CN101049963A - Method for preparing laminar alpha zirconium phosphate with high crystallinity and even particle diameter - Google Patents
Method for preparing laminar alpha zirconium phosphate with high crystallinity and even particle diameter Download PDFInfo
- Publication number
- CN101049963A CN101049963A CN 200710099379 CN200710099379A CN101049963A CN 101049963 A CN101049963 A CN 101049963A CN 200710099379 CN200710099379 CN 200710099379 CN 200710099379 A CN200710099379 A CN 200710099379A CN 101049963 A CN101049963 A CN 101049963A
- Authority
- CN
- China
- Prior art keywords
- solution
- zirconium phosphate
- hydrochloric acid
- alpha zirconium
- zrp
- 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.)
- Pending
Links
Images
Landscapes
- Catalysts (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
Abstract
This invention discloses a method for preparing lamellar alpha-zirconium phosphate with high crystallinity and uniform particle sizes. The method comprises: mixing and reacting two reactant solutions in a colloid mill rotating at a high speed to obtain crystal seed with uniform and small grain sizes, transferring to a hydrothermal reaction kettle, and crystallizing. The method has such advantages as simple process and easy operation. The obtained lamellar alpha-zirconium phosphate has high crystallinity and uniform particle sizes.
Description
Technical field
The invention belongs to the inorganic layered compounds preparing technical field, the preparation method of a kind of high-crystallinity and uniform particle diameter laminar alpha zirconium phosphate particularly is provided, promptly at first with of the colloidal mill short mix reaction of two kinds of reactant solutions by running up, generate the nucleus of the tiny homogeneous of particle diameter, then it is transferred in the hydrothermal reaction kettle crystallization to generate degree of crystallinity height and the controlled alpha zirconium phosphate of size distribution homogeneous.
Background technology
Alpha zirconium phosphate (α-Zr (HPO
4)
2H
2O, abbreviation α-ZrP), be a cationoid type lamellar compound.α-ZrP has ion-exchange performance preferably, acid-proof alkaline, higher thermostability, selects shape absorption and catalytic performance, the main basic materials that are used as ion-exchanger, catalyzer and support of the catalyst, biomolecules fixing agent and self-assembly composite membrane etc. have broad application prospects in fields such as catalysis, medicine, electrochemistry, photochemistry, biology, environmental protection.And the degree of crystallinity of α-ZrP and size distribution thereof have material impact to its physicochemical property and application.As the α-ZrP with high-crystallinity and uniform particle diameter is template, can access the superpolymer of narrow molecular weight distribution when carrying out in-situ polymerization again behind the intercalation monomer molecule.
Preparation α-ZrP mainly contains four kinds of methods such as circumfluence method, sol-gel method, direct precipitation method and hydrothermal method at present.The not high and size distribution heterogeneity of the α that circumfluence method and sol-gel method prepare-ZrP degree of crystallinity; α-ZrP the degree of crystallinity of direct precipitation method preparation is higher, but needs to use hydrofluoric acid in the preparation process, to the seriously corroded of equipment; The degree of crystallinity of the synthetic α-ZrP that obtains of hydrothermal method is higher, but the formation of hydrothermal method nucleus and the growth of crystal grain are carried out synchronously usually, so product cut size distribution range broad.As at document (1) China YouSe Acta Metallurgica Sinica, 2001,11 (5): in 895, people such as Zhang Rui adopt hydrothermal method to synthesize α-ZrP, and electromicroscopic photograph shows α-ZrP particle diameter heterogeneity, particle size distribution range broad.
Summary of the invention
The object of the invention is to provide the preparation method of a kind of high-crystallinity and uniform particle diameter laminar alpha zirconium phosphate, the formation and the crystal growth that solve traditional water thermal reaction method nucleus when preparation α-ZrP are carried out synchronously, synthetic α-ZrP product particle diameter heterogeneity, the problem of particle size distribution range broad.
The inventive method is at first with the colloidal mill short mix reaction of two kinds of reactant solutions by running up, generate the nucleus of the tiny homogeneous of particle diameter, then it is transferred in the hydrothermal reaction kettle crystallization to generate degree of crystallinity height and the controlled alpha zirconium phosphate of size distribution homogeneous.Concrete processing step is as follows:
A. with ZrOCl
28H
2O, concentrated hydrochloric acid (36-38wt%) join wiring solution-forming I in the deionized water; Strong phosphoric acid (85wt%), concentrated hydrochloric acid (36-38wt%) are joined wiring solution-forming II in the deionized water.Solution I and solution II are joined rotating speed simultaneously under 15-30 ℃ room temperature be that reaction back suspension liquid hightails colloidal mill in 3000-5000 rev/min the colloidal mill.According to two kinds of mixed cumulative volumes of solution are calculated, each reacting material concentration is respectively: ZrOCl
28H
2O concentration is 0.044-0.36mol/L, and phosphoric acid concentration is 2.0-10mol/L, and concentration of hydrochloric acid is 0.50-4.0mol/L.
B. steps A gained suspension liquid is transferred in the polytetrafluoroethylcontainer container, filling degree is 40-80%, polytetrafluoroethylcontainer container is sealed in the hydrothermal reaction kettle, at 180-240 ℃ of hydrothermal treatment consists 48-192 hour, water heating kettle is naturally cooled to room temperature, opening the still suction filtration, is 6-7 with deionized water wash filter cake to filtrate pH value, and filter cake is got product after the drying in 50-60 ℃ of air atmosphere.
Adopt day island proper Tianjin XRD-6000 type x-ray powder diffraction instrument to characterize product structure, its XRD test result shows that product is the single α-ZrP of crystalline phase as shown in Figure 1, and peak shape is sharp-pointed, shows product degree of crystallinity height.Adopt FDAC S-4700 field emission scanning electron microscope to characterize the pattern of α-ZrP, test result is seen Fig. 2, Fig. 3 and shown in Figure 4, and α-ZrP is regular hexagon, the size homogeneous, and its particle diameter is adjustable in the scope of 0.4-2.8 μ m.
Effect of the present invention and advantage are: adopt the inventive method can obtain degree of crystallinity height and the controlled α-ZrP of size distribution homogeneous, and technology is simple, easy to operate.
Description of drawings
The serve as reasons XRD spectra of α-ZrP that the embodiment 1 that adopts the inventive method prepares of Fig. 1.X-coordinate is angle 2 θ, and unit is ° (degree), and ordinate zou is a diffracted intensity, and unit is a.u. (absolute units).
Fig. 2 is the field emission scanning electron microscope photo of α-ZrP of being prepared by embodiment 1.
Fig. 3 is the field emission scanning electron microscope photo of α-ZrP of being prepared by embodiment 2.
Fig. 4 is the field emission scanning electron microscope photo of α-ZrP of being prepared by embodiment 3.
Embodiment:
Embodiment 1:
With 1.707g ZrOCl
28H
2O, 10mL concentrated hydrochloric acid (36-38wt%) join wiring solution-forming I in the 15mL water; 81.5mL strong phosphoric acid (85wt%), 10mL concentrated hydrochloric acid (36-38wt%) are joined wiring solution-forming II in the 5mL water.It is short mix reaction in 5000 rev/mins the colloidal mill that solution I and solution II are at room temperature joined rotating speed simultaneously, and reaction back suspension liquid hightails colloidal mill.
Get the 80mL suspension liquid in the 100mL polytetrafluoroethylcontainer container, polytetrafluoroethylcontainer container is sealed in the hydrothermal reaction kettle, 240 ℃ of hydrothermal treatment consists 192 hours, hydrothermal reaction kettle is naturally cooled to room temperature, open the still suction filtration, with deionized water wash filter cake to filtrate pH value is 6, and filter cake is dry in 50 ℃ of air atmospheres, obtains product of the present invention.
Adopt day island proper Tianjin XRD-6000 type x-ray powder diffraction instrument to characterize product structure, its XRD test result as shown in Figure 1, be 11.6 °, 19.8 °, 24.9 ° at angle 2 θ and located the three strongest ones peak, (002), (110) and (112) crystal face of the corresponding α-ZrP of difference, peak shape is sharp-pointed, shows that product is single α-ZrP of crystalline phase and degree of crystallinity height.Adopt FDAC S-4700 field emission scanning electron microscope to characterize the pattern of α-ZrP, test result is seen Fig. 2, can find out the hexagon of α-ZrP for rule, the size homogeneous, and particle size distribution range is narrow, and the median size size is 2.8 μ m.
Embodiment 2:
With 13.650g ZrOCl
28H
2O, 4.95mL concentrated hydrochloric acid (36-38wt%) join wiring solution-forming I in the 30mL water; 68.55mL strong phosphoric acid (85wt%), 4.95mL concentrated hydrochloric acid (36-38wt%) are joined wiring solution-forming II in the 12mL water.It is short mix reaction in 3000 rev/mins the colloidal mill that solution I and solution II are at room temperature joined rotating speed simultaneously, and reaction back suspension liquid hightails colloidal mill.
Get the 60mL suspension liquid in the 100mL polytetrafluoroethylcontainer container, polytetrafluoroethylcontainer container is sealed in the hydrothermal reaction kettle, 240 ℃ of hydrothermal treatment consists 48 hours, hydrothermal reaction kettle is naturally cooled to room temperature, open the still suction filtration, with deionized water wash filter cake to filtrate pH value is 7, and filter cake is dry in 60 ℃ of air atmospheres, obtains product of the present invention.
XRD test shows product is the single high-crystallinity α-ZrP of crystalline phase, the field emission scanning electron microscope test result as shown in Figure 3, the size homogeneous, the median size size is 2.0 μ m.
Embodiment 3:
With 13.650g ZrOCl
28H
2O, 2.5mL concentrated hydrochloric acid (36-38wt%) join wiring solution-forming I in the 55mL water; 17.2mL strong phosphoric acid (85wt%), 2.5mL concentrated hydrochloric acid (36-38t%) are joined wiring solution-forming II in the 45mL water.It is short mix reaction in 5000 rev/mins the colloidal mill that solution I and solution II are at room temperature joined rotating speed simultaneously, and reaction back suspension liquid hightails colloidal mill.
Get the 40mL suspension liquid in the 100mL polytetrafluoroethylcontainer container, polytetrafluoroethylcontainer container is sealed in the hydrothermal reaction kettle, 180 ℃ of hydrothermal treatment consists 144 hours, hydrothermal reaction kettle is naturally cooled to room temperature, open the still suction filtration, with deionized water wash filter cake to filtrate pH value is 6, and filter cake is dry in 55 ℃ of air atmospheres, obtains product of the present invention.
XRD test shows product is the single high-crystallinity α-ZrP of crystalline phase, the field emission scanning electron microscope test result as shown in Figure 4, the size homogeneous, the median size size is 0.4 μ m.
Embodiment 4:
With 6.828g ZrOCl
28H
2O, 10mL concentrated hydrochloric acid (36-38wt%) join wiring solution-forming I in the 45mL water; 17.2mL strong phosphoric acid (85wt%), 10mL concentrated hydrochloric acid (36-38wt%) are joined wiring solution-forming II in the 35mL water.It is short mix reaction in 4000 rev/mins the colloidal mill that solution I and solution II are at room temperature joined rotating speed simultaneously, and reaction back suspension liquid hightails colloidal mill.
Get the 40mL suspension liquid in the 100mL polytetrafluoroethylcontainer container, polytetrafluoroethylcontainer container is sealed in the hydrothermal reaction kettle, 240 ℃ of hydrothermal treatment consists 96 hours, hydrothermal reaction kettle is naturally cooled to room temperature, open the still suction filtration, with deionized water wash filter cake to filtrate pH value is 6.5, and filter cake is dry in 50 ℃ of air atmospheres, obtains product of the present invention.
XRD and field emission scanning electron microscope test shows product are the stratiform α-ZrP of the higher and size homogeneous of degree of crystallinity, and the median size size is 1.0 μ m.
Embodiment 5:
With 6.828g ZrOCl
28H
2O, 20mL concentrated hydrochloric acid (36-38wt%) join wiring solution-forming I in the 33mL water; 34.3mL strong phosphoric acid (85wt%), 20mL concentrated hydrochloric acid (36-38wt%) are joined wiring solution-forming II in the 10mL water.It is short mix reaction in 4500 rev/mins the colloidal mill that solution I and solution II are at room temperature joined rotating speed simultaneously, and reaction back suspension liquid hightails colloidal mill.
Get the 70mL suspension liquid in the 100mL polytetrafluoroethylcontainer container, polytetrafluoroethylcontainer container is sealed in the hydrothermal reaction kettle, 210 ℃ of hydrothermal treatment consists 48 hours, hydrothermal reaction kettle is naturally cooled to room temperature, open the still suction filtration, with deionized water wash filter cake to filtrate pH value is 7, and filter cake is dry in 55 ℃ of air atmospheres, obtains product of the present invention.
XRD and field emission scanning electron microscope test shows product are the stratiform α-ZrP of the higher and size homogeneous of degree of crystallinity, and the median size size is 0.6 μ m.
Claims (2)
1, the preparation method of a kind of high-crystallinity and uniform particle diameter laminar alpha zirconium phosphate is characterized in that, processing step is:
(1) with ZrOCl
28H
2O, concentrated hydrochloric acid 36-38wt% join wiring solution-forming I in the deionized water; Strong phosphoric acid 85wt%, concentrated hydrochloric acid 36-38wt% are joined wiring solution-forming II in the deionized water; Solution I and solution II are joined under 15-30 ℃ room temperature in the colloidal mill that rotating speed is the 3000-5000 revolutions per minute simultaneously, and reaction back suspension liquid breaks away from colloidal mill;
(2) step (1) gained suspension liquid is transferred in the polytetrafluoroethylcontainer container, filling degree is 40-80%, polytetrafluoroethylcontainer container is sealed in the hydrothermal reaction kettle, at 180-240 ℃ of hydrothermal treatment consists 48-192 hour, water heating kettle is naturally cooled to room temperature, opening the still suction filtration, is 6-7 with deionized water wash filter cake to filtrate pH value, and filter cake is obtained alpha zirconium phosphate after the drying in 50-60 ℃ of air atmosphere.
, the preparation method of alpha zirconium phosphate as claimed in claim 1, it is characterized in that according to two kinds of mixed cumulative volumes of solution are calculated, each reacting material concentration is respectively: ZrOCl
28H
2O concentration is 0.044-0.36mol/L, and phosphoric acid concentration is 2.0-10mol/L, and concentration of hydrochloric acid is 0.50-4.0mol/L.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200710099379 CN101049963A (en) | 2007-05-18 | 2007-05-18 | Method for preparing laminar alpha zirconium phosphate with high crystallinity and even particle diameter |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200710099379 CN101049963A (en) | 2007-05-18 | 2007-05-18 | Method for preparing laminar alpha zirconium phosphate with high crystallinity and even particle diameter |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN101049963A true CN101049963A (en) | 2007-10-10 |
Family
ID=38781601
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 200710099379 Pending CN101049963A (en) | 2007-05-18 | 2007-05-18 | Method for preparing laminar alpha zirconium phosphate with high crystallinity and even particle diameter |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN101049963A (en) |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104627979A (en) * | 2015-01-26 | 2015-05-20 | 合肥学院 | Carbon nanotube/alpha-zirconium phosphate composite powder and preparation method thereof |
| CN106348270A (en) * | 2016-08-23 | 2017-01-25 | 广东工业大学 | Preparation method for reducing polydispersity of discotic colloids |
| CN106517126A (en) * | 2016-10-31 | 2017-03-22 | 广东工业大学 | Control method for liquid crystal phase transition of disk-shaped colloid |
| CN106995209A (en) * | 2016-01-25 | 2017-08-01 | 中国科学院大连化学物理研究所 | A kind of Ψ-type Zirconium phosphate crystal nanometer sheet and its preparation and application |
| CN108485058A (en) * | 2018-03-02 | 2018-09-04 | 华南理工大学 | A kind of preparation method for the easy-stripping type laminar nano basic zirconium phosphate that size is controllable |
| CN110015889A (en) * | 2019-04-24 | 2019-07-16 | 宁波泰科先进陶瓷有限公司 | A kind of ZTA ceramic material preparation method and its material of preparation |
| CN113198326A (en) * | 2021-03-22 | 2021-08-03 | 山东格兰克环保新材料有限公司 | Composite ultrafiltration membrane material and preparation method thereof |
-
2007
- 2007-05-18 CN CN 200710099379 patent/CN101049963A/en active Pending
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104627979A (en) * | 2015-01-26 | 2015-05-20 | 合肥学院 | Carbon nanotube/alpha-zirconium phosphate composite powder and preparation method thereof |
| CN106995209A (en) * | 2016-01-25 | 2017-08-01 | 中国科学院大连化学物理研究所 | A kind of Ψ-type Zirconium phosphate crystal nanometer sheet and its preparation and application |
| CN106348270A (en) * | 2016-08-23 | 2017-01-25 | 广东工业大学 | Preparation method for reducing polydispersity of discotic colloids |
| CN106517126A (en) * | 2016-10-31 | 2017-03-22 | 广东工业大学 | Control method for liquid crystal phase transition of disk-shaped colloid |
| CN106517126B (en) * | 2016-10-31 | 2019-02-22 | 广东工业大学 | A kind of control method of disk like colloid liquid crystal phase transition |
| CN108485058A (en) * | 2018-03-02 | 2018-09-04 | 华南理工大学 | A kind of preparation method for the easy-stripping type laminar nano basic zirconium phosphate that size is controllable |
| CN110015889A (en) * | 2019-04-24 | 2019-07-16 | 宁波泰科先进陶瓷有限公司 | A kind of ZTA ceramic material preparation method and its material of preparation |
| CN110015889B (en) * | 2019-04-24 | 2021-11-02 | 宁波泰科先进陶瓷有限公司 | Preparation method of ZTA ceramic material and material prepared by same |
| CN113198326A (en) * | 2021-03-22 | 2021-08-03 | 山东格兰克环保新材料有限公司 | Composite ultrafiltration membrane material and preparation method thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101049963A (en) | Method for preparing laminar alpha zirconium phosphate with high crystallinity and even particle diameter | |
| Liu et al. | Hydrothermal synthesis of microscale boehmite and gamma nanoleaves alumina | |
| Chemseddine et al. | Nanostructuring titania: control over nanocrystal structure, size, shape, and organization | |
| Song et al. | Synthesis and characterization of magnesium hydroxide by batch reaction crystallization | |
| US10005077B2 (en) | Zeolite nanosheet membrane | |
| Shahini et al. | Gel–sol synthesis and aging effect on highly crystalline anatase nanopowder | |
| CN103172081B (en) | High-molecular organic polymer template synthesized compound pore structure molecular sieve and preparation method thereof | |
| Chen et al. | Comparison of the evolution and growth processes of films of M/Al-layered double hydroxides with M= Ni or Zn | |
| Huang et al. | Direct synthesis of mesoporous TiO2 modified with phosphotungstic acid under template-free condition | |
| CN101033062A (en) | Method of preparing layered alpha-titanium phosphate | |
| Chen et al. | Surfactant-additive-free synthesis of 3D anatase TiO 2 hierarchical architectures with enhanced photocatalytic activity | |
| CN102897734A (en) | Calcium phosphate nano-structures and preparation method thereof | |
| CN102942193B (en) | Method for synthesizing novel thin layer ZSM-5 zeolite with boron-containing framework | |
| Neale et al. | Size and shape control of nanocrystallites in mesoporous TiO 2 films | |
| CN105668589A (en) | Method for preparing SAPO-11 molecular sieve with high crystallinity | |
| Feng et al. | Preparation of novel porous hydroxyapatite sheets with high Pb2+ adsorption properties by self-assembly non-aqueous precipitation method | |
| Che et al. | Ordered mesoporous tin oxide with crystalline pore walls: Preparation and thermal stability | |
| CN103086398B (en) | Method for synthesizing porous NaY molecular sieve microspheres | |
| CN101058416A (en) | Method of preparing ordered nano hydroxyl apatite polycrystal powder | |
| CN102634842B (en) | Method for preparing {001} and {100} surface-exposed anatase TiO2 nano single crystals | |
| CN1915824A (en) | Method for preparing Nano alpht-A12O3 through catalyzing calcinations in low tempeature | |
| Sun et al. | Single crystal forms induced diverse interface structures in TiO 2 (B)/anatase dual-phase nanocomposites | |
| CN1214978C (en) | Ordered mesoporous molecnlar sieve material with wltrahigh hydrothermal stability and synthesis method thereof | |
| CN103962171A (en) | Aluminum silicon molecular sieve-aluminum oxide composite material and in-situ growth preparation method thereof | |
| Supothina et al. | Effect of stirring and temperature on synthesis yield and crystallization of hydrothermally synthesized K2W4O13 nanorods |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C02 | Deemed withdrawal of patent application after publication (patent law 2001) | ||
| WD01 | Invention patent application deemed withdrawn after publication |