CN106110908A - The preparation method of aromatic polyamides hydridization NF membrane - Google Patents
The preparation method of aromatic polyamides hydridization NF membrane Download PDFInfo
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- CN106110908A CN106110908A CN201610521666.0A CN201610521666A CN106110908A CN 106110908 A CN106110908 A CN 106110908A CN 201610521666 A CN201610521666 A CN 201610521666A CN 106110908 A CN106110908 A CN 106110908A
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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
- B01D67/0002—Organic membrane manufacture
- B01D67/0009—Organic membrane manufacture by phase separation, sol-gel transition, evaporation or solvent quenching
- B01D67/0011—Casting solutions therefor
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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
- B01D69/122—Separate manufacturing of ultra-thin membranes
Abstract
This reality disclosure of the invention preparation method of a kind of aromatic polyamides hydridization NF membrane, including step 1: anhydrous Lithium chloride (LiCl) and acetamide (DMAc) are put in the boiling flask of cleaning and mix, ultrasonic make anhydrous Lithium chloride dissolve, obtain mixed solution；Step 2: be 0～1.5%PMIA(poly(isophthaloyl metaphenylene diamine) by mass fraction) metal-organic framework material (MOFs) add in the mixed solution in step 1, ultrasonic 30min so that it is dispersed；Step 3: adding aromatic polyamide fibers in the solution after step 2 is ultrasonic, mechanical agitation is fully dissolved to it under 90 C, obtains casting solution；Step 4: casting solution is put into vacuum drying oven and carries out vacuum defoamation process；Step 5: the casting solution after deaeration being processed is poured on glass plate and carries out preparing aromatic polyamides hydridization NF membrane.The preparation method of hydridization NF membrane of the present invention is simple, process is easily controllable, low to monovalent salt and divalent salts rejection, high to organic dye molecule rejection, is with a wide range of applications.
Description
Technical field
The present invention relates to filter membrane, a kind of aromatic polyamides hydridization NF membrane based on metal-organic framework material
Preparation method.
Background technology
Nanofiltration (NF), between ultrafiltration and reverse osmosis, has relatively low operation pressure and higher permeation flux.At present,
Nanofiltration is used widely, at pharmacy, biological engineering, food engineering at aspects such as drinking water production, waste water process, beverage concentrations
Etc. in non-solution system, nanofiltration also shows that broad prospect of application.
Membrane material and membrane structure have important impact to the separation permeance property of film, and along with the extensive of membrane technology should
With, every Separation Indexes of film is had higher requirement by people.Traditional inorganic material and organic material are due to by " lifting up
Seesaw " constraint of phenomenon, and it is difficult to prepare the separation film of higher performance.In recent years, inorganic and organic materials hydridization is prepared miscellaneous
Change film (mixed substrate membrane containing nano-grade molecular sieve), material characteristics complement and optimization can be realized, be a researcher direction carrying out exploring.
Aromatic polyamides (PMIA) is the high polymer material of a kind of excellent performance, has excellent chemical stability, is resistant to
Highly basic and high temperature, organic solvent resistance is good, and mechanical strength is high, hence it is evident that be better than other macromolecular materials such as cellulose, by extensively
General for NF membrane with the preparation of reverse osmosis membrane.Currently used most method of preparing of aromatic polyamide nanofiltration membrane is to prop up in porous
Ultra-thin top layer is made in various ways on support layer.
Metal organic frame (MOFs) material is the hybrid inorganic-organic materials that a kind is zeolite structured, has Gao Bibiao
Area, controlled voidage, the duct of functionalization, specific molecular is had affinity and the characteristic such as structure flexibly.MOFs
Higher adsorption capacity and adsorptive selectivity, storing or having fabulous application as adsorbent/desorbent at hydrogen, methane etc.
Prospect.In recent years, the hybridized film filled MOFs or the research of composite membrane have become one of focus improving film properties.
At present, MOFs hybridized film is existing substantial amounts of report in gas separates, but the report separated for liquid also compares
Few, the present invention is directed to existing filter membrane the highest to organic dye molecule rejection, and preparation process complexity is unmanageable.
Summary of the invention
For the shortcoming of prior art, the invention provides the preparation method of a kind of aromatic polyamides hydridization NF membrane.
The preparation method of aromatic polyamides hydridization NF membrane, comprises the steps:
Step 1: anhydrous Lithium chloride (LiCl) and acetamide (DMAc) are put into cleaning boiling flask in mix, ultrasonic make anhydrous
Lithium chloride dissolves, and obtains mixed solution；
Step 2: the metal-organic framework material (MOFs) that mass fraction is 0～1.5wt% aromatic polyamides is added in step 1
Mixed solution in, ultrasonic 30～35min so that it is dispersed；
Step 3: adding aromatic polyamide fibers in the solution after step 2 is ultrasonic, mechanical agitation is to it under 90～100 C
Fully dissolve, obtain casting solution；
Step 4: casting solution is put into vacuum drying oven and carries out vacuum defoamation process；
Step 5: the casting solution after deaeration being processed is poured on glass plate and carries out preparing aromatic polyamides hydridization NF membrane.
In one embodiment of the invention, described anhydrous Lithium chloride (LiCl) is 10-for 0.1-5 part, acetamide (DMAc)
50 parts, aromatic polyamide fibers be 0.5-10 part.
In one embodiment of the invention, described anhydrous Lithium chloride (LiCl) is 0.1-5g, acetamide (DMAc) is 10-50g,
Aromatic polyamide fibers is 0.5-10g.
In one embodiment of the invention, described metal-organic framework material (MOFs) is p-phthalic acid aluminum (MIL-53
(Al)).
In one embodiment of the invention, described aromatic polyamide fibers is poly(isophthaloyl metaphenylene diamine) (PMIA).
In one embodiment of the invention, step 4 vacuum defoamation process after also through the pre-heat treatment, described the pre-heat treatment be by
Dried casting solution seals in the baking oven being placed on 60 ~ 65 C.
In one embodiment of the invention, the masking in step 5 includes initial film processed and molding telolemma；Described initial film processed is
First by scraping hymenotome laminating and being perpendicular to the position of described glass plate, scrape the most rapidly, prepare initial film；Molding telolemma is to make
The initial film obtained is put into rapidly in baking oven, immerses coagulation forming in the pure water under room temperature after certain time immediately, prepares telolemma.
In one embodiment of the invention, the temperature of described baking oven is 60 ~ 65 C, and described initial film is placed in described baking oven
Time be 20 ~ 30min.As multiple in Nano filtering composite membrane, reverse osmosis composite membrane, positive osmosis composite membrane, gas separation membrane, seepage slope
Close film.
The method have the advantages that
MOFs hybridized film is used for liquid and separates by the present invention, and by blending method, the addition adding MOFs, MOFs in casting solution is bright
The aobvious structure changing film.The addition of MOFs need to reach by the filter effect of aromatic polyamides hydridization NF membrane in particular range
Optimum.Experimental data can be seen that the water flux of film is improved along with the raising of MOFs content in casting solution, and membrance separation
Can there is no significant change.
The preparation method of hydridization NF membrane of the present invention is simple, process is easily controllable, can be used for other various separation processes
Prepared by composite membrane.The aromatic polyamides hydridization NF membrane flux prepared is higher, especially low to monovalent salt and divalent salts rejection, right
Organic dye molecule rejection is high, is with a wide range of applications during dye desalination.
Detailed description of the invention
Below in conjunction with embodiment, the invention will be further described.
First hydridization NF membrane prepared by the present invention uses pure water precompressed 0.5h under 1.0Mpa pressure, the most at room temperature
Hydridization NF membrane performance is tested for feed liquid respectively with pure water and 500mg/L sodium sulfate and 500mg/L xylenol orange mixed liquor.Film leads to
The computing formula of amount is as follows.
Wherein F is the pure water flux (L/m of film2H), V is the volume (L) of permeate, and A is the effective area (m of film2), t is
Testing time (h).
Rejection R is calculated by concentration of raw material and permeate concentration, as follows.
Wherein R is solute rejection, CfIt is the concentration of material liquid, CpIt is the concentration of permeate.
Inorganic salt solution concentration uses electrical conductivity method, and for the weak solution of single electrolyte, its electrical conductivity just becomes with concentration
Ratio, then conveniently calculate with can directly substitute with the conductivity value of material liquid with permeate in formula.The concentration of dyestuff uses dyestuff
Concentration use spectrophotometer method measure.
All films all carry out 3 tests, and 3 times test result is averaged.
Comparative example 1
1) anhydrous Lithium chloride (LiCl) and 26.25g acetamide (DMAc) that quality is 0.75g are put in clean boiling flask
Mixing, ultrasonic makes LiCl dissolve.
2) adding dry aromatic polyamide fibers (PMIA) 3g in the solution of (1), under 90 C, mechanical agitation is to it
Fully dissolve.
3) being put into by the casting solution that (2) obtain after vacuum drying oven carries out vacuum defoamation process, sealing is stored in 60 C's
In baking oven.
4) casting solution completely of deaeration is poured on dry, clean, smooth glass plate, hymenotome will be scraped and be perpendicular to glass
Glass plate rapid striking initial film, and put into rapidly in the baking oven of 60 DEG C, after solvent evaporation 20min certain time, immerse immediately
Coagulation forming in pure water under room temperature.
The hybridized film product prepared is at 25 DEG C, under 1.0Mpa, with sodium sulfate and the 500mg/L xylenol orange of 500mg/L
Mixed liquor is dye wastewater, and test compound NF membrane is to sodium sulfate, the rejection of xylenol orange dye molecule and corresponding
Water flux, acquired results is shown in Table 1.
Embodiment 1
Difference from comparative example 1 is, after step 1), the MOFs that quality is 0.015g is put into DMAc(26.25g)/LiCl
(0.75g), in solution, ultrasonic 30min so that it is dispersed, remaining step is the most identical.
The hybridized film product prepared is at 25 DEG C, under 1.0Mpa, with sodium sulfate and the 500mg/L xylenol orange of 500mg/L
Mixed liquor is dye wastewater, and test compound NF membrane is to sodium sulfate, the rejection of xylenol orange dye molecule and corresponding
Water flux, acquired results is shown in Table 1.
Embodiment 2
Difference from comparative example 1 is, after step (1), the MOFs that quality is 0.03g is put into DMAc(26.25g)/LiCl
(0.75g), in solution, ultrasonic 30min so that it is dispersed, remaining step is the most identical.
The hybridized film product prepared is at 25 DEG C, under 1.0Mpa, with sodium sulfate and the 500mg/L xylenol orange of 500mg/L
Mixed liquor is dye wastewater, and test compound NF membrane is to sodium sulfate, the rejection of xylenol orange dye molecule and corresponding
Water flux, acquired results is shown in Table 1.
Embodiment 3
Difference from comparative example 1 is, after step (1), the MOFs that quality is 0.045g is put into DMAc(26.25g)/LiCl
(0.75g), in solution, ultrasonic 30min so that it is dispersed, remaining step is the most identical.
The hybridized film product prepared is at 25 DEG C, under 1.0Mpa, with sodium sulfate and the 500mg/L xylenol orange of 500mg/L
Mixed liquor is dye wastewater, and test compound NF membrane is to sodium sulfate, the rejection of xylenol orange dye molecule and corresponding
Water flux, acquired results is shown in Table 1
Table 1
| Embodiment | MOFs content (wt%) | Pure water flux (L/m2H) | Sodium sulfate rejection (%) | Xylenol orange rejection (%) |
| Comparative example 1 | 0 | 30.33 | 37.11 | 97.32 |
| Embodiment 1 | 0. 5 | 34.91 | 36.68 | 98.31 |
| Embodiment 2 | 1.0 | 34.66 | 37.99 | 98.02 |
| Embodiment 3 | 1.5 | 36.97 | 37.35 | 97.87 |
Comparative example 2
1) anhydrous Lithium chloride (LiCl) and 17.5g acetamide (DMAc) that quality is 0.5g are put in clean boiling flask mixed
Close, ultrasonic make LiCl dissolve.
2) adding dry aromatic polyamide fibers (PMIA) 2g in the solution of (1), under 90 C, mechanical agitation is to it
Fully dissolve.
3) being put into by the casting solution that (2) obtain after vacuum drying oven carries out vacuum defoamation process, sealing is stored in 60 C's
In baking oven.
4) casting solution completely of deaeration is poured on dry, clean, smooth glass plate, hymenotome will be scraped and be perpendicular to glass
Glass plate rapid striking initial film, and put into rapidly in the baking oven of uniform temperature, after solvent evaporation certain time, immerse room immediately
Coagulation forming in pure water under Wen.
The hybridized film product prepared is at 25 DEG C, and under 1.0Mpa, sodium sulfate and 500mg/L Ponceau S with 500mg/L mix
Conjunction liquid is dye wastewater, and test compound NF membrane is to sodium sulfate, the rejection of Ponceau S dye molecule and corresponding water
Flux, acquired results is shown in Table 2.
Embodiment 4:
Difference from comparative example 2 is, after step (1), the MOFs that quality is 0.01g is put into DMAc(17.5g)/LiCl
(0.5g), in solution, ultrasonic 30min so that it is dispersed, remaining step is the most identical.
The hybridized film product prepared is at 25 DEG C, and under 1.0Mpa, sodium sulfate and 500mg/L Ponceau S with 500mg/L mix
Conjunction liquid is dye wastewater, and test compound NF membrane is to sodium sulfate, the rejection of Ponceau S dye molecule and corresponding water
Flux, acquired results is shown in Table 2.
Embodiment 5:
Difference from comparative example 2 is, after step (1), the MOFs that quality is 0.02g is put into DMAc(17.5g)/LiCl
(0.5g), in solution, ultrasonic 30min so that it is dispersed, remaining step is the most identical.
The hybridized film product prepared is at 25 DEG C, and under 1.0Mpa, sodium sulfate and 500mg/L Ponceau S with 500mg/L mix
Conjunction liquid is dye wastewater, and test compound NF membrane is to sodium sulfate, the rejection of Ponceau S dye molecule and corresponding water
Flux, acquired results is shown in Table 2.
Embodiment 6:
Difference from comparative example 2 is, after step (1), the MOFs that quality is 0.03g is put into DMAc(17.5g)/LiCl
(0.5g), in solution, ultrasonic 30min so that it is dispersed, remaining step is the most identical.
The hybridized film product prepared is at 25 DEG C, and under 1.0Mpa, sodium sulfate and 500mg/L Ponceau S with 500mg/L mix
Conjunction liquid is dye wastewater, and test compound NF membrane is to sodium sulfate, the rejection of Ponceau S dye molecule and corresponding water
Flux, acquired results is shown in Table 2.
Table 2
| Embodiment | MOFs content (wt%) | Pure water flux (L/m2H) | Sodium sulfate rejection (%) | Ponceau S rejection (%) |
| Comparative example 2 | 0 | 32.73 | 36.38 | 99.32 |
| Embodiment 4 | 0. 5 | 36.71 | 35.78 | 99.77 |
| Embodiment 5 | 1.0 | 37.11 | 35.08 | 99.39 |
| Embodiment 6 | 1.5 | 37.53 | 36.28 | 99.59 |
Comparative example 3
1) anhydrous Lithium chloride (LiCl) and 52.5g acetamide (DMAc) that quality is 1.5g are put in clean boiling flask mixed
Close, ultrasonic make LiCl dissolve.
2) adding dry aromatic polyamide fibers (PMIA) 6g in the solution of (1), under 90 C, mechanical agitation is to it
Fully dissolve.
3) being put into by the casting solution that (2) obtain after vacuum drying oven carries out vacuum defoamation process, sealing is stored in 60 C's
In baking oven.
4) casting solution completely of deaeration is poured on dry, clean, smooth glass plate, hymenotome will be scraped and be perpendicular to glass
Glass plate rapid striking initial film, and put into rapidly in the baking oven of uniform temperature, after solvent evaporation certain time, immerse room immediately
Coagulation forming in pure water under Wen.
The hybridized film product prepared is at 25 DEG C, under 1.0Mpa, with sodium chloride and the 500mg/L xylenol orange of 500mg/L
Mixed liquor is dye wastewater, and test compound NF membrane is to sodium chloride, the rejection of xylenol orange dye molecule and corresponding
Water flux, acquired results is shown in Table 3.
Embodiment 7
Difference from comparative example 3 is, after step (1), the MOFs that quality is 0.03g is put into DMAc(52.5g)/LiCl
(1.5g), in solution, ultrasonic 30min so that it is dispersed, remaining step is the most identical.
The hybridized film product prepared is at 25 DEG C, under 1.0Mpa, with sodium chloride and the 500mg/L xylenol orange of 500mg/L
Mixed liquor is dye wastewater, and test compound NF membrane is to sodium chloride, the rejection of xylenol orange dye molecule and corresponding
Water flux, acquired results is shown in Table 2.
Embodiment 8
Difference from comparative example 3 is, after step (1), the MOFs that quality is 0.06g is put into DMAc(52.5g)/LiCl
(1.5g), in solution, ultrasonic 30min so that it is dispersed, remaining step is the most identical.
The hybridized film product prepared is at 25 DEG C, under 1.0Mpa, with sodium chloride and the 500mg/L xylenol orange of 500mg/L
Mixed liquor is dye wastewater, and test compound NF membrane is to sodium chloride, the rejection of xylenol orange dye molecule and corresponding
Water flux, acquired results is shown in Table 2.
Embodiment 9
Difference from comparative example 3 is, after step (1), the MOFs that quality is 0.09g is put into DMAc(52.5g)/LiCl
(1.5g), in solution, ultrasonic 30min so that it is dispersed, remaining step is the most identical.
The hybridized film product prepared is at 25 DEG C, under 1.0Mpa, with sodium chloride and the 500mg/L xylenol orange of 500mg/L
Mixed liquor is dye wastewater, and test compound NF membrane is to sodium chloride, the rejection of xylenol orange dye molecule and corresponding
Water flux, acquired results is shown in Table 3.
Table 3
| Embodiment | MOFs content (wt%) | Pure water flux (L/m2H) | Sodium chloride rejection (%) | Xylenol orange rejection (%) |
| Comparative example 3 | 0 | 31.77 | 10.30 | 98.32 |
| Embodiment 7 | 0. 5 | 36.51 | 10.68 | 98.17 |
| Embodiment 8 | 1.0 | 35.11 | 11.01 | 98.08 |
| Embodiment 9 | 1.5 | 34.96 | 9.29 | 98.19 |
Comparative example 4
1) anhydrous Lithium chloride (LiCl) and 105g acetamide (DMAc) that quality is 3g are put in clean boiling flask and are mixed,
Ultrasonic LiCl is made to dissolve.
2) adding dry aromatic polyamide fibers (PMIA) 12g in the solution of (1), under 90 C, mechanical agitation is to it
Fully dissolve.
3) being put into by the casting solution that (2) obtain after vacuum drying oven carries out vacuum defoamation process, sealing is stored in 60 C's
In baking oven.
4) casting solution completely of deaeration is poured on dry, clean, smooth glass plate, hymenotome will be scraped and be perpendicular to glass
Glass plate rapid striking initial film, and put into rapidly in the baking oven of uniform temperature, after solvent evaporation certain time, immerse room immediately
Coagulation forming in pure water under Wen.
The hybridized film product prepared is at 25 DEG C, and under 1.0Mpa, sodium chloride and 500mg/L Ponceau S with 500mg/L mix
Conjunction liquid is dye wastewater, and test compound NF membrane is to sodium chloride, the rejection of Ponceau S dye molecule and corresponding water
Flux, acquired results is shown in Table 4.
Embodiment 10
Difference from comparative example 4 is, after step (1), the MOFs that quality is 0.06g is put into DMAc(105g)/LiCl
(3g), in solution, ultrasonic 30min so that it is dispersed, remaining step is the most identical.
The hybridized film product prepared is at 25 DEG C, and under 1.0Mpa, sodium chloride and 500mg/L Ponceau S with 500mg/L mix
Conjunction liquid is dye wastewater, and test compound NF membrane is to sodium chloride, the rejection of Ponceau S dye molecule and corresponding water
Flux, acquired results is shown in Table 2.
Embodiment 11
Difference from comparative example 4 is, after step (1), the MOFs that quality is 0.12g is put into DMAc(105g)/LiCl
(3g), in solution, ultrasonic 30min so that it is dispersed, remaining step is the most identical.
The hybridized film product prepared is at 25 DEG C, and under 1.0Mpa, sodium chloride and 500mg/L Ponceau S with 500mg/L mix
Conjunction liquid is dye wastewater, and test compound NF membrane is to sodium chloride, the rejection of Ponceau S dye molecule and corresponding water
Flux, acquired results is shown in Table 2.
Embodiment 12
Difference from comparative example 4 is, after step (1), the MOFs that quality is 0.18g is put into DMAc(105g)/LiCl
(3g), in solution, ultrasonic 30min so that it is dispersed, remaining step is the most identical.
The hybridized film product prepared is at 25 DEG C, and under 1.0Mpa, sodium chloride and 500mg/L Ponceau S with 500mg/L mix
Conjunction liquid is dye wastewater, and test compound NF membrane is to sodium chloride, the rejection of Ponceau S dye molecule and corresponding water
Flux, acquired results is shown in Table 4.
Table 4
| Embodiment | MOFs content (wt%) | Pure water flux (L/m2H) | Sodium chloride rejection (%) | Ponceau S rejection (%) |
| Comparative example 4 | 0 | 33.99 | 10.32 | 99.32 |
| Embodiment 10 | 0. 5 | 40.71 | 9.72 | 99.72 |
| Embodiment 11 | 1.0 | 38.41 | 11.01 | 99.79 |
| Embodiment 12 | 1.5 | 37.79 | 11.23 | 99.59 |
Comparative example 5
1) anhydrous Lithium chloride (LiCl) and 28g acetamide (DMAc) that quality is 0.85g are put in clean boiling flask mixed
Close, ultrasonic make LiCl dissolve.
2) adding dry aromatic polyamide fibers (PMIA) 4g in the solution of (1), under 90 C, mechanical agitation is to it
Fully dissolve.
3) being put into by the casting solution that (2) obtain after vacuum drying oven carries out vacuum defoamation process, sealing is stored in 65 C's
In baking oven.
4) casting solution completely of deaeration is poured on dry, clean, smooth glass plate, hymenotome will be scraped and be perpendicular to glass
Glass plate rapid striking initial film, and put into rapidly in the baking oven of uniform temperature, after solvent evaporation certain time, immerse room immediately
Coagulation forming in pure water under Wen.
The hybridized film product prepared is at 25 DEG C, and under 1.0Mpa, sodium chloride and 500mg/L Ponceau S with 500mg/L mix
Conjunction liquid is dye wastewater, and test compound NF membrane is to sodium chloride, the rejection of Ponceau S dye molecule and corresponding water
Flux, acquired results is shown in Table 4.
Embodiment 13
Difference from comparative example 4 is, after step (1), the MOFs that quality is 0.02g is put into DMAc(28g)/LiCl
(0.85g), in solution, ultrasonic 30min so that it is dispersed, remaining step is the most identical.
The hybridized film product prepared is at 25 DEG C, and under 1.0Mpa, sodium chloride and 500mg/L Ponceau S with 500mg/L mix
Conjunction liquid is dye wastewater, and test compound NF membrane is to sodium chloride, the rejection of Ponceau S dye molecule and corresponding water
Flux, acquired results is shown in Table 2.
Embodiment 14
Difference from comparative example 4 is, after step (1), the MOFs that quality is 0.04g is put into DMAc(28g)/LiCl
(0.85g), in solution, ultrasonic 30min so that it is dispersed, remaining step is the most identical.
The hybridized film product prepared is at 25 DEG C, and under 1.0Mpa, sodium chloride and 500mg/L Ponceau S with 500mg/L mix
Conjunction liquid is dye wastewater, and test compound NF membrane is to sodium chloride, the rejection of Ponceau S dye molecule and corresponding water
Flux, acquired results is shown in Table 2.
Embodiment 15
Difference from comparative example 4 is, after step (1), the MOFs that quality is 0.06g is put into DMAc(28g)/LiCl
(0.85g), in solution, ultrasonic 30min so that it is dispersed, remaining step is the most identical.
The hybridized film product prepared is at 25 DEG C, and under 1.0Mpa, sodium chloride and 500mg/L Ponceau S with 500mg/L mix
Conjunction liquid is dye wastewater, and test compound NF membrane is to sodium chloride, the rejection of Ponceau S dye molecule and corresponding water
Flux, acquired results is shown in Table 4.
Table 5
| Embodiment | MOFs content (wt%) | Pure water flux (L/m2H) | Sodium chloride rejection (%) | Ponceau S rejection (%) |
| Comparative example 5 | 0 | 35.09 | 10.01 | 99.25 |
| Embodiment 13 | 0. 5 | 36.43 | 8.92 | 99.91 |
| Embodiment 14 | 1.0 | 39.09 | 10.98 | 99.68 |
| Embodiment 15 | 1.5 | 37.85 | 11.13 | 99.59 |
Described aromatic polyamides hydridization NF membrane flux is higher, low, to organic dye molecule to monovalent salt and divalent salts rejection
Rejection is high, has great potential application foreground during dye desalination.
Above-mentioned specific embodiment is used only to illustrate the present invention, rather than is to limit the invention, in the present invention
Objective and scope of the claims in, any replacement not paying creative work that the present invention is made and change,
Fall within the protection domain of patent of the present invention.
Claims (7)
1. the preparation method of an aromatic polyamides hydridization NF membrane, it is characterised in that comprise the steps:
Step 1: anhydrous Lithium chloride (LiCl) and acetamide (DMAc) are put into cleaning boiling flask in mix, ultrasonic make anhydrous
Lithium chloride dissolves, and obtains mixed solution；
Step 2: the metal-organic framework material (MOFs) that mass fraction is aromatic polyamides 0.5 ~ 1.5wt% is added in step 1
Mixed solution in, ultrasonic 30min so that it is dispersed；
Step 3: adding aromatic polyamide fibers in the solution after step 2 is ultrasonic, mechanical agitation is the most molten to it under 90 C
Solve, obtain casting solution；
Step 4: casting solution is put into vacuum drying oven and carries out vacuum defoamation process；
Step 5: the casting solution after deaeration being processed is poured on glass plate and carries out preparing aromatic polyamides hydridization NF membrane.
2. the preparation method of aromatic polyamides hydridization NF membrane as claimed in claim 1, it is characterised in that described metal is organic
Frame material (MOFs) is p-phthalic acid aluminum (MIL-53(Al)).
3. the preparation method of aromatic polyamides hydridization NF membrane as claimed in claim 1, it is characterised in that described anhydrous chlorination
Lithium (LiCl) be 0.1-5 part, acetamide (DMAc) be 10-50 part, aromatic polyamide fibers be 0.5-10 part.
4. the preparation method of aromatic polyamides hydridization NF membrane as claimed in claim 1, it is characterised in that described fragrance polyamides
Amine fiber is poly(isophthaloyl metaphenylene diamine) (PMIA).
5. the preparation method of aromatic polyamides hydridization NF membrane as claimed in claim 1, it is characterised in that step 4 vacuum takes off
Also through the pre-heat treatment after bubble process, described the pre-heat treatment is the baking oven being sealed by dried casting solution and being placed on 60 ~ 65 C
In.
6. the preparation method of aromatic polyamides hydridization NF membrane as claimed in claim 1, it is characterised in that the system in step 5
Film includes initial film processed and molding telolemma；Described initial film processed is first will to scrape hymenotome laminating and be perpendicular to the position of described glass plate
Put, scrape the most rapidly, prepare initial film；Molding telolemma is prepared initial film to be put into rapidly in baking oven, after certain time
Immerse coagulation forming in the pure water under room temperature immediately, prepare telolemma.
7. the preparation method of aromatic polyamides hydridization NF membrane as claimed in claim 6, it is characterised in that the temperature of described baking oven
Degree is 60 ~ 65 C, and it is 20 ~ 30min that described initial film is placed on the time in described baking oven.
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