CN113457466A - Oxidized hyperbranched polyethyleneimine nanofiltration membrane, preparation method and application - Google Patents
Oxidized hyperbranched polyethyleneimine nanofiltration membrane, preparation method and application Download PDFInfo
- Publication number
- CN113457466A CN113457466A CN202110795153.XA CN202110795153A CN113457466A CN 113457466 A CN113457466 A CN 113457466A CN 202110795153 A CN202110795153 A CN 202110795153A CN 113457466 A CN113457466 A CN 113457466A
- Authority
- CN
- China
- Prior art keywords
- hyperbranched polyethyleneimine
- oxidized
- nanofiltration membrane
- polyethyleneimine
- hyperbranched
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Images
Classifications
-
- 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
-
- 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
-
- 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
-
- 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
-
- 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
-
- 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
-
- 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 salt in 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 the ultrafiltration membrane and the reverse osmosis membrane, and has a nano-scale membrane aperture and a charge effect, so that low-valence molecular salt is allowed to pass through and higher-molecular-weight organic matters and multivalent ions are intercepted, and 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 is taken as an important polyamine positively charged polyelectrolyte, and a plurality of reports for preparing nanofiltration membranes by polyethyleneimine modification are provided at present, but most of the hyperbranched polyethyleneimine is prepared by an interfacial polymerization method using an organic solvent. CN108905624A discloses that polyethyleneimine reacts with polyhydric alcohol and trimesoyl chloride to obtain a polyesteramide amphoteric charge composite nanofiltration membrane, and the organic phase of the nanofiltration membrane is n-hexane. CN111330447A discloses a method for preparing quaternized polyethyleneimine by reacting with acyl chloride monomer, wherein the organic phase is n-hexane. CN111187413A discloses a sulfonated polyethyleneimine prepared by reacting polyethyleneimine with sultone and ammonia water, and then 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 acyl chloride, wherein 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 conditions, 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 having great application potential in the field of water treatment.
The technical scheme is as follows:
the oxidized hyperbranched polyethyleneimine nanofiltration membrane 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 on the supporting layer.
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 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 70000 Da.
The mass concentration of the hyperbranched polyethyleneimine in the hyperbranched polyethyleneimine aqueous solution is 0.05-50%, the mass concentration of the hyperbranched polyethyleneimine aqueous 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 adding 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.
The invention can control the agglomeration degree of the oxidized hyperbranched polyethyleneimine by controlling the oxidation degree of the hyperbranched polyethyleneimine, 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 control of the oxidation degree is low, so that the aperture of the oxidized hyperbranched polyethyleneimine nanofiltration membrane is small, the separation performance on salt ions is good, and the interception of the dye can be realized.
Preferably, 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 0.1-2: 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: 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 30 wt% 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 aperture of 0.1 mu m as a supporting layer, placing the oxidized hyperbranched polyethyleneimine suspension on the supporting layer, carrying out vacuum filtration to form a membrane, wherein the vacuum degree is 0.05MPa, and drying at 45 ℃ for 2h 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 fig. 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 20.1 wt%, 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 to separate 50mg/L Evans Blue (EB) solution at a pressure of 4bar, and the result is shown in FIG. 3, where the flux is 0.9L m-2h-1bar-1The rejection 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 30 wt% 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.
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 0.05MPa, and drying at 45 ℃ for 2h 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. 3-2h-1bar-1The 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.
Under the pressure of 4bar, the obtained oxidized hyperbranched polyethyleneimineThe membrane separates 50mg/L rhodamine B (RhB) solution, and the result is shown in figure 3, the flux is 1.2L m-2h-1bar-1The 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 aqueous solution, adding 5mL of chemically pure sodium hypochlorite into the hyperbranched polyethyleneimine aqueous solution, reacting for 2min at 25 ℃, 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 oxidized hyperbranched polyethyleneimine film obtained was separated from a 50mg/L solution of chrome black T (EBT) at a pressure of 4bar, and the flux was 1.2L m as shown in FIG. 3-2h-1bar-1The 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 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 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-2h-1bar-1The 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-2h-1bar-1The 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 in 10mL of deionized water, uniformly stirring to obtain a hyperbranched polyethyleneimine aqueous solution, adding 12g of analytically pure ammonium persulfate into the hyperbranched polyethyleneimine aqueous solution, reacting at 25 ℃ for 3 hours, 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.
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-2h-1bar-1The rejection was 66.6%.
Claims (10)
1. The oxidized hyperbranched polyethyleneimine nanofiltration membrane is characterized by comprising 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 on the supporting layer.
2. The oxidized hyperbranched polyethyleneimine nanofiltration membrane according to claim 1, wherein the support layer is a microfiltration membrane with a pore diameter of 10-450 nm, 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 or 2, wherein the preparation method 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.
4. The method for preparing an oxidized hyperbranched polyethyleneimine nanofiltration membrane according to claim 3, wherein the oxidant is at least one of hydrogen peroxide, sodium hypochlorite and ammonium persulfate.
5. The method for preparing the oxidized hyperbranched polyethyleneimine nanofiltration membrane according to claim 3, wherein the molecular weight of the hyperbranched polyethyleneimine is 600-70000 Da; the mass concentration of the hyperbranched polyethyleneimine in the hyperbranched polyethyleneimine water solution is 0.05-50%.
6. The method for preparing an oxidized hyperbranched polyethyleneimine nanofiltration membrane according to claim 3, wherein the mass ratio of the addition amount of the oxidant to the hyperbranched polyethyleneimine aqueous solution is 0.1-10: 1.
7. the method for preparing the oxidized hyperbranched polyethyleneimine nanofiltration membrane according to claim 3, 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 0.1-2: 1.
8. the method for preparing the oxidized hyperbranched polyethyleneimine nanofiltration membrane according to claim 3, 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 0.5-1.5: 1.
9. the method for preparing the oxidized hyperbranched polyethyleneimine nanofiltration membrane according to claim 3, wherein 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.
10. The use of the oxidized hyperbranched polyethyleneimine nanofiltration membrane according to claim 1 or 2 in the field of water treatment.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202110795153.XA CN113457466B (en) | 2021-07-14 | 2021-07-14 | Oxidized hyperbranched polyethyleneimine nanofiltration membrane, preparation method and application |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202110795153.XA CN113457466B (en) | 2021-07-14 | 2021-07-14 | Oxidized hyperbranched polyethyleneimine nanofiltration membrane, preparation method and application |
Publications (2)
Publication Number | Publication Date |
---|---|
CN113457466A true CN113457466A (en) | 2021-10-01 |
CN113457466B CN113457466B (en) | 2023-03-07 |
Family
ID=77880200
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN202110795153.XA Active CN113457466B (en) | 2021-07-14 | 2021-07-14 | Oxidized hyperbranched polyethyleneimine nanofiltration membrane, preparation method and application |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN113457466B (en) |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN114479449A (en) * | 2022-03-16 | 2022-05-13 | 山东交通学院 | Composite material for ground restoration and bearing reinforcement engineering, preparation method and application |
CN115262232A (en) * | 2022-08-26 | 2022-11-01 | 兰州理工大学 | Amine-rich polyacrylonitrile-based nano composite fiber membrane as well as preparation method and application thereof |
Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
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 |
-
2021
- 2021-07-14 CN CN202110795153.XA patent/CN113457466B/en active Active
Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
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 |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN114479449A (en) * | 2022-03-16 | 2022-05-13 | 山东交通学院 | Composite material for ground restoration and bearing reinforcement engineering, preparation method and application |
CN115262232A (en) * | 2022-08-26 | 2022-11-01 | 兰州理工大学 | Amine-rich polyacrylonitrile-based nano composite fiber membrane as well as preparation method and application thereof |
CN115262232B (en) * | 2022-08-26 | 2024-03-22 | 兰州理工大学 | Amino-rich polyacrylonitrile-based nano composite fiber membrane and preparation method and application thereof |
Also Published As
Publication number | Publication date |
---|---|
CN113457466B (en) | 2023-03-07 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
Li et al. | Polyelectrolytes self-assembly: versatile membrane fabrication strategy | |
CN102294177B (en) | Sulfobetaine type amphion-containing reverse osmosis composite film | |
CN102553460B (en) | Method for preparing pollution-resistant low-pressure reverse osmosis membrane | |
CN113457466B (en) | Oxidized hyperbranched polyethyleneimine nanofiltration membrane, preparation method and application | |
CN107344074B (en) | Preparation method of high-flux solvent-resistant organic/inorganic hybrid composite membrane doped with aminated graphene quantum dots | |
CN102553461B (en) | Inorganic/organic composite nanofiltration membrane and preparation method thereof | |
CN110449049B (en) | Nanofiltration membrane, preparation method and application of nanofiltration membrane in separation of pigment wastewater monovalent mixed salt | |
CN111921387B (en) | Preparation method of polydopamine modified imidazolyl nanoparticle composite nanofiltration membrane | |
CN113289498B (en) | Positively charged nanofiltration membrane and preparation method thereof | |
Febrianto et al. | Polyetherimide nanofiltration membranes modified by interfacial polymerization for treatment of textile dyes wastewater | |
CN106345323A (en) | Preparation method for anti-pollution hydrophilic positive permeable membrane | |
CN114288876B (en) | Preparation method of crown ether functionalized nanofiltration membrane for extracting lithium from magnesium-lithium mixed solution | |
CN114797490A (en) | Preparation method of high-selectivity separation membrane for separating anionic salt | |
CN114870641A (en) | Piperazinyl primary positively charged nanofiltration membrane and preparation method thereof | |
CN101332415A (en) | Polyamide reverse osmosis composite membrane containing biphenyl structure and production method thereof | |
CN110743383B (en) | Modification method for improving permeation flux of polyamide composite membrane | |
CN117181019A (en) | Nitrogen-containing hybrid macrocyclic cycloparaffin polyamide composite membrane, and preparation method and application thereof | |
CN110548400A (en) | Large-flux reverse osmosis membrane and preparation method thereof | |
KR100322235B1 (en) | Fabrication of high permeable reverse osmosis membranes | |
CN104801209A (en) | Ultralow-pressure nanofiltration membrane prepared from imidazole sulfonate grafted polyether sulfone | |
CN116143233A (en) | Preparation method of debrominated seawater desalination reverse osmosis membrane and reverse osmosis membrane prepared by same | |
CN117427509B (en) | Self-assembled dendritic macromolecule polyamide nano-film for efficient separation of lithium and magnesium and preparation method thereof | |
Zhou et al. | A facile method to fabricate anti-fouling nanofiltration membrane with aminated lignin | |
CN116943461B (en) | Nanofiltration membrane and preparation method and application thereof | |
CN114471197B (en) | Mixed charged nanofiltration membrane and preparation method and application thereof |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
PB01 | Publication | ||
PB01 | Publication | ||
SE01 | Entry into force of request for substantive examination | ||
SE01 | Entry into force of request for substantive examination | ||
GR01 | Patent grant | ||
GR01 | Patent grant |