CN112138545A - Gallic acid-based positively charged composite nanofiltration membrane and preparation method thereof - Google Patents

Gallic acid-based positively charged composite nanofiltration membrane and preparation method thereof Download PDF

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CN112138545A
CN112138545A CN201910568707.5A CN201910568707A CN112138545A CN 112138545 A CN112138545 A CN 112138545A CN 201910568707 A CN201910568707 A CN 201910568707A CN 112138545 A CN112138545 A CN 112138545A
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membrane
gallic acid
polyethyleneimine
solution
nanofiltration membrane
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黄中华
唐梦頔
张震
林晓璐
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Nanjing University of Science and Technology
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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
    • B01D71/40—Polymers of unsaturated acids or derivatives thereof, e.g. salts, amides, imides, nitriles, anhydrides, esters
    • B01D71/42—Polymers of nitriles, e.g. polyacrylonitrile
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D61/00—Processes of separation using semi-permeable membranes, e.g. dialysis, osmosis or ultrafiltration; Apparatus, accessories or auxiliary operations specially adapted therefor
    • B01D61/02—Reverse osmosis; Hyperfiltration ; Nanofiltration
    • B01D61/027—Nanofiltration
    • 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
    • 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
    • B01D69/02—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor characterised by their properties
    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2325/00—Details relating to properties of membranes
    • B01D2325/16—Membrane materials having positively charged functional groups
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2325/00—Details relating to properties of membranes
    • B01D2325/36—Hydrophilic membranes
    • 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

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  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Nanotechnology (AREA)
  • Water Supply & Treatment (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Hydrology & Water Resources (AREA)
  • Environmental & Geological Engineering (AREA)
  • Organic Chemistry (AREA)
  • Manufacturing & Machinery (AREA)
  • Separation Using Semi-Permeable Membranes (AREA)

Abstract

The invention discloses a gallic acid-based positively charged composite nanofiltration membrane and a preparation method thereof. The method is characterized in that a polyacrylonitrile hydrolysis membrane is used as a supporting layer, the supporting layer is soaked in a homogeneous composite solution formed by gallic acid and polyethyleneimine, and the positively charged composite nanofiltration membrane is prepared after thermal crosslinking. The method has simple operation, no pollution and no by-product, and the pure water permeability coefficient of the prepared composite nanofiltration membrane is 74.214 L.m‑2·h‑1·MPa‑1The molecular weight cut-off is 958Da, which belongs to the nano-filtration membrane category, the isoelectric point of the membrane surface is 7.2, and the membrane has good hydrophilicity and anti-pollution performance, and has good removal effect on trace-trace organic pollutants in water.

Description

Gallic acid-based positively charged composite nanofiltration membrane and preparation method thereof
Technical Field
The invention belongs to the technical field of preparation of separation membranes, and relates to a gallic acid-based positively-charged composite nanofiltration membrane and a preparation method thereof.
Background
The nanofiltration technology has low operation pressure, strong selective separation performance, unique charge effect and good interception effect on organic matters with molecular mass of 150-1000, and the relative molecular mass of most of medicines and personal care products (PPCPs) is between the two, so the nanofiltration membrane treatment technology has potential advantages in removing trace-trace PPCPs organic pollutants in the environment. Benes et al (Lee K P, et al. pH stable film composite polymeric membranes by interfacial polymerization [ J ]. Journal of Membrane Science,2015,478:75-84.) found that positively charged PEI/CC/Polyethersulfone (PES) nanofiltration membranes had good separation performance and excellent acid and base resistance (pH 1-13). Chung (Sun S P, Chung T S, Hatton T A. high branched polyethylene induced Cross-linking of polyamine-imide nanofilation Hollow Fiber Membranes for Effective Removal of Ciprofloxacin [ J ] Environmental Science & Technology,2011,45(9): 4003) 4009) and the like research the separation performance of positively charged PEI/PAI Nanofiltration Membranes prepared by a chemical Cross-linking method on Ciprofloxacin at different pH values, and the result shows that PEI-60K/PA has the best separation performance and pollution resistance.
Gallic Acid (GA) is a natural carboxyl-containing polyphenol compound widely existing in plants such as grapes and tea leaves, has the characteristics of oxidation resistance, water solubility, antibacterial property and the like, is widely applied in the fields of food, biology, medicinal chemistry and the like, but the technical development in the aspect of water treatment is not complete. GA contains abundant phenol groups, the groups are easily oxidized into quinoid structures in an alkaline environment, so that Michael addition or Schiff base reaction is carried out on the groups and hydrophilic or hydrophobic organic molecules containing sulfydryl, amino or imino, and carboxyl in the molecular structure can improve the hydrophilicity of a membrane, so that the substance has reaction activity, can be used for further surface modification of the membrane, realizes the functionalization of the membrane, and plays an increasingly important role in the field of membrane application.
The Polyethyleneimine (PEI) is a water-soluble polymer with higher cation density and stronger adsorbability, and as active primary amine and secondary amine on a molecular chain can react with epoxy groups, carboxylic acid and isocyanate, and a large number of amine groups on the molecular chain of the PEI are in a protonated state, the positively-charged PEI nanofiltration membrane has high hydrophilicity, high separability and high stability. PEI has good water solubility, high charge density and low cost. The positively charged nanofiltration membrane prepared by the method has the characteristics of high separability and strong stability. The separation performance for PPCPs, dyes and heavy metals is good. The nanofiltration membrane prepared by the method can adsorb and separate negatively charged bacteria, toxins and colloidal particles in a water source. Wang (Li X, Wang R, Wicaksana F, et al.preparation of high performance Nanofilteration (NF) membranes associated with aquaporin Z [ J]Journal of Membrane Science,2014,450: 181-188), etc. by crosslinking dopamine with polyethyleneimine and introducing aquaporins at the Membrane surface, forming unique water channels, achieving nanofiltration Membrane operation at 1.0bar, and having 36.6 L.m.-2·h-1·MPa-1Water flux and excellent rejection properties.
Disclosure of Invention
The invention aims to provide a gallic acid-based positively-charged composite nanofiltration membrane with high water flux and excellent PPCPs rejection rate and a preparation method thereof.
The technical solution for realizing the purpose of the invention is as follows:
a preparation method of a positively charged composite nanofiltration membrane based on gallic acid, which takes a PAN hydrolytic membrane as a basal membrane, takes gallic acid and polyethyleneimine as reaction substances, utilizes Schiff base reaction and Michael addition reaction between the gallic acid and the polyethyleneimine and electrostatic attraction action between a compound formed by the gallic acid and the polyethyleneimine and the PAN hydrolytic membrane, and adopts a surface coating method to prepare the positively charged composite nanofiltration membrane based on a biological material, and comprises the following steps:
step 1, soaking a Polyacrylonitrile (PAN) ultrafiltration membrane in water for more than 12 hours, hydrolyzing a soaked substrate membrane in a 2-2.5 mol/L NaOH solution for 1-2 hours at the constant temperature of 40-50 ℃ in a water bath, then putting the hydrolyzed PAN substrate membrane into a 0.2-0.3 mol/L HCl solution for acidification for 2-3 hours, and taking out to generate a polyacrylonitrile hydrolyzed membrane;
and 2, reacting 0.20-0.30% gallic acid solution and 0.30-0.40% polyethyleneimine solution at a pH of 7.5-8.5 for 9-12 h, soaking the polyacrylonitrile hydrolyzed membrane in homogeneous solution obtained by reacting gallic acid and polyethyleneimine for 1-2 h, performing thermal crosslinking at 40-45 ℃ for 25-35 min after water washing, and soaking in water for preservation to obtain the gallic acid-based positively-charged composite nanofiltration membrane.
Preferably, in step 2, the concentration of gallic acid is 0.20%, the concentration of polyethyleneimine is 0.30%, and the reaction time is 9 h.
Preferably, in step 2, the molecular weight of the polyethyleneimine is 600, 1800 or 10000 Da.
Preferably, in step 2, the soaking time is 1h, and the thermal crosslinking time is 30 min.
The invention also provides the gallic acid-based positively charged composite nanofiltration membrane prepared by the preparation method.
Compared with the prior art, the invention has the following advantages:
the invention has simple process, and is natural and environment-friendly. The prepared composite membrane has higher flux, good stability, hydrophilicity and anti-pollution performance, and excellent effect on interception of trace-trace organic PPCPs in water, and the highest interception rate can reach 91.35%.
Drawings
Fig. 1 is a graph showing the permeability coefficient of pure water of a positively charged composite nanofiltration membrane based on gallic acid, which was obtained under the preparation conditions of 0.20% concentration of gallic acid, 0.30% concentration of polyethyleneimine, 9 hours of reaction time at pH 8.5, 1800 molecular weight of polyethyleneimine, 1 hour of soaking time, and 30 minutes of thermal crosslinking time.
Fig. 2 is a graph showing the retention curve of gallic acid-based positively-charged composite nanofiltration membrane on a series of organic matters with different molecular weights, wherein the gallic acid concentration is 0.20%, the polyethyleneimine concentration is 0.30%, the reaction time is 9h under the condition that the pH value is 8.5, the polyethyleneimine molecular weight is 1800, the soaking time is 1h, and the thermal crosslinking time is 30 min.
Fig. 3 is a graph showing the change of Zeta potential on the surface of the positively charged composite nanofiltration membrane with pH, which is obtained under the preparation conditions of 0.20% of gallic acid, 0.30% of polyethyleneimine, 8.5 pH, 9h of reaction time, 1800 molecular weight of polyethyleneimine, 1h of soaking time and 30min of thermal crosslinking time.
FIG. 4 is a surface view and a cross-sectional view of a PAN hydrolysis film in scanning electron microscope (a) and (c), respectively. The figure (b) and the figure (d) are a scanning electron microscope surface image and a cross section image of the gallic acid-based positively-charged composite nanofiltration membrane obtained under the preparation conditions that the concentration of gallic acid of the PAN hydrolysis membrane is 0.20%, the concentration of polyethyleneimine is 0.30%, the reaction time is 9h under the condition that the pH value is 8.5, the molecular weight of polyethyleneimine is 1800, the soaking time is 1h and the thermal crosslinking time is 30 min.
Fig. 5 is a contact angle diagram of the PAN hydrolysis membrane and the composite nanofiltration membrane obtained under the preparation conditions that the concentration of gallic acid is 0.20%, the concentration of polyethyleneimine is 0.30%, the reaction time is 6h and 9h under the condition that the pH is 8.5, the molecular weight of polyethyleneimine is 1800 and 10000, the soaking time is 1h, and the thermal crosslinking time is 30 min. Wherein M1 is PAN-H, M2 is GA/PEI1800-6H, M3 is GA/PEI1800-9H, M4 is GA/PEI10000-6H, and M5 is GA/PEI 10000-9H.
Fig. 6 is a graph showing the results of interception of PPCPs by a gallic acid-based positively-charged composite nanofiltration membrane obtained under the conditions of a gallic acid concentration of 0.20%, a polyethyleneimine concentration of 0.30%, a reaction time of 9 hours at pH 8.5, a polyethyleneimine molecular weight of 1800, a soaking time of 1 hour, and a thermal crosslinking time of 30 min.
Detailed Description
The invention is described in further detail below with reference to the figures and examples.
Example 1
Soaking 12 polyacrylonitrile ultrafiltration membranes in deionized water for 12 hours, hydrolyzing the soaked substrate membrane in 2mol/L NaOH solution for 1 hour at the constant temperature of 45 ℃ in a water bath, then putting the hydrolyzed PAN substrate membrane in 0.2mol/L HCl for acidification for 3 hours at normal temperature, and taking out the hydrolyzed PAN substrate membrane to generate the polyacrylonitrile hydrolyzed membrane. Weighing a polyethyleneimine (Mw is 1800) sample, dissolving the polyethyleneimine in deionized water to prepare a polyethyleneimine solution with the mass concentration of 0.3%, weighing a gallic acid sample, dissolving the gallic acid sample in the prepared polyethyleneimine solution to prepare a gallic acid solution with the mass concentration of 0.05, 0.10, 0.15, 0.20, 0.25 and 0.30%, adding a buffer solution with the pH of 8.5, reacting for 9h, soaking a polyacrylonitrile hydrolysis membrane in the homogeneous solution after the reaction of gallic acid and polyethyleneimine is finished for 1h, washing with water, and thermally crosslinking for 30min in an oven at 40 ℃ to obtain 2 composite membranes prepared under the condition of 6 gallic acid concentrations.
The composite membrane prepared under the conditions of 0.05, 0.10, 0.15, 0.20, 0.25 and 0.30 percent of gallic acid solution is used for treating 500mg/L of Na2SO4The retention rate of the solution is 13.44%, 15.26%, 19.80%, 24.51%, 25.06% and 27.24% in sequence; for MgCl of 500mg/L2The retention rate of the solution is 45.79%, 49.97%, 60.16%, 69.30%, 69.69% and 70.22% in sequence. Therefore, the rejection rate of the composite membrane prepared under the condition of 0.20% gallic acid solution is high, the increase of the concentration is not obvious, and the flux is influenced. Therefore, 0.20% is the optimum concentration of gallic acid.
Example 2
Soaking 12 polyacrylonitrile ultrafiltration membranes in deionized water for 12 hours, hydrolyzing the soaked substrate membrane in 2mol/L NaOH solution for 1 hour at the constant temperature of 45 ℃ in a water bath, then putting the hydrolyzed PAN substrate membrane in 0.2mol/L HCl for acidification for 3 hours at normal temperature, and taking out the hydrolyzed PAN substrate membrane to generate the polyacrylonitrile hydrolyzed membrane. Weighing a gallic acid sample, dissolving the gallic acid sample in deionized water to prepare a gallic acid solution with the mass concentration of 0.2%, weighing a polyethyleneimine (Mw is 1800) sample, dissolving the polyethyleneimine in the prepared gallic acid solution to prepare a polyethyleneimine solution with the mass concentration of 0.15, 0.20, 0.25, 0.30, 0.35 and 0.40%, adding a buffer solution with the pH of 8.5, reacting for 9h, soaking a polyacrylonitrile hydrolysis membrane in a homogeneous solution obtained by the reaction of gallic acid and polyethyleneimine for 1h, washing with water, and carrying out thermal crosslinking for 30min in an oven at 40 ℃ to obtain 2 composite membranes prepared under the condition of 6 gallic acid concentrations.
The composite membrane prepared under the condition of 0.15, 0.20, 0.25, 0.30, 0.35 and 0.40 percent of polyethyleneimine solution is used for treating 500mg/L of Na2SO4The retention rate of the solution is 30.14%, 35.40%, 41.03%, 45.38%, 43.02% and 42.11% in sequence; for MgCl of 500mg/L2The retention rate of the solution is 74.39%, 75.57%, 76.36%, 83.93%, 81.19% and 78.84% in sequence. Therefore, the rejection rate of the composite membrane prepared under the condition of 0.30% polyethyleneimine solution is high, the increase of the rejection rate by continuously increasing the concentration is not obvious, and the flux is influenced. Therefore, 0.30% is the optimum concentration of polyethyleneimine.
Example 3
10 polyacrylonitrile ultrafiltration membranes are taken and put in deionized water for soaking for 12 hours, then the soaked basement membrane is hydrolyzed in 2mol/L NaOH solution for 1 hour at the temperature of constant temperature heating of water bath and 45 ℃, then the hydrolyzed PAN basement membrane is put in 0.2mol/L HCl for acidification for 3 hours at normal temperature, and the polyacrylonitrile hydrolysis membrane is generated after being taken out. Weighing a polyethyleneimine (Mw is 1800) sample, dissolving the polyethyleneimine in deionized water to prepare a polyethyleneimine solution with the mass concentration of 0.3%, weighing a gallic acid sample, dissolving the gallic acid sample in the prepared polyethyleneimine solution to prepare a 0.20% gallic acid solution, adding a buffer solution with the pH of 8.5, reacting for 3 hours, 6 hours, 9 hours, 12 hours and 24 hours, soaking a polyacrylonitrile hydrolysis membrane in the homogeneous solution after the reaction of gallic acid and polyethyleneimine is finished for 1 hour, washing with water, and thermally crosslinking in an oven at 40 ℃ for 30 minutes to obtain 2 composite membranes prepared under the condition of 5 gallic acid concentrations.
The composite membrane prepared under the conditions of reacting polyethyleneimine with gallic acid for 3h, 6h, 9h, 12h and 24h is used for reacting 500mg/L of Na2SO4The retention rate of the solution is 8.55%, 20.34%, 32.86%, 39.21% and 39.21% in sequence; for MgCl of 500mg/L2The retention rate of the solution is 38.87%, 54.54%, 66.95%, 67.99% and 71.39% in sequence. Therefore, the rejection rate of the composite membrane prepared under the condition that polyethyleneimine reacts with gallic acid for 9 hours is high, and the reaction is continuously increasedThe increase in rejection rate is not significant and also affects throughput. Therefore, 9h is the optimal reaction time.
Example 4
Soaking 6 polyacrylonitrile ultrafiltration membranes in deionized water for 12h, hydrolyzing the soaked substrate membrane in 2mol/L NaOH solution for 1h at the constant temperature of 45 ℃ in a water bath, then acidifying the hydrolyzed PAN substrate membrane in 0.2mol/L HCl for 3h at normal temperature, and taking out to generate the polyacrylonitrile hydrolyzed membrane. Weighing a polyethyleneimine (Mw is 600, 1800 and 10000) sample, dissolving the sample in deionized water to prepare a polyethyleneimine solution with the mass concentration of 0.3%, weighing a gallic acid sample, dissolving the gallic acid sample in the prepared polyethyleneimine solution to prepare a gallic acid solution with the mass concentration of 0.20%, adding a buffer solution with the pH value of 8.5, reacting for 9 hours, soaking a polyacrylonitrile hydrolysis membrane in a homogeneous solution obtained by the reaction of the gallic acid and the polyethyleneimine for 1 hour, washing with water, and thermally crosslinking for 30 minutes in a drying oven at 40 ℃ to obtain 2 composite membranes prepared under the condition of 3 polyethyleneimine molecular weights.
The composite membrane prepared under the condition of polyethyleneimine molecular weight of 600, 1800 and 10000 is used for treating 500mg/L Na2SO4The retention rate of the solution is 35.76%, 41.57% and 49.55% in sequence; for MgCl of 500mg/L2The retention rate of the solution is 63.30%, 72.44% and 83.10% in sequence. Therefore, the rejection rate of the composite membrane prepared under the condition that the molecular weight of the polyethyleneimine is 1800 is high, the increase of the rejection rate by continuously increasing the reaction time is not obvious, and the flux is influenced. Accordingly, 1800 is the optimum molecular weight for the polyethyleneimine.
As can be seen from the above examples, in the method for preparing a positively-charged composite nanofiltration membrane based on a biomaterial according to the present invention, by examining the influence of factors such as the concentration of polyethyleneimine, the concentration of gallic acid, the reaction time of polyethyleneimine and gallic acid, and the molecular weight of polyethyleneimine on the membrane performance, the optimal membrane-forming conditions were obtained as follows: the concentration of polyethyleneimine is 0.30%, the concentration of gallic acid is 0.20%, the reaction time is 9h, and the molecular weight of polyethyleneimine is 1800.
As can be seen from FIG. 1, the radicals prepared under the optimum conditionsThe pure water permeability coefficient of the gallic acid positively charged composite nanofiltration membrane is 74.214 L.m-2·h-1·MPa-1. Referring to FIG. 2, the molecular weight cut-off of the composite membrane is 958Da, and belongs to the nanofiltration membrane category. As can be seen from fig. 3, the membrane surface is positively charged under acidic and neutral conditions, and the isoelectric point is 7.2. As can be seen from FIG. 4, the surface skin thickness of the PAN hydrolysis film was 0.623. mu.m, and the surface skin thickness of the composite film produced under the optimum conditions was 1.032. mu.m. As can be seen from fig. 5, the contact angle of the PAN hydrolyzed membrane was 48 °, and the contact angle of the composite membrane manufactured under the optimal conditions was reduced to 33 °, indicating that the hydrophilic property of the base membrane was improved to some extent by the hydrophilic substance on the membrane surface. As can be seen from fig. 6, the retention rates of the composite membrane on the Atenolol (ATE), the Carbamazepine (CBZ), the Ibuprofen (IBU) and the Amlodipine (AML) are 88.04%, 86.59%, 73.83% and 91.35% in sequence.

Claims (5)

1. The preparation method of the gallic acid-based positively-charged composite nanofiltration membrane is characterized by comprising the following steps of:
step 1, soaking a PAN ultrafiltration membrane in water for more than 12 hours, hydrolyzing a soaked substrate membrane in a 2-2.5 mol/L NaOH solution for 1-2 hours at the constant temperature of 40-50 ℃ in a water bath, then putting the hydrolyzed PAN substrate membrane into a 0.2-0.3 mol/L HCl solution for acidification for 2-3 hours, and taking out to generate a polyacrylonitrile hydrolyzed membrane;
and 2, reacting 0.20-0.30% gallic acid solution and 0.30-0.40% polyethyleneimine solution at a pH of 7.5-8.5 for 9-12 h, soaking the polyacrylonitrile hydrolyzed membrane in homogeneous solution obtained by reacting gallic acid and polyethyleneimine for 1-2 h, performing thermal crosslinking at 40-45 ℃ for 25-35 min after water washing, and soaking in water for preservation to obtain the gallic acid-based positively-charged composite nanofiltration membrane.
2. The process according to claim 1, wherein in step 2, the concentration of gallic acid is 0.20%, the concentration of polyethyleneimine is 0.30%, and the reaction time is 9 hours.
3. The method according to claim 1, wherein in step 2, the molecular weight of the polyethyleneimine is 600, 1800 or 10000 Da.
4. The method according to claim 1, wherein the soaking time is 1 hour and the thermal crosslinking time is 30min in step 2.
5. The gallic acid-based positively charged composite nanofiltration membrane prepared by the preparation method according to any one of claims 1 to 4.
CN201910568707.5A 2019-06-27 2019-06-27 Gallic acid-based positively charged composite nanofiltration membrane and preparation method thereof Pending CN112138545A (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114452840A (en) * 2022-01-28 2022-05-10 中山大学 Graphene oxide modified separation membrane based on electrostatic spraying and preparation and application thereof

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Publication number Priority date Publication date Assignee Title
CN105126650A (en) * 2015-08-16 2015-12-09 哈尔滨工业大学宜兴环保研究院 Antibiotic separating nanofiltration membrane preparation method
CN106268323A (en) * 2016-09-14 2017-01-04 南京理工大学 A kind of n-trimethyl chitosan chloride/polyacrylic acid composite nanometer filtering film and preparation method thereof
CN109046033A (en) * 2018-07-20 2018-12-21 南京理工大学 Polyethyleneimine/carboxymethyl chitosan composite nanometer filtering film and preparation method thereof

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105126650A (en) * 2015-08-16 2015-12-09 哈尔滨工业大学宜兴环保研究院 Antibiotic separating nanofiltration membrane preparation method
CN106268323A (en) * 2016-09-14 2017-01-04 南京理工大学 A kind of n-trimethyl chitosan chloride/polyacrylic acid composite nanometer filtering film and preparation method thereof
CN109046033A (en) * 2018-07-20 2018-12-21 南京理工大学 Polyethyleneimine/carboxymethyl chitosan composite nanometer filtering film and preparation method thereof

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114452840A (en) * 2022-01-28 2022-05-10 中山大学 Graphene oxide modified separation membrane based on electrostatic spraying and preparation and application thereof

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Application publication date: 20201229