CN101733110A - Three-dimensional ordered macroporous oxide catalyst for diesel soot purification and preparation method thereof - Google Patents
Three-dimensional ordered macroporous oxide catalyst for diesel soot purification and preparation method thereof Download PDFInfo
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- CN101733110A CN101733110A CN200810225707A CN200810225707A CN101733110A CN 101733110 A CN101733110 A CN 101733110A CN 200810225707 A CN200810225707 A CN 200810225707A CN 200810225707 A CN200810225707 A CN 200810225707A CN 101733110 A CN101733110 A CN 101733110A
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Abstract
The invention relates to a three-dimensional ordered macroporous (3DOM) complex metal oxide catalyst for diesel soot purification and a preparation method thereof. The invention firstly provides an oxidization catalyst for combustion of soot particles discharged by a diesel vehicle, which is a simple metal oxide or complex metal oxide which selects more than one from rare-earth metal, transition metal and alkalinous metal as active components and has the 3DOM structure, wherein the average pore diameter is 50nm-1mum. The utilization of the catalyst with the 3DOM structure is beneficial to the diffusion of soot particles, improves the utilization rate of the active surface area of the catalyst, and greatly decreases the combustion temperature of the soot particles. The invention also provides a preparation method of the catalyst, comprising the step of dipping a colloidal crystal template through an organic complex agent solution that contains the active component of the catalyst, and then roasting to obtain the catalyst.
Description
Technical field
The present invention relates to emission of diesel engine soot particulate purification techniques, specifically, relate to a kind of three-dimensional ordered macroporous oxide catalyst for diesel soot purification and preparation method thereof, belong to environmental technology field.
Background technology
Improve the activity of soot particulate (PM) catalyst for clarifying of exhaust gas from diesel vehicle discharging, reduce the ignition temperature of soot particulate, thereby making the soot particulate trap can long time continuous working, be to reduce the most direct method of diesel emission soot particulate.Because the elimination of soot reaction is one gas-solid (soot)-the deep oxidation course of reaction of (catalyst) three-phase complexity, the raising of catalyst activity is not only closely related with the redox property of oxide catalyst itself, and is also closely related with the exposure level of solid catalyst and PM simultaneously.The catalyst of same active component, high more with the engagement capacity of soot, activity is good more.But, because the granularity of soot particulate is big (diameter of single soot particle is greater than 25nm), be difficult to enter in catalyst or the carrier micropore and react, even super large mesoporous molecular sieve (the about 20nm in maximum diameter of hole), the diffusion of soot particulate also has certain resistance, soot particulate can only contact with the outer surface of catalyst, thereby the utilization rate of active surface area is reduced greatly.
The composite metal oxide that Ca-Ti ore type, perovskite-like type, spinel-type, scheelite type or Ce based solid solution type etc. have a fixed structure have flexibly can " chemical tailoring " design feature and unique physical property (as ferromagnetism, ferroelectricity, superconductivity, thermal conductance, adsorptivity etc.), this type of catalyst also has advantages of high catalytic activity for the burning of soot.Several perovskite and perovskite-like serial nano ultrafine dust catalyst that can be used for the burning of catalyzed diesel tail gas carbon granule are disclosed among the Chinese patent CN1743067A, adopt this type of catalyst that the carbon granule ignition temperature is obviously reduced, make it to reach the desired temperature range of diesel car tail gas refining.Although this type of catalyst is a nano superfine micro, can improve the contact performance of catalyst and carbon granule, but the aperture of this catalyst is less than 10nm, soot particulate is difficult to enter in the catalyst duct and reacts, can only contact with the outer surface of catalyst, activity of such catalysts specific area utilization rate is low.Therefore it is significant for the diesel soot burning to prepare macroporous catalyst.
The definition of pure according to the world in applied chemistry federation (IUPAC), large pore material is meant the porous material of aperture greater than 50nm, and can be divided into ordered big hole material and unordered large pore material according to the order and the randomness in its duct.Three-dimensional ordered macroporous material (3DOM material, Three-dimensionally Ordered Macroporous Materials) has specific composition and cycle ordered big hole two specific characters, the aperture is big, pore size distribution is even, the duct is neat and orderly, compare with other porous materials, its unique pore passage structure helps material and enters in the hole from all directions, reduce the diffusional resistance of material, for the diffusion of material provides optimum flow rate and higher efficient, wide application prospect is arranged in various fields such as catalyst, carrier materials.
The method of the three-dimensional ordered macroporous material of preparation mainly is the colloidal crystal template method at present, generally comprise following steps: at first, by manual method mono-dispersion microballoon is piled into and is similar to the class material that natural opal (opal) has ordered 3 D structure, be so-called colloidal crystal (or synthetic opal), it is face-centered cubic (fcc) structure, wherein micelle accounts for 74% (volume ratio), and air accounts for 26% (volume ratio); Secondly, liquid precursor is filled into the gap of colloidal crystal, and is converted into solid skeletal in position; At last, microballoon is removed, the position, space between original microballoon obtains solid skeletal, and originally the position that occupies of microballoon then becomes interconnective hole, and last resulting ordered 3 D structure is opaline antistructure, is called as anti-opal.
A kind of macroporous Pt/CeO that is used for water gas shift reaction is disclosed among the open CN101199929A of Chinese patent
2Catalysts and its preparation method, this catalyst are the three-dimensional ordered macroporous CeO of template preparation with the polystyrene colloid crystal
2Be carrier, supporting precious metals pt is active component.This three-dimensional ordered macroporous supported carrier type catalyst is used for water gas shift reaction and has the advantages that activity is high, selectivity is good and have good stability.
Mostly the disclosed technical scheme of report of the relevant macropore metal oxide that has existed at present is to adopt the source of organic salt such as the alkoxide, oxalates, acetate of metal as active component.But the alkoxide precursor of transition metal and lanthanide series metal is difficult to preparation, and cost is very high, is unsuitable for preparing the 3DOM composite metal oxide; Though there are not such problem in the oxalates of common metal and acetate, but each metal is different with the reactivity of acid, alkali, different solubilities in reaction medium such as the oxalates that generates, acetate, this will cause the stoichiometric proportion of the metal oxide that obtains after the roasting and original stoichiometric proportion inconsistent, is difficult to obtain the composite metal oxide of needed chemical composition; At present, metal organic salt only is used to prepare the simple metal oxide.
In view of there are above-mentioned problems in metal organic salt, some present researchs begin to pay close attention to and utilize the inorganic salts of active component to prepare metal oxide, and nitrate is common common salt, if can be with nitrate as raw material, cost will reduce greatly.But the fusing point of nitrate is very low, and when utilizing the colloidal crystal template legal system to be equipped with metal oxide, when colloidal crystal template was not also removed, nitrate just decomposed, and is difficult to obtain the 3DOM structure.Way by complexing can be converted into nitrate the higher metal precursor of fusing point, and this presoma can penetrate into colloidal crystal template and be converted into corresponding metal oxide and do not melt, thereby obtains three-dimensional ordered macroporous structure.People such as Wu Quanzhou are at " nitrate prepares three-dimensional ordered macroporous metal oxide materials research " (chemical journal, 2005 the 63rd the 10th phases of volume, report 891-896): can adopt citric acid to come metal ion in the complexing nitrate, be translated into the higher complex compound of fusing point, by further roasting, obtain three-dimensional ordered macroporous metal oxide materials: Al
2O
3, CeO
2, Cr
2O
3, NiO, MgO, In
2O
3, CeO
2/ Al
2O
3, Cr
2O
3/ Al
2O
3And NiO/Al
2O
3The disclosed process of the document is the technical scheme that preparation has the simple metal oxide of three-dimensional ordered macroporous structure, because spontaneous combustion takes place in citric acid (approximately 100-300 ℃) easily at a lower temperature, therefore, reaction condition control is improper, might cause obtaining the 3DOM structure.In addition, citric acid is originally as solid, and is convenient not as liquid complexing agent in operation as complexing agent, and for example the lemon aqueous acid will just can obtain being similar to the solution of colloid through refluxing for a long time, could be used as complexing agent then.And, because citric acid is to the coordination ability difference of different metal ion, when adopting citric acid to prepare the three-dimensional ordered macroporous composite metal oxide of Ca-Ti ore type, perovskite-like type, spinel-type, scheelite type, Ce based solid solution type as complexing agent, the composition of resulting composite metal oxide be difficult to and precursor solution in the metal molar ratio be consistent, be difficult to be met the composite metal oxide that stoichiometric proportion requires.
In view of three-dimensional ordered macroporous structure has above-mentioned characteristics; manufacture metal oxide with three-dimensional ordered macroporous structure; for example simple metal oxide and Ca-Ti ore type, perovskite-like type, spinel-type, scheelite type, Ce based solid solution type composite metal oxide; used as emission of diesel engine soot particulate burning catalyst; for improving activity of such catalysts surface utilization rate; reduce the ignition temperature of carbon soot particles; reduce exhaust gas from diesel vehicle and pollute, the protection environment is significant.
Summary of the invention
For solving the problems of the technologies described above, the object of the present invention is to provide a kind of soot particulate burning catalyst, it is the composite metal oxide of types such as a kind of simple metal oxide or Ca-Ti ore type, perovskite-like type, spinel-type, scheelite type, Ce based solid solution type, the contact area of this catalyst and carbon soot particles is bigger, and the utilization rate of active surface area is also higher.
The present invention also aims to provide the burning of above-mentioned carbon soot particles to use the Preparation of catalysts method, the simple metal oxide or the composite metal oxide that utilize the colloidal crystal template method to prepare to have higher catalytic activity and three-dimensional ordered macroporous structure.
For achieving the above object, the present invention at first provides a kind of emission of diesel engine soot particulate burning oxidation catalyst, it is a kind of three-dimensional ordered macroporous oxide catalyst for diesel soot purification, be as active component and simple metal oxide or composite metal oxide by more than one the element in rare earth metal, transition metal and the alkalinous metal etc. with three-dimensional ordered macroporous structure, wherein, composite metal oxide is Ca-Ti ore type, perovskite-like type, spinel-type, scheelite type or Ce based solid solution type composite metal oxide.
The present inventor is by discovering, utilization has when than the catalyst of macropore the diesel vehicle soot particle being handled, carbon soot particles can enter catalyst inside, contact with the active surface in the inner duct of catalyst, its ignition temperature is more much lower than currently used other cleaning catalysts.But, because the granularity of soot big (diameter of single soot particle is greater than 25nm) will make carbon soot particles can enter the inner duct of catalyst smoothly, must satisfy certain aperture requirement, promptly require catalyst to have macroporous structure.And according to the definition of IUPAC, the aperture is called macropore greater than the hole of 50nm, so, diesel soot purification of the present invention macropore metal oxide catalyst, the average pore size 50nm-1 μ m in its inner duct belongs to the macropore metal oxide catalyst.
The aperture of the pore structure of macropore metal oxide catalyst provided by the invention is big, and pore size distribution is even, the duct is neat and orderly, belong to three-dimensional ordered macroporous structure, therefore, emission of diesel engine soot particulate burning provided by the invention is a kind of three-dimensional ordered macroporous metal oxide catalyst with oxidation catalyst, unique pore passage structure helps material and enters in the hole from all directions, reduced the diffusional resistance of carbon soot particles, for the diffusion of carbon soot particles provides optimum flow rate and higher efficient.
Emission of diesel engine soot particulate burning provided by the invention can be simple metal oxide, Ca-Ti ore type, perovskite-like type, spinel-type, scheelite type or Ce based solid solution type composite metal oxide with oxidation catalyst.The chemical composition of simple metal oxide can be expressed as M
aO
b, in the formula, M is any one in the metallic element, for example: Li, Na, K, Mg, Al, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Zr, Nb, Mo, Pb, Ce, Pr, Nd, Sm, Eu etc.; The chemical composition of composite metal oxide can be expressed as Ln
1-xA
xM
1-yB
yO
3, Ln
2-zA
zM
1-yB
yO
4, Ln
1-xA
xM
2-wB
wO
4, Ln
1-xA
xM
1-yB
yO
4, Ce
1-mZr
mO
2Or Ce
1-m-nZr
mPr
nO
2, in the formula, Ln is a rare earth metal, and A is an alkalinous metal, comprises alkali metal or alkaline-earth metal, and M is a transition metal, and B is the transition metal that is different from M, and x=0-0.95, y=0-0.95, z=0-1.95, w=0-1.95, m=0-0.99, n=0-0.99; Wherein, rare earth metal comprises one or more among La, Ce, Pr, Nd and the Sm etc.; Transition metal comprises one or more among Fe, Co, Mn, Ni, Cu and the Cr etc.; Alkalinous metal comprises alkali metal and/or alkaline-earth metal, comprises among Li, Na, K, Rb, Cs, Mg, Ca, Sr and the Ba etc. one or more.
According to concrete technical scheme of the present invention, above-mentioned oxidation catalyst provided by the invention can be that the organic complex agent solution that will contain the salt of its active component floods colloidal crystal template as maceration extract, obtains through roasting then.
The present invention also provides the preparation method of above-mentioned oxidation catalyst, and it may further comprise the steps:
The salt that will contain active component is dissolved in the organic complexing agent according to predetermined stoichiometric proportion mixing, and adds cosolvent, obtains the complex catalyst precursor liquid solution;
Utilize resulting complex catalyst precursor liquid solution as maceration extract, the adding colloidal crystal template floods repeatedly, drying, is warming up to 450 ℃-1000 ℃ of target temperatures then in air atmosphere, insulation 4-10h.
According to concrete technical scheme of the present invention, contain in the complex catalyst precursor liquid solution of salt, organic complexing agent and cosolvent of active component, the total concentration of metal ion may be controlled to 0.05-3mol/L.
According to concrete technical scheme of the present invention, the air velocity in the air atmosphere may be controlled to 30-300mL/min, and the intensification of being adopted can be to 450 ℃-1000 ℃ of target temperatures with the heating rate temperature programming below the 2 ℃/min.
For the performance of the metal oxide catalyst that guarantees to obtain, the salt of the active component that is adopted among the preparation method provided by the invention can be the inorganic salts that active component can be provided, and preferably adopts nitrate.The present invention utilizes organic complexing agent that nitrate is converted into the higher metal precursor of fusing point by the method for complexing, and this presoma can penetrate into colloidal crystal template and be converted into corresponding metal oxide and do not melt, thereby obtains three-dimensional ordered macroporous structure.Take technical scheme provided by the invention, can avoid occurring to obtain the problem of the metal oxide of 3DOM structure when colloidal crystal template is removed because the low nitrate that causes containing active component of the fusing point of nitrate does not decompose.
Be applicable to that organic complexing agent of the present invention is liquid dihydroxylic alcohols or polyalcohol, for example ethylene glycol, glycerine etc.When adopting ethylene glycol to be organic complexing agent, the ethylene glycol solution of metal nitrate can be under lower temperature, the oxidation of original position nitrate before being burnt, template takes place, generate the corresponding metal glyoxylate, glyoxylate can be converted into corresponding metal oxide by further roasting, and with the polymer template removal, thereby obtain the 3DOM metal oxide materials.
In order to dilute the salt that contains active component and the mixed solution of organic complexing agent, reduce its viscosity, can in mixed solution, add a certain amount of cosolvent, help precursor solution like this and under the effect of capillary force, infiltrate template, further be converted into solid skeletal.Be applicable to that cosolvent of the present invention can be this area cosolvent commonly used, for example methyl alcohol, ethanol etc.
Colloidal crystal template of the present invention can be the copolymer template (P (S-MMA)) of polymethyl methacrylate (PMMA) template, polystyrene (PS) template, styrene and methyl methacrylate or the PS, PMMA template etc. that the surface has carboxyl functional group, both can be the finished product that is purchased, also can prepare voluntarily.Wherein, the preparation of polymethyl methacrylate template or polystyrene moulding etc. can adopt the method that may further comprise the steps to carry out:
1, adopt the emulsifier-free emulsion polymerization legal system to be equipped with monodisperse polymer micro-sphere
Under nitrogen protection, acetone and redistilled water are mixed, and be preheated to 60-90 ℃ with water-bath, add monomers methyl methacrylate or styrene, continue to be heated to 60-90 ℃ with water-bath;
Under nitrogen protection, the initiator solution that adds 60-90 ℃, wherein, this initator can comprise the initator that potassium peroxydisulfate and azodiisobutyronitrile etc. are used always when the preparation colloidal crystal template, continue to stir 2-30h, obtain single polymethyl methacrylate or polystyrene microsphere emulsion of disperseing; Preferably, should make the surperficial smoother of the microballoon that obtains, size ratio adopts this microballoon can make the metal oxide of final acquisition have form and structure preferably than homogeneous;
2, adopt centrifugal deposition method or evaporation deposition method to prepare colloidal crystal template
The microballoon emulsion is placed centrifuge tube, with 1000-10000rpm, preferred 1000-5000rpm, rotating speed centrifugal treating 1-30h, the preferred processing time is 10-20h, obtains closelypacked colloidal crystal template, perhaps the microballoon emulsion is placed in the Flat bottom container, with the slowly evaporation in drying box of 40-80 ℃ temperature, the microballoon deposition obtains colloidal crystal template.
According to specific embodiments of the present invention, can adopt the preparation method who comprises following concrete parameter and concrete steps to prepare polymethyl methacrylate template or polystyrene moulding:
30-100ml acetone and the mixing of 50-300ml redistilled water are obtained mixed liquor, and water-bath is heated to 60-90 ℃, adds 30-120ml monomers methyl methacrylate or styrene then, and water-bath is heated to 60-90 ℃;
The 60-90 ℃ of aqueous solution that adds initiator potassium persulfate 0.001g-0.500g and azodiisobutyronitrile 0.001g-0.500g, continue to stir 2-30h, obtain single polymethyl methacrylate or polystyrene microsphere emulsion of disperseing, entire reaction course is carried out under nitrogen protection, the particle diameter of gained mono-dispersion microballoon can be by regulating the control in monomer consumption, initiator amount, mixing speed, reaction temperature and reaction time, and the particle diameter of thus obtained microsphere is between 100nm-1 μ m;
The microballoon emulsion is placed centrifuge tube, rotating speed centrifugal treating 10-20h with 1000rpm-5000rpm obtains closelypacked colloidal crystal template, perhaps the microballoon emulsion is placed in the Flat bottom container, with the slowly evaporation in drying box of 40-80 ℃ temperature, the microballoon deposition obtains colloidal crystal template.
The present invention also provides a kind of method of purification of diesel car discharging soot particulate, and it comprises the process that the burning of the soot particulate that adopts above-mentioned oxidation catalyst catalytic diesel oil car discharging purifies.
Emission of diesel engine soot particulate burning provided by the invention is the simple metal oxide with three-dimensional ordered macroporous structure with oxidation catalyst; Ca-Ti ore type; the perovskite-like type; spinel-type; scheelite type or Ce based solid solution type composite metal oxide; the regular duct of its inside and big aperture are enough to make soot particulate diffusion smoothly in its duct; soot particulate can not only be contacted with the activity of such catalysts outer surface; but also carbon soot particles is diffused in the duct from all directions; fully contact with activity of such catalysts inner surface especially activated centre; the utilization rate on soot particulate catalyst activity surface is improved greatly; the ignition temperature of soot particulate is reduced significantly; in the temperature range of exhaust gas from diesel vehicle discharging, carbon granule substantially can completing combustion.
The present invention adopts the simple oxide with three-dimensional ordered macroporous structure and the composite metal oxide (Ca-Ti ore type, perovskite-like type, spinel-type, scheelite type or Ce based solid solution type etc.) of colloidal crystal template method preparation, its preparation process is simple, and course of reaction is controlled easily.
Three-dimensional ordered macroporous oxide catalyst, its average pore size is between 50nm-1 μ m, the duct is neat and orderly, soot particulate can be diffused in the duct from all directions, fully contact with the activity of such catalysts center, so the utilization rate of catalyst activity surface area improves greatly, thereby the ignition temperature of soot particulate is reduced significantly, the soot particulate burning can be CO
2Temperature be reduced in the delivery temperature scope of exhaust gas from diesel vehicle.By activity of such catalysts being compared can learning, the three-dimensional ordered macroporous oxide catalyst of the present invention's preparation has better catalytic activity than corresponding conventional catalyst, nanoparticle catalyst and unordered macroporous catalyst.
Description of drawings
Fig. 1 a and Fig. 1 b are the 3DOM CeO of embodiment 1 preparation
2Stereoscan photograph;
Fig. 1 c is the 3DOM LaFeO of embodiment 2 preparations
3Stereoscan photograph;
Fig. 1 d is the 3DOM La of embodiment 3 preparations
0.9K
0.1FeO
3Stereoscan photograph;
Fig. 1 e is the 3DOM LaFe of embodiment 4 preparations
0.7Co
0.3O
3Stereoscan photograph;
Fig. 1 f is the 3DOM ZrO of embodiment 5 preparations
2Stereoscan photograph;
Fig. 1 g is the 3DOMAl of embodiment 6 preparations
2O
3Stereoscan photograph;
Fig. 2 a is the unordered macropore CeO of Comparative Examples 1 preparation
2Stereoscan photograph;
Fig. 2 b is the unordered macropore LaFeO of Comparative Examples 2 preparations
3Stereoscan photograph;
Fig. 2 c is the unordered macropore La of Comparative Examples 3 preparations
0.9K
0.1FeO
3Stereoscan photograph;
Fig. 3 is embodiment 1-3, the 3DOM CeO of 7 preparations
2, 3DOM LaFeO
3, 3DOMLa
0.9K
0.1FeO
3And Ce
0.75Zr
0.25O
2X ray diffracting spectrum;
Fig. 4 is the 3DOM CeO of embodiment 1-3 preparation
2, 3DOM LaFeO
3And 3DOMLa
0.9K
0.1FeO
3The catalytic oxidation soot particulate generates CO
2The graph of relation of Pressure, Concentration, Temperature.
The specific embodiment
Below introduce realization of the present invention and the beneficial effect that had by specific embodiment, but should not constitute any qualification to practical range of the present invention in view of the above.
The evaluation method of catalyst activity:
Use fixed-bed micro-reactor-gas-chromatography detection system;
Concrete parameter: catalyst sample 100mg, the mass ratio of catalyst and soot particulate are 10: 1;
Concrete steps: utilize ultrasonic auxiliary method, be about to load weighted catalyst and soot particulate and place small beaker, stir with spoon, again to wherein adding 3ml ethanol, ultrasonic 3-10min enters in the duct of catalyst sample soot particulate, and wherein, the control gas flow is 50ml/min, the volume content of NO is 2000ppm in the gas, O
2Volume content be 5%, surplus is He;
After in carbon soot particles enters the catalyst sample duct, heat, wherein, heating rate is controlled to be about 2 ℃/min.
Evaluation method: the oxidability power of catalyst adopts the ignition temperature of soot particulate to represent, wherein, and the initiation temperature (T of soot particulate
10), the temperature (T of correspondence when burn rate is maximum
50) and after-flame temperature (T
90), represent that respectively carbon-smoke combustion finishes 10%, 50% and the temperature spot of 90% o'clock correspondence, its computational methods are the CO that produce by to carbon black burning in the temperature programmed oxidation reaction
2Carry out integration, CO with the curve of CO
2Be T with 10%, 50%, 90% the pairing temperature spot of numerical value of CO integral area sum
10, T
50And T
90
The aperture of catalyst is determined according to the SEM photo.
The colloidal crystal template preparation method:
1) adopt the emulsifier-free emulsion polymerization legal system to be equipped with monodisperse polymer micro-sphere
With 50ml acetone and 150ml redistilled water, join in the 1000ml four neck flasks, be preheated to 70 ℃ with 70 ℃ of water-baths, 70ml monomers methyl methacrylate (or styrene) is joined in the four good neck flasks of preheating; In the preheating reactant, take by weighing initiator potassium persulfate K
2S
2O
80.090g and azodiisobutyronitrile (AIBN) 0.1538g, separate with 150ml is water-soluble, water-bath is heated to 70 ℃; When the question response monomer is preheated to 70 ℃, add 70 ℃ initiator solution, continue stirring reaction 2-10h, promptly getting solid content is single polymethyl methacrylate (or polystyrene) microballoon emulsion of disperseing of 5-10%;
2) adopt centrifugal deposition method or evaporation deposition method to prepare colloidal crystal template
An amount of microballoon emulsion is placed centrifuge tube, and the rotating speed centrifugal treating 10-20h with 1000-5000rpm obtains closelypacked colloidal crystal template;
Perhaps an amount of microballoon emulsion is placed in the Flat bottom container (for example beaker), with the slowly evaporation in drying box of 40-80 ℃ temperature, the microballoon deposition obtains colloidal crystal template.
Embodiment 13DOM CeO
2The simple metal oxide
The particle diameter that takes a morsel is the poly (methyl methacrylate) micro-sphere emulsion of 446nm, and the rotating speed centrifugal treating 10h with 3000rpm obtains the PMMA colloidal crystal template, air dry;
Take by weighing a certain amount of cerous nitrate, be dissolved in the ethylene glycol, gained solution is transferred in the volumetric flask, with methanol constant volume (the methyl alcohol volume fraction is 5-50%), GOLD FROM PLATING SOLUTION is joined by institute, and to belong to ion concentration be 2.0mol/L, obtains 3DOM CeO
2Precursor solution;
The PMMA colloidal crystal template good to drying drips 3DOM CeO
2Precursor solution, up to solution submergence PMMA template, to be impregnated fully after, suction filtration is removed redundant solution, obtains the compound of presoma/PMMA, air dry, place tube furnace with the heating rate of≤2 ℃/min temperature to be risen to 500 ℃ then, roasting (insulation) 5h obtains 3DOM CeO
2
Fig. 1 a and Fig. 1 b are the 3DOM CeO of present embodiment preparation
2Different amplification ESEM (SEM) photo.By 3DOM CeO among the figure
2Whole pattern as can be seen, 3DOM CeO
2Have three-dimensional ordered macroporous structure, average pore size is about 248nm; The 3DOM CeO of present embodiment preparation
2X ray diffracting spectrum as shown in Figure 3, its diffraction maximum is pure CeO
2The characteristic diffraction peak of fluorite type cubic structure, this result shows that the composition of the catalyst of present embodiment preparation is CeO
2
Comparative Examples 1 unordered macropore CeO
2
The 3DOM CeO that takes a morsel and obtain among the embodiment 1
2Precursor solution, place Muffle furnace, with the heating rate of≤2 ℃/min temperature is risen to 500 ℃, roasting 5h obtains having the CeO of unordered cellular macroporous structure
2, promptly unordered macropore CeO
2, its surface topography is shown in Fig. 2 a.
Activity rating 1
According to the evaluation method of above-mentioned catalyst activity 3DOM CeO to embodiment 1 preparation
2, Comparative Examples 1 preparation unordered macropore CeO
2And non-macropore CeO
2Estimate 3DOM CeO
2The activity rating result (wherein, ordinate is CO as shown in Figure 4
2Concentration, ordinate are temperature), above-mentioned three kinds of activity of such catalysts evaluating datas see Table 1.
Ultrasonic auxiliary soot particulate enters 3DOM CeO
2With unordered macropore CeO
2The duct in, with this understanding, 3DOM CeO
2Make the initiation temperature of carbon soot particles burning be lower than 294 ℃, peak temperature (T
50) be 386 ℃, the after-flame temperature is lower than 412 ℃, with unordered macropore CeO
2Compare its initiation temperature (T
10), the temperature (T of correspondence when burn rate is maximum
50) and after-flame temperature (T
90) all lower, T wherein
10 Low 70 ℃, T
50Low 67 ℃.
More non-macropore CeO
2, unordered macropore CeO
2With 3DOM CeO
2For the catalytic activity of the burning of soot, its catalytic activity is in proper order: 3DOM CeO
2＞unordered macropore CeO
2＞non-macropore CeO
2
Table 1:
| Catalyst | ??T 10/℃ | ??T 50/℃ | ??T 90/℃ |
| ??3DOM?CeO 2 | ??294 | ??386 | ??412 |
| Unordered macropore CeO 2 | ??338 | ??405 | ??436 |
| Non-macropore CeO 2 | ??368 | ??436 | ??509 |
Embodiment 23DOM LaFeO
3Composite metal oxide
The particle diameter that takes a morsel is the polystyrene microsphere emulsion of 367nm, and the rotating speed centrifugal treating 20h with 3000rpm obtains the PS colloidal crystal template, air dry;
Take by weighing lanthanum nitrate, ferric nitrate by stoichiometric proportion (mol ratio 1: 1), to wherein adding ethylene glycol, magnetic agitation 2h, the solution that obtains is transferred in the volumetric flask, with methanol constant volume (volume fraction of methyl alcohol is 30%), GOLD FROM PLATING SOLUTION is joined by institute, and to belong to ion concentration be 1.5mol/L, obtains 3DOM LaFeO
3Precursor solution, this solution is 3DOM LaFeO
3The precursor solution of O composite metallic oxide catalyst;
With 3DOM LaFeO
3Precursor solution be added drop-wise in the dry PS colloidal crystal template, up to solution submergence PS template, to be impregnated fully after, suction filtration is removed redundant solution, obtain the compound of presoma/PS, air dry places tube furnace with the heating rate of＜2 ℃/min temperature to be risen to 600 ℃ then, roasting 5h obtains 3DOM LaFeO
3
Fig. 1 c is the 3DOM LaFeO of present embodiment preparation
3Stereoscan photograph.As can be seen from Figure, use the 3DOM LaFeO of PS colloidal crystal in the present embodiment as the template preparation
3Have regular three-dimensional ordered macroporous structure, average pore size is about 320nm; The 3DOM LaFeO of present embodiment preparation
3X ray diffracting spectrum as shown in Figure 3, its result shows the 3DOM LaFeO of present embodiment preparation
3Has perovskite structure.
Comparative Examples 2 unordered macropore LaFeO
3
The 3DOM LaFeO that takes a morsel
3Precursor solution place in the crucible, the heating rate with≤2 ℃/min in Muffle furnace rises to 600 ℃ with temperature, roasting 5h obtains having the LaFeO of unordered cellular macroporous structure
3, promptly unordered macropore LaFeO
3
Fig. 2 b is the unordered macropore LaFeO of this Comparative Examples preparation
3Stereoscan photograph, as can be seen from Figure, this Comparative Examples is with the precursor solution LaFeO that directly roasting obtains in Muffle furnace
3Be cellular macroporous structure, average pore size is greater than 50nm.
According to the evaluation method of above-mentioned catalyst activity 3DOM LaFeO to embodiment 2 preparations
3, Comparative Examples 2 preparation unordered macropore LaFeO
3And non-macropore LaFeO
3Estimate 3DOMLaFeO
3The activity rating result (abscissa is a temperature, and ordinate is CO as shown in Figure 4
2Concentration), above-mentioned three kinds of activity of such catalysts evaluating datas see Table 2;
Ultrasonic down auxiliary, soot particulate enters 3DOM LaFeO
3With unordered macropore LaFeO
3The duct in, the ignition temperature of soot particulate reduces.
Contrast 3DOM LaFeO
3, unordered macropore LaFeO
3With non-macropore LaFeO
3The catalytic activity data of the catalyst of three kinds of different-shapes can be learnt 3DOM LaFeO
3The ignition temperature of corresponding carbon soot particles is minimum, and is the highest to the catalytic activity of the burning of soot.
Table 2:
| Catalyst | ??T 10/℃ | ??T 50/℃ | ??T 90/℃ |
| ??3DOM?LaFeO 3 | ??348 | ??416 | ??444 |
| Unordered macropore LaFeO 3 | ??368 | ??444 | ??455 |
| Non-macropore LaFeO 3 | ??386 | ??488 | ??530 |
Embodiment 33DOMLa
0.9K
0.1FeO
3Composite metal oxide
The particle diameter that takes a morsel is the poly (methyl methacrylate) micro-sphere emulsion of 487nm, and the rotating speed centrifugal treating 15h with 2000rpm discards supernatant liquor, obtains the PMMA colloidal crystal template, air dry;
Take by weighing lanthanum nitrate, potassium nitrate and ferric nitrate by stoichiometric proportion (mol ratio 9: 1: 10), to wherein adding ethylene glycol, magnetic agitation 2h, gained solution is transferred in the volumetric flask, with methanol constant volume (the methyl alcohol volume fraction is 40%), GOLD FROM PLATING SOLUTION is joined by institute, and to belong to ion concentration be 2.0mol/L, obtains 3DOMLa
0.9K
0.1FeO
3Precursor solution, this solution is 3DOM La
0.9K
0.1FeO
3The precursor solution of O composite metallic oxide catalyst;
In the good PS colloidal crystal mould of drying, drip 3DOM La
0.9K
0.1FeO
3Precursor solution, up to solution submergence PMMA template, to be impregnated fully after, suction filtration is removed redundant solution, obtains the compound of presoma/PMMA, air dry, place tube furnace with the heating rate of≤2 ℃/min temperature to be risen to 650 ℃ then, roasting 5h obtains 3DOM La
0.9K
0.1FeO
3
Fig. 1 d is the 3DOM La of present embodiment preparation
0.9K
0.1FeO
3Stereoscan photograph.As can be seen from Figure, use the La of PMMA colloidal crystal as the template preparation
0.9K
0.1FeO
3Have three-dimensional ordered macroporous structure, belong to three-dimensional ordered macroporous catalyst, average pore size is about 400nm; The 3DOM La of present embodiment preparation
0.9K
0.1FeO
3X ray diffracting spectrum as shown in Figure 3, its result shows the 3DOM La of present embodiment preparation
0.9K
0.1FeO
3Be perofskite type oxide.
Comparative Examples 3 unordered macropore La
0.9K
0.1FeO
3
3DOM La takes a morsel
0.9K
0.1FeO
3Precursor solution place in the crucible, the heating rate with≤2 ℃/min in Muffle furnace rises to 650 ℃ with temperature, roasting 5h obtains having the La of unordered cellular macroporous structure
0.9K
0.1FeO
3, promptly unordered macropore La
0.9K
0.1FeO
3
Fig. 2 c is the unordered macropore La of this Comparative Examples preparation
0.9K
0.1FeO
3Stereoscan photograph, as can be seen from Figure, with the precursor solution La that directly roasting obtains in Muffle furnace
0.9K
0.1FeO
3Be cellular unordered macroporous catalyst, average pore size is greater than 50nm.
Activity rating 3
According to the evaluation method of above-mentioned catalyst activity 3DOMLa to embodiment 3 preparations
0.9K
0.1FeO
3, Comparative Examples 3 preparation unordered macropore La
0.9K
0.1FeO
3And non-macropore La
0.9K
0.1FeO
3Estimate 3DOM La
0.9K
0.1FeO
3The activity rating result as shown in Figure 4; Above-mentioned three kinds of activity of such catalysts evaluating datas see Table 3.
Ultrasonic down auxiliary, soot particulate enters 3DOM La
0.9K
0.1FeO
3With unordered macropore La
0.9K
0.1FeO
3The duct in, the ignition temperature of soot particulate reduces, with non-macropore La
0.9K
0.1FeO
3, unordered macropore La
0.9K
0.1FeO
3Compare 3DOM La
0.9K
0.1FeO
3The ignition temperature of corresponding carbon soot particles is minimum, and is the highest to the catalytic activity of the burning of soot.
Table 3:
| Catalyst | ??T 10/℃ | ??T 50/℃ | ??T 90/℃ |
| ??3DOM?La 0.9K 0.1FeO 3 | ??305 | ??366 | ??379 |
| Unordered macropore La 0.9K 0.1FeO 3 | ??325 | ??370 | ??390 |
| Non-macropore La 0.9K 0.1FeO 3 | ??334 | ??445 | ??503 |
Embodiment 43DOM LaFe
0.7Co
0.3O
3Composite metal oxide
The particle diameter that takes a morsel is the poly (methyl methacrylate) micro-sphere emulsion of 362nm, and the rotating speed centrifugal treating 1h with 7200rpm discards supernatant liquor, obtains the PMMA colloidal crystal template, air dry;
Take by weighing lanthanum nitrate, ferric nitrate and cobalt nitrate by stoichiometric proportion (mol ratio 10: 7: 3), to wherein adding ethylene glycol, magnetic agitation 2h, gained solution is transferred in the volumetric flask, with methanol constant volume (the methyl alcohol volume fraction is 35%), GOLD FROM PLATING SOLUTION is joined by institute, and to belong to ion concentration be 2.0mol/L, obtains 3DOMLaFe
0.7Co
0.3O
3Precursor solution, this solution is 3DOM LaFe
0.7Co
0.3O
3The precursor solution of O composite metallic oxide catalyst; It is added drop-wise in the dry good PMMA template, up to solution submergence PMMA template, to be impregnated fully after, suction filtration is removed redundant solution, obtain the compound of presoma/PMMA, air dry places tube furnace with the heating rate of≤2 ℃/min temperature to be risen to 650 ℃ then, roasting 5h obtains 3DOM LaFe
0.7Co
0.3O
3
Fig. 1 e is the 3DOM LaFe of present embodiment preparation
0.7Co
0.3O
3Stereoscan photograph.As can be seen from Figure, use the LaFe of PMMA colloidal crystal as the template preparation
0.7Co
0.3O
3Have three-dimensional ordered macroporous structure, belong to three-dimensional ordered macroporous catalyst, average pore size is about 268nm.
Embodiment 53DOM ZrO
2The simple metal oxide
The particle diameter that takes a morsel is the poly (methyl methacrylate) micro-sphere emulsion of 446nm, and the rotating speed centrifugal treating 10h with 3000rpm discards supernatant liquor, obtains the PMMA colloidal crystal template, air dry;
Take by weighing zirconium nitrate,, gained solution is transferred in the volumetric flask, obtain 3DOM ZrO its mixed liquor that is dissolved in ethylene glycol and ethanol (50%)
2Precursor solution, in order to the good PMMA template of impregnation drying, to be impregnated fully after, suction filtration is removed redundant solution, obtains the compound of presoma/PMMA, air dry, place tube furnace with the heating rate of≤2 ℃/min temperature to be risen to 500 ℃ then, roasting 5h obtains 3DOM ZrO
2
Fig. 1 f is the 3DOM ZrO of present embodiment preparation
2Stereoscan photograph.As can be seen from Figure, use the ZrO of PMMA colloidal crystal as the template preparation
2Have three-dimensional ordered macroporous structure, belong to three-dimensional ordered macroporous catalyst, average pore size is about 378nm.
Embodiment 63DOM Al
2O
3The simple metal oxide
The particle diameter that takes a morsel is the polystyrene microsphere emulsion of 144nm, and the rotating speed centrifugal treating 20h with 5500rpm obtains the PS colloidal crystal template, air dry;
Take by weighing aluminum nitrate, to wherein adding ethylene glycol, magnetic agitation 2h transfers to the solution that obtains in the volumetric flask, and with methanol constant volume (volume fraction of methyl alcohol is 30%), GOLD FROM PLATING SOLUTION is joined by institute, and to belong to ion concentration be 1.5mol/L, and this solution is 3DOM Al
2O
3Precursor solution;
PS colloidal crystal template 3DOM Al with drying
2O
3Precursor solution dipping, to be impregnated fully after, suction filtration is removed redundant solution, obtains the compound of presoma/PS, air dry places tube furnace with the heating rate of＜2 ℃/min temperature to be risen to 700 ℃ then, roasting 5h obtains 3DOMAl
2O
3
Fig. 1 g is the 3DOM Al of present embodiment preparation
2O
3Stereoscan photograph.As can be seen from Figure, use the 3DOM Al of PS colloidal crystal in the present embodiment as the template preparation
2O
3Have regular three-dimensional ordered macroporous structure, average pore size is about 100nm.
Embodiment 73DOM Ce
0.75Zr
0.25O
2Composite metal oxide
The particle diameter that takes a morsel is the poly (methyl methacrylate) micro-sphere emulsion of 454nm, and the rotating speed centrifugal treating 10h with 3000rpm obtains the PMMA colloidal crystal template, air dry;
Take by weighing cerous nitrate, zirconium nitrate by stoichiometric proportion (mol ratio 3: 1), to the mixed liquor that wherein adds ethylene glycol and ethanol (volume fraction of ethanol is 50%), magnetic agitation 2h, gained solution is transferred in the volumetric flask, use the ethanol constant volume, GOLD FROM PLATING SOLUTION is joined by institute, and to belong to ion concentration be 2.0mol/L, obtains 3DOM Ce
0.75Zr
0.25O
2Precursor solution; The PMMA template that drying is good is impregnated into 3DOMCe
0.75Zr
0.25O
2Precursor solution in, to be impregnated fully after, suction filtration is removed redundant solution, obtains the compound of presoma/PMMA, air dry places tube furnace with the heating rate of≤2 ℃/min temperature to be risen to 650 ℃ then, roasting 5h obtains 3DOM Ce
0.75Zr
0.25O
2
The 3DOM Ce of present embodiment preparation
0.75Zr
0.25O
2X ray diffracting spectrum as shown in Figure 3, at the spectrogram and the pure CeO of the catalyst sample of present embodiment preparation
2The fluorite type cubic structure, ZrO does not appear
2Characteristic peak, this explanation 3DOM Ce
0.75Zr
0.25O
2Exist with a kind of crystalline phase, phase-splitting do not occur.
Claims (10)
1. an emission of diesel engine soot particulate burns and uses oxidation catalyst, it is as active component and simple metal oxide or composite metal oxide with three-dimensional ordered macroporous structure by more than one the element in rare earth metal, transition metal and the alkalinous metal, wherein, described composite metal oxide is Ca-Ti ore type, perovskite-like type, spinel-type, scheelite type or Ce based solid solution type composite metal oxide, wherein, the average pore size of this catalyst is 50nm-1 μ m.
2. oxidation catalyst as claimed in claim 1, wherein, the chemical composition of described simple metal oxide is M
aO
b, in the formula, M is any one in the metallic element.
3. oxidation catalyst as claimed in claim 1, wherein, the chemical composition of described composite metal oxide is Ln
1-xA
xM
1-yB
yO
3, Ln
2-zA
zM
1-yB
yO
4, Ln
1-xA
xM
2-wB
wO
4, Ln
1-xA
xM
1-yB
yO
4, Ce
1-mZr
mO
2Or Ce
1-m-nZr
mPr
nO
2, in the formula, Ln is a rare earth metal, and A is an alkalinous metal, comprises alkali metal or alkaline-earth metal, and M is a transition metal, and B is the transition metal that is different from M, and x=0-0.95, y=0-0.95, z=0-1.95, w=0-1.95, m=0-0.99, n=0-0.99;
Described rare earth metal comprises one or more among La, Ce, Pr, Nd and the Sm;
Described transition metal comprises one or more among Fe, Co, Mn, Ni, Cu and the Cr;
Described alkalinous metal comprises alkali metal and/or alkaline-earth metal, comprises among Li, Na, K, Rb, Cs, Mg, Ca, Sr and the Ba one or more.
4. as each described oxidation catalyst of claim 1-3, wherein, this oxidation catalyst is that the organic complex agent solution that will contain the salt of its active component floods colloidal crystal template as maceration extract, the process roasting obtains then, and described organic complexing agent is liquid dihydroxylic alcohols or polyalcohol.
5. the preparation method of each described oxidation catalyst of claim 1-4, it may further comprise the steps:
The nitrate that will contain active component is dissolved in the organic complexing agent according to predetermined stoichiometric proportion mixing, and adds cosolvent, obtains the complex catalyst precursor liquid solution, and wherein, described organic complexing agent is ethylene glycol or glycerine, and described cosolvent is methyl alcohol or ethanol;
Utilize resulting complex catalyst precursor liquid solution as maceration extract, the adding colloidal crystal template floods repeatedly, drying, is warming up to 450 ℃-1000 ℃ then in air atmosphere, insulation 4-10h.
6. preparation method as claimed in claim 5, wherein, in the complex catalyst precursor liquid solution of described nitrate, organic complexing agent and the cosolvent that contains active component, the total concentration of metal ion is 0.05-3mol/L.
7. preparation method as claimed in claim 5, wherein, the air velocity in the described air atmosphere is 30-300mL/min.
8. preparation method as claimed in claim 5, wherein, with the following heating rate temperature programming to 450 of 2 ℃/min ℃-1000 ℃.
9. preparation method as claimed in claim 5, wherein, the preparation method of described colloidal crystal template may further comprise the steps:
Under nitrogen protection, acetone and redistilled water are mixed, and be preheated to 60-90 ℃ with water-bath, add monomers methyl methacrylate or styrene, continue to be heated to 60-90 ℃ with water-bath;
Under nitrogen protection, add 60-90 ℃ initiator solution, continue to stir 2-10h, obtain single polymethyl methacrylate or polystyrene microsphere emulsion of disperseing;
The microballoon emulsion is placed centrifuge tube, rotating speed centrifugal treating 1-30h with 1000-10000rpm obtains closelypacked colloidal crystal template, perhaps the microballoon emulsion is placed in the Flat bottom container, with the slowly evaporation in drying box of 40-80 ℃ temperature, the microballoon deposition obtains colloidal crystal template.
10. the method for purification of diesel car discharging soot particulate, it comprises the process that the burning of the soot particulate that adopts each described oxidation catalyst catalytic diesel oil car discharging of claim 1-4 purifies.
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| CN115487800A (en) * | 2022-09-16 | 2022-12-20 | 四川大学 | CeO with stable macroporous structure 2 -ZrO 2 Catalytic material, preparation method and application thereof |
| CN115487800B (en) * | 2022-09-16 | 2023-11-14 | 四川大学 | CeO with stable macroporous structure 2 -ZrO 2 Catalytic material, preparation method and application thereof |
| CN116510720A (en) * | 2023-06-20 | 2023-08-01 | 南昌大学 | Preparation method and application of catalyst for eliminating soot particles of diesel vehicle |
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