CN1043190C - Method for preparing inorganic ceramic membrane - Google Patents
Method for preparing inorganic ceramic membrane Download PDFInfo
- Publication number
- CN1043190C CN1043190C CN94112148A CN94112148A CN1043190C CN 1043190 C CN1043190 C CN 1043190C CN 94112148 A CN94112148 A CN 94112148A CN 94112148 A CN94112148 A CN 94112148A CN 1043190 C CN1043190 C CN 1043190C
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- Prior art keywords
- ceramic membrane
- inorganic ceramic
- acid
- preparation
- aluminium
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
- C04B41/009—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone characterised by the material treated
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
- C04B41/45—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements
- C04B41/50—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements with inorganic materials
- C04B41/5025—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements with inorganic materials with ceramic materials
- C04B41/5031—Alumina
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Ceramic Engineering (AREA)
- Materials Engineering (AREA)
- Structural Engineering (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
Abstract
The present invention relates to a preparation method for inorganic ceramic films. Al2O3. H2O is used as a raw material; transparent or translucent monodisperse collosol with small granule diameters is prepared through acidolysis, solation and refluxing aging; a binding agent is added in the collosol, and a film coating solution is prepared; the film coating solution is uniformly coated on micropore ceramic; after natural drying, temperature programming drying and temperature programming calcination, an inorganic ceramic film with a uniform surface is prepared. The film has the advantages of good film forming performance, low price, etc., and can be widely used for film reactions.
Description
The present invention is a kind of Al of using
2O
3H
2O prepares the method for inorganic ceramic membrane.
In the membrane catalytic reaction process,, can improve the equilibrium conversion of reversible reaction and save separation energy because it is that catalytic reaction and membrane separation technique are combined; Improve parallel cascade reaction purpose product selectivity; So obtained developing rapidly in recent years.Obtained extensive use at aspects such as reverse osmosis, hyperfiltration, secondary filter, dialysis, infiltration gasification, gas separation, fluid separation applications.For example aspect medical treatment and biotechnology, become the important means of separation.Reclaim in hydrogen, the natural gas in the concentrating of wastewater treatment aspect chemical industry, ethanol water, synthesis ammonia plant or the refinery exhaust and remove CO
2And H
2The enrichment of oxygen and nitrogen concentrates etc. in S, the air.
The film of component film catalyst generally has two kinds of inorganic ceramic membrane and organic films.Inoranic membrane has the chemical stability, corrosion resistance of remarkable hear resistance, height, mechanical strength, good solvent resistance preferably, and the aperture of film can accurate premium properties such as control grade.The disadvantage of organic film is a non-refractory, thus in the chemical reaction that under the need hot conditions, carries out, extensive use inorganic ceramic membrane.
Inorganic ceramic membrane adopts the sol-gel process preparation mostly.The primary raw material of preparation inorganic ceramic membrane all was to use aluminium alcoholates in the past.In document US 3941719 and US3944658, introduced sol-gel process (Sol-gel), at first aluminium alcoholates hydrolysis under acid condition, under acid condition, carry out polycondensation reaction then, through aging, make aluminium colloidal sol again, in this colloidal sol, add binding agent then and make coating liquid, coating liquid evenly is coated onto on the carrier, makes film.Such preparation method since aluminium alcoholates to need with alcohols, light alkene, aluminium, hydrogen be that raw material makes, make preparation cost higher, also more complicated of preparation method has influenced industrial extensive use in addition.For overcoming the shortcoming for preparing inorganic ceramic membrane with aluminium alcoholates, we have invented the new preparation method of inorganic ceramic membrane.
The present invention adopts Al
2O
3H
2O makes the method for feedstock production inorganic ceramic membrane, and its process is at first with Al
2O
3H
2The O powder joins in the distilled water that is preheated to 80～90 ℃, make aluminium: the water ratio is 1: 100～200 (mol ratios), stir, and then in distilled water, add organic acid, the mixture of inorganic acid or inorganic acid and storng-acid cation exchange resin, wherein organic acid is formic acid or acetate; Inorganic acid is nitric acid, hydrochloric acid or crosses chloric acid; Storng-acid cation exchange resin is that [solid content of resin is 51.32% to styrene cross-linking type cationic ion-exchange resin, the weight exchanging equivalent is a 4.56MN/ gram (butt)], its sour addition is the hydrogen ion that makes in the batching: aluminum ratio is 1: 1～10.0 (mol ratios), and this suspension is warming up to 85～99 ℃ then; Wore out 8～80 hours under keeping refluxing, obtain the aluminium colloidal sol of transparent or semitransparent monodispersity, through the laser light scattering particle size analyzer determination, its result is average grain diameter＜100 nanometers, particle size distribution range 10～150 nanometers.In this aluminium colloidal sol, add binding agent, be made into the coating liquid that aluminium content is 0.2～1.2 mol concentration, concentration range is 0.4～0.7 mol preferably, and wherein binding agent is polyvinyl alcohol, methylcellulose or hydroxy-methyl cellulose, and its addition is 20～40% (weight) of colloidal sol amount.Then this coating liquid evenly is applied to the surface of micropore ceramics, through air dry, the temperature programming drying, temperature-programmed calcination to 450～600 ℃, better sintering temperature is 500～550 ℃, make surface inorganic ceramic membrane uniformly, wherein the material of micropore ceramics is aluminium oxide, silica, cordierite, zirconia, titanium oxide or their mixture.
The present invention is owing to adopt industrial Al
2O
3H
2O is a raw material, and the cost of material of preparation inorganic ceramic membrane is reduced greatly, and preparation process is also simpler in addition, and having overcome with aluminium alcoholates is the shortcoming of raw material.
[embodiment 1]
400 milliliters of distilled water are preheated to 80 ℃, add 9 gram Al
2O
3H
2The O powder stirs half an hour; Treat Al
2O
3H
2After the O powder is uniformly dispersed, in this distilled water, add 2MHClO in distilled water
410 milliliters, then add styrene cross-linking type cationic ion-exchange resin 20 grams again, make it to be made into suspension, this suspension is warming up to 85 ℃, carry out reflux digestion 20 hours, and filtered resin and a small amount of deposit then, obtain the more transparent monodisperse aluminium collosol of outward appearance.This monodisperse aluminium collosol is measured through laser light scattering instrument; Micelle average grain diameter 83 nanometers, particle diameter is distributed as 40～140 nanometers.The polyvinyl alcohol that this colloidal sol is added 30% (weight) aluminium colloidal sol amount, being made into aluminium content is 0.2 mol coating liquid, select 12 * 300 * 1.5 millimeters pellumina carriers of φ for use, 25 ℃ of vacuum evaporations 5 minutes, one night of air dry, temperature programming is dried to 150 ℃, temperature-programmed calcination to 580 ℃ again, the film pipe after obtaining being coated with once, then, use identical coating liquid again, filmed 5 seconds at 25 ℃, normal pressure, then with identical method drying and roasting, twice so repeatedly, make the film pipe,, measure H with static method at 30 ℃
2, N
2The separation of the infiltration capacity of gas and two kinds of gases.Measurement result, N
2Infiltration capacity is 0.337 * 10
-5Mole/rice
2Second handkerchief; H
2Infiltration capacity is 1.026 * 10
-5Mole/rice
2Second handkerchief, composite membrane is 3.04 to the separation of hydrogen nitrogen.[embodiment 2]
340 milliliters of distilled water are preheated to 85 ℃, add 10 gram Al
2O
3H
2The O powder stirs half an hour; Treat Al
2O
3H
2After the O powder is uniformly dispersed, in this distilled water, add 2MHNO in distilled water
330 milliliters, make it to be made into suspension, this suspension is warming up to 90 ℃, carried out reflux digestion 20 hours, filter a small amount of deposit then, obtain the more transparent monodisperse aluminium collosol of outward appearance, this monodisperse aluminium collosol is measured through laser light scattering instrument, micelle average grain diameter 52 nanometers, particle size distribution range 25～90 nanometers.No supported film is made in the slowly dry also roasting of this colloidal sol, this film is adsorbed instrument with Digisorb-2600, under liquid nitrogen temperature, measure with volumetric method, its pore volume is 0.270 a milliliter/gram, 258.0 meters of specific surfaces
2/ gram, most probable bore dia 37.1 , average pore diameter 41.9 account for 98% of total hole volume less than the hole of 45.6 .[embodiment 3]
360 milliliters of distilled water are preheated to 90 ℃, add 13 gram Al
2O
3H
2The O powder stirs half an hour; Treat Al
2O
3H
2After the O powder is uniformly dispersed, in this distilled water, add 2MCH in distilled water
3The COOH30 milliliter, make it to be made into suspension, this suspension is warming up to 90 ℃, carried out reflux digestion 50 hours, filter a small amount of deposit then, obtain the translucent monodisperse aluminium collosol of outward appearance, this monodisperse aluminium collosol is measured through laser light scattering instrument, micelle average grain diameter 87 nanometers, particle size distribution range 40～130 nanometers.The methylcellulose of 20% (weight) aluminium colloidal sol amount will be added in this colloidal sol, being made into aluminium content is 0.5 mol coating liquid, select the oxidation titanium film carrier of 12 * 300 * 2 millimeters of φ for use, under the condition of 25 ℃ of 5 seconds times of filming, film, air dry then, temperature programming drying, temperature-programmed calcination to 540 ℃.5 times so repeatedly, the film pipe that makes film is at every turn measured H with static method at 30 ℃
2, N
2Infiltration capacity and to N
2, H
2Separation, test result such as table 1:
[embodiment 4]
| The number of times of filming | Nitrogen infiltration capacity * 10 5Mole/rice 2Second handkerchief | Hydrogen permeate amount * 10 -5Mole/rice 2Second handkerchief | The teleblem separation | The composite membrane separation |
| 1 | 1.052 | 2.759 | 2.82 | 2.62 |
| 2 | 0.458 | 1.262 | 2.82 | 2.76 |
| 3 | 0.395 | 1.202 | 3.40 | 3.05 |
| 4 | 0.352 | 1.081 | 3.07 | |
| 5 | 0.274 | 0.934 | 3.41 |
400 milliliters of distilled water are preheated to 90 ℃, add 7 gram Al
2O
3H
2The O powder stirs half an hour; Treat Al
2O
3H
2After the O powder is uniformly dispersed, in this distilled water, add 2MHClO in distilled water
46 milliliters, make it to be made into suspension, this suspension is warming up to 99 ℃, carried out reflux digestion 80 hours, filter a small amount of deposit then, obtain the translucent monodisperse aluminium collosol of outward appearance, this monodisperse aluminium collosol is measured through laser light scattering instrument, micelle average grain diameter 118 nanometers, particle size distribution range 56～195 nanometers.The hydroxy-methyl cellulose of 40% (weight) aluminium colloidal sol amount will be added in the colloidal sol, and be made into the coating liquid (being coated with usefulness 2,3,4,5 times) that aluminium content is 1.1 mol (be coated with for the first time and use) and 0.7 mol respectively, select the silicon oxide film carrier of 12 * 30 * 2 millimeters of φ for use.Film all at 25 ℃ at every turn, film 5～10 seconds time, pass through air dry then, the temperature programming drying, temperature-programmed calcination to 470 ℃ system film forming pipe, after filming at every turn, with static method test membrane performance, test result such as table 2:
| The number of times of filming | Nitrogen infiltration capacity * 10 -5Mole/rice 2Second handkerchief | Hydrogen permeate amount * 10 -5Mole/rice 2Second handkerchief | The teleblem separation | The composite membrane separation |
| 1 | 0.939 | 2.554 | 2.85 | 2.72 |
| 2 | 0.481 | 1.383 | 3.01 | 2.87 |
| 3 | 0.436 | 1.279 | 2.93 | |
| 4 | / | / | / | / |
| 5 | 0.340 | 1.168 | / | 3.43 |
Claims (7)
1, a kind of Al that uses
2O
3H
2O prepares the method for inorganic ceramic membrane, it is characterized in that earlier Al
2O
3H
2The O powder joins in the distilled water that is preheated to 80～90 ℃, makes aluminium: the water ratio is 1: 100～200 (mol ratios), stirs; And then in distilled water, add the mixture of organic acid, inorganic acid or storng-acid cation exchange resin and inorganic acid; Make the hydrogen ion in the batching: aluminum ratio is 1: 1～10 (mol ratios); This suspension is warming up to 85～99 ℃, wore out 8～80 hours under keeping refluxing; Obtain transparent or semitransparent monodisperse aluminium collosol, in this colloidal sol, add binding agent and be made into the coating liquid that aluminium content is 0.2～1.2 mol concentration, then this coating liquid evenly is applied to the surface of micropore ceramics, through air dry, temperature programming drying, temperature-programmed calcination to 450～600 ℃, make surface inorganic ceramic membrane uniformly.
2, the preparation method of inorganic ceramic membrane according to claim 1 is characterized in that the organic acid that adds is formic acid or acetate in distilled water; Inorganic acid is nitric acid, hydrochloric acid or crosses chloric acid; Storng-acid cation exchange resin is a styrene cross-linking type cationic ion-exchange resin.
3, the preparation method of inorganic ceramic membrane according to claim 1 is characterized in that the binding agent that adds is polyvinyl alcohol, methylcellulose or hydroxy-methyl cellulose in colloidal sol.
4, the preparation method of inorganic ceramic membrane according to claim 1 is characterized in that coating liquid concentration is 0.4～0.7 mol.
5, the preparation method of inorganic ceramic membrane according to claim 1, the temperature that it is characterized in that temperature-programmed calcination is 500～550 ℃.
6, the preparation method of inorganic ceramic membrane according to claim 1, the addition that it is characterized in that binding agent are 20～40% (weight) of aluminium colloidal sol amount.
7, the preparation method of inorganic ceramic membrane according to claim 1, the material that it is characterized in that micropore ceramics are aluminium oxide, silica, cordierite, zirconia, titanium oxide or their mixture.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN94112148A CN1043190C (en) | 1994-05-03 | 1994-05-03 | Method for preparing inorganic ceramic membrane |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN94112148A CN1043190C (en) | 1994-05-03 | 1994-05-03 | Method for preparing inorganic ceramic membrane |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1111165A CN1111165A (en) | 1995-11-08 |
| CN1043190C true CN1043190C (en) | 1999-05-05 |
Family
ID=5035949
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN94112148A Expired - Fee Related CN1043190C (en) | 1994-05-03 | 1994-05-03 | Method for preparing inorganic ceramic membrane |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1043190C (en) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1304095C (en) * | 2004-06-16 | 2007-03-14 | 南京理工大学 | Method for preparing alumina ceramic membrance by ion exchange |
| CN101564652B (en) * | 2009-05-25 | 2011-08-10 | 北京化工大学 | Preparation method of nanofiltration membrane by particle packing method |
| CN102728235A (en) * | 2011-04-07 | 2012-10-17 | 北京化工大学 | Method for manufacturing alumina ceramic membrane |
| CN103230746B (en) * | 2013-04-17 | 2015-02-18 | 滨州学院 | Membrane coating apparatus and method of inorganic microfiltration membrane |
| CN110937880A (en) * | 2018-09-25 | 2020-03-31 | 中国石油化工股份有限公司 | Integral alumina material and preparation method thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3941719A (en) * | 1972-08-17 | 1976-03-02 | Owens-Illinois, Inc. | Transparent activated nonparticulate alumina and method of preparing same |
| US3944658A (en) * | 1972-08-17 | 1976-03-16 | Owens-Illinois, Inc. | Transparent activated nonparticulate alumina and method of preparing same |
-
1994
- 1994-05-03 CN CN94112148A patent/CN1043190C/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3941719A (en) * | 1972-08-17 | 1976-03-02 | Owens-Illinois, Inc. | Transparent activated nonparticulate alumina and method of preparing same |
| US3944658A (en) * | 1972-08-17 | 1976-03-16 | Owens-Illinois, Inc. | Transparent activated nonparticulate alumina and method of preparing same |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1111165A (en) | 1995-11-08 |
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