CN102491388A - Preparation method of nano mesoporous alumina - Google Patents
Preparation method of nano mesoporous alumina Download PDFInfo
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- CN102491388A CN102491388A CN2011103993402A CN201110399340A CN102491388A CN 102491388 A CN102491388 A CN 102491388A CN 2011103993402 A CN2011103993402 A CN 2011103993402A CN 201110399340 A CN201110399340 A CN 201110399340A CN 102491388 A CN102491388 A CN 102491388A
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Abstract
The invention provides a preparation method of nano mesoporous alumina and relates to a nano material. The preparation method of nano mesoporous alumina has the advantages that a surfactant does not need to be added in the preparation process, preparation process is simple and environment-friendly and green, cost is low, prepared alumina has large specific surface area and proper pore size distribution, and application prospect is wide. The preparation method has the following steps of: adding gardenia in deionized water and then boiling; cooling and then leaching, wherein a filtrate is a gardenia extraction liquid; dissolving aluminum nitrate in the gardenia extraction liquid so that the concentration of the mixed liquid is 0.04-0.2mol/L; adding ammonium hydroxide so as to obtain biomass aluminum sol; ageing the biomass aluminum sol to obtain biomass alumina gel; and leaching the biomass alumina gel, drying a filter cake and then roasting, so as to obtain nano mesoporous alumina.
Description
Technical field
The present invention relates to a kind of nano material, especially relate to a kind of preparation method who utilizes the mesoporous nano aluminum oxide of natural gardenia extract and aluminium salt complexing action.
Background technology
Aluminum oxide, particularly γ-Al
2O
3, have suitable specific surface area, pore volume and pore size distribution, excellent mechanical intensity and thermostability are widely used in chemical industry as catalyzer, carrier and sorbent material.The preparation of aluminum oxide adopts acid-base neutralisation to generate pseudo-boehmite usually, forms aluminum oxide through roasting again.Can be divided into following several types according to raw material: (1) acid precipitation method; It is the neutralization reaction of aluminium salt and alkali; The aluminium salt that adopts has aluminum chloride, aluminum nitrate and Tai-Ace S 150 etc., and alkali has ammoniacal liquor, sodium hydroxide and Pottasium Hydroxide etc., and Chinese patent ZL94107295.9 discloses a kind of preparation method of aluminum oxide; It carries out preparing activated alumina after the neutralization reaction to contain aluminum ions acidic aqueous solution and to contain or do not contain aluminum ions alkaline aqueous solution, and used method is an acid system.(2) alkaline precipitation, promptly aluminate with acid neutralization reaction, used aluminium salt mainly is sodium metaaluminate and potassium metaaluminate, used acid has nitric acid, sulfuric acid, hydrochloric acid and carbonic acid gas etc.; It is the method for feedstock production activated alumina with sodium metaaluminate and carbonic acid gas that Chinese patent ZL02158286.6 discloses a kind of, is alkaline process.(3) the metathesis neutralization reaction of aluminium salt and aluminate, pseudobochmite powder that the open support of the catalyst of Chinese patent ZL98801104.2 is used and preparation method thereof is metathesis neutralization reaction method.
In order to obtain suitable pore size distribution, on above-mentioned preparation process basis, need to add template usually.Mostly template is tensio-active agent, is divided into aniorfic surfactant, cationic surfactant, non-ionics and some superpolymer etc.People such as Lee (Hyun Chul Lee et al.; Synthesis of Unidirectional Alumina Nanostructures without Added Organic Solvents; Journal of the American Chemical Society; 2003,10 (125), 2882-2883) investigated 4 kinds of tensio-active agent: CH of interpolation
3(CH
2)
15N (CH
3)
3-Br, CH
3(CH
2)
15-(PEO)
2-OH, CH
3(CH
2)
14COOH and CH
3(CH
2)
15NH
2To the aluminum oxide The properties that makes.Chinese patent ZL200610113015.4 discloses a kind of natural phant root of kudzu vine that utilizes and is template, through the nitric acid pre-treatment, soaks through aluminum trichloride solution again, and ammonia is smoked to be soaked, and high-temperature roasting obtains gama-alumina.It is characterized in that this layer stephanoporate gamma-aluminum oxide has and the similar pore passage structure of wild root of kudzu vine stem pore passage structure, its existing pore size distribution is mesoporous 6～7nm's, has the aperture to be distributed in the macropore of hundreds of nanometer to tens micron again; This layer stephanoporate gamma-aluminum oxide is after through 600～1000 ℃ calcining, and its specific surface area is still up to 170～180m
2/ g, pore capacities reaches 0.3～0.4cm
3/ g.
Summary of the invention
The object of the present invention is to provide a kind of preparation process to need not to add tensio-active agent; Preparation technology is simple; Cost is low, and is environmentally friendly, environmental protection; The aluminum oxide that makes has than bigger serface and suitable pore size distribution, has the preparation method of the mesoporous nano aluminum oxide of wide application prospect.
The present invention includes following steps:
1) cape jasmine is added in the deionized water, boil, cooling back suction filtration, filtrating is the cape jasmine extract;
2) aluminum nitrate is dissolved in the cape jasmine extract of step 1) gained, concentration is 0.04～0.2mol/L, adds volatile caustic, gets biomass aluminium colloidal sol;
3) with step 2) the biomass aluminium colloidal sol of gained is aging, the biomass alumina gel;
4) with the biomass alumina gel suction filtration of step 3) gained, again with behind the filtration cakes torrefaction, roasting promptly gets the mesoporous nano aluminum oxide.
In step 1), the mass ratio of said cape jasmine and water can be 1: (25～200), the said time of boiling can be 5～10min.
In step 2) in, said adding volatile caustic to pH value is 6～10.
In step 3), said aging, preferably under agitation aging, the aged temperature can 60～90 ℃, and the aged time can be 4～50h.
In step 4), said exsiccant temperature can be 60～120 ℃, and the exsiccant time can be 12～36h; The temperature of said roasting can be 500～800 ℃, and the time of roasting can be 2～6h.
The preparation method of mesoporous nano aluminum oxide provided by the invention and mechanism: contain a large amount of electronegativity groups in the cape jasmine; Like hydroxyl, carboxyl, ester group and amino etc.; In boiling part, these groups in the cape jasmine are dissolved in the extract, contain a large amount of groups in the cape jasmine extract that therefore obtains.Aluminum nitrate is dissolved in the cape jasmine extract, trivalent aluminium ion Al
3+Be easy to through coordination and these electronegativity group complexings.After adding alkali lye, the aluminum ion slowly-releasing of complexing is white lake and interacts with cape jasmine biomass organo-functional group.Through certain thermal treatment, the alumina precursor dehydration is converted into the mesoporous nano aluminum oxide, and the remaining a small amount of group in simultaneous oxidation aluminium surface shows the good adsorption performance in the process of absorption heavy metal.The present invention adds the natural gardenia extract on the traditional technology basis, the preparation process need not to add tensio-active agent; Preparation technology is simple, and cost is low, and is environmentally friendly; Environmental protection, the aluminum oxide that makes have bigger specific surface area and suitable pore size distribution, are with a wide range of applications.
Description of drawings
X-ray diffractogram behind the alumina lap powdered that Fig. 1 makes for the embodiment of the invention 1.In Fig. 1, X-coordinate be diffraction angle 2 θ (°), ordinate zou is an intensity.
X-ray diffractogram behind the alumina lap powdered that Fig. 2 makes for the embodiment of the invention 4.In Fig. 2, X-coordinate be diffraction angle 2 θ (°), ordinate zou is an intensity.
The isothermal nitrogen adsorption of the aluminum oxide that Fig. 3 makes for the embodiment of the invention 1-desorption line.In Fig. 3, X-coordinate is relative pressure (P/P
0), ordinate zou is absorption volume (cm
3/ g).
The pore size distribution curve of the aluminum oxide that Fig. 4 makes for the embodiment of the invention 1.In Fig. 4, X-coordinate is bore dia (nm), and ordinate zou is dV/dD (cm
3/ g/nm).
The infrared spectrogram of the aluminum oxide after the absorption that the dried powder of cape jasmine extract that Fig. 5 makes for the present invention, the aluminum oxide that reference example 1 makes, aluminum oxide that embodiment 1 makes and embodiment 16 make.In Fig. 5, X-coordinate is wave number (cm
-1), ordinate zou is a transmittance; The dried powder of cape jasmine extract that a makes for the present invention; B is the aluminum oxide that reference example 1 makes; The aluminum oxide that c makes for embodiment 1; Aluminum oxide after the absorption that d makes for embodiment 16.
Embodiment
Below describe through specific embodiment, but do not limit the scope that application of the present invention is asked for protection.
Embodiment 1
Take by weighing cape jasmine 9.00g, add the 450mL deionized water, promptly the mass ratio of cape jasmine and water is 1: 50, boils 8min, cooling and suction filtration.Take by weighing 7.502g nine water aluminum nitrate crystal, be dissolved in the 300mL cape jasmine extract, in this solution, drip volatile caustic to pH=9, put into the water bath with thermostatic control magnetic stirring apparatus, in 80 ℃ of down aging 24h with dropper; Take out suction filtration, filter cake places loft drier, dry 24h under 80 ℃, and grinding is placed in the retort furnace, is warming up to 600 ℃ of roasting 4h by 10 ℃/min of temperature rise rate; After being cooled to room temperature, with the gained solids through compressing tablet (20kN pressure), break into pieces and sieve and obtain 60～80 purpose alumina particles.Its main character is seen table 1.
The nanometer gama-alumina that the makes last X ray diffracting spectrum of pulverizing is seen Fig. 1.In 2 θ=66.8 °, 60.2 °, 45.7 °, 37.3 °, 33.5 ° and 18.9 ° of diffraction peaks of locating correspond respectively to (440) of gama-alumina crystal face, (511), (400), (311), (220) and (111).
The isothermal nitrogen adsorption of the nanometer gama-alumina that makes-desorption line is seen Fig. 3.Hysteresis loop shape among the figure shows that this aluminum oxide had both had the tubulose pore of the both ends open of H1 type representative between H1 type and H2 type, have the thin neck of H2 type representative and the hole of the tubular or ink bottle shape of wide body again.The pore size distribution curve of the nanometer gama-alumina that makes is seen Fig. 4.Curve is to calculate through BJH (Barrett, Joyner and Halenda) method among the figure, and the aluminum oxide aperture narrow distribution that as can be seen from Figure 4 makes concentrates on 4～6nm.
Reference example 1
The preparation method is similar with embodiment 1, and its difference is to change the cape jasmine extract into deionized water.
Fig. 5 is the dried powder of cape jasmine extract (a), the aluminum oxide that reference example 1 makes (b), the infrared spectrogram of the aluminum oxide (d) after the absorption that aluminum oxide that embodiment 1 makes (c) and embodiment 16 make.(curve is a) at 1519cm for the dried powder of cape jasmine extract among the figure
-1, 1077cm
-1And 1048cm
-1Absorption peak is arranged.At 1519cm
-1The peak of position is the sum of fundamental frequencies peak (δ N-H+vC-N) of stretching vibration of flexural vibration and the C-N key of N-H key amino in the biomass.At 1077cm
-1The peak of position is the sum of fundamental frequencies peak (δ O-H+vC-O) of stretching vibration of flexural vibration and C-O key of the O-H key of hydroxyl.At 1048cm
-1The peak of position is-the C=CCOOR group in the stretching vibration peak of C-O key.Embodiment 1 prepared aluminum oxide (curve c) also has absorption peak in the corresponding position, explain to contain remaining functional group on the aluminum oxide that makes.(after being the alumina adsorption nickel ion that makes of embodiment 1, in the infrared spectrum of curve (d), the absorption peak position changes or disappears, and explains that the absorption of nickel ion is relevant with these functional groups at embodiment 16.And the prepared aluminum oxide of reference example 1 (the preparation process is not added the cape jasmine extract, curve b) does not then contain these functional groups.Adsorptive capacity is described what also bigger relation is arranged with the functional group of prepared alumina surface.
Embodiment 2～4
The preparation method is similar with embodiment 1, its difference be with cape jasmine and water ratio change 1: 200 into, 1: 100 and 1: 25.
X ray diffracting spectrum behind the alumina lap powdered that embodiment 4 makes is seen Fig. 2.Do not see tangible gama-alumina characteristic peak among the figure, be unformed aluminum oxide.
Table 1 embodiment 1～4 product main character
| Sample | Cape jasmine and water ratio | Specific surface area (m 2/g) | Pore volume (cm 3/g) | Mean pore size (nm) | The thing phase |
| Embodiment 2 | 1∶200 | 322 | 0.359 | 2.21 | γ |
| Embodiment 3 | 1∶100 | 338 | 0.292 | 3.79 | γ |
| Embodiment 1 | 1∶50 | 313 | 0.378 | 4.87 | γ |
| Embodiment 4 | 1∶25 | 93.7 | 0.0684 | 2.48 | Unformed |
Embodiment 5～8
The preparation method is similar with embodiment 1, and its difference is to change volatile caustic titration end point pH value into 6,7,8 and 10.
Table 2 embodiment 5～8 product main character
| Sample | Titration end point pH value | Specific surface area (m 2/g) | Pore volume (cm 3/g) | Mean pore size (nm) | The thing phase |
| Embodiment 5 | pH＝6 | 225 | 0.223 | 4.52 | γ |
| Embodiment 6 | pH＝7 | 258 | 0.374 | 4.15 | γ |
| Embodiment 7 | pH＝8 | 268 | 0.322 | 4.52 | γ |
| Embodiment 1 | pH＝9 | 313 | 0.378 | 4.87 | γ |
| Embodiment 8 | pH＝10 | 306 | 0.356 | 3.90 | γ |
Embodiment 9～11
The preparation method is similar with embodiment 1, and its difference is to change aging temperature into 60 ℃, 70 ℃ and 90 ℃.
Table 3 embodiment 9～11 product main character
| Sample | Aging temperature (℃) | Specific surface area (m 2/g) | Pore volume (cm 3/g) | Mean pore size (nm) | The thing phase |
| Embodiment 9 | 60 | 173 | 0.221 | 4.31 | |
| Embodiment | |||||
| 10 | 70 | 189 | 0.184 | 4.37 | Unformed |
| Embodiment 1 | 80 | 313 | 0.378 | 4.87 | γ |
| Embodiment 11 | 90 | 286 | 0.309 | 4.88 | γ |
Embodiment 12～15
The preparation method is similar with embodiment 1, and its difference is to change digestion time into 4h, 12h, 16h and 50h.
Table 4 embodiment 12～15 product main character
| Sample | Digestion time (h) | Specific surface area (m 2/g) | Pore volume (cm 3/g) | Mean pore size (nm) | The thing phase |
| Embodiment 12 | 4 | 283 | 0.481 | 6.03 | Unformed |
| Embodiment 13 | 12 | 266 | 0.276 | 4.26 | Unformed |
| Embodiment 14 | 16 | 246 | 0.224 | 4.01 | Unformed |
| Embodiment 1 | 24 | 313 | 0.378 | 4.87 | γ |
| Embodiment 15 | 50 | 273 | 0.377 | 4.82 | γ |
Embodiment 16
Embodiment 1 gained aluminum oxide as sorbent material, in 30 ℃ of following absorbed Ni ions, is measured the adsorption activity of sorbent material to nickel ion, and its active result sees table 5.
Reference example 2
Aluminum oxide (its specific surface area 169m that reference example 1 is made
2/ g, pore volume 0.291cm
3/ g, mean pore size 4.97nm) as sorbent material, investigate its activity with embodiment 16 identical activity rating conditions, the result sees table 5.
Reference example 3
Commercial alumina (is taken from Zibo safe photoinitiator chemical ltd, its specific surface area 307m
2/ g, pore volume 0.746cm
3/ g, mean pore size 4.51nm) as sorbent material, investigate its activity with embodiment 16 identical activity rating conditions, the result sees table 5.
Table 5 adsorbent activity evaluation result
| Embodiment 16 | Reference example 2 | Reference example 3 | |
| Adsorptive capacity (mg/g aluminum oxide) | 3.96 | 0.250 | 0.568 |
Embodiment 17
Activity rating condition according to embodiment 16 is carried out the adsorption-desorption regeneration tests, and its active result sees table 6.
Table 6 adsorbent reactivation activity rating result
| Number of times | Adsorptive capacity (mg/g aluminum oxide) | Desorption rate (mg/g aluminum oxide) | Desorption rate (%) |
| 1 | 3.96 | 3.42 | 86.4 |
| 2 | 3.24 | 3.15 | 97.2 |
| 3 | 3.06 | 2.71 | 88.6 |
Claims (8)
1. the preparation method of a mesoporous nano aluminum oxide is characterized in that may further comprise the steps:
1) cape jasmine is added in the deionized water, boil, cooling back suction filtration, filtrating is the cape jasmine extract;
2) aluminum nitrate is dissolved in the cape jasmine extract of step 1) gained, concentration is 0.04～0.2mol/L, adds volatile caustic, gets biomass aluminium colloidal sol;
3) with step 2) the biomass aluminium colloidal sol of gained is aging, the biomass alumina gel;
4) with the biomass alumina gel suction filtration of step 3) gained, again with behind the filtration cakes torrefaction, roasting promptly gets the mesoporous nano aluminum oxide.
2. the preparation method of a kind of mesoporous nano aluminum oxide as claimed in claim 1 is characterized in that in step 1), and the mass ratio of said cape jasmine and water is 1: 25～200.
3. the preparation method of a kind of mesoporous nano aluminum oxide as claimed in claim 1 is characterized in that in step 1), and the said time of boiling is 5～10min.
4. the preparation method of a kind of mesoporous nano aluminum oxide as claimed in claim 1 is characterized in that in step 2) in, said adding volatile caustic to pH value is 6～10.
5. the preparation method of a kind of mesoporous nano aluminum oxide as claimed in claim 1 is characterized in that in step 3), and is said aging, is under agitation aging.
6. like the preparation method of claim 1 or 4 described a kind of mesoporous nano aluminum oxide, it is characterized in that 60～90 ℃ of said aged temperature, the aged time is 4～50h.
7. the preparation method of a kind of mesoporous nano aluminum oxide as claimed in claim 1 is characterized in that in step 4), and said exsiccant temperature is 60～120 ℃, and the exsiccant time is 12～36h.
8. the preparation method of a kind of mesoporous nano aluminum oxide as claimed in claim 1 is characterized in that in step 4), and the temperature of said roasting is 500～800 ℃, and the time of roasting is 2～6h.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105460963A (en) * | 2015-12-11 | 2016-04-06 | 李金秀 | Preparation method of nanometer mesoporous alumina |
| CN106512918A (en) * | 2016-11-16 | 2017-03-22 | 上海绿强新材料有限公司 | An alkali-modified alumina material having a high specific surface area, a preparing method thereof and applications of the material |
| CN110790291A (en) * | 2018-08-01 | 2020-02-14 | 中国石油化工股份有限公司 | Preparation method of pseudo-boehmite |
| CN110882684A (en) * | 2019-12-02 | 2020-03-17 | 厦门大学 | Alumina carrier with secondary pore structure and preparation method and application thereof |
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|---|---|---|---|---|
| CN100558638C (en) * | 2006-09-07 | 2009-11-11 | 中国科学院理化技术研究所 | Layer stephanoporate gamma-aluminum oxide and its production and use |
| CN101804346A (en) * | 2009-11-03 | 2010-08-18 | 厦门大学 | Nanometer palladium catalyst for hydrogenation of anthraquinone and preparation method thereof |
-
2011
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN100558638C (en) * | 2006-09-07 | 2009-11-11 | 中国科学院理化技术研究所 | Layer stephanoporate gamma-aluminum oxide and its production and use |
| CN101804346A (en) * | 2009-11-03 | 2010-08-18 | 厦门大学 | Nanometer palladium catalyst for hydrogenation of anthraquinone and preparation method thereof |
Non-Patent Citations (2)
| Title |
|---|
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| 盛景云等: "一种新的γ-Al2O3制备方法", 《厦门大学学报(自然科学版)》, vol. 42, no. 5, 30 September 2003 (2003-09-30), pages 626 - 628 * |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105460963A (en) * | 2015-12-11 | 2016-04-06 | 李金秀 | Preparation method of nanometer mesoporous alumina |
| CN105460963B (en) * | 2015-12-11 | 2017-05-10 | 李金秀 | Preparation method of nanometer mesoporous alumina |
| CN106512918A (en) * | 2016-11-16 | 2017-03-22 | 上海绿强新材料有限公司 | An alkali-modified alumina material having a high specific surface area, a preparing method thereof and applications of the material |
| CN106512918B (en) * | 2016-11-16 | 2019-05-14 | 上海绿强新材料有限公司 | A kind of alkali modification alumine with high specific surface area material and its preparation method and application |
| CN110790291A (en) * | 2018-08-01 | 2020-02-14 | 中国石油化工股份有限公司 | Preparation method of pseudo-boehmite |
| CN110790291B (en) * | 2018-08-01 | 2022-07-12 | 中国石油化工股份有限公司 | Preparation method of pseudo-boehmite |
| CN110882684A (en) * | 2019-12-02 | 2020-03-17 | 厦门大学 | Alumina carrier with secondary pore structure and preparation method and application thereof |
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