CN114432903B - Composite membrane with acid resistance and preparation method and application thereof - Google Patents

Composite membrane with acid resistance and preparation method and application thereof Download PDF

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CN114432903B
CN114432903B CN202011227922.8A CN202011227922A CN114432903B CN 114432903 B CN114432903 B CN 114432903B CN 202011227922 A CN202011227922 A CN 202011227922A CN 114432903 B CN114432903 B CN 114432903B
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acid resistance
chloride
polyamine
composite film
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CN114432903A (en
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张杨
于浩
潘国元
刘轶群
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Sinopec Beijing Research Institute of Chemical Industry
China Petroleum and Chemical Corp
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Sinopec Beijing Research Institute of Chemical Industry
China Petroleum and Chemical Corp
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
    • B01D69/12—Composite membranes; Ultra-thin membranes
    • B01D69/125—In situ manufacturing by polymerisation, polycondensation, cross-linking or chemical reaction
    • 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
    • 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
    • B01D69/02—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
    • 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
    • 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
    • B01D2325/30—Chemical resistance
    • 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
    • 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

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  • Organic Chemistry (AREA)
  • Separation Using Semi-Permeable Membranes (AREA)

Abstract

The invention relates to a composite membrane with acid resistance and a preparation method and application thereof. The composite membrane comprises a bottom layer, a middle porous supporting layer and a surface separation layer, wherein the separation layer is a polysulfonamide separation layer, and the polysulfonamide separation layer has a structure shown in a formula (1):

Description

Composite membrane with acid resistance and preparation method and application thereof
Technical Field
The invention relates to the field of membranes, in particular to a composite membrane with acid resistance and a preparation method and application thereof.
Background
Nanofiltration is a pressure-driven membrane separation process between reverse osmosis and ultrafiltration, the pore size range of the nanofiltration membrane is about several nanometers, the removal of monovalent ions and organic matters with the molecular weight less than 200 is poor, and the removal rate of divalent or multivalent ions and organic matters with the molecular weight between 200 and 500 is high. Can be widely used in the fields of fresh water softening, seawater softening, drinking water purification, water quality improvement, oil-water separation, wastewater treatment and recycling, and the classification, purification, concentration and the like of chemical products such as dye, antibiotic, polypeptide, polysaccharide and the like.
At present, most commercial nanofiltration membranes use polysulfone ultrafiltration membranes as a supporting layer, interfacial polymerization of polyamine aqueous phase and polyacyl chloride organic phase is carried out in situ on the upper surface of the ultrafiltration membrane, and the final product is a composite nanofiltration membrane. The common aqueous phase monomer is piperazine or piperazine substituted amine, the organic phase is trimesoyl chloride or a multifunctional acyl halide, as disclosed in patent numbers US4769148 and US4859384, a large amount of unreacted acyl chloride groups are hydrolyzed into carboxylic acid, so that the surface of the nanofiltration membrane is negatively charged, and by utilizing the charge effect, the polypiperazine amide composite nanofiltration membrane has higher retention rate on high-valence anions and adjustable retention rate on monovalent anions. In addition, patent nos. US4765897, US4812270 and US4824574 also provide a method how to convert polyamide composite reverse osmosis membranes into nanofiltration membranes. However, due to the limitation of the material characteristics, the traditional polyamide nanofiltration membrane is degraded in an extreme pH environment, and the polyamide nanofiltration membrane is only used for neutral media or weak-acid and weak-alkaline media close to neutral because the pH range of the polyamide nanofiltration membrane is generally 2-11.
In recent years, researchers have developed various nanofiltration membranes, and various commercial products have appeared. In addition, many new materials, such as sulfonated polyether ketone, sulfonated polyether sulfone, and the like, are also applied to the field of nanofiltration.
Reported in the literature "Sulfonated poly (etherketotone) based composite membranes for nanofilamentation of acidic and alkaline media, J.Membr.Sci.,381,81-89,2011": the sulfonated polyether-ether-ketone has acid resistance, a nanofiltration membrane material with excellent interception performance can be obtained through Crosslinking, the crosslinked polyether-ether-ketone material has strong solvent resistance, and dyes can be separated from polar solvents such as isopropanol and acetone (Crosslinking of modified poly (ether ketone) membranes for use in solvent solvents nanofilation, 447,212-221 and 2013).
The document shows that acid and alkali resistant and high temperature resistant nanofiltration membrane HYDRACoRe70pHT is used for recovering waste alkali liquor in sugar industry, and the membrane science and technology is 32,11-15,2006: the commercial sulfonated polyether sulfone composite nanofiltration membrane is a HYDRACoRe series developed by Nindon electrician-Heidenen, can be used in strong acid and strong alkali solutions, and is widely applied to the recovery of waste alkali.
The nanofiltration membranes capable of stable long-term operation at pH =0 to 14 were reported in patent nos. US5265734, EP0392982 (A3) to be exclusively SelRO MPS34 developed by KOCH, which was first developed by israel scientists and was first applied to pervaporation.
AMS company develops an acid-resistant, alkali-resistant and solvent-resistant composite nanofiltration membrane, and a separation layer is made of polyamine (US 9943811) and is prepared by interfacial polymerization reaction of polyamine and cyanuric chloride or a derivative thereof.
Documents (Journal of Membrane Science 523 (2017) 487-496) and (Journal of Membrane Science 478 (2015) 75-84) report that a polyaniline separation layer is modified on a porous support layer by interfacial polymerization, and a composite Membrane has strong permeation and separation stability in a medium environment with pH =0 to 14.
The literature (Journal of Membrane Science 572 (2019) 489-495) utilizes a phase inversion and post-treatment method to prepare a polyvinylidene fluoride nanofiltration Membrane material which has strong stability in strong acid and strong alkali environments.
The literature "Acid stable thin-film composite membrane for nanofilation prediction from naphthalene-1,3,6-trisulfonylchloride (NTSC) and piperazine (PIP)" reports: the sulfonamide material has strong acid resistance, and the composite nanofiltration membrane obtained by interfacial polymerization of a polybasic sulfonyl chloride monomer and piperazine can keep stable separation performance in the environment with pH = 0. The acid-resistant nanofiltration membrane Duracid NF1812C developed by GE company is a three-layer composite structure, and the material of the separation layer is polysulfonamide (patent number US 7138058), which can be kept stable under the conditions of 20% hydrochloric acid, sulfuric acid and phosphoric acid, and can be kept stable under the conditions of 70 ℃ and 20% sulfuric acid.
Although the literature and the patent have reports on polysulfonamides as a separation layer of an acid-resistant nanofiltration membrane, the water flux and the salt rejection rate of the acid-resistant nanofiltration membrane reported in the literature are low due to the limitation of the molecular structure. Therefore, the polysulfonamide composite nanofiltration membrane with a novel cross-linked structure is developed, the water permeability and the salt interception performance of the nanofiltration membrane are improved, and the application of the nanofiltration membrane in the treatment of waste acid water is of great significance.
Disclosure of Invention
The invention aims to overcome the defect of poor acid resistance of the existing nanofiltration membrane, and provides a composite membrane with acid resistance, a preparation method thereof, and application of the composite membrane and the composite membrane prepared by the method in the field of water treatment.
In order to achieve the above objects, one of the objects of the present invention is to provide a composite membrane having acid resistance, comprising a bottom layer, an intermediate porous support layer, and a separation layer of a surface layer, wherein the separation layer is a polysulfonamide separation layer, wherein polysulfonamide has a structure represented by formula (1):
Figure 289955DEST_PATH_IMAGE001
（1）。
the composite membrane comprises a three-layer structure: a porous support layer is attached to one surface of the bottom layer of the lowest layer, and a polysulfonamide dense separation layer with a cross-linking structure is attached to the surface of the porous support layer, wherein the polysulfonamide contains a structure shown as a formula (1).
According to the present invention, the base layer and the porous support layer are not particularly limited, and may be made of various existing materials having a certain strength and being capable of being used for nanofiltration and reverse osmosis membranes.
The bottom layer can be non-woven fabrics, and the material of non-woven fabrics is one or the mixture of polyethylene and polypropylene.
The porous support layer material may be one or a mixture of several of polyethersulfone, polysulfone, polyaromatic ether, polybenzimidazole, polyetherketone, polyetheretherketone, polyacrylonitrile, polyvinylidene fluoride, and polyaryletherketone, which can be known to those skilled in the art and will not be described herein again.
The polysulfonamide separation layer is obtained by interfacial polymerization of sulfonamide and derivatives thereof, polyamine and polybasic sulfonyl chloride.
<xnotran> , , ,4- ,2- ,3- , , , , N- , , 4325 zxft 4325- ,4- -N- , ,4- , 3536 zxft 3536- ,4- (2- ) ,4- -6- -3926 zxft 3926- ,4- ,3- ,2- , 3528 zxft 3528- -5- , , ,4- -1- , 3835 zxft 3835- , 3924 zxft 3924- ,4- , 3534 zxft 3534- -3- ,3- ,4- ,5- -2- ,4- ; </xnotran> More preferably, it is one or a mixture of more of sulfonamide, 4-aminobenzenesulfonamide, 2-aminobenzenesulfonamide, 3-aminobenzenesulfonamide, 1,3-benzenedisulfonamide, 4-amino-N-methylbenzenesulfonamide, 4- (2-aminoethyl) benzenesulfonamide, 4-amino-6-chloro-1,3-benzenedisulfonamide and 4-acetamidobenzenesulfonamide.
Preferably, the polyamine is one or more of m-phenylenediamine, p-phenylenediamine, o-phenylenediamine, 1,3,5-triaminobenzene, melamine, piperazine, ethylene diamine, 1,2-propane diamine, 1,4-butane diamine, diethylene triamine, tetraethylene pentamine, polyethylene polyamine, polyethylene imine and polyether amine; more preferably one or more of polyethyleneimine, 1,3,5-triaminobenzene, and polyethylene polyamine.
Preferably, the polybasic sulfonyl chloride is one or more of 1,3-benzene disulfonyl chloride, 1,2-benzene disulfonyl chloride, 1,4-benzene disulfonyl chloride, 2,4-disulfonylchloromesitylene, biphenyl-4,4' -disulfonyl chloride, 4,5-dichloro-1,3-benzene disulfonyl chloride, 2,6-naphthalene disulfonyl chloride, 1,3-naphthalene disulfonyl chloride, 2,7-naphthalene disulfonyl chloride, 1,3,5-benzene trisulfonyl chloride, 1,3,6-naphthalene trisulfonyl chloride; more preferably 1,3-benzene disulfonyl chloride, 2,4-disulfonylchloromesitylene, 1,3,5-benzene trisulfonyl chloride, 1,3,6-naphthalene trisulfonyl chloride.
According to the invention, the thicknesses of the bottom layer, the porous supporting layer and the separating layer are not particularly limited and can be selected conventionally in the field, but in order to enable the three layers to have a better synergistic cooperation effect, the obtained composite nanofiltration membrane can have excellent acid resistance, higher water flux and salt rejection, and preferably, the thickness of the bottom layer is 30 to 150 μm, and preferably 50 to 120 μm; the thickness of the porous support layer is 10 to 100 micrometers, preferably 30 to 60 micrometers; the thickness of the polysulfonamide separation layer is 10 to 500nm, and preferably 50 to 300nm.
Another object of the present invention is to provide a method for preparing the acid-resistant composite film, comprising the steps of:
(1) Preparing a porous support layer on one surface of the base layer;
(2) And a separation layer obtained by interfacial polymerization of components including sulfonamide and its derivatives, polyamine, and polysulfonyl chloride on the other surface of the porous support layer.
According to the present invention, the method of step (1) may be selected conventionally in the art, and preferably by a phase inversion method, a porous support layer may be obtained by applying a polymer solution of a porous support layer material to one surface of a substrate and performing phase inversion.
The phase inversion process may preferably be: dissolving a polymer material of a support layer in a solvent to obtain a polymer solution with the concentration of 10 to 20 weight percent, and defoaming for 10 to 180min at the temperature of 20 to 40 ℃; and then coating the polymer solution on a bottom layer to obtain an initial film, soaking the initial film in water at the temperature of 10 to 30 ℃ for 10 to 60min, and carrying out phase inversion layer on the porous polymer film of the support layer.
Among them, the solvent may be N, N-dimethylformamide, N-dimethylacetamide, N-methylpyrrolidone, dimethylsulfoxide, or the like.
According to the invention, step (2) is to obtain the polysulfonamide separating layer by interfacial polymerization of sulfonamide and derivatives thereof, polyamine and polybasic sulfonyl chloride.
According to the present invention, there is provided, the sulfonamide and derivatives thereof are preferably at least one selected from the group consisting of sulfonamide, benzenesulfonamide, 4-aminobenzenesulfonamide, 2-aminobenzenesulfonamide, 3-aminobenzenesulfonamide, methylsulfonamide, ethylsulfonamide, propylsulfonamide, N-butylbenzenesulfonamide, perfluorobutylsulfonamide, 1,3-benzenedisulfonamide, 4-amino-N-methylbenzenesulfonamide, perfluorooctylsulfonamide, 4-carboxybenzenesulfonamide, 3,5-difluorobenzenesulfonamide, 4- (2-aminoethyl) benzenesulfonamide, 4-amino-6-chloro-1,3-benzenedisulfonamide, 4-methoxybenzenesulfonamide, 3-chlorobenzenesulfonamide, 2-chlorobenzenesulfonamide, 2,3-dichlorothiophene-5-sulfonamide, p-toluenesulfonamide, o-toluenesulfonamide, 4-cyanophenyl-1-sulfonamide, 2,6-difluorobenzenesulfonamide, 32 zxft 3232-difluorobenzenesulfonamide, 3238-dichlorothiophene-3-nitrobenzenesulfonamide, 4-chlorobenzenesulfonamide, 324-chlorobenzenesulfonamide, and 4-chlorobenzenesulfonamide; more preferably, it is one or a mixture of more of sulfonamide, 4-aminobenzenesulfonamide, 2-aminobenzenesulfonamide, 3-aminobenzenesulfonamide, 1,3-benzenedisulfonamide, 4-amino-N-methylbenzenesulfonamide, 4- (2-aminoethyl) benzenesulfonamide, 4-amino-6-chloro-1,3-benzenedisulfonamide and 4-acetamidobenzenesulfonamide.
According to the invention, the polyamine is preferably one or a mixture of more of m-phenylenediamine, p-phenylenediamine, o-phenylenediamine, 1,3,5-triaminobenzene, melamine, piperazine, ethylene diamine, 1,2-propane diamine, 1,4-butane diamine, diethylene triamine, tetraethylene pentamine, polyethylene polyamine, polyethylene imine and polyether amine; more preferably polyethyleneimine, 1,3,5-triamino, polyethylene polyamine.
According to the invention, the multi-element sulfonyl chloride is preferably one or a mixture of 1,3-benzene disulfonyl chloride, 1,2-benzene disulfonyl chloride, 1,4-benzene disulfonyl chloride, 2,4-disulfonylchloromesitylene, biphenyl-4,4' -disulfonyl chloride, 2,6-naphthalene disulfonyl chloride, 1,3-naphthalene disulfonyl chloride, 2,7-naphthalene disulfonyl chloride, 1,3,5-benzene trisulfonyl chloride and 1,3,6-naphthalene trisulfonyl chloride; more preferably 1,3-benzene disulfonyl chloride, 2,4-disulfonylchloride mesitylene, 1,3,6-naphthalene trisulfonyl chloride.
According to the invention, in the step (2), the process of mixing and contacting the porous support layer with the aqueous phase containing sulfonamide and its derivative, polyamine and the organic phase containing polybasic sulfonyl chloride comprises the following steps: firstly, the other surface of the porous supporting layer is contacted with water phase containing sulfamide and derivatives thereof and polyamine, and then contacted with organic phase containing polybasic sulfonyl chloride after liquid drainage, and heat treatment is carried out.
According to the invention, the concentration of the sulfamide and the derivatives thereof, the polyamine and the polybasic sulfonyl chloride in the interface polymerization process is not particularly limited as long as the obtained nanofiltration membrane can combine excellent acid resistance, higher water flux and salt rejection rate.
Preferably, the concentration of the sulfonamide and the derivatives thereof in the aqueous phase is 0.05 to 5wt%, preferably 0.1 to 2wt%; the concentration of the polyamine is 0.05 to 5wt%, preferably 0.1 to 2wt%.
Preferably, the content of the polybasic sulfonyl chloride in the organic phase is 0.025 to 1wt%, preferably 0.05 to 0.5wt%.
According to the invention, the mass concentration ratio of the sulfamide and the derivatives thereof, the polyamine and the polybasic sulfonyl chloride in the interface polymerization process is not particularly limited as long as the obtained nanofiltration membrane can combine excellent acid resistance, higher water flux and desalination rate.
Preferably, the ratio of the sum of the mass concentration of the sulfonamide and the derivative thereof and the polyamine to the mass concentration of the polybasic sulfonyl chloride is (0.1 to 50): 1, preferably (0.5 to 10): 1, most preferably (0.5 to 5): 1.
according to the present invention, the kind of the solvent of the organic phase is not particularly limited as long as it can dissolve the polybasic sulfonyl chloride, and preferably, the solvent of the organic phase is one or more of n-hexane, dodecane, n-heptane, alkane solvent oils (Isopar E, isopar G, isopar H, isopar L and Isopar m).
According to the invention, in the interfacial polymerization process, the contact time of the porous support layer with the water phase and the organic phase is not particularly limited as long as the obtained nanofiltration membrane can have excellent acid resistance, high water flux and high desalination rate, and the contact time of the porous support layer with the water phase containing sulfonamide and derivatives thereof and polyamine is preferably 5s to 100s, and is preferably 10s to 60s; the time for contacting the organic phase containing a polyvalent sulfonyl chloride is 10s to 200s, preferably 20s to 120s.
According to the invention, the post-treatment conditions of interfacial polymerization are not particularly limited, as long as the monomer can be completely polymerized, the nanofiltration membrane can have excellent acid resistance, high water flux and high salt rejection, and the heat treatment temperature is preferably 40 to 150 ℃, and preferably 50 to 120 ℃; the heat treatment time is 0.5 to 20 minutes, preferably 1 to 10 minutes.
It is a further object of the present invention to provide a composite film having acid resistance obtained by the preparation method.
The fourth purpose of the invention is to provide the composite membrane and the application of the composite membrane prepared by the preparation method in the field of water treatment.
The inventor of the invention has found through intensive research that the sulfonamide group with the structure shown in the formula (1) is introduced into the molecular structure of the polysulfonamide, and H on N is very active under the strong electron withdrawing action of adjacent groups and is easy to dissociate into hydrogen ions in water, so that N shows electronegativity. According to the southeast effect, the introduction of the electronegative ion group can increase the rejection rate of the polysulfonamide nanofiltration composite membrane on divalent anion salts. On the other hand, the introduction of more ionic groups helps to improve the hydrophilicity of the membrane and increase the water flux.
Additional features and advantages of the invention will be set forth in the detailed description which follows.
Detailed Description
The following describes in detail specific embodiments of the present invention. It should be understood that the detailed description and specific examples, while indicating the present invention, are given by way of illustration and explanation only, not limitation.
In the following examples and comparative examples:
(1) The water flux of the composite nanofiltration membrane is obtained by testing the following method: the composite nanofiltration permeable membrane is put into a membrane pool, after prepressing for 0.5 hour under 1.2MPa, the water permeability of the nanofiltration membrane within 1 hour is measured under the conditions of the pressure of 2.0MPa and the temperature of 25 ℃, and the water permeability is calculated by the following formula:
j = Q/(A.t), wherein J is water flux, Q is water flux (L), and A is effective membrane of the composite nanofiltration membraneArea (m) 2 ) T is time (h);
(2) The salt rejection of the composite nanofiltration membrane is obtained by testing the following method: the composite nanofiltration membrane is loaded into a membrane pool, after prepressing for 0.5h under 0.2MPa, the concentration change of sodium sulfate raw water solution with initial concentration of 1000ppm and sodium sulfate in permeate liquid within 1h is measured under the conditions of pressure of 0.5MPa and temperature of 25 ℃, and the composite nanofiltration membrane is obtained by calculating according to the following formula:
R=（C p -C f ）/C p x 100%, wherein R is the salt rejection, C p Is the concentration of sodium sulfate in the stock solution, C f The concentration of sodium sulfate in the permeate;
(3) And (3) testing the acid resistance of the composite nanofiltration membrane: soaking the composite nanofiltration membrane in a solution containing 20 wt% of H 2 SO 4 And (3) testing the water flux and the salt rejection rate of the composite nanofiltration membrane in the water solution for 2 months.
In addition, in the following examples and comparative examples:
branched polyethyleneimines (weight average molecular weight 25000), polyethylenepolyamines, melamine, 1,3,5-triaminobenzene, sulfonamide, benzenesulfonamide, 4-aminobenzenesulfonamide, 3-aminobenzenesulfonamide, methylsulfonamide, 1,3-benzenedisulfonamide, 4-amino-N-methylbenzenesulfonamide, 1,3-benzenedisulfonyl chloride, 2,4-disulfonylchloromesitylene, biphenyl-4,4' -disulfonyl chloride, 1,3-naphthalene disulfonyl chloride, 1,3,5-benzenetrisulfonyl chloride, 1,3,6-naphthalene trisulfonyl chloride, and the like, are available from Bailingwei Techno, inc., and other reagents are available from national drug group Chemicals, inc.
The supporting layer is prepared by adopting a phase inversion method, and the 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 120min; then, the polysulfone solution was coated on a polyethylene nonwoven fabric (75 μm thick) using a doctor blade to obtain an initial film, which was then soaked in water at a temperature of 25 ℃ for 60min so that the polysulfone layer on the surface of the polyethylene nonwoven fabric was phase-converted into a porous film, and finally washed 3 times to obtain a support layer having a total thickness of 115 μm.
Example 1
Contacting the upper surface of the polysulfone support layer with an aqueous solution containing 0.25 wt% of sulfonamide and 0.25 wt% of polyethyleneimine, and discharging liquid after contacting for 60s at 25 ℃; then, the upper surface of the supporting layer is contacted with Isopar E solution containing 0.25 weight percent of 1,3-benzene disulfonyl chloride again, and is contacted for 60s at 25 ℃ for liquid drainage; then, the film was put into an oven and heated at 70 ℃ for 3min to obtain a composite film. The thickness of the separating layer was 193nm as measured by scanning electron microscopy.
Soaking the obtained composite membrane N1 in water for 24h, and measuring water flux and Na pair at 25 deg.C under 0.5MPa 2 SO 4 The salt rejection of (2) is shown in Table 1. Soaking the membrane in 20% by mass of H 2 SO 4 After 2 months in the water solution, the water flux and the salt rejection rate of the composite nanofiltration membrane are tested, and the results are shown in table 1.
Example 2
Contacting the upper surface of the polysulfone support layer with an aqueous solution containing 1.8 wt% of 4-aminobenzenesulfonamide and 0.2 wt% of 1,3,5-triaminobenzene, and discharging liquid after contacting for 60s at 25 ℃; then, the upper surface of the supporting layer is contacted with Isopar E solution containing 0.5 weight percent of 2,4-disulfonyl chloride mesitylene again, and the liquid is discharged after the contact for 60s at the temperature of 25 ℃; then, the film was put into an oven and heated at 70 ℃ for 3min to obtain a composite film. The thickness of the separating layer was 232nm as measured by scanning electron microscopy.
Soaking the obtained composite membrane N2 in water for 24h, and measuring water flux and Na pair at 25 deg.C under 0.5MPa 2 SO 4 The salt rejection of (2) is shown in Table 1. Soaking the membrane in 20% by mass of H 2 SO 4 After 2 months in the water solution, the water flux and the salt rejection rate of the composite nanofiltration membrane are tested, and the results are shown in table 1.
Example 3
Contacting the upper surface of the polysulfone support layer with an aqueous solution containing 0.1 wt% of 1,3-benzenedisulfonamide and 0.9 wt% of polyethylene polyamine, and discharging liquid after contacting for 60s at 25 ℃; then, the upper surface of the supporting layer is contacted with Isopar E solution containing 0.15 weight percent of biphenyl-4,4' -disulfonyl chloride again, and is contacted for 60 seconds at 25 ℃ for liquid drainage; then, the film was put into an oven and heated at 70 ℃ for 3min to obtain a composite film. The thickness of the separating layer was 205nm as measured by scanning electron microscopy.
Soaking the obtained composite membrane N3 in water for 24h, and measuring water flux and Na pair at 25 deg.C under 0.5MPa 2 SO 4 The salt rejection of (2) is shown in Table 1. Soaking the membrane in 20% by mass of H 2 SO 4 After 2 months in the water solution, the water flux and the salt rejection rate of the composite nanofiltration membrane are tested, and the results are shown in table 1.
Example 4
Contacting the upper surface of the polysulfone supporting layer with an aqueous solution containing 0.1 wt% of melamine and 0.1 wt% of 4-amino-N-methylbenzenesulfonamide, and discharging liquid after contacting for 60s at 25 ℃; then, the upper surface of the supporting layer is contacted with Isopar E solution containing 0.05 weight percent of 1,3-naphthalene disulfonyl chloride for 60 seconds at 25 ℃ and then drained; then, the film was put into an oven and heated at 70 ℃ for 3min to obtain a composite film. The thickness of the separating layer was 160nm as measured by scanning electron microscopy.
Soaking the obtained composite membrane N4 in water for 24h, and measuring water flux and Na pair at 25 deg.C under 0.5MPa 2 SO 4 The salt rejection of (2) is shown in Table 1. Soaking the membrane in 20% by mass of H 2 SO 4 After 2 months in the water solution, the water flux and the salt rejection rate of the composite nanofiltration membrane are tested, and the results are shown in table 1.
Example 5
A composite membrane was prepared as in example 1, except that 3-aminobenzenesulfonamide was used in place of sulfonamide to obtain composite membrane N5.
Soaking the obtained composite membrane N5 in water for 24h, and measuring water flux and Na pair at 25 deg.C under 0.5MPa 2 SO 4 The salt rejection of (2) is shown in Table 1. Soaking the membrane in 20% by mass of H 2 SO 4 After 2 months in the water solution, the water flux and the salt rejection rate of the composite nanofiltration membrane are tested, and the results are shown in table 1.
Example 6
A composite membrane was prepared as in example 1, except that methanesulfonamide was used instead of sulfonamide to provide composite membrane N6.
Soaking the obtained composite membrane N6 in water for 24h, and measuring water flux and Na pair at 25 deg.C under 0.5MPa 2 SO 4 The salt rejection of (2) is shown in Table 1. Soaking the membrane in 20% by mass of H 2 SO 4 After 2 months in the water solution, the water flux and the salt rejection rate of the composite nanofiltration membrane are tested, and the results are shown in table 1.
Example 7
A composite membrane was prepared as in example 1, except that benzenesulfonamide was used instead of sulfonamide, to give composite membrane N7.
Soaking the obtained composite membrane N7 in water for 24h, and measuring water flux and Na pair at 25 deg.C under 0.5MPa 2 SO 4 The salt rejection of (2) is shown in Table 1. Soaking the membrane in 20% by mass of H 2 SO 4 After 2 months in the water solution, the water flux and the salt rejection rate of the composite nanofiltration membrane are tested, and the results are shown in table 1.
Example 8
A composite membrane was prepared as in example 1, except that 1,3,5-benzenetrisulfonyl chloride was used instead of 1,3-benzenedisulfonyl chloride, to give composite membrane N8.
Soaking the obtained composite membrane N8 in water for 24h, and measuring water flux and Na pair at 25 deg.C under 0.5MPa 2 SO 4 The salt rejection of (2) is shown in Table 1. Soaking the membrane in 20% by mass of H 2 SO 4 After 2 months in the water solution, the water flux and the salt rejection rate of the composite nanofiltration membrane are tested, and the results are shown in table 1.
Example 9
A composite membrane was prepared as in example 1, except that 1,3,6-naphthalenetrisulfonyl chloride was used instead of 1,3-benzenedisulfonyl chloride, to give composite membrane N9.
Soaking the obtained composite membrane N9 in water for 24h, and measuring water flux and Na pair at 25 deg.C under 0.5MPa 2 SO 4 The salt rejection of (1) is shown in the table1 is shown. Soaking the membrane in 20% by mass of H 2 SO 4 After 2 months in the water solution, the water flux and the salt rejection rate of the composite nanofiltration membrane are tested, and the results are shown in table 1.
Comparative example 1
Contacting the upper surface of the polysulfone supporting layer with an aqueous solution containing 0.5 weight percent of polyethyleneimine, and discharging liquid after contacting for 60s at 25 ℃; then, the upper surface of the supporting layer is contacted with Isopar E solution containing 0.25 weight percent of 1,3-benzene disulfonyl chloride again, and is contacted for 60s at 25 ℃ for liquid drainage; then, the film was put into an oven and heated at 70 ℃ for 3min to obtain a composite film. The thickness of the separating layer was 220nm as measured by scanning electron microscopy.
Soaking the obtained composite membrane D1 in water for 24h, and measuring water flux and Na at 25 deg.C under 0.5MPa 2 SO 4 The salt rejection of (2) is shown in Table 1. Soaking the membrane in 20% by mass of H 2 SO 4 After 2 months in the water solution, the water flux and the salt rejection rate of the composite nanofiltration membrane are tested, and the results are shown in table 1.
Comparative example 2
Contacting the upper surface of the polysulfone supporting layer with an aqueous solution containing 0.5 weight percent of sulfonamide, and discharging liquid after contacting for 60s at 25 ℃; then, the upper surface of the supporting layer is contacted with Isopar E solution containing 0.25 weight percent of 1,3,6-naphthalene trisulfonyl chloride again, and liquid drainage is carried out after the contact for 60s at 25 ℃; then, the film was put into an oven and heated at 70 ℃ for 3min to obtain a composite film. The thickness of the separating layer was 230nm as measured by scanning electron microscopy.
Soaking the obtained composite membrane D2 in water for 24h, and measuring water flux and Na under the conditions of 0.5MPa of pressure and 25 DEG C 2 SO 4 The salt rejection of (2) is shown in Table 1. Soaking the membrane in 20% by mass of H 2 SO 4 After 2 months in the water solution, the water flux and the salt rejection rate of the composite nanofiltration membrane are tested, and the results are shown in table 1.
The results in table 1 show that, when the sulfonamide group having the structure of formula (1) is introduced into the molecular structure of polysulfonamide, H on N is very active under the strong electron withdrawing action of the adjacent group, and is easily dissociated into hydrogen ions in water, so that N exhibits electronegativity. According to the southward effect, the introduction of electronegative ionic groups can increase the rejection rate of the polysulfonamide nanofiltration membrane on divalent anion salts. On the other hand, the introduction of more ionic groups helps to improve the hydrophilicity of the membrane and increase the water flux. The obtained composite membrane has excellent acid resistance, higher water flux and desalination rate.
TABLE 1
Figure 909155DEST_PATH_IMAGE002

Claims (14)

1. A composite membrane having acid resistance comprising a bottom layer, an intermediate porous support layer and a separation layer of a top layer, said separation layer being a polysulfonamide separation layer wherein the polysulfonamide has the structure shown in formula (1):
Figure 862149DEST_PATH_IMAGE001
（1）；
the separation layer is obtained by interfacial polymerization of sulfonamide or its derivative and polyamine with polybasic sulfonyl chloride, wherein the sulfonamide or its derivative is at least one of sulfonamide, benzenesulfonamide, 4-aminobenzenesulfonamide, 2-aminobenzenesulfonamide, 3-aminobenzenesulfonamide, methylsulfonamide, ethylsulfonamide, propylsulfonamide, N-butylbenzenesulfonamide, perfluorobutylsulfonamide, 1,3-benzenedisulfonamide, 4-amino-N-methylbenzenesulfonamide, perfluorooctylsulfonamide, 4-carboxybenzenesulfonamide, 3,5-difluorobenzenesulfonamide, 4- (2-aminoethyl) benzenesulfonamide, 4-amino-6-chloro-1,3-benzenedisulfonamide, 4-methoxybenzenesulfonamide, 3-chlorobenzenesulfonamide, 2-chlorobenzenesulfonamide, 2,3-dichlorothiophene-5-sulfonamide, p-toluenesulfonamide, o-toluenesulfonamide, 4-cyanophenyl-1-sulfonamide, 3835 zxft 3935-difluorobenzenesulfonamide, 24-difluorobenzenesulfonamide, 3524-3534-dichlorothiophene-5-sulfonamide, 3-chlorobenzenesulfonamide, 3534-chlorobenzenesulfonamide, 4-chlorobenzenesulfonamide, 3-3534, and at least one of chlorobenzene sulfonamide; the polyamine is at least one of m-phenylenediamine, p-phenylenediamine, o-phenylenediamine, 1,3,5-triaminobenzene, melamine, piperazine, ethylenediamine, 1,2-propanediamine, 1,4-butanediamine, diethylenetriamine, tetraethylenepentamine, polyethylene polyamine, polyethylene imine and polyether amine; the polybasic sulfonyl chloride is at least one of 1,3-benzene disulfonyl chloride, 1,2-benzene disulfonyl chloride, 1,4-benzene disulfonyl chloride, 2,4-disulfonylchloromesitylene, biphenyl-4,4' -disulfonyl chloride, 4,5-dichloro-1,3-benzene disulfonyl chloride, 2,6-naphthalene disulfonyl chloride, 1,3-naphthalene disulfonyl chloride, 2,7-naphthalene disulfonyl chloride, 1,3,5-benzene trisulfonyl chloride, 1,3,6-naphthalene trisulfonyl chloride.
2. The composite film having acid resistance according to claim 1, wherein:
the material of the porous supporting layer is at least one of polyether sulfone, polysulfone, polyaromatic ether, polybenzimidazole, polyether ketone, polyether ether ketone, polyacrylonitrile, polyvinylidene fluoride and polyaryletherketone.
3. The composite film having acid resistance of any one of claims 1~2 wherein:
the thickness of the bottom layer is 30 to 150 mu m; the thickness of the porous supporting layer is 10 to 100 mu m; the thickness of the polysulfonamide separation layer is 10 to 500nm.
4. The composite film having acid resistance according to claim 3, wherein:
the thickness of the bottom layer is 50 to 120 mu m; the thickness of the porous support layer is 30 to 60 micrometers; the thickness of the polysulfonamide separation layer is 50 to 300nm.
5. A method of making a composite film having acid resistance according to any one of claims 1~4 comprising the steps of:
(1) Preparing a porous support layer on one surface of the base layer;
(2) A separation layer is obtained on the other surface of the porous support layer by interfacial polymerization of a component comprising a sulfonamide or derivative thereof, a polyamine, and a polybasic sulfonyl chloride.
6. The method for preparing a composite film having acid resistance according to claim 5, wherein:
in the step (2), the other surface of the porous supporting layer is firstly contacted with water containing sulfamide or derivatives thereof and polyamine, and then contacted with organic phase containing polybasic sulfonyl chloride after liquid drainage, and heat treatment is carried out.
7. The method for preparing a composite film having acid resistance according to claim 6, wherein:
in the water phase, the concentration of the sulfamide or the derivatives thereof is 0.05 to 5wt%; the concentration of the polyamine is 0.05 to 5wt%; and/or the presence of a gas in the gas,
in the organic phase, the content of the polybasic sulfonyl chloride is 0.025 to 1wt%.
8. The method for preparing a composite film having acid resistance according to claim 7, wherein:
in the water phase, the concentration of the sulfamide or the derivatives thereof is 0.1 to 2wt%; the concentration of the polyamine is 0.1 to 2wt%; and/or the presence of a gas in the gas,
in the organic phase, the content of the polybasic sulfonyl chloride is 0.05 to 0.5wt%.
9. The method for preparing a composite film having acid resistance according to claim 7, wherein:
the ratio of the sum of the concentrations of the sulfonamide or the derivative thereof and the polyamine to the concentration of the polybasic sulfonyl chloride is (0.1 to 50): 1.
10. the method for preparing a composite film having acid resistance according to claim 9, wherein:
the ratio of the sum of the concentrations of the sulfonamide or the derivative thereof and the polyamine to the concentration of the polybasic sulfonyl chloride is (0.5 to 10): 1.
11. the method for preparing a composite film having acid resistance according to claim 6, wherein:
the contact time of the porous support layer and a water phase containing sulfamide or derivatives thereof and polyamine is 5 to 100s; and/or the presence of a gas in the gas,
the time for the porous supporting layer to contact with the organic phase containing the polybasic sulfonyl chloride is 10 to 200s; and/or the presence of a gas in the atmosphere,
the heat treatment temperature is 40 to 150 ℃; the heat treatment time is 0.5 to 20 minutes.
12. The method for preparing a composite film having acid resistance according to claim 11, wherein:
the contact time of the porous support layer and a water phase containing sulfamide or derivatives thereof and polyamine is 10 to 60s; and/or the presence of a gas in the gas,
the contact time of the porous support layer and an organic phase containing the polybasic sulfonyl chloride is 20 to 120s; and/or the presence of a gas in the gas,
the heat treatment temperature is 50 to 120 ℃; the heat treatment time is 1 to 10 minutes.
13. A composite film having acid resistance obtained by the production method according to any one of claims 5 to 12.
14. Use of the acid-resistant composite film according to any one of claims 1~4 or the acid-resistant composite film obtained by the preparation method according to any one of claims 5 to 12 in the field of water treatment.
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