CN109603586A - A kind of preparation method of the high-flux nanofiltration membrane based on new buffer system - Google Patents
A kind of preparation method of the high-flux nanofiltration membrane based on new buffer system Download PDFInfo
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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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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
- B01D67/0002—Organic membrane manufacture
- B01D67/0006—Organic membrane manufacture by chemical reactions
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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
- B01D69/10—Supported membranes; Membrane supports
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Abstract
The invention belongs to Nano filtering composite membrane technical field, a kind of preparation method of the high-flux nanofiltration membrane based on new buffer system.The present invention is by first coating the aqueous phase solution containing polyamine and one or more faintly acid salts or weak acid and tetramethylammonium hydroxide on polysulfones counterdie, after drying in the shade, it is coated with the oil-phase solution that polynary acyl chlorides is dissolved in Isopar G (a kind of Isopars), then it will be post-processed at a certain temperature by the film of coating, finally obtained nanofiltration membrane.Wherein contain the one or more ammonium salts for being dissolved in water in the water phase of coating liquid.It is an advantage of the invention that this patent buffering is simple and easy to control compared with the existing technology, good rejection was not only maintained, but also greatly improve water flux, reproducibility is preferable, and preparation cost is cheap.
Description
Technical field
The invention belongs to Nano filtering composite membrane technical field, a kind of preparation of the high-flux nanofiltration membrane based on new buffer system
Method.
Background technique
Nanofiltration (nanofiltration, NF) is a kind of novel pressure driving UF membrane between reverse osmosis between ultrafiltration
Process, because its seperation film is mostly from reverse osmosis membrane derivation, and operating pressure is lower, and be otherwise known as " low pressure reverse osmosis " in early days
Or " loose reverse osmosis ".Nanofiltration membrane generally by being constituted with highly selective cortex with the porous sub-layer to play a supportive role, but its
Generally there are very big differences for chemical composition.Currently, commercialization nanofiltration membrane material mainly have it is polyamide-based (Film Tec, Toray,
ATM, Trisep), polyvinyl alcohol-polyamide-based (Hydranautics, Nitto Denko), sulfonated polysulfone class (Nitto
) and acetate fiber class (Toray, Trisep) etc. Denko.Aromatic polyamide nanofiltration membrane is to sell most, work currently on the market
Most widely used one kind nanofiltration membrane, compound film properties depend primarily on duct, thickness, roughness and the hydrophily of film in industry
Etc. the chemical characteristics such as architectural characteristics and the degree of cross linking, functional group and chemical bond.The different of monomer directly determine in interfacial polymerization process
The comprehensive performance of composite membrane, therefore in order to prepare the nanofiltration membrane with ideal membrane structure and separating property, design and synthesis are not
Same monomer is widely studied.Nanofiltration membrane is mainly used for water process and sewage treatment, due to polymeric membrane such as PES, PVDF,
PSF etc. has hydrophobicity, and in use vulnerable to fouling membrane, protein is generally readily adsorbed in coarse and hydrophobic film
Surface, so the structure and morphology of nanofiltration film surface decides service life of the nanofiltration membrane in water treatment procedure.Such as, it is desirable to preparation is high
The nanofiltration membrane of flux, increasing film surface roughness is that a good selection must then subtract if it is desired to improving the contamination resistance of film
The roughness of few film surface.If it is possible to which that meeting is so that nanofiltration membrane according to the configuration of surface of actual use situation building film
Application it is more extensive.Mainly pass through the type and concentration, interfacial polymerization of monomer to the regulation of nanometer filtering film water flux at this stage
Temperature, reaction time and the time of post-processing and temperature are realized.In general, buffer system is essentially all by weak acid
And its mixed solution of salt, weak base and its salt composition.Tetramethylammonium hydroxide has strong basicity, 120 DEG C of boiling point, is heated to boiling point
Shi Yi resolves into trimethylamine and methanol, and in the preparation process of seawater film, heat treatment temperature is generally above 120 DEG C.So handle
Tetramethylammonium hydroxide is added to buffer system, and alkalinity can slowly weaken during heat treatment, decomposes the front three generated
Amine can be with the faintly acid salt or weak acid one new buffer system of formation in system.It is used in the present invention and contains tetramethyl hydrogen
The buffer system of amine-oxides and weak acid prepares high-throughput nanofiltration membrane.The nanofiltration membrane prepared under this buffer system, works as heat
Treatment temperature is having just enter into heat treatment in a flash at 120 DEG C or more, and the pH value of system is higher, and alkalinity is larger, so reaction
Than faster, the compacted zone of formation is also finer and close, over time, system pH value becomes smaller, and reaction tends to gentle, due to
Tetramethylammonium hydroxide can generate trimethylamine and methanol when decomposing, and can escape separating layer, to a certain extent adjustable separation
Layer structure, improves water flux.Research of the invention is exactly with slow containing tetramethylammonium hydroxide and faintly acid salt or weak acid
System is rushed to prepare nanofiltration membrane and improve the water flux of nanofiltration membrane.
Summary of the invention
The present invention is intended to provide a kind of novel buffer system prepares high-flux nanofiltration membrane and preparation method thereof.This research
The buffering of one or more faintly acid salts or weak acid and tetramethylammonium hydroxide as reaction is added in interface polymerization reaction
System.The preparation process of this novel high flux nanofiltration membrane is that first coating contains polyamine and one or more on polysulfones counterdie
The aqueous phase solution of faintly acid salt or weak acid and tetramethylammonium hydroxide is coated with polynary acyl chlorides and is dissolved in Isopar L (a kind different
Structure alkane solvent) in oil-phase solution, high-flux nanofiltration membrane is prepared by interfacial polymerization.By to coating liquid each component and type
It is in optimized selection, post-processing temperature is regulated and controled, prepared the nanofiltration membrane of high water flux.
The present invention is achieved through the following technical solutions:
A kind of preparation method of the high-flux nanofiltration membrane based on new buffer system, it is characterized in that: on polysulfones counterdie, first
The aqueous phase solution containing polyamine and one or more faintly acid salts or weak acid and tetramethylammonium hydroxide is coated, after drying in the shade,
It is coated with the oil-phase solution that polynary acyl chlorides is dissolved in Isopar G (a kind of Isopars), then by the film by coating
It is post-processed at a certain temperature, finally obtained nanofiltration membrane.Wherein contain the one kind for being dissolved in water in the water phase of coating liquid
Or a variety of ammonium salts.
Preferably, the macromolecule contained in aqueous phase solution in above-mentioned preparation method has m-phenylene diamine (MPD) (MPD), piperazine
(PIP), one of polyethyleneimine or a variety of, and the high molecule mass percentage in water phase is 0.1-5.0%.Aqueous phase solution
Tetramethylammonium hydroxide, ammonium chloride, etamon chloride, boric acid, citric acid, one of triethylamine hydrochloride or more can be contained
Kind, the ammonium salt quality in water phase is very 0.1-10%.As more preferably selecting, the macromolecule of aqueous phase solution is m-phenylene diamine (MPD)
(MPD), and m-phenylene diamine (MPD) (MPD) mass percent is 0.1-3%.As more preferably selecting, the tetramethylammonium hydroxide in water phase
Quality is very 0.1-5%.
Preferably, the macromolecule contained in oil-phase solution in above-mentioned preparation method has pyromellitic trimethylsilyl chloride (TMC), oneself two
Acyl chlorides (APC), one or more, and the solute polymer mass percent in oily phase of hexamethylene diisocyanate (HDI)
For 0.1-4.0%.As more preferably selecting, the macromolecule in oil-phase solution is pyromellitic trimethylsilyl chloride (TMC), and TMC mass percentage
Than for 0.1-3.5%.
Preferably, faintly acid salt or weak acid in above-mentioned preparation method are ammonium chloride, boric acid, triethylamine hydrochloride
One or more, and the mass percent in water phase is 0.1-6%.
Preferably, the post-processing temperature of composite membrane is 100 DEG C -150 DEG C in above-mentioned preparation method.As more preferably selecting,
The post-processing temperature of reverse osmosis membrane is 120 DEG C -140 DEG C.
In the present invention, polysulfones counterdie can be the counterdie that any producer provides, the type of the performance difference of counterdie, counterdie
Result of the invention is had no and is directly affected, therefore can choose business polysulfones counterdie or self-control, this is also of the invention general
Logical applicable, progress commercial applications provide possibility.
In the present invention, this novel buffer system raw material is easy to get, and each component is all highly soluble in water, in production line
Any one production technology for changing production line is completely dispensed in production process, therefore is also generally suitable, progress of the invention
Commercial applications provide possibility.
The post-processing temperature of nanofiltration membrane can be controlled by baking oven, and especially at 120 DEG C -140 DEG C, performance is more excellent
More.
The utility model has the advantages that passing through the method for interfacial polymerization using this patent the method, it is only necessary to tetramethyl hydroxide be added
Ammonium and one or more of acidulous materials can prepare the excellent high-flux nanofiltration membrane of cutoff performance.And relative to existing skill
Art this patent buffering is simple and easy to control, has not only maintained good rejection, but also greatly improve water flux, reproducibility is preferable, is prepared into
This is cheap.
Specific embodiment
A specific embodiment of the invention is illustrated below:
Following embodiment provides the preparation method of the high-flux nanofiltration membrane based on new buffer system.Following embodiments only mention
It is provided as explanation rather than limiting the invention.
Polysulfones counterdie used in following embodiment is self-control counterdie.The film date of manufacture to experiment the date less than 30 days, the phase
Between be stored in 2% aqueous solution of sodium bisulfite.Before carrying out interfacial reaction and preparing composite membrane, for 24 hours in advance by polysulfones counterdie
It is soaked in pure water.
A kind of film properties of the preparation method of high-flux nanofiltration membrane based on new buffer system are done in following embodiment
It evaluates out: sodium sulphate solution salt rejection rate and water flux.Test pressure when performance evaluation is 100psi, and concentrated water flow is 1.0L/
Min, environment temperature are 25 DEG C, and concentrated water pH value is 6.5~7.5, and concentrated water is that sodium sulphate concentration is 1000ppm.
In following embodiment, salt rejection rate is defined as concentrated water and produces the difference of the concentration of water divided by concentrated water concentration；Water flux definition
For water volume of the unit time through unit area composite separating film, unit L/m in above-mentioned test process2·h(LMH)。
Each of the above data point is averaged to obtain by 9 samples.
Comparative example
Constantly change the post-processing temperature of water phase solubility and oily phase solubility and baking oven, but uses most common buffering
The acid-base accommodation system (CSA) of system/triethylamine (TEA) system, is prepared for different nanofiltration membranes.It is tested by experiment, it is made
Standby nanofiltration membrane film is up to 99.7% to the rejection of 1000ppm aqueous sodium persulfate solution, and water flux is up to 65LMH.Performance
Test pressure when evaluation is 100psi, and concentrated water flow is 1.0L/min, and environment temperature is 25 DEG C, and concentrated water pH value is 6.5
~7.5, concentrated water is aqueous sodium persulfate solution, concentration 1000ppm.
Embodiment 1
Piperazine (PIP) aqueous solution of configuration 0.1% and the tetramethylammonium hydroxide that mass fraction 1% is added, 1% chlorination
Ammonium is uniformly mixed, is reconfigured 0.2% pyromellitic trimethylsilyl chloride (TMC) oil-phase solution.It is molten that water phase is first coated on polysulfones counterdie
Liquid outwells extra solution after 60s, dries in the shade, then oil-phase solution is coated on the film to dry in the shade, after 30s, outwells extra oily phase
Solution, and 5min is heat-treated in 120 DEG C of baking ovens.Thus the high-flux nanofiltration membrane based on new buffer system of method preparation is being surveyed
Pressure testing power is 100psi, and concentrated water flow is 1.0L/min, and environment temperature is 25 DEG C, and concentrated water pH value is 6.5~7.5, concentrated water
For sodium sulphate aqueous solution, concentration is under the experiment condition of 1000ppm, and measuring its water flux is 80LMH, salt rejection rate 99.7%.
Embodiment 2
Piperazine (PIP) aqueous solution of configuration 0.1% and the tetramethylammonium hydroxide that mass fraction 1% is added, 2% chlorination
Ammonium is uniformly mixed, is reconfigured 0.2% pyromellitic trimethylsilyl chloride (TMC) oil-phase solution.It is molten that water phase is first coated on polysulfones counterdie
Liquid outwells extra solution after 60s, dries in the shade, then oil-phase solution is coated on the film to dry in the shade, after 30s, outwells extra oily phase
Solution, and 5min is heat-treated in 120 DEG C of baking ovens.Thus the high-flux nanofiltration membrane based on new buffer system of method preparation is being surveyed
Pressure testing power is 100psi, and concentrated water flow is 1.0L/min, and environment temperature is 25 DEG C, and concentrated water pH value is 6.5~7.5, concentrated water
For sodium sulphate aqueous solution, concentration is under the experiment condition of 1000ppm, and measuring its water flux is 82LMH, salt rejection rate 99.7%.
Embodiment 3
Piperazine (PIP) aqueous solution of configuration 0.1% and the tetramethylammonium hydroxide that mass fraction 2% is added, 1.5% chlorine
Change ammonium, is uniformly mixed, is reconfigured 0.2% pyromellitic trimethylsilyl chloride (TMC) oil-phase solution.It is molten that water phase is first coated on polysulfones counterdie
Liquid outwells extra solution after 60s, dries in the shade, then oil-phase solution is coated on the film to dry in the shade, after 30s, outwells extra oily phase
Solution, and 5min is heat-treated in 120 DEG C of baking ovens.Thus the high-flux nanofiltration membrane based on new buffer system of method preparation is being surveyed
Pressure testing power is 100psi, and concentrated water flow is 1.0L/min, and environment temperature is 25 DEG C, and concentrated water pH value is 6.5~7.5, concentrated water
For sodium sulphate aqueous solution, concentration is under the experiment condition of 1000ppm, and measuring its water flux is 100LMH, salt rejection rate 99.6%.
Embodiment 4
Piperazine (PIP) aqueous solution of configuration 0.1% and the tetramethylammonium hydroxide that mass fraction 1.5% is added, 1% chlorine
Change ammonium, is uniformly mixed, is reconfigured 0.2% pyromellitic trimethylsilyl chloride (TMC) oil-phase solution.It is molten that water phase is first coated on polysulfones counterdie
Liquid outwells extra solution after 60s, dries in the shade, then oil-phase solution is coated on the film to dry in the shade, after 30s, outwells extra oily phase
Solution, and 5min is heat-treated in 120 DEG C of baking ovens.Thus the high-flux nanofiltration membrane based on new buffer system of method preparation is being surveyed
Pressure testing power is 100psi, and concentrated water flow is 1.0L/min, and environment temperature is 25 DEG C, and concentrated water pH value is 6.5~7.5, concentrated water
For sodium sulphate aqueous solution, concentration is under the experiment condition of 1000ppm, and measuring its water flux is 85LMH, salt rejection rate 99.7%.
Embodiment 5
Piperazine (PIP) aqueous solution of configuration 0.1% and the tetramethylammonium hydroxide that mass fraction 2% is added, 1% chlorination
Ammonium is uniformly mixed, is reconfigured 0.2% pyromellitic trimethylsilyl chloride (TMC) oil-phase solution.It is molten that water phase is first coated on polysulfones counterdie
Liquid outwells extra solution after 60s, dries in the shade, then oil-phase solution is coated on the film to dry in the shade, after 30s, outwells extra oily phase
Solution, and 5min is heat-treated in 120 DEG C of baking ovens.Thus the high-flux nanofiltration membrane based on new buffer system of method preparation is being surveyed
Pressure testing power is 100psi, and concentrated water flow is 1.0L/min, and environment temperature is 25 DEG C, and concentrated water pH value is 6.5~7.5, concentrated water
For sodium sulphate aqueous solution, concentration is under the experiment condition of 1000ppm, and measuring its water flux is 88LMH, salt rejection rate 99.7%.
Embodiment 6
Piperazine (PIP) aqueous solution of configuration 0.1% and the tetramethylammonium hydroxide that mass fraction 1% is added, 3% chlorination
Ammonium is uniformly mixed, is reconfigured 0.2% pyromellitic trimethylsilyl chloride (TMC) oil-phase solution.It is molten that water phase is first coated on polysulfones counterdie
Liquid outwells extra solution after 60s, dries in the shade, then oil-phase solution is coated on the film to dry in the shade, after 30s, outwells extra oily phase
Solution, and 5min is heat-treated in 120 DEG C of baking ovens.Thus the high-flux nanofiltration membrane based on new buffer system of method preparation is being surveyed
Pressure testing power is 100psi, and concentrated water flow is 1.0L/min, and environment temperature is 25 DEG C, and concentrated water pH value is 6.5~7.5, concentrated water
For sodium sulphate aqueous solution, concentration is under the experiment condition of 1000ppm, and measuring its water flux is 81LMH, salt rejection rate 99.7%.
Embodiment 7
Piperazine (PIP) aqueous solution of configuration 0.1% and the tetramethylammonium hydroxide that mass fraction 1.5% is added, 1.5%
Ammonium chloride is uniformly mixed, is reconfigured 0.2% pyromellitic trimethylsilyl chloride (TMC) oil-phase solution.First water phase is coated on polysulfones counterdie
Solution outwells extra solution after 60s, dries in the shade, then oil-phase solution is coated on the film to dry in the shade, after 30s, outwells extra oil
Phase solution, and 5min is heat-treated in 120 DEG C of baking ovens.Thus the high-flux nanofiltration membrane based on new buffer system of method preparation exists
Test pressure is 100psi, and concentrated water flow is 1.0L/min, and environment temperature is 25 DEG C, and concentrated water pH value is 6.5~7.5, dense
Water is sodium sulphate aqueous solution, and concentration is under the experiment condition of 1000ppm, and measuring its water flux is 88LMH, and salt rejection rate is
99.8%.
Embodiment 8
Piperazine (PIP) aqueous solution of configuration 0.15% and the tetramethylammonium hydroxide that mass fraction 1% is added, 1% chlorine
Change ammonium, is uniformly mixed, is reconfigured 0.2% pyromellitic trimethylsilyl chloride (TMC) oil-phase solution.It is molten that water phase is first coated on polysulfones counterdie
Liquid outwells extra solution after 60s, dries in the shade, then oil-phase solution is coated on the film to dry in the shade, after 30s, outwells extra oily phase
Solution, and 5min is heat-treated in 120 DEG C of baking ovens.Thus the high-flux nanofiltration membrane based on new buffer system of method preparation is being surveyed
Pressure testing power is 100psi, and concentrated water flow is 1.0L/min, and environment temperature is 25 DEG C, and concentrated water pH value is 6.5~7.5, concentrated water
For sodium sulphate aqueous solution, concentration is under the experiment condition of 1000ppm, and measuring its water flux is 83LMH, salt rejection rate 99.7%.
Embodiment 9
Piperazine (PIP) aqueous solution of configuration 0.1% and the tetramethylammonium hydroxide that mass fraction 1.8% is added, 1% chlorine
Change ammonium, is uniformly mixed, is reconfigured 0.2% pyromellitic trimethylsilyl chloride (TMC) oil-phase solution.It is molten that water phase is first coated on polysulfones counterdie
Liquid outwells extra solution after 60s, dries in the shade, then oil-phase solution is coated on the film to dry in the shade, after 30s, outwells extra oily phase
Solution, and 5min is heat-treated in 120 DEG C of baking ovens.Thus the high-flux nanofiltration membrane based on new buffer system of method preparation is being surveyed
Pressure testing power is 100psi, and concentrated water flow is 1.0L/min, and environment temperature is 25 DEG C, and concentrated water pH value is 6.5~7.5, concentrated water
For sodium sulphate aqueous solution, concentration is under the experiment condition of 1000ppm, and measuring its water flux is 91LMH, salt rejection rate 99.7%.
Claims (9)
1. a kind of preparation method of the high-flux nanofiltration membrane based on new buffer system, it is characterized in that: first being applied on polysulfones counterdie
Aqueous phase solution is covered, contains polyamine, one or more faintly acid salts or weak acid and tetramethylammonium hydroxide in aqueous phase solution；
After drying in the shade, it is coated with oil-phase solution, oil-phase solution is that polynary acyl chlorides is dissolved in Isopar G；Then by the film by coating one
It is post-processed at a temperature of fixed, finally obtained nanofiltration membrane；
Wherein, the ammonium salt for being dissolved in water is contained in the aqueous phase solution of coating liquid, specifically: tetramethylammonium hydroxide, ammonium chloride, tetrem
Ammonium chloride, boric acid, one of citric acid or triethylamine hydrochloride or a variety of, the ammonium salt quality in water phase are very
0.1-10%.
2. a kind of preparation method according to claim 1, which is characterized in that the macromolecule also contained in the aqueous phase solution
Substance has the quality percentage of m-phenylene diamine (MPD), one of piperazine or polyethyleneimine or a variety of, and the polymer substance in water phase
Than for 0.1-5.0%.
3. a kind of preparation method according to claim 2, which is characterized in that between the polymer substance of the aqueous phase solution is
Phenylenediamine, and m-phenylene diamine (MPD) mass percent is 0.1-3%.
4. a kind of preparation method according to claim 1, which is characterized in that the ammonium salt in the aqueous phase solution is tetramethyl
Ammonium hydroxide, and the mass percent in water phase is 0.1-5%.
5. a kind of preparation method according to claim 1, which is characterized in that the macromolecule contained in the oil-phase solution adds
Add agent, specifically: pyromellitic trimethylsilyl chloride, Adipoyl Chloride or hexamethylene diisocyanate it is one or more, and in oily phase
The mass percent of polymeric additive is 0.1-4.0%.
6. a kind of preparation method according to claim 5, which is characterized in that the polymeric additive of the oil-phase solution
For pyromellitic trimethylsilyl chloride, and mass percent is 0.1-3.5%.
7. a kind of preparation method according to claim 1, which is characterized in that the faintly acid salt or weak acid are chlorination
The one or more of ammonium, boric acid or triethylamine hydrochloride, and the mass percent in aqueous phase solution is 0.1-6%.
8. a kind of preparation method according to claim 1, which is characterized in that the post-processing temperature of the composite membrane is 100
℃-150℃。
9. a kind of preparation method according to claim 8, which is characterized in that the post-processing temperature of the composite membrane is 120
℃-140℃。
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110449045A (en) * | 2019-08-01 | 2019-11-15 | 蓝星（杭州）膜工业有限公司 | A kind of preparation method of the high-flux nanofiltration membrane based on new buffer system |
| CN110449044A (en) * | 2019-08-01 | 2019-11-15 | 蓝星（杭州）膜工业有限公司 | A kind of preparation method of the high-performance nanofiltration membrane based on building Multi-network |
| CN111450714A (en) * | 2020-04-17 | 2020-07-28 | 蓝星（杭州）膜工业有限公司 | Method for preparing composite nanofiltration membrane by using multi-element buffer system |
| CN114797505A (en) * | 2021-01-28 | 2022-07-29 | 欧美新材料(浙江)有限公司 | Preparation method of loose polyamine aqueous phase solution and hollow fiber composite nanofiltration membrane |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110449045A (en) * | 2019-08-01 | 2019-11-15 | 蓝星（杭州）膜工业有限公司 | A kind of preparation method of the high-flux nanofiltration membrane based on new buffer system |
| CN110449044A (en) * | 2019-08-01 | 2019-11-15 | 蓝星（杭州）膜工业有限公司 | A kind of preparation method of the high-performance nanofiltration membrane based on building Multi-network |
| CN111450714A (en) * | 2020-04-17 | 2020-07-28 | 蓝星（杭州）膜工业有限公司 | Method for preparing composite nanofiltration membrane by using multi-element buffer system |
| CN114797505A (en) * | 2021-01-28 | 2022-07-29 | 欧美新材料(浙江)有限公司 | Preparation method of loose polyamine aqueous phase solution and hollow fiber composite nanofiltration membrane |
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