30)：1, more preferably 25：1.Of the invention preferred Embodiment in, the molecular sieve be BEA, the silica alumina ratio of the BEA is preferably (15~25)：1, more preferably 19：1.
In the present invention, in the formula (I), the CeO2- X and the mass ratio of molecular sieve are preferably 1：(1~10), it is more excellent Elect 1 as：5.
In the present invention, the catalyst B has formula shown in formula (II)：
M@CeO2/ molecular sieve formula (II)；
Wherein, M is selected from Rh, Pt or Pd, preferably Pt.In the present invention, the M@CeO2For catalyst B activearm Point, molecular sieve is catalyst A carrier.In the preferred embodiment of the invention, the M is Rh, and the catalyst B is Rh@ CeO2/ molecular sieve；The M is Pt, and the catalyst B is Pt@CeO2/ molecular sieve；The M is Pd, and the catalyst B is Pd@CeO2/ molecular sieve.In the present invention, in the formula (II), M and CeO2Mol ratio be preferably 1：(8~32), more preferably 1：16.
In the present invention, in the formula (II), the molecular sieve is preferably selected from ZSM-5, MCM-56 or BEA, more preferably MCM-56.The present invention is not particularly limited to the source of the molecular sieve, using above-mentioned ZSM- well known to those skilled in the art 5th, MCM-56 and BEA commercial goods or laboratory own product.In the preferred embodiment of the invention, the molecular sieve is ZSM-5, the ZSM-5 silica alumina ratio are preferably (5~20)：1, more preferably 12：1.In the preferred embodiment of the invention, institute Molecular sieve is stated for MCM-56, the silica alumina ratio of the MCM-56 is preferably (15~30)：1, more preferably 25：1.Of the invention preferred Embodiment in, the molecular sieve be BEA, the silica alumina ratio of the BEA is preferably (15~25)：1, more preferably 19：1.
In the present invention, in the formula (II), the M@CeO2Mass ratio with molecular sieve is 1：(1~10), more preferably For 1：5.
In the present invention, the mass ratio of the catalyst A and catalyst B are preferably (0.5~3)：1, more preferably 1：1.
Present invention also offers a kind of preparation method of the two-part catalyst described in above-mentioned technical proposal, including following step Suddenly：
A) cerium source, X ' sources and triethylamine are subjected to hydro-thermal reaction in the first solvent, obtain CeO2- X nano particle；It is described X ' sources are selected from copper source, source of iron or manganese source；
B) M ' sources, cerium source and ammoniacal liquor are subjected to coprecipitation reaction in the second solvent, obtain M@CeO2Nuclear shell structure nano Particle；M ' the sources are selected from rhodium source, platinum source or palladium source；
C) CeO for obtaining step a)2The M@CeO that-X nano particle and step b) are obtained2Core-shell structure nanometer particle is distinguished Loaded with molecular sieve, respectively obtain catalyst A and catalyst B；
D) catalyst A is arranged on inlet end, catalyst B is arranged on outlet side, obtained for exhaust gas from diesel vehicle processing Two-part catalyst；
The step a) and b) no order limitation.
Cerium source, X ' sources and triethylamine are carried out hydro-thermal reaction by the present invention in the first solvent first, obtain CeO2- X nano Particle.In the present invention, the cerium source is preferably cerous nitrate；X ' the sources are selected from copper source, source of iron or manganese source, wherein, the copper Source is preferably copper nitrate, and the source of iron is preferably ferric nitrate, and the manganese source is preferably the manganese nitrate solution that mass fraction is 50%； First solvent is preferably the ethanol solution of polyvinylpyrrolidone, and polyvinylpyrrolidone ethanol is molten in first solvent Liquid preferred mass concentration is 10g/L~30g/L.The present invention does not have to the source of the cerium source, X ' sources, triethylamine and the first solvent It is specifically limited, use above-mentioned cerous nitrate well known to those skilled in the art, copper nitrate, ferric nitrate, mass fraction for 50% nitre The commercial goods of sour manganese solution, polyvinylpyrrolidone and ethanol.
The present invention is not particularly limited to the mode of the hydro-thermal reaction, using technical side well known to those skilled in the art Case.In the present invention, the hydrothermal temperature is preferably 160 DEG C~200 DEG C, more preferably 180 DEG C；The hydro-thermal is anti- The time answered is preferably 20h~30h, more preferably 24h.
In the present invention, the CeO obtained2The average grain diameter of-X nano particle is preferably 3nm~5nm.
Meanwhile, M ' sources, cerium source and ammoniacal liquor are carried out coprecipitation reaction by the present invention in the second solvent, obtain M@CeO2Nucleocapsid Structure nano particle.In the present invention, the M ' sources are selected from rhodium source, platinum source or palladium source, wherein, rhodium source is preferably that rhodium nitrate is molten Liquid, the platinum source is preferably platinum acid chloride solution, and the palladium source is preferably palladium nitrate solution；The cerium source is preferably that cerous nitrate is molten Liquid；The ammoniacal liquor is preferably the ammoniacal liquor that mass concentration is 25%；Second solvent is preferably the aqueous solution or the iodate of KBr The aqueous solution of potassium, the mass concentration of second solvent is preferably 0.3g/L~0.4g/L, more preferably 0.375g/L.The present invention The source of the M ' sources, cerium source, ammoniacal liquor and the second solvent is not particularly limited, using well known to those skilled in the art above-mentioned Rhodium nitrate solution, platinum acid chloride solution, palladium nitrate solution, cerous nitrate solution, mass concentration are 25% ammoniacal liquor, KBr and iodate The commercial goods of potassium.
The present invention is not particularly limited to the mode of the coprecipitation reaction, using technology well known to those skilled in the art Scheme.In the present invention, preferably 50 DEG C~70 DEG C of the temperature of the coprecipitation reaction, more preferably 60 DEG C；It is described coprecipitated The time of shallow lake reaction is preferably 0.5h~1.5h, more preferably 1h.
In the present invention, the M@CeO obtained2The average grain diameter of core-shell structure nanometer particle is preferably 45nm~55nm, more Preferably 50nm.
Obtain the CeO2- X nano particle and M@CeO2It is of the invention by obtained CeO after core-shell structure nanometer particle2-X Nano-particle and obtained M@CeO2Core-shell structure nanometer particle is loaded with molecular sieve respectively, respectively obtain catalyst A and Catalyst B.In the present invention, the molecular sieve is identical with described in above-mentioned technical proposal, will not be repeated here.The present invention is right The mode of the load is not particularly limited, using the skill well known to those skilled in the art by nanometer particle load to molecular sieve Art scheme, is particularly preferred as：
Nano-particle is dispersed in deionized water or ethanol, after being uniformly dispersed, adds after molecular sieve ultrasound 0.5h and stirs 4h makes it uniform, after being evaporated and being dried overnight, is calcined, obtains the molecular sieve of nanometer particle load.In the present invention, it is described The temperature of calcining is preferably 400 DEG C~600 DEG C, more preferably 500 DEG C；The time of the calcining is preferably 1h~8h, more preferably For 2h.
In the present invention, by CeO2- X nano particle and M@CeO2Core-shell structure nanometer particle is born with molecular sieve respectively After load, the catalyst A and catalyst B respectively obtained is identical with described in above-mentioned technical proposal, will not be repeated here.
Respectively obtain after the catalyst A and catalyst B, catalyst A is set inlet end by the present invention, catalyst B is set In outlet side, the two-part catalyst for exhaust gas from diesel vehicle processing is obtained.The present invention is to the catalyst A/ catalyst B two Set-up mode in segmentation catalyst is not particularly limited, it is preferred to use by catalyst A/ catalyst B tablettings, grinding, screening takes 40-60 mesh granular sizes are directly used, or catalyst A/ catalyst B is coated on matrix obtained coated catalysts A/ coatings and urged Agent B is reused.In the present invention, the coating matrix of the coated catalysts A/ coated catalysts B is preferably honeycomb pottery Porcelain basal body or metal beehive carrier.
The two-part catalyst can be used for moving source or fixed combustion device includes various motor car engines and fire coal electricity The purification of factory's tail gas nitrogen oxide.It is placed in when using in exhaust pipe, reducing agent and tail is sprayed into by two-part catalyst inlet end Gas is mixed, wherein, NH3The ratio for counting consumption and NO is 0.8~1.2.
The invention provides a kind of two-part catalyst handled for exhaust gas from diesel vehicle, including：The catalyst A of inlet end With the catalyst B of outlet side；The catalyst A has formula：CeO2- X/ molecular sieves；Wherein, X is selected from CuO, Fe2O3Or MnO2； The catalyst B has formula：M@CeO2/ molecular sieve；Wherein, M is selected from Rh, Pt or Pd.Compared with prior art, the present invention is carried The two-part catalyst of confession for exhaust gas from diesel vehicle processing, have in wide temperature range to nitrogen oxides high eradicating efficacy and Selectivity, and particulate matter can be eliminated to a certain extent.Test result indicates that, the two-part catalyst that the present invention is provided exists 150-550 DEG C, high-speed 240000h-1Under the conditions of, with active, the good stability of the conversion of nitrogen oxides higher than 80% with And in high temperature excellent N2Selectivity；And the soot particulate matter during tail gas can be eliminated at 450 DEG C or so.
In addition, the two-part catalyst preparation process that provides of the present invention is simple, mild condition, cost are low, and not only to ring Border is not polluted, and is also had urea concurrently and is decomposed and eliminate escape NH3Effect.
In addition, catalyst is easy to be coated in ceramic honey comb or metal beehive carrier in the two-part catalyst that the present invention is provided Deng coated catalysts are obtained on matrix, it is expected to be directly used in diesel car tail gas refining, to meet the more strict discharge mark of state six It is accurate.
In order to further illustrate the present invention, it is described in detail below by following examples.Following examples of the present invention Raw materials used is commercial goods.
Embodiment 1
(1) CeO is prepared2-Fe2O3Nano-particle：
Weigh 5.4g polyvinylpyrrolidones (PVP-K30) and be dissolved in 360mL absolute ethyl alcohols；Treat that PVP is completely dissolved backward molten 0.7422g cerous nitrates and 0.0218g ferric nitrates are added in liquid, stirring is added dropwise to 1.82g triethylamines to after being completely dissolved, is stirred for It is transferred to after 10min in reactor, 180 DEG C of hydro-thermal reaction 24h, it is stand-by to take out constant volume (0.0008g/mL) after having reacted.
The CeO2-Fe2O3The TEM photos of nano-particle are as shown in figure 1, as shown in Figure 1, CeO2-Fe2O3Nano-particle Average grain diameter is 3nm~5nm.
(2) Rh@CeO are prepared2Core-shell structure nanometer particle：
7.5mg KBrs are added in the beaker equipped with 20mL deionized waters, are sequentially added after 60 DEG C of stirring in water bath dissolvings 0.03M rhodium nitrate solution 0.417mL, 0.1M cerous nitrate solution 2mL, are added dropwise to the water-reducible 0.05mL of 5mL deionizations Mass concentration be 25% ammoniacal liquor, finally 60 DEG C stirring keep 1h, centrifugation precipitated, washing repeatedly after 100 DEG C drying It is stand-by.
The Rh@CeO2The TEM photos of core-shell structure nanometer particle are as shown in Fig. 2 as shown in Figure 2, Rh@CeO2Nucleocapsid knot The average grain diameter of structure nano-particle is 50nm or so.
(3) CeO is prepared2-Fe2O3/ZSM-5：
Take the CeO of constant volume in step (1)2-Fe2O3Nanoparticle sol solution 250mL, adds 1g molecular sieve ZSM-5 (n (SiO2)/n(Al2O34h is stirred after)=12), ultrasonic 0.5h makes it uniform, and 100 DEG C of stirrings are evaporated, and 100 DEG C are dried overnight, air In 1 DEG C/min be warming up to 500 DEG C holding 2h, obtain CeO2-Fe2O3/ ZSM-5, i.e. catalyst A；Finally by catalyst A tablettings, grind Mill, screening takes 40-60 mesh granular sizes standby.
(4) Rh@CeO are prepared2/ZSM-5：
Weigh the Rh@CeO in 0.2g steps (2)2Core-shell structure nanometer particle is scattered in 20mL deionized waters, plus Enter 1g molecular sieves ZSM-5 (n (SiO2)/n(Al2O34h is stirred after)=12), ultrasonic 0.5h makes it uniform, and 80 DEG C of heating stirrings are steamed Dry, 100 DEG C of gained sample is dried overnight, and 1 DEG C/min is warming up to 500 DEG C of holding 2h in air, obtains Rh@CeO2/ ZSM-5, i.e., Catalyst B；Finally by catalyst B tablettings, grinding, screening takes 40-60 mesh granular sizes standby.
(5) 25mg catalyst A is arranged on to the inlet end of tubular fixed-bed reactor, 25mg catalyst B is arranged on tubular type The outlet side of fixed bed reactors, obtains the two-part catalyst for exhaust gas from diesel vehicle processing.
Embodiment 2
(1) CeO is prepared2-Fe2O3Nano-particle：
Weigh 5.4g polyvinylpyrrolidones (PVP-K30) and be dissolved in 360mL absolute ethyl alcohols；Treat that PVP is completely dissolved backward molten 0.4661g cerous nitrates and 0.0186g ferric nitrates are added in liquid, stirring is added dropwise to 1.22g triethylamines to after being completely dissolved, is stirred for It is transferred to after 10min in reactor, 180 DEG C of hydro-thermal reaction 24h, it is stand-by to take out constant volume (0.0008g/mL) after having reacted.
(2) Rh@CeO are prepared2Core-shell structure nanometer particle：Be the same as Example 1.
(3) CeO is prepared2-Fe2O3/ZSM-5：Be the same as Example 1.
(4) Rh@CeO are prepared2/ZSM-5：Be the same as Example 1.
(5) 25mg catalyst A is arranged on to the inlet end of tubular fixed-bed reactor, 25mg catalyst B is arranged on tubular type The outlet side of fixed bed reactors, obtains the two-part catalyst for exhaust gas from diesel vehicle processing.
Embodiment 3
(1) CeO is prepared2-Fe2O3Nano-particle：
Weigh 3.6g polyvinylpyrrolidones (PVP-K30) and be dissolved in 240mL absolute ethyl alcohols；Treat that PVP is completely dissolved backward molten 0.4687g cerous nitrates and 0.0290g ferric nitrates are added in liquid, stirring is added dropwise to 1.22g triethylamines to after being completely dissolved, is stirred for It is transferred to after 10min in reactor, 180 DEG C of hydro-thermal reaction 24h, it is stand-by to take out constant volume (0.0008g/mL) after having reacted.
(2) Rh@CeO are prepared2Core-shell structure nanometer particle：Be the same as Example 1.
(3) CeO is prepared2-Fe2O3/ZSM-5：Be the same as Example 1.
(4) Rh@CeO are prepared2/ZSM-5：Be the same as Example 1.
(5) 25mg catalyst A is arranged on to the inlet end of tubular fixed-bed reactor, 25mg catalyst B is arranged on tubular type The outlet side of fixed bed reactors, obtains the two-part catalyst for exhaust gas from diesel vehicle processing.
Embodiment 4
(1) CeO is prepared2-Fe2O3Nano-particle：
Weigh 3.6g polyvinylpyrrolidones (PVP-K30) and be dissolved in 240mL absolute ethyl alcohols；Treat that PVP is completely dissolved backward molten 0.4166g cerous nitrates and 0.0580g ferric nitrates are added in liquid, stirring is added dropwise to 1.22g triethylamines to after being completely dissolved, is stirred for It is transferred to after 10min in reactor, 180 DEG C of hydro-thermal reaction 24h, it is stand-by to take out constant volume (0.0008g/mL) after having reacted.
(2) Rh@CeO are prepared2Core-shell structure nanometer particle：Be the same as Example 1.
(3) CeO is prepared2-Fe2O3/ZSM-5：Be the same as Example 1.
(4) Rh@CeO are prepared2/ZSM-5：Be the same as Example 1.
(5) 25mg catalyst A is arranged on to the inlet end of tubular fixed-bed reactor, 25mg catalyst B is arranged on tubular type The outlet side of fixed bed reactors, obtains the two-part catalyst for exhaust gas from diesel vehicle processing.
Embodiment 5
(1) CeO is prepared2-Fe2O3Nano-particle：Be the same as Example 4.
(2) Rh@CeO are prepared2Core-shell structure nanometer particle：Be the same as Example 1.
(3) CeO is prepared2-FeO/MCM-56：
Take the CeO of constant volume in step (1)2-Fe2O3Nanoparticle sol solution 130mL, adds 0.5g molecular sieves MCM-56 (n(SiO2)/n(Al2O34h is stirred after)=25), ultrasonic 0.5h makes it uniform, and 100 DEG C of stirrings are evaporated, and 100 DEG C are dried overnight, empty 1 DEG C/min is warming up to 500 DEG C of holding 2h in gas, obtains CeO2-Fe2O3/ MCM-56, i.e. catalyst A；The CeO2-Fe2O3/ MCM-56 TEM photos are as shown in Figure 3；Finally by catalyst A tablettings, grinding, screening takes 40-60 mesh granular sizes standby.
(4) Rh@CeO are prepared2/MCM-56：
Weigh the Rh@CeO in 0.2g steps (2)2Core-shell structure nanometer particle is scattered in 20mL deionized waters, plus Enter 1g molecular sieves MCM-56 (n (SiO2)/n(Al2O34h is stirred after)=25), ultrasonic 0.5h makes it uniform, and 80 DEG C of heating stirrings are steamed Dry, 100 DEG C of gained sample is dried overnight, and 1 DEG C/min is warming up to 500 DEG C of holding 2h in air, obtains Rh@CeO2/ MCM-56, i.e., Catalyst B；The Rh@CeO2/ MCM-56 TEM photos are as shown in Figure 4；Finally by catalyst B tablettings, grinding, screening takes 40- 60 mesh granular sizes are standby.
(5) 25mg catalyst A is arranged on to the inlet end of tubular fixed-bed reactor, 25mg catalyst B is arranged on tubular type The outlet side of fixed bed reactors, obtains the two-part catalyst for exhaust gas from diesel vehicle processing.
Embodiment 6
(1) CeO is prepared2-Fe2O3Nano-particle：Be the same as Example 4.
(2) Rh@CeO are prepared2Core-shell structure nanometer particle：Be the same as Example 1.
(3) CeO is prepared2-Fe2O3/BEA：
Take the CeO of constant volume in step (1)2-Fe2O3Nanoparticle sol solution 130mL, adds 0.51g molecular sieve BEA (n (SiO2)/n(Al2O34h is stirred after)=19), ultrasonic 0.5h makes it uniform, and 100 DEG C of stirrings are evaporated, and 100 DEG C are dried overnight, air In 1 DEG C/min be warming up to 500 DEG C holding 2h, obtain CeO2-Fe2O3/ BEA, i.e. catalyst A；Finally by catalyst A tablettings, grind Mill, screening takes 40-60 mesh granular sizes standby.
(4) Rh@CeO are prepared2/MCM-56：
Weigh the Rh@CeO in 0.2g steps (2)2Core-shell structure nanometer particle is scattered in 20mL deionized waters, plus Enter 1g molecular sieves BEA (n (SiO2)/n(Al2O34h is stirred after)=19), ultrasonic 0.5h makes it uniform, and 80 DEG C of heating stirrings are evaporated, 100 DEG C of gained sample is dried overnight, and 1 DEG C/min is warming up to 500 DEG C of holding 2h in air, obtains Rh@CeO2/ BEA, i.e. catalyst B；Finally by catalyst B tablettings, grinding, screening takes 40-60 mesh granular sizes standby.
(5) 25mg catalyst A is arranged on to the inlet end of tubular fixed-bed reactor, 25mg catalyst B is arranged on tubular type The outlet side of fixed bed reactors, obtains the two-part catalyst for exhaust gas from diesel vehicle processing.
Embodiment 7
(1) CeO is prepared2- CuO nano-particles：
Weigh 5.4g polyvinylpyrrolidones (PVP-K30) and be dissolved in 360mL absolute ethyl alcohols；Treat that PVP is completely dissolved backward molten 0.7422g cerous nitrates and 0.0217g copper nitrates are added in liquid, stirring is added dropwise to 1.82g triethylamines to after being completely dissolved, is stirred for It is transferred to after 10min in reactor, 180 DEG C of hydro-thermal reaction 24h, it is stand-by to take out constant volume (0.0008g/mL) after having reacted.
(2) Pt@CeO are prepared2Core-shell structure nanometer particle：
7.5mg KIs are added in the beaker equipped with 20mL deionized waters, are sequentially added after 60 DEG C of stirring in water bath dissolvings 0.03M platinum acid chloride solution 0.417mL, 0.1M cerous nitrate solution 2mL, are added dropwise to the water-reducible 0.05mL of 5mL deionizations Mass concentration be 25% ammoniacal liquor, finally 60 DEG C stirring keep 1h, centrifugation precipitated, washing repeatedly after 100 DEG C drying It is stand-by.
(3) CeO is prepared2-CuO/ZSM-5：
Take the CeO of constant volume in step (1)2- CuO nanoparticle sol solution 250mL, add 1g molecular sieve ZSM-5 (n (SiO2)/n(Al2O34h is stirred after)=12), ultrasonic 0.5h makes it uniform, and 100 DEG C of stirrings are evaporated, and 100 DEG C are dried overnight, air In 1 DEG C/min be warming up to 500 DEG C holding 2h, obtain CeO2- CuO/ZSM-5, i.e. catalyst A；Finally by catalyst A tablettings, grind Mill, screening takes 40-60 mesh granular sizes standby.
(4) Pt@CeO are prepared2/ZSM-5：
Weigh the Pt@CeO in 0.2g steps (2)2Core-shell structure nanometer particle is scattered in 20mL deionized waters, plus Enter 1g molecular sieves ZSM-5 (n (SiO2)/n(Al2O34h is stirred after)=24), ultrasonic 0.5h makes it uniform, and 80 DEG C of heating stirrings are steamed Dry, 100 DEG C of gained sample is dried overnight, and 1 DEG C/min is warming up to 500 DEG C of holding 2h in air, obtains Pt@CeO2/ ZSM-5, i.e., Catalyst B；Finally by catalyst B tablettings, grinding, screening takes 40-60 mesh granular sizes standby.
(5) 25mg catalyst A is arranged on to the inlet end of tubular fixed-bed reactor, 25mg catalyst B is arranged on tubular type The outlet side of fixed bed reactors, obtains the two-part catalyst for exhaust gas from diesel vehicle processing.
Embodiment 8
(1) CeO is prepared2- CuO nano-particles：Be the same as Example 7.
(2) Pt@CeO are prepared2Core-shell structure nanometer particle：Be the same as Example 7.
(3) CeO is prepared2-CuO/MCM-56：
Take the CeO of constant volume in step (1)2- CuO nanoparticle sol solution 250mL, add 1g molecular sieve MCM-56 (n (SiO2)/n(Al2O34h is stirred after)=25), ultrasonic 0.5h makes it uniform, and 100 DEG C of stirrings are evaporated, and 100 DEG C are dried overnight, air In 1 DEG C/min be warming up to 500 DEG C holding 2h, obtain CeO2- CuO/MCM-56, i.e. catalyst A；Finally by catalyst A tablettings, grind Mill, screening takes 40-60 mesh granular sizes standby.
(4) Pt@CeO are prepared2/MCM-56：
Weigh the Pt@CeO in 0.2g steps (2)2Core-shell structure nanometer particle is scattered in 20mL deionized waters, plus Enter 1g molecular sieves MCM-56 (n (SiO2)/n(Al2O34h is stirred after)=25), ultrasonic 0.5h makes it uniform, and 80 DEG C of heating stirrings are steamed Dry, 100 DEG C of gained sample is dried overnight, and 1 DEG C/min is warming up to 500 DEG C of holding 2h in air, obtains Pt@CeO2/ MCM-56, i.e., Catalyst B；Finally by catalyst B tablettings, grinding, screening takes 40-60 mesh granular sizes standby.
(5) 25mg catalyst A is arranged on to the inlet end of tubular fixed-bed reactor, 25mg catalyst B is arranged on tubular type The outlet side of fixed bed reactors, obtains the two-part catalyst for exhaust gas from diesel vehicle processing.
Embodiment 9
(1) CeO is prepared2- CuO nano-particles：
Weigh 3.6g polyvinylpyrrolidones (PVP-K30) and be dissolved in 240mL absolute ethyl alcohols；Treat that PVP is completely dissolved backward molten 0.4661g cerous nitrates and 0.0193g copper nitrates are added in liquid, stirring is added dropwise to 1.22g triethylamines to after being completely dissolved, is stirred for It is transferred to after 10min in reactor, 180 DEG C of hydro-thermal reaction 24h, it is stand-by to take out constant volume (0.0008g/mL) after having reacted.
(2) Pt@CeO are prepared2Core-shell structure nanometer particle：Be the same as Example 7.
(3) CeO is prepared2-CuO/MCM-56：
Take the CeO of constant volume in step (1)2- CuO nanoparticle sol solution 125.6mL, add 0.5g molecular sieves MCM-56 (n(SiO2)/n(Al2O34h is stirred after)=25), ultrasonic 0.5h makes it uniform, and 100 DEG C of stirrings are evaporated, and 100 DEG C are dried overnight, empty 1 DEG C/min is warming up to 500 DEG C of holding 2h in gas, obtains CeO2- CuO/MCM-56, i.e. catalyst A；Finally by catalyst A tablettings, Grinding, screening takes 40-60 mesh granular sizes standby.
(4) Pt@CeO are prepared2/MCM-56：Be the same as Example 8.
(5) 25mg catalyst A is arranged on to the inlet end of tubular fixed-bed reactor, 25mg catalyst B is arranged on tubular type The outlet side of fixed bed reactors, obtains the two-part catalyst for exhaust gas from diesel vehicle processing.
Embodiment 10
(1) CeO is prepared2- CuO nano-particles：
Weigh 3.6g polyvinylpyrrolidones (PVP-K30) and be dissolved in 240mL absolute ethyl alcohols；Treat that PVP is completely dissolved backward molten 0.4687g cerous nitrates and 0.0290g copper nitrates are added in liquid, stirring is added dropwise to 1.22g triethylamines to after being completely dissolved, is stirred for It is transferred to after 10min in reactor, 180 DEG C of hydro-thermal reaction 24h, it is stand-by to take out constant volume (0.0008g/mL) after having reacted.
(2) Pt@CeO are prepared2Core-shell structure nanometer particle：Be the same as Example 7.
(3) CeO is prepared2-CuO/MCM-56：
Take the CeO of constant volume in step (1)2- CuO nanoparticle sol solution 123mL, add 0.5g molecular sieve MCM-56 (n (SiO2)/n(Al2O34h is stirred after)=25), ultrasonic 0.5h makes it uniform, and 100 DEG C of stirrings are evaporated, and 100 DEG C are dried overnight, air In 1 DEG C/min be warming up to 500 DEG C holding 2h, obtain CeO2- CuO/MCM-56, i.e. catalyst A；Finally by catalyst A tablettings, grind Mill, screening takes 40-60 mesh granular sizes standby.
(4) Pt@CeO are prepared2/MCM-56：Be the same as Example 8.
(5) 25mg catalyst A is arranged on to the inlet end of tubular fixed-bed reactor, 25mg catalyst B is arranged on tubular type The outlet side of fixed bed reactors, obtains the two-part catalyst for exhaust gas from diesel vehicle processing.
Embodiment 11
(1) CeO is prepared2- CuO nano-particles：
Weigh 3.6g polyvinylpyrrolidones (PVP-K30) and be dissolved in 240mL absolute ethyl alcohols；Treat that PVP is completely dissolved backward molten 0.4166g cerous nitrates and 0.0580g copper nitrates are added in liquid, stirring is added dropwise to 1.22g triethylamines to after being completely dissolved, is stirred for It is transferred to after 10min in reactor, 180 DEG C of hydro-thermal reaction 24h, it is stand-by to take out constant volume (0.0008g/mL) after having reacted.
(2) Pt@CeO are prepared2Core-shell structure nanometer particle：Be the same as Example 7.
(3) CeO is prepared2-CuO/MCM-56：
Take the CeO of constant volume in step (1)2- CuO nanoparticle sol solution 130mL, add 0.5g molecular sieve MCM-56 (n (SiO2)/n(Al2O34h is stirred after)=25), ultrasonic 0.5h makes it uniform, and 100 DEG C of stirrings are evaporated, and 100 DEG C are dried overnight, air In 1 DEG C/min be warming up to 500 DEG C holding 2h, obtain CeO2- CuO/MCM-56, i.e. catalyst A；Finally by catalyst A tablettings, grind Mill, screening takes 40-60 mesh granular sizes standby.
(4) Pt@CeO are prepared2/MCM-56：Be the same as Example 8.
(5) 25mg catalyst A is arranged on to the inlet end of tubular fixed-bed reactor, 25mg catalyst B is arranged on tubular type The outlet side of fixed bed reactors, obtains the two-part catalyst for exhaust gas from diesel vehicle processing.
Embodiment 12
(1) CeO is prepared2- CuO nano-particles：Be the same as Example 10.
(2) Pt@CeO are prepared2Core-shell structure nanometer particle：
7.5mg KIs are added in the beaker equipped with 20mL deionized waters, are sequentially added after 60 DEG C of stirring in water bath dissolvings 0.03M platinum acid chloride solution 0.417mL, 0.1M cerous nitrate solution 4mL, are added dropwise to the water-reducible 0.05mL of 5mL deionizations Mass concentration be 25% ammoniacal liquor, finally 60 DEG C stirring keep 1h, centrifugation precipitated, washing repeatedly after 100 DEG C drying It is stand-by.
(3) CeO is prepared2-CuO/MCM-56：Be the same as Example 10.
(4) Pt@CeO are prepared2/MCM-56：Be the same as Example 8.
(5) 25mg catalyst A is arranged on to the inlet end of tubular fixed-bed reactor, 25mg catalyst B is arranged on tubular type The outlet side of fixed bed reactors, obtains the two-part catalyst for exhaust gas from diesel vehicle processing.
Embodiment 13
(1) CeO is prepared2- CuO nano-particles：Be the same as Example 10.
(2) Pt@CeO are prepared2Core-shell structure nanometer particle：
7.5mg KIs are added in the beaker equipped with 20mL deionized waters, are sequentially added after 60 DEG C of stirring in water bath dissolvings 0.03M platinum acid chloride solution 0.8.34mL, 0.1M cerous nitrate solution 2mL, are added dropwise to the water-reducible 0.05mL of 5mL deionizations Mass concentration be 25% ammoniacal liquor, finally 60 DEG C stirring keep 1h, centrifugation precipitated, washing repeatedly after 100 DEG C drying It is stand-by.
(3) CeO is prepared2-CuO/MCM-56：Be the same as Example 10.
(4) Pt@CeO are prepared2/MCM-56：Be the same as Example 8.
(5) 25mg catalyst A is arranged on to the inlet end of tubular fixed-bed reactor, 25mg catalyst B is arranged on tubular type The outlet side of fixed bed reactors, obtains the two-part catalyst for exhaust gas from diesel vehicle processing.
Embodiment 14
(1) CeO is prepared2- CuO nano-particles：Be the same as Example 10.
(2) Pt@CeO are prepared2Core-shell structure nanometer particle：Be the same as Example 7.
(3) CeO is prepared2-CuO/BEA：
Take the CeO of constant volume in step (1)2- CuO nanoparticle sol solution 130mL, add 0.5g molecular sieve BEA (n (SiO2)/n(Al2O34h is stirred after)=19), ultrasonic 0.5h makes it uniform, and 100 DEG C of stirrings are evaporated, and 100 DEG C are dried overnight, air In 1 DEG C/min be warming up to 500 DEG C holding 2h, obtain CeO2- CuO/BEA, i.e. catalyst A；Finally by catalyst A tablettings, grinding, Screening takes 40-60 mesh granular sizes standby.
(4) Pt@CeO are prepared2/BEA：
Weigh the Pt@CeO in 0.2g steps (2)2Core-shell structure nanometer particle is scattered in 20mL deionized waters, plus Enter 1g molecular sieves BEA (n (SiO2)/n(Al2O34h is stirred after)=19), ultrasonic 0.5h makes it uniform, and 80 DEG C of heating stirrings are evaporated, 100 DEG C of gained sample is dried overnight, and 1 DEG C/min is warming up to 500 DEG C of holding 2h in air, obtains Pt@CeO2/ BEA, i.e. catalyst B；Finally by catalyst B tablettings, grinding, screening takes 40-60 mesh granular sizes standby.
(5) 25mg catalyst A is arranged on to the inlet end of tubular fixed-bed reactor, 25mg catalyst B is arranged on tubular type The outlet side of fixed bed reactors, obtains the two-part catalyst for exhaust gas from diesel vehicle processing.
Embodiment 15
(1) CeO is prepared2-Fe2O3Nano-particle：Be the same as Example 4.
(2) Pd@CeO are prepared2Core-shell structure nanometer particle：
7.5mg KBrs are added in the beaker equipped with 20mL deionized waters, are sequentially added after 60 DEG C of stirring in water bath dissolvings 0.03M palladium nitrate solution 0.417mL, 0.1M cerous nitrate solution 2mL, are added dropwise to the water-reducible 0.05mL of 5mL deionizations Mass concentration be 25% ammoniacal liquor, finally 60 DEG C stirring keep 1h, centrifugation precipitated, washing repeatedly after 100 DEG C drying It is stand-by.
(3) CeO is prepared2-Fe2O3/ZSM-5：Be the same as Example 4.
(4) Pd@CeO are prepared2/ZSM-5：
Weigh the Pd@CeO in 0.2g steps (2)2Core-shell structure nanometer particle is scattered in 20mL deionized waters, plus Enter 1g molecular sieves ZSM-5 (n (SiO2)/n(Al2O34h is stirred after)=12), ultrasonic 0.5h makes it uniform, and 80 DEG C of heating stirrings are steamed Dry, 100 DEG C of gained sample is dried overnight, and 1 DEG C/min is warming up to 500 DEG C of holding 2h in air, obtains Pd@CeO2/ ZSM-5, i.e., Catalyst B；Finally by catalyst B tablettings, grinding, screening takes 40-60 mesh granular sizes standby.
(5) 25mg catalyst A is arranged on to the inlet end of tubular fixed-bed reactor, 25mg catalyst B is arranged on tubular type The outlet side of fixed bed reactors, obtains the two-part catalyst for exhaust gas from diesel vehicle processing.
Embodiment 16
(1) CeO is prepared2-Fe2O3Nano-particle：Be the same as Example 15.
(2) Pd@CeO are prepared2Core-shell structure nanometer particle：Be the same as Example 15.
(3) CeO is prepared2-Fe2O3/MCM-56：Be the same as Example 5.
(4) Pd@CeO are prepared2/MCM-56：
Weigh the Pd@CeO in 0.2g steps (2)2Core-shell structure nanometer particle is scattered in 20mL deionized waters, plus Enter 1g molecular sieves MCM-56 (n (SiO2)/n(Al2O34h is stirred after)=25), ultrasonic 0.5h makes it uniform, and 80 DEG C of heating stirrings are steamed Dry, 100 DEG C of gained sample is dried overnight, and 1 DEG C/min is warming up to 500 DEG C of holding 2h in air, obtains Pd@CeO2/ MCM-56, i.e., Catalyst B；Finally by catalyst B tablettings, grinding, screening takes 40-60 mesh granular sizes standby.
(5) 25mg catalyst A is arranged on to the inlet end of tubular fixed-bed reactor, 25mg catalyst B is arranged on tubular type The outlet side of fixed bed reactors, obtains the two-part catalyst for exhaust gas from diesel vehicle processing.
Embodiment 17
(1) CeO is prepared2-Fe2O3Nano-particle：Be the same as Example 15.
(2) Pd@CeO are prepared2Core-shell structure nanometer particle：Be the same as Example 15.
(3) CeO is prepared2-Fe2O3/BEA：Be the same as Example 6.
(4) Pd@CeO are prepared2/BEA：
Weigh the Pd@CeO in 0.2g steps (2)2Core-shell structure nanometer particle is scattered in 20mL deionized waters, plus Enter 1g molecular sieves BEA (n (SiO2)/n(Al2O34h is stirred after)=19), ultrasonic 0.5h makes it uniform, and 80 DEG C of heating stirrings are evaporated, 100 DEG C of gained sample is dried overnight, and 1 DEG C/min is warming up to 500 DEG C of holding 2h in air, obtains Pd@CeO2/ BEA, i.e. catalyst B；Finally by catalyst B tablettings, grinding, screening takes 40-60 mesh granular sizes standby.
(5) 25mg catalyst A is arranged on to the inlet end of tubular fixed-bed reactor, 25mg catalyst B is arranged on tubular type The outlet side of fixed bed reactors, obtains the two-part catalyst for exhaust gas from diesel vehicle processing.
Embodiment 18
(1) CeO is prepared2-MnO2Nano-particle：
Weigh 3.6g polyvinylpyrrolidones (PVP-K30) and be dissolved in 240mL absolute ethyl alcohols；Treat that PVP is completely dissolved backward molten It is 50% manganese nitrate solution that 0.4687g cerous nitrates and 0.04294g mass fractions are added in liquid, and stirring is dripped to after being completely dissolved 1.22g triethylamines are added, are stirred for being transferred in reactor after 10min, 180 DEG C of hydro-thermal reaction 24h, constant volume is taken out after having reacted (0.0008g/mL) is stand-by.
(2) Pt@CeO are prepared2Core-shell structure nanometer particle：Be the same as Example 7.
(3) CeO is prepared2-MnO2/ZSM-5：
Take the CeO of constant volume in step (1)2-MnO2Nanoparticle sol solution 130mL, adds 0.5g molecular sieve ZSM-5 (n (SiO2)/n(Al2O34h is stirred after)=12), ultrasonic 0.5h makes it uniform, and 100 DEG C of stirrings are evaporated, and 100 DEG C are dried overnight, air In 1 DEG C/min be warming up to 500 DEG C holding 2h, obtain CeO2-MnO2/ ZSM-5, i.e. catalyst A；Finally by catalyst A tablettings, grind Mill, screening takes 40-60 mesh granular sizes standby.
(4) Pt@CeO are prepared2/ZSM-5：Be the same as Example 7.
(5) 25mg catalyst A is arranged on to the inlet end of tubular fixed-bed reactor, 25mg catalyst B is arranged on tubular type The outlet side of fixed bed reactors, obtains the two-part catalyst for exhaust gas from diesel vehicle processing.
Embodiment 19
(1) CeO is prepared2-MnO2Nano-particle：Be the same as Example 18.
(2) Pt@CeO are prepared2Core-shell structure nanometer particle：Be the same as Example 7.
(3) CeO is prepared2-MnO2/MCM-56：
Take the CeO of constant volume in step (1)2-MnO2Nanoparticle sol solution 130mL, adds 0.5g molecular sieve MCM-56 (n (SiO2)/n(Al2O34h is stirred after)=25), ultrasonic 0.5h makes it uniform, and 100 DEG C of stirrings are evaporated, and 100 DEG C are dried overnight, air In 1 DEG C/min be warming up to 500 DEG C holding 2h, obtain CeO2-MnO2/ MCM-56, i.e. catalyst A；Finally by catalyst A tablettings, grind Mill, screening takes 40-60 mesh granular sizes standby.
(4) Pt@CeO are prepared2/MCM-56：Be the same as Example 8.
(5) 25mg catalyst A is arranged on to the inlet end of tubular fixed-bed reactor, 25mg catalyst B is arranged on tubular type The outlet side of fixed bed reactors, obtains the two-part catalyst for exhaust gas from diesel vehicle processing.
Embodiment 20
(1) CeO is prepared2-MnO2Nano-particle：Be the same as Example 18.
(2) Pt@CeO are prepared2Core-shell structure nanometer particle：Be the same as Example 7.
(3) CeO is prepared2-MnO2/BEA：
Take the CeO of constant volume in step (1)2-MnO2Nanoparticle sol solution 130mL, adds 0.5g molecular sieve BEA (n (SiO2)/n(Al2O34h is stirred after)=19), ultrasonic 0.5h makes it uniform, and 100 DEG C of stirrings are evaporated, and 100 DEG C are dried overnight, air In 1 DEG C/min be warming up to 500 DEG C holding 2h, obtain CeO2-MnO2/ BEA, i.e. catalyst A；Finally by catalyst A tablettings, grinding, Screening takes 40-60 mesh granular sizes standby.
(4) Pt@CeO are prepared2/BEA：Be the same as Example 14.
(5) 25mg catalyst A is arranged on to the inlet end of tubular fixed-bed reactor, 25mg catalyst B is arranged on tubular type The outlet side of fixed bed reactors, obtains the two-part catalyst for exhaust gas from diesel vehicle processing.
Embodiment 21
(1) to mix to slurries uniform with 30% Ludox by the catalyst A for preparing embodiment 8；
(2) to mix to slurries uniform with 30% Ludox by the catalyst B for preparing embodiment 8；
(2) a diameter of 17mm is taken, calcining 2h goes the removal of impurity to length at 700 DEG C in atmosphere for 17mm cordierite, obtains Cordierite honeycomb ceramic matrix；
(3) cordierite honeycomb ceramic matrix is immersed in the homogenate in step (1) and step (2) respectively, taken after 10min Go out, dried in 100 DEG C of baking ovens and be calcined 2h at 10h, 500 DEG C of Muffle furnace, respectively obtain the ceramic honeycomb catalyst A and coating of coating Ceramic honeycomb catalyst B；
(4) it is 0.5 that will take mass ratio：The ceramic honeycomb catalyst A of the 1 coating and ceramic honeycomb catalyst B of coating, its In, the ceramic honeycomb catalyst A of coating is arranged on the inlet end of tubular fixed-bed reactor, the ceramic honeycomb catalyst B of coating The outlet side of tubular fixed-bed reactor is arranged on, the two-part catalyst for exhaust gas from diesel vehicle processing is obtained.
Embodiment 22
(1) to mix to slurries uniform with 25% Alumina gel by the catalyst A for preparing embodiment 8；
(2) to mix to slurries uniform with 25% Alumina gel by the catalyst B for preparing embodiment 8；
(2) a diameter of 17mm is taken, calcining 2h goes the removal of impurity to length at 700 DEG C in atmosphere for 17mm cordierite, obtains Cordierite honeycomb ceramic matrix；
(3) cordierite honeycomb ceramic matrix is immersed in the homogenate in step (1) and step (2) respectively, taken after 10min Go out, dried in 100 DEG C of baking ovens and be calcined 2h at 10h, 500 DEG C of Muffle furnace, respectively obtain the ceramic honeycomb catalyst A and coating of coating Ceramic honeycomb catalyst B；
(4) it is 1 that will take mass ratio：The ceramic honeycomb catalyst A of the 1 coating and ceramic honeycomb catalyst B of coating, its In, the ceramic honeycomb catalyst A of coating is arranged on the inlet end of tubular fixed-bed reactor, the ceramic honeycomb catalyst B of coating The outlet side of tubular fixed-bed reactor is arranged on, the two-part catalyst for exhaust gas from diesel vehicle processing is obtained.
Embodiment 23
(1) to mix to slurries uniform with 30% Ludox by the catalyst A for preparing embodiment 8；
(2) to mix to slurries uniform with 30% Ludox by the catalyst B for preparing embodiment 8；
(2) a diameter of 17mm is taken, length is that 17mm metal beehive carriers are cleaned in supersonic wave cleaning machine, in horse after drying Not 900 DEG C of calcining 2h go the removal of impurity in stove, obtain metal beehive carrier；
(3) metal beehive carrier is immersed in respectively in the homogenate in step (1) and step (2), taken out after 10min, 100 Dried in DEG C baking oven at 10h, 500 DEG C of Muffle furnace and be calcined 2h, respectively obtain the metal honeycomb catalyst A of coating and the metal of coating Honeycomb catalyst B；
(4) it is 2 that will take mass ratio：The metal honeycomb catalyst A of the 1 coating and metal honeycomb catalyst B of coating, its In, the metal honeycomb catalyst A of coating is arranged on the inlet end of tubular fixed-bed reactor, the metal honeycomb catalyst B of coating The outlet side of tubular fixed-bed reactor is arranged on, the two-part catalyst for exhaust gas from diesel vehicle processing is obtained.
The active of two-part catalyst nitrogen oxides reduction of the offer of the embodiment of the present invention 1~23 is detected, Experiment condition is as follows：
Reacting gas is NO：500ppm, NH3：500ppm, O2：5%, Ar are Balance Air；
Total gas flow rate is 100mL/min, and reaction velocity (GHSV) is 240000mL/g/h；
Reaction temperature interval is from 150 DEG C to 550 DEG C；
Gas uses Mass Spectrometer Method.
Testing result is shown in Table 1.
The activity for the two-part catalyst nitrogen oxides reduction that the embodiment of the present invention 1~23 of table 1 is provided
Data
As shown in Table 1, the two-part catalyst that the embodiment of the present invention 1~20 is provided is in 150-550 DEG C, high-speed 240000h-1Under the conditions of, it is excellent with active, the good stability of the conversion of nitrogen oxides higher than 80% and in high temperature N2Selectivity.
Comparative example 1
The catalyst B that 25mg embodiments 8 are prepared is arranged on the inlet end of tubular fixed-bed reactor, and 25mg is implemented The catalyst A that example 8 is prepared is arranged on the outlet side of tubular fixed-bed reactor, obtains two for exhaust gas from diesel vehicle processing Segmentation catalyst.
Comparative example 2
The catalyst A mixing that catalyst B and the 25mg embodiment 8 that 25mg embodiments 8 are prepared is prepared, flat Two parts of inlet ends for being separately positioned on tubular fixed-bed reactor and outlet side are divided into, is obtained for exhaust gas from diesel vehicle processing Two-part catalyst.
The activity of the two-part catalyst nitrogen oxides reduction provided under the same conditions comparative example 1~2 is carried out Detection, testing result is shown in Table 2.
The activity data for the two-part catalyst nitrogen oxides reduction that the comparative example 1~2 of table 2 is provided
As shown in Table 2, catalytic performance is drastically reduced after 300 DEG C of the two-part catalyst that comparative example 1~2 is provided.
Comparative example 3
The catalyst A that 50mg embodiments 10 are prepared is divided into two parts and is separately positioned on tubular fixed-bed reactor Inlet end and outlet side, obtain for exhaust gas from diesel vehicle processing two-part catalyst.
Comparative example 4
The catalyst B that 50mg embodiments 10 are prepared is divided into two parts and is separately positioned on tubular fixed-bed reactor Inlet end and outlet side, obtain for exhaust gas from diesel vehicle processing two-part catalyst.
The activity of the two-part catalyst nitrogen oxides reduction provided under the same conditions comparative example 3~4 is carried out Detection, and contrasted with embodiment 10, as a result as shown in Figure 5.As shown in Figure 5, the two-part that the embodiment of the present invention 10 is provided Catalyst compares comparative example 3~4, has high eradicating efficacy and selectivity to nitrogen oxides in wide temperature range.
The performance that the two-part catalyst that the embodiment of the present invention 9, comparative example 1~2 are provided removes soot particulate matter is examined Survey, experiment condition is as follows：
0.0028g carbon blacks are mixed with the catalyst of tubular fixed-bed reactor inlet end；Reacting gas is NO： 500ppm, O2：5%, Ar are Balance Air；
Total gas flow rate is 40mL/min, and reaction velocity (GHSV) is 96000mL/g/h；
Reaction temperature interval is from 150 DEG C to 700 DEG C；
Gas uses Mass Spectrometer Method.
Testing result is shown in Table 3.
The two-part catalyst that the embodiment 9 of table 3, comparative example 1~2 are provided removes the performance number of soot particulate matter
According to
Group Ts(℃) Tm(℃) Te(℃)
Embodiment 9 200 476 563
Comparative example 1 400 605 668
Comparative example 2 450 610 673
In table 3, Ts is that carbon black is converted into CO2Initial temperature, Tm be carbon black be converted into CO2Peak temperature, Te is carbon black It is converted into CO2End temp.As shown in Table 3, the two-part catalyst that the embodiment of the present invention 9 is provided has compared to comparative example 1~2 There are the performance for preferably removing soot particulate matter, the soot particulate matter during tail gas can be eliminated at 450 DEG C or so.
NH is aoxidized to the two-part catalyst that the embodiment of the present invention 7 is provided3Performance detected that experiment condition is as follows：
Reacting gas is NH3：Concentration is respectively 1000ppm, 500ppm, 200ppm, 100ppm, O2：5%, Ar are balance Gas, total gas flow rate is 40ml/min, and reaction velocity (GHSV) is 96000mL/g/h；
Reaction temperature interval is from 150 DEG C to 550 DEG C；
Gas uses Mass Spectrometer Method.
Testing result is shown in Table 4.
The two-part catalyst that the embodiment 7 of table 4 is provided is in different NH3NH is aoxidized under concentration3Performance data
As shown in Table 4, the two-part catalyst that the embodiment of the present invention 7 is provided, which has, eliminates escape NH3Effect.
The described above of the disclosed embodiments, enables professional and technical personnel in the field to realize or using the present invention.It is right A variety of modifications of these embodiments will be apparent for those skilled in the art, and as defined herein one As principle can realize in other embodiments without departing from the spirit or scope of the present invention.Therefore, the present invention will It will not be intended to be limited to the embodiments shown herein, and be to fit to consistent with principles disclosed herein and features of novelty Most wide scope.

Claims (10)

1. a kind of two-part catalyst handled for exhaust gas from diesel vehicle, including：The catalyst A of inlet end and the catalysis of outlet side Agent B；
The catalyst A has formula shown in formula (I)：
CeO2- X/ molecular sieve formula (I)s；
Wherein, X is selected from CuO, Fe2O3Or MnO2；
The catalyst B has formula shown in formula (II)：
M@CeO2/ molecular sieve formula (II)；
Wherein, M is selected from Rh, Pt or Pd.
2. two-part catalyst according to claim 1, it is characterised in that in the formula (I), CeO2Mol ratio with X is (3~19)：1.
3. two-part catalyst according to claim 1, it is characterised in that in the formula (I), the molecular sieve is selected from ZSM-5, MCM-56 or BEA；
The CeO2- X and the mass ratio of molecular sieve are 1：(1~10).
4. two-part catalyst according to claim 1, it is characterised in that in the formula (II), M and CeO2Mol ratio For 1：(8~32).
5. two-part catalyst according to claim 1, it is characterised in that in the formula (II), the molecular sieve is selected from ZSM-5, MCM-56 or BEA；
The M@CeO2Mass ratio with molecular sieve is 1：(1~10).
6. two-part catalyst according to claim 1, it is characterised in that the mass ratio of the catalyst A and catalyst B For (0.5~3)：1.
7. a kind of preparation method of the two-part catalyst described in any one of claim 1~6, comprises the following steps：
A) cerium source, X ' sources and triethylamine are subjected to hydro-thermal reaction in the first solvent, obtain CeO2- X nano particle；X ' the sources Selected from copper source, source of iron or manganese source；
B) M ' sources, cerium source and ammoniacal liquor are subjected to coprecipitation reaction in the second solvent, obtain M@CeO2Core-shell structure nanometer particle； M ' the sources are selected from rhodium source, platinum source or palladium source；
C) CeO for obtaining step a)2The M@CeO that-X nano particle and step b) are obtained2Core-shell structure nanometer particle is respectively with dividing Son sieve is loaded, and respectively obtains catalyst A and catalyst B；
D) catalyst A is arranged on inlet end, the outlet side that catalyst B is arranged on obtains two for exhaust gas from diesel vehicle processing Segmentation catalyst；
The step a) and b) no order limitation.
8. preparation method according to claim 7, it is characterised in that the temperature of hydro-thermal reaction described in step a) is 160 DEG C~200 DEG C, the time is 20h~30h.
9. preparation method according to claim 7, it is characterised in that the temperature 50 C of coprecipitation reaction described in step b) ~70 DEG C, the time is 0.5h~1.5h.
10. preparation method according to claim 7, it is characterised in that CeO described in step c)2- X nano particle is averaged Particle diameter is 3nm~5nm；The M@CeO2The average grain diameter of core-shell structure nanometer particle is 45nm~55nm.
CN201710485488.5A 2017-06-23 2017-06-23 Two-stage catalyst for diesel vehicle tail gas treatment and preparation method thereof Active CN107233912B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201710485488.5A CN107233912B (en) 2017-06-23 2017-06-23 Two-stage catalyst for diesel vehicle tail gas treatment and preparation method thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201710485488.5A CN107233912B (en) 2017-06-23 2017-06-23 Two-stage catalyst for diesel vehicle tail gas treatment and preparation method thereof

Publications (2)

Publication Number Publication Date
CN107233912A true CN107233912A (en) 2017-10-10
CN107233912B CN107233912B (en) 2020-04-07

Family

ID=59987766

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201710485488.5A Active CN107233912B (en) 2017-06-23 2017-06-23 Two-stage catalyst for diesel vehicle tail gas treatment and preparation method thereof

Country Status (1)

Country Link
CN (1) CN107233912B (en)

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108435220A (en) * 2018-04-26 2018-08-24 中国科学院长春应用化学研究所 A kind of combined type SCR denitration that anti-poisoning capability is strong and its application
CN110052287A (en) * 2019-05-17 2019-07-26 湘潭大学 A kind of the core-shell structure molecular sieve catalyst and preparation method of Collaborative Control NO and toluene
CN110385124A (en) * 2018-04-16 2019-10-29 浙江大学 One kind passing through segmentation reaction preparation MnOx-CeO2The method of mixed oxide catalyst
CN112279266A (en) * 2020-12-29 2021-01-29 中化学科学技术研究有限公司 Cu-SSZ-13@ SSZ-13 core-shell type molecular sieve and preparation method and application thereof
CN113385221A (en) * 2021-07-14 2021-09-14 安徽元琛环保科技股份有限公司 Ultra-high temperature catalyst based on metal honeycomb carrier and preparation method thereof
CN113457730A (en) * 2021-06-17 2021-10-01 江苏博霖环保科技有限公司 Preparation method of porous SCR catalyst for treating diesel engine tail gas
CN115155559A (en) * 2022-08-02 2022-10-11 中国科学院赣江创新研究院 Denitration catalyst and preparation method and application thereof
CN117797860A (en) * 2024-02-27 2024-04-02 中汽研汽车检验中心（天津）有限公司 Treatment of N in vehicle exhaust 2 Sectional catalyst of O and preparation method

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102814192A (en) * 2012-07-24 2012-12-12 中国科学院长春应用化学研究所 Cerium/molecular sieve catalyst used for selective catalytic reduction of nitrogen oxides and preparation method thereof
CN104005823A (en) * 2014-06-06 2014-08-27 四川中自尾气净化有限公司 Catalytic converter for treating exhaust gas of motorcycle and preparation method of catalytic converter
CN105597748A (en) * 2015-11-13 2016-05-25 无锡威孚环保催化剂有限公司 Segmented type ternary catalyst and preparation method thereof
CN105964253A (en) * 2016-05-13 2016-09-28 无锡威孚环保催化剂有限公司 Gasoline car particle capturing catalyst and preparation method thereof

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102814192A (en) * 2012-07-24 2012-12-12 中国科学院长春应用化学研究所 Cerium/molecular sieve catalyst used for selective catalytic reduction of nitrogen oxides and preparation method thereof
CN104005823A (en) * 2014-06-06 2014-08-27 四川中自尾气净化有限公司 Catalytic converter for treating exhaust gas of motorcycle and preparation method of catalytic converter
CN105597748A (en) * 2015-11-13 2016-05-25 无锡威孚环保催化剂有限公司 Segmented type ternary catalyst and preparation method thereof
CN105964253A (en) * 2016-05-13 2016-09-28 无锡威孚环保催化剂有限公司 Gasoline car particle capturing catalyst and preparation method thereof

Cited By (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110385124A (en) * 2018-04-16 2019-10-29 浙江大学 One kind passing through segmentation reaction preparation MnOx-CeO2The method of mixed oxide catalyst
CN108435220A (en) * 2018-04-26 2018-08-24 中国科学院长春应用化学研究所 A kind of combined type SCR denitration that anti-poisoning capability is strong and its application
CN110052287A (en) * 2019-05-17 2019-07-26 湘潭大学 A kind of the core-shell structure molecular sieve catalyst and preparation method of Collaborative Control NO and toluene
CN112279266A (en) * 2020-12-29 2021-01-29 中化学科学技术研究有限公司 Cu-SSZ-13@ SSZ-13 core-shell type molecular sieve and preparation method and application thereof
CN112279266B (en) * 2020-12-29 2021-04-06 中化学科学技术研究有限公司 Cu-SSZ-13@ SSZ-13 core-shell type molecular sieve and preparation method and application thereof
CN113457730A (en) * 2021-06-17 2021-10-01 江苏博霖环保科技有限公司 Preparation method of porous SCR catalyst for treating diesel engine tail gas
CN113385221A (en) * 2021-07-14 2021-09-14 安徽元琛环保科技股份有限公司 Ultra-high temperature catalyst based on metal honeycomb carrier and preparation method thereof
CN115155559A (en) * 2022-08-02 2022-10-11 中国科学院赣江创新研究院 Denitration catalyst and preparation method and application thereof
CN115155559B (en) * 2022-08-02 2023-04-25 中国科学院赣江创新研究院 Denitration catalyst and preparation method and application thereof
CN117797860A (en) * 2024-02-27 2024-04-02 中汽研汽车检验中心（天津）有限公司 Treatment of N in vehicle exhaust 2 Sectional catalyst of O and preparation method
CN117797860B (en) * 2024-02-27 2024-05-03 中汽研汽车检验中心（天津）有限公司 Treatment of N in vehicle exhaust2Sectional catalyst of O and preparation method

Also Published As

Publication number Publication date
CN107233912B (en) 2020-04-07

Similar Documents

Publication Publication Date Title
CN107233912A (en) A kind of two-part catalyst handled for exhaust gas from diesel vehicle and preparation method thereof
CN101530787B (en) Oxidation catalyst for purifying tail gas of diesel vehicles and preparation method thereof
JP4317345B2 (en) Low concentration CO-containing exhaust gas treatment method
EP3045220B1 (en) Exhaust gas treatment method and denitrification/so3 reduction apparatus
US8506892B2 (en) Exhaust gas purifying device for diesel engine
CN101069849A (en) Carbon oxide and volatile organic compound oxidation decomposing catalyst
WO2012121085A1 (en) Catalyst for exhaust gas purification, method for producing same, and exhaust gas purification method using same
CN107921416A (en) Nitrous oxide for exhaust system removes catalyst
CN110773153B (en) Supported manganese-based medium-low temperature denitration catalyst, preparation method and application thereof
KR101626541B1 (en) The Catalysts for Selective Oxidation of NH3 to N2 and Their Preparation Methods
CN114247448A (en) Oxidation type catalyst for diesel engine exhaust aftertreatment and manufacturing method thereof
CN106807432A (en) A kind of Pt Pd bimetallic catalysts for NO oxidations and preparation method thereof
JP2006289211A (en) Ammonia oxidation catalyst
CN108479762A (en) A kind of manganese oxide catalyst and its preparation method and application
CN105562031A (en) Catalyst for reducing content of NOx in FCC smoke
CN113117693A (en) Pd-Cu/TiO for catalytic oxidation of CO2Bimetallic catalyst and preparation method and application thereof
CN112657541A (en) Preparation method of molecular sieve based low-temperature environment-friendly SCR denitration catalyst
CN111686716B (en) WOxLow-temperature SCR (selective catalytic reduction) flue gas denitration catalyst with modified carbon nano tube loaded with metal oxide, and preparation method and application thereof
CN109589960A (en) A kind of wall-flow type low precious metal content catalyst, preparation method and applications
CN110327918A (en) It is a kind of to remove NH simultaneously3Catalyst and the preparation of escape and CO
CN107965371A (en) A kind of arrangement for catalytic purification of vehicle exhaust
CN101632926B (en) Exhaust gas catalysts and exhaust-gas catalytic converter
CN105764600B (en) Exhaust treatment system
JP3474514B2 (en) Low temperature denitration catalyst and low temperature denitration method
CN102814192B (en) Cerium/molecular sieve catalyst used for selective catalytic reduction of nitrogen oxides and preparation method thereof

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant