CN104671750A - Preparation method of composite ZrO2-Al2O3 ceramic micro-filtration membrane - Google Patents
Preparation method of composite ZrO2-Al2O3 ceramic micro-filtration membrane Download PDFInfo
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- CN104671750A CN104671750A CN201410821184.8A CN201410821184A CN104671750A CN 104671750 A CN104671750 A CN 104671750A CN 201410821184 A CN201410821184 A CN 201410821184A CN 104671750 A CN104671750 A CN 104671750A
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Abstract
The invention discloses a preparation method of a composite ZrO2-Al2O3 ceramic micro-filtration membrane. The method comprises the following steps: (1) burdening zirconia powder and alumina powder, and carrying out ball-milling; (2) adding an additive lanthanum nitrate, and carrying out ball-milling; and (3) forming a film from the milled slurry, drying and sintering. The powder components of the composite membrane layer prepared by the preparation method gradually change; the pore size distribution of the membrane layer is relatively narrow; the thickness of the membrane layer is moderate, so that the micro-filtration membrane has relatively high permeation flux and separation coefficient; the particle size collocation of the powder of a transition membrane layer is reasonable; the surface roughness of the membrane layer is improved; relatively large membrane layer pollution is not easily caused in the actual separation process; zirconia with good chemical stability is utilized in the membrane layer; and the acid and alkali resistance of the membrane layer is improved. The price of the zirconia is higher than that of aluminum oxide, but the amount in preparation of the membrane layer is relatively small; meanwhile, the service life of an inorganic membrane can be prolonged; and the composite ZrO2-Al2O3 ceramic micro-filtration membrane is better than a simple aluminum oxide ceramic membrane or zirconia ceramic membrane in the market at present in performance.
Description
Technical field
The present invention relates to compound ZrO
2-Al
2o
3the preparation method of ceramic microfiltration membrane, belongs to ceramic membrane preparation field.
Background technology
Along with the increase of mankind's environmental consciousness and the improvement of existing membrane technique, the separation efficiency that membrane sepn has is high, can not produce the appreciation that the advantages such as secondary pollution receive increasing manufacturer, and particularly mineral membrane chemical stability is good, physical strength is high, long service life; System operation is easy, stable, and maintenance cost is low; Biochemical treatment can adopt integration apparatus, and whole process can realize Automated condtrol etc. and is applied to widely in caustic environment by many producers relative to the feature of organic membrane, such as, and high temperature, highly basic, strong acid, strong organic solvent etc.
Generally all contain acid or alkali in the waste water that modern chemical industry produces in producing, if adopt chemical method to remove, add chemical reagent except needs and increase except processing costs, the more important thing is and can produce secondary pollution.The use of mineral membrane just can well solve such shortcoming, and the concentrated solution obtained after process can also be recycled, and reduces processing costs.Such condition is for the environment of pH value between 3 ~ 11, is less than 3 or be greater than 11 for pH value, and conventional mineral membrane is as Al
2o
3film in this environment life-time service can cause the reduction of breaking of rete and supporter intensity because of being corroded of mould material, thus greatly shortens the work-ing life of mineral membrane.Therefore, for such environment for use, the mould material system that new chemical stability is good must be developed.
ZrO
2al is compared because having
2o
3better chemical stability and become research emphasis.ZrO
2the relative Al of material
2o
3the another one advantage had has good hydrophilic oleophobic property.ZrO
2middle Zr
4+in+4 valencys, have and compare Al
3+much higher mass-to-charge ratio, thus polarity is stronger, for profit system, ZrO
2there is good oleophobic property.This feature is for use ZrO
2film process oily(waste)water then rete pollutes few, and permeation flux is large.Thus.For ZrO
2the research of the preparation technology of film just has very important practice significance.
For ZrO
2the preparation of film, report more in document be adopt sol-gel legal system for ZrO
2ultra-filtration membrane, and large for flux, the ZrO that use range is wider
2the preparation of microfiltration membrane then generally adopts dip-coating preparation.No matter adopt any method, if adopt sintering strength good, the Al of cost relative moderate
2o
3as supporter, ZrO will be there is
2rete and Al
2o
3because of the difference (ZrO of material character between supporter
2thermal expansivity be 10.8 × 10
-6, Al
2o
3thermal expansivity be 8.8 × 10
-6) and the heat treatment performance mismatch problem caused.Heat treatment performance does not mate accumulated stress and in drying and sintering process, produces the defects such as tiny crack by directly causing rete, has a strong impact on ZrO
2the performance of microfiltration membrane.Therefore, the principle of utilizing works mechanics, solves the problem of rete cracking for raising ZrO
2the performance of microfiltration membrane, the Application Areas reducing product cost and expansion mineral membrane will have important science and practical application meaning.
Summary of the invention
The object of the present invention is to provide bonding force between a kind of rete good, not easily produce tiny crack, membrane permeation flux
Greatly, oily(waste)water rete can be processed and pollute few compound ZrO
2-Al
2o
3the preparation method of ceramic microfiltration membrane.
Compound ZrO of the present invention
2-Al
2o
3the preparation method of ceramic microfiltration membrane, comprises the steps:
(1) zirconia powder and aluminum oxide powder are prepared burden according to volume required ratio, add the deionized water identical with powder quality, ball milling 12 hours on shaft type ball mill;
(2) additive lanthanum nitrate is made into the solution of 8%, adjust ph is 8.5 to add according to 2% of powder quality, ball milling 24 hours;
(3) different volumes after above-mentioned ball milling is adopted dip-coating method film forming than the slurry of batching, then wet film is placed in the loft drier drying that humidity is 70%, the 5-10% of original moisture is accounted for the moisture contained, according to the temperature rise rate of 1 DEG C/min, will there is the rete sintering of different volumes than batching successively.
During step (3) sintering, according to from containing low volumetric concentration ZrO
2composite film to containing high volumetric concentration ZrO
2composite film sinter successively.
The volume proportion of step (1) described zirconia powder and aluminum oxide powder is respectively containing 20% volumetric concentration ZrO
2and containing 80% volumetric concentration ZrO
2.
Step (1) described zirconia powder particle diameter 4um, aluminum oxide powder particle diameter 2.5um.
The powder content gradually variational of the composite film that preparation method of the present invention obtains, rete pore size distribution is narrower, and thicknesses of layers is moderate, thus has larger permeation flux and separation factor; The diameter of particle collocation of transition rete rationally, improves the surfaceness of rete, not easily causes larger rete to pollute in substantial sepn process; Employ the good zirconium white of chemical stability in rete, improve the performance of the acid-alkali-corrosive-resisting of rete.Although zirconic cost ratio aluminum oxide is high, in the preparation of rete, usage quantity is less, greatly can also increase the work-ing life of mineral membrane simultaneously, than alumina ceramic membrane simple in the market or zirconia ceramics film properties excellence.
The composite film that preparation method of the present invention obtains can be used for the transition layer that alumina support and zirconium white filter rete, can improve the performance difference between supporter in thermal treatment, reduces the possibility of the film cracking that rete causes because of thermal treatment.Because the character between the character of composite membrane and adjacent rete is close, easily sinter in sintering process, the combination degree between rete is fine, avoids heterogeneous asymmetric membrane in preparation process, produces the phenomenon that rete and supporter peel off; The microfiltration membrane of the composite membrane prepared of this technology inherently excellent property, simultaneously also can as sol-gel legal system for ZrO
2the supporter that ultra-filtration membrane is good.Because nature difference between rete is little, reduce the thermal stresses that the difference because of material character causes to greatest extent and concentrate, improve ZrO
2optimal experimental design technique, improves finished product rate; The ZrO that chemical stability is good is added in composite membrane
2, relative Al
2o
3separatory membrane, has expanded the use range of ceramic membrane, has improve the work-ing life of separatory membrane; Relative ZrO
2separatory membrane, although performance is close, decreases the ZrO that price is higher
2usage quantity, reduce the manufacturing cost of ceramic membrane.
Embodiment
Following embodiment further illustrates using as the explaination to the technology of the present invention content for content of the present invention; but flesh and blood of the present invention is not limited in described in following embodiment, those of ordinary skill in the art can and should know any simple change based on connotation of the present invention or replace all should belong to protection domain of the presently claimed invention.
embodiment 1
Compound ZrO of the present invention
2-Al
2o
3the preparation method of ceramic microfiltration membrane, comprises the preparation of composite mortar and the preparation of compound transition rete, and concrete preparation adopts following step:
(1) zirconia powder (particle diameter 4um) and aluminum oxide powder (particle diameter 2.5um) are respectively 0,20%, 40%, 60%, 80%, 100% batching according to zirconium white volume ratio, add the deionized water identical with powder quality, ball milling 12 hours on shaft type ball mill;
(2) additive lanthanum nitrate is made into the solution of 8%, adjust ph is 8.5 to add according to 2% of powder quality, and ball milling obtains respectively containing the zirconic compound ZrO of 0,20%, 40%, 60%, 80%, 100% volume ratio for 24 hours
2-Al
2o
3slurry;
(3) different volumes after above-mentioned ball milling is adopted dip-coating method film forming than the slurry of batching, then wet film is placed in the loft drier drying that humidity is 70%, the 5-10% of original moisture is accounted for the moisture contained, according to the temperature rise rate of 1 DEG C/min, to there is the rete sintering of different volumes than batching successively, during sintering, according to from containing low volumetric concentration ZrO
2composite film to containing high volumetric concentration ZrO
2composite film sinter successively, obtain compound ZrO
2-Al
2o
3ceramic microfiltration membrane.The film of this example gained composite film can a few aperture 0.2um, is less than conventional ZrO at present
2or Al
2o
3ceramic membrane can a few aperture, permeation flux is 1600 l/ (m
2hbar), higher than commonly using ZrO at present
2or Al
2o
3the permeation flux of ceramic membrane.
Claims (4)
1. compound ZrO
2-Al
2o
3the preparation method of ceramic microfiltration membrane, comprises the steps:
(1) zirconia powder and aluminum oxide powder are prepared burden according to volume required ratio, add the deionized water identical with powder quality, ball milling 12 hours on shaft type ball mill;
(2) additive lanthanum nitrate is made into the solution of 8%, adjust ph is 8.5 to add according to 2% of powder quality, ball milling 24 hours;
(3) different volumes after above-mentioned ball milling is adopted dip-coating method film forming than the slurry of batching, then wet film is placed in the loft drier drying that humidity is 70%, the 5-10% of original moisture is accounted for the moisture contained, according to the temperature rise rate of 1 DEG C/min, will there is the rete sintering of different volumes than batching successively.
2. compound ZrO as claimed in claim 1
2-Al
2o
3the preparation method of ceramic microfiltration membrane, is characterized in that, during step (3) sintering, according to from containing low volumetric concentration ZrO
2composite film to containing high volumetric concentration ZrO
2composite film sinter successively.
3. compound ZrO as claimed in claim 1
2-Al
2o
3the preparation method of ceramic microfiltration membrane, is characterized in that, the volume proportion of step (1) described zirconia powder and aluminum oxide powder is respectively containing 20% volumetric concentration ZrO
2and containing 80% volumetric concentration ZrO
2.
4. compound ZrO as claimed in claim 1
2-Al
2o
3the preparation method of ceramic microfiltration membrane, is characterized in that, step (1) described zirconia powder particle diameter 4um, aluminum oxide powder particle diameter 2.5um.
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|---|---|---|---|
| CN201410821184.8A CN104671750B (en) | 2014-12-26 | 2014-12-26 | Compound ZrO2‑Al2O3The preparation method of ceramic micro filter film |
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|---|---|---|---|
| CN201410821184.8A CN104671750B (en) | 2014-12-26 | 2014-12-26 | Compound ZrO2‑Al2O3The preparation method of ceramic micro filter film |
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| CN104671750A true CN104671750A (en) | 2015-06-03 |
| CN104671750B CN104671750B (en) | 2017-06-20 |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105771675A (en) * | 2016-03-24 | 2016-07-20 | 景德镇陶瓷学院 | Ceramic membrane having asymmetric structure, and preparation method of ceramic membrane |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2009220074A (en) * | 2008-03-18 | 2009-10-01 | Nikkato:Kk | Alumina substrate for separation membrane with superior corrosion resistance and manufacturing method of the same |
| CN102701778A (en) * | 2012-06-01 | 2012-10-03 | 清华大学 | Preparation method for ceramic film with hierarchical pore structure |
| CN103074660A (en) * | 2013-01-30 | 2013-05-01 | 长安大学 | Preparation method of ZrO2/Al2O3 composite membrane on surfaces of aluminium and aluminium alloy |
| CN103408200A (en) * | 2013-08-27 | 2013-11-27 | 武汉钢铁(集团)公司 | Cold rolling oily wastewater treatment process |
-
2014
- 2014-12-26 CN CN201410821184.8A patent/CN104671750B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2009220074A (en) * | 2008-03-18 | 2009-10-01 | Nikkato:Kk | Alumina substrate for separation membrane with superior corrosion resistance and manufacturing method of the same |
| CN102701778A (en) * | 2012-06-01 | 2012-10-03 | 清华大学 | Preparation method for ceramic film with hierarchical pore structure |
| CN103074660A (en) * | 2013-01-30 | 2013-05-01 | 长安大学 | Preparation method of ZrO2/Al2O3 composite membrane on surfaces of aluminium and aluminium alloy |
| CN103408200A (en) * | 2013-08-27 | 2013-11-27 | 武汉钢铁(集团)公司 | Cold rolling oily wastewater treatment process |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105771675A (en) * | 2016-03-24 | 2016-07-20 | 景德镇陶瓷学院 | Ceramic membrane having asymmetric structure, and preparation method of ceramic membrane |
| CN105771675B (en) * | 2016-03-24 | 2018-11-06 | 景德镇陶瓷大学 | A kind of unsymmetric structure ceramic membrane and preparation method thereof |
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| CN104671750B (en) | 2017-06-20 |
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