Be used for the liquefied petroleum gas is the three-way catalyst of the purifying vehicle exhaust of fuel
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 liquefied petroleum 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 liquefied petroleum gas (be called for short LPG, down with) has combustion characteristics near gasoline, and octane number is than the gasoline height, and the thermal efficiency is big.LPG 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 LPG automobile, thereby the LPG fuel vehicle has obtained using widely.
At present, the LPG 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 LPG 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 LPG vehicle exhaust.Therefore the tail-gas from gasoline automobiles cleaning catalyst can not well adapt to the LPG car, is necessary the tai-gas clean-up catalyst of researching and developing out the LPG automobile specified at the operating mode and the discharging characteristics of LPG 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, in order to improve the hear resistance of coating, the dispersiveness of catalytic active component.Usually in the matrix of aluminium oxide, introduce alkaline earth oxide or transition metal oxide or rare earth oxide (as La, Ce etc.).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.
The foreign literature of specializing in the LPG cleaning catalyst for tail gases of automobiles is few.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), the compound of metal B (is selected from I
A, II
A, rare earth and IV
BFamily).
Patent JP2004249214 has related to the catalyst that a kind of dimethyl ether automobile and LPG purifying vehicle exhaust are used.Catalyst preparation process: flood inorganic porous carrier (ceramic fibre, porous ceramics, molecular sieve etc.) with chromium chloride and chloroplatinic acid aqueous solution, heat then and reduce.
Choudhary etc. have prepared the ZrO that the Mn that is used for controlling LPG vehicle exhaust propane content mixes
2Catalyst has been studied different precipitating reagents, ZrO
2Crystal formation, Mn/Zr ratio, sintering temperature, reaction temperature, air speed are to influence [the Proceedings-Inian Academy of Science of catalyst performance, Chemical Sciences, 115 (4), 287-298 (English) 2003 Indian Academy ofSciences].
Summary of the invention
It is the three-way catalyst of the 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 liquefied petroleum gas, to overcome the defective that the tail-gas from gasoline automobiles cleaning catalyst is not suitable for the LPG purifying vehicle exhaust, satisfy the operating mode and the discharging characteristics of LPG vehicle exhaust, reach the needs of LPG 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 lanthana of rare earth oxide, cerium oxide, praseodymium oxide or neodymia;
Said catalytic active component is the mixture of palladium-rhodium-cerium-nickel metal oxide;
In optimized technical scheme of the present invention, the weight ratio of cerium zirconium sosoloid is 8: 2~2: 8, described cerium zirconium sosoloid also comprises other elements of cerium zirconium sosoloid gross weight 0.2~8%, 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 that 4: 6~6: 4 cerium zirconium sosoloid is the best wherein with cerium zirconium ratio;
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 part by weight 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 palladium-rhodium in the catalyst-cerium-nickel metal oxide is 0.5~6% of catalyst weight, the weight ratio of palladium-rhodium in the catalyst-cerium-nickel is 3~6: 2~4: 15~20: 20~25, palladium 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, coating is coated on the cordierite honeycomb ceramic, and 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) then step (1) has been contained the cordierite honeycomb ceramic monolith of coating, adopting equi-volume impregnating to be immersed in weight concentration is in 0.5~6% the aqueous solution that contains palladium salt, rhodium salt, nickel 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 palladium salt, rhodium salt, cerium salt and nickel salt, the weight ratio of palladium salt, rhodium salt, cerium salt and nickel salt is 3~6: 2~4: 15~20: 20~25;
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 palladium salt is selected from palladium bichloride or palladium nitrate;
Said rhodium salt is selected from radium chloride or rhodium nitrate;
Said nickel salt is selected from nickel 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 the cordierite honeycomb ceramic monolith that step (1) has been contained coating material adopts equi-volume impregnating to flood with palladium salt, rhodium salt solution earlier, dry, 400~600 ℃ of roastings 3~6 hours, flood with nickel salt, cerium salt solution again, dry then, 500~800 ℃ of roastings 3~6 hours;
The weight concentration of palladium salt, rhodium salt solution is 0.1~1.5%;
The weight concentration of nickel salt, cerium salt solution is 0.5~4.5%; Or
Step (1) has been contained cated cordierite honeycomb ceramic monolith adopts equi-volume impregnating to flood with nickel salt, cerium salt solution earlier, drying, 500~800 ℃ of roastings 3~6 are flooded with palladium salt, rhodium salt again, drying, 400~600 ℃ of roastings 3~6 hours;
The weight concentration of palladium salt, rhodium salt solution is 0.1~1.5%;
The weight concentration of nickel salt, cerium salt solution is 0.5~4.5%.
Adopt the catalyst that said method obtained, for a kind of being used for the liquefied petroleum 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 LPG purifying vehicle exhaust.As the initiation temperature to CO is 200 ℃, is 206 ℃ to the initiation temperature of HC, is 211 ℃ 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 LPG running cars service life.In catalytic active component, introduce base metal nickel and rare earth cerium, greatly reduce the consumption of precious metal palladium, 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 palladium chloride 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 nickel nitrate 0.26 gram, 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 palladium 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%, C
3H
6Gas 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 LPG 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 nickel nitrate 2.0 grams, cerous nitrate 1.5 grams add deionized water to 25ml 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; Measuring concentration is the palladium chloride 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 nickel, 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 palladium chloride aqueous solution 2.46ml of 0.0122 gram/ml, concentration is the radium chloride aqueous solution 1.12ml of 0.0215 gram/ml, add nickel nitrate 1.45 grams, cerous nitrate 1.10 grams add deionized water to 25ml after the dissolving, make active component precursor salt mixed solution, adopt equi-volume impregnating that activity component impregnation was 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: