CN108295812B - Graphene oxide composite membrane for selectively removing metal ions in water, and preparation method and application thereof - Google Patents
Graphene oxide composite membrane for selectively removing metal ions in water, and preparation method and application thereof Download PDFInfo
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- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
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- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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Abstract
The invention relates to a graphene oxide composite membrane for selectively removing metal ions in water, and a preparation method and application thereof, and belongs to the technical field of wastewater treatment. The graphene oxide composite membrane is mainly prepared from graphene oxide, an ammonia-carboxyl complexing agent and an organic polymeric flocculant; the mass ratio of the graphene oxide to the aminocarboxylate complexing agent is 1: 5-10, and the mass ratio of the aminocarboxylate complexing agent to the organic polymeric flocculant is 1-5: 1. According to the graphene oxide composite membrane, the complexing agent and the organic polymeric flocculant are doped into the graphene oxide, so that the selective adsorption capacity of the material is enhanced, the rejection rate of the material is improved, and the stability of the material in a water environment can be enhanced due to the addition of the organic polymeric flocculant, so that the material can be recycled.
Description
Technical Field
The invention relates to a graphene oxide composite membrane for selectively removing metal ions in water, and a preparation method and application thereof, and belongs to the technical field of wastewater treatment.
Background
In 1940 evaluation, assessment and ranking sections (point positions) of surface water of China, which are published in 2016, the I type, the II type, the III type, the IV type, the V type and the inferior V type respectively account for 2.4 percent, 37.5 percent, 27.9 percent, 16.8 percent, 6.9 percent and 8.6 percent. Of 6124 groundwater water quality monitoring points, monitoring points with water quality of good grade, poor grade and range grade account for 10.1%, 25.4%, 4.4%, 45.4% and 14.7% respectively. In water body pollution, besides water body eutrophication, heavy metals are also important pollution factors, and the heavy metals and compounds thereof are one of the categories in the blacklist of Chinese environmental priority pollutants.
At present, methods for removing heavy metals in water mainly comprise a chemical precipitation method, an ion exchange method, an electrochemical method, an adsorption method and the like. Compared with other traditional treatment methods, the adsorption method has the advantages of low cost, high efficiency, energy conservation, cyclic utilization, environmental protection and the like. The selection of the adsorbent is particularly important, and a plurality of researchers at home and abroad are dedicated to seeking a more appropriate novel efficient adsorption material. The graphene oxide is a product obtained by chemically oxidizing and stripping graphite powder, has a large specific surface area and a large number of hydrophilic groups such as carboxyl and hydroxyl, and is beneficial to adsorption and diffusion of pollutants. In recent years, there have been a lot of studies on the treatment of heavy metals, dyes, small-molecule organic pollutants, and the like with graphene oxide adsorbing materials. A series of graphene oxide and functional modified materials thereof are prepared by royal jelly, and the adsorption capacity of the graphene oxide to copper ions is 50.95mg/g (the royal jelly, the graphene oxide and the functional modified materials thereof are used for enriching the mechanism of heavy metal ions in water research [ D ], Hunan university, 2016.4); trivinyl triamine and triethylene tetramine are mixed with graphene oxide to prepare gel spheres with three-dimensional grid porous structures, adsorption of the gel spheres on lead ions, copper ions, rhodamine B, methylene blue and congo red in industrial wastewater is studied, and the removal effect on cationic pollutants is good (Zhukai, research on preparation and performance of graphene oxide hydrogel [ D ], Yanshan university, 2016.5).
Graphene oxide is a good adsorbent, but due to its strong hydrophilicity, it is easily dispersed in an aqueous solution, and it is difficult to separate after adsorption, so that the solidification of graphene oxide has become a current research hotspot. The modified single-walled carbon nanotube cross-linked graphene oxide film is prepared from the reed by a vacuum filtration method, and under the optimal condition, the hybrid film can be used for Sr in radioactive wastewater2+The retention rate is 70 percent, and the flux reaches 390.6L/(m)2H) complexing Sr by addition of ethylenediaminetetraacetic acid2+Forming complex with larger molecular size, and improving the removal capability to 86.3% (Lu Li, preparation and performance research of graphene oxide base film [ D)]2016.6 Zhejiang university). However, most of the methods are applied to removal of single metal ions at present, and researches on treatment of wastewater containing multiple metal ions are few, and the problems of poor selectivity exist at the same time.
Disclosure of Invention
The invention aims to provide a graphene oxide composite membrane for selectively removing metal ions with high selectivity and high removal rate.
The invention also provides a preparation method of the graphene oxide composite membrane and application of the graphene oxide composite membrane in selectively removing metal ions in water.
In order to achieve the above purpose, the graphene oxide composite membrane for selectively removing metal ions in water according to the present invention adopts the following technical scheme:
a graphene oxide composite membrane for selectively removing metal ions in water is mainly prepared from graphene oxide, an ammonia-carboxyl complexing agent and an organic polymeric flocculant; the mass ratio of the graphene oxide to the aminocarboxylate complexing agent is 1: 5-10, and the mass ratio of the aminocarboxylate complexing agent to the organic polymeric flocculant is 1-5: 1.
According to the graphene oxide composite membrane for selectively removing the metal ions in the water, the graphene oxide can increase the size of an original two-dimensional pore channel through pi-pi interaction, electrostatic interaction and an H-bond cross-linked aminocarboxylic complexing agent, so that the screening effect of the channel is improved, and a three-dimensional network structure is formed at the same time. The organic polymeric flocculant can also react with hydrophilic groups in the graphene oxide and the aminocarboxylic acid complexing agent, so that the network structure is changed, the network strength is improved, the stability of the material in a water environment is enhanced, and the material can be recycled. The aminocarboxylate complexing agent can also form a large-size cyclic chelate with heavy metals, has the minimum pH value allowing complexation with various ions, can realize respective complexation of metal ions by adjusting the pH range of the solution, enhances the selective adsorption capacity of the material, and improves the retention rate of the material.
The complexone is amino polybasic acid or amino polybasic carboxylic acid salt containing ammonia nitrogen and carboxyl oxygen coordination atoms.
Preferably, the aminocarboxylic acid complexing agent is at least one of ethylenediamine tetraacetic acid, cyclohexanediamine tetraacetate, ethylene glycol diethyl ether diamine tetraacetic acid, ethylenediamine tetrapropionic acid, ethylenediamine tetrapropionate and triethylene tetramine.
The edetate is at least one of sodium salt and potassium salt of ethylenediamine tetraacetic acid.
The cyclohexanediamine tetraacetate is a sodium salt of cyclohexanediamine tetraacetate.
The ethylene glycol diethyl ether diamine tetraacetic acid salt is sodium salt of ethylene glycol diethyl ether diamine tetraacetic acid.
The ethylene diamine tetrapropionate is sodium salt of ethylene diamine tetrapropionic acid.
The ethylene diamine tetraacetic acid is a commonly used aminocarboxylic complexing agent, six atoms capable of forming coordination bonds with metal ions are arranged in each molecule, and an easily soluble and stable cyclic complex can be formed with the metal ions with the valences of 1-4; meanwhile, the complexation reaction of the ethylene diamine tetraacetic acid and the metal ions has the minimum pH limit, so that different heavy metal ions in the wastewater can be selectively removed by controlling the pH value of the solution, and the practical application is facilitated. Because of the low solubility of ethylenediaminetetraacetic acid in water, disodium salts of ethylenediaminetetraacetic acid are commonly used as the aminocarboxylic complexing agent. Preferably, the complexone is disodium edetate.
The flocculant is a natural organic polymer flocculant.
The organic polymeric flocculant is at least one of sodium alginate and chitosan. Sodium alginate is a natural polymer material, has the characteristics of no toxicity, good viscosity, good film forming property and the like, has a large amount of carboxyl and hydroxyl, is an organic polymer flocculant with good adsorption property, and can react with various divalent and trivalent cations to form gel with stable property. Particularly, the ordered three-dimensional reticular graphene oxide composite membrane can be prepared by using ethylene diamine tetraacetic acid and/or disodium ethylene diamine tetraacetic acid as a complexing agent and sodium alginate as an organic polymeric flocculant, so that the adsorption material is solidified, and the specific surface area of the material is enhanced.
The thickness of the graphene oxide composite film is 0.08-0.12 mm.
The preparation method of the graphene oxide composite membrane for selectively removing metal ions in water adopts the technical scheme that:
a preparation method of the graphene oxide composite membrane comprises the following steps: uniformly dispersing graphene oxide, an ammonia-carboxyl complexing agent and an organic polymeric flocculant in a solvent to obtain a mixed dispersion liquid; and then preparing the mixed dispersion liquid into a membrane to obtain the membrane.
The preparation method of the graphene oxide composite membrane is simple in preparation, mild in condition, less in required reagent amount, low in cost, good in stability in water environment and high in rejection rate.
Preferably, the aminocarboxylic acid complexing agent is at least one of ethylenediamine tetraacetic acid, cyclohexanediamine tetraacetate, ethylene glycol diethyl ether diamine tetraacetic acid, ethylenediamine tetrapropionic acid, ethylenediamine tetrapropionate and triethylene tetramine.
The edetate is at least one of sodium salt and potassium salt of ethylenediamine tetraacetic acid.
The cyclohexanediamine tetraacetate is a sodium salt of cyclohexanediamine tetraacetate.
The ethylene glycol diethyl ether diamine tetraacetic acid salt is sodium salt of ethylene glycol diethyl ether diamine tetraacetic acid.
The ethylene diamine tetrapropionate is sodium salt of ethylene diamine tetrapropionic acid.
Further preferably, the complexone is disodium edetate.
The flocculant is a natural organic polymer flocculant. The organic polymeric flocculant is at least one of sodium alginate and chitosan.
The solvent is water.
Before the mixed dispersion liquid is formed into a film, the pH of the mixed dispersion liquid is adjusted to 6-8. H released in the use process of the graphene oxide composite membrane can be reduced by adjusting the pH of the mixed dispersion liquid to be 6-8+Or OH-And the influence of the fluctuation of the pH of the treatment liquid on the selective removal of the metal ions is reduced.
In the dispersion liquid, the concentration of the graphene oxide is 1-5 g/L.
The membrane preparation from the mixed dispersion liquid comprises the steps of carrying out suction filtration on the mixed dispersion liquid to prepare a composite membrane, and then washing and drying the obtained composite membrane. Before the mixed dispersion liquid is prepared into a membrane, when the pH value of the mixed dispersion liquid is adjusted to 6-8, the mixed dispersion liquid is prepared into the membrane, namely the mixed dispersion liquid after the pH value is adjusted is prepared into the membrane, and the obtained composite membrane is washed and dried.
In the suction filtration process, the area of the filter membrane correspondingly occupied by every 1-3 mL of the mixed dispersion liquid is 400 pi mm2. That is to say every 400 pi mm in the suction filtration process2The filter membrane with the area is only used for carrying out suction filtration on 1-3 mL of mixed dispersion liquid.
The suction filtration membrane adopted by suction filtration is a water-based microporous filtration membrane. The aperture of the water system microporous filter membrane is 0.22-0.45 mu m.
The drying temperature is 20-35 ℃.
The technical scheme adopted by the application of the graphene oxide composite membrane in the aspect of selectively removing metal ions in water is as follows:
the application of the graphene oxide composite membrane in selectively removing metal ions in water comprises the steps of adjusting the pH value of wastewater to be treated to be 2-8, and then filtering by using the graphene oxide composite membrane.
The graphene oxide composite membrane disclosed by the invention is applied to selectively removing metal ions in water, is simple to operate, and can realize adsorption of various metal ions in a water sample to be detected by adjusting the pH value of the water sample.
The water sample to be detected contains Mg2+、Cu2+、Fe3+、Zn2+、Cd2+、Pb2+、Cr6+At least one of the above.
Drawings
Fig. 1 is an SEM image of the surface of the graphene oxide composite membrane of example 1;
fig. 2 is an SEM image of a cross section of the graphene oxide composite membrane of example 1;
fig. 3 is an SEM image of the graphene oxide composite membrane fracture surface network structure of example 1.
Detailed Description
The technical solution of the present invention will be further described with reference to the following embodiments.
Example 1
The graphene oxide composite membrane for selectively removing metal ions in water is mainly prepared from graphene oxide, an ammonia-carboxyl complexing agent and a natural organic polymeric flocculant; the mass ratio of the graphene oxide to the ammonia-carboxyl complexing agent to the natural organic polymeric flocculant is 1:10: 2; the complexone is disodium ethylene diamine tetraacetate, and the natural organic polymeric flocculant is sodium alginate.
The preparation method of the graphene oxide composite membrane for selectively removing metal ions in water in the embodiment comprises the following steps:
1) adding graphene oxide into deionized water, and performing ultrasonic treatment for 2 hours to uniformly disperse the graphene oxide to obtain 5g/L graphene oxide dispersion liquid; then adding an ammonia-carboxyl complexing agent and a natural organic polymeric flocculant into the graphene oxide dispersion liquid, and stirring at room temperature for 12 hours to obtain a mixed dispersion liquid;
2) washing water system microporous filter membrane with diameter of 50mm and pore diameter of 0.22 μm with high purity water, and placing in vacuum filtration device(the effective filtration area of the aqueous microporous membrane is 400 pi mm2) And then taking 3mL of the obtained mixed dispersion, adjusting the pH to 7, then dropwise adding the mixed dispersion onto a water-based microporous filter membrane, turning on a power supply for suction filtration to obtain a brown-yellow composite membrane, taking down the composite membrane after the suction filtration is stopped, then washing with high-purity water, and then airing at room temperature to obtain the graphene oxide composite membrane with the thickness of 0.08-0.12 mm.
The SEM image of the surface of the graphene oxide composite film prepared in this example is shown in fig. 1, and as can be seen from fig. 1, the surface of the film has no porous structure and has characteristic wrinkles of graphene oxide; as shown in fig. 2 and 3, the graphene oxide composite membrane has an orderly stacked three-dimensional network structure, has more pores and a large specific surface area, and is favorable for adsorbing and removing metal ions.
Example 2
The graphene oxide composite membrane for selectively removing metal ions in water is mainly prepared from graphene oxide, an ammonia-carboxyl complexing agent and a natural organic polymeric flocculant; the mass ratio of the graphene oxide to the complexone and the natural organic polymeric flocculant is 1:5: 5; the complexone is disodium ethylene diamine tetraacetate, and the natural organic polymeric flocculant is sodium alginate.
The preparation method of the graphene oxide composite membrane for selectively removing metal ions in water in the embodiment comprises the following steps:
1) adding graphene oxide into deionized water, and performing ultrasonic treatment for 2 hours to uniformly disperse the graphene oxide to obtain 1g/L graphene oxide dispersion liquid; then adding an ammonia-carboxyl complexing agent and a natural organic polymeric flocculant into the graphene oxide dispersion liquid, and stirring at room temperature for 12 hours to obtain a mixed dispersion liquid;
2) washing water system microporous filter membrane with diameter of 50mm and pore diameter of 0.45 μm with high purity water, and placing in vacuum filtration device (effective filtration area of water system microporous filter membrane is 400 π mm)2) (ii) a Then taking 1mL of the obtained mixed dispersion, adjusting pH to 6, dripping the mixed dispersion on a water system microporous filter membrane, switching on a power supply for suction filtration to obtain a brown yellow composite membrane, taking down the composite membrane after the suction filtration is stopped, and then flushing the composite membrane with high-purity waterAnd washing, and airing at room temperature to obtain the graphene oxide composite membrane with the thickness of 0.08-0.12 mm.
Example 3
The graphene oxide composite membrane for selectively removing metal ions in water is mainly prepared from graphene oxide, an ammonia-carboxyl complexing agent and a natural organic polymeric flocculant; the mass ratio of the graphene oxide to the complexone and the natural organic polymeric flocculant is 1:7.5: 3; the complexone is disodium ethylene diamine tetraacetate, and the natural organic polymeric flocculant is sodium alginate.
The preparation method of the graphene oxide composite membrane for selectively removing metal ions in water in the embodiment comprises the following steps:
1) adding graphene oxide into deionized water, and performing ultrasonic treatment for 2 hours to uniformly disperse the graphene oxide to obtain 2.5g/L graphene oxide dispersion liquid; then adding an ammonia-carboxyl complexing agent and a natural organic polymeric flocculant into the graphene oxide dispersion liquid, and stirring for 2 hours at room temperature to obtain a mixed dispersion liquid;
2) washing water system microporous filter membrane with diameter of 50mm and pore diameter of 0.45 μm with high purity water, and placing in vacuum filtration device (effective filtration area of water system microporous filter membrane is 400 π mm)2) (ii) a And then taking 2mL of the obtained mixed dispersion, adjusting the pH to 8, dropwise adding the obtained mixed dispersion onto a water-based microporous filter membrane, turning on a power supply for suction filtration to obtain a brown-yellow composite membrane, taking down the composite membrane after the suction filtration is stopped, washing with high-purity water, and airing at room temperature to obtain the graphene oxide composite membrane with the thickness of 0.08-0.12 mm.
Example 4
The graphene oxide composite membrane for selectively removing metal ions in water is mainly prepared from graphene oxide, an ammonia-carboxyl complexing agent and a natural organic polymeric flocculant; the mass ratio of the graphene oxide to the complexone and the natural organic polymeric flocculant is 1:7.5: 3; the complexone is ethylenediamine tetra propionic acid, and the natural organic polymer flocculant is chitosan.
The preparation method of the graphene oxide composite membrane for selectively removing metal ions in water in the embodiment comprises the following steps:
1) adding graphene oxide into deionized water, and performing ultrasonic treatment for 2 hours to uniformly disperse the graphene oxide to obtain 1g/L graphene oxide dispersion liquid; then adding an ammonia-carboxyl complexing agent and a natural organic polymeric flocculant into the graphene oxide dispersion liquid, and stirring at room temperature for 12 hours to obtain a mixed dispersion liquid;
2) washing water system microporous filter membrane with diameter of 50mm and pore diameter of 0.45 μm with high purity water, and placing in vacuum filtration device (effective filtration area of water system microporous filter membrane is 400 π mm)2) (ii) a And then taking 2mL of the obtained mixed dispersion, adjusting the pH to 7, dropwise adding the obtained mixed dispersion onto a water-based microporous filter membrane, turning on a power supply for suction filtration to obtain a brown-yellow composite membrane, taking down the composite membrane after the suction filtration is stopped, washing with high-purity water, and airing at room temperature to obtain the graphene oxide composite membrane with the thickness of 0.08-0.12 mm.
Comparative example
The preparation method of the graphene oxide composite membrane of the comparative example comprises the following steps:
1) carrying out ultrasonic treatment on 10ml of 5g/L graphene oxide for 2h to obtain a uniform graphene oxide aqueous dispersion, adding 0.1g of sodium alginate, stirring for 12h, and adjusting the pH value to 7 to obtain a membrane preparation solution.
2) Washing a water system microporous filter membrane with a diameter of 50mm and a diameter of 0.22 μm with high-purity water, and installing the filter membrane in a vacuum filtration device (the effective filtration area of the water system microporous filter membrane is 400 pi mm)2) Dripping 3mL of the film preparation solution on a water-system microporous filter membrane, switching on a power supply, and performing suction filtration; and after the suction filtration is stopped, taking down the membrane to show a brown yellow color, then washing with high-purity water, and airing at room temperature to obtain the graphene oxide composite membrane.
Experimental example 1
Separately preparing Mg2+、Cu2+、Pb2+、Fe3+、Zn2+、Cd2+The water sample A to be detected, the water sample B to be detected, the water sample C to be detected, the water sample D to be detected, the water sample E to be detected and the water sample F to be detected, which are 10mg/L in concentration, are respectively subjected to vacuum filtration by using the graphene oxide composite membrane in the embodiment 1 after the pH of the water sample A to be detected is adjusted to 7 and the pH of the water sample B to be detected is adjusted to 4, and the graphene oxide composite membrane in the embodiment 2 is adopted after the pH of the water sample C to be detected is adjusted to 7Vacuum filtration, namely performing vacuum filtration by using the graphene oxide composite membrane in the embodiment 3 after adjusting the pH of the water sample D to be detected to be 7, performing vacuum filtration by using the graphene oxide composite membrane in the embodiment 4 after adjusting the pH of the water sample E to be detected to be 6, filtering by using the graphene oxide composite membrane in the comparative example after adjusting the pH of the water sample F to be detected to be 7, and determining Mg in filtrate by using an inductively coupled plasma atomic emission spectrometer2+、Cu2+、Pb2+、Fe3+、Zn2+、Cd2+And the removal rate was calculated, the results are shown in table 1.
Table 1 removal rates of graphene oxide composite films of examples 1 to 4 and comparative example for different metal ions
As can be seen from the data in table 1, the composite membrane prepared by the comparative example without the complexing agent has the adsorption and retention effects on the metal ions, but the removal rate is low, the selectivity is poor, and the competitive adsorption is caused by the difference in affinity between the graphene oxide composite membrane and the metal ions and mainly determined by the ionic radius and electronegativity of the metal ions. The graphene oxide composite membrane prepared in the embodiment 1-4 can generate a cyclic chelate due to the complexation with metal ions by adding the aminocarboxylate complexing agent, so that the membrane interception is facilitated, and the feasibility of the reaction between the aminocarboxylate complexing agent and the metal ions can be controlled by adjusting the pH value of the solution, so that the composite membrane has the effect of selectively removing metal cations.
Experimental example 2
Installing the graphene oxide composite films of examples 1-4 and comparative example in a vacuum filtration device, and preparing a film containing 10mg/L Cr6+Adjusting the pH of the solution to 7 and 2, and performing suction filtration on the graphene oxide composite membrane prepared in the embodiment 1; preparing Cr containing 10mg/L6+Solution, pH 2 adjusted using examples 2-4And carrying out suction filtration on the graphene oxide composite membrane prepared by the comparative example. And during suction filtration, adding 10mL of each solution into a filter cup, carrying out suction filtration at room temperature, and taking out the filtrate. Measurement of Cr in filtrate by inductively coupled plasma atomic emission spectrometer6+And the removal rate was calculated, the results are shown in table 2.
TABLE 2 graphene oxide composite films of examples 1 to 4 and comparative examples vs Cr6+Removal rate of
As can be seen from the data in Table 2, the composite film prepared by the comparative example which does not contain the complexing agent is Cr6+The removal capability is weak, and the composite membrane added with the complexone contains a large amount of amino groups, so that the amino groups are protonated under the acidic condition of pH 2, and at the time, Cr is6+In the form of Cr2O7 -、HCrO4 -Plasma form, and is removed by electrostatic binding. With the increase of pH, the negative charges on the surface of the graphene oxide composite membrane increase, and the graphene oxide composite membrane and Cr6+Presence of CrO4 2-The form generates electrostatic repulsive force, and the removal rate is reduced.
The graphene oxide composite films of examples 1 to 4 were compared with a single graphene oxide film for Cr under acidic conditions6+The ions have better selective removal capability.
Experimental example 3
Preparation of Mg2+、Cu2+、Pb2+、Fe3+、Zn2+、Cd2+The ion concentration is 10mg/L solution, then the pH is adjusted to 7, as a water sample to be treated, the graphene oxide composite membrane of the embodiment 1 is adopted to filter 10mL of the water sample to be treated, then the water sample is soaked in 0.1mol/L hydrochloric acid solution and oscillated for 2h, then a large amount of water is washed to carry out regeneration treatment, the processes are repeated, the concentration of each metal ion in filtrate obtained by filtering after each graphene oxide composite membrane is regenerated is detected, the removal rate of each ion filtered at this time is calculated, and the result is shown in Table 3.
Table 3 removal rate of different metal ions after regeneration of graphene oxide composite film of example 1
As can be seen from the data in table 3, the graphene oxide composite membrane prepared in example 1 has a large adsorption removal rate for each metal ion after 4 times of regeneration, which indicates that the membrane has good stability and regeneration capability.
Claims (8)
1. The utility model provides a graphite oxide complex film for metal ion's in selectivity gets rid of water which characterized in that: mainly prepared from graphene oxide, an ammonia-carboxyl complexing agent and an organic polymeric flocculant; the mass ratio of the graphene oxide to the aminocarboxylate complexing agent is 1: 5-10, and the mass ratio of the aminocarboxylate complexing agent to the organic polymeric flocculant is 1-5: 1; the aminocarboxylic complexing agent is at least one of ethylene diamine tetraacetic acid, cyclohexanediamine tetraacetic acid, ethylene glycol diethyl ether diamine tetraacetic acid, ethylene diamine tetrapropionic acid and triethylene tetramine; the organic polymeric flocculant is at least one of sodium alginate and chitosan;
the preparation method of the graphene oxide composite membrane for selectively removing the metal ions in water comprises the following steps: uniformly dispersing graphene oxide, an ammonia-carboxyl complexing agent and an organic polymeric flocculant in a solvent to obtain a mixed dispersion liquid; and then carrying out suction filtration on the mixed dispersion liquid to prepare a composite membrane, and washing and drying the obtained composite membrane to obtain the composite membrane.
2. The graphene oxide composite film according to claim 1, wherein: the thickness of the graphene oxide composite film is 0.08-0.12 mm.
3. A method for preparing the graphene oxide composite membrane according to claim 1, wherein: the method comprises the following steps: uniformly dispersing graphene oxide, an ammonia-carboxyl complexing agent and an organic polymeric flocculant in a solvent to obtain a mixed dispersion liquid; and then preparing the mixed dispersion liquid into a membrane to obtain the membrane.
4. The method for preparing a graphene oxide composite film according to claim 3, wherein: before the mixed dispersion liquid is formed into a film, the pH of the mixed dispersion liquid is adjusted to 6-8.
5. The method for preparing a graphene oxide composite film according to claim 3, wherein: the membrane preparation from the mixed dispersion liquid comprises the steps of carrying out suction filtration on the mixed dispersion liquid to prepare a composite membrane, and then washing and drying the obtained composite membrane.
6. The method for preparing a graphene oxide composite film according to claim 5, wherein: in the suction filtration process, the area of the filter membrane correspondingly occupied by every 1-3 mL of the mixed dispersion liquid is 400 pi mm2。
7. The method for preparing a graphene oxide composite film according to claim 5, wherein: the drying temperature is 20-35 ℃.
8. The application of the graphene oxide composite membrane according to claim 1 in selectively removing metal ions in wastewater, which is characterized in that: the method comprises the steps of adjusting the pH value of wastewater to be treated to 2-8, and then filtering with the graphene oxide composite membrane.
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