CN103977842A - Method for coating motor vehicle exhaust cleaning catalyst - Google Patents
Method for coating motor vehicle exhaust cleaning catalyst Download PDFInfo
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- CN103977842A CN103977842A CN201410244144.1A CN201410244144A CN103977842A CN 103977842 A CN103977842 A CN 103977842A CN 201410244144 A CN201410244144 A CN 201410244144A CN 103977842 A CN103977842 A CN 103977842A
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Abstract
The invention provides a method for coating a motor vehicle exhaust cleaning catalyst. The method comprises the following steps: (1) pretreating a carrier; (2) sensitizing the carrier; (3) activating the carrier; and (4) carrying out electroless-deposition. The method for coating the motor vehicle exhaust cleaning catalyst overcomes technical bottlenecks of a traditional impregnation method, a precipitation method, a vacuum coating method and the like, enables the uniform load of precious metal catalysts in wall-flow-type honeycomb ceramic carrier micropores as well as on straight-through-type honeycomb ceramic carrier coatings to be realized successfully; moreover, the precious metal catalysts prepared by the invention have the particle size of 50-100nm, have performances of nano particles, have large specific surface areas, improve the catalytic reaction speed and reaction activities greatly compared with those of great-size catalysts under the same condition; additionally, precious metal salt is used for the method, and is low in price, so that the using quantity of precious metal can be reduced greatly; techniques of high-temperature forging and the like are not required; the method is simple to operate, can be realized, and is wide in carrier application range.
Description
Technical field
The invention belongs to air contaminant treatment and environment protection catalytic Material Field, be specifically related to a kind of Vehicle Exhaust Gas Cleaning Catalysts painting method.
Background technology
Along with economic fast development, people grow with each passing day to the demand of motor vehicles, output and the recoverable amount of domestic motor vehicle sharply increase, tail gas pollution of motor-driven vehicle problem is also more and more serious, interrelated data shows: the big cities such as Beijing, Shanghai, Guangzhou, motor-vehicle tail-gas has become the main source of atmosphere pollution.Particularly diesel engine becomes the major impetus of motor vehicle just gradually because of features such as its thermal efficiency are high, fuel economy is good, the life-span is long.But in diesel engine vent gas, contain a large amount of nitrogen oxide (NO
x) and the discharge of particle (PM), especially particle, limited it and applied.There is continuing blind haze weather in most areas, China central and east in 2013, especially Beijing, capital haze reaches 60 days, urge the proposition of Cheng Liao state V vehicle exhaust standard and in the enforcement of Beijing area, in this standard, increase granular material discharged restriction, and increased crucial emission control parts (catalytic converter) inspection requirements.Therefore the discharge of strict control diesel particulate has become the task of top priority.
Automobile pollution control measure are divided into emission controls by improving combustion and the outer two class technology of controlling of machine, and wherein catalytic converter is one of outer exhaust purifying method of the most effective machine.For diesel engine, catalytic converter can adsorb and holds back soot particulate, is CO by the rapid conversion under the effect of catalyst such as part particulate, CO, THC in tail gas simultaneously
2, H
2o, N
2deng innocuous substance.The cleaning catalyst of one of Main Means polluting as cleaning of off-gas is subject to researcher's extensive concern in recent years.Wherein noble metal catalyst is because of advantages such as its good low temperature ignition is active, catalytic activity is high, good stability, life-span length, and it occupies extremely important status in motor-driven vehicle gas disposal.Noble metal for purifying vehicle exhaust mainly contains rhodium (Rh), platinum (Pt), palladium (Pd) at present, and Rh has the NOx of promotion and is optionally reduced to N
2, also showed good sulfur poisoning-resistant ability; Pt has good Catalytic Combustion Effect to soot particulate in diesel engine vent gas; Pt, Pd have very high activity to the oxidation of CO, HC.But Precious Metals Resources is in short supply, expensive, limited its application aspect tail gas catalyzed, so people reduce noble metal dosage at finding method always, keep the method for its catalytic activity simultaneously.
It in diesel car tail gas refining field, is the removal efficiency of raising soot particulate (soot), the general porous material that adopts is as carrier, present stage concentrates on and prepares forming method, pore structure parameter and regeneration techniques the research of honeycomb ceramic filter, and the coating few people of catalyst in micropore on its filtering surface are related to.
The conventional method of noble-metal coated has at present:
1) infusion process, carrier is immersed in the solution containing one or more noble metal precursor things, by the capillary pressure in carrier duct, make liquid (noble metal) be penetrated into carrier space inner, the required catalyst that can make after the steps such as the carrier drying after dipping, Muffle furnace roasting.Can be divided into excessive infusion process and equi-volume impregnating again, excessive infusion process is that the volume of dipping solution is greater than carrier bulk, and the method noble-metal-supported evenly but can not control noble-metal-supported amount, is not many times that load capacity is the bigger the better.Incipient impregnation is that carrier bulk is consistent with maceration extract volume, and maceration extract can just enter the inside, hole completely, although can control eaily noble-metal-supported amount, its decentralization is very poor, and particle disperses inhomogeneous.Use the publication of this technique to have CN1239017A, CN1055302A, CN1191127C etc.
2) vacuum covering technology, is about to honeycomb ceramic carrier one end and immerses slurry, at the other end, aspirates by force, and after reaching a certain height, carrier Rotate 180 °, uses the same method the other end is applied.Vacuum covering technique has guaranteed that carrier duct can apply spreading mass, and eyelet can not occur all to fill in, but its structure and driver are complicated, have increased the cost of Catalyst Production, and is difficult to realize evenly and applying in micropore.Use the publication of this technique to have CN203370699U, CN103386391A etc.
3) precipitation method, refer to aqueous metal salt are added in agitator, carrier is put into solution and floods, after add precipitating reagent, active component is precipitated at carrier surface, generate solid sediment.After having precipitated, by with the washing of sedimentary carrier, filter, the catalyst finished product of dry, roasting system.The method is simple to operate, and feasibility is high, but due to the impact of the uncontrollable precipitating reagent concentration of the prepared catalyst of the precipitation method on shaping particles, the position shaped granule radius therefore having is larger, inhomogeneous.Use the publication of this technique to have CN1927459B etc.
In sum, existing noble-metal coated method cost is high, complex procedures, and is difficult to use in the coating of honeycomb ceramic filter micropore inner catalyst.
Summary of the invention
Shortcoming of the prior art, the invention provides a kind of Vehicle Exhaust Gas Cleaning Catalysts and applies new method in view of the above, and by adopt the synthetic route of bottom-up in water, growth has the noble metal catalyst of nanocluster structure.
A Vehicle Exhaust Gas Cleaning Catalysts painting method, comprises the steps:
(1) support pretreatment
Described carrier is honeycomb ceramic filter or through type ceramic honey comb, and described carrier is soaked in nitric acid, cleans post-drying;
(2) carrier sensitization
The carrier of handling well in step (1) is immersed in sensitizing solution, and the solvent of described sensitizing solution is deionized water and CH
3oH, solute is SnCl
2and C
2hF
3o
2;
(3) carrier activation
By in step (2) through the carrier of sensitization, take out and first use washed with methanol, then use pure water rinsing, immerse afterwards in activating solution; Described activating solution is by AgNO
3be dissolved in wiring solution-forming in pure water, then with ammoniacal liquor, carry out titration until brown silver oxide precipitation disappears, obtain activating solution;
(4) electroless deposition
Preparation precious metal salt solution: precious metal salt solution is the aqueous solution that contains one or more soluble-salts in platinum, palladium, rhodium;
Configuration plating solution: described plating solution is that described precious metal salt solution is added to complexing agent, and described complexing agent is ammoniacal liquor; Ammoniacal liquor, as complexing agent, both can be stablized pH value in plating solution, again can with precious metal ion complexing, therefore add suitable ammoniacal liquor, can keep bath stability, can accelerate reaction rate again.
Deposition reaction: by activated carrier in step (3), take out and first use washed with methanol, then use pure water rinsing, immerse afterwards in plating solution; In carrier immerses plating solution, start reaction and in terminal procedure, constantly add reducing agent to reacting, described reducing agent is a kind of in hydrazine hydrate, hypophosphites, phosphite, borine, trimethylamine, formaldehyde.
As optimal way, described step (1) support pretreatment is further: carrier is honeycomb ceramic filter or through type ceramic honey comb, and the nitric acid dousing carrier with 5～30% 24 hours is cleaned with pure water, dries 10 hours at 90～120 ℃.
As optimal way, described step (2) carrier sensitization is further: the carrier of handling well in step (1) is put into sensitizing solution, stop 30～90min, the solvent of described sensitizing solution is deionized water and the CH of volume ratio 1:1
3oH, solute is SnCl
2and C
2hF
3o
2, SnCl
2concentration be 17～27mmol/L, C
2hF
3o
2concentration be 60～80mmol/L.
As optimal way, described step (3) carrier activation is further: by step (2) through the carrier of sensitization, take out and first use washed with methanol, then use pure water rinsing, immerse afterwards in activating solution, stop 10～30min, described activating solution is by AgNO
3be dissolved in the solution that is made into 30～40mmol/L in pure water, then with 37% ammoniacal liquor, carry out titration until brown silver oxide precipitation disappears, obtain activating solution.
As optimal way, in described step (4), preparation precious metal salt solution is further:
(4.1) preparation precious metal salt solution, described precious metal salt solution solute is one or more soluble-salts that contain platinum, palladium, rhodium, and solvent is pure water, and concentration is 0.1～10mmol/L;
As optimal way, in described step (4), before immersing plating solution, carrier comprises:
(4.2) preparation surfactant solution, described surfactant solution solute is neopelex, and solvent is pure water, and concentration is 0.01～0.3mol/L; Described surfactant adds in plating solution as stabilizing agent, and stabilizing agent is conducive to bath stability, and can reduce reaction stress.
As optimal way, in described step (4), preparation plating solution is further:
(4.3) preparation plating solution A, described plating solution A be by the precious metal salt solution making and ammoniacal liquor by volume 1:1.5～1:4 mix and make.
As optimal way, in described step (4), preparation plating solution also comprises:
(4.4) preparation plating solution B, described plating solution B is described reductant solution or the volume ratio described surfactant solution that is 1:10～1:50 and the mixed liquor of reductant solution, and described reductant solution is selected from the following solution that concentration is 1-10mol/L: hydrazine hydrate aqueous solution, the hypophosphites aqueous solution, the phosphite aqueous solution, the borine aqueous solution, trimethylamine aqueous solution, formalin.
As optimal way, in described step (4), deposition reaction is further:
(4.5) by activated carrier in step (3), take out and first use washed with methanol, use again pure water rinsing, immerse afterwards in plating solution A, afterwards plating solution B is added and in plating solution A, obtain plating solution C, wherein the volume ratio of plating solution B and plating solution A is 1:1～1:3, at 40～70 ℃, in this solution, soak 20min～150min, and upgrade once described plating solution C every 25～50min, in the middle of the interval of twice renewal plating solution, in plating solution, add once described reductant solution, the described reductant solution adding and the volume ratio of plating solution B are 1:2.
For making noble metal in plating solution become nonactive being all deposited before, this method adopts low concentration, repeatedly precipitates.
Because reducing agent is unstable in plating solution, easily hydrolysis does not therefore add reducing agent when preparation plating solution A simultaneously, but now with the current when carrying out electroless deposition, is first mixed with B plating solution, then when electroless deposition, joins in A plating solution again.
Because precious metal ion in plating solution is precipitable complete about half an hour, so will upgrade primary sedimentation solution every 25～50min.Can make like this precious metal ion complete reaction in plating solution, maximization of economic benefit.
As optimal way, after electroless deposition, also comprise step:
(4.6) after electroless deposition, sample is clean by pure water rinsing, and at 25% HNO
3in solution, soak 12～24h, take out totally by pure water rinsing, dry at 120 ℃, make noble metal nano catalyst.
As mentioned above, the present invention has following beneficial effect: broken through the technical bottlenecks such as traditional infusion process, the precipitation method, vacuum coat method, successfully realized the uniform load of noble metal catalyst in wall-flow type honeycomb ceramic carrier micropore and on through type honeycomb ceramic carrier coating, and noble metal catalyst particle diameter prepared by the present invention is 50～100nm, the performance with nano particle, its specific area is large, and catalytic, reactivity improve a lot than large scale catalyst under equal conditions.In addition this technique is used precious metal salt, and price is relatively low, and plating solution also can repeatedly utilize, and therefore can significantly reduce noble metal dosage, and without techniques such as high-temperature calcinations, simple to operate, easily realize.Carrier in the method is applied widely, except carrying out the growth in situ of micropore noble metal catalyst for diesel particulate filter (DPF), also can be used for the load of through type honeycomb ceramic carrier active component in vehicle exhaust processing.
Accompanying drawing explanation
Fig. 1 is the process chart of this method;
Fig. 2 be take honeycomb ceramic filter as the prepared single platinum catalyst scanning electron microscope (SEM) photograph of carrier in embodiment 1.
Fig. 3 is the prepared single platinum nano catalyst EDX figure of embodiment 1.
Fig. 4 be take single platinum catalyst scanning electron microscope (SEM) photograph that through type ceramic honey comb prepared as carrier in embodiment 3.
Fig. 5 is the prepared single platinum nano catalyst EDX figure of embodiment 3.
Fig. 6 is the prepared single platinum nano catalyst of embodiment 4.
Fig. 7 is the prepared single platinum nano catalyst EDX figure of embodiment 4.
The specific embodiment
Below, by specific instantiation explanation embodiments of the present invention, those skilled in the art can understand other advantages of the present invention and effect easily by the disclosed content of this description.The present invention can also be implemented or be applied by the other different specific embodiment, and the every details in this description also can be based on different viewpoints and application, carries out various modifications or change not deviating under spirit of the present invention.
The process chart of Fig. 1 for using the inventive method to carry out Vehicle Exhaust Gas Cleaning Catalysts coating, as shown in the figure, the noble metal catalyst painting method of the present embodiment, comprises the following steps:
(1) support pretreatment
Described carrier is honeycomb ceramic filter or through type ceramic honey comb, and described carrier is soaked in nitric acid, cleans post-drying;
(2) carrier sensitization
The carrier of handling well in step (1) is immersed in sensitizing solution, and the solvent of described sensitizing solution is deionized water and CH
3oH, solute is SnCl
2and C
2hF
3o
2;
(3) carrier activation
By in step (2) through the carrier of sensitization, take out and first use washed with methanol, then use pure water rinsing, immerse afterwards in activating solution; Described activating solution is by AgNO
3be dissolved in wiring solution-forming in pure water, then with ammoniacal liquor, carry out titration until brown silver oxide precipitation disappears, obtain activating solution;
(4) electroless deposition
Preparation precious metal salt solution: precious metal salt solution is the solution that contains one or more soluble-salts in platinum, palladium, rhodium;
Configuration plating solution: described plating solution is that described precious metal salt solution is added to complexing agent, and described complexing agent is ammoniacal liquor;
Deposition reaction: by activated carrier in step (3), take out and first use washed with methanol, then use pure water rinsing, immerse afterwards in plating solution; In carrier immerses plating solution, start reaction and in terminal procedure, constantly add reducing agent to reacting, described reducing agent is a kind of in hydrazine hydrate, hypophosphites, phosphite, borine, trimethylamine, formaldehyde.
Embodiment 1
The present embodiment is prepared as example with single platinum catalyst, is intended to illustrate Nobel-metal catalyst preparation method disclosed by the invention.
(1) support pretreatment
Carrier is wall-flow type wall-flow type cordierite honeycomb ceramic carrier, purchased from Yixing prince's potting Co., Ltd, and Φ 127 * 118mm, 200 orders, break into pieces, get 5% nitric acid dousing carrier 24 hours for 2cm square, with pure water, clean, and dry 10 hours at 90 ℃.Stand-by.
(2) carrier sensitization
The carrier of handling well in step (1) is put into sensitizing solution, stop 60min, preparation 250ml sensitizing solution, the solvent of described sensitizing solution is deionized water and the CH of volume ratio 1:1
3oH, solute is SnCl
2and C
2hF
3o
2, SnCl
2concentration be 22mmol/L, C
2hF
3o
2concentration be 70mmol/L.
(3) carrier activation
By in step (2) through the carrier of sensitization, take out and first use washed with methanol, use again pure water rinsing, immerse afterwards in activating solution, stop 20min, described activating solution is that AgNO3 is dissolved in to the solution that is made into 35mmol/L in pure water, then with 37% ammonia spirit, carries out titration until brown silver oxide precipitation disappears, and obtains activating solution.
(4) electroless deposition
(4.1) preparation precious metal salt solution, described precious metal salt solution solute K
2ptCl
6, solvent is pure water, concentration is 1mmol/L;
(4.2) preparation surfactant solution, described surfactant solution solute is neopelex, and solvent is pure water, and concentration is 0.14mol/L;
(4.3) preparation plating solution A, described plating solution A be by the precious metal salt solution making in (4.1) and ammoniacal liquor by volume 1:1.5 mix and make; Ammoniacal liquor is the ammoniacal liquor of commercially available 37% concentration;
(4.4) preparation plating solution B, described plating solution B adds reductant solution to mix the surfactant solution making in (4.2) to make, reductant solution is 1mol/L hydrazine hydrate aqueous solution, and wherein the volume ratio of surfactant solution and reductant solution is 1:25;
(4.5) by activated carrier in step (3), take out and first use washed with methanol, use again pure water rinsing, immerse afterwards in plating solution A, plating solution B is added and in plating solution A, obtains plating solution C, wherein the volume ratio of plating solution B and plating solution A is 1:1.5, at 55 ℃, in this solution, soak 120min, in precipitation process, every 40min, upgrade a plating solution, upgrade the hydrazine hydrate aqueous solution that adds a 1mol/L in the middle of plating solution interval for twice, upgrade plating solution after 20min add hydrazine hydrate one time, the volume ratio of the hydrazine hydrate solution adding and plating solution B is 1:2.
(4.6) after electroless deposition, sample is clean by pure water rinsing, and at 25% HNO
3in solution, soak 12h, take out totally by pure water rinsing, dry at 120 ℃, make single platinum catalyst.
Embodiment 2
(1) support pretreatment
Carrier is honeycomb ceramic filter, and the nitric acid dousing carrier with 30% 24 hours is cleaned with pure water, dries 10 hours at 120 ℃.
(2) carrier sensitization
The carrier of handling well in step (1) is put into sensitizing solution, stop 90min, the solvent of described sensitizing solution is deionized water and the CH of volume ratio 1:1
3oH, solute is SnCl
2and C
2hF
3o
2, SnCl
2concentration be 27mmol/L, C
2hF
3o
2concentration be 80mmol/L.
(3) carrier activation
By in step (2) through the carrier of sensitization, take out and first use washed with methanol, then use pure water rinsing, immerse afterwards in activating solution, stop 30min, described activating solution is by AgNO
3be dissolved in the solution that is made into 40mmol/L in pure water, then with 37% ammoniacal liquor, carry out titration until brown silver oxide precipitation disappears, obtain activating solution.
(4) electroless deposition
(4.1) preparation precious metal salt solution, described precious metal salt solution solute is Pd (NH
3)
4cl
2, solvent is pure water, concentration is 5mmol/L;
(4.2) preparation surfactant solution, described surfactant solution solute is neopelex, and solvent is pure water, and concentration is 0.3mol/L;
(4.3) preparation plating solution A, described plating solution A be by the precious metal salt solution making in (4.1) and ammoniacal liquor by volume 1:2 mix and make; Ammoniacal liquor is the ammoniacal liquor of commercially available 37% concentration;
(4.4) preparation plating solution B, described plating solution B adds reducing agent to make the surfactant solution making in (4.2), and reducing agent is NaH
2pO
2h
2the O aqueous solution, concentration is 7.5mol/L, wherein the volume ratio of reductant solution and surfactant is 50:1;
(4.5) by activated carrier in step (3), take out and first use washed with methanol, use again pure water rinsing, immerse afterwards in plating solution A, afterwards plating solution B is added in plating solution A, wherein the volume ratio of plating solution B and plating solution A is 1:3, at 70 ℃, in this solution, soak 150min, in precipitation process, every 40min, will upgrade primary sedimentation solution, upgrade in the middle of plating solution interval, need in plating solution, add 7.5mol/L NaH one time for twice
2pO
2h
2the O aqueous solution, upgrade plating solution after 20min add NaH one time
2pO
2h
2the O aqueous solution, the NaH adding
2pO
2h
2the volume ratio of O solution and plating solution B is 1:2.
(4.6) after electroless deposition, sample is clean by pure water rinsing, and at 25% HNO
3in solution, soak 24h, take out totally by pure water rinsing, dry at 120 ℃, make single palladium nanocatalyst.
Embodiment 3
(1) support pretreatment
Carrier is through type ceramic honey comb, and the nitric acid dousing carrier with 5% 24 hours is cleaned with pure water, dries 10 hours at 90 ℃.
(2) carrier sensitization
The carrier of handling well in step (1) is put into sensitizing solution, stop 30min, the solvent of described sensitizing solution is deionized water and the CH of volume ratio 1:1
3oH, solute is SnCl
2and C
2hF
3o
2, SnCl
2concentration be 17mmol/L, C
2hF
3o
2concentration be 60mmol/L.
(3) carrier activation
By in step (2) through the carrier of sensitization, take out and first use washed with methanol, then use pure water rinsing, immerse afterwards in activating solution, stop 20min, described activating solution is by AgNO
3be dissolved in the solution that is made into 30mmol/L in pure water, then with 37% ammoniacal liquor, carry out titration until brown silver oxide precipitation disappears, obtain activating solution.
(4) electroless deposition
(4.1) preparation precious metal salt solution, described precious metal salt solution solute is Pt (NH
3)
2(NO
2)
2, solvent is pure water, concentration is 0.1mmol/L;
(4.2) preparation surfactant solution, described surfactant solution solute is neopelex, and solvent is pure water, and concentration is 0.1mol/L;
(4.3) preparation plating solution A, described plating solution A be by the precious metal salt solution making in (4.1) and ammoniacal liquor by volume 1:2 mix and make; Ammoniacal liquor is the ammoniacal liquor of commercially available 37% concentration;
(4.4) preparation plating solution B, described plating solution B adds reducing agent to make the surfactant solution making in (4.2), and reducing agent is Na
2hPO
35H
2o, concentration is 8mol/L, wherein the volume ratio of reductant solution and surfactant is 15:1;
(4.5) by activated carrier in step (3), take out and first use washed with methanol, use again pure water rinsing, immerse afterwards in plating solution A, afterwards plating solution B is added in plating solution A, wherein the volume ratio of plating solution B and plating solution A is 1:1, at 40 ℃, in this solution, soaks 80min, in precipitation process, reducing agent is 8mol/L Na
2hPO
35H
2o solution, and need to upgrade primary sedimentation solution every 30min, upgrade in the middle of plating solution interval, need in plating solution, add 8mol/L Na one time for twice
2hPO
35H
2the O aqueous solution, the Na adding
2hPO
35H
2the volume ratio of the O aqueous solution and plating solution B is 1:2.
(4.6) after electroless deposition, sample is clean by pure water rinsing, and at 25% HNO
3in solution, soak 12h, take out totally by pure water rinsing, dry at 120 ℃, make single platinum noble metals nanocatalyst.
Embodiment 4
(1) support pretreatment
Carrier is honeycomb ceramic filter, and the nitric acid dousing carrier with 10% 24 hours is cleaned with pure water, dries 10 hours at 100 ℃.
(2) carrier sensitization
The carrier of handling well in step (1) is put into sensitizing solution, stop 50min, the solvent of described sensitizing solution is deionized water and the CH of volume ratio 1:1
3oH, solute is SnCl
2and C
2hF
3o
2, SnCl
2concentration be 20mmol/L, C
2hF
3o
2concentration be 65mmol/L.
(3) carrier activation
By in step (2) through the carrier of sensitization, take out and first use washed with methanol, then use pure water rinsing, immerse afterwards in activating solution, stop 18min, described activating solution is by AgNO
3be dissolved in the solution that is made into 35mmol/L in pure water, then with 37% ammoniacal liquor, carry out titration until brown silver oxide precipitation disappears, obtain activating solution.
(4) electroless deposition
(4.1) preparation precious metal salt solution, described precious metal salt solution solute is Na
2pt (OH)
6, solvent is pure water, concentration is 2mmol/L;
(4.2) preparation surfactant solution, described surfactant solution solute is neopelex, and solvent is pure water, and concentration is 0.01mol/L;
(4.3) preparation plating solution A, described plating solution A be by the precious metal salt solution making in (4.1) and ammoniacal liquor by volume 1:3 mix and make; Ammoniacal liquor is the ammoniacal liquor of commercially available 37% concentration;
(4.4) preparation plating solution B, described plating solution B adds reducing agent to make the surfactant solution making in (4.2), and reducing agent is 7mol/L NaBH
4the aqueous solution, wherein the volume ratio of reductant solution and surfactant solution is 28:1;
(4.5) by activated carrier in step (3), take out and first use washed with methanol, then use pure water rinsing, immerse afterwards in plating solution A, afterwards plating solution B is added in plating solution A, wherein the volume ratio of plating solution B and plating solution A is 1:1.6, soaks 100min, in precipitation process at 50 ℃ in this solution, in precipitation process, every 50min, to upgrade primary sedimentation solution, upgrade in the middle of plating solution interval, need in plating solution, add 7mol/LNaBH one time
4the aqueous solution, the NaBH adding
4the volume ratio of the aqueous solution and plating solution B is 1:2.
(4.6) after electroless deposition, sample is clean by pure water rinsing, and at 25% HNO
3in solution, soak 14h, take out totally by pure water rinsing, dry at 120 ℃, make single platinum nano catalyst.
Embodiment 5
(1) support pretreatment
Carrier is honeycomb ceramic filter or through type ceramic honey comb, and the nitric acid dousing carrier with 12% 24 hours is cleaned with pure water, dries 10 hours at 110 ℃.
(2) carrier sensitization
The carrier of handling well in step (1) is put into sensitizing solution, stop 70min, the solvent of described sensitizing solution is deionized water and the CH of volume ratio 1:1
3oH, solute is SnCl
2and C
2hF
3o
2, SnCl
2concentration be 25mmol/L, C
2hF
3o
2concentration be 70mmol/L.
(3) carrier activation
By in step (2) through the carrier of sensitization, take out and first use washed with methanol, then use pure water rinsing, immerse afterwards in activating solution, stop 25min, described activating solution is by AgNO
3be dissolved in the solution that is made into 36mmol/L in pure water, then with 37% ammoniacal liquor, carry out titration until brown silver oxide precipitation disappears, obtain activating solution.
(4) electroless deposition
(4.1) preparation precious metal salt solution, described precious metal salt solution solute is PdCl
2, solvent is pure water, concentration is 2.5mmol/L;
(4.2) preparation surfactant solution, described surfactant solution solute is neopelex, and solvent is pure water, and concentration is 0.11mol/L;
(4.3) preparation plating solution A, described plating solution A be by the precious metal salt solution making in (4.1) and ammoniacal liquor by volume 1:2.5 mix and make; Ammoniacal liquor is the ammoniacal liquor of commercially available 37% concentration;
(4.4) preparation plating solution B, described plating solution B adds reducing agent to make the surfactant solution making in (4.2), the formalin that reducing agent is 2mol/L, wherein the volume ratio of reducing agent and surfactant solution is 30:1.
(4.5) by activated carrier in step (3), take out and first use washed with methanol, then use pure water rinsing, immerse afterwards in plating solution A, afterwards plating solution B is added in plating solution A, wherein the volume ratio of plating solution B and plating solution A is 1:1.4, soaks 90min at 60 ℃, in precipitation process in this solution, every 40min, to upgrade primary sedimentation solution, upgrade for twice in the middle of plating solution interval, to the formalin that adds a 2mol/L in plating solution, the volume ratio of the formalin adding and plating solution B is 1:2.
(4.6) after electroless deposition, sample is clean by pure water rinsing, and at 25% HNO
3in solution, soak 10h, take out totally by pure water rinsing, dry at 120 ℃, make noble metal nano catalyst.
Embodiment 6
(1) support pretreatment
Carrier is honeycomb ceramic filter, and the nitric acid dousing carrier with 15% 24 hours is cleaned with pure water, dries 10 hours at 120 ℃.
(2) carrier sensitization
The carrier of handling well in step (1) is put into sensitizing solution, stop 80min, the solvent of described sensitizing solution is deionized water and the CH of volume ratio 1:1
3oH, solute is SnCl
2and C
2hF
3o
2, SnCl
2concentration be 25mmol/L, C
2hF
3o
2concentration be 80mmol/L.
(3) carrier activation
By in step (2) through the carrier of sensitization, take out and first use washed with methanol, then use pure water rinsing, immerse afterwards in activating solution, stop 22min, described activating solution is by AgNO
3be dissolved in the solution that is made into 38mmol/L in pure water, then with 37% ammoniacal liquor, carry out titration until brown silver oxide precipitation disappears, obtain activating solution.
(4) electroless deposition
(4.1) preparation precious metal salt solution, described precious metal salt solution solute is Pd (NH
3)
4cl
2, solvent is pure water, concentration is 2mmol/L;
(4.2) preparation surfactant solution, described surfactant solution solute is neopelex, and solvent is pure water, and concentration is 0.3mol/L;
(4.3) preparation plating solution A, described plating solution A be by the precious metal salt solution making in (4.1) and ammoniacal liquor by volume 1:4 mix and make; Ammoniacal liquor is the ammoniacal liquor of commercially available 37% concentration;
(4.4) preparation plating solution B, described plating solution B adds reducing agent to make the surfactant solution making in (4.2), the trimethylamine aqueous solution that reducing agent is 2mol/L, wherein the volume ratio of reducing agent and surfactant solution is 10:1;
(4.5) by activated carrier in step (3), take out and first use washed with methanol, use again pure water rinsing, immerse afterwards in plating solution A, afterwards plating solution B is added in plating solution A, wherein the volume ratio of plating solution B and plating solution A is 1:2, at 66 ℃, in this solution, soak 150min, in precipitation process, every 40min, to upgrade primary sedimentation solution, upgrade in the middle of plating solution interval, need to be to the trimethylamine aqueous solution that adds a 2mol/L in plating solution, the volume ratio of the trimethylamine aqueous solution adding and plating solution B is 1:2.
(4.6) after electroless deposition, sample is clean by pure water rinsing, and at 25% HNO
3in solution, soak 18h, take out totally by pure water rinsing, dry at 120 ℃, make single palladium nanocatalyst.
Embodiment 7
(1) support pretreatment
Carrier is through type ceramic honey comb, and the nitric acid dousing carrier with 25% 24 hours is cleaned with pure water, dries 10 hours at 100 ℃.
(2) carrier sensitization
The carrier of handling well in step (1) is put into sensitizing solution, stop 70min, the solvent of described sensitizing solution is deionized water and the CH of volume ratio 1:1
3oH, solute is SnCl
2and C
2hF
3o
2, SnCl
2concentration be 20mmol/L, C
2hF
3o
2concentration be 63mmol/L.
(3) carrier activation
By in step (2) through the carrier of sensitization, take out and first use washed with methanol, then use pure water rinsing, immerse afterwards in activating solution, stop 10min, described activating solution is by AgNO
3be dissolved in the solution that is made into 40mmol/L in pure water, then with 37% ammoniacal liquor, carry out titration until brown silver oxide precipitation disappears, obtain activating solution.
(4) electroless deposition
(4.1) preparation precious metal salt solution, described precious metal salt solution solute is Na
3rhCl
6, solvent is pure water, concentration is 10mmol/L;
(4.3) preparation plating solution A, described plating solution A be by the precious metal salt solution making in (4.1) and ammoniacal liquor by volume 1:2 mix and make; Ammoniacal liquor is the ammoniacal liquor of commercially available 37% concentration;
(4.4) preparation plating solution B, described plating solution B is reductant solution, the hydrazine hydrate aqueous solution that reducing agent is 1mol/L;
(4.5), by activated carrier in step (3), take out and first use washed with methanol, then use pure water rinsing, immerse afterwards in plating solution A, afterwards plating solution B is added in plating solution A, wherein the volume ratio of plating solution B and plating solution A is 1:2, at 62 ℃, in this solution, soak 20min, carry out electroless deposition.
(4.6) after electroless deposition, sample is clean by pure water rinsing, and at 25% HNO
3in solution, soak 12h, take out totally by pure water rinsing, dry at 120 ℃, make single rhodium nanocatalyst.
Fig. 2 be take honeycomb ceramic filter as the prepared single platinum catalyst surface sweeping Electronic Speculum figure of carrier in embodiment 1, use the K of 1mmol/L
2ptCl
6as noble metal precipitation solution, hydrazine hydrate is reducing agent.A) be wherein the SEM figure of blank carrier, b), c), d) be catalyst granules SEM figure under different scale, the noble metal catalyst that as we can see from the figure prepared by the present invention is evenly distributed on honeycomb ceramic filter micropore hole wall surface, decentralization is high, density is large, and single Pt catalyst granule particle diameter is distributed as 50～100nm.
Fig. 3 is the prepared single platinum nano catalyst EDX figure of embodiment 1, and in figure, the platinum load capacity of gauge point is 7.44% (w/w), and the load capacity of zonule platinum is 1.08% (w/w).
Fig. 4 be take single platinum catalyst scanning electron microscope (SEM) photograph that through type ceramic honey comb prepared as carrier in embodiment 3, use the Pt (NH of 0.1mmol/L
3)
2(NO
2)
2as noble metal precipitation solution, Na
2hPO
35H
2o is reducing agent.Wherein scheming is a) the SEM figure of 2.48 * 1.78 μ m, figure b) be the SEM image after amplifying in white box in a), platinum nano catalyst distributes at through type honeycomb ceramic carrier duct surface uniform, and density is larger, one-tenth popped rice shape, particle size range 50～150nm.
Fig. 5 is the prepared single platinum nano catalyst EDX figure of embodiment 3, and in figure, in marked region, the load capacity of platinum is 13.25% (w/w).
Fig. 6 is the prepared single platinum nano catalyst of embodiment 4, uses the Na of 2mmol/L
2pt (OH)
6as noble metal precipitation solution, NaBH
4for reducing agent.Figure is a) empty carrier, c) and d) be respectively the SEM figure after the load platinum catalyst of different scale b),, Pt nanoparticle distributes very intensive at honeycomb ceramic filter hole wall surface, and formed platinum cluster structure (figure d), greatly increased the contact area of soot particulate and catalyst.
Fig. 7 is the prepared single platinum nano catalyst EDX figure of embodiment 4, and in figure, in marked region, the load capacity of platinum is 14.85% (w/w).
Above-described embodiment is illustrative principle of the present invention and effect thereof only, but not for limiting the present invention.Any person skilled in the art scholar all can, under spirit of the present invention and category, modify or change above-described embodiment.Therefore, such as in affiliated technical field, have and conventionally know that the knowledgeable, not departing from all equivalence modifications that complete under disclosed spirit and technological thought or changing, must be contained by claim of the present invention.
Claims (10)
1. a Vehicle Exhaust Gas Cleaning Catalysts painting method, is characterized in that, comprises the steps:
(1) support pretreatment
Described carrier is honeycomb ceramic filter or through type ceramic honey comb, and described carrier is soaked in nitric acid, cleans post-drying;
(2) carrier sensitization
The carrier of handling well in step (1) is immersed in sensitizing solution, and the solvent of described sensitizing solution is deionized water and CH
3oH, solute is SnCl
2and C
2hF
3o
2;
(3) carrier activation
By in step (2) through the carrier of sensitization, take out and first use washed with methanol, then use pure water rinsing, immerse afterwards in activating solution; Described activating solution is by AgNO
3be dissolved in wiring solution-forming in pure water, then with ammoniacal liquor, carry out titration until brown silver oxide precipitation disappears, obtain activating solution;
(4) electroless deposition
Preparation precious metal salt solution: precious metal salt solution is the aqueous solution that contains one or more soluble-salts in platinum, palladium, rhodium;
Configuration plating solution: described plating solution is that described precious metal salt solution is added to complexing agent, and described complexing agent is ammoniacal liquor;
Deposition reaction: by activated carrier in step (3), take out and first use washed with methanol, then use pure water rinsing, immerse afterwards in plating solution; In carrier immerses plating solution, start reaction and in terminal procedure, constantly add reducing agent to reacting, described reducing agent is a kind of in hydrazine hydrate, hypophosphites, phosphite, borine, trimethylamine, formaldehyde.
2. Vehicle Exhaust Gas Cleaning Catalysts painting method according to claim 1, it is characterized in that described step (1) support pretreatment is further: carrier is honeycomb ceramic filter or through type ceramic honey comb, nitric acid dousing carrier with 5～30% 24 hours, with pure water, clean, at 90～120 ℃, dry 10 hours.
3. Vehicle Exhaust Gas Cleaning Catalysts painting method according to claim 1, it is characterized in that described step (2) carrier sensitization is further: the carrier of handling well in step (1) is put into sensitizing solution, stop 30～90min, the solvent of described sensitizing solution is deionized water and the CH of volume ratio 1:1
3oH, solute is SnCl
2and C
2hF
3o
2, SnCl
2concentration be 17～27mmol/L, C
2hF
3o
2concentration be 60～80mmol/L.
4. Vehicle Exhaust Gas Cleaning Catalysts painting method according to claim 1, it is characterized in that described step (3) carrier activation is further: by step (2) through the carrier of sensitization, take out and first use washed with methanol, use again pure water rinsing, immerse afterwards in activating solution, stop 10～30min, described activating solution is by AgNO
3be dissolved in the solution that is made into 30～40mmol/L in pure water, then with 37% ammoniacal liquor, carry out titration until brown silver oxide precipitation disappears, obtain activating solution.
5. Vehicle Exhaust Gas Cleaning Catalysts painting method according to claim 1, is characterized in that in described step (4), preparation precious metal salt solution is further:
(4.1) preparation precious metal salt solution, described precious metal salt solution solute is one or more soluble-salts that contain platinum, palladium, rhodium, and solvent is pure water, and concentration is 0.1～10mmol/L.
6. Vehicle Exhaust Gas Cleaning Catalysts painting method according to claim 1, is characterized in that before carrier immerses plating solution, comprising in described step (4):
(4.2) preparation surfactant solution, described surfactant solution solute is neopelex, and solvent is pure water, and concentration is 0.01～0.3mol/L.
7. Vehicle Exhaust Gas Cleaning Catalysts painting method according to claim 6, is characterized in that in described step (4), preparation plating solution is further:
(4.3) preparation plating solution A, described plating solution A be by the precious metal salt solution making and ammoniacal liquor by volume 1:1.5～1:4 mix and make.
8. Vehicle Exhaust Gas Cleaning Catalysts painting method according to claim 7, is characterized in that in described step (4), preparation plating solution also comprises:
(4.4) preparation plating solution B, described plating solution B is described reductant solution or the volume ratio described surfactant solution that is 1:10～1:50 and the mixed liquor of reductant solution, and described reductant solution is selected from the following solution that concentration is 1-10mol/L: hydrazine hydrate aqueous solution, the hypophosphites aqueous solution, the phosphite aqueous solution, the borine aqueous solution, trimethylamine aqueous solution, formalin.
9. Vehicle Exhaust Gas Cleaning Catalysts painting method according to claim 8, is characterized in that in described step (4), deposition reaction is further:
(4.5) by activated carrier in step (3), take out and first use washed with methanol, use again pure water rinsing, immerse afterwards in plating solution A, afterwards plating solution B is added and in plating solution A, obtain plating solution C, wherein the volume ratio of plating solution B and plating solution A is 1:1～1:3, at 40～70 ℃, in this solution, soak 20min～150min, and upgrade once described plating solution C every 25～50min, in the middle of the interval of twice renewal plating solution, in plating solution, add once described reductant solution, the described reductant solution adding and the volume ratio of plating solution B are 1:2.
10. Vehicle Exhaust Gas Cleaning Catalysts painting method according to claim 1, is characterized in that after electroless deposition, also comprises step:
(4.6) after electroless deposition, sample is clean by pure water rinsing, and at 25% HNO
3in solution, soak 12～24h, take out totally by pure water rinsing, dry at 120 ℃, make noble metal nano catalyst.
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Cited By (3)
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| CN105664939A (en) * | 2016-01-06 | 2016-06-15 | 中自环保科技股份有限公司 | Catalytic converter for treating motorcycle tail gas and preparation method thereof |
| CN110833831A (en) * | 2019-11-07 | 2020-02-25 | 上海纳米技术及应用国家工程研究中心有限公司 | Preparation method of chromium-cobalt-based nitric oxide normal-temperature normal-pressure catalyst, product and application thereof |
| CN114959665A (en) * | 2022-04-25 | 2022-08-30 | 金川集团股份有限公司 | Preparation method of colloidal palladium activation solution for electroless copper plating of printed circuit board |
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| EP1994982A1 (en) * | 2007-03-30 | 2008-11-26 | Fujifilm Corporation | Catalyst body which uses an anodized layer |
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| CN105664939A (en) * | 2016-01-06 | 2016-06-15 | 中自环保科技股份有限公司 | Catalytic converter for treating motorcycle tail gas and preparation method thereof |
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| CN110833831A (en) * | 2019-11-07 | 2020-02-25 | 上海纳米技术及应用国家工程研究中心有限公司 | Preparation method of chromium-cobalt-based nitric oxide normal-temperature normal-pressure catalyst, product and application thereof |
| CN114959665A (en) * | 2022-04-25 | 2022-08-30 | 金川集团股份有限公司 | Preparation method of colloidal palladium activation solution for electroless copper plating of printed circuit board |
| CN114959665B (en) * | 2022-04-25 | 2024-03-01 | 金川集团股份有限公司 | Preparation method of colloid palladium activating solution for electroless copper plating of printed circuit board |
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|---|---|
| CN103977842B (en) | 2015-12-02 |
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