CN100431677C - Process for producing Al2O3-SiO2-ZrO2 compound ceramic separation film using microwave heating process - Google Patents
Process for producing Al2O3-SiO2-ZrO2 compound ceramic separation film using microwave heating process Download PDFInfo
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- CN100431677C CN100431677C CNB2006101561704A CN200610156170A CN100431677C CN 100431677 C CN100431677 C CN 100431677C CN B2006101561704 A CNB2006101561704 A CN B2006101561704A CN 200610156170 A CN200610156170 A CN 200610156170A CN 100431677 C CN100431677 C CN 100431677C
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Abstract
The invention relates to a method for preparing Al2O3-SiO2-ZrO2 ceramic composite separating film, wherein it comprises that: using microwave heating method to prepare Al2O3-SiO2-ZrO2 composite gel to be plated on the porous alpha- Al2O3 ceramic tube; sintering at 900-1000Deg. C, to obtain the Al2O3-SiO2-ZrO2 composite film. The inventive film is used to treat middle water. And the inventive production has short time and high quality. The mol ratio between Al2O3, SiO2, and ZrO2 is 8:2. 3:1-10:2. 3:1; the pH value is 3. 4-4. 5; the microwave power is 500-900W; the heating time is tens seconds. The ceramic tube plated with composite gel is heated in microwave oven for several minutes, to be dried; the composite film after sintered has main crystal phase as gamma-Al2O3 and t-ZrO2, while SiO2 is not shaped. The test has proved that: after 1200Deg. C sintering, there is no phase change from gamma-Al2O3 to alpha-Al2O3. The inventive film has reach drinking water standard.
Description
Technical field:
The present invention relates to the technology of preparing of ceramic membrane material, relate in particular to a kind of Al
2O
3-SiO
2-ZrO
2The heating using microwave preparation method of composite ceramic film.
Background technology:
The membrane science technology be many subject crossing such as material science and process engineering in conjunction with, interpenetrate and the frontier that produces.The film separation process has become important new and high technology and the sustainable development technical foundation that solves the contemporary energy, resource and problem of environmental pollution.Pellumina is to use more a kind of membrane material at present, but the not anti-strong acid of aluminium oxide, γ-Al
2O
3Film is being higher than under 500 ℃ the hot conditions not really stablely, can phase transformation generate α-Al about 1000 ℃
2O
37% Volume Changes can take place in the phase transition process in phase.The present invention adopts microwave heating technique, by adding some oxides such as SiO
2And ZrO
2Wait and improve and modify Al
2O
3The performance of film and structure.
Summary of the invention:
The objective of the invention is to prepare Al fast with microwave heating method
2O
3-SiO
2-ZrO
2Complex sol, and then be applied to porous α-Al
2O
3Earthenware (apparent porosity 35%; Average pore size 4 μ m) on, the method with microwave drying makes colloidal sol change gel layer into again, is fired into Al then
2O
3-SiO
2-ZrO
2Composite ceramic separation membrane.The introducing of microwave heating method makes the system film cycle shorten greatly, has improved efficient.
Its preparation method is as follows;
(1) heating using microwave prepares boehmite sol:
Al (NO in molar ratio
3)
3: NH
3H
2O=1: 1 with Al (NO
3)
3Crystal joins in the ammonia spirit, and without stirring, placing power is the micro-wave oven of 500～800W, and heating 20-80 took out after second, and agitating solution cools off it in whipping process, repeat above-mentioned steps until Al (NO
3)
3Crystal all dissolves, and the solution clear has Tyndall phenomenon, promptly makes boehmite sol;
(2) heating using microwave prepares Al
2O
3-SiO
2-ZrO
2Complex sol:
With ethyl orthosilicate and zirconium oxychloride is raw material, prepares by a certain percentage to join in the absolute ethyl alcohol, adds boehmite sol again, and the mol ratio that makes complex sol is Al
2O
3: SiO
2: ZrO
2=8: 2.3: 1～10: 2.3: 1, stir, regulate pH value=3.4～4.5, microwave power is that 500～900W heating 20-80 promptly obtains Al after second
2O
3-SiO
2-ZrO
2Complex sol;
(3) with α-Al
2O
3The earthenware matrix is immersed in above-mentioned Al
2O
3-SiO
2-ZrO
2In the complex sol, take out after 10 seconds, place micro-wave oven 500～900W heating 10 minutes, make film under microwave condition, after the drying, promptly make Al
2O
3-SiO
2-ZrO
2Composite ceramic separation membrane.
From accompanying drawing 1 as can be seen, composite membrane is calcined under different temperatures, and the XRD figure spectrum that obtains is not quite similar.In the time of 1000 ℃, begin to occur very weak γ-Al
2O
3Diffraction maximum and t-ZrO
2Diffraction maximum, and along with the rising of temperature, γ-Al
2O
3The intensity of diffraction maximum increases gradually, and peak width narrows down, and illustrates that the crystal formation of this crystal is tending towards complete, and crystal grain is grown up gradually, γ-Al
2O
3Remain to 1200 ℃ always the crystalline phase variation does not take place yet.Principal crystalline phase to 1200 ℃ of composite membranes is γ-Al
2O
3With amorphous state SiO
2And t-ZrO
2
With porous α-Al
2O
3Earthenware is soaked in 24h in 5% the watery hydrochloric acid, is adsorbed on the impurity on surface with removing, uses the distilled water cleaning down again, places 120 ℃ of dry 24h of drying box then, 600 ℃ of roasting 2h.
Matrix is immersed in the colloidal sol, put into micro-wave oven and take out after heating a period of time, then matrix is pulled out from sol solutions.After filming earthenware is put into micro-wave oven and heat 10min, make film under microwave condition after the drying, put into resistance furnace and be warming up to 900～1200 ℃ with the speed of 3 ℃/min, insulation 2h cools off naturally with stove.
With the Al that makes
2O
3-SiO
2-ZrO
2Ceramic thin sheet carries out sewage disposal, and composite membrane is as shown in table 1 to the filter effect of sewage;
Table 1 composite membrane is to the filter result of sewage
Characteristics of the present invention are: the method with heating using microwave is incorporated into Al first
2O
3The preparation that is composite ceramic film is central next, and test shows, needs 18h to compare with the water-bath heating, adopts the method for heating using microwave only just can prepare boehmite sol with tens of seconds under the power of 500～900W, has saved the time greatly; The main difference of the present invention and prior art is at preparation Al
2O
3-SiO
2-ZrO
2During complex sol, the colloidal sol quality that obtains is good, work simplification, and the time shortens greatly.
Table 2 illustrates boehmite sol performance that heating using microwave and water-bath add hot preparation relatively;
Table 2 heating using microwave and water-bath add the boehmite sol of hot preparation
(
*Annotate: good being divided into difference according to the colloidal sol transparency is 1～5,5 grades, and 1 is best, and 5 for the poorest)
As can be seen from Table 2, it is convenient and swift to use micro-wave oven to prepare boehmite sol much smaller than the time of water-bath heating the time of heating using microwave; For the colloidal sol with concentration, the transparency of microwave legal system is good, and gelling time is long, helps a large amount of preparations, and long preservation is better than the water-bath heating.
Another of heating using microwave
Point is that technology is easy, and equipment is simple.Equipment and technology comparison when table 3 is equipped with boehmite sol for microwave heating method and alkoxide process and inorganic salts legal system.
Table 3 heating using microwave and alkoxide process, equipment and technology comparison when the inorganic salts legal system is equipped with boehmite sol
The composite membrane porcelain film of making is carried out the drainage experiment, adopt the sewage after sewage treatment plant handles to carry out running test, advanced treating has been carried out in industrial water outlet (middle water) to Sewage Plant, the data of finding treated water sample colourity, turbidity (NTU) and fluoride all significantly decrease, and the content of iron and total coli group is within the scope of national drinking water standard.(according to country's " drinking water sanitary standard ", iron: 0.3mg/L total coli group: 3/L).
Description of drawings:
Fig. 1 is n
Al2O3: n
SiO2: n
ZrO2=Al
2O
3: SiO
2: ZrO
2(mol ratio) is 1O: the X-ray diffractogram of 2.3: 1 composite membrane behind the different temperatures sintering.
The specific embodiment:
Embodiment 1
Al (NO in molar ratio
3)
3: NH
3H
2O=1: 1 with Al (NO
3)
3Crystal joins in the ammonia spirit, and without stirring, placing power is the micro-wave oven of 800W, heats after 30 seconds and takes out, and agitating solution cools off it in whipping process, repeat above-mentioned steps until Al (NO
3)
3Crystal all dissolves, and promptly makes boehmite sol;
Embodiment 2
With ethyl orthosilicate and zirconium oxychloride is raw material, joins in the absolute ethyl alcohol after preparing by a certain percentage, adds boehmite sol again, and the mol ratio that makes complex sol is Al
2O
3: SiO
2: ZrO
2=1O: 2.3: 1, stir, regulate pH value=4, microwave power is that the 800W heating promptly obtained Al after 60 seconds
2O
3-SiO
2-ZrO
2Complex sol;
Embodiment 3
By carrier being carried out use Al again after the preliminary treatment
2O
3-SiO
2-ZrO
2Complex sol is filmed to its three times, and adopting and placing power is the micro-wave oven of 900W, heats after 10 minutes and takes out.And heat up with the speed of 3 ℃/min, calcining heat is 1000 ℃, and it is even to make fenestra, and the aperture is about the composite membrane of 2～4 μ m.
Claims (3)
1. one kind is adopted heating using microwave to prepare Al
2O
3-SiO
2-ZrO
2The method of composite ceramic separation membrane is characterized in that this method may further comprise the steps:
(1) heating using microwave prepares boehmite sol:
Al (NO in molar ratio
3)
3: NH
3H
2O=1: 1 with Al (NO
3)
3Crystal joins in the ammonia spirit, and without stirring, placing power is the micro-wave oven of 500～900W, heats after 20 1 80 seconds and takes out, and agitating solution cools off it in whipping process, repeat above-mentioned steps until Al (NO
3)
3Crystal all dissolves, and the solution clear has Tyndall phenomenon, promptly makes boehmite sol;
(2) heating using microwave prepares Al
2O
3-SiO
2-ZrO
2Complex sol:
With ethyl orthosilicate and zirconium oxychloride is raw material, prepares by a certain percentage to join in the absolute ethyl alcohol, adds boehmite sol again, and the mol ratio that makes complex sol is Al
2O
3: SiO
2: ZrO
2=8: 2.3: 1～10: 2.3: 1, stir, regulate pH value=3.4～4.5, microwave power is that 500～900W heating 20-80 promptly obtains Al after second
2O
3-SiO
2-ZrO
2Complex sol;
(3) with α-Al
2O
3The earthenware matrix is immersed in above-mentioned Al
2O
3-SiO
2-ZrO
2In the complex sol, take out after 10 seconds, place micro-wave oven 500～900W heating 10 minutes, make film under microwave condition, after the drying, promptly make Al
2O
3-SiO
2-ZrO
2Composite ceramic separation membrane.
2. a method for preparing boehmite sol is characterized in that Al (NO in molar ratio
3)
3: NH
3H
2O=1: 1 with Al (NO
3)
3Crystal joins in the ammonia spirit, and without stirring, placing power is the micro-wave oven of 500～800W, and heating 20-80 took out after second, and agitating solution cools off it in whipping process, repeat above-mentioned steps until Al (NO
3)
3Crystal all dissolves, and the solution clear has Tyndall phenomenon, promptly makes boehmite sol.
3. Al with the preparation of the described method of claim 1
2O
3-SiO
2-ZrO
2The method that composite ceramic separation membrane is disposed of sewage; The water drainage was handled during the composite membrane that employing is made carried out, and the content of iron and total coli group is within the scope of national drinking water standard.
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|---|---|---|---|
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|---|---|---|---|
| CNB2006101561704A CN100431677C (en) | 2006-12-30 | 2006-12-30 | Process for producing Al2O3-SiO2-ZrO2 compound ceramic separation film using microwave heating process |
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| CN100431677C true CN100431677C (en) | 2008-11-12 |
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| CN101721919B (en) * | 2008-10-30 | 2012-09-26 | 中国石油化工股份有限公司 | Method for preparing tubular support dense oxide film |
| US9512041B2 (en) * | 2010-12-17 | 2016-12-06 | General Electric Company | Ceramic membranes |
| CN104014252B (en) * | 2014-05-06 | 2016-02-17 | 三达膜科技（厦门）有限公司 | A kind of preparation method of ceramic film support |
| CN110052181A (en) * | 2019-04-30 | 2019-07-26 | 西安工程大学 | A kind of preparation method of zirconia-supported hydrophobic silica composite membrane |
| JP2023513812A (en) * | 2020-02-17 | 2023-04-03 | インスティテュート ストローマン アーゲー | Glass-ceramic and its manufacturing method |
| CN113659164B (en) * | 2021-08-11 | 2022-11-11 | 南京大学 | Preparation method of fuel cell platinum-based alloy catalyst |
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| US20030101866A1 (en) * | 2000-04-20 | 2003-06-05 | Andreas Noack | Separation of fluid mixtures using membranized sorption bodies |
| CN1459434A (en) * | 2002-05-23 | 2003-12-03 | 山东大学 | Hard alloy powder surface ceramic coating material and its preparation process |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20030101866A1 (en) * | 2000-04-20 | 2003-06-05 | Andreas Noack | Separation of fluid mixtures using membranized sorption bodies |
| CN1459434A (en) * | 2002-05-23 | 2003-12-03 | 山东大学 | Hard alloy powder surface ceramic coating material and its preparation process |
Non-Patent Citations (10)
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| Al2O3-SiO2-ZrO2-TiO2复合膜的制备与研究. 王黔平，马雪刚，王永刚.河北理工学院学报，第27卷第3期. 2005 |
| Al2O3-SiO2-ZrO2-TiO2复合膜的制备与研究. 王黔平，马雪刚，王永刚.河北理工学院学报，第27卷第3期. 2005 * |
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Application publication date: 20070711 Assignee: Taizhou Changhang Environmental Protection Technology Co., Ltd. Assignor: Hebei Univ. of Science & Technology Contract record no.: 2010330000584 Denomination of invention: Method for preparing Al*O*-SiO*-ZrO* composite ceramic separation membrane by microwave heating Granted publication date: 20081112 License type: Exclusive License Record date: 20100421 |
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