CN109433023B - Graphene oxide nanofiltration membrane with graphite-like carbon nitride intercalation, and preparation method and application thereof - Google Patents
Graphene oxide nanofiltration membrane with graphite-like carbon nitride intercalation, and preparation method and application thereof Download PDFInfo
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- Y02A20/124—Water desalination
- Y02A20/131—Reverse-osmosis
Abstract
The invention discloses a graphene oxide nanofiltration membrane with a graphite-like carbon nitride intercalation layer, and a preparation method and application thereof, wherein the preparation method of the graphene oxide nanofiltration membrane with the graphite-like carbon nitride intercalation layer comprises the following steps: preparing graphene oxide into a graphene oxide dispersion liquid; preparing graphite-like carbon nitride into uniformly dispersed carbon nitride dispersion liquid; adding ascorbic acid into the graphene oxide aqueous dispersion liquid and continuously stirring to obtain a partially reduced graphene oxide dispersion liquid; mixing the carbon nitride dispersion liquid and the partially reduced graphene oxide dispersion liquid, and performing ultrasonic treatment to obtain a uniformly mixed casting solution; and performing vacuum filtration on the uniformly mixed membrane casting solution on the organic filter membrane subjected to dopamine pretreatment to form a membrane by adopting a vacuum filtration mode, and drying to obtain the carbon nitride intercalated graphene oxide nanofiltration membrane, wherein the carbon nitride intercalated graphene oxide nanofiltration membrane can realize higher water flux and has higher interception on salt ions. The preparation method is simple in preparation process and mild in condition, and can be used for industrial desalination.
Description
Technical Field
The invention belongs to the technical field of membrane separation, and particularly relates to a preparation method of a graphene oxide nanofiltration membrane similar to a graphite carbon nitride intercalation, which is applied to removal of salt ions.
Background
The ever-increasing demand for drinking water, as well as for irrigation water, is one of the most significant challenges of this century. Seawater desalination is an effective solution to solve the problem, and research on seawater desalination in membrane separation technology is becoming more and more hot, wherein nanofiltration is a pressure-driven membrane separation process between ultrafiltration and reverse osmosis. The surface of the membrane is charged, and has certain desalting capacity under the combined action of sieving effect and charge effect. The nanofiltration technology has the characteristics of low energy consumption, low investment, low maintenance cost, easy operation, high reliability and high flux, is widely applied to a plurality of fields of chemical industry, environmental protection, food, medicine, ocean, metallurgy and the like, and mainly focuses on two fields of drinking water production and wastewater treatment. The nanofiltration technology can be used for treating underground water and surface water, and can also be used for pretreatment in the desalination industry. The introduction of nanofiltration processes is also considered to be a major technological breakthrough in the desalination industry.
The key factors determining the membrane performance are the preparation of the membrane material and the microstructure of the membrane, the polymeric nanofiltration membrane has considerable separation performance and is widely applied due to easy manufacture and relatively low cost, but the traditional polymer membrane at present has some non-negligible defects, such as poor chemical and thermal properties, easy pollution, physical aging and the like. The application of the novel nano material in the aspect of membrane separation has great potential in the aspects of changing the structure of a membrane material and optimizing the performance of the membrane. Graphene Oxide (GO) has many natural characteristics that make it a very potential separation membrane starting material, and the integrity of pure graphene oxide membrane is maintained only by the hydrogen bonding between oxygen-containing functional groups of nanosheets, so pure GO membrane has low structural and physicochemical stability. The graphene oxide membrane can be improved in stability in water by performing moderate partial reduction modification on the graphene oxide, but the reduced graphene oxide nanofiltration membrane has lower permeation flux. Substances with different sizes are inserted between the graphene oxide layers, so that different separation purposes can be achieved, and meanwhile, the permeation flux can be improved.
Disclosure of Invention
The invention aims to provide a graphene oxide nanofiltration membrane with a graphite-like carbon nitride intercalation layer and a preparation method thereof.
The graphene oxide nanofiltration membrane with the graphite-like carbon nitride intercalation is prepared by the following steps:
(1) dipping the organic filter membrane in a dopamine Tris buffer solution, and slowly oscillating and polymerizing for 12-30h at 25-30 ℃ to ensure that dopamine is self-polymerized on the membrane surface to form the organic filter membrane with a Polydopamine (PDA) layer; the concentration of the dopamine Tris buffer solution is 0.5-4g/L, and the pH value is 8.0-8.5;
(2) adding graphene oxide into deionized water, and performing ultrasonic dispersion to obtain a uniform graphene oxide dispersion liquid; the concentration of the graphene oxide dispersion liquid is 0.02-0.5 g/L;
(3) adding graphite-like carbon nitride into deionized water, and performing ultrasonic dispersion to obtain a uniform graphite-like carbon nitride dispersion liquid; the concentration of the graphite-like carbon nitride dispersion liquid is 0.01-1 g/L;
(4) adding an ascorbic acid solution with the concentration of 0.1-2g/L into the graphene oxide dispersion liquid obtained in the step (2), carrying out reduction reaction for 0.5-8h under the stirring condition, and then carrying out ultrasonic treatment for 0.5-2h to obtain a partially reduced graphene oxide dispersion liquid; the volume ratio of the ascorbic acid solution to the graphene oxide dispersion liquid is 1-5: 1;
(5) adding the graphite-like carbon nitride dispersion liquid obtained in the step (3) into the partially reduced graphene oxide dispersion liquid obtained in the step (4), stirring for 1-10h, and performing ultrasonic treatment for 0.2-2h to uniformly mix the graphite-like carbon nitride dispersion liquid and the partially reduced graphene oxide dispersion liquid to obtain a mixed liquid; the addition amount of the obtained graphite-like carbon nitride dispersion liquid is calculated by the mass of the graphite-like carbon nitride, and the addition amount of the partially reduced graphene oxide dispersion liquid is calculated by the mass of the graphene oxide; the mass ratio of the graphene oxide to the graphite-like carbon nitride is 2-10: 1;
(6) and (2) taking the organic filter membrane of the Polydopamine (PDA) layer obtained in the step (1) as a bottom membrane, carrying out vacuum filtration on the mixed solution obtained in the step (5) on the bottom membrane, and drying the membrane subjected to vacuum filtration at 50-80 ℃ for 5-60min to obtain the carbon nitride intercalated graphene oxide nanofiltration membrane.
Further, in the step (1), the organic filter membrane is an ultrafiltration membrane or a microfiltration membrane.
Furthermore, in the step (1), the material of the organic filter membrane is polysulfone, polyacrylonitrile, nylon, polyvinylidene fluoride, mixed cellulose ester or cellulose acetate.
Further, in the step (1), the concentration of the Tris buffer solution is preferably 2g/L, and the pH is preferably 8.5.
Further, in the step (1), the polymerization time is preferably 20 to 24 hours.
Further, in the step (2), the concentration of the graphene oxide dispersion liquid is preferably 0.1 to 0.25 g/L.
Further, in the step (3), the concentration of the graphite-like carbon nitride dispersion is preferably 0.1 to 0.5 g/L.
Further, in the step (4), the reduction time is preferably 1 to 2.5 hours.
Further, in the step (6), the organic filter membrane of the Polydopamine (PDA) layer prepared in the step (1) is slowly washed by deionized water before the mixed solution is subjected to suction filtration.
Still further, in the step (6), the drying temperature is preferably 60 ℃, and the drying time is preferably 10-30 min.
The graphene oxide and the carbon nitride nanosheets described in the method of the present invention are bonded together by electrostatic interaction, such that carbon nitride can be intercalated between the graphene oxide layers.
The carbon nitride intercalated graphene oxide nanofiltration membrane prepared by the method is used for filtering and removing salt ions.
Compared with the prior art, the invention has the beneficial effects that:
the method is simple to operate, does not need harsh conditions, and has mild conditions; the method comprises the following steps of pretreating an organic filter membrane basement membrane by using dopamine, so that the hydrophilicity of the organic filter membrane and the binding force between the organic filter membrane and graphene oxide are enhanced; the ascorbic acid is utilized to partially reduce the graphene oxide, so that the environment is protected, the reduced graphene oxide can still keep stable dispersion, and the stability of the reduced graphene oxide in a water environment is improved; the distance between graphene oxide sheet layers is regulated and controlled by utilizing the intercalation of the two-dimensional graphite carbon nitride nanosheets, so that the membrane flux is greatly improved, the effective interception of salt ions is further realized, and meanwhile, the permeation flux of the graphene oxide nanofiltration membrane is improved, and the method can be widely applied to the field of industrial desalination.
Drawings
FIG. 1 is a scanning electron micrograph of the surface and cross section of the film of example 1;
FIG. 2 is an EDS line scan of a membrane section of example 1;
fig. 3 is XPS survey spectra of example 2 and comparative example 1.
Detailed Description
The present invention will be described in further detail with reference to the following examples, but the present invention is not limited to the following examples.
Example 1
(1) Adopting an organic filter membrane as a polysulfone ultrafiltration membrane, adding 0.121g of Tris (trihydroxymethyl aminomethane) into 100ml of deionized water, adjusting the pH to 8.5, then adding 0.2g of levodopa to prepare a dopamine Tris buffer solution with the concentration of 2g/L, placing the polysulfone membrane into the dopamine buffer solution, shaking and oscillating for 24 hours at 30 ℃ to ensure that dopamine is self-polymerized on the surface of the polysulfone membrane to form a polydopamine layer, and washing with the deionized water for several times after the reaction is finished;
(2) dispersing 0.005g of graphite-like carbon nitride into 50ml of deionized water, stirring for 2h, and performing ultrasonic treatment for 2h to prepare carbon nitride dispersion liquid with the concentration of 0.1 g/L;
(3) dispersing 0.005g of graphene oxide into 50ml of deionized water, performing ultrasonic dispersion for 2h to prepare a graphene oxide dispersion liquid with the concentration of 0.1g/L, then adding 40ml of 0.5g/L ascorbic acid solution, stirring for 2h, performing ultrasonic treatment for 0.5h to prepare a partially reduced graphene oxide solution, then taking 3ml of the obtained partially reduced graphene oxide solution, adding 0.75ml of the prepared carbon nitride dispersion liquid according to the mass ratio of the graphene oxide to the carbon nitride of 4:1, stirring for 2h, performing ultrasonic treatment for 0.5h to uniformly mix the solution, casting the uniformly mixed membrane solution on a polysulfone ultrafiltration membrane treated by dopamine to prepare a membrane by adopting a vacuum filtration manner, and drying the obtained membrane in an oven at 60 ℃ for 10min to obtain the graphene oxide nanofiltration membrane of the carbon nitride.
Respectively using 1000ppm of Na at 25 ℃ and 0.3MPa2SO4、NaCl、MgSO4And MgCl2The water flux and salt rejection of the membrane material were determined. The water flux of the nanofiltration membrane is measured to be 17.45L m-2h-1bar-1To Na2SO4、NaCl、MgSO4And MgCl2The retention rate is 70.83%, 23.40%, 23.25% and 10.45% in sequence.
Example 2
(1) An organic filter membrane is adopted as a polysulfone ultrafiltration membrane, 0.121g of Tris (trihydroxymethyl aminomethane) is added into 100ml of deionized water, the pH value is adjusted to 8.5, then 0.2g of levodopa is added to prepare 2g/L dopamine Tris buffer solution, the polysulfone membrane is placed into the dopamine buffer solution, shaking and shaking are carried out for 24 hours at the temperature of 30 ℃, dopamine is enabled to be self-polymerized into a poly-dopamine layer on the surface of the polysulfone membrane, and the poly-dopamine layer is washed by the deionized water for several times after the reaction is finished.
(2) Dispersing 0.005g of graphite-like carbon nitride into 50ml of deionized water, stirring for 2h, and performing ultrasonic treatment for 2h to prepare carbon nitride dispersion liquid with the concentration of 0.1 g/L;
(3) dispersing 0.005g of graphene oxide into 50ml of deionized water, performing ultrasonic dispersion for 2h to prepare a graphene oxide dispersion liquid with the concentration of 0.1g/L, then adding 40ml of 0.5g/L ascorbic acid solution, stirring for 2h, performing ultrasonic treatment for 0.5h to prepare a partially reduced graphene oxide solution, then taking 3ml of the obtained partially reduced graphene oxide solution, adding 0.5ml of the prepared carbon nitride dispersion liquid according to the mass ratio of the graphene oxide to the carbon nitride of 6:1, stirring for 2h, performing ultrasonic treatment for 0.5h to uniformly mix the solution, casting the uniformly mixed membrane solution on a polysulfone ultrafiltration membrane treated by dopamine to prepare a membrane by adopting a vacuum filtration manner, and drying the obtained membrane in an oven at 60 ℃ for 10min to obtain the graphene oxide nanofiltration membrane of the carbon nitride.
(4) Respectively using 1000ppm of Na at 25 ℃ and 0.3MPa2SO4、NaCl、MgSO4And MgCl2The water flux and salt rejection of the membrane material were determined. The water flux of the nanofiltration membrane is measured to be 8.85L m-2h-1bar-1To Na2SO4、NaCl、MgSO4And MgCl2The retention rates are 85.86%, 30.17%, 29.53% and 12.58% in sequence.
Example 3
(1) An organic filter membrane is adopted as a polysulfone ultrafiltration membrane, 0.121g of Tris (trihydroxymethyl aminomethane) is added into 100ml of deionized water, the pH value is adjusted to 8.5, then 0.2g of levodopa is added to prepare 2g/L dopamine Tris buffer solution, the polysulfone membrane is placed into the dopamine buffer solution, shaking and shaking are carried out for 24 hours at the temperature of 30 ℃, dopamine is enabled to be self-polymerized into a poly-dopamine layer on the surface of the polysulfone membrane, and the poly-dopamine layer is washed by the deionized water for several times after the reaction is finished.
(2) Dispersing 0.005g of graphite-like carbon nitride into 50ml of deionized water, stirring for 2h, and performing ultrasonic treatment for 2h to prepare carbon nitride dispersion liquid with the concentration of 0.1 g/L;
(3) dispersing 0.005g of graphene oxide into 50ml of deionized water, performing ultrasonic dispersion for 2h to prepare a graphene oxide dispersion liquid with the concentration of 0.1g/L, then adding 40ml of 0.5g/L ascorbic acid solution, stirring for 2h, performing ultrasonic treatment for 0.5h to prepare a partially reduced graphene oxide solution, then taking 3ml of the obtained partially reduced graphene oxide solution, adding 0.375ml of the prepared carbon nitride dispersion liquid according to the mass ratio of the graphene oxide to the carbon nitride of 8:1, stirring for 2h, performing ultrasonic treatment for 0.5h to uniformly mix the solution, casting the uniformly mixed membrane liquid on a polysulfone ultrafiltration membrane treated by dopamine to prepare a membrane by adopting a vacuum filtration manner, and drying the obtained membrane in an oven at 60 ℃ for 10min to obtain the graphene oxide nanofiltration membrane of the carbon nitride.
(4) Respectively using 1000ppm of Na at 25 ℃ and 0.3MPa2SO4、NaCl、MgSO4And MgCl2The water flux and salt rejection of the membrane material were determined. The water flux of the nanofiltration membrane is measured to be 7.54L m-2h-1bar-1To Na2SO4、NaCl、MgSO4And MgCl2The retention rate is 86.73 percent, 33.67 percent, 30.07 percent and 13.83 percent in sequence.
Example 4
(1) An organic filter membrane is adopted as a polysulfone ultrafiltration membrane, 0.121g of Tris (trihydroxymethyl aminomethane) is added into 100ml of deionized water, the pH value is adjusted to 8.5, then 0.2g of levodopa is added to prepare 2g/L dopamine Tris buffer solution, the polysulfone membrane is placed into the dopamine buffer solution, shaking and shaking are carried out for 24 hours at the temperature of 30 ℃, dopamine is enabled to be self-polymerized into a poly-dopamine layer on the surface of the polysulfone membrane, and the poly-dopamine layer is washed by the deionized water for several times after the reaction is finished.
(2) Dispersing 0.005g of graphite-like carbon nitride into 50ml of deionized water, stirring for 2h, and performing ultrasonic treatment for 2h to prepare carbon nitride dispersion liquid with the concentration of 0.1 g/L;
(3) dispersing 0.005g of graphene oxide into 50ml of deionized water, performing ultrasonic dispersion for 2h to prepare a graphene oxide dispersion liquid with the concentration of 0.1g/L, then adding 40ml of 0.5g/L ascorbic acid solution, stirring for 2h, performing ultrasonic treatment for 0.5h to prepare a partially reduced graphene oxide solution, then taking 3ml of the obtained partially reduced graphene oxide solution, adding 0.3ml of the prepared carbon nitride dispersion liquid according to the mass ratio of the graphene oxide to the carbon nitride of 10:1, stirring for 2h, performing ultrasonic treatment for 0.5h to uniformly mix the solution, casting the uniformly mixed membrane solution on a polysulfone ultrafiltration membrane treated by dopamine to prepare a membrane by adopting a vacuum filtration mode, and drying the obtained membrane in an oven at 60 ℃ for 10min to obtain the graphene oxide nanofiltration membrane of the carbon nitride.
(4) Respectively using 1000ppm of Na at 25 ℃ and 0.3MPa2SO4、NaCl、MgSO4And MgCl2The water flux and salt rejection of the membrane material were determined. The water flux of the nanofiltration membrane is measured to be 6.75L m-2h-1bar-1To Na2SO4、NaCl、MgSO4And MgCl2The retention rate is 85.56%, 30.31%, 32.41% and 14.27% in sequence.
Comparative example 1
(1) An organic filter membrane is adopted as a polysulfone ultrafiltration membrane, 0.121g of Tris (trihydroxymethyl aminomethane) is added into 100ml of deionized water, the pH value is adjusted to 8.5, then 0.2g of levodopa is added to prepare 2g/L dopamine Tris buffer solution, the polysulfone membrane is placed into the dopamine buffer solution, shaking and shaking are carried out for 24 hours at the temperature of 30 ℃, dopamine is enabled to be self-polymerized into a poly-dopamine layer on the surface of the polysulfone membrane, and the poly-dopamine layer is washed by the deionized water for several times after the reaction is finished.
(2) Dispersing 0.005g of graphene oxide into 50ml of deionized water, performing ultrasonic dispersion for 2h to prepare a graphene oxide dispersion liquid with the concentration of 0.1g/L, then adding 40ml of 0.5g/L ascorbic acid solution, stirring for 2h, performing ultrasonic treatment for 0.5h to prepare a partially reduced graphene oxide solution, preparing a membrane by performing vacuum filtration on the uniformly mixed membrane casting solution on a polysulfone ultrafiltration membrane treated by dopamine to prepare a membrane, and drying the obtained membrane in an oven at 60 ℃ for 10min to obtain the carbon nitride intercalated graphene oxide nanofiltration membrane.
(3) Respectively using 1000ppm of Na at 25 ℃ and 0.3MPa2SO4、NaCl、MgSO4And MgCl2The water flux and salt rejection of the membrane material were determined. The water flux of the nanofiltration membrane is measured to be 4.12L m-2h-1bar-1To Na2SO4、NaCl、MgSO4And MgCl2The retention rate is 90.4%, 37.95%, 53.71% and 32.36% in sequence.
Claims (10)
1. The utility model provides an application of graphite nitrogenization carbon intercalation's oxidation graphite alkene nanofiltration membrane in salt ion filtering and removing which characterized in that: the graphene oxide nanofiltration membrane is prepared by the following steps:
(1) dipping the organic filter membrane in a dopamine Tris buffer solution, and slowly oscillating and polymerizing for 12-30h at 25-30 ℃ to ensure that dopamine is self-polymerized on the membrane surface to form the organic filter membrane of a polydopamine layer; the concentration of the dopamine Tris buffer solution is 0.5-4g/L, and the pH value is 8.0-8.5;
(2) adding graphene oxide into deionized water, and performing ultrasonic dispersion to obtain a uniform graphene oxide dispersion liquid; the concentration of the graphene oxide dispersion liquid is 0.02-0.5 g/L;
(3) adding graphite-like carbon nitride into deionized water, and performing ultrasonic dispersion to obtain a uniform graphite-like carbon nitride dispersion liquid; the concentration of the graphite-like carbon nitride dispersion liquid is 0.01-1 g/L;
(4) adding an ascorbic acid solution with the concentration of 0.1-2g/L into the graphene oxide dispersion liquid obtained in the step (2), carrying out reduction reaction for 0.5-8h under the stirring condition, and then carrying out ultrasonic treatment for 0.5-2h to obtain a partially reduced graphene oxide dispersion liquid; the volume ratio of the ascorbic acid solution to the graphene oxide dispersion liquid is 1-5: 1;
(5) adding the graphite-like carbon nitride dispersion liquid obtained in the step (3) into the partially reduced graphene oxide dispersion liquid obtained in the step (4), stirring for 1-10h, and performing ultrasonic treatment for 0.2-2h to uniformly mix the graphite-like carbon nitride dispersion liquid and the partially reduced graphene oxide dispersion liquid to obtain a mixed liquid; the addition amount of the graphite-like carbon nitride dispersion liquid is calculated by the mass of the graphite-like carbon nitride, and the addition amount of the partially reduced graphene oxide dispersion liquid is calculated by the mass of the graphene oxide; the mass ratio of the graphene oxide to the graphite-like carbon nitride is 2-10: 1;
(6) and (2) taking the organic filter membrane of the polydopamine layer obtained in the step (1) as a bottom membrane, carrying out vacuum filtration on the mixed solution obtained in the step (5) on the bottom membrane, and drying the membrane subjected to vacuum filtration at 50-80 ℃ for 5-60min to obtain the carbon nitride intercalated graphene oxide nanofiltration membrane.
2. The use of claim 1, wherein: in the step (1), the organic filter membrane is an ultrafiltration membrane or a microfiltration membrane.
3. The use of claim 1, wherein: in the step (1), the organic filter membrane is made of polysulfone, polyacrylonitrile, nylon, polyvinylidene fluoride, mixed cellulose ester or cellulose acetate.
4. The use of claim 1, wherein: in the step (1), the concentration of the Tris buffer solution is 2g/L, and the pH value is 8.5.
5. The use of claim 1, wherein: in the step (1), the polymerization time is 20-24 h.
6. The use of claim 1, wherein: in the step (2), the concentration of the graphene oxide dispersion liquid is 0.1-0.25 g/L.
7. The use of claim 1, wherein: in the step (3), the concentration of the graphite-like carbon nitride dispersion liquid is 0.1-0.5 g/L.
8. The use of claim 1, wherein: in the step (4), the reduction time is 1-2.5 h.
9. The use of claim 1, wherein: and (6) slowly cleaning the organic filter membrane of the polydopamine layer prepared in the step (1) by using deionized water before the suction filtration of the mixed solution.
10. The use of claim 1, wherein: in the step (6), the drying temperature is 60 ℃, and the drying time is 10-30 min.
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