CN104895652B - Reduce the granular material discharged catalyzed diesel particulate filter of diesel vehicle and preparation method - Google Patents
Reduce the granular material discharged catalyzed diesel particulate filter of diesel vehicle and preparation method Download PDFInfo
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Abstract
It is used to reduce granular material discharged catalyzed diesel particulate filter of diesel vehicle and preparation method thereof the invention discloses a kind of.The activated alumina and cerium zirconium sosoloid of rare-earth oxide modified are coated uniformly on diesel particulate filter carrier by the present invention using vacuum extraction method, then impregnate active component（Cu、Cs、Pt）, prepare catalyzed diesel particulate filter.The addition of starch pore creating material improves the microcellular structure of active coating, reduces carrier back pressure, while adding the specific surface area and pore volume of active coating, substantially increases catalytic oxidation activity of the catalyzed diesel particulate filter for soot.The preparation process of vacuum extraction method is simple and easy to do, and the load factor of active coating is high, and the adhesion with honeycomb substrate is strong, and the catalyzed diesel particulate filter of preparation has preferable catalytic performance.
Description
Technical field
It is used to reduce the granular material discharged catalyzed diesel particulate filter of diesel vehicle and its system the present invention relates to a kind of
Preparation Method, specifically, is uniformly applied the activated alumina and cerium zirconium sosoloid of rare-earth oxide modified using vacuum extraction method
Overlay on diesel particulate filter carrier, then impregnate active component（Cu、Cs、Pt）, prepare catalyzed diesel particle
Filter.
Background technology
Soot particulate matter in exhaust gas from diesel vehicle mainly includes solid matter dry carbon cigarette（DS, about 40 ~ 50%）, it is soluble organic
Thing（SOF, about 35 ~ 45%）And sulfate, moisture, ashes and other components（About 5-10%）.The particulate matter of emission of diesel engine
Quantity is 20 ~ 100 times of gasoline engine, and the particulate that diameter is less than 10 μm enters nasal cavity, throat and lung from air, causes stimulation
Property cough, harm to the human body is maximum.There are some researches show some heavy metal elements and nytron adsorbed on carbon soot particles
Thing, such as polycyclic aromatic hydrocarbon（PAHs）, there is strong carcinogenic mutagenesis to human body, the probability for causing human body to suffer from respiratory disease is big
Increase.In addition, carbon soot particles light weight, can suspend in an atmosphere, one of primary pollution source as city has a strong impact on for a long time
Environmental quality, to human lives brings many harmful effects.
Method on reducing carbon soot particles discharge, increasingly strict row can not be met by depending merely on improvement engine technology
Put standard.Meanwhile, do not have cost effectiveness using fuel additive, its own, which is discharged into air, may also result in secondary dirt
Dye.In order to reduce the discharge of soot particulate, current widely used wall-flow type carbon soot particles filter both at home and abroad（Diesel
Particulate Filter, DPF）.Wall-flow type honeycomb ceramic carrier has the parallel channels similar to normal cellular ceramics, but not
Same is adjacent duct two ends alternating plug-hole.Exhaust gas from diesel vehicle enters behind DPF ducts, because the end in duct is plugged, gas
Body is discharged after internal stephanoporate thin wall, and DPF walls are designed to suitable porosity so that tail gas can be passed through, and is reduced
The pressure drop of system, and carbon soot particles therein are filtered, and are deposited on hole wall.DPF filter efficiency is higher, generally may be used
Up to more than 90%, part soluble organic fraction can also be captured, and structural strength is high, heat shock resistance and resistance to mechanical lasing capability
It is stronger.Wall-flow type honeycomb ceramic carrier has obvious breakthrough, filter wall thickness reduction, identical in production technology in recent years
Filter efficiency under shed cross-sectional area increases, so as to reduce pressure drop loss.Therefore, in the quite a long time from now on
Interior, honeycomb ceramic filter will be the diesel emission particulate filter of most main flow.
It is micro- that Chinese patent CN103206287A discloses a kind of diesel engine for the carrier coating for having and improving filter capability
Grain filter.The diesel particulate filter is deposited on the aluminum oxide coating layer on porous ceramic matrices suitable surface by porous ceramic matrices suitable,
At least one noble metal for selecting in the group constituted from platinum, palladium and rhodium, and from cerium oxide, zirconium oxide, lanthana and yittrium oxide
At least one metal oxide selected in the group of composition is constituted.
Chinese patent CN103375227A discloses a kind of diesel particulate filter with oxidation catalytic activity coating.Should
Diesel particulate filter is by wall-flow filter（It is made up of cordierite, carborundum, mullite or aluminium titanates）, with large surface
Long-pending indifferent oxide carrier（By aluminum oxide, the aluminum oxide of doping, titanium dioxide, cerium oxide, zirconium oxide, cerium zirconium mixed oxidization
The mixture composition of two or more in thing, silica or these oxides）And active component（By platinum, palladium, gold or
Their mixture composition）Constitute.
Above-mentioned existing patented technology is all using catalytic active component of the noble metal as diesel particulate filter, production
Cost is high, is unfavorable for large-scale popularization and application.
The content of the invention
It is an object of the present invention to provide a kind of be used to reduce the granular material discharged catalyzed diesel particle mistake of diesel vehicle
Filter and preparation method thereof, described catalyzed diesel particulate filter has relatively low production cost, the relatively low carrier back of the body
Pressure and preferably catalytic performance.
The present invention is uniformly coated the activated alumina and cerium zirconium sosoloid of rare-earth oxide modified using vacuum extraction method
On diesel particulate filter carrier, active component is then impregnated（Cu、Cs、Pt）, prepare catalyzed diesel particle mistake
Filter, the composition and its weight percent content of active coating are：
The activated alumina 50.0 ~ 75.0% of lanthana modification,
Cerium zirconium sosoloid 25.0 ~ 50.0%,
Copper 0.5 ~ 5.0%,
Caesium 0.5 ~ 5.0%,
Platinum 0.05 ~ 1.5%.
The preparation method of catalyzed diesel particulate filter of the present invention is vacuum extraction method, is specifically included as follows
Step：
1. the activated alumina of lanthana modification, Alumina gel, cerium zirconium sosoloid and pore creating material are scattered in deionized water
In, slurry is made after being emulsified 0.5 ~ 1 hour in mulser；
2. above-mentioned slurry is coated uniformly on diesel particulate filter carrier using special vacuum extraction device,
Then dry 8 ~ 16 hours, be calcined 2 ~ 6 hours at 500 ~ 700 DEG C at 100 ~ 120 DEG C successively；
3. in Pt (NO3)2、Cu(NO3)2·3H2O and CsNO3Mixed aqueous solution in impregnate 1 ~ 3 hour, then exist successively
100 ~ 120 DEG C of dryings 2 ~ 6 hours, after 450 ~ 650 DEG C of roastings 2 ~ 6 hours, prepare catalyzed diesel particulate filter.
Described pore creating material includes one kind in polyethylene glycol, polyvinyl alcohol, tween, starch, methylcellulose and urea
Or multiple combinations are used, the weight percent content shared by pore creating material is the 0.1 ~ 5.0% of slurry gross weight.
One of remarkable advantage of catalyzed diesel particulate filter of the present invention is that the addition of starch pore creating material changes
The microcellular structure of active coating has been apt to it, has reduced carrier back pressure, while adds the specific surface area and pore volume of active coating, significantly
Improve catalytic oxidation activity of the catalyzed diesel particulate filter for soot.
The two of the remarkable advantage of catalyzed diesel particulate filter of the present invention are that Pt addition is directly facilitated
The complete catalysts oxidation of carbon soot particles, Cu and Cs addition reduce the production cost of catalyst, further increase its for
The catalytic oxidation activity of soot.
The remarkable advantage of the preparation method of catalyzed diesel particulate filter of the present invention is that described vacuum is taken out
The preparation process of formulation is simple and easy to do, and the load factor of active coating is high, and the adhesion with honeycomb substrate is strong, the catalytic type bavin of preparation
Oil machine particulate filter has preferable catalytic performance.
Embodiment
Comparative example
The activated alumina and 80 grams of solid contents of 73.6 grams of lanthana modifications are added to 246.4 grams for 8% Alumina gel
In ionized water, slurry is made after being emulsified 0.5 hour in mulser；It is using special vacuum extraction device that above-mentioned slurry is uniform
It is coated on the diesel particulate filter carrier that volume is 74.5 milliliters, is then dried 12 hours at 120 DEG C successively, 600
DEG C roasting 2 hours, it is taken out after natural cooling, that is, prepares catalyzed diesel particulate filter.
Embodiment 1
Alumina gel, 21.6 grams of cerium zirconium sosoloids by the activated alumina of 52 grams of lanthana modifications, 80 grams of solid contents for 8%
It is added to a certain amount of pore creating material in 236.4 grams of deionized waters, slurry is made after being emulsified 1 hour in mulser；Using special
Above-mentioned slurry is coated uniformly on the diesel particulate filter carrier that volume is 74.5 milliliters by vacuum extraction device, so
Dried 12 hours at 120 DEG C successively afterwards, be calcined 2 hours at 600 DEG C, it is taken out after natural cooling, that is, prepares catalytic type bavin
Oil machine particulate filter.Different pore creating materials are as shown in table 1 for the influence of active coating performance.
Influence of the different pore creating materials of table 1 for active coating performance
| Pore creating material | Addition (%) | Upper carrying capacity (g/L) | Back pressure (kPa) | Expulsion rate (%) |
| Without pore creating material | 0 | 45.5 | 0.21 | 0.57 |
| Macrogol 4000 | 1.25 | 45.7 | 0.22 | 0.3 |
| Macrogol 4000 | 2.5 | 37.9 | 0.22 | 1.0 |
| Macrogol 4000 | 3.75 | 26.1 | 0.24 | 1.7 |
| 0.5% polyvinyl alcohol | 2.5 | 31.9 | 0.23 | 1.8 |
| 0.5% polyvinyl alcohol | 1.0 | 29.1 | 0.22 | 0.82 |
| Starch | 1.25 | 40.7 | 0.21 | 0.50 |
| Starch | 2.5 | 45.5 | 0.18 | 0.61 |
| Starch | 3.75 | 50.2 | 0.24 | 0.73 |
| Starch | 5.0 | 40.1 | 0.23 | 2.30 |
| Methylcellulose | 0.25 | 44.3 | 0.23 | 0.36 |
| Methylcellulose | 0.125 | 36.2 | 0.23 | 0.51 |
| Urea | 2.5 | 30.0 | 0.23 | 0.93 |
| Tween 80 | 2.5 | 42.7 | 0.20 | 4.1 |
Embodiment 2
The Alumina gel and 37.6 grams of cerium zirconium sosoloids for being 8% by the activated alumina of 36 grams of lanthana modifications, 80 grams of solid contents
It is added in 246.4 grams of deionized waters, slurry is made after being emulsified 0.5 hour in mulser；Filled using special vacuum extraction
Put and above-mentioned slurry is coated uniformly on the diesel particulate filter carrier that volume is 74.5 milliliters, then successively at 120 DEG C
Dry 12 hours, be calcined 2 hours at 600 DEG C, it is taken out after natural cooling, that is, prepares catalyzed diesel particle filtering
Device, is designated as A samples.
Embodiment 3
The Alumina gel and 21.6 grams of cerium zirconium sosoloids for being 8% by the activated alumina of 52 grams of lanthana modifications, 80 grams of solid contents
It is added in 246.4 grams of deionized waters, slurry is made after being emulsified 0.5 hour in mulser；Filled using special vacuum extraction
Put and above-mentioned slurry is coated uniformly on the diesel particulate filter carrier that volume is 74.5 milliliters, then successively at 120 DEG C
Dry 12 hours, be calcined 2 hours at 600 DEG C, it is taken out after natural cooling, that is, prepares catalyzed diesel particle filtering
Device, is designated as B samples.
Embodiment 4
Alumina gel, 21.6 grams of cerium zirconium sosoloids by the activated alumina of 52 grams of lanthana modifications, 80 grams of solid contents for 8%
It is added to 10 grams of starch pore creating materials in 236.4 grams of deionized waters, slurry is made after being emulsified 1 hour in mulser；Using special
Above-mentioned slurry is coated uniformly on the diesel particulate filter carrier that volume is 74.5 milliliters by vacuum extraction device, so
Dried 12 hours at 120 DEG C successively afterwards, be calcined 2 hours at 600 DEG C, it is taken out after natural cooling, that is, prepares catalytic type bavin
Oil machine particulate filter, is designated as C sample.
Embodiment 5
Catalyzed diesel particulate filter prepared by the embodiment 3 that volume is 3.6 milliliters, in 3.2 milliliters of Pt
(NO3)2In the aqueous solution（Pt(NO3)2Concentration is 1.225g/L）Dipping takes out after 1 hour, then small in 120 DEG C of dryings 4 successively
When, it is calcined 4 hours at 550 DEG C, it is taken out after natural cooling, that is, prepares catalyzed diesel particulate filter, D samples are designated as
Product.
Embodiment 6
Catalyzed diesel particulate filter prepared by the embodiment 3 that volume is 3.6 milliliters, in 3.2 milliliters of Pt
(NO3)2With Cu (NO3)2In mixed aqueous solution（Pt(NO3)2Concentration is 1.225g/L, Cu (NO3)2Concentration is 7.667g/L）Dipping
Take out, then dried 4 hours at 120 DEG C successively after 1.5 hours, be calcined 4 hours, take out it after natural cooling, i.e., at 550 DEG C
Catalyzed diesel particulate filter is prepared, E samples are designated as.
Embodiment 7
Catalyzed diesel particulate filter prepared by the embodiment 3 that volume is 3.6 milliliters, in 3.2 milliliters of mixing waters
In solution（Pt(NO3)2Concentration is 1.225g/L, Cu (NO3)2Concentration is 2.548g/L, CsNO3Concentration is 1.031g/L）Dipping 2
Take out, then dried 4 hours at 120 DEG C successively after hour, be calcined 4 hours at 550 DEG C, it is taken out after natural cooling, that is, made
For catalyzed diesel particulate filter is gone out, F samples are designated as.
Embodiment 8
Catalyzed diesel particulate filter prepared by the embodiment 3 that volume is 3.6 milliliters, in 3.2 milliliters of mixing
In the aqueous solution（Pt(NO3)2Concentration is 1.225g/L, Cu (NO3)2Concentration is 7.667g/L, CsNO3Concentration is 3.125g/L）Dipping
Take out, then dried 4 hours at 120 DEG C successively after 2.5 hours, be calcined 4 hours, take out it after natural cooling, i.e., at 550 DEG C
Catalyzed diesel particulate filter is prepared, G samples are designated as.
Table 2 is various catalyzed diesel particulate filters for the catalytic oxidation activity of soot, the catalysis oxidation of soot
Activity rating condition is：Air speed is 40000h-1, from 60 DEG C with 5 DEG C of min-1Heating rate rise to 700 DEG C.Can from table 2
Go out, the addition of starch pore creating material improves catalytic oxidation activity of the catalyzed diesel particulate filter for soot, and Pt's adds
Enter to have directly facilitated the complete catalysts oxidation of carbon soot particles, Cu and Cs addition reduce the production cost of catalyst, further
Improve the catalytic oxidation activity for soot.
Catalytic oxidation activity of the catalyzed diesel particulate filter of table 2 for soot
| Catalyst | Comparative example | A | B | C | D | E | F | G |
| T10/℃ | 536 | 543 | 487 | 483 | 441 | 394 | 337 | 365 |
| T50/℃ | 580 | 582 | 560 | 520 | 512 | 504 | 488 | 503 |
| T90/℃ | 601 | 625 | 599 | 580 | 550 | 525 | 526 | 550 |
Claims (3)
1. a kind of be used to reduce the granular material discharged catalyzed diesel particulate filter of diesel vehicle, it is characterised in that uses vacuum
The slurries that extraction process forms the activated alumina of lanthana modification, cerium zirconium sosoloid, Alumina gel and pore creating material after emulsification are applied
Overlay on diesel particulate filter carrier, then impregnate active component, the composition and its weight percent content of active coating
For：
2. preparing being used for described in claim 1 reduces the side of the granular material discharged catalyzed diesel particulate filter of diesel vehicle
Method, it is characterised in that the preparation method is vacuum extraction method, specifically includes following steps：
The activated alumina of lanthana modification, Alumina gel, cerium zirconium sosoloid and pore creating material are scattered in deionized water, in emulsification
Slurry is made after being emulsified 0.5~1 hour in machine；Above-mentioned slurry is coated uniformly on by diesel engine using special vacuum extraction device
On particulate filter carrier, then dry 8~16 hours, be calcined 2~6 hours at 500~700 DEG C at 100~120 DEG C successively；
Finally in Pt (NO3)2、Cu(NO3)2·3H2O and CsNO3Mixed aqueous solution in impregnate 1~3 hour, then successively 100~
120 DEG C of dryings 2~6 hours, after 450~650 DEG C of roastings 2~6 hours, prepare catalyzed diesel particulate filter.
3. according to claim 2 be used to reduce the system of the granular material discharged catalyzed diesel particulate filter of diesel vehicle
Preparation Method, it is characterised in that described pore creating material includes polyethylene glycol, polyvinyl alcohol, tween, starch, methylcellulose and urine
One or more in element are applied in combination, the weight percent content shared by pore creating material for slurry gross weight 0.1~
5.0%.
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| CN106807384B (en) * | 2016-11-09 | 2019-10-29 | 浙江科技学院 | A kind of preparation method and application of copper zinc catalyst |
| CN110813301A (en) * | 2018-08-07 | 2020-02-21 | 天津大学 | High-dispersion supported perovskite catalyst and preparation method and application thereof |
| CN110201666B (en) * | 2019-06-20 | 2022-01-25 | 中自环保科技股份有限公司 | Gasoline engine particle trapping catalyst and preparation method thereof |
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| CN1630556B (en) * | 2002-02-15 | 2012-10-03 | 株式会社Ict | Catalyst for clarifying exhaust emission from internal combustion engine, method for preparation thereof and method for clarifying exhaust emission from internal combustion engine |
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| CN101721997A (en) * | 2009-11-10 | 2010-06-09 | 华东理工大学 | Integral type metal carrier three-way catalyst and preparation method thereof |
| CN102039146A (en) * | 2010-11-18 | 2011-05-04 | 华东理工大学 | Catalyst for purifying exhaust gas of natural gas engine and preparation method thereof |
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