CN107376664A - A kind of preparation method towards acid system selfreparing seperation film - Google Patents
A kind of preparation method towards acid system selfreparing seperation film Download PDFInfo
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- CN107376664A CN107376664A CN201710676939.3A CN201710676939A CN107376664A CN 107376664 A CN107376664 A CN 107376664A CN 201710676939 A CN201710676939 A CN 201710676939A CN 107376664 A CN107376664 A CN 107376664A
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/02—Inorganic material
- B01D71/028—Molecular sieves
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
- B01D67/0039—Inorganic membrane manufacture
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
- B01D67/0079—Manufacture of membranes comprising organic and inorganic components
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
- B01D69/02—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor characterised by their properties
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/06—Organic material
- B01D71/40—Polymers of unsaturated acids or derivatives thereof, e.g. salts, amides, imides, nitriles, anhydrides, esters
- B01D71/42—Polymers of nitriles, e.g. polyacrylonitrile
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2323/00—Details relating to membrane preparation
- B01D2323/46—Impregnation
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2325/00—Details relating to properties of membranes
- B01D2325/30—Chemical resistance
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
Abstract
A kind of preparation method towards acid system selfreparing seperation film, belong to technical field of membrane separation.Its step includes：By anionic polymer sodium salt solution dip-coating to substrate or the surface of molecular screen membrane, Static Adsorption is dried afterwards for a period of time；This film immersion is subjected to ionomer in divalent salt solutions again.The acid resistance seperation film being prepared according to the method described above can be used for the separation of organic matter/aqueous systems under acid condition.After running a period of time, after film properties decay, film immersion is repaired in sodium salt solution, is impregnated in afterwards in certain density divalent metal salting liquid and is crosslinked a period of time, is dried under certain temperature, you can recovers film properties.Film prepared by this method has excellent separating property, acid resistance to organic matter/aqueous systems, and effectively extends the life-span of film.This method preparation condition is gentle, cost economy, is easy to industrial amplification.
Description
Technical field
The invention belongs to technical field of membrane separation, more particularly to a kind of preparation side towards acid system selfreparing seperation film
Method.
Background technology
Dehydration of organic solvent has great importance in fields such as petrochemical industry, bio-fuels.Infiltration evaporation with it is traditional
The technologies such as extracting rectifying are compared, with its cleaning, energy-conservation and efficiently the advantages of be widely used in the research of dehydration of organic solvent.So
And infiltrating and vaporizing membrane performance degradation in acid system is obvious, the life-span of film turns into key of the seperation film in acid system application
Problem.One layer of compacted zone (patent No. can be formed on film surface using the crosslinking of anti-acid polymer divalent salts：
201610476454.5).However, the longtime running under sour environment, some small charged ions (H in such as HCl+) can compensate
The electric charge of polymer, and the ion for the divalent salts being crosslinked is replaced, so as to which swelling or loosely organized, seperation film infiltration occur for film
The decline of performance is vaporized, causes the life-span of film to reduce, cost increase.In order to strengthen the acid resistance of seperation film, film can be utilized
Self-repair function strengthens its operation stability and life-span.
The content of the invention
The present invention provides a kind of preparation method for repairing acid resistance film, makes anionic polymer sodium salt using infusion process
Dip-coating is to substrate or the surface of molecular screen membrane, after drying, with divalent salt solutions cross linked anionic type polymer sodium salt so as to
Film surface or the surface of molecular screen membrane form one layer of compacted zone.After running in acid condition, by post-processing and repeating crosslinking
So as to be repaired to the performance degradation in film running.The film prepared using this kind of method is had to organic matter/aqueous systems
Excellent separating property, acid resistance and long-time stability.
A kind of acid resistance can repair the preparation method of seperation film, it is characterised in that comprise the following steps：
(1) certain density anionic polymer sodium salt solution, vacuum defoamation after stirring are prepared at room temperature；
(2) under certain temperature, basement membrane or molecular screen membrane are immersed in anionic polymer sodium salt solution, Static Adsorption
After a period of time, dry；
(3) basement membrane after step (2) dip-coating anionic polymer sodium salt or molecular screen membrane are immersed in certain density two
A period of time is crosslinked in valency metal salt solution, is dried；
(4) the acid resistance seperation film with certain number of plies is made in repeat step (2)-(3) for several times；
(5) seperation film of preparation is used into infiltration evaporation organic solvent/aqueous systems under acid condition separate, the timing of operation one
Between film properties decay after, film immersion is repaired in sodium salt solution, it is molten to be impregnated in certain density divalent metal salt afterwards
A period of time is crosslinked in liquid, is dried under certain temperature, you can recover film properties.
(6) repeat step (5) can performance degradation be repeatedly repaiied in acidic organic solvent/aqueous systems running to film
It is multiple.
The present invention relates to the preparation method that a kind of acid resistance can repair seperation film, it is characterised in that acidproof anionic
Polymer sodium salt can be sodium alginate, Sodium Polyacrylate, concentration 0.5wt%-5wt%, dip time 10-60min, impregnate
Temperature is 10-50 DEG C.
The divalent metal salinity that the present invention is used to be crosslinked is 0.05-0.5mol/L；Crosslinking time is 10-60min.For
The divalent metal of the divalent metal salt of crosslinking is selected from Cu2+、Ba2+、Ca2+、Co2+、Zn2+、Pb2+、Cd2+、Mn2+And Ni2+In one kind
Or it is several, divalent metal salt is soluble salt, such as nitrate, hydrochloride.Described basement membrane is organic polymer basement membrane, nothing
Machine ceramics basement membrane, described molecular screen membrane can be NaA, CHA, MOR, ZSM types.Described sodium salt is sodium chloride, sodium carbonate, carbonic acid
Hydrogen sodium, sodium phosphate, sodium nitrate, sodium phosphite, sodium sulfite, sodium acetate, sodium formate, sodium propionate, PAA, sodium benzoate,
Sodium hypochlorite, sodium chlorate, sodium perchlorate, sodium pyrophosphate, sodium thiosulfate, sodium peroxydisulfate, sodium metasilicate, sodium bromate, sodium bromide, iodine
Change sodium.Sodium salt concentration is 0.05-0.5mol/L；Repair time is 10-60min.
The acid resistance that the present invention is prepared can repair the separation that seperation film is used for organic matter/aqueous systems under acid condition,
Separated particularly for the infiltration evaporation of ethanol/water system under acid condition, acid condition is that pH scopes are 2~6.It is prepared by the present invention
Obtained acid resistance can repair seperation film available for long-term Effec-tive Function under acid condition.
The principle of technical solution of the present invention is：Hydrophilic acidproof anionic polymerization is impregnated in basement membrane or molecular screen membrane surface
Thing sodium salt layer is as separating layer or makes up the intergranular defect of molecular sieve, then passes through divalent ion and replace anionic polymer sodium salt
Na in layer+Ionomer is carried out, strengthens the stability of anionic polymer sodium salt.In acid feed liquid after long-term operation, by
In a large amount of H+Displacement causes crosslinked divalent salts ion to be lost in so as to the swelling of film or loosely organized with destroying.Further profit
Use Na+Enter line replacement to film, then fine and close infiltrating and vaporizing membrane is cross-linked to form to film using divalent ion again, repair or multiple
Film after reparation is applied to long-term industrial acid system separation.
Embodiment
The present invention is elaborated with reference to specific embodiment, but the present invention is not limited to following examples.
Embodiment 1
For the NaA molecular sieve membrane used for fine and close vapor permeable membrance, film effective area is 11.23cm2, anion used
Type polymer sodium salt is sodium alginate, viscosity 1.05-1.15Pas, divalent salts CaCl2, sodium salt NaCl, solvent for use
It is water.
Preparation condition and method：
(1) at room temperature, the sodium alginate soln that mass fraction is 1% is prepared, is transferred to after stirring in bottle,suction, very
Reciprocal of duty cycle is maintained at -0.09MPa deaerations 1h；
(2) at room temperature, NaA molecular sieve membrane is immersed in sodium alginate soln, Static Adsorption for a period of time after, dry；
(3) NaA molecular sieve membrane after dip-coating sodium alginate is immersed in the CaCl that concentration is 0.1mol/L230min in solution,
And dried at 40 DEG C；
(4) 4 obtained acid resistance sodium alginate NaA Modified Membranes of repeat step (2)-(3).
The sodium alginate NaA molecular sieve membrane of above-mentioned preparation is subjected to infiltration evaporation performance test in infiltration evaporation membrane cisterna.
Test condition is：The ethanol/water system that the ethanol content that feeding liquid is pH=3 is 90%, evaluation temperature are 75 DEG C, film downstream
Pressure is 200Pa.
The infiltration evaporation film properties measured are：Permeation flux is 900gm-2·h-1, water content is in permeate
99.0%.After operation 40 hours, film properties decline, permeation flux 705gm-2·h-1, water content is 96.8% in permeate
(5) film immersion is repaired in NaCl salting liquids by the film after performance degradation, is impregnated in finite concentration afterwards
Divalent metal salting liquid in be crosslinked 30min, at 40 DEG C dry.
Sodium alginate NaA molecular sieve membrane after above-mentioned reparation is subjected to infiltration evaporation performance survey in infiltration evaporation membrane cisterna
Examination.Test condition is：The ethanol/water system that the ethanol content that feeding liquid is pH=3 is 90%, evaluation temperature is 75 DEG C, under film
Trip lateral pressure is 200Pa.
The infiltration evaporation film properties measured are：Permeation flux is 860gm-2·h-1, water content is in permeate
99.6%, continue to run with 60 hours and have no decay.
Embodiment 2
For the polyacrylonitrile (PAN) used for basement membrane, film effective area is 28cm2, anionic polymer sodium salt used is
Sodium alginate, viscosity 1.05-1.15Pas, divalent salts CaCl2, sodium salt NaCl, solvent for use is water.
Preparation condition and method：
(1) at room temperature, the sodium alginate soln that mass fraction is 1% is prepared, is transferred to after stirring in bottle,suction, very
Reciprocal of duty cycle is maintained at -0.09MPa deaerations 1h；
(2) at room temperature, by PAN film immersions in sodium alginate soln, Static Adsorption for a period of time after, dry；
(3) film immersion after dip-coating sodium alginate is in the CaCl that concentration is 0.1mol/L230min in solution, and at 40 DEG C
Lower drying；
(4) 4 obtained acid resistance sodium alginate/PAN films of repeat step (2)-(3).
The sodium alginate of above-mentioned preparation/PAN films are subjected to infiltration evaporation performance test in infiltration evaporation membrane cisterna.Test-strips
Part is：The ethanol/water system that the ethanol content that feeding liquid is pH=2 is 90%, evaluation temperature are 75 DEG C, and film downstream lateral pressure is
200Pa。
The infiltration evaporation film properties measured are：Permeation flux is 2591gm-2·h-1, water content is in permeate
96.6%.After operation 8 hours, film properties decline, permeation flux 2689gm-2·h-1, water content is 83.9% in permeate
(5) film immersion is repaired in NaCl salting liquids by the film after performance degradation, is impregnated in finite concentration afterwards
Divalent metal salting liquid in be crosslinked 30min, at 40 DEG C dry.
Sodium alginate NaA molecular sieve membrane after above-mentioned reparation is subjected to infiltration evaporation performance survey in infiltration evaporation membrane cisterna
Examination.Test condition is：The ethanol/water system that the ethanol content that feeding liquid is pH=3 is 90%, evaluation temperature is 75 DEG C, under film
Trip lateral pressure is 200Pa.
The infiltration evaporation film properties measured are：Permeation flux is 8791gm-2·h-1, water content is in permeate
99.1%.
Claims (9)
1. a kind of acid resistance can repair the preparation method of seperation film, it is characterised in that comprise the following steps：
(1) certain density anionic polymer sodium salt solution, vacuum defoamation after stirring are prepared at room temperature；
(2) under certain temperature, basement membrane or molecular screen membrane are immersed in anionic polymer sodium salt solution, one section of Static Adsorption
After time, dry；
(3) basement membrane after step (2) dip-coating anionic polymer sodium salt or molecular screen membrane are immersed in certain density divalence gold
Belong to and a period of time is crosslinked in salting liquid, dry；
(4) the acid resistance seperation film with certain number of plies is made in repeat step (2)-(3) for several times.
2. the preparation method of seperation film can be repaired according to a kind of acid resistance described in claim 1, it is characterised in that also include with
Lower step：
(5) seperation film of preparation is used into infiltration evaporation organic solvent/aqueous systems under acid condition separate, runs certain time film
After performance degradation, film immersion is repaired in sodium salt solution, is impregnated in afterwards in certain density divalent metal salting liquid
Crosslinking for a period of time, is dried under certain temperature, you can recovers film properties.
3. the preparation method of seperation film can be repaired according to a kind of acid resistance described in claim 2, it is characterised in that repeat step
(5) to film, performance degradation is repeatedly repaired in acidic organic solvent/aqueous systems running.
4. the preparation method of seperation film can be repaired according to a kind of acid resistance described in claim 1, it is characterised in that acid resistance is cloudy
Ionomer sodium salt can be sodium alginate, Sodium Polyacrylate, concentration 0.5wt%-5wt%, dip time 10-
60min, dipping temperature are 10-50 DEG C.
5. the preparation method of seperation film can be repaired according to a kind of acid resistance described in claim 1, it is characterised in that for being crosslinked
Divalent metal salinity be 0.05-0.5mol/L；Crosslinking time is 10-60min.
6. the preparation method of seperation film can be repaired according to a kind of acid resistance described in claim 1, it is characterised in that for being crosslinked
The divalent metal of divalent metal salt be selected from Cu2+、Ba2+、Ca2+、Co2+、Zn2+、Pb2+、Cd2+、Mn2+And Ni2+In one kind or several
Kind, divalent metal salt is soluble salt.
7. the preparation method of seperation film can be repaired according to a kind of acid resistance described in claim 1, it is characterised in that described base
Film is organic polymer basement membrane, inorganic ceramic basement membrane, and described molecular screen membrane is NaA, CHA, MOR, ZSM types.
8. the preparation method of seperation film can be repaired according to a kind of acid resistance described in claim 1, it is characterised in that described use
In reparation sodium salt for sodium chloride, sodium carbonate, sodium acid carbonate, sodium phosphate, sodium nitrate, sodium phosphite, sodium sulfite, sodium acetate,
Sodium formate, sodium propionate, PAA, sodium benzoate, sodium hypochlorite, sodium chlorate, sodium perchlorate, sodium pyrophosphate, sodium thiosulfate,
Sodium peroxydisulfate, sodium metasilicate, sodium bromate, sodium bromide, sodium iodide；Sodium salt concentration is 0.05-0.5mol/L；Repair time is 10-
60min。
9. the acid resistance being prepared according to any one of claim 1-8 method can repair seperation film, applied under acid condition
The infiltration evaporation separation of ethanol/water system, acid condition is that pH scopes are 2~6.
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| CN201710676939.3A CN107376664B (en) | 2017-08-09 | 2017-08-09 | Preparation method of self-repairing separation membrane for acid system |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115364693A (en) * | 2021-11-16 | 2022-11-22 | 中国科学院生态环境研究中心 | Method for repairing water treatment performance of polyamide composite membrane |
| CN116116235A (en) * | 2023-02-02 | 2023-05-16 | 中复新水源科技有限公司 | Reverse osmosis membrane with self-healing function and preparation method thereof |
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| CN116116235A (en) * | 2023-02-02 | 2023-05-16 | 中复新水源科技有限公司 | Reverse osmosis membrane with self-healing function and preparation method thereof |
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