CN111921388A - Borate intercalation modified graphene oxide composite nanofiltration membrane and preparation method thereof - Google Patents
Borate intercalation modified graphene oxide composite nanofiltration membrane and preparation method thereof Download PDFInfo
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- B01D61/00—Processes of separation using semi-permeable membranes, e.g. dialysis, osmosis or ultrafiltration; Apparatus, accessories or auxiliary operations specially adapted therefor
- B01D61/02—Reverse osmosis; Hyperfiltration ; Nanofiltration
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- B01D69/125—In situ manufacturing by polymerisation, polycondensation, cross-linking or chemical reaction
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/44—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis
- C02F1/442—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis by nanofiltration
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Abstract
The invention discloses a borate intercalation modified graphene oxide composite nanofiltration membrane and a preparation method thereof. The modified graphene oxide is modified by adopting borate as an intercalation molecule, and then the modified graphene oxide is connected with a hydrolyzed polyacrylonitrile film through polyethyleneimine to obtain the composite nanofiltration membrane. According to the invention, borate is used as an inorganic covalent cross-linking agent to intercalate and modify the layered graphene oxide nanosheets, the distance between graphene oxide layers is increased before film formation, so that the problem of environmental pollution caused by organic small molecule intercalation is solved, and the distance between graphene oxide layers is increased so as to improve the permeation flux and separation performance of the film; and the reaction condition of the preparation process is mild, and the cost is low.
Description
Technical Field
The invention belongs to the technical field of nanofiltration membranes, and particularly relates to a borate intercalation modified graphene oxide composite nanofiltration membrane and a preparation method thereof.
Background
Due to the proliferation of the world population, the demand for water resources has far exceeded the supply capacity of natural water resources, and nearly 80% of the world population is facing the threat of water safety. The lack of water resources meeting the use requirements almost becomes the main crisis of human society. Nanofiltration, reverse osmosis and forward osmosis membrane processes are among the most effective strategies for the removal of traditional and emerging contaminants in water, and all require the use of a semipermeable membrane with excellent performance.
Graphene oxide is an ideal nanofiltration membrane forming material, the surface of the graphene oxide contains a large number of oxygen-containing functional groups such as epoxy groups, carboxyl groups, hydroxyl groups, carbonyl groups and the like, wherein the carboxyl groups are protonated in water to enable the membrane to be negatively charged, and an ultrathin membrane with good mechanical properties can be prepared. However, graphene oxide is easy to agglomerate and stack, so that graphene oxide pore channels are blocked, and the mass transfer resistance of water molecules is increased. By an intercalation modification method, a cross-linking agent can be added in the preparation process to realize the bridge function between graphene oxide layers, increase the interlayer spacing and fully utilize the capillary effect of the graphene oxide.
At present, in the preparation of graphene oxide membranes, the widely used cross-linking agents are mostly amine cross-linking agents such as dopamine, ethylenediamine, propylenediamine and the like, and other cross-linking agents such as trimesoyl chloride and the like, the cross-linking agents are all organic cross-linking agents, and the membranes prepared from the organic cross-linking agents are easily oxidized in the water treatment process and the cleaning process, so that the cross-linking effect is lost, graphene oxide on the surfaces of the membranes is finally dropped, and the water treatment performance of the membranes is further influenced. In addition, the use of organic cross-linking agents in the film-making process also causes certain environmental pollution. Therefore, it is important to select a suitable crosslinking agent in the preparation of the graphene oxide film. Borate, as an inorganic crosslinking agent, can solve the environmental problems and the problem of being easily oxidized caused by the organic crosslinking agent.
The graphene oxide contains a large number of oxygen-containing functional groups, has a cross-linking reaction basis with borate, and is intercalated and modified by the borate serving as an inorganic covalent cross-linking agent, so that the distance between graphene oxide layers is increased before film formation, the permeation flux and the pollutant retention rate are expected to be greatly improved, and the nanofiltration performance of the film is improved.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides a borate intercalation modified graphene oxide composite nanofiltration membrane, wherein borate is used as an inorganic covalent cross-linking agent to intercalate and modify layered graphene oxide nanosheets, the distance between graphene oxide layers is increased before membrane formation, so that the problem of environmental pollution caused by organic small molecule intercalation is solved, and the distance between graphene oxide layers is increased to improve the permeation flux and separation performance of the membrane.
In order to achieve the purpose, the invention adopts the following technical scheme:
a borate intercalation modified graphene oxide composite nanofiltration membrane is prepared by modifying modified graphene oxide by adopting borate as an intercalation molecule, and then connecting the modified graphene oxide with a hydrolyzed polyacrylonitrile membrane through polyethyleneimine to obtain the composite nanofiltration membrane; the borate is sodium tetraborate or potassium tetraborate.
The preparation method of the graphene oxide composite nanofiltration membrane comprises the following steps:
step 1, immersing the polyacrylonitrile membrane into a sodium hydroxide solution, standing and washing to obtain a hydrolyzed polyacrylonitrile membrane, wherein the concentration of the sodium hydroxide solution is 0.5-2 mol/L;
step 2, immersing the hydrolyzed polyacrylonitrile membrane obtained in the step 1 into a polyethyleneimine solution, standing and washing to obtain a base membrane, wherein the concentration of the polyethyleneimine solution is 0.5-2 g/L;
step 3, adding graphene oxide into deionized water, performing ultrasonic dispersion to obtain a graphene oxide dispersion solution, then adding borate, and oscillating to obtain a borate intercalation modified graphene oxide solution, wherein the concentration of the graphene oxide is 0.1-2 g/L, and the concentration of the borate is 0.1-2 g/L;
and 4, immersing the base membrane obtained in the step 2 into the solution obtained in the step 3, standing, washing and drying to obtain the borate intercalation modified graphene oxide nanofiltration membrane.
Further, the standing time in the step 1 is 0.5-5 h, the temperature is 40-70 ℃, and the washing is to wash the redundant sodium hydroxide solution by deionized water.
Further, the solvent of the sodium hydroxide solution in the step 1 is deionized water.
Further, the standing time in the step 2 is 0.5-5 h, the temperature is 40-70 ℃, and the washing is to wash the redundant polyethyleneimine solution by using deionized water.
Further, the solvent of the polyethyleneimine solution in the step 2 is deionized water.
Further, the time of ultrasonic dispersion in the step 3 is 0.5h-2h, the time of oscillation is 6h-24h, and the temperature is 40-70 ℃.
Further, the standing time in the step 4 is 0.5-5 h, the temperature is 40-70 ℃, the washing is to wash the redundant solution by using deionized water, and the drying temperature is 20-25 ℃.
Has the advantages that:
1. according to the invention, borate is used as a crosslinking agent for intercalation modification of graphene oxide, the vibration is carried out for full reaction, the distance between graphene oxide layers is increased before film formation, and the permeation flux and separation performance of the nanofiltration membrane are improved.
2. According to the invention, inorganic cross-linking agent borate is used as an intercalation micromolecule, and graphene oxide is modified by intercalation, so that the problems of environmental pollution and easy oxidation of organic cross-linking agents such as diamine monomers are solved.
3. The preparation method has the advantages of mild reaction conditions, low cost and good industrial production and application prospects.
Drawings
FIG. 1 shows the comparison of pure water fluxes between examples of the present invention and comparative examples.
FIG. 2 is a comparison of the dye retention of examples of the present invention and comparative examples.
Detailed Description
The invention will be further illustrated with reference to the following specific examples. It should be understood that these examples are for illustrative purposes only and are not intended to limit the scope of the present invention. Further, it should be understood that various changes or modifications of the present invention may be made by those skilled in the art after reading the teaching of the present invention, and such equivalents may fall within the scope of the present invention as defined in the appended claims.
The reagents used in the examples of the invention were as follows: the single-layer graphene oxide is purchased from Nanjing Xiancheng nanometer material science and technology Limited; sodium tetraborate pentahydrate, analytically and purchasably arranged in a chemical reagent factory of the Pangolidae; polyethyleneimine, sodium hydroxide and analytical reagent purchased from an alatin chemical reagent; the polyethylene cyanide film is purchased from Xiamen national science and technology Co. Methyl orange, methylene blue, purchased from alatin chemicals.
The important parameters for evaluating the nanofiltration performance of the composite nanofiltration membrane prepared by the invention are mainly two: retention of dye and permeation flux of solvent. Wherein the retention of the dye is defined as:
wherein, CfDenotes the feed solution concentration, CpRepresents the concentration of the permeated liquid; the dye concentration is expressed as the absorbance of the solution.
The permeate flux is defined as: the volume of liquid per membrane area per unit time is expressed in L.m-2·h-1The formula is as follows:
wherein V represents the volume of the permeated solution and has a unit of L; a represents the effective membrane area in m2(ii) a t represents time in units of h.
Example 1
(1) And (3) immersing the polyacrylonitrile membrane into a sodium hydroxide solution, standing for 2h at 40 ℃, and washing the redundant sodium hydroxide solution by using deionized water to obtain the hydrolyzed polyacrylonitrile membrane, wherein the concentration of the sodium hydroxide is 2 mol/L.
(2) And (2) immersing the hydrolyzed polyacrylonitrile membrane obtained in the step (1) into a polyethyleneimine solution, standing for 1h at 40 ℃, and washing the redundant polyethyleneimine solution with deionized water to obtain a base membrane, wherein the concentration of polyethyleneimine is 1 g/L.
(3) Dissolving graphene oxide in deionized water, performing ultrasonic treatment for 1h to obtain a graphene oxide dispersion liquid, adding sodium tetraborate, and oscillating at 60 ℃ for 12h to obtain a sodium tetraborate intercalation modified graphene oxide solution. Wherein the concentration of the graphene oxide is 1g/L, and the concentration of the sodium tetraborate is 0.2 g/L.
(4) And (3) immersing the base membrane obtained in the step (2) into the mixed solution prepared in the step (3), standing for 1h at 40 ℃, washing the redundant mixed solution with deionized water, and airing the membrane at room temperature to obtain the sodium tetraborate intercalated modified graphene oxide nanofiltration membrane.
Under the same experimental conditions, the graphene oxide composite nanofiltration membrane modified by intercalation without adding borate is used as a comparative example. The results of the experiment are shown in table 1:
table 1 pure water flux and contaminant rejection for example 1 and comparative examples
The data in table 1 show that the flux of the graphene oxide nanofiltration membrane modified by 0.2g/L sodium tetraborate intercalation is increased by 56.2% and the rejection rate of methyl orange is increased by 39.0% compared with the nanofiltration membrane without borate.
Example 2
(1) And (3) immersing the polyacrylonitrile membrane into a sodium hydroxide solution, standing for 2h at 40 ℃, and washing the redundant sodium hydroxide solution by using deionized water to obtain the hydrolyzed polyacrylonitrile membrane, wherein the concentration of the sodium hydroxide is 2 mol/L.
(2) And (2) immersing the hydrolyzed polyacrylonitrile membrane obtained in the step (1) into a polyethyleneimine solution, standing for 1h at 40 ℃, and washing the redundant polyethyleneimine solution with deionized water to obtain a base membrane, wherein the concentration of polyethyleneimine is 1 g/L.
(3) Dissolving graphene oxide in deionized water, performing ultrasonic treatment for 1h to obtain a graphene oxide dispersion liquid, adding sodium tetraborate, and oscillating at 60 ℃ for 12h to obtain a borate intercalation modified graphene oxide solution. Wherein the concentration of the graphene oxide is 1g/L, and the concentration of the sodium tetraborate is 0.4 g/L.
(4) And (3) immersing the base membrane obtained in the step (2) into the mixed solution prepared in the step (3), standing for 1h at 40 ℃, washing the redundant mixed solution with deionized water, and airing the membrane at room temperature to obtain the borate intercalation modified graphene oxide nanofiltration membrane.
Under the same experimental conditions, the graphene oxide composite nanofiltration membrane modified by intercalation without adding borate is used as a comparative example. The results of the experiment are shown in table 2:
table 2 pure water flux and contaminant rejection for example 2 and comparative examples
The data in table 2 show that the flux of the 0.4g/L sodium tetraborate intercalation-modified graphene oxide nanofiltration membrane is increased by 25.0%, the methyl orange rejection rate is increased by 61.3%, and the methylene blue rejection rate is increased by 3.4% compared with the nanofiltration membrane without borate.
As can be seen from fig. 1 and 2, the composite nanofiltration membrane of the present invention has greatly improved permeation flux and contaminant rejection rate compared to an unmodified graphene oxide membrane.
Claims (9)
1. The utility model provides a borate intercalation modified graphene oxide composite nanofiltration membrane which characterized in that: modifying and modifying graphene oxide by using borate as an intercalation molecule, and then connecting the modified graphene oxide with a hydrolyzed polyacrylonitrile film through polyethyleneimine to obtain a composite nanofiltration membrane; the borate is sodium tetraborate or potassium tetraborate.
2. The preparation method of the composite nanofiltration membrane of claim 1, wherein the preparation method comprises the following steps: the method comprises the following steps:
step 1, immersing the polyacrylonitrile membrane into a sodium hydroxide solution, standing and washing to obtain a hydrolyzed polyacrylonitrile membrane, wherein the concentration of the sodium hydroxide solution is 0.5-2 mol/L;
step 2, immersing the hydrolyzed polyacrylonitrile membrane obtained in the step 1 into a polyethyleneimine solution, standing and washing to obtain a base membrane, wherein the concentration of the polyethyleneimine solution is 0.5-2 g/L;
step 3, adding graphene oxide into deionized water, performing ultrasonic dispersion to obtain a graphene oxide dispersion solution, then adding borate, and oscillating to obtain a borate intercalation modified graphene oxide solution, wherein the concentration of the graphene oxide is 0.1-2 g/L, and the concentration of the borate is 0.1-2 g/L;
and 4, immersing the base membrane obtained in the step 2 into the solution obtained in the step 3, standing, washing and drying to obtain the borate intercalation modified graphene oxide nanofiltration membrane.
3. The method of claim 2, wherein: in the step 1, the standing time is 0.5 to 5 hours, the temperature is 40 to 70 ℃, and the washing is to wash the redundant sodium hydroxide solution by deionized water.
4. The method of claim 2, wherein: the solvent of the sodium hydroxide solution in the step 1 is deionized water.
5. The method of claim 2, wherein: and (3) standing for 0.5-5 h in the step (2), and washing at 40-70 ℃, wherein the redundant polyethyleneimine solution is washed by deionized water.
6. The method of claim 2, wherein: the solvent of the polyethyleneimine solution in the step 2 is deionized water.
7. The method of claim 2, wherein: the time of ultrasonic dispersion in the step 3 is 0.5h-2h, the time of oscillation is 6h-24h, and the temperature is 40-70 ℃.
8. The method of claim 2, wherein: and the standing time in the step 4 is 0.5-5 h, the temperature is 40-70 ℃, the washing is to wash the redundant solution by using deionized water, and the drying temperature is 20-25 ℃.
9. Use of a composite nanofiltration membrane according to claim 1 in wastewater treatment.
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| CN115445451A (en) * | 2022-10-11 | 2022-12-09 | 天津工业大学 | Preparation method of amine molecular intercalation double-reduction graphene oxide composite membrane |
| CN115621463A (en) * | 2022-10-21 | 2023-01-17 | 厦门凯纳石墨烯技术股份有限公司 | Graphene composite conductive agent, preparation method and application |
| WO2023212813A1 (en) * | 2022-05-03 | 2023-11-09 | Ora Graphene Audio Inc. | Filtration system |
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