CN1184699A - Mesopore molecular sieve inorganic composite film used for water purification - Google Patents
Mesopore molecular sieve inorganic composite film used for water purification Download PDFInfo
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- CN1184699A CN1184699A CN97116931A CN97116931A CN1184699A CN 1184699 A CN1184699 A CN 1184699A CN 97116931 A CN97116931 A CN 97116931A CN 97116931 A CN97116931 A CN 97116931A CN 1184699 A CN1184699 A CN 1184699A
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- molecular sieve
- mesopore molecular
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Abstract
In the prepn. porous ceramics membrane is used as matrix, the mesoporous molecular sieve film is combined on its surface. By using the surfacial chemical plating technology, a hydrophobic organic film is prepared on the mesoporous surface of the molecular sieve. When using for water treatment,the external layer microfiltering structure can filter away the bacteria, virus and macro molecule, while the mesoporous molecular sieve film of internal layer surface can absorb and sieve the soluble harmful matter in the water. Said composite film is easy to regenerate, it can be used in the deep treatment of daily life used water, and also can be used in the waste water purifying treatment.
Description
The present invention discloses a kind of preparation method of inorganic compounding molecular screen membrane, and it is the application that belongs to novel environmental material in the water body purification.
In recent years, the application development of film aspect purification techniques is very fast, and as carrying out water treatment with milipore filter, this adventitia has been widely used in the biological technology products separation.Membrane technology is better than conventional method as a kind of separation means.Yet there are many fatal shortcomings in organic high molecular layer, and its film-strength is not enough, poor heat resistance, and easily biological-degradable is easily by organic solvent swelling and acid and alkali-resistance not.Simple in addition membrane technology just utilizes the duct to dam to carry out isolation of purified, and little molecule and harmful element can not effectively separate, and therefore adopt organic high molecular layer still can not be used for ambient water fully and handle.The appearance of inorganic material film, film and membrane process The Application of Technology field have greatly been opened up, this is on the one hand because inoranic membrane has characteristics such as high strength that macromolecular material lacks, high temperature resistant, resistance to chemical attack, new on the other hand inoranic membrane preparation technology's fast development also makes the even inoranic membrane preparation in high performance aperture become possibility, and the developmental research of inoranic membrane has at present become the important directions of membrane technology development.Abroad, ceramic micro filter film has been used for the clarification of fruit juice, drinks, degerming, milk the aspect such as concentrate.The inoranic membrane of preparation small-bore also has certain difficulty at present, and the contradiction between permeability and the selectivity is a difficult problem.The organic/inorganic composite membrane that the various countries researcher has developed various ways has in recent years made full use of the selectivity of organic polymer and the stability of inoranic membrane, but the bond strength between inoranic membrane and the organic polymer can become subject matter.Molecular sieve is used for environmental protection at present; especially use still few in the water body purification; it particularly is the matrix skeleton with the inorganic ceramic; with mesopore molecular sieve in its surface recombination film forming; and carrying out chemical modification on mesoporous inner surface, inorganic substances compound membrane at home and abroad still is not reported to be used for water body purification to prepare efficiently.
The object of the present invention is to provide a kind of mesopore molecular sieve inorganic composite film that is used for water body purification.It not only removes the organic pollution in the water body, reduces the harmful element in the water body again dramatically, is used for water body purification effectively.
In order to achieve the above object, the present invention is achieved through the following technical solutions.It is to make basement membrane with the inorganic ceramic pipe of special pore size distribution; Get ethyl orthosilicate, positive butyl titanate, tetramethylammonium hydroxide aqueous solution, be mixed into the mesopore molecular sieve gel with softex kw (template agent), carry out surface recombination in ceramic membrane surface, it is attached to carry out chemical plating at the mesopore molecular sieve internal surface of hole then, and the aperture that it is characterized in that ceramic-film tube is 100～400nm; Gel solution mole proportioning: (0.2～0.8) ethyl orthosilicate: (0.01～0.05) positive butyl titanate: (0.03～0.09) TMAH (25% aqueous solution): 56 water: (0.1～0.5) softex kw: (0～0.5) auxiliary agent, amount by the control auxiliary agent, change template agent structure effect in the coagulant liquid, the aperture of molecular screen membrane is changed; The auxiliary agent that joins in the gel is ethanol and isopropanol mixture, and its mol ratio is 2: 1; The surface recombination of mesopore molecular sieve gel and basement membrane adopts the rotary dipping technology; Chemical plating is (10～15% vinyltrimethoxy silanes+2～5% dimethylsilane+80～888% dimethylbenzene) with the machine mixture.The speed of the rotary dipping of mesopore molecular sieve film gel and basement membrane is 450～600rpm; Dip time is 0.5～2 minute.The attached condition of chemical plating on surface is to add hot reflux 5 hours at 110 ℃, and 80～90 ℃ of dryings 48 hours.
The concrete preparation method of mesopore molecular sieve inorganic composite film of the present invention is as follows.
Get the certain size inorganic ceramic membrane parent tube (internal diameter 10mm, external diameter 14mm, long 100mm) of commodity selling, or adopt ripe ceramic membrane preparation technology self-control.Require aperture average out to 400nm.Clean secondary respectively with ethanol and deionized water, to remove the organic matter and the impurity on surface.Under 100 ℃ to film pipe vacuum drying 24 hours with standby.Get ethyl orthosilicate (TEOS), positive butyl titanate Ti (OC
4H
9)
4TMAH (25% aqueous solution) (TMA) OH mixes, adding softex kw (CTMA) Br is the template agent, is auxiliary agent with ethanol and isopropyl alcohol (mol ratio 2: 1) mixed liquor A, is made into three kinds of molecular sieve gel liquid 0.8TEOS of following mole proportioning: 0.02Ti (OC
4H
9)
4: 0.08 (TMA) OH: 56H
2O: 0.5CTMABr: (0～0.5) A, wherein the mole of A is taken as 0,0.25,0.5 respectively and will handles the sealing of stand-by ceramic-film tube bottom surface, is fixed on the electric rotating machine, under certain rotation speed (450～600rpm), slowly immerse in the gel solution, the control time is 1 minute.The film pipe that skin is scribbled gel mould is dried 2hr down at 120 ℃, calcines 5hr down at 540 ℃～600 ℃, forms the mesopore molecular sieve film.Can adopt repeatedly dip-coating-drying-method for calcinating to the gel of above-mentioned three kinds of variable concentrations, to form molecular sieve rete complete and that have the special pore size distribution gradient.Embathe respectively with watery hydrochloric acid and deionized water again, be washed till neutrality, again 120 ℃ of following vacuum drying.Prepare the organic polymer soln of following mass percent: (10～15% vinyltrimethoxy silanes+5% dimethylsilane+80～85% dimethylbenzene)-Zeolite composite film that obtains is immersed in the organic mixture solution, temperature is 110 ℃, and the control time is 5hr.Take out the back cooling, embathe several times, to remove potential solvent and free silane with xylene extraction.Then in drying box with temperature drying 48hr less than 90 ℃.Form the organic film of one deck at the mesopore molecular sieve bore area like this.
To outer surface, its aperture is descending from the film tube hub for the inorganic compounding molecular screen membrane of above-mentioned preparation.The employing inorganic ceramic membrane is a matrix, and film strength is increased, acid and alkali-resistance, and the thickness of functional membrane is little, the permeability rate height.Lip-deep chemical modification of mesopore molecular sieve film and plating are attached, make the oil contaminants in its organic pollution to solubility, particularly water body, and strong suction-operated is arranged.Strengthened the absorption effect of damming of mesopore molecular sieve film.The molecular screen membrane of the ceramic membrane of micro-filtration structure and wide spectrum absorption screening characteristics can 100% filtering water body in harmful bacteria, virus and big organic molecule.In addition heavy metal ion, little organic molecule harmful in the water there is strong adsorption capacity.Composite inorganic molecular screen membrane of the present invention is easy to regeneration, to saturated or weary film body, can adopt hydrochloric acid to embathe, and is washed till the neutral heavy metal ion that gets final product wash-out absorption with getting ionized water again.To the organic pollution that absorption is held back, can adopt suitable organic solvent extraction regeneration on the one hand, available water steam desorption can use repeatedly in addition.Therefore it is a kind of high-performance, reproducible mesopore molecular sieve inorganic composite film.This inoranic membrane has characteristics easy to use, can make the filter core mode, is equipped with overcoat.Former water is entered by the film tube hub, flows out from the tube outside, and it is inserted the water body pipe-line system, directly uses.
Embodiment: get internal diameter 10mm, external diameter 14mm, long 100mm inorganic ceramic membrane pipe (average pore size 400nm) is used ethanol and washed with de-ionized water respectively, 100 ℃ of following vacuum drying.Take by weighing chemical pure ethyl orthosilicate 166.4g, positive butyl titanate 6.7g, TMAH (25% aqueous solution) 30.4g, softex kw 218.4g, ethanol 3.7g isopropyl alcohol 5.0g, water 1026g mixes to stir forming gel.Above-mentioned ceramic-film tube is immersed in the coagulant liquid with the 600rpm rotation, and the control dip time is 1 minute.Can adopt dip-coating one a dry method for calcinating repeatedly.Drying is 2 hours under 120 ℃, calcined 5 hours down, take by weighing vinyltrimethoxy silane 150.0g then, dimethylsilane 50.0g for 600 ℃, dimethylbenzene 800.0g, mix wiring solution-forming, the earthenware that is compounded with mesopore molecular sieve is immersed in this organic solution, 110 ℃ of hot refluxs 5 hours, take out cooling, clean with dimethylbenzene, descended dry 48 hours at 90 ℃ again, so just make a kind of mesopore molecular sieve inorganic composite film finished product.Make use-case: 1. certain mark-on domestic water, behind this combined filtration, the front and back testing result sees Table 1: (mg/l) 0.003 0.0005 0.004 0.05 0.01 0.002 02. certain waste water water body after (mg/l) 1.6 0.098 0.008 1.20 1 0.29 10000 purified before the plumbous mercury cadmium of project benzo purified than the thin castor number of hexachloro-benzene chloroform, contain a large amount of organic pollutions, processing through this compound sieve membrane, testing result sees Table 2: project TOC (mg/l) apparent colour turbidity purifies preceding 41000 brown, 200 is colourless, transparent after muddy the purification
Claims (3)
1. preparation method who is used for the mesopore molecular sieve inorganic composite film of water body purification, it is to make basement membrane with the inorganic ceramic pipe of special pore size distribution; Get ethyl orthosilicate, positive butyl titanate, tetramethylammonium hydroxide aqueous solution, be mixed into the mesopore molecular sieve gel with softex kw (template agent), carry out surface recombination in ceramic membrane surface, it is attached to carry out chemical plating at the mesopore molecular sieve internal surface of hole then, and it is characterized in that: the micropore of ceramic-film tube is 100～400nm; Gel solution mole proportioning, ethyl orthosilicate: positive butyl titanate: TMAH (25% aqueous solution): softex kw: auxiliary agent: water is (0.2～0.8): (0.01～0.05): (0.03～0.09): (0.1～0.5): (0～0.5): 56, the auxiliary agent that joins in the gel is ethanol and isopropanol mixture, and its mol ratio is 2: 1; The surface recombination of mesopore molecular sieve gel and basement membrane adopts the rotary dipping technology; Chemical plating is (10～15%) vinyltrimethoxy silane+(2～5%) dimethylsilane+(80～88%) dimethylbenzene with the machine mixture.
2. the mesopore molecular sieve inorganic composite film that is used for water body purification according to claim 1 is characterized in that, rotary dipping is to carry out under 450～600rpm rotating condition, and dip time is 0.5～2 minute.
3. the mesopore molecular sieve inorganic composite film that is used for water body purification according to claim 1 is characterized in that, the chemical plating in sieve membrane hole is attached to be to carry out under 5 hours 110 ℃ of hot refluxs, then 80～90 ℃ dry 48 hours down.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN97116931A CN1184699A (en) | 1997-09-29 | 1997-09-29 | Mesopore molecular sieve inorganic composite film used for water purification |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN97116931A CN1184699A (en) | 1997-09-29 | 1997-09-29 | Mesopore molecular sieve inorganic composite film used for water purification |
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| CN1184699A true CN1184699A (en) | 1998-06-17 |
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|---|---|---|---|
| CN97116931A Pending CN1184699A (en) | 1997-09-29 | 1997-09-29 | Mesopore molecular sieve inorganic composite film used for water purification |
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1113811C (en) * | 2001-08-14 | 2003-07-09 | 复旦大学 | Preparation method of mesonic pore molecular sieve carrier material |
| WO2007071166A1 (en) * | 2005-12-23 | 2007-06-28 | Beijing Lanjing Innovation And Technology Co., Ltd | Composite membrane based on superfine metal-powder sinter, its preparation method and seawater desalination system |
| CN100341783C (en) * | 2005-04-07 | 2007-10-10 | 中国科学院大连化学物理研究所 | Method for preparing molecular sieve membrane on porous ceramic carrier by utilizing hydrothermal synthesis |
| CN100386364C (en) * | 2006-01-09 | 2008-05-07 | 武汉理工大学 | Method of preparing metallic sulfide nano-particle and mesopore film composite material |
| CN100455354C (en) * | 2007-03-27 | 2009-01-28 | 天津大学 | Method for producing zeolite molecular sieve film carrier noble metal catalyst |
| CN100462133C (en) * | 2006-05-17 | 2009-02-18 | 景德镇陶瓷学院 | Composite modified A1203 ceramic microfiltering film |
| CN109529523A (en) * | 2018-11-26 | 2019-03-29 | 吉林大学 | Molecular sieve core-mesoporous organosilicon hollow shell multi-stage porous composite material and preparation method |
| CN110668844A (en) * | 2019-10-17 | 2020-01-10 | 天津大学 | Microwave sintering preparation method of black molecular adsorption layer on ceramic surface |
-
1997
- 1997-09-29 CN CN97116931A patent/CN1184699A/en active Pending
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1113811C (en) * | 2001-08-14 | 2003-07-09 | 复旦大学 | Preparation method of mesonic pore molecular sieve carrier material |
| CN100341783C (en) * | 2005-04-07 | 2007-10-10 | 中国科学院大连化学物理研究所 | Method for preparing molecular sieve membrane on porous ceramic carrier by utilizing hydrothermal synthesis |
| WO2007071166A1 (en) * | 2005-12-23 | 2007-06-28 | Beijing Lanjing Innovation And Technology Co., Ltd | Composite membrane based on superfine metal-powder sinter, its preparation method and seawater desalination system |
| CN100386364C (en) * | 2006-01-09 | 2008-05-07 | 武汉理工大学 | Method of preparing metallic sulfide nano-particle and mesopore film composite material |
| CN100462133C (en) * | 2006-05-17 | 2009-02-18 | 景德镇陶瓷学院 | Composite modified A1203 ceramic microfiltering film |
| CN100455354C (en) * | 2007-03-27 | 2009-01-28 | 天津大学 | Method for producing zeolite molecular sieve film carrier noble metal catalyst |
| CN109529523A (en) * | 2018-11-26 | 2019-03-29 | 吉林大学 | Molecular sieve core-mesoporous organosilicon hollow shell multi-stage porous composite material and preparation method |
| CN110668844A (en) * | 2019-10-17 | 2020-01-10 | 天津大学 | Microwave sintering preparation method of black molecular adsorption layer on ceramic surface |
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