CN111760473A - Composite semipermeable membrane, preparation method and application - Google Patents

Composite semipermeable membrane, preparation method and application Download PDF

Info

Publication number
CN111760473A
CN111760473A CN201910257503.XA CN201910257503A CN111760473A CN 111760473 A CN111760473 A CN 111760473A CN 201910257503 A CN201910257503 A CN 201910257503A CN 111760473 A CN111760473 A CN 111760473A
Authority
CN
China
Prior art keywords
arginine
layer
semipermeable membrane
composite semipermeable
membrane according
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.)
Pending
Application number
CN201910257503.XA
Other languages
Chinese (zh)
Inventor
张杨
刘轶群
潘国元
于浩
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Sinopec Beijing Research Institute of Chemical Industry
China Petroleum and Chemical Corp
Original Assignee
Sinopec Beijing Research Institute of Chemical Industry
China Petroleum and Chemical Corp
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Sinopec Beijing Research Institute of Chemical Industry, China Petroleum and Chemical Corp filed Critical Sinopec Beijing Research Institute of Chemical Industry
Priority to CN201910257503.XA priority Critical patent/CN111760473A/en
Publication of CN111760473A publication Critical patent/CN111760473A/en
Pending legal-status Critical Current

Links

Classifications

    • 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
    • B01D71/66—Polymers having sulfur in the main chain, with or without nitrogen, oxygen or carbon only
    • B01D71/68—Polysulfones; Polyethersulfones
    • 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
    • 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
    • B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
    • B01D69/12—Composite membranes; Ultra-thin membranes
    • 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
    • C02F1/441—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis by reverse osmosis
    • 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

Landscapes

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

Abstract

The invention discloses a composite semipermeable membrane and a preparation method and application thereof. The composite membrane comprises a support layer, a separation layer and a reinforcing layer, wherein the separation layer is positioned on one surface of the support layer, the reinforcing layer is positioned on the other surface of the support layer, the support layer is a polymer porous membrane, and the separation layer is a polyamide separation layer containing guanidyl. The separation layer is prepared by interfacial polymerization reaction of an aqueous phase containing polyamine, arginine and derivatives thereof and a catalyst and an organic phase containing polyacyl chloride. In the interfacial polymerization process, under the action of a catalyst, an amido group of arginine and derivatives thereof reacts with an acyl chloride group to form an amido bond, and the guanidyl is fixed in a polyamide separation layer, so that the antibacterial activity of the membrane is improved, the biological pollution resistance of the composite semipermeable membrane in long-term operation is improved, and the service life of the membrane is prolonged.

Description

Composite semipermeable membrane, preparation method and application
Technical Field
The invention relates to the technical field of water treatment, in particular to a composite semipermeable membrane, a preparation method thereof and application of the composite semipermeable membrane in a water treatment process.
Background
Nanofiltration and reverse osmosis semi-permeable membranes are currently the most widely used water treatment technologies that rely on pressure-driven separation. The pore diameter range of the nanofiltration membrane is about a few nanometers, the nanofiltration membrane has poor removal rate on monovalent ions and organic matters with the molecular weight less than 200, and has higher removal rate on divalent or multivalent ions and organic matters with the molecular weight between 200 and 500, so that the nanofiltration membrane can be widely applied to the fields of water softening, drinking water purification, water quality improvement, oil-water separation, wastewater treatment and recycling, seawater softening, grading, purification and concentration of chemical products such as dyes, antibiotics, polypeptides, polysaccharides and the like. Compared with a nanofiltration membrane, the reverse osmosis membrane has smaller aperture and good removal rate of monovalent ions, and is mainly applied to desalination of seawater and brackish water, preparation of boiler feed water, industrial pure water and electronic grade ultrapure water, production of drinking pure water, wastewater treatment and special separation processes.
Membrane materials are the core of membrane technology. Most of the separation layer materials of the commercial composite nanofiltration membranes and reverse osmosis membranes are aromatic polyamide. The aromatic polyamide has the advantages of high desalting rate, good water permeability, excellent chemical stability, low operation pressure and the like. However, none of the currently used composite membranes have antibacterial or bactericidal capabilities, which requires that the membranes be periodically sterilized and cleaned with a special chemical during actual operation. The use of biocides not only increases the cost of the film, but also causes the film to degrade, thereby reducing its useful life.
At present, in order to improve the biological pollution resistance of a nanofiltration membrane or a reverse osmosis membrane, antibacterial inorganic nanoparticles or high polymer materials with antibacterial performance are often introduced into a functional layer or the surface of the functional layer. The Ag nano particles have broad-spectrum bactericidal performanceIn many documents and patents, nano silver is modified on a nano filtration membrane or a reverse osmosis membrane to improve the biological contamination resistance of the membrane. CN101874989A (time wonton technologies ltd) discloses that silver nanoparticles are fixed on the surface of a reverse osmosis membrane which has been prepared by interfacial polymerization, and then the surface of the reverse osmosis membrane is coated with an aqueous phase containing nano silver and m-phenylenediamine, and the surface of the membrane is crosslinked again. Elimelch group of subjects dipped polyamide composite reverse osmosis membranes in AgNO-containing solution3After draining, the solution is immersed in the aqueous solution containing NaBH4In-situ reaction is utilized to generate nano silver on the surface of the membrane in the aqueous solution. CN102527252A discloses a reverse osmosis membrane material with good antibacterial property, which is obtained by coating a layer of sericin macromolecule on the surface of a polyamide composite membrane and crosslinking. CN108057348A discloses that quaternary ammonium salt functional layer with bactericidal performance is grafted on the surface of polyamide separation layer by RAFT active polymerization method.
The guanidino has broad-spectrum bactericidal activity, has a bactericidal effect on gram-positive bacteria, gram-negative bacteria, fungi, yeasts and the like, and the safety of the guanidino is approved by the FDA and the EPA in the United states. Few patents and documents report that guanidino is introduced into a polyamide layer to improve the bacteriostatic activity of the composite membrane.
Disclosure of Invention
The invention provides a composite semipermeable membrane and a preparation method thereof, aiming at solving the problem of poor contamination resistance of nanofiltration and reverse osmosis membranes in the prior art. In the interfacial polymerization process, under the action of a curing catalyst, the amino and acyl chloride are subjected to interfacial polymerization to form an amide group, so that the guanidine group is fixed in a polyamide separation layer, the antibacterial activity of the membrane is improved, and the biological pollution resistance of the membrane in long-term operation is improved.
An object of the present invention is to provide a composite semipermeable membrane comprising a support layer, a separation layer and a reinforcing layer, the separation layer being provided on one surface of the support layer, the reinforcing layer being provided on the other surface of the support layer, the support layer being a polymer porous membrane, the separation layer being a polyamide separation layer containing guanidine groups.
In the present invention, the support layer is not particularly limited and may be selected conventionally in the art, for example, the polymer porous membrane of the support layer may be a membrane of one or more of polysulfone, polyethersulfone, sulfonated polyethersulfone, polytetrafluoroethylene, polyetherketone, or polyacrylonitrile, and more preferably, a polysulfone porous support layer.
In the present invention, the source of the polymer porous membrane of the support layer is not particularly limited, and may be selected conventionally in the art, for example, commercially available, and in a preferred case, may be self-prepared by a phase inversion method. The phase inversion method is well known to those skilled in the art, and may be, for example, a gas phase gel method, a solvent evaporation gel method, a thermal gel method, or an immersion gel method, and preferably an immersion gel method. In a preferred embodiment, a primary membrane is formed by coating a coating solution containing polysulfone on a reinforcing layer, and then the primary membrane is converted into a support layer using a phase inversion method to obtain a polysulfone porous support layer.
The reinforced layer is positioned on one surface of the supporting layer, so that the supporting layer is more favorably formed, and the composite film has better mechanical property. In addition, the reinforcing layer is not particularly limited in the present invention, and may be selected conventionally in the art, for example, one or more of a polyester layer, a polyethylene layer, or a polypropylene layer, preferably a polyester layer, and more preferably a polyester nonwoven fabric support layer. The source of the enhancement layer is not particularly limited and may be a conventional choice in the art, for example, commercially available.
Preferably, the separating layer is made by interfacial polymerization of an aqueous phase containing polyamine, arginine and derivatives thereof, and a catalyst, and an organic phase containing a polyacyl chloride. The interfacial polymerization method employs a process method generally used in the art.
The type of the polyamine is not particularly limited in the present invention and may be conventionally selected in the art, and for example, one or more of m-phenylenediamine, p-phenylenediamine, o-phenylenediamine, piperazine and pyromellitic triamine may be preferable, and m-phenylenediamine may be more preferable. The solvent of the aqueous phase containing the polyamine may be any of various inert liquid substances capable of dissolving the polyamine, for example, water or a mixture of water and at least one of alcohol, ketone and ether, preferably water.
The type of the poly-acid chloride is not particularly limited in the present invention, and may be conventionally selected in the art, and for example, one or more of trimesoyl chloride, isophthaloyl chloride and terephthaloyl chloride may be preferably used, and trimesoyl chloride may be more preferably used.
The solvent of the organic phase containing the polybasic acid chloride can be various inert liquid substances capable of dissolving the polybasic acid chloride, for example, can be an organic solvent, and preferably can be one or more of n-hexane, dodecane, n-heptane, alkane solvent oil (Isopar E, Isopar G, Isopar H, Isopar L and Isopar M).
The arginine and its derivatives are not particularly limited in the present invention, but L-arginine, N ' - (4-methoxy-2, 3, 6-trimethylbenzenesulfonyl) -L-arginine, L-arginine-L-pyroglutamate, N ' -nitro-L-arginine, N ' -nitro-D-arginine, N-monomethyl-L-arginine monoacetate, D-arginine hydrochloride, N-benzoyl-L-arginine ethyl ester hydrochloride, N- α -carbonylphenoxy-D-arginine, L-arginine methyl ester dihydrochloride, FMOC-L-arginine (N-fluorenylmethoxycarbonyl-L-arginine), one or more of N-benzyloxycarbonyl-L-arginine, N-p-toluenesulfonyl-L-arginine, NA-2, 4-dinitrobenzene-L-arginine, and FMOC-D-arginine (N-fluorenylmethoxycarbonyl-D-arginine).
The catalyst is not particularly limited in the present invention, as long as it can promote the reaction of amino group and acyl chloride group, and is preferably a pyridine compound, more preferably one or a mixture of pyridine, 2-methylpyridine or 4-dimethylaminopyridine.
The thicknesses of the supporting layer, the separating layer and the reinforcing layer are not particularly limited and can be selected conventionally in the field, but in order to enable the layers to have a better synergistic cooperation effect, the obtained composite membrane can better have an excellent salt rejection rate and a higher water flux, and under the preferable condition, the thickness of the supporting layer is 30-60 micrometers, and more preferably 35-45 micrometers; the thickness of the separation layer is 0.05-0.3 micrometer, and more preferably 0.1-0.2 micrometer; the thickness of the enhancement layer is 50-100 microns, and more preferably 60-80 microns.
The second purpose of the invention is to provide a preparation method of the composite semipermeable membrane, which comprises the following steps:
(1) preparing a supporting layer on one surface of the reinforcing layer to obtain the supporting layer with the reinforcing layer attached to the surface;
(2) preparing a polyamide separation layer containing guanidine groups on the other surface of the support layer;
(3) and (4) carrying out heat treatment to obtain the composite semipermeable membrane.
Wherein, the method of step (1) can be selected conventionally in the field, and preferably adopts a phase inversion method, and a supporting layer polymer solution can be coated on one surface of the reinforcing layer, and the supporting layer with the surface adhered with the reinforcing layer can be obtained through phase inversion.
For example, a doctor blade is used to scrape the polymer solution of the support layer on one surface of the reinforced layer, and the polymer solution is converted into a solid state through phase inversion, so as to obtain the support layer with the reinforced layer attached on the surface.
The phase inversion method may specifically be: dissolving the polymer of the support layer in a solvent to obtain a polymer solution with the concentration of 10-20 wt%, and defoaming at 20-40 ℃ for 30-180 min; and then coating the polymer solution on the enhancement layer to obtain an initial membrane, and soaking the initial membrane in water at the temperature of 10-30 ℃ for 20-60 min, so that the polysulfone layer on the surface of the enhancement layer is converted into a polymer porous membrane supporting layer through phase conversion.
The solvent may be N, N-dimethylformamide, N-dimethylacetamide, N-methylpyrrolidone, dimethylsulfoxide, or the like.
In the step (2), the other surface of the supporting layer is contacted with water containing polyamine, arginine, derivatives thereof and a catalyst, and liquid is discharged; then contacting with organic phase containing polybasic acyl chloride, discharging liquid to obtain polyamide separation layer.
The porous support layer of the adhesion enhancement layer is contacted with an aqueous phase containing polyamine, arginine and derivatives thereof, and a catalyst, and an organic phase containing a polyacyl chloride in a sequential manner and an interfacial polymerization reaction occurs.
The aqueous phase contains polyamine, arginine and derivatives thereof and a catalyst, wherein the content of the polyamine is 0.5-10 wt%, preferably 1-8 wt%, and more preferably 1-5 wt%; the content of the arginine and the derivative thereof is 0.05-10 wt%, preferably 0.1-8 wt%, and more preferably 0.1-5 wt%; the content of the catalyst is 0.005 to 5% by weight, preferably 0.01 to 3% by weight, and more preferably 0.01 to 1% by weight.
The content of the polybasic acyl chloride in the organic phase containing the polybasic acyl chloride is 0.025-1 wt%, preferably 0.05-0.5 wt%.
In the process of preparing the separation layer, the weight ratio of the dosage of arginine and derivatives thereof, the catalyst and the polyamine can be 0.01-10: 0.001-5: 1, preferably 0.05-1: 0.005-0.5: 1.
in the process of preparing the separation layer, the mass concentration ratio of the use amount of polyamine to the use amount of polyacyl chloride is 1-100: 1, preferably 10 to 50: 1.
the contact time of the support layer with the aqueous phase or the organic phase is not particularly limited and may be conventionally selected in the art, the contact time of the porous support layer with the aqueous phase containing polyamine, arginine and derivatives thereof, and the catalyst may be 5s to 100s, more preferably 10s to 60s, and the temperature may be normal temperature; the time for contacting the organic phase containing the polybasic acid chloride may be 5 to 100 seconds, more preferably 10 to 60 seconds, and the temperature may be room temperature.
In the step (3), the heat treatment conditions are not particularly limited, and the heat treatment temperature is preferably 40 to 150 ℃, more preferably 50 to 120 ℃; the heat treatment time is 0.5 to 20 minutes, preferably 1 to 10 minutes.
The invention can adopt the following technical scheme:
the composite semipermeable membrane of the present invention comprises a support layer, a separation layer on one surface of the support layer, and a reinforcing layer on the other surface of the support layer; the separation layer is prepared by interfacial polymerization reaction of a water phase containing polyamine, arginine and derivatives thereof and a catalyst and an organic phase containing polyacyl chloride, and the support layer is a polysulfone porous support layer.
The invention also aims to provide the application of the composite semipermeable membrane in the water treatment process.
In the interfacial polymerization process, under the action of a curing catalyst, arginine or derivatives thereof are subjected to interfacial polymerization with acyl chloride to form an amide group, and the guanidine group is fixed in a polyamide separation layer, so that the antibacterial activity of the membrane is improved, the biological pollution resistance of the membrane in long-term operation is improved, and the service life of the membrane is prolonged, thereby completing the invention.
The composite semipermeable membrane provided by the invention has high water permeability and salt rejection rate, excellent biological pollution resistance, simple preparation method and great industrial application prospect.
Detailed Description
The present invention will be further described with reference to the following examples.
In the following examples and comparative examples:
(1) the water flux of the composite semipermeable membrane was measured by the following method: the composite semipermeable membrane is put into a membrane pool, after prepressing for 0.5 hour under 1.2MPa, the water permeability of the composite semipermeable membrane is measured under the conditions of the pressure of 1.55MPa and the temperature of 25 ℃ within 1 hour, and the water permeability is calculated by the following formula:
j is Q/(A.t), wherein J is water flux (L/m)2h) Q is water permeability (L), A is effective membrane area (m) of the composite reverse osmosis membrane2) T is time (h);
(2) the salt rejection of the composite semipermeable membrane was measured by the following method: loading the composite semipermeable membrane into a membrane pool, prepressing for 0.5h under 1.2MPa, measuring the concentration change of sodium chloride in a sodium chloride raw water solution with initial concentration of 2000ppm and a permeate liquid within 1h under the conditions of pressure of 1.55MPa and temperature of 25 ℃, and calculating by the following formula:
R＝(Cp-Cf)/Cp× 100% where R is the salt rejection, CpIs the concentration of sodium chloride in the stock solution, CfIs the concentration of sodium chloride in the permeate;
(3) the section appearance of the membrane is observed by a Hitachi S-4800 type high-resolution Field Emission Scanning Electron Microscope (FESEM), and the thickness of the membrane is obtained.
(4) Testing the bacteriostatic performance of the membrane: fixing a certain amount of CFU (circulating fluid Unit) bacterial liquid to a membrane sample to be detected by adopting a filtering method according to the guiding principle of microbial limit of the second part of Chinese pharmacopoeia 2010 edition, reversely pasting the CFU bacterial liquid to a proper culture medium, culturing for 24 hours, taking down a membrane, printing and dyeing the membrane to a disposable sterile filter membrane, transferring the filter membrane to a culture plate according to a microbial limit measuring method, culturing for 48 hours, and inspecting the antibacterial activity of the membrane by using a microbial counting method;
in addition, in the following examples and preparations, L-arginine, N '- (4-methoxy-2, 3, 6-trimethylbenzenesulfonyl) -L-arginine, L-arginine-L-pyroglutamate, N' -nitro-L-arginine, N-monomethyl-L-arginine monoacetate, pyridine, 2-methylpyridine or 4-dimethylaminopyridine, and trimesoyl chloride and m-phenylenediamine were purchased from Bailingwei scientific Co., Ltd; isopar E is available from Shilange chemical Co., Ltd; other chemicals were purchased from the national pharmaceutical group chemicals, ltd.
The preparation of the supporting layer on the surface of the reinforcing layer is prepared by adopting a phase inversion method, and the preparation method comprises the following specific steps:
dissolving a certain amount of polysulfone (the number average molecular weight is 80000) in N, N-dimethylformamide to prepare a polysulfone solution with the concentration of 18 weight percent, and defoaming at 25 ℃ for 120 min; then, a polysulfone solution is coated on the polyester non-woven fabric by using a scraper to obtain an initial membrane, and then the initial membrane is soaked in water with the temperature of 25 ℃ for 60min, so that a polysulfone layer on the surface of the polyester non-woven fabric is subjected to phase conversion into a porous membrane, and finally the porous membrane supporting layer is obtained by 3 times of water washing.
Example 1
This example is intended to illustrate the composite semipermeable membrane provided by the present invention and the production method thereof.
Contacting the upper surface of a polysulfone porous membrane with an aqueous solution containing 2 wt% of m-phenylenediamine, 1 wt% of L-arginine and 0.1 wt% of 4-dimethylaminopyridine, and discharging liquid after contacting for 10s at 25 ℃; then, the upper surface of the polysulfone porous membrane is contacted with Isopar E solution containing 0.1 weight percent of trimesoyl chloride for 10 seconds at 25 ℃, and then liquid is discharged; then, the membrane was placed in an oven and heated at 70 ℃ for 5min to obtain a composite semipermeable membrane N1. The thickness of the reinforcing layer was 72 microns, the thickness of the support layer was 41 microns, and the thickness of the separation layer was 0.18 microns.
The composite semipermeable membrane N1 obtained was immersed in water for 24 hours, and then the water flux and the salt rejection to NaCl were measured under conditions of a pressure of 1.55MPa and a temperature of 25 ℃, and the results are shown in table 1. In addition, the antibacterial activity was examined by the microbial count method, and the results are shown in table 1.
Example 2
This example is intended to illustrate the composite semipermeable membrane provided by the present invention and the production method thereof.
Contacting the upper surface of a polysulfone porous membrane with a solution containing 0.5 wt% of m-phenylenediamine aqueous solution, 5 wt% of N' - (4-methoxy-2, 3, 6-trimethylbenzenesulfonyl) -L-arginine and 1 wt% of pyridine, and discharging liquid after contacting for 10s at 25 ℃; then, the upper surface of the polysulfone porous membrane is contacted with Isopar E solution containing 0.025 weight percent of trimesoyl chloride for 10 seconds at 25 ℃, and then liquid is discharged; then, the membrane was placed in an oven and heated at 100 ℃ for 3min to obtain a composite semipermeable membrane N2. The thickness of the reinforcing layer was 72 microns, the thickness of the support layer was 41 microns, and the thickness of the separation layer was 0.15 microns.
The composite semipermeable membrane N2 obtained was immersed in water for 24 hours, and then the water flux and the salt rejection to NaCl were measured under conditions of a pressure of 1.55MPa and a temperature of 25 ℃, and the results are shown in table 1. In addition, the antibacterial activity was examined by the microbial count method, and the results are shown in table 1.
Example 3
This example is intended to illustrate the composite semipermeable membrane provided by the present invention and the production method thereof.
Contacting the upper surface of polysulfone porous membrane with 4 wt% m-phenylenediamine aqueous solution, 0.5 wt% N-monomethyl-L-arginine monoacetate and 0.05 wt% 2-methylpyridine, discharging liquid after contacting for 10s at 25 ℃; then, the upper surface of the polysulfone porous membrane is contacted with Isopar E solution containing 1 weight percent of trimesoyl chloride again, and is contacted for 10s at 25 ℃ for discharging liquid; then, the membrane was placed in an oven and heated at 120 ℃ for 2min to obtain a composite semipermeable membrane N3. The thickness of the reinforcing layer was 72 microns, the thickness of the support layer was 41 microns, and the thickness of the separation layer was 0.25 microns.
The composite semipermeable membrane N3 obtained was immersed in water for 24 hours, and then the water flux and the salt rejection to NaCl were measured under conditions of a pressure of 1.55MPa and a temperature of 25 ℃, and the results are shown in table 1. In addition, the antibacterial activity was examined by the microbial count method, and the results are shown in table 1.
Example 4
This example is intended to illustrate the composite semipermeable membrane provided by the present invention and the production method thereof.
A composite semipermeable membrane N4 was obtained according to the process described in example 1, except that L-arginine was replaced with N' -nitro-L-arginine. The thickness of the reinforcing layer was 72 microns, the thickness of the support layer was 41 microns, and the thickness of the separation layer was 0.17 microns.
The obtained composite membrane N4 was immersed in water for 24 hours, and then the water flux and the salt rejection to NaCl were measured under conditions of a pressure of 1.55MPa and a temperature of 25 ℃, and the results are shown in table 1. In addition, the antibacterial activity was examined by the microbial count method, and the results are shown in table 1.
Example 5
This example is intended to illustrate the composite semipermeable membrane provided by the present invention and the production method thereof.
The composite semipermeable membrane N5 was produced according to the process of example 1, except that L-arginine-L-pyroglutamate was used instead of L-arginine. The thickness of the reinforcing layer was 72 microns, the thickness of the support layer was 41 microns, and the thickness of the separation layer was 0.14 microns.
The composite semipermeable membrane N5 obtained was immersed in water for 24 hours, and then the water flux and the salt rejection to NaCl were measured under conditions of a pressure of 1.55MPa and a temperature of 25 ℃, and the results are shown in table 1. In addition, the antibacterial activity was examined by the microbial count method, and the results are shown in table 1.
Comparative example 1
A composite semipermeable membrane M1 was prepared according to the method of example 1, except that arginine and its derivatives and the catalyst were not contained in the aqueous phase. The thickness of the reinforcing layer was 72 microns, the thickness of the support layer was 41 microns, and the thickness of the separation layer was 0.18 microns.
The results of measuring the water flux and the salt rejection to NaCl under the conditions of a pressure of 1.55MPa and a temperature of 25 ℃ after immersing the obtained composite membrane M1 in water for 24 hours are shown in table 1. In addition, the antibacterial activity was examined by the microbial count method, and the results are shown in table 1.
TABLE 1
Film Salt rejection% Pure water flux L/m2h The sterilization rate%
N1 99.15 40.2 96.9
N2 99.02 41.5 92.5
N3 99.20 38.7 96.1
N4 98.87 40.9 90.8
N5 99.10 38.8 85.8
M1 98.50 36.5 0
As can be seen from the results of examples 1 to 5 above, the composite semipermeable membrane provided by the present invention has high water flux and salt rejection rate, and has excellent bactericidal rate.
Moreover, the preparation method provided by the invention is simple and has great industrial application prospect.
The preferred embodiments of the present invention have been described in detail, however, the present invention is not limited to the specific details of the above embodiments, and various simple modifications may be made to the technical solution of the present invention within the technical idea of the present invention, and these simple modifications are within the protective scope of the present invention.
It should be noted that the various features described in the above embodiments may be combined in any suitable manner without departing from the scope of the invention. The invention is not described in detail in order to avoid unnecessary repetition.

Claims (17)

1. A composite semipermeable membrane, characterized in that the composite membrane comprises a support layer, a separation layer and a reinforcing layer, the separation layer is provided on one surface of the support layer, the reinforcing layer is provided on the other surface of the support layer, the support layer is a polymer porous membrane, and the separation layer is a polyamide separation layer containing guanidine groups.
2. The composite semipermeable membrane according to claim 1, wherein:
the polymer porous membrane of the support layer is one or more of polysulfone, polyethersulfone, sulfonated polyethersulfone, polytetrafluoroethylene, polyetherketone or polyacrylonitrile.
3. The composite semipermeable membrane according to claim 1, wherein:
the enhancement layer is one or more of a polyester layer, a polyethylene layer or a polypropylene layer.
4. The composite semipermeable membrane according to claim 1, wherein:
the separation layer is prepared by interfacial polymerization reaction of an aqueous phase containing polyamine, arginine and derivatives thereof and a catalyst and an organic phase containing polyacyl chloride.
5. The composite semipermeable membrane according to claim 4, wherein:
the polyamine is selected from at least one of m-phenylenediamine, p-phenylenediamine, o-phenylenediamine, piperazine or benzenetriamine;
the polybasic acyl chloride is selected from at least one of trimesoyl chloride, isophthaloyl dichloride or terephthaloyl dichloride;
the arginine and its derivatives are selected from L-arginine, N ' - (4-methoxy-2, 3, 6-trimethylbenzenesulfonyl) -L-arginine, L-arginine-L-pyroglutamate, N ' -nitro-L-arginine, N ' -nitro-D-arginine, N-monomethyl-L-arginine monoacetate, D-arginine hydrochloride, N-benzoyl-L-arginine ethyl ester hydrochloride, N-alpha-carbonylphenoxy-D-arginine, L-arginine methyl ester dihydrochloride, N-fluorenylmethoxycarbonyl-L-arginine, N-benzyloxycarbonyl-L-arginine, N-p-toluenesulfonyl-L-arginine, L-arginine, One or more of NA-2, 4-dinitrobenzene-L-arginine and N-fluorenylmethyloxycarbonyl-D-arginine;
the catalyst is a pyridine compound, preferably at least one of pyridine, 2-methylpyridine or 4-dimethylaminopyridine.
6. The composite semipermeable membrane according to claim 1, wherein:
the thickness of the supporting layer is 30-60 micrometers; the thickness of the separation layer is 0.05-0.3 microns; the thickness of the enhancement layer is 50-100 microns.
7. The composite semipermeable membrane according to claim 6, wherein:
the thickness of the supporting layer is 35-45 micrometers; the thickness of the separation layer is 0.1-0.2 microns; the thickness of the enhancement layer is 60-80 microns.
8. A method for producing the composite semipermeable membrane according to any one of claims 1 to 7, characterized by comprising the steps of:
(1) preparing a support layer on one surface of the reinforcing layer;
(2) preparing a separation layer of polyamide containing guanidine groups on the other surface of the support layer;
(3) and (4) carrying out heat treatment to obtain the composite semipermeable membrane.
9. The method for producing a composite semipermeable membrane according to claim 8, wherein:
in the step (1), a supporting layer polymer solution is coated on one surface of the reinforcing layer, and the supporting layer with the surface attached with the reinforcing layer is obtained through phase inversion.
10. The method for producing a composite semipermeable membrane according to claim 8, wherein:
in the step (2), the other surface of the supporting layer is contacted with water containing polyamine, arginine, derivatives thereof and a catalyst, and liquid is discharged; then contacting with organic phase containing polybasic acyl chloride, discharging liquid to obtain polyamide separation layer.
11. The method for producing a composite semipermeable membrane according to claim 10, wherein:
the aqueous phase contains polyamine, arginine and derivatives thereof and a catalyst, wherein the content of the polyamine is 0.5-10 wt%; the content of the arginine and the derivative thereof is 0.05-10 wt%; the content of the catalyst is 0.005-5 wt%;
the organic phase containing polybasic acyl chloride contains 0.025-1 wt% of polybasic acyl chloride.
12. The method for producing a composite semipermeable membrane according to claim 11, wherein:
the water phase containing polyamine, arginine and derivatives thereof and a catalyst, wherein the content of the polyamine is 1-8 wt%; the content of the arginine and the derivative thereof is 0.1-8 wt%; the catalyst content is 0.01-3 wt%;
the content of the polybasic acyl chloride in the organic phase containing the polybasic acyl chloride is 0.05-0.5 wt%.
13. The method for producing a composite semipermeable membrane according to claim 10, wherein:
the contact time with the water phase or the organic phase is 5s to 100s, and the temperature is normal temperature.
14. The method for producing a composite semipermeable membrane according to claim 10, wherein:
the mass concentration ratio of polyamine to polyacyl chloride is 1-100: 1, preferably 10 to 50: 1.
15. the method for producing a composite semipermeable membrane according to claim 10, wherein:
the weight ratio of arginine and derivatives thereof, catalyst and polyamine is 0.01-10: 0.001-5: 1.
16. the method for producing a composite semipermeable membrane according to claim 8, wherein:
in the step (3), the heat treatment temperature is 40-150 ℃, and preferably 50-120 ℃; the heat treatment time is 0.5 to 20 minutes, preferably 1 to 10 minutes.
17. Use of the composite semipermeable membrane according to any one of claims 1 to 7 in water treatment process.
CN201910257503.XA 2019-04-01 2019-04-01 Composite semipermeable membrane, preparation method and application Pending CN111760473A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201910257503.XA CN111760473A (en) 2019-04-01 2019-04-01 Composite semipermeable membrane, preparation method and application

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201910257503.XA CN111760473A (en) 2019-04-01 2019-04-01 Composite semipermeable membrane, preparation method and application

Publications (1)

Publication Number Publication Date
CN111760473A true CN111760473A (en) 2020-10-13

Family

ID=72718130

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201910257503.XA Pending CN111760473A (en) 2019-04-01 2019-04-01 Composite semipermeable membrane, preparation method and application

Country Status (1)

Country Link
CN (1) CN111760473A (en)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113750800A (en) * 2021-10-26 2021-12-07 天津工业大学 Preparation method of arginine modified composite nanofiltration membrane

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101112675A (en) * 2006-07-27 2008-01-30 中国科学院大连化学物理研究所 Method for modifying compound film surface
EP2517782A1 (en) * 2009-12-24 2012-10-31 Toray Industries, Inc. Composite semipermeable membrane and method for producing same
CN104437110A (en) * 2014-12-15 2015-03-25 彭博 High-flux polyamide composite film
CN109012240A (en) * 2018-07-17 2018-12-18 时代沃顿科技有限公司 A kind of antibacterial contamination-resistance composite reverse osmosis membrane and preparation method thereof

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101112675A (en) * 2006-07-27 2008-01-30 中国科学院大连化学物理研究所 Method for modifying compound film surface
EP2517782A1 (en) * 2009-12-24 2012-10-31 Toray Industries, Inc. Composite semipermeable membrane and method for producing same
CN104437110A (en) * 2014-12-15 2015-03-25 彭博 High-flux polyamide composite film
CN109012240A (en) * 2018-07-17 2018-12-18 时代沃顿科技有限公司 A kind of antibacterial contamination-resistance composite reverse osmosis membrane and preparation method thereof

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113750800A (en) * 2021-10-26 2021-12-07 天津工业大学 Preparation method of arginine modified composite nanofiltration membrane

Similar Documents

Publication Publication Date Title
Miller et al. Surface modification of water purification membranes
Homayoonfal et al. Amoxicillin separation from pharmaceutical solution by pH sensitive nanofiltration membranes
Moghadam et al. Improved antifouling properties of TiO2/PVDF nanocomposite membranes in UV‐coupled ultrafiltration
KR101185701B1 (en) Composite semipermeable membrane
WO2018120476A1 (en) Supramolecular composite nano-filtration membrane and preparation method therefor and use thereof
Wang et al. Fabrication of non-woven composite membrane by chitosan coating for resisting the adsorption of proteins and the adhesion of bacteria
CN107466312B (en) Method for reducing surface fouling
US20050173341A1 (en) Blended polymer media for treating aqueous fluids
JP6534607B2 (en) Reverse osmosis membrane or nanofiltration membrane and method for producing them
CN112023727B (en) Anti-pollution antibacterial reverse osmosis membrane, preparation method and application thereof
WO2015068657A1 (en) Composite semi-permeable membrane
KR101487575B1 (en) Reverse osmosis membrane having a high fouling resistance and manufacturing method thereof
JP2012250192A (en) Composite semipermeable membrane and manufacturing method thereof
CN112870990B (en) Antibacterial and pollution-resistant reverse osmosis composite membrane and preparation method thereof
CN108786498B (en) Surface-modified anti-adhesion and anti-biological-pollution reverse osmosis membrane and preparation method thereof
CN110354682B (en) Reverse osmosis membrane resisting biological pollution and preparation method and application thereof
US20150328592A1 (en) Thin film composite reserve osmosis membrane with antifouling properties and method of preparation of the same
CN102512997B (en) Hydrophilic polyethersulfone with cardo alloy ultrafiltration membrane and preparation method thereof
Ma et al. Novel dopamine-modified cellulose acetate ultrafiltration membranes with improved separation and antifouling performances
RU2717512C2 (en) Chlorine-resistant hydrophilic filtration membranes based on polyaniline
CN111760473A (en) Composite semipermeable membrane, preparation method and application
CN111888943B (en) Preparation method of reverse osmosis membrane containing buffer layer free interface polymerization
KR20150016019A (en) Polyamide water-treatment membranes having properies of high salt rejection and high flux and manufacturing method thereof
KR20130076498A (en) Reverse osmosis membrane having ultra hydrophilic layer and method of manufacturing the same
KR101944118B1 (en) Reverse Osmosis membrane having excellent fouling resistance and manufacturing method 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
RJ01 Rejection of invention patent application after publication
RJ01 Rejection of invention patent application after publication

Application publication date: 20201013