CN105621463A - Method for synthesizing macroporous aluminium oxide - Google Patents
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Abstract
The invention provides a method for synthesizing macroporous aluminium oxide. Composition of the aluminium oxide contains amorphous aluminium oxide which has two-stage pores. The synthetic method comprises the following steps: firstly mixing carbon black and alkali lye and stirring, preparing an aluminium salt solution, mixing filtered and dried carbon black and the aluminium salt solution and stirring, carrying out ultrasonic treatment, drying the mixture, and treating successively in nitrogen, oxygen, nitrogen atmospheres so as to obtain aluminium oxide. According to the method, expensive organic additives are not used, operation steps are simple and feasible, and production cost is low.
Description
Technical field
The invention belongs to porous inorganic material synthesis field, specifically a kind of method synthesizing macroporous aluminium oxide.
Background technology
Classification according to IUPAC, porous material can be divided into three major types: large pore material (direct > 50nm), mesoporous material (2nm��directly��50nm) and poromerics (direct < 2nm). Due to poromerics and mesoporous material Industrial Catalysis with the field such as separate and apply with succeeding, so being always up research and the focus of application. In recent years, compensate for conventional small pore molecular sieve along with large pore material in the field such as bulky molecular catalysis, separation and mesoporous material is difficult to the shortcoming that allows macromole to enter within duct, and the advantage that some other physical chemical characteristics embodies, the sight of the researcher attracted gradually, becomes the popular domain of research.
CN102040235A, a kind of three-dimensional ordered macroporous alumina and preparation method thereof, disclose a kind of three-dimensional ordered macroporous alumina and preparation method thereof. The method is also adopt template to prepare large pore material, comprises the following steps: monodispersed polymer microballoon is assembled into glue crystal template, then fills alumina sol prepared by ad hoc approach in template, and last drying and roasting obtain macroporous aluminium oxide.
At present, industry expands the aperture of aluminium oxide frequently with following two method, and one is add the various expanding agent of people in extrusion process, and two is carry out hydrothermal treatment consists or high-temperature process after extrusion shapes.
CN103055948A, the preparation method of macropore alumina supporter, it is burn the light ash powder generated for expanding agent with crops stem shell, is simultaneously introduced triethanolamine aqueous solution, adopts kneading method to prepare macroporous aluminium oxide. Prepared macroporous aluminium oxide has diplopore distribution, bore dia and accounts for the 50%-70% of total pore volume at the pore volume of 10-20nm, and the bore dia pore volume more than 100nm accounts for the 20%-30% of total pore volume.
CN1087289A, method for preparing macropore alumina supporter, the alumina support moment of molding is warming up to 500-650 DEG C, and at high temperature maintains a few hours, it is possible to reach to expand the purpose in aperture.
CN1209355A, macropore alumina supporter and preparation method thereof, is that boehmite raw material first carries out peptization or transconversion into heat, and the material after extruded moulding processes with containing by the compound of ion, it is possible to the aperture of aluminium oxide.
Macroporous aluminium oxide material can be prepared in addition with other technology, such as CN101863499A, the preparation method of a kind of macroporous-mesoporous alumina, prepare a kind of aluminium oxide overlapping duct containing 5��40nm and 50��150nm two. This patent comprises the following steps: reaction promoter and aluminium salt are first dissolved in organic solvent solution by a., then template adds above-mentioned solution and dissolves, and the pH value of solution controls 3.5��6.0; B. the solution of a step preparation is carried out burin-in process so that it is in progressively elimination system, organic solvent and moisture obtain macroporous-mesoporous alumina presoma; C. macroporous-mesoporous alumina powder body is obtained through 400��800 DEG C of calcination process. The template that this patent uses is expensive triblock copolymer.
CN101200297A, the preparation method of integral macroporous alumina, this patent adopts template synthesis to go out macroporous aluminium oxide. Preparation includes procedure below: first adopt reverse concentrated emulsions method to prepare monoblock type macropore organic formwork with styrene and divinylbenzene for monomer; Al is prepared for predecessor again with aluminum isopropylate. or boehmite2O3The hydrosol; Then by Al2O3The hydrosol is filled in monoblock type macropore organic formwork; Finally by the monolithic devices organic/inorganic composite drying after filling, roasting elimination template, obtain integral macroporous alumina. The Integral macroporous alumina obtained has the macropore duct that micron order interconnects, and aperture is 1��50 ��m.
CN102311133A, a kind of Integral macroporous alumina and preparation method thereof, the preparation method disclosing a kind of Integral macroporous alumina. Preparation process is: after aluminum source, Polyethylene Glycol and low-carbon (LC) alcohol and water at least one mix homogeneously, is added by low-carbon (LC) epoxyalkane in described mixture, through aging, soak, dry and roasting obtains Integral macroporous alumina. Its aperture of gained Integral macroporous alumina is at 0.05��10 ��m.
CN102311134A, a kind of spherical integral macroporous alumina and preparation method thereof, disclose a kind of spherical integral macroporous alumina and preparation method thereof. The method comprises the following steps: by polymer microballoon emulsion, alumina sol and coagulant with certain proportion mix homogeneously, this mixture is scattered in oil phase, form w/o type drop, then above-mentioned mixed phase system is reheated, make the alumina sol balling-up in aqueous phase, from oil phase, isolate the gel micro-ball of molding afterwards, then obtain described spherical integral macroporous alumina after aged in aqueous ammonia medium, dry and roasting. The macropore diameter of this aluminium oxide is homogeneous controlled in the scope less than 1 ��m, and the size of spheroidal particle is controlled, and mechanical strength is higher.
Existing large pore material, although especially existing a lot of the disclosing of the preparation method of macroporous aluminium oxide is reported, but still has some defects to need to overcome, and the template assemblies of such as colloid crystal templating is consuming time long, and preparation cost is high, it is difficult to industrialized production; The macropore ratio of the large pore material that some technology obtains and content are too low, and macropore diameter is generally higher than 200nm, and the excessive using value in aperture is relatively low, and pore diameter range is difficult to prepare at 100��200nm macropore with high using value. Therefore, studying novel, especially the preparation method of the macropore carbon of Cheap highly effective just has very real meaning.
Summary of the invention
For the deficiencies in the prior art, the invention provides a kind of method synthesizing macroporous aluminium oxide. The present invention provides aluminium oxide to have abundant macropore, and preparation method is simple, and production cost is low.
The present invention provides a kind of aluminium oxide, and described aluminium oxide has the feature that constituent is gama-alumina, has three grades of ducts, the aperture in first order duct is 3��4nm, the aperture in duct, the second level is 40��50nm, and the aperture in third level duct is 100��200nm, and specific surface area is 200��300m2/g��
The method of synthesis macroporous aluminium oxide of the present invention, comprises the following steps:
(1) being mixed with aqueous slkali by white carbon black, under 50��90 DEG C of conditions, stir process 0.5��3h, then filters, the solid matter dry 5��15h at 100��150 DEG C that will be filtrated to get;
(2) aluminium salt is mixed homogeneously with water, obtain solution A;
(3) solution A obtained to step (2) adds the white carbon black that step (1) obtains, ultrasonic Treatment 1��10h after mix homogeneously;
(4) solution obtained to step (3) adds ammonium salt, ultrasonic Treatment 1��5h after mix homogeneously, then stir under 80��100 DEG C of conditions, until mixture becomes viscous pasty state, finally dried under 100��120 DEG C of conditions;
(5) material that step (4) obtains is placed in nitrogen atmosphere, heat treatment 3��5h at 400��600 DEG C;
(6) material that step (5) obtains is placed in oxygen atmosphere, heat treatment 3��10h at 400��600 DEG C;
(7) after the material obtained until step (6) is down to room temperature, it is placed in nitrogen atmosphere, at 300��400 DEG C of heat treatment 1��3h, then is warming up to 500��800 DEG C of heat treatment 3��10h.
The present invention synthesizes in the method for macroporous aluminium oxide, and described in step (1), the granularity of white carbon black is 30��50nm.
The present invention synthesizes in the method for macroporous aluminium oxide, aqueous slkali described in step (1) is one or both in sodium hydroxide, potassium hydroxide, described alkaline concentration is 0.01��0.1mol/L, and the mass ratio of white carbon black and aqueous slkali is 1:5��1:50, it is preferable that 1:10��1:20.
The present invention synthesizes in the method for macroporous aluminium oxide, and the aluminium salt described in step (2) is aluminum nitrate and/or aluminum chloride; The mass ratio of described aluminium salt and water is 1:4��1:10, it is preferable that 1:5��1:8.
The present invention synthesizes in the method for macroporous aluminium oxide, aluminium salt described in step (3), white carbon black mass ratio be 1:0.5��1:3, it is preferable that 1:0.8��1:2.5.
The present invention synthesizes in the method for macroporous aluminium oxide, and ammonium salt described in step (4) is ammonium carbonate or ammonium nitrate, and wherein, the mass ratio of ammonium salt and aluminium salt is 1:4��1:10, it is preferable that 1:5��1:8.
The present invention synthesizes in the method for macroporous aluminium oxide, and in nitrogen atmosphere described in step (5), nitrogen flow rate is 100��500mL/min, it is preferred to 150��450mL/min.
The present invention synthesizes in the method for macroporous aluminium oxide, and the heat treatment described in step (5) processes 3.5��4.5h at 450��550 DEG C.
The present invention synthesizes in the method for macroporous aluminium oxide, and step (5) and the heat treatment heating rate described in step (6) are 1��10 DEG C/min, heats up with constant heating rate.
The present invention synthesizes in the method for macroporous aluminium oxide, and in the oxygen atmosphere described in step (6), oxygen gas flow rate is 200��500mL/min, it is preferred to 150��450mL/min.
The present invention synthesizes in the method for macroporous aluminium oxide, and the heat treatment described in step (6) processes 4��8h at 450��550 DEG C.
The present invention synthesizes in the method for macroporous aluminium oxide, and heat treatment described in step (7) carries out in nitrogen atmosphere, and nitrogen flow rate is at 100��500mL/min.
The present invention synthesizes in the method for macroporous aluminium oxide, and heat treated heating rate described in step (7) is 1��3 DEG C/min, heats up with constant heating rate.
Aluminium oxide provided by the invention has abundant macropore, can be used as catalyst carrier, adsorbent, chromatographic column filler, it is possible to as the synthesis masterplate of inorganic organic material.
Compared with prior art, aluminium oxide provided by the invention and synthetic method thereof have the advantage that
(1) present invention provides two-stage duct aluminium oxide to have the physicochemical characteristic of uniqueness, has two-stage duct, and wherein the aperture integrated distribution scope in first order duct is 30��40nm, and the aperture integrated distribution scope in duct, the second level is 100��200nm. Such pore passage structure is very beneficial for the transmission diffusion of macromolecular substances, has prominent advantage in bulky molecular catalysis process and adsorption separation process.
(2) in the inventive method, using the white carbon black through base extraction as hard template, required multistage pore canal aluminium oxide can be obtained, use base extraction white carbon black, the Surface electric property that can make white carbon black changes, the white carbon black promoting a part of single dispersing form is assembled, and makes several carbon black particle assemble and forms miniature coherent condition, in order to forms the template needed for macropore duct; And remaining white carbon black still keeps monodisperse status, it is possible to as the template needed for medium duct. And adopt ammonium salt and aluminium species plastic as the presoma of aluminium oxide, it is advantageously possible for generate less aluminium oxide particles, thus mesoporous at 3 ~ 5nm of aperture integrated distribution can be obtained; And the calcination steps through step (7) obtains gama-alumina. The preparation method of macroporous aluminium oxide of the present invention is simple, and topmost being characterized by does not use expensive poisonous organic formwork agent or additive, and cost is low.
(3) in the inventive method, by controlling the ratio of various material, ultrasonic, stirring, the operating procedure such as roasting, control the dispersity of carbon black particle (including single dispersing and miniature state of aggregation). Especially preparation method described in step (3), is stir in a heated condition, first by the moisture slow evaporation in mixture, until mixture becomes viscous pasty state, is then dried process again, is a kind of dynamically dry combination dried with static state. This drying mode can make the carbon black particle of aluminum and state of aggregation and single dispersing state be in Homogeneous phase mixing state all the time, avoid aluminum with white carbon black owing to density variation is separated, cause that aluminum cannot wrap up white carbon black effectively, and then cause that the aluminium oxide prepared is that aperture is less than 5nm common small-bore aluminium oxide.
Accompanying drawing explanation
Fig. 1 is the SEM photograph of the aluminium oxide of embodiment 1 synthesis.
Detailed description of the invention
Below by specific embodiment, the preparation method of material with carbon element of the present invention is described in detail, but is not limited to embodiment. In embodiment, the granularity of white carbon black used is about 40nm, and manufacturer is Shandong Ao Long Group Co., Ltd.
Embodiment 1
(1) 5g white carbon black is mixed with 50mL0.02mol/L sodium hydroxide solution, under 70 DEG C of conditions, stir 2h, then filter, the solid sample dry 10h under 100 DEG C of conditions that will obtain;
(2) 5g aluminum nitrate is mixed with 50mL distilled water, stir process 20min;
(3) in the solution of step (2), add the white carbon black that step (1) obtains, stir 1h, then ultrasonic Treatment 5h; It is subsequently adding 2g ammonium carbonate, stirs 2h, then ultrasonic Treatment 5h;
(4) solution prepared by step (3) is placed in 80 DEG C of stirred in water bath process, makes moisture evaporate, until solution becomes viscous pasty state, then dry under 100 DEG C of conditions;
(5) being placed in tube furnace by the material that step (4) obtains, pass into nitrogen, nitrogen flow rate is 300mL/min, with 2 DEG C/min from room temperature to 450 DEG C, and constant temperature 3.5h; Then passing to oxygen, oxygen gas flow rate is 300mL/min, constant temperature 5h at 450 DEG C, then room temperature it is cooled to, then passing to nitrogen, nitrogen flow rate is 300mL/min, with 2 DEG C/min from room temperature to 350 DEG C, constant temperature 1.5h, then it is warming up to 700 DEG C with 2 DEG C/min, constant temperature 5h, obtain aluminium oxide, being numbered CL1, the duct at different levels aperture integrated distribution of gained sample and reference area result are in Table 1.
Embodiment 2
(1) 6g white carbon black is mixed with 100mL0.02mol/L sodium hydroxide solution, under 70 DEG C of conditions, stir 2h; Then filter, the solid sample dry 10h under 100 DEG C of conditions that will obtain;
(2) 5g aluminum nitrate is mixed with 60mL distilled water, stir 20min;
(3) in the solution of step (2), add the white carbon black that step (1) obtains, stir 1h, then ultrasonic Treatment 7h; It is subsequently adding 2g ammonium carbonate, stirs 2h, then ultrasonic Treatment 5h;
(4) solution prepared by step (3) is placed in 80 DEG C of stirred in water bath process, makes moisture evaporate, until solution becomes viscous pasty state, then dry under 100 DEG C of conditions;
(5) being placed in tube furnace by the material that step (4) obtains, pass into nitrogen, nitrogen flow rate is 200mL/min, with 2 DEG C/min from room temperature to 450 DEG C, and constant temperature 4h; Then passing to oxygen, oxygen gas flow rate is 300mL/min, constant temperature 5h at 450 DEG C, then room temperature it is cooled to, then passing to nitrogen, nitrogen flow rate is 400mL/min, with 2 DEG C/min from room temperature to 350 DEG C, constant temperature 2h, then it is warming up to 650 DEG C with 2 DEG C/min, constant temperature 6h, obtain aluminium oxide, being numbered CL2, the duct at different levels aperture integrated distribution of gained sample and reference area result are in Table 1.
Embodiment 3
(1) 8g white carbon black is mixed with 80mL0.02mol/L sodium hydroxide solution, under 60 DEG C of conditions, stir 2h; Then filter, the solid sample dry 10h under 100 DEG C of conditions that will obtain;
(2) 4g aluminum nitrate is mixed with 50mL distilled water, stir 20min;
(3) in the solution of step (2), add the white carbon black that step (1) obtains, stir 1h, then ultrasonic Treatment 5h; It is subsequently adding 2.5g ammonium carbonate, stirs 2h, then ultrasonic Treatment 5h;
(4) solution prepared by step (3) is placed in 80 DEG C of stirred in water bath process, makes moisture evaporate, until solution becomes viscous pasty state, then dry under 100 DEG C of conditions;
(5) being placed in tube furnace by the material that step (4) obtains, pass into nitrogen, nitrogen flow rate is 260mL/min, with 1 DEG C/min from room temperature to 500 DEG C, and constant temperature 4h; Then passing to oxygen, oxygen gas flow rate is 300mL/min, 500 DEG C of constant temperature 5h, then room temperature it is cooled to, then passing to nitrogen, nitrogen flow rate is 300mL/min, with 2 DEG C/min from room temperature to 350 DEG C, constant temperature 1.5h, then it is warming up to 700 DEG C with 2 DEG C/min, constant temperature 5h, obtain aluminium oxide, being numbered CL3, the duct at different levels aperture integrated distribution of gained sample and reference area result are in Table 1.
Embodiment 4
(1) 12g white carbon black is mixed with 50mL0.02mol/L sodium hydroxide solution, under 70 DEG C of conditions, stir 2h, then filter, the solid sample dry 10h under 100 DEG C of conditions that will obtain;
(2) 6g aluminum nitrate is mixed with 100mL distilled water, stir 20min;
(3) in the solution of step (2), add the white carbon black that step (1) obtains, stir 1h, then ultrasonic Treatment 3h; It is subsequently adding 2.8g ammonium carbonate, stirs 2h, then ultrasonic Treatment 5h;
(4) solution prepared by step (3) is placed in 80 DEG C of stirred in water bath process, makes moisture evaporate, until solution becomes viscous pasty state, then dry under 100 DEG C of conditions;
(5) being placed in tube furnace by the material that step (4) obtains, pass into nitrogen, nitrogen flow rate is 300mL/min; With 1 DEG C/min from room temperature to 530 DEG C, constant temperature 4h; Then passing to oxygen, oxygen gas flow rate is 300mL/min, 500 DEG C of constant temperature 5h, then room temperature it is cooled to, then passing to nitrogen, nitrogen flow rate is 300mL/min, with 2 DEG C/min from room temperature to 350 DEG C, constant temperature 1.5h, then it is warming up to 700 DEG C with 2 DEG C/min, constant temperature 5h, obtain aluminium oxide, being numbered CL4, the duct at different levels aperture integrated distribution of gained sample and reference area result are in Table 1.
Embodiment 5
(1) 4.5g white carbon black is mixed with 50mL0.06mol/L sodium hydroxide solution, under 50 DEG C of conditions, stir 2h; Then filter, the solid sample dry 10h under 100 DEG C of conditions that will obtain;
(2) 5g aluminum nitrate is mixed with 50mL distilled water, stir 20min;
(3) in the solution of step (2), add the white carbon black that step (1) obtains, stir 1h, then ultrasonic Treatment 5h; It is subsequently adding 2.8g ammonium carbonate, stirs 2h, then ultrasonic Treatment 5h;
(4) solution prepared by step (3) is placed in 80 DEG C of stirred in water bath process, makes moisture evaporate, until solution becomes viscous pasty state, then dry under 100 DEG C of conditions;
(5) being placed in tube furnace by the material obtained of step (4), pass into nitrogen, nitrogen flow rate is 300mL/min, with 1 DEG C/min from room temperature to 530 DEG C, and constant temperature 4h; Then passing to oxygen, oxygen flow speed is 300mL/min, 500 DEG C of constant temperature 8h, then room temperature it is cooled to, then passing to nitrogen, nitrogen flow rate is 300mL/min, with 2 DEG C/min from room temperature to 350 DEG C, constant temperature 1.5h, then it is warming up to 650 DEG C with 2 DEG C/min, constant temperature 5h, obtain aluminium oxide, being numbered CL5, the duct at different levels aperture integrated distribution of gained sample and reference area result are in Table 1.
Comparative example 1
(1) 5g aluminum nitrate is mixed with 50mL distilled water, stir 20min;
(2) solution obtained to step (1) adds 5g white carbon black, stir 1h, then ultrasonic Treatment 5h; It is subsequently adding 2g ammonium carbonate, stirs 2h, then ultrasonic Treatment 5h;
(3) solution prepared by step (2) is placed in 80 DEG C of stirred in water bath process, makes moisture evaporate, until solution becomes viscous pasty state, then dry under 100 DEG C of conditions;
(4) being placed in tube furnace by the material that step (3) obtains, pass into nitrogen, nitrogen flow rate is 300mL/min; With 2 DEG C/min from room temperature to 450 DEG C, constant temperature 3.5h; Then pass to oxygen, oxygen gas flow rate is 300mL/min, 450 DEG C of constant temperature 5h, then is cooled to room temperature, then pass to nitrogen, nitrogen flow rate is 300mL/min, with 2 DEG C/min from room temperature to 350 DEG C of constant temperature 1.5h, then is warming up to 650 DEG C, constant temperature 5h, obtaining aluminium oxide, be numbered CL6, the duct at different levels aperture integrated distribution of gained sample and reference area result are in Table 1.
Comparative example 2
(1) 5g white carbon black is mixed with 60mL0.02mol/L sodium hydroxide solution, under 70 DEG C of conditions, stir 2h; Then filter, the solid sample dry 10h under 100 DEG C of conditions that will obtain;
(2) 5g aluminum nitrate is mixed with 50mL distilled water, stir 20min;
(3) in the solution of step (2), add the white carbon black that step (1) obtains, stir 1h, then ultrasonic Treatment 5h; It is subsequently adding 2g ammonium carbonate, stirs 2h, then ultrasonic Treatment 5h;
(4) material step (3) prepared is directly dry under 100 DEG C of conditions, is subsequently placed in tube furnace, passes into nitrogen, and nitrogen flow rate is 300mL/min; With 2 DEG C/min from room temperature to 450 DEG C, constant temperature 3.5h; Then pass to oxygen, oxygen flow speed is 300mL/min, 450 DEG C of constant temperature 5h, then is cooled to room temperature, then pass to nitrogen, nitrogen flow rate is 300mL/min, with 2 DEG C/min from room temperature to 350 DEG C of constant temperature 1.5h, then is warming up to 650 DEG C, constant temperature 5h, obtaining aluminium oxide, be numbered CL7, the duct at different levels aperture integrated distribution of gained sample and reference area result are in Table 1.
Comparative example 3
(1) 5g aluminum nitrate is mixed with 50mL distilled water, stir 20min;
(2) solution obtained to step (1) adds 5g white carbon black, stir 1h, then ultrasonic Treatment 5h; It is subsequently adding 2g ammonium carbonate, stirs 2h, then ultrasonic Treatment 5h;
(3) solution step (2) obtained is dry under 100 DEG C of conditions, is subsequently placed in tube furnace, passes into nitrogen, and nitrogen flow rate is 300mL/min; With 2 DEG C/min from room temperature to 450 DEG C, constant temperature 3.5h; Then passing to oxygen, oxygen flow speed is 300mL/min, 450 DEG C of constant temperature 5h, it is cooled to room temperature, then passing to nitrogen, nitrogen flow rate is 300mL/min, with 2 DEG C/min from room temperature to 350 DEG C, constant temperature 1.5h, then it is warming up to 650 DEG C with 2 DEG C/min, constant temperature 5h, obtain aluminium oxide, being numbered CL8, the duct at different levels aperture integrated distribution of gained sample and reference area result are in Table 1.
Table 1 embodiment and comparative example gained sample physico-chemical property
Claims (19)
1. the method synthesizing macroporous aluminium oxide, described aluminium oxide constituent is gama-alumina, has three grades of ducts, the aperture in first order duct is 3��4nm, the aperture in duct, the second level is 40��50nm, and the aperture in third level duct is 100��200nm, and specific surface area is 200��300m2/ g; The method of described synthesis macroporous aluminium oxide comprises the steps:
(1) being mixed with aqueous slkali by white carbon black, under 50��90 DEG C of conditions, stir process 0.5��3h, then filters, the solid matter dry 5��15h at 100��150 DEG C that will be filtrated to get;
(2) aluminium salt is mixed homogeneously with water, obtain solution A;
(3) solution A obtained to step (2) adds the white carbon black that step (1) obtains, ultrasonic Treatment 1��10h after mix homogeneously;
(4) solution obtained to step (3) adds ammonium salt, ultrasonic Treatment 1��5h after mix homogeneously, then stir under 80��100 DEG C of conditions, until solution becomes viscous pasty state, finally dried under 100��120 DEG C of conditions;
(5) material that step (4) obtains is placed in nitrogen atmosphere, heat treatment 3��5h at 400��600 DEG C;
(6) material that step (5) obtains is placed in oxygen atmosphere, heat treatment 3��10h at 400��600 DEG C;
(7) after the material obtained until step (6) is down to room temperature, it is placed in nitrogen atmosphere, at 300��400 DEG C of heat treatment 1��3h, then heats to 500��800 DEG C of heat treatment 3��10h.
2. in accordance with the method for claim 1, it is characterised in that: described in step (1), the granularity of white carbon black is 30��50nm.
3. in accordance with the method for claim 1, it is characterised in that: aqueous slkali described in step (1) is one or both in sodium hydroxide, potassium hydroxide.
4. in accordance with the method for claim 1, it is characterised in that: alkaline concentration described in step (1) is 0.01��0.1mol/L.
5. in accordance with the method for claim 1, it is characterised in that: the mass ratio of white carbon black described in step (1) and aqueous slkali is 1:5��1:50, it is preferable that 1:10��1:20.
6. in accordance with the method for claim 1, it is characterised in that: the aluminium salt described in step (2) is aluminum nitrate and/or aluminum chloride.
7. in accordance with the method for claim 1, it is characterised in that: the mass ratio of aluminium salt described in step (2) and water is 1:4��1:10, it is preferable that 1:5��1:8.
8. in accordance with the method for claim 1, it is characterised in that: aluminium salt described in step (3), white carbon black mass ratio be 1:0.5��1:3, it is preferable that 1:0.8��1:2.5.
9. in accordance with the method for claim 1, it is characterised in that: ammonium salt described in step (4) is ammonium carbonate or ammonium nitrate.
10. in accordance with the method for claim 1, it is characterised in that: the mass ratio of ammonium salt described in step (4) and aluminium salt is 1:4��1:10, it is preferable that 1:5��1:8.
11. in accordance with the method for claim 1, it is characterised in that: in nitrogen atmosphere described in step (5), nitrogen flow rate is 100��500mL/min, it is preferred to 150��450mL/min.
12. in accordance with the method for claim 1, it is characterised in that: the heat treatment described in step (5) processes 3.5��4.5h at 450��550 DEG C.
13. in accordance with the method for claim 1, it is characterised in that: step (5) and the heat treatment heating rate described in step (6) they are 1��10 DEG C/min.
14. the method described in claim 1 or 13, it is characterised in that: step (5) and the heat treatment described in step (6) heat up with constant heating rate.
15. in accordance with the method for claim 1, it is characterised in that: in oxygen atmosphere described in step (6), oxygen gas flow rate is 200��500mL/min, it is preferred to 150��450mL/min.
16. in accordance with the method for claim 1, it is characterised in that: the heat treatment described in step (6) processes 4��8h at 450��550 DEG C.
17. in accordance with the method for claim 1, it is characterised in that: in nitrogen atmosphere described in step (7), nitrogen flow rate is 100��500mL/min.
18. in accordance with the method for claim 1, it is characterised in that: heat treated heating rate described in step (7) is 1��3 DEG C/min.
19. the method described in claim 1 or 18, it is characterised in that: heat treatment described in step (7) heats up with constant heating rate.
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