CN110386613A - A kind of preparation method for the mesoporous alumina hydrate microspherical of graduation that crystal form is controllable - Google Patents
A kind of preparation method for the mesoporous alumina hydrate microspherical of graduation that crystal form is controllable Download PDFInfo
- Publication number
- CN110386613A CN110386613A CN201910783043.4A CN201910783043A CN110386613A CN 110386613 A CN110386613 A CN 110386613A CN 201910783043 A CN201910783043 A CN 201910783043A CN 110386613 A CN110386613 A CN 110386613A
- Authority
- CN
- China
- Prior art keywords
- microspherical
- alumina hydrate
- graduation
- crystal form
- preparation
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J13/00—Colloid chemistry, e.g. the production of colloidal materials or their solutions, not otherwise provided for; Making microcapsules or microballoons
- B01J13/02—Making microcapsules or microballoons
-
- 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
- C01F7/00—Compounds of aluminium
- C01F7/02—Aluminium oxide; Aluminium hydroxide; Aluminates
- C01F7/04—Preparation of alkali metal aluminates; Aluminium oxide or hydroxide therefrom
- C01F7/14—Aluminium oxide or hydroxide from alkali metal aluminates
- C01F7/144—Aluminium oxide or hydroxide from alkali metal aluminates from aqueous aluminate solutions by precipitation due to cooling, e.g. as part of the Bayer process
-
- 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
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/50—Agglomerated particles
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/12—Surface area
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/14—Pore volume
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/16—Pore diameter
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/16—Pore diameter
- C01P2006/17—Pore diameter distribution
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Geology (AREA)
- Inorganic Chemistry (AREA)
- Dispersion Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Compounds Of Alkaline-Earth Elements, Aluminum Or Rare-Earth Metals (AREA)
Abstract
The present invention relates to a kind of preparation methods of the controllable mesoporous alumina hydrate microspherical of graduation of crystal form.It the described method comprises the following steps: taking certain formamide to be added rapidly in sodium aluminate solution, stir evenly；Then the solution is added rapidly in water heating kettle, heating hydrolysis a period of time, the white precipitate of generation is filtered after cooling, and is successively washed with water and dehydrated alcohol, obtains filter cake；By filtration cakes torrefaction, the flower-shaped mesoporous alumina hydrate microspherical of different crystal forms assembled by two-dimensional nano piece is obtained.The flower-shaped hydrated alumina microballoon of different crystal forms prepared by the present invention has good texture property, and changing hydro-thermal time, hydrothermal temperature and formamide additive amount can be such that its pore structure parameter changes in following range: 103.7~250.1m of specific surface area20.20~0.35cm of/g, Kong Rong3/ g, 4.3~5.4nm of average pore size, and aperture integrated distribution is in 3.3~5.2nm.
Description
Technical field
The invention belongs to aluminium oxide preparation technical fields, and in particular to a kind of mesoporous aqua oxidation of the graduation that crystal form is controllable
The preparation method of aluminium microballoon.
Background technique
The hydrated alumina (boehmite, bayerite and gibbsite etc.) and aluminium oxide of different crystal forms are extensive
Apply in the fields such as electronics, petrochemical industry, refractory material, ceramics, abrasive material, papermaking, pharmacy and aviation, especially active oxygen
Changing aluminium has Lewis-acid sites abundant and high surface area, is often used as catalyst or catalyst carrier.Heterogeneous catalysis is anti-
In answering in order to solve catalyst agglomeration inactivation, the problems such as friction is impaired and recycling is lost, it is certain to usually require that catalyst has
Particle diameter distribution, material can be increased on the characteristics of taking into account nano material high surface area well by preparing catalyst microspheres
Partial size and reduction fluid resistance.In addition, noble metal catalyst is essentially eggshell type structure, ball type carrier is more conducive to noble metal
In the distribution of carrier surface.To sum up, select simple, quick, extensive, low energy consumption, the method prepared product of high yield mutually stable
Ball-aluminium oxide hydrate is the important directions of high-performance advanced material development.
Aluminium oxide after different hydrated alumina roastings usually by being made.The preparation side of hydrated alumina microballoon at present
Method mainly has ball-milling method, spray drying process, homogeneous precipitation method, colloidal sol --- gel method, drop ball, template and hydro-thermal method etc.,
Wherein ball-milling method and spray drying process have been widely used, but the most size of alumina balls that they are prepared is inhomogenous, ball
Shape degree is not high, and is required to large-scale equipment.Present colloidal sol --- gel method generally can be equal to prepare partial size in conjunction with drop ball
One, the aluminum oxide micro-sphere of good dispersion, but silicon source can mostly select the organic aluminium salt of higher cost, and long preparation period.Xu etc.
People (Xu D., Jiang H., Li M.A novel method for synthesizing well-defined boehmite
hollow microspheres[J].Journal of Colloid and Interface Science,2017,504,660-
668.) use sol-gel method, select propylene oxide making gel auxiliary agent, formed without oil droplet successfully prepare it is solid to sky
The aluminum oxide micro-sphere of heart transformation, but preparation process is complicated, the period is long.And template generally prepares the lesser hollow oxidation of density
Aluminium, and the more difficult recycling of template, cause at high cost.Hydro-thermal method is the method for a comparative maturity, Cai et al. (Cai W., Yu
J.,Mann S.Template-free hydrothermal fabrication of hierarchically organized
γ-AlOOH hollow microspheres[J].Microporous&Mesoporous Materials,2009,122,42-
47；Ge J.,Deng K.,Cai W.,et al.Effect of structure-directing agents on facile
hydrothermal preparation of hierarchical γ-Al2O3 and their adsorption
performance toward Cr(VI)and CO2[J].Journal of colloid and interface science,
2013,401,34-39.) using urea as precipitating reagent, using hydro-thermal method respectively from aluminum sulfate and sodium aluminate be prepared for graduation intend it is thin
Diaspore microballoon.But the crystal form that this method obtains is uncontrollable, and select sodium aluminate as silicon source when also need to add surface-active
Agent.It is finally exactly Bayer process and CO2The liquid-phase precipitation methods such as method, this is industrially to prepare chemical aluminum oxide at present to be widely used
Method.The intermediate of the aluminium industrially leached from bauxite exists in the form of sodium aluminate solution, but also rarely has in temperature at present
The relevant report of the controllable mesoporous micron-size spherical aluminium oxide of crystal form is prepared from sodium aluminate solution under conditions of.
Summary of the invention
To solve the shortcomings and deficiencies of the prior art, the purpose of the present invention is to provide a kind of easy to operate, conditions
Mild method prepares the controllable mesoporous flower-shaped hydrated alumina microballoon of crystal form.
The object of the invention is achieved through the following technical solutions:
A kind of preparation method for the mesoporous alumina hydrate microspherical of graduation that crystal form is controllable, comprising the following steps:
(1) sodium aluminate is dissolved in the water, and stirring and dissolving at room temperature, certain formamide is then taken to be added rapidly to aluminium
In acid sodium solution, continue to stir evenly to form solution；
(2) solution that step (1) obtains is added rapidly in water heating kettle, the water heating kettle is further heated to certain temperature
A period of time is spent and hydrolyzed, the white precipitate of generation is filtered after cooling, and is successively washed with water and dehydrated alcohol, is filtered
Cake；By filtration cakes torrefaction, the flower-shaped mesoporous alumina hydrate microspherical of different crystal forms assembled by two-dimensional nano piece is obtained.
Preferably, the ratio of sodium aluminate and water is 2.46g:50~66mL in step (1)；The volume ratio of water and formamide is
1:0.06~0.4.
Preferably, the volume ratio of water and formamide is 66:4,58:12 or 50:20 in step (1).
Preferably, the time stirred twice in step (1) is respectively 10~30min, 0.5~1min.
Preferably, hydrolysis temperature is 25~180 DEG C in step (2).
Preferably, hydrolysis time is 2~48h in step (2).
Preferably, filter cake described in step (2) is in 60 DEG C of dry 12h.
The flower-shaped mesoporous alumina hydrate microspherical that the present invention synthesizes is the boehmite being assembled by nanometer sheet, bayerite
Or both mixture.With the extension of hydro-thermal time at 25 DEG C, it may appear that apparent unformed hydrated alumina is thin to intending
The conversion stage of diaspore, bayerite；With the increase of formamide additive amount at 25 DEG C, in boehmite crystal form stage product
Structure is more stable and crystallinity is higher；As hydrothermal temperature is increased to 180 DEG C from 25 DEG C, bayerite crystal form fades away,
And the crystallinity of the boehmite generated is higher.The average grain diameter of obtained aluminum oxide micro-sphere is 1.02~1.66 μm, compares table
Area is 103.7~250.1cm20.20~0.35cm of/g, Kong Rongwei3/ g, average pore size are 4.3~5.4nm, and aperture collection
In be distributed in 3.3~5.2nm.
Compared with prior art, the present invention has following major advantage:
1, using sodium aluminate as silicon source, formamide is precipitating reagent and pattern regulator, by the control of hydrothermal condition, mild
The meso-porous alumina hydrate microballoon of different crystal forms is prepared under hydrothermal condition.With the extension of time, will appear bright at 25 DEG C
Stage of the aobvious unformed hydrated alumina to boehmite, bayerite crystal transfer；As formamide adds at 25 DEG C
The increase of amount, it is more stable higher with crystallinity forming boehmite stage product；As the temperature rises, bayerite is brilliant
Type is not in, and the crystallization degree of pseudo-boehmite generated is higher.
2, the hydrated alumina crystal form prepared is controllable, and formamide additive amount is bigger, is more easy to get boehmite；
The hydro-thermal time extends, it may appear that the transformation of the opposite bayerite phase of boehmite；Hydrothermal temperature is higher, and thin water is intended in easier generation
Aluminium stone phase, and crystallinity is higher.
3, the hydrated alumina obtained under different condition all has flower-like microsphere pattern, and temperature more polymolecularity more
Good, the average grain diameter of microballoon is at 1.02~1.66 μm.
4, the flower-shaped hydrated alumina microballoon for the different crystal forms prepared has good texture property, when changing hydro-thermal
Between, hydrothermal temperature and formamide additive amount its pore structure parameter can be made to change in following range: specific surface area 103.7~
250.1m20.20~0.35cm of/g, Kong Rong3/ g, 4.3~5.4nm of average pore size, and aperture integrated distribution is in 3.3~5.2nm.
Detailed description of the invention
Fig. 1 is the SEM photograph of microballoon prepared by embodiment 1.
Fig. 2 is the SEM photograph of microballoon prepared by embodiment 2.
Fig. 3 is the SEM photograph of microballoon prepared by embodiment 3.
Fig. 4 is the SEM photograph of microballoon prepared by embodiment 4.
Fig. 5 is the SEM photograph of microballoon prepared by embodiment 5.
Fig. 6 is the SEM photograph of microballoon prepared by embodiment 6.
Fig. 7 is the SEM photograph of microballoon prepared by embodiment 7.
Fig. 8 is the XRD spectrum of the microballoon of each embodiment preparation.
Fig. 9 is the nitrogen adsorption-desorption isothermal curve and pore size distribution curve that each embodiment prepares microballoon.
Specific embodiment
Below with reference to embodiment and attached drawing, the present invention is described in further detail, but embodiments of the present invention are unlimited
In this.In the test of embodiment, room temperature is 25 DEG C.
Embodiment 1
2.46g sodium aluminate is dissolved in 58mL deionized water, and magnetic agitation 15min forms sodium aluminate solution at 25 DEG C
Liquid；Then it is added in above-mentioned solution with the formamide that pipette draws 12mL, continues magnetic agitation 1min and form solution；Then
The solution is added rapidly in the stainless steel water heating kettle of inner liner polytetrafluoroethylene, puts it into and hydrolyzes 2h in 25 DEG C of baking oven
Afterwards, the white precipitate of generation is filtered, and be successively washed with deionized twice, dehydrated alcohol washed once, then at 60 DEG C
Air dry oven in dry 12h to get arriving pseudo boehmite microsphere.
As shown in table 1 and Fig. 1, Fig. 8, Fig. 9, obtained is the flower-shaped pseudo boehmite microsphere being assembled by nanometer sheet,
The average grain diameter of microballoon is 1.02 μm, specific surface area 154.8m2/ g, Kong Rongwei 0.26cm3/ g, average pore size 5.3nm, hole
Diameter distribution concentrates on 3.6nm.
Embodiment 2
2.46g sodium aluminate is dissolved in 58mL deionized water, and magnetic agitation 15min forms sodium aluminate solution at 25 DEG C
Liquid；Then it is added in above-mentioned solution with the formamide that pipette draws 12mL, continues magnetic agitation 1min and form solution；Then
The solution is added rapidly in the stainless steel water heating kettle of inner liner polytetrafluoroethylene, puts it into 25 DEG C of baking oven and hydrolyzes for 24 hours
Afterwards, the white precipitate of generation is filtered, and be successively washed with deionized twice, dehydrated alcohol washed once, then at 60 DEG C
Air dry oven in dry 12h to get arriving bayerite microballoon.
As shown in table 1 and Fig. 2, Fig. 8, Fig. 9, obtained is the flower-shaped bayerite microballoon being assembled by nanometer sheet, microballoon
Average grain diameter be 1.23 μm, specific surface area 122.8m2/ g, Kong Rongwei 0.20cm3/ g, average pore size 5.3nm, aperture point
Cloth concentrates on 3.4nm.
Embodiment 3
2.46g sodium aluminate is dissolved in 66mL deionized water, and magnetic agitation 15min forms sodium aluminate solution at 25 DEG C
Liquid；Then it is added in above-mentioned solution with the formamide that pipette draws 4mL, continues magnetic agitation 1min and form solution；Then
The solution is added rapidly in the stainless steel water heating kettle of inner liner polytetrafluoroethylene, puts it into and hydrolyzes 2h in 25 DEG C of baking oven
Afterwards, the white precipitate of generation is filtered, and be successively washed with deionized twice, dehydrated alcohol washed once, then at 60 DEG C
Air dry oven in dry 12h to get the mixing microballoon for arriving bayerite and boehmite.
As shown in table 1 and Fig. 3, Fig. 8, Fig. 9, obtained is the flower-shaped bayerite being assembled by nanometer sheet and to intend thin water aluminium
Microballoon, the average grain diameter of microballoon are 1.02 μm, specific surface area 103.7m2/ g, Kong Rongwei 0.2cm3/ g, average pore size are
5.2nm, pore-size distribution concentrate on 3.3nm.
Embodiment 4
2.46g sodium aluminate is dissolved in 50mL deionized water, and magnetic agitation 15min forms sodium aluminate solution at 25 DEG C
Liquid；Then it is added in above-mentioned solution with the formamide that pipette draws 20mL, continues magnetic agitation 1min and form solution；Then
The solution is added rapidly in the stainless steel water heating kettle of inner liner polytetrafluoroethylene, puts it into 25 DEG C of baking oven and hydrolyzes for 24 hours
Afterwards, the white precipitate of generation is filtered, and be successively washed with deionized twice, dehydrated alcohol washed once, then at 60 DEG C
Air dry oven in dry 12h to get arriving pseudo boehmite microsphere.
As shown in table 1 and Fig. 4, Fig. 8, Fig. 9, obtained is that be assembled by nanometer sheet flower-shaped intends thin water aluminium microballoon, micro-
The average grain diameter of ball is 1.36 μm, specific surface area 179.7m2/ g, Kong Rongwei 0.35cm3/ g, average pore size 5.4nm, aperture
Distribution concentrates on 3.7nm.
Embodiment 5
2.46g sodium aluminate is dissolved in 58mL deionized water, and magnetic agitation 15min forms sodium aluminate solution at 25 DEG C
Liquid；Then it is added in above-mentioned solution with the formamide that pipette draws 12mL, continues magnetic agitation 1min and form solution；Then
The solution is added rapidly in the stainless steel water heating kettle of inner liner polytetrafluoroethylene, puts it into and hydrolyzes 2h in 60 DEG C of baking oven
Afterwards, the white precipitate of generation is filtered, and be successively washed with deionized twice, dehydrated alcohol washed once, then at 60 DEG C
Air dry oven in dry 12h to get arriving pseudo boehmite microsphere.
As shown in table 1 and Fig. 5, Fig. 8, Fig. 9, obtained is the flower-shaped pseudo boehmite microsphere being assembled by nanometer sheet,
The average grain diameter of microballoon is 1.66 μm, specific surface area 159.7m2/ g, Kong Rongwei 0.29cm3/ g, average pore size 5.2nm, hole
Diameter distribution concentrates on 3.3nm.
Embodiment 6
2.46g sodium aluminate is dissolved in 58mL deionized water, and magnetic agitation 15min forms sodium aluminate solution at 25 DEG C
Liquid；Then it is added in above-mentioned solution with the formamide that pipette draws 12mL, continues magnetic agitation 1min and form uniform clear liquid；
Then the solution is added rapidly in the stainless steel water heating kettle of inner liner polytetrafluoroethylene, puts it into water in 120 DEG C of baking oven
After solving 2h, the white precipitate of generation is filtered, and be successively washed with deionized twice, dehydrated alcohol washed once, then exist
12h is dried in 60 DEG C of air dry oven to get pseudo boehmite microsphere is arrived.
As shown in table 1 and Fig. 6, Fig. 8, Fig. 9, obtained is the flower-shaped pseudo boehmite microsphere being assembled by nanometer sheet,
The average grain diameter of microballoon is 1.34 μm, specific surface area 250.1m2/ g, Kong Rongwei 0.27cm3/ g, average pore size 4.3nm, hole
Diameter distribution concentrates on 3.4nm.
Embodiment 7
2.46g sodium aluminate is dissolved in 58mL deionized water, and magnetic agitation 15min forms sodium aluminate solution at 25 DEG C
Liquid；Then it is added in above-mentioned solution with the formamide that pipette draws 12mL, continues magnetic agitation 1min and form uniform clear liquid,
Then the solution is added rapidly in the stainless steel water heating kettle of inner liner polytetrafluoroethylene, puts it into water in 180 DEG C of baking oven
After solving 2h, the white precipitate of generation is filtered, and be successively washed with deionized twice, dehydrated alcohol washed once, then exist
12h is dried in 60 DEG C of air dry oven to get pseudo boehmite microsphere is arrived.
As shown in table 1 and Fig. 7, Fig. 8, Fig. 9, obtained is the flower-shaped pseudo boehmite microsphere being assembled by nanometer sheet,
The average grain diameter of microballoon is 1.40 μm, specific surface area 171.9m2/ g, Kong Rongwei 0.30cm3/ g, average pore size 5.0nm, hole
Diameter distribution concentrates on 5.2nm.
As shown in Figure 8, at room temperature with the extension of reaction time, hydrated alumina show it is unformed, intend thin water aluminium
The obvious transition process of stone, bayerite.The additional amount of formamide is bigger at room temperature, and the crystallinity of the boehmite of formation is got over
Height, stability are stronger；With the rising of reaction temperature, the sample of preparation shows preferable boehmite crystalline phase, and
The dispersibility of microballoon is better.
The pore structure parameter of different samples has a certain difference it can be seen from table 1 and Fig. 9, range distribution are as follows: ratio
103.7~254.8m of surface area20.20~0.36cm of/g, Kong Rong3/ g, 4.3~5.4nm of average pore size, pore-size distribution concentrate on
3.3~5.2nm.In conjunction with crystal form variation as can be seen that the content and crystallinity of boehmite are higher, the specific surface area of microballoon is got over
Height, Kong Rongyue are big, and the pore-size distribution of sample is concentrated mainly on 3.3-3.7nm, 180 DEG C of hydro-thermal back apertures distributions before 180 DEG C
Concentrate on 5.2nm, the aperture increases of integrated distribution.As shown in Figure 9, the aluminium oxide that prepared by embodiment 1- embodiment 7 is shown as
Typical IV thermoisopleth shows that these samples are mesopore material；Its hysteresis loop shows as H2 and H3 mixed type, shows to deposit in solid
The ink-bottle pore gap to be formed and slot-shaped hole are accumulated in sheet-like particle.
Can significantly it be found out by Fig. 1-Fig. 7, related flower-like microsphere is to be assembled by nanometer sheet, but have portion between microballoon
Divide bonding；As formamide additive amount increases the raising with reaction temperature, the dispersibility of microballoon increases.
Pore structure parameter, average grain diameter and the crystal form information of hydrated alumina microballoon prepared by each embodiment of table 1
The above embodiment is a preferred embodiment of the present invention, but embodiments of the present invention are not by above-described embodiment
Limitation, other any changes, modifications, substitutions, combinations, simplifications made without departing from the spirit and principles of the present invention,
It should be equivalent substitute mode, be included within the scope of the present invention.
Claims (10)
1. a kind of preparation method of the controllable mesoporous alumina hydrate microspherical of graduation of crystal form, which is characterized in that including following step
It is rapid:
(1) sodium aluminate is dissolved in the water, and stirring and dissolving obtains sodium aluminate solution at room temperature, and certain formamide is then taken to add
Enter into sodium aluminate solution, continues to stir evenly to form solution；
(2) solution that step (1) obtains is added in water heating kettle, when which is heated to one section of certain temperature hydrolysis
Between, the white precipitate of generation is filtered after cooling, and washs, obtains filter cake；By filtration cakes torrefaction, it is micro- to obtain mesoporous hydrated alumina
Ball.
2. a kind of preparation method of the controllable mesoporous alumina hydrate microspherical of graduation of crystal form according to claim 1,
It is characterized in that, the ratio of sodium aluminate and water is 2.46g:50~66mL in step (1)；The volume ratio of water and formamide is 1:0.06
~0.4.
3. a kind of preparation method of the controllable mesoporous alumina hydrate microspherical of graduation of crystal form according to claim 1,
It is characterized in that, the volume ratio of water and formamide is 66:4,58:12 or 50:20 in step (1).
4. a kind of preparation method of the controllable mesoporous alumina hydrate microspherical of graduation of crystal form according to claim 1,
It is characterized in that, the time stirred twice in step (1) is respectively 10~30min, 0.5~1min.
5. a kind of preparation method of the controllable mesoporous alumina hydrate microspherical of graduation of crystal form according to claim 1,
It is characterized in that, hydrolysis temperature is 25~180 DEG C in step (2).
6. a kind of preparation method of the controllable mesoporous alumina hydrate microspherical of graduation of crystal form according to claim 1,
It is characterized in that, hydrolysis time is 2~48h in step (2).
7. a kind of preparation method of the controllable mesoporous alumina hydrate microspherical of graduation of crystal form according to claim 1,
It is characterized in that, washing, which refers to, described in step (2) is successively washed with water and dehydrated alcohol.
8. a kind of preparation method of the controllable mesoporous alumina hydrate microspherical of graduation of crystal form according to claim 1,
It is characterized in that, filter cake described in step (2) is in 60 DEG C of dry 12h.
9. a kind of mesoporous alumina hydrate microspherical as made from any one of claim 1-8 the method.
10. mesoporous alumina hydrate microspherical according to claim 9, which is characterized in that the meso-porous alumina microballoon
Average grain diameter be 1.02~1.66 μm, specific surface area is 103.7~250.1cm20.20~0.35cm of/g, Kong Rongwei3/ g, it puts down
Equal aperture is 4.3~5.4nm, and aperture integrated distribution is in 3.3~5.2nm.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910783043.4A CN110386613B (en) | 2019-08-23 | 2019-08-23 | Preparation method of hierarchical mesoporous hydrated alumina microspheres with controllable crystal forms |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910783043.4A CN110386613B (en) | 2019-08-23 | 2019-08-23 | Preparation method of hierarchical mesoporous hydrated alumina microspheres with controllable crystal forms |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN110386613A true CN110386613A (en) | 2019-10-29 |
| CN110386613B CN110386613B (en) | 2022-04-29 |
Family
ID=68289382
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201910783043.4A Active CN110386613B (en) | 2019-08-23 | 2019-08-23 | Preparation method of hierarchical mesoporous hydrated alumina microspheres with controllable crystal forms |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN110386613B (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110652957A (en) * | 2019-11-14 | 2020-01-07 | 广州大学 | Preparation method and application of pseudo-boehmite microspheres |
| CN112374514A (en) * | 2020-11-11 | 2021-02-19 | 广州大学 | Method for rapidly preparing bayer stone microspheres with uniform particle size by double hydrolysis at room temperature |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1317527A (en) * | 1971-07-14 | 1973-05-23 | Mitsubishi Chem Ind | Process for preparing pure hydrated alumina |
| CN101367535A (en) * | 2008-10-09 | 2009-02-18 | 武汉理工大学 | Hydrothermal method for preparing gamma-AL2O3 hollow microsphere polishing material without mould plate |
| CN103011215A (en) * | 2012-12-10 | 2013-04-03 | 中国科学院合肥物质科学研究院 | Boehmite micro-nano structure sphere and preparation method thereof |
| CN103232049A (en) * | 2013-03-17 | 2013-08-07 | 青岛科技大学 | Preparation method of alpha-Al2O3 cage-structure hollow microspheres |
| CN106830024A (en) * | 2017-02-16 | 2017-06-13 | 曲阜师范大学 | A kind of red mud is the hydro-thermal thermal conversion process that raw material prepares active boehmite and aluminum oxide porous microballoon |
| CN108726544A (en) * | 2018-07-02 | 2018-11-02 | 陕西学前师范学院 | Nanometer sheet self assembly hierarchical structure γ-AlOOH tiny balloons, preparation method and application |
| CN110065959A (en) * | 2019-05-08 | 2019-07-30 | 广州大学 | A kind of η-Al2O3Microballoon and its preparation method and application |
-
2019
- 2019-08-23 CN CN201910783043.4A patent/CN110386613B/en active Active
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1317527A (en) * | 1971-07-14 | 1973-05-23 | Mitsubishi Chem Ind | Process for preparing pure hydrated alumina |
| CN101367535A (en) * | 2008-10-09 | 2009-02-18 | 武汉理工大学 | Hydrothermal method for preparing gamma-AL2O3 hollow microsphere polishing material without mould plate |
| CN103011215A (en) * | 2012-12-10 | 2013-04-03 | 中国科学院合肥物质科学研究院 | Boehmite micro-nano structure sphere and preparation method thereof |
| CN103232049A (en) * | 2013-03-17 | 2013-08-07 | 青岛科技大学 | Preparation method of alpha-Al2O3 cage-structure hollow microspheres |
| CN106830024A (en) * | 2017-02-16 | 2017-06-13 | 曲阜师范大学 | A kind of red mud is the hydro-thermal thermal conversion process that raw material prepares active boehmite and aluminum oxide porous microballoon |
| CN108726544A (en) * | 2018-07-02 | 2018-11-02 | 陕西学前师范学院 | Nanometer sheet self assembly hierarchical structure γ-AlOOH tiny balloons, preparation method and application |
| CN110065959A (en) * | 2019-05-08 | 2019-07-30 | 广州大学 | A kind of η-Al2O3Microballoon and its preparation method and application |
Non-Patent Citations (4)
| Title |
|---|
| JIATAI WANG ET AL.: "Facile size-controlled synthesis of well-dispersed spherical amorphous alumina nanoparticles via homogeneous precipitation", 《CERAMICS INTERNATIONAL》 * |
| JIE LI ET AL.: "Novel application of red mud Facile hydrothermal thermal conversion synthesis of hierarchical porous AlOOH and Al2O3 microspheres as adsorbents for dye removal", 《CHEMICAL ENGINEERING JOURNAL》 * |
| SOURAV GHOSH ET AL.: "Morphologically Tuned Aluminum Hydrous Oxides and Their Calcined Products", 《JOURNAL OF THE AMERICAN CERAMIC SOCIETY》 * |
| YOU ZHU ET AL.: "Synthesis of Three-Quarter-Sphere-Like γ-AlOOH Superstructures with High Adsorptive Capacity", 《EUR. J. INORG. CHEM.》 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110652957A (en) * | 2019-11-14 | 2020-01-07 | 广州大学 | Preparation method and application of pseudo-boehmite microspheres |
| CN110652957B (en) * | 2019-11-14 | 2022-02-18 | 广州大学 | Preparation method and application of pseudo-boehmite microspheres |
| CN112374514A (en) * | 2020-11-11 | 2021-02-19 | 广州大学 | Method for rapidly preparing bayer stone microspheres with uniform particle size by double hydrolysis at room temperature |
| CN112374514B (en) * | 2020-11-11 | 2022-09-30 | 广州大学 | Method for rapidly preparing bayer stone microspheres with uniform particle size by double hydrolysis at room temperature |
Also Published As
| Publication number | Publication date |
|---|---|
| CN110386613B (en) | 2022-04-29 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN100494066C (en) | Method for preparing ordered mesoporous aluminium oxide | |
| CN101704538B (en) | Hydrothermal method for preparing series of special-shaped graded pseudo-boehmite | |
| CN107081155B (en) | A kind of catalyst and preparation method for catalytic gasoline hydrogenation desulfurization | |
| CN105397103A (en) | Nano-silver/graphene composite material and preparation method thereof | |
| CN109942012B (en) | Nanoscale flaky boehmite and preparation method thereof | |
| CN106994361B (en) | A kind of alumina support and preparation method with macroporous structure | |
| CN108726544A (en) | Nanometer sheet self assembly hierarchical structure γ-AlOOH tiny balloons, preparation method and application | |
| CN110386613A (en) | A kind of preparation method for the mesoporous alumina hydrate microspherical of graduation that crystal form is controllable | |
| US20080311031A1 (en) | Methods For Production of Metal Oxide Nano Particles With Controlled Properties, and Nano Particles and Preparations Produced Thereby | |
| CN105668647A (en) | High-specific surface area perovskite nano-LaCoO3 porous hollow sphere material and preparation method thereof | |
| CN110201655B (en) | One-step method for preparing hollow TiO2Method and application of nano-microspheres | |
| CN104860357B (en) | Mono-dispersed nano sheet and/or nano-rings and preparation thereof and application | |
| CN111362295A (en) | Ordered large-mesoporous cerium oxide material with high specific surface area and preparation method thereof | |
| Benu et al. | Reverse micelle-mediated synthesis of plate-assembled hierarchical three-dimensional flower-like gamma-alumina particles | |
| Yu et al. | Hydrothermal synthesis and photocatalytic activity of mesoporous titania hollow microspheres | |
| CN113736094B (en) | Synthesis method of hierarchical porous ZIF-9 | |
| CN109516482B (en) | Preparation method of boehmite powder with different morphologies | |
| CN109647404B (en) | yolk/shell type catalyst, preparation method thereof and application thereof in catalytic hydrogen production | |
| CN110937620A (en) | Non-stoichiometric zinc-aluminum spinel and preparation method thereof | |
| CN103058259A (en) | Preparation method for chestnut-shaped copper sulphide hollow micron sphere composed of nanosheets | |
| CN112811450A (en) | Preparation method of spherical nano-micron alumina | |
| CN109338466B (en) | Preparation of single crystal Fe2O3Method for self-assembling nano-particle into elliptical micro-nano structure | |
| CN105253904A (en) | Alumina micro-nano powder preparation method | |
| CN109304226A (en) | A kind of hydrocracking catalyst and its preparation method and application of fecund heavy naphtha and boat coal | |
| CN110835103A (en) | Preparation method of cobalt-copper phosphate microspheres and application of cobalt-copper phosphate microspheres in catalyzing ammonia borane hydrolysis to produce hydrogen |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |