CN109734127A - A kind of monodisperse zirconium oxide porous microsphere and preparation method thereof - Google Patents
A kind of monodisperse zirconium oxide porous microsphere and preparation method thereof Download PDFInfo
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- CN109734127A CN109734127A CN201910189035.7A CN201910189035A CN109734127A CN 109734127 A CN109734127 A CN 109734127A CN 201910189035 A CN201910189035 A CN 201910189035A CN 109734127 A CN109734127 A CN 109734127A
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- zirconium oxide
- porous microsphere
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Abstract
The invention discloses a kind of monodisperse zirconium oxide porous microspheres and preparation method thereof, and stirring in n,N-Dimethylformamide, which is added, in oxalic acid dissolves it sufficiently；Zirconium-n-propylate is added drop-wise in n,N-Dimethylformamide DMF and is made it dissolve；Two kinds of solution are uniformly mixed；It pours into polytetrafluoroethylliner liner, white precipitate is prepared and is filtered to obtain filter cake；Gained filter cake is dried to obtain white powder and is ground up, sieved；It obtains white powder and after heat treatment obtains porous microsphere.Operation of the present invention is simple, and equipment requirement is low, and parameter area is relatively wide easily controllable, and repeatability is high, and gained porous mono-dispersion microsphere partial size and aperture are adjustable, and the strength of materials is high, is suitble to business promotion and large-scale application.
Description
Technical field
The invention belongs to inorganic micro-nano powder preparation technical fields, and in particular to a kind of monodisperse zirconium oxide porous microsphere
And preparation method thereof.
Background technique
Sub-micron and nanoporous microballoon, because of its unique design feature and small-size effect, in catalysis, environment work
The fields such as journey, pharmaceutical carrier have highly important application, are the hot spots of current scientific research circle research.
Porous structure microballoon and preparation method thereof mainly has collosol and gel, emulsion method, template etc. at present.Although synthesis two
The method of silica porous ball is varied, but the synthesis that these methods are applied to zirconium oxide porous microsphere still has some offices
Limit, main reason is that zirconium ion is compared with silica material with very big difference with interactions such as solvent and its pore creating materials,
It is difficult to synthesize the ideal structure and function of people's demand.Simultaneous oxidation zirconium particle surface hydroxyl in synthesis and drying process is easy
Hard aggregation occurs for condensation, and the mono-dispersion microballoon that uniformly agglomerates into of primary particle is more difficult to control.
Although having been reported that about passing throughMethod has obtained monodisperse zirconium oxide microballoons, but is amorphous structure, calcining
Post-processing obtains the preferable monodisperse particles of crystallinity, but since calcination process is shunk, is unable to get porous microsphere.Therefore such as
What manufacture monodisperse zirconium oxide porous microsphere meets the market demand, is current urgent problem to be solved.
Summary of the invention
In view of the above-mentioned deficiencies in the prior art, the technical problem to be solved by the present invention is that providing a kind of monodisperse oxygen
Change zirconium porous microsphere and preparation method thereof, simple and easy, the monodisperse porous zirconium oxide microballoons size uniformity of preparation, pore-size distribution
Uniformly.
The invention adopts the following technical scheme:
A kind of monodisperse zirconium oxide porous microsphere preparation method, comprising the following steps:
S1, dissolve it sufficiently stirring in oxalic acid addition n,N-Dimethylformamide (DMF)；
S2, zirconium-n-propylate is added drop-wise in n,N-Dimethylformamide (DMF) and is made it dissolve；
S3, it the solution in step S2 is added drop-wise in the solution of step S1 is uniformly mixed it；
S4, the solution in step S3 is poured into polytetrafluoroethylliner liner, white precipitate is prepared；
S5, it is filtered white precipitate obtained by step S4 to obtain filter cake；
S6, it is dried filter cake obtained by step S5 to obtain white powder；
S7, white powder obtained by step S6 is ground up, sieved；
S8, porous microsphere will be obtained after the white powder heat treatment in step S7 after sieving.
Specifically, 5~10min of magnetic agitation dissolves oxalic acid and n,N-Dimethylformamide sufficiently in step S1.
Specifically, 2~5min of magnetic agitation dissolves zirconium-n-propylate and n,N-Dimethylformamide sufficiently in step S2.
Specifically, the mass ratio of oxalic acid and zirconium-n-propylate is 2.5~3.0, and 10~20min of magnetic agitation makes in step S3
It is uniformly mixed.
Specifically, in step S4, reaction temperature is 150~200 DEG C of heat preservations 15~for 24 hours, raw material solid content 250 in reaction solution
~400g/l.
Specifically, in step S5, respectively with alcohol and distillation water washing 3~6 times.
Specifically, in step S6, drying temperature is 60~100 DEG C, drying time is 12~for 24 hours.
Specifically, be sieved 800~2000 mesh in step S7.
Specifically, in step S8, heat treatment specifically: control 2~5 DEG C/min of heating rate calcines 2 at 550~800 DEG C
~3h.
Another technical solution of the invention is a kind of monodisperse zirconium oxide porous microsphere, and monodisperse zirconium oxide is porous micro-
The partial size of ball is 250~500nm.
Compared with prior art, the present invention at least has the advantages that
A kind of monodisperse zirconium oxide porous microsphere of the present invention and preparation method thereof, using the organic solvent DMF for being dissolved in water,
Its removal easy to clean in later period separation process；Oxalic acid and zirconium-n-propylate are used simultaneously, effectively prevent conventional method introducing
The shortcomings that initial reaction caused by moisture is uneven, overcomes primary particle misgrowth and aggregation；Oxalic acid and zirconium ion are mutual
The monodisperse white presoma precipitating that effect is formed, has not only been successfully introduced into organic principle but also stable structure, will not be subsequent
It is damaged during clear and sieving.The organic principle of introducing can remove during subsequent calcination；Pass through oxalic acid and zirconium
Aperture can also be adjusted in proportion between ion；The partial size that presoma is also adjustable by reacting solid content accounting obtains
Obtain the porous mono-dispersion microsphere of different-grain diameter.Gained porous mono-dispersion microsphere structural strength is high, and good dispersion can satisfy load
Etc. application requirements.
Further, magnetic agitation is easy to operate, salable operation, avoids introducing a large amount of water in large-scale production process
Divide equal impurity reactant.
Further, pass through the ratio of raw material reactant, thus it is possible to vary the ratio of the organic principle of introducing, at last heat
It can effective adjustment aperture size during reason.
Further, the partial size of the adjustable monodisperse presoma of solid content is adjusted；The range of reaction temperature of the application compared with
Extensively, to production has easily controllable meaning on a large scale later.
Further, the washing that process passes through water and alcohol is filtered, organic solvent can be removed and other are unreacted miscellaneous
Matter, while being also avoided that in subsequent drying process and hard aggregation occurs, improve product quality.
Further, suction filtration cleaning solvent is completely removed, prevents follow-up heat treatment process from reuniting, misgrowth etc.
Situation.
Further, organic principle is easily removed, required porous mono-dispersion microsphere is obtained.
In conclusion operation of the present invention is simple, equipment requirement is low, and parameter area is relatively wide easily controllable, and repeatability is high, gained
Porous mono-dispersion microsphere partial size and aperture are adjustable, and the strength of materials is high, are suitble to business promotion and large-scale application.
Below by drawings and examples, technical scheme of the present invention will be described in further detail.
Detailed description of the invention
Fig. 1 is monodisperse zirconium oxide porous microsphere shape appearance figure prepared by the present invention；
Fig. 2 is porous mono-dispersion microsphere grain size distribution prepared by the present invention；
Fig. 3 is porous mono-dispersion microsphere graph of pore diameter distribution of the present invention.
Specific embodiment
The present invention provides a kind of monodisperse zirconium oxide porous microspheres and preparation method thereof, by oxalic acid and N, N- dimethyl methyl
The DMF solution that zirconium-n-propylate is added after amide mixing, which is uniformly mixed, obtains mixed solution, and mixed solution is put into polytetrafluoroethyl-ne
Reaction obtains white precipitate in alkene liner, is filtered to obtain filter cake to white precipitate, obtains white powder through being dried again
Body is simultaneously ground, and after heat treatment obtains porous microsphere.
A kind of preparation method of monodisperse zirconium oxide porous microsphere of the present invention, comprising the following steps:
S1, oxalic acid is added in n,N-Dimethylformamide (DMF), 5~10min of magnetic stirrer keeps it sufficiently molten
Solution；
S2, zirconium-n-propylate is added drop-wise in n,N-Dimethylformamide (DMF), 2~5min of magnetic agitation makes it dissolve；
In S3, the solution the solution fast drop in step S2 to step S1, the mass ratio of oxalic acid and zirconium-n-propylate is
2.5~3.0, continuing 10~20min of stirring is uniformly mixed it；
S4, the solution in step S3 is poured into polytetrafluoroethylliner liner, 150~200 DEG C of heat preservations 15~for 24 hours, it obtains white
Color precipitates, 250~400g/l of raw material solid content in reaction solution；
S5, white precipitate obtained by step S4 is filtered, respectively with alcohol and distillation water washing 3~6 times, it is extra to remove
DMF or impurity, obtain filter cake；
S6, by filter cake obtained by step S5 60~100 DEG C dry 12~for 24 hours, remove alcohol and moisture, then obtain white
Powder；
S7, powder obtained by step S6 is ground up, sieved 800~2000 mesh, avoids the occurrence of big agglomeration；
S8, the powder after being sieved in step S7 is heat-treated under certain temperature, removes organic principle, obtains porous micro-
Ball.
Heat treatment specifically: control heating rate is 2~5 DEG C/min, in 550~800 DEG C of 2~3h of calcining.
The partial size of the final monodisperse zirconium oxide porous microsphere obtained using this preparation system can be between 250~500nm
It is adjustable, specifically include 250nm, 300nm, 400nm or 500nm etc..
In order to make the object, technical scheme and advantages of the embodiment of the invention clearer, below in conjunction with the embodiment of the present invention
In attached drawing, technical scheme in the embodiment of the invention is clearly and completely described, it is clear that described embodiment is
A part of the embodiment of the present invention, instead of all the embodiments.The present invention being described and shown in usually here in attached drawing is real
The component for applying example can be arranged and be designed by a variety of different configurations.Therefore, below to the present invention provided in the accompanying drawings
The detailed description of embodiment be not intended to limit the range of claimed invention, but be merely representative of of the invention selected
Embodiment.Based on the embodiments of the present invention, those of ordinary skill in the art are obtained without creative efforts
The every other embodiment obtained, shall fall within the protection scope of the present invention.
Embodiment 1
S1, oxalic acid is added in n,N-Dimethylformamide (DMF), magnetic stirrer 5min dissolves it sufficiently；
S2, zirconium-n-propylate is added drop-wise in n,N-Dimethylformamide (DMF), magnetic agitation 2min makes it dissolve；
S3, the step S2 solution prepared is added drop-wise in the solution of step S1, the mass ratio of oxalic acid and zirconium-n-propylate is
2.5, continuing stirring 20min is uniformly mixed it；
S4, the solution in step S3 is poured into polytetrafluoroethylliner liner, is kept the temperature for 24 hours at 150 DEG C, obtains white precipitate,
Raw material solid content is 250g/l in reaction solution；
S5, white precipitate obtained by step S4 is filtered, respectively three times with alcohol and distillation water washing, it is extra to remove
DMF or impurity, obtain filter cake；
S6, filter cake obtained by step S5 is dried for 24 hours at 60 DEG C, removes alcohol and moisture, then obtains white powder；
S7, powder obtained by step S6 is ground up, sieved 800 mesh, avoids the occurrence of big agglomeration；
S8, control heating rate are 2 DEG C/min, by the powder after step S7 sieving in 550 DEG C of calcining 2h, removal it is organic at
Point, obtain the porous microsphere of 250nm.
Embodiment 2
S1, oxalic acid is added in n,N-Dimethylformamide (DMF), magnetic stirrer 8min dissolves it sufficiently；
S2, zirconium-n-propylate is added drop-wise in n,N-Dimethylformamide (DMF), the mass ratio of oxalic acid and zirconium-n-propylate is
2.8, magnetic agitation 3min makes it dissolve；
In S3, the solution the solution fast drop in step S2 to step S1, continuing stirring 15min keeps its mixing equal
It is even；
S4, the solution in step S3 is poured into polytetrafluoroethylliner liner, 180 DEG C of heat preservation 20h obtain white precipitate, instead
Answer raw material solid content 320g/l in liquid；
S5, white precipitate obtained by step S4 is filtered, respectively with alcohol and distillation water washing 4 times, it is extra to remove
DMF or impurity, obtain filter cake；
S6, by filter cake obtained by step S5 in 80 DEG C of dry 18h, removal alcohol and moisture, then obtain white powder；
S7, powder obtained by step S6 is ground up, sieved 1400 mesh, avoids the occurrence of big agglomeration；
S8, control heating rate are 3.5 DEG C/min, by the powder after being sieved in step S7 in 680 DEG C of calcining 2.5h, removal
Organic principle obtains the porous microsphere of 300nm.
Embodiment 3
S1, oxalic acid is added in n,N-Dimethylformamide (DMF), magnetic stirrer 10min dissolves it sufficiently；
S2, zirconium-n-propylate is added drop-wise in n,N-Dimethylformamide (DMF), the mass ratio of oxalic acid and zirconium-n-propylate is
3.0, magnetic agitation 4min makes it dissolve；
In S3, the solution the solution fast drop in step S2 to step S1, continuing stirring 15min keeps its mixing equal
It is even；
S4, the solution in step S3 is poured into polytetrafluoroethylliner liner, 200 DEG C of heat preservation 15h obtain white precipitate, instead
Answer raw material solid content 400g/l in liquid；
S5, white precipitate obtained by step S4 is filtered, respectively with alcohol and distillation water washing 5 times, it is extra to remove
DMF or impurity, obtain filter cake；
S6, by filter cake obtained by step S5 in 100 DEG C of dry 12h, removal alcohol and moisture, then obtain white powder；
S7, powder obtained by step S6 is ground up, sieved 2000 mesh, avoids the occurrence of big agglomeration；
S8, control heating rate are 5 DEG C/min, by the powder after being sieved in step S7 in 800 DEG C of calcining 3h, are removed organic
Ingredient obtains the porous microsphere of 400nm.
Embodiment 4
S1, oxalic acid is added in n,N-Dimethylformamide (DMF), magnetic stirrer 7min dissolves it sufficiently；
S2, zirconium-n-propylate is added drop-wise in n,N-Dimethylformamide (DMF), the mass ratio of oxalic acid and zirconium-n-propylate is
2.6, magnetic agitation 5min makes it dissolve；
In S3, the solution the solution fast drop in step S2 to step S1, continuing stirring 10min keeps its mixing equal
It is even；
S4, the solution in step S3 is poured into polytetrafluoroethylliner liner, 160 DEG C of heat preservation 18h obtain white precipitate, instead
Answer raw material solid content 300g/l in liquid；
S5, white precipitate obtained by step S4 is filtered, respectively with alcohol and distillation water washing 6 times, it is extra to remove
DMF or impurity, obtain filter cake；
S6, by filter cake obtained by step S5 in 90 DEG C of dry 20h, removal alcohol and moisture, then obtain white powder；
S7, powder obtained by step S6 is ground up, sieved 1000 mesh, avoids the occurrence of big agglomeration；
S8, control heating rate are 4 DEG C/min, by the powder after being sieved in step S7 in 750 DEG C of calcining 3h, are removed organic
Ingredient obtains the porous microsphere of 500nm.
Referring to Fig. 1, present invention gained porous microsphere structural integrity, morphological rules, particle diameter distribution is uniform, and particle surface is thick
It is rough, it is made of many little particles, hole is full of between little particle.
Fig. 2 and Fig. 3 are please referred to, the porous mono-dispersion microsphere particle diameter distribution of the application is uniform, further illustrates monodisperse
Property good feature, and resulting materials pore-size distribution is relatively uniform, further illustrates that the preparation method controllable degree of application is high.
The above content is merely illustrative of the invention's technical idea, and this does not limit the scope of protection of the present invention, all to press
According to technical idea proposed by the present invention, any changes made on the basis of the technical scheme each falls within claims of the present invention
Protection scope within.
Claims (10)
1. a kind of monodisperse zirconium oxide porous microsphere preparation method, which comprises the following steps:
S1, dissolve it sufficiently stirring in oxalic acid addition n,N-Dimethylformamide；
S2, it zirconium-n-propylate is added drop-wise in n,N-Dimethylformamide makes it dissolve；
S3, it the solution in step S2 is added drop-wise in the solution of step S1 is uniformly mixed it；
S4, the solution in step S3 is poured into polytetrafluoroethylliner liner, white precipitate is prepared；
S5, it is filtered white precipitate obtained by step S4 to obtain filter cake；
S6, it is dried filter cake obtained by step S5 to obtain white powder；
S7, white powder obtained by step S6 is ground up, sieved；
S8, porous microsphere will be obtained after the white powder heat treatment in step S7 after sieving.
2. monodisperse zirconium oxide porous microsphere preparation method according to claim 1, which is characterized in that in step S1, magnetic
Power, which stirs 5~10min, dissolves oxalic acid and n,N-Dimethylformamide sufficiently.
3. monodisperse zirconium oxide porous microsphere preparation method according to claim 1, which is characterized in that in step S2, magnetic
Power, which stirs 2~5min, dissolves zirconium-n-propylate and n,N-Dimethylformamide sufficiently.
4. monodisperse zirconium oxide porous microsphere preparation method according to claim 1, which is characterized in that in step S3, grass
The mass ratio of acid and zirconium-n-propylate is 2.5~3.0, and 10~20min of magnetic agitation is uniformly mixed it.
5. monodisperse zirconium oxide porous microsphere preparation method according to claim 1, which is characterized in that in step S4, instead
Answer temperature be 150~200 DEG C heat preservation 15~for 24 hours, 250~400g/l of raw material solid content in reaction solution.
6. monodisperse zirconium oxide porous microsphere preparation method according to claim 1, which is characterized in that in step S5, point
It Yong not alcohol and distillation water washing 3~6 times.
7. monodisperse zirconium oxide porous microsphere preparation method according to claim 1, which is characterized in that in step S6, do
Dry temperature be 60~100 DEG C, drying time be 12~for 24 hours.
8. monodisperse zirconium oxide porous microsphere preparation method according to claim 1, which is characterized in that in step S7, mistake
Sieve 800~2000 mesh.
9. monodisperse zirconium oxide porous microsphere preparation method according to claim 1, which is characterized in that in step S8, heat
Processing specifically: control 2~5 DEG C/min of heating rate, in 550~800 DEG C of 2~3h of calcining.
10. the monodisperse zirconium oxide porous microsphere that one kind is prepared method according to claim 1, which is characterized in that monodisperse
The partial size of zirconium oxide porous microsphere is 250~500nm.
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Citations (4)
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|---|---|---|---|---|
| US20030113254A1 (en) * | 2001-12-17 | 2003-06-19 | Vladimir Belov | Method for manufacturing stabilized zirconia |
| CN101337192A (en) * | 2007-07-04 | 2009-01-07 | 中国科学院大连化学物理研究所 | Meso-microporous metal-organic compound and preparation method thereof |
| CN104324728A (en) * | 2014-11-05 | 2015-02-04 | 中国科学院上海硅酸盐研究所 | Mesoporous composite oxide catalyst for purifying tail gases and preparation method thereof |
| CN106450288A (en) * | 2016-11-04 | 2017-02-22 | 济南大学 | Preparation method and application of porous cobalt oxide |
-
2019
- 2019-03-13 CN CN201910189035.7A patent/CN109734127A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20030113254A1 (en) * | 2001-12-17 | 2003-06-19 | Vladimir Belov | Method for manufacturing stabilized zirconia |
| CN101337192A (en) * | 2007-07-04 | 2009-01-07 | 中国科学院大连化学物理研究所 | Meso-microporous metal-organic compound and preparation method thereof |
| CN104324728A (en) * | 2014-11-05 | 2015-02-04 | 中国科学院上海硅酸盐研究所 | Mesoporous composite oxide catalyst for purifying tail gases and preparation method thereof |
| CN106450288A (en) * | 2016-11-04 | 2017-02-22 | 济南大学 | Preparation method and application of porous cobalt oxide |
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