CN104895652A - Catalytic diesel particulate filter reducing particulate matter emission of diesel vehicle and manufacturing method of filter - Google Patents
Catalytic diesel particulate filter reducing particulate matter emission of diesel vehicle and manufacturing method of filter Download PDFInfo
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- CN104895652A CN104895652A CN201510275106.7A CN201510275106A CN104895652A CN 104895652 A CN104895652 A CN 104895652A CN 201510275106 A CN201510275106 A CN 201510275106A CN 104895652 A CN104895652 A CN 104895652A
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Abstract
The invention discloses a catalytic diesel particulate filter reducing particulate matter emission of a diesel vehicle and a manufacturing method of the filter. A vacuum extraction method is adopted for evenly coating a diesel particulate filter carrier with rare earth oxide modified activated aluminum oxide and a ceria-zirconium solid solution, then, the diesel particulate filter carrier is dipped into active components (Cu, Cs and Pt), and the catalytic diesel particulate filter is made. The micro-hole structure of an active coating is improved by adding starch pore-forming agents, the back pressure of the carrier is reduced, meanwhile, the specific surface area and the pore volume of the active coating are increased, and the catalytic oxidation activity of the catalytic diesel particulate filter on carbon black is greatly improved. The manufacturing process of the vacuum extraction method is easier and more convenient to perform, the load rate of the active coating is high, the binding force between the catalytic diesel particulate filter and a honeycomb carrier is strong, and the manufactured catalytic diesel particulate filter has good catalytic performance.
Description
Technical field
The present invention relates to a kind of catalyzed diesel particulate filter granular material discharged for reducing diesel-oil vehicle and preparation method thereof, specifically, vacuum extraction method is adopted evenly to be coated on diesel particulate filter carrier by the activated alumina of rare-earth oxide modified and cerium zirconium sosoloid, then impregnated activated component (Cu, Cs, Pt), prepares catalyzed diesel particulate filter.
Background technique
Soot particulate matter in exhaust gas from diesel vehicle mainly comprises the dry soot of solid matter (DS, about 40 ~ 50%), dissolved organic matter (SOF, about 35 ~ 45%) and sulphate, moisture, ashes and other components (about 5-10%).The particulate matter quantity of emission of diesel engine is 20 ~ 100 times of petrol engine, and the particulate that diameter is less than 10 μm enters nasal cavity, throat and lung from air, causes irritable cough, maximum to harm.There are some researches show, some heavy metal elements that carbon soot particles adsorbs and hydrocarbon, as polycyclic aromatic hydrocarbon (PAHs), to have strong carcinogenic mutagenesis to human body, the probability causing human body to suffer from respiratory disease increases.In addition, carbon soot particles quality is light, can suspend in an atmosphere for a long time, one of primary pollution source becoming city, have a strong impact on environmental quality, bring many harmful effects to human lives.
About the method reducing carbon soot particles discharge, depend merely on and improve the emission standard that engine technology cannot meet increasingly stringent.Meanwhile, use fuel additive not have cost effectiveness, himself be discharged in air and also may cause secondary pollution.In order to reduce the discharge of soot particulate, extensively adopt wall-flow type carbon soot particles filter (Diesel Particulate Filter, DPF) both at home and abroad at present.Wall-flow type honeycomb ceramic carrier has the parallel channels being similar to normal cellular pottery, but replaces plug-hole unlike adjacent two ends, duct.After exhaust gas from diesel vehicle enters DPF duct, because the end in duct is plugged, gas is discharged after the stephanoporate thin wall of inside, DPF wall is designed to the porosity be applicable to, and tail gas can be passed through smoothly, reduces the Pressure Drop of system, and carbon soot particles is wherein filtered, be deposited on hole wall.The filter efficiency of DPF is higher, usually can reach more than 90%, and part soluble organic fraction also can be captured, and structural strength is high, heat shock resistance and resistance to mechanical lasing capability stronger.Wall-flow type honeycomb ceramic carrier has had obvious breakthrough in production technology in recent years, filter wall thickness reduction, and identical filter efficiency under shed cross-section area increases, thus reduces pressure drop loss.Therefore, within the quite a long time from now on, honeycomb ceramic filter will be the diesel emission particulate filter of most main flow.
Chinese patent CN103206287A discloses a kind of diesel particulate filter with the carrier coating improving filter capability.This diesel particulate filter is by porous ceramic matrices suitable, be deposited on the aluminum oxide coating layer of porous ceramic matrix surface, the at least one precious metal selected from the group that platinum, palladium and rhodium are formed, and at least one metallic oxide selected from the group that cerium oxide, zirconium oxide, lanthana and yittrium oxide are formed is formed.
Chinese patent CN103375227A discloses a kind of diesel particulate filter with oxidation catalytic activity coating.This diesel particulate filter is made up of wall-flow filter (being made up of steinheilite, silicon carbide, mullite or aluminium titanates), the indifferent oxide carrier (being made up of two or more mixture in the aluminium oxide of aluminium oxide, doping, titanium dioxide, cerium oxide, zirconium oxide, cerium Zr mixed oxide, silica or these oxides) with large surface area and active component (being made up of platinum, palladium, gold or their mixture).
Above-mentioned existing patented technology all adopts precious metal as the catalytic active component of diesel particulate filter, and cost of production is high, is unfavorable for applying on a large scale.
Summary of the invention
The object of the invention is to, there is provided a kind of catalyzed diesel particulate filter granular material discharged for reducing diesel-oil vehicle and preparation method thereof, described catalyzed diesel particulate filter has lower cost of production, lower carrier back pressure and good catalytic performance.
The present invention adopts vacuum extraction method to be evenly coated on diesel particulate filter carrier by the activated alumina of rare-earth oxide modified and cerium zirconium sosoloid, then impregnated activated component (Cu, Cs, Pt), prepare catalyzed diesel particulate filter, the composition of active coating and weight percent content thereof 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, specifically comprises the steps:
1. be scattered in deionized water by the activated alumina of lanthana modification, Alumina gel, cerium zirconium sosoloid and pore creating material, in mulser, emulsification made slurry after 0.5 ~ 1 hour;
2. adopt special vacuum extraction device to be evenly coated on diesel particulate filter carrier by above-mentioned slurry, then successively 100 ~ 120 DEG C of dryings 8 ~ 16 hours, 500 ~ 700 DEG C of roastings 2 ~ 6 hours;
3. at Pt (NO
3)
2, Cu (NO
3)
23H
2o and CsNO
3mixed aqueous solution in dipping 1 ~ 3 hour, then successively 100 ~ 120 DEG C of dryings 2 ~ 6 hours, after 2 ~ 6 hours, prepare catalyzed diesel particulate filter 450 ~ 650 DEG C of roastings.
Described pore creating material comprise in polyethyleneglycol, polyvinyl alcohol, tween, starch, methyl cellulose and urea one or more combinationally use, the weight percent content shared by pore creating material is 0.1 ~ 5.0% of slurry gross weight.
One of remarkable advantage of catalyzed diesel particulate filter of the present invention is, starch pore creating material add the microcellular structure improving active coating, reduce carrier back pressure, add specific surface area and the pore volume of active coating simultaneously, substantially increase the catalytic oxidation activity of catalyzed diesel particulate filter for soot.
Two of the remarkable advantage of catalyzed diesel particulate filter of the present invention is, Pt adds the complete catalysts oxidation directly facilitating carbon soot particles, Cu and Cs adds the cost of production reducing catalyzer, further increases its catalytic oxidation activity for soot.
The remarkable advantage of the preparation method of catalyzed diesel particulate filter of the present invention is, the preparation process of described vacuum extraction method is simple and easy to do, the load factor of active coating is high, strong with the combination force of honeycomb substrate, the catalyzed diesel particulate filter of preparation has good catalytic performance.
Embodiment
Comparative example
The Alumina gel being 8% by the activated alumina of 73.6 grams of lanthana modifications and 80 grams of solid contents joins in 246.4 grams of deionized waters, and in mulser, emulsification made slurry after 0.5 hour; Adopting special vacuum extraction device above-mentioned slurry to be evenly coated in volume is on the diesel particulate filter carrier of 74.5 milliliters, then successively 120 DEG C of dryings 12 hours, 600 DEG C of roastings 2 hours, by it taking-up after naturally cooling, namely prepare catalyzed diesel particulate filter.
Embodiment 1
Be that the Alumina gel of 8%, 21.6 grams of cerium zirconium sosoloids and a certain amount of pore creating material join in 236.4 grams of deionized waters by the activated alumina of 52 grams of lanthana modifications, 80 grams of solid contents, in mulser, emulsification made slurry after 1 hour; Adopting special vacuum extraction device above-mentioned slurry to be evenly coated in volume is on the diesel particulate filter carrier of 74.5 milliliters, then successively 120 DEG C of dryings 12 hours, 600 DEG C of roastings 2 hours, by it taking-up after naturally cooling, namely prepare catalyzed diesel particulate filter.Different pore creating material is as shown in table 1 for the impact of active coating performance.
The different pore creating material of table 1 is for the impact of 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 |
| Methyl cellulose | 0.25 | 44.3 | 0.23 | 0.36 |
| Methyl cellulose | 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
By the activated alumina of 36 grams of lanthana modifications, 80 grams of solid contents be 8% Alumina gel and 37.6 grams of cerium zirconium sosoloids join in 246.4 grams of deionized waters, in mulser, emulsification made slurry after 0.5 hour; Adopting special vacuum extraction device above-mentioned slurry to be evenly coated in volume is on the diesel particulate filter carrier of 74.5 milliliters, then successively 120 DEG C of dryings 12 hours, 600 DEG C of roastings 2 hours, naturally by it taking-up after cooling, namely prepare catalyzed diesel particulate filter, be designated as A sample.
Embodiment 3
By the activated alumina of 52 grams of lanthana modifications, 80 grams of solid contents be 8% Alumina gel and 21.6 grams of cerium zirconium sosoloids join in 246.4 grams of deionized waters, in mulser, emulsification made slurry after 0.5 hour; Adopting special vacuum extraction device above-mentioned slurry to be evenly coated in volume is on the diesel particulate filter carrier of 74.5 milliliters, then successively 120 DEG C of dryings 12 hours, 600 DEG C of roastings 2 hours, naturally by it taking-up after cooling, namely prepare catalyzed diesel particulate filter, be designated as B sample.
Embodiment 4
Be the Alumina gel of 8% by the activated alumina of 52 grams of lanthana modifications, 80 grams of solid contents, 21.6 grams of cerium zirconium sosoloids and 10 grams of starch pore creating materials join in 236.4 grams of deionized waters, in mulser, emulsification made slurry after 1 hour; Adopting special vacuum extraction device above-mentioned slurry to be evenly coated in volume is on the diesel particulate filter carrier of 74.5 milliliters, then successively 120 DEG C of dryings 12 hours, 600 DEG C of roastings 2 hours, naturally by it taking-up after cooling, namely prepare catalyzed diesel particulate filter, be designated as C sample.
Embodiment 5
Be catalyzed diesel particulate filter prepared by the embodiment 3 of 3.6 milliliters by volume, at the Pt (NO of 3.2 milliliters
3)
2(Pt (NO in the aqueous solution
3)
2concentration is 1.225g/L) flood after 1 hour and take out, then successively 120 DEG C of dryings 4 hours, 550 DEG C of roastings 4 hours, by it taking-up after naturally cooling, namely prepare catalyzed diesel particulate filter, be designated as D sample.
Embodiment 6
Be catalyzed diesel particulate filter prepared by the embodiment 3 of 3.6 milliliters by volume, at the Pt (NO of 3.2 milliliters
3)
2with Cu (NO
3)
2(Pt (NO in mixed aqueous solution
3)
2concentration is 1.225g/L, Cu (NO
3)
2concentration is 7.667g/L) flood after 1.5 hours and take out, then successively 120 DEG C of dryings 4 hours, 550 DEG C of roastings 4 hours, by it taking-up after naturally cooling, namely prepare catalyzed diesel particulate filter, be designated as E sample.
Embodiment 7
Be catalyzed diesel particulate filter prepared by the embodiment 3 of 3.6 milliliters by volume, (Pt (NO in 3.2 milliliters of mixed aqueous solutions
3)
2concentration is 1.225g/L, Cu (NO
3)
2concentration is 2.548g/L, CsNO
3concentration is 1.031g/L) flood after 2 hours and take out, then successively 120 DEG C of dryings 4 hours, 550 DEG C of roastings 4 hours, by it taking-up after naturally cooling, namely prepare catalyzed diesel particulate filter, be designated as F sample.
Embodiment 8
Be catalyzed diesel particulate filter prepared by the embodiment 3 of 3.6 milliliters by volume, (Pt (NO in the mixed aqueous solution of 3.2 milliliters
3)
2concentration is 1.225g/L, Cu (NO
3)
2concentration is 7.667g/L, CsNO
3concentration is 3.125g/L) flood after 2.5 hours and take out, then successively 120 DEG C of dryings 4 hours, 550 DEG C of roastings 4 hours, by it taking-up after naturally cooling, namely prepare catalyzed diesel particulate filter, be designated as G sample.
Table 2 is the catalytic oxidation activity of various catalyzed diesel particulate filter for soot, and the catalytic oxidation activity appreciation condition of soot is: air speed is 40000h
-1, from 60 DEG C with 5 DEG C of min
-1heating rate rise to 700 DEG C.As can be seen from Table 2, adding of starch pore creating material improves the catalytic oxidation activity of catalyzed diesel particulate filter for soot, Pt adds the complete catalysts oxidation directly facilitating carbon soot particles, Cu and Cs adds the cost of production reducing catalyzer, further increases the catalytic oxidation activity for soot.
Table 2 catalyzed diesel particulate filter is for the catalytic oxidation activity of soot
| Catalyzer | Comparative example | A | B | C | D | E | F | G |
| T 10/℃ | 536 | 543 | 487 | 483 | 441 | 394 | 337 | 365 |
| T 50/℃ | 580 | 582 | 560 | 520 | 512 | 504 | 488 | 503 |
| T 90/℃ | 601 | 625 | 599 | 580 | 550 | 525 | 526 | 550 |
Claims (3)
1. one kind for reducing the granular material discharged catalyzed diesel particulate filter of diesel-oil vehicle, it is characterized in that, by vacuum extraction method, the activated alumina of rare-earth oxide modified and cerium zirconium sosoloid are coated on diesel particulate filter carrier, then impregnated activated component (Cu, Cs, Pt), the composition of active coating and weight percent content thereof 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%.
2. prepare the method for the catalyzed diesel particulate filter granular material discharged for reducing diesel-oil vehicle according to claim 1, it is characterized in that, this preparation method is vacuum extraction method, specifically comprises the steps:
Be scattered in deionized water by the activated alumina of lanthana modification, Alumina gel, cerium zirconium sosoloid and pore creating material, in mulser, emulsification made slurry after 0.5 ~ 1 hour; Special vacuum extraction device is adopted evenly to be coated on diesel particulate filter carrier by above-mentioned slurry, then successively 100 ~ 120 DEG C of dryings 8 ~ 16 hours, 500 ~ 700 DEG C of roastings 2 ~ 6 hours; Last at Pt (NO
3)
2, Cu (NO
3)
23H
2o and CsNO
3mixed aqueous solution in dipping 1 ~ 3 hour, then successively 100 ~ 120 DEG C of dryings 2 ~ 6 hours, after 2 ~ 6 hours, prepare catalyzed diesel particulate filter 450 ~ 650 DEG C of roastings.
3. the preparation method of the catalyzed diesel particulate filter granular material discharged for reducing diesel-oil vehicle according to claim 2, it is characterized in that, described pore creating material comprise in polyethyleneglycol, polyvinyl alcohol, tween, starch, methyl cellulose and urea one or more combinationally use, the weight percent content shared by pore creating material is 0.1 ~ 5.0% of slurry gross weight.
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| CN105413652A (en) * | 2015-11-06 | 2016-03-23 | 中国第一汽车股份有限公司 | Preparation method of particle filter carrier material mixture containing diatom ooze |
| CN106807384A (en) * | 2016-11-09 | 2017-06-09 | 浙江科技学院 | A kind of preparation method and application of copper zinc catalyst |
| CN110201666A (en) * | 2019-06-20 | 2019-09-06 | 中自环保科技股份有限公司 | A kind of gasoline engine granule capturing catalyst and preparation method thereof |
| CN110813301A (en) * | 2018-08-07 | 2020-02-21 | 天津大学 | High-dispersion supported perovskite catalyst and preparation method and application thereof |
| CN111821971A (en) * | 2020-07-30 | 2020-10-27 | 中自环保科技股份有限公司 | Integral catalyst for catalytic regeneration of soot and preparation method thereof |
| CN112610309A (en) * | 2020-12-16 | 2021-04-06 | 中南大学 | Diesel catalytic particle trap coated with CeZrK/rGO nano solid solution catalyst |
| CN112958067A (en) * | 2021-02-06 | 2021-06-15 | 昆明贵研催化剂有限责任公司 | Gasoline vehicle particle trapping catalyst and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN105413652A (en) * | 2015-11-06 | 2016-03-23 | 中国第一汽车股份有限公司 | Preparation method of particle filter carrier material mixture containing diatom ooze |
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| CN112958067A (en) * | 2021-02-06 | 2021-06-15 | 昆明贵研催化剂有限责任公司 | Gasoline vehicle particle trapping catalyst and preparation method thereof |
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