CN104229843A - Method for preparing three-dimensional ordered macroporous aluminum oxide by utilizing dual templates - Google Patents
Method for preparing three-dimensional ordered macroporous aluminum oxide by utilizing dual templates Download PDFInfo
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- CN104229843A CN104229843A CN201310240778.5A CN201310240778A CN104229843A CN 104229843 A CN104229843 A CN 104229843A CN 201310240778 A CN201310240778 A CN 201310240778A CN 104229843 A CN104229843 A CN 104229843A
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Abstract
The invention discloses a method for preparing three-dimensional ordered macroporous aluminum oxide by utilizing dual templates. The method comprises the following steps: firstly, preparing polymethyl methacrylate (PMMA) microspheres with a uniform grain size, and assembling the PMMA microspheres into a PMMA hard template by virtue of a centrifugal method; then, soaking the PMMA hard template into an alcohol solution containing aluminum nitrate nonahydrate and a surfactant F127; and finally, carrying out suction filtration, drying and roasting to obtain the three-dimensional ordered macroporous (3DOM) aluminum oxide. According to the method disclosed by the invention, the advantages of soft and hard templates are delicately combined to synthesize three-dimensional ordered Al2O3 with a mesoporous-macroporous gradient hole structure by one step, and thus, the method is especially suitable for preparing novel hydrogenation catalysts for treating heavy oil and residual oil.
Description
Technical field
The present invention relates to a kind of preparation method of aluminum oxide, particularly a kind of double-template legal system that utilizes is for the preparation method of three-dimensional ordered macroporous alumina.
Background technology
The preparation of current industrial aluminum oxide realizes mainly through precipitation, dry and roasting oxidation aluminium presoma, adopts the alumina ratio surface-area that obtains in this way and pore volume is mostly less than 250m
2/ g and 0.5cm
3/ g, pore size distribution wider and be difficult to regulation and control, greatly limit aluminum oxide as the application of support of the catalyst in petrochemical industry.After M41S series mesopore molecular sieve is successfully synthesized, extensively carry out the study on the synthesis of meso-porous alumina in the world.Generally speaking, major part research adopts template synthesis method, specifically, can be divided into following a few class: anion surfactant, cats product, nonionogenic tenside, organic molecule and ionic liquid etc.The meso-porous alumina of these methods synthesis shows larger specific surface area and to a certain degree controlled pore size distribution, but owing to the reason such as easily to undergo phase transition in the more difficult control of speed of reaction and reaction process, its pore passage structure is nearly all unordered vermiform, spongy or scaffolding shape, hole wall mostly is amorphous structure, its thermostability and hydrothermal stability poor, these shortcomings seriously limit aluminum oxide application industrially.The common trait of ordered porous materials has rule and uniform pore passage structure, comprising the dimension in the size and dimension of duct and window, duct, the trend in duct, the composition of hole wall and character, and the size dimension in duct is the feature finally wanted in vesicular structure.Especially There-dimensional ordered macroporous materials (3DOM), hole wall both can be made up of single dispersion metal, metal oxide, the crystal that can be made up of polycomponent again or sosoloid, Inorganic-organic hybrid, superpolymer form, there is good compatibility, be easy to construct the new function material that not only there is specific composition but also have cycle ordered big hole architecture.Compared with other materials, the pore passage structure of its uniqueness is conducive to material and enters inside, duct from all directions, reduce material diffusional resistance, the diffusion for material provides optimum flow rate and higher efficiency, has broad application prospects in the field such as fractionation by adsorption and support of the catalyst.
Summary of the invention
The object of the invention is to provide a kind of advantage in conjunction with soft or hard two kinds of templates, and disposable synthesis has mesopore-macropore graded pore structure Al
2o
3preparation method.
Concrete preparation process of the present invention is as follows:
(1) by method that emulsifier-free is polymerized, the add-on controlling monomers methyl methacrylate (MMA) is 2%-10%, and initiator potassium persulfate add-on is 0.05-0.4g, and stir speed (S.S.) is 350rpm, temperature of reaction is 70 DEG C, prepares the polymethylmethacrylate emulsion of uniform particle sizes.
(2) the polymethylmethacrylate emulsion will prepared in step 1), is assembled into PMMA hard template under the action of the centrifugal, and rotating speed is 1000-3000rpm.And at 40-80 DEG C freeze-day with constant temperature 6-8 hour.Said PMMA template is hard template.
(3) be made into the aluminum nitrate ethanolic soln of 0.5-2.0mol/L with nine water aluminum nitrates, soft template and 95% ethanol, concentration preferably controls at 0.8-1.0mol/L, and in mixed solution, soft template content is 5-10 × 10
-3mol/L, concentration preferably controls in 6-8 × 10
-3mol/L.Said soft template is F127.
(4) continuous whipping step 3) gained solution, obtain transparent mixed solution, stop adding step 2 after stirring) the PMMA hard template that obtains.Infiltrating time is 2-6 hour.
(5) mixture of step 4) gained is carried out suction filtration, solids freeze-day with constant temperature 6-8 hour at 40-80 DEG C of gained.Said temperature preferably controls at 40-60 DEG C.
(6) will by 5) material of gained is at 650-950 DEG C of roasting 3-6 hour, and sequence of control temperature rise rate is 1-5 DEG C/min, and removing hard template PMMA and soft template, obtain the three-dimensional ordered macroporous Al with mesopore-macropore graded pore structure
2o
3.Said maturing temperature preferably 750-850 DEG C, programmed rate is preferably 1-2 DEG C/min.
Adopt preparation method of the present invention, overcome at present industry preparation alumina ratio surface-area and pore volume size, pore size distribution is wider and be difficult to the shortcoming that regulates and controls, can prepare the three-dimensional ordered macroporous Al of mesopore-macropore graded pore structure
2o
3.
The three-dimensional ordered macroporous Al of the mesopore-macropore graded pore structure adopting the inventive method to prepare
2o
3can directly as various sorbent material and catalyzer, as the carrier of the catalyzer such as hydrotreatment, catalytic cracking reformation.
The three-dimensional ordered macroporous Al of the mesopore-macropore graded pore structure adopting the inventive method to prepare
2o
3, be especially suitable for use as the support of the catalyst of heavy oil and residual oil and various distillate hydrogenation process.
Below in conjunction with the drawings and specific embodiments, the present invention is described further.
Accompanying drawing explanation
Fig. 1 is the SEM figure of PMMA template prepared by the present invention
Fig. 2 is that the present invention schemes at the SEM of sample after different maturing temperature
Fig. 3 is the TEM figure of the present invention's sample after 800 DEG C of roastings
Embodiment
Embodiment 1
In four-hole boiling flask, add 650ml deionized water, constant temperature 30 minutes in 70 DEG C of water-baths, controlling stirring velocity with constant speed stirrer is 350rpm, and passes into nitrogen and protect reaction.Add a certain amount of 13.75ml methyl methacrylate, continue stirring 15 minutes.Take 0.2g Potassium Persulphate, be dissolved in 20mL water, be preheated to 70 DEG C, solution is added in flask, stir lower continuation reaction 60 minutes, obtain milky emulsion.Emulsion is assembled into PMMA hard template through centrifugal, and its character lists in table 1.
Embodiment 2-3
Preparation method is similar to embodiment 1, and the consumption of methyl methacrylate is become 27.5ml, 55ml, and its character lists in table 1.Fig. 1 is the SEM figure of PMMA template prepared by embodiment 2, the as can be seen from the figure order of hard template, and in hexagonal array.
The character of table 1 embodiment 1-3 product
Embodiment 4-5
Preparation method is similar to embodiment 1, and be 0.1g, 0.4g by the quantitative change of initiator potassium persulfate, its character lists in table 2.
The character of table 2 embodiment 4-5 product
Embodiment 6
By the Al (NO of 0.1g F127 and 10mmol
3)
39H
2o adds in 95wt% ethanolic soln, be stirred to and dissolve completely, then the PMMA hard template assembled is added, suction filtration removing excess liq after complete wetting, and at 40-60 DEG C after drying, rise to 700 DEG C of roastings 5 hours with the temperature rise rate of 1 DEG C/min, obtain the three-dimensional ordered macroporous Al of mesopore-macropore graded pore structure
2o
3.The character of product lists in table 3.
The character of table 3 embodiment 6-7 product
Embodiment 7
Preparation method is similar to embodiment 1, maturing temperature is changed into 800 DEG C, and the character of product lists in table 3.
As can be seen from the upper figure of the SEM of Fig. 2, when maturing temperature is 700,800 DEG C, all there is compact arranged ordered big hole structure in obtained aluminum oxide.And when temperature reaches 800 DEG C, its macroporous structure destroys not yet.Illustrate that the macroporous aluminium oxide material that the method prepares has good thermostability.As shown in the TEM photo of Fig. 3, the hole wall of sample exists aperture comparatively concentrate mesoporous, this demonstrate after 800 DEG C of roastings, the present invention has prepared the three-dimensional ordered macroporous Al of mesopore-macropore graded pore structure
2o
3.
Claims (5)
1. utilize double-template to prepare the method for three-dimensional ordered macroporous alumina, it is characterized in that the concrete steps of preparation method are as follows:
(1) by method that emulsifier-free is polymerized, the add-on controlling monomers methyl methacrylate (MMA) is 2%-10%, and initiator potassium persulfate add-on is 0.05-0.4g, and stir speed (S.S.) is 350rpm, temperature of reaction is 70 DEG C, prepares the polymethylmethacrylate emulsion of uniform particle sizes;
(2) the polymethylmethacrylate emulsion will prepared in step 1), is assembled into PMMA hard template under the action of the centrifugal, and rotating speed is 1000-3000rpm.And at 40-80 DEG C freeze-day with constant temperature 6-8 hour;
(3) be made into the aluminum nitrate ethanolic soln of 0.5-2.0mol/L with nine water aluminum nitrates, soft template and 95% ethanol, in mixed solution, soft template content is 5-10 × 10
-3mol/L;
(4) continuous whipping step 3) gained solution, obtain transparent mixed solution, stop adding step 2 after stirring) the PMMA hard template that obtains;
(5) infiltrating time is the mixture of step 4) gained was carried out suction filtration in 2-6 hour, solids freeze-day with constant temperature 6-8 hour at 40-80 DEG C of gained;
(6) will by 5) material of gained is at 650-950 DEG C of roasting 3-6 hour, and sequence of control temperature rise rate is 1-5 DEG C/min, and removing hard template PMMA and soft template, obtain the three-dimensional ordered macroporous Al with mesopore-macropore graded pore structure
2o
3.
2. want the double-template that utilizes described in 1 to prepare the method for three-dimensional ordered macroporous alumina according to right, it is characterized in that said soft or hard template is respectively F127 and PMMA template.
3. want the double-template that utilizes described in 1 to prepare the method for three-dimensional ordered macroporous alumina according to right, it is characterized in that the concentration of aluminum nitrate ethanolic soln in said step 3) is 0.8-1.0mol/L, soft template content is 6-8 × 10
-3mol/L.
4. want the double-template that utilizes described in 1 to prepare the method for three-dimensional ordered macroporous alumina according to right, it is characterized in that in said step 5), drying temperature is 40-60 DEG C.
5. want the double-template that utilizes described in 1 to prepare the method for three-dimensional ordered macroporous alumina according to right, it is characterized in that the maturing temperature in said step 6) is 750-850 DEG C, programmed rate is 1-2 DEG C/min.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105664909A (en) * | 2015-12-30 | 2016-06-15 | 中国石油大学(北京) | Ordered macroporous/ordered mesoporous composite-pore Ce/Zr metal oxide catalyst |
| CN106145919A (en) * | 2016-07-05 | 2016-11-23 | 陕西科技大学 | A kind of preparation method of three-dimensional netted ferrite microwave absorbing material |
| CN106925286A (en) * | 2015-12-30 | 2017-07-07 | 中国石油天然气股份有限公司 | The classification orientation preparation method of deasphalted oil Hydrodemetalation catalyst |
| CN110394197A (en) * | 2019-08-09 | 2019-11-01 | 辽宁石油化工大学 | A kind of orderly grade porous aluminum oxide carrier and its preparation method and application |
| CN110947288A (en) * | 2020-01-17 | 2020-04-03 | 南京大学 | Preparation method of composite decarbonizing liquid suitable for low-pressure and low-heat working conditions |
| CN112958106A (en) * | 2021-03-04 | 2021-06-15 | 青岛科技大学 | Preparation method of 3DOM (three-dimensional object model) bulk hydrogenation catalyst |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102040235A (en) * | 2009-10-21 | 2011-05-04 | 中国石油化工股份有限公司 | Three-dimensional ordered macroporous alumina and preparation method thereof |
-
2013
- 2013-06-18 CN CN201310240778.5A patent/CN104229843A/en active Pending
Patent Citations (1)
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| CN102040235A (en) * | 2009-10-21 | 2011-05-04 | 中国石油化工股份有限公司 | Three-dimensional ordered macroporous alumina and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| DEZHI HAN ET AL.: "Hierarchically ordered meso/macroporous γ-alumina for enhanced hydrodesulfurization performance", 《MICROPOROUS AND MESOPOROUS MATERIALS》, vol. 158, 16 March 2012 (2012-03-16), pages 1 - 6, XP028489657, DOI: doi:10.1016/j.micromeso.2012.03.022 * |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105664909A (en) * | 2015-12-30 | 2016-06-15 | 中国石油大学(北京) | Ordered macroporous/ordered mesoporous composite-pore Ce/Zr metal oxide catalyst |
| CN106925286A (en) * | 2015-12-30 | 2017-07-07 | 中国石油天然气股份有限公司 | The classification orientation preparation method of deasphalted oil Hydrodemetalation catalyst |
| CN105664909B (en) * | 2015-12-30 | 2018-07-24 | 中国石油大学(北京) | A kind of order mesoporous compound duct cerium zirconium metal oxide catalyst of ordered big hole- |
| CN106925286B (en) * | 2015-12-30 | 2019-06-11 | 中国石油天然气股份有限公司 | The classification of deasphalted oil Hydrodemetalation catalyst orients preparation method |
| CN106145919A (en) * | 2016-07-05 | 2016-11-23 | 陕西科技大学 | A kind of preparation method of three-dimensional netted ferrite microwave absorbing material |
| CN110394197A (en) * | 2019-08-09 | 2019-11-01 | 辽宁石油化工大学 | A kind of orderly grade porous aluminum oxide carrier and its preparation method and application |
| CN110947288A (en) * | 2020-01-17 | 2020-04-03 | 南京大学 | Preparation method of composite decarbonizing liquid suitable for low-pressure and low-heat working conditions |
| CN110947288B (en) * | 2020-01-17 | 2021-09-28 | 南京大学 | Preparation method of composite decarbonizing liquid suitable for low-pressure and low-heat working conditions |
| CN112958106A (en) * | 2021-03-04 | 2021-06-15 | 青岛科技大学 | Preparation method of 3DOM (three-dimensional object model) bulk hydrogenation catalyst |
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