CN109999666A - High-throughput charged positive electricity anti-acid nanofiltration membrane, preparation method and application - Google Patents
High-throughput charged positive electricity anti-acid nanofiltration membrane, preparation method and application Download PDFInfo
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- CN109999666A CN109999666A CN201910365990.1A CN201910365990A CN109999666A CN 109999666 A CN109999666 A CN 109999666A CN 201910365990 A CN201910365990 A CN 201910365990A CN 109999666 A CN109999666 A CN 109999666A
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D61/00—Processes of separation using semi-permeable membranes, e.g. dialysis, osmosis or ultrafiltration; Apparatus, accessories or auxiliary operations specially adapted therefor
- B01D61/02—Reverse osmosis; Hyperfiltration ; Nanofiltration
- B01D61/027—Nanofiltration
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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
- B01D67/0002—Organic membrane manufacture
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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
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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
- B01D71/06—Organic material
- B01D71/56—Polyamides, e.g. polyester-amides
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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
- B01D71/06—Organic material
- B01D71/66—Polymers having sulfur in the main chain, with or without nitrogen, oxygen or carbon only
- B01D71/68—Polysulfones; Polyethersulfones
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/44—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis
- C02F1/442—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis by nanofiltration
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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
- B01D2325/16—Membrane materials having positively charged functional groups
Abstract
A kind of high-throughput charged positive electricity anti-acid nanofiltration membrane, preparation method and application.The preparation method is reacted the following steps are included: ultrafiltration membranes are immersed in configured aqueous phase solution, obtains ultrafiltration membranes one after dry；Ultrafiltration membranes one are immersed in oil-phase solution and are reacted, ultrafiltration membranes two are obtained；High-throughput charged positive electricity anti-acid nanofiltration membrane is obtained after ultrafiltration membranes two are heat-treated.For nanofiltration membrane prepared by the present invention under the premise of guaranteeing acid resistance and salt rejection rate, flux improves 100%~250%, in addition, the preparation method is simply easy to realize industrial production, is with a wide range of applications；High-throughput charged positive electricity anti-acid nanofiltration membrane prepared by the present invention is improved to polyvalent cation rejection and saturating sour rate.
Description
Technical field
The present invention relates to membrane preparation technology fields, and in particular to a kind of high-throughput charged positive electricity anti-acid nanofiltration membrane, its preparation
Methods and applications.
Background technique
Nanofiltration is the membrane separation technique risen in recent years, due to property the characteristics of its own, to molecular weight 200
Organic matter between~1000Da has higher removal effect, and can retain the part ion beneficial to human body.Nanofiltration at present is
It is widely used in the fields such as purification of water quality, Industrial Wastewater Treatment, wherein nanofiltration is applied relatively extensively in strong acidic environment,
As highly acid liquid to be processed (extract waste liquid, acidic cleaning solution, electroplating industry acid-bearing wastewater, metal industry and demould spent acid by industrial acids
Liquid, fermentation acid waste water etc.) in heavy metal recovery, acid recovery and biomass separation and the purifying of water etc., thus prepare
Anti-acid nanofiltration membrane is very necessary, to improve rejection and hydrionic transmitance to polyvalent metal ion, prepares lotus positive electricity
Acid resistance nanofiltration membrane is most important.Currently, preparing nanofiltration membrane (amides nanofiltration membrane) using diamines and acyl chlorides interfacial polymerization
Conventional means, but intolerant to strong acid, so anti-acid nanofiltration membrane mostly uses polyamines and cyanuric trichloride or contains trimerization at present
The oligomer of cyanogen chlorine reacts, and has better acid resistance than amides nanofiltration membrane.But most anti-acid nanofiltration membranes are
Nanofiltration membrane with negative electric charge, the rejection and saturating sour rate to polyvalent cation are to be improved, and flux is lower, only in 2.0~3.0LMH/
bar.To promote the application value of nanofiltration membrane in acid condition, the anti-acid nanofiltration membrane for preparing high-throughput charged positive electricity very must
It wants.
Summary of the invention
In view of this, one of main object of the present invention be to propose a kind of high-throughput charged positive electricity anti-acid nanofiltration membrane, its
Preparation method and application, at least be partially solved at least one of above-mentioned technical problem.
To achieve the goals above, it as one aspect of the present invention, provides a kind of high-throughput charged positive electricity anti-acid and receives
The Preparation Method of filter membrane, the preparation method comprises the following steps:
S1: ultrafiltration membranes being immersed in configured aqueous phase solution and are reacted, and obtains ultrafiltration membranes one after dry；
S2: ultrafiltration membranes one being immersed in oil-phase solution and are reacted, and obtains ultrafiltration membranes two；
S3: high-throughput charged positive electricity anti-acid nanofiltration membrane is obtained after ultrafiltration membranes two are heat-treated.
As another aspect of the present invention, a kind of high-throughput charged positive electricity anti-acid nanofiltration membrane is additionally provided.
As an additional aspect of the present invention, it is net in water quality to additionally provide a kind of high-throughput charged positive electricity anti-acid nanofiltration membrane
Change, the application of field of industrial waste water treatment.
Based on the above-mentioned technical proposal it is found that high-throughput charged positive electricity anti-acid nanofiltration membrane of the invention, preparation method and answering
With one of at least having the advantage that compared with the existing technology:
1, technical characterstic of the invention is to control oily phase concentration and heat treatment process, will have by the method for interfacial polymerization
There is the complex functional layer of C-N key to be coated in the surface of ultrafiltration membranes, the lotus positive electricity for preparing high-throughput (30-150LMH/MPa) is resistance to
Acid type nanofiltration membrane, surface Zeta potential is up to 15-30mV.
2, nanofiltration membrane prepared by the present invention is guaranteeing acid resistance and under the premise of salt rejection rate, flux improves 20%~
500%, in addition, the preparation method is simply easy to realize industrial production, it is with a wide range of applications.
3, the present invention prepared by high-throughput charged positive electricity anti-acid nanofiltration membrane improve to polyvalent cation rejection and thoroughly
Sour rate.
Detailed description of the invention
Fig. 1 is lotus positive electricity anti-acid nanofiltration membrane (curve a) and Tao Shi NF270 nanofiltration membrane in comparative example 1 in embodiment 1
(curve b) is to 2g/LMgCl2Rejection with soaking time change curve comparison diagram；
Fig. 2 is the salt rejection rate (figure A) and saturating sour rate (figure B) figure of the lotus positive electricity anti-acid nanofiltration membrane in embodiment 1；
Fig. 3 be in comparative example 2 in AMS-A3012 (a) and the present embodiment 3 the high-throughput charged acidproof nanofiltration membrane (b) of positive electricity it is logical
Measure comparison diagram.
Specific embodiment
To make the objectives, technical solutions, and advantages of the present invention clearer, below in conjunction with specific embodiment, and reference
Attached drawing, the present invention is described in further detail.
The invention discloses a kind of preparation methods of high-throughput charged positive electricity anti-acid nanofiltration membrane, which is characterized in that the system
Preparation Method the following steps are included:
S1: ultrafiltration membranes being immersed in configured aqueous phase solution and are reacted, and obtains ultrafiltration membranes one after dry；
S2: ultrafiltration membranes one being immersed in oil-phase solution and are reacted, and obtains ultrafiltration membranes two；
S3: high-throughput charged positive electricity anti-acid nanofiltration membrane is obtained after ultrafiltration membranes two are heat-treated.
Wherein, heat treatment temperature is 20-100 DEG C, is, for example, 70 DEG C in the step S3, heat treatment time 1min-
It 120min, is, for example, 5min.
Wherein, the step S1- step S3 reacts under normal pressure.
Wherein, it is rinsed, and is stored in ionized water with deionized water after the step S3.
Wherein, it after the step S3, with citric acid treatment, is then rinsed with deionized water, and be stored in deionization
In water.
Wherein, the concentration of the citric acid is 2-15wt%, is, for example, 10wt%, and the processing time is 1-20min, for example
For 5min.
Wherein, in the step S1 aqueous phase solution configuration method are as follows: sequentially add aqueous phase monomers in deionized water, tie up
Sour agent and surfactant, and be uniformly dispersed, as aqueous phase solution；
The aqueous phase monomers are polyethyleneimine, polyvinylamine, polyethylene aniline, polyphenyl methylamine, diethylenetriamine, more second
Any one or more of combination of alkene polyamines, for example, polyethyleneimine, the molecular weight of the polyethyleneimine are 600-
It 25000, is, for example, 1800.
Wherein, the aqueous phase monomers A can also be respectively the mass mixings such as 600,1800,10000,25000 for molecular weight
Polyethyleneimine mixture；
The acid binding agent is triethylamine, pyridine, 4-dimethylaminopyridine, n,N-diisopropylethylamine, sodium hydroxide, hydrogen
Any one or more of potassium oxide, sodium bicarbonate, sodium carbonate, saleratus, potassium carbonate, acid binding agent are, for example, triethylamine；
The surfactant is neopelex, dodecyl sodium sulfate, lauryl sodium sulfate, hexadecane
Base dimethyl benzyl ammonium chloride, octadecyltrimethylammonium chloride, tri-n-octyl methyl ammonium chloride, benzyltriethylammoinium chloride, four
Any one or more of conventional surfactants such as butyl ammonium chloride, surfactant are, for example, dodecyl sodium sulfate.
Wherein, the concentration of the aqueous phase monomers is 5-25g/L, for example, 10g/L；
The concentration of the acid binding agent is 0.1-5wt%, is, for example, 0.5wt%；
The concentration of the surfactant is 0.02-0.08wt%, is, for example, 0.05wt%.
Wherein, in the step S2 oil-phase solution preparation method are as follows: cyanuric trichloride is dissolved in organic solvent；Trimerization
The concentration of cyanogen chlorine is 0.01-5g/L, is, for example, 2g/L；
Wherein, the organic solvent is any one or more of n-hexane, hexamethylene, toluene, benzene, ethyl acetate, is had
Solvent is, for example, n-hexane.
Wherein, ultrafiltration membranes are immersed in 2-15min in configured aqueous phase solution in the step S1, are, for example,
10min；
Drying means is to dry in the step S1；
The reaction time is 20-500s, is, for example, 180s in the step S2；
Reaction temperature in the step S2 is 5-45 DEG C, is, for example, 10 DEG C；Reaction humidity 20-80%, it is, for example,
40%.
Wherein, the ultrafiltration membranes be polyether sulfone, polysulfones, it is poly- between any in stupid two formyls m-phenylene diamine (MPD) ultrafiltration membrane
Kind, for example, polyether sulfone.
The molecular cut off of the ultrafiltration membranes is 30KDa-100KDa, for example, 30KDa.
The invention also discloses a kind of high-throughput charged positive electricity anti-acid nanofiltration membranes that the preparation method obtains.
Wherein, the flux of the high-throughput charged positive electricity anti-acid nanofiltration membrane is 30-150LMH/MPa.
Wherein, the surface Zeta potential of the high-throughput charged positive electricity anti-acid nanofiltration membrane is 15-30mV.
The invention also discloses the high-throughput charged positive electricity anti-acid nanofiltration membranes described in one kind at purification of water quality, industrial wastewater
The application in reason field.
In one embodiment of the invention, for example, by using following preparation method:
The invention discloses a kind of preparation methods of high-throughput charged positive electricity anti-acid nanofiltration membrane, belong to membrane preparation technology neck
Domain.Polyethyleneimine, dodecyl sodium sulfate are added sequentially in deionized water first, prepare aqueous phase solution；Again by trimerization
Cyanogen chlorine is dissolved in organic solvent, prepares oil-phase solution, finally by ultrafiltration membranes liquid haptoreaction compatible with water under atmospheric pressure,
Then removal redundant solution, then again with oil-phase solution haptoreaction for a period of time, after being heat-treated, rushed with deionized water
It washes, and is stored in the anti-acid nanofiltration membrane for arriving the lotus positive electricity in ionized water.Nanofiltration membrane prepared by the present invention has
It is high to polyvalent cation rejection, lead to the high feature of acid rate, it is easy to operate, it easily realizes industrialization, is with a wide range of applications.
In a preferred embodiment of the present invention, the present invention is for example, by using following technical solution:
A kind of preparation method of high-throughput charged positive electricity anti-acid nanofiltration membrane, method includes the following steps:
(1) it configures aqueous phase solution: sequentially adding 5-25g/L aqueous phase monomers, the acid binding agent of 0.1-5wt% in deionized water
It with the surfactant of 0.02-0.08wt%, and is uniformly dispersed, configures aqueous phase solution；
(2) it configures oil-phase solution: cyanuric trichloride is dissolved in n-hexane, hexamethylene, toluene, benzene, one in ethyl acetate
In the solution of kind or several organic solvents, concentration 0.01-5g/L；
(3) interfacial polymerization process: under normal pressure, being immersed in 2-15min in aqueous phase solution for ultrafiltration membranes, and taking-up is dried,
It is dipped in the environment of 10-60 DEG C and humidity are 30-90% into oil-phase solution and reacts 20-500s；
(4) it is heat-treated: obtained film in step (3) is heat-treated, heat treatment temperature is 30-100 DEG C, when processing
Between be 1-120min.
(5) film obtained in step (4) citric acid treatment: is subjected to citric acid treatment, concentration 2-15wt%, processing
Time is 1-20min, obtains the high-throughput charged positive electricity anti-acid nanofiltration membrane.
Wherein, the aqueous phase monomers are polyethyleneimine, polyvinylamine, polyethylene aniline, polyphenyl methylamine, divinyl three
Amine, the multi-functional amine substance such as polyethylene polyamine and any combination thereof, preferably polyethyleneimine, molecular weight is in 600-
25000, preferably 1800, polyethyleneimine amine concentration is 5-25g/L, and concentration is preferably 10g/L；
Further preferably, aqueous phase monomers are the poly- second that molecular weight is respectively the mass mixings such as 600,1800,10000,25000
The mixture of alkene imines, concentration 10g/L.
Wherein, the acid binding agent is triethylamine, pyridine, 4-dimethylaminopyridine, n,N-diisopropylethylamine, hydroxide
One or more of sodium, potassium hydroxide, sodium bicarbonate, sodium carbonate, saleratus, potassium carbonate, preferably triethylamine, concentration are preferred
For 0.5wt%.
Wherein, the surfactant be neopelex, dodecyl sodium sulfate, lauryl sodium sulfate,
Cetalkonium chloride, octadecyltrimethylammonium chloride, tri-n-octyl methyl ammonium chloride, benzyl triethyl ammonium chlorination
One or more of conventional surfactants such as ammonium, tetrabutylammonium chloride.Wherein, preferably dodecyl sodium sulfate, concentration
Preferably 0.05wt%.
Wherein, the ultrafiltration membranes be polyether sulfone, polysulfones, it is poly- between in the ultrafiltration membranes such as stupid two formyls m-phenylene diamine (MPD) one
Kind, preferably polyether sulfone；Molecular cut off is in 30-100KDa, preferably 30KDa.
Wherein, the oil phase solvent is preferably n-hexane, and the oily phase concentration is preferably 0.01-1.5g/L, wherein
Most preferably 0.1g/L.
Wherein, the temperature in the step (3) be 5-45 DEG C, preferably 10 DEG C, humidity 20-80%, preferably 40%.
Wherein, the temperature of heat treatment is preferably 70 DEG C, time 5min.
Wherein, the concentration of citric acid is preferably 10wt%, and the processing time is 5min.
Explanation is further elaborated to technical solution of the present invention below by way of specific embodiment combination attached drawing.It should be noted that
, following specific embodiments are only as example, the scope of protection of the present invention is not limited thereto.
Chemicals used in following embodiments and raw material are commercially available gained or are made by oneself by well known preparation method
It obtains.Heretofore described molecular weight is weight average molecular weight amount.
Embodiment 1
Weigh 5g molecular weight be 1800 polyethylene industry amine, 1.0g triethylamine, 0.15g dodecyl sodium sulfate, add from
Sub- water is fully dispersed with stirring 12 hours to its to 500ml；0.1g cyanuric trichloride is weighed, the n-hexane of 500ml is dissolved in
In solvent, it is sufficiently stirred 12 hours；The poly (ether-sulfone) ultrafiltration membrane of immersion in deionized water is first impregnated into 10min in aqueous phase solution,
Taking-up is dried, and is dipped in oil-phase solution under the conditions of 25 DEG C and is reacted 2min, and 30 DEG C of heat treatment 120min is carried out to it,
It is cleaned up followed in turn by deionized water, at normal temperature, measures its flux, be 40LMH/MPa, measure it to 2g/LMgCl2's
Rejection is 91%, and the Zeta potential on its surface be 16mV, by the high-throughput charged positive electricity anti-acid nanofiltration membrane 25 DEG C,
It is impregnated in the hydrochloric acid of 3wt%, and measures it to 2g/LMgCl2Rejection with the curve graph of time change, curve as shown in figure 1
Shown in a, the results showed that lotus positive electricity anti-acid nanofiltration membrane is to MgCl2Rejection do not reduce significantly with time change, say
The high-throughput charged positive electricity anti-acid nanofiltration membrane is illustrated with good acid resistance.
The high-throughput charged positive electricity anti-acid nanofiltration membrane is measured to 3%HCl and 2g/L MgCl2Saturating sour rate and Mg2+Ion is cut
Stay rate.As shown in Fig. 2, histogram A is the high-throughput charged positive electricity anti-acid nanofiltration membrane to Mg2+The rejection figure of ion, retention
Rate is 90%；Histogram B is the saturating sour rate figure of this high-throughput charged positive electricity anti-acid nanofiltration membrane, and acid rate is 99% thoroughly.
Embodiment 2
Polyethyleneimine, the 1.0g sodium hydroxide that 1.25g molecular weight is 600,1800,10000,25000 are weighed respectively,
0.15g neopelex adds deionized water to 500ml, fully dispersed with stirring 12 hours to its；Weigh 0.025g tri-
Paracyanogen chlorine is dissolved in the n-hexane solvent of 500ml, is sufficiently stirred 12 hours；Polysulfones in deionized water will be impregnated
Ultrafiltration membrane first impregnates 10min in aqueous phase solution, and taking-up dries, is dipped in oil-phase solution and reacts under the conditions of 25 DEG C
3min, 70 DEG C of heat treatment 5min is carried out to it, and subsequent deionized water cleaning measures its flux at normal temperature, is 80LMH/
MPa measures it to 2/LMgCl2Rejection be 92%, and the Zeta potential on its surface be 26mV.
Embodiment 3
Polyethyleneimine, the 1.0g sodium hydroxide that 1.25g molecular weight is 600,1800,10000,25000 are weighed respectively,
0.15g neopelex adds deionized water to 500ml, fully dispersed with stirring 12 hours to its；Weigh 0.025g tri-
Paracyanogen chlorine is dissolved in the n-hexane solvent of 500ml, is sufficiently stirred 12 hours；Polysulfones in deionized water will be impregnated
Ultrafiltration membrane first impregnates 10min in aqueous phase solution, and taking-up dries, is dipped in oil-phase solution and reacts under the conditions of 25 DEG C
3min carries out 70 DEG C of heat treatment 5min to it, followed in turn by 10wt% citric acid cleaning 5min, then again with deionized water
Cleaning, measures its flux at normal temperature, is 150LMH/MPa, measures it to 2/LMgCl2Rejection be 92%, and its surface
Zeta potential be 18mV.
Embodiment 4
Polyethyleneimine, the 1.0g sodium hydroxide that 12.5g molecular weight is 1800 are weighed, 0.15g lauryl sodium sulfate adds
Deionized water is fully dispersed with stirring 12 hours to its to 500ml；0.5g cyanuric trichloride is weighed, the first of 500ml is dissolved in
In benzene solvent, it is sufficiently stirred 12 hours；Stupid two formyls m-phenylene diamine (MPD) ultrafiltration membrane is first in water between in deionized water poly- will be impregnated
Phase solution impregnates 10min, and taking-up dries, is dipped in oil-phase solution under the conditions of 25 DEG C and reacts 3min, carries out 100 to it
DEG C heat treatment 5min, then use 10wt% citric acid treatment 20min, then cleaned up again with deionized water, at normal temperature
Its flux is measured, is 35LMH/MPa, measures it to 2g/LMgCl2Rejection be 95%, surface Zeta potential be 19mV.
Comparative example 1
Commercially available Tao Shi NF270 nanofiltration membrane is impregnated in 50 DEG C, the hydrochloric acid of 1mol/L, and measures it to MgCl2Cut
Stay rate with the curve graph of time change, as shown in figure 1 shown in curve b, the results showed that commercially available Tao Shi NF270 nanofiltration membrane pair
MgCl2Rejection gradually decrease as time went on, illustrate that commercially available Tao Shi NF270 acid resistance is poor.
Comparative example 2
The high-throughput charged positive electricity anti-acid tested in the flux and embodiment 3 of the acidproof nanofiltration membrane of commercially available AMS-A3012 is received
The flux of filter membrane compares, and as shown in histogram a (AMS-A3012) in Fig. 3, which is only 22LMH/MPa, and histogram
The flux of b (the high-throughput charged acidproof nanofiltration membrane of positive electricity) is up to 150LMH/MPa.Illustrate that high-throughput charged positive electricity anti-acid nanofiltration membrane exists
Nanofiltration membrane more acidproof than the A3012 of AMS company has very big advantage on flux.
Comparative example 3
Weigh respectively 1.25g molecular weight be 600,1800,10000,25000 polyethyleneimine, 1.0g sodium hydroxide,
0.15g neopelex adds deionized water to 500ml, fully dispersed with stirring 12 hours to its；Weigh 0.025g tri-
Paracyanogen chlorine is dissolved in the n-hexane solvent of 500ml, is sufficiently stirred 12 hours；Polysulfones in deionized water will be impregnated
Ultrafiltration membrane first impregnates 10min in aqueous phase solution, and taking-up dries, is dipped in oil-phase solution and reacts under the conditions of 25 DEG C
3min, and cleaned with deionized water, its flux is measured at normal temperature, is 363LMH/MPa, is measured it to 2/LMgCl2Retention
Rate is 18%.Compared with Example 2, through the nanofiltration membrane of Overheating Treatment, greatly improved salt rejection rate, but flux have it is certain under
Drop.
Particular embodiments described above has carried out further in detail the purpose of the present invention, technical scheme and beneficial effects
Describe in detail bright, it should be understood that the above is only a specific embodiment of the present invention, is not intended to restrict the invention, it is all
Within the spirit and principles in the present invention, any modification, equivalent substitution, improvement and etc. done should be included in protection of the invention
Within the scope of.
Claims (10)
1. a kind of preparation method of high-throughput charged positive electricity anti-acid nanofiltration membrane, which comprises the following steps:
S1: ultrafiltration membranes being immersed in configured aqueous phase solution and are reacted, and obtains ultrafiltration membranes one after dry；
S2: ultrafiltration membranes one being immersed in oil-phase solution and are reacted, and obtains ultrafiltration membranes two；
S3: high-throughput charged positive electricity anti-acid nanofiltration membrane is obtained after ultrafiltration membranes two are heat-treated.
2. preparation method as described in claim 1, which is characterized in that
Heat treatment temperature is 20-100 DEG C, preferably 70 DEG C in the step S3, heat treatment time 1min-120min, preferably
5min；
Preferably, the step S1- step S3 reacts under normal pressure.
3. preparation method as described in claim 1, which is characterized in that
It is rinsed, and is stored in ionized water with deionized water after the step S3；
Preferably, with citric acid treatment, then being rinsed with deionized water, and be stored in deionization after the step S3
In water；
Preferably, the concentration of the citric acid is 2-15wt%, preferably 10wt%, the processing time is 1-20min, preferably
For 5min.
4. preparation method as described in claim 1, which is characterized in that
The configuration method of aqueous phase solution in the step S1 are as follows: sequentially add aqueous phase monomers, acid binding agent and table in deionized water
Face activating agent, and being uniformly dispersed, as aqueous phase solution；
The aqueous phase monomers are that polyethyleneimine, polyvinylamine, polyethylene aniline, polyphenyl methylamine, diethylenetriamine, more ethylene are more
The molecular weight of any one or more of combination of amine, preferably polyethyleneimine, the polyethyleneimine is 600-25000, preferably
1800；
Preferably, the aqueous phase monomers A is the poly- second that molecular weight is respectively the mass mixings such as 600,1800,10000,25000
The mixture of alkene imines；
The acid binding agent is triethylamine, pyridine, 4-dimethylaminopyridine, n,N-diisopropylethylamine, sodium hydroxide, hydroxide
Any one or more of potassium, sodium bicarbonate, sodium carbonate, saleratus, potassium carbonate, the preferred triethylamine of acid binding agent；
The surfactant is neopelex, dodecyl sodium sulfate, lauryl sodium sulfate, cetyl two
Methylbenzyl ammonium chloride, octadecyltrimethylammonium chloride, tri-n-octyl methyl ammonium chloride, benzyltriethylammoinium chloride, the tetrabutyl
Any one or more of ammonium chloride, the preferred dodecyl sodium sulfate of surfactant.
5. preparation method as claimed in claim 4, which is characterized in that
The concentration of the aqueous phase monomers is 5-25g/L, preferably 10g/L；
The concentration of the acid binding agent is 0.1-5wt%, preferably 0.5wt%；
The concentration of the surfactant is 0.02-0.08wt%, preferably 0.05wt%.
6. preparation method as described in claim 1, which is characterized in that
The preparation method of oil-phase solution in the step S2 are as follows: cyanuric trichloride is dissolved in organic solvent；Cyanuric trichloride it is dense
Degree is 0.01-5g/L, preferably 2g/L；
Preferably, the organic solvent is any one or more of n-hexane, hexamethylene, toluene, benzene, ethyl acetate, have
The preferred n-hexane of solvent.
7. preparation method as described in claim 1, which is characterized in that
Ultrafiltration membranes are immersed in 2-15min, preferably 10min in configured aqueous phase solution in the step S1；
Drying means is to dry in the step S1；
The reaction time is 20-500s, preferably 180s in the step S2；
Reaction temperature in the step S2 is 5-45 DEG C, preferably 10 DEG C；Reaction humidity 20-80%, preferably 40%.
8. preparation method as described in claim 1, which is characterized in that
Any one of stupid two formyls m-phenylene diamine (MPD) ultrafiltration membrane, preferred, polyethers between the ultrafiltration membranes are polyether sulfone, polysulfones, gather
Sulfone；
The molecular cut off of the ultrafiltration membranes is 30KDa-100KDa, preferably 30KDa.
9. the high-throughput charged positive electricity anti-acid nanofiltration membrane that the preparation method as described in claim any one of 1-8 obtains；
Preferably, the flux of the high-throughput charged positive electricity anti-acid nanofiltration membrane is 30-150LMH/MPa；
Preferably, the surface Zeta potential of the high-throughput charged positive electricity anti-acid nanofiltration membrane is 15-30mV.
10. as claimed in claim 9 high-throughput charged positive electricity anti-acid nanofiltration membrane is in purification of water quality, field of industrial waste water treatment
Using.
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