CN115814622A - MOF material composite nanofiltration membrane, preparation method and application - Google Patents
MOF material composite nanofiltration membrane, preparation method and application Download PDFInfo
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- CN115814622A CN115814622A CN202211301624.8A CN202211301624A CN115814622A CN 115814622 A CN115814622 A CN 115814622A CN 202211301624 A CN202211301624 A CN 202211301624A CN 115814622 A CN115814622 A CN 115814622A
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- 239000013154 zeolitic imidazolate framework-8 Substances 0.000 claims abstract description 85
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- NGNBDVOYPDDBFK-UHFFFAOYSA-N 2-[2,4-di(pentan-2-yl)phenoxy]acetyl chloride Chemical compound CCCC(C)C1=CC=C(OCC(Cl)=O)C(C(C)CCC)=C1 NGNBDVOYPDDBFK-UHFFFAOYSA-N 0.000 claims 1
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A20/00—Water conservation; Efficient water supply; Efficient water use
- Y02A20/124—Water desalination
- Y02A20/131—Reverse-osmosis
Abstract
The invention relates to a composite nanofiltration membrane made of an MOF material, a preparation method and application, and belongs to the technical field of nanofiltration membrane preparation. The ZIF-8 intermediate layer is successfully synthesized by a method of simple PEG participation post-heat treatment, the addition of the PEG can remarkably adjust the particle size of the ZIF-8 intermediate layer, solvent-resistant organic nanofiltration membranes are prepared on the ZIF-8 intermediate layers with different particle sizes, the addition of the ZIF-8 intermediate layer can improve the flux by more than one time and improve the interception, and the ZIF-8 with different particle sizes shows different fluxes. In addition, the TETA crosslinked ZIF-8 film had good organic solvent resistance.
Description
Technical Field
The invention relates to a composite nanofiltration membrane made of an MOF material, a preparation method and application, and belongs to the technical field of nanofiltration membrane preparation.
Background
The Organic Solvent Nanofiltration (OSN) technology is a novel technology for separating and purifying organic solvents, and the selection of membrane materials and the preparation method of a selection layer play an important role in the performance of the membrane materials 1-3 . Currently, materials such as Polyimide (PI), polyphenylsulfone (PPSU), etc. are used to prepare OSN thin film composite membranes (TFCs), but conventional TFC membranes are further limited in their use by the "Trade-off" effect.
In recent years, the introduction of an interlayer method for improving membrane performance by adding nanoparticles to a TFC membrane has attracted extensive attention by researchers, and the porosity and relatively good compatibility of MOFs with membrane substrates, compared to inorganic nanomaterials, make MOFs uniquely advantageous as interlayers 4-6 . As a subclass of MOF materials, ZIF synthesis conditions are simple, have excellent chemical stability and are widely applied to the field of membrane separation, but the poor interfacial compatibility between ZIF and a membrane substrate and the solvent synthesis conditions of ZIF limit the further use of an intermediate layer of the ZIF membrane 7 。
Some researchers have added nucleation sites by modifying the surface of the membrane 8 Secondary growth of the silicon oxide 4 Convection growth of 9 Electrochemical assisted synthesis 10 The ZIF intermediate layer enhances the compatibility of ZIF and the membrane, and reduces the interface defect and non-selective gap of the ZIF and the membrane, but the methods need additional functional modification treatment on the membrane and have complicated steps. On the other hand, the synthesis of the intermediate layer can be completed in an organic solvent system for a long time, and the use of a large amount of organic solvent causes environmental pollution and actual operation of plant equipmentRaising higher challenges, therefore, a green fast approach to ZIF interlayer synthesis is urgently needed.
Reference documents:
1.Sun,S.P.；Chan,S.Y.；Xing,W.H.；Wang,Y.；Chung,T.S.,Facile Synthesis of Dual-Layer Organic Solvent Nanofiltration(OSN)Hollow Fiber Membranes.Acs Sustainable Chemistry&Engineering 2015,3(12),3019-3023.
2.Lu,T.D.；Zhao,L.L.；Yong,W.F.；Wang,Q.；Duan,L.；Sun,S.P.,Highly solvent-durable thin-film molecular sieve membranes with insoluble polyimide nanofibrous substrate.Chemical Engineering Journal 2021,409.
3.Szekely,G.；Jimenez-Solomon,M.F.；Marchetti,P.；Kim,J.F.；Livingston,A.G.,Sustainability assessment of organic solvent nanofiltration:from fabrication to application.Green Chemistry 2014,16(10),4440-4473.
4.Wang,L.；Fang,M.；Liu,J.；He,J.；Li,J.；Lei,J.,Layer-by-Layer Fabrication of High-Performance Polyamide/ZIF-8Nanocomposite Membrane for Nanofiltration Applications.ACS Appl Mater Interfaces 2015,7(43),24082-24093.
5.Ren,Z.Y.；Luo,J.Q.；Wan,Y.H.,Highly permeable biocatalytic membrane prepared by3D modification:Metal-organic frameworks ameliorate its stability for micropollutants removal.Chemical Engineering Journal 2018,348,389-398.
6.Zhang,X.F.；Feng,Y.；Wang,Z.G.；Jia,M.M.；Yao,J.F.,Fabrication of cellulose nanofibrils/UiO-66-NH2 composite membrane for CO2/N-2separation.Journal of Membrane Science 2018,568,10-16.
7.Zhou,Y.C.；Jia,M.M.；Zhang,X.F.；Yao,J.F.,Etched ZIF-8as a Filler in Mixed-Matrix Membranes for Enhanced CO2/N-2Separation.Chemistry-a European Journal 2020,26(35),7918-7922.
8.Zhao,X.X.；Zhang,H.；Xu,S.；Wang,Y.,ZIF-8membrane synthesized via covalent-assisted seeding on polyimide substrate for pervaporation dehydration.Aiche Journal 2019,65(8).
10.Shi,Q.；Chen,Z.；Song,Z.；Li,J.；Dong,J.,Synthesis of ZIF-8and ZIF-67by steam-assisted conversion and an investigation of their tribological behaviors.Angew Chem Int Ed Engl 2011,50(3),672-675.
disclosure of Invention
The invention mainly aims to prepare the ZIF intermediate layer in a green and rapid manner in the process of preparing the multi-layer nanofiltration membrane so as to improve the performance of the OSN membrane. The technical idea of the patent is that a ZIF intermediate layer grows in situ on the surface of a polymer film by a heating method after the surface of the film is coated with a mixture of PEG and ZIF precursors.
The technical scheme is as follows:
a nanofiltration membrane compounded by an MOF material comprises a base membrane, an intermediate layer and an interfacial polymerization layer, wherein the intermediate layer contains ZIF particles and polyethylene glycol, and the interfacial polymerization layer is a polyamide material.
The ZIF particles are selected from one or more of ZIF-8, ZIF-7, ZIF-1, ZIF-12, ZIF-90, ZIF-62, ZIF-78 and ZIF-71.
The molecular weight of the polyethylene glycol is 100-4000, preferably 150-1500.
The weight ratio of the ZIF particles to the polyethylene glycol is 1:0.2-2.
The particle size of the ZIF particles is 100-400nm.
The thickness of the interfacial polymerization layer is 100-300nm.
The polyamide material is obtained by polymerizing amine monomers and acyl chloride monomers.
The preparation method of the MOF material composite nanofiltration membrane comprises the following steps:
and 2, preparing the polyamide layer on the surface of the base film with the middle layer by an interfacial polymerization method.
In the step 1, the weight ratio of the zinc salt to the imidazolyl ligand to the polyethylene glycol is 1:1.5-4:0.5-5.
In the step 1, the grinding time is 5-30min, the heat treatment time is 5-30min, and the heat treatment temperature is 70-90 ℃.
In the step 2, the interfacial polymerization method is to coat the aqueous phase solution containing the amine monomer and then coat the oil phase solution containing the acyl chloride monomer.
The concentration of the water phase solution is 0.05-0.5wt%, and the concentration of the oil phase solution is 0.05-0.2wt%.
The amine monomer is one or a mixture of more of triethylene tetramine, diethylenetriamine and polyethyleneimine; the acyl chloride monomer is trimesic acid chloride.
The MOF material composite nanofiltration membrane is applied to liquid filtration.
The liquid filtration is selected from one of the filtration of solution containing inorganic salt and the filtration of small molecular compound.
A method of regulating the size of ZIF-8 nanoparticles, comprising the steps of:
during the preparation of ZIF-8 nanoparticles, polyethylene glycol was also added and ground.
In the method, the size of the nano-particles is increased by increasing the dosage of the polyethylene glycol, or the size of the nano-particles is reduced by reducing the dosage of the polyethylene glycol.
Advantageous effects
The invention adopts a heating method after coating PEG and ZIF precursor mixture on the surface of the membrane to grow the ZIF intermediate layer on the surface of the polymer membrane in situ, wherein the PEG contains a flexible chain segment group, and the method has the advantages that: 1) The addition of PEG introduces a large number of nucleation sites on the surface of the membrane, thereby avoiding the need of additional modification on the surface of the membrane; 2) The PEG has hydrophilic and hydrophobic groups, so that the solubility of metal ions and organic ligands can be increased, and the use of an organic solvent is avoided; accelerating ZIF crystal growth under post-heating conditions, so that the reaction is rapidly carried out, and the apparent morphology of the ZIF material can be regulated and controlled by regulating the dosage of PEG; in addition, PEG can be used as a pore-retaining agent of the membrane during heat treatment in the experimental process, so that the collapse of the membrane pores during heating is avoided, and the advantages can enable green rapid synthesis of the ZIF intermediate layer.
Drawings
FIG. 1: (a) XRD pattern, (b) FTIR spectra of all samples, (c) SEM image of PI film substrate, (d) PI-ZIF-8SEM image, (e) partially magnified SEM image of PI-ZIF-8, and (f) cross section of PI-ZIF-8.
FIG. 2: (a) XRD patterns of samples, (b) XRD patterns of ZIF-8 prepared with different amounts of PEG, (c) Zn (OAC) with and without PEG 2 -DSC curve of 2-imidazole mixture; (d0) The SEM images of the amounts of PEG added of 0mL, 1mL, 2mL, and 3mL were obtained for (d 1), (d 2), and (d 3), respectively.
FIG. 3: (a) XRD patterns of samples heated at different times; SEM images of ZIF-8 prepared by heating at different times were (b) 5 minutes, (c) 15 minutes, and (d) 25 minutes, respectively.
FIG. 4: FTIR spectra of the films after interfacial polymerization.
FIG. 5: (a) and (d), SEM pictures of interfacial polymerization without intermediate layer, (b) and (e), SEM pictures of interfacial polymerization with small ZIF-8 particle intermediate layer, (c) and (f), SEM pictures of interfacial polymerization with large ZIF-8 particle intermediate layer.
FIG. 6: different interfacial polymerization concentrations and membrane properties with or without intermediate layer, (b) rejection and performance of the membrane in methanol solution, (c) weight loss ratio of the membrane with and without TETA crosslinking, (d) flux and rejection performance of ZIF-8-IP membrane in different organic solvents.
FIG. 7: (a) Relationship of solvent Performance to solvent Performance (b) Long-term stability experiments of PI-ZIF-IP membranes.
FIG. 8: photographs of the membrane after soaking in DMF with or without TETA cross-linking.
Detailed Description
Preparation of the Material
The base film used was a polyimide film, prepared according to the prior art.
The preparation method of the membrane comprises the following steps:
1g of Zn (OAc) 2 2.5g 2-methylimidazole and PEG 200 (1 mL, 2mL, 3 mL) with different x mL contents were added to the mill, the mixture was milled for 10min, and then the mixture was coated on the surface of a PI membrane, and the PI membrane was placed in an ovenHeating at 80 deg.C for y min (5 min,15min, 25min), cooling to room temperature, washing with deionized water and methanol, and naming as PI-ZIF-x, y.
The prepared film was soaked with z-concentration triethylene tetramine (TETA) (0.2 wt%, 0.1wt%, 0.05 wt%) for 2min, after which the excess liquid was removed with a roller, and then 0.1wt% TMC solution was poured on the surface thereof and reacted for 1 min, and the film was expressed as PI-ZIF x, y-z.
Meanwhile, in order to better characterize the configuration of the synthesized crystal, a ZIF crystal is synthesized. 1g of Zn (OAc) are used 2 2.5g 2-methylimidazole and PEG 200 (1 mL, 2mL, 3 mL) with different x mL contents are heated for different time y min, then washed three times with deionized water and methanol, and freeze-dried, and the samples are named as ZIF-x, y respectively.
Flux and selectivity test
The membranes were tested for permeability and selectivity using a cross-flow and dead-end test. The permeation amount was calculated using the following formula (1).
P is permeability in L m -2 h -1 bar -1 J is the volume flow of the permeability coefficient, A is the membrane area, and the effective area is 3.14cm -2 And delta P is transmembrane pressure difference, the pressure used in the research is 6bar, the membrane needs to be pre-communicated for 30min under the pressure of 8bar before formal testing is started so as to overcome the influence of pressure on membrane flux, the dyes used in the research, namely rhodanine blue, oxytetracycline, tetracycline and vitamin B12, are all 20ppm, and the concentrations of the rhodanine blue, oxytetracycline, tetracycline and vitamin B12 are measured by an ultraviolet-visible spectrophotometer. The rejection performance of the membrane was calculated using equation (2), c p And c f Is the concentration of solute in the permeate and solution.
Characterization of crystal form, functional group and apparent morphology
An area a XRD spectrum shown in figure 1 shows that a pure polyimide (P84) film has wider dispersion peaks at 2Theta of 17 degrees, 22 degrees and 25 degrees, which indicates that the pure PI film has an amorphous structure, and simultaneously, with the addition of ZIF-8, characteristic diffraction peaks belonging to ZIF-8 appear at 2Theta of 7.5 degrees, 10.7 degrees, 13 degrees and 15 degrees, which correspond to crystal faces (110), (200), (211) and (220) of the ZIF-8, which indicates that a ZIF-8 seed crystal layer can be successfully synthesized on the surface of the polyimide film by a PEG-involved solvent heat treatment method.
From the b infrared spectrum of fig. 1, it can be seen that: after PEG heat treatment and water washing are carried out on the surface of the membrane, PEG still exists in an infrared spectrogram, wherein: 1029. 1447 and 2866cm -1 Respectively corresponding to the stretching vibration of-C-O-C in PEG, -CH 2 The stretching vibration and the bending vibration show that although PEG is a substance with better water solubility, most of PEG can be removed in the process of washing with water, but part of PEG still remains on the surface of the membrane, and the surface of the membrane can be well modified by the existence of the PEG. Meanwhile, a characteristic peak of ZIF-8 can be observed in an infrared spectrogram, wherein the peak is 3133cm -1 Represents a C-H vibration peak of unsaturated hydrocarbon on an imidazole ring, and is 2925cm -1 Representing C-H stretching vibration in methyl at 1575cm -1 The peak at (a) is the C = N stretching vibration in the imidazole ring, which is consistent with the XRD pattern results and the SEM pictures described below.
While the surface of the pure PI film is smooth and flat in the c of the FIG. 1, the ZIF-8 particles uniformly and densely grown on the surface of the PI film can be seen from the d and e of the FIG. 1, the particle size of the ZIF-8 particles is analyzed to be about 110nm, compared with the ZIF-8 particles grown on the polymer film in situ, twice grown and other methods, the PEG modification introduces a large number of nucleation sites on the film substrate, thereby avoiding the need of additional modification on the film substrate. According to the film cross section, the ZIF-8 particle PI film has good interface compatibility, no obvious layering phenomenon exists between the ZIF-8 particles and the film substrate, and the particles uniformly grow in the film surface.
Appearance and crystal form representation in crystal formation process
FIG. 2, a, shows XRD patterns of ZIF-8 precursor and the product formed during synthesis with or without PEG addition, which is dense without PEG additionUnlike the conventional literature, the structure of the Zn (dense dia (Zn)) phase is different in that only Zn (OAc) is used in the conventional literature 2 Only amorphous melts can be formed with imidazole ligands, even dense phase Zn (Zn) can not be formed, but the dense phase Zn can be formed in the work, presumably because the zinc source and imidazole are fully combined due to full grinding, and partial imidazole is melted due to heat brought by grinding while the grinding plays a role of an initiator, and a dense phase Zn structure is formed after post-heat treatment.
By inspecting the appearance of the film obtained by the post-heat treatment method of the surfactant, after the PEG is added, the generated product is yellow, but after the PEG is washed by water, the yellow color disappears, the yellow color is a eutectic mixture and can only appear after high-temperature treatment, and the fact that the ZIF-8 crystal can be formed by adding the PEG is shown. Further DSC analysis of the crystallization of ZIF-8 shows Zn (OAc) in the absence of PEG 2 And 2-methylimidazole at 94-107 ℃ shows two strong absorption peaks, which is the process of losing two molecules of crystal water by zinc acetate dihydrate, while in the sample added with PEG, a new absorption peak appears at 88 ℃, and because the melting peak of PEG 200 is-65 ℃, a new absorption peak appears at 88 ℃ possibly as a crystal peak for generating ZIF-8.
The addition amount of PEG can remarkably regulate and control the size and the morphology of ZIF-8 particles, as shown in d0-d3 of figure 2, when no PEG is added, an amorphous compact phase Zn structure is formed, the particle size is about 2um, small particles grow on the surface of the particles, and at the moment, a ZIF-8 crystal form is not formed. When 1mL of PEG was added, a ZIF-8 structure was formed, the particle size of which was 120nm cubic structure (cubic), and when 2mL of PEG was added, the ZIF-8 particle size changed to 250nm cubic structure, while when the amount of PEG added was 3mL, the ZIF-8 particle size did not change significantly, but the ZIF-8 configuration changed to Truncated Rhambyc Dodecahedral (TRD) configuration, and it is more remarkable that, in the literature, under experimental conditions without PEG, even when heated at 120 ℃ for 24 hours, both generated only an amorphous melt mixture 9, and under the conditions of PEG existence, ZIF-8 crystals could be formed at a lower temperatureBody, possible reasons are: the Janus characteristics of PEG with hydrophilic and hydrophobic functional groups enable the PEG to increase the solubility of metal ions and organic ligands, so that the ligands are in full contact with a metal source, and crystals grow under a certain temperature condition. When 1mL of PEG is added, the concentration of ZIF-8 crystals is too low during nucleation and the crystals with a smaller [100 ] content because the surfactant is used in too little amount and the ligand and the metal source are only partially dissolved in the surfactant]The ZIF-8 configuration of crystal face, and when the addition amount of PEG is 2mL, the metal source and the ligand can be well combined to form a complex with [110 ]]The crystal face of the ZIF-8 of the Rhambic Dodecahedral (RD) according to Wulff's rule, the 110 crystal face growing slowest in the ZIF-8 determines the final appearance of the ZIF-8, meanwhile, the ZIF-8 with RD configuration can be a stable equilibrium form of the ZIF-8, when the content of the added PEG is 3mL, because a large amount of hydrophobic groups-CH are contained in a PEG chain 2 CH 2 And a hydrophilic group-CH 2 -O-CH 2 Structure, the hydrophobic group in PEG adsorbs on the hydrophobic ZIF-8 surface to act as capping agent, reducing the growth rate of leaching (capping agents), and the crystal morphology is changed from RD configuration to TRD configuration.
The heating time also affects the morphology of ZIF-8 as shown in FIG. 3 a: if the precursor is not heated, it is merely ground, even in the case of adding PEG, only a mixture of dia Zn and a small amount of ZIF-8 is produced, and the precursor is heated for various times, as shown in a of FIG. 3, even in the case of heating for 5min, the ZIF-8 configuration can be formed, however, when the heating time is increased, the typical phenomenon of austenite ripening (Ostwald ripening) of ZIF-8 is found, and in b of FIG. 3, the ZIF-8 is formed by the aggregation of ZIF-8 small particles without regular shape, without distinct boundaries, and as the heating time is increased, the ZIF-8 crystals continuously grow into crystals with a size of about 150nm, and as the heating time is further increased (Ostwald ripening), the ZIF-8 particles gradually grow and aggregate together.
The heat treatment time of the middle layer of the nanofiltration membrane adopted in the subsequent membrane performance test is controlled to be 15min.
Influence of ZIF-8 interlayer on interfacial polymerization morphology
PEG dosage of 1mL and 2mL are selected as the middle layer to carry out subsequent interfacial polymerization reaction so as to explore the influence of the particle size on membrane flux and interception. ZIF-8 interlayers with different sizes and thicknesses can be synthesized by using different PEG dosages, and the influence of different ZIF-8 interlayers on an interface polymerization layer is researched.
In the IR spectrum (FIG. 4), at 1542, 1610 and 1660cm -1 The peaks at (a), corresponding to the N-H bend of the amide II, aromatic amide and amide I bands, are chemical groups of the PA layer formed by the reaction of TETA with TMC, indicating successful preparation of the interfacial polymeric layer. The surface of the composite nanofiltration membrane formed by TETA and TMC interfacial polymerization is nodular, and the granular protrusions are formed by polymerization of aliphatic polyamine and are different from the surface of polymerization of aromatic polyamine. The surface of the base film after interfacial polymerization is shown to form a compact functional layer, and the thickness of the formed interfacial polymerization layer is about 195nm.
As shown in fig. 5, the interface polymerization layer modified by the middle layer of the smaller ZIF-8 nanoparticles formed by 1mL PEG has a plurality of Worm-like structures (whose thickness is reduced to 120 nm), and the polyamide structure formed by the middle layer of the larger ZIF-8 particles modified by 2mL PEG forms a Worm-like structure on the surface of the membrane, and also forms a vesicle with larger particles on the surface of the membrane, and the thickness of the interface polymerization layer is 285nm, which is presumed to be the reason why the smaller ZIF-8 particles form a thin interface polymerization layer, (1) the introduction of ZIF-8 enhances the absorption of TETA by the ZIF-8, thereby enhancing the concentration of Amine Monomers on the surface (Enhanced uptake of Amine Monomers), (2) the Controlled Release of Amine Monomers, and the existence of the ZIF-8 layer can significantly reduce the Release rate of the Amine Monomers, thereby reducing the thickness of the interface polymerization layer by more than one time (Controlled Release of Amine Monomers); (3) CO is produced after interfacial polymerization according to nano-foaming theory 2 The pore diameter of the membrane surface can be obviously reduced by adding the air bubbles and the ZIF-8, so that nano bubbles are better restrained, and the appearance of the membrane surface is changed (Enhanced defined Effect for interactive treated Nanobubbles). While larger ZIF-8 particles may form thicker interfacial polymeric layers because: ZIF-8 particles themselves have a particle size of about 250nm, ZThe IF-8 particles adsorb TETA monomers, so that interfacial polymerization is started along the ZIF-8 particles to form a thicker interfacial polymerization layer, the interfacial polymerization layer without the ZIF-8 intermediate layer is more compact, and the addition of the ZIF-8 particles enables the interfacial polymerization layer to have a multi-bending wrinkle appearance, which is beneficial to the improvement of membrane flux.
Membrane flux and rejection
As shown in Table 1, when the PI film substrate and the PI film substrate are directly put into an oven for heating at 80 ℃ through PEG coating ZIF-8 crystal, the film flux is remarkably changed, and the film flux without PEG modification is reduced to 5.3L m -2 h -1 bar -1 The flux of the PEG-coated PI membrane is almost unchanged, which indicates that PEG has good protection effect on the membrane pores during heating.
TABLE 1 Membrane Performance before and after heating with or without PEG
As shown in a of fig. 6, the membrane flux and interception are adjusted by adjusting the concentration of TETA, the interception of rhodanine blue by the aqueous solution is tested, because TETA is a long linear polymer, the degree of crosslinking after the reaction of TETA and TMC is higher, the functional layer is compact, no intermediate layer is directly subjected to interfacial polymerization to obtain a polyamide membrane flux which is lower, and when the TETA concentration is 1% -1.5%, the membrane fluxes are respectively 8.69 and 5.37L m -2 h -1 bar -1 Meanwhile, the retention is more than 98.85 percent, when the concentration of TETA is further reduced to 0.5 percent, the flux of the membrane is increased to 12.27L m -2 h -1 bar -1 However, the rhodanine blue retention at this point was reduced to 91.37%, probably because the TETA concentration was too low to form a dense polymer network with TMC.
When a small ZIF-8 intermediate layer is added, interfacial polymerization is carried out, and the membrane flux rises to 19.37 percent, 15.53 percent and 12.27L m respectively when the TETA concentration is 0.5 to 1.5 percent -2 h -1 bar -1 Flux was increased by about 1 fold compared to no intermediate layer, and the reason for the increase in flux may be: (1) Water molecules far from the pore region need to travel a long distance to complete the transmission without any interlayer, andthe presence of porous ZIF-8 allows to reduce the transport distance through water molecules and thus to increase the water flux, the so-called "channeling Mechanism" (Gutter Mechanism). (2) The existence of the intermediate layer can reduce the polyamide entering the aperture of the base membrane, which causes the generation of bottleneck phenomenon ("bottleneck") and on the other hand, the existence of the intermediate layer can control the release of amine monomer, so that the thickness of an interface polymeric layer is reduced, thereby increasing the membrane flux, the interception of the nanofiltration membrane with the ZIF-8 intermediate layer at the TETA concentration of 1% -1.5% is all around 98.52%, but the interception of the ZIF-8 intermediate layer at 0.5% is 95.57%, compared with the absence of the ZIF-8 intermediate layer, the interception and the flux are both improved, and the reason for the improved interception is probably that the uniform interface polymeric layer is formed due to the addition of the ZIF-8, and the aperture of the membrane is reduced at the same time, thereby effectively promoting the release of the amine monomer. When larger ZIF-8 particles are added as an interlayer, the retention phase of the ZIF-8 particles is not obviously changed when the larger ZIF-8 particles are added as the interlayer, but the flux is slightly lower than that of the interlayer of the smaller ZIF-8 particles and higher than that without the interlayer, presumably because the thicker interlayer formed by the larger ZIF-8 particles increases the resistance in the transmission process and causes the flux to be reduced, and compared with an interfacial polymerization layer without the interlayer, the polyamide structure formed by the larger ZIF-8 particles is looser, and the permeability of the ZIF-8 particles is enhanced by the porosity of the ZIF-8 particles.
In order to evaluate the stability of the composite membrane in an organic solvent, the membrane is respectively soaked in DMF and methanol to test the weight loss ratio, as shown in the figure, the membrane before and after the TETA crosslinking is respectively soaked in DMF, the figure (8) can be seen, PI which is not subjected to TETA crosslinking can be easily dissolved in DMF, only a non-woven fabric layer is left, and a ZIF-8-PI membrane which is subjected to the TETA crosslinking part can have good stability in DMF. As shown in c of fig. 6, the weight loss ratio of the film subjected to TETA overall crosslinking is significantly reduced, which indicates that TETA can realize crosslinking of the base film while modifying ZIF-8, thereby achieving good solvent resistance.
In addition, the TETA monomer can participate in the interfacial polymerization reaction process and can also participate in the crosslinking of a PI molecular chain so as to solve the problems of swelling and dissolving of the membrane in an organic solvent. Therefore, the retention performance of the ZIF-8-IP membrane on tetracycline in an organic solvent system is tested, and the ZIF-8-IP membrane has good tetracycline retention performanceThe interception effect of the method can reach 15.57, 3.66, 1.03, 13.37 and 0.13L m fluxes of methanol, ethanol, acetonitrile and DMF respectively -2 h -1 bar -1 The TETA modified membrane can resist polar solvents such as DMF and the like and keeps a certain retention. Meanwhile, the retention condition of the ZIF-8-IP membrane on small-molecule drugs in a methanol solvent system is tested, and as shown in the figure, due to the fact that a polyamide layer obtained by a TETA rigid molecular structure is compact, the retention on drug molecules in the methanol solvent system is maintained at a high level. Meanwhile, the long-term stability of the PI-ZIF-IP membrane in methanol is tested, and the fact that the rejection rate of the membrane is basically not obviously changed and the flux of the membrane is reduced to about 90% in a long-term cross flow test of 100 hours can be seen, so that the membrane has good long-term stability.
Claims (10)
1. A nanofiltration membrane compounded by MOF materials comprises a base membrane, an intermediate layer and an interfacial polymerization layer, and is characterized in that the intermediate layer contains ZIF particles and polyethylene glycol, and the interfacial polymerization layer is a polyamide material.
2. The MOF material composite nanofiltration membrane according to claim 1, wherein the ZIF particles are selected from one or a mixture of ZIF-8, ZIF-7, ZIF-1, ZIF-12, ZIF-90, ZIF-62, ZIF-78 and ZIF-71;
the molecular weight of the polyethylene glycol is 100-4000, preferably 150-1500.
3. The MOF material composite nanofiltration membrane according to claim 1, wherein the weight ratio of the ZIF particles to the polyethylene glycol is 1:0.2-2.
4. A MOF material composite nanofiltration membrane according to claim 1, wherein the ZIF particles have a particle size of 100 to 400nm;
the thickness of the interfacial polymerization layer is 100-300nm;
the polyamide material is obtained by polymerizing amine monomers and acyl chloride monomers.
5. A method of preparing a MOF material composite nanofiltration membrane according to claim 1, comprising the steps of:
step 1, grinding and mixing zinc salt, imidazolyl ligand and polyethylene glycol, coating the mixture on the surface of a base film, performing heat treatment, and cleaning to obtain the base film with an intermediate layer;
and 2, preparing the polyamide layer on the surface of the base film with the middle layer by an interfacial polymerization method.
6. The preparation method of the nanofiltration membrane compounded by the MOF material according to claim 5, wherein in the step 1, the weight ratio of the zinc salt to the imidazolyl ligand to the polyethylene glycol is 1:1.5-4:0.5 to 5;
grinding for 5-30min, heat treating for 5-30min at 70-90 deg.C.
7. The method for preparing the nanofiltration membrane made of the MOF material composite of claim 5, wherein in the step 2, the interfacial polymerization method comprises coating an aqueous phase solution containing the amine monomer and then coating an oil phase solution containing the acid chloride monomer.
8. A method of preparing a nanofiltration membrane composited with an MOF material according to claim 7, wherein the concentration of the aqueous phase solution is 0.05 to 0.5wt%, and the concentration of the oil phase solution is 0.05 to 0.2wt%;
the amine monomer is one or a mixture of more of triethylene tetramine, diethylenetriamine and polyethyleneimine; the acyl chloride monomer is trimesic acid chloride.
9. Use of a nanofiltration membrane composited with a MOF material according to claim 7 for liquid filtration.
10. A method for regulating the size of ZIF-8 nanoparticles, comprising the steps of: during the preparation of the ZIF-8 nano-particles, polyethylene glycol is also added and ground; in the method, the size of the nano-particles is increased by increasing the dosage of the polyethylene glycol, or the size of the nano-particles is reduced by reducing the dosage of the polyethylene glycol.
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