CN104289253A - Catalyst used for purifying tail gas of automobile internal combustion engine, and preparation method thereof - Google Patents
Catalyst used for purifying tail gas of automobile internal combustion engine, and preparation method thereof Download PDFInfo
- Publication number
- CN104289253A CN104289253A CN201410011696.8A CN201410011696A CN104289253A CN 104289253 A CN104289253 A CN 104289253A CN 201410011696 A CN201410011696 A CN 201410011696A CN 104289253 A CN104289253 A CN 104289253A
- Authority
- CN
- China
- Prior art keywords
- catalyst
- carrier
- combustion engine
- rare earth
- preparation
- 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
Links
Landscapes
- Catalysts (AREA)
- Exhaust Gas Treatment By Means Of Catalyst (AREA)
Abstract
The invention relates to a catalyst belonging to the field of environmental protection, and a preparation method thereof, and particularly relates to a preparation method of a catalyst suitable for purifying a tail gas of an automobile internal combustion engine. The catalyst used for purifying the tail gas of the automobile internal combustion engine is characterized in that the catalyst comprises cordierite honeycomb ceramic as a carrier, active Al2O3, a transition metal, a noble metal and a rare earth active polymer. The rare earth oxide greatly increases mechanical strength of the catalyst carrier; and variable valences and unique oxygen-storing function effectively increase catalytic activity. Meanwhile, the rare earth oxide can increase the capacity of lead and sulfur poisoning resistance of the catalyst.
Description
Technical field
The present invention relates to a kind of Catalysts and its preparation method of field of Environment Protection, be particularly useful for the method for preparing catalyst of car combustion engine tail gas clean-up.
Background technology
Automobile is the most universal vehicles of modern society, and the environmental problem brought thus can not be ignored.The pollution of use to environment of automobile mainly contains the air pollution that noise pollution and exhaust emissions cause.The pollutant of motor vehicle emission is mainly derived from internal combustion engine, and in its harmful components, CO, HC and NOx are the main atmosphere pollution compositions of automotive emissions control, very large to the health hazard of the mankind.In China, purifying vehicle exhaust is the most effectual way solving pollution emission, has become an instant task.
Automobile exhaust pollution controls to be divided into control and machine in machine to control two kinds outward.By improving performance and the production technology of catalyst and carrier thereof, improving car combustion engine combustion technology, the ability of three-way catalyst gas extraction system treatment and purification pernicious gas can be improved.Install catalytic cleaner, carrying out process to pernicious gas is the most effective method of the outer tail gas clean-up of machine, and catalyst is again the key of clean-up effect.Therefore the cleaning catalyst for tail gases of automobiles developing practicality and high efficiency is one of Optimal action controlling motor vehicle exhaust emission.
Catalytic cleaning of car tail gas is exactly that harmful CO and HC is oxidized to CO
2and H
2o, is reduced into N by NOx
2.Catalyst is functionally divided into oxidized form and reduced form two parts.Along with the improvement of engine and catalyst preparation technology, achieving can the chemical environment of compatible two kinds of functions, and namely oxidation and induction two kinds of activated centres coexist on same catalyst, have occurred three-way catalyst TWC (three-way catalyst).Catalyst converter the most frequently used at present uses honeycomb type catalysis (honeycomb catalyst).Ceramic honeycomb body is carrier, and its outer appendix has the aluminum oxide coating layer of high-specific surface area, more impregnated activated component.So, cleaning catalyst for tail gases of automobiles primarily of carrier, coating and active material three part composition.
The research and development of Foreign Automobile tail-gas catalyst experienced by altogether: oxidation catalyst, bimetallic catalyst, trimetallic catalyst, triple effect palladium catalyst and NOx store the double teachers such as reduced form three-element catalytic material, and overview is one section of method of purification, two sections of methods of purification and three-element catalytic method.Domestic from last century the mid-80 automobile exhaust pollution control research.Mainly be divided into noble metal catalyst and non-precious metal catalyst two kinds, what adopt the reaction of this technology to carry out at typical condition is very slow.
What late 1970s to the beginning of the eighties occurred is double bed type heat platinum, rhodium catalyst, and the redox reaction of catalyst is that segmentation is carried out, and reduction catalyst is positioned at leading portion, separates by supplementing air with back segment oxidation catalyst.This set is conducive to from carrying out in chemical atmosphere.Typical catalyst is Pt-Rh.In leading portion, NOx is reduced N by CO
2, CO and HC is oxidized to CO by back segment
2and H
2o.But this kind of catalytic structure complexity, troublesome poeration, and likely again oxidized after NOx reduction.
20th century, the mid-80 was to the beginning of the nineties, brought into use the Pt-Rh-Pd three-way catalyst of a new generation.This generation palladium catalyst has better heat-resistant stability at internal layer; Rhodium is more conducive to the reduction of NOx at skin; Platinum plays positive coordinative role between palladium rhodium.Can have effect to CO, HC and NOx, therefore the performance of catalyst there is obvious improvement simultaneously.But easily there is heat ageing and poisoning in three-way catalyst.Have developed NOx on this basis further and store reduced form three-element catalytic material.This catalyst is made up of noble metal, alkali metal or alkaline-earth metal, rare earth oxide.General principle is: NOx adsorption during Exhaust Gas lean atmosphere, is reduced to N by NOx during dense atmosphere
2.Under excess oxygen, NOx is first oxidized on noble metal, then stores thing with NOx and reacts, and forms nitrate.
Research finds, the lower catalytic activity of temperature is higher, and linear with the particle diameter of precious metal palladium, platinum, rhodium.Therefore, noble metal is that nano superfine micro is dispersed in aluminium oxide and can improves catalytic activity.For REINFORCED Al
2o
3stability and fusing point, higher than Pt itself, with the addition of other noble metals such as rare earth and Rh, Ir, Ru wherein.Though Pt-supported catalyst has higher catalytic activity and good low temperature active, high, the anti-sintering of its cost and sulfur poisoning resistance poor.
In catalyst, add non-noble metal compound, common is rare earth oxide, replaces or partly replaces the noble metal in catalyst, reducing the cost of catalyst while improving catalyst activity.With rare-earth composite oxide catalyst La-Co/ γ-Al
2o
3for representative.The characteristic of combining nano material high surface and rare earth catalyst obtains nano rare earth three-way catalyst, can improve catalyst cryogenic effect and extending catalyst life-span.
As from the foregoing, when needing on the one hand the cold start-up of catalyst, low temperature active is good, conversion ratio is high, and not easily thermal failure and poison deactivation occurs; On the other hand, the necessary cost of its preparation process is reasonable, and manufacturing process can not be too complicated.The target realized as above becomes problem demanding prompt solution.
Summary of the invention
In order to realize above-mentioned target, during acquisition cold start-up, low temperature active is good, conversion ratio is high, and not easily there is the catalyst of thermal failure and poison deactivation, the preparation process cost of this catalyst is lower simultaneously, and manufacturing process is uncomplicated, the invention provides a kind of catalyst for car combustion engine tail gas clean-up, it is characterized in that, described catalyst comprises cordierite honeycomb ceramic, active A l as carrier
2o
3, transition metal, noble metal and active rare-earth polymer.
Described active A l
2o
3be attached on cordierite honeycomb ceramic carrier, described cordierite honeycomb ceramic carrier apply γ-Al
2o
3after colloidal sol, form described active A l through oven dry and roasting
2o
3.
Described transition metal is manganese, and described manganese is by soluble manganese salt repeatedly impregnated carrier and applying; Described noble metal is palladium, and described palladium is by soluble palladium salt repeatedly impregnated carrier and applying.
Described active rare-earth polymer is Ce (NO
3)
36H
2o, described Ce (NO
3)
36H
2o and citric acid and 1,3,5-benzenetricarboxylic acid (BTC) mixes in the ratio of 1:1 ~ 2:0.5 ~ 1.5 and is dissolved in 350 mL dimethyl formamides (DMF), after dust technology with 5% ~ 20% regulates pH to faintly acid, carry out hydro-thermal reaction, reaction time is 12 ~ 24 h, and reaction temperature is 150 ~ 300 DEG C.
On the other hand, the present invention also provides a kind of preparation method for diesel engine vent gas cleaning catalyst, it is characterized in that: step a, forms the carrier containing transition metal and noble metal; Step b, carrier is hydro-thermal reaction in the DMF solution of rare earth; Step c, hydro-thermal reaction product is through washing, oven dry and hydrogen reducing.
Described step a, comprises a1 step: infusion process is by γ-Al
2o
3colloidal sol is coated on a certain amount of cordierite, dry in the shade, Muffle furnace annealing; Also comprise a2 step: the carrier of a1 process is immersed palladium salting liquid, and freeze-day with constant temperature, and repeated impregnations and drying, make multi-load precious metal palladium as far as possible; Also comprise a3 step: the carrier of a2 process is immersed soluble manganese salting liquid, and freeze-day with constant temperature, and repeated impregnations and drying, make multi-load transition metal manganese as far as possible.
Described step b comprises b1 step: rare earth Cerium, citric acid, BTC mixing is dissolved in DMF, and dust technology regulates pH to faintly acid and constantly stirs; Also comprise b2 step: described hydro-thermal reaction produces the Porous coordination polymer of rare earth Cerium, and the reaction time is 12 ~ 24 h, and reaction temperature is 150 ~ 300 DEG C.
Rare earth Cerium in described b1 step is Ce (NO
3)
36H
2o, described Ce (NO
3)
36H
2o and citric acid and 1,3,5-benzenetricarboxylic acid (BTC) mix in the ratio of 1:1 ~ 2:0.5 ~ 1.5 and are dissolved in 350 mL dimethyl formamides (DMF), and the dust technology with 5% ~ 20% regulates pH to faintly acid.
In described b2 step, hydro-thermal reaction produces the Porous coordination polymer reaction time of rare earth Cerium is 18 ~ 24 h, and reaction temperature is 160 ~ 220 DEG C.
Described step c, comprises c1 step: after described hydro-thermal reaction product washs after filtration, calcines 8 hours under 500 DEG C of nitrogen atmospheres; Also comprise c2 step: the carrier of c1 process is put into tube furnace 350 ° of C ~ 600 ° C hydrogen reducing 1.5 h ~ 3 h.
The rare earth oxide generated improves the mechanical strength of catalyst carrier greatly, and variable valence and unique storage oxygen function effectively improve catalytic activity.Meanwhile, rare earth oxide can improve the ability of the anti-lead of catalyst, sulfur poisoning.
Specific embodiment
The present invention discloses a kind of catalyst for car combustion engine tail gas clean-up, and described catalyst comprises cordierite honeycomb ceramic, active A l as carrier
2o
3, transition metal, noble metal and active rare-earth polymer.By cordierite honeycomb ceramic as carrier, can obtain that quality is light, the honeycomb type catalysis material of regular shape.Active A l
2o
3be attached on cordierite honeycomb ceramic carrier, described cordierite honeycomb ceramic carrier apply γ-Al
2o
3after colloidal sol, form described active A l through oven dry and roasting
2o
3.Ceramic honeycomb body is carrier, and its outer appendix has the aluminum oxide coating layer of high-specific surface area, more impregnated activated component.Concrete, transition metal is manganese, and described manganese is by soluble manganese salt repeatedly impregnated carrier and be coated on carrier; Noble metal is palladium, and described palladium is by soluble palladium salt repeatedly impregnated carrier and on coated carrier.Duct can be formed like this enrich and the large structure of specific area; MOF=metal node+organic linker, the latter is by chemical synthesis, and chemical schedulable is large.Structures and characteristics adjustability simultaneously from molecular structure to coherent condition is large.Active rare-earth polymer is the living polymer containing Ce, described Ce (NO
3)
36H
2o and citric acid and 1,3,5-benzenetricarboxylic acid (BTC) mixes in the ratio of 1:1 ~ 2:0.5 ~ 1.5 and is dissolved in 350 mL dimethyl formamides (DMF), after dust technology with 5% ~ 20% regulates pH to faintly acid, reaction time is 12 ~ 24 h, and reaction temperature is that 150 ~ 300 DEG C of hydro-thermal reactions produce.Formed based on rare earth metal Porous coordination polymer, add a small amount of noble metal and the transition metal vehicle tail gas cleaning catalyst as active component, there is the advantages such as long service life, efficient and sulfur poisoning-resistant and lead poisoning ability are strong.
The present invention on the other hand also disclose a kind of preparation method for diesel engine vent gas cleaning catalyst, comprises order enforcement:
Step a, forms the carrier containing transition metal and noble metal;
Step b, carrier is hydro-thermal reaction in the DMF solution of rare earth;
Step c, hydro-thermal reaction product is through washing, oven dry and hydrogen reducing.
In an embodiment, step a specifically comprises: step a1: infusion process is by γ-Al
2o
3colloidal sol is coated on a certain amount of cordierite, dry in the shade, Muffle furnace annealing; A2 step: the carrier through a1 process immerses palladium salting liquid, freeze-day with constant temperature, and repeated impregnations and drying, to make on carrier multi-load precious metal palladium as far as possible; A3 step: the carrier through a2 process immerses soluble manganese salting liquid, freeze-day with constant temperature.Repeated impregnations and drying repeatedly, multi-load transition metal manganese as far as possible, thus form the carrier containing transition metal and noble metal.The final structure that formation duct is enriched, specific area is large; MOF=metal node+organic linker, the latter is by chemical synthesis, and chemical schedulable is large.Structures and characteristics adjustability simultaneously from molecular structure to coherent condition is large.
An alternative embodiment of the invention provides a kind of with the synthetic method of the Porous coordination polymer of transition metal, noble metal, the rare earth metal auto-exhaust catalyst that is active component, comprises the following steps: a1 step: ceramic honey comb surface coating Al
2o
3form secondary carrier: infusion process is by Al
2o
3be coated on a certain amount of cordierite, dry in the shade, Muffle furnace annealing; A2 step: dip-coating noble metal: immersed in precious metal solution by a1 step gained carrier, fully soaks into rear fan and purges, and in oven drying.Repeat above-mentioned dipping, purging, dry run until solution is all coated on cordierite carrier; A3 step: dip-coating transition metal: a2 step gained carrier is immersed in transition metal solution, in like manner through repeatedly flooding, purging, dry run by whole for liquid dip-coating on carrier; B1 step: the Porous coordination polymer of dip-coating rare earth metal: by rare earth metal, acid and active component by a certain percentage Homogeneous phase mixing be dissolved in organic solvent, regulate pH stirring at room temperature.B2 step: b1 step gained carrier is immersed hydro-thermal reaction in this solution, and the reaction time is 12 ~ 24 h, and reaction temperature is 150 ~ 300 DEG C.C1 step: by b2 step after hydro-thermal reaction product washs after filtration, calcines 8 hours under 500 ° of C nitrogen atmospheres.C2 step: the Porous coordination polymer cordierite carrier of the dip-coating transition metal of b2 step process, noble metal, rare earth oxide 350 ° of C ~ 600 ° C hydrogen reducing 1.5 h ~ 3 h in tube furnace.After cooling, noble metal is uniformly distributed in each mesh surface of ceramic monolith with nanometer or submicron particles form, so carrier is entire body black.In the present embodiment, the present invention discloses a kind of preparation method for diesel engine vent gas cleaning catalyst, comprise a step be embodied in be easier to operate a1, a2, a3 step, b step is embodied in b1, b2 step being easier to operate, and c step is embodied in c1, c2 step being easier to operate.Rare earth oxide improves the mechanical strength of catalyst carrier greatly, and variable valence and unique storage oxygen function effectively improve catalytic activity.Meanwhile, rare earth oxide can improve the ability of the anti-lead of catalyst, sulfur poisoning.
In order to synthetic rare earth metal Cerium Porous coordination polymer, wherein the operation of step b is most important.After the carrier that step a defines coating transition metal and noble metal, preparation is needed to comprise the DMF solution of rare earth metal Cerium, and hydro-thermal reaction under given conditions, to form rare earth metal Cerium Porous coordination polymer.
One embodiment of the present of invention are, according to the carrier containing transition metal and noble metal that step a is formed, carry out next step operation.Step b comprises b1 step: rare earth Cerium, citric acid, BTC mixing is dissolved in DMF, and dust technology regulates pH to faintly acid and constantly stirs, and obtains the DMF solution of rare earth metal Cerium; B2 step: the DMF solution that the carrier containing transition metal and noble metal formed by step a is immersed in the rare earth metal Cerium that b1 step is formed carries out hydro-thermal reaction, reaction time is 12 ~ 24 h, reaction temperature is 150 ~ 300 DEG C, and hydro-thermal reaction produces the Porous coordination polymer of rare earth Cerium.The Porous coordination polymer structure produced due to hydro-thermal reaction is different, and its catalytic effect being carried on amount on active carrier and identical load amount situation is different.
In another embodiment of the present invention, according to the carrier containing transition metal and noble metal that step a is formed, carry out next step operation.Step b comprises b1 step, and the rare earth Cerium in b1 step is Ce (NO
3)
36H
2o, this Ce (NO
3)
36H
2o and citric acid and 1,3,5-benzenetricarboxylic acid (BTC) mixes in the ratio of 1:1 ~ 2:0.5 ~ 1.5 and is dissolved in 350 mL dimethyl formamides (DMF), dust technology with 5% ~ 20% regulates pH to faintly acid (between pH=3 ~ 6), stirring at room temperature, obtains the DMF solution of rare earth metal Cerium.B2 step: the DMF solution that the carrier containing transition metal and noble metal formed by step a is immersed in the rare earth metal Cerium that b1 step is formed carries out hydro-thermal reaction, reaction time is 18 ~ 24 h, reaction temperature is 160 ~ 220 DEG C, and hydro-thermal reaction produces the Porous coordination polymer of rare earth Cerium.In this Porous coordination polymer structure, the exposed group on surface hates acidity.Through EDS test, when the load capacity be carried on active carrier is 5% ~ 10%, 120 DEG C measure denitration efficiency and can reach 90%.
In another embodiment of the invention, according to the carrier containing transition metal and noble metal that step a is formed, carry out next step operation.Step b comprises b1 step, under room temperature, by Ce (NO
3)
36H
2o, citric acid and Isosorbide-5-Nitrae-pyridine carboxylic acid hydrochloride is dissolved in the DMF of 350 mL according to the ratio uniform mixing of 1:1 ~ 2:1.5 ~ 3.5, and the dust technology of 5% ~ 20% regulates pH to faintly acid (between pH=3 ~ 6), stirs 2 hours, obtains the DMF solution of rare earth metal Cerium.B2 step: the DMF solution that the cordierite honeycomb ceramic carrier containing transition metal and noble metal formed by step a is immersed in the rare earth metal Cerium that b1 step is formed carries out hydro-thermal reaction, reaction temperature is 180 ° of C, constant temperature 24 hours, hydro-thermal reaction produces the Porous coordination polymer of rare earth Cerium.Then subsequent step c1 is carried out to the Porous coordination polymer of this rare earth Cerium: calcine 8 hours under 500 ° of C nitrogen atmospheres after filtration washing.Exposed in this Porous coordination polymer structure have basic group again at the existing acidic-group of surface group.Wherein basic group is easy to hate the cordierite of acidic-group to be combined with surface, effectively improves catalytic effect.Through EDS test, when the load capacity be carried on active carrier is 5% ~ 10%, 120 DEG C measure denitration efficiency and can reach 99%, and comparatively the catalytic activity of 1,3,5-benzenetricarboxylic acid is high by 5%.
In another embodiment of the present invention, according to the carrier containing transition metal and noble metal that step a is formed, carry out next step operation.Step b comprises b1 step: under room temperature, by Ce (NO
3)
36H
2o, citric acid and Isosorbide-5-Nitrae-pyridine acetic acid hydrochloride are dissolved in the DMF of 350 mL according to the ratio uniform mixing of 1:1 ~ 2:1.5 ~ 3.5, and the dust technology of 5% ~ 20% regulates pH to faintly acid (between pH=2 ~ 5), stirs 2 hours, obtains the DMF solution of rare earth metal Cerium.B2 step: the DMF solution that the cordierite honeycomb ceramic carrier containing transition metal and noble metal formed by step a is immersed in the rare earth metal Cerium that b1 step is formed carries out hydro-thermal reaction, and hydrothermal temperature is 180 ° of C, constant temperature 24 hours in reactor.Then follow-up step c1 is carried out to the Porous coordination polymer of this rare earth Cerium: calcine 8 hours under 500 ° of C nitrogen atmospheres after filtration washing.Exposed in this Porous coordination polymer structure have basic group again at the existing acidic-group of surface group.Wherein basic group is easy to hate the cordierite of acidic-group to be combined with surface, effectively improves catalytic effect.Through EDS test, when the load capacity be carried on active carrier is 5% ~ 10%, 100 DEG C measure denitration efficiency and can reach 99%, and comparatively the catalytic activity of 1,3,5-benzenetricarboxylic acid is high by 10%.
Rare earth oxide improves the mechanical strength of catalyst carrier greatly, and variable valence and unique storage oxygen function effectively improve catalytic activity.Meanwhile, rare earth oxide can improve the ability of the anti-lead of catalyst, sulfur poisoning.
The DMF solution that the carrier containing transition metal and noble metal that above step produces is immersed in rare earth metal Cerium carries out the reactant of hydro-thermal reaction, after filtration, calcines 8 hours after washing into neutrality under 500 ° of C nitrogen atmospheres.Then calcined product is placed in tube furnace hydrogen reducing 1.5 h ~ 3 h under ° C condition of 350 ° of C ~ 600.After cooling, noble metal is uniformly distributed in each mesh surface of ceramic monolith with nanometer or submicron particles form, so carrier is entire body black.
Claims (10)
1. for a catalyst for car combustion engine tail gas clean-up, it is characterized in that, described catalyst comprises cordierite honeycomb ceramic, active A l as carrier
2o
3, transition metal, noble metal and active rare-earth polymer.
2. the catalyst for car combustion engine tail gas clean-up according to claim 1, is characterized in that: described active A l
2o
3being attached on cordierite honeycomb ceramic carrier, is apply γ-Al by described cordierite honeycomb ceramic carrier
2o
3after colloidal sol, through drying and roasting formation.
3. the catalyst for car combustion engine tail gas clean-up according to claim 2, is characterized in that: described transition metal is manganese, and described manganese is by soluble manganese salt repeatedly impregnated carrier and applying; Described noble metal is palladium, and described palladium is by soluble palladium salt repeatedly impregnated carrier and applying.
4. the catalyst for car combustion engine tail gas clean-up according to claim 1, is characterized in that: described active rare-earth polymer is Ce (NO
3)
36H
2o, described Ce (NO
3)
36H
2o and citric acid and 1,3,5-benzenetricarboxylic acid (BTC) mixes in the ratio of 1:1 ~ 2:0.5 ~ 1.5 and is dissolved in 350 mL dimethyl formamides (DMF), after dust technology with 5% ~ 20% regulates pH to faintly acid, hydro-thermal reaction produces, reaction time is 12 ~ 24 h, and reaction temperature is 150 ~ 300 DEG C.
5. for a preparation method for car combustion engine tai-gas clean-up catalyst, it is characterized in that: step a, form the carrier containing transition metal and noble metal; Step b, carrier is hydro-thermal reaction in the DMF solution of rare earth; Step c, hydro-thermal reaction product is through washing, oven dry and hydrogen reducing.
6. the preparation method for car combustion engine tai-gas clean-up catalyst according to claim 5, it is characterized in that: described step b comprises b1 step: rare earth Cerium, citric acid, BTC mixing is dissolved in DMF, dust technology regulates pH to faintly acid and constantly stirs; B2 step: described hydro-thermal reaction produces the Porous coordination polymer of rare earth Cerium, and the reaction time is 12 ~ 24 h, and reaction temperature is 150 ~ 300 DEG C.
7. the preparation method for car combustion engine tai-gas clean-up catalyst according to claim 6, is characterized in that: the rare earth Cerium in described b1 step is Ce (NO
3)
36H
2o, described Ce (NO
3)
36H
2o and citric acid and 1,3,5-benzenetricarboxylic acid (BTC) mix in the ratio of 1:1 ~ 2:0.5 ~ 1.5 and are dissolved in 350mL dimethyl formamide (DMF), and the dust technology with 5% ~ 20% regulates pH to faintly acid.
8. the preparation method for car combustion engine tai-gas clean-up catalyst according to claim 7, is characterized in that: in described b2 step, hydro-thermal reaction produces the Porous coordination polymer reaction time of rare earth Cerium is 18 ~ 24 h, and reaction temperature is 160 ~ 220 DEG C.
9. the preparation method for car combustion engine tai-gas clean-up catalyst according to any one of claim 5-8, is characterized in that: described step a, comprises a1 step: infusion process is by γ-Al
2o
3colloidal sol is coated on a certain amount of cordierite, dry in the shade, Muffle furnace annealing; A2 step: the carrier of a1 process is immersed palladium salting liquid, freeze-day with constant temperature, and repeated impregnations and drying steps, as far as possible multi-load precious metal palladium; A3 step: the carrier of a2 process is immersed soluble manganese salting liquid, freeze-day with constant temperature, and repeated impregnations and drying steps, as far as possible multi-load transition metal manganese.
10. the preparation method for car combustion engine tai-gas clean-up catalyst according to claim 9, is characterized in that: described step c, comprises c1 step: described hydro-thermal reaction product washs after filtration, calcines 8 hours under 500 ° of C nitrogen atmospheres; C2 step: the carrier of c1 process is put into tube furnace 350 ° of C ~ 600 ° C hydrogen reducing 1.5 h ~ 3 h.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410011696.8A CN104289253B (en) | 2014-01-10 | 2014-01-10 | It is a kind of for catalyst of car combustion engine tail gas clean-up and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410011696.8A CN104289253B (en) | 2014-01-10 | 2014-01-10 | It is a kind of for catalyst of car combustion engine tail gas clean-up and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN104289253A true CN104289253A (en) | 2015-01-21 |
| CN104289253B CN104289253B (en) | 2017-09-15 |
Family
ID=52309340
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201410011696.8A Expired - Fee Related CN104289253B (en) | 2014-01-10 | 2014-01-10 | It is a kind of for catalyst of car combustion engine tail gas clean-up and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN104289253B (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104785302A (en) * | 2015-04-21 | 2015-07-22 | 北京大学包头创新研究院 | Selective catalytic reduction denitration catalyst, preparation method and application thereof |
| CN104841426A (en) * | 2015-04-28 | 2015-08-19 | 内蒙古硕鑫工业科技有限公司 | Catalyst for purifying automobile exhaust and preparation method of catalyst |
| CN109569627A (en) * | 2018-12-19 | 2019-04-05 | 中自环保科技股份有限公司 | One kind catalyst containing Pd and preparation method thereof |
| CN114011444A (en) * | 2021-12-02 | 2022-02-08 | 苏州彼定新材料科技有限公司 | Noble metal catalyst based on rare earth carrier and preparation method thereof |
| CN114345331A (en) * | 2020-10-13 | 2022-04-15 | 北京锋测生物科技有限公司 | Method for preparing supported platinum group catalyst by using laser |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1502407A (en) * | 2002-11-19 | 2004-06-09 | 南昌大学 | Catalyst for purifying exhausted gas of car and preparation process thereof |
| CN103464152A (en) * | 2013-09-29 | 2013-12-25 | 福州大学 | Catalyst for tail gas purification and preparation method thereof |
-
2014
- 2014-01-10 CN CN201410011696.8A patent/CN104289253B/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1502407A (en) * | 2002-11-19 | 2004-06-09 | 南昌大学 | Catalyst for purifying exhausted gas of car and preparation process thereof |
| CN103464152A (en) * | 2013-09-29 | 2013-12-25 | 福州大学 | Catalyst for tail gas purification and preparation method thereof |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104785302A (en) * | 2015-04-21 | 2015-07-22 | 北京大学包头创新研究院 | Selective catalytic reduction denitration catalyst, preparation method and application thereof |
| CN104785302B (en) * | 2015-04-21 | 2019-05-10 | 北京大学包头创新研究院 | Denitrifying catalyst with selective catalytic reduction and its preparation method and application |
| CN104841426A (en) * | 2015-04-28 | 2015-08-19 | 内蒙古硕鑫工业科技有限公司 | Catalyst for purifying automobile exhaust and preparation method of catalyst |
| CN109569627A (en) * | 2018-12-19 | 2019-04-05 | 中自环保科技股份有限公司 | One kind catalyst containing Pd and preparation method thereof |
| CN109569627B (en) * | 2018-12-19 | 2020-10-23 | 中自环保科技股份有限公司 | Pd-containing catalyst and preparation method thereof |
| CN114345331A (en) * | 2020-10-13 | 2022-04-15 | 北京锋测生物科技有限公司 | Method for preparing supported platinum group catalyst by using laser |
| CN114011444A (en) * | 2021-12-02 | 2022-02-08 | 苏州彼定新材料科技有限公司 | Noble metal catalyst based on rare earth carrier and preparation method thereof |
| CN114011444B (en) * | 2021-12-02 | 2023-12-22 | 苏州彼定新材料科技有限公司 | Rare earth carrier-based noble metal catalyst and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN104289253B (en) | 2017-09-15 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP5185942B2 (en) | Vanadium-free catalyst for selective catalytic reduction and process for producing the same | |
| JP4833453B2 (en) | Exhaust gas purification catalyst and its production and use | |
| CN103433057B (en) | Three-way catalyst for purifying automobile exhaust and preparation method thereof | |
| CN100455352C (en) | Honeycomb metal wire net carrier catalyst for catalytically reducing nitrogen oxide and preparing method thereof | |
| BR112017028424B1 (en) | NITROUS OXIDE REMOVAL CATALYST COMPOSITE, EMISSION TREATMENT SYSTEM, AND, METHOD TO TREAT EXHAUST GASES | |
| EP2127729A1 (en) | Exhaust gas purification catalyst | |
| CN105289641B (en) | A kind of cobalt cerium-carrying manganese oxide catalyst and preparation method thereof | |
| WO2005075059A1 (en) | Precious metal catalyst stabilized with iron oxide for the removal of pollutants from exhaust gases from leanburn engines | |
| CN101479037A (en) | Exhaust gas purifying catalyst and its manufacturing method | |
| CN104289253A (en) | Catalyst used for purifying tail gas of automobile internal combustion engine, and preparation method thereof | |
| CN110075862A (en) | Compound non-noble metal oxide catalyst for catalytic combustion and preparation method thereof | |
| JP6348110B2 (en) | Catalyst composition | |
| CN102065997B (en) | Oxidation catalyst for commercial vehicles comprising diesel motor | |
| CN101618323B (en) | Structural catalyst for catalyzing and reducing nitrogen oxide and preparation method thereof | |
| JPH11276907A (en) | Catalyst for purifying exhaust gas and its production | |
| JPH05285387A (en) | Catalyst for purification of exhaust gas and purification method | |
| US20230070493A1 (en) | Twc catalysts for gasoline engine exhaust gas treatments | |
| JPH08281110A (en) | Catalyst for purifying exhaust gas and its production | |
| JP3251009B2 (en) | Exhaust gas purification catalyst | |
| CN108043397B (en) | Integral vehicle tail gas purification catalyst with porous structure and preparation method thereof | |
| JP6108289B2 (en) | CO oxidation catalyst and method for producing the same | |
| KR101438885B1 (en) | Catalyst for conversion nitrogen oxides into ammonia and manufacturing method for the same | |
| JPH08266900A (en) | Exhaust gas purifying catalyst and its production | |
| JP4624598B2 (en) | Exhaust gas purification catalyst and production method thereof | |
| JP2007084391A (en) | Exhaust gas purifying device for automobile and hydrogen producing catalyst |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| CB02 | Change of applicant information |
Address after: Peking University Science Park 014010 the Inner Mongolia Autonomous Region Jiuyuan District of Baotou city planning new equipment Park District 2 Building 2 layer Applicant after: Packet header innovation research institute of Peking University Address before: 014010 room B, block, management committee, equipment manufacturing park, Qingshan District, the Inner Mongolia Autonomous Region, China Applicant before: BAOTOU RESEARCH INSTITUTE, COLLEGE OF ENGINEERING, PKU |
|
| COR | Change of bibliographic data | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20170915 Termination date: 20210110 |
|
| CF01 | Termination of patent right due to non-payment of annual fee |