CN102173442B - Preparation method for aperture-adjustable alumina oxide - Google Patents
Preparation method for aperture-adjustable alumina oxide Download PDFInfo
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- CN102173442B CN102173442B CN 201110045648 CN201110045648A CN102173442B CN 102173442 B CN102173442 B CN 102173442B CN 201110045648 CN201110045648 CN 201110045648 CN 201110045648 A CN201110045648 A CN 201110045648A CN 102173442 B CN102173442 B CN 102173442B
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Abstract
The invention discloses a preparation method for aperture-adjustable alumina oxide. The preparation method is characterized by comprising the steps of: 1), dissolving n-butyl alcohol or cyclohexane in deionized water through high shear emulsification to prepare even emulsion base fluid I; dissolving a certain amount of dispersing agent in an aluminum sulfate or sodium aluminate solution through emulsification to prepare solutions II and III respectively; 2) under a certain temperature and the mixing conditions, adding the solutions II and III accounting for 60 percent of the total reaction solution into the base fluid I sequentially to react fully so as to obtain the serous fluid containing a reaction precursor; then merging at constant speed and adding the rest solutions II and III are into the serous fluid containing the reaction precursor for full reaction; 3) aging the reacted serous fluid and then carrying out extraction filtration, washing with a great quantity of deionized water and alcohol to obtain a simulated thin diaspore filter cake; 4) subjecting the simulated thin diaspore filter cake and the emulsion obtained by certain amount of organic solvent and the dispersing agent through high shear emulsification to atmospheric distillation; and 5) drying, heating and roasting the obtained products and removing the dispersing agent to obtain the alumina powder.
Description
Technical field
The invention belongs to field of inorganic material preparing technology, relate to a kind of preparation method of aluminum oxide, particularly a kind of preparation method of aperture-adjustable alumina oxide.
Background technology
Aluminum oxide is very widely inorganic oxide of a kind of industrial application.It is often used as catalytic carrier, is used for the hydrofining of purifying vehicle exhaust, oil product etc.In addition, aluminum oxide can also be used as sorbent material and siccative.Aluminum oxide of different nature is selected in the different application field, and wherein pore size distribution is the important parameter that affects the aluminum oxide performance.A1
2O
3Generally made through 500～900 ℃ of high temperature dehydrations by pseudo-boehmite, the preparation technology of pseudo-boehmite and roasting condition have determined its use properties to a great extent, and therefore preparation pseudo-boehmite stable, superior performance is to obtain high-performance A1
2O
3Important means.
At present, can reach the purpose of adjustment aperture by the compound that in preparation process, adds the elements such as titanium, silicon, phosphorus, but have a strong impact on the purity of aluminum oxide.Or adopt tensio-active agent as template, and obtain having the aluminum oxide of certain pore size structure by the interface interaction of inorganic-organic phase in the solution, but its synthetic route is complicated, cost is higher, can't realize industrialization.The present invention has overcome the restriction of aperture size, effectively controls the form of precursor pseudo-boehmite by changing reaction conditions, effectively improves aperture and the performance of aluminum oxide, thereby enlarges its range of application.Synthetic route of the present invention is simpler, and is with low cost, realizes easily industrialization.
Summary of the invention
The object of the invention is to provide the within the specific limits preparation method of controlled high purity alumina powder of a kind of aperture, and is easy and simple to handle, with low cost, but the alumina powder jointed mean pore size of gained modulation in the 5-25nm scope, and have simultaneously higher specific surface area.
The present invention is a kind of preparation method of aperture-adjustable alumina oxide, it is characterized in that, comprises following concrete steps:
1) by high-shear emulsifying an amount of organism solvent is dissolved in the appropriate amount of deionized water, make homogeneous latex emulsion I as the reaction base fluid, homogeneous latex emulsion reaction base fluid I comprises the mixture of organism solvent, n-butanol or hexanaphthene and deionized water, or the mixture of propyl carbinol and hexanaphthene and deionized water;
By high-shear emulsifying with an amount of dispersion agent; Fully be dissolved in the sodium aluminate solution of the Tai-Ace S 150 of strength of solution 0.1-1.0mol/L or strength of solution 1.0-6.0mol/L, make respectively transparent homogeneous solution II and III; Described dispersion agent comprises ionic dispersant, non-ionic dispersing agent, and ionic dispersant comprises quaternary ammonium salt cationic surfactant, is selected from alkyl trimethyl quaternary ammonium salt; And fluorine surfactant, be selected from the fluorocarbon surfactant of C8-C15; Non-ionic dispersing agent refers to polymeric alcohol, is selected from polyvinyl alcohol and polyoxyethylene glycol;
2) under the certain temperature, II and the III that will account for first total reaction solution 10-60% under the agitation condition successively join among the reaction base fluid I, make two kinds of solution fully react 5-30min, obtain containing the slurries that react precursor; Then the II of remainder and III and stream are at the uniform velocity joined and contain in the slurries that react precursor, it is fully reacted; Whole reaction keeps certain temperature, is controlled at 45-100 ℃, and mixing speed is controlled at 50-800rpm, and pH is controlled at 6.0-9.0, and reaction continues 10min-120min;
3) carry out suction filtration with moving into Büchner funnel behind the aging 30-60min under the reacted slurries room temperature condition, remove most of sulfate radical and sodium ion with a large amount of deionized water wash, except anhydrating and residual ion, obtain the pseudo-boehmite filter cake with an amount of washing with alcohol;
4) pseudo-boehmite and an amount of organism solvent, dispersion agent are carried out air distillation 0.5-3h through high-shear emulsifying gained emulsion;
5) with above-mentioned products therefrom 110 ℃ of dryings, 550 ℃ of temperature-programmed calcination 3.0h remove dispersion agent, obtain alumina powder jointed;
According to preparation method of the present invention, it is characterized in that, in step (2), in the reaction with part II and the III of 10-50%, prepare first a certain amount of slurries that react precursor that contain with I, will remain again II and III during subsequent reactions and stream at the uniform velocity joins and contains in the slurries that react precursor.
According to preparation method of the present invention, it is characterized in that, pseudo-boehmite and an amount of organism solvent, dispersion agent are carried out air distillation 0.5-2h through high-shear emulsifying gained emulsion.
According to preparation method of the present invention, it is characterized in that, in step (4), by change dispersion agent different sorts and different amounts, and control certain reaction conditions, effectively regulate and control the different average pore diameters of aluminum oxide.
The present invention realizes the modulation in aluminum oxide aperture by the usage quantity that adopts dissimilar dispersion agents and change dispersion agent, and technique is simple, and is cheap, is conducive to realize industrial production.
The present invention compares with background technology, and the beneficial effect that has is:
1. working condition is gentle, and is with low cost, is fit to suitability for industrialized production.
2. utilize the guide effect of dispersion agent, by adjusting dispersant and usage quantity, and control the effective adjustment aperture size of certain preparation condition.
3. by the temperature-programmed calcination process, progressively remove dispersion agent, keep the powder pore passage structure, and obtain high specific surface area.
4. the aluminum oxide of present method preparation integrates high-specific surface area and wide aperture, but and the aperture Effective Regulation, have wide application prospect.
Description of drawings
Fig. 1 is embodiment 4 gained pseudo-boehmite XRD spectra.
Fig. 2 is the pore size distribution curve of embodiment 4 gained alumina powders.
Embodiment
Embodiment 1:
(1) by high-shear emulsifying the propyl carbinol of 1.5L 99.9% is joined and obtain homogeneous latex emulsion I in the 1.5L deionized water, by high-shear emulsifying the 0.15g cetyl trimethylammonium bromide fully is dissolved in and makes transparent homogeneous solution II in the alum liquor that 450mL concentration is 0.93mol/L, and concentration be in the sodium aluminate solution of 5.88mol/L as reaction soln III, the consumption of solution III is 420mL.
(2) under the certain temperature, first 60% II and III priority are reacted with I under the agitation condition, obtain containing the slurries that react precursor, then remaining 40% II and III and stream are at the uniform velocity joined and contain in the slurries that react precursor, temperature of reaction is controlled at 75 ℃, pH is controlled at 7.0, continues 60min by changing the reaction of reaction feed speed control;
(3) carry out suction filtration with moving into Büchner funnel behind the aging 45min under the reacted slurries room temperature condition, remove most of sulfate radical and sodium ion with a large amount of deionized water wash, except anhydrating and residual ion, obtain the pseudo-boehmite filter cake with an amount of washing with alcohol.
(4) above-mentioned filter cake and 500ml propyl carbinol, 0.15g cetyl trimethylammonium bromide are carried out air distillation 0.5h through the emulsion that high-shear emulsifying obtains.
(4) with above-mentioned products therefrom 110 ℃ of dryings, 550 ℃ of temperature-programmed calcination 3.0h remove dispersion agent, obtain alumina powder jointed.The program of temperature-programmed calcination is from 4.5h to 300 ℃ of 25 ℃ of intensification, at 300 ℃ of lower insulation 2h, from 2h to 550 ℃ of 300 ℃ of intensification, at 550 ℃ of lower insulation 3h, from 3h to 25 ℃ of 550 ℃ of cooling.
(5) other reaction conditions is constant, and cetyl trimethylammonium bromide content in the step (1) is increased to 0.2%, 0.5% and 1.0% successively.N
2Alumina powder jointed specific surface area, mean pore size and the pore volume of adsorption desorption analyzing and testing gained sees Table 1.
Embodiment 2:
Other reaction conditions is constant to change dispersion agent in the step (1) into Macrogol 2000.The analytical results of product see Table 2.
Embodiment 3:
Other reaction conditions is constant to change dispersion agent in the step (1) into nona oxy benzene sulfonic acid sodium salt of perfluoro.The products therefrom analytical results sees Table 3.
Embodiment 4:
Other reaction conditionss are with embodiment 1, and the add-on with three kinds of tensio-active agents is controlled to be 0.2% respectively, the precursor amount changed into add first 12% II and III, and rear and stream adds remaining 82% II and III, make to contain the slurries that react precursor.The aging 60min of reaction rear slurry, post-processed is seen Fig. 1 with the XRD spectra of 1,110 ℃ of oven dry of embodiment product.A among the figure, b, c, d are respectively and do not add dispersion agent, add cetyl trimethylammonium bromide, Macrogol 2000, the XRD spectra of nona oxy benzene sulfonic acid sodium salt of perfluoro products therefrom.As can be seen from the figure, the pseudo-boehmite characteristic peak does not change behind the adding dispersion agent, illustrates that its crystal formation does not change, and the cutting edge of a knife or a sword value reduces, and cutting edge of a knife or a sword is wide to broaden, and illustrates that powder diameter diminishes.N
2The adsorption desorption analytical results detects alumina powder jointed specific surface area, mean pore size and the pore volume of gained and sees Table 4.The pore size distribution curve of three kinds of powders is seen Fig. 2.
Table 1. embodiment 1 products obtained therefrom N
2Adsorption desorption analyzing and testing result
Table 2. embodiment 2 products obtained therefrom N
2Adsorption desorption analyzing and testing result
Table 3. embodiment 3 products obtained therefrom N
2Adsorption desorption analyzing and testing result
Table 4. embodiment 4 products obtained therefrom N
2Adsorption desorption analyzing and testing result
Claims (4)
1. the preparation method of an aperture-adjustable alumina oxide is characterized in that, comprises following concrete steps:
1) by high-shear emulsifying an amount of organism solvent is dissolved in the appropriate amount of deionized water, make homogeneous latex emulsion I as the reaction base fluid, homogeneous latex emulsion I comprises the mixture of organism solvent, n-butanol or hexanaphthene and deionized water, or the mixture of propyl carbinol and hexanaphthene and deionized water;
Respectively an amount of dispersion agent fully is dissolved in by high-shear emulsifying in the sodium aluminate solution of the Tai-Ace S 150 of strength of solution 0.1-1.0mol/L and strength of solution 1.0-6.0mol/L, makes respectively transparent homogeneous solution II and III; Described dispersion agent is selected from ionic dispersant or non-ionic dispersing agent, does not comprise other materials, and ionic dispersant comprises quaternary ammonium salt cationic surfactant, is selected from alkyl trimethyl quaternary ammonium salt; And fluorine surfactant, be selected from the fluorocarbon surfactant of C8-C15; Non-ionic dispersing agent refers to polymeric alcohol, is selected from polyvinyl alcohol and polyoxyethylene glycol;
2) under the certain temperature, II and the III that will account for first total reaction solution 10-60% under the agitation condition successively join among the reaction base fluid I, make two kinds of solution fully react 5-30min, obtain containing the slurries that react precursor; Then the II of remainder and III and stream are at the uniform velocity joined and contain among the base fluid I that reacts precursor, it is fully reacted; Whole reaction keeps certain temperature, is controlled at 45-100 ℃, and mixing speed is controlled at 50-800rpm, and pH is controlled at 6.0-9.0, and reaction continues 10min-120min;
3) carry out suction filtration with moving into Büchner funnel behind the aging 30-60min under the reacted slurries room temperature condition, remove most of sulfate radical and sodium ion with a large amount of deionized water wash, except anhydrating and residual ion, obtain the pseudo-boehmite filter cake with an amount of washing with alcohol;
4) pseudo-boehmite and an amount of organism solvent, dispersion agent are carried out air distillation 0.5-3h through high-shear emulsifying gained emulsion;
5) with above-mentioned products therefrom 110 ℃ of dryings, 550 ℃ of temperature-programmed calcination 3.0h remove dispersion agent, obtain alumina powder jointed.
2. method according to claim 1, it is characterized in that, in step (2), in the reaction with part II and the III of 10-50%, prepare first a certain amount of slurries that react precursor that contain with I, will remain again II and III during subsequent reactions and stream at the uniform velocity joins and contains in the slurries that react precursor.
3. method according to claim 1 is characterized in that, pseudo-boehmite and an amount of organism solvent, dispersion agent are carried out air distillation 0.5-2h through high-shear emulsifying gained emulsion.
4. method according to claim 1 is characterized in that, in step (4), by change dispersion agent different sorts and different amounts, and controls certain reaction conditions, effectively regulates and control the different average pore diameters of aluminum oxide.
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| CN103787393B (en) * | 2012-11-01 | 2016-06-22 | 中国石油化工股份有限公司 | A kind of preparation method of aluminium oxide |
| CN104692429B (en) * | 2015-02-16 | 2017-03-01 | 北京化工大学 | A kind of controllable method for preparing of bigger serface macropore volume boehmite |
| CN111377467A (en) * | 2018-12-28 | 2020-07-07 | 中国石油化工股份有限公司 | Alumina and preparation method thereof |
| CN114433252B (en) * | 2020-11-03 | 2024-03-05 | 中国石油天然气股份有限公司 | Catalytic cracking catalyst and preparation method thereof |
| CN113912092A (en) * | 2021-12-01 | 2022-01-11 | 扬州中天利新材料股份有限公司 | Preparation method of alumina ultrafine powder with purity of 5N |
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| CN100348493C (en) * | 2005-05-10 | 2007-11-14 | 中国石油天然气股份有限公司 | Preparation tech. for producing pseudoboehmite |
| CN100548884C (en) * | 2007-11-09 | 2009-10-14 | 中国铝业股份有限公司 | The preparation method of pseudo-boehmite |
| CN101618886B (en) * | 2008-07-04 | 2011-05-18 | 中国石油化工股份有限公司 | Aluminum hydroxide and preparation method thereof |
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