CN112295418B - Polyethylene-based composite graphene oxide nanofiltration membrane and preparation method thereof - Google Patents
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- B01D61/02—Reverse osmosis; Hyperfiltration ; Nanofiltration
- B01D61/027—Nanofiltration
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- B01D—SEPARATION
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- B01D2325/36—Hydrophilic membranes
Abstract
The invention relates to a polyethylene substrate composite graphene oxide nanofiltration membrane and a preparation method thereof, wherein a polyethylene substrate is chemically eroded by an oxidant to generate active sites, then a graphene oxide lamella containing metal ions is coated, the lamella and the polyethylene substrate are firmly bonded together under the action of hydrogen bonds, and a functional nanofiltration membrane is realized by utilizing a molecular sieve effect formed by channels among the graphene oxide lamella and negative charges carried on the lamella according to a Dow effect. The ultrathin polyolefin film is used as the substrate, the film structure is symmetrical, and the polyethylene substrate has great advantages in transmission capacity due to low transmission resistance; the polyethylene has high tensile strength, solvent resistance and ageing resistance, and has longer service life; the preparation process of the nanofiltration membrane has the advantages of novel method, strong functionality and strong selectivity of added ions, can adjust the filtration level according to requirements, and has wide prospect in future industrial application.
Description
Technical Field
The invention relates to the technical field of nanofiltration membranes, in particular to a polyethylene-based composite graphene oxide nanofiltration membrane and a preparation method thereof.
Background
With the rapid development of industrialization, the problems of water pollution and water resource shortage are increasingly remarkable, and how to scientifically solve the problem of water utilization is an important subject of human sustainable development strategy. The water treatment technology taking the membrane process as the core can effectively separate the required water molecules from useless impurities, thereby realizing the regeneration of water resources. The nanofiltration membrane mainly prepared by the interfacial polymerization method has a relatively loose separation layer, the pore diameter of the membrane pore is 1-2 nm, ions with different valence states can be effectively separated, and the method is widely applied to industry.
The commercial nanofiltration membrane usually takes a non-woven fabric composite polymer as a supporting layer, and the separation layer is attached to the supporting layer to form a composite reverse osmosis membrane, so that the strength of the membrane product is ensured, and the separation capability of the cortex is effectively exerted. However, the nanofiltration membrane in this mode is excellent in rejection capacity, but the water flux produced is still at a low level. Graphene is used as a novel 2-dimensional nano material, a graphene oxide sheet layer subjected to oxidation modification can carry oxygen-containing groups such as hydroxyl, carboxyl, ether bond and the like, and the appearance of the material provides a thought for preparing a novel functional nanofiltration membrane. By stacking graphene oxide sheet layers, a regular nano channel can be formed, water molecules pass through the nano channel, and larger salt ions can be intercepted to form a molecular sieving effect; and the negative charges carried on the graphene oxide sheet layer can separate monovalent salt from divalent salt through charging, so that the separation function of the nanofiltration membrane is realized.
In the selection of the material of the support layer, in order to ensure sufficient mechanical strength, the thickness of the support layer is usually larger than 120 μm, which causes great resistance during the filtration process, resulting in attenuation of flux and generation of concentration polarization. Polyolefin materials such as polyethylene, polypropylene and other thermoplastic resins have excellent mechanical strength and physical and chemical properties, and microporous membrane products with the thickness less than 10 microns and the strength higher than that of traditional non-woven fabrics can be prepared. In addition, the polyolefin material has excellent acid-base resistance and ageing resistance, and the service life of the film can be greatly prolonged.
However, it must be seen that polyolefin materials have low surface energy, high hydrophobicity, reduced flux levels, and membranes are prone to fouling, and thus are essential for hydrophilic modification of membranes. The common surface treatment mode comprises surface coating of a hydrophilic layer, surface physical treatment (such as corona, ultraviolet irradiation, low-temperature plasma and the like), surface grafting and the like, in order to ensure the strength of the membrane without damaging the membrane structure, the application adopts a chemical method to carry out surface treatment, and a polyolefin membrane is immersed into an oxidant to generate functional group active sites such as hydroxyl, carboxyl, amino, ether bond and the like on the membrane surface, so that the contact angle of the membrane surface is obviously reduced, and the pad is used for subsequent modification.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provides a polyethylene-based composite graphene oxide nanofiltration membrane and a preparation method thereof. According to the preparation method, the polyethylene active substrate and the graphene oxide lamella are bonded through hydrogen bond force generated between the metal ions and the oxygen-containing groups, and the polyvinyl alcohol cross-linking reinforcing skin layer is coated on the polyethylene active substrate, so that the hydrophilicity is improved, and the functional nanofiltration membrane is prepared.
The purpose of the application is realized by the following technical scheme:
the polyethylene-based composite graphene oxide nanofiltration membrane has pure water flux of 55-85L/m under 0.5MPa2h, the retention rate of the divalent salt is more than 92%.
A polyethylene substrate composite graphene oxide nanofiltration membrane is characterized in that a polyethylene substrate membrane is immersed in an oxidant for erosion, then is coated with graphene oxide micro-sheets under the assistance of pressure to form a salt-blocking layer, and finally is coated with polyvinyl alcohol for crosslinking to obtain a hydrophilic and firm cortex.
A preparation method of a polyethylene substrate composite graphene oxide nanofiltration membrane comprises the following specific steps:
(1) cleaning a polyethylene substrate with isopropanol, drying, modifying in an oxidant, immersing for a fixed period of time, taking out, and airing at room temperature;
the average thickness of the polyethylene substrate is between 5 and 30 micrometers, and preferably 9 to 20 micrometers; the average pore diameter is between 0.02 and 0.2 microns, and preferably between 0.05 and 0.1 micron;
The oxidant is one of hypochlorite, perchlorate, permanganate, trivalent cobalt salt, persulfate, sodium peroxide, peracetic acid, sodium percarbonate, sodium perborate, potassium dichromate, chromic acid, fuming sulfuric acid and nitric acid;
the concentration of the oxidant is 100-5000 ppm;
the immersion time is 0.25-30 hours;
(2) preparing a graphene oxide solution, and adding metal ions and a dispersing agent;
the sheet diameter of the graphene oxide is 1-100 micrometers, and preferably 5-50 micrometers;
the concentration of the graphene oxide in the graphene oxide solution is 10-100 ppm;
the metal ions are potassium ions, lithium ions, zinc ions, calcium ions, magnesium ions, aluminum ions, manganese ions, iron ions, cobalt ions, copper ions, chromium ions and the like, wherein divalent metal ions are preferred;
the content of metal ions in the graphene oxide solution is 5-10 ppm;
the dispersing agent is polyvinylpyrrolidone, the molecular weight is 3000-45000, and preferably 5000-16000;
the content of polyvinylpyrrolidone in the graphene oxide solution is 5 ppm;
the solvent is ethanol water solution, and the mixture ratio is ethanol: the water is 10: 0-7: 3;
(4) Loading the graphene oxide solution on a modified polyethylene substrate under the pressure of 0.1Mpa, and then putting the modified polyethylene substrate into an oven for heat treatment;
the heat treatment temperature is 50-80 ℃, and the heat treatment time is 5-20 min;
(4) immersing the nascent nanofiltration membrane obtained in the step (3) into a polyvinyl alcohol solution containing a cross-linking agent, then putting the solution into an oven for thermal cross-linking to obtain a polyethylene-based composite graphene oxide nanofiltration membrane, and drying and storing the polyethylene-based composite graphene oxide nanofiltration membrane;
the mass fraction of the polyvinyl alcohol in the polyvinyl alcohol solution is 0.5-10%;
the mass fraction of the cross-linking agent in the polyvinyl alcohol solution is 0.1-2%.
The molecular weight of the polyvinyl alcohol is 60000-180000, preferably 84000-120000
The cross-linking agent is one of glyoxal, glutaraldehyde, p-tolualdehyde, crotonaldehyde, maleic anhydride, glycidyl methacrylate, trihydroxymethyl aminomethane oxalic acid, malonic acid, citric acid, boric acid, epichlorohydrin and silane coupling agent.
The solvent is water;
the soaking time in the polyvinyl alcohol solution is 5-20 minutes, the heat treatment temperature is 50-80 ℃, and the soaking time is 1-20 min.
Compared with the prior art, the invention has the following positive effects:
this application utilizes thin and high polyethylene of intensity as the basement membrane, compares with conventional polysulfone ultrafiltration basement, and the high selective nanofiltration membrane of flux can be realized to its loose membrane main part, can be used to solve the general lower problem of nanofiltration membrane flux at present.
According to the method, a polyethylene substrate is chemically corroded by an oxidant, so that active sites are excited on the surface of polyethylene, and the surface tension is obviously reduced after corrosion; different from the modes of corona, oxygen plasma, irradiation and the like, the composite membrane has weaker chemical erosion force, has smaller damage to the membrane, does not influence the service life of the membrane, and provides a precondition for the subsequent preparation of the composite membrane.
According to the method, the stacking of graphene oxide functional sheets is used as an interception layer, the gaps among the sheets are used for screening ions with different sizes, and negative charges loaded on the sheets generate a charge effect to separate monovalent ions and divalent ions, so that a natural nanofiltration system is formed; the metal ions are used for complexing to reinforce the bonding force between the sheet layer and the substrate, and the mechanical strength and the performance stability are both greatly improved.
Compared with the conventional interfacial polymerization process, the process for compounding the graphene oxide on the polyethylene substrate is simple and easy to operate, has strong controllability, and has the capacity of continuous large-scale industrial production.
Drawings
FIG. 1 is a schematic diagram of the mechanism of action of metal ions
FIG. 2 SEM surface topography, where (1) and (2) are GO raw membranes and (3) and (4) are GO & Zn ion composite membranes;
the labels in the figures are:
1. Graphene oxide lamellae;
2. a polyethylene substrate.
Detailed Description
The specific embodiment of the invention provides an ethylene-based composite graphene oxide nanofiltration membrane and a preparation method thereof.
The specific methods for membrane performance testing and characterization in the examples and comparative examples are as follows:
thickness: the thickness of the plastic film and the sheet is measured by using a German Mark film thickness gauge C1216 according to the measuring method of GB/T6672-2001, the same sample is tested for 5 times, and the average value is taken as the average thickness.
Pure water flux: and (3) measuring by adopting a nanofiltration tester (self-made).
Retention rate: the measurement was carried out by using a conductivity meter (DDS-307A, Rehmagnet, Shanghai).
Flux and rejection: the pure water flux is an important parameter for representing the water permeability of the separation membrane, and the membrane is pre-pressed for 1 hour by using deionized water as a feed liquid under the pressure of 0.6MPa to ensure that the effluent is stable; then, pure water flux test was carried out at 0.5MPa, and the effective membrane area of the test apparatus was 28.5cm2. The calculation formula is as follows:
wherein Q is the volume (L) of pure water passing therethrough, Δ t is the time (h) of passing therethrough, and A is the effective area (cm) of the permeable membrane2)。
Retention performance: the retention rate (R) is two indexes. After the membrane pre-compaction is finished, the MgSO with 2000mg/L of MgSO4And 500mg/L of NaCl solution to be tested, adjusting the pressure to 0.5MPa, and testing at room temperature of 25 ℃. The calculation formula is as follows:
CPAnd CFThe permeate and feed concentrations (mg/L), respectively, are generally considered to be linearly related to the salt concentration, and thus the salt cut-off R can be calculated using conductivity instead of concentration.
Example 1
Polyethylene (Mn ═ 6X 10)6) The basement membrane (thickness 14 microns, average pore diameter 0.05 μm, porosity 42%) is cleaned and dried, immersed in a sodium hypochlorite solution of 2500ppm for 0.5 hour, taken out, washed with clear water and air-dried at room temperature.
A 75ppm graphene oxide solution (sheet diameter 80 μm) was prepared, and the solvent was 70% ethanol aqueous solution containing 5ppm of metal lithium ions and 5ppm of polyvinylpyrrolidone (Mw 30000).
Fixing a polyethylene substrate, coating a graphene oxide solution under the pressure of 1MPa, transferring the polyethylene substrate to an oven for heat treatment, treating the polyethylene substrate at 80 ℃ for 10min, taking out the polyethylene substrate, and storing the polyethylene substrate at room temperature to obtain the polyethylene substrate composite nanofiltration membrane 1.
The performance test results show that the surface water contact angle is reduced to 62.6 degrees after chemical erosion; the pure water flux of the membrane 1 was 66.7LMH, the rejection for divalent salt was 92.2%, the rejection for monovalent salt was 17.3%, and the divalent salt separation ratio was 5.33; compared with a comparative example, the high-concentration oxidant can shorten the erosion time, meanwhile, the active sites are more, so that the graphene oxide lamella is combined more firmly, the retention rate is improved to a certain extent, and correspondingly, the flux is reduced by a small amount.
The ultrathin polyolefin film is used as the substrate, the symmetrical film structure is realized, the thickness is only about one tenth of that of the latter film, and the polyethylene substrate has great advantage in transmission capacity due to the lower transmission resistance; the polyethylene has high tensile strength, solvent resistance and ageing resistance, and has longer service life; the preparation process of the nanofiltration membrane has the advantages of novel method, strong functionality and strong selectivity of added ions, can adjust the filtration level according to requirements, and has wide prospect in future industrial application.
Example 2
The metal lithium ion was replaced with aluminum ion, and the content of polyvinylpyrrolidone (Mw 8000) was 2.5ppm, under the same conditions as in example 1. And then the polyethylene substrate composite nanofiltration membrane 2 is obtained.
Performance tests showed a pure water flux of 68.8LMH, a divalent salt cut-off of 93.6%, a monovalent salt cut-off of 18.6%, and a divalent salt separation ratio of 5.03; after monovalent metal ions are converted into divalent metal ions, more empty tracks can be coupled with active sites on graphene sheets and a substrate, so that the sheet spacing is further reduced, the rejection rate is improved, and the monovalent salt is improved relatively obviously.
Example 3
Replacing the polyethylene substrate with (Mn ═ 4.2X 10)6) Base film of (2), thickness 21 μm, averageThe aperture is 0.1 μm, the porosity is 38%, and the other conditions are the same as the example 2, so as to obtain the polyethylene-based composite nanofiltration membrane 3.
The test of example 3 was performed, after changing to the macroporous substrate, the chemically etched surface water contact angle was reduced to 58.4 °, the pure water flux was increased to 78.4LMH, the divalent salt rejection was 91.7%, the monovalent salt rejection was 15.2%, and the divalent salt separation ratio was 6.03; after the polyethylene substrate is replaced by the substrate with larger pore size, the flux is obviously improved by 14 percent compared with that of the example 2, and the interception is only slightly reduced, which shows that the substrate with larger pore size has very obvious effect on improving the flux.
Example 4
Polyethylene (Mn ═ 4.2X 10)6) The base film (thickness 21 μm, average pore diameter 0.1 μm, porosity 38%) was washed and air-dried, immersed in a sodium hypochlorite solution of 5000ppm for 0.25 hour, then taken out, rinsed with clear water and air-dried at room temperature.
A 50ppm graphene oxide solution (sheet diameter 80 μm) was prepared, and the solvent was a 90% ethanol aqueous solution containing 5ppm of metal zinc ions and 5ppm of polyvinylpyrrolidone (Mw: 5000).
The polyethylene substrate was fixed, coated with graphene oxide solution under 1MPa pressure, and then immersed in 0.5 wt.% aqueous polyvinyl alcohol solution with 0.1 wt.% glutaraldehyde content as a crosslinking agent. And taking out after 5min, transferring to an oven, carrying out heat treatment at 70 ℃ for 15min, taking out, and storing at room temperature to obtain the polyethylene-based composite nanofiltration membrane 4.
The test of example 4 showed that the pure water flux was increased to 81.5LMH, and the divalent salt retention was 91.3%, the monovalent salt retention was 15.6%, and the divalent salt separation ratio was 5.83; after polyvinyl alcohol crosslinking modification, the overall hydrophilicity of the membrane is improved, the flux is further improved, the interception is slightly reduced, and the separation ratio is still kept about 6.
Example 5
The content of zinc ions in example 4 was increased to 10ppm, and the content of polyvinylpyrrolidone (Mw: 5000) was increased to 10ppm, and the conditions were not changed to obtain a polyethylene-based composite nanofiltration membrane 5.
The performance test of example 5 showed a pure water flux of 84.7LMH, a divalent salt cut-off of 88.1%, a monovalent salt cut-off of 14.7%, and a divalent salt separation ratio of 5.99; at this time, it can be seen that multiple hydrogen bond coupling is formed between the sheet layers by increasing the metal ion content, so that the interlayer spacing is increased, the flux is increased, and the interception is reduced to 90%. Therefore, in order to ensure effective interception capability, the content of metal ions needs to be controlled to a certain level, and the metal ions are not required to be too high.
Comparative example 1
Polyethylene (Mn 3X 10)6) The basement membrane (thickness 20 microns, average pore diameter 0.07 μm, porosity 45%) is cleaned, dried, immersed in 200ppm sodium hypochlorite solution for 24 hours, and then taken out.
Preparing 50ppm of graphene oxide (with the plate diameter of 50 microns) dispersion liquid, wherein the solvent is absolute ethyl alcohol.
Fixing a polyethylene substrate, coating a graphene oxide solution under the assistance of 1MPa pressure, transferring the polyethylene substrate into an oven for heat treatment, treating the polyethylene substrate at 80 ℃ for 5min, taking out the polyethylene substrate, and drying and storing the polyethylene substrate at room temperature to obtain the composite nanofiltration membrane 0-1.
Comparative example 2
Polyethylene (Mn 3X 10)6) The basement membrane (thickness 20 microns, average pore diameter 0.07 μm, porosity 45%) is cleaned, dried, immersed in 500ppm sodium hypochlorite solution for 10 hours, and then taken out.
A 50ppm graphene oxide solution (sheet diameter 50 μm) was prepared in a 70% ethanol aqueous solution containing 5ppm of metal lithium ions and 5ppm of polyvinylpyrrolidone (Mw 30000).
Fixing a polyethylene substrate, coating a graphene oxide solution under the pressure of 1MPa, transferring the polyethylene substrate into an oven for heat treatment, treating the polyethylene substrate at 80 ℃ for 5min, taking out the polyethylene substrate, and storing the polyethylene substrate at room temperature to obtain the composite nanofiltration membrane 0-2.
TABLE 1 permeation and rejection performance of the modified reverse osmosis membranes of the examples.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, several modifications and decorations can be made without departing from the concept of the present invention, and these modifications and decorations should also be regarded as being within the protection scope of the present invention.
Claims (8)
1. The preparation method of the polyethylene-based composite graphene oxide nanofiltration membrane is characterized in that the pure water flux of the polyethylene-based composite graphene oxide nanofiltration membrane is 55-85L/m under 0.5MPa2h, the retention rate of divalent salt is more than 92%;
the preparation method of the polyethylene substrate composite graphene oxide nanofiltration membrane comprises the following specific steps:
(1) cleaning a polyethylene substrate by using isopropanol, drying, modifying in an oxidant, immersing for a fixed period of time, taking out, and airing at room temperature;
(2) preparing a graphene oxide solution, and adding metal ions and a dispersing agent;
(3) loading the graphene oxide solution on a modified polyethylene substrate under the pressure of 0.1Mpa, and then putting the modified polyethylene substrate into an oven for heat treatment;
(4) immersing the nascent nanofiltration membrane obtained in the step (3) into a polyvinyl alcohol solution containing a cross-linking agent, then putting the solution into an oven for thermal cross-linking to obtain a polyethylene-based composite graphene oxide nanofiltration membrane, and drying and storing the nanofiltration membrane;
in the step (2), the metal ions are potassium ions, lithium ions, zinc ions, calcium ions, magnesium ions, aluminum ions, manganese ions, iron ions, cobalt ions, copper ions and chromium ions.
2. The preparation method of the polyethylene substrate composite graphene oxide nanofiltration membrane as claimed in claim 1, wherein the polyethylene substrate membrane is immersed in an oxidant for erosion, then coated with graphene oxide micro-sheets under the assistance of pressure to form a salt-trapping layer, and finally coated with polyvinyl alcohol for crosslinking to obtain a hydrophilic and firm skin layer.
3. The method for preparing the polyethylene substrate composite graphene oxide nanofiltration membrane as claimed in claim 1, wherein in the step (1),
the average thickness of the polyethylene substrate is 9-20 micrometers; the average pore diameter is 0.05-0.1 micron.
4. The method for preparing a polyethylene substrate composite graphene oxide nanofiltration membrane according to claim 1, wherein in the step (1), the oxidant is one of hypochlorite, perchlorate, permanganate, trivalent cobalt salt, persulfate, sodium peroxide, peracetic acid, sodium percarbonate, sodium perborate, potassium dichromate, chromic acid, oleum, and nitric acid.
5. The preparation method of the polyethylene substrate composite graphene oxide nanofiltration membrane according to claim 1, wherein in the step (2), the sheet diameter of the graphene oxide is 5-50 microns.
6. The preparation method of the polyethylene-based composite graphene oxide nanofiltration membrane according to claim 1, wherein in the step (2), the dispersing agent is polyvinylpyrrolidone with a molecular weight of 5000-16000.
7. The preparation method of the polyethylene-based composite graphene oxide nanofiltration membrane according to claim 1, wherein in the step (4), the molecular weight of the polyvinyl alcohol is 84000-120000.
8. The preparation method of the polyethylene-based composite graphene oxide nanofiltration membrane according to claim 1, wherein in the step (4), the mass fraction of the polyvinyl alcohol in the polyvinyl alcohol solution is 0.5-10%;
the mass fraction of the cross-linking agent in the polyvinyl alcohol solution is 0.1-2%;
the cross-linking agent is one of glyoxal, glutaraldehyde, p-tolualdehyde, crotonaldehyde, maleic anhydride, glycidyl methacrylate, tris (hydroxymethyl) aminomethane oxalic acid, malonic acid, citric acid, boric acid, epichlorohydrin and a silane coupling agent;
the solvent is water;
the soaking time in the polyvinyl alcohol solution is 5-20 minutes, the heat treatment temperature is 50-80 ℃, and the soaking time is 1-20 min.
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