CN113509839A - Acid/alkali-resistant composite nanofiltration membrane and preparation method and application thereof - Google Patents
Acid/alkali-resistant composite nanofiltration membrane and preparation method and application thereof Download PDFInfo
- Publication number
- CN113509839A CN113509839A CN202010271899.6A CN202010271899A CN113509839A CN 113509839 A CN113509839 A CN 113509839A CN 202010271899 A CN202010271899 A CN 202010271899A CN 113509839 A CN113509839 A CN 113509839A
- Authority
- CN
- China
- Prior art keywords
- nanofiltration membrane
- composite nanofiltration
- polyamine
- diisocyanate
- layer
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Images
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- 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
- 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
- B01D69/10—Supported membranes; Membrane supports
- B01D69/105—Support pretreatment
-
- 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
-
- 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
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/12—Layered products comprising a layer of synthetic resin next to a fibrous or filamentary layer
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/28—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B5/00—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts
- B32B5/02—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by structural features of a fibrous or filamentary layer
-
- 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
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2262/00—Composition or structural features of fibres which form a fibrous or filamentary layer or are present as additives
- B32B2262/02—Synthetic macromolecular fibres
- B32B2262/0253—Polyolefin fibres
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Nanotechnology (AREA)
- Water Supply & Treatment (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
Abstract
The invention relates to an acid/alkali resistant composite nanofiltration membrane, and a preparation method and application thereof. The composite nanofiltration membrane comprises a bottom layer, a middle porous supporting layer and a surface separation layer, wherein the separation layer is a polyurea separation layer. The polyurea separating layer is obtained by interfacial polymerization of polyamine and polyisocyanate. A large number of intermolecular hydrogen bonds (carbonyl and imino or amino in carbamido) can be formed in the molecular structure of the polyurea, and the molecular structure of the separation layer is more compact due to the existence of the hydrogen bonds, so that the stability of the separation layer in an acid/alkali medium is improved. The composite nanofiltration membrane can stably run in an aqueous solution with the pH value of 0-14, has high desalination rate and water permeability and strong acid/alkali resistance, and the preparation method is simple and has great industrial application prospect.
Description
Technical Field
The invention relates to the field of functional films, in particular to an acid/alkali resistant composite nanofiltration membrane and a preparation method and application thereof.
Background
Nanofiltration is a pressure-driven membrane separation process between reverse osmosis and ultrafiltration, the pore diameter 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 US 482474 also provide a method how to convert a polyamide composite reverse osmosis membrane into a nanofiltration membrane. However, due to the limitation of the characteristics of the materials, the traditional polyamide nanofiltration membrane can be degraded in an extreme pH environment, particularly under a strong alkali condition, and the polyamide nanofiltration membrane can only be used for a neutral medium or a weak acid and weak alkali medium 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.
The document "Acid stable thin-film composite membrane for nanofilation prediction from naphthalene-1,3,6-trisulfonylchloride (NTSC) and piperazine (PIP), J.Membr.Sci., 415-: 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 of pH 0.
Reported in the literature "Sulfonated poly (etherketone) 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 and strong alkali resistance, a nanofiltration membrane material with excellent interception performance can be obtained through Crosslinking, and the crosslinked polyether-ether-ketone material has strong solvent resistance and can separate dyes (Crosslinking of modified poly (ether ketone) membranes for use in solvent nanofilation, 447, 212-containing 221,2013) in polar solvents such as isopropanol, acetone and the like.
The application of acid and alkali resistant and high temperature resistant nanofiltration membrane HYDRACoRe70pHT in the recovery of waste alkali liquor in sugar industry, and the report of membrane science and technology, 32,11-15,2006: the commercial sulfonated polyether sulfone composite nanofiltration membrane is 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 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 No. US7138058), 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.
Patent No. US5265734, EP0392982(a3) reported that nanofiltration membranes capable of stable operation at pH 0-14 for long periods of time were only SelRO MPS34 developed by KOCH corporation, which was first developed by israel scientists and was first applied to pervaporation.
The AMS company develops an acid-resistant, alkali-resistant and solvent-resistant composite nanofiltration membrane, and the separation layer is made of polyamine (US9943811) which is prepared by interfacial polymerization reaction of polyamine and cyanuric chloride or derivatives thereof.
The literature (Journal of Membrane Science 523(2017)487-496) and the literature (Journal of Membrane Science 478(2015)75-84) report that a polyaniline separation layer is modified on a porous support layer by using an interfacial polymerization method, and a composite nanofiltration Membrane has strong permeation and separation stability in a medium environment with the pH value of 0-14.
The literature (Journal of Membrane Science 572(2019)489-495) prepares a polyvinylidene fluoride nanofiltration Membrane material by using a phase inversion and post-treatment method, and the material has strong stability in strong acid and strong alkali environments.
Disclosure of Invention
The invention aims to overcome the defects of poor acid resistance and poor alkali resistance of the existing nanofiltration membrane, and provides an acid/alkali resistant composite nanofiltration membrane, a preparation method thereof, and application of the composite nanofiltration membrane and the composite nanofiltration membrane prepared by the method in the field of water treatment.
The composite nanofiltration membrane comprises a bottom layer, a middle porous supporting layer and a surface separation layer, wherein the separation layer is a polyurea separation layer.
The composite nanofiltration membrane comprises a three-layer structure: the bottom layer of the substrate is provided with a porous support layer on one surface, and a dense polyurea separation layer with a cross-linked structure on the other surface.
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 capable of being used for a nanofiltration membrane. 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 material of the porous support layer is 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 polyurea separating layer is obtained by interfacial polymerization of polyamine and polyisocyanate.
The polyamine comprises at least one of aliphatic polyamine and aromatic amine. The aliphatic polyamine is preferably at least one of piperazine, ethylenediamine, 1, 2-propanediamine, 1, 4-butanediamine, diethylenetriamine, tetraethylenepentamine, polyethyleneimine, polyethylene polyamine and polyether amine; the aromatic amine is preferably at least one selected from m-phenylenediamine, p-phenylenediamine, o-phenylenediamine, 1,3, 5-triaminobenzene and melamine.
The polyisocyanate is preferably selected from m-xylylene diisocyanate, o-xylylene diisocyanate, isophorone diisocyanate, 1, 6-hexamethylene diisocyanate, toluene-2, 6-diisocyanate, 1, 4-phenylene diisocyanate, toluene-2, 4-diisocyanate, 4' -methylenebis (phenyl isocyanate), at least one of 1, 3-phenylene diisocyanate, 3 ' -dichloro-4, 4 ' -diisocyanate biphenyl, dicyclohexylmethane-4, 4 ' -diisocyanate, trimethylhexamethylene diisocyanate, L-lysine-ethyl ester-diisocyanate, 1, 4-cyclohexyl diisocyanate, and 4-chloro-6-methyl-m-phenylene diisocyanate; more preferably at least one selected from the group consisting of m-xylylene diisocyanate, o-xylylene diisocyanate, 1, 4-phenylene diisocyanate, 1, 3-phenylene diisocyanate, 4 '-methylenebis (phenylisocyanate), 3' -dichloro-4, 4 '-diisocyanatobiphenyl, dicyclohexylmethane-4, 4' -diisocyanate and 1, 4-cyclohexyl diisocyanate.
The polyamine preferably includes aliphatic polyamines and aromatic amines, and more preferably a mixture of polyethyleneimine, polyethylenepolyamine, and any two of m-phenylenediamine, p-phenylenediamine, and 1,3, 5-triaminobenzene.
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 better synergistic cooperation, the obtained composite nanofiltration membrane can better have excellent acid and alkali resistance, higher water flux and higher desalination rate, and preferably, the thickness of the bottom layer is 30-150 μm, and preferably 50-120 μm; the thickness of the porous supporting layer is 10-100 mu m, and preferably 30-60 mu m; the thickness of the polyurea separating layer is 10-500 nm, and preferably 50-300 nm.
The invention also aims to provide a preparation method of the acid/alkali resistant composite nanofiltration membrane, which comprises the following steps:
(1) preparing a porous support layer on one surface of the base layer:
(2) the polyurea separation layer is obtained by interfacial polymerization of a polyamine with a polyisocyanate 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 support layer material to one surface of a substrate layer 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 10-20 wt%, and defoaming at 20-40 ℃ for 10-180 min; and then coating the polymer solution on the bottom layer to obtain an initial membrane, soaking the initial membrane in water at the temperature of 10-30 ℃ for 10-60 min, and passing through a phase inversion layer to form the support layer polymer porous membrane.
Among them, the solvent may be N, N-dimethylformamide, N-dimethylacetamide, N-methylpyrrolidone, dimethylsulfoxide, or the like.
According to the present invention, the process of contacting the other surface of the porous support layer with the aqueous phase containing the polyamine and the organic phase containing the polyisocyanate in sequence in step (2) comprises: firstly, the porous supporting layer is contacted with water containing polyamine, drained, then contacted with organic phase containing polyisocyanate, and then heat treated.
According to the invention, the polyamine is one or a mixture of more of m-phenylenediamine, p-phenylenediamine, o-phenylenediamine, 1,3, 5-triaminobenzene, melamine, piperazine, ethylenediamine, 1, 2-propanediamine, 1, 4-butanediamine, diethylenetriamine, tetraethylenepentamine, polyethyleneimine and polyether amine; preferably an aliphatic polyamine mixed with an aromatic amine; more preferably a mixture of polyethyleneimine, polyethylenepolyamine, and any two of m-phenylenediamine, p-phenylenediamine, and 1,3, 5-triaminobenzene. The polybasic isocyanate is m-xylylene diisocyanate, o-xylylene diisocyanate, isophorone diisocyanate, 1, 6-hexamethylene diisocyanate, toluene-2, 6-diisocyanate, 1, 4-phenylene diisocyanate, toluene-2, 4-diisocyanate, 4' -methylenebis (phenyl isocyanate), 1, 3-phenylene diisocyanate, 3 ' -dichloro-4, 4 ' -diisocyanate biphenyl, dicyclohexylmethane-4, 4 ' -diisocyanate, trimethylhexamethylene diisocyanate, m-xylylene diisocyanate, L-lysine-ethyl ester-diisocyanate, 1, 4-cyclohexyl diisocyanate, 4-chloro-6-methyl m-phenylene diisocyanate.
According to the present invention, the kind of the solvent of the organic phase is not particularly limited as long as the polyisocyanate can be dissolved, 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, the concentration of polyamine and polyisocyanate in the interfacial polymerization process is not particularly limited as long as the obtained nanofiltration membrane has excellent acid and alkali resistance and high water flux and desalination rate, and preferably, in a water phase containing polyamine, the content of the polyamine is 0.2-10 wt%, more preferably 0.5-5 wt%; when the polyamine comprises aliphatic polyamine and aromatic amine, the mass ratio of the aliphatic polyamine to the aromatic amine is (0.05-100): 1, preferably (0.1 to 10): 1; the content of the polyisocyanate in the organic phase containing the polyisocyanate is 0.025 to 1 wt%, preferably 0.05 to 0.5 wt%.
According to the invention, the mass concentration ratio of the polyamine and the polyisocyanate in the interfacial polymerization process is not particularly limited as long as the obtained nanofiltration membrane can combine excellent acid and alkali resistance, high water flux and high salt rejection rate, and the mass concentration ratio of the polyamine and the polyisocyanate is preferably (0.5-100): 1, more preferably (1 to 50): 1.
according to the invention, in the interface 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 has excellent acid and alkali resistance, high water flux and high desalination rate, and preferably, the contact time of the porous support layer with the water phase containing polyamine is 5-100 s, preferably 10-60 s; the time for contacting the polyisocyanate-containing organic phase is 10 to 200 seconds, preferably 20 to 120 seconds.
According to the invention, the post-treatment conditions of the interfacial polymerization are not particularly limited, as long as the monomers can be completely polymerized, the nanofiltration membrane can have excellent acid and alkali resistance and higher water flux and desalination rate, and the heat treatment temperature is preferably 40-150 ℃, and preferably 50-120 ℃; the heat treatment time is 0.5 to 20 minutes, preferably 1 to 10 minutes.
The invention also aims to provide the acid/alkali resistant composite nanofiltration membrane prepared by the preparation method provided by the invention.
The fourth purpose of the invention is to provide the composite nanofiltration membrane with acid/alkali resistance and the application of the composite nanofiltration membrane with acid/alkali resistance obtained by the preparation method in the field of water treatment.
The inventor of the present invention has found through intensive research that, on one hand, the polyurea functional layer provided by the present invention has a molecular structure containing both flexible chain breaks provided by aliphatic amine and stable rigid chain breaks provided by aromatic amine, the flexible chain breaks are beneficial to the improvement of water flux of the membrane, and the rigid chain breaks are beneficial to the improvement of acid/alkali resistance of the membrane, and by adjusting the ratio of the flexible chain breaks to the rigid chain breaks in the molecular structure, the composite nanofiltration membrane material having good water permeability and salt cut-off property and excellent acid/alkali resistance can be prepared. On the other hand, a large number of intermolecular hydrogen bonds (carbonyl and imino or amino groups in urea groups) can be formed in the molecular structure of the polyurea, and the molecular structure of the separation layer is more compact due to the existence of the hydrogen bonds, so that the stability of the separation layer in an acid/alkali medium is improved. The composite nanofiltration membrane can stably operate in an aqueous solution with the pH value of 0-14, has high desalination rate and water permeability (water flux), has strong acid/alkali resistance, is simple in preparation method, and has great industrial application prospects.
Additional features and advantages of the invention will be set forth in the detailed description which follows.
Drawings
The accompanying drawings, which are included to provide a further understanding of the invention and are incorporated in and constitute a part of this specification, illustrate embodiments of the invention and together with the description serve to explain the principles of the invention and not to limit the invention. In the drawings:
FIG. 1 shows the salt rejection and water flux of the composite nanofiltration membrane prepared in example 1 with H at 20%2SO4Variation of soaking time in aqueous solution;
figure 2 is a graph of salt rejection and water flux of the composite nanofiltration membrane prepared in example 1 as a function of soaking time in a 20% aqueous NaOH solution;
figure 3 is a graph of the salt rejection and water flux of the composite nanofiltration membrane prepared in example 1 as a function of soaking time in a 20% aqueous phosphoric acid solution;
figure 4 is a graph of salt rejection and water flux of the composite nanofiltration membranes prepared in example 1 as a function of soaking time in 20% aqueous HCl.
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 is Q/(A.t), wherein J is water flux, Q is water flux (L), and A is effective membrane area (m) of the composite nanofiltration membrane2) T is time (h);
(2) the salt rejection of the composite nanofiltration membrane is obtained by testing the following method: loading the composite nanofiltration membrane into a membrane pool, prepressing for 0.5h under 1.2MPa, measuring the concentration change of the magnesium sulfate raw water solution with initial concentration of 2000ppm and the magnesium sulfate in the permeate liquid within 1h under the conditions of pressure of 2.0MPa and temperature of 25 ℃, and calculating by the following formula:
R＝(Cp-Cf)/Cpx 100%, wherein R is the salt rejection, CpIs the concentration of magnesium sulfate in the stock solution, CfIs the concentration of magnesium sulfate in the permeate;
(3) and (3) testing the acid resistance of the composite nanofiltration membrane: the composite nanofiltration membrane membranes are respectively soaked in a solution containing 20 mass percent of H2SO420% by mass of HCl and 20% by mass of H3PO4Soaking the composite nanofiltration membrane in the aqueous solution for 6 months, and then testing the change of the water flux and the salt rejection rate of the composite nanofiltration membrane every other week;
(4) and (3) testing alkali resistance of the composite nanofiltration membrane: the composite nanofiltration membrane is soaked in an alkali aqueous solution containing 20 mass percent of NaOH for 6 months, and then the changes of the water flux and the salt rejection rate of the composite nanofiltration membrane are tested every other week.
In addition, in the following examples and comparative examples:
branched polyethyleneimines (weight average molecular weight 25000), piperazine, m-phenylenediamine, 1,3, 5-triaminobenzene, p-phenylenediamine, tetraethylenepentamine, diethylenetriamine, m-xylylene diisocyanate, 1, 6-hexamethylene diisocyanate, toluene-2, 6-diisocyanate, 1, 4-phenylene diisocyanate, toluene-2, 4-diisocyanate, polyethylene polyamine, 4 ' -methylenebis (phenylisocyanate), 1, 3-phenylene diisocyanate, 3 ' -dichloro-4, 4 ' -diisocyanate biphenyl, o-xylylene diisocyanate, 4-chloro-6-methylisophenyldiisocyanate, isophorone diisocyanate, 1, 4-cyclohexyl diisocyanate and the like are available from Bailingwei scientific Co, other chemicals were purchased from the national pharmaceutical group chemicals, ltd.
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 120 min; 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 polyester nonwoven fabric was phase-converted into a porous film, and finally washed with water 3 times to obtain a film having a total thickness of 115 μm.
Example 1
Contacting the upper surface of the polysulfone supporting layer with an aqueous solution containing 1 wt% of m-phenylenediamine and 1 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 0.2 weight percent of 4, 4' -methylene bis (phenyl isocyanate) and is contacted for 60 seconds at the temperature of 25 ℃ for liquid drainage; and then, putting the membrane into an oven, and heating for 3min at 70 ℃ to obtain the composite nanofiltration membrane. The thickness of the separating layer was 215nm as measured by scanning electron microscopy.
Soaking the obtained composite nanofiltration membrane N1 in water for 24h, and measuring water flux and p-MgSO at 25 deg.C and 2.0MPa4The salt rejection of (2) is shown in Table 1. The membranes were immersed in 20 mass% of H, respectively2SO420% by mass of HCl and 20% by mass of H3PO4And 20 mass percent NaOH in water solution for 6 months, and then testing the change of the water flux and the salt rejection rate of the composite nanofiltration membrane every other week, and the results are shown in figures 1-4。
Example 2
Contacting the upper surface of the polysulfone support layer with an aqueous solution containing 3 wt% of 1,3, 5-triaminobenzene and 2 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 0.5 weight percent of 3,3 '-dichloro-4, 4' -diisocyanate biphenyl, and the liquid is discharged after the contact for 60s at 25 ℃; and then, putting the membrane into an oven, and heating for 3min at 70 ℃ to obtain the composite nanofiltration membrane. The thickness of the separating layer was 248nm as measured by scanning electron microscopy.
Soaking the obtained composite nanofiltration membrane N2 in water for 24h, and measuring water flux and p-MgSO at 25 deg.C and 2.0MPa4The salt rejection of (2) is shown in Table 1. After the membrane was immersed in aqueous solutions of 20 mass% HCl and 20 mass% NaOH for 6 months, the water flux and salt rejection of the composite nanofiltration membrane were measured, and the results are shown in table 1.
Example 3
Contacting the upper surface of the polysulfone support layer with an aqueous solution containing 0.3 wt% of p-phenylenediamine and 0.2 wt% of tetraethylenepentamine, 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 m-xylylene diisocyanate, and the liquid is discharged after the contact for 60s at 25 ℃; and then, putting the membrane into an oven, and heating for 3min at 70 ℃ to obtain the composite nanofiltration membrane. The thickness of the separating layer was 185nm as measured by scanning electron microscopy.
Soaking the obtained composite nanofiltration membrane N3 in water for 24h, and measuring water flux and p-MgSO at 25 deg.C and 2.0MPa4The salt rejection of (2) is shown in Table 1. After the membrane was immersed in aqueous solutions of 20 mass% HCl and 20 mass% NaOH for 6 months, the water flux and salt rejection of the composite nanofiltration membrane were measured, and the results are shown in table 1.
Example 4
Contacting the upper surface of the polysulfone supporting layer with an aqueous solution containing 0.4 wt% of melamine and 0.1 wt% of piperazine, and discharging liquid after contacting for 60s at 25 ℃; then, the upper surface of the supporting layer is contacted with Isopar E solution containing 0.025 weight percent of 1, 4-phenylene diisocyanate and is contacted with the solution for 60 seconds at 25 ℃ for liquid drainage; and then, putting the membrane into an oven, and heating for 3min at 70 ℃ to obtain the composite nanofiltration membrane. The thickness of the separating layer was 180nm as measured by scanning electron microscopy.
Soaking the obtained composite nanofiltration membrane N4 in water for 24h, and measuring water flux and p-MgSO at 25 deg.C and 2.0MPa4The salt rejection of (2) is shown in Table 1. After the membrane was immersed in aqueous solutions of 20 mass% HCl and 20 mass% NaOH for 6 months, the water flux and salt rejection of the composite nanofiltration membrane were measured, and the results are shown in table 1.
Example 5
The procedure was carried out as in example 1 for the preparation of a composite nanofiltration membrane, except that 1, 3-benzenediisocyanate was used instead of 4, 4' -methylenebis (phenylisocyanate) to give a composite nanofiltration membrane N5.
Soaking the obtained composite nanofiltration membrane N5 in water for 24h, and measuring water flux and p-MgSO at 25 deg.C and 2.0MPa4The salt rejection of (2) is shown in Table 1. After the membrane was immersed in aqueous solutions of 20 mass% HCl and 20 mass% NaOH for 6 months, the water flux and salt rejection of the composite nanofiltration membrane were measured, and the results are shown in table 1.
Example 6
The procedure was carried out as in example 1 for the preparation of a composite nanofiltration membrane, except that o-xylylene diisocyanate was used instead of 4, 4' -methylenebis (phenylisocyanate) to give a composite nanofiltration membrane N6.
Soaking the obtained composite nanofiltration membrane N6 in water for 24h, and measuring water flux and p-MgSO at 25 deg.C and 2.0MPa4The salt rejection of (2) is shown in Table 1. After the membrane was immersed in aqueous solutions of 20 mass% HCl and 20 mass% NaOH for 6 months, the water flux and salt rejection of the composite nanofiltration membrane were measured, and the results are shown in table 1.
Example 7
A composite nanofiltration membrane was prepared as in example 1, except that 4-chloro-6-methyl-m-phenylene diisocyanate was used in place of 4, 4' -methylenebis (phenyl isocyanate) to provide a composite nanofiltration membrane N7.
Soaking the obtained composite nanofiltration membrane N7 in water for 24h, and measuring water flux and p-MgSO at 25 deg.C and 2.0MPa4The salt rejection of (2) is shown in Table 1. After the membrane was immersed in aqueous solutions of 20 mass% HCl and 20 mass% NaOH for 6 months, the water flux and salt rejection of the composite nanofiltration membrane were measured, and the results are shown in table 1.
Example 8
The procedure was followed for the preparation of a composite nanofiltration membrane as in example 1, except that isophorone diisocyanate was used instead of 4, 4' -methylenebis (phenyl isocyanate) to give a composite nanofiltration membrane N8.
Soaking the obtained composite nanofiltration membrane N8 in water for 24h, and measuring water flux and p-MgSO at 25 deg.C and 2.0MPa4The salt rejection of (2) is shown in Table 1. After the membrane was immersed in aqueous solutions of 20 mass% HCl and 20 mass% NaOH for 6 months, the water flux and salt rejection of the composite nanofiltration membrane were measured, and the results are shown in table 1.
Example 9
The procedure was carried out as in example 1 for the preparation of composite nanofiltration membranes, with the difference that 1, 4-cyclohexyl diisocyanate was used instead of 4, 4' -methylenebis (phenylisocyanate) to obtain composite nanofiltration membrane N9.
Soaking the obtained composite nanofiltration membrane N9 in water for 24h, and measuring water flux and p-MgSO at 25 deg.C and 2.0MPa4The salt rejection of (2) is shown in Table 1. After the membrane was immersed in aqueous solutions of 20 mass% HCl and 20 mass% NaOH for 6 months, the water flux and salt rejection of the composite nanofiltration membrane were measured, and the results are shown in table 1.
Example 10
A composite nanofiltration membrane was prepared as in example 1, except that m-phenylenediamine was used in an amount of 0.25 wt%, polyethyleneimine was used in an amount of 2.5 wt%, and 4, 4' -methylenebis (phenylisocyanate) was used in an amount of 0.055 wt%, to give a composite nanofiltration membrane N10.
Soaking the obtained composite nanofiltration membrane N10 in water for 24h, and then putting the membrane in the waterMeasuring water flux and p-MgSO at 25 deg.C and 2.0MPa4The salt rejection of (2) is shown in Table 1. After the membrane was immersed in aqueous solutions of 20 mass% HCl and 20 mass% NaOH for 6 months, the water flux and salt rejection of the composite nanofiltration membrane were measured, and the results are shown in table 1.
Example 11
Contacting the upper surface of the polysulfone supporting layer with an aqueous solution containing 1 wt% of m-phenylenediamine and 1 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 0.2 weight percent of toluene-2, 6-diisocyanate, and the liquid is discharged after the contact for 60s at 25 ℃; then, the membrane was placed in an oven and heated at 70 ℃ for 3min to obtain a composite nanofiltration membrane N11. The thickness of the separating layer was 205nm as measured by scanning electron microscopy.
Soaking the obtained composite nanofiltration membrane N11 in water for 24h, and measuring water flux and p-MgSO at 25 deg.C and 2.0MPa4The salt rejection of (2) is shown in Table 1. After the membrane was immersed in aqueous solutions of 20 mass% HCl and 20 mass% NaOH for 6 months, the water flux and salt rejection of the composite nanofiltration membrane were measured, and the results are shown in table 1.
Example 12
Contacting the upper surface of the polysulfone supporting layer with an aqueous solution containing 1 wt% of m-phenylenediamine and 1 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 0.2 weight percent of toluene-2, 4-diisocyanate, and the liquid is discharged after the contact for 60s at 25 ℃; then, the membrane was placed in an oven and heated at 70 ℃ for 3min to obtain a composite nanofiltration membrane N12. The thickness of the separating layer was 200nm as measured by scanning electron microscopy.
Soaking the obtained composite nanofiltration membrane N12 in water for 24h, and measuring water flux and p-MgSO at 25 deg.C and 2.0MPa4The salt rejection of (2) is shown in Table 1. After the membrane was immersed in aqueous solutions of 20 mass% HCl and 20 mass% NaOH for 6 months, the water flux and salt rejection of the composite nanofiltration membrane were measured, and the results are shown in table 1.
Example 13
Contacting the upper surface of the polysulfone supporting layer with an aqueous solution containing 1 wt% of m-phenylenediamine and 1 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 0.2 weight percent of 1, 6-hexamethylene diisocyanate and is contacted for 60 seconds at 25 ℃, and then liquid drainage is carried out; then, the membrane was placed in an oven and heated at 70 ℃ for 3min to obtain a composite nanofiltration membrane N13. The thickness of the separating layer was 215nm as measured by scanning electron microscopy.
Soaking the obtained composite nanofiltration membrane N13 in water for 24h, and measuring water flux and p-MgSO at 25 deg.C and 2.0MPa4The salt rejection of (2) is shown in Table 1. After the membrane was immersed in aqueous solutions of 20 mass% HCl and 20 mass% NaOH for 6 months, the water flux and salt rejection of the composite nanofiltration membrane were measured, and the results are shown in table 1.
Example 14
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 0.025 weight percent of 1, 4-phenylene diisocyanate and is contacted with the solution for 60 seconds at 25 ℃ for liquid drainage; and then, putting the membrane into an oven, and heating for 3min at 70 ℃ to obtain the composite nanofiltration membrane. The thickness of the separating layer was 188nm as measured by scanning electron microscopy.
Soaking the obtained composite nanofiltration membrane N14 in water for 24h, and measuring water flux and p-MgSO at 25 deg.C and 2.0MPa4The salt rejection of (2) is shown in Table 1. After the membrane was immersed in aqueous solutions of 20 mass% HCl and 20 mass% NaOH for 6 months, the water flux and salt rejection of the composite nanofiltration membrane were measured, and the results are shown in table 1.
Example 15
Contacting the upper surface of the polysulfone support layer with an aqueous solution containing 0.5 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 0.025 weight percent of 4, 4' -methylene bis (phenyl isocyanate) and is contacted for 60 seconds at 25 ℃, and then liquid drainage is carried out; and then, putting the membrane into an oven, and heating for 3min at 70 ℃ to obtain the composite nanofiltration membrane. The thickness of the separating layer was 193nm as measured by scanning electron microscopy.
Soaking the obtained composite nanofiltration membrane N15 in water for 24h, and measuring water flux and p-MgSO at 25 deg.C and 2.0MPa4The salt rejection of (2) is shown in Table 1. After the membrane was immersed in aqueous solutions of 20 mass% HCl and 20 mass% NaOH for 6 months, the water flux and salt rejection of the composite nanofiltration membrane were measured, and the results are shown in table 1.
As can be seen from FIGS. 1 to 4, the composite nanofiltration membrane using polyurea as the separation layer was 20 mass% H2SO420% by mass of HCl and 20% by mass of H3PO4And 20 mass% NaOH in water, and soaking in the above extremely acidic or alkaline solution for more than 200 days for MgSO4The retention rate of the catalyst is still kept above 90 percent. The water flux increases significantly with increasing soaking time, indicating swelling of the polyurea cross-linked structure in extremely acidic or alkaline solutions.
TABLE 1 comparison of acid and base resistance of the example and comparative example films
Claims (14)
1. The composite nanofiltration membrane with acid/alkali resistance is characterized by comprising a bottom layer, a middle porous supporting layer and a surface separation layer, wherein the separation layer is a polyurea separation layer.
2. The composite nanofiltration membrane having acid/alkali 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 nanofiltration membrane having acid/alkali resistance according to claim 1, wherein:
the polyurea separating layer is obtained by interfacial polymerization of polyamine and polyisocyanate.
4. The composite nanofiltration membrane having acid/alkali resistance according to claim 3, wherein:
the polyamine comprises at least one of aliphatic polyamine and aromatic amine; the aliphatic polyamine is preferably at least one of piperazine, ethylenediamine, 1, 2-propanediamine, 1, 4-butanediamine, diethylenetriamine, tetraethylenepentamine, polyethyleneimine, polyethylene polyamine and polyether amine; the aromatic amine is preferably at least one of m-phenylenediamine, p-phenylenediamine, o-phenylenediamine, 1,3, 5-triaminobenzene and melamine; and/or the presence of a gas in the gas,
the polybasic isocyanate is selected from m-xylylene diisocyanate, o-xylylene diisocyanate, isophorone diisocyanate, 1, 6-hexamethylene diisocyanate, toluene-2, 6-diisocyanate, 1, 4-phenylene diisocyanate, toluene-2, 4-diisocyanate, 4' -methylene bis (phenyl isocyanate), 1, 3-phenylene diisocyanate, 3 ' -dichloro-4, 4 ' -diisocyanate biphenyl, dicyclohexylmethane-4, 4 ' -diisocyanate, trimethylhexamethylene diisocyanate, L-lysine-ethyl ester-diisocyanate, 1, 4-cyclohexyl diisocyanate, 4-chloro-6-methyl-m-phenylene diisocyanate.
5. The composite nanofiltration membrane having acid/alkali resistance according to claim 4, wherein:
the polyamine includes aliphatic polyamines and aromatic amines.
6. The composite nanofiltration membrane having acid/alkali resistance according to claim 1, wherein:
the thickness of the bottom layer is 30-150 mu m, preferably 50-120 mu m; the thickness of the porous supporting layer is 10-100 mu m, and preferably 30-60 mu m; the thickness of the polyurea separating layer is 10-500 nm, and preferably 50-300 nm.
7. A method for preparing the composite nanofiltration membrane with acid/alkali resistance according to any one of claims 1 to 6, wherein the method comprises the following steps:
(1) preparing a porous support layer on one surface of the base layer:
(2) the polyurea separation layer is obtained by interfacial polymerization of a polyamine with a polyisocyanate on the other surface of the porous support layer.
8. The preparation method of the composite nanofiltration membrane according to claim 7, wherein the preparation method comprises the following steps:
in the step (2), the other surface of the porous support layer is contacted with an aqueous phase containing polyamine and an organic phase containing polyisocyanate in sequence, and then heat treatment is performed.
9. The preparation method of the composite nanofiltration membrane according to claim 8, wherein the preparation method comprises the following steps:
in an aqueous phase containing polyamine, the content of the polyamine is 0.2-10 wt%, preferably 0.5-5 wt%; and/or the presence of a gas in the gas,
the polyamine comprises aliphatic polyamine and aromatic amine, and the mass ratio of the aliphatic polyamine to the aromatic amine is (0.05-100): 1, preferably (0.1 to 10): 1, and/or,
the content of the polyisocyanate in the organic phase containing the polyisocyanate is 0.025 to 1 wt%, preferably 0.05 to 0.5 wt%.
10. The preparation method of the composite nanofiltration membrane according to claim 9, wherein the preparation method comprises the following steps:
the mass concentration ratio of the polyamine to the polyisocyanate is (0.5-100): 1, preferably (1 to 50): 1.
11. the preparation method of the composite nanofiltration membrane according to claim 8, wherein the preparation method comprises the following steps:
the contact time of the porous supporting layer and the water phase containing the polyamine is 5-100 s, preferably 10-60 s; and/or the presence of a gas in the gas,
the time for contacting the porous supporting layer with the organic phase containing the polyisocyanate is 10-200 s, preferably 20-120 s.
12. The preparation method of the composite nanofiltration membrane according to claim 8, wherein the preparation method comprises the following steps:
the conditions of the heat treatment include: 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.
13. The composite nanofiltration membrane obtained by the preparation method according to any one of claims 7 to 12, wherein the composite nanofiltration membrane has acid/alkali resistance.
14. Use of the acid/alkali resistant composite nanofiltration membrane according to any one of claims 1 to 6 or the preparation method according to any one of claims 7 to 12 in the field of water treatment.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010271899.6A CN113509839B (en) | 2020-04-09 | 2020-04-09 | Acid/alkali-resistant composite nanofiltration membrane and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010271899.6A CN113509839B (en) | 2020-04-09 | 2020-04-09 | Acid/alkali-resistant composite nanofiltration membrane and preparation method and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN113509839A true CN113509839A (en) | 2021-10-19 |
| CN113509839B CN113509839B (en) | 2023-03-17 |
Family
ID=78060040
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202010271899.6A Active CN113509839B (en) | 2020-04-09 | 2020-04-09 | Acid/alkali-resistant composite nanofiltration membrane and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN113509839B (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114573171A (en) * | 2022-01-21 | 2022-06-03 | 广东台泉环保科技有限公司 | Salt lake lithium extraction intelligent energy-saving system equipment |
| CN115970521A (en) * | 2023-02-28 | 2023-04-18 | 中国科学院长春应用化学研究所 | Acid-resistant nanofiltration membrane and preparation method and application thereof |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5173335A (en) * | 1990-07-31 | 1992-12-22 | E. I. Du Pont De Nemours And Company | Method of producing multilayer reverse osmosis membrane of polyamide-urea |
| CN101502762A (en) * | 2009-02-12 | 2009-08-12 | 东华大学 | Method for preparing high-throughput flat aromatic/aliphatic copolymerized carbamide porous membrane |
| CN101631889A (en) * | 2007-04-16 | 2010-01-20 | 株式会社爱发科 | Polyurea film and film thereof |
| CN104010718A (en) * | 2011-10-18 | 2014-08-27 | 帝国创新有限公司 | Membranes for separation |
| CN107148311A (en) * | 2014-08-13 | 2017-09-08 | Iab离子交换股份有限公司 | The method for preparing the nonpolluting coating being made up of utilized thin film composite membranes for counter-infiltration and nanofiltration, the utilized thin film composite membranes and application thereof |
-
2020
- 2020-04-09 CN CN202010271899.6A patent/CN113509839B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5173335A (en) * | 1990-07-31 | 1992-12-22 | E. I. Du Pont De Nemours And Company | Method of producing multilayer reverse osmosis membrane of polyamide-urea |
| CN101631889A (en) * | 2007-04-16 | 2010-01-20 | 株式会社爱发科 | Polyurea film and film thereof |
| CN101502762A (en) * | 2009-02-12 | 2009-08-12 | 东华大学 | Method for preparing high-throughput flat aromatic/aliphatic copolymerized carbamide porous membrane |
| CN104010718A (en) * | 2011-10-18 | 2014-08-27 | 帝国创新有限公司 | Membranes for separation |
| CN107148311A (en) * | 2014-08-13 | 2017-09-08 | Iab离子交换股份有限公司 | The method for preparing the nonpolluting coating being made up of utilized thin film composite membranes for counter-infiltration and nanofiltration, the utilized thin film composite membranes and application thereof |
Non-Patent Citations (3)
| Title |
|---|
| MARCEL MULDER著 李琳译: "《膜技术基本原理 第2版》", 31 July 1999, 清华大学出版社 * |
| 刘茉娥等: "《膜分离技术》", 31 August 1998, 化学工业出版社 * |
| 崔绍波等: "界面聚合技术及其应用研究进展", 《化工进展》 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114573171A (en) * | 2022-01-21 | 2022-06-03 | 广东台泉环保科技有限公司 | Salt lake lithium extraction intelligent energy-saving system equipment |
| CN115970521A (en) * | 2023-02-28 | 2023-04-18 | 中国科学院长春应用化学研究所 | Acid-resistant nanofiltration membrane and preparation method and application thereof |
| CN115970521B (en) * | 2023-02-28 | 2024-08-23 | 中国科学院长春应用化学研究所 | Acid-resistant nanofiltration membrane and preparation method and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN113509839B (en) | 2023-03-17 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN113509840B (en) | Composite nanofiltration membrane and preparation method and application thereof | |
| US5616249A (en) | Nanofiltration apparatus and processes | |
| Bargeman | Recent developments in the preparation of improved nanofiltration membranes for extreme pH conditions | |
| CA2069510C (en) | Dry high flux semipermeable membranes | |
| US5744039A (en) | Composite semipermeable membrane and production method thereof | |
| CA3142200C (en) | Forward osmosis membrane, forward osmosis membrane module, and manufacturing method thereof | |
| CN103068476A (en) | Solvent resistant polyamide nanofiltration membranes | |
| CN108176258A (en) | For the film of separation | |
| CN114146566B (en) | Preparation method of high-performance polyolefin substrate reverse osmosis membrane, reverse osmosis membrane and application | |
| CN114146567B (en) | Preparation process of epoxy modified reverse osmosis membrane, reverse osmosis membrane and application of reverse osmosis membrane | |
| CN113509839B (en) | Acid/alkali-resistant composite nanofiltration membrane and preparation method and application thereof | |
| EP0421676B1 (en) | Interfacially polymerized membranes, and reverse osmosis separation of organic solvent solutions using them | |
| CN110354682B (en) | Reverse osmosis membrane resisting biological pollution and preparation method and application thereof | |
| Wei et al. | One-step fabrication of recyclable polyimide nanofiltration membranes with high selectivity and performance stability by a phase inversion-based process | |
| Zhang et al. | Tailoring molecular structure in the active layer of thin-film composite membrane for extreme pH condition | |
| CN114432901B (en) | Composite membrane with acid resistance and alkali resistance as well as preparation method and application thereof | |
| CN115105967B (en) | Acid-resistant alkali-resistant nanofiltration membrane and preparation method and application thereof | |
| CN113634136A (en) | Nanofiltration membrane and preparation method and application thereof | |
| WO2023222117A1 (en) | Separation membrane, preparation method therefor and use thereof | |
| CN107970779B (en) | Reverse osmosis membrane and preparation method and application thereof | |
| CA3110147A1 (en) | Forward osmosis membrane and membrane module including same | |
| de Grooth | A tale of two charges: zwitterionic polyelectrolyte multilayer membranes | |
| CN111760472A (en) | Composite membrane and preparation method and application thereof | |
| CN114432903B (en) | Composite membrane with acid resistance and preparation method and application thereof | |
| KR20230065910A (en) | Composite semipermeable membrane, spiral membrane element, water treatment system, and water treatment method |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |