CN1239237C - Preparing method for nanometer multi-microporous ceramic composite membrane for water treatment - Google Patents
Preparing method for nanometer multi-microporous ceramic composite membrane for water treatment Download PDFInfo
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- CN1239237C CN1239237C CN 02136000 CN02136000A CN1239237C CN 1239237 C CN1239237 C CN 1239237C CN 02136000 CN02136000 CN 02136000 CN 02136000 A CN02136000 A CN 02136000A CN 1239237 C CN1239237 C CN 1239237C
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Abstract
The present invention provides a method for preparing a nanometer microporous ceramic composite membrane for water treatment, a hydrothermal molecule self-recognizing method is used, and that is to say, a hexagonal phase-recognizing structure formed by interacting polyethylene glycol or hexadecyl trimethyl ammonium chloride or hexadecyltrimethylammonium bromide with tetraethyl orthosilicate, TEOS, presedimentation silicon dioxide colloid, SiO2, Al2O3, etc., and the polyethylene glycol or the hexadecyl trimethyl ammonium chloride or the hexadecyltrimethylammonium bromide is used as a guiding agent; a microporous ceramic nanometer ion screening material with a nanometer dimension is obtained after the organic guiding agent is eliminated by heat treatment, and the microporous ceramic nanometer ion screening material, high molecular polymers, etc. are sliced compositely to be manufactured into an inorganic-organic composite membrane. Because the method has the advantages of wide material sources, simple technology and low production cost, the cost and the operation cost of sea water or brackish water desalination devices assembled by nanometer microporous composite membrane components and desalination engineering can be greatly reduced, drinking water with low price and good quality can be obtained, and the present invention has the obvious social benefits and economic benefits.
Description
1, technical field
The present invention relates to a kind of ceramic material that is used for water treatment, specifically a kind of preparation method of ion sub-sieve nanometer multi-microporous ceramic composite membrane.The nanometer micropore material is by SiO
2With Al
2O
3Be base material, be powder shaped, have the hardness height, chemical property is stable, and density is little, can carry out the performance of a series of excellences such as sub-sieve to ion and molecule, can be widely used in water treatment, environmental protection, fields such as petroleum industry.
2, technical background
Existing seawater, misery or salt water are processed into the method for treating water of drinking water, adopt has film evaporation method, hyperfiltration, dialysis or the like more.Though the water quality of utilizing said method to handle can reach the standard of drinking water,, operating cost and the engineering equipment cost of handling water are very expensive.Employed critical material organic film material has poor stability in the water treatment facilities, intensity is low, not corrosion-resistant, and have easily be degraded, drawbacks such as crowfoot cracks, inefficacy, cleaning difficulty, therefore, be difficult for extensive use and popularize.
3, summary of the invention
The objective of the invention is to overcome the problem of above existence, it is compound that employing inorganic ceramic ion sub-sieve material and high-molecular organic material carry out two-phase, makes inorganic-organic asymmetric compound film and be used for the nanoporous pottery of the ion sub-sieve of seawater or brackish water desalination.A kind of good stability, intensity height, corrosion-resistant are provided, and the preparation method who is difficult for the ion sub-sieve nanometer multi-microporous ceramic composite membrane that is used for water treatment facilities of degraded, not crowfoot cracks, easy cleaning.
Method of the present invention is to utilize the hydro-thermal molecule from the knowledge method, promptly utilizes polyethylene glycol or hexadecyltrimethylammonium chloride or softex kw as directed agents and ethyl orthosilicate, the silicon dioxide colloid of preformed precipitate, SiO
2, Al
2O
3Know each other the attitude structure Deng six sides that interact to form, remove organic directed agents by heat treatment after, obtain the multi-microporous ceramic nanoparticle sub-sieve material of nano-scale.Make inorganic-organic hybrid films with materials such as multi-microporous ceramic nanoparticle sub-sieve material and high molecular polymer are composite layered again.
The preparation method of nanometer multi-microporous ceramic composite membrane for water treatment of the present invention comprises the preparation of multi-microporous ceramic nano-powder, the preparation of the organic basement membrane of micropore and the preparation of inorganic-organic hybrid films:
Concrete preparation process is as follows:
(1) preparation of multi-microporous ceramic nano-powder: surfactant and the fineness of 20-30% are mixed at the nano-powder raw material of 5-100 nanometer 75-80%, heat 100-300 ℃, be incubated 2-10 hour, material self-organizing generation organic matter is known the attitude structure mutually with the liquid crystal of inorganic matter under this temperature, this structure has the lattice paprmeter of nano-scale mutually, the 300-1300 ℃ of high temperature that heats up is then removed surfactant, and it is standby to generate the multi-microporous ceramic nano-powder;
(2) preparation of the organic basement membrane of micropore: the high molecular polymer with 40～50% joins in 30～40% the excessive transition solvent and stirs, adding 10～20% pore former again mixes and is mixed with casting solution, with the casting solution blade coating after on the surface of template, template is sunk in the precipitating bath solution immediately, non-transition solvent in transition solvent in the casting solution and the precipitating bath solution exchanges mutually, make the casting solution of initial steady state produce unstable state and then liquid-liquid phase separation formation micropore basal membrane takes place, template is taken out from precipitating bath solution, micropore basal membrane is peeled off from template to make micropore basal membrane standby;
(3) preparation of inorganic-organic hybrid films: the multi-microporous ceramic nano-powder with 3 ‰～1% joins in the dispersant that polyacrylic acid or aliphatic acid forms and stirs, make the aggregate of porous ceramics nano-powder be separated into single multi-microporous ceramic nano-powder particle or a plurality of multi-microporous ceramic nano-powder particle cluster aggressiveness is evenly distributed in the dispersant, dispersant coated equably make the ion rete of forming by multi-microporous ceramic nano-powder particle on the basement membrane, use the casting solution blade coating again on multi-microporous ceramic nano-powder particle ion rete, form second layer micropore basal membrane through the precipitating bath solution-treated and just make an inorganic organic hybrid films.
Surfactant is: the mixture of one or more in poly-ethanol, hexadecyltrimethylammonium chloride or the softex kw;
The nano-powder raw material is: SiO
2, Al
2O
3, ethyl orthosilicate one or more mixture.
High molecular polymer is: the mixture of one or more of polyether sulfone, polyethersulfone ketone or aromatic polyamides high molecular polymer;
The transition solvent is: the mixture of one or more of dimethylacetylamide or dimethyl sulfoxide (DMSO);
Pore former is: the mixture of one or more of PVP, sodium acetate or sodium nitrate;
The precipitation body lotion is: water or 30～60% ethanol water.
4, embodiment
Prescription and preparation method:
Prescription one,
1, the weight of preparation multi-microporous ceramic powder material is composed as follows:
(1) amount of surfactant accounts for 25% of raw material composition;
(2) nano-powder raw material consumption accounts for 75% of raw material composition.
2, the weight proportion of each raw material of casting solution is as follows:
(1) high molecular polymer: 40%
(2) transition solvent: dimethylacetylamide or dimethyl sulfoxide (DMSO) 40%
(3) pore former: PVP or sodium acetate or sodium nitrate 18%
(4) inorganic monomer molecule: nanoporous ceramic powder 2%.
Precipitating bath solution is the ethanol water of water or 30～60%.
Prescription two,
1, the weight of preparation multi-microporous ceramic powder material is composed as follows:
(1) amount of surfactant accounts for 20% of raw material composition;
(2) nano-powder raw material consumption accounts for 80% of raw material composition.
2, the weight proportion of each raw material of casting solution is as follows:
(1) high molecular polymer: 40%
(2) transition solvent: dimethylacetylamide or dimethyl sulfoxide (DMSO) 37%
(3) pore former: PVP or sodium acetate or sodium nitrate 20%
(4) inorganic monomer molecule: nanoporous ceramic powder 3%.
Precipitating bath solution is the ethanol water of water or 30～60%.
The preparation of nanometer multi-microporous ceramic powder:
(1) growth of precursor organic/inorganic liquid crystalline phase, utilize have parents' character be two ends contain respectively hydrophilic and hydrophobic group because of the poly-ethanol of surfactant, hexadecyltrimethylammonium chloride or softex kw and fineness be nano level SiO
2, Al
2O
3, the self-organizing under the environment of heating of ethyl orthosilicate powder generate organic matter and inorganic matter liquid crystal knowledge attitude structure mutually.And this structure has the lattice paprmeter of nano-scale mutually.Utilize high-temperature heat treatment method to remove organic surface active agent then and generate nanometer multi-microporous ceramic powder with many micropore canals.
Heat treatment is divided into two stages: in 100～300 ℃ of relatively low temperature ranges, and amorphous organic directed agents gel particles generation crystal transfer, and follow dehydration, generate no water particle.Organic surface active agent is also burnouted in this stage.In temperature rises to 300～1300 ℃ of scopes, generate the multi-microporous ceramic nano-powder that is interconnected and contacts with surrounding environment.
The preparation method of nanometer multi-microporous ceramic composite membrane:
(1) preparation of basement membrane: in proportion high molecular polyether sulfone material is added solvent dimethylacetylamide or dimethyl sulfoxide (DMSO), pore former sodium acetate or sodium nitrate etc. carry out hybrid modulation, and the press filtration deaeration is mixed with casting solution.Through the solvent evaporation, cold water dipping or heat treated are made basement membrane (supporting layer) then.
(2) preparation of molecular screen membrane: the aforementioned multi-microporous ceramic nano-powder that makes is added dispersant (polyacrylic acid in proportion; Aliphatic acid etc.) in, make the aggregate of nano particle be separated into single nano particle, the small agglomerates of nano particle few in number is evenly distributed in the organic media, coat equably then and form ion sub-sieve layer on the micropore basal membrane, because nanometer effect and affinity reach to capillary action, make particle-filled being fixed on organic micropore basal membrane, make it two tablings, containing.
(3) preparation of inorganic-organic interlayer composite membrane: in proportion with the macromolecule aromatic polyamides or (PPESK) and solvent dimethylacetylamide or dimethyl sulfoxide (DMSO)), pore former (PVP or sodium acetate, sodium nitrate etc. carry out hybrid modulation and become casting solution, are coated on the molecular sieve rete; Exchange the casting solution that makes initial thermodynamics stable state mutually by transition solvent in the casting solution and precipitating bath solution and produce unstable state and liquid-liquid takes place be separated into the micropore compacted zone, thereby make inorganic-organic hybrid films.
Nanometer multi-microporous ceramic composite membrane of the present invention can be prepared into the chip film, also can be prepared into hollow membrane.
Compound film sheet or hollow membrane be will prepare and rolled film element or hollow fibre membrane component made by existing general rolled film or hollow-fibre membrane group technological standards size and technological standards.Then membrane component is contained in the cylindrical pressure vessel, promptly constitutes the membrane module that seawater or brackish water desalination are used.
The advantage of many porous nanos composite membrane of the present invention is as follows:
1, divides the screen capacity height to the molecule in water or the Normal Atmospheric Temperature Liquid or ion; Utilize nano ceramics ion sub-sieve material The asymmetric pellicle of inorganic-organic that material is prepared into; To the sodium chloride in the seawater (NaCl) and contain pigment, The former water of divalent salts, trivalent salt ion or molecule carries out pressure filtration, and removal efficiency is up to 99%～99.5%.
2, the present invention is because adopting the composite film material that becomes with Polymer materialspreparation with the nanometer multi-microporous ceramic material, It has taken into account the advantage of inoranic membrane and organic film material, has high-flexibility, intensity height, anti-degraded, corrosion resistant The property, stability is stronger than conventional organic or inorganic membrane material, because its area is big, and the porosity height, it produces water Flux is big, power consumption is low, easier maintenance, cleaning and maintenance. So, can guarantee that it has stable property Energy and quality. Because material source of the present invention is wide, technology is simple, production cost is low, so applying nano Seawater or bitter salt water desalting equipment and desalting engineering cost and the operating cost meeting of the assembling of many microporous compound films element Greatly reduce, thereby obtain drinking water of high quality and at a reasonable price.
3, this membrane material is not the simple adduction of inorganic phase and organic phase, but by inorganic phase and organic phase In nanometer range, carry out 0-2 and be compounded to form, exist stronger or more weak chemical bond or tighter between two-phase interface Close chimeric, containing. Many specific physiques that they compound will realize collecting inorganic-organic, nano particle in New material all over the body, it has taken into account the advantage of inoranic membrane and organic film material. Thereby have good popularization and make Use value.
Claims (1)
1. the preparation method of a nanometer multi-microporous ceramic composite membrane for water treatment is characterized in that concrete preparation process is as follows:
(1) preparation of multi-microporous ceramic nano-powder: surfactant and the fineness of 20-25% are mixed at the nano-powder raw material of 5-100 nanometer 75-80%, heat 100-300 ℃, be incubated 2-10 hour, material self-organizing generation organic matter is known the attitude structure mutually with the liquid crystal of inorganic matter under this temperature, this structure has the lattice paprmeter of nano-scale mutually, the 300-1300 ℃ of high temperature that heats up is then removed surfactant, and it is standby to generate the multi-microporous ceramic nano-powder;
Surfactant is: the mixture of one or more in poly-ethanol, hexadecyltrimethylammonium chloride or the softex kw;
The nano-powder raw material is: SiO
2, Al
2O
3, one or more the mixture in the ethyl orthosilicate.
(2) preparation of the organic basement membrane of micropore: the high molecular polymer with 40～50% joins in 30～40% the transition solvent and stirs, adding 10～20% pore former again mixes and is mixed with casting solution, with the casting solution blade coating after on the surface of template, template is sunk in the precipitating bath solution immediately, non-transition solvent in transition solvent in the casting solution and the precipitating bath solution exchanges mutually, make the casting solution of initial steady state produce unstable state and then liquid-liquid phase separation formation micropore basal membrane takes place, template is taken out from precipitating bath solution, micropore basal membrane is peeled off from template to make micropore basal membrane standby;
High molecular polymer is: the mixture of one or more of polyether sulfone, polyethersulfone ketone or aromatic polyamides high molecular polymer;
The transition solvent is: the mixture of one or more in dimethylacetylamide or the dimethyl sulfoxide (DMSO);
Pore former is: the mixture of one or more in PVP, sodium acetate or the sodium nitrate;
(3) preparation of inorganic-organic hybrid films: the multi-microporous ceramic nano-powder with 3 ‰～1% joins in the dispersant that polyacrylic acid or aliphatic acid forms and stirs, make the aggregate of porous ceramics nano-powder be separated into single multi-microporous ceramic nano-powder particle or a plurality of multi-microporous ceramic nano-powder particle cluster aggressiveness is evenly distributed in the dispersant, dispersant coated equably make the ion rete of forming by multi-microporous ceramic nano-powder particle on the basement membrane, use the casting solution blade coating again on multi-microporous ceramic nano-powder particle ion rete, form second layer micropore basal membrane through the precipitating bath solution-treated and just make inorganic-organic hybrid films.
The precipitation body lotion is: water or 30～60% ethanol water.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 02136000 CN1239237C (en) | 2002-12-24 | 2002-12-24 | Preparing method for nanometer multi-microporous ceramic composite membrane for water treatment |
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|---|---|---|---|
| CN 02136000 CN1239237C (en) | 2002-12-24 | 2002-12-24 | Preparing method for nanometer multi-microporous ceramic composite membrane for water treatment |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1509805A CN1509805A (en) | 2004-07-07 |
| CN1239237C true CN1239237C (en) | 2006-02-01 |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102872819A (en) * | 2012-08-28 | 2013-01-16 | 常州大学 | Composite adsorbing material for removing nitrate from water and preparation method of same |
Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100394215C (en) * | 2005-05-26 | 2008-06-11 | 财团法人工业技术研究院 | Three-D nano-porous film and its manufacturing method |
| CN1305553C (en) * | 2005-06-22 | 2007-03-21 | 南京工业大学 | Process for preparing organic and inorganic composite film by autoassembling tech |
| CN101265123B (en) * | 2008-04-18 | 2010-12-01 | 南京工业大学 | Method for preparing small aperture ceramic film |
| EP2402071B1 (en) * | 2009-02-27 | 2019-04-03 | Mitsubishi Chemical Corporation | Inorganic porous support-zeolite membrane composite, production method thereof, and separation method using the composite |
| CN102008901B (en) * | 2010-09-28 | 2012-11-21 | 朱惠芬 | Preparation method of multifunctional water treatment nano material composite membrane |
| CN107233870A (en) * | 2017-07-03 | 2017-10-10 | 安徽省鸿鑫生物科技有限公司 | A kind of preparation method and applications of sewage treating material |
| CN107174963B (en) * | 2017-07-17 | 2020-05-08 | 天津大学 | Method for preparing PES ultrafiltration membrane by using eutectic solvent |
| US20190177237A1 (en) | 2017-12-11 | 2019-06-13 | Saudi Arabian Oil Company | Ceramic membranes |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102872819A (en) * | 2012-08-28 | 2013-01-16 | 常州大学 | Composite adsorbing material for removing nitrate from water and preparation method of same |
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