CN104525180A - Preparation method for cerium-zirconium-aluminum-lanthanum-based oxygen storage material of mesoporous structure - Google Patents
Preparation method for cerium-zirconium-aluminum-lanthanum-based oxygen storage material of mesoporous structure Download PDFInfo
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Abstract
The invention discloses a preparation method for a cerium-zirconium-aluminum-lanthanum-based oxygen storage material of a mesoporous structure. The preparation method sequentially includes the following steps that a mixed salt solution A containing cerium salt, zirconium salt, aluminum salt, lanthanum salt and doping element salt, a precipitant solution B and a mesporous structure template solution C are prepared; under mechanical or magnetic stirring, the solution A and the solution B are added into the template solution C in a flow-merging mode and aged after reaction, after aging, cleaning is performed, or neutralizing agents are added so that the mixed solution can be neutralized; then filtering or centrifuging is performed, and water and dispersing agents are added into an obtained precipitate so that the precipitate can be stirred to be homogeneous dispersion gel; obtained supernatant is used for dissolving the mixed salt or preparing the template solution C; the gel is infiltrated through absolute ethyl alcohol after being dried through air blowing, then smashed after drying is performed again and roasted inside a muffle furnace to obtain the cerium-zirconium-aluminum-lanthanum-based oxygen storage material of the mesoporous structure. The cerium-zirconium-aluminum-lanthanum-based oxygen storage material prepared through the preparation method is of a thick-pore-wall structure not prone to collapsing at a high temperature and is good in comprehensive performance has a high specific surface area and a large pore volume, and is good in oxygen storage performance and low in reducing peak temperature.
Description
Technical field
The present invention relates to hydrogen-storing material technical field, particularly relate to a kind of preparation method of the meso-hole structure cerium zirconium aluminium lanthanum based oxygen storage material for high standard purifying vehicle exhaust.
Background technology
The exhaust emissions that the fast development of auto industry brings has become one of topmost pollution sources in city, and for this reason, country improves constantly motor vehicle exhaust emission classification standard.2013, China implemented integrally state four exhaust emission standard, Beijing executed state five exhaust emission standard.Adopt electronic fuel injection (EFI) to control air-fuel ratio (A/F), and install triple effect catalytic converter (TWC) additional, the CO in tail gas, oxidizing hydrocarbon are become CO
2and H
2o, by NO
xbe reduced to N
2, effectively can reduce the discharge of dusty gas in vehicle exhaust; And use cleaning catalyst to be that vehicle exhaust thoroughly purifies the most effective means.
At present, auto-exhaust catalyst mainly by noble metal active component, auxiliary agent hydrogen-storing material and the carrier γ-Al for supporting active component such as Pt, Rh, Pd of catalytic action
2o
3composition.Hydrogen-storing material is to the dispersion of noble metal and stable play a part key, can improve high high-temp stability and the oxygen storage capacity of noble metal, expands its air-fuel ratio operation window, stablize γ-Al
2o
3the specific area of carrier, prevention γ-Al
2o
3the phase in version caused because of sintering and raising carrier γ-Al
2o
3high high-temp stability.Say in a way, the quality that catalyst stores oxygen performance decides the performance of three-way catalyst.Along with the upgrading of tail gas clean-up standard, the performance of catalyst is had higher requirement and certainly will need to increase bullion content.For this reason, development high-performance hydrogen-storing material becomes study hotspot to improve catalyst performance, as far as possible minimizing noble metal dosage, and the preparation of high-performance hydrogen-storing material is catalyst source core technology of preparing.
Cerium oxide has obtained investigation and application widely in hydrogen-storing material, its development experience three phases: the first stage is CeO
2application, but CeO
2poor heat stability, low temperature oxygen storage capacity is weak, and grow up rapidly higher than 800 DEG C of crystal grain, specific area declines to a great extent, and causes storing oxygen performance and reduces rapidly; Second stage is the application of binary cerium base oxide, and zirconium ion is introduced CeO
2lattice defines defect fluorite type solid solution, overcomes CeO
2the shortcomings such as high high-temp stability is poor, the dispersal ability of cryogenic oxygen is weak, significantly improve heat endurance and Oxygen storage capacity, but Ce-Zr hydrogen-storing material still can not meet the discharge standard needs of constantly upgrading; Phase III is the application of ternary cerium base oxide, namely adopts noble metal, transition metal, alkaline-earth metal, rare earth metal and Al
2o
3deng to cerium zirconium sosoloid modification doping, strengthen the high-temperature aging resisting of hydrogen-storing material further, improve its oxygen storage capacity.
The hydrogen-storing material with excellent combination properties such as high-specific surface area, large pore volume, suitable pore-size distribution, good high-temperature aging resisting performance, the cryogenic reducting performances storing oxygen performance and excellence is the essential condition of new three-effect catalysis hydrogen-storing material.
At present, in catalyst coat, cerium zirconium sosoloid is dispersed in carrier γ-Al
2o
3in, in fact, two-way interaction, cerium zirconium sosoloid stablizes γ-Al
2o
3the specific area of carrier, prevention γ-Al
2o
3the phase in version caused because of sintering, raising carrier γ-Al
2o
3high high-temp stability; Aluminium oxide then suppresses sintering and the grain growth of cerium zirconium sosoloid under high temperature.There is research with cerium zirconia material Modification on Al
2o
3, demonstrate hydrogen-storing material and Al
2o
3common feature, cerium zirconium-alumina composite oxide is called as third generation hydrogen-storing material.With cerium zirconio material and the mutual modification of aluminium oxide, prepare Ce-Zr-Al based composite, the high temperature ageing resistance improving hydrogen-storing material becomes new study hotspot.
But, although Ce-Zr-Al based composite significantly can improve the high temperature ageing resistance of hydrogen-storing material, large specific area is had after high temperature ageing, but oxygen storage capacity does not have obvious reduction containing the cerium zirconium hydrogen-storing material of aluminium, the temperature rise of hydrogen reducing peak, pore volume is little, existing research display combination property is poor, patent also seldom has the report of the integrated datas such as correlation ratio surface, pore volume, oxygen storage capacity, hydrogen reducing performance, research also obtains its effect mainly with making catalyst, in fact, the performance of hydrogen-storing material itself is also very important.The patent No. 200510020615.1 discloses a kind of Ce-Zr-Al based oxygen stored material and preparation method thereof, and after 1000 DEG C of roasting 5h, specific area reaches as high as 110m
2/ more than g, at least can reach 38m
2/ more than g, but the hydrogen-storing material aperture that the method is prepared is less, and high temperature ageing resistace is still poor.Patent 201210148884 discloses a kind of preparation method of Ce-Zr-Al based oxygen stored material, adopts boehmite to obtain Ce-Zr-Al based oxygen stored material specific area after 1000 DEG C of roasting 10h and is greater than 60m
2/ g, after 1100 DEG C of roasting 10h, specific area is greater than 40m
2/ g; Patent CN103084161A (publication date 2013.5.8) discloses a kind of cerium zirconium aluminum based multiple oxide rare earth oxygen storage material and preparation method thereof, and its alumina raw material selects macropore γ-Al
2o
3or pore volume>=0.9cm
3the macropore boehmite of/g, and by adding surface conditioning agent, ensureing that sediment presoma has larger aperture, pore volume after baking, improving the high temperature ageing resistance of material; The combination property data such as oxygen storage capacity, pore volume, reducing property but these patents are not all correlated with.Patent 201110204326 discloses a kind of catalyst carrier material and the manufacture method thereof with oxygen storage capacity, patent CN103566923A discloses a kind of Cerium zirconium aluminum composite oxide oxygen storage material and preparation method thereof, large pore volume and specific area is all obtained afterwards, also the relevant combination property such as oxygen storage capacity, reducing property data although fresh and aging.Therefore, research and development one had both had high-specific surface area, large pore volume, the hydrogen-storing material of the excellent combination property of the Oxygen storage capacity had again and lower reduction peak temperature, be meet the high standard purifying vehicle exhaust market of upgrading at present in the urgent need to.
Summary of the invention
The technical problem to be solved in the present invention overcomes the deficiencies in the prior art, provides a kind of and have high-specific surface area, the good combination property of large pore volume, better Oxygen storage capacity and lower reduction peak temperature and the preparation method of the low Ce-Zr-Al based oxygen stored material of cost.
For solving the problems of the technologies described above, the technical scheme that the present invention proposes is:
A preparation method for meso-hole structure cerium zirconium aluminium lanthanum based oxygen storage material, comprises the following steps:
1) by the salt mixed dissolution of cerium salt, zirconates, aluminium salt, lanthanum salt and doping M element, then add hydrogen peroxide, be adjusted to required concentration, volume stirring, obtain mixing salt solution A;
2) precipitating reagent be dissolved in water and be diluted to desired concn, volume, being precipitated agent solution B;
3) will be adjusted to desired concn and volume after surfactant dissolves, reconciliation statement surface-active agent solution pH value, obtains meso-hole structure template solution C;
4) under machinery or magnetic stirring being carried out to described meso-hole structure template solution C, and stream adds described mixing salt solution A and described precipitant solution B, keep PH to be greater than 7 by coutroi velocity in course of reaction, reaction temperature is 25 ~ 60 DEG C, and preserving heat after reaction ends continues to stir;
5) 85 ~ 95 DEG C of aging steps 4) after mixed liquor 2 ~ 24h, clean or add nertralizer and fully stir and make mixed liquor be neutral;
6) to step 5) after neutral mixed liquor suction filtration or centrifugal, suction filtration or centrifugal after precipitation add suitable quantity of water and pull an oar and add dispersant, stir into dispersed gel; Suction filtration or centrifugal supernatant are used for above-mentioned steps 1) dissolve salt-mixture or for above-mentioned steps 3) in dissolve surfactant;
7) described gel is infiltrated with absolute ethyl alcohol after 100 ~ 120 DEG C of forced air dryings, then pulverize after spray-dried, Rotary drying or oven drying, obtained precursor powder;
8) described precursor powder is placed in Muffle furnace 500 ~ 600 DEG C of roasting 4-10h i.e. obtained meso-hole structure cerium zirconium aluminium lanthanum based oxygen storage material.
Above-mentioned preparation method, preferably, described step 1) in, cerium salt is the combination of one or more in cerous nitrate, ammonium ceric nitrate, cerium chloride and cerous acetate; Zirconates is the combination of one or more of zirconium nitrate, zirconyl nitrate, zirconium oxychloride and acetic acid zirconium; The Alumina gel that aluminium salt is aluminum nitrate or is made up of boehmite; Doping M element is the combination of one or more elements removed in rare earth element in other element of cerium and lanthanum, alkali earth metal, transition element, Bi and V.
Above-mentioned preparation method, preferably, described rare earth element is one or more in Y, Pr, Nd and Tb; Described alkali earth metal is one or more in Ca, Sr, Ba and Mg; Described transition element is one or more in Mn, Cu, Fe and Ni.
Above-mentioned preparation method, preferably, described step 1) in, the addition of hydrogen peroxide and the mol ratio of cerium salt are 1: 1 ~ 1: 2; In mixing salt solution A, the total concentration of salt-mixture is 0.1 ~ 2mol/L.
Above-mentioned preparation method, preferably, described step 2) in, precipitating reagent is one or more in ammoniacal liquor, ammonium carbonate and carbonic hydroammonium, and in precipitant solution B, the concentration of precipitating reagent is with NH
4 +count 0.1 ~ 3mol/L.
Above-mentioned preparation method, preferably, described step 3) in, surfactant is any combination of one or more of one or more and polyacrylamide, polyvinyl alcohol, Macrogol 2000, Macrogol 4000, Macrogol 6000, PEG 8000, silane coupler and NPE in triethanolamine, softex kw, Cetyltrimethylammonium bromide, quaternised polyacrylamide.
Above-mentioned preparation method, preferably, described step 3) in, the interpolation total amount of surfactant be calculate product material mass 3 ~ 30%, meso-hole structure template solution C concentration be 0.001 ~ 0.05mol/L, PH be 10 ~ 12.
Above-mentioned preparation method, preferably, described step 4) in, pH value is controlled by mixing salt solution A and precipitant solution B flow velocity, and at the end of reaction, PH is 8.0 ~ 9.5.
Above-mentioned preparation method, preferably, described step 5) in, nertralizer is one or more in acetic acid, oxalic acid, maleic acid, citric acid, tartaric acid, dust technology, watery hydrochloric acid and 1-amino-8-naphthol-3,6-disulfonic acid; Described step 6) in, dispersant is the one or more combination in polyvinyl alcohol, Macrogol 2000, Macrogol 4000, Macrogol 6000, PEG 8000, APES, Brij-35, sodium polyphosphate, sodium metasilicate, calgon and ethylenediamine tetra-acetic acid; The addition of described dispersant is 20 ~ 60% of reaction product quality.
Above-mentioned preparation method, preferably, described step 8) in, meso-hole structure cerium zirconium aluminium lanthanum based oxygen storage material product general formula is: m (Ce
xzr
yla
zm
1-x-y-z): n (Al
2o
3), wherein, x:0.25-0.7, y:0.2-0.6, z:0.01-0.1, m:0.3-0.9, n:0.1-0.7.
The present invention carries out improvement according to mesoporous material molecular sieve formation basic theory makes not givey aperture structure under formation thick hole wall high temperature, in conjunction with the hydrogen-storing material of suitable element composition and doped chemical and process adjustments acquisition good combination property.1992, the scientist of Mobil company breaks through the principle of the molecular formula ion lifting plate effect of single solvation in traditional micro-pore zeolite sieve synthesis procedure, with surfactant self assembly successfully synthesize have bigger serface, duct rule and adjustable ordered mesoporous material molecular sieve.But, the hole wall that the molecular sieve of single templated synthesis produces is thinner, easily decompose in boiling water and subside, organic macromolecule adds specific area, order and the hole body crystal property that can change mesoporous material product, contribute to the generation of thick hole wall product, organic polymer inclusion is in surfactant templates agent colloidal sol liquid crystal micella extexine simultaneously, and template becomes globular micelle from rod-shaped micelle, its pattern is spherical in shape, and low power tem observation is " honeycomb ceramics ".
Compared with prior art, the invention has the advantages that:
1) improve according to mesoporous material molecular sieve formation basic theory, make not givey aperture structure under formation thick hole wall high temperature, mesoporous material molecular sieve surface activating agent template is utilized to form with suitable element and doped chemical and process adjustments combine to have prepared and both have high-specific surface area, large pore volume, the hydrogen-storing material of the excellent combination property of the Oxygen storage capacity had again and lower reduction peak temperature, be particularly suitable for high standard purifying vehicle exhaust market demand, and technique is simple, cost is low, is easy to industrial implementation;
2) the present invention carries out neutralisation treatment to implementation process waste water and recycles as far as possible, and easily, wastewater treatment is few, and saves water source in presoma cleaning.
Accompanying drawing explanation
Fig. 1 is that cerium zirconium aluminium lanthanum based oxygen storage material ageing prod XRD prepared by embodiment 1 schemes.
Fig. 2 is that cerium zirconium aluminium lanthanum based oxygen storage material ageing prod XRD prepared by embodiment 2 schemes.
Fig. 3 is that cerium zirconium aluminium lanthanum based oxygen storage material ageing prod XRD prepared by embodiment 3 schemes.
Fig. 4 is cerium zirconium aluminium lanthanum based oxygen storage material fresh products hydrogen reducing collection of illustrative plates prepared by embodiment 3.
Fig. 5 is cerium zirconium aluminium lanthanum based oxygen storage material ageing prod hydrogen reducing collection of illustrative plates prepared by embodiment 3.
Fig. 6 is that cerium zirconium aluminium lanthanum based oxygen storage material ageing prod XRD prepared by embodiment 4 schemes.
Detailed description of the invention
For the ease of understanding the present invention, hereafter will do to describe more comprehensively, meticulously to the present invention in conjunction with Figure of description and preferred embodiment, but protection scope of the present invention is not limited to following specific embodiment.
Unless otherwise defined, hereinafter used all technical terms are identical with the implication that those skilled in the art understand usually.The object of technical term used herein just in order to describe specific embodiment is not be intended to limit the scope of the invention.
Embodiment 1:
A preparation method for meso-hole structure cerium zirconium aluminium lanthanum based oxygen storage material of the present invention, concrete operation step is as follows:
By CeO
2: ZrO
2: La
2o
3: Y
2o
3: Al
2o
3the weight ratio of=11:7:1:1:19 takes the nitrate of corresponding cerous nitrate, zirconium nitrate, aluminum nitrate, lanthanum nitrate and doped chemical yttrium, add water mixed dissolution, and add the hydrogen peroxide with the amount of cerous nitrate same substance, add water and to stir and the total concentration adjusting salt-mixture in solution is 0.8mol/L, obtain mixing salt solution A; Ammonium carbonate and ammoniacal liquor are mixed with precipitating reagent by amount of substance than for 1:1, this precipitating reagent are dissolved in water and are diluted to precipitating reagent total concentration (with NH
4 +meter) for 1.2mol/L and volume is identical with mixing salt solution A, be precipitated agent solution B; By surfactant, (surfactant is Cetyltrimethylammonium bromide and silane coupler, the two mol ratio is 1:1, addition is calculate product material mass 5%) be dissolved in water, its volume is made to be 1/10 of reacting tank body, adjust PH=12 with ammoniacal liquor, obtaining concentration is 0.005mol/L meso-hole structure template solution C.
Fully stir meso-hole structure template solution C under constant temperature tank body 45 DEG C of conditions, with identical flow velocity and stream adds mixing salt solution A and precipitant solution B, record solution PH=8.5 after reaction terminates, then insulation continues to stir 1h, then 90 DEG C of ageing 16h, and cleaning is to neutral.Centering mixture suction filtration again, sediment after suction filtration adds water and fully pulls an oar, add dispersant (polyvinyl alcohol that dispersant is amount of substance ratio is 1:0.1 and calgon mixture, addition is calculate product material mass 20%) again, make its uniformly dispersion gel; By gel when 120 DEG C of forced air dryings are extremely half-dried, add absolute ethyl alcohol and infiltrate, then after Rotary drying, be placed in Muffle furnace 600 DEG C of roasting 5h and obtain meso-hole structure cerium zirconium aluminium lanthanum based oxygen storage material fresh products; Again cerium zirconium aluminium lanthanum based oxygen storage material fresh products 1000 DEG C of roasting 4h in Muffle furnace are obtained ageing prod.
Test obtained cerium zirconium aluminium lanthanum based oxygen storage material fresh products and ageing prod thereof, recording fresh products specific area is 157.551m
2/ g, pore volume is 0.524cc/g, and oxygen storage capacity is 594.3656 μm of ol/g, H
2reduction peak temperature 505 DEG C; The specific area of ageing prod is 60.179m
2/ g, pore volume is 0.423cc/g, and oxygen storage capacity is 385.156 μm of ol/g, H
2reduction peak temperature 525 DEG C; Be illustrated in figure 1 the XRD figure of ageing prod, the product after as can be seen from the figure aging is still single cerium zirconium sosoloid.
Embodiment 2:
A preparation method for meso-hole structure cerium zirconium aluminium lanthanum based oxygen storage material of the present invention, concrete operation step is as follows:
By CeO
2: ZrO
2: La
2o
3: Bi
2o
3: Al
2o
3the weight ratio of=10.0:8.6:0.9:0.5:20 takes the nitrate of corresponding cerous nitrate, zirconium nitrate, aluminum nitrate, lanthanum nitrate and doped chemical bismuth, add water mixed dissolution, and add hydrogen peroxide by cerous nitrate and hydrogen peroxide amount of substance than for 1:2, add water and stir and regulate the total concentration of salt-mixture in solution to be 0.5mol/L, obtain mixing salt solution A; Be precipitating reagent with ammoniacal liquor, add water and regulate precipitant concentration (with NH
4 +meter) for 1.0mol/L and volume is identical with mixing salt solution A, be precipitated agent solution B; By surfactant, (surfactant is quaternised polyacrylamide and polyvinyl alcohol, the two amount of substance compares 1:1, addition is calculate product amount of substance 5%) dissolve, add water and make volume be 1/10 of reacting tank body, adjust PH=11 with ammoniacal liquor, obtaining concentration is 0.0035mol/L meso-hole structure template solution C.
Fully meso-hole structure template solution C is stirred under constant temperature tank body 45 DEG C of conditions, with identical flow velocity and stream adds mixing salt solution A and precipitant solution B, reaction end records pH value of solution=9.0, then continues to stir 1h, 85 DEG C of ageing 20h, drip nertralizer citric acid to solution while stirring in neutral.Centering solution suction filtration again, sediment after suction filtration adds water and fully pulls an oar, and (dispersant is Macrogol 4000 and ethylenediamine tetra-acetic acid, and the two amount of substance is than being 1:0.1 to add dispersant, addition is calculate product amount of substance 20%), make its uniformly dispersion gel.Dispersion gel in 120 DEG C of forced air dryings to add during partial desiccation absolute ethyl alcohol infiltrate, more spray-dried after, be placed in Muffle furnace 600 DEG C of roasting 5h and obtain meso-hole structure cerium zirconium aluminium lanthanum based oxygen storage material fresh products.Fresh sample 1000 DEG C of roasting 4h in Muffle furnace are obtained ageing prod.
Test obtained meso-hole structure cerium zirconium aluminium lanthanum based oxygen storage material fresh products and ageing prod thereof, recording fresh products specific area is 162.198m
2/ g, pore volume is 0.538cc/g, and oxygen storage capacity is 624.228 μm of ol/g, H
2reduction peak temperature 515 DEG C; Ageing prod specific area is 64.545m
2/ g, pore volume is 0.264cc/g, and oxygen storage capacity is 412.326 μm of ol/g, H
2reduction peak temperature 536 DEG C; Be illustrated in figure 2 the XRD figure of ageing prod, the product after as can be seen from the figure aging is still single cerium zirconium sosoloid.
Embodiment 3:
A preparation method for meso-hole structure cerium zirconium aluminium lanthanum based oxygen storage material of the present invention, concrete operation step is as follows:
By CeO
2: ZrO
2: La
2o
3: MnO:Al
2o
3the nitrate of the weight ratio of=10.6:8.0:0.7:0.7:20 takes corresponding cerous nitrate, zirconium nitrate, boehmite are made Alumina gel, lanthanum nitrate and doped chemical manganese, add water mixed dissolution, and add hydrogen peroxide by cerous nitrate and the amount of substance of hydrogen peroxide than for 1:1, add water and to stir and the total concentration adjusting salt-mixture in solution is 0.6mol/L, obtain mixing salt solution A; Be precipitating reagent with ammoniacal liquor, the adjustment precipitant concentration that adds water is (with NH
4 +meter) for 1.0mol/L and volume is identical with mixing salt solution A volume, be precipitated agent solution B; By surfactant, (surfactant is quaternised polyacrylamide and NPE, the amount of substance of the two compares 1:1, addition is calculate product amount of substance 5%) dissolve, add water and make volume be 1/10 of reacting tank body, adjust PH=12 with ammoniacal liquor, obtaining concentration is 0.005mol/L meso-hole structure template solution C.
Fully meso-hole structure template solution C is stirred at 25 DEG C, with identical flow velocity and stream adds mixing salt solution A and precipitant solution B, reaction end records solution PH=9.0, then continues to stir 1h, 85 DEG C of ageing 24h, drip nertralizer oxalic acid solution while stirring to neutral.Centering mixed solution suction filtration, supernatant after suction filtration stores stand-by, sediment adds water and fully pulls an oar, (dispersant is Macrogol 2000 and sodium polyphosphate to add dispersant again, the two amount of substance is than being 1:0.1, addition is calculate product amount of substance 30%), make its uniformly dispersion gel.Gel infiltrates in 120 DEG C of forced air dryings to adding absolute ethyl alcohol during partial desiccation, after spray-dried, be placed in Muffle furnace 600 DEG C of roasting 5h and obtain meso-hole structure cerium zirconium aluminium lanthanum based oxygen storage material fresh products.Fresh sample 1000 DEG C of roasting 4h in Muffle furnace are obtained ageing prod.
Test obtained meso-hole structure cerium zirconium aluminium lanthanum based oxygen storage material fresh products and ageing prod thereof, the specific area recording fresh products is 160.423m
2/ g, pore volume is 0.475cc/g, and oxygen storage capacity is 604.73656 μm of ol/g, H
2reduction peak temperature 495 DEG C; The specific area of ageing prod is 64.246m
2/ g, pore volume is 0.334cc/g, and oxygen storage capacity is 404.3853 μm of ol/g, H
2reduction peak temperature is 517.3 DEG C.
Be illustrated in figure 3 ageing prod XRD, the product after as can be seen from the figure aging is still single cerium zirconium sosoloid; Be illustrated in figure 4 the hydrogen reducing collection of illustrative plates of the present embodiment cerium zirconium aluminium lanthanum based oxygen storage material fresh products, as can be seen from the figure cerium zirconium aluminium lanthanum based oxygen storage material reduction peak temperature is low and wide; Be illustrated in figure 5 the hydrogen reducing collection of illustrative plates of the present embodiment cerium zirconium aluminium lanthanum based oxygen storage material ageing prod, as can be seen from the figure cerium zirconium aluminium lanthanum based oxygen storage material ageing prod reduction peak temperature compares with fresh sample and changes little, illustrates that cerium zirconium aluminium lanthanum based oxygen storage material has good high-temperature aging resisting performance.
Embodiment 4:
A preparation method for meso-hole structure cerium zirconium aluminium lanthanum based oxygen storage material of the present invention, concrete operation step is as follows:
By CeO
2: ZrO
2: La
2o
3: MnO:Al
2o
3the nitrate of the weight ratio of=10.6:8.0:0.7:0.7:20 takes corresponding cerous nitrate, zirconium nitrate, boehmite are made Alumina gel, lanthanum nitrate and doped chemical manganese, add the supernatant mixed dissolution in embodiment 3 after suction filtration, and add the hydrogen peroxide with the amount of cerous nitrate same substance, in adjustment solution, salt-mixture total concentration is 0.5mol/L, obtains mixing salt solution A; Be precipitating reagent with ammoniacal liquor, the concentration of the adjustment precipitating reagent that adds water is (with NH
4 +meter) for 1.0mol/L and volume is identical with mixing salt solution A, be precipitated agent solution B; By surfactant, (surfactant is quaternised polyacrylamide and NPE, the amount of substance of the two is than being 1:1, addition is calculate product material amount 5%) dissolve, the supernatant added in embodiment 3 after suction filtration makes volume be 1/10 of reacting tank body, adjust PH=11 with ammoniacal liquor, obtaining concentration is 0.005mol/L meso-hole structure template solution C.
Fully meso-hole structure template solution C is stirred at 25 DEG C, with identical flow velocity and stream adds mixing salt solution A and precipitant solution B, solution PH=9.0 are recorded after reaction terminates, then continue to stir 1h, 85 DEG C of ageing 16h, limit agitation and dropping nertralizer oxalic acid solution to solution is neutral, after suction filtration, sediment adds water and fully pulls an oar, (dispersant is Macrogol 2000 and sodium polyphosphate to add dispersant again, both amount of substances are than being 1:0.1, addition is calculate product material amount 30%), make its uniformly gel, 120 DEG C of forced air dryings infiltrate to adding absolute ethyl alcohol during partial desiccation, after Rotary drying, be placed in Muffle furnace 600 DEG C of roasting 5h and obtain cerium zirconium aluminium lanthanum based oxygen storage material fresh products.Fresh sample 1000 DEG C of roasting 4h in Muffle furnace are obtained ageing prod.
Test obtained meso-hole structure cerium zirconium aluminium lanthanum based oxygen storage material fresh products and ageing prod thereof, the specific area recording fresh products is 173.564m
2/ g, pore volume are 0.567cc/g, and oxygen storage capacity is 608.159 μm of ol/g, H
2reduction peak temperature 497 DEG C, the specific area of ageing prod is 60.463m
2/ g, pore volume are 0.316cc/g, and oxygen storage capacity is 401.335 μm of ol/g, H
2reduction peak temperature 520 DEG C.Be illustrated in figure 6 ageing prod XRD to scheme, the product after as can be seen from the figure aging is still single cerium zirconium sosoloid.
Claims (10)
1. a preparation method for meso-hole structure cerium zirconium aluminium lanthanum based oxygen storage material, comprises the following steps:
1) by the salt mixed dissolution of cerium salt, zirconates, aluminium salt, lanthanum salt and doping M element, then add hydrogen peroxide, be adjusted to required concentration, volume stirring, obtain mixing salt solution A;
2) precipitating reagent be dissolved in water and be diluted to desired concn, volume, being precipitated agent solution B;
3) will be adjusted to desired concn and volume after surfactant dissolves, reconciliation statement surface-active agent solution pH value, obtains meso-hole structure template solution C;
4) under machinery or magnetic stirring being carried out to described meso-hole structure template solution C, and stream adds described mixing salt solution A and described precipitant solution B, keep PH to be greater than 7 by coutroi velocity in course of reaction, reaction temperature is 25 ~ 60 DEG C, and preserving heat after reaction ends continues to stir;
5) 85 ~ 95 DEG C of aging steps 4) after mixed liquor 2 ~ 24h, clean or add nertralizer and fully stir and make mixed liquor be neutral;
6) to step 5) after neutral mixed liquor suction filtration or centrifugal, suction filtration or centrifugal after precipitation add suitable quantity of water and pull an oar and add dispersant, stir into dispersed gel; Suction filtration or centrifugal supernatant are used for above-mentioned steps 1) dissolve salt-mixture or for above-mentioned steps 3) in dissolve surfactant;
7) described gel is infiltrated with absolute ethyl alcohol after 100 ~ 120 DEG C of forced air dryings, then pulverize after spray-dried, Rotary drying or oven drying, obtained precursor powder;
8) described precursor powder is placed in Muffle furnace 500 ~ 600 DEG C of roasting 4-10h i.e. obtained meso-hole structure cerium zirconium aluminium lanthanum based oxygen storage material.
2. preparation method as claimed in claim 1, is characterized in that: described step 1) in, cerium salt is the combination of one or more in cerous nitrate, ammonium ceric nitrate, cerium chloride and cerous acetate; Zirconates is the combination of one or more of zirconium nitrate, zirconyl nitrate, zirconium oxychloride and acetic acid zirconium; The Alumina gel that aluminium salt is aluminum nitrate or is made up of boehmite; Doping M element is the combination of one or more elements removed in rare earth element in other element of cerium and lanthanum, alkali earth metal, transition element, Bi and V.
3. preparation method as claimed in claim 2, is characterized in that: described rare earth element is one or more in Y, Pr, Nd and Tb; Described alkali earth metal is one or more in Ca, Sr, Ba and Mg; Described transition element is one or more in Mn, Cu, Fe and Ni.
4. preparation method as claimed in claim 1, is characterized in that: described step 1) in, the addition of hydrogen peroxide and the mol ratio of cerium salt are 1: 1 ~ 1: 2; In mixing salt solution A, the total concentration of salt-mixture is 0.1 ~ 2mol/L.
5. preparation method as claimed in claim 1, is characterized in that: described step 2) in, precipitating reagent is one or more in ammoniacal liquor, ammonium carbonate and carbonic hydroammonium, and in precipitant solution B, the concentration of precipitating reagent is with NH
4 +count 0.1 ~ 3mol/L.
6. preparation method as claimed in claim 1, it is characterized in that: described step 3) in, surfactant is any combination of one or more of one or more and polyacrylamide, polyvinyl alcohol, Macrogol 2000, Macrogol 4000, Macrogol 6000, PEG 8000, silane coupler and NPE in triethanolamine, softex kw, Cetyltrimethylammonium bromide, quaternised polyacrylamide.
7. preparation method as claimed in claim 6, it is characterized in that: described step 3) in, the interpolation total amount of surfactant be calculate product material mass 3 ~ 30%, meso-hole structure template solution C concentration be 0.001 ~ 0.05mol/L, PH be 10 ~ 12.
8. preparation method as claimed in claim 1, is characterized in that: described step 4) in, pH value is controlled by mixing salt solution A and precipitant solution B flow velocity, and at the end of reaction, PH is 8.0 ~ 9.5.
9. preparation method as claimed in claim 1, is characterized in that: described step 5) in, nertralizer is one or more in acetic acid, oxalic acid, maleic acid, citric acid, tartaric acid, dust technology, watery hydrochloric acid and 1-amino-8-naphthol-3,6-disulfonic acid; Described step 6) in, dispersant is the one or more combination in polyvinyl alcohol, Macrogol 2000, Macrogol 4000, Macrogol 6000, PEG 8000, APES, Brij-35, sodium polyphosphate, sodium metasilicate, calgon and ethylenediamine tetra-acetic acid; The addition of described dispersant is 20 ~ 60% of reaction product quality.
10. the preparation method as described in any one of claim 1 ~ 9, is characterized in that: described step 8) in, meso-hole structure cerium zirconium aluminium lanthanum based oxygen storage material product general formula is: m (Ce
xzr
yla
zm
1-x-y-z): n (Al
2o
3), wherein, x:0.25-0.7, y:0.2-0.6, z:0.01-0.1, m:0.3-0.9, n:0.1-0.7.
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| CN117619338B (en) * | 2024-01-24 | 2024-03-26 | 北京师范大学珠海校区 | Lanthanum-aluminum composite hydroxide dephosphorization material and preparation method and application thereof |
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