CN109569308A - A kind of acid absorbent system prepares the preparation method of high-flux reverse osmosis membrane - Google Patents
A kind of acid absorbent system prepares the preparation method of high-flux reverse osmosis membrane Download PDFInfo
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- CN109569308A CN109569308A CN201811368677.5A CN201811368677A CN109569308A CN 109569308 A CN109569308 A CN 109569308A CN 201811368677 A CN201811368677 A CN 201811368677A CN 109569308 A CN109569308 A CN 109569308A
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- 238000002360 preparation method Methods 0.000 title claims abstract description 42
- 239000002253 acid Substances 0.000 title claims abstract description 31
- 239000012528 membrane Substances 0.000 title claims abstract description 23
- 238000001223 reverse osmosis Methods 0.000 title claims abstract description 20
- 239000002250 absorbent Substances 0.000 title claims abstract description 11
- 230000002745 absorbent Effects 0.000 title claims abstract description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 92
- 239000012071 phase Substances 0.000 claims abstract description 58
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 claims abstract description 46
- 239000013535 sea water Substances 0.000 claims abstract description 25
- 150000003839 salts Chemical class 0.000 claims abstract description 22
- 229920002492 poly(sulfone) Polymers 0.000 claims abstract description 17
- 239000008346 aqueous phase Substances 0.000 claims abstract description 16
- 239000002131 composite material Substances 0.000 claims abstract description 11
- 150000001263 acyl chlorides Chemical class 0.000 claims abstract description 10
- 229920000768 polyamine Polymers 0.000 claims abstract description 8
- 239000011248 coating agent Substances 0.000 claims abstract description 7
- 238000000576 coating method Methods 0.000 claims abstract description 7
- 239000007788 liquid Substances 0.000 claims abstract description 6
- CNPVJWYWYZMPDS-UHFFFAOYSA-N 2-methyldecane Chemical compound CCCCCCCCC(C)C CNPVJWYWYZMPDS-UHFFFAOYSA-N 0.000 claims abstract description 3
- 238000001035 drying Methods 0.000 claims abstract description 3
- WZCQRUWWHSTZEM-UHFFFAOYSA-N 1,3-phenylenediamine Chemical compound NC1=CC=CC(N)=C1 WZCQRUWWHSTZEM-UHFFFAOYSA-N 0.000 claims description 33
- 229940018564 m-phenylenediamine Drugs 0.000 claims description 33
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims description 26
- IJOOHPMOJXWVHK-UHFFFAOYSA-N chlorotrimethylsilane Chemical compound C[Si](C)(C)Cl IJOOHPMOJXWVHK-UHFFFAOYSA-N 0.000 claims description 25
- 235000019270 ammonium chloride Nutrition 0.000 claims description 13
- 238000012805 post-processing Methods 0.000 claims description 7
- GLUUGHFHXGJENI-UHFFFAOYSA-N Piperazine Chemical compound C1CNCCN1 GLUUGHFHXGJENI-UHFFFAOYSA-N 0.000 claims description 6
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 6
- 229920002521 macromolecule Polymers 0.000 claims description 6
- 229920000642 polymer Polymers 0.000 claims description 5
- 239000000126 substance Substances 0.000 claims description 5
- ILWRPSCZWQJDMK-UHFFFAOYSA-N triethylazanium;chloride Chemical compound Cl.CCN(CC)CC ILWRPSCZWQJDMK-UHFFFAOYSA-N 0.000 claims description 5
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims description 4
- 239000004327 boric acid Substances 0.000 claims description 4
- 239000005057 Hexamethylene diisocyanate Substances 0.000 claims description 3
- 230000008859 change Effects 0.000 claims description 3
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 claims description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 2
- 229920002873 Polyethylenimine Polymers 0.000 claims description 2
- 239000003795 chemical substances by application Substances 0.000 claims description 2
- YMBCJWGVCUEGHA-UHFFFAOYSA-M tetraethylammonium chloride Chemical compound [Cl-].CC[N+](CC)(CC)CC YMBCJWGVCUEGHA-UHFFFAOYSA-M 0.000 claims description 2
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims 3
- 239000000654 additive Substances 0.000 claims 2
- 230000000996 additive effect Effects 0.000 claims 2
- PWAXUOGZOSVGBO-UHFFFAOYSA-N adipoyl chloride Chemical compound ClC(=O)CCCCC(Cl)=O PWAXUOGZOSVGBO-UHFFFAOYSA-N 0.000 claims 1
- XWBDWHCCBGMXKG-UHFFFAOYSA-N ethanamine;hydron;chloride Chemical compound Cl.CCN XWBDWHCCBGMXKG-UHFFFAOYSA-N 0.000 claims 1
- GFAUNYMRSKVDJL-UHFFFAOYSA-N formyl chloride Chemical compound ClC=O GFAUNYMRSKVDJL-UHFFFAOYSA-N 0.000 claims 1
- 229910052760 oxygen Inorganic materials 0.000 claims 1
- 239000001301 oxygen Substances 0.000 claims 1
- 125000003698 tetramethyl group Chemical group [H]C([H])([H])* 0.000 claims 1
- 239000000243 solution Substances 0.000 abstract description 69
- 230000004907 flux Effects 0.000 abstract description 23
- 239000007853 buffer solution Substances 0.000 abstract description 20
- 150000003863 ammonium salts Chemical class 0.000 abstract description 5
- 230000003139 buffering effect Effects 0.000 abstract description 5
- 238000005516 engineering process Methods 0.000 abstract description 2
- 235000002639 sodium chloride Nutrition 0.000 description 31
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 27
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical group [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 24
- 238000000034 method Methods 0.000 description 13
- 229960002668 sodium chloride Drugs 0.000 description 12
- 239000011780 sodium chloride Substances 0.000 description 12
- 238000012360 testing method Methods 0.000 description 12
- 238000002474 experimental method Methods 0.000 description 11
- 239000007864 aqueous solution Substances 0.000 description 10
- 238000006243 chemical reaction Methods 0.000 description 9
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 5
- MIOPJNTWMNEORI-GMSGAONNSA-N (S)-camphorsulfonic acid Chemical compound C1C[C@@]2(CS(O)(=O)=O)C(=O)C[C@@H]1C2(C)C MIOPJNTWMNEORI-GMSGAONNSA-N 0.000 description 4
- 238000012695 Interfacial polymerization Methods 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 3
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 3
- BAVYZALUXZFZLV-UHFFFAOYSA-N Methylamine Chemical compound NC BAVYZALUXZFZLV-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 238000010612 desalination reaction Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000010406 interfacial reaction Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000012074 organic phase Substances 0.000 description 2
- 238000006068 polycondensation reaction Methods 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 239000004952 Polyamide Substances 0.000 description 1
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical compound [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 238000005660 chlorination reaction Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000001728 nano-filtration Methods 0.000 description 1
- 239000003002 pH adjusting agent Substances 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- -1 tetramethyl hydroxide Chemical compound 0.000 description 1
Classifications
-
- 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
-
- 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
- B01D67/0081—After-treatment of organic or inorganic membranes
- B01D67/0088—Physical treatment with compounds, e.g. swelling, coating or impregnation
-
- 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
- C02F1/441—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis by reverse osmosis
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
- C02F2103/08—Seawater, e.g. for desalination
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A20/00—Water conservation; Efficient water supply; Efficient water use
- Y02A20/124—Water desalination
- Y02A20/131—Reverse-osmosis
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
Abstract
A kind of acid absorbent system prepares the preparation method of high-flux reverse osmosis membrane.The invention discloses reverse osmosis composite membrane technical field, a kind of preparation method of the high-throughput seawater film based on new buffer system.The present invention passes through on polysulfones counterdie, first coat the aqueous phase solution containing polyamine and one or more faintly acid salts or weak acid and tetramethylammonium hydroxide, 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 reverse osmosis seawater film.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 reverse osmosis composite membrane technical field, a kind of system of the high-throughput seawater film based on new buffer system
Preparation Method.
Background technique
Water flux is one of main performance of reverse osmosis membrane.Water flux is higher, it is meant that processing same volume liquid
Energy consumption is lower.Reverse osmosis development mainly experienced two stages, and nineteen sixty, Loeb and Sourirajan had developed asymmetry
The autofrettage of film, obtained film is at 10MPa, and the removal efficiency to salt is 98.6%, permeable sensible 10.8LMH.It reduces later
Transmembrane pressure, increasing water flux becomes always the high performance most important target of desalination membrane pursuit.The end of the seventies J.E.Cadotte
Polymerization is prepared for first composite membrane, becomes the milestone of low-pressure high-throughput desalination membrane development.
The operating pressure of current ultra-low-pressure reverse osmosis or nanofiltration membrane is less than 0.5MPa, and water flux is in 30~60LMH.It grinds
Ultralow pressure high throughput reverse osmosis composite membrane processed is the important goal that scholars study composite membrane.Reverse osmosis membrane generally by
Prepared by polyamines and acyl chlorides interfacial polymerization, in interfacial reaction, polyamines and acyl chlorides polycondensation reaction are also given birth to while generating polyamide
At side reaction hydrogen chloride, the accumulation in reaction zone will limit the progress of polycondensation reaction forward direction, therefore select suitable buffering
System facilitates the formation of the higher active separating layer of molecular weight except the hydrogen chloride in dereaction, so that rejection be prepared more
High seperation film.Koo etc. studied the acid absorbent of different systems, used the suction of camphorsulfonic acid (CSA)/triethylamine (TEA) system
Compound film properties prepared by sour agent are the most excellent.Researcher also is then together by triethylamine hydrochloride and camphorsulfonic acid
(CSA)/triethylamine (TEA) system has also prepared the composite membrane haveing excellent performance as acid absorbent.In general, alkaline change
Learn substance all can serve as acid absorbent, they are as follows to the promotion mechanism of interfacial polymerization: by taking triethylamine as an example, triethylamine molecule and
M-phenylene diamine (MPD) molecule is diffused into the reaction zone of organic phase from water phase together, very due to the reactivity of triethylamine and acyl chlorides
It is low, therefore triethylamine only generates ammonium salt with hcl reaction, without not dissolving in organic phase with the ammonium salt of acyl chloride reaction, generation, from
And byproduct hydrogen chloride is taken out of reaction zone.However, acid absorbent, which is added, can improve the PH of reaction system, excessively high PH can accelerate
Therefore while acid absorbent is added, one or more acidic materials (pH adjusting agent) should be also added to adjust in the hydrolysis of acyl chlorides
The pH value of section system.In general, buffer system is essentially all that the mixing that is made of weak acid and its salt, weak base and its salt is molten
Liquid.Tetramethylammonium hydroxide has strong basicity, 120 DEG C of boiling point, is heated to easily resolve into trimethylamine and methanol when boiling point, in seawater
In the preparation process of film, heat treatment temperature is generally above 120 DEG C.So tetramethylammonium hydroxide is added to buffer system,
Alkalinity can slowly weaken during heat treatment, and decomposing the trimethylamine that generates can be with faintly acid salt in system or weak
Acid forms a new buffer system.Height is prepared using the buffer system containing tetramethylammonium hydroxide and weak acid in the present invention
The seawater film of flux.The seawater film prepared under this buffer system is having just enter into when heat treatment temperature is at 120 DEG C or more
In a flash, the pH value of system is higher for heat treatment, and alkalinity is larger, so reaction ratio is faster, the compacted zone of formation also compares cause
Close, over time, system pH value becomes smaller, and reaction tends to gentle, due to that can generate three when tetramethylammonium hydroxide is decomposed
Methylamine and methanol can escape separating layer, to a certain extent adjustable separating layer structure, improve water flux.Of the invention grinds
Study carefully and exactly prepares seawater film with the buffer system containing tetramethylammonium hydroxide and faintly acid salt or weak acid and improve seawater
The water flux of film.
Summary of the invention
The present invention is intended to provide a kind of novel buffer system prepares high-throughput seawater film 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 seawater film 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, pass through interfacial polymerization and prepare high-throughput seawater film.By to coating liquid each component and type
It is in optimized selection, post-processing temperature is regulated and controled, prepared the seawater film of high water flux.
The present invention is achieved through the following technical solutions:
A kind of novel acid absorbent system prepares the preparation method of high-flux reverse osmosis membrane, it is characterized in that: at polysulfones bottom
On film, the aqueous phase solution containing polyamine and one or more faintly acid salts or weak acid and tetramethylammonium hydroxide is first 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), it then will be by applying
The film covered is post-processed at a certain temperature, finally obtained reverse osmosis seawater film.Wherein contain in the water phase of coating liquid
It is dissolved in one or more ammonium salts of water.
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 reverse osmosis seawater film can be controlled by baking oven, especially at 120 DEG C -140 DEG C, performance compared with
It is superior.
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 reverse osmosis seawater film of high throughput of cutoff performance.And relative to
Prior art this patent buffering is simple and easy to control, has not only maintained good rejection, but also greatly improve water flux, and reproducibility is preferable,
Preparation cost is cheap.
Specific embodiment
A specific embodiment of the invention is illustrated below:
Following embodiment provides the preparation method of the high-throughput seawater film 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.
Evaluation: chlorination is made to the film properties of the high-flux reverse osmosis membrane based on new acid absorbent system in following embodiment
Sodium salt rejection rate and water flux.Test pressure when performance evaluation is 550psi, and concentrated water flow is 1.0L/min, and environment temperature is
25 DEG C, concentrated water pH value is 6.5~7.5, and concentrated water is sodium-chloride water solution, concentration 32000ppm.
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
System triethylamine hydrochloride/triethylamine system is prepared for different reverse osmosis seawater films.It is tested by experiment, prepared is anti-
Permeable membrane is up to 99.6% to the rejection of 32000ppm sodium-chloride water solution, and water flux is up to 55LMH.When performance evaluation
Test pressure be 550psi, concentrated water flow be 1.0L/min, environment temperature is 25 DEG C, and concentrated water pH value is 6.5~7.5,
Concentrated water is sodium-chloride water solution, concentration 32000ppm.
Embodiment 1
The m-phenylene diamine (MPD) aqueous solution of configuration quality score 3% and the tetramethylammonium hydroxide that mass fraction 1% is added, 1%
Ammonium chloride, be uniformly mixed, be reconfigured 0.2% pyromellitic trimethylsilyl chloride (TMC) oil-phase solution.First water is coated on polysulfones counterdie
Phase solution outwells extra solution after 60s, dries in the shade, then oil-phase solution is coated on the film to dry in the shade, and after 30s, it is extra to outwell
Oil-phase solution, and 5min is heat-treated in 120 DEG C of baking ovens.Thus the high-throughput seawater film based on new buffer system of method preparation
It is 550psi in test pressure, 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 sodium-chloride water solution, and concentration is under the experiment condition of 32000ppm, and measuring its water flux is 65LMH, and salt rejection rate is
99.7%.
Embodiment 2
The m-phenylene diamine (MPD) aqueous solution of configuration quality score 3% and the tetramethylammonium hydroxide that mass fraction 1.5% is added,
1% ammonium chloride is uniformly mixed, is reconfigured 0.2% pyromellitic trimethylsilyl chloride (TMC) oil-phase solution.First applied on polysulfones counterdie
Aqueous phase solution is covered, extra solution is outwelled after 60s, is dried in the shade, then oil-phase solution is coated on the film to dry in the shade, after 30s, is outwelled more
Remaining oil-phase solution, and 5min is heat-treated in 130 DEG C of baking ovens.Thus the high throughput sea based on new buffer system of method preparation
Moisture film is 550psi in test pressure, and concentrated water flow is 1.0L/min, and environment temperature is 25 DEG C, concentrated water pH value is 6.5~
7.5, concentrated water is sodium-chloride water solution, and concentration is under the experiment condition of 32000ppm, and measuring its water flux is 68LMH, salt rejection rate
It is 99.7%.
Embodiment 3
The m-phenylene diamine (MPD) aqueous solution of configuration quality score 3% and the tetramethylammonium hydroxide that mass fraction 1% is added, 1%
Ammonium chloride, be uniformly mixed, be reconfigured 0.3% pyromellitic trimethylsilyl chloride (TMC) oil-phase solution.First water is coated on polysulfones counterdie
Phase solution outwells extra solution after 60s, dries in the shade, then oil-phase solution is coated on the film to dry in the shade, and after 30s, it is extra to outwell
Oil-phase solution, and 5min is heat-treated in 120 DEG C of baking ovens.Thus the high-throughput seawater film based on new buffer system of method preparation
It is 550psi in test pressure, 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 sodium-chloride water solution, and concentration is under the experiment condition of 32000ppm, and measuring its water flux is 62LMH, and salt rejection rate is
99.7%.
Embodiment 4
The m-phenylene diamine (MPD) aqueous solution of configuration quality score 3% and the tetramethylammonium hydroxide that mass fraction 1% is added, 2%
Ammonium chloride, be uniformly mixed, be reconfigured 0.2% pyromellitic trimethylsilyl chloride (TMC) oil-phase solution.First water is coated on polysulfones counterdie
Phase solution outwells extra solution after 60s, dries in the shade, then oil-phase solution is coated on the film to dry in the shade, and after 30s, it is extra to outwell
Oil-phase solution, and 5min is heat-treated in 120 DEG C of baking ovens.Thus the high-throughput seawater film based on new buffer system of method preparation
It is 550psi in test pressure, 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 sodium-chloride water solution, and concentration is under the experiment condition of 32000ppm, and measuring its water flux is 70LMH, and salt rejection rate is
99.7%.
Embodiment 5
The m-phenylene diamine (MPD) aqueous solution of configuration quality score 3% and the tetramethylammonium hydroxide that mass fraction 2% is added, 1%
Ammonium chloride, be uniformly mixed, be reconfigured 0.3% pyromellitic trimethylsilyl chloride (TMC) oil-phase solution.First water is coated on polysulfones counterdie
Phase solution outwells extra solution after 60s, dries in the shade, then oil-phase solution is coated on the film to dry in the shade, and after 30s, it is extra to outwell
Oil-phase solution, and 5min is heat-treated in 120 DEG C of baking ovens.Thus the high-throughput seawater film based on new buffer system of method preparation
It is 550psi in test pressure, 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 sodium-chloride water solution, and concentration is under the experiment condition of 32000ppm, and measuring its water flux is 72LMH, and salt rejection rate is
99.7%.
Embodiment 6
The m-phenylene diamine (MPD) aqueous solution of configuration quality score 3% and the tetramethylammonium hydroxide that mass fraction 2.5% is added,
1% ammonium chloride is uniformly mixed, is reconfigured 0.2% pyromellitic trimethylsilyl chloride (TMC) oil-phase solution.First applied on polysulfones counterdie
Aqueous phase solution is covered, extra solution is outwelled after 60s, is dried in the shade, then oil-phase solution is coated on the film to dry in the shade, after 30s, is outwelled more
Remaining oil-phase solution, and 5min is heat-treated in 120 DEG C of baking ovens.Thus the high throughput sea based on new buffer system of method preparation
Moisture film is 550psi in test pressure, and concentrated water flow is 1.0L/min, and environment temperature is 25 DEG C, concentrated water pH value is 6.5~
7.5, concentrated water is sodium-chloride water solution, and concentration is under the experiment condition of 32000ppm, and measuring its water flux is 75LMH, salt rejection rate
It is 99.7%.
Embodiment 7
The m-phenylene diamine (MPD) aqueous solution of configuration quality score 3% and the tetramethylammonium hydroxide that mass fraction 3% is added, 1%
Ammonium chloride, be uniformly mixed, be reconfigured 0.2% pyromellitic trimethylsilyl chloride (TMC) oil-phase solution.First water is coated on polysulfones counterdie
Phase solution outwells extra solution after 60s, dries in the shade, then oil-phase solution is coated on the film to dry in the shade, and after 30s, it is extra to outwell
Oil-phase solution, and 5min is heat-treated in 140 DEG C of baking ovens.Thus the high-throughput seawater film based on new buffer system of method preparation
It is 550psi in test pressure, 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 sodium-chloride water solution, and concentration is under the experiment condition of 32000ppm, and measuring its water flux is 78LMH, and salt rejection rate is
99.7%.
Embodiment 8
The m-phenylene diamine (MPD) aqueous solution of configuration quality score 3% and the tetramethylammonium hydroxide that mass fraction 4% is added, 1%
Ammonium chloride, be uniformly mixed, be reconfigured 0.2% pyromellitic trimethylsilyl chloride (TMC) oil-phase solution.First water is coated on polysulfones counterdie
Phase solution outwells extra solution after 60s, dries in the shade, then oil-phase solution is coated on the film to dry in the shade, and after 30s, it is extra to outwell
Oil-phase solution, and 5min is heat-treated in 130 DEG C of baking ovens.Thus the high-throughput seawater film based on new buffer system of method preparation
It is 550psi in test pressure, 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 sodium-chloride water solution, and concentration is under the experiment condition of 32000ppm, and measuring its water flux is 75LMH, and salt rejection rate is
99.7%.
Embodiment 9
The m-phenylene diamine (MPD) aqueous solution of configuration quality score 3% and the tetramethylammonium hydroxide that mass fraction 4% is added, 1%
Ammonium chloride, be uniformly mixed, be reconfigured 0.3% pyromellitic trimethylsilyl chloride (TMC) oil-phase solution.First water is coated on polysulfones counterdie
Phase solution outwells extra solution after 60s, dries in the shade, then oil-phase solution is coated on the film to dry in the shade, and after 30s, it is extra to outwell
Oil-phase solution, and 3min is heat-treated in 140 DEG C of baking ovens.Thus the high-throughput seawater film based on new buffer system of method preparation
It is 550psi in test pressure, 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 sodium-chloride water solution, and concentration is under the experiment condition of 32000ppm, and measuring its water flux is 78LMH, and salt rejection rate is
99.7%.
Claims (10)
1. a kind of acid absorbent system prepares the preparation method of high-flux reverse osmosis membrane, it is characterized in that: first applied on polysulfones counterdie
One layer of aqueous phase solution is covered, wherein aqueous phase solution contains polyamine, one or more faintly acid salts or weak acid and tetramethyl hydrogen-oxygen
Change ammonium；After drying in the shade, it is coated with oil-phase solution, wherein oil-phase solution is the solution that polynary acyl chlorides is dissolved in Isopar G；Then
It will be post-processed at a certain temperature by the film of coating, finally obtained reverse osmosis seawater film；
Wherein contain tetramethylammonium hydroxide, ammonium chloride, etamon chloride, boric acid, citric acid or three in the water phase of coating liquid
One of ethylamine hydrochloride is a variety of.
2. preparation method according to claim 1, which is characterized in that contain in the aqueous phase solution in the preparation method
Polymer substance m-phenylene diamine (MPD), one of piperazine or polyethyleneimine or a variety of, and the quality of the polymer substance in water phase
Percentage is 0.1-5.0%.
3. preparation method according to claim 2, which is characterized in that contain in the aqueous phase solution in the preparation method
Polymer substance m-phenylene diamine (MPD), and the mass percent of the polymer substance in water phase is 0.1-3.0%.
4. preparation method according to claim 1, which is characterized in that polyamine in the aqueous phase solution in the preparation method
Shared mass percent is 0.1-10%.
5. the preparation method according to claim 4, which is characterized in that the polyamine of the aqueous phase solution in the preparation method
For tetramethylammonium hydroxide, and quality of the tetramethylammonium hydroxide in aqueous phase solution is very 0.1-5%.
6. preparation method according to claim 1, which is characterized in that also added containing macromolecule in the oil-phase solution
Agent, there is a pyromellitic trimethylsilyl chloride, one or more, and the macromolecule in oily phase of Adipoyl Chloride or hexamethylene diisocyanate
The mass percent of additive is 0.1-4.0%.
7. preparation method according to claim 6, which is characterized in that the polymeric additive in the oil-phase solution is equal
Three formyl chloride of benzene, and the mass percent of pyromellitic trimethylsilyl chloride is 0.1-3.5%.
8. preparation method according to claim 1, which is characterized in that faintly acid salt or weak acid in the preparation method
For ammonium chloride, the one or more of boric acid or triethylamine hydrochloride, and the mass percent in aqueous phase solution is 0.1-
6%.
9. preparation method according to claim 1, which is characterized in that the post-processing temperature of composite membrane in the preparation method
It is 100 DEG C -150 DEG C.
10. preparation method according to claim 1, which is characterized in that the post-processing temperature of composite membrane in the preparation method
Degree is 120 DEG C -140 DEG C.
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