CN116272394A - Preparation method and application of organic-inorganic hybrid nanofiltration membrane - Google Patents
Preparation method and application of organic-inorganic hybrid nanofiltration membrane Download PDFInfo
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- 239000012528 membrane Substances 0.000 title claims abstract description 64
- 238000001728 nano-filtration Methods 0.000 title claims abstract description 47
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- 229910004298 SiO 2 Inorganic materials 0.000 claims abstract description 36
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 34
- 238000001354 calcination Methods 0.000 claims abstract description 22
- 239000011248 coating agent Substances 0.000 claims abstract description 12
- 238000000576 coating method Methods 0.000 claims abstract description 12
- 238000002156 mixing Methods 0.000 claims abstract description 12
- 238000000926 separation method Methods 0.000 claims abstract description 9
- 239000000463 material Substances 0.000 claims abstract description 4
- 238000000034 method Methods 0.000 claims description 30
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 18
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 15
- 238000006243 chemical reaction Methods 0.000 claims description 13
- 239000013078 crystal Substances 0.000 claims description 12
- 239000007864 aqueous solution Substances 0.000 claims description 11
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 9
- 229910052710 silicon Inorganic materials 0.000 claims description 9
- 239000010703 silicon Substances 0.000 claims description 9
- DUNKXUFBGCUVQW-UHFFFAOYSA-J zirconium tetrachloride Chemical compound Cl[Zr](Cl)(Cl)Cl DUNKXUFBGCUVQW-UHFFFAOYSA-J 0.000 claims description 8
- 238000006460 hydrolysis reaction Methods 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 5
- 238000010438 heat treatment Methods 0.000 claims description 5
- 238000005406 washing Methods 0.000 claims description 5
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 4
- 229910052726 zirconium Inorganic materials 0.000 claims description 4
- 238000004729 solvothermal method Methods 0.000 claims description 3
- 238000001914 filtration Methods 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims description 2
- 150000003754 zirconium Chemical class 0.000 claims description 2
- 239000000126 substance Substances 0.000 claims 1
- 239000002131 composite material Substances 0.000 abstract description 10
- 239000000919 ceramic Substances 0.000 abstract description 8
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 abstract 2
- 235000012239 silicon dioxide Nutrition 0.000 abstract 1
- 239000000377 silicon dioxide Substances 0.000 abstract 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 33
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 26
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 22
- BSDOQSMQCZQLDV-UHFFFAOYSA-N butan-1-olate;zirconium(4+) Chemical compound [Zr+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] BSDOQSMQCZQLDV-UHFFFAOYSA-N 0.000 description 18
- 229960001193 diclofenac sodium Drugs 0.000 description 17
- JGMJQSFLQWGYMQ-UHFFFAOYSA-M sodium;2,6-dichloro-n-phenylaniline;acetate Chemical compound [Na+].CC([O-])=O.ClC1=CC=CC(Cl)=C1NC1=CC=CC=C1 JGMJQSFLQWGYMQ-UHFFFAOYSA-M 0.000 description 17
- 230000000052 comparative effect Effects 0.000 description 12
- 230000004907 flux Effects 0.000 description 12
- 239000008367 deionised water Substances 0.000 description 11
- 229910021641 deionized water Inorganic materials 0.000 description 11
- 239000011148 porous material Substances 0.000 description 9
- 230000014759 maintenance of location Effects 0.000 description 6
- 238000001878 scanning electron micrograph Methods 0.000 description 5
- 239000004952 Polyamide Substances 0.000 description 4
- 239000004372 Polyvinyl alcohol Substances 0.000 description 4
- 230000007547 defect Effects 0.000 description 4
- 229920002647 polyamide Polymers 0.000 description 4
- 229920002451 polyvinyl alcohol Polymers 0.000 description 4
- 238000001027 hydrothermal synthesis Methods 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 238000001223 reverse osmosis Methods 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 238000009210 therapy by ultrasound Methods 0.000 description 3
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000010348 incorporation Methods 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 230000001737 promoting effect Effects 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- OHVLMTFVQDZYHP-UHFFFAOYSA-N 1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-2-[4-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]piperazin-1-yl]ethanone Chemical compound N1N=NC=2CN(CCC=21)C(CN1CCN(CC1)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)=O OHVLMTFVQDZYHP-UHFFFAOYSA-N 0.000 description 1
- LDXJRKWFNNFDSA-UHFFFAOYSA-N 2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-1-[4-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]piperazin-1-yl]ethanone Chemical compound C1CN(CC2=NNN=C21)CC(=O)N3CCN(CC3)C4=CN=C(N=C4)NCC5=CC(=CC=C5)OC(F)(F)F LDXJRKWFNNFDSA-UHFFFAOYSA-N 0.000 description 1
- JLVVSXFLKOJNIY-UHFFFAOYSA-N Magnesium ion Chemical compound [Mg+2] JLVVSXFLKOJNIY-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 238000010668 complexation reaction Methods 0.000 description 1
- 238000010612 desalination reaction Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000009396 hybridization Methods 0.000 description 1
- 229910001425 magnesium ion Inorganic materials 0.000 description 1
- 238000001471 micro-filtration Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 239000013535 sea water Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 239000000271 synthetic detergent Substances 0.000 description 1
- 238000000108 ultra-filtration Methods 0.000 description 1
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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
-
- 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
- B01D61/027—Nanofiltration
-
- 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
-
- 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
- C02F1/442—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis by nanofiltration
-
- 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
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Nanotechnology (AREA)
- Water Supply & Treatment (AREA)
- Inorganic Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Environmental & Geological Engineering (AREA)
- Organic Chemistry (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
Abstract
The invention belongs to the technical field of preparation of organic-inorganic hybrid membrane materials, and in particular relates to a preparation method and application of an organic-inorganic hybrid nanofiltration membrane for respectively preparing high-concentration SiO (silicon dioxide) 2 ‑ZrO 2 Sol and low concentration SiO 2 ‑ZrO 2 Sol of high concentration SiO 2 ‑ZrO 2 Coating the sol on a carrier and calcining to obtain SiO 2 ‑ZrO 2 Layer to low concentration SiO 2 ‑ZrO 2 Mixing UiO-66-NH into sol 2 Post-coating on SiO 2 ‑ZrO 2 On the layer and calcined. The obtained composite membrane can be used as nanofiltration membrane to separate organic or inorganic matters from water, and is suitable for intercepting and separating DCF water solution. The organic-inorganic hybrid ceramic nanofiltration membrane has the advantages of excellent separation performance, high hydrothermal stability, good reproducibility and the like.
Description
Technical Field
The invention belongs to the technical field of preparation of organic-inorganic hybrid membrane materials, and particularly relates to a preparation method and application of an organic-inorganic hybrid nanofiltration membrane.
Background
Nanofiltration (NF) is a membrane separation technology between ultrafiltration and reverse osmosis, which has the advantages of higher membrane flux, low monovalent ion rejection and high multivalent ion rejection rate compared to reverse osmosis technology, and therefore, nanofiltration membranes are also called "loose reverse osmosis membranes". Nanofiltration is commonly applied to sea water desalination and industrial separation and purification due to its advantages of high separation efficiency, low operating pressure, low pollution, etc. In the aspect of water softening, the nanofiltration membrane can also remove synthetic detergents, magnesium ion hardness components and soluble organic matters in the aqueous solution.
Nanofiltration membranes used commercially are typically polyamide nanofiltration membranes, which are typically composed of a porous support layer and a polyamide selective layer (PA), the pore substrate typically acting as a mechanical support, and the polyamide layer determining the water flux and selectivity of the membrane. Although polyamide nanofiltration membranes have been commercialized and widely used in the water treatment industry, in the practical application process, there are problems of a 'trade-off' effect between water flux and retention rate, insufficient pollution resistance, reduced service life of the nanofiltration membrane, and the like, thereby increasing running cost. In addition, the thickness of the membrane layer of the nanofiltration membrane has a larger influence on flux, and the thicker the membrane layer is, the lower the flux is, but the thinner the membrane layer is, the more the nanofiltration membrane is likely to be in missing.
Therefore, how to obtain nanofiltration membranes with high retention rate, ideal water flux and good membrane integrity is still an aim in the field as before.
Disclosure of Invention
In order to solve the technical problems, the invention provides a preparation method of an organic-inorganic hybrid nanofiltration membrane,
(1) Preparation of high concentration SiO respectively 2 -ZrO 2 Sol and low concentration SiO 2 -ZrO 2 The sol is used for preparing the gel,
specifically, after a period of hydrolysis reaction of a silicon source, adding zirconium salt into the silicon source, heating the silicon source, and continuing the hydrolysis reaction to obtain SiO 2 -ZrO 2 The sol is used for preparing the gel,
the molar ratio of silicon to zirconium is 1:1, heating to 100-120 ℃ for hydrolysis reaction for 12-18 h,
high concentration SiO 2 -ZrO 2 The mass concentration of the sol is 2.0-5.0%, and the low concentration SiO is 2 -ZrO 2 The mass concentration of the sol is 0.5 to 1.0 percent,
(2) High concentration SiO obtained in step (1) 2 -ZrO 2 Coating the sol on a carrier and calcining to obtain SiO 2 -ZrO 2 The layer of the material is formed from a layer,
repeating the step (2) for 2 to 6 times to obtain high-concentration SiO 2 -ZrO 2 The operation of sol coating and calcination,
(3) To the low concentration SiO obtained in step (1) 2 -ZrO 2 Mixing UiO-66-NH into sol 2 Fully mixing and then coating the mixture on the SiO obtained in the step (2) 2 -ZrO 2 On the layer and calcining to obtain UIO-66-NH 2 /SiO 2 -ZrO 2 The hybrid layer is formed by a layer of silicon,
wherein UiO-66-NH 2 The preparation method comprises dispersing zirconium chloride and 2-amino-1, 4-phthalic acid in N, N-dimethylformamide, adding acetic acid, performing solvothermal reaction, filtering out the product after reaction, washing, and drying to obtain UiO-66-NH 2 The crystal is formed by a crystal body,
the temperature of the solvothermal reaction is 130-160 ℃, the reaction time is 24-40 h,
UiO-66-NH 2 Mixing low-concentration SiO according to the mass concentration of 0.05 to 0.6 percent 2 -ZrO 2 In the sol, the water in the sol,
repeating the operation of coating and calcining the mixed sol in the step (3) for 2 to 6 times.
The invention also provides an application of the organic-inorganic hybrid nanofiltration membrane for separating organic matters or inorganic matters from water, and further the organic-inorganic hybrid nanofiltration membrane is used for intercepting and separating an aqueous solution of DCF.
The invention has the beneficial effects that:
the invention adjusts the pore size of the film after the film is formed by calcining the coated sol by controlling the concentration of the coated sol, and the nano-scale pore size is formed on the surface of the micro-filtration carrier with relatively large original pore size by the synergistic effect of the sol with different concentrations between the layers after the film is formed, so that the nano-scale pore size is successfully used for nano-filtration separation; incorporation of hydrophilic and porous UiO-66-NH into nanofiltration layers 2 Promoting the water flux of the nanofiltration membrane and UiO-66-NH 2 Are rigid particles per se, and are easy to cause film defects when used as film forming components, and UiO-66-NH is adopted in the scheme 2 With SiO 2 -ZrO 2 Mixing the sol, forming a film, and mixing Zr and UIO-66-NH 2 The carboxyl groups which do not form coordination generate the mutual attraction and complexation effect, thereby greatly promoting the integrity of the film layer after calcining and film forming. In conclusion, the organic-inorganic hybrid ceramic nanofiltration membrane has the advantages of excellent separation performance, high hydrothermal stability, good reproducibility and the like.
Drawings
FIG. 1 is a graph showing the comparison of particle size distribution of sols of different concentrations prepared in example 1,
FIG. 2 is UiO-66-NH prepared in step (4) of example 1 2 /SiO 2 -ZrO 2 SEM images of the surface of the hybrid layer,
FIG. 3 is a cross-sectional SEM image of a composite film finally prepared in example 1,
FIG. 4 is a SiO produced in the step (3) in comparative example 1 2 -ZrO 2 SEM image of the surface of the separation layer,
FIG. 5 is a SiO produced in step (3) in comparative example 3 2 SEM image of the surface of the separation layer,
FIG. 6 is UiO-66-NH prepared in step (4) of comparative example 4 2 /SiO 2 SEM image of the surface of the hybrid layer.
Detailed Description
The invention is further described below in connection with embodiments. The following embodiments are only for more clearly illustrating the technical aspects of the present invention, and should not be used to limit the scope of the present invention.
Example 1
(1) 1.0g of tetraethyl orthosilicate (TEOS) is dissolved in 19.8g of Ethanol (ETOH), then 0.28g of water and 0.06g of hydrochloric acid (the mass concentration is 35 percent, the same applies below) are added and stirred for 60 minutes, then 3.80g of zirconium n-butoxide (ZrBT) is added, finally 215g of deionized water is added and heated to 100 ℃ for stirring reaction for 12 hours, thus obtaining high-concentration SiO with the mass fraction of 2.0 percent 2 -ZrO 2 The sol is used for preparing the gel,
1.0g of tetraethyl orthosilicate (TEOS) is dissolved in 19.8g of Ethanol (ETOH), then 0.28g of water and 0.06g of hydrochloric acid are added and stirred for 60 minutes, then 3.80g of zirconium n-butoxide (ZrBT) is added, finally 455g of deionized water is added and heated to 100 ℃ and stirred for reaction for 12 hours, thus obtaining low-concentration SiO with the mass fraction of 1.0 percent 2 -ZrO 2 The sol is used for preparing the gel,
the influence of the concentration of the sol on the particle size is shown in figure 1;
(2) Taking a hollow flat ceramic membrane as a carrier (aperture 500 nm), and carrying out the high-concentration SiO in the step (1) 2 -ZrO 2 The sol is evenly coated on a carrier, put into a muffle furnace with 550 ℃ for calcination for 20min, and the process is repeated for 4 times to obtain SiO 2 -ZrO 2 A layer;
(3) 0.88g of zirconium chloride (ZrCl) 4 ) And 0.68g of 2-amino-1, 4-phthalic acid (H) 2 BDC-NH 2 ) Respectively dissolving in 42ml of N, N-Dimethylformamide (DMF), mixing the two solutions, performing ultrasonic treatment for 10min, adding 10ml of acetic acid (with mass concentration of 10%, the same applies below), placing into a hydrothermal reaction kettle, reacting at 150deg.C for 20h, taking out the product, centrifuging, washing, and drying at 60deg.C to obtain UiO-66-NH 2 The crystal is formed by a crystal body,
UiO-66-NH to be used herein 2 The crystals were mixed into the low concentration SiO in step (1) at a mass concentration of 0.6% 2 -ZrO 2 Obtaining mixed sol from sol;
(4) Uniformly coating the mixed sol obtained in the step (3) on the SiO obtained in the step (2) 2 -ZrO 2 Calcining the layer in a muffle furnace at 550deg.C for 20min, and repeating the process for 2 times to obtainUiO-66-NH 2 /SiO 2 -ZrO 2 A hybrid layer.
FIG. 2 shows UIO-66-NH 2 /SiO 2 -ZrO 2 The surface of the hybridization layer is continuous and has no defect and good integrity,
FIG. 3 shows that the film thickness of example 1 on the carrier is about 200nm, and the thickness is smaller, which is beneficial to the water flux of the nanofiltration membrane.
Nanofiltration test was performed on the composite membrane finally prepared in example 1 by means of polyvinyl alcohol (PEG) with molecular weight 200/400/600/800/1000, and the membrane pore size was 1.0nm, which falls into the nanofiltration membrane range.
The composite film finally prepared in example 1 was used for 0.05 g.L -1 Separating the aqueous solution of diclofenac sodium (DCF), operating at 0.6MPa and 70 ℃ for 50h,
nanofiltration performance to DCF aqueous solution: flux of 14.25 L.m -2 ·h -1 The retention rate of DCF is above 98.1%, and the hydrothermal stability is excellent.
Example 2
(1) 1.0g of tetraethyl orthosilicate (TEOS) is dissolved in 19.8g of Ethanol (ETOH), then 0.28g of water and 0.06g of hydrochloric acid are added and stirred for 60 minutes, then 3.80g of zirconium n-butoxide (ZrBT) is added, finally 215g of deionized water is added and heated to 100 ℃ and stirred for reaction for 12 hours, thus obtaining high-concentration SiO with mass fraction of 2.0 percent 2 -ZrO 2 The sol is used for preparing the gel,
1.0g of tetraethyl orthosilicate (TEOS) is dissolved in 19.8g of Ethanol (ETOH), then 0.28g of water and 0.06g of hydrochloric acid are added and stirred for 60 minutes, then 3.80g of zirconium n-butoxide (ZrBT) is added, finally 455g of deionized water is added and heated to 100 ℃ and stirred for reaction for 12 hours, thus obtaining low-concentration SiO with the mass fraction of 1.0 percent 2 -ZrO 2 Sol;
(2) Taking a hollow flat ceramic membrane as a carrier (aperture 500 nm), and carrying out the high-concentration SiO in the step (1) 2 -ZrO 2 The sol is evenly coated on a carrier, put into a muffle furnace with 550 ℃ for calcination for 20min, and the process is repeated for 4 times to obtain SiO 2 -ZrO 2 A layer;
(3) 0.88g of zirconium chloride (ZrCl) 4 ) And 0.68g of 2-amino-1, 4-benzenedimethanamideAcid (H) 2 BDC-NH 2 ) Respectively dissolving in 42ml of N, N-Dimethylformamide (DMF), mixing the two solutions, performing ultrasonic treatment for 10min, adding 10ml of acetic acid, placing in a hydrothermal reaction kettle, reacting at 150deg.C for 20 hr, taking out the product, centrifuging, washing, and drying at 60deg.C to obtain UiO-66-NH 2 The crystal is formed by a crystal body,
UiO-66-NH to be used herein 2 The crystals were mixed into the low concentration SiO in step (1) at a mass concentration of 0.5% 2 -ZrO 2 Obtaining mixed sol from sol;
(4) Uniformly coating the mixed sol obtained in the step (3) on the SiO obtained in the step (2) 2 -ZrO 2 Calcining the layer in a muffle furnace at 550deg.C for 20min, repeating the process for 2 times to obtain UiO-66-NH 2 /SiO 2 -ZrO 2 A hybrid layer.
The total thickness of the film formed on the support was about 200nm.
Nanofiltration test was performed on the composite membrane finally prepared in example 2 by means of polyvinyl alcohol (PEG) with molecular weight 200/400/600/800/1000, and the membrane pore size was 1.1nm, which falls into the nanofiltration membrane range.
The composite film finally prepared in example 2 was used for 0.05 g.L -1 Separating the aqueous solution of diclofenac sodium (DCF), operating at 0.6MPa and 70 ℃ for 50h,
nanofiltration performance to DCF aqueous solution: flux of 12.61 L.m -2 ·h -1 The retention rate of DCF is above 98.7%, and the hydrothermal stability is excellent.
Comparative example 1
No UiO-66-NH is introduced 2 The rest of the procedure is the same as in example 1:
(1) 1.0g of tetraethyl orthosilicate (TEOS) is dissolved in 19.8g of Ethanol (ETOH), then 0.28g of water and 0.06g of hydrochloric acid are added and stirred for 60 minutes, then 3.80g of zirconium n-butoxide (ZrBT) is added, finally 215g of deionized water is added and heated to 100 ℃ and stirred for reaction for 12 hours, thus obtaining high-concentration SiO with mass fraction of 2.0 percent 2 -ZrO 2 The sol is used for preparing the gel,
1.6g of tetraethyl orthosilicate (TEOS) was dissolved in 19.8g of Ethanol (ETOH), then 0.28g of water and 0.06g of hydrochloric acid were added andstirring for 60 min, adding 6.08g of zirconium n-butoxide (ZrBT), adding 455g of deionized water, heating to 100deg.C, stirring for reaction for 12 hr to obtain low concentration SiO with mass fraction of 1.6% 2 -ZrO 2 Sol;
(2) Taking a hollow flat ceramic membrane as a carrier (aperture 500 nm), and carrying out the high-concentration SiO in the step (1) 2 -ZrO 2 The sol is evenly coated on a carrier, put into a muffle furnace with 550 ℃ for calcination for 20min, and the process is repeated for 4 times to obtain SiO 2 -ZrO 2 A layer;
(3) The low concentration SiO in the step (1) is treated 2 -ZrO 2 The sol is uniformly coated on the SiO obtained in the step (2) 2 -ZrO 2 Calcining the layer in a muffle furnace at 550deg.C for 20min, repeating the process for 2 times to obtain SiO 2 -ZrO 2 And separating the layers.
The total thickness of the film formed on the support was about 200nm, as can be seen in FIG. 4 SiO 2 -ZrO 2 The separating layer has smooth and continuous surface, no defect and good integrity.
Nanofiltration test was performed on the composite membrane finally prepared in comparative example 1 by means of polyvinyl alcohol (PEG) having a molecular weight of 200/400/600/800/1000, and the membrane pore size was 1.2nm, which falls into the nanofiltration membrane range.
The composite film finally prepared in comparative example 1 was used for 0.05g.L -1 Separating the aqueous solution of diclofenac sodium (DCF), operating at 0.6MPa and 70 ℃ for 50h,
nanofiltration performance to DCF aqueous solution: flux of 8.25 L.m -2 ·h -1 The retention rate for DCF was 92%.
Comparative example 2
No incorporation of low concentration SiO 2 -ZrO 2 Sol and UiO-66-NH 2 The rest of the procedure is the same as in example 1:
(1) 1.0g of tetraethyl orthosilicate (TEOS) is dissolved in 19.8g of Ethanol (ETOH), then 0.28g of water and 0.06g of hydrochloric acid are added and stirred for 60 minutes, then 3.80g of zirconium n-butoxide (ZrBT) is added, finally 215g of deionized water is added and heated to 100 ℃ and stirred for reaction for 12 hours, thus obtaining high-concentration SiO with mass fraction of 2.0 percent 2 -ZrO 2 Sol;
(2) Taking a hollow flat ceramic membrane as a carrier (aperture 500 nm), and carrying out the high-concentration SiO in the step (1) 2 -ZrO 2 The sol is evenly coated on a carrier, put into a muffle furnace with 550 ℃ for calcination for 20min, and the process is repeated for 6 times to obtain SiO 2 -ZrO 2 And separating the layers.
The composite membrane finally prepared in comparative example 2 was tested by means of polyvinyl alcohol (PEG) having a molecular weight of 200/400/600/800/1000, and a membrane pore size of 2nm was obtained.
The composite film finally prepared in comparative example 2 was used for 0.05g.L -1 Separating the aqueous solution of diclofenac sodium (DCF), operating at 0.6MPa and 70 ℃ for 50h,
nanofiltration performance to DCF aqueous solution: flux of 9.0 L.m -2 ·h -1 The retention rate of DCF is lower than 50%.
Comparative example 3
No zirconium source and UiO-66-NH are introduced into the low concentration film-forming sol 2 The rest of the procedure is the same as in example 1:
(1) 1.0g of tetraethyl orthosilicate (TEOS) is dissolved in 19.8g of Ethanol (ETOH), then 0.28g of water and 0.06g of hydrochloric acid are added and stirred for 60 minutes, then 3.80g of zirconium n-butoxide (ZrBT) is added, finally 215g of deionized water is added and heated to 100 ℃ and stirred for reaction for 12 hours, thus obtaining high-concentration SiO with mass fraction of 2.0 percent 2 -ZrO 2 The sol is used for preparing the gel,
1.6g of tetraethyl orthosilicate (TEOS) is dissolved in 19.8g of Ethanol (ETOH), then 0.28g of water and 0.06g of hydrochloric acid are added and stirred for 60 minutes, then 3.30g of tetraethyl orthosilicate (TEOS) is added, finally 455g of deionized water is added and heated to 100 ℃ and stirred for reaction for 12 hours, thus obtaining low-concentration SiO with the mass percentage of 1.6 percent 2 Sol;
(2) Taking a hollow flat ceramic membrane as a carrier (aperture 500 nm), and carrying out the high-concentration SiO in the step (1) 2 -ZrO 2 The sol is evenly coated on a carrier, put into a muffle furnace with 550 ℃ for calcination for 20min, and the process is repeated for 4 times to obtain SiO 2 -ZrO 2 A layer;
(3) The low concentration SiO in the step (1) is treated 2 Sol uniform coatingCoating the SiO obtained in the step (2) 2 -ZrO 2 Calcining the layer in a muffle furnace at 550deg.C for 20min, repeating the process for 2 times to obtain SiO 2 And separating the layers.
FIG. 5 is a diagram showing SiO 2 The separating layer has smooth and continuous surface, no defect and good integrity.
Comparative example 4
Under the condition that a zirconium source is not introduced into the low-concentration film-forming sol, uiO-66-NH is added 2 The rest of the procedure is the same as in example 1:
(1) 1.0g of tetraethyl orthosilicate (TEOS) is dissolved in 19.8g of Ethanol (ETOH), then 0.28g of water and 0.06g of hydrochloric acid are added and stirred for 60 minutes, then 3.80g of zirconium n-butoxide (ZrBT) is added, finally 215g of deionized water is added and heated to 100 ℃ and stirred for reaction for 12 hours, thus obtaining high-concentration SiO with mass fraction of 2.0 percent 2 -ZrO 2 The sol is used for preparing the gel,
1.0g of tetraethyl orthosilicate (TEOS) is dissolved in 19.8g of Ethanol (ETOH), then 0.28g of water and 0.06g of hydrochloric acid are added and stirred for 60 minutes, then 2.06g of tetraethyl orthosilicate (TEOS) is added, finally 455g of deionized water is added and heated to 100 ℃ and stirred for reaction for 12 hours, thus obtaining low-concentration SiO with the mass percentage of 1.0 percent 2 Sol;
(2) Taking a hollow flat ceramic membrane as a carrier (aperture 500 nm), and carrying out the high-concentration SiO in the step (1) 2 -ZrO 2 The sol is evenly coated on a carrier, put into a muffle furnace with 550 ℃ for calcination for 20min, and the process is repeated for 4 times to obtain SiO 2 -ZrO 2 A layer;
(3) 0.88g of zirconium chloride (ZrCl) 4 ) And 0.68g of 2-amino-1, 4-phthalic acid (H) 2 BDC-NH 2 ) Respectively dissolving in 42ml of N, N-Dimethylformamide (DMF), mixing the two solutions, performing ultrasonic treatment for 10min, adding 10ml of acetic acid, placing in a hydrothermal reaction kettle, reacting at 150deg.C for 20 hr, taking out the product, centrifuging, washing, and drying at 60deg.C to obtain UiO-66-NH 2 The crystal is formed by a crystal body,
UiO-66-NH to be used herein 2 The crystals were mixed into the low concentration SiO in step (1) at a mass concentration of 0.6% 2 Obtaining mixed sol from sol;
(4) Will step by stepThe mixed sol in the step (3) is uniformly coated on the SiO obtained in the step (2) 2 -ZrO 2 Calcining the layer in a muffle furnace at 550deg.C for 20min, repeating the process for 2 times to obtain UiO-66-NH 2 /SiO 2 A hybrid layer.
FIG. 6 shows that, compared with comparative example 3, siO 2 Introduction of UiO-66-NH into the layer 2 After that, the membrane was obviously split during the membrane formation, and the membrane could not be used as a filter membrane.
Claims (10)
1. The preparation process of organic-inorganic hybridized nanofiltration membrane includes the following steps:
(1) Preparation of high concentration SiO respectively 2 -ZrO 2 Sol and low concentration SiO 2 -ZrO 2 The sol is used for preparing the gel,
(2) High concentration SiO obtained in step (1) 2 -ZrO 2 Coating the sol on a carrier and calcining to obtain SiO 2 -ZrO 2 The layer of the material is formed from a layer,
(3) To the low concentration SiO obtained in step (1) 2 -ZrO 2 Mixing UiO-66-NH into sol 2 Fully mixing and then coating the mixture on the SiO obtained in the step (2) 2 -ZrO 2 On the layer and calcining to obtain UIO-66-NH 2 /SiO 2 -ZrO 2 A hybrid layer.
2. The method for preparing the organic-inorganic hybrid nanofiltration membrane according to claim 1, wherein the method comprises the following steps: in the step (1), after a period of hydrolysis reaction of a silicon source, adding zirconium salt into the silicon source, heating the silicon source, and continuing the hydrolysis reaction to obtain SiO 2 -ZrO 2 And (3) sol.
3. The method for preparing the organic-inorganic hybrid nanofiltration membrane according to claim 2, wherein the method comprises the following steps: in the step (1), the molar ratio of silicon to zirconium is 1:1, heating to 100-120 ℃ for hydrolysis reaction for 12-18 h.
4. The method for preparing the organic-inorganic hybrid nanofiltration membrane according to claim 1, wherein the method comprises the following steps: in the step (1), high-concentration SiO 2 -ZrO 2 Mass of solThe concentration is 2.0-5.0%, and the concentration is low SiO 2 -ZrO 2 The mass concentration of the sol is 0.5-1.0%.
5. The method for preparing the organic-inorganic hybrid nanofiltration membrane according to claim 1, wherein the method comprises the following steps: repeating the step (2) for 2 to 6 times to obtain high-concentration SiO 2 -ZrO 2 Sol coating and calcining.
6. The method for preparing the organic-inorganic hybrid nanofiltration membrane according to claim 1, wherein the method comprises the following steps: in step (3), uiO-66-NH 2 The preparation method comprises dispersing zirconium chloride and 2-amino-1, 4-phthalic acid in N, N-dimethylformamide, adding acetic acid, performing solvothermal reaction, filtering out the product after reaction, washing, and drying to obtain UiO-66-NH 2 And (5) a crystal.
7. The method for preparing the organic-inorganic hybrid nanofiltration membrane according to claim 1, wherein the method comprises the following steps: in step (3), uiO-66-NH is reacted with 2 Mixing low-concentration SiO according to the mass concentration of 0.05 to 0.6 percent 2 -ZrO 2 In the sol.
8. The method for preparing the organic-inorganic hybrid nanofiltration membrane according to claim 1, wherein the method comprises the following steps: repeating the operation of coating and calcining the mixed sol in the step (3) for 2 to 6 times.
9. Use of an organic-inorganic hybrid nanofiltration membrane obtained by the preparation process according to any one of claims 1 to 8 for separating organic or inorganic substances from water.
10. Use of an organic-inorganic hybrid nanofiltration membrane according to claim 9, wherein: the organic-inorganic hybrid nanofiltration membrane is used for interception and separation of the aqueous solution of DCF.
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