CN101792164A - Method for preparing nano aluminum oxide through vacuum freeze drying technology - Google Patents
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Abstract
The invention relates to a method for preparing nano aluminum oxide with high specific surface area through vacuum freeze drying technology. The method comprises the following steps that: an organic phase is prepared, inorganic aluminum salt is mixed with the organic phase when agitation is conducted to obtain a micro-emulsion liquid system, and alkaline precipitant is added into the micro-emulsion liquid system for reaction to obtain aluminum hydroxide sediment; and after filtration and washing, vacuum freeze drying is conducted to the aluminum hydroxide sediment under conditions with temperature of negative 30 DEG C to negative 70 DEG C after pre-freezing, the freeze drying time is 2-96h to obtain aluminum hydroxide solid powder, and the aluminum hydroxide solid powder is calcined to finally obtain nano aluminum oxide. The preparation method of the invention combines the vacuum freeze drying technology with the reverse-phase micro-emulsion, the obtained nano aluminum oxide is gamma-aluminum oxide phase, the dispersity is good, the particles are even, the average grain size is 5-20nm, the specific surface area of the obtained nano aluminum oxide reaches 400-600m<2>/g and the pore volume is 1.5-2.5cm<3>/g. The invention has the advantages that the production process of the preparation method is controllable, the repetitiveness is high, the mass production can be realized, the stability is very high and the nano aluminum oxide can be used as the standard substance with high specific surface area.
Description
Technical field
The present invention relates to a kind of method of preparing nano aluminum oxide through vacuum freeze drying technology, particularly relate to and a kind ofly adopt Vacuum Freezing ﹠ Drying Technology to combine to prepare the method for nano aluminium oxide with microemulsion method.
Background technology
Alumina powder jointed material is a kind of widely used Industrial products, because alumina powder jointed material has characteristics such as high temperature resistant, anti-oxidant, wear-resistant, good insulating, surface-area are big, as catalyzer or catalyst support material, be applied in the fields such as top coat of the many catalyst for hydrogenation carriers of petrochemical industry, catalyst carrier for purifying vehicle tail gas for many years always.In recent years, along with the develop rapidly of China's oil chemical industry and nano material industry, to high-specific area nano Al
20
3Research and development become and become increasingly active.Wherein, the high-specific area nano A1 that how prepares dependable performance, has good quality with the technology of stable and controllable
2O
3Product is the main flow research direction in this field all the time.
A lot of about the preparation patent of different specific surface area aluminum oxide both at home and abroad.U.S. Pat 4248852 (a kind of preparation method who is applicable to support of the catalyst with aluminum oxide, in February, 1981 is open) in aluminum oxide be that pH value swing method prepares, this method can be controlled pore volume, the pore size distribution of the aluminum oxide of acquisition, but this method complex process, efficient are low.China patent CN101024503A (a kind of method for preparing ordered mesoporous aluminium oxide, in August, 2007 is open) makes inorganic aluminum salting liquid react into glue with precipitant solution in supergravity reactor, and the final gama-alumina specific surface area that obtains is 250-300m
2/ g.Patent CN1317189C (a kind of preparation method of mesoporous aluminas, in May, 2007 is open) is a presoma with aluminium colloidal sol, and tensio-active agent, high molecular polymer are structure directing agent, Hydrothermal Preparation mesopore gama-alumina, and its specific surface area is 250-350m
2/ g.Shortcomings such as there is complex process in above-mentioned alumina preparation method, the production process controllability is relatively poor and the aluminium oxide particles size is big, size-grade distribution is wide, particle agglomeration is relatively more serious, specific surface area is lower.
Microemulsion method is a kind of effective ways of nano materials, and the characteristics of this method are that the size distribution of synthetic product is easy to control, good process repeatability.Nano particle diameter with this method preparation is evenly distributed, and can regulate its microstructure by the structural parameter that change microemulsion, and then crystalline state, pattern, particle diameter and the distribution etc. of regulation and control nanoparticle, with the various types of materials of preparation desired properties.
Vacuum Freezing ﹠ Drying Technology combines as vacuum technique and low temperature technique, and is developed and receive much attention in 20 th century later.In the vacuum lyophilization process, to need the cooling of exsiccant wet stock to be frozen into solid or gel earlier, solid or gel are in the environment of low temperature, high vacuum, the solvent composition in solid or the gel are directly distilled without liquid process, thereby obtain the exsiccant powder.Lot of documents and experimental study show, adopts vacuum freeze-drying method to prepare nano-powder, advantage such as have that particle diameter is little and even, specific surface area is high, hard aggregation is few, purity is high, good uniformity, sintering temperature are low.This technological method is reliable, easy and simple to handle, good reproducibility, uses the nano-function powder of vacuum freeze-drying method preparation to have broad application prospects in fields such as space flight, electronics, military affairs, biologies.
At present, it is few to utilize vacuum freeze-drying method to prepare the patent report of high-specific area nano material both at home and abroad, as China patent CN101050128A (improvement of freeze dehydration method for preparing porous material, in October, 2007 open) mainly studied organic additive control to the porous material microstructure in freeze-drying.Patent CN1962547A (method of preparing alumina porous ceramic using gelatin wrapping-freeze drying process, in May, 2007 is open) is a presoma with the aluminum isopropylate, and pyrohydrolysis obtains alumina sol, has prepared alumina porous ceramic by lyophilize.Patent CN101037345A (method of preparing mullite porous ceramic by gel refrigeration drying process, in September, 2007 is open) is a raw material with silicon-dioxide aerosol and alumina sol, has prepared mullite porous ceramic by the lyophilize moulding process.At nano material characteristic and the present situation of specific surface area reference material development both at home and abroad, the present invention adopts Vacuum Freezing ﹠ Drying Technology to combine with microemulsion method, performance advantage has separately been synthesized the nano aluminium oxide with high-specific surface area, to satisfy the different field user demand.
Summary of the invention
The objective of the invention is to: adopt Vacuum Freezing ﹠ Drying Technology to prepare the alumina powder jointed of high-specific surface area, large pore volume in conjunction with microemulsion method; Solve that existing aluminium oxide particles size is big, size-grade distribution is wide, particle agglomeration is relatively more serious and the general lower problem of specific surface area; Use as reference material, provide unified data both at home and abroad, but provide traceability for the calibration of specific surface area analysis instrument the basic physical properties of various high-specific area nano powders (comprising aluminum oxide); A kind of technology is controlled, the preparation method of the nano alumina material with high-specific surface area of good reproducibility thereby provide.
The object of the present invention is achieved like this:
Preparation provided by the invention has the method for the nano alumina material of high-specific surface area, adopts Vacuum Freezing ﹠ Drying Technology in conjunction with microemulsion method, specifically comprises the steps:
1) preparation organic phase: the consumption that at first calculates required oil phase A, surfactant B and cosurfactant C, according to volume ratio surfactant B: cosurfactant C=1: 1～5: 1, oil phase A: (surfactant B+cosurfactant C)=1: 1～5: 1 batchings; Oil phase A, the surfactant B for preparing joined in the reaction vessel successively with cosurfactant C mix, form even organic phase;
2) under electronic stirring, be that the inorganic aluminate aqueous solution of 0.05M-3.0M mixes with the organic phase that step 1) obtains with concentration range, the molar ratio range of the tensio-active agent in control water and the step 1) is 10-40, formation stable microemulsion liquid system;
3) under electronic stirring, between 15 ℃-80 ℃, alkaline precipitating agent is added drop-wise to step 2) in the microemulsion system that obtains, rate of addition is 1ml/min-40ml/min, mix, under the alkaline condition of pH=7-13, inorganic aluminate and alkaline precipitating agent are reacted in minute water nuclear, reaction times is 1-10h, generates the aluminium hydroxide slurry;
4) the aluminium hydroxide slurry that step 3) is obtained under 15 ℃-80 ℃, pH value are condition between the 7-13, wore out 5-50 hour;
5) the aluminium hydroxide slurries filtration that step 4) is obtained washs successively with deionized water and organic solvent respectively, obtains aluminum hydroxide filter cake;
6) aluminum hydroxide filter cake that step 5) is obtained, place the cold-trap of vacuum freeze drier to carry out pre-freeze, pre-freeze is with the complete glaciation of the water of free state in the wet stock, for drying stage is prepared, the rate of temperature fall of pre-freeze process is 0.1-20 ℃/min, the pre-freeze temperature is-20 ℃～-90 ℃, and the pre-freeze time is 2-48h;
7) with step 6) through the gel masses after the pre-freeze, be to carry out lyophilize under-30 ℃～-70 ℃ the condition in temperature, freeze-drying time is 2-96h, obtains the aluminium hydroxide pressed powder;
8) the aluminium hydroxide pressed powder that step 7) is obtained grinds evenly, again in 300 ℃ of-1000 ℃ of following roasting 2-10 hours, promptly obtains having the nano alumina material of high-specific surface area.
In above-mentioned technical scheme, described oil phase is to contain a kind of in alkane, sherwood oil, lubricant base, oleic acid or the stearic acid of six to eight carbon atoms or with the mixing more than 2 kinds of arbitrary proportion.
In above-mentioned technical scheme, described tensio-active agent is a kind of in Triton X-100, alkyl trimethyl ammonium halide, alkyl dimethyl ammonium halide, alkyl ammonium halide, alcoxyl phthalein amine series, Aerosol OT (AOT), alkyl sodium sulfonate, sodium alkyl benzene sulfonate, sodium alkyl sulfate, fatty alcohol-polyoxyethylene ether series, alkylphenol polyoxyethylene series, nonyl benzene polyethenoxy ether class, tween (the polyoxyethylene sorbitol acid anhydride fatty acid ester) series or with the mixing more than 2 kinds of arbitrary proportion.
In above-mentioned technical scheme, described cosurfactant is a kind of or mixing more than 2 kinds in Fatty Alcohol(C12-C14 and C12-C18) or the aliphatic amide, as: propyl carbinol, n-hexyl alcohol, Pentyl alcohol, n-Octanol, aniline, acrylamide, N-N-isopropylacrylamide, vinylformic acid, methacrylic acid, sodium acrylate or N-vinyl pyridine.
In above-mentioned technical scheme, described inorganic aluminate is from anhydrous or contain a kind of in aluminum nitrate, Tai-Ace S 150 or the aluminum chloride of crystal water or with the mixing more than 2 kinds of arbitrary proportion.
In above-mentioned technical scheme, described alkaline precipitating agent adds with aqueous solution form from a kind of in volatile salt, bicarbonate of ammonia, ammonia, ammoniacal liquor, urea, hexamethylenetetramine, ammonium citrate, alkali-metal oxyhydroxide and the alkali-metal carbonate or with the mixing more than 2 kinds of arbitrary proportion.
In above-mentioned technical scheme, described step 3) and 4) in, the speed of electronic stirring is 500r/min-2000r/min;
In above-mentioned technical scheme, washing is to use deionized water wash 1-10 time in the described step 5), uses the 10-2000ml deionized water at every turn; Use organic solvent washing 1-10 time afterwards again, use the 10-2000ml organic solvent at every turn, organic solvent is a kind of in ethanol, methyl alcohol, the acetone or with the mixing more than 2 kinds of arbitrary proportion; Said process constitutes once washing process fully.
In above-mentioned technical scheme, in the described step 7), the vacuum tightness in the freeze drier is 0.1-100Pa, can adopt the mode that single pump vacuumizes or double pump vacuumizes simultaneously to reach required vacuum tightness.
In above-mentioned technical scheme, in the described step 8), the temperature rise rate in the retort furnace is 0.5-20 ℃/min, the temperature increasing schedule that can adopt speed change to heat up or at the uniform velocity heat up, and perhaps two kinds of temperature increasing schedules interosculate.
Fields such as the nano alumina material of this method preparation is mainly used in that the specific surface area reference material is synthetic, fine chemistry industry, biological ceramics, matrix material, optics, semiconductor material and catalysis belong to Vacuum Freezing ﹠ Drying Technology and combine with microemulsion method and prepare the field of nano material.
The present invention compared with prior art has following advantage:
1. preparation method of the present invention has controlled, the repeatable strong characteristics of production process strictness.
2. preparation method of the present invention adopts Vacuum Freezing ﹠ Drying Technology in conjunction with microemulsion method, can avoid the agglomeration in the nano material building-up process effectively, the weave construction of powder and pore distribution are preserved to greatest extent, thereby improve the specific surface area and the pore volume of material significantly; Solve that existing aluminium oxide particles size is big, size-grade distribution is wide, particle agglomeration is relatively more serious and the general lower problem of specific surface area.The character of resulting nano aluminium oxide is as follows: be gama-alumina thing phase, median size 5-20nm, specific surface area 400-600m
2/ g, pore volume 1.5-2.5cm
3/ g, mean pore size 5-20nm.The nano aluminium oxide that obtains has high homogeneity and stability, both has been applicable to all types of industries field and scientific research, also meets the requirement as high-specific surface area and pore volume reference material.
Description of drawings
The transmission electron microscope photograph of the high-specific area nano aluminum oxide that Figure 1A makes for method of the present invention
The nano alumina powder jointed high-resolution-ration transmission electric-lens photo that Figure 1B makes for method of the present invention
Embodiment
In order to make purpose of the present invention, technical scheme and advantage clearer, the present invention is described in further details below in conjunction with drawings and Examples.
Embodiment 1
Adopt the method for preparing nano alumina material of the present invention, the concrete preparation process of the gama-alumina material that obtains is as follows:
1) according to tensio-active agent: cosurfactant=1.2: 1 (volume ratio), oil phase: (tensio-active agent+cosurfactant)=1.3: 1 (volume ratio) batching, take by weighing 290ml hexanaphthene (oil phase), 120ml Triton X-100 (tensio-active agent) and 100ml propyl carbinol (cosurfactant), and drop to successively in the reaction vessel, mix and electronic stirring;
2) be added drop-wise in the above-mentioned organic phase with the speed of 2ml/min aluminum nitrate aqueous solution 100ml, stir while dripping and the mol ratio of control water and tensio-active agent is 15, formation aluminum nitrate reverse micro emulsion 1.0M;
3) under 25 ℃ the ammonium carbonate solution 100ml of 2.0M at the uniform velocity being added drop-wise in the aluminum nitrate reverse micro emulsion in the stirring with the speed of 2ml/min, is to stop to drip the alkaline precipitating agent ammonium carbonate solution at 9 o'clock until the pH value, and reaction 3h generates the aluminium hydroxide slurry; In 60 ℃, again the aluminium hydroxide slurry that generates was worn out 48 hours then;
4) step 3) is obtained aging after slurries filtration, the filter cake that obtains is used 1000ml deionized water and 300ml absolute ethanol washing successively; Filtration and washing process all repeat to carry out three times;
5) aluminum hydroxide filter cake that step 4) is obtained places the cold-trap of vacuum freezing drying oven to carry out pre-freeze, and pre-freeze is with the complete glaciation of the water of free state in the wet stock, for drying stage is prepared, the rate of temperature fall of pre-freeze process is 2 ℃/min, and the pre-freeze temperature is-60 ℃, and the pre-freeze time is 16h;
6) step 5) is carried out lyophilize through the gel masses after the pre-freeze in loft drier, wherein, the vacuum tightness in the loft drier is that 10Pa (mode that adopts single pump to vacuumize), temperature are to carry out lyophilize under-60 ℃ the condition, and freeze-drying time is 48h;
7) the aluminium hydroxide pressed powder that step 6) is obtained grinds evenly, places retort furnace to heat up, and temperature rise rate is 5 ℃/min, is warming up to 500 ℃ of roastings 3 hours, promptly obtains the high-specific area nano alumina material of present embodiment preparation; Nano alumina powder jointed as shown in the figure pattern, Figure 1A are nano alumina powder jointed transmission electron microscope photo, and Figure 1B is nano alumina powder jointed high-resolution-ration transmission electric-lens photo.
Embodiment 2
The preparation method is identical with embodiment 1, and difference is that the pre-freeze temperature is-40 ℃, and products obtained therefrom is the high-specific area nano alumina material of present embodiment preparation.
Embodiment 3
The preparation method is identical with embodiment 1, and difference is that the pre-freeze temperature is-50 ℃, and products obtained therefrom is the high-specific area nano alumina material of present embodiment preparation.
Embodiment 4
The preparation method is identical with embodiment 1, and difference is that the pre-freeze time is 4h, and products obtained therefrom is the high-specific area nano alumina material of present embodiment preparation.
Embodiment 5
The preparation method is identical with embodiment 1, and difference is that the pre-freeze time is 6h, and products obtained therefrom is the high-specific area nano alumina material of present embodiment preparation.
Embodiment 6
The preparation method is identical with embodiment 1, and difference is that the pre-freeze time is 8h, and products obtained therefrom is the high-specific area nano alumina material of present embodiment preparation.
Embodiment 7
The preparation method is identical with embodiment 1, and difference is that the pre-freeze time is 12h, and products obtained therefrom is the high-specific area nano alumina material of present embodiment preparation.
Embodiment 8
The preparation method is identical with embodiment 1, and difference is that the pre-freeze time is 24h, and products obtained therefrom is the high-specific area nano alumina material of present embodiment preparation.
Embodiment 9
The preparation method is identical with embodiment 1, and difference is that the pre-freeze time is 48h, and products obtained therefrom is the high-specific area nano alumina material of present embodiment preparation.
Embodiment 10
The preparation method is identical with embodiment 1, and difference is that rate of temperature fall is 0.5 ℃/min, and products obtained therefrom is the high-specific area nano alumina material of present embodiment preparation.
Embodiment 11
The preparation method is identical with embodiment 1, and difference is that rate of temperature fall is 1 ℃/min, and products obtained therefrom is the high-specific area nano alumina material of present embodiment preparation.
Embodiment 12
The preparation method is identical with embodiment 1, and difference is that rate of temperature fall is 3 ℃/min, and products obtained therefrom is the high-specific area nano alumina material of present embodiment preparation.
Embodiment 13
The preparation method is identical with embodiment 1, and difference is that vacuum tightness is 20Pa in the loft drier, and products obtained therefrom is the high-specific area nano alumina material of present embodiment preparation.
Embodiment 14
The preparation method is identical with embodiment 1, and difference is that vacuum tightness is 15Pa in the loft drier, and products obtained therefrom is the high-specific area nano alumina material of present embodiment preparation.
Embodiment 15
The preparation method is identical with embodiment 1, and difference is that vacuum tightness is 5Pa in the loft drier, and products obtained therefrom is the high-specific area nano alumina material of present embodiment preparation.
Embodiment 16
The preparation method is identical with embodiment 1, and difference is that freeze-drying time is 4h, and products obtained therefrom is the high-specific area nano alumina material of present embodiment preparation.
Embodiment 17
The preparation method is identical with embodiment 1, and difference is that freeze-drying time is 8h, and products obtained therefrom is the high-specific area nano alumina material of present embodiment preparation.
Embodiment 18
The preparation method is identical with embodiment 1, and difference is that freeze-drying time is 12h, and products obtained therefrom is the high-specific area nano alumina material of present embodiment preparation.
Embodiment 19
The preparation method is identical with embodiment 1, and difference is that freeze-drying time is 24h, and products obtained therefrom is the high-specific area nano alumina material of present embodiment preparation.
Embodiment 20
The preparation method is identical with embodiment 1, and difference is that freeze-drying time is 64h, and products obtained therefrom is the high-specific area nano alumina material of present embodiment preparation.
Embodiment 21
The preparation method is identical with embodiment 1, and difference is that freeze-drying time is 72h, and products obtained therefrom is the high-specific area nano alumina material of present embodiment preparation.
Embodiment 22
The preparation method is identical with embodiment 1, and difference is that calcining temperature is 600 ℃, and products obtained therefrom is the high-specific area nano alumina material of present embodiment preparation.
Embodiment 23
The preparation method is identical with embodiment 1, and difference is that calcining temperature is 700 ℃, and products obtained therefrom is the high-specific area nano alumina material of present embodiment preparation.
Embodiment 24
The preparation method is identical with embodiment 1, and difference is that calcining temperature is 450 ℃, and products obtained therefrom is the high-specific area nano alumina material of present embodiment preparation.
The character of table 1 embodiment 1～24 gained aluminum oxide
| Embodiment | Specific surface area (m 2/g) | Pore volume (cm 3/g) | Mean pore size (nm) | The thing phase |
| ??1 | ??551.5 | ??2.02 | ??7.6 | ??γ-Al 20 3 |
| ??2 | ??465.2 | ??1.85 | ??9.6 | ??γ-Al 20 3 |
| ??3 | ??496.5 | ??2.00 | ??10.2 | ??γ-Al 20 3 |
| ??4 | ??457.6 | ??1.84 | ??12.4 | ??γ-Al 20 3 |
| ??5 | ??475.8 | ??1.86 | ??11.2 | ??γ-Al 20 3 |
| ??6 | ??476.0 | ??1.89 | ??11.4 | ??γ-Al 20 3 |
| ??7 | ??499.7 | ??1.93 | ??9.6 | ??γ-Al 20 3 |
| ??8 | ??548.6 | ??2.03 | ??7.4 | ??γ-Al 20 3 |
| ??9 | ??555.5 | ??2.03 | ??7.3 | ??γ-Al 20 3 |
| Embodiment | Specific surface area (m 2/g) | Pore volume (cm 3/g) | Mean pore size (nm) | The thing phase |
| ??10 | ??466.4 | ??1.81 | ??12.3 | ??γ-Al 20 3 |
| ??11 | ??516.2 | ??1.96 | ??10.4 | ??γ-Al 20 3 |
| ??12 | ??543.0 | ??1.99 | ??7.8 | ??γ-Al 20 3 |
| ??13 | ??476.6 | ??1.88 | ??13.1 | ??γ-Al 20 3 |
| ??14 | ??477.6 | ??1.84 | ??12.4 | ??γ-Al 20 3 |
| ??15 | ??555.4 | ??2.17 | ??7.7 | ??γ-Al 20 3 |
| ??16 | ??440.8 | ??1.77 | ??13.6 | ??γ-A1 20 3 |
| ??17 | ??491.3 | ??1.85 | ??11.5 | ??γ-Al 20 3 |
| ??18 | ??500.9 | ??1.84 | ??11.5 | ??γ-Al 20 3 |
| ??19 | ??514.8 | ??1.90 | ??10.8 | ??γ-Al 20 3 |
| ??20 | ??543.1 | ??2.00 | ??8.6 | ??γ-Al 20 3 |
| ??21 | ??511.0 | ??1.93 | ??12.0 | ??γ-Al 20 3 |
| ??22 | ??474.5 | ??1.73 | ??14.5 | ??γ-Al 20 3 |
| ??23 | ??400.8 | ??1.55 | ??16.3 | ??γ-Al 20 3 |
| ??24 | ??593.2 | ??2.26 | ??8.4 | ??γ-Al 20 3 |
Embodiment 25
The preparation method is identical with embodiment 1, and it is the high-specific area nano alumina material of present embodiment preparation that difference is to have used 330ml hexanaphthene, products obtained therefrom.
Embodiment 26
The preparation method is identical with embodiment 1, and it is the high-specific area nano alumina material of present embodiment preparation that difference is to have used 240ml hexanaphthene, products obtained therefrom.
Embodiment 27
The preparation method is identical with embodiment 1, and difference is that feeding rate is 5ml/min, and products obtained therefrom is the high-specific area nano alumina material of present embodiment preparation.
Embodiment 28
The preparation method is identical with embodiment 1, and difference is that feeding rate is 20ml/min, and products obtained therefrom is the high-specific area nano alumina material of present embodiment preparation.
Embodiment 29
The preparation method is identical with embodiment 1, and difference is to use the ammonia soln of 3.0M to replace the ammonium carbonate solution of 2.0M, and products obtained therefrom is the high-specific area nano alumina material of present embodiment preparation.
Embodiment 30
The preparation method is identical with embodiment 1, and difference is that the mol ratio of water and tensio-active agent is 20, and products obtained therefrom is the high-specific area nano alumina material of present embodiment preparation.
Embodiment 31
The preparation method is identical with embodiment 1, and difference is that the mol ratio of water and tensio-active agent is 30, and products obtained therefrom is the high-specific area nano alumina material of present embodiment preparation.
Embodiment 32
The preparation method is identical with embodiment 1, difference is under 40 ℃ the ammonium carbonate solution 100ml of 2.0M at the uniform velocity is added drop-wise in the aluminum nitrate microemulsion in the stirring with the speed of 10ml/min, and products obtained therefrom is the high-specific area nano alumina material of present embodiment preparation.
Embodiment 33
The preparation method is identical with embodiment 1, difference is under 20 ℃ the ammonium carbonate solution 100ml of 2.0M at the uniform velocity is added drop-wise in the aluminum nitrate microemulsion in the stirring with the speed of 10ml/min, and products obtained therefrom is the high-specific area nano alumina material of present embodiment preparation.
Embodiment 34
The preparation method is identical with embodiment 1, and difference is that the pH value is 10, and products obtained therefrom is the high-specific area nano alumina material of present embodiment preparation.
Embodiment 35
The preparation method is identical with embodiment 1, and difference is that the pH value is 8, and products obtained therefrom is the high-specific area nano alumina material of present embodiment preparation.
Embodiment 36
The preparation method is identical with embodiment 1, and difference is to have used 290ml oleic acid, 120ml Triton X-100 and 100ml propyl carbinol to mix and stirs, and products obtained therefrom is the high-specific area nano alumina material of present embodiment preparation.
Embodiment 37
The preparation method is identical with embodiment 1, difference has been to use mixture (volume ratio 1: 1), 120ml Triton X-100 and the 100ml propyl carbinol of 290ml sherwood oil and hexanaphthene to mix and has stirred, and products obtained therefrom is the high-specific area nano alumina material of present embodiment preparation.
Embodiment 38
The preparation method is identical with embodiment 1, and difference is to have used 290ml hexanaphthene, 120ml Triton X-100 and 100ml aniline to mix and stirs, and products obtained therefrom is the high-specific area nano alumina material of present embodiment preparation.
Embodiment 39
The preparation method is identical with embodiment 1, difference has been to use 290ml hexanaphthene, 120ml Triton X-100 and 100ml propyl carbinol to mix with the mixture (volume ratio 1: 1) of acrylamide and has stirred, and products obtained therefrom is the high-specific area nano alumina material of present embodiment preparation.
Embodiment 40
The preparation method is identical with embodiment 1, and difference is to have used 290ml hexanaphthene, 120ml cetyl trimethylammonium bromide (CTAB) and 100ml propyl carbinol to mix and stirs, and products obtained therefrom is the high-specific area nano alumina material of present embodiment preparation.
Embodiment 41
The preparation method is identical with embodiment 1, difference has been to use the mixture (volume ratio 1: 1) and the mixing of 100ml propyl carbinol of 290ml hexanaphthene, 120ml Triton X-100 and two octadecyl ammonium chloride and has stirred, and products obtained therefrom is the high-specific area nano alumina material of present embodiment preparation.
Embodiment 42
The preparation method is identical with embodiment 1, and difference has been to use the aluminum sulfate aqueous solution 100ml of 1.0M, and products obtained therefrom is the high-specific area nano alumina material of present embodiment preparation.
The character of the nano alumina material that embodiment 25-42 is prepared is as follows: be gama-alumina thing phase, median size 5-20nm, specific surface area 400-600m
2/ g, pore volume 1.5-2.5cm
3/ g, mean pore size 5-20nm.
Should be noted that and understand, under the situation that does not break away from the desired the spirit and scope of the present invention of accompanying Claim, can make various modifications and improvement the present invention of foregoing detailed description.Therefore, the scope of claimed technical scheme is not subjected to the restriction of given any specific exemplary teachings.
Claims (9)
1. the method for a preparing nano aluminum oxide through vacuum freeze drying technology comprises the steps:
1) preparation organic phase: the consumption that at first calculates required oil phase A, surfactant B and cosurfactant C, according to volume ratio surfactant B: cosurfactant C=1: 1～5: 1, oil phase A: (surfactant B+cosurfactant C)=1: 1～5: 1 batchings; Oil phase A, the surfactant B for preparing joined in the reaction vessel successively with cosurfactant C mix, form even organic phase;
2) mixing while stirring, is that the inorganic aluminate aqueous solution of 0.05M-3.0M mixes with the organic phase that step 1) obtains with concentration range, and the molar ratio range of the tensio-active agent in control water and the step 1) is 10-40, forms the stable microemulsion liquid system;
3) mix while stirring, between 15 ℃-80 ℃, alkaline precipitating agent is added drop-wise to step 2) in the microemulsion system that obtains, mix, wherein, rate of addition is 1ml/min-40ml/min, under the alkaline condition of pH=7-13, stop to drip alkaline precipitating agent, inorganic aluminate and alkaline precipitating agent are reacted in minute water nuclear, reaction times is 1-10h, generates the aluminium hydroxide slurry;
4) the aluminium hydroxide slurry that step 3) is obtained under 15 ℃-80 ℃, pH value are condition between the 7-13, wore out 5-50 hour;
5) the aluminium hydroxide slurries filtration that step 4) is obtained washs successively with deionized water and organic solvent respectively, obtains aluminum hydroxide filter cake;
6) aluminum hydroxide filter cake that step 5) is obtained, place the cold-trap of vacuum freeze drier to carry out pre-freeze, described pre-freeze is the complete glaciation of water with free state in the aluminum hydroxide filter cake wet stock, for drying stage is prepared, the rate of temperature fall of pre-freeze process is 0.1-20 ℃/min, the pre-freeze temperature is-20 ℃-90 ℃, and the pre-freeze time is 2-48h;
7) with step 6) through the gel masses after the pre-freeze, be to carry out lyophilize under-30 ℃～-70 ℃ the condition in temperature, freeze-drying time is 2-96h, obtains the aluminium hydroxide pressed powder;
8) the aluminium hydroxide pressed powder that step 7) is obtained grinds evenly, again in 300 ℃ of-1000 ℃ of following roasting 2-10 hours, promptly obtains having the nano alumina material of high-specific surface area.
2. the method for preparing nano aluminum oxide through vacuum freeze drying technology according to claim 1, it is characterized in that: described oil phase A contains a kind of in alkane, sherwood oil, lubricant base, oleic acid or the stearic acid of six to eight carbon atoms, or with the mixing more than 2 kinds of arbitrary proportion.
3. the method for preparing nano aluminum oxide through vacuum freeze drying technology according to claim 1, it is characterized in that: described surfactant B is Triton X-100, alkyl trimethyl ammonium halide, alkyl dimethyl ammonium halide, alkyl ammonium halide, alcoxyl phthalein amine series, Aerosol OT, alkyl sodium sulfonate, sodium alkyl benzene sulfonate, sodium alkyl sulfate, fatty alcohol-polyoxyethylene ether series, alkylphenol polyoxyethylene series, nonyl benzene polyethenoxy ether class or tween, or with the mixing more than 2 kinds in they of arbitrary proportion.
4. the method for preparing nano aluminum oxide through vacuum freeze drying technology according to claim 1, it is characterized in that: described cosurfactant C is propyl carbinol, n-hexyl alcohol, Pentyl alcohol, n-Octanol, aniline, acrylamide, N-N-isopropylacrylamide, vinylformic acid, methacrylic acid, sodium acrylate or N-vinyl pyridine, perhaps with the mixing more than 2 kinds in they of arbitrary proportion.
5. the method for preparing nano aluminum oxide through vacuum freeze drying technology according to claim 1 is characterized in that: described inorganic aluminate is anhydrous or contains a kind of in aluminum nitrate, Tai-Ace S 150 or the aluminum chloride of crystal water or with the mixing 2 kind or more of arbitrary proportion in them.
6. the method for preparing nano aluminum oxide through vacuum freeze drying technology according to claim 1, it is characterized in that: described precipitation agent is a kind of in volatile salt, bicarbonate of ammonia, ammonia, ammoniacal liquor, urea, hexamethylenetetramine, ammonium citrate, alkali-metal oxyhydroxide or the alkali-metal carbonate or with the two or more mixing of arbitrary proportion, adds with aqueous solution form.
7. the method for preparing nano aluminum oxide through vacuum freeze drying technology according to claim 1 is characterized in that: wash in the described step 5) and be to use deionized water wash 1-10 time, use the 10-2000ml deionized water at every turn; Use organic solvent washing 1-10 time afterwards again, use the 10-2000ml organic solvent at every turn;
Wherein said organic solvent is one or more the mixing in ethanol, methyl alcohol, the acetone.
8. the method for preparing nano aluminum oxide through vacuum freeze drying technology according to claim 1, it is characterized in that: the lyophilize condition in the described step 7) is: the vacuum tightness in the loft drier is 0.1-100Pa.
9. the method for preparing nano aluminum oxide through vacuum freeze drying technology according to claim 1, it is characterized in that: roasting condition is in the described step 8):, the temperature rise rate in the retort furnace is 0.5-20 ℃/min.
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