CN100493703C - Triple-effect catalyst for purifying natural gas-fueled automobile exhaust gas and preparation method thereof - Google Patents
Triple-effect catalyst for purifying natural gas-fueled automobile exhaust gas and preparation method thereof Download PDFInfo
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- CN100493703C CN100493703C CNB2006101477776A CN200610147777A CN100493703C CN 100493703 C CN100493703 C CN 100493703C CN B2006101477776 A CNB2006101477776 A CN B2006101477776A CN 200610147777 A CN200610147777 A CN 200610147777A CN 100493703 C CN100493703 C CN 100493703C
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- Y—GENERAL 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
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A50/00—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
- Y02A50/20—Air quality improvement or preservation, e.g. vehicle emission control or emission reduction by using catalytic converters
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- Y—GENERAL 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
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02T—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO TRANSPORTATION
- Y02T10/00—Road transport of goods or passengers
- Y02T10/10—Internal combustion engine [ICE] based vehicles
- Y02T10/12—Improving ICE efficiencies
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Abstract
The invention relates to a three-effect catalyst which can purify the vehicle tail gas as natural gas (CNG), wherein it comprises carrier, coat on the carrier and catalysis active component coated on the coat layer. The invention is characterized in that: said carrier is iolite honeycomb ceramic material whose porous capacity is 0.25-0.35ml/g; the coat layer is the mixture of cerium zirconium sosoloid, rare-earth oxide and alumina; the catalysis active component is the mixture of platinum, rhodium, cerium metal oxides. The invention has better three-effect catalysis purify property on the CNG tail gas, with better high-temperature resistance, while its maximum application temperature is 1000Deg. C, and when the vehicle has driven 80000km, it can meet the Europe II discharge standard. And the invention uses rare-earth cerium to reduce the consumption of platinum and rhodium.
Description
Technical field
The present invention relates to a kind of integral catalyzer of rare earth based low precious metal content, being specifically related to be used for the natural gas is the catalytic cleaning of car tail gas catalyst of fuel.
Background technology
Pillar industry as China---automobile industry development is rapid, and new car output and automobile pollution significantly increase.Reach 2,500 ten thousand, 5,000,000 of annual new car output by China's automobile pollution in 2004.In automobile institute discharge tail gas, mainly containing harmful substances has: carbon monoxide (CO), hydrocarbon (HC), nitrogen oxide (NOx) etc.Emission of automobile wastes has become the primary pollution source of China's large-and-medium size cities atmosphere, therefore must effectively administer emission of automobile wastes.The most effective improvement method is to reduce the pollutant emission of bicycle at present.Vehicle exhaust is carried out catalytic purification before discharging be the effective ways that reduce the bicycle discharging, and its basic principle is the effect by catalyst, CO, HC, NOx simultaneous oxidation or be reduced to carbon dioxide (CO
2), nitrogen (N
2) and steam (H
2O), so be referred to as vehicle tail gas triple effect cleaning catalyst (Three-way Catalyst:TWC).
Developing of automobile industry has also significantly increased the demand to oil, and the China's oil resource is in short supply day by day, and rising in 1993 becomes net import of oil state.Imported crude oil was 100,000,000 tons in 2004.The recent international crude oil price skyrockets, and fuel price is also constantly soaring thereupon, and therefore from China's energy resource structure, environmental protection, resources characteristic, the substitute fuel automobile of development cleaning is subjected to the support energetically of China governments at all levels.
Advantages such as natural gas (be called for short CNG, down with) has combustion characteristics near gasoline, and octane number is than the gasoline height, and the thermal efficiency is big.CNG is used for motor vehicle fuel, because its chemical composition is simple and have high hydrogen-carbon ratio, and is easy to completing combustion, compares with gasoline motor car exhausted gas, and CO and HC all have significantly decline.It is simple simultaneously gasoline car to be adapted as the required retrofit technology of CNG automobile, thereby the CNG fuel vehicle has obtained using widely.
At present, the CNG automobile all is to convert on the basis of the gasoline car of typing, and employed tai-gas clean-up catalyst designs at the operating mode and the discharging characteristics of gasoline car, can not well adapt to the tail gas clean-up of CNG automobile.As: it is higher or the like that lower, the HC of CO concentration mostly is saturated hydrocarbons, NOx content height, operating temperature in the CNG vehicle exhaust.Therefore the tail-gas from gasoline automobiles cleaning catalyst can not well adapt to the CNG car, is necessary the tai-gas clean-up catalyst of researching and developing out the CNG automobile specified at the operating mode and the discharging characteristics of CNG vehicle exhaust.
Consisting of of the common auto-exhaust catalyst that adopts in the world: on ceramic honeycomb or metal alloy carrier, apply the coating (Washcoat) of bigger serface, and then the supported catalyst active component.Catalytic active component is generally noble metals such as Pt, Rh, Pd, according to actual needs, both can adopt single noble metal component, also can adopt many noble metal component.Because the noble metal resource-constrained costs an arm and a leg, the consumption that therefore reduces noble metal becomes the research focus.Coating material adopts activated alumina usually, for hear resistance and the dispersiveness of catalytic active component, introducing alkaline earth oxide or transition metal oxide or the rare earth oxide (as La, Ce etc.) in the matrix of aluminium oxide usually that improves coating.Since Libby in 1971 proposed rare earth oxide is applied to cleaning catalyst for tail gases of automobiles, the application of rare earth in cleaning catalyst for tail gases of automobiles become the application of rare earth maximum.
Generally speaking, the vehicle tail gas triple effect catalyst of function admirable should possess: 1) have lower initiation temperature, the discharging of pollutant when reducing cold start-up; 2) very high purification efficiency adapts to more and more strict emission control standards; 3) can bear big air speed load; 4) higher heat resistance and mechanical strength are arranged; 6) have sufficiently long service life; 7) rational cost etc.
Patent EP0624399 has related to the catalyst that internal combustion engine (with liquid fuel, LPG or CNG) tail gas clean-up that a kind of spark ignition or other modes light a fire is used.Supported porous coating on pottery and metallic carrier, this coating contain high-temperature inorganic oxide, ferriferous oxide, cerium oxide, metal A and (are selected from I
B, VI
B, VII
BWith VIII family) and the compound of metal B (be selected from I
A, II
A, rare earth and IV
BFamily).
Patent CN1876230 has related to a kind of purification catalyst for natural gas and auto tail gas, is coated with catalytic active component on described porous ceramics carrier, calculates with every liter of porous ceramics carrier, contains the CeO of 20/L～40g/L in the catalytic active component
2And 1.6g/L～3.2g/L metal Pd.Also contain La in the catalytic active component that is coated with on described porous ceramics carrier, calculate with every liter of porous ceramics carrier, the content of described La is 0.1g/L～0.5g/L.
People such as author Zhao Bin have investigated Pd, Pt, Pd-Rh and the Pt-Rh influence to purification catalyst for natural gas and auto tail gas.Prepared with La-Al
2O
3, La-Al
2O
3+ CeO
2-ZrO
2And La-Al
2O
3+ CeO
2-ZrO
2MnO
xNatural gas and auto tail gas purification palladium catalyst for carrier.The result shows, Pd/Al
2O
3+ CeO
2ZrO
2The MnOx catalyst can reduce CH
4Initiation temperature and improve the reactivity worth [noble metal 2004,25 (3), 33-35] of catalyst
Summary of the invention
It is the three-way catalyst and preparation method thereof of purifying vehicle exhaust of fuel that the technical issues that need to address of the present invention provide a kind of being used for the natural gas, to overcome the defective that the tail-gas from gasoline automobiles cleaning catalyst is not suitable for the CNG purifying vehicle exhaust, satisfy the operating mode and the discharging characteristics of CNG vehicle exhaust, reach the needs of CNG purifying vehicle exhaust.
Three-way catalyst of the present invention comprises carrier, be coated in the coating on the carrier and be coated in catalyst activity component on the coating;
Said carrier is selected from the cordierite honeycomb ceramic material that pore volume is the 0.25-0.35ml/ gram;
Said coating is selected from the mixture of cerium zirconium sosoloid, rare earth oxide and aluminium oxide, and cerium zirconium sosoloid refers to the solid mixture of cerium and zirconium, the preferred lanthanum of rare earth, cerium, praseodymium;
Said catalytic active component is platinum-rhodium-ce metal hopcalite;
In optimized technical scheme of the present invention, the weight ratio of cerium zirconium sosoloid is 7:3～3:7, described cerium zirconium sosoloid also comprises other elements of cerium zirconium sosoloid gross weight 0.2～3%, and these other elements are selected from one or more of elements such as oxide, alkaline-earth metal, aluminium or silicon of other rare earth elements;
Be the best than the cerium zirconium sosoloid that is 4:6～6:4 wherein with the cerium zirconium;
Other rare earth oxides are the oxide or the barium monoxide of lanthanide series, wherein are best with the lanthana;
The weight of coating accounts for 15～25% of vehicle weight;
In the coating, the weight ratio of cerium zirconium sosoloid, rare earth oxide and aluminium oxide is: cerium zirconium sosoloid: rare earth oxide: aluminium oxide=1:0.1～0.6:8～20;
The weight of active component platinum-rhodium in the catalyst-ce metal oxide is 0.5～6% of catalyst weight, the weight ratio of platinum-rhodium in the catalyst-cerium is 3～6:2～4:15～30, platinum content is 0.1～0.4 grams per liter catalyst in the catalyst, and rhodium content is 0.05～0.2 grams per liter catalyst.
Preparation of catalysts method of the present invention may further comprise the steps:
(1) the cordierite honeycomb ceramic monolith being immersed in weight concentration is in 50～30% the coating water slurry 5～15 minutes, oven dry, 400～600 ℃ of roastings 3～6 hours.Said coating water slurry is the mixture of cerium zirconium sosoloid, rare earth oxide, aluminium oxide, tackifier and water.Wherein, the weight ratio of cerium zirconium sosoloid, rare earth oxide and aluminium oxide as previously mentioned, the weight of tackifier is 0.5～5% of cerium zirconium sosoloid, rare earth oxide and aluminium oxide gross weight, said tackifier are nitric acid;
(2) the cordierite honeycomb ceramic monolith that contains coating that then step (1) is prepared, adopting equi-volume impregnating to be immersed in weight concentration is in 0.5～6% the aqueous solution that contains platinum salt, rhodium salt and cerium salt 5～10 minutes, dry, 500～800 ℃ of roastings 3～6 hours promptly make catalyst behind hydrogen reducing;
In the aqueous solution of platinum salt, rhodium salt, cerium salt, the weight ratio of platinum salt, rhodium salt, cerium salt is 3～6:2～4:15～30;
Said hydrogen reducing is a kind of method of routine, the description in the same document (Roberta Brayber, Dacid dosSantos Cunha, Francois Bozon-Berduraz.Catalysis Today, 2003,78,419～432);
Said platinum salt is selected from chloroplatinic acid or platinum nitrate;
Said rhodium salt is selected from radium chloride or rhodium nitrate;
Said cerium salt is selected from cerous nitrate;
According to the present invention, preferably can be under vacuum condition, cordierite honeycomb ceramic-like ceramic monolith is immersed in the coating paste 5～10 minutes;
Or
After adopting equi-volume impregnating to flood with platinum salt, rhodium salt solution earlier the cordierite honeycomb ceramic monolith that contains coating material of step (1) preparation, drying, 400～600 ℃ of roastings are after 3～6 hours, flood with cerium salt solution again, dry then, 500～800 ℃ of roastings 3～6 hours;
The weight concentration of platinum salt, rhodium salt solution is 0.1～1.5%;
The weight concentration of cerium salt solution is 0.5～4.5%;
Or
Adopt equi-volume impregnating to flood with cerium salt solution earlier the cordierite honeycomb ceramic monolith that contains coating of step (1) preparation, drying, 500～800 ℃ of roastings 3～6 are flooded with platinum salt, rhodium salt again, drying, 400～600 ℃ of roastings 3～6 hours;
The weight concentration of platinum salt, rhodium salt solution is 0.1～1.5%;
The weight concentration of cerium salt solution is 0.5～4.5%.
Adopt the prepared catalyst of said method, for a kind of being used for the natural gas is the monoblock type three-way catalyst of rare earth based low precious metal content of purifying vehicle exhaust of fuel.
Catalyst of the present invention has good three-effect catalysis purifying property to the CNG purifying vehicle exhaust.As the initiation temperature to CO is 185 ℃, is 210 ℃ to the initiation temperature of HC, is 218 ℃ to the initiation temperature of NOx, has good low temperature ignition performance.Have the air-fuel ratio operation window of broad and good resistance to elevated temperatures simultaneously, maximum operation (service) temperature can reach 1000 ℃, and still can meet European II discharge standard behind 80,000 kilometers of the CNG running cars service life.In catalytic active component, introduce base metal rare earth cerium, greatly reduce the consumption of noble metal platinum, rhodium.
The specific embodiment
Embodiment 1
It is stand-by that 2.346 gram pore volumes are that 0.3ml/ gram cordierite honeycomb carrier is placed in 110 ℃ of drying boxes, takes by weighing 20 gram γ-Al
2O
3, after 3 gram cerium zirconium powders, 0.3 gram lanthanum nitrate mix, add 80 milliliters of deionized waters, stir at normal temperatures, be 4 with the nitre acid for adjusting pH value simultaneously, make coating paste.
Then in vacuum tank, with carrier impregnation in the coating slurries 5 minutes, take out the back and uses air purge, at 110 ℃ of dry 10h, standby behind the roasting 3h in 400 ℃ of air again.
Measuring concentration is the chloroplatinic acid aqueous solution 0.82ml of 0.0122 gram/ml.Measuring concentration is the radium chloride aqueous solution 0.34ml of 0.0215 gram/ml, adds deionized water to 25ml, makes active component precursor salt solution, adopts equi-volume impregnating activity component impregnation being applied on the carrier of coating 110 ℃ of dry 10h, 500 ℃ of roasting 3h; Take by weighing cerous nitrate 0.19 gram.Add deionized water after the dissolving to 25ml, make active component precursor salt solution, on the carrier that is coated with platinum rhodium component, 110 ℃ of dry 10h behind 700 ℃ of roasting 3h, use H to the employing equi-volume impregnating with the active component single-steeping
2At 250 ℃ of following preliminary treatment 2h, promptly obtain catalyst 1 of the present invention
#
The test of catalyst performance is carried out in the stainless steel fixed bed reactors.With CO gas concentration 1.5%, CH
4Gas concentration 1500ppm, NO gas concentration 1000ppm, O
2Gas concentration 0～5%, balanced gas N
2, being made into analog gas, air speed is 40000h
-1, gas composition is analyzed by five component exhaust gas analyzers.
Catalyst air-fuel ratio evaluating characteristics carries out in the stainless steel fixed bed reactors.Simulation gas is the same.Under 450 ℃ of conditions, fix N O, CO, HC, N
2Flow velocity, change O
2Concentration, the conversion ratio of measuring N O, CO, HC is with oxygen content change.
80,000 kilometers roadway experiments of catalyst life test on the CNG automobile, carrying out.The automotive performance mechanism for testing issue that report has country to authorize.
Embodiment 2
Stand-by 2.356 grams for 0.33ml/ gram cordierite honeycomb carrier is placed in 110 ℃ of drying boxes, take by weighing 30 gram γ-Al
2O
3, after 4 gram cerium zirconium powders, 1.5 gram lanthanum nitrates mix, add 80 milliliters of deionized waters, stir at normal temperatures, be 4 with the nitre acid for adjusting pH value simultaneously, make coating paste.
Then in vacuum tank, with carrier impregnation in the coating slurries 5 minutes, take out the back and uses air purge, at 110 ℃ of dry 10h, standby behind the roasting 5h in 500 ℃ of air again.
Take by weighing cerous nitrate 1.5 grams, add deionized water after the dissolving, make active component precursor salt solution, adopt equi-volume impregnating activity component impregnation being applied on the carrier of coating 110 ℃ of dry 10h, 800 ℃ of roasting 4h to 25ml; Measuring concentration is the chloroplatinic acid aqueous solution 3.42ml of 0.0122 gram/ml.Measuring concentration is the radium chloride aqueous solution 2.14ml of 0.0215 gram/ml, adds deionized water to 25ml, makes active component precursor salt solution, adopt equi-volume impregnating active component solution to be immersed in again on the carrier that is coated with the cerium component, 110 ℃ of dry 10h behind 500 ℃ of roasting 4h, use H
2At 250 ℃ of following preliminary treatment 2h, promptly obtain catalyst 2 of the present invention
#
Embodiment 3
Stand-by 2.354 grams for the cordierite honeycomb carrier of 0.32ml/ gram is placed in 110 ℃ of drying boxes, take by weighing 40 and restrain γ-Al
2O
3, after 5 gram cerium zirconium powders, 1.7 gram lanthanum nitrates mix, add 80 milliliters of deionized waters, stir at normal temperatures, be 4 with the nitre acid for adjusting pH value simultaneously, make coating paste.
Then in vacuum tank, with carrier impregnation in the coating slurries 5 minutes, take out the back and uses air purge, at 110 ℃ of dry 10h, standby behind the roasting 4h in 600 ℃ of air again.
Measuring concentration is the chloroplatinic acid aqueous solution 2.46ml of 0.0122 gram/ml, concentration is the radium chloride aqueous solution 1.12ml of 0.0215 gram/ml, add cerous nitrate 1.10 grams, add deionized water after the dissolving to 25ml, make active component precursor salt mixed solution, adopt equi-volume impregnating activity component impregnation being applied on the carrier of coating 110 ℃ of dry 10h, behind 700 ℃ of roasting 5h, use H
2At 250 ℃ of following preliminary treatment 2h, promptly obtain catalyst 3 of the present invention
#
Analog reslt is as follows:
Claims (5)
1. being used for the natural gas is the three-way catalyst of the purifying vehicle exhaust of fuel, comprises carrier, is coated in the coating on the carrier and is coated in catalytic active component on the coating, it is characterized in that:
Said carrier is selected from the cordierite honeycomb ceramic material that pore volume is the 0.25-0.35mL/ gram;
Said coating is selected from the mixture of cerium zirconium sosoloid, rare earth oxide and aluminium oxide, and rare earth is selected from lanthanum, cerium or praseodymium; The weight of coating accounts for 15～25% of vehicle weight; In the coating, the weight ratio of cerium zirconium sosoloid, rare earth oxide and aluminium oxide is: cerium zirconium sosoloid: rare earth oxide: aluminium oxide=1:0.1～0.6:8～20;
Said catalytic active component is platinum-rhodium-ce metal hopcalite; The weight of active component is 0.5～6% of catalyst weight; The weight ratio of platinum-rhodium in the catalyst-cerium is 3～6:2～4:15～30.
Consisting of of described cerium zirconium sosoloid: cerium oxide is 3:7～7:3 to zirconic weight ratio.
2. three-way catalyst according to claim 1 is characterized in that: described cerium zirconium sosoloid also comprises other elements of cerium zirconium sosoloid gross weight 0.2～3%, and these other elements are selected from more than one in lanthanide series, alkaline-earth metal, aluminium or the element silicon.
3. three-way catalyst according to claim 1 is characterized in that, platinum content is 0.1～0.4 grams per liter catalyst in the catalyst, and rhodium content is 0.05～0.2 grams per liter catalyst.
4. prepare the described Preparation of catalysts method of claim 1, may further comprise the steps:
(1) the cordierite honeycomb ceramic monolith being immersed in weight concentration is in 30～50% the coating water slurry 5～15 minutes, oven dry, 400～600 ℃ of roastings 3～6 hours, said coating water slurry is the mixture of cerium zirconium sosoloid, rare earth oxide, aluminium oxide, tackifier and water, wherein, the weight ratio of cerium zirconium sosoloid, rare earth oxide and aluminium oxide as previously mentioned, the weight of tackifier is 0.1～2% of cerium zirconium sosoloid, rare earth oxide and aluminium oxide gross weight, and said tackifier are nitric acid;
(2) the cordierite honeycomb ceramic monolith that contains coating that then step (1) is prepared, adopting equi-volume impregnating to be immersed in weight concentration is in 0.5～6% the aqueous solution that contains platinum salt, rhodium salt and cerium salt 5～10 minutes, dry, 500～800 ℃ of roastings 3～6 hours promptly make catalyst behind hydrogen reducing;
In the aqueous solution of platinum salt, rhodium salt and cerium salt, the weight ratio of platinum salt, rhodium salt, cerium salt is 3～6:2～4:15～30;
Said platinum salt is platinum nitrate;
Said rhodium salt is rhodium nitrate;
Said cerium salt is selected from cerous nitrate;
Or
After adopting equi-volume impregnating to flood with platinum salt, rhodium salt solution earlier the cordierite honeycomb ceramic monolith that contains coating of step (1) preparation, drying, 400～600 ℃ of roastings are after 3～6 hours, flood with cerium salt solution again, dry then, 500～800 ℃ of roastings 3～6 hours;
The weight concentration of platinum salt, rhodium salt solution is 0.1～1.5%;
The weight concentration of cerium salt solution is 0.5～4.5%.
Or
Adopt equi-volume impregnating to flood with cerium salt solution earlier the cordierite honeycomb ceramic monolith that contains coating of step (1) preparation, drying, 500～800 ℃ of roastings 3～6 hours are flooded with platinum salt, rhodium salt again, drying, 400～600 ℃ of roastings 3～6 hours;
The weight concentration of platinum salt, rhodium salt solution is 0.1～1.5%;
The weight concentration of cerium salt solution is 0.5～4.5%.
5. method according to claim 4 is characterized in that, under vacuum condition, the cordierite honeycomb ceramic monolith is immersed in the coating water slurry 5～10 minutes.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2006101477776A CN100493703C (en) | 2006-12-22 | 2006-12-22 | Triple-effect catalyst for purifying natural gas-fueled automobile exhaust gas and preparation method thereof |
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|---|---|---|---|
| CNB2006101477776A CN100493703C (en) | 2006-12-22 | 2006-12-22 | Triple-effect catalyst for purifying natural gas-fueled automobile exhaust gas and preparation method thereof |
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| CN100493703C true CN100493703C (en) | 2009-06-03 |
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Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101748460B (en) * | 2008-12-03 | 2011-04-13 | 中国科学院金属研究所 | Method for coating nanometer rare earth oxide or composite material thereof catalyst by electrochemical method |
| CN102039146A (en) * | 2010-11-18 | 2011-05-04 | 华东理工大学 | Catalyst for purifying exhaust gas of natural gas engine and preparation method thereof |
| CN102003254B (en) * | 2010-11-18 | 2015-08-19 | 华东理工大学 | Catalytic converter for purifying exhaust of natural gas automobile |
| KR101507325B1 (en) * | 2013-12-20 | 2015-03-31 | 희성촉매 주식회사 | A catalyst member for purifying exhuast gas and washcoat therefor |
| CN106413858A (en) * | 2014-06-06 | 2017-02-15 | 克林迪塞尔技术公司 | Rhodium-iron catalysts |
| CN105435785B (en) * | 2015-12-04 | 2018-02-06 | 中自环保科技股份有限公司 | A kind of resistant to sulfur natural gas tai-gas clean-up catalyst and preparation method thereof |
| CN106179397B (en) * | 2016-06-27 | 2019-04-30 | 翁夏翔 | A kind of palladium ruthenium type gasoline automotive catalyst and preparation method thereof |
| CN109046348A (en) * | 2018-08-24 | 2018-12-21 | 无锡威孚环保催化剂有限公司 | A kind of gasoline vehicle tail gas multicomponent catalyst and preparation method thereof |
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Granted publication date: 20090603 Termination date: 20161222 |