CN111841341B - Composite ultrafiltration membrane of amino acid-metal complex bonded graphene oxide and preparation method thereof - Google Patents

Composite ultrafiltration membrane of amino acid-metal complex bonded graphene oxide and preparation method thereof Download PDF

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CN111841341B
CN111841341B CN201911020685.5A CN201911020685A CN111841341B CN 111841341 B CN111841341 B CN 111841341B CN 201911020685 A CN201911020685 A CN 201911020685A CN 111841341 B CN111841341 B CN 111841341B
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graphene oxide
amino acid
ultrafiltration membrane
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CN111841341A (en
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王炳涛
舒婷
周福平
高德
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Ningbo Institute of Technology of ZJU
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
    • B01D71/02—Inorganic material
    • B01D71/022—Metals
    • 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
    • B01D61/14—Ultrafiltration; Microfiltration
    • B01D61/145—Ultrafiltration
    • 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
    • B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
    • B01D69/12—Composite membranes; Ultra-thin membranes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
    • B01D71/02—Inorganic material
    • B01D71/021—Carbon
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
    • B01D71/06—Organic material
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    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
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Abstract

The invention discloses a composite ultrafiltration membrane of amino acid-metal complex bonded graphene oxide and a preparation method thereof, and is characterized in that: the ultrafiltration membrane is prepared by chemically bonding amino acid and metal ions on the surface of graphene oxide, dispersing the formed graphene oxide-amino acid-metal ion complex in a high molecular solution, and then preparing the graphene oxide-amino acid-metal ion complex by a non-solvent phase conversion method. The method has the advantages of overcoming the defects of easy adhesion of organic pollutants to block membrane pores, low separation efficiency, difficult cleaning, low flux recovery rate and the like of the traditional polymer membrane material in the ultrafiltration separation process.

Description

Composite ultrafiltration membrane of amino acid-metal complex bonded graphene oxide and preparation method thereof
Technical Field
The invention belongs to the technical field of functional high-molecular-weight membrane materials, and particularly relates to a composite ultrafiltration membrane of amino acid-metal complex bonded graphene oxide and a preparation method thereof.
Background
The gradual shortage of fresh water resources seriously restricts the development of global economy and the improvement of the living standard of people. The recycling of domestic sewage and industrial wastewater can effectively relieve the water resource crisis. The membrane separation technology is favored by people because of energy conservation, high efficiency, simple operation and no chemical pollution, and becomes an important means for treating the urban domestic sewage. However, the traditional polymer membrane material has the hydrophobic property, so that membrane pollution is easy to occur in the sewage treatment process, and the problems of membrane pore blocking, water flux reduction, separation efficiency reduction, difficulty in cleaning and the like are caused, so that the application of the membrane separation technology is greatly limited.
The prior research proves that the introduction of a hydrophilic component into a membrane matrix and the improvement of the self-hydrophilic performance of the membrane material are important means for improving the anti-pollution performance of the membrane material. Graphene is a novel carbon nanomaterial consisting of a single layer of carbon atoms and having a lamellar structure, the thickness of the graphene is only 1nm, and the graphene has ultrahigh strength, large specific surface area and excellent gas-liquid separation performance. Graphene oxide GO is an important derivative of graphene, and the surface of the graphene oxide GO is rich in a large number of polar groups such as hydroxyl, carboxyl, epoxy and the like, so that the graphene oxide GO has good hydrophilic performance and can stably exist in an aqueous solution for a long time. Adding silver-loaded graphene oxide GO into a polyvinyl alcohol ultrafiltration membrane as reported in patent CN106582327A, a membrane separation material with excellent anti-pollution performance is obtained; however, the introduction effect of the single hydrophilic substance is not ideal, and the high flux and strong antifouling property are not ideal.
Disclosure of Invention
Aiming at the defects in the prior art, the invention provides the composite ultrafiltration membrane of the amino acid-metal complex bonded graphene oxide, which can overcome the defects that organic pollutants are easy to adhere to block membrane pores, the separation efficiency is low, the membrane is not easy to clean, the flux recovery rate is low and the like in the ultrafiltration separation process of the traditional polymer membrane material.
In order to achieve the purpose, the invention adopts the technical scheme that: the composite ultrafiltration membrane is prepared by chemically bonding amino acid and metal ions on the surface of graphene oxide, dispersing the formed graphene oxide-amino acid-metal ion complex in a high molecular solution, and then preparing the graphene oxide-amino acid-metal ion complex by a non-solvent phase conversion method.
The amino acid is one or more of lysine, arginine, serine and glutamic acid, and lysine is preferred.
The metal ion is Cu 2+ 、Mg 2+ 、Zn 2+ 、Ni 2+ Preferably Zn 2+ 。
The polymer of the present invention is preferably polysulfone PSf (polysulfone is a thermoplastic resin containing a chain unit in the main chain of the molecule).
The invention also provides a preparation method of the amino acid-metal complex bonded graphene oxide composite ultrafiltration membrane, which comprises the following steps:
(1) uniformly dispersing Graphene Oxide (GO) in an aqueous solution, adding A NHS (N-hydroxysuccinimide)/EDC (1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride) catalyst to activate A carboxyl functional group on the surface of GO, adding an amino acid, and reacting to generate amino acid surface modified graphene oxide GO-A;
(2) respectively dispersing the GO-A prepared in the step 1) and metal salts in water, then dropwise adding the metal salts (metal salt aqueous solution) into the GO-A aqueous dispersion to obtain A mixed reaction solution, after completely mixing, adding ethanol, violently stirring, centrifuging, filtering and drying to obtain graphene oxide-amino acid-metal ion complex GO-A-M;
(3) selecting A high molecular polymer as A membrane matrix, dissolving the membrane matrix in dimethylacetamide (DMAc), then adding GO-A-M and A pore-forming agent PVP-K30, performing ultrasonic dispersion and standing vacuum deaeration, then pouring the mixed solution on A glass plate, scraping the mixed solution into A liquid membrane with the thickness of 150 mu M, and then immersing the liquid membrane into A coagulating bath to be cured into A membrane, thus obtaining the ultrafiltration membrane.
In the invention, the graphene oxide aqueous solution in the step (1), the GO-A in the step (2) and the metal salt are respectively dispersed in water, and preferably ultrasonically dispersed.
The graphene oxide described in step (1) of the present invention: the mass ratio of the amino acids is 5: 1-1: 5, preferably 1: 1; the molar ratio of NHS/EDC in the NHS/EDC catalyst in the step (1) is 1:1, and the mass ratio of EDC to graphene oxide is 4: 1.
In the step (2), the mass ratio of GO-A to metal salt is 15: 1-5: 1, and 8:1 is preferred.
The metal ion of the metal salt in the step (2) of the invention is Cu 2+ 、Mg 2+ 、Zn 2+ 、Ni 2+ Preferably Zn 2+ 。
The adding amount of the ethanol in the step (2) is 1-10 mL, preferably 3 mL; the amount of ethanol added was in accordance with the ratio of the mixed reaction solution, and 30ml of the mixed reaction solution: 1-10 mL of ethanol; the specific amount of addition herein is not limited by unit, as long as the ethanol satisfies the above mixing ratio.
The addition amount of GO-A-M in the step (3) is 0.1-3% (mass percentage content), preferably 1%. GO-A-M is herein its content in the mixture of the final polymer, dimethylacetamide, GO-A-M and porogen PVP-K30.
The adding amount of the pore-foaming agent PVP-K30 in the step (3) is 1-5% by mass; the porogen here is its content in the final polymer, dimethylacetamide, GO-A-M and the porogen PVP-K30.
All materials of the coagulating bath in the step (3) of the invention are one or more of deionized water, ethanol and isobutanol, and preferably deionized water.
The invention has the advantages and beneficial effects that:
1. according to the invention, the amino acid-metal ion complex is adopted to modify the graphene oxide, the modification mode further improves the polar components on the surface of the graphene oxide, and endows the graphene oxide with better hydrophilic performance, the reaction condition is mild, the operation is simple and convenient, the graphene oxide can be uniformly dispersed in a polymer ultrafiltration membrane matrix through conventional solution blending, the agglomeration phenomenon is avoided, and the compatibility is good.
2. The ultrafiltration membrane containing graphene-amino acid prepared by the invention has large water flux (the highest pure water flux is 215 L.m) -2 ·h -1 ) The removal rate of organic pollutants is high (the highest retention rate of bovine serum albumin BSA can reach 95%), the cleaning is easy after pollution, the recovery rate of water flux is high (the lowest irreversible pollution proportion is 7.3%, the highest recovery rate of water flux can reach 94%), and the like. In addition, the ultrafiltration membrane still keeps higher membrane flux and pollution resistance after multiple tests, the preparation process of the ultrafiltration membrane is simple, the repeatability is good, and the large-scale production is easy to realize.
3. According to the invention, A specific catalyst is adopted to activate carboxyl functional groups on the surface of GO, and the catalyst enables the carboxyl on the surface of GO to become more active and easy to generate chemical reaction, so that amino acid surface modified graphene oxide GO-A is generated by the reaction, and the combination of the amino acid surface modified graphene oxide GO-A and the graphene oxide GO-A is more compact through the chemical reaction. The ethanol is added in the step (2) of the invention, so that the GO-amino acid-metal salt complex generated after the reaction can be completely dispersed in water, and the complex reaction is more sufficient.
4. In the prior art, amino acid is grafted on graphene oxide by an alkaline method, but the regularity of a carbon sheet layer of the graphene oxide is damaged under an alkaline condition, so that the use effect of the graphene oxide is influenced; in addition, the amino acid is not a chemical reaction but a physical reaction under the alkaline condition, and is combined together through the hydrogen bonding between the graphene oxide and the amino acid, the amino acid connected by the method is not firm and is easy to change along with the change of the pH value of the solution, and the connected amino acid is easy to fall off in the subsequent application process. The method is carried out under a neutral condition, and the amino acid is connected to the graphene oxide through a chemical reaction (carboxyl on the graphene oxide reacts with amine on the amino acid to form an amide chemical bond), so that the graphene oxide is firm and cannot fall off. In addition, metal ions are introduced on the basis of graphene oxide-amino acid, amino acid chemically grafted on the surface of graphene oxide and metal ions are subjected to a complex reaction to form an amino acid-metal ion complex, so that the graphene oxide-amino acid-metal ions are mutually fused on a molecular level and firmly exist without falling, and the simple physical mixing is not performed.
Drawings
FIG. 1 SEM and AFM images of the surface, cross-sectional profile of PSf ultrafiltration membrane and PSf/GO-Lys-Zn ultrafiltration membrane.
FIG. 2 is a graph comparing water flux and BSA retention for PSf ultrafiltration membranes and PSf/GO-Lys-Zn ultrafiltration membranes.
FIG. 3 is a graph comparing the water flux recovery rate and the reversible fouling rate of PSf ultrafiltration membranes and PSf/GO-Lys-Zn ultrafiltration membranes.
Detailed Description
The present invention will be described in further detail below by way of examples, but the present invention is not limited to only the following examples.
As mentioned in the invention
Example 1
Graphene oxide surface lysine-zinc ion functionalization: uniformly dispersing 50mg of graphene oxide GO in an aqueous solution by using ultrasound to prepare 1mg/mL GO dispersion liquid, then adding 0.25g of NHS/EDC catalyst, and stirring for 30min at 20 ℃. And then adding 50mg of lysine Lys, stirring for 24 hours at normal temperature, centrifuging, washing with water, and drying to obtain GO-Lys. Then ZnCl is put into 2 Slowly dripping the aqueous solution into GO-Lys water dispersion (the mass ratio of GO-Lys: ZnCl) 2 8:1) and adding after the solution is completely mixed3mL of ethanol, stirring for 3min, centrifuging, filtering and drying to obtain GO-Lys-Zn.
Preparation of PSf-based ultrafiltration membrane: uniformly ultrasonically dispersing GO-Lys-Zn with the mass percent concentration of 1% in DMAc solution of polysulfone PSf with the mass percent concentration of 19%, simultaneously adding 3% of PVP-K30 pore-forming agent, standing and defoaming for 8 hours after the mixture is completely dissolved, pouring the solution after standing on a glass plate, scraping a membrane with the thickness controlled at 150 mu m, and immediately immersing the glass plate into deionized water to prepare the ultrafiltration membrane containing graphene-amino acid. The pure water flux of the ultrafiltration membrane is 215 L.m -2 ·h -1 The retention rate of BSA is 95%, the irreversible contamination ratio is 7.3%, and the recovery rate of water flux is 94%. The methods and standards for detecting the water flux, the retention rate, the reversible pollution and the like are tested according to the GB/T32360-2015 ultrafiltration membrane test method.
Example 2
And (3) carrying out lysine-copper ion functionalization on the surface of graphene oxide: uniformly dispersing 50mg of graphene oxide GO in an aqueous solution by using ultrasound to prepare 1mg/mL GO dispersion liquid, then adding 0.25g of NHS/EDC catalyst, and stirring for 30min at 20 ℃. And then adding 50mg of lysine Lys, stirring for 24 hours at normal temperature, centrifuging, washing with water, and drying to obtain GO-Lys. Then adding CuCl 2 Slowly dripping the aqueous solution into GO-Lys water dispersion (the mass ratio of GO-Lys: CuCl) 2 1: 8), adding 3mL of ethanol after the solution is completely mixed, stirring for 3min, centrifuging, filtering and drying to obtain GO-Lys-Cu. Preparation of PSf-based ultrafiltration membrane: uniformly dispersing 1% GO-Lys-Cu in DMAc solution with the concentration of 19% polysulfone PSf by ultrasonic, simultaneously adding 3% PVP-K30 pore-forming agent, standing and defoaming for 8 hours after the mixture is completely dissolved, pouring the pouring liquid on a glass plate, scraping the film, controlling the thickness to be 150 mu m, and then immersing the glass plate into deionized water to prepare the ultrafiltration membrane containing graphene-amino acid. The pure water flux of the ultrafiltration membrane is 197 L.m -2 ·h -1 The retention rate of BSA is 91%, the irreversible contamination ratio is 14%, and the recovery rate of water flux is 90%.
Example 3
Carrying out serine-zinc ion functionalization on the surface of graphene oxide: 50mg in aqueous solution by sonicationGraphene oxide GO is uniformly dispersed to prepare 1mg/mL GO dispersion liquid, and then 0.5g of NHS/EDC catalyst is added and stirred for 30min at 20 ℃. And then adding 100mg of serine Ser, stirring for 24 hours at normal temperature, centrifuging, washing with water, and drying to obtain GO-Ser. Then ZnCl is put into 2 Slowly dripping the aqueous solution into GO-Ser water dispersion (the mass ratio of GO-Ser: ZnCl) 2 1: 5), adding 3mL of ethanol after the solution is completely mixed, stirring for 3min, centrifuging, filtering and drying to obtain GO-Ser-Zn. Preparation of PSf-based ultrafiltration membrane: uniformly dispersing 1% of GO-Ser-Zn in DMAc solution with the concentration of 19% of polysulfone PSf by ultrasonic waves, simultaneously adding 3% of PVP-K30 pore-forming agent, standing and defoaming for 8 hours after completely dissolving, pouring liquid on a glass plate, scraping a membrane, controlling the thickness to be 150 mu m, and then immersing the glass plate into deionized water to prepare the ultrafiltration membrane containing graphene-amino acid. The pure water flux of the ultrafiltration membrane is 173 L.m -2 ·h -1 The retention rate of BSA is 92%, the irreversible contamination ratio is 21%, and the recovery rate of water flux is 89%.
Example 4
Carrying out serine-magnesium ion functionalization on the surface of graphene oxide: uniformly dispersing 50mg of graphene oxide GO in an aqueous solution by ultrasound to prepare 1mg/mL GO dispersion liquid, then adding 0.5g of NHS/EDC catalyst, and stirring for 30min at 20 ℃. And then adding 100mg of serine Ser, stirring for 24 hours at normal temperature, centrifuging, washing with water, and drying to obtain GO-Ser. Then MgCl 2 Slowly dripping the aqueous solution into GO-Ser water dispersion (the mass ratio of GO-Ser to MgCl) 2 1: 8), adding 3mL of ethanol after the solution is completely mixed, stirring for 3min, centrifuging, filtering and drying to obtain GO-Ser-Mg. Preparation of PSf-based ultrafiltration membrane: uniformly dispersing 1% of GO-Ser-Mg in DMAc solution with the concentration of 19% of polysulfone PSf by ultrasonic waves, simultaneously adding 3% of PVP-K30 pore-forming agent, standing and defoaming for 8 hours after completely dissolving, pouring liquid on a glass plate, scraping a membrane, controlling the thickness to be 150 mu m, and then immersing the glass plate into deionized water to prepare the ultrafiltration membrane containing graphene-amino acid. The pure water flux of the ultrafiltration membrane is 204 L.m -2 ·h -1 The retention rate of BSA is 91%, the irreversible contamination ratio is 13%, and the recovery rate of water flux is 93%.
FIGS. 1-3 are graphs comparing the structural performance of the ultrafiltration membrane prepared in example 1 (PSf/GO-Lys-Zn ultrafiltration membrane) with that of a pure polymer ultrafiltration membrane (PSf ultrafiltration membrane). As can be seen from the attached figure 1, compared with a pure PSf ultrafiltration membrane, the surface pore density and the pore diameter of the ultrafiltration membrane prepared in the embodiment 1 are both obviously increased, which plays an important role in greatly improving the water flux of the ultrafiltration membrane; furthermore, the example 1 ultrafiltration membrane has longer and denser penetrating pores in the fingers of the sub-layer compared with the cross-sectional area of the membrane, which helps to reduce the flow resistance of the permeated water and increase the water flux of the membrane. The cross-sectional view of the ultrafiltration membrane of example 1 shows no agglomerated GO-Lys-Zn particles or lamellae, which is almost the same as the cross-sectional view of a pure PSf ultrafiltration membrane, indicating that the added GO-Lys-Zn has good compatibility with the PSf matrix. The AFM profile of the ultrafiltration membrane of example 1 also clearly shows that the surface roughness of the PSf/GO-Lys-Zn ultrafiltration membrane is not increased but rather decreased compared to the pure PSf ultrafiltration membrane, which indicates that GO-Lys-Zn is well fused with the PSf matrix.
FIG. 2 demonstrates that the ultrafiltration membrane prepared in example 1 of this patent exhibits a greatly improved retention of both water flux and BSA over pure polymer ultrafiltration membranes.
Fig. 3 shows that the ultrafiltration membrane prepared in the patent example 1 has excellent anti-pollution performance, and the water flux recovery rate is obviously improved compared with that of a pure polymer ultrafiltration membrane, wherein the irreversible pollution rate is greatly reduced, and the reversible pollution rate is greatly improved.

Claims (5)

1. The composite ultrafiltration membrane of amino acid-metal complex bonded graphene oxide is characterized in that: the ultrafiltration membrane is prepared by chemically bonding amino acid and metal ions on the surface of graphene oxide, dispersing a formed graphene oxide-amino acid-metal ion complex in a high molecular solution and then preparing the graphene oxide-amino acid-metal ion complex by a non-solvent phase inversion method, wherein the high molecular in the high molecular solution is polysulfone, the amino acid is one or more of lysine, arginine, serine and glutamic acid, and the metal ions are Cu 2+ 、Mg 2+ 、Zn 2+ 、Ni 2+ One or more of the above;
the preparation method of the composite ultrafiltration membrane of the amino acid-metal complex bonded graphene oxide comprises the following steps:
(1) uniformly dispersing Graphene Oxide (GO) in an aqueous solution, adding an NHS/EDC catalyst to activate carboxyl functional groups on the surface of GO, adding amino acid, and reacting to generate amino acid surface modified graphene oxide GO-A;
(2) respectively dispersing GO-A and metal salts prepared in the step (1) in water, then dropwise adding the metal salts into GO-A water dispersion to obtain mixed reaction liquid, after the metal salts are completely mixed, adding ethanol, violently stirring, centrifuging, filtering and drying to obtain graphene oxide-amino acid-metal ion complex GO-A-M;
(3) selecting A high molecular polymer as A membrane matrix, dissolving the membrane matrix in dimethylacetamide, then adding GO-A-M and A pore-forming agent PVP-K30, ultrasonically dispersing, standing, vacuum defoaming, then pouring the mixed solution on A glass plate, scraping into A liquid membrane with the thickness of 150 mu M, and then immersing into A coagulating bath to solidify into A membrane to obtain the ultrafiltration membrane.
2. The composite ultrafiltration membrane bonded with graphene oxide through an amino acid-metal complex compound according to claim 1, characterized in that: and (3) respectively dispersing the graphene oxide aqueous solution in the step (1), the GO-A and the metal salt in the step (2) in water by adopting ultrasonic dispersion.
3. The amino acid-metal complex bonded graphene oxide composite ultrafiltration membrane of claim 1, wherein: the graphene oxide in the step (1): the mass ratio of the amino acid is 5: 1-1: 5; the molar ratio of NHS/EDC in the NHS/EDC catalyst in the step (1) is 1:1, and the mass ratio of EDC to graphene oxide is 4: 1.
4. The amino acid-metal complex bonded graphene oxide composite ultrafiltration membrane of claim 1, wherein: the mass ratio of GO-A to metal salt in the step (2) is 15: 1-5: 1.
5. The amino acid-metal complex bonded graphene oxide composite ultrafiltration membrane of claim 1, wherein: the adding amount of the ethanol in the step (2) is 1-10 mL; the addition amount of GO-A-M in the step (3) is 0.1-3% by mass percentage; the adding amount of the pore-foaming agent PVP-K30 in the step (3) is 1-5% by mass; and (3) all materials of the coagulating bath in the step (3) are one or more of deionized water, ethanol and isobutanol.
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