CN100343491C - Electric direct heating type three-efficiency purifier for automobile exhaust - Google Patents

Electric direct heating type three-efficiency purifier for automobile exhaust Download PDF

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CN100343491C
CN100343491C CNB2004100206528A CN200410020652A CN100343491C CN 100343491 C CN100343491 C CN 100343491C CN B2004100206528 A CNB2004100206528 A CN B2004100206528A CN 200410020652 A CN200410020652 A CN 200410020652A CN 100343491 C CN100343491 C CN 100343491C
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heating
silicon carbide
catalyst
electrically direct
carrier
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CN1704565A (en
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张劲松
杨振明
曹小明
刘强
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Institute of Metal Research of CAS
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    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02ATECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
    • Y02A50/00TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
    • Y02A50/20Air quality improvement or preservation, e.g. vehicle emission control or emission reduction by using catalytic converters
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02TCLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO TRANSPORTATION
    • Y02T10/00Road transport of goods or passengers
    • Y02T10/10Internal combustion engine [ICE] based vehicles
    • Y02T10/12Improving ICE efficiencies

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Abstract

The present invention discloses an electric direct heating type automobile tail gas purifying device which comprises a power supply, an electric direct heating type tail gas purifier and a honeycomb ceramic main catalyst, wherein the electric direct heating type tail gas purifier and the honeycomb ceramic main catalyst are arranged in a purifier packing outer shell connected with an exhausting pipe, and the electric direct heating type tail gas purifier is composed of a foam ceramic electric direct heating type catalyst unit. The foam ceramic electric direct heating type catalyst unit is composed of a triple-effect tail gas purifying catalyst which uses conductive silicon carbide foam ceramics as a carrier, graphite electrode bases arranged at both ends of the conductive silicon carbide foam ceramics carrier and a metal electrode respectively connected with the two graphite electrode bases. The power supply can supply power for the conductive silicon carbide foam ceramics carrier by the metal electrode. The catalyst of the present invention has the characteristics of good and controllable electrical conductivity, good effect, simple automobile improvement and low cost. The early purification of pollutants discharged at the cold starting period of the automobile can be realized, and the discharging result can reach strict purification standards.

Description

The device that a kind of vehicle exhaust electrically direct-heating triple effect purifies
Technical field
The present invention relates to the device that a kind of vehicle tail gas triple effect purifies, specifically a kind of be catalyst carrier with the conductive silicon carbide foam ceramic, can effectively eliminate cold-starting automobile and pollute, have the electrically direct-heating purification plant of intelligent control system.
Background technique
Along with the increase of economic development and automobile pollution, the environmental pollution that vehicle exhaust causes has become serious social concern.For better controlling tail gas pollution, China has worked out a series of emission control regulations.The rules that current China carries out in most of area are equivalent to the EU-I standard, and the EU-II standard of will carrying out in an all-round way in 1 day July in 2004.
Compare with the advance of purification standard, the present situation of China's automobile industry and purification technics but allows of no optimist: automobile making technology and production line are relatively backward on the one hand, unless carry out huge fund input, otherwise be difficult to the automobile of a large amount of production low emissions; On the other hand, because the leading position of external tail gas clean-up technology and patent, exhaust purifier of China or import or the production of employing foreign technology, thus under one's control for a long time in the tail gas clean-up field.Therefore, to have new type purification technology independent intellectual property right, that can be complementary with China auto manufacturing present situation be extremely urgent task in exploitation.
Studies show that installing under the situation of common triple effect auto-exhaust catalyst, about 90% pollutant emission concentrates on the cold start-up stage in the vehicle behavior test process, just in the automobile starting 200 seconds.Therefore, further reduce pollutant emission, just must reduce the discharge amount in cold start-up stage, corresponding with it technology is exactly the cold start-up purification technics.
The exhaust temperature that adopts Electric heating to improve the cold start-up stage is a kind of effective cold start-up technology, considerable patent and research article is arranged abroad, but do not appear in the newspapers as yet at home.Comprehensive various document, current as can be known electric-heating technology has following characteristics: be the power supply of electric heating purifier with high-tension power supply unit 1., be generally direct current or the ac power supply of 24V or 36V; 2. all adopt the honeycomb metallic carrier as conducting medium; 3. for reducing thermal capacitance, the volume ratio of electric heater is less, generally between 50~100ml; 4. on the metal electric heater catalytically active coatings is arranged, the content of noble metal active constituent element can reach 5/L than higher, can carry out part to tail gas and purify in the energising heating.
Adopt Electric heating can obviously reduce the pollutant discharge amount in cold start-up stage, make the emission test result reach higher standard.But also there is following significant disadvantages in existing electric-heating technology: 1. power supply unit complexity, need carry out essence transformation or additional second source to existing vehicle power, and the automobile making cost will be increased substantially; 2. the oxidative stability of honeycomb metallic carrier is relatively poor, and working life is short; 3. owing to the greatest differences of expansion coefficient, adhesive strength is lower between aluminium oxide active coating and the metallic carrier, thereby under the service condition of this temperature fluctuation very high frequency of automobile exhaust, coating is peeled off from carrier surface easily, causes purifying ability to descend; 4. the electric heater volume is little, so in the cold start-up process, the catalytic purification of electric heater can only play booster action.Because the existence of above-mentioned defective, electric heating purification technics major part is in the laboratory research stage, really moves towards market seldom.
Summary of the invention
Defective at traditional electrical heating purification technics, the object of the present invention is to provide a kind of device of new electrically direct-heating purifying automobile tail gas, equip this device and can eliminate the pollutant of automobile in a large number, make the vehicle behavior test result can satisfy higher antipollution law in the discharging of cold start-up stage.
For achieving the above object, the technical solution used in the present invention is:
The device that a kind of vehicle exhaust electrically direct-heating triple effect purifies, comprise power supply, the ceramic honey comb primary catalyst, the ceramic honey comb primary catalyst is installed in the purifier package casing that links to each other with the petrol engine outlet pipe, also comprise electrically direct-heating exhaust purifier and automatically controlled part, wherein the electrically direct-heating exhaust purifier is in the ceramic honey comb primary catalyst is installed on the purifier package casing that links to each other with the petrol engine outlet pipe, constitute by foamed ceramics electrically direct-heating catalyst elements, foamed ceramics electrically direct-heating catalyst elements is for being the three-way catalyst of carrier with the conductive silicon carbide foam ceramic, be installed on the graphite electrode pedestal at conductive silicon carbide foam ceramic carrier two ends, constitute with the metal film that two graphite electrode pedestals link to each other respectively, power supply constitutes the loop by metal film and conductive silicon carbide foam ceramic carrier, is the power supply of conductive silicon carbide foam ceramic carrier; Automatically controlled part links to each other with electrically direct-heating exhaust purifier electrode.
Described automatically controlled part is made up of control unit and (PCC) power, described control unit is powered by the power supply processing unit, comprise frequency signal processing unit, water temperature signal processing unit, governor circuit, wherein: the frequency signal processing unit is core with the monostable flipflop, the frequency signal that input termination automobile rotational speed sensor produces, its output signal is connected to an input end of governor circuit; The water temperature signal processing unit is a core with first triode, and its base stage connects the water temperature signal that the automobile cooling-water temperature sensor produces, and emitter is to another input end of governor circuit; Described governor circuit is made up of the first~two comparator, NAND gate circuit and timer, the first~two comparator is connected to the linear voltage of frequency signal processing unit processes and the amplification voltage signal of water temperature signal processing unit respectively, its output terminal links to each other with timer through NAND gate circuit, second triode successively, and timer output end is connected to (PCC) power; Described (PCC) power is that secondary promotes structure, and its output terminal links to each other with the electrode of load; In addition, the output terminal of first contactor of (PCC) power links to each other with the output terminal of the second comparator U4 of governor circuit.
Described (PCC) power is made up of the 3rd triode, first contactor and second contactor, and wherein the 3rd triode input signal is the timer output end signal, and its emitter is connected to the secondary contactor, and the afterbody contactor connects load; Its current collection level all links to each other with 12V with the secondary contactor.
Described power supply processing unit adopts the three-terminal voltage-stabilizing module to provide 9V power supply to governor circuit, and the three-terminal voltage-stabilizing module input meets 12V through the lock switch.
Described load is the electrically direct-heating exhaust purifier.
Described metal film is connected on the graphite base by brazing mode.
Described electrically direct-heating exhaust purifier is one or at least two foamed ceramics electrically direct-heating catalyst elements compositions, when purifier is made of two or two above unit, it between each unit relation in parallel, be linked to be an integral body by the mode of welding between the electrode, the volume of electrically direct-heating exhaust purifier is controlled between 100~400ml, and THICKNESS CONTROL is in 10~50mm scope.
Described three-way catalyst is a carrier with the conductive silicon carbide foam ceramic, and catalyzer floating coat content is between 100~150g/L catalyst carrier, and the weight ratio of each material is in the coating: Al 2O 3: CeO 2: La 2O 3: BaO=(55~80): (25~35): (1~5): (2~10), the weight ratio of Pt and Rh is 5 in the catalyzer: (1~0.1), Pt and Rh total content are 2~5g/L catalyst carrier, described foam silicon carbon pottery is the mark meter by weight, its composition is made up of 90%~98% silicon carbide and 10%~2% silicon, and its resistance is between 50~70m Ω.
Described foam silicon carbide ceramics is an elementary cell with polygonal closed loop, and each elementary cell is interconnected to form three-dimensional networks; Constitute relative density 〉=99% of the ceramic muscle of polygonal closed loop unit, average grain size is at 50nm~10 μ m.
The preparation process of described three-way catalyst is specific as follows:
1. be to soak 5~10 minutes in the NaOH of 2~5M or the KOH solution conductive silicon carbide foam ceramic in concentration, remove its surperficial impurity such as greasy dirt, afterwards water clean, oven dry in 1~4 hour in 100~150 ℃ of air atmospheres again;
2. get γ-Al 2O 3110~160 parts, CeO 250~70 parts, La 2O 34~20 parts of 2~10 parts, BaO add 500 parts in water after the mixing, ball milling obtained coating paste in 2~4 hours;
3. foamed ceramics was flooded in slurry 2~5 minutes, blow away unnecessary slurry, placed 100~150 ℃ of air atmospheres then dry 20~30 minutes, flood slip after the cooling once more with pressurized air.So repeat repeatedly, until making coating levels reach 100~150g/L catalyst carrier, at last in 450~500 ℃ of roastings 4~5 hours, the coating preparation finishes;
4. get H 2PtCl 610~15 parts, RhCl 30.5~2 parts, add water and be mixed with mixed solution for 500 parts, the foamed ceramics that will have active coating then vacuum impregnation 10~15 minutes in solution, the pottery after will flooding is afterwards dried in baking oven, 100~150 ℃ of oven temperatures, 20~30 minutes time; Sample after the oven dry 450~500 ℃ of reductase 12~4 hour in hydrogen atmosphere, can obtain with the conductive silicon carbide foam ceramic is the vehicle tail gas triple effect catalyzer of carrier.
Compared with prior art, the present invention has more following beneficial effect:
1. adopting conductive silicon carbide foam ceramic is catalyst carrier, and the resistance of this foamed ceramic carrier can be adjusted as required flexibly.
2. the active catalytic coating in the preparation of conductive silicon carbide foam ceramic carrier surface combines closely difficult drop-off, long service life with carrier.
3. this device adopts Vehicular accumulator cell as power supply, need not increase second source, and the automobile improvement scope is little, and cost is low.
4. control system intellectuality can be adjusted heated condition according to conditions such as water temperature, engine speed in good time.
5. adopt the mode of soldering to prepare metal film, it is minimum that contact resistance is reduced to, and improved energy utilization efficiency.
6. the electrically direct-heating exhaust purifier is formed in parallel by one or several electrically direct-heating catalyst elements, and total volume is between 100ml~400ml, and this structure can guarantee the working life of purifier, can reach good purifying effect again.
7. adopt electrically direct-heating tail gas clean-up intelligent control unit, this unit can be from control unit receiving gate lock-switch signal, engine speed and cooling water water temperature signal, and the state of whether switching on from main control electrically direct-heating system according to above-mentioned signal; In addition, this control unit can freely be set the electrically direct-heating upper limit of current"on"time.
Description of drawings
Fig. 1 is an electrically direct-heating exhaust gas cleaner schematic representation.
Fig. 2 is the schematic representation of a foamed ceramics electrically direct-heating catalyst elements.
Fig. 3 is an electric control part parallel circuit schematic diagram of the present invention.
Embodiment
Preparation active oxidation aluminium paint on the conductive silicon carbide foam ceramic carrier, and dipping noble metal active constituent element can obtain the foamed ceramics three-way catalyst, employing is according to " foam silicon carbon stupalith of a kind of high strength dense and preparation method thereof " (Metal Inst., Chinese Academy of Sciences's application, application number 03134039.3) conductive silicon carbide foam ceramic of being done is a catalyst carrier, and its resistance is controlled between 50~70m Ω.
Its preparation process is specific as follows:
1. be to soak 5~10 minutes in the NaOH of 2~5M or the KOH solution conductive silicon carbide foam ceramic in concentration, remove its surperficial impurity such as greasy dirt, afterwards water clean, oven dry in 1~4 hour in 100~150 ℃ of air atmospheres again;
2. get γ-Al 2O 3110~160 parts, CeO 250~70 parts, La 2O 34~20 parts of 2~10 parts, BaO add 500 parts in water after the mixing, ball milling obtained coating paste in 2~4 hours;
3. foamed ceramics is flooded in slurry, blow away unnecessary slurry, placed 100~150 ℃ of air atmospheres then dry 20~30 minutes, flood slip after the cooling once more with pressurized air.So repeat repeatedly, until making coating levels reach 100~150g/ (L catalyzer), at last in 450~500 ℃ of roastings 4~5 hours, the coating preparation finishes;
4. get H 2PtCl 610~15 parts, RhCl 30.5~2 parts, add water and be mixed with mixed solution for 500 parts, the foamed ceramics that will have active coating then vacuum impregnation 10~15 minutes in solution, the pottery after will flooding is afterwards dried in baking oven, 100~150 ℃ of oven temperatures, 20~30 minutes time; Sample after the oven dry 450~500 ℃ of reductase 12~4 hour in hydrogen atmosphere, can obtain with the conductive silicon carbide foam ceramic is the vehicle tail gas triple effect catalyzer of carrier.
Catalyzer floating coat content is between 100~150g/ (L catalyzer), and the weight ratio of each material is in the coating: Al 2O 3: CeO 2: La 2O 3: BaO=(55~80): (25~35): (1~5): (2~10);
The weight ratio of PT and Rh is 5: (1~0.1), total content are 2~5g/ (L catalyzer).
5. select catalyst elements after one or more preparations finish for use according to the specific requirement of the resistance of catalyzer and bullion content, if adopt a plurality of catalyst elements, it then between each unit relation in parallel, and connect into an integral body by the mode of weld plate on metal film, can obtain required electrically direct-heating exhaust purifier after the thick corrosion resistant plate encapsulation of 2mm.
Shown in Fig. 1~2, the electrically direct-heating exhaust gas cleaner comprises ceramic honey comb primary catalyst 9, electrically direct-heating exhaust purifier 12 and automatically controlled part, wherein electrically direct-heating exhaust purifier 12 is in ceramic honey comb primary catalyst 9 is installed on the purifier package casing 8 that links to each other with the petrol engine outlet pipe, electrically direct-heating exhaust purifier 12 is made of foamed ceramics electrically direct-heating catalyst elements, foamed ceramics electrically direct-heating catalyst elements is for being the three-way catalyst of carrier with the conductive silicon carbide foam ceramic, be installed on the graphite electrode pedestal 15 at conductive silicon carbide foam ceramic carrier 14 two ends, 16, with two graphite electrode pedestals 15,16 metal films 10 that link to each other respectively, 11 constitute, power supply is by metal film 10,11 constitute loops with conductive silicon carbide foam ceramic carrier 14, are 14 power supplies of conductive silicon carbide foam ceramic carrier; Automatically controlled part links to each other with electrically direct-heating exhaust purifier 12 electrodes.
Behind the automobile starting, vehicle exhaust is discharged by petrol engine 1, arrives electrically direct-heating exhaust purifier 12 via outlet pipe 13; At this moment, the cooling water water temperature and the controlled unit 4 of tach signal that are monitored by engine cooling water cooling-water temperature sensor 2 and speed probe 3 receive, and then transmit signals to (PCC) power 5, when the cooling water water temperature is lower than 30 ℃ and engine speed and changes greater than 800, (PCC) power 5 is connected circuit, Vehicular accumulator cell 6 promptly begins to give the electrically direct-heating exhaust purifier 12 power supplies by cable 7, and can be set current"on"time by control unit; 10 and 11 is two electrodes of electrically direct-heating exhaust purifier 12, and an end is soldered on the conductive silicon carbide foam ceramic, and the other end links to each other with cable; Tail gas is heated and obtains part and purifies through the electrically direct-heating exhaust purifier time, and then the ceramic honey comb primary catalyst 9 of flowing through, and is further purified.8 is the purifier package casing, and ceramic honey comb primary catalyst 9 is the EU-II standard tail-gas catalyst that Dalian Hua Ke Automobile Parts Company produces, and volume is 1.5 liters.
14 is the conductive silicon carbide foam ceramic carrier among Fig. 2; 15,16 is the graphite electrode pedestal, and its effect is to play transitional function between metal film and foamed ceramics; 10,11 is metal film, is connected with graphite base by brazing mode.A complete electrically direct-heating exhaust purifier can be combined by one or more catalyst elements.Under combined situation, each catalyst elements is linked to be an integral body by the mode of welding between the electrode.The volume of purifier is controlled between 100~400ml, and THICKNESS CONTROL is in 10~50mm scope.
As shown in Figure 3, the automatically controlled part of the present invention is made up of control unit 4, (PCC) power 5, described control unit 4 is powered by the power supply processing unit, comprise frequency signal processing unit, water temperature signal processing unit, governor circuit, wherein: the frequency signal processing unit is a core with monostable flipflop U1, input end (4 pin) connects the frequency signal that automobile rotational speed sensor 3 produces, and converts it into linear voltage, and its output signal (through 6 pin) is connected to an input end of governor circuit; The water temperature signal processing unit is a core with the first triode T1, and water temperature signal is amplified, and its base stage connects the water temperature signal that automobile cooling-water temperature sensor 2 produces, and its emitter is input to the voltage signal that amplifies another input end of governor circuit; Described governor circuit is by the first~two comparator U3~U4, NAND gate circuit U5 and timer U6 form, the first~two comparator U3~U4 carries out judgment processing to frequency signal and water temperature signal respectively, and (wherein the first comparator U3 homophase termination is through the linear voltage of frequency signal processing unit processes, the second comparator U4 negative termination is by the amplification voltage signal of water temperature signal processing unit processes), output terminal carries out the logical AND operation through NAND gate circuit U5, carry out power amplification through the second triode T2 again, be connected to timer U6 then and carry out the signal lag processing, at last the signal after the delay process is delivered to (PCC) power 5; Described (PCC) power 5 is made up of the 3rd triode T3, the first contactor J1 and the second contactor J2, promotes structure with secondary and meets load R1; Be specially: described the 3rd triode T3 input signal is a timer U6 output end signal, and its emitter is connected to the secondary contactor, and the afterbody contactor connects on two electrodes 10 and 11 of load R1; The 3rd triode T3 current collection level all links to each other with Vehicular accumulator cell 12V with the secondary contactor; Described load R1 is an electrically direct-heating exhaust purifier 12; The power supply processing unit adopts three-terminal voltage-stabilizing module U2 to provide 9V power supply to governor circuit, and three-terminal voltage-stabilizing module U2 input end meets Vehicular accumulator cell 12V through the lock K switch; In addition, the output terminal of the first contactor J1 links to each other with the output terminal of the second comparator U4, and in order to keep the high level in the second comparator U4 working procedure, load R1 of the present invention is an electrically direct-heating exhaust purifier 12.
In the present embodiment, monostable flipflop U1 adopts the CD4098 chip; The first~three triode T1~T3 adopts chip BU406; Three-terminal voltage-stabilizing module U2 adopts chip 7809; The first~two comparator U3~U4 co-used chip LM339; NAND gate circuit U5 adopts the CD4011 chip, circuit connects two AND NOT gate utilizing in the chip, one of them AND NOT gate input end connects the output terminal of the first~two comparator U3~U4 respectively, and with another AND NOT gate polyphone, output terminal is connected to the second triode T2 base stage; Timer U6 adopts 555 chips, carries out signal lag and handles; The first contactor J1 (9V) and the second contactor J2 (400A) are responsible for powering to load R1.
Its working principle is as follows: when the lock K switch is opened, and the tach signal of control unit 4 identification automobiles; When tach signal<800 rev/min, (PCC) power 5 is waited for; When tach signal>800 rev/min, the water temperature signal of control unit 4 identification automobiles; When water temperature signal during greater than preset temperature, (PCC) power 5 is waited for; When water temperature signal during less than preset temperature, (PCC) power 5 is connected, and heats to catalyst carrier by automobile mounted storage battery, and control unit 4 begins to clock simultaneously; Equal Preset Time when the time, control unit 4 disconnects (PCC) power 5, stops Vehicular accumulator cell and heats to catalyst carrier; Finish once circulation, wait for that the lock K switch is opened next time.
Exhaust gas cleaner of the present invention mainly is made of above-mentioned electrically direct-heating exhaust purifier and intelligent control unit two-part, catalyzer in the purifier is carrier with the conductive silicon carbide foam ceramic, have good, controlled electric conductivity, be coated with catalyst coat on the carrier; Intelligent control unit can receive cooling water water temperature and the engine rotational speed signal from the control unit platform, and the state of whether switching on from main control electrically direct-heating cleaning system according to signal.Under the situation of vehicle power power supply, can realize purification in advance that the cold-starting automobile stage is discharged pollutants making emission result reach stricter purification standard.Characteristics effective, that automobile improvement is simple, cost is low that this method has.
Embodiment and relevant comparative example
Each embodiment all carries out at Automobile Detection center, Changchun with relevant comparative example, and the experiment vehicle is a CA7180A2E type red flag car, and the EU-III mode is adopted in test.
Embodiment 1
1. be to soak 8 minutes in the NaOH solution of 3M conductive silicon carbide foam ceramic in concentration, remove its surperficial impurity such as greasy dirt, afterwards water clean, oven dry in 2 hours in 120 ℃ of air atmospheres again;
2. get γ-Al 2O 3120 grams, CeO 260 grams, La 2O 36 grams, BaO 12 grams add water 500 grams after the mixing, ball milling obtained coating paste in 3 hours;
3. foamed ceramics is flooded in slurry, blow away unnecessary slurry, placed 120 ℃ of air atmospheres then dry 20 minutes, flood slip after the cooling once more with pressurized air.So repeat repeatedly, until making coating levels reach 120g/ (L catalyzer), at last in 450 ℃ of roastings 5 hours, the coating preparation finishes;
4. get H 2PtCl 610 grams, RhCl 32 grams add water 500 gram and are mixed with mixed solution, the foamed ceramics that will have active coating then vacuum impregnation 12 minutes in solution, and the pottery after will flooding is afterwards dried in baking oven, 120 ℃ of oven temperatures, 30 minutes time; Sample after the oven dry 500 ℃ of reductase 12s hour in hydrogen atmosphere, can obtain with the conductive silicon carbide foam ceramic is the vehicle tail gas triple effect catalyzer of carrier.
5. select catalyst elements after one or more preparations finish for use according to the specific requirement of the resistance of catalyzer and bullion content, if adopt a plurality of catalyst elements, it then between each unit relation in parallel, and connect into an integral body by the mode of weld plate on metal film, can obtain required electrically direct-heating exhaust purifier after the thick corrosion resistant plate encapsulation of 2mm.
Embodiment 2
Difference from Example 1 is:
1. be to soak 10 minutes in the NaOH solution of 2M conductive silicon carbide foam ceramic in concentration, remove its surperficial impurity such as greasy dirt, afterwards water clean, oven dry in 4 hours in 100 ℃ of air atmospheres again;
2. get γ-Al 2O 3110 grams, CeO 270 grams, La 2O 35 grams, BaO 15 grams add water 500 grams after the mixing, ball milling obtained coating paste in 2 hours;
3. foamed ceramics is flooded in slurry, blow away unnecessary slurry, placed 100 ℃ of air atmospheres then dry 30 minutes, flood slip after the cooling once more with pressurized air.So repeat repeatedly, until making coating levels reach 130g/ (L catalyzer), at last in 460 ℃ of roastings 4.5 hours, the coating preparation finishes;
4. get H 2PtCl 610 grams, RhCl 32 grams add water 500 gram and are mixed with mixed solution, the foamed ceramics that will have active coating then vacuum impregnation 10 minutes in solution, and the pottery after will flooding is afterwards dried in baking oven, 100 ℃ of oven temperatures, 30 minutes time; Sample after the oven dry in hydrogen atmosphere 450 ℃ the reduction 4 hours, can obtain with the conductive silicon carbide foam ceramic is the vehicle tail gas triple effect catalyzer of carrier.
Embodiment 3
Difference from Example 1 is:
1. be to soak 5 minutes in the NaOH solution of 4M conductive silicon carbide foam ceramic in concentration, remove its surperficial impurity such as greasy dirt, afterwards water clean, oven dry in 1 hour in 150 ℃ of air atmospheres again;
2. get γ-Al 2O 3130 grams, CeO 250 grams, La 2O 32 grams, BaO 8 grams add water 500 grams after the mixing, ball milling obtained coating paste in 4 hours;
3. foamed ceramics is flooded in slurry, blow away unnecessary slurry, placed 150 ℃ of air atmospheres then dry 20 minutes, flood slip after the cooling once more with pressurized air.So repeat repeatedly, until making coating levels reach 100g/ (L catalyzer), at last in 500 ℃ of roastings 4 hours, the coating preparation finishes;
4. get H 2PtCl 610 grams, RhCl 32 grams add water 500 gram and are mixed with mixed solution, the foamed ceramics that will have active coating then vacuum impregnation 15 minutes in solution, and the pottery after will flooding is afterwards dried in baking oven, 150 ℃ of oven temperatures, 20 minutes time; Sample after the oven dry in hydrogen atmosphere 480 ℃ the reduction 3 hours, can obtain with the conductive silicon carbide foam ceramic is the vehicle tail gas triple effect catalyzer of carrier.
Embodiment 4
Difference from Example 1 is:
1. be to soak 5 minutes in the NaOH solution of 5M conductive silicon carbide foam ceramic in concentration, remove its surperficial impurity such as greasy dirt, afterwards water clean, oven dry in 4 hours in 100 ℃ of air atmospheres again;
2. get γ-Al 2O 3160 grams, CeO 260 grams, La 2O 38 grams, BaO 8 grams add water 500 grams after the mixing, ball milling obtained coating paste in 3 hours;
3. foamed ceramics is flooded in slurry, blow away unnecessary slurry, placed 150 ℃ of air atmospheres then dry 20 minutes, flood slip after the cooling once more with pressurized air.So repeat repeatedly, until making coating levels reach 150g/ (L catalyzer), at last in 480 ℃ of roastings 4 hours, the coating preparation finishes;
4. get H 2PtCl 610 grams, RhCl 31 gram adds water 500 gram and is mixed with mixed solution, the foamed ceramics that will have active coating then vacuum impregnation 12 minutes in solution, and the pottery after will flooding is afterwards dried in baking oven, 150 ℃ of oven temperatures, 20 minutes time; Sample after the oven dry 500 ℃ of reductase 12s hour in hydrogen atmosphere, can obtain with the conductive silicon carbide foam ceramic is the vehicle tail gas triple effect catalyzer of carrier.
Embodiment 5
With the EXAMPLE l difference be:
1. be to soak lO minute in the NaOH solution of 2M conductive silicon carbide foam ceramic in concentration, remove its surperficial impurity such as greasy dirt, afterwards water clean, oven dry in 1 hour in 150 ℃ of air atmospheres again;
2. get γ-Al 2O 3150 grams, CeO 260 grams, La 2O 310 grams, BaO 10 grams add water 500 grams after the mixing, ball milling obtained coating paste in 2 hours;
3. foamed ceramics is flooded in slurry, blow away unnecessary slurry, placed 100 ℃ of air atmospheres then dry 30 minutes, flood slip after the cooling once more with pressurized air.So repeat repeatedly, until making coating levels reach 120g/ (L catalyzer), at last in 450 ℃ of roastings 5 hours, the coating preparation finishes;
4. get H 2PtCl 610 grams, RhCl 30.2 gram adds water 500 gram and is mixed with mixed solution, the foamed ceramics that will have active coating then vacuum impregnation 10 minutes in solution, and the pottery after will flooding is afterwards dried in baking oven, 100 ℃ of oven temperatures, 30 minutes time; Sample after the oven dry in hydrogen atmosphere 450 ℃ the reduction 4 hours, can obtain with the conductive silicon carbide foam ceramic is the vehicle tail gas triple effect catalyzer of carrier.
Embodiment 6
Difference from Example 1 is:
1. be to soak 10 minutes in the KOH solution of 2M conductive silicon carbide foam ceramic in concentration, remove its surperficial impurity such as greasy dirt, afterwards water clean, oven dry in 4 hours in 100 ℃ of air atmospheres again;
2. get γ-Al 2O 3120 grams, CeO 260 grams, La 2O 310 grams, BaO 20 grams add water 500 grams after the mixing, ball milling obtained coating paste in 2 hours;
3. foamed ceramics is flooded in slurry, blow away unnecessary slurry, placed 100 ℃ of air atmospheres then dry 30 minutes, flood slip after the cooling once more with pressurized air.So repeat repeatedly, until making coating levels reach 100g/ (L catalyzer), at last in 450 ℃ of roastings 5 hours, the coating preparation finishes;
4. get H 2PtCl 610 grams, RhCl 32 grams add water 500 gram and are mixed with mixed solution, the foamed ceramics that will have active coating then vacuum impregnation 10 minutes in solution, and the pottery after will flooding is afterwards dried in baking oven, 100 ℃ of oven temperatures, 30 minutes time; Sample after the oven dry in hydrogen atmosphere 450 ℃ the reduction 4 hours, can obtain with the conductive silicon carbide foam ceramic is the vehicle tail gas triple effect catalyzer of carrier.
Embodiment 7
Difference from Example 1 is:
4. be to soak 8 minutes in the KOH solution of 3M conductive silicon carbide foam ceramic in concentration, remove its surperficial impurity such as greasy dirt, afterwards water clean, oven dry in 2 hours in 120 ℃ of air atmospheres again;
2. get γ-Al 2O 3110 grams, CeO 250 grams, La 2O 34 grams, BaO 6 grams add water 500 grams after the mixing, ball milling obtained coating paste in 3 hours;
3. foamed ceramics is flooded in slurry, blow away unnecessary slurry, placed 120 ℃ of air atmospheres then dry 25 minutes, flood slip after the cooling once more with pressurized air.So repeat repeatedly, until making coating levels reach 120g/ (L catalyzer), at last in 480 ℃ of roastings 4.5 hours, the coating preparation finishes;
4. get H 2PtCl 610 grams, RhCl 32 grams add water 500 gram and are mixed with mixed solution, the foamed ceramics that will have active coating then vacuum impregnation 12 minutes in solution, and the pottery after will flooding is afterwards dried in baking oven, 120 ℃ of oven temperatures, 25 minutes time; Sample after the oven dry in hydrogen atmosphere 480 ℃ the reduction 4.5 hours, can obtain with the conductive silicon carbide foam ceramic is the vehicle tail gas triple effect catalyzer of carrier.
Embodiment 8
Difference from Example 1 is:
1. be to soak 5 minutes in the KOH solution of 5M conductive silicon carbide foam ceramic in concentration, remove its surperficial impurity such as greasy dirt, afterwards water clean, oven dry in 1 hour in 150 ℃ of air atmospheres again;
2. get γ-Al 2O 3160 grams, CeO 270 grams, La 2O 38 grams, BaO 16 grams add water 500 grams after the mixing, ball milling obtained coating paste in 4 hours;
3. foamed ceramics is flooded in slurry, blow away unnecessary slurry, placed 150 ℃ of air atmospheres then dry 20 minutes, flood slip after the cooling once more with pressurized air.So repeat repeatedly, until making coating levels reach 150g/ (L catalyzer), at last in 500 ℃ of roastings 4 hours, the coating preparation finishes;
4. get H 2PtCl 610 grams, RhCl 32 grams add water 500 gram and are mixed with mixed solution, the foamed ceramics that will have active coating then vacuum impregnation 15 minutes in solution, and the pottery after will flooding is afterwards dried in baking oven, 150 ℃ of oven temperatures, 20 minutes time; Sample after the oven dry in hydrogen atmosphere 500 ℃ the reduction 4 hours, can obtain with the conductive silicon carbide foam ceramic is the vehicle tail gas triple effect catalyzer of carrier.
Embodiment 9
Difference from Example 1 is:
1. be to soak 8 minutes in the KOH solution of 4M conductive silicon carbide foam ceramic in concentration, remove its surperficial impurity such as greasy dirt, afterwards water clean, oven dry in 2 hours in 120 ℃ of air atmospheres again;
2. get γ-Al 2O 3110 grams, CeO 250 grams, La 2O 32 grams, BaO 4 grams add water 500 grams after the mixing, ball milling obtained coating paste in 3 hours;
3. foamed ceramics is flooded in slurry, blow away unnecessary slurry, placed 120 ℃ of air atmospheres then dry 25 minutes, flood slip after the cooling once more with pressurized air.So repeat repeatedly, until making coating levels reach 100g/ (L catalyzer), at last in 450 ℃ of roastings 5 hours, the coating preparation finishes;
4. get H 2PtCl 6L0 gram, RhCl 30.2 gram adds water 500 gram and is mixed with mixed solution, the foamed ceramics that will have active coating then vacuum impregnation 12 minutes in solution, and the pottery after will flooding is afterwards dried in baking oven, 120 ℃ of oven temperatures, 25 minutes time; Sample after the oven dry in hydrogen atmosphere 450 ℃ the reduction 5 hours, can obtain with the conductive silicon carbide foam ceramic is the vehicle tail gas triple effect catalyzer of carrier.
Embodiment 10
Difference from Example 1 is:
1. be to soak 10 minutes in the KOH solution of 3M conductive silicon carbide foam ceramic in concentration, remove its surperficial impurity such as greasy dirt, afterwards water clean, oven dry in 1 hour in 150 ℃ of air atmospheres again;
2. get γ-Al 2O 3150 grams, CeO 260 grams, La 2O 36 grams, BaO 16 grams add water 500 grams after the mixing, ball milling obtained coating paste in 4 hours;
3. foamed ceramics is flooded in slurry, blow away unnecessary slurry, placed 100 ℃ of air atmospheres then dry 30 minutes, flood slip after the cooling once more with pressurized air.So repeat repeatedly, until making coating levels reach 150g/ (L catalyzer), at last in 500 ℃ of roastings 4 hours, the coating preparation finishes;
4. get H 2PtCl 6L0 gram, PhCl 32 grams add water 500 gram and are mixed with mixed solution, the foamed ceramics that will have active coating then vacuum impregnation 10 minutes in solution, and the pottery after will flooding is afterwards dried in baking oven, 150 ℃ of oven temperatures, 20 minutes time; Sample after the oven dry in hydrogen atmosphere 500 ℃ the reduction 4 hours, can obtain with the conductive silicon carbide foam ceramic is the vehicle tail gas triple effect catalyzer of carrier.
Embodiment and relevant comparative example the results are shown in Table 1.Test 1~10 among the table l and be embodiment, experiment 11~13 is relevant comparative example.Each embodiment is compared with the EU-III standard with the result of comparative example, can find that emission result exceeds standard under the situation of not assembling the electrically direct-heating exhaust purifier comprehensively; Though and resulting result increases than comparative example 12 under comparative example 11 and 13 two kind of condition, still have big gap apart from the EU-III standard.And the result of embodiment 1-10 has all reached the EU-III standard, and has higher surplus capacity.Show that under power on condition, the electrically direct-heating exhaust purifier can play the purifying effect of expection.
Table 1
Experiment numbers Profile (mm 3) Resistance (m Ω) Current"on"time Pt, Rh content (g/L) and weight ratio Emission result (g/km)
CO THC NOx
1 90×75×50 54 120 2.5(5∶1) 0.4774 0.1096 0.1239
2 90×75×50 54 90 2.5(5∶1) 0.5734 0.133 0.0904
3 90×75×50 58 100 2.5(5∶1) 0.4162 0.0962 0.0922
4 90×75×50 64 90 2.5(5∶0.5) 0.4845 0.1323 0.1336
5 90×75×50 64 105 2.5(5∶0.1) 0.5334 0.1198 0.1274
6 90×75×30 58 100 2.5(5∶1) 0.5471 0.1276 0.1074
7 90×75×20 60 100 2.5(5∶1) 0.5071 0.1252 0.1187
8 90×75×50 54 100 4(5∶1) 0.4935 0.1131 0.0946
9 90×75×50 54 100 5(5∶0.1) 0.5013 0.0985 0.1004
10 90×75×50 54 100 2(5∶1) 0.6159 0.1128 0.1201
11 90×75×30 55 120 0 0.7778 0.1657 0.1511
12 No electrically direct-heating purifier only uses the honeycomb ceramic carrier primary catalyst 2.168 0.28 0.2403
13 90×75×50 54 0 2.5(5∶1) 1.968 0.2632 0.2149
The EU-III standard limited value 2.3 0.2 0.15

Claims (9)

1, the device that a kind of vehicle exhaust electrically direct-heating triple effect purifies, comprise power supply, ceramic honey comb primary catalyst (9), ceramic honey comb primary catalyst (9) is installed in the purifier package casing (8) that links to each other with the petrol engine outlet pipe, also comprise electrically direct-heating exhaust purifier (12) and automatically controlled part, wherein electrically direct-heating exhaust purifier (12) is in ceramic honey comb primary catalyst (9) is installed on the purifier package casing (8) that links to each other with the petrol engine outlet pipe, constitute by foamed ceramics electrically direct-heating catalyst elements, foamed ceramics electrically direct-heating catalyst elements is for being the three-way catalyst of carrier with the conductive silicon carbide foam ceramic, be installed on the graphite electrode pedestal (15 at conductive silicon carbide foam ceramic carrier (14) two ends, 16), with two graphite electrode pedestals (15,16) metal film (10 that links to each other respectively, 11) constitute, power supply is by metal film (10,11) constitute the loop with conductive silicon carbide foam ceramic carrier (14), be conductive silicon carbide foam ceramic carrier (14) power supply; Automatically controlled part links to each other with electrically direct-heating exhaust purifier (12) electrode; It is characterized in that:
Described automatically controlled part is made up of control unit (4) and (PCC) power (5), described control unit (4) is powered by the power supply processing unit, comprise frequency signal processing unit, water temperature signal processing unit, governor circuit, wherein: the frequency signal processing unit is a core with monostable flipflop (U1), the frequency signal that input termination automobile rotational speed sensor produces, its output signal is connected to an input end of governor circuit; The water temperature signal processing unit is a core with first triode (T1), and its base stage connects the water temperature signal that the automobile cooling-water temperature sensor produces, and emitter is to another input end of governor circuit; (form by U3~U4), NAND gate circuit (U5) and timer (U6) by the first~two comparator for described governor circuit, (U3~U4) is connected to the linear voltage of frequency signal processing unit processes and the amplification voltage signal of water temperature signal processing unit respectively to first~two comparator, its output terminal links to each other with timer (U6) through NAND gate circuit (U5), second triode (T2) successively, and timer (U6) output terminal is connected to (PCC) power (5); Described (PCC) power (5) promotes structure for secondary, and its output terminal links to each other with the electrode of load (R1); In addition, the output terminal of first contactor (J1) of (PCC) power (5) links to each other with the output terminal of second comparator (U4) of governor circuit.
2, the device that purifies according to the described vehicle exhaust electrically direct-heating of claim 1 triple effect, it is characterized in that: described (PCC) power (5) is made up of the 3rd triode (T3), first contactor (J1) and second contactor (J2), wherein the 3rd triode (T3) input signal is timer (U6) output end signal, its emitter is connected to the secondary contactor, and the afterbody contactor connects load (R1); Its current collection level all links to each other with 12V with the secondary contactor.
3, the device that purifies according to the described vehicle exhaust electrically direct-heating of claim 1 triple effect, it is characterized in that: described power supply processing unit adopts three-terminal voltage-stabilizing module (U2) to provide 9V power supply to governor circuit, and three-terminal voltage-stabilizing module (U2) input end meets 12V through lock switch (K).
4, the device that purifies according to the described vehicle exhaust electrically direct-heating of claim 1 triple effect is characterized in that: described load (R1) is electrically direct-heating exhaust purifier (12).
5, the device that purifies according to the described vehicle exhaust electrically direct-heating of claim 1 triple effect, it is characterized in that: described metal film (10,11) is connected on the graphite base (15,16) by brazing mode.
6, the device that purifies according to the described vehicle exhaust electrically direct-heating of claim 1 triple effect, it is characterized in that: described electrically direct-heating exhaust purifier (12) is one or at least two foamed ceramics electrically direct-heating catalyst elements compositions, when purifier is made of two or two above unit, it between each unit relation in parallel, be linked to be an integral body by the mode of welding between the electrode, the volume of electrically direct-heating exhaust purifier (12) is controlled between 100~400ml, and THICKNESS CONTROL is in 10~50mm scope.
7, the device that purifies according to the described vehicle exhaust electrically direct-heating of claim 1 triple effect, it is characterized in that: described three-way catalyst, with the conductive silicon carbide foam ceramic is carrier, catalyzer floating coat content is between 100~150g/L catalyst carrier, and the weight ratio of each material is in the coating: Al 2O 3: CeO 2: La 2O 3: BaO=(55~80): (25~35): (1~5): (2~10), the weight ratio of Pt and Rh is 5 in the catalyzer: (1~0.1), Pt and Rh total content are 2~5g/L catalyst carrier, described foam silicon carbon pottery is the mark meter by weight, its composition is made up of 90%~98% silicon carbide and 10%~2% silicon, and its resistance is between 50~70m Ω.
8, the device that purifies according to the described vehicle exhaust electrically direct-heating of claim 7 triple effect, it is characterized in that: described foam silicon carbide ceramics is an elementary cell with polygonal closed loop, and each elementary cell is interconnected to form three-dimensional networks; Constitute relative density 〉=99% of the ceramic muscle of polygonal closed loop unit, average grain size is at 50nm~10 μ m.
9, the device that purifies according to the described vehicle exhaust electrically direct-heating of claim 7 triple effect is characterized in that the preparation process of described three-way catalyst is specific as follows:
1. be to soak 5~10 minutes in the NaOH of 2~5M or the KOH solution conductive silicon carbide foam ceramic in concentration, remove its surperficial impurity such as greasy dirt, afterwards water clean, oven dry in 1~4 hour in 100~150 ℃ of air atmospheres again;
2. get γ-Al 2O 3110~160 parts, CeO 250~70 parts, La 2O 34~20 parts of 2~10 parts, BaO add 500 parts in water after the mixing, ball milling obtained coating paste in 2~4 hours;
3. foamed ceramics was flooded in slurry 2~5 minutes, blow away unnecessary slurry, placed 100~150 ℃ of air atmospheres then dry 20~30 minutes, flood slip after the cooling once more with pressurized air.So repeat repeatedly, until making coating levels reach 100~150g/L catalyst carrier, at last in 450~500 ℃ of roastings 4~5 hours, the coating preparation finishes;
4. get H 2PtCl 610~15 parts, RhCl 30.5~2 parts, add water and be mixed with mixed solution for 500 parts, the foamed ceramics that will have active coating then vacuum impregnation 10~15 minutes in solution, the pottery after will flooding is afterwards dried in baking oven, 100~150 ℃ of oven temperatures, 20~30 minutes time; Sample after the oven dry 450~500 ℃ of reductase 12~4 hour in hydrogen atmosphere, can obtain with the conductive silicon carbide foam ceramic is the vehicle tail gas triple effect catalyzer of carrier.
CNB2004100206528A 2004-06-02 2004-06-02 Electric direct heating type three-efficiency purifier for automobile exhaust Expired - Fee Related CN100343491C (en)

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