CN104667914A - Diesel engine tail gas denitration catalyst and preparation method thereof - Google Patents
Diesel engine tail gas denitration catalyst and preparation method thereof Download PDFInfo
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- CN104667914A CN104667914A CN201310653823.XA CN201310653823A CN104667914A CN 104667914 A CN104667914 A CN 104667914A CN 201310653823 A CN201310653823 A CN 201310653823A CN 104667914 A CN104667914 A CN 104667914A
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- Y02A50/20—Air quality improvement or preservation, e.g. vehicle emission control or emission reduction by using catalytic converters
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Abstract
The invention relates to a catalyst and a preparation method thereof, particularly relates to a diesel engine tail gas denitration catalyst and a preparation method thereof, and belongs to the technical field of environmental protection. The denitration catalyst comprises a denitration catalyst A layer and a denitration catalyst B layer, and is characterized in that the denitration catalyst A layer adopts honeycomb ceramic as a base body, adopts attapulgite and one or more oxides of aluminum, titanium and zirconium as a carrier and adopts precious metal such as platinum, rhodium and palladium to be loaded on the carrier, the mass percent of the aluminum, titanium and zirconium oxide accounts for less than 35 percent of the total mass of the carrier, and the element ratio of the precious metal platinum, rhodium and palladium loaded on the carrier is as follows: 5 to 10 percent of platinum, 1 to 2 percent of rhodium and 3 to 6 percent of palladium; the mass of the precious metal accounts for 0.2 to 1 percent of the total mass of the carrier; the denitration catalyst B layer adopts honeycomb ceramic as a base body, adopts attapulgite as a carrier and adopts cerium, lanthanum and praseodymium oxides to be loaded on the carrier, wherein the mass of cerium in the oxide accounts for 50 to 95 percent of the mass of all oxides, and the mass of all the metal oxides accounts for 1 to 5 percent of the total mass of the carrier. By adopting the technical scheme, the catalyst has advantages and beneficial effects that NOx, CO and HC in diesel engine tail gas can be adequately purified.
Description
Technical field
The present invention relates to a kind of Catalysts and its preparation method, particularly a kind of diesel engine vent gas denitrating catalyst and preparation method thereof, belongs to environmental technology field.
Background technology
At present, in the air of China big city more than 50% NO
xpollute from automotive emission, particularly exhaust emissions of diesel engine.In addition, city atmospheric environment quality-monitoring result also showed in recent years, and exhaust pollution of diesel engines becomes primary pollution source.
In diesel engine vent gas, oxygen content is high, and under excess oxygen, the reduction reaction of nitrogen oxide is very difficult, and exhaust temperature is lower than gasoline engine tail gas 200 DEG C, makes widely used three-way catalyst on automobile not directly apply to diesel engine.Current employing EGR Technology (EGR), the particulate material (PM) that emits in a large amount of Diesel engines and other noxious emissions is made directly to introduce the wearing and tearing that cylinder can increase piston ring and cylinder sleeve, also can dilute lubricating oil accelerate it and go bad; Selective reduction technology (SCR) is adopted to only can be used in fixing NO
xon pollution sources, need the flow accurately controlling ammonia simultaneously, remove NO simultaneously
xall by traditional treatment technology is optimized combination with the technology of PM, thus reach the object removing NOx and PM, its result does not still break away from complicated equipment and accurate control, the waste of fuel oil can be caused simultaneously or increase the addition etc. of reducing agent, its stability also cannot be guaranteed, and cost intensive.
Summary of the invention
Technical problem to be solved by this invention is: provide a kind of diesel engine vent gas denitrating catalyst and preparation method thereof, can with the NO in the abundant purification of diesel tail gas of this catalyst
x.
The technical solution adopted for the present invention to solve the technical problems is: diesel engine vent gas denitrating catalyst disclosed by the invention comprises denitrating catalyst A layer and denitrating catalyst B layer, and denitrating catalyst A layer mainly carries out NO
xreduction reaction, denitrating catalyst B layer mainly carries out NO
xabsorption.
Denitrating catalyst A layer take ceramic honey comb as matrix, with one or more oxides in attapulgite and aluminium, titanium, zirconium for carrier and the platinum, rhodium, the palladium noble metal that are carried on carrier, the ratio that described aluminium, titanium, Zirconium oxide quality account for carrier gross mass is less than 35%, be carried on the platinum on carrier, rhodium, palladium noble metal, its element ratio is platinum 5-10, rhodium 1-2, palladium 3-6; Noble metal quality accounts for the 0.2-1% of carrier gross mass.
Because in diesel engine vent gas, oxygen content is high, temperature, lower than the specified temp of denitrating catalyst, cannot realize sufficient NO
xpurifying property.The present invention proposes and use one or more oxides in attapulgite and aluminium, titanium, zirconium to be carrier, utilize attapulgite absorption property, the NO in absorption tail gas
x, CO, HC, and issue raw reduction reaction in the catalysis of platinum, rhodium, palladium noble metal, its key reaction equation is as follows:
2NO+2CO-
catalyst-N2+2CO
2
HC+NO
2-
catalyst-N2+H
2o+CO
2
Denitrating catalyst B layer take ceramic honey comb as matrix, take attapulgite as carrier and the oxide being carried on cerium, lanthanum and praseodymium on carrier, the quality of the cerium wherein described in oxide accounts for the 50-95% of all oxides quality, and the quality of described all metal oxides accounts for the 1-5% of carrier gross mass.
Tail gas after denitrating catalyst A layer, a part of NO
x, there is reduction reaction, a part of NO in addition in CO, HC
x, CO, HC flow to catalyst B layer.Research finds: in catalyst B layer, attapulgite inhales the NO in tail gas
x, CO, HC, and in carrier the oxide of cerium not by electronics occupied orbital or unpaired electron track and NO
xthe electron orbit had can form binding molecule sub-track, therefore when lower than specific temperature (about 200 DEG C), can be used as adsorbent and preserves NO for a long time
x.
The invention discloses the renovation process of denitrating catalyst B layer, when the absorption of catalyst B layer reaches capacity, heat to 400 DEG C to catalyst B layer, the electronics acceptance of its metal oxide reduces, and absorption NO
xthermal vibration also come to life, therefore this carrier not only discharges stored oxygen in high-temperature region, also discharges adsorbed NO
x.
The preparation method of diesel engine vent gas denitrating catalyst A layer disclosed by the invention, comprises the following steps:
(1) get in attapulgite and aluminium, titanium, one or more oxide Homogeneous phase mixing of zirconium and the aqueous solution, stir;
(2) get in platinum, rhodium, palladium noble metal chlorate Homogeneous phase mixing and the aqueous solution, add ammoniacal liquor and be adjusted to pH value 3-5;
(3) by said mixture high-speed stirred half an hour, rear standing 1-3 hour;
(4) get blank ceramic honey comb and be dipped in 5-10 minute in described mixture; Take out, centrifugal segregation additional size, 50-120 DEG C completely dry after, 400-600 DEG C of roasting 3-4 hour; Obtain catalyst A layer.
The preparation method of diesel engine vent gas denitrating catalyst B layer disclosed by the invention, comprises the following steps:
(1) get attapulgite and cerium, lanthanum and praseodymium oxide Homogeneous phase mixing and the aqueous solution in;
(2) by said mixture high-speed stirred half an hour, rear standing 1-3 hour;
(3) get blank ceramic honey comb and be dipped in 5-10 minute in described mixture; Take out, centrifugal segregation additional size, 50-120 DEG C completely dry after, 400-600 DEG C of roasting 3-4 hour; Obtain catalyst B layer.
Owing to adopting technique scheme, the advantage that the present invention has and good effect are: the NO in the abundant purification of diesel tail gas of energy
x, CO, HC.
Detailed description of the invention
The present invention adopts two-stage denitration pattern, and comprise denitrating catalyst A layer and denitrating catalyst B layer, denitrating catalyst A layer mainly carries out NO
xreduction reaction, denitrating catalyst B layer mainly carries out NO
xabsorption, diesel engine vent gas, can by NO after denitrating catalyst A layer and denitrating catalyst B layer
xabundant purification.
Embodiment 1: take in the attapulgite of certain mass and aluminium, titanium, one or more oxide Homogeneous phase mixing of zirconium and the aqueous solution, wherein aluminium, titanium, Zirconium oxide quality account for 30% of carrier gross mass.Take in the platinum of certain mass, rhodium, palladium noble metal chlorate Homogeneous phase mixing and the aqueous solution, noble metal quality accounts for 0.5% of carrier gross mass, and its element ratio is platinum 6, rhodium 1, palladium 3, adds ammoniacal liquor and is adjusted to pH value 3.5; By said mixture high-speed stirred half an hour, latter standing 2 hours; Get blank ceramic honey comb and to be dipped in described mixture 8 minutes; Take out, centrifugal segregation additional size, 100 DEG C dry completely after, 500 DEG C of roastings 3 hours, obtain denitrating catalyst catalyst A layer.
Embodiment 2: take in the attapulgite of certain mass and aluminium, titanium, one or more oxide Homogeneous phase mixing of zirconium and the aqueous solution, wherein aluminium, titanium, Zirconium oxide quality account for 25% of carrier gross mass.Take in the platinum of certain mass, rhodium, palladium noble metal chlorate Homogeneous phase mixing and the aqueous solution, noble metal quality accounts for 0.6% of carrier gross mass, and its element ratio is platinum 5, rhodium 1, palladium 4, adds ammoniacal liquor and is adjusted to pH value 4.5; By said mixture high-speed stirred half an hour, latter standing 1 hour; Get blank ceramic honey comb and to be dipped in described mixture 10 minutes; Take out, centrifugal segregation additional size, 120 DEG C dry completely after, 450 DEG C of roastings 4 hours, obtain denitrating catalyst catalyst A layer.
Embodiment 3: take in the attapulgite of certain mass and the oxide Homogeneous phase mixing of cerium, lanthanum and praseodymium and the aqueous solution, wherein the oxide mass of cerium, lanthanum and praseodymium accounts for 2% of carrier gross mass, and cerium oxide quality accounts for 60% of all oxides quality; By said mixture high-speed stirred half an hour, latter standing hour; Get blank ceramic honey comb and to be dipped in described mixture 8 minutes; Take out, centrifugal segregation additional size, 100 DEG C dry completely after, 500 DEG C of roastings 3.5 hours, obtain denitrating catalyst catalyst B layer.
Embodiment 4: take in the attapulgite of certain mass and the oxide Homogeneous phase mixing of cerium, lanthanum and praseodymium and the aqueous solution, wherein the oxide of cerium, lanthanum and praseodymium accounts for carrier gross mass 3%, and cerium oxide accounts for 70% of all oxides quality; By said mixture high-speed stirred half an hour, latter standing 2 hours; Get blank ceramic honey comb and to be dipped in described mixture 10 minutes; Take out, centrifugal segregation additional size, 110 DEG C dry completely after, 450 DEG C of roastings 4 hours, obtain denitrating catalyst catalyst B layer.
Claims (3)
1. diesel engine vent gas denitrating catalyst and preparation method thereof, denitrating catalyst comprises denitrating catalyst A layer and denitrating catalyst B layer, it is characterized in that: denitrating catalyst A layer take ceramic honey comb as matrix, with one or more oxides in attapulgite and aluminium, titanium, zirconium for carrier and the platinum, rhodium, the palladium noble metal that are carried on carrier, the ratio that described aluminium, titanium, Zirconium oxide quality account for carrier gross mass is less than 35%, be carried on the platinum on carrier, rhodium, palladium noble metal, its element ratio is platinum 5-10, rhodium 1-2, palladium 3-6; Noble metal quality accounts for the 0.2-1% of carrier gross mass; Denitrating catalyst B layer take ceramic honey comb as matrix, take attapulgite as carrier and the oxide being carried on cerium, lanthanum and praseodymium on carrier, the quality of the cerium wherein described in oxide accounts for the 50-95% of all oxides quality, and the quality of described all metal oxides accounts for the 1-5% of carrier gross mass.
2. a kind of diesel engine vent gas denitrating catalyst according to claim 1 and preparation method thereof, is characterized in that: the preparation method of denitrating catalyst A layer, comprises the following steps:
(1) get in attapulgite and aluminium, titanium, one or more oxide Homogeneous phase mixing of zirconium and the aqueous solution, stir;
(2) get in platinum, rhodium, palladium noble metal chlorate Homogeneous phase mixing and the aqueous solution, add ammoniacal liquor and be adjusted to pH value 3-5;
(3) by said mixture high-speed stirred half an hour, rear standing 1-3 hour;
(4) get blank ceramic honey comb and be dipped in 5-10 minute in described mixture; Take out, centrifugal segregation additional size, 50-120 DEG C completely dry after, 400-600 DEG C of roasting 3-4 hour.
3. a kind of diesel engine vent gas denitrating catalyst according to claim 1 and preparation method thereof, is characterized in that: the preparation method of denitrating catalyst B layer, comprises the following steps:
(1) get attapulgite and cerium, lanthanum and praseodymium oxide Homogeneous phase mixing and the aqueous solution in;
(2) by said mixture high-speed stirred half an hour, rear standing 1-3 hour;
(3) get blank ceramic honey comb and be dipped in 5-10 minute in described mixture; Take out, centrifugal segregation additional size, 50-120 DEG C completely dry after, 400-600 DEG C of roasting 3-4 hour.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310653823.XA CN104667914A (en) | 2013-11-29 | 2013-11-29 | Diesel engine tail gas denitration catalyst and preparation method thereof |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310653823.XA CN104667914A (en) | 2013-11-29 | 2013-11-29 | Diesel engine tail gas denitration catalyst and preparation method thereof |
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|---|---|
| CN104667914A true CN104667914A (en) | 2015-06-03 |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106111150A (en) * | 2016-06-16 | 2016-11-16 | 浙江三龙催化剂有限公司 | Boats and ships denitrating catalyst |
| CN117696044A (en) * | 2024-01-24 | 2024-03-15 | 兰州大学 | Attapulgite-doped rare earth SCR catalyst and preparation method thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1593756A (en) * | 2004-07-05 | 2005-03-16 | 南京大学 | Preparation method of metal honeycomb supported catalyst |
| US20080187477A1 (en) * | 2007-02-06 | 2008-08-07 | Mitsubishi Heavy Industries, Ltd. | Catalyst for treating exhaust gases, method for producing the same, and method for treating exhaust gases |
| CN103052444A (en) * | 2010-06-10 | 2013-04-17 | 巴斯夫欧洲公司 | Nox storage catalyst with improved hydrocarbon conversion activity |
| CN103157488A (en) * | 2011-12-08 | 2013-06-19 | 江苏东大热能机械制造有限公司 | Medium-low-temperature denitrification catalyst taking attapulgite as support for flue gas and preparation method for same |
-
2013
- 2013-11-29 CN CN201310653823.XA patent/CN104667914A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1593756A (en) * | 2004-07-05 | 2005-03-16 | 南京大学 | Preparation method of metal honeycomb supported catalyst |
| US20080187477A1 (en) * | 2007-02-06 | 2008-08-07 | Mitsubishi Heavy Industries, Ltd. | Catalyst for treating exhaust gases, method for producing the same, and method for treating exhaust gases |
| CN103052444A (en) * | 2010-06-10 | 2013-04-17 | 巴斯夫欧洲公司 | Nox storage catalyst with improved hydrocarbon conversion activity |
| CN103157488A (en) * | 2011-12-08 | 2013-06-19 | 江苏东大热能机械制造有限公司 | Medium-low-temperature denitrification catalyst taking attapulgite as support for flue gas and preparation method for same |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106111150A (en) * | 2016-06-16 | 2016-11-16 | 浙江三龙催化剂有限公司 | Boats and ships denitrating catalyst |
| CN117696044A (en) * | 2024-01-24 | 2024-03-15 | 兰州大学 | Attapulgite-doped rare earth SCR catalyst and preparation method thereof |
| CN117696044B (en) * | 2024-01-24 | 2024-06-11 | 兰州大学 | Attapulgite-doped rare earth SCR catalyst and preparation method thereof |
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Application publication date: 20150603 |
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