CN110449046A - Modified antipollution complex reverse osmosis membrane of a kind of MOF and preparation method thereof - Google Patents
Modified antipollution complex reverse osmosis membrane of a kind of MOF and preparation method thereof Download PDFInfo
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- CN110449046A CN110449046A CN201910723696.3A CN201910723696A CN110449046A CN 110449046 A CN110449046 A CN 110449046A CN 201910723696 A CN201910723696 A CN 201910723696A CN 110449046 A CN110449046 A CN 110449046A
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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
- B01D61/025—Reverse osmosis; Hyperfiltration
-
- 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
-
- 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
- B01D69/12—Composite membranes; Ultra-thin membranes
-
- 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
-
- 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
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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
- C02F1/50—Treatment of water, waste water, or sewage by addition or application of a germicide or by oligodynamic treatment
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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
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
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- 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
Abstract
The invention belongs to field of sea water desalting technology, and in particular to modified antipollution complex reverse osmosis membrane of a kind of MOF and preparation method thereof.The complex reverse osmosis membrane, including polysulfone supporting layer and desalination layer, the desalination layer is the polyamide composite film of the double carboxylate metal's organic framework materials of supported copper-Isosorbide-5-Nitrae-benzene, and the aperture of the double carboxylate metal's organic framework materials of the copper-Isosorbide-5-Nitrae-benzene is 0.52nm.The present invention also provides a kind of preparation methods of the modified antipollution complex reverse osmosis membrane of MOF.The modified antipollution complex reverse osmosis membrane of MOF prepared by the present invention, organic pollutant is effectively reduced in the absorption on complex reverse osmosis membrane surface, the copper ion of film surface plays bactericidal effect simultaneously, so that complex reverse osmosis membrane has both the function of anti-organic pollution and microbial contamination；While salt rejection rate remains unchanged, the water flux of complex reverse osmosis membrane obviously rises.
Description
Technical field
The invention belongs to field of sea water desalting technology, and in particular to a kind of modified antipollution complex reverse osmosis membrane of MOF and its
Preparation method.
Background technique
To solve the problems, such as that the shortage of water resources that the world today faces provides the production used indirectly, life is used for sea water desalination
Water has become an important very effective approach of global water supply.Being converted seawater by reverse osmosis method can
With direct way.In all kinds of reverse osmosis membranes, polyamide composite reverse osmosis membrane, due to its excellent separating property and through performance
Mainstream as current reverse osmosis membrane.In the practical application of reverse osmosis membrane, since organic matter and microorganism are in the suction of film surface
It draws wrong conclusions by false analogy and causes the decline of water flux, therefore preparation keeps high water flux for a long time and resistant to pollution reverse osmosis membrane becomes urgent need
It wants.
In recent years some patents disclose the methods for preparing anti-pollution reverse osmosis membrane.These methods include United States Patent (USP)
US8875906B2 is disclosed to coat silver nanotube in polysulfone supporting layer, and United States Patent (USP) 20150224450A1 is disclosed in polyamides
Crosslinking curing has zwitterionic carbon nanotube in amine separating layer, and United States Patent (USP) US6551536 is disclosed to be separated in polyamide
Doped nano titanium dioxide particle and United States Patent (USP) US20140238939A1 are disclosed in polyamide separating layer surface grafting in layer
Doped quaternary ammonium salt class antibacterials.
However, the limitation of the above prior art is, antibacterial action can be played to microorganism, but organic matter is adhered to
It pollutes caused by the film surface and does not act on significantly.In addition, the modified particles of stable against biological contamination are added in reverse osmosis membrane, it is past
Increase toward the defect point that will lead to reverse osmosis membrane, so that the salt rejection rate of reverse osmosis membrane reduces.
In consideration of it, proposing the present invention.
Summary of the invention
In order to solve the defect for polluting not obvious effect that reverse osmosis membrane existing in the prior art adheres to organic matter,
The invention reside in provide modified anti-pollution reverse-osmosis composite membrane of a kind of MOF and preparation method thereof.The present invention passes through in compound reverse osmosis
Double carboxylate metal organic frame (MOF) materials of supported copper-Isosorbide-5-Nitrae-benzene in the desalination layer of permeable membrane, so that complex reverse osmosis membrane has
Pollution-resistant, while salt rejection rate remains unchanged, water flux is promoted.
The present invention is achieved through the following technical solutions:
A kind of modified antipollution complex reverse osmosis membrane of MOF, including polysulfone supporting layer and desalination layer, the desalination layer are load
The polyamide composite film of the double carboxylate metal's organic framework materials of copper-Isosorbide-5-Nitrae-benzene, and the double carboxylate metals of the copper-Isosorbide-5-Nitrae-benzene have
The aperture of machine frame frame material is nano micro-flake structure, and microplate thickness in monolayer is 30nm, aperture 0.52nm, and being conducive to diameter is
The hydrone of 0.26nm passes through, and retains the sodium ion that diameter is 0.72nm.
The present invention also provides a kind of preparation methods of the modified antipollution complex reverse osmosis membrane of MOF, including walk as follows
It is rapid:
(1) preparation of the double carboxylate metal's organic framework materials of copper -1,4- benzene
A, dimethylformamide is mixed as the first mixed solvent with acetonitrile, the double carboxylic acids of Isosorbide-5-Nitrae benzene is mixed in first
In bonding solvent, 30-60min is stirred, obtains the double carboxylic acid solutions of uniform Isosorbide-5-Nitrae benzene；
B, dimethylformamide is mixed with acetonitrile as the second mixed solvent；
C, dimethylformamide is mixed with acetonitrile as third mixed solvent, by Cu (NO3)2·3H2O is dissolved in third
In the mixed solvent stirs 30-60min, obtains uniform copper nitrate solution；
D, successively by the copper nitrate solution of 1,4 benzene of step a double carboxylic acid solutions, the second mixed solvent of step b and step c
It is added slowly in reactor, is then reacted, after blue precipitate is collected by centrifugation, be redispersed in dimethylformamide
In, it is dry after repeated centrifugation 3 times, obtain the double carboxylate metal's organic framework materials of copper-Isosorbide-5-Nitrae-benzene；
(2) preparation of polysulfone supporting layer
Polysulfones solid particle is dissolved in DMF solution, and polysulfones solution is made, and then vacuum defoamation, cooling exists polysulfones solution
Film forming is coated in polyester non-woven fabric substrate, is then immersed in 20 DEG C of deionized waters after solidification processing 240s, is obtained that there is porous knot
The polysulfone supporting layer of structure；
(3) preparation of complex reverse osmosis membrane
The double carboxylate metal's organic framework materials of copper -1,4- benzene that step (1) obtains are added to pyromellitic trimethylsilyl chloride
In hexane solution, ultrasonic disperse 40min, obtains mixed solution at 40 DEG C.M-phenylene diamine (MPD) aqueous solution is coated in step (2) to obtain
Polysulfone supporting layer on, air purging, then by the mixed solution be coated in polysulfone supporting layer on, carry out interface polymerization reaction,
Then dry, rinsing, then immerse in glycerine water solution, 8min is impregnated at 60 DEG C, it is modified anti-to obtain MOF for 60 DEG C of drying after taking-up
Pollution compound reverse osmosis membrane.
The polymerization reaction of pyromellitic trimethylsilyl chloride and m-phenylene diamine (MPD) generates netted desalination layer during interface polymerization reaction
While, the double carboxylate metal's organic framework materials of meeting supported copper-Isosorbide-5-Nitrae-benzene in situ generate polyurethane composite membrane, with polysulfones branch
Support layer forms the modified antipollution complex reverse osmosis membrane of MOF together.
Preferably, the volume ratio of the first in the mixed solvent dimethylformamide and acetonitrile described in step (1) is (1.5-
3): 1, the volume ratio of the second in the mixed solvent dimethylformamide and acetonitrile is 1:1, the third in the mixed solvent diformazan
The volume ratio of base formamide and acetonitrile is 1:(2-5).
Preferably, the concentration of the double carboxylic acids of Isosorbide-5-Nitrae benzene is 10-25mg/mL in the double carboxylic acid solutions of Isosorbide-5-Nitrae benzene described in step (1)；Institute
State Cu (NO in copper nitrate solution3)2·3H2The concentration of O is 10-50mg/mL；It is in step d that the double carboxylic acids of 1,4 benzene of step a are molten
The copper nitrate solution of liquid, the second mixed solvent of step b and step c is successively added slowly to reaction according to the volume ratio of 3:2:3
In device；The reaction is to react for 24 hours at 40 DEG C.
Preferably, the mass fraction of polysulfones solution described in step (2) is 20wt%-25wt%, by polysulfones solid particle
When being dissolved in DMF solution, need to stir 6-8h under the conditions of 50 DEG C；The film thickness of the coating film forming is 50 μm.
Preferably, in mixed solution described in step (3) the double carboxylate metal's organic framework materials of copper-Isosorbide-5-Nitrae-benzene quality
Score is 0.02wt%~0.16wt%, preferably 0.09wt%-0.12wt%, more preferably 0.12wt%；Three formyl of equal benzene
The mass fraction of chlorine is 0.01wt%~0.04wt%, preferably 0.02wt%；The mass fraction of the m-phenylene diamine (MPD) aqueous solution
For 1.5wt%.
Preferably, the time of interface polymerization reaction described in step (3) is 150s；The drying is to do at a temperature of 60 DEG C
Dry 5min；The rinsing is successively respectively to rinse 15min with the ethanol water of 10%wt and 40 DEG C of distilled water respectively.
Beneficial effects of the present invention:
(1) it is micro- that double carboxylate metal organic frame (MOF) nanometers of copper -1,4- benzene are added in the present invention in complex reverse osmosis membrane
Piece belongs to two-dimensional structure (2D MOF), aperture 0.52nm, can permit the hydrone that diameter is 0.26nm and passes through, but is straight
Diameter is that the sodium ion of 0.72nm is but trapped and can not pass through.In addition, the introducing of mantoquita so that complex reverse osmosis membrane surface parent
It is aqueous substantially to enhance, organic pollutant is effectively reduced in the absorption on complex reverse osmosis membrane surface, while the copper ion of film surface
Bactericidal effect is played, so that complex reverse osmosis membrane has both the function of anti-organic pollution and microbial contamination.
(2) in addition, the double carboxylate metal's organic framework materials of copper-Isosorbide-5-Nitrae-benzene prepared by the present invention are nano micro-flake shapes,
And thickness in monolayer is 30nm or so, is added in the desalination layer of complex reverse osmosis membrane, effectively reduces complex reverse osmosis membrane desalination
The thickness of layer significantly improves water flux, while salt rejection rate remains unchanged to reduce osmotic resistance；Meanwhile copper-Isosorbide-5-Nitrae-benzene is double
Carboxylate metal's organic framework materials can gradually discharge the copper ion with bactericidal effect, and microplate surface in use
It is smooth, there is high-hydrophilic, the attachment of organic pollutant can be reduced, improve the stable against biological contamination and organic contamination of reverse osmosis membrane
Ability.
Detailed description of the invention
Fig. 1 is the SEM figure of the double carboxylate metal's organic framework materials of copper -1,4- benzene prepared by embodiment 1.
Specific embodiment
Below will by specific embodiment, the present invention will be further described in detail, but not limited to this.
One, the preparation of the modified antipollution complex reverse osmosis membrane of MOF
Embodiment 1
(1) preparation of the double carboxylate metal's organic framework materials of copper -1,4- benzene
Dimethylformamide is mixed at room temperature using the volume ratio of 2:1 as the first mixed solvent with acetonitrile, and Isosorbide-5-Nitrae benzene is double
Carboxylic acid is dissolved in the first in the mixed solvent with the concentration of 10mg/mL, stirs 30 minutes at room temperature, obtains the double carboxylics of uniform Isosorbide-5-Nitrae benzene
Acid solution.
Dimethylformamide is mixed at room temperature using the volume ratio of 1:1 as the second mixed solvent with acetonitrile；By diformazan
Base formamide is mixed at room temperature using the volume ratio of 1:2 as third mixed solvent with acetonitrile.By nitrate trihydrate copper Cu (NO3)2·
3H2O is dissolved in third in the mixed solvent with the concentration of 10mg/mL, stirs 30 minutes at room temperature, it is molten to obtain uniform copper nitrate
Liquid.By Isosorbide-5-Nitrae benzene double carboxylic acid solutions, the second mixed solvent, copper nitrate solution is successively added slowly to examination according to the volume ratio of 3:2:3
Guan Zhong is divided into 3 layers of liquid in test tube.Test tube is placed in convection oven, 40 DEG C are reacted 24 hours.After the reaction was completed, In
It is centrifuged 5 minutes on centrifuge with the revolving speed of 10000rpm, collects blue precipitate, be scattered in dimethylformamide.Repeat with
It is 24 hours dry at 60 DEG C after upper centrifugal separation processes 3 times, the double carboxylate metal's organic frame materials of resulting copper-Isosorbide-5-Nitrae-benzene
Material, which is placed in vacuum desiccator, to be retained to use.
The SEM figure of the double carboxylate metal's organic framework materials of copper-Isosorbide-5-Nitrae-benzene of preparation is as shown in Figure 1, it can be seen that receive
Rice micro sheet structure, and thickness in monolayer is in 30nm or so.
(2) preparation of polysulfone supporting layer
Polysulfones solid particle is added in DMF solution, mass fraction 20wt%, 50 DEG C heating stirring 6 hours, be made poly-
Sulfolane solution.Polysulfones solution after deaeration filtering, is cooled to room temperature under -0.1MPa vacuum.Polysulfones solution automatic film applicator is existed
Film forming is coated in polyester non-woven fabric substrate, film thickness is controlled at 50 μm.Non-woven fabrics after coating is immersed in coagulating bath immediately,
Coagulating bath is 20 DEG C of deionized waters.After handling 240s, the polysulfone supporting layer with porous structure is obtained.
(3) preparation of the modified antipollution complex reverse osmosis membrane of MOF
The double carboxylate metal's organic framework materials of copper -1,4- benzene that step (1) obtains are added to pyromellitic trimethylsilyl chloride
In hexane solution, ultrasonic disperse 40min (ultrasonic disperse condition: 3000 is surpassed using Mission mix Sonicator at 40 DEG C
Sound dispersion machine, power 100W), obtain containing the double carboxylate metal's organic framework materials of 0.03wt% copper-Isosorbide-5-Nitrae-benzene and
The n-hexane mixed solution (oily phase) of 0.02wt% pyromellitic trimethylsilyl chloride.Mass fraction is water-soluble for the m-phenylene diamine (MPD) of 1.5wt%
Liquid is coated in polysulfone supporting layer, and air purging removes excessive aqueous solution.The double carboxylic acids of 0.03wt% copper -1,4- benzene will be contained
The n-hexane mixed solution of salt metal organic frame and 0.02wt% pyromellitic trimethylsilyl chloride is coated in above-mentioned coated m-phenylene diamine (MPD)
Polysulfone supporting layer on, control interface polymerization time be 150s, then heat 5min in 60 DEG C of convection oven.It uses respectively
The ethanol water of 10wt% and 40 DEG C of distilled water respectively rinse 15min.Diaphragm after rinsing is placed in the glycerol liquor of 10wt%
In solution, 8min is impregnated at 60 DEG C, is dried in 60 DEG C of baking ovens after taking-up, and the modified antipollution complex reverse osmosis membrane of MOF is obtained.
Embodiment 2
Compared with Example 1, difference is only that, by the double carboxylate metal's organic framework materials of copper-Isosorbide-5-Nitrae-benzene in n-hexane
Mass fraction in mixed solution replaces with 0.06wt%, other are the same as embodiment 1.
Embodiment 3
Compared with Example 1, difference is only that, by the double carboxylate metal's organic framework materials of copper-Isosorbide-5-Nitrae-benzene in n-hexane
Mass fraction in mixed solution replaces with 0.09wt%, other are the same as embodiment 1.
Embodiment 4
Compared with Example 1, difference is only that, by the double carboxylate metal's organic framework materials of copper-Isosorbide-5-Nitrae-benzene in n-hexane
Mass fraction in mixed solution replaces with 0.12wt%, other are the same as embodiment 1.
Embodiment 5
Compared with Example 1, difference is only that, by the double carboxylate metal's organic framework materials of copper-Isosorbide-5-Nitrae-benzene in n-hexane
Mass fraction in mixed solution replaces with 0.15wt%, other are the same as embodiment 1.
Embodiment 6
Identical as (1) the step of embodiment 1~(2), difference is the double carboxylate metals of copper-Isosorbide-5-Nitrae-benzene in step (3)
Organic framework materials are dissolved in m-phenylene diamine (MPD) aqueous solution, step (3) in the present embodiment specifically:
The double carboxylate metal's organic framework materials of copper -1,4- benzene are added to (water in 1.5wt% m-phenylene diamine (MPD) aqueous solution
Phase), (ultrasonic disperse condition: use 3000 ultrasonic disperse of Mission mix Sonicator within ultrasonic disperse 40 minutes at 40 DEG C
Machine, power 100W), the mass fraction of the double carboxylate metal's organic framework materials of copper-Isosorbide-5-Nitrae-benzene is 0.12wt%.Copper-will be contained
The m-phenylene diamine (MPD) aqueous solution of the double carboxylate metal's organic framework materials of Isosorbide-5-Nitrae-benzene is coated in polysulfone supporting layer, and air purging removes
Remove excessive aqueous solution.The hexane solution of 0.02wt% pyromellitic trimethylsilyl chloride is coated in polysulfone supporting layer, control interface
Polymerization time is 150s, then heats 5min in 60 DEG C of convection oven.Respectively with the ethanol water of 10wt% and 40 DEG C
Distilled water rinse 15min.Diaphragm after rinsing is placed in the glycerine water solution of 10wt%, 8min is impregnated at 60 DEG C, is taken out
It is dried in 60 DEG C of baking ovens afterwards, obtains the modified antipollution complex reverse osmosis membrane of MOF.
Comparative example 1
Compared with Example 1, difference is: omitting three formyl of equal benzene in the step (1) and step (3) in embodiment 1
The double carboxylate metal's organic framework materials of copper-Isosorbide-5-Nitrae-benzene are added without in the hexane solution of chlorine, other are the same as embodiment 1.
Two, performance test
(1) penetrating power is tested
For the complex reverse osmosis membrane that the penetrating power for testing complex reverse osmosis membrane, Example 1~6 and comparative example 1 obtain,
It is tested on cross-current type diaphragm check-out console, test condition is 2000ppm NaCl aqueous solution, 225psi operating pressure, temperature 25
DEG C, pH value 7.Test result is as shown in table 1:
Table 1
| Number | Explanation | Water flux (gfd) | Salt rejection rate (%) |
| Embodiment 1 | Oily mutually addition 0.03wt% metal-organic framework material | 33.7 | 98.8 |
| Embodiment 2 | Oily mutually addition 0.06wt% metal-organic framework material | 35.4 | 98.7 |
| Embodiment 3 | Oily mutually addition 0.09wt% metal-organic framework material | 38.9 | 98.8 |
| Embodiment 4 | Oily mutually addition 0.12wt% metal-organic framework material | 40.6 | 98.7 |
| Embodiment 5 | Oily mutually addition 0.15wt% metal-organic framework material | 41.5 | 98.5 |
| Embodiment 6 | Water phase adds 0.12wt% metal-organic framework material | 33.2 | 98.6 |
| Comparative example 1 | It is not added with metal-organic framework material | 31.2 | 98.7 |
(2) anti-microbial property test
In order to test the stable against biological contamination ability of anti-pollution reverse osmosis membrane, answered what Examples 1 to 6 and comparative example 1 obtained
Reverse osmosis membrane diaphragm is closed to be soaked respectively not in inoculum (Escherichia coli and golden staphylococci, CFU=106/mL), at 37 DEG C
Culture is taken out after 3 hours, places certain time, is calculated its bacterium and is reduced percentage.According to formula: R%=100 × (A-B), meter
It calculates number of bacteria and reduces percentage R, wherein A is the number of bacteria at 0 moment, and B is the number of bacteria after 24 hours.Test result is such as
Shown in table 2:
Table 2
(3) resistance to organic contamination performance test
In order to test anti-pollution reverse osmosis membrane resistance to organic contamination ability, Examples 1 to 6 and comparative example 1 are obtained
Complex reverse osmosis membrane diaphragm is tested on cross-current type diaphragm monitor station, water-soluble with 2000ppm NaCl and 200ppm bovine serum albumin
Liquid is as feeding liquid, and 225psi operating pressure, temperature DEG C, adjusting pH is 4.7.By 48 hours Contamination measurements, each film is recorded
The water flux of piece sample changes, and water flux attenuation rate r is according to formula r=100 × (J1-J2) calculate, wherein J1It is logical for initial water
Amount, J2For the water flux after 48 hours Contamination measurements.Test result is as shown in table 3:
Table 3
By the experimental result of table 1~3 it is found that when the double carboxylate metal's organic framework materials of oily Xiang Zhongtong-Isosorbide-5-Nitrae-benzene
When mass fraction is 0.12wt%, preferable antibacterial effect can be obtained, at the same the performance of resistance to organic contamination and biological pollution compared with
It is good.With the increase of the double carboxylate metal's organic framework materials mass fractions in oily phase of copper-Isosorbide-5-Nitrae-benzene, the water of reverse osmosis membrane is logical
After amount increases therewith, but the mass fraction of metal-organic framework material is more than 0.12wt%, the reduction of salt rejection rate can be caused.
Compared to the double carboxylate metal's organic framework materials of copper-Isosorbide-5-Nitrae-benzene are added in water phase, the double carboxylic acids of copper-Isosorbide-5-Nitrae-benzene are added in oily phase
Salt metal-organic framework material can obtain higher water flux, better antibacterial and resistance to organic contamination performance.This may be because
For polyamide desalination layer is the functional layer of reverse osmosis membrane, determines the water flux and anti-fouling performance of reverse osmosis membrane.Copper -1,4-
The double carboxylate metal's organic framework materials of benzene are hydrophilic nano particle, are added to the oily phase (n-hexane of pyromellitic trimethylsilyl chloride
Solution) in, be conducive to diffusion of the water phase (m-phenylene diamine (MPD) aqueous solution) to oily phase, advantageously form more uniform polyamide desalination
Layer.
Claims (8)
1. a kind of modified antipollution complex reverse osmosis membrane of MOF, which is characterized in that described de- including polysulfone supporting layer and desalination layer
Salt deposit is the polyamide composite film of the double carboxylate metal's organic framework materials of supported copper-Isosorbide-5-Nitrae-benzene, and the double carboxylics of the copper-Isosorbide-5-Nitrae-benzene
Hydrochlorate metal-organic framework material is nano micro-flake structure, and microplate thickness in monolayer is 30nm, aperture 0.52nm.
2. a kind of preparation method of the modified antipollution complex reverse osmosis membrane of MOF as described in claim 1, which is characterized in that packet
Include following steps:
(1) preparation of the double carboxylate metal's organic framework materials of copper -1,4- benzene
A, dimethylformamide is mixed with acetonitrile as the first mixed solvent, the double carboxylic acids of Isosorbide-5-Nitrae benzene are molten in the first mixing
In agent, 30-60min is stirred, obtains the double carboxylic acid solutions of uniform Isosorbide-5-Nitrae benzene；
B, dimethylformamide is mixed with acetonitrile as the second mixed solvent；
C, dimethylformamide is mixed with acetonitrile as third mixed solvent, by Cu (NO3)2·3H2O is dissolved in third mixing
In solvent, 30-60min is stirred, uniform copper nitrate solution is obtained；
D, successively slowly by the copper nitrate solution of 1,4 benzene of step a double carboxylic acid solutions, the second mixed solvent of step b and step c
It is added in reactor, is then reacted, after blue precipitate is collected by centrifugation, is redispersed in dimethylformamide, weight
It is dry after being centrifuged 3 times again, obtain the double carboxylate metal's organic framework materials of copper-Isosorbide-5-Nitrae-benzene；
(2) preparation of polysulfone supporting layer
Polysulfones solid particle is dissolved in DMF solution, and polysulfones solution, then vacuum defoamation, cooling, by polysulfones solution in polyester is made
Film forming is coated on nonwoven fabric base bottom, is then immersed in 20 DEG C of deionized waters after solidification processing 240s, is obtained that there is porous structure
Polysulfone supporting layer；
(3) preparation of complex reverse osmosis membrane
The double carboxylate metal's organic framework materials of copper -1,4- benzene that step (1) obtains are added to the hexane of pyromellitic trimethylsilyl chloride
In solution, ultrasonic disperse 40min, obtains mixed solution at 40 DEG C.M-phenylene diamine (MPD) aqueous solution is gathered coated in what step (2) obtained
On sulfone supporting layer, air purging, then the mixed solution is coated in polysulfone supporting layer, interface polymerization reaction is carried out, then
Dry, rinsing, then immerse in glycerine water solution, 8min is impregnated at 60 DEG C, 60 DEG C of drying after taking-up obtain the modified antipollution of MOF
Complex reverse osmosis membrane.
3. a kind of preparation method of the modified antipollution complex reverse osmosis membrane of MOF according to claim 2, which is characterized in that
The volume ratio of first in the mixed solvent dimethylformamide and acetonitrile described in step (1) is (1.5-3): 1, second mixing
The volume ratio of dimethylformamide and acetonitrile is 1:1 in solvent, the third in the mixed solvent dimethylformamide and acetonitrile
Volume ratio is 1:(2-5).
4. a kind of preparation method of the modified antipollution complex reverse osmosis membrane of MOF according to claim 2, which is characterized in that
The concentration of the double carboxylic acids of 1,4 benzene is 10-25mg/mL in the double carboxylic acid solutions of 1,4 benzene described in step (1)；In the copper nitrate solution
Cu(NO3)2·3H2The concentration of O is 10-50mg/mL；The double carboxylic acid solution of 1,4 benzene of step a, step b second are mixed in step d
The copper nitrate solution of bonding solvent and step c are successively added slowly in reactor according to the volume ratio of 3:2:3；Described in step d
Reaction is to react for 24 hours at 40 DEG C.
5. a kind of preparation method of the modified antipollution complex reverse osmosis membrane of MOF according to claim 2, which is characterized in that
The mass fraction of polysulfones solution described in step (2) is 20wt%-25wt%, when polysulfones solid particle is dissolved in DMF solution, is needed
6-8h is stirred under the conditions of 50 DEG C；The film thickness of the coating film forming is 50 μm.
6. a kind of preparation method of the modified antipollution complex reverse osmosis membrane of MOF according to claim 2, which is characterized in that
The mass fraction of the double carboxylate metal's organic framework materials of copper -1,4- benzene is 0.02wt% in mixed solution described in step (3)
~0.16wt%, the mass fraction of pyromellitic trimethylsilyl chloride are 0.01wt%~0.04wt%；The matter of the m-phenylene diamine (MPD) aqueous solution
Amount score is 0.5wt%-1.5wt%.
7. a kind of preparation method of the modified antipollution complex reverse osmosis membrane of MOF according to claim 6, which is characterized in that
The mass fraction of the double carboxylate metal's organic framework materials of copper -1,4- benzene is 0.09wt% in mixed solution described in step (3)
~0.12wt%, the mass fraction of pyromellitic trimethylsilyl chloride are 0.02wt%.
8. a kind of preparation method of the modified antipollution complex reverse osmosis membrane of MOF according to claim 2, which is characterized in that
The time of interface polymerization reaction described in step (3) is 150s；The drying is dry 5min at a temperature of 60 DEG C；The rinsing
Successively respectively to rinse 15min with the ethanol water of 10%wt and 40 DEG C of distilled water respectively.
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| CN111939774A (en) * | 2020-08-11 | 2020-11-17 | 哈尔滨工业大学 | Method for preparing composite nanofiltration membrane by growing nano particles after etching |
| CN112481639A (en) * | 2020-12-01 | 2021-03-12 | 中国海洋大学 | Preparation method and application of hierarchical porous nickel-based metal organic framework electrocatalytic material |
| CN112657352A (en) * | 2020-11-30 | 2021-04-16 | 同济大学 | Polyamide thin film layer composite reverse osmosis film and preparation method and application thereof |
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| CN111939774A (en) * | 2020-08-11 | 2020-11-17 | 哈尔滨工业大学 | Method for preparing composite nanofiltration membrane by growing nano particles after etching |
| CN112657352A (en) * | 2020-11-30 | 2021-04-16 | 同济大学 | Polyamide thin film layer composite reverse osmosis film and preparation method and application thereof |
| CN112481639A (en) * | 2020-12-01 | 2021-03-12 | 中国海洋大学 | Preparation method and application of hierarchical porous nickel-based metal organic framework electrocatalytic material |
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| US11254691B1 (en) | 2021-02-22 | 2022-02-22 | Kuwait Institute For Scientific Research | Method for making metal organic frameworks and thin film nanocomposite membranes using the same |
| CN113880316A (en) * | 2021-11-17 | 2022-01-04 | 青岛延晖环保科技有限公司 | Method for desalting seawater by using biological membrane |
| CN114452842A (en) * | 2022-01-11 | 2022-05-10 | 上海电力大学 | CNC/Cu-MOF-74 composite material surface modified PVDF membrane, and preparation method and application thereof |
| CN114870656A (en) * | 2022-05-17 | 2022-08-09 | 北京碧水源膜科技有限公司 | Preparation method of zwitterionic polymer mixed matrix composite membrane |
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