CN106348327B - Ultra-large pore pseudo-boehmite and preparation method thereof - Google Patents
Ultra-large pore pseudo-boehmite and preparation method thereof Download PDFInfo
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- CN106348327B CN106348327B CN201610799935.XA CN201610799935A CN106348327B CN 106348327 B CN106348327 B CN 106348327B CN 201610799935 A CN201610799935 A CN 201610799935A CN 106348327 B CN106348327 B CN 106348327B
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
- C01F7/00—Compounds of aluminium
- C01F7/02—Aluminium oxide; Aluminium hydroxide; Aluminates
- C01F7/44—Dehydration of aluminium oxide or hydroxide, i.e. all conversions of one form into another involving a loss of water
- C01F7/447—Dehydration of aluminium oxide or hydroxide, i.e. all conversions of one form into another involving a loss of water by wet processes
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/12—Surface area
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/14—Pore volume
Abstract
The invention discloses a super-large pore pseudo-boehmite and a preparation method thereof, relating to the field of chemical industry. The pore volume of the ultra-large pore pseudo-boehmite sample synthesized in the laboratory is more than 1.5ml/g, and the specific surface is more than 400m2The/g is far beyond the standard of the common industrial large-pore pseudo-boehmite and is the leading level of the international range.
Description
Technical Field
The invention relates to the field of chemical industry, in particular to a super-macroporous pseudo-boehmite and a preparation method thereof.
Background
At present, the traditional synthesis process for synthesizing the pseudoboehmite mainly comprises the following three processes:
1. a precipitation method: aluminum salts such as aluminum chloride, aluminum nitrate, aluminum sulfate and the like are taken as precursors, and sodium hydroxide is taken as a precipitator; taking aluminate as a precursor and acid or carbon dioxide as a precipitator; taking aluminum salt as acid and aluminate as alkali, and performing parallel flow precipitation; precipitating, gelatinizing, aging, filtering, washing and drying to obtain the product.
2. An aluminum alkoxide method:
the SB powder is a high-quality pseudoboehmite which is successfully developed by German Condea company and produced by taking high-purity aluminum cyclone and higher alcohol (n-amyl alcohol and n-hexyl alcohol) as raw materials. The production comprises a circulating process of 'aluminum hydroxide-alumina-aluminum alkoxide-aluminum hydroxide'. The SB powder has good crystal form, easily controlled pore structure, large specific surface area and high purity, and is widely used in the field of catalysis. However, the organic solvent used in the method has certain toxicity and high production cost.
3. Post-treatment method for hydration of quick-release powder
Besides, there is a kind of post-treatment process for quick-removing powder hydration. The quick-release powder is flash-roasted aluminium hydroxide, and after hydration treatment, various alumina family materials (such as bayerite, boehmite, pseudoboehmite and the like) can be prepared. The process is simple and convenient, the process cost is low, but the prior industrialized technology only uses the pseudo-boehmite to produce the common pseudo-boehmite, the pore volume is lower, and the pseudo-boehmite is often accompanied by the hetero-phase of the bayerite, so the process does not become the mainstream of preparation and still has larger space for improvement.
In the traditional method, the preparation limit pore volume of 1.2ml/g is not broken through in the industry, and once the pore volume is larger, the performance of the catalyst is possibly further improved in the petrochemical field. The precipitation method and the aluminum alkoxide method have more steps, relatively complex process and high process cost. Although the post-treatment method of the quick-release powder hydration is simple and convenient, the performance of the product produced at present is poor, the pore volume is low, and most products are only used in the field of refractory materials.
Disclosure of Invention
The invention aims to solve the technical problem of providing the ultra-large pore pseudo-boehmite and the preparation method thereof, and opens up a flexible, economic and environment-friendly brand new preparation route.
In order to achieve the above purpose, the present invention provides the following technical solutions: a super-macroporous pseudo-boehmite and a preparation method thereof are characterized in that: the pore volume of the ultra-large pore pseudo-boehmite is more than or equal to 1.5ml/g and the specific surface is more than or equal to 400m measured in a low-temperature nitrogen adsorption and desorption experiment2The preparation method of the thermal ultra-large pore pseudo-boehmite comprises the following steps: and putting the quick-release powder into an aqueous solution containing ammonium carbonate and an auxiliary agent, stirring to fully hydrate the quick-release powder and combine the quick-release powder with a template agent, filtering to obtain a filter cake, drying the filter cake, and heating to eliminate the ammonium carbonate and the auxiliary agent to obtain the ultra-macroporous pseudo-boehmite.
Preferably, the quick-release powder is a solid powder product obtained by flash roasting gibbsite, the component of the quick-release powder is rho-alumina, and the mass ratio of the quick-release powder to the aqueous solution is 1: 3-5.
Preferably, the concentration of the ammonium carbonate in the aqueous solution is 20-40%.
Preferably, the temperature of the hydration reaction is 30-90 ℃.
Preferably, the auxiliary agent is one or a combination of several of isopropanol, ethylene glycol and n-butanol in any proportion, and the mass concentration of the auxiliary agent in the aqueous solution is 0.2-5%, preferably 0.5-1%.
Preferably, the quick-release powder is put into the aqueous solution containing ammonium carbonate and the auxiliary agent, the stirring speed is 100-300 r/min, and the stirring time is 0.5-8 hours.
Preferably, the drying temperature of the filter cake is 100 ℃, and the drying time is 6-12 h.
Preferably, the heating decomposition temperature of the filter cake is 150-250 ℃, and the heating time is 2-6 h.
The beneficial effect of adopting above technical scheme is: the ultra-large pore pseudo-boehmite and the preparation method thereof have the advantages of simple operation, low equipment investment, excellent performance and no pollution, and compared with the traditional route, the method opens up a flexible, economic and environment-friendly brand new preparation route. The pore volume of the ultra-large pore pseudo-boehmite sample synthesized in the laboratory is more than 1.5ml/g, and the specific surface is more than 400m2The/g is far beyond the standard of the common industrial large-pore pseudo-boehmite and is the leading level of the international range.
Drawings
The following describes embodiments of the present invention in further detail with reference to the accompanying drawings.
FIG. 1 is a graph showing the relationship between diffraction intensity and temperature of a super-large pore pseudo-boehmite prepared by the method of the present invention.
Detailed Description
The following describes in detail the specific embodiments of a super large pore pseudo-boehmite and its preparation method according to the present invention with reference to the accompanying drawings.
Example 1:
120g of ammonium carbonate and 2g of isopropanol are dissolved in 300g of water, the temperature is maintained at 60 ℃, then 100g of quick-release powder is put into the solution at a rotation speed of 150 revolutions per minute, and stirring is continued for 4 hours. And after stirring is finished, filtering the suspension to obtain a solid filter cake, and drying the filter cake in an oven at 100 ℃ for 8 hours. After drying, the solid sample is placed in a muffle furnace to be roasted for 4 hours at the temperature of 200 ℃ to obtain the ultra-large pore pseudo-boehmite, and the BET specific surface area obtained by a nitrogen adsorption and desorption test is 441m2The volume of the pores is 1.60ml/g, and the XRD results of the sample are shown in figure 1.
Example 2:
150g of ammonium carbonate and 2g of n-butanol are dissolved in 300g of water, the temperature is maintained at 75 ℃, then 80g of quick-release powder is added to the solution at 200 revolutions per minute, and stirring is continued for 5 h. And after stirring is finished, filtering the suspension to obtain a solid filter cake, and drying the filter cake in an oven at 100 ℃ for 12 hours. After drying, placing the solid sample in a muffle furnace for roasting at 200 ℃ for 3h to obtain the ultra-large pore pseudo-boehmite, and obtaining the BET specific surface area of 433m through a nitrogen adsorption and desorption test2The pore volume is 1.52 ml/g.
Example 3:
160g of ammonium carbonate and 4g of ethylene glycol are dissolved in 300g of water, the temperature is maintained at 55 ℃, then 110g of quick-release powder is put into the solution at a rotation speed of 250 revolutions per minute, and stirring is continued for 6 h. And after stirring is finished, filtering the suspension to obtain a solid filter cake, and drying the filter cake in an oven at 100 ℃ for 6 hours. After drying, placing the solid sample in a muffle furnace for roasting at 220 ℃ for 4h to obtain the ultra-macroporous pseudo-boehmite, and obtaining a BET specific surface area of 427m through a nitrogen adsorption and desorption test2The pore volume is 1.56 ml/g.
Example 4:
180g of ammonium carbonate and 4g of isopropanol are dissolved in 300g of water, the temperature is maintained at 60 ℃, then 110g of quick-release powder is put into the solution at a rotation speed of 250 revolutions per minute, and stirring is continued for 6 h. And after stirring is finished, filtering the suspension to obtain a solid filter cake, and drying the filter cake in an oven at 100 ℃ for 6 hours. After drying, the solid sample is placed in a muffle furnace to be roasted for 4 hours at the temperature of 200 ℃ to obtain the ultra-large pore pseudo-boehmite, and the BET specific surface area obtained by a nitrogen adsorption and desorption test is 455m2The pore volume was 1.61 ml/g.
The above is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, many variations and modifications can be made without departing from the inventive concept of the present invention, which falls into the protection scope of the present invention.
Claims (8)
1. A preparation method of ultra-large pore pseudo-boehmite is characterized by comprising the following steps: adding the quick-release powder into an aqueous solution containing ammonium carbonate and an auxiliary agent, stirring to ensure that the quick-release powder is fully mixed with water and combined with the ammonium carbonate and the auxiliary agent, then filtering to obtain a filter cake, drying the filter cake, heating to eliminate the ammonium carbonate and the auxiliary agent to obtain the ultra-macroporous pseudo-boehmite,
the auxiliary agent is one or a combination of more of isopropanol, ethylene glycol and n-butanol in any proportion, and the mass concentration of the auxiliary agent in the aqueous solution is 0.2-5%;
the pore volume of the ultra-large pore pseudo-boehmite is more than or equal to 1.5ml/g and the specific surface is more than or equal to 400m measured in a low-temperature nitrogen adsorption and desorption experiment2/g。
2. The method for preparing the ultra-large pore pseudo-boehmite according to claim 1, characterized in that: the quick-release powder is a solid powder product obtained after flash roasting of gibbsite, the component of the quick-release powder is rho-alumina, and the mass ratio of the quick-release powder to the aqueous solution is 1: 3-5.
3. The method for preparing the ultra-large pore pseudo-boehmite according to claim 1, characterized in that: the concentration of the ammonium carbonate in the aqueous solution is 20-40%.
4. The method for preparing the ultra-large pore pseudo-boehmite according to claim 1, characterized in that: the temperature of the hydration reaction is 30-90 ℃.
5. The method for preparing the ultra-large pore pseudo-boehmite according to claim 1, characterized in that: the mass concentration of the auxiliary agent in the water solution is 0.5-1%.
6. The method for preparing the ultra-large pore pseudo-boehmite according to claim 1, characterized in that: the quick-release powder is put into an aqueous solution containing ammonium carbonate and an auxiliary agent, the stirring speed is 100-300 r/min, and the stirring time is 0.5-8 hours.
7. The method for preparing the ultra-large pore pseudo-boehmite according to claim 1, characterized in that: the drying temperature of the filter cake is 100 ℃, and the drying time is 6-12 h.
8. The method for preparing the ultra-large pore pseudo-boehmite according to claim 1, characterized in that: the heating decomposition temperature of the filter cake is 150-250 ℃, and the heating time is 2-6 h.
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0264010A (en) * | 1988-07-14 | 1990-03-05 | Condea Chem Gmbh | Production of boehmite alumina |
| CN1807247A (en) * | 2006-02-14 | 2006-07-26 | 张立省 | Pseudoboehmite preparing method using catalyst carrier and its cleaning production process |
| CN102910655A (en) * | 2012-11-20 | 2013-02-06 | 中国海洋石油总公司 | Method for preparing pseudoboehmite by quick removal powder |
| CN103708511A (en) * | 2013-12-19 | 2014-04-09 | 中国铝业股份有限公司 | Technology for producing pseudo-boehmite |
| CN105883871A (en) * | 2016-04-17 | 2016-08-24 | 北京化工大学 | Preparation method of bohemite |
-
2016
- 2016-08-29 CN CN201610799935.XA patent/CN106348327B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0264010A (en) * | 1988-07-14 | 1990-03-05 | Condea Chem Gmbh | Production of boehmite alumina |
| CN1807247A (en) * | 2006-02-14 | 2006-07-26 | 张立省 | Pseudoboehmite preparing method using catalyst carrier and its cleaning production process |
| CN102910655A (en) * | 2012-11-20 | 2013-02-06 | 中国海洋石油总公司 | Method for preparing pseudoboehmite by quick removal powder |
| CN103708511A (en) * | 2013-12-19 | 2014-04-09 | 中国铝业股份有限公司 | Technology for producing pseudo-boehmite |
| CN105883871A (en) * | 2016-04-17 | 2016-08-24 | 北京化工大学 | Preparation method of bohemite |
Non-Patent Citations (3)
| Title |
|---|
| Preparation of Pseudoboehmite with a Large Pore Volume and a Large Pore Size by Using a Membrane-Dispersion Microstructured Reactor through the Reaction of CO2 and a NaAlO2 Solution;Yujun et al.,;《Industrial & Engineering Chemistry Research》;20110224;3889-3894 * |
| 活性氧化铝再水合制备拟薄水铝石的形态研究;李晓云等;《电子显微学报》;20111231;第517-520页 * |
| 铵盐水热改性对氧化铝孔结构的影响;熊莹等;《硅酸盐通报》;20140630;第1287-1292页 * |
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Effective date of registration: 20180511 Address after: 315042 room 388, 2 building, 66 business building, academician Road, Ningbo high tech Zone, Zhejiang. Applicant after: Ningbo ino new Mstar Technology Ltd Address before: No. 926 Xixi Road, Hangzhou, Zhejiang Applicant before: Chen Miao |
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