CN113522047B - D-amino acid chemical grafting modified water treatment ultrafiltration membrane and preparation method thereof - Google Patents
D-amino acid chemical grafting modified water treatment ultrafiltration membrane and preparation method thereof Download PDFInfo
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- C02F1/44—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis
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Abstract
The invention discloses a D-amino acid chemical grafting modified water treatment ultrafiltration membrane and a preparation method thereof, wherein the preparation method mainly takes D-amino acid as functional molecules, takes a PAN ultrafiltration membrane as a base membrane, takes nitrile groups on the surface of the base membrane as reaction groups, and covalently grafts D-amino acid molecules on the surface of the membrane through reactions such as hydrolysis, activation, carboxylation and the like so as to construct an anti-pollution surface on the PAN ultrafiltration membrane. The preparation method disclosed by the invention is simple and efficient in process, the grafting amount of the D-amino acid can be regulated and controlled through the added concentration, and the modified functional layer is stable in structure and easy to realize industrial production. The obtained ultrafiltration membrane for water treatment has biological pollution resistance and organic pollution, can effectively control membrane pollution under the ultrafiltration operation condition, and realizes long-term stable operation of an ultrafiltration membrane separation technology in water treatment.
Description
Technical Field
The invention relates to the technical field of membranes, in particular to a D-amino acid chemical grafting modified water treatment ultrafiltration membrane and a preparation method thereof.
Background
In the face of the severe situation of global water resource shortage, the development and utilization of unconventional water resource have become a necessary issue. Due to the advantages of excellent pollutant retention capacity, operability at normal temperature and low pressure, stable effluent quality and the like, the ultrafiltration membrane separation technology plays an increasingly important role in the utilization process of unconventional water resources in recent years. However, membrane pollution is always a bottleneck for restricting the popularization and application of the technology, wherein biological pollution is a key factor for causing irreversible pollution of the ultrafiltration membrane and is most difficult to control.
The essence of membrane biological pollution is that microorganisms in inlet water adhere and aggregate on the surface of a membrane to form a biological membrane, and biological colonies consisting of the microorganisms and extracellular polymers secreted by the microorganisms block membrane pores, so that the permeability of the membrane is reduced. At present, the modification of the water treatment membrane for resisting biological pollution mainly reduces the deposition and the attachment of organic matters on the surface of the membrane by improving the hydrophilicity of the water treatment membrane, thereby reducing the growth speed of microorganisms on the surface of the membrane. However, microorganisms adhered to the surface of the membrane generally have strong biological activity, can rapidly reproduce and form a biological membrane by utilizing nutrients in water, and are difficult to control effectively.
The D-amino acid biological signal molecules can inhibit the adhesion of microorganisms on the surface of a carrier by regulating and controlling the expression of bacterial cells, and promote the dispersion and depolymerization of a mature biological membrane, thereby fundamentally solving the biological pollution of the membrane. Various water treatment materials (such as polyether sulfone, polyvinylidene fluoride, polyamide and the like) show excellent biological pollution resistance after being modified by D-amino acid.
At present, the functional modification modes of the membrane by using the D-amino acid mainly comprise a physical coating method, a physical adsorption method, a blending method and the like. These methods usually require the introduction of linkers having functional groups (such as polydopamine, polyvinyl alcohol, chitosan, etc.) during the modification process to provide reactive sites for binding with D-amino acids; or blending D-amino acid with the nano particles, and modifying the D-amino acid to the surface of the membrane by an immersion precipitation method. However, the functional layer of the modified membrane prepared by the method is mainly combined with the base membrane by electrostatic adsorption or hydrogen bond action, and is easy to fall off under the shearing force of water in the water treatment process, so that the stability is poor; in addition, the preparation process of the modified membrane also has the problems of low grafting ratio of D-amino acid, easy blockage of membrane pores by introduced linking agents and the like, and the severe phenomenon affects the separation performance of the membrane. Therefore, a simple, efficient and controllable membrane modification method is not available at present to solve the problems of unstable functional layer and reduced separation performance of the existing D-amino acid modified membrane.
The information disclosed in this background section is only for enhancement of understanding of the general background of the invention and is not to be taken as an acknowledgement or any form of suggestion that this information forms the prior art already known to a person skilled in the art.
Disclosure of Invention
The invention aims to overcome the defects in the prior art and provides a D-amino acid chemical grafting modified water treatment ultrafiltration membrane and a preparation method thereof. The method has the advantages of simple and efficient process, controllable D-amino acid grafting amount, stable structure of the modified functional layer and easy realization of industrial production. The obtained ultrafiltration membrane for water treatment has biological pollution resistance and organic pollution, can effectively control membrane pollution under the ultrafiltration operation condition, and realizes long-term stable operation of the ultrafiltration membrane separation technology in water treatment.
The invention adopts the following specific technical scheme:
in a first aspect, the invention provides a preparation method of a D-amino acid chemical grafting modified water treatment ultrafiltration membrane, which comprises the following specific steps:
s1: soaking a polyacrylonitrile ultrafiltration membrane serving as a base membrane in a strong alkaline solution for hydrolysis reaction to convert nitrile groups on the surface of the base membrane into carboxyl groups; then washing the residual alkali liquor on the surface of the membrane to obtain a hydrolyzed base membrane;
s2: taking a mixture solution containing N-hydroxysuccinimide and carbodiimide hydrochloride as an activating agent, and carrying out an activating reaction on carboxyl on the surface of the hydrolyzed base film at room temperature; subsequently, washing the residual activating agent on the surface of the membrane to obtain an activated base membrane;
s3: immersing the activated base membrane into a D-amino acid solution to perform amidation reaction between activated carboxyl on the membrane surface and amino of D-amino acid, and covalently grafting the D-amino acid on the surface of the activated base membrane; and washing and drying the obtained product to obtain the D-amino acid chemical grafting modified water treatment ultrafiltration membrane.
Preferably, the polyacrylonitrile ultrafiltration membrane has the molecular weight cut-off of 50kDa to 100kDa.
Preferably, the strong alkali solution is a KOH solution or a NaOH solution with the concentration of 0.1-10 mol/L.
Preferably, the hydrolysis reaction is carried out for 0.5 to 20 hours at a temperature of 10 to 300 ℃.
Preferably, the mixture solution is obtained by dissolving N-hydroxysuccinimide and carbodiimide hydrochloride in a 2-mercaptoethanesulfonic acid buffer solution.
Further, the pH value of the 2-mercaptoethanesulfonic acid buffer solution is 4.0-9.0.
Further, in the mixture solution, the concentration ratio of N-hydroxysuccinimide to carbodiimide hydrochloride is 1 to 2 to 1, wherein the concentration of N-hydroxysuccinimide is 10 to 200mmol/L, and the concentration of carbodiimide hydrochloride is 10 to 500mmol/L.
Preferably, the D-amino acid is D-tyrosine with the concentration of 5-5000 mu mol/L.
Preferably, the amidation reaction time is 2-24 h, and the pH during the reaction is 5-10.
In a second aspect, the invention provides a D-amino acid chemical grafting modified water treatment ultrafiltration membrane obtained by the preparation method of any one of the first aspect.
Compared with the prior art, the invention has the following beneficial effects:
(1) The preparation method provided by the invention adopts the nitrile group hydrolysis reaction and the amidation reaction with controllable processes, has simple and controllable process, and is easy to realize industrial production.
(2) The D-amino acid chemical grafting modified water treatment ultrafiltration membrane prepared by the invention has the advantages that the modified functional layer is chemically bonded with the base membrane, the structure is stable, and the D-amino acid chemical grafting modified water treatment ultrafiltration membrane is not easy to fall off in the water treatment process.
(3) The D-amino acid chemical grafting modified water treatment ultrafiltration membrane prepared by the invention has obviously improved biological pollution resistance, organic pollution resistance and hydrophilic performance, and is beneficial to long-term stability in the water treatment process.
Drawings
FIG. 1 is a molecular structural formula of D-tyrosine;
FIG. 2 is a flow chart of the preparation of the D-amino acid chemical grafting modified water treatment ultrafiltration membrane.
Detailed Description
The invention will be further elucidated and described with reference to the drawings and the detailed description. The technical features of the embodiments of the present invention can be combined correspondingly without mutual conflict.
As shown in figure 2, the invention provides a preparation method of a D-amino acid chemical grafting modified water treatment ultrafiltration membrane, which mainly takes D-amino acid as functional molecules, takes a PAN ultrafiltration membrane as a base membrane, takes nitrile groups on the surface of the base membrane as reaction groups, and covalently grafts D-amino acid molecules on the surface of the membrane through reactions such as hydrolysis, activation, carboxylation and the like so as to construct an anti-pollution surface on the PAN ultrafiltration membrane. The method comprises the following specific steps:
s1: a Polyacrylonitrile (PAN) ultrafiltration membrane is used as a base membrane, and the surface of the base membrane of the material contains a large number of nitrile groups (-CN), so that chemical grafting modification is easy to perform. Soaking the base film in strong alkali solution of certain concentration for hydrolysis to convert the nitrile group in the surface of the base film into carboxyl group. And then washing the residual alkali liquor on the surface of the membrane to obtain the hydrolyzed membrane.
In the step, the cut-off molecular weight of the polyacrylonitrile ultrafiltration membrane can be 50kDa to 100kDa; the strong alkali solution can be KOH solution or NaOH solution with the concentration of 0.1-10 mol/L; the time of the hydrolysis reaction can be 0.5-20 h, and the temperature can be 10-300 ℃.
S2: the carboxyl groups on the surface of the hydrolyzed base film obtained by the step S1 are subjected to an activation reaction at room temperature using a mixture solution containing N-hydroxysuccinimide (NHS) and carbodiimide hydrochloride (EDC) as an activating agent. And then washing the residual activating agent on the surface of the membrane to obtain an activated base membrane. Wherein the mixture solution is obtained by dissolving N-hydroxysuccinimide and carbodiimide hydrochloride in 2-mercaptoethane sulfonic acid (MES) buffer solution.
In this step, the pH of the 2-mercaptoethanesulfonic acid buffer solution may be 4.0 to 9.0; the concentration ratio of the N-hydroxysuccinimide to the carbodiimide hydrochloride can be 1 to 2, to 5, wherein the concentration of the N-hydroxysuccinimide can be 10 to 200mmol/L, and the concentration of the carbodiimide hydrochloride can be 10 to 500mmol/L;
s3: and (3) immersing the activated base membrane prepared in the step (S2) into a D-amino acid solution, taking the activated carboxyl as a reaction site, carrying out amidation reaction between the activated carboxyl on the surface of the membrane and the amino of the D-amino acid so as to covalently graft the D-amino acid on the surface of the activated base membrane, washing and drying to obtain the D-amino acid chemical grafting modified water treatment ultrafiltration membrane.
Wherein, the time of the amidation reaction can be 2 to 24 hours, and the pH value in the reaction process is controlled between 5 and 10.
In this step, D-tyrosine can be used at a concentration of 5 to 5000. Mu. Mol/L, and the amount of grafting can be controlled by the concentration of D-tyrosine. The molecular structure of D-tyrosine is shown in figure 1, because the R group of D-tyrosine contains phenolic hydroxyl group, can participate in hydrogen bond formation, has strong hydrophilicity, and the inhibition of D-tyrosine on biomembrane formation and the promotion effect of biomembrane disintegration are most obvious in known D-amino acid signal molecules, D-tyrosine is preferably adopted as D-amino acid.
Example 1
The embodiment prepares a D-amino acid chemical grafting modified water treatment ultrafiltration membrane, and the preparation steps are as follows:
s1: and soaking the PAN ultrafiltration membrane in 2.5mol/L NaOH solution, and hydrolyzing for 2h at the temperature of 65 ℃ to convert nitrile groups on the surface of the base membrane into carboxyl groups. And after the hydrolysis is finished, washing the membrane to remove the residual alkali liquor on the surface of the membrane to obtain the hydrolyzed base membrane.
S2: the obtained hydrolyzed membrane was immersed in MES buffer solution (50mM, pH 8.0) containing 25mM NHS and 50mM EDC, activated at room temperature for 2 hours, and then washed three times with ultrapure water to remove unreacted reagents on the membrane surface, to obtain an activated membrane.
S3: and soaking the obtained activated base membrane in 300 mu mol/L D-tyrosine solution, reacting for 6 hours at room temperature, washing the reacted membrane with deionized water for 3 times to remove adsorbed amino acid, and drying to obtain the D-amino acid chemical grafting modified water treatment ultrafiltration membrane.
The obtained D-amino acid chemically grafted and modified water treatment ultrafiltration membrane is compared with a commercial PAN ultrafiltration membrane to test the hydrophilic performance and the anti-pollution performance. The method comprises the following specific steps: measuring the water contact angle of the surface of the film by using a contact angle measuring instrument; and (3) taking sludge mixed liquor (the sludge concentration is 4000-5000 mg/L) of an aerobic tank of a sewage treatment plant as feed liquor, and determining the anti-pollution performance of the membrane by adopting the cross-flow MBR. The measurement results are shown in table 1, compared with the commercial PAN ultrafiltration membrane, the hydrophilicity of the D-amino acid chemical grafting modified water treatment ultrafiltration membrane is improved by 16%, the biological pollution resistance is improved by 54%, and the organic pollution resistance is improved by 58%.
Example 2
The embodiment prepares a D-amino acid chemical grafting modified water treatment ultrafiltration membrane, and the preparation steps are as follows:
s1: and soaking the PAN ultrafiltration membrane in 2mol/L KOH solution, and hydrolyzing for 1.5h at the temperature of 70 ℃ to convert nitrile groups on the surface of the base membrane into carboxyl groups. And after the hydrolysis is finished, washing the membrane to remove the residual alkali liquor on the surface of the membrane to obtain the hydrolyzed base membrane.
S2: the obtained hydrolyzed membrane was immersed in MES buffer solution (50mM, pH 8.0) containing 25mM NHS and 50mM EDC, activated at room temperature for 2 hours, and then rinsed three times with ultrapure water to remove unreacted reagents on the membrane surface, to obtain an activated membrane.
S3: and soaking the obtained activated base membrane in 300 mu mol/L D-tyrosine solution, reacting for 6h at room temperature, washing the reacted membrane with deionized water for 3 times to remove adsorbed amino acid, and drying to obtain the D-amino acid chemical grafting modified water treatment ultrafiltration membrane.
The obtained D-amino acid chemical grafting modified water treatment ultrafiltration membrane is compared with a commercial PAN ultrafiltration membrane to test the hydrophilic performance and the anti-pollution performance, the testing method is the same as the embodiment, and the details are not repeated. The measurement results are shown in table 1, compared with the commercial PAN ultrafiltration membrane, the hydrophilicity of the D-amino acid chemical grafting modified water treatment ultrafiltration membrane is improved by 16%, the biological pollution resistance is improved by 52%, and the organic pollution resistance is improved by 54%.
Example 3
The embodiment prepares a D-amino acid chemical grafting modified water treatment ultrafiltration membrane, and the specific preparation steps are as follows:
s1: and soaking the PAN ultrafiltration membrane in 2.5mol/L NaOH solution, and hydrolyzing for 2h at the temperature of 65 ℃ to convert nitrile groups on the surface of the base membrane into carboxyl groups. And after the hydrolysis is finished, washing the membrane to remove the residual alkali liquor on the surface of the membrane to obtain the hydrolyzed base membrane.
S2: the obtained hydrolyzed membrane was immersed in MES buffer solution (50mM, pH 8.0) containing 25mM NHS and 50mM EDC, activated at room temperature for 2 hours, and then rinsed three times with ultrapure water to remove unreacted reagents on the membrane surface, to obtain an activated membrane.
S3: and soaking the obtained activated base membrane in 200 mu mol/L D-tyrosine solution, reacting for 8h at room temperature, washing the reacted membrane with deionized water for 3 times to remove adsorbed amino acid, and drying to obtain the D-amino acid chemical grafting modified water treatment ultrafiltration membrane.
The obtained D-amino acid chemically grafted and modified water treatment ultrafiltration membrane and a commercial PAN ultrafiltration membrane are compared to test the hydrophilic performance and the anti-pollution performance, the test method is the same as the embodiment, and the description is omitted. The measurement results are shown in table 1, compared with the commercial PAN ultrafiltration membrane, the hydrophilicity of the D-amino acid chemical grafting modified water treatment ultrafiltration membrane is improved by 15%, the biological pollution resistance is improved by 35%, and the organic pollution resistance is improved by 30%.
Example 4
The embodiment prepares a D-amino acid chemical grafting modified water treatment ultrafiltration membrane, and the specific preparation steps are as follows:
s1: and soaking the PAN ultrafiltration membrane in 2.5mol/L NaOH solution, and hydrolyzing for 2h at the temperature of 65 ℃ to convert nitrile groups on the surface of the base membrane into carboxyl groups. And after the hydrolysis is finished, washing the membrane to remove the residual alkali liquor on the surface of the membrane to obtain the hydrolyzed base membrane.
S2: the obtained hydrolyzed membrane was immersed in MES buffer solution (50mM, pH 8.0) containing 25mM NHS and 50mM EDC, activated at room temperature for 2 hours, and then rinsed three times with ultrapure water to remove unreacted reagents on the membrane surface, to obtain an activated membrane.
S3: and soaking the obtained activated base membrane in 500 mu mol/L D-tyrosine solution, reacting for 3 hours at room temperature, washing the reacted membrane with deionized water for 3 times to remove adsorbed amino acid, and drying to obtain the D-amino acid chemical grafting modified water treatment ultrafiltration membrane.
The obtained D-amino acid chemical grafting modified water treatment ultrafiltration membrane is compared with a commercial PAN ultrafiltration membrane to test the hydrophilic performance and the anti-pollution performance, the testing method is the same as the embodiment, and the details are not repeated. The measurement results are shown in table 1, compared with the commercial PAN ultrafiltration membrane, the hydrophilicity of the D-amino acid chemical grafting modified water treatment ultrafiltration membrane is improved by 18%, the biological pollution resistance is improved by 37%, and the organic pollution resistance is improved by 34%.
TABLE 1 comparison of the Performance of the modified membranes obtained in the examples with commercial PAN Ultrafiltration membranes (comparative example)
Therefore, the preparation method has simple and efficient process, the grafting amount of the D-amino acid can be regulated and controlled by the added concentration, the modified functional layer has stable structure, and the industrial production is easy to realize. The obtained ultrafiltration membrane for water treatment has biological pollution resistance and organic pollution, can effectively control membrane pollution under the ultrafiltration operation condition, and realizes long-term stable operation of an ultrafiltration membrane separation technology in water treatment.
The above-described embodiments are merely preferred embodiments of the present invention, and are not intended to limit the present invention. Various changes and modifications may be made by one of ordinary skill in the pertinent art without departing from the spirit and scope of the present invention. Therefore, the technical scheme obtained by adopting the mode of equivalent replacement or equivalent transformation is within the protection scope of the invention.
Claims (5)
1. A preparation method of a D-amino acid chemical grafting modified water treatment ultrafiltration membrane is characterized by comprising the following steps:
s1: soaking a polyacrylonitrile ultrafiltration membrane serving as a base membrane in a strong alkaline solution for hydrolysis reaction to convert nitrile groups on the surface of the base membrane into carboxyl groups; then washing the residual alkali liquor on the surface of the membrane to obtain a hydrolyzed base membrane;
s2: taking a mixture solution containing N-hydroxysuccinimide and carbodiimide hydrochloride as an activating agent, and carrying out an activating reaction on carboxyl on the surface of the hydrolyzed base film at room temperature; subsequently, washing the residual activating agent on the surface of the membrane to obtain an activated base membrane;
s3: immersing the activated base membrane into a D-amino acid solution to ensure that amidation reaction occurs between activated carboxyl on the surface of the membrane and amino of D-amino acid, wherein the amidation reaction time is 2-24 h, the pH value in the reaction process is 5-10, and the D-amino acid is covalently grafted on the surface of the activated base membrane; then washing and drying the obtained product to obtain a D-amino acid chemical grafting modified water treatment ultrafiltration membrane;
in the mixture solution, the concentration ratio of N-hydroxysuccinimide to carbodiimide hydrochloride is 1; the mixture solution is obtained by dissolving N-hydroxysuccinimide and carbodiimide hydrochloride in 2-mercaptoethane sulfonic acid buffer solution, and the pH value of the 2-mercaptoethane sulfonic acid buffer solution is 4.0-9.0;
the D-amino acid is D-tyrosine with the concentration of 5-5000 mu mol/L.
2. The preparation method of the D-amino acid chemical grafting modified water treatment ultrafiltration membrane according to claim 1, wherein the molecular weight cut-off of the polyacrylonitrile ultrafiltration membrane is 50kDa to 100kDa.
3. The preparation method of the D-amino acid chemical grafting modified water treatment ultrafiltration membrane according to claim 1, wherein the strong alkaline solution is a KOH solution or a NaOH solution with the concentration of 0.1-10 mol/L.
4. The preparation method of the D-amino acid chemical grafting modified water treatment ultrafiltration membrane according to claim 1, characterized in that the hydrolysis reaction time is 0.5-20 h, and the temperature is 10-300 ℃.
5. A D-amino acid chemical grafting modified water treatment ultrafiltration membrane obtained by the preparation method of any one of claims 1 to 4.
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