CN105948098B - A kind of spherical lanthana - Google Patents
A kind of spherical lanthana Download PDFInfo
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- CN105948098B CN105948098B CN201610260597.2A CN201610260597A CN105948098B CN 105948098 B CN105948098 B CN 105948098B CN 201610260597 A CN201610260597 A CN 201610260597A CN 105948098 B CN105948098 B CN 105948098B
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- lanthana
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- ethylene glycol
- surface area
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
- C01F17/00—Compounds of rare earth metals
- C01F17/20—Compounds containing only rare earth metals as the metal element
- C01F17/206—Compounds containing only rare earth metals as the metal element oxide or hydroxide being the only anion
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/30—Particle morphology extending in three dimensions
- C01P2004/32—Spheres
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/62—Submicrometer sized, i.e. from 0.1-1 micrometer
Abstract
The invention discloses a kind of spherical lanthana, the average grain diameter of the spherical lanthana is 150nm~1.2 μm, and the specific surface area after being calcined at 1000 DEG C is 1 7m2/ g, the specific surface area after being calcined at 500 DEG C is 120 144m2/g.The invention also discloses the preparation method of the spherical lanthana, comprise the following steps：(1) lanthanum salt, water and ethylene glycol, polyvinylpyrrolidone and short chain organic acid, the laggard water-filling thermal response of stirring and dissolving are mixed；(2) reacted 18 hours at 160 240 DEG C；Centrifugation obtains sediment after cooling, and dry sediment obtains spherical lanthana.Lanthana pattern globulate prepared by the present invention and have that more uniform pattern, better crystallinity degree, good dispersion, heat endurance are high, specific surface area is big；Application suitable for motor-vehicle tail-gas.
Description
Technical field
The invention belongs to micro Nano material to synthesize field, and in particular to a kind of spherical lanthana.
Background technology
Rare earth element has the 4f electron orbits of uniqueness, and the motion mode of electronics has rare earth element and is different from it in track
The optics, electricity and magnetic property of its element.Lanthana is as one kind in light rare earth oxide, in precision optics glass, glimmering
Luminescent material, solid electrolyte battery, ceramic capacitor and gas sensor etc. have important application.In addition, lanthana is same
Sample is good catalysis material, is widely used in heterogeneous catalysis field.In Vehicle Exhaust Gas Cleaning Catalysts, lanthana and oxygen
Auxiliary agent can be all used as by changing cerium, improve the decentralization of noble metal, suppress the growth of noble metal crystal grain, improve catalytic activity；Lanthanum base calcium
Titanium ore type oxide equally just has good catalytic activity because fault of construction produces Lacking oxygen.
The method for synthesizing lanthana is various, and the lanthana of traditional precipitation method and sol-gal process synthesis is mostly amorphous,
It is poor to there is heat endurance, the deficiencies of high temperature easy-sintering, application in high temperature environments is limited.The La that conventional method obtains2O3Typically
To be amorphous, crystallinity is low, heat endurance is poor, typically by adulterating come increasing specific surface area and heat endurance, through 1000 DEG C of roastings
It is less than 1m than surface after burning2/ g is low applied to motor-vehicle tail-gas catalytic efficiency.
CN200910089538.3 discloses a kind of lanthana microballoon as dimension standard material, the lanthana microballoon
For inorganic organic hybrid microballoon, it is made up of lanthana and polyvinylpyrrolidonemolecules molecules, wherein lanthana and polyvinyl pyrrole
The weight ratio of alkanone is 11-16:1, the inorganic organic hybrid microballoon is polycrystalline structure, belongs to cubic system, crystal structure is
Fluorite type, structure cell are face-centred cubic structure, and microballoon form factor is less than 1.2, size range 90nm-450nm, the phase of size value
5 are less than to uncertainty } 0.The need of above method Hydrothermal Synthesiss twice, operating method is cumbersome, and obtained lanthana microballoon exists
Its specific surface area is less than 1m after 1000 DEG C of high-temperature roastings2/ g is also low applied to motor-vehicle tail-gas catalytic efficiency.
The content of the invention
The shortcomings that it is an object of the invention to overcome prior art, there is provided a kind of better crystallinity degree, good dispersion, have it is more equal
The spherical lanthana of one pattern.
To reach above-mentioned purpose, present invention employs following technical proposals：
A kind of spherical lanthana, the average grain diameter of spherical lanthana is 150nm~1.2 μm, after being calcined at 1000 DEG C
Specific surface area is 1-7m2/g。
Preferably, the specific surface area after being calcined at 500 DEG C is 120-144m2/g。
Preferably, the preparation method of the spherical lanthana comprises the following steps：
(1) lanthanum salt, water and ethylene glycol, polyvinylpyrrolidone and short chain organic acid, the laggard water-filling heat of stirring and dissolving are mixed
Reaction；
(2) 1-8 hours are reacted at 160-240 DEG C；Centrifugation obtains sediment after cooling, and dry sediment obtains spherical oxygen
Change lanthanum.
Preferably, step (1) reclaimed water and the volume ratio of ethylene glycol are 6-10:50-80.
Preferably, lanthanum salt and polyvinylpyrrolidone mol ratio are (200-270):1, short chain organic acid and water and ethylene glycol
The volume ratio of sum is 1：50-88, the mass ratio of lanthanum salt and water and ethylene glycol sum is 4-8:63-92.
Preferably, first lanthanum salt is dissolved in water and ethylene glycol in the step (1), then adds polyvinylpyrrolidone
Stir and stirred after to the solution of transparent clarification, adding short chain organic acid to the solution of transparent clarification.
Preferably, the lanthanum salt is La (NO3)3·6H2O or LaCl3·7H2O。
Preferably, the short chain organic acid is selected from glacial acetic acid, propionic acid, n-butyric acie and n-caproic acid.
Application of the spherical lanthana of the present invention in motor-vehicle tail-gas.
Compared with prior art, the present invention has the advantages that：
1st, the present invention prepares short, easy to operate, easy to control, the easy repetition of lanthana reacted time, using suitable organic acid
And its dosage, the lanthana pattern globulate of synthesis and have that more uniform pattern, better crystallinity degree, good dispersion, heat endurance be high, ratio
Surface area is big.
2nd, the present invention uses ethylene glycol as solvent, and with lanthanum stronger coordination can occur for ethylene glycol, makes it in synthesis rank
Section controls nanocrystalline growth.In addition, the viscosity of ethylene glycol is high, nucleation and growth rate can be reduced, so as to get product morphology
Evenly, it is regular.The spherical secondary structure with compared with low-surface-energy can also be formed simultaneously so that the spherical lanthana heat of preparation is steady
Qualitative height.
The addition of water have adjusted viscosity, avoid spheric granules from sticking together.Meanwhile the present invention is lived using PVP as surface
Property agent, and with water and ethylene glycol in the range of proper ratio, it is spherical that lanthana, which is not only prepared, and its have it is more uniform
Pattern, better crystallinity degree, good dispersion, heat endurance are high, specific surface area is big.
In addition, the addition of PVP and short chain organic acid has regulated and controled pattern, PVP is adsorbed in spherical surface, limits the size of particle diameter
And prevent the adhesion between spheric granules；Short chain organic acid influence spheric granules size, short chain organic acid due to exist carboxyl and
Alkyl, the carboxyl of one end can and La3+Coordination, the alkyl of the other end can modify nano-particle and influence the phase between nano-particle
Interaction.
Brief description of the drawings
The X ray diffracting spectrum of lanthana in Fig. 1 embodiments 1
SEM electron microscope of the lanthana after 750 DEG C of roastings in Fig. 2 embodiments 1
Embodiment
In order to make the purpose , technical scheme and advantage of the present invention be clearer, with reference to embodiments, to the present invention
It is further elaborated, but the scope of protection of present invention is not limited to the scope of embodiment expression.
The used composition of raw materials that each embodiment and comparative example prepare lanthana is as follows：
Embodiment 1
A kind of spherical lanthana is prepared, has and comprises the following steps：
(1) La (NO are weighed3)3·6H2O is dissolved in the mixed liquor of deionized water and ethylene glycol, stirring to being completely dissolved,
Polyvinylpyrrolidone (PVP, molecular weight M=58000) is added, stir about 1h, obtains the solution of transparent clarification, adds third
Acid, continue to stir 0.5h；
(2) mixed liquor for obtaining transparent clarification is transferred in 100ml polytetrafluoroethyllining linings, is put into stainless steel cauldron, and 200
DEG C reaction 200min；
(3) after question response kettle is cooled to room temperature, product is centrifuged into 5min with 10000r/min rotating speed, obtains sediment,
Again with alternately washing 3 times of deionized water and ethanol, lanthana is obtained with after 80 DEG C of dry 12h.
Test prepares：(1) lanthana prepared by embodiment 1 is dried, and with mortar grinder into fine powder, will wherein one
Half is calcined 1h in 500 DEG C, 2 DEG C/min of heating rate, obtains carbonic acid dioxy lanthanum；Wherein second half 4h will be calcined in 1000 DEG C, risen
Warm 3 DEG C/min of speed, obtained lanthanum oxide powder.
(2) XRD is tested：Lanthana prepared by embodiment 1 is carried out into XRD to test to obtain X ray diffracting spectrum, such as Fig. 1 institutes
Show, the results showed that the lanthana being prepared is hexagonal crystal phase.
(3) SEM is tested：Lanthana prepared by embodiment 1 carries out SEM sem tests, its pattern as shown in Fig. 2
Figure it is seen that embodiment 1 prepare lanthana for particle diameter in the spherical of 150~300nm.
Comparative example 1-1
A kind of spherical lanthana, its prepare when use molecular weight for 58000 polyvinylpyrrolidone, remaining raw material and
Preparation method and each performance test are the same as embodiment 1.
Comparative example 1-2
A kind of spherical lanthana, deionized water is not with ethylene glycol in OK range when it is prepared, and remaining raw material is with preparing
Method and respectively test with embodiment 1.
Comparative example 1-3
A kind of spherical lanthana, its prepare when deionized water with ethylene glycol and polyvinylpyrrolidone three not suitable
In the range of, remaining raw material is with preparation method and test with embodiment 1.
Comparative example 1-4
A kind of spherical lanthana, polyvinylpyrrolidone, remaining raw material are replaced using lauryl sodium sulfate when it is prepared
With preparation method and test with embodiment 1.
The test result such as following table of all of above embodiment and comparative example：
Data above shows, it is 58000 polyvinylpyrrolidone as surface-active that comparative example 1-1, which does not use molecular weight,
Agent, the lanthana prepared relative to embodiment 1, the larger pattern of its average grain diameter is irregular and agglomeration occurs, through 500 DEG C,
After 1000 DEG C of roastings, heat endurance is worse relative to embodiment 1, and after especially 1000 DEG C roastings, its specific surface area is lower, phase
For embodiment 1, it is not suitable for vehicle exhaust gas systems.
Comparative example 1-2 deionized waters and ethylene glycol is not in OK range, the lanthana that is prepared relative to embodiment 1, its
The larger pattern of average grain diameter is irregular and agglomeration occurs, and after 500 DEG C, 1000 DEG C of roastings, heat endurance is relative to reality
It is worse to apply example 1, after especially 1000 DEG C roastings, its specific surface area is lower, and it is not suitable for motor-vehicle tail-gas relative to embodiment 1
Catalyst.
Comparative example 1-3 deionized waters and ethylene glycol and polyvinylpyrrolidone is not in OK range, relative to embodiment 1
The lanthana of preparation, the larger pattern of its average grain diameter is irregular and agglomeration occurs, and after 500 DEG C, 1000 DEG C of roastings, heat is steady
Qualitative property is worse relative to embodiment 1, and after especially 1000 DEG C roastings, its specific surface area is lower, and relative to embodiment 1, it is uncomfortable
For vehicle exhaust gas systems.
Comparative example 1-4 replaces polyvinylpyrrolidone using lauryl sodium sulfate, the oxidation prepared relative to embodiment 1
Lanthanum, the larger pattern of its average grain diameter is irregular and agglomeration occurs, and after 500 DEG C, 1000 DEG C of roastings, heat endurance is relative
Worse in embodiment 1, after especially 1000 DEG C roastings, its specific surface area is lower, and relative to embodiment 1, it is not suitable for motor vehicle
Tail-gas catalyst.
The announcement and teaching of book according to the above description, those skilled in the art in the invention can also be to above-mentioned embodiment party
Formula is changed and changed.Therefore, the invention is not limited in embodiment disclosed and described above, to the present invention's
Some modifications and changes should also be as falling into the scope of the claims of the present invention.In addition, although used in this specification
Some specific terms, but these terms are merely for convenience of description, do not form any restrictions to the present invention.
Claims (7)
1. a kind of spherical lanthana, it is characterised in that the average grain diameter of spherical lanthana is 150nm~1.2 μm, at 1000 DEG C
Specific surface area after roasting is 1-7m2/ g, wherein, the preparation method of the spherical lanthana comprises the following steps：
(1) lanthanum salt, water and ethylene glycol, polyvinylpyrrolidone and short chain organic acid, the laggard water-filling thermal response of stirring and dissolving are mixed；
(2) 1-8 hours are reacted at 160-240 DEG C；Centrifugation obtains sediment after cooling, and dry sediment obtains spherical oxidation
Lanthanum,
Wherein, step (1) reclaimed water and the volume ratio of ethylene glycol are 6-10:50-80.
2. spherical lanthana as claimed in claim 1, it is characterised in that the specific surface area after being calcined at 500 DEG C is 120-
144m2/g。
3. spherical lanthana as claimed in claim 1, it is characterised in that lanthanum salt is with polyvinylpyrrolidone mol ratio
(200-270):1, short chain organic acid is 1 with the volume ratio of water and ethylene glycol sum：50-88, lanthanum salt and water and ethylene glycol sum
Mass ratio be 4-8:63-92.
4. spherical lanthana as claimed in claim 1, it is characterised in that in the step (1) first by lanthanum salt be dissolved in water and
In ethylene glycol, then add polyvinylpyrrolidone and stir to the solution of transparent clarification, add after short chain organic acid stir to
The solution of transparent clarification.
5. the spherical lanthana as described in claim any one of 1-4, it is characterised in that the lanthanum salt is La (NO3)3·6H2O
Or LaCl3·7H2O。
6. the spherical lanthana as described in claim any one of 1-4, it is characterised in that the short chain organic acid is selected from ice second
Acid, propionic acid, n-butyric acie and n-caproic acid.
7. application of the spherical lanthana of claim 1 or 2 in motor-vehicle tail-gas.
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| CN110790297B (en) * | 2018-07-31 | 2022-01-18 | 盛和资源(江苏)稀土有限公司 | Production process of lanthanum oxide |
| CN110359043B (en) * | 2019-07-27 | 2021-03-26 | 西北师范大学 | Preparation method of titanium-based lanthanum oxide nanoflower film with dielectric wetting low-voltage response |
| JP2023508816A (en) * | 2019-10-23 | 2023-03-06 | ネオ パフォーマンス マテリアルズ （シンガポール） プライベート リミテッド | Moderately dispersed Dy2O3 particles |
| CN111017980A (en) * | 2019-12-26 | 2020-04-17 | 宣城晶瑞新材料有限公司 | Preparation method of high-purity nano lanthanum oxide material |
| KR102261151B1 (en) * | 2020-02-27 | 2021-06-07 | 비드오리진(주) | Spherical inorganic particles having surface bump and method for preparing same |
| CN113087729B (en) * | 2021-04-01 | 2022-11-04 | 山东大学 | Lanthanum complex precursor, lanthanum oxide fiber and preparation method and application of lanthanum zirconate fiber derived from lanthanum oxide fiber |
| CN113651351A (en) * | 2021-08-16 | 2021-11-16 | 广东工业大学 | Samarium oxide and preparation and application thereof |
| CN115231605B (en) * | 2022-07-26 | 2024-02-06 | 宣城市晶和环保新材料科技有限公司 | Preparation method of high-purity nano lanthanum oxyfluoride |
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| CN103571334B (en) * | 2013-11-05 | 2015-02-18 | 上海华明高纳稀土新材料有限公司 | Cerium oxide polishing powder and preparation method thereof |
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