CN1161183C - Ternary catalyst for automobile tail gas and its preparation method - Google Patents
Ternary catalyst for automobile tail gas and its preparation method Download PDFInfo
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- CN1161183C CN1161183C CNB021250006A CN02125000A CN1161183C CN 1161183 C CN1161183 C CN 1161183C CN B021250006 A CNB021250006 A CN B021250006A CN 02125000 A CN02125000 A CN 02125000A CN 1161183 C CN1161183 C CN 1161183C
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Abstract
The present invention discloses a ternary catalyst for automobile tail gas and a preparation method thereof. The ternary catalyst is characterized in that the ternary catalyst adopts a first carrier of home-made cordierite honeycomb ceramics modified by the tailings of misch metal and transition metal oxides, a second carrier of a modified aluminium oxide coating, and the active constituents of the precious metals of Pt, Rh and Pd. The modified aluminum oxide has a double-layer structure, wherein inner modified aluminum oxide is directly coated on the base body of the modified cordierite ceramics, outer modified aluminum oxide is coated on the inner modified aluminum oxide, and the active constituents of the precious metals are loaded on the modified aluminium oxide coating; the modifiers of the modified aluminum oxide are the cheap tailings, transition metal oxides and/or alkali-earth oxides. With the application of the catalyst in the preparation process provided by the present invention, a ternary purifier made by adding a cushion layer and an outer shell can be used for implementing the purification of the automobile tail gas.
Description
Technical field
The present invention relates to the processing of purifying vehicle exhaust, a kind of specifically three-way catalyst that is used for purifying vehicle exhaust and preparation method thereof.
Background technology
Vehicle exhaust is the worldwide main source of atmospheric pollution, and it is one of most effectual way of carrying out the tail gas pollution control that catalytic cleaner is installed.The most frequently used catalytic cleaner is a ternary cleaner at present, and under the situation of control air-fuel ratio, it can purify the main harmful poisonous substance in NOx, CH, three kinds of tail gas of CO simultaneously.And the core of ternary cleaner is exactly a three-way catalyst.
It is carrier that existing cleaning catalyst for tail gases of automobiles generally is to use metal or ceramic honeycomb, uses noble metal (Pt, Pd, Rh) to be active component, and transition metal and alkaline-earth metal are for helping active component.
Almost the performance of whole rare earth oxides all was studied when the exploitation three-way catalyst.Rare earth can play promoter, activator, dispersant, function of stabilizer in catalyst.The three-way catalyst that uses nearly all contains cerium oxide at present, and this mainly gives the credit to the storage oxygen function of cerium oxide.And transition metal plays the assistance catalytic action mainly as the electronics auxiliary agent in catalyst.
Alkali earth metal is the main function of stabilizer that rises in catalyst, and they stablize the crystalline structure effect at play the same with the part rare earth, suppress the transformation mutually of aluminium oxide, improve the stability of aluminum oxide coating layer, thereby improves the heat endurance of catalyst.
Pt in the catalyst, Pd, Rh are one of principal elements that constitutes the Catalyst Production cost.People wish to be used for tail gas clean-up with the base metal catalysts that does not add noble metal for this reason.Experiment shows that base metal catalysts is that the activity that equates with noble metal is arranged when middle warm area (400～600 ℃) and medium air speed.The characteristics of this class catalyst are that ability to take oxygen is strong and firm, and desorption is difficult, the oxygen supply speed of catalyst is affected, thereby when low temperature, high pollution substrate concentration and high-speed, exposes the deadly defect of oxidation rate than noble metal difference.And aspect durability, anti-S poisoning aspect is all far away from noble metal catalyst.Therefore a large amount of on the market at present cleaning catalysts that are still the platinum group element that use.For the catalyst that is used for purifying vehicle exhaust, people have carried out a large amount of research and developments, and a large amount of documents has been arranged, and (Ye Qing, gold is equal, Chen Yongbao, kingly way.Beijing University of Technology's journal, 26 (1), 2000, the present situation development and the trend of P112:117. vehicle tail gas triple effect catalyst.; Cai Shengyou, yellow brave. functional material, 29 (3), 1998, P225:228.Al
2O
3The applicating and exploitation of base coating technology in the catalytic cleaning of car tail gas device.; Peace qin, Feng Changgen, Ceng Qingxuan, Wang second place, You Shaoxiong. chemistry circular, (3), 2001, P135:140. ceramic honeycomb carrier γ-Al2O3 coating progress.; Weng Duan, Li Zhenhong, Wu Xiaodong, Xu Cenghua, Chen Huapeng, stone is of heap of stone. rare earth, 22 (5) effects of 2001, P55:58. rare earth in automobile exhaust purifier.; Mai Liqiang, Zou Zhengguang, Cui Tianshun. Technical Colleges Of Guilin's journal, 19 (2), 1999, P188:199.TWC handles the progress of vehicle exhaust .), patent is seen in report.
By adding rare earth and preparation method's improvement, the noble metal dosage of three-way catalyst drops to several grams from every liter tens early stage gram.Existing noble metal representative formula is that Pt: Pd: Rh is (5: 0: 1), (1: 10: 1), (0: 10: 1) or full palladium catalyst, and consumption is 1.4～4.2 gram per unit volumes.Noble metal dosage is still the principal element of decision catalyst cost, along with the further strictness of worldwide noble metal resource anxiety and Abgasgesetz, requires to improve the low temperature active and the endurance quality of catalyst on the one hand; To reduce the consumption of noble metal on the other hand.Be necessary the cleaning catalyst for tail gases of automobiles that research cost is lower, active better, endurance quality is stronger.
At present industrial typical preparation method be a coating process, and slurries are made in activated alumina, metal oxide auxiliary agent and the mixing of precious metal salt composition instrument, and then is coated on the ceramic matrix (as patent application: 00124737.9).The characteristics of this method are that technology is simple.Weak point is, has the noble metal of part to be covered by compositions such as activated alumina and auxiliary agents, can not all be exposed to the surface of catalyst and can not get effective utilization; Secondly, the catalyst of this method preparation, coating easily hardens, fragility is big, and coating is poor with the compatibility of pottery, through impacts such as repeatedly cold cycling and mechanical oscillation, finally can cause coating to break, come off, the active component on the coating also comes off thereupon, and reduce the service life of catalyst.
Change aluminium oxide into the aluminium glue dip-coating, form aluminum oxide coating layer after, flood auxiliary agent and active component more respectively, this method can be improved the compatibility of coating and pottery (as patent application: 99105254.4,99105250.1).Weak point is, complex process need just can reach required load capacity through dip-coating repeatedly repeatedly, and this mainly is because the aluminium glue water content is big, and the primary coating amount is less, and the excessive coating of primary coating amount is easy to crack.The activated alumina load capacity is on the low side, and the effective surface area that provides is less, and makes active component Pt, Pd, Rh better not to disperse and influence activity of such catalysts and endurance quality.
Summary of the invention
In order to overcome the deficiency of catalyst in the existing ternary cleaner, the invention provides that a kind of cost of being made up of modified ceramic, modified aluminas and noble metal is low, relative less, the active height of noble metal dosage, stable again ternary catalyst for automobile tail gas and preparation method thereof at high temperature.
The technical solution adopted for the present invention to solve the technical problems is: with modified ceramic is first carrier, with modified oxidized aluminized coating is second carrier, with precious metals pt, Pd, Rh is active component, it is characterized in that: described modified ceramic is for through mishmetal, transition metal modified cordierite honeycomb ceramic.Described modified oxidized aluminized coating is divided into inside and outside two-layer, and interior modified oxidized aluminized coating is applied directly on the modified ceramic, and on the modified oxidized aluminized coating, active component was coated on the modified oxidized aluminium lamination in outer modified oxidized aluminized coating was coated on.The modifier of wherein said modified aluminas is mishmetal, transition elements, alkaline-earth metal.
Catalyst of the present invention, described cordierite honeycomb ceramic are the porous cordierite ceramics of 400～600 hole/square inches of producing of Shentai Shentai New Inorganic Material Co., Ltd., or the character porous ceramics close with it on the market.Its inside is straight parallel reduction of fractions to a common denominator cloth, and the interface, duct is a square.After its usefulness mishmetal, transition metal oxide modification, as first carrier of catalyst.Our researcher is by finding cordierite ceramic comparative study both domestic and external: homemade pottery is that with the main difference of external pottery the intensity of homemade pottery is relatively poor under the identical condition of wall thickness.After the present invention improves homemade pottery by employing mishmetal and transition metal oxide, its intensity is significantly improved, simultaneously by duct surface Modification to pottery, increased the roughness of hole wall, easier hanging makes that simultaneously pottery is better with the degree of adhesion of interior modified oxidized aluminized coating.The modifier of modified ceramic of the present invention, wherein mishmetal is carbonic acid or the nitric acid rare earth mine tailing behind the valuable rare earth element of extraction, and it consists of Ce:15～50%, La:20～75%, Y, Nd, Pr:2～8%, the percentage composition sum of mentioned component should equal 100%.
Catalyst of the present invention, in every liter of described cellular ceramic substrate matrix, the amount of modified oxidized aluminized coating, internal layer is 30～120g, and skin is 20～90g, and specific area reaches 20～40 square metres/milliliter.
In the catalyst of the present invention, the used rare earth of modified oxidized aluminized coating is the mishmetal mine tailing behind the valuable rare earth element of extraction, and it consists of Ce:15～50%, La:20～75%, Y, Nd, Pr:2～8%, the percentage composition sum of mentioned component should equal 100%.In per 100 gram modified aluminas quality, contain and mix rare earth oxide 7～20g.As everyone knows, Ce mainly plays a part to store the oxygen agent in three-way catalyst, and other rare earth such as La mainly rises and stablizes γ-Al
2O
3Crystal phase structure and the effect that improves stability, the used cheap mishmetal mine tailing cost of the present invention is lower, effect is preferable.
Catalyst of the present invention is characterized in that the ectonexine modified aluminas adopts different modified formulas.Alkaline earth oxide, mishmetal modification are mainly used in the internal layer modification.Alkaline earth oxide is one or more in Ca, Mg, Sr, the Ba oxide.We are by discovering, the adhesion of modified oxidized aluminized coating and ceramic matrix is one of key performance that influences catalyst service life.Pottery is poor with the adhesion of coating, and then catalyst is in use through water.Cold and hot, big air speed gas shock, coating easily comes off, and makes catalyst lose its function; And adhesion is good, and then cold and hot, the big air speed of ability is impacted.Combine closely between mishmetal and the alkaline earth oxide modification that catalyst inner layer of the present invention is selected for use through us, and to the modification of blank pottery, the adhesion between undercoating and the pottery is good, coating and pottery, the while is again main oxygen memory block.Used alkaline earth oxide is counted 5～20g with modified aluminas in every 100g.
The main modifier of outer modified oxidized aluminized coating is mishmetal, transition metal oxide and alkaline earth oxide.In 100 gram modified aluminas, wherein the amount of mixed rare-earth oxide is 10～25 grams, and alkaline earth oxide is one or more in the oxide of Ca, Mg, Sr, Ba, and its consumption is 10～20 grams; At skin, alkaline earth oxide can improve the adsorption capacity of catalyst to NOx, can promote the conversion of NOx to a certain extent.Transition metal oxide is mainly TiO
2, ZnO, NiO, Fe
2O
3, among the MnO one or more, wherein the effect talked about in coating of every kind of element has nothing in common with each other.As aluminium oxide through TiO
2, after the ZnO modification, it is to harmful poisonous substance SO
2Suction-operated weaken, help the poisonous substance desorption and the poisoning that slows down catalyst, simultaneously through TiO
2Etc. modified oxidized aluminized coating, make carrier and CeO
2With noble metal, particularly the interaction of Rh weakens, thereby helps the stable catalysis efficiency that improved Rh of Rh under the condition of high temperature.Ni itself just has catalytic performance, it can promote water gas shift reaction on the one hand, produce more reducing substances, improve the catharsis of catalyst to NOx, the adding of Ni on the other hand, can measure than chemical reaction at activation CO, HC under the lower temperature, NOx, make the initiation temperature of catalyst reduce.
Catalyst of the present invention, the catalytic active component of using as Pt, Pd, its ratio of Rh is: 5～10: 3～6: 0.5～2; The noble metal overall control is at every liter of catalyst of 0.4～1.2g.The minimizing of noble metal dosage has benefited from special γ-Al on the one hand
2O
3The modification mode of coating and ectonexine structure; Be the special coating method of noble metal on the other hand.By in precious metal solution, adding chelating agent or stabilizing agent, using NH simultaneously
3The pH value that water increases solution is 3～5.Can delay the diffusion velocity of precious metal ion like this, make noble metal mainly be coated on outer modified oxidized aluminized coating.The adding of stabilizing agent simultaneously can prevent from the dry run to make the gathering once again of precious metal ion because of diffusion.General effect is, noble metal mainly is distributed in external coating, and utilization rate improves, and does not assemble, and metallic is little, and active surface area is big, the specific activity height.
Catalyst of the present invention, its preparation method may further comprise the steps:
1), in proportion with mixed rare earth nitrates, transition metal nitrate, alkaline earth nitrate, soluble in water, join respectively ceramic modified solution, internal layer modification liquid, outer modification liquid.Get blank ceramic honey comb, γ-Al
2O
3, with blotting infusion process, flood above-mentioned three solution respectively, after 50～180 ℃ of oven dry,, make modified ceramic, interior modified aluminas, outer modified aluminas respectively in 450～900 ℃ of roasting 3-5 hours;
2), the modified aluminas that step 1) is made is with aluminium oxide: the ratio of lapping liquid=1: 1 places the ball milling instrument in grinding 6～12 hours.Obtaining proportion respectively is 1.2～1.6, and viscosity is the inside and outside modified oxidized aluminized coating slurries of 10～90CP;
3), modified ceramic was dipped in earlier in the internal layer slurry 5～10 minutes, take out, centrifugal removal redundant sizing agent is at 50-120 ℃ fully after the oven dry, 400～600 ℃ of roastings 3～4 hours;
4), the pottery that is coated with the internal layer modified aluminas that again step 3) made, be dipped in the outer slurry 5～10 minutes, take out, centrifugal removal redundant sizing agent is at 50～120 ℃ fully after the oven dry, 400～600 ℃ of roastings 3～4 hours;
5), be made into certain density solution with the solubility chlorination salt of noble metal is soluble in water, wherein add a spot of stabilizing agent, regulating pH value with ammoniacal liquor is 3～5, the pottery that step 4) is obtained was dipped in the precious metal solution 10～120 seconds, excessive solution is blown away in taking-up, 50～120 ℃ make its bone dry after, in 200～850 ℃ of roastings 4～6 hours, catalyst.
The invention has the beneficial effects as follows improving of preparation method the compatibility of coating and pottery improved the heat endurance of catalyst simultaneously, make catalyst have the long life; Adopt modification of cheap mishmetal mine tailing and special noble metal mode of loading, improved the noble metal decentralization, noble metal dosage is relatively low, and total amount is 0.4～1.2g/L, and the catalyst cost is low, and is active good.
Description of drawings
Fig. 1 is the conversion ratio (λ=1) of FD type three-way catalyst.
Fig. 2 is the car load condition tail gas discharge value of FD three unique catalytic converter.
Fig. 3 is the light off characteristics curve (aging before) of FD three-way catalyst, among the figure abscissa be the catalyst inlet temperature (℃), ordinate is conversion ratio (%).
Fig. 4 is the air-fuel ratio characteristic curve (aging back) of FD three-way catalyst, among the figure abscissa be the catalyst inlet temperature (℃), ordinate is conversion ratio (%).
The specific embodiment
Embodiment 1
1. the modification of cordierite honeycomb ceramic.
Get mixed rare earth nitrates 600g, ferric nitrate 100g, aluminum nitrate 800g, soluble in water, be made into the aqueous solution of 2000mL.With a blank volume is 1 liter of cordierite, claims its quality, is dipped in to prepare solution central 10 minutes, takes out and blows away excessive solution.Behind 110 ℃ of bone dries,, obtain modified ceramic in 450～900 ℃ of temperature-programmed calcinations 4 hours.
2. γ-Al
2O
3Modification
Get mixed rare earth nitrates 350g, magnesium nitrate 160g, barium nitrate 20g, the 700ml aqueous solution that is made into soluble in water is with blotting dipping 2000g γ-Al
2O
3, through 110 ℃ of dryings fully after, in 400～600 ℃ of temperature-programmed calcinations 3 hours, obtain interior modified aluminas.
Get mixed rare earth nitrates 400g, alkaline earth nitrate 200g, transition metal nitrate 220g, the 700ml aqueous solution that is made into soluble in water is with blotting dipping 2000g γ-A1
2O
3, through 110 ℃ of dryings fully after, in 400～600 ℃ of temperature-programmed calcinations 3 hours, obtain outer modified aluminas.
3. coating is flooded
With the ectonexine modification γ-Al that obtains
2O
3, with solid: the lapping liquid ratio is that 1: 1 ratio was ground 10 hours in the ball milling instrument, obtains the modified oxidized aluminum slurry of ectonexine respectively.
Get 1 liter of modified ceramic, in being dipped in the modified oxidized aluminum slurry 3～5 minutes, take out and remove redundant sizing agent, in 50～120 ℃ fully the oven dry after, in 450 ℃ of roastings 2 hours, obtain scribbling the pottery of modified oxidized aluminized coating, be 30～120g in the amount of every liter of ceramic matrix aluminum oxide coating layer.
The pottery of modified oxidized aluminized coating in scribbling was immersed in the outer modified oxidized aluminum slurry 3～5 minutes, redundant sizing agent is removed in taking-up, in 50～120 ℃ fully the oven dry after, in 450 ℃ of roastings 2 hours, obtain scribbling the pottery of inside and outside two-layer modified oxidized aluminized coating, in every liter of ceramic matrix, the amount of outer modified oxidized aluminized coating is 10～30g.
4. noble metal floods
Press Pt, Pd, the Rh ratio is 6: 4: 1 a ratio, takes by weighing Pt, Pd, the soluble-salt of Rh is made into the solution of 7.6g/L, adds polyvinyl alcohol 2000: 0.001g, chelating agent: 0.10g in every liter; Urea: 0.02g, transferring noble metal PH with the ammoniacal liquor of 3mol/L is 3～5.The pottery with two coatings that obtains is dipped in the precious metal solution, controls the noble metal load capacity by the control dip time.Complete through 110 ℃ of dryings, in 200～850 ℃ of temperature-programmed calcinations 10 hours, obtain catalyst of the present invention, the noble metal total content of the catalyst of gained is 0.4～1.2g.
Press the catalyst of embodiment preparation; make the FD ternary cleaner behind cushioned layer and the shell; detect through Tianjin country car quality supervision and test center, its every performance meets " HCRJ007-1999 gasoline car exhaust gas catalytic converter " Environment Protect in China product and assert technical conditions (shown in Fig. 1,3,4).
According to catalyst noble metal total amount of the present invention is 0.4～1.2g, and entrucking is used can reach GB18352.2-2001, the discharge standard (as shown in Figure 2) that national second stage is implemented.
Claims (6)
1. three-way catalyst that is used for vehicle exhaust, it is characterized in that: with modified ceramic is first carrier, with modified oxidized aluminized coating is second carrier, precious metals pt, Rh, Pd are active component, it is characterized in that: described modified ceramic is for through mishmetal, transition metal modified cordierite honeycomb ceramic; Described modified oxidized aluminized coating divides inside and outside two-layer, inside and outside modified oxidized aluminized coating adopts different modified formulas, interior aluminum oxide coating layer alkaline earth oxide, mishmetal modification, external oxidation aluminized coating mishmetal, transition metal oxide and alkaline earth oxide modification, interior modified oxidized aluminized coating is applied directly on the modified ceramic, on the modified oxidized aluminized coating, active component was coated on the modified aluminas in outer modified oxidized aluminized coating was coated on.
2. catalyst according to claim 1, it is characterized in that: described cordierite honeycomb ceramic is the cordierite honeycomb ceramic of 400～600 hole/square inches, its inside is straight parallel reduction of fractions to a common denominator cloth, the interface, duct is a square, after its usefulness mishmetal, transition metal oxide modification, as first carrier of catalyst.
3. catalyst according to claim 1 is characterized in that: catalyst of the present invention, in every liter of described honeycomb ceramic carrier matrix, the amount of modified oxidized aluminized coating, internal layer is 30～120g, and skin is 20～90g, and specific area reaches 20～40 square metres/milliliter.
4. catalyst according to claim 1, it is characterized in that: in the catalyst of the present invention, the used mishmetal of modified oxidized aluminized coating is the mishmetal mine tailing behind the valuable rare earth element of extraction, it consists of Ce:15～50%, La:20～75%, Y, Nd, Pr:2～8%, the percentage composition sum of mentioned component should equal 100%; Used alkaline earth oxide is Ca, Mg, Sr, Ba oxide; Used transition metal oxide is TiO
2, ZnO, NiO, Fe
2O
3, MnO.
5. catalyst according to claim 1 is characterized in that: catalyst of the present invention, and the catalytic active component of using as Pt, Pd, Rh, its ratio is: 5～10: 3～6: 0.5～2, the noble metal overall control is at every liter of catalyst of 0.4～1.2g.
6. preparation method who is used for ternary catalyst for automobile tail gas is characterized in that: catalyst of the present invention, and its preparation method may further comprise the steps:
1), in proportion with mixed rare earth nitrates, transition metal nitrate, alkaline earth nitrate, soluble in water, join respectively ceramic modified solution, internal layer modification liquid, outer modification liquid; Get blank ceramic honey comb, γ-Al respectively
2O
3, with blotting infusion process, flood above-mentioned three solution respectively, after 50～180 ℃ of oven dry,, make modified ceramic, interior modified aluminas, outer modified aluminas respectively in 450～900 ℃ of roasting 3-5 hours;
2), the modified aluminas that step 1) is made is with aluminium oxide: the ratio of lapping liquid=1: 1 places the ball milling instrument in grinding 6～12 hours.Obtaining proportion respectively is 1.2～1.6, and viscosity is the inside and outside modified oxidized aluminized coating slurries of 10～90CP;
3), modified ceramic was dipped in earlier in the internal layer slurry 5～10 minutes, take out, centrifugal removal redundant sizing agent is at 50-120 ℃ fully after the oven dry, 400～600 ℃ of roastings 3～4 hours;
4), the pottery that is coated with the internal layer modified aluminas that again step 3) made, be dipped in the outer slurry 5～10 minutes, take out, centrifugal removal redundant sizing agent is at 50～120 ℃ fully after the oven dry, 400～600 ℃ of roastings 3～4 hours;
5), be made into certain density solution with the solubility chlorination salt of noble metal is soluble in water, wherein add a spot of stabilizing agent, regulating pH value with ammoniacal liquor is 3～5, the pottery that step 4) is obtained was dipped in the precious metal solution 10～120 seconds, take out and remove excessive solution, 50～120 ℃ make its bone dry after, in 200～850 ℃ of roastings 4～6 hours, catalyst.
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| CN101357332B (en) * | 2007-07-31 | 2013-04-10 | 比亚迪股份有限公司 | Automobile tail gas cleaning catalyst and its preparation method |
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