CN113457466B - Oxidized hyperbranched polyethyleneimine nanofiltration membrane, preparation method and application - Google Patents
Oxidized hyperbranched polyethyleneimine nanofiltration membrane, preparation method and application Download PDFInfo
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- CN113457466B CN113457466B CN202110795153.XA CN202110795153A CN113457466B CN 113457466 B CN113457466 B CN 113457466B CN 202110795153 A CN202110795153 A CN 202110795153A CN 113457466 B CN113457466 B CN 113457466B
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
- B01D67/0002—Organic membrane manufacture
- B01D67/0006—Organic membrane manufacture by chemical reactions
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
- B01D69/10—Supported membranes; Membrane supports
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/06—Organic material
- B01D71/58—Other polymers having nitrogen in the main chain, with or without oxygen or carbon only
- B01D71/60—Polyamines
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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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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F5/00—Softening water; Preventing scale; Adding scale preventatives or scale removers to water, e.g. adding sequestering agents
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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
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/308—Dyes; Colorants; Fluorescent agents
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A20/00—Water conservation; Efficient water supply; Efficient water use
- Y02A20/124—Water desalination
- Y02A20/131—Reverse-osmosis
Abstract
The invention discloses an oxidized hyperbranched polyethyleneimine nanofiltration membrane, which comprises a supporting layer and an oxidized hyperbranched polyethyleneimine layer, wherein the oxidized hyperbranched polyethyleneimine layer is obtained by performing vacuum filtration on an oxidized hyperbranched polyethyleneimine turbid liquid onto the supporting layer. The invention also discloses a preparation method of the oxidized hyperbranched polyethyleneimine nanofiltration membrane, which comprises the steps of adding an oxidant into the hyperbranched polyethyleneimine aqueous solution for reaction, adding deionized water for dilution after precipitation is separated out to obtain an oxidized hyperbranched polyethyleneimine suspension, placing the oxidized hyperbranched polyethyleneimine suspension on a support layer for vacuum filtration to form a membrane, and drying to obtain the oxidized hyperbranched polyethyleneimine nanofiltration membrane. The preparation method is simple, mild in condition and free of the auxiliary action of an organic solvent. The oxidized hyperbranched polyethyleneimine nanofiltration membrane can intercept dye pollutants in water and remove salts in the water, and has great application potential in the field of water treatment.
Description
Technical Field
The invention belongs to the technical field of high polymer materials, and particularly relates to an oxidized hyperbranched polyethyleneimine nanofiltration membrane, and a preparation method and application thereof.
Background
The membrane separation technology is used as a high-efficiency, energy-saving and environment-friendly water treatment technology and is widely applied to the field of sewage treatment. The nanofiltration membrane is a functional semipermeable membrane between an ultrafiltration membrane and a reverse osmosis membrane, and has a nano-scale membrane aperture and a charge effect, allows low-valence molecular salt to pass through, and intercepts organic matters and multivalent ions with higher molecular weight, so that the nanofiltration membrane has unique separation performance and higher separation precision. Compared with other separation membranes, the nanofiltration membrane has the advantages of large membrane flux, low osmotic pressure, selective separation, low operation pressure, low energy consumption and the like. At present, nanofiltration membranes are widely applied to the aspects of hard water softening, brine desalination, drinking water purification, target substance purification and concentration, sewage treatment, reclaimed water recycling and the like. The commercial polyamine nanofiltration membrane is mainly of a composite membrane structure and comprises a polymer ultrafiltration membrane supporting layer and a selection layer obtained by interfacial polymerization on the polymer ultrafiltration membrane supporting layer by taking polyamine and polybasic acyl chloride as monomers, wherein the compactness and the charging performance of the polyamide selection layer play a key role in the interception of ions.
The hyperbranched polyethyleneimine has a highly branched structure, is difficult to crystallize, has no intertwined molecular chains, is excellent in water solubility, and has a large number of active functional group amino groups at the tail ends of branched chains. Hyperbranched polyethyleneimine as an important polyamine positively charged polyelectrolyte has been reported to be prepared into nanofiltration membranes by polyethyleneimine modification, but most of the hyperbranched polyethyleneimine is prepared by an interfacial polymerization method using an organic solvent. CN108905624A discloses a polyesteramide amphoteric charge composite nanofiltration membrane obtained by reacting polyethyleneimine with polyhydric alcohol and trimesoyl chloride, wherein an organic phase of the composite nanofiltration membrane is n-hexane. CN111330447A discloses a quaternized polyethyleneimine prepared by reacting with an acyl chloride monomer, the organic phase of which is n-hexane. CN111187413A discloses a sulfonated polyethyleneimine prepared by reacting polyethyleneimine with sultone and ammonia water, and reacting with aromatic acyl chloride through interfacial polymerization reaction, wherein the organic phase is organic alcohol; CN102151499A discloses a polyamide nanofiltration membrane prepared by interfacial polymerization of polyvinylamine and polybasic acid chloride, and the organic phase of the nanofiltration membrane is n-hexane. Because the interfacial polymerization method uses an organic solvent in the preparation process, the requirements of increasingly strict environmental regulations and production cost cannot be met, and the industrial production is difficult.
Disclosure of Invention
The invention provides an oxidized hyperbranched polyethyleneimine nanofiltration membrane, which is simple in preparation method, mild in preparation process condition, free of the auxiliary action of an organic solvent, capable of preparing a separation membrane with a dye retention function or a desalination function by controlling the oxidation degree of hyperbranched polyethyleneimine, and has great application potential in the field of water treatment.
The technical scheme is as follows:
the utility model provides an oxidation hyperbranched polyethyleneimine nanofiltration membrane, includes supporting layer and oxidation hyperbranched polyethyleneimine layer, oxidation hyperbranched polyethyleneimine layer obtain on being filtered the supporting layer by oxidation hyperbranched polyethyleneimine turbid liquid vacuum suction.
Because a large number of amine groups exist in the hyperbranched polyethyleneimine molecules, the hyperbranched polyethyleneimine can be completely dissolved in water and cannot be formed into a film through simple suction filtration, because the effect of intramolecular hydrogen bonds is smaller than that of intermolecular hydrogen bonds between the hyperbranched polyethyleneimine molecules and water molecules; when oxidant is added for oxidation, the amine group on the hyperbranched polyethyleneimine molecule is oxidized into a nitro group, a ketone group, an aldehyde group and other groups, the intramolecular hydrogen bond action is enhanced, the aggregation is caused, and then the hyperbranched polyethyleneimine is separated out from water.
The invention selects water as a reaction solvent, utilizes an environment-friendly oxidation reagent to oxidize the hyperbranched polyethyleneimine in the water, and can prepare a film through simple suction filtration after the oxidized hyperbranched polyethyleneimine is separated out from the water.
The support layer is a microfiltration membrane with the aperture of 10-450 nm, and comprises but is not limited to a mixed cellulose microfiltration membrane, a polyether sulfone microfiltration membrane, a polystyrene microfiltration membrane, a polyvinylidene fluoride microfiltration membrane and a polyacrylonitrile microfiltration membrane.
The invention also provides a preparation method of the oxidized hyperbranched polyethyleneimine nanofiltration membrane, which comprises the following steps: adding an oxidant into the hyperbranched polyethyleneimine water solution for reaction, adding water for dilution after precipitation in a reaction system is separated out to obtain an oxidized hyperbranched polyethyleneimine suspension, placing the oxidized hyperbranched polyethyleneimine suspension on a supporting layer for vacuum filtration to form a membrane, and drying to obtain the oxidized hyperbranched polyethyleneimine nanofiltration membrane.
The oxidant is at least one of hydrogen peroxide, sodium hypochlorite and ammonium persulfate.
The molecular weight of the hyperbranched polyethyleneimine is 600-70000 Da.
Preferably, the molecular weight of the hyperbranched polyethyleneimine is at least one of 600Da, 1800Da, 10000Da and 70000Da.
The mass concentration of the hyperbranched polyethyleneimine in the hyperbranched polyethyleneimine water solution is 0.05% -50%, the mass concentration of the hyperbranched polyethyleneimine water solution is too low, and the oxidized hyperbranched polyethyleneimine layer of the prepared oxidized hyperbranched polyethyleneimine nanofiltration membrane is not compact enough.
Preferably, the mass concentration of the hyperbranched polyethyleneimine in the hyperbranched polyethyleneimine water solution is 0.1-20%.
The mass ratio of the addition amount of the oxidant to the hyperbranched polyethyleneimine water solution is 0.1-10: 1, the addition amount of the oxidant is too low, so that the precipitated oxidized hyperbranched polyethyleneimine precipitates too little, and the preparation of the oxidized hyperbranched polyethyleneimine nanofiltration membrane is not facilitated.
According to the invention, the degree of oxidation of the hyperbranched polyethyleneimine can be controlled, so that the agglomeration degree of the oxidized hyperbranched polyethyleneimine can be controlled, the addition amount of the oxidant is large, the oxidation degree is high, the particles agglomerated by the oxidized hyperbranched polyethyleneimine are large, the aperture of the oxidized hyperbranched polyethyleneimine nanofiltration membrane prepared by vacuum filtration is large, and the oxidized hyperbranched polyethyleneimine nanofiltration membrane has good separation performance on dye molecules; on the contrary, the oxidation degree is controlled to be low, so that the aperture of the oxidized hyperbranched polyethyleneimine nanofiltration membrane is small, salt ions can be well separated, and the interception of the dye can be realized.
Preferably, the oxidizing agent is hydrogen peroxide or sodium hypochlorite; the mass ratio of the addition amount of the oxidant to the hyperbranched polyethyleneimine water solution is 0.1-2: 1. when the mass ratio is selected, the prepared oxidized hyperbranched polyethyleneimine nanofiltration membrane has better separation performance on dye molecules.
Preferably, the oxidant is sodium hypochlorite or ammonium persulfate; the mass concentration of the hyperbranched polyethyleneimine in the hyperbranched polyethyleneimine water solution is 0.5-2%; the mass ratio of the addition amount of the oxidant to the hyperbranched polyethyleneimine water solution is 0.5-1.5: 1. when the mass ratio is selected, the prepared oxidized hyperbranched polyethyleneimine nanofiltration membrane has good separation performance on salt ions.
The reaction conditions are as follows: 10-40 ℃ for 1-200 min.
The vacuum degree of the vacuum filtration is 0.01-0.1 MPa; the drying temperature is 30-100 ℃, and the drying time is 10-180 min.
The invention also provides application of the oxidized hyperbranched polyethyleneimine nanofiltration membrane in sewage treatment and hard water softening.
The oxidized hyperbranched polyethyleneimine nanofiltration membrane has good interception stability on dye pollutants in water, the retention rate of the dye reaches over 90 percent, and the dye comprises Evans blue, brilliant blue, rhodamine B or chrome black T, but is not limited thereto. Meanwhile, the oxidized hyperbranched polyethyleneimine nanofiltration membrane has a removal effect on salt in water, the rejection rate of the salt is over 60 percent, and the salt comprises copper sulfate, calcium chloride or sodium chloride, but is not limited thereto.
Compared with the prior art, the invention has the following advantages:
(1) The preparation method of the oxidized hyperbranched polyethyleneimine nanofiltration membrane disclosed by the invention is simple, mild in condition, free of the auxiliary action of an organic solvent, free of the complicated purification process of the product, green and environment-friendly in synthesis process, and meets the requirement of green chemistry.
(2) In the preparation process of the oxidized hyperbranched polyethyleneimine nanofiltration membrane disclosed by the invention, the separation membrane with a dye retention function or a desalination function can be prepared by controlling the oxidation degree of hyperbranched polyethyleneimine.
(3) The oxidized hyperbranched polyethyleneimine nanofiltration membrane disclosed by the invention has good and long-term retention stability on dye pollutants in water, the retention rate of the dye reaches over 90%, the softening effect on hard water can be realized, the retention rate of salt reaches over 60%, and the oxidized hyperbranched polyethyleneimine nanofiltration membrane has great application potential in the field of water treatment.
Drawings
Fig. 1 is an oxidized hyperbranched polyethyleneimine and an oxidized hyperbranched polyethyleneimine nanofiltration membrane prepared in example 1, wherein a is an SEM picture of the oxidized hyperbranched polyethyleneimine, and B is an optical picture of the oxidized hyperbranched polyethyleneimine nanofiltration membrane.
FIG. 2 is an infrared spectrum of hyperbranched polyethyleneimine and oxidized hyperbranched polyethyleneimine prepared in example 1.
Fig. 3 shows the separation performance of the oxidized hyperbranched polyethyleneimine nanofiltration membranes prepared in examples 1 to 4 on dyes, EB: evans blue, BB: brilliant blue, rhB: rhodamine B, EBT: and (4) chrome black T.
FIG. 4 shows the salt separation performance of the oxidized hyperbranched polyethyleneimine nanofiltration membranes prepared in examples 5 to 7.
FIG. 5 is an SEM picture of the oxidized hyperbranched polyethyleneimine nanofiltration membrane prepared in example 6.
FIG. 6 is an SEM picture of the oxidized hyperbranched polyethyleneimine nanofiltration membrane prepared in example 7.
Detailed Description
Comparative example:
respectively taking 50mg of hyperbranched polyethyleneimine with the molecular weights of 600Da, 1800Da, 10000Da and 70000Da, dissolving the hyperbranched polyethyleneimine in 20mL of deionized water, adding 50mL of deionized water for dilution, taking a mixed cellulose microfiltration membrane with the pore diameter of 0.1 mu m as a supporting layer, and performing vacuum filtration to form a membrane. However, due to the excellent water solubility of the hyperbranched polyethyleneimine, the hyperbranched polyethyleneimine water solution completely permeates from the support layer in the vacuum filtration process, and a film cannot be formed.
Example 1
Dissolving 25mg of hyperbranched polyethyleneimine with the molecular weight of 1800Da in 5mL of deionized water, uniformly stirring to obtain a hyperbranched polyethyleneimine aqueous solution, adding 0.5mL of 30wt% hydrogen peroxide, reacting at 25 ℃ for 3h, and adding 30mL of deionized water for dilution after precipitation is separated out from the reaction system to obtain an oxidized hyperbranched polyethyleneimine suspension. Wherein, the oxidized hyperbranched polyethyleneimine precipitate separated out from the reaction system is light yellow, and the microscopic morphology is shown in figure 1A.
And (2) taking a mixed cellulose microfiltration membrane with the pore diameter of 0.1 mu m as a supporting layer, placing the oxidized hyperbranched polyethyleneimine suspension on the supporting layer, performing vacuum filtration to form a membrane, wherein the vacuum degree is 0.05MPa, and drying at 45 ℃ for 2 hours to obtain the oxidized hyperbranched polyethyleneimine nanofiltration membrane.
The optical picture of the oxidized hyperbranched polyethyleneimine nanofiltration membrane is shown in fig. 1B, and the oxidized hyperbranched polyethyleneimine membrane is deposited on the mixed cellulose support layer in a suction filtration mode and can completely cover the support layer.
The infrared spectrograms of the hyperbranched polyethyleneimine and the oxidized hyperbranched polyethyleneimine are shown in figure 2, and the amine group of the hyperbranched polyethyleneimine is oxidized into a nitro group, a ketone group, an aldehyde group and other groups in the oxidation process.
The results of EDX elemental analysis of the oxidized hyperbranched polyethyleneimine nanofiltration membrane are shown in table 1. From the experimental data in the table, it can be seen that the oxygen content of the oxidized hyperbranched polyethyleneimine is 20.1wt%, and the hyperbranched polyethyleneimine does not contain oxygen, i.e. the hyperbranched polyethyleneimine has been partially oxidized.
The obtained oxidized hyperbranched polyethyleneimine nanofiltration membrane was used for separating 50mg/L Evans Blue (EB) solution under the pressure of 4bar, and the result is shown in FIG. 3, wherein the flux is 0.9L m -2 h -1 bar -1 The rejection rate was 91.9%.
Table 1 EDX data of the oxidized hyperbranched polyethyleneimine nanofiltration membranes prepared in example 1
Example 2
Dissolving 25mg of hyperbranched polyethyleneimine with the molecular weight of 10000Da in 5mL of deionized water, uniformly stirring to obtain a hyperbranched polyethyleneimine aqueous solution, adding 2mL of 30wt% hydrogen peroxide into the hyperbranched polyethyleneimine aqueous solution, reacting at 25 ℃ for 3 hours, and adding 30mL of deionized water for dilution after precipitation is separated out from the reaction system to obtain an oxidized hyperbranched polyethyleneimine suspension.
And (2) taking a mixed cellulose microfiltration membrane with the pore diameter of 0.1 mu m as a supporting layer, placing the oxidized hyperbranched polyethyleneimine suspension on the supporting layer, performing vacuum filtration to form a membrane, wherein the vacuum degree is 0.05MPa, and drying at 45 ℃ for 2 hours to obtain the oxidized hyperbranched polyethyleneimine nanofiltration membrane.
The obtained oxidized hyperbranched polyethyleneimine membrane was separated from a 50mg/L Brilliant Blue (BB) solution at a pressure of 4bar, and the flux was 1.1L m as shown in FIG. 3 -2 h -1 bar -1 The rejection was 98.6%.
Example 3
Dissolving 25mg of hyperbranched polyethyleneimine with the molecular weight of 600Da in 5mL of deionized water, uniformly stirring to obtain a hyperbranched polyethyleneimine aqueous solution, adding 1mL of chemically pure sodium hypochlorite, reacting at 25 ℃ for 2min, and adding 30mL of deionized water for dilution after precipitates are separated out from the reaction system to obtain an oxidized hyperbranched polyethyleneimine suspension.
And (2) taking a mixed cellulose microfiltration membrane with the aperture of 0.1 mu m as a supporting layer, placing the oxidized hyperbranched polyethyleneimine suspension on the supporting layer, performing vacuum filtration to form a membrane, wherein the vacuum degree is 0.1MPa, and drying at 45 ℃ for 1h to obtain the oxidized hyperbranched polyethyleneimine nanofiltration membrane.
The obtained oxidized hyperbranched polyethyleneimine membrane is used for separating 50mg/L rhodamine B (RhB) solution under the pressure of 4bar, and the result is shown in figure 3, wherein the flux is 1.2L m -2 h -1 bar -1 The rejection was 99.9%.
Example 4
Dissolving 25mg of hyperbranched polyethyleneimine with the molecular weight of 70000Da in 5mL of deionized water, uniformly stirring to obtain a hyperbranched polyethyleneimine water solution, adding 5mL of chemically pure sodium hypochlorite, reacting at 25 ℃ for 2min, and adding 30mL of deionized water for dilution after precipitation is separated out from the reaction system to obtain an oxidized hyperbranched polyethyleneimine suspension.
And (2) taking a mixed cellulose microfiltration membrane with the aperture of 0.1 mu m as a supporting layer, placing the oxidized hyperbranched polyethyleneimine suspension on the supporting layer, performing vacuum filtration to form a membrane, wherein the vacuum degree is 0.1MPa, and drying at 45 ℃ for 1h to obtain the oxidized hyperbranched polyethyleneimine nanofiltration membrane.
The obtained oxidized hyperbranched polyethyleneimine membrane pair is subjected to pressure of 4barThe separation was carried out using a 50mg/L chrome black T (EBT) solution, and the flux was 1.2L m as shown in FIG. 3 -2 h -1 bar -1 The rejection was 99.0%.
Example 5
Respectively taking 50mg of hyperbranched polyethyleneimine with the molecular weight of 10000Da and 1800Da, dissolving in 5mL of deionized water, uniformly stirring to obtain a hyperbranched polyethyleneimine aqueous solution, adding 6mL of chemically pure sodium hypochlorite, reacting at 25 ℃ for 2min, and adding 30mL of deionized water for dilution after precipitation is separated out from the reaction system to obtain an oxidized hyperbranched polyethyleneimine suspension.
And (2) taking a mixed cellulose microfiltration membrane with the aperture of 0.1 mu m as a supporting layer, placing the oxidized hyperbranched polyethyleneimine turbid liquid on the supporting layer, performing vacuum filtration to form a membrane, wherein the vacuum degree is 0.1MPa, and drying at 45 ℃ for 1h to obtain the oxidized hyperbranched polyethyleneimine nanofiltration membrane.
The prepared oxidized hyperbranched polyethyleneimine nanofiltration membrane is used for separating 10g/L copper sulfate solution under the pressure of 4bar, and the result is shown in figure 4, wherein the flux is 0.7L m -2 h -1 bar -1 The rejection was 99.0%.
Example 6
Respectively taking 50mg of hyperbranched polyethyleneimine with the molecular weight of 600Da and 1800Da, dissolving the hyperbranched polyethyleneimine into 10mL of deionized water, uniformly stirring to obtain a hyperbranched polyethyleneimine aqueous solution, adding 8g of analytically pure ammonium persulfate, reacting at 25 ℃ for 1h, and adding 50mL of deionized water for dilution after precipitation is separated out from the reaction system to obtain an oxidized hyperbranched polyethyleneimine suspension.
And (2) taking a mixed cellulose microfiltration membrane with the aperture of 0.1 mu m as a supporting layer, placing the oxidized hyperbranched polyethyleneimine suspension on the supporting layer, performing vacuum filtration to form a membrane, wherein the vacuum degree is 0.1MPa, and drying at 45 ℃ for 1h to obtain the oxidized hyperbranched polyethyleneimine nanofiltration membrane.
SEM surface morphology representation is carried out on the oxidized hyperbranched polyethyleneimine nanofiltration membrane, and the result is shown in figure 5, wherein the surface of the oxidized hyperbranched polyethyleneimine nanofiltration membrane has a plurality of granular structures which are closely stacked in batches, and the surface is rough.
The prepared oxidized hyperbranched polyethyleneimine nanofiltration membrane is used for separating 10g/L calcium chloride solution under the pressure of 4bar, and the result is shown in figure 4, wherein the flux is 1.1L m -2 h -1 bar -1 The rejection was 80.1%.
Example 7
Respectively taking 50mg of hyperbranched polyethyleneimine with the molecular weight of 1800Da, 10000Da and 70000Da, dissolving the hyperbranched polyethyleneimine into 10mL of deionized water, uniformly stirring to obtain hyperbranched polyethyleneimine water solution, adding 12g of analytically pure ammonium persulfate into the hyperbranched polyethyleneimine water solution, reacting for 3 hours at 25 ℃, and adding 50mL of deionized water for dilution after precipitation is separated out from the reaction system to obtain oxidized hyperbranched polyethyleneimine suspension.
And (2) taking a mixed cellulose microfiltration membrane with the aperture of 0.1 mu m as a supporting layer, placing the oxidized hyperbranched polyethyleneimine suspension on the supporting layer, performing vacuum filtration to form a membrane, wherein the vacuum degree is 0.1MPa, and drying at 45 ℃ for 1h to obtain the oxidized hyperbranched polyethyleneimine nanofiltration membrane.
The surface morphology of the oxidized hyperbranched polyethyleneimine nanofiltration membrane is characterized by SEM, and the result is shown in FIG. 6, compared with the example 6, the surface of the oxidized hyperbranched polyethyleneimine nanofiltration membrane prepared by the method is smoother and smoother, which indicates that the oxidized hyperbranched polyethyleneimine is stacked more uniformly and tightly.
The prepared oxidized hyperbranched polyethyleneimine nanofiltration membrane is used for separating 10g/L sodium chloride solution under the pressure of 4bar, and the result is shown in figure 4, wherein the flux is 1.4L m -2 h -1 bar -1 The rejection was 66.6%.
Claims (8)
1. The preparation method of the oxidized hyperbranched polyethyleneimine nanofiltration membrane is characterized in that the oxidized hyperbranched polyethyleneimine nanofiltration membrane comprises a supporting layer and an oxidized hyperbranched polyethyleneimine layer;
adding an oxidant into the hyperbranched polyethyleneimine aqueous solution for reaction, and adding water for dilution after precipitation in a reaction system to obtain the oxidized hyperbranched polyethyleneimine suspension; placing the oxidized hyperbranched polyethyleneimine turbid liquid on a support layer, performing vacuum filtration to form a film, and drying to obtain an oxidized hyperbranched polyethyleneimine nanofiltration membrane;
the oxidant is at least one of hydrogen peroxide, sodium hypochlorite and ammonium persulfate;
the mass concentration of the hyperbranched polyethyleneimine in the hyperbranched polyethyleneimine water solution is 0.05% -50%;
the mass ratio of the addition amount of the oxidant to the hyperbranched polyethyleneimine water solution is 0.1 to 10:1.
2. the preparation method of the oxidized hyperbranched polyethyleneimine nanofiltration membrane according to claim 1, wherein the support layer is a microfiltration membrane with a pore size of 10 to 450nm, and the microfiltration membrane is any one of a mixed cellulose microfiltration membrane, a polyethersulfone microfiltration membrane, a polystyrene microfiltration membrane, a polyvinylidene fluoride microfiltration membrane and a polyacrylonitrile microfiltration membrane.
3. The preparation method of the oxidized hyperbranched polyethyleneimine nanofiltration membrane according to claim 1, wherein the molecular weight of the hyperbranched polyethyleneimine is 600 to 70000Da.
4. The method for preparing the oxidized hyperbranched polyethyleneimine nanofiltration membrane according to claim 1, wherein the oxidant is hydrogen peroxide or sodium hypochlorite; the mass ratio of the addition amount of the oxidant to the hyperbranched polyethyleneimine water solution is 0.1 to 2:1.
5. the method for preparing the oxidized hyperbranched polyethyleneimine nanofiltration membrane according to claim 1, wherein the oxidant is sodium hypochlorite or ammonium persulfate; the mass concentration of the hyperbranched polyethyleneimine in the hyperbranched polyethyleneimine water solution is 0.5% -2%; the mass ratio of the addition amount of the oxidant to the hyperbranched polyethyleneimine water solution is 0.5 to 1.5:1.
6. the method for preparing the oxidized hyperbranched polyethyleneimine nanofiltration membrane according to claim 1, wherein the reaction conditions are as follows: 10 to 40 ℃,1 to 200 min; the vacuum degree of the vacuum filtration is 0.01 to 0.1MPa; the drying temperature is 30 to 100 ℃, and the drying time is 10 to 180min.
7. The oxidized hyperbranched polyethyleneimine nanofiltration membrane prepared by the method for preparing the oxidized hyperbranched polyethyleneimine nanofiltration membrane according to any one of claims 1 to 6.
8. The use of an oxidized hyperbranched polyethyleneimine nanofiltration membrane according to claim 7 in the field of water treatment.
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| WO2015073161A1 (en) * | 2013-11-12 | 2015-05-21 | Ppg Industries Ohio, Inc. | Coated microporous materials having filtration and adsorption properties and their use in fluid purification processes |
| CN106139922A (en) * | 2015-04-14 | 2016-11-23 | 华东理工大学 | Ultra-high throughput NF membrane and preparation method thereof |
| CN111013399A (en) * | 2019-12-25 | 2020-04-17 | 福州大学 | Bionic nanofiltration membrane for extracting humic acid in landfill leachate membrane concentrated solution and preparation method thereof |
| CN111992042A (en) * | 2020-09-10 | 2020-11-27 | 德州学院 | Method for improving water flux of polyelectrolyte nanofiltration membrane |
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