CN107349807A - A kind of Fe（BTC）Big flux polyamide nano composite membrane inlayed and its production and use - Google Patents
A kind of Fe（BTC）Big flux polyamide nano composite membrane inlayed and its production and use 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
- B01D71/56—Polyamides, e.g. polyester-amides
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
- B01D67/0079—Manufacture of membranes comprising organic and inorganic components
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
- B01D69/12—Composite membranes; Ultra-thin membranes
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- B—PERFORMING OPERATIONS; TRANSPORTING
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Abstract
The invention discloses a kind of preparation method of Fe (BTC) big flux polyamide nano composite membranes inlayed：Raw material milipore filter is dissolved into N, in N solvent dimethylformamides, stirring at room temperature obtains casting solution, casting film shaping, obtains PSF support membranes；M-phenylene diamine (MPD) is dissolved in deionized water and obtains 0.1~8wt% m-phenylene diamine (MPD) aqueous phase solutions, pyromellitic trimethylsilyl chloride is dissolved in n-hexane, obtained pyromellitic trimethylsilyl chloride organic phase solution；Take described m-phenylene diamine (MPD) aqueous phase solution to be uniformly added dropwise on described PSF support membranes, then take the pyromellitic trimethylsilyl chloride organic phase solution to continue uniformly to be added dropwise on the PSF support membranes after handling through aqueous phase solution, obtain PA membrane；Gained PA membrane is immersed in the mixed solution of ferric iron compound, water and ethanol, then the film after processing is immersed in the mixed solution of trimesic acid, water and ethanol and obtains Fe (BTC)/PA films；Film prepared by the present invention has high selectivity, high-throughout separating property.
Description
Technical field
Present invention relates particularly to a kind of polyamide reverse osmose membrane inlayed based on metal-organic framework materials and its preparation side
Method and purposes.
Background technology
Counter-infiltration is the membrane separating process using pressure difference as motive force, possesses separation process without phase transformation, selectivity height, efficiency high
And energy consumption it is low the features such as.
Polyamide is a kind of high polymer material for being commonly used to prepare composite membrane cortex, and it has good stability, hydrophilic
Property and mechanical strength, can high temperature resistant, highly basic and organic solvent.Current commercialized nanofiltration and reverse osmosis membrane are gathered from aromatic series more
Acid amides, such film achieve wide range of industrial applications in the whole world, including water process, solution decolourize, medicine concentrates and purifies and biochemical
Material concentration etc..For polyamide composite film as most widely used composite membrane kind, polyamide composite film has rejection high, leads to
Larger, the features such as chemical stability is excellent, and pH range is wide, and operating pressure is low is measured, although the energy profit of large-scale water process at present
Improved constantly with rate, but energy consumption problem is always the subject matter in desalination field, raising water flux, pressure needed for reduction, from
And it is most important means at this stage to reduce energy consumption, it has now been found that added into polyamide material porous inorganic material prepare it is new
Organic/inorganic film, which can turn into, improves infiltrative effective means, and the porous inorganic material having been reported has silica, molecule
Sieve, CNT and graphene etc..
The organic framework material of metal one is newfound polyporous materials in recent years, has the duct or hole of nano-scale
Cave, and duct type complexity is various；Its porosity is high, specific surface area is big, density is small, chemical stability is good, and pore structure is controllable.
The organic framework material of metal one for possessing nanoscale duct shows excellent gas/liquid adsorptive selectivity, it is developed into performance
Excellent gas separation membrane or infiltration evaporation membrane material；In addition, the organic framework material of metal one can improve NF membrane desalination offer
Extra nanochannel, in the case where not influenceing rejection, improve its permeability.Fe (BTC) is Fe (III) and terephthaldehyde
The tricarboxylic acid polymer of acid, has higher specific surface area, water stability, heat endurance.
Traditional law system is for Fe (BTC)/PA composite membranes.Fe (BTC) nano particle is synthesized first, then is doped to polyamide
In layer, Fe (BTC)/PA composite membranes are obtained.Although comparing property of polyamide composite membrane has been achieved for obvious progress,
During MOF nano particles are mixed into PA membrane, easily cause reunion and non-selectivity hole of the nano particle inside it
The generation of gap, so as to cause the decline of film properties.
The content of the invention
To solve the shortcomings of the prior art, the purpose of the present invention is the hypotonicity for aromatic polyamide film,
A kind of Fe (BTC) is prepared using the architectural characteristic of Fe (BTC) metal-organic framework materials using the method for fabricated in situ to inlay
Polyamide nano composite membrane, realization prepare big flux, the target of high rejection PA membrane.
To achieve the above object, the present invention adopts the following technical scheme that：
The polyamide nano composite membrane that Fe (BTC) of the present invention is inlayed can be prepared in accordance with the following steps：
(1) raw material milipore filter is dissolved into DMF solvent, stirring at room temperature obtains casting solution, by institute
The casting solution ultrasound stated, the bubble in 20~40h removing solution is stood, at 20~50 DEG C, described casting solution is laid on
On smooth glass plate, scraped with scraper to shaping, obtain PSF support membranes；The addition of described DMF solvent
Amount is calculated as 5~10ml/g with the quality of described milipore filter；
(2) m-phenylene diamine (MPD) is dissolved in deionized water and obtains 0.1~8wt% m-phenylene diamine (MPD) aqueous phase solutions, by equal benzene front three
Acyl chlorides is dissolved in n-hexane, the pyromellitic trimethylsilyl chloride organic phase solution that 30~60min of ultrasound is obtained；Take described m-phenylene diamine (MPD) water
Phase solution is uniformly added dropwise on described PSF support membranes and stands 2~8min, removes unnecessary aqueous phase solution, then take the equal benzene
Three formyl chloride organic phase solutions continue uniformly to be added dropwise on the PSF support membranes after handling through aqueous phase solution, stand 2~8min, remove
Unnecessary organic phase solution is removed, after standing 2~10min, the film after being handled, by the film after the processing at 40~60 DEG C
5~15min is dried, obtains PA membrane；The amount of described pyromellitic trimethylsilyl chloride material is calculated as 100 with the volume of n-hexane~
700mmol/L；The addition of described m-phenylene diamine (MPD) aqueous phase solution is calculated as 0.7~1.4ml/cm with the area of PSF support membranes2；
The addition of described pyromellitic trimethylsilyl chloride organic phase solution is calculated as 0.7~1.4ml/cm with the area of PSF support membranes2；
(3) ferric iron compound is dissolved in the mixed solution of water and ethanol and obtains reaction solution A, trimesic acid is dissolved in water
With reaction solution B is obtained in the mixed solution of ethanol, PA membrane obtained by step (2) is immersed in described reaction solution A, room temperature
20~40h of lower standing, then the film after processing is immersed in described reaction solution B, 12~24h is reacted at 60~80 DEG C,
Products therefrom is placed in standing 24h in deionized water and obtains Fe (BTC)/PA films；The amount of the material of described ferric iron compound with
The total volume meter of the mixed solution of water and ethanol is 100~700mmol/L；The amount of the material of described trimesic acid with water and
The total volume meter of the mixed solution of ethanol is 100~700mmol/L.
Further, in step (1), described milipore filter is polysulfones, polyether sulfone, polyethylene or polypropylene, preferably polysulfones.
Further, in step (1), the frequency of the ultrasonic deaeration is 30~50KHz, and the time is 0.2~3h.
Further, in step (1), described PSF support film thicknesses are 100~300 μm.
Further, in step (3), described ferric iron compound is：Ferric trichloride, ferric nitrate or ferric sulfate.
Further, in step (3), the volume ratio 1 of described deionized water and ethanol:1~10；Further, it is preferably
1:1。
Further, in step (3), preferably described reaction temperature is 60 DEG C, reaction time 40h.
Application of the polyamide nano composite membrane that Fe (BTC) of the present invention is inlayed in desalinating process.
Compared with prior art, the advantage of the invention is that：
Method of the present invention utilizes existing carboxylic group and Fe in aramid layer3+Coordination, be follow-up Fe
(BTC) particle synthesis provides uniformly, scattered coordination site, it is compound to be successfully prepared the polyamide nano that Fe (BTC) inlays
Film, the film of synthesis has obtained good improvement in dispersiveness and compatibility, while has high selectivity, high-throughout separation property
Energy.
Brief description of the drawings
Fig. 1 is the ESEM surface for the polyamide nano composite membrane that Fe (BTC) inlays and sectional view in example 1；
Fig. 2 is the ESEM surface of PA membrane and sectional view in comparative example.
Embodiment
With reference to specific embodiment, the present invention is described in detail in, but the present invention is not limited to following embodiments,
Do not depart from present invention and scope, change should be all included in the technical scope of the present invention.
The separating property test for the polyamide nano composite membrane that Fe (BTC) of the present invention is inlayed can be in accordance with the following steps
Carry out：
The compound water separating membrane solution system of polyamide nano inlayed using flat board membrane performance tester measure Fe (BTC)
Reverse osmosis separation performance：Feed liquid is respectively concentration 2000ppm NaCl, 2000ppm MgSO4, 2000ppm Na2SO4,
2000ppm CaCl2, 2000ppm KCl, operation temperature is 25 DEG C, and operating pressure is respectively 0.2Mpa, 0.4Mpa, 0.6Mpa,
0.8MPa。
The test of the evaluation of nanofiltration separation performance, i.e. membrane flux and rejection
1) permeation flux (J), is the index for reflecting membrane permeability, and its defined formula is：
J=V/ (S*t*P)
J represents flux (L m-2h-1bar-1), S represents the effective area (m of film-2), t represents time (h), P representative pressures
(bar)。
2) rejection (R), the selectivity of film is reflected, its defined formula is：
R=(Cf–Cp)/Cf100%
In formula, CfWith CpRespectively concentration of the solute component in feed liquid and penetrating fluid.
Example 1
(1) polysulfones 5mg is dissolved into 20ml DMF solvents, obtains casting solution ultrasound 20min standings
12h, casting solution is laid on to smooth 100cm at 50 DEG C2On glass plate, scraped on a glass to film forming with 200 μm of scrapers,
Immediately obtained film is put into water rapidly, after being fully formed, obtain PSF support membranes be put into it is standby in deionized water.
(2) m-phenylene diamine (MPD) 0.4g is dissolved in 20ml deionized waters and obtains 2% m-phenylene diamine (MPD) aqueous phase solution, take 0.02g equal
The formyl chloride of benzene three is dissolved in 20ml n-hexanes and obtains 0.1% pyromellitic trimethylsilyl chloride organic phase solution；Take described m-phenylene diamine (MPD) aqueous phase
Solution 5ml is uniformly added dropwise in described PSF support membranes 7.065cm2Upper standing 2min, removes unnecessary aqueous phase solution, then takes institute
State pyromellitic trimethylsilyl chloride organic phase solution 5ml to continue uniformly to be added dropwise on the PSF support membranes after handling through aqueous phase solution, stand
2min, unnecessary organic phase solution is removed, after standing 2min, the film after being handled, by the film after the processing at 40 DEG C
5min is dried, obtains PA membrane；
(3) it is 1 ferric trichloride 0.972g to be dissolved in into water and ethanol volume ratio：In 1 mixed solution 60ml, then to mixed liquor
PA membrane obtained by middle addition, stands 20h at room temperature；It is 1 that 2.52g trimesic acids are dissolved in into water and ethanol volume ratio：1 it is mixed
Close in solution 120ml, then add PA membrane, react 12h at 60 DEG C, products therefrom is placed in deionized water and obtains Fe
(BTC)/PA films.
Gained Fe (BTC)/PA films are subjected to performance test；To Fe (BTC) type metal-organic framework materials/polyamide nano
Composite membrane carries out surface analysis, as shown in figure 1, its under 0.6Mpa to 2000ppm NaCl rejection 92.55%, simultaneously
Water flux reaches 5.662L m-2h-1bar-1。
Example 2
(1) polysulfones 5mg is dissolved into 20ml DMF solvents, obtains casting solution ultrasound 20min standings
12h, casting solution is laid on to smooth 100cm at 50 DEG C2On glass plate, scraped on a glass to film forming with 200 μm of scrapers,
Immediately obtained film is put into water rapidly, after being fully formed, obtain PSF support membranes be put into it is standby in deionized water.
(2) m-phenylene diamine (MPD) 0.4g is dissolved in 20ml deionized waters and obtains 2% m-phenylene diamine (MPD) aqueous phase solution, take 0.02g equal
The formyl chloride of benzene three is dissolved in 20ml n-hexanes and obtains 0.1% pyromellitic trimethylsilyl chloride organic phase solution；Take described m-phenylene diamine (MPD) aqueous phase
Solution 5ml is uniformly added dropwise in described PSF support membranes 7.065cm2Upper standing 2min, removes unnecessary aqueous phase solution, then takes institute
State pyromellitic trimethylsilyl chloride organic phase solution 5ml to continue uniformly to be added dropwise on the PSF support membranes after handling through aqueous phase solution, stand
2min, unnecessary organic phase solution is removed, after standing 2min, the film after being handled, by the film after the processing at 40 DEG C
5min is dried, obtains PA membrane；
(3) it is 1 ferric trichloride 6.804g to be dissolved in into water and ethanol volume ratio：It is configured to react in 1 mixed solution 60ml
Liquid A, it is 1 that 17.651g trimesic acids are dissolved in into water and ethanol volume ratio：Reaction solution B is configured in 1 mixed solution 120ml,
PA membrane obtained by step (2) is immersed in reaction solution A, 40h is stood at room temperature, then the film after processing is placed in and submerged again
In reaction solution B, 12h is reacted at 80 DEG C, products therefrom is placed in deionized water, obtain Fe (BTC)/PA films.
Gained Fe (BTC)/PA films are subjected to performance test；To Fe (BTC) type metal-organic framework materials/polyamide nano
Composite membrane carries out surface analysis, and surface analysis is carried out to Fe (BTC) type metal-organic framework materials/polyamide nano composite membrane,
It was found that with example 1 in Fe (BTC) type metal-organic framework materials/polyamide nano composite membrane surface topography do not have it is big not
Together, its under 0.6Mpa to 2000ppm NaCl rejection 93.85%, while water flux reaches 5.214L m-2h-1bar-1。
Example 3
(1) polyethylene 5mg is dissolved into 20ml DMF solvents, it is quiet obtains casting solution ultrasound 20min
12h is put, casting solution is laid on to smooth 100cm at 50 DEG C2On glass plate, with 200 μm of scrapers scrape on a glass into
Film, immediately obtained film is put into water rapidly, after being fully formed, obtain PSF support membranes be put into it is standby in deionized water
With.
(2) m-phenylene diamine (MPD) 0.4g is dissolved in 20ml deionized waters and obtains 2% m-phenylene diamine (MPD) aqueous phase solution, take 0.02g equal
The formyl chloride of benzene three is dissolved in 20ml n-hexanes and obtains 0.1% pyromellitic trimethylsilyl chloride organic phase solution；Take described m-phenylene diamine (MPD) aqueous phase
Solution 5ml is uniformly added dropwise in described PSF support membranes 7.065cm2Upper standing 2min, removes unnecessary aqueous phase solution, then takes institute
State pyromellitic trimethylsilyl chloride organic phase solution 5ml to continue uniformly to be added dropwise on the PSF support membranes after handling through aqueous phase solution, stand
2min, unnecessary organic phase solution is removed, after standing 2min, the film after being handled, by the film after the processing at 40 DEG C
5min is dried, obtains PA membrane；
(3) it is 1 ferric trichloride 6.804g to be dissolved in into water and ethanol volume ratio：It is configured to react in 1 mixed solution 60ml
Liquid A, it is 1 that 17.651g trimesic acids are dissolved in into water and ethanol volume ratio：Reaction solution B is configured in 1 mixed solution 120ml,
PA membrane obtained by step (2) is immersed in reaction solution A, 40h is stood at room temperature, then the film after processing is placed in and submerged again
In reaction solution B, 12h is reacted at 60 DEG C, products therefrom is placed in deionized water, obtain Fe (BTC)/PA films.
Gained Fe (BTC)/PA films are subjected to performance test；To Fe (BTC) type metal-organic framework materials/polyamide nano
Composite membrane carries out surface analysis, and surface analysis is carried out to Fe (BTC) type metal-organic framework materials/polyamide nano composite membrane,
It was found that with example 1 in Fe (BTC) type metal-organic framework materials/polyamide nano composite membrane surface topography do not have it is big not
Together, its under 0.6Mpa to 2000ppm NaCl rejection 93.21%, while water flux reaches 5.354L m-2h-1bar-1。
Example 4
(1) polyether sulfone 5mg is dissolved into 20ml DMF solvents, it is quiet obtains casting solution ultrasound 20min
12h is put, casting solution is laid on to smooth 100cm at 50 DEG C2On glass plate, with 200 μm of scrapers scrape on a glass into
Film, immediately obtained film is put into water rapidly, after being fully formed, obtain PSF support membranes be put into it is standby in deionized water
With.
(2) m-phenylene diamine (MPD) 0.4g is dissolved in 20ml deionized waters and obtains 2% m-phenylene diamine (MPD) aqueous phase solution, take 0.02g equal
The formyl chloride of benzene three is dissolved in 20ml n-hexanes and obtains 0.1% pyromellitic trimethylsilyl chloride organic phase solution；Take described m-phenylene diamine (MPD) aqueous phase
Solution 5ml is uniformly added dropwise in described PSF support membranes 7.065cm2Upper standing 8min, removes unnecessary aqueous phase solution, then takes institute
State pyromellitic trimethylsilyl chloride organic phase solution 5ml to continue uniformly to be added dropwise on the PSF support membranes after handling through aqueous phase solution, stand
8min, unnecessary organic phase solution is removed, after standing 2min, the film after being handled, by the film after the processing at 40 DEG C
5min is dried, obtains PA membrane；
(3) it is 1 ferric trichloride 6.804g to be dissolved in into water and ethanol volume ratio：It is configured to react in 1 mixed solution 60ml
Liquid A, it is 1 that 17.651g trimesic acids are dissolved in into water and ethanol volume ratio：Reaction solution B is configured in 1 mixed solution 120ml,
PA membrane obtained by step (2) is immersed in reaction solution A, 40h is stood at room temperature, then the film after processing is placed in and submerged again
In reaction solution B, 24h is reacted at 80 DEG C, products therefrom is placed in deionized water, obtain Fe (BTC)/PA films.
Resulting Fe (BTC)/PA films are subjected to performance test；Fe (BTC) type metal-organic framework materials/polyamide is received
Rice composite membrane carries out surface analysis,
Surface analysis is carried out to Fe (BTC) type metal-organic framework materials/polyamide nano composite membrane, found and example 1
In the surface topography of Fe (BTC) type metal-organic framework materials/polyamide nano composite membrane there is no big difference, its
To 2000ppm NaCl rejection 94.03% under 0.6Mpa, while water flux reaches 5.122L m-2h-1bar-1。
Example 5
(1) polysulfones 5mg is dissolved into 20ml DMF solvents, obtains casting solution ultrasound 20min standings
12h, casting solution is laid on to smooth 100cm at 50 DEG C2On glass plate, scraped on a glass to film forming with 200 μm of scrapers,
Immediately obtained film is put into water rapidly, after being fully formed, obtain PSF support membranes be put into it is standby in deionized water.
(2) m-phenylene diamine (MPD) 0.4g is dissolved in 20ml deionized waters and obtains 2% m-phenylene diamine (MPD) aqueous phase solution, take 0.02g equal
The formyl chloride of benzene three is dissolved in 20ml n-hexanes and obtains 0.1% pyromellitic trimethylsilyl chloride organic phase solution；Take described m-phenylene diamine (MPD) aqueous phase
Solution 5ml is uniformly added dropwise in described PSF support membranes 7.065cm2Upper standing 2min, removes unnecessary aqueous phase solution, then takes institute
State pyromellitic trimethylsilyl chloride organic phase solution 5ml to continue uniformly to be added dropwise on the PSF support membranes after handling through aqueous phase solution, stand
2min, unnecessary organic phase solution is removed, after standing 2min, the film after being handled, by the film after the processing at 40 DEG C
5min is dried, obtains PA membrane；
(3) it is 1 ferric trichloride 6.804g to be dissolved in into water and ethanol volume ratio：It is configured to react in 1 mixed solution 60ml
Liquid A, it is 1 that 17.651g trimesic acids are dissolved in into water and ethanol volume ratio：Reaction solution B is configured in 1 mixed solution 120ml,
PA membrane obtained by step (2) is immersed in reaction solution A, 40h is stood at room temperature, then the film after processing is placed in and submerged again
In reaction solution B, 24h is reacted at 80 DEG C, products therefrom is placed in deionized water, obtain Fe (BTC)/PA films.
Gained Fe (BTC)/PA films are subjected to performance test；To Fe (BTC) type metal-organic framework materials/polyamide nano
Composite membrane carries out surface analysis,
Surface analysis is carried out to Fe (BTC) type metal-organic framework materials/polyamide nano composite membrane, found and example 1
In the surface topography of Fe (BTC) type metal-organic framework materials/polyamide nano composite membrane there is no big difference, its
To 2000ppm NaCl rejection 94.25% under 0.6Mpa, while water flux reaches 5.145L m-2h-1bar-1。
Comparative example
(1) polysulfones 5mg is dissolved into 20ml DMF solvents, obtains casting solution ultrasound 60min standings
12h, casting solution is laid on to smooth 100cm at 50 DEG C2On glass plate, scraped on a glass to film forming with 200 μm of scrapers,
Immediately obtained film is put into water rapidly, after being fully formed, obtain PSF support membranes be put into it is standby in deionized water.
(2) m-phenylene diamine (MPD) 0.4g is dissolved in 20ml deionized waters and obtains 2% m-phenylene diamine (MPD) aqueous phase solution, take 0.02g equal
The formyl chloride of benzene three is dissolved in 20ml n-hexanes and obtains 0.1% pyromellitic trimethylsilyl chloride organic phase solution；Take described m-phenylene diamine (MPD) aqueous phase
Solution 5ml is uniformly added dropwise in described PSF support membranes 7.065cm2Upper standing 2min, removes unnecessary aqueous phase solution, then takes institute
State pyromellitic trimethylsilyl chloride organic phase solution 5ml to continue uniformly to be added dropwise on the PSF support membranes after handling through aqueous phase solution, stand
2min, unnecessary organic phase solution is removed, after standing 2min, the film after being handled, by the film after the processing at 40 DEG C
5min is dried, obtains PA membrane；
Surface analysis is carried out to PA membrane, as shown in Fig. 2 it exists under 0.6Mpa to 2000ppm NaCl rejection
96.38%, while water flux reaches 1.312L m-2h-1bar-1。
Claims (9)
- A kind of 1. preparation method for the big flux polyamide nano composite membrane that Fe (BTC) is inlayed, it is characterised in that：Described method Prepared as follows：(1) raw material milipore filter is dissolved into DMF solvent, stirring at room temperature obtains casting solution, will be described Casting solution ultrasound, the bubble in 20~40h removing solution is stood, at 20~50 DEG C, described casting solution is laid on smooth Glass plate on, scraped with scraper to shaping, obtain PSF support membranes；The addition of described DMF solvent with The quality of described milipore filter is calculated as 5~10ml/g；(2) m-phenylene diamine (MPD) is dissolved in deionized water and obtains 0.1~8wt% m-phenylene diamine (MPD) aqueous phase solutions, by pyromellitic trimethylsilyl chloride It is dissolved in n-hexane, the pyromellitic trimethylsilyl chloride organic phase solution that 30~60min of ultrasound is obtained；Take described m-phenylene diamine (MPD) aqueous phase molten Liquid is uniformly added dropwise on described PSF support membranes and stands 2~8min, removes unnecessary aqueous phase solution, then takes the benzene front three Acyl chlorides organic phase solution continues uniformly to be added dropwise on the PSF support membranes after handling through aqueous phase solution, stands 2~8min, removes more Remaining organic phase solution, after standing 2~10min, the film after being handled, the film after the processing is dried at 40~60 DEG C 5~15min, obtain PA membrane；The amount of described pyromellitic trimethylsilyl chloride material is calculated as 100 with the volume of n-hexane~ 700mmol/L；The addition of described m-phenylene diamine (MPD) aqueous phase solution is calculated as 0.7~1.4ml/cm with the area of PSF support membranes2； The addition of described pyromellitic trimethylsilyl chloride organic phase solution is calculated as 0.7~1.4ml/cm with the area of PSF support membranes2；(3) ferric iron compound is dissolved in the mixed solution of water and ethanol and obtains reaction solution A, trimesic acid is dissolved in water and second Reaction solution B is obtained in the mixed solution of alcohol, PA membrane obtained by step (2) is immersed in described reaction solution A, it is quiet at room temperature 20~40h is put, is then immersed in the film after processing in described reaction solution B, 12~24h, gained are reacted at 60~80 DEG C Product is placed in standing 24h in deionized water and obtains Fe (BTC)/PA films；The amount of the material of described ferric iron compound with water and The total volume meter of the mixed solution of ethanol is 100~700mmol/L；The amount of the material of described trimesic acid is with water and ethanol The total volume meter of mixed solution be 100~700mmol/L.
- 2. the big flux polyamide nano composite membrane that Fe (BTC) according to claim 1 is inlayed, it is characterised in that：Step (1) in, described milipore filter is polysulfones, polyether sulfone, polyethylene or polypropylene.
- 3. the big flux polyamide nano composite membrane that Fe (BTC) according to claim 2 is inlayed, it is characterised in that：Step (1) in, described milipore filter is polysulfones.
- 4. the big flux polyamide nano composite membrane that Fe (BTC) according to claim 1 is inlayed, it is characterised in that：Step (1) in, the frequency of the ultrasonic deaeration is 30~50KHz, and the time is 0.2~3h.
- 5. the big flux polyamide nano composite membrane that Fe (BTC) according to claim 1 is inlayed, it is characterised in that：Step (1) in, described PSF support film thicknesses are 100~300 μm.
- 6. big flux Fe (BTC)/polyamide nano complex reverse osmosis membrane according to claim 1, it is characterised in that:Step (3) in, described ferric iron compound is：Ferric trichloride, ferric nitrate or ferric sulfate.
- 7. big flux Fe (BTC)/polyamide nano complex reverse osmosis membrane according to claim 1, it is characterised in that:Step (3) in, the volume ratio 1 of described deionized water and ethanol:1~10.
- 8. big flux Fe (BTC)/polyamide nano complex reverse osmosis membrane according to claim 1, it is characterised in that:Step (3) in, described reaction temperature is 60 DEG C, reaction time 40h.
- 9. big flux Fe (BTC)/polyamide nano is compound made from a kind of preparation method as described in one of claim 1~8 Application of the reverse osmosis membrane in desalinating process.
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Citations (10)
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