CN1724128A - Process for preparing organic and inorganic composite film by autoassembling tech - Google Patents
Process for preparing organic and inorganic composite film by autoassembling tech Download PDFInfo
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- CN1724128A CN1724128A CN 200510040661 CN200510040661A CN1724128A CN 1724128 A CN1724128 A CN 1724128A CN 200510040661 CN200510040661 CN 200510040661 CN 200510040661 A CN200510040661 A CN 200510040661A CN 1724128 A CN1724128 A CN 1724128A
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Abstract
A process for preparing the composite organic-inorganic membrane by self-assembling technique includes such steps as mixing ethyl silicate, de-ionized water, absolute alcohol and acid catalyst, heating to obtain SiO2 sol, ageing, coating it on the one surface of Al2O3 ceramic substrate, drying, calcining, washing to obtain SiO2-Al2O3 substrate, preparing poly-cationic electrolyte solution and poly-anionic electrolyte solution by use of hydrochloric acid, immersing the SiO2 side of said substrate in the poly-cationic solution and washing with clean water, immersing in polyanionic solution and washing with clean water, and repeating said alternative immersing and washing steps to form nano-class compact membrane layer.
Description
Technical field
The present invention relates to a kind of preparation method's of the film that is used to separate, particularly preparing organic and inorganic composite film by autoassembling tech method.
Background technology
Film separate as a kind of separation method have the selectivity height, simple to operate, energy consumption is low, take up an area of less, advantage such as pollution-free, become a kind of unit operations in the separation field in recent years gradually, and formed suitable industry size.From the evolution of membrane separation technique, the research of organic separation membrane starting early develops soon, is widely used.Organic film pliability is good, the selectivity height, and preparation process is simple, technology comparative maturity, and low price, but its poor heat stability, not acid and alkali resistance and organic solvent, adverse circumstances are short following service life, and easily block not easy cleaning and repeated use.The end of the seventies, the research of inoranic membrane began to cause people's extensive concern.Inoranic membrane is compared with organic film, has advantages such as heat endurance, chemical stability and mechanical stability are good, not aging, life-span length, easy cleaning.Yet inoranic membrane also has shortcomings such as material is more crisp, processing difficulties cost height.The mid-80, someone takes up the preparation research of organic and inorganic composite separating film, hope can be got up both advantages, make it both to have the stability of inoranic membrane, have the surface characteristic that organo-functional group is given again, the preparation of composite membrane and application have become one of the main developing direction in membrane science field.At present, the general employing makes methods such as organic matter grafting on ceramic membrane, interfacial polymerization, organic matter portion of hot solution have the machine inorganic substances compound membrane, but under test mostly, or permeability of the membrane can be undesirable, or cost is too high.
Summary of the invention
The object of the invention provides a kind of method of preparing organic and inorganic composite film by autoassembling tech, and the composite membrane that it makes contains fine and close organic film, be applicable to the infiltration evaporation separation process, and method is simple, and cost is low.
This method may further comprise the steps:
1) be 1 with ethyl orthosilicate, deionized water, absolute ethyl alcohol and acid catalyst with mol ratio: 4-10: 1-100: 0.05-0.5 mixes, 50-80 ℃ of following agitating heating 2～5 hours, SiO
2Colloidal sol, the ageing of constant temperature lower seal;
2) with SiO
2The colloidal sol coated is at tubular type or chip Al
2O
3On one side of ceramic micro filter film matrix;
3) with ceramic micro filter film matrix drying, subsequently in 500～550 ℃ of following roastings 2～5 hours, with the SiO of gained
2-Al
2O
3The inorganic substances compound membrane matrix is with acetone, and ethanol, deionized water clean for several times in turn;
4) polycation electrolyte and mixed in hydrochloric acid are mixed with cationic aqueous solution, polycation electrolyte concentration is 0.01mol/L in the solution, and concentration of hydrochloric acid is 0.01mol/L;
5) polyanion electrolyte and mixed in hydrochloric acid are mixed with anionic water solution, polyanion electrolyte concentration is 0.01mol/L in the solution, and concentration of hydrochloric acid is 0.01mol/L;
6) with the SiO of step 3) gained
2/ Al
2O
3The SiO of inorganic substances compound membrane matrix
2One side use washed with de-ionized water in the cationic solution of step 4) dipping back, places the anion solutions dipping back of step 5) use washed with de-ionized water again, floods 5～30 minutes at every turn, repeats the above several times of operating, and gets polymer-SiO
2-Al
2O
3Organic/inorganic composite film.
The number of repetition of dip operation can be decided according to polymer organic layer thickness needs in the step 6).
Said polycation electrolyte is: a kind of or its mixture in PAH salt, poly-dipropenyl dimethyl ammonium chloride, polyvinyl alcohol, collagen, shitosan, poly-D-lysine, the polyvinyl inferior amine salt hydrochlorate.
Said polyanion electrolyte is: a kind of or its mixture in kayexalate, polyvinyl sulfonate, dextran sulfate, chondroitin sulfate, sodium alginate, Sodium Polyacrylate, polymethylacrylic acid, heparin, the heparin sulfate.
The said sealing ageing of step 1) temperature is 25～50 ℃, and said acid catalyst is red fuming nitric acid (RFNA) or concentrated hydrochloric acid.
This method is based on the preparation technology of the organic/inorganic composite film of self-assembling technique, uses sol method at ceramic matrix surface coated SiO earlier
2Transition zone carries out modification to inorganic supporting body, utilizes SiO
2Easy hydroxylated character, alternating deposit polycation layer and polyanion layer repeatedly on its surface have promptly prepared the organic/inorganic composite film with permeance property by self-assembling technique.Organic substance is compounded on the inorganic substrate with fine polyion particle deposition, spontaneously be arranged in the ordered space structure by Electrostatic Absorption power, thereby form nano level fine and close organic film on inorganic micro filtering membrane, this film has extremely good Pervaporation Separation.Time and the number of times of the present invention by changing the zwitterion alternating impregnating can be realized control to organic film thickness.The inventive method technology simple economy, good reproducibility, degree of controllability height.
Description of drawings
Fig. 1 is the composite membrane schematic cross-section.
Fig. 2 is the influence of operating temperature to permeation flux.
Fig. 3 is the influence of operating temperature to permeate water content.
Fig. 1 represents the cross section schematic construction of the organic/inorganic composite film that the inventive method is made, and film lower floor is the porous ceramic matrices suitable as supporter, and the centre is SiO
2Coating, it is modified porous ceramic matrices suitable, makes it electrically charged, and the upper strata is a molecule self assembly separating layer, is at SiO by polycation and polyanion electrolyte
2The assembling of laminar surface alternating deposit forms.
Fig. 2 represents the influence of operating temperature to permeation flux, and the visual penetration flux increases along with the rising of feed temperature, and the rising of feed temperature helps improving permeation flux.
Fig. 3 represents the influence of operating temperature to permeate water content, and water content increases along with the rising of feed temperature in the visual penetration liquid, and promptly composite membrane increases the selectivity of water, and the rising of feed temperature helps improving the selectivity of composite membrane to water.
The specific embodiment
Embodiment 1
The preparation of organic/inorganic composite film
Place 60 ℃ water-bath to reflux 2 hours in the mixture of ethyl orthosilicate 50ml, absolute ethyl alcohol 50ml, deionized water 30ml, nitric acid 5ml, get silicon dioxide gel, seal ageing in 25 ℃ the baking oven.
With the silicon dioxide gel coated for preparing at Al
2O
3The inboard of porous ceramic film pipe placed 25 ℃ of baking oven inner dryings 3 days, after 4 hours, promptly coated SiO in the ceramic-film tube inboard 500 ℃ of following roastings again
2Rete cleans in turn with acetone, ethanol, deionized water, and the after backwashing 5 times of laying equal stress on is then at pure N
2Dry up in the atmosphere.
With adding hydrochloric acid in the poly diallyldimethylammonium chloride, be mixed with cationic solution, wherein poly diallyldimethylammonium chloride concentration is 0.01mol/L, concentration of hydrochloric acid is 0.01mol/L.Add hydrochloric acid in the kayexalate, be mixed with anion solutions, wherein kayexalate concentration is 0.01mol/L, and concentration of hydrochloric acid is 0.01mol/L.
Poly diallyldimethylammonium chloride solution is poured in the pipe of the ceramic-film tube of above-mentioned processing, the sealing two ends mouth of pipe, behind impregnated 5 minutes of the inwall of pipe, intraluminal fluid is inclined to, placed the deionized water soaking and washing 5 minutes, use again with quadrat method the inwall of pipe by kayexalate solution impregnation 5 minutes, use the deionized water soaking and washing.Constantly repeat above-mentioned dipping, cleaning process 50 times, with the ceramic-film tube inner surface of gained at pure N
2Dry up in the atmosphere, obtain polymer/SiO
2/ Al
2O
3Film.
Embodiment 2
Go up the infiltration evaporation performance test of routine composite membrane
On homemade infiltration evaporation experimental provision, carry out the Separation Research of the ethanol/water mixture of composite membrane, the feed ethanol weight concentration is 95% (being water content 5%), the infiltration measuring pressure is 500Pa, experimental result such as Fig. 2 and Fig. 3.
The water content of the visible material liquid of Fig. 3 is increased to 16% of per-meate side from 5%, composite membrane penetrated preferably water, thus make the ethanol of material liquid obtain further concentrating.
Claims (5)
1. the method for preparing organic and inorganic composite film by autoassembling tech is characterized in that may further comprise the steps:
1) be 1 with ethyl orthosilicate, deionized water, absolute ethyl alcohol and acid catalyst with mol ratio: 4-10: 1-100: 0.05-0.5 mixes, 50-80 ℃ of following agitating heating 2～5 hours, SiO
2Colloidal sol, the ageing of constant temperature lower seal;
2) with SiO
2The colloidal sol coated is at tubular type or chip Al
2O
3On one side of ceramic micro filter film matrix;
3) with after the ceramic micro filter film matrix drying, in 500～550 ℃ of following roastings 2～5 hours, with the SiO of gained
2-Al
2O
3The inorganic substances compound membrane matrix cleans for several times in turn with acetone, ethanol, deionized water;
4) polycation electrolyte and hydrochloric acid are mixed with the cation mixed aqueous solution, the cation Polyelectrolyte Concentration is 0.01mol/L in the solution, and concentration of hydrochloric acid is 0.01mol/L;
5) polyanion electrolyte and hydrochloric acid are mixed with are mixed into anionic water solution, anionic polyelectrolyte concentration is 0.01mol/L in the solution, and concentration of hydrochloric acid is 0.01mol/L;
6) with the SiO of step 3) gained
2/ Al
2O
3The SiO of inorganic substances compound membrane matrix
2One side use washed with de-ionized water in the cationic solution of step 4) dipping back, places the anion solutions dipping back of step 5) use washed with de-ionized water again, floods 5～30 minutes at every turn, repeats the above several times of operating, and gets polymer-SiO
2-Al
2O
3Organic/inorganic composite film.
2. the method for preparing organic and inorganic composite film by autoassembling tech according to claim 1 is characterized in that said polycation electrolyte is: a kind of or its mixture in PAH salt, poly-dipropenyl dimethyl ammonium chloride, polyvinyl alcohol, collagen, shitosan, poly-D-lysine, the polyvinyl inferior amine salt hydrochlorate.
3. the method for preparing organic and inorganic composite film by autoassembling tech according to claim 1 is characterized in that said polyanion electrolyte is: a kind of or its mixture in kayexalate, polyvinyl sulfonate, dextran sulfate, chondroitin sulfate, sodium alginate, Sodium Polyacrylate, polymethylacrylic acid, heparin, the heparin sulfate.
4. the method for preparing organic and inorganic composite film by autoassembling tech according to claim 1 is characterized in that said acid catalyst is red fuming nitric acid (RFNA) or concentrated hydrochloric acid.
5. according to the method for claim 1 or 2 or 3 or 4 described preparing organic and inorganic composite film by autoassembling tech, it is characterized in that the said sealing ageing of step 1) temperature is 25～50 ℃.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102548646A (en) * | 2009-04-09 | 2012-07-04 | 国立大学法人山口大学 | Charge-mosaic membrane |
| CN103223308A (en) * | 2013-04-22 | 2013-07-31 | 北京工业大学 | Composite nanofiltration membrane prepared based on aliphatic sulfonate condensation product |
| CN104307390A (en) * | 2014-11-05 | 2015-01-28 | 华玉叶 | Composite membrane |
| CN104772044A (en) * | 2015-03-13 | 2015-07-15 | 南京工业大学 | Method for improving inorganic/organic composite membrane performance through interface modification |
| CN106178994A (en) * | 2016-08-23 | 2016-12-07 | 东华理工大学 | A kind of preparation method of antibacterial NF membrane |
| CN106215718A (en) * | 2016-09-28 | 2016-12-14 | 东莞市联洲知识产权运营管理有限公司 | A kind of hollow fiber nanofiltration membrane based on ε polylysine and preparation method thereof |
| CN106334447A (en) * | 2016-09-28 | 2017-01-18 | 东莞市联洲知识产权运营管理有限公司 | Anti-pollution composite nano filtering membrane for direct dye waste liquid treatment |
| CN106422805A (en) * | 2016-10-12 | 2017-02-22 | 佛山迅拓奥科技有限公司 | Preparing method for antibacterial nanofiltration membrane with ultrafiltration membrane as base membrane |
| KR20170060642A (en) * | 2015-11-24 | 2017-06-02 | 한국기계연구원 | Cermic membrane having excellent fouling resistance by surface modification and water treatment method using the same |
| CN107174975A (en) * | 2017-06-18 | 2017-09-19 | 长沙无道工业设计有限公司 | A kind of desalinization composite membrane for producing hydrogen-rich direct drinking and preparation method thereof |
| CN108601235A (en) * | 2017-12-28 | 2018-09-28 | 广东光华科技股份有限公司 | The method of insulating substrate electroplating surface metal |
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| CN1058908C (en) * | 1997-06-20 | 2000-11-29 | 清华大学 | Method for prepn. of ultra filtering silica membrane used for seawater desalination |
| KR100313661B1 (en) * | 1999-10-13 | 2001-11-15 | 김충섭 | Polyion complex membranes for separation of organic mixtures, and preparation thereof |
| CN1239237C (en) * | 2002-12-24 | 2006-02-01 | 王旭生 | Preparing method for nanometer multi-microporous ceramic composite membrane for water treatment |
| CN1287888C (en) * | 2003-05-23 | 2006-12-06 | 中国科学技术大学 | Prepn process of negatively charged hybridized inorganic-organic membrane |
| CN1194801C (en) * | 2003-07-09 | 2005-03-30 | 天津大学 | Preparation method of nanometer Al2O3Sio2 polysulfone composite film having intermediate phase structure |
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2005
- 2005-06-22 CN CNB2005100406618A patent/CN1305553C/en active Active
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| CN102548646B (en) * | 2009-04-09 | 2015-12-02 | 国立大学法人山口大学 | Charge embedded film |
| CN102548646A (en) * | 2009-04-09 | 2012-07-04 | 国立大学法人山口大学 | Charge-mosaic membrane |
| CN103223308A (en) * | 2013-04-22 | 2013-07-31 | 北京工业大学 | Composite nanofiltration membrane prepared based on aliphatic sulfonate condensation product |
| CN103223308B (en) * | 2013-04-22 | 2015-01-07 | 北京工业大学 | Composite nanofiltration membrane prepared based on aliphatic sulfonate condensation product |
| CN104307390A (en) * | 2014-11-05 | 2015-01-28 | 华玉叶 | Composite membrane |
| CN104772044A (en) * | 2015-03-13 | 2015-07-15 | 南京工业大学 | Method for improving inorganic/organic composite membrane performance through interface modification |
| KR20170060642A (en) * | 2015-11-24 | 2017-06-02 | 한국기계연구원 | Cermic membrane having excellent fouling resistance by surface modification and water treatment method using the same |
| CN106178994A (en) * | 2016-08-23 | 2016-12-07 | 东华理工大学 | A kind of preparation method of antibacterial NF membrane |
| CN106334447A (en) * | 2016-09-28 | 2017-01-18 | 东莞市联洲知识产权运营管理有限公司 | Anti-pollution composite nano filtering membrane for direct dye waste liquid treatment |
| CN106215718A (en) * | 2016-09-28 | 2016-12-14 | 东莞市联洲知识产权运营管理有限公司 | A kind of hollow fiber nanofiltration membrane based on ε polylysine and preparation method thereof |
| CN106422805A (en) * | 2016-10-12 | 2017-02-22 | 佛山迅拓奥科技有限公司 | Preparing method for antibacterial nanofiltration membrane with ultrafiltration membrane as base membrane |
| CN107174975A (en) * | 2017-06-18 | 2017-09-19 | 长沙无道工业设计有限公司 | A kind of desalinization composite membrane for producing hydrogen-rich direct drinking and preparation method thereof |
| CN107174975B (en) * | 2017-06-18 | 2020-06-09 | 玛雅森林(北京)国际科技有限公司 | Seawater desalination composite membrane for producing hydrogen-rich direct drinking water and preparation method thereof |
| CN108601235A (en) * | 2017-12-28 | 2018-09-28 | 广东光华科技股份有限公司 | The method of insulating substrate electroplating surface metal |
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