CN106492876A - A kind of preparation method of LD-diesel oxidation catalyst - Google Patents
A kind of preparation method of LD-diesel oxidation catalyst Download PDFInfo
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- CN106492876A CN106492876A CN201610907608.1A CN201610907608A CN106492876A CN 106492876 A CN106492876 A CN 106492876A CN 201610907608 A CN201610907608 A CN 201610907608A CN 106492876 A CN106492876 A CN 106492876A
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- 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
- B01D53/944—Simultaneously removing carbon monoxide, hydrocarbons or carbon making use of oxidation catalysts
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- 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
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- 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
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- 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
- B01J29/80—Mixtures of different zeolites
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2256/00—Main component in the product gas stream after treatment
- B01D2256/22—Carbon dioxide
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- 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
-
- 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
- B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
- B01J2229/10—After treatment, characterised by the effect to be obtained
- B01J2229/18—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself
- B01J2229/183—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself in framework positions
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Abstract
The present invention relates to a kind of oxidation catalyst preparation method of diesel exhaust discharge, comprises the following steps：Aluminum oxide, sieve particle and rare earth material deionized water are stirred and evenly mixed, mixed slurry is made；Noble metal platinum Pt and noble metal X are mixed by a certain percentage, noble metal mixed solution is made；Noble metal mixed solution is added in mixed slurry, it is 2～5 stirring 8～30 hours to adjust pH value, obtains paintable catalyst pulp；Catalyst pulp is coated on carrier, is carried out drying after coating is good, calcined, catalyst is obtained.The light diesel oxidation catalyst preparation method that the present invention is provided is simple, add the ageing resistace that rare earth element improves catalyst, and palladium noble metal replacement part platinum noble metals are introduced, cost is significantly reduced, and Pt Pd also improve the catalyzed conversion performance of catalyst.
Description
Technical field
The present invention relates to catalyst of diesel exhaust discharge and preparation method thereof.
Background technology
In the exhaust gas component of light-duty diesel vehicle engine emission, carbon monoxide (CO), THC (HC), nitrogen oxidation
Thing (NOx) and black smoke (PM), are all the pollutant components strictly controlled by Abgasgesetz.In order to reach discharge standard, diesel vehicle
Tail gas control can adopt two kinds of means of engine technology (internal purification technology) and post-processing technology.Diesel vehicle dynamical system is led to
Internal purification technology is crossed, the discharge of NOx and PM can be reduced and made to reach limited value of discharge standard, but the discharge of CO and HC must be led to
Later treatment technology can be only achieved limited value of discharge standard.Diesel oil oxidation type catalyst (Diesel Oxidation Catalyst,
DOC) it is conventional diesel oil post-processing technology.
DOC catalyst can be used to remove the dissolved organic matter (SOF) in CO, the HC and particulate matter in diesel exhaust,
Its reaction mechanism is that CO, HC and SOF are reacted with oxygen under the catalytic action of DOC catalyst, gives birth to carbon dioxide and water, such as
Shown in following chemical reaction equation：
CO+O2→CO2(1)
HC+O2→CO2+H2O (2)
SOF+O2→CO2+H2O (3)
Above-mentioned reaction needs effectively and rapidly to carry out under the catalytic action of DOC catalyst.And actually driving a vehicle
Cheng Zhong, due to the longtime running of engine, highest delivery temperature can reach 450 DEG C～500 DEG C, if DOC long-lasting catalytics
The condition of high temperature is in, as the noble metal of catalyst main active, it may occur that sintering phenomenon causes catalyst aging, catalysis
Effect failure.DOC catalyst can normal work determine that can discharge reach standard.Therefore, DOC ageing resistaces just into
The key of the technology.
Content of the invention
For above-mentioned technical problem, the present invention proposes a kind of LD-diesel oxidation catalyst.Solve existing diesel oil oxygen
There is high temperature ageing in change type catalyst, the ageing resistace for improving catalyst can cause to make by increasing bullion content
The increase of cost,
Technical scheme：
In order to solve problem above, the invention provides a kind of diesel oil oxidation type catalyst, its preparation process includes：
A kind of preparation method of light diesel oxidation catalyst, it is characterised in that comprise the following steps：
Step 1, aluminum oxide, sieve particle and rare earth material deionized water are stirred and evenly mixed, mixed slurry is made；
Step 2, noble metal platinum Pt and noble metal X are mixed by a certain percentage, noble metal mixed solution is made；
Step 3, noble metal mixed solution is added in mixed slurry, and it is 2～5 stirring 8～30 hours to adjust pH value, obtains
Arrive paintable catalyst pulp；
Step 4, catalyst pulp is coated on carrier, is carried out drying, is calcined, catalyst is obtained after coating is good.
In step 4, the catalyst pulp of 60～140g of uniform coating on every liter of carrier；Calcination process is at 400～600 DEG C
1～5 hour, drying course was 2～5 hours at 80～200 DEG C.
Above-mentioned preparation method is characterised by：
Mass percent (wt%) of the aluminum oxide in mixed slurry solid constituent is 10～50%, and aluminum oxide can be
γ-Al2O3Or by γ-Al2O3The material being prepared from；
Mass percent (wt%) of the sieve particle in mixed slurry solid constituent is 10～40%, and molecular sieve can be with
It is the zeolite molecular sieves such as beta-molecular sieve, ZSM-5, or the molecular sieve material being prepared from by zeolite molecular sieves such as beta-molecular sieve, ZSM-5
Material；
Rare earth material adopts cerium zirconium material, cerium zirconium ratio=0.5:1～1:0, cerium zirconium material is in mixed slurry solid constituent
Mass percent (wt%) be 10～60%；
The noble metal that catalyst is adopted is platinum noble metals and noble metal X, and noble metal X is other platinum group noble metals, adds ratio
Example Pt：X=1.5:1～1:0, the precursor of noble metal can be complex compound, organic salt, inorganic salts etc., and noble metal is in mixed slurry
Mass percent (wt%) in solid constituent is 0.1～5%；In step 4, on every liter of carrier, 60～140g's of uniform coating urges
Agent slurry；Calcination process is that drying course is 2～5 hours at 80～200 DEG C 1～5 hour at 400～600 DEG C.
The light diesel oxidation catalyst of the present invention, it is characterised in that：Including carrier and coating.Described carrier can be with
It is metal or ceramic honeycomb carrier；Described coating includes the constituents such as aluminum oxide, molecular sieve, rare earth material, noble metal, its
Middle 10～50wt% of alumina content, 10～40wt% of molecular sieve content, 10～60wt% of rare earth material, bullion content 0.1
～5wt%.
Beneficial effect：
The light diesel oxidation catalyst preparation method that the present invention is provided is simple, adds rare earth element and improves catalyst
Ageing resistace, and introduce palladium noble metal replace part platinum noble metals, significantly reduce cost, and Pt-Pd also improved
The catalyzed conversion performance of catalyst.
Description of the drawings
Fig. 1 is the transformation efficiency comparison diagram that 1 fresh state of the embodiment of the present invention, aging state ESC steady-cycle in stable state test CO.
Fig. 2 is the transformation efficiency comparison diagram that 1 fresh state of the embodiment of the present invention, aging state ESC steady-cycle in stable state test HC.
Fig. 3 is the transformation efficiency comparison diagram that 2 fresh state of the embodiment of the present invention, aging state ESC steady-cycle in stable state test CO.
Fig. 4 is the transformation efficiency comparison diagram that 2 fresh state of the embodiment of the present invention, aging state ESC steady-cycle in stable state test HC.
Specific embodiment
For the ease of the understanding of those skilled in the art, the present invention is made further with accompanying drawing with reference to embodiment
Bright.
Catalytic conversion efficiency can be higher as the leading indicator for weighing DOC ageing resistaces, catalyzed conversion temperature, DOC
Catalytic performance is better, and DOC ageing resistaces are also better, the catalytic conversion efficiency for improving catalyst using following approach：
1) improve the bullion content of catalyst or add other noble metals.The increase of bullion content can be improved and be urged
Change transformation efficiency, but also increase the cost of manufacture of catalyst simultaneously, improve the price of catalyst.DOC catalyst is commonly used
Be platinum noble metals, on the high side, can replace part platinum noble metals with the relatively low palladium noble metal of price, reduces cost same
When, the interphase interaction of platinum-palladium can also improve the catalytic performance of catalyst.
2) formula of improved catalysts, such as adds auxiliary agent (rare earth oxide etc.) in the catalyst.By adding rare earth unit
Element such as lanthanum, cerium etc., can improve the high-temperature stability of noble metal, to a certain extent also can reduces cost.
Embodiment 1
Step 1：Take 400g γ-Al2O3, (cerium zirconium compares 2 for 600g sieve particles and 500g cerium zirconium materials:1), add go from
Sub- water is stirred and evenly mixed, and mixed slurry is obtained；Take 71.43g platinum nitrate solutions and after 23.8g palladium nitrate solutions are well mixed, add
Mixed slurry is arrived, content of the noble metal in mixed slurry is 1%, it is 2～5 to adjust pH value, stirs 8 hours, obtains coating
Catalyst pulp.
Step 2：Catalyst pulp is coated on the ceramic monolith of cylinder, uniform coating 120g on every liter of ceramic monolith
Catalyst pulp.
Step 3：Coated carrier is dried 3 hours at 800 DEG C, is calcined 1 hour at 600 DEG C.
Embodiment 2
Step 1：Take 600 γ-Al2O3, (cerium zirconium compares 4 for 428.6g sieve particles and 750g cerium zirconium materials:1), add go from
Sub- water is stirred and evenly mixed, and mixed slurry is obtained；Take 238.1g platinum nitrate solutions and after 99.2g palladium nitrate solutions are well mixed, add
Mixed slurry is arrived, content of the noble metal in mixed slurry is 2.5%, it is 2～5 to adjust pH value, stirs 15 hours, obtains applying
The catalyst pulp for covering.
Step 2：Catalyst pulp is coated on the ceramic monolith of cylinder, uniform coating 100g on every liter of ceramic monolith
Catalyst pulp.
Step 3：Coated carrier is dried 2 hours at 120 DEG C, is calcined 2 hours at 550 DEG C.
Experimental example 3
Catalyst carrier in embodiment 1 and embodiment 2 is respectively taken 1, to carry out high temperature within 15 hours old for calcining at 750 DEG C
Change, then fresh carrier (being obtained in embodiment 1 and 2) and aging carrier are encapsulated respectively, its catalyzed conversion effect is examined
Survey.
Fig. 1-4 is the fresh state of the embodiment of the present invention, the transformation efficiency contrast of aging state ESC steady-cycle in stable state test CO and HC
Figure.
Testing standard：《QCT829-2010》、《GB17691-2005》
Test result：
More than 90%, the transformation efficiency of HC is up to the transformation efficiency of catalyst fresh carrier CO in embodiment 1
To 94%；The transformation efficiency of aging support C O, HC is compared and fresh carrier, although decreased, but amplitude very little, CO turn
Change transformation efficiency up to more than 90 % that efficiency majority operating mode has reached more than 90%, HC.
More than 90%, the transformation efficiency of HC is up to the transformation efficiency of catalyst fresh carrier CO in embodiment 2
98%；Substantially more than 90%, the transformation efficiency of HC is up to 96% to the transformation efficiency of aging support C O, with fresh carrier
Compare, fall very little.
From test result it can be seen that the diesel oxidation catalyst of present invention offer is somewhat obvious：
1st, after high-temperature calcination is aging, the transformation efficiency of CO, HC reduces amplitude very little compared to fresh to catalyst,
High value is remained in that, the ageing resistace of catalyst is good.
2nd, catalyst using noble metal platinum palladium be improved to by single platinum combine, reduce catalyst cost, also improve
The catalytic performance of catalyst.
3rd, add rare earth element in catalyst, improve the situation of precious metal high-temperature sintering, improve the anti-ageing of catalyst
The property changed.
Above embodiment technological thought only to illustrate the invention, it is impossible to which protection scope of the present invention is limited with this, all
It is any change for being done on the basis of technical scheme according to technological thought proposed by the present invention, each falls within present invention protection model
Within enclosing.The technology that the present invention is not directed to can be realized by existing technology.
Claims (7)
1. a kind of preparation method of light diesel oxidation catalyst, it is characterised in that comprise the following steps：
Step 1, aluminum oxide, sieve particle and rare earth material deionized water are stirred and evenly mixed, mixed slurry is made；
Step 2, noble metal platinum Pt and noble metal X are mixed by a certain percentage, noble metal mixed solution is made；
Step 3, noble metal mixed solution is added in mixed slurry, and it is 2～5 stirring 8～30 hours to adjust pH value, and obtaining can
The catalyst pulp of coating；
Step 4, catalyst pulp is coated on carrier, is carried out drying, is calcined, catalyst is obtained after coating is good.
2. the preparation method of catalyst according to claim 1, it is characterised in that：Aluminum oxide is in mixed slurry solid constituent
In mass percent be 10～50%, aluminum oxide be γ-Al2O3By γ-Al2O3The material being prepared from.
3. the preparation method of catalyst according to claim 1, it is characterised in that：Sieve particle is in mixed slurry solid
Mass percent in composition is 10～40%, and molecular sieve is the zeolite molecular sieve such as beta-molecular sieve, ZSM-5, or by beta-molecular sieve,
The molecular screen material that the zeolite molecular sieves such as ZSM-5 are prepared from.
4. the preparation method of catalyst according to claim 1, it is characterised in that：Rare earth material adopts cerium zirconium material, cerium
Zirconium ratio=0.5:1～1:0, mass percent of the cerium zirconium material in mixed slurry solid constituent is 10～60%.
5. the preparation method of catalyst according to claim 1, it is characterised in that：Noble metal X is other platinum group noble metals,
Adding proportion Pt：X=1.5:1～1:0, the precursor of noble metal can be complex compound, organic salt, inorganic salts etc., and noble metal is mixed
It is 0.1～5% to close the mass percent in slurry solids composition.
6. the preparation method of catalyst according to claim 1, it is characterised in that：In step 4, uniformly apply on every liter of carrier
Cover the catalyst pulp of 60～140g；Calcination process is that drying course is 2 at 80～200 DEG C 1～5 hour at 400～600 DEG C
～5 hours.
7. a kind of light diesel oxidation catalyst, it is characterised in that：Including carrier and coating.Described carrier can be metal
Or ceramic honeycomb carrier；Described coating includes the constituents such as aluminum oxide, molecular sieve, rare earth material, noble metal, wherein aoxidizes
10～50wt% of aluminium content, 10～40wt% of molecular sieve content, 10～60wt% of rare earth material, bullion content 0.1～
5wt%.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107649126A (en) * | 2017-10-27 | 2018-02-02 | 南京依柯卡特排放技术股份有限公司 | Biradical noble metal DOC catalyst and preparation method for diesel exhaust purification |
| CN107983345A (en) * | 2017-12-05 | 2018-05-04 | 南京依柯卡特排放技术股份有限公司 | Exhaust emissions of diesel engine DOC oxidation catalyst preparation methods |
| CN109465027A (en) * | 2018-11-14 | 2019-03-15 | 中国科学院城市环境研究所 | A kind of beta-molecular sieve catalyst of catalysis oxidation soot particulate and its preparation method and application |
| CN112412588A (en) * | 2019-08-20 | 2021-02-26 | 汪利峰 | Diesel engine tail gas aftertreatment catalyst unit |
| CN116273204A (en) * | 2023-03-14 | 2023-06-23 | 潍柴动力股份有限公司 | Preparation method and equipment of DOC catalyst |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107649126A (en) * | 2017-10-27 | 2018-02-02 | 南京依柯卡特排放技术股份有限公司 | Biradical noble metal DOC catalyst and preparation method for diesel exhaust purification |
| CN107983345A (en) * | 2017-12-05 | 2018-05-04 | 南京依柯卡特排放技术股份有限公司 | Exhaust emissions of diesel engine DOC oxidation catalyst preparation methods |
| CN109465027A (en) * | 2018-11-14 | 2019-03-15 | 中国科学院城市环境研究所 | A kind of beta-molecular sieve catalyst of catalysis oxidation soot particulate and its preparation method and application |
| CN112412588A (en) * | 2019-08-20 | 2021-02-26 | 汪利峰 | Diesel engine tail gas aftertreatment catalyst unit |
| CN116273204A (en) * | 2023-03-14 | 2023-06-23 | 潍柴动力股份有限公司 | Preparation method and equipment of DOC catalyst |
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Application publication date: 20170315 |