CN1209289C - Prepn. of aluminium sol - Google Patents
Prepn. of aluminium sol Download PDFInfo
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- CN1209289C CN1209289C CN 00110421 CN00110421A CN1209289C CN 1209289 C CN1209289 C CN 1209289C CN 00110421 CN00110421 CN 00110421 CN 00110421 A CN00110421 A CN 00110421A CN 1209289 C CN1209289 C CN 1209289C
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- colloidal sol
- preparation
- aluminium colloidal
- acid
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Abstract
The present invention relates to a preparation method of aluminium sol, which is characterized in that inorganic aluminum salts are used as raw material under the condition of room temperature; precipitates are prepared by a method of adding excess alkali, so the pH value is larger than 9; the precipitates are added with acid as a dispergation catalyst after washed; the range of the molar ratio of (H<+>)/(Al<3+>) is from 0.07 to 0.50; stable clear aluminium sol is formed under the action of ultrasonic waves; the ultrasonic waves comprise the physical parameters that the frequency is from 20 to 50KHz, and the sound intensity is from 50 to 150W. The present invention has the advantages of low cost of the raw material and simple and controllable method, and the prepared aluminium sol has the advantages of uniform granularity, high particle dispersancy and good stability.
Description
The preparation that the present invention relates to provides a kind of presoma---the technology of preparing of alumina sol of alumina material especially.
Aluminum oxide is the carrier that is most widely used in the Industrial Catalysis agent carrier, and aluminum oxide is low price not only, and the desired crystalline phase of various catalyzed reaction, and rerum naturas such as surface-area and pore size distribution range can obtain by the change of preparation condition.Known aluminum oxide has multiple crystalline phase, as γ-Al
2O
3, η-Al
2O
3, θ-Al
2O
3, κ-Al
2O
3, χ-Al
2O
3, α-Al
2O
3α-Al wherein
2O
3Be stable state, other is called activated alumina, and its crystalline phase all changes into the α phase when high temperature.Because most commercial catalystss are selected γ-Al
2O
3Be carrier.Its presoma comprises boehmite, other crystalline phases such as pseudo-boehmite.Boehmite wherein, two kinds of oxyhydroxide of pseudo-boehmite are transformed into γ-Al
2O
3Temperature be different.Formula (1), (2) have specifically been explained two kinds of presomas and have been become γ-Al
2O
3And δ-Al
2O
3Temperature.
Therefrom can find if be that presoma not only can be converted into γ-Al under lower temperature with the pseudo-boehmite
2O
3, and have higher thermostability.
For the general industry catalyzer, the pore size distribution of different carriers aluminum oxide can be a micropore, mesopore, and macropore or several hole exist simultaneously.Wherein micropore derives from the interlayer dehydration and the dehydration of hydrate crystallite of alumina hydrate layer shape structure, and the aperture of Xing Chenging is relevant with the crystalline phase of hydrate therefrom.Between the simple particle of oxide hydrate and the space between the offspring forms mesopore, so the size of mesopore depends on the size of primary particle, the factors such as size of shape and accumulation mode and offspring.Macropore is to add suitable weighting agent in the process of extrusion moulding.Form macropore because of after the filling effect roasting of space, the aperture of macropore and the size of particles of weighting agent have good corresponding relation.Through a large amount of practices, people come more and more clearly to recognize that what catalytic performance was had material impact is not total pore volume of catalyzer, but its pore size distribution, be effective pore volume. therefore how prepare according to different catalyzed reactions and have different qualities and (comprise the aperture, pore volume) alumina supporter has caused people's attention, becomes an emphasis of research.D.L Trimm, A.Stanislaus people such as (D.L Trimm, A.Stanislaus Applied Catalysis, 21 (1986) 215-238) have well summed up in the traditional preparation process method every preparation factor to the influence of pore structure.General preparation γ-Al
2O
3Key step comprise: become glue, washing, drying, moulding, roasting.The seventies, B.E.Yoldas (B.E.Yoldas, J.Appl.Chem.Biotechnol, 1973,23.803) adopt sol-gel method to obtain the alumina material of novel homogeneous pore structure, have opened up the new approach for preparing aluminum oxide.From then on be presoma becomes the preparation alumina material through sol-gel process another important method with aluminium colloidal sol.This is because can regulate and control preparation parameter with comparalive ease by sol-gel method, thereby obtains the controlled catalyzer of various physico-chemical properties.Compare with the traditional catalyst preparation method, sol-gel process for preparing has advantage in the following aspects:
1. can access high homogeneous, the material of high-specific surface area.
2. the pore size distribution homogeneous of material is controlled.
3. the metal component high dispersing makes catalyzer have the very high reactive behavior and the ability of anti-carbon deposit on carrier.
4. can access active ingredient and be distributed in lip-deep catalyzer with high degree of dispersion.
5. the easier composition of control material.
6. the catalyzer (crystalline form or amorphous) that can prepare different structure according to concrete needs.
7. can access physical strength that is fit to reaction conditions and material with higher anti-deactivation.(M.A.Caugui and J.M.Rodriguez-Izquierdo J of Non-Crystalline Solids147&148(1992)724-738)。
Sol-gel method has two kinds, and a kind of is particle method (Particulate method), and another kind is polymerization (Polymeric method).In particle method, metal alkoxide hydrolysis in excessive water, form the precipitation of gluey oxyhydroxide or hydrous oxide, add acid or alkaline hydrolysis glue then, form stable colloidal sol, when this colloidal sol was converted into gel, micelle accumulated in and forms solid-state material together, and wherein the interaction force between the micelle is electrostatic force, hydrogen bond, Van der Waals force.In polymerization, the hydrolysis rate and the hydrolysis degree of strict control metal alkoxide allow the metal alkoxide partial hydrolysis, introduce the OH key on metal, and these have the mutual condensation polymerization of metal alcoholate of OH key, form organic and inorganic polymerizable molecular colloidal sol.When these colloidal sols were converted into gel, polymerizable molecular continued condensation in medium, formed oxide network texture (Texture) by chemical bond.(Larry L.Hench and K.West Chem Rev 1990 90 33-72)。
Sol-gel method is widely used in the synthetic of catalytic material as a kind of low temperature method of preparation inorganic materials in recent years.And aluminium colloidal sol becomes the important presoma of numerous material synthetic just gradually because its distinctive character, as catalyzer of ceramic membrane, controllable aperture or the like.Since often of a specified duration, the preparation method of aluminium colloidal sol mainly concentrates on hydrolysis alkoxide, acidolysis glue SB powder, homogeneous precipitation method etc.But these preparation methods mainly carry out being higher than under 80 ℃ the temperature condition, generate the bayerite that acid can not dispergation easily because if operating process is lower than certain temperature.And the used raw material of these preparation methods is expensive alkoxide and SB powder.And aluminum oxide is a kind of important materials that is widely used in Industrial Catalysis agent carrier and other industrial circles, how therefore to seek to go out to send the controlled alumina material of the various basic physicochemical property of preparation from the raw material of cheapness and have extremely important using value and economic worth.
The object of the present invention is to provide a kind of preparation method of aluminium colloidal sol, its employed cost of material is cheap, the method simple controllable, and prepared aluminium colloidal sol homogeneous grain diameter, particle high dispersing, stability are better.
The invention provides a kind of preparation method of aluminium colloidal sol, it is characterized in that: under the condition of room temperature, be raw material, obtain precipitation, make the pH value greater than 9 by the method that adds excessive alkali with the inorganic aluminate; Clean the back and add acid as dispergation catalyzer, [H
+]/[Al
3+] scope of mol ratio is 0.07-0.50, under action of ultrasonic waves, form stable, aluminium colloidal sol clearly, hyperacoustic physical parameter is: frequency 20-50KHz, sound intensity 50-150W.
There is aluminum nitrate in employed aluminium source among the present invention, Tai-Ace S 150, the inorganic aluminate of aluminum chloride; Employed alkali is ammoniacal liquor, sodium hydroxide, and the mineral alkali of potassium hydroxide is preferably ammoniacal liquor; Employed acid as catalyzer is nitric acid, sulfuric acid, and the mineral acid of hydrochloric acid and the organic acid of Glacial acetic acid are good with nitric acid.
The present invention is at ambient temperature with cheap al inorganic salt and adopt other assist measure to make homogeneous grain diameter, particle high dispersing, stability aluminium colloidal sol preferably.And utilize
27Analysis means such as Al NMR, XRD characterize the basic physicochemical property of this colloidal sol, have found the different new phenomenon of the resulting aluminium colloidal sol of some and traditional preparation process method.Preparation method of the present invention has simple to operately, controls advantage easily.Utilize reported method of the present invention not only for the aluminum oxide that has the industrial application background from the preparation of the raw material of cheapness provide may, and provide new material for the physicochemical property of research nanometer system.
Accompanying drawing 1 is the preparation process figure of aluminium colloidal sol.
Accompanying drawing 2 is particle size distribution figures of the aluminium colloidal sol for preparing by various different conditions;
Wherein A represents aluminium colloidal sol (0.42M[H
+]/[Al
3+]=0.24) size-grade distribution
B represents aluminium colloidal sol (0.42M[H
+]/[Al
3+]=0.27) size-grade distribution
C represents aluminium colloidal sol (0.42M[H
+]/[Al
3+]=0.30) size-grade distribution
D represents aluminium colloidal sol (0.42M[H
+]/[Al
3+]=0.09) size-grade distribution
Accompanying drawing 3 is aluminium colloidal sol (0.12M, [H
+]/[Al
3+]=0.09)
27Al NMR spectrogram.
Accompanying drawing 4 is aluminium colloidal sol (0.42M, [H
+]/[Al
3+]=0.27)
27Al NMR spectrogram.
Accompanying drawing 5 is XRD figure of the gel that obtains after aluminium colloidal sol (0.42M) vacuum-drying
Wherein " " represents the characteristic peak of boehmite
Accompanying drawing 6 is XRD figure of the gel that obtains after aluminium colloidal sol (0.12M) vacuum-drying.
" " represents the characteristic peak of boehmite
" * " represents the characteristic peak of promise diaspore
Accompanying drawing 7 is transmission electron microscope pictures of aluminium colloidal sol (0.42M).
The preparation of example 1 aluminium colloidal sol:
The preparation process of this aluminium colloidal sol is: 2.5% excessive ammonia soln progressively is added drop-wise to and produces precipitation in the 25ml 0.96M aluminum nitrate solution, and the pH value that makes final solution is greater than 9.20.Centrifugal then, with washing in twice distilled water of precipitation adding 50ml that obtains repeatedly, about the pH of system value is near 7.4.Then add 0.94M nitric acid in proportion and effect 10 minutes in ultrasonic water bath, with the ultrasonic cleaning machine of commercial 50Kz80W as ultrasonic source.Preparation flow figure such as accompanying drawing 1.System remains under the condition of room temperature in whole process of preparation, even the temperature of ultrasonic water bath still is no more than 40 ℃ in the ultrasonic wave effect after 10 minutes.To obtain aluminium colloidal sol sample then is positioned over and carries out drying in the vacuum drying oven.Keeping vacuum tightness in whole drying process is 60mmHg.Then the gel sample that obtains is carried out various signs or does further processing.
Example 2 results of grain size analysis:
Adopt Coulter N
4The plus laser particle analyzer has been measured the size-grade distribution with the aluminium colloidal sol of this patent reported method preparation.A in the accompanying drawing 2, B, three figure of C represent same concentrations (0.42M) respectively but add the different aluminium colloidal sol (1) of acid amount, (2), (3) sample ([H
+]/[Al
3+] be respectively 0.24, particle size distribution figure 0.27.0.30).From figure, can find in these three colloidal sol samples to concentrate between 20nm and the 50nm greater than the size-grade distribution of the particle of 90wt%.And along with the increase that adds the acid amount, the particle of sol system increases gradually, and size distribution is widened gradually.To represent concentration be 0.12mol/L to D in the accompanying drawing 2, [H
+]/[Al
3+The particle size distribution figure of the aluminium colloidal sol sample of]=0.09.Above size-grade distribution characterization result shows can prepare the comparatively aluminium colloidal sol of homogeneous of size-grade distribution with this method.In experimentation, the aluminum nitrate solution with different concns prepares aluminium colloidal sol respectively.The concentration that found that aluminum nitrate has great influence to the required acid amount of dispergation and the pH value of final colloidal sol.Concrete outcome sees Table-1.The gel that obtains after the vacuum-drying is put into retort furnace arrive different temperature with the linear temperature rise rate roasting of 5 ℃/min.The sample that obtains is measured specific surface area and pore size distribution with low-temperature nitrogen adsorption method.Concrete data see Table-2, table-3.From the data of table-2, table-3, can see of the influence of precursor sol granularity to material structure.Along with the increase of colloidal sol granularity, the specific surface area of the aluminum oxide that finally obtains reduces, but pore volume increases.Same sample is under different treatment temps, and specific surface area increases afterwards to have earlier and reduces.And pore volume and aperture are increasing always, and distribute from the micropore of broad and to become the homogeneous mesopore.
Table-1:
Aluminum nitrate concentration [H
+]/[Al
3+] the final collosol concentration of final colloidal sol
(mol/L) molar ratio pH value (mol/L)
0.20 0.09 4.59 0.12
0.96 0.27 4.17 0.42
Table-2:
Colloidal sol most probable granularity maturing temperature specific surface area pore volume aperture
Sample distribution (nm) (℃) (m2/g) (ml/g) (nm)
1 24.6 350 191.66 0.02 0.8-1.8
2 41.9 350 178.57 0.04 1-1.8
Table-3:
Colloidal sol most probable granularity maturing temperature specific surface area pore volume aperture
Sample distribution (nm) (℃) (m
2/ g) (ml/g) (nm)
2 41.9 350 178.57 0.04 1-1.8
2 41.9 450 265.72 0.08 1.4-2
2 41.9 550 158.37 0.13 3.8
Example 3
27Al NMR analytical results:
Accompanying drawing 3,4 has shown
27The result of Al NMR, the spike at 62ppm place ownership is the aluminium of four-coordination in the drawings, the spike at 0ppm place can belong to the monomer for hexa-coordinate aluminium, is the dimer that the wide bag at center belongs to hexa-coordinate aluminium with 4ppm.Owing to occurred the aluminium peak of four-coordination in the spectrogram, thinking of therefore can be sure oing exists Al in this aluminium colloidal sol
13Positively charged ion.Comparative drawings figs 3 and 4 can be found being lower concentration or all having Al in the aluminium colloidal sol of high density by the inventive method preparation
13Positively charged ion, different just their concentration different.
Example 4 XRD analysis results:
Resulting aluminium colloidal sol drying under the room temperature vacuum condition can be obtained gel, and the X-ray diffraction analysis result shows that its main crystalline phase is a pseudo-boehmite, also has simultaneously other crystal phase structure such as promise diaspore etc.That accompanying drawing 5 shows is the X-ray powder diffraction figure of gel sample (0.42M pH=4.17) after the process vacuum-drying.Wherein main crystalline phase is a pseudo-boehmite.That accompanying drawing 6 shows is the X-ray powder diffraction figure of gel sample (0.12M pH=4.65) after the process vacuum-drying.The characteristic diffraction peak that has significantly occurred the promise diaspore among the figure illustrates to have the promise diaspore in this sol system.The crystal phase structure of the aluminium hydroxide that this reports in document and the acidity of system and digestion time have the theory of confidential relation to meet.A bigger endotherm(ic)peak is arranged about 100 ℃ in the DTA spectrogram of the alumina gel after the room temperature vacuum-drying, mainly is that gel media water removes and causes; The exothermic peak that exists about 200 ℃ causes owing to nitrate radical decomposes; 300 ℃ endotherm(ic)peak be since the pseudo-boehmite crystalline phase to γ-Al
2O
3Crystal transition causes.Proved further that from the analytical results of DTA the composition the gel mainly is a pseudo-boehmite.
Example 5 tem analysis results:
Accompanying drawing 7 is TEM figure of aluminium colloidal sol.Can find that from TEM figure this sol particles is mainly spheroidal particle.The particle of the aluminium colloidal sol that this has the people to think in bibliographical information to obtain with the nitric acid dispergation should be that rectangular viewpoint is distinct.(Z.R.Ismagilov，M.N.Shepeleva，R.A.Shkrabina，U.B.Fenelonov，Applied Catalysis，69(1991)65-73)
The pH value of comparative example 1 colloidal sol:
The pH value of the colloidal sol by the preparation of this patented method will significantly be higher than the aluminium colloidal sol that obtains from the Yoldas process.Usually the pH value of the aluminium colloidal sol that obtains by the Yoldas preparation method is about 3.60.And the pH value of the colloidal sol that makes with this patent reported method is greater than 4.10.[(1).T.Assih，A.Ayral，M.Abenoza，and J.Phalippou，J.Mater.Sci.，23(1988)3326.(2).C.J.Brinker，G.W.Scherer，“Sol-gel Science”Academic Press.Inc.1990.(3).H.B.ZHAO，A.W.Li，J.H.Gu，G.X.Xiong，H.Brunner，J.Mater.Sci.，34(1999)2987-2996)
The type of comparative example 2 aluminium molecular clusterings:
By
27Contain Al in the aluminium colloidal sol that the characterization result of Al NMR can be found to make with this patent
13The aluminium molecular clustering.Then do not contain this aluminium molecular clustering by being higher than in the aluminium colloidal sol that 80 ℃ of hydrolysis alkoxide process and acidolysis SB powder method obtain.(Edisson Morgado JR，Yiu Lau Lam，Sonia Maria C.Menezes，Linda F.Nazar.J.Colloid.Interface Sci.，1995，176，432)
The effect of comparative example 3 acid
Acting on of nitric acid also significantly is different from hydrolysis alkoxide process and acidolysis SB powder method in this preparation process.It is generally acknowledged that what play is the effect of dispergation in the process of preparation colloidal sol in acid.Therefore in the process of the colloidal sol for preparing different concns, the sour aluminum ratio that uses is approximately uniform.And when preparing aluminium colloidal sol with this patent method, we find that employed sour aluminum ratio is distinct in the process of the colloidal sol of preparation different concns.The data of table in-1 clearly demonstration this point.We think that nitric acid role in this preparation process is not only the effect of playing dispergation thus, and the generation Al that reacts of the coacervate before the acid that part arranged and the dispergation
13 7+Positively charged ion.
Claims (6)
1. the preparation method of an aluminium colloidal sol is characterized in that: under the condition of room temperature, be raw material with the inorganic aluminate, obtain precipitation by the method that adds excessive alkali, make the pH value greater than 9; Clean the back and add acid as dispergation catalyzer, [H
+]/[Al
3+] scope of mol ratio is 0.07-0.50, under action of ultrasonic waves, form stable, aluminium colloidal sol clearly, hyperacoustic physical parameter is: frequency 20-50KHz, sound intensity 50-150W.
2. according to the preparation method of the described aluminium colloidal sol of claim 1, it is characterized in that: employed aluminium source is selected from a kind of in aluminum nitrate, Tai-Ace S 150 and the aluminum chloride.
3. according to the preparation method of the described aluminium colloidal sol of claim 1, it is characterized in that: employed alkali is selected from a kind of in ammoniacal liquor, sodium hydroxide and the potassium hydroxide.
4. according to the preparation method of the described aluminium colloidal sol of claim 3, it is characterized in that: employed alkali is ammoniacal liquor.
5. according to the preparation method of the described aluminium colloidal sol of claim 1, it is characterized in that: employed acid as catalyzer is selected from a kind of in nitric acid, sulfuric acid, hydrochloric acid and the Glacial acetic acid.
6. according to the preparation method of the described aluminium colloidal sol of claim 5, it is characterized in that: employed acid as catalyzer is nitric acid.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 00110421 CN1209289C (en) | 2000-05-17 | 2000-05-17 | Prepn. of aluminium sol |
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|---|---|---|---|
| CN 00110421 CN1209289C (en) | 2000-05-17 | 2000-05-17 | Prepn. of aluminium sol |
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|---|---|
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| CN1209289C true CN1209289C (en) | 2005-07-06 |
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Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100448774C (en) * | 2004-08-31 | 2009-01-07 | 中国石油化工股份有限公司 | Method for preparing colloidal sol containing chloride and aluminium |
| CN1313374C (en) * | 2004-10-29 | 2007-05-02 | 中国石油化工股份有限公司 | Gama-Al2O3 preparation method |
| CN103785485B (en) * | 2012-11-03 | 2016-04-27 | 中国石油化工股份有限公司 | A kind of preparation method of clean binding agent |
| CN103910369B (en) * | 2014-03-14 | 2016-02-10 | 开封大学 | A kind of preparation method of nano aluminium oxide |
| CN105617883B (en) * | 2015-12-28 | 2018-04-20 | 山东省科学院海洋仪器仪表研究所 | A kind of method using alumine hydroxide colloid to polypropylene filter hydrophilic modifying |
| CN107473735B (en) * | 2017-09-29 | 2019-08-02 | 无锡特科精细陶瓷有限公司 | A kind of preparation method of alumina titanate ceramics |
| CN108212030B (en) * | 2017-12-20 | 2021-02-19 | 广东邦普循环科技有限公司 | Aluminum sol and preparation method thereof |
| CN110876948B (en) * | 2018-09-05 | 2022-11-15 | 中国石油化工股份有限公司 | Aluminum sol, preparation method and application thereof, and preparation method of catalytic cracking catalyst |
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