CN104556178A - Preparation method for polycrystal gamma-aluminum oxide - Google Patents
Preparation method for polycrystal gamma-aluminum oxide Download PDFInfo
- Publication number
- CN104556178A CN104556178A CN201310495666.4A CN201310495666A CN104556178A CN 104556178 A CN104556178 A CN 104556178A CN 201310495666 A CN201310495666 A CN 201310495666A CN 104556178 A CN104556178 A CN 104556178A
- Authority
- CN
- China
- Prior art keywords
- alumina
- gama
- gamma
- accordance
- particle
- 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
Landscapes
- Catalysts (AREA)
Abstract
The invention discloses a preparation method for a polycrystal gamma-aluminum oxide. The preparation method comprises the following steps: immersing gamma-aluminum oxide into ammonia water to perform closed hydro-thermal treatment; performing solid-liquid separation, drying and roasting to obtain the polycrystal gamma-aluminum oxide. The polycrystal gamma-aluminum oxide particles prepared by the method disclosed by the invention have the shapes of polyhedrons; the method is simple and feasible, low in cost and high in operability; the polycrystal gamma-aluminum oxide can serve as a raw material for forming an aluminum oxide carrier; through proper treatment, the distribution concentricity of the dimensions of the pores formed by secondary particles in a carrier material can be remarkably improved; the catalytic performance of the catalyst is improved.
Description
Technical field
The present invention relates to a kind of preparation method of polycrystalline gama-alumina, belong to field of inorganic material preparing technology.
Background technology
Gama-alumina, as a kind of solid support material widely used in field of hydrogenation, has the catalytic activity that high pore volume, high-specific surface area etc. are higher usually.Research finds: active gama-alumina powder is normally made up of the once oxidation aluminum nanocrystalline grain being not more than 100nm on microcosmic, these little crystal grain due to the reason of interfacial energy reunite formed together size micron order and above irregular, without the second particle of solid shape, and form polycrystalline gamma phase.Pore properties is the important controling parameters of of active gama-alumina.The hole of activated alumina is divided three classes by [Industrial Catalysis, the 6th phase, 14-18 page in 2000]: the intercrystalline hole of the primary particle of coalescing particle; Micropartical intercrystalline hole (offspring); And alumina product shaping time formed defective hole.Wherein, the intercrystalline hole of primary particle belongs to the less micropore of size, mesoporous, for hydrogenation catalyst especially heavy resid hydrogenation, belong to inactive pore; The micropartical intercrystalline hole that offspring is formed belongs to relatively large hole, is important material mass transfer and the reaction duct of the catalyzer taking aluminum oxide as carrier.Originated as can be seen from the duct of above-mentioned activated alumina, the irregular and ununiformity of aluminum oxide secondary particle can cause the ununiformity of pore dimension between second particle, i.e. the dispersivity of pore distribution.This will produce adverse influence to the performance of monolith catalytic performance.
The aluminum hydroxide gel that CN200910011627.6, CN200910206229.X and CN200910011626.1 adopt fused salt titania nanoparticle legal system standby is raw material, after shaping and roasting, obtain comparatively regular rod-like nano aluminum oxide secondary particle, this bar-shaped nanoparticle is piled up and is formed skeleton construction, there is aperture large, porosity is high, and outer surface orifice is comparatively large, the advantages such as duct penetrability is good.
Above patent can produce larger impact to the pore structure of material by the adjustment of aluminum oxide secondary particle form.But the process of this fused salt titania nanoparticle method regulation and control second particle pattern and size is comparatively loaded down with trivial details, is unconventional preparation method.
Summary of the invention
For the deficiencies in the prior art, the invention provides a kind of preparation method of polycrystalline gama-alumina.Polycrystalline gamma-alumina particle prepared by the inventive method has polyhedron pattern, and method is simple, with low cost, has stronger operability.
Polycrystalline gamma-alumina preparation method of the present invention, comprises following content: immersed by gama-alumina in ammoniacal liquor and carry out airtight hydrothermal treatment consists, then solid-liquid separation, and dry, roasting, obtains polycrystalline gama-alumina.
In the inventive method, described gama-alumina can be commercially available prod, also can prepare by art methods, and wherein the grain-size of gama-alumina is not more than 100nm, is preferably 3-50nm.
The invention provides a kind of preparation method of gama-alumina, comprise following content: by pseudo-boehmite under 450-750 DEG C of condition, roasting 1-12 hour, preferred 500-650 DEG C of roasting 3-6 hour, obtains gama-alumina.
Wherein said pseudo-boehmite also can be the element modified pseudo-boehmite of at least one in silicon, boron, phosphorus, titanium or zirconium etc.
In the inventive method, described ammonia concn is 5-15mol/L, with molar amount, and ammoniacal liquor/Al
3+ratio is 0.5-20, is preferably 1-5.
In the inventive method, the consumption of described ammoniacal liquor at least can the complete submergence by handled material.
In the inventive method, described airtight hydrothermal condition is: hydrothermal treatment consists 2-24 hour at 90-150 DEG C, hydrothermal treatment consists 3-8 hour at being preferably 90-130 DEG C.
In the inventive method, described drying conditions is: in the inventive method, and the drying temperature described in step (2) is not more than 200 DEG C, dry 12-24 hour at being preferably 80-120 DEG C.
In the inventive method, described roasting condition is: 400-750 DEG C of roasting 1-12 hour, preferred 500-650 DEG C roasting 3-8 hour.
Polycrystalline gamma-alumina particle prepared by the inventive method, particle size is 1000-5000nm, and the gama-alumina nanocrystal that particle is less than 100nm by size forms.
Polycrystalline gamma of the present invention-alumina powder jointed, has mesoporous, the large pore distribution of comparatively concentrating in 10-100nm scope.
Compared with existing irregular gama-alumina second particle, gama-alumina second particle of the present invention has the polyhedron-shaped of approximate rule.Meanwhile, the gama-alumina second particle obtained by gama-alumina once little crystal grain form, be formed as polycrystalline gama-alumina, therefore can keep the activity of the irregular alumina particle of conventional polysilicon.Polyhedral aluminum oxide of the present invention unity on pattern and size is relatively high, can as the raw material of shaped alumina alumina supporter, through suitably process, the centrality of the pore size distribution formed by offspring in solid support material can be significantly improved, thus improve the catalytic performance of catalyzer.
Accompanying drawing explanation
Fig. 1 is the stereoscan photograph of polyhedral gama-alumina prepared by embodiment 1.
Fig. 2 is the transmission electron microscope photo of polyhedral gama-alumina prepared by embodiment 1.
Fig. 3 is the XRD spectra of polyhedral gama-alumina prepared by embodiment 1.
Fig. 4 is the pore size distribution$ figure of polyhedral gama-alumina prepared by embodiment 1.
Embodiment
Below by embodiment to the inventive method detailed description in addition.Polyhedral gama-alumina particle size is measured according to scanning electron microscope image, and measure 20 particles at random, each particle measures the maximal margin that can observe, and gets the diameter of its mean value as particle.The little crystal grain of composition Polyhedral Particles, by transmission electron microscope observing, observes its size range.Crystal formation adopts X-ray diffraction to characterize.Pore distribution adopts low temperature nitrogen physisorphtion to measure.
Embodiment 1
5 grams, commercially available pseudo-boehmite powder, roasting 6 hours at 500 DEG C, cool to room temperature, then to be immersed in the ammoniacal liquor of the excessive 0.5M that it floods completely to major general (with molar amount, ammoniacal liquor/Al
3+ratio is 1.0), then airtight and be warmed up to 130 DEG C of hydrothermal treatment consists 3 hours.Then at 120 DEG C dry 12 hours, product roasting 3 hours at 650 DEG C.Scanning electron microscopic observation is known, and product morphology is the particle of polyhedral.Particle mean size is 2389nm.After sample grinding also ultrasonic disperse, known with transmission electron microscope observing, Polyhedral Particles is made up of the little crystal grain of 3-50nm.Because simply grinding and supersound process can not destroy single crystal particle, therefore Polyhedral Particles is not large single crystal crystal grain.The XRD result of product shows, it is gama-alumina.Therefore, polyhedral particle is polycrystalline gama-alumina.Physical adsorption test shows, it has the narrower pore distribution of 30-60nm.
Embodiment 2
By commercially available 5 grams, modified zirconia pseudo-boehmite powder, roasting 5 hours at 600 DEG C, cool to room temperature, then to be immersed in the ammoniacal liquor of the excessive 10M that it floods completely to major general (with molar amount, ammoniacal liquor/Al
3+ratio is 2.0), then airtight and be warmed up to 120 DEG C of hydrothermal treatment consists 8 hours.Then at 120 DEG C dry 12 hours, by product roasting 8 hours at 500 DEG C.Scanning electron microscopic observation product is known, and its pattern is the particle of polyhedral.Particle mean size is 1278nm.After sample grinding also ultrasonic disperse, known with transmission electron microscope observing, Polyhedral Particles is made up of the little crystal grain of 3-50nm.Because simply grinding and supersound process can not destroy single crystal particle, therefore Polyhedral Particles is not large single crystal crystal grain.The XRD result of product shows, it is gama-alumina.Therefore, polyhedral particle is polycrystalline gama-alumina.Physical adsorption test shows, it has the narrower pore distribution of 20-30nm.
Embodiment 3
By 5 grams, commercially available pseudo-boehmite powder, roasting 5 hours at 550 DEG C, cool to room temperature, then to be immersed in the ammoniacal liquor of the excessive 5M that it floods completely to major general (with molar amount, ammoniacal liquor/Al
3+ratio is 5), then airtight and be warmed up to 90 DEG C of hydrothermal treatment consists 3 hours.Then by the roasting 5 hours at 550 DEG C of the product after at 100 DEG C dry 24 hours.Scanning electron microscopic observation product is known, and its pattern is the particle of polyhedral.Particle mean size is 4842nm.After sample grinding also ultrasonic disperse, known with transmission electron microscope observing, Polyhedral Particles is made up of the little crystal grain of 3-50nm.Because simply grinding and supersound process can not destroy single crystal particle, therefore Polyhedral Particles is not large single crystal crystal grain.The XRD result of product shows, it is gama-alumina.Therefore, polyhedral particle is polycrystalline gama-alumina.Physical adsorption test shows, it has the narrower pore distribution of 54-73nm.
Embodiment 4
By 5 grams, commercially available pseudo-boehmite powder, roasting 5 hours at 650 DEG C, cool to room temperature, then to be immersed in the ammoniacal liquor of the excessive 15M that it floods completely to major general (with molar amount, ammoniacal liquor/Al
3+ratio is 3), then airtight and be warmed up to 130 DEG C of hydrothermal treatment consists 3 hours.Then by the roasting 5 hours at 550 DEG C of the product after at 80 DEG C dry 24 hours.Scanning electron microscopic observation is known, and product morphology is the particle of polyhedral.Particle mean size is 1634nm.After sample grinding also ultrasonic disperse, known with transmission electron microscope observing, Polyhedral Particles is made up of the little crystal grain of 3-50nm.Because simply grinding and supersound process can not destroy single crystal particle, therefore Polyhedral Particles is not large single crystal crystal grain.The XRD result of product shows, it is gama-alumina.Therefore, polyhedral particle is polycrystalline gama-alumina.Physical adsorption test shows, it has the narrower pore distribution of 14-27nm.
Claims (10)
1. a preparation method for polycrystalline gama-alumina, is characterized in that comprising following content: immersed by gama-alumina in ammoniacal liquor and carry out airtight hydrothermal treatment consists, then solid-liquid separation, and dry, roasting, obtains polycrystalline gama-alumina.
2. in accordance with the method for claim 1, it is characterized in that: described gama-alumina is commercially available prod or prepares by art methods, and wherein the grain-size of gama-alumina is not more than 100nm.
3. according to the method described in claim 1 or 2, it is characterized in that: the preparation method of gama-alumina comprises following content: by pseudo-boehmite under 450-750 DEG C of condition, and roasting 1-12 hour, obtains gama-alumina.
4. in accordance with the method for claim 3, it is characterized in that: described pseudo-boehmite is one or more the element modified pseudo-boehmites in silicon, boron, phosphorus, titanium or zirconium.
5. in accordance with the method for claim 1, it is characterized in that: described ammonia concn is 5-15mol/L, with molar amount, ammoniacal liquor/Al
3+ratio is 0.5-20, is preferably 1-5.
6. in accordance with the method for claim 1, it is characterized in that: the consumption of ammoniacal liquor at least can the complete submergence by handled material.
7. in accordance with the method for claim 1, it is characterized in that: described airtight hydrothermal condition is: hydrothermal treatment consists 2-24 hour at 90-150 DEG C.
8. in accordance with the method for claim 1, it is characterized in that: described drying temperature is dry 12-24 hour at 80-120 DEG C.
9. in accordance with the method for claim 1, it is characterized in that: described roasting condition is: 400-750 DEG C of roasting 1-12 hour.
10. polycrystalline gamma-alumina particle of preparing of method according to claim 1, it is characterized in that: particle size is 1000-5000nm, particle is made up of the gama-alumina nanocrystal being less than 100nm, and the mean pore size of polycrystalline gamma-alumina powder jointed is between 10-100nm.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310495666.4A CN104556178B (en) | 2013-10-22 | 2013-10-22 | A kind of preparation method of polycrystalline gama-alumina |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310495666.4A CN104556178B (en) | 2013-10-22 | 2013-10-22 | A kind of preparation method of polycrystalline gama-alumina |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN104556178A true CN104556178A (en) | 2015-04-29 |
| CN104556178B CN104556178B (en) | 2016-03-30 |
Family
ID=53073383
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201310495666.4A Active CN104556178B (en) | 2013-10-22 | 2013-10-22 | A kind of preparation method of polycrystalline gama-alumina |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN104556178B (en) |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105858783A (en) * | 2016-04-18 | 2016-08-17 | 北京化工大学 | Application of nanometer flaky aluminum oxide to removal of fluorine ions from water |
| CN105905974A (en) * | 2016-06-27 | 2016-08-31 | 北京化工大学 | Application of phosphorus-modified nano flaky aluminium oxide in removal of cadmium ions in water |
| CN106334570A (en) * | 2015-07-09 | 2017-01-18 | 中国石油化工股份有限公司 | N-alkane isomerization catalyst and preparation method thereof |
| CN106334581A (en) * | 2015-07-09 | 2017-01-18 | 中国石油化工股份有限公司 | N-alkane isomerization catalyst and preparation method thereof |
| CN112707426A (en) * | 2019-10-25 | 2021-04-27 | 中国石油化工股份有限公司 | Gamma-alumina crystal grain and preparation method thereof |
| CN112707423A (en) * | 2019-10-25 | 2021-04-27 | 中国石油化工股份有限公司 | Preparation method of self-assembled octahedral particles of polycrystalline alumina |
| CN112978776A (en) * | 2019-12-02 | 2021-06-18 | 中国石油化工股份有限公司 | Gamma-alumina octahedral particle and preparation method thereof |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE3730947A1 (en) * | 1987-07-17 | 1989-01-26 | Espanola Alumina Sa | Process for producing a special aluminium oxide from the fine powder formed during the calcination of metallurgical aluminium oxide |
| CN101323977A (en) * | 2008-07-10 | 2008-12-17 | 上海交通大学 | Preparation of big length to diameter ratio aluminum oxide nanowire |
| CN102259901A (en) * | 2011-05-23 | 2011-11-30 | 华东理工大学 | Hierarchical aluminium oxide and catalysis application thereof |
| CN102311132A (en) * | 2010-07-07 | 2012-01-11 | 中国石油化工股份有限公司 | Rod-like one-dimensional polycrystalline gamma-Al2O3 nanocrystal grains and preparation method thereof |
| CN102311134A (en) * | 2010-07-07 | 2012-01-11 | 中国石油化工股份有限公司 | Spherical integral macroporous alumina and preparation method thereof |
-
2013
- 2013-10-22 CN CN201310495666.4A patent/CN104556178B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE3730947A1 (en) * | 1987-07-17 | 1989-01-26 | Espanola Alumina Sa | Process for producing a special aluminium oxide from the fine powder formed during the calcination of metallurgical aluminium oxide |
| CN101323977A (en) * | 2008-07-10 | 2008-12-17 | 上海交通大学 | Preparation of big length to diameter ratio aluminum oxide nanowire |
| CN102311132A (en) * | 2010-07-07 | 2012-01-11 | 中国石油化工股份有限公司 | Rod-like one-dimensional polycrystalline gamma-Al2O3 nanocrystal grains and preparation method thereof |
| CN102311134A (en) * | 2010-07-07 | 2012-01-11 | 中国石油化工股份有限公司 | Spherical integral macroporous alumina and preparation method thereof |
| CN102259901A (en) * | 2011-05-23 | 2011-11-30 | 华东理工大学 | Hierarchical aluminium oxide and catalysis application thereof |
Non-Patent Citations (1)
| Title |
|---|
| 刘辉等: ""微波水热合成γ-ＡlOOH和γ-Ａl２O３片状自组装微球"", 《功能材料》 * |
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106334570A (en) * | 2015-07-09 | 2017-01-18 | 中国石油化工股份有限公司 | N-alkane isomerization catalyst and preparation method thereof |
| CN106334581A (en) * | 2015-07-09 | 2017-01-18 | 中国石油化工股份有限公司 | N-alkane isomerization catalyst and preparation method thereof |
| CN106334570B (en) * | 2015-07-09 | 2019-03-22 | 中国石油化工股份有限公司 | A kind of catalyst for normal paraffin isomerization and preparation method thereof |
| CN105858783A (en) * | 2016-04-18 | 2016-08-17 | 北京化工大学 | Application of nanometer flaky aluminum oxide to removal of fluorine ions from water |
| CN105905974A (en) * | 2016-06-27 | 2016-08-31 | 北京化工大学 | Application of phosphorus-modified nano flaky aluminium oxide in removal of cadmium ions in water |
| CN112707426A (en) * | 2019-10-25 | 2021-04-27 | 中国石油化工股份有限公司 | Gamma-alumina crystal grain and preparation method thereof |
| CN112707423A (en) * | 2019-10-25 | 2021-04-27 | 中国石油化工股份有限公司 | Preparation method of self-assembled octahedral particles of polycrystalline alumina |
| CN112707426B (en) * | 2019-10-25 | 2022-10-11 | 中国石油化工股份有限公司 | Gamma-alumina crystal grain and preparation method thereof |
| CN112978776A (en) * | 2019-12-02 | 2021-06-18 | 中国石油化工股份有限公司 | Gamma-alumina octahedral particle and preparation method thereof |
| CN112978776B (en) * | 2019-12-02 | 2023-01-10 | 中国石油化工股份有限公司 | Gamma-alumina octahedral particle and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN104556178B (en) | 2016-03-30 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN104556178B (en) | A kind of preparation method of polycrystalline gama-alumina | |
| Poolakkandy et al. | Soft-template-assisted synthesis: a promising approach for the fabrication of transition metal oxides | |
| CN104556163B (en) | Prism-shaped polycrystalline gama-alumina and preparation method thereof | |
| Wang et al. | Mesoporous titania nanotubes: Their preparation and application as electrode materials for rechargeable lithium batteries | |
| Zhu et al. | Shape-controlled synthesis of porous Co 3 O 4 nanostructures for application in supercapacitors | |
| Chen et al. | Templated synthesis of hierarchically porous manganese oxide with a crystalline nanorod framework and its high electrochemical performance | |
| Du et al. | Dendrimer-like hybrid particles with tunable hierarchical pores | |
| CN101565210B (en) | Method for preparing cobaltosic oxide powders with high tapping density by combining nanostructure | |
| WO2008048716A2 (en) | Nanostructured metal oxides comprising internal voids and methods of use thereof | |
| CN103936027B (en) | Controlled SAPO-34 zeolitic material of colored shape of nanometer sheet assembling and preparation method thereof | |
| Ma et al. | Controllable synthesis and characterization of porous FeVO 4 nanorods and nanoparticles | |
| CN102583476A (en) | Method for preparing mesoporous gamma-Al2O3 by dynamic hydrothermal method | |
| CN104556162B (en) | Sheet polycrystalline gama-alumina and preparation method thereof | |
| Yu et al. | Hydrothermal synthesis and photocatalytic activity of mesoporous titania hollow microspheres | |
| Liu et al. | Gelatin-assisted sol–gel derived TiO2 microspheres for hydrogen storage | |
| CN107601581A (en) | A kind of double pore dimension structure nano crystalline substance cobalt acetate powders and preparation method thereof | |
| CN104437458A (en) | Cerium-zirconium-based composite oxide catalytic material and preparation method thereof | |
| Liu et al. | Directed growth of TiO2 nanorods into microspheres | |
| Nair et al. | Influence of Peptization and Ethanol Washing on the Pore‐Structure Evolution of Sol‐Gel‐Derived Alumina Catalyst Supports | |
| Xin et al. | A universal route to fabricate hierarchically ordered macro/mesoporous oxides with enhanced intrinsic activity | |
| Eggen et al. | Surface roughness and chemical properties of porous inorganic films | |
| Liang et al. | P123 assisted synthesis and characterization of urchin-like γ-Al 2 O 3 hollow microspheres | |
| CN104001489A (en) | High-photocatalytic-activity flower-shaped porous titanium dioxide nano material and preparation method thereof | |
| CN106745039A (en) | A kind of size adjustable simultaneously has nanometer Ti-Si zeolite molecular sieve of ultra-high yield and preparation method thereof | |
| CN102730739A (en) | Synthetic method of porous cerium dioxide nano rod capable of adjusting pore diameter |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |