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CN109304107B - A kind of large flux forward osmosis hollow fiber membrane and preparation method thereof - Google Patents

A kind of large flux forward osmosis hollow fiber membrane and preparation method thereof Download PDF

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CN109304107B
CN109304107B CN201710628674.XA CN201710628674A CN109304107B CN 109304107 B CN109304107 B CN 109304107B CN 201710628674 A CN201710628674 A CN 201710628674A CN 109304107 B CN109304107 B CN 109304107B
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hollow fiber
fiber membrane
solution
preparation
monomer
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CN109304107A (en
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朱丽静
宋海明
曾志翔
王立平
薛群基
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Ningbo Institute of Material Technology and Engineering of CAS
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Ningbo Institute of Material Technology and Engineering of CAS
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
    • B01D71/06—Organic material
    • B01D71/76—Macromolecular material not specifically provided for in a single one of groups B01D71/08 - B01D71/74
    • B01D71/82—Macromolecular material not specifically provided for in a single one of groups B01D71/08 - B01D71/74 characterised by the presence of specified groups, e.g. introduced by chemical after-treatment
    • 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
    • B01D61/002—Forward osmosis or direct osmosis
    • 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
    • B01D69/08—Hollow fibre membranes
    • B01D69/087—Details relating to the spinning process
    • B01D69/088—Co-extrusion; Co-spinning
    • 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
    • C02F1/445—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis by forward osmosis
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2325/00—Details relating to properties of membranes
    • B01D2325/24—Mechanical properties, e.g. strength
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
    • C02F2103/08—Seawater, e.g. for desalination

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

Abstract

本发明公开了一种大通量正渗透中空纤维膜及其制备方法。所述的制备方法包括：提供包含聚合物、功能单体、引发剂、添加剂和溶剂的混合反应体系，加热所述混合反应体系使功能单体发生聚合‑交联反应而形成半互穿网络结构，得到纺丝液；以及，以纺丝的方式将所述纺丝液与包含酰氯单体的芯液经喷丝口共挤出，之后浸入包含胺类单体的凝固浴中固化形成中空纤维膜，且在固化成膜的同时使酰氯单体与胺类单体在中空纤维膜的内壁和外壁瞬间发生界面聚合，生成疏松的超薄聚酰胺功能层，获得大通量正渗透中空纤维膜。本发明的中空纤维膜正渗透水通量大、力学强度优异，同时其制备方法简便易行，易于大规模生产和应用。The invention discloses a large flux forward osmosis hollow fiber membrane and a preparation method thereof. The preparation method includes: providing a mixed reaction system comprising a polymer, a functional monomer, an initiator, an additive and a solvent, and heating the mixed reaction system to cause the functional monomer to undergo a polymerization-crosslinking reaction to form a semi-interpenetrating network structure , to obtain a spinning solution; and, co-extruding the spinning solution and a core solution containing an acid chloride monomer through a spinneret in a spinning manner, and then immersing it in a coagulation bath containing an amine monomer to solidify to form a hollow fiber membrane, and the acid chloride monomer and amine monomer are instantly interfacially polymerized on the inner and outer walls of the hollow fiber membrane while curing to form a membrane, resulting in a loose ultra-thin polyamide functional layer to obtain a high-flux forward osmosis hollow fiber membrane. . The hollow fiber membrane of the present invention has large forward osmosis water flux and excellent mechanical strength, and at the same time, the preparation method thereof is simple and feasible, and is easy to be produced and applied on a large scale.

Description

Large-flux forward osmosis hollow fiber membrane and preparation method thereof
Technical Field
The invention belongs to the technical field of membrane separation, and particularly relates to a large-flux forward osmosis hollow fiber membrane and a preparation method thereof.
Background
The forward osmosis process is a new membrane separation technology in recent years and is an important means for realizing seawater desalination. It is driven by solute concentration difference at two sides of the membrane, no external driving force is needed, energy is saved and consumption is reduced. And the concentrated raw material liquid can be further processed, the diluted draw solution can be subjected to a re-concentration technology to extract pure water therein, and the concentrated draw solution is obtained again, so that the cyclic utilization of the draw solution is realized, the operation cost is low, and the additional value is high.
The interface polymerization is one of the most common methods for preparing the forward osmosis membrane, the classical interface polymerization process is that a support membrane is firstly immersed into an aqueous solution containing active monomers or prepolymers, the membrane is taken out after a certain period of time, redundant aqueous phase solution on the surface of the membrane is removed, then the sample is immersed into an organic solution containing another active monomer, the two active monomers only react at the interface to form a skin layer, and a compact polymer skin layer is formed on the surface of the base membrane through proper heat treatment, so that the forward osmosis water flux is smaller. And the common forward osmosis membrane is a flat membrane, so the space utilization rate is low. Therefore, the above problems in the prior art are urgently solved.
Disclosure of Invention
The invention aims to provide a high-flux forward osmosis hollow fiber membrane and a preparation method thereof, so as to overcome the defects in the prior art.
In order to achieve the purpose, the technical scheme adopted by the invention comprises the following steps:
the embodiment of the invention provides a preparation method of a high-flux forward osmosis hollow fiber membrane, which comprises the following steps:
providing a mixed reaction system at least comprising a polymer, a functional monomer, an initiator, an additive and a solvent, and heating the mixed reaction system in a protective atmosphere to enable the functional monomer to generate polymerization-crosslinking reaction to form a semi-interpenetrating network structure to obtain a spinning solution;
and co-extruding the spinning solution and a core solution containing an acyl chloride monomer through a spinning nozzle, then immersing the spinning solution and the core solution into a coagulating bath containing an amine monomer for solidification to form a hollow fiber membrane, and enabling the acyl chloride monomer and the amine monomer to instantly generate interfacial polymerization on the inner wall and the outer wall of the hollow fiber membrane while solidifying to form a membrane to generate a loose ultrathin polyamide functional layer, thereby obtaining the high-flux forward osmosis hollow fiber membrane.
In some embodiments of the invention, the method of making comprises:
(1) uniformly mixing at least a polymer, a functional monomer and an additive in a solvent in a protective atmosphere, heating to 20-130 ℃, adding an initiator, and reacting at 60-150 ℃ for 0.5-60 hours to enable the functional monomer to perform polymerization-crosslinking reaction to form a semi-interpenetrating network structure, thereby obtaining a spinning solution;
(2) and (2) taking an acyl chloride monomer solution as a core solution, taking an amine monomer solution as a coagulating bath, co-extruding the spinning solution obtained in the step (1) and the core solution through a spinning nozzle, staying in the air for 0.5-60 seconds, then immersing into the coagulating bath for solidification to form a film, and carrying out heat treatment at 60-120 ℃ for 0.5-10 minutes to obtain the high-flux forward osmosis hollow fiber film.
The embodiment of the invention also provides the large-flux forward osmosis hollow fiber membrane prepared by the method.
Preferably, the high flux forward osmosis hollow fiber membrane comprises:
the hollow fiber membrane body comprises a semi-interpenetrating network structure mainly formed by polymerizing and crosslinking functional monomers;
and loose ultrathin polyamide functional layers at least distributed on the inner wall and the outer wall of the hollow fiber membrane body.
Compared with the prior art, the invention has the advantages that:
(1) according to the preparation method of the high-flux forward osmosis hollow fiber membrane, provided by the invention, an acyl chloride monomer solution and an amine monomer solution are respectively used as a core solution and a coagulating bath, interfacial polymerization is completed in the spinning process, and a loose ultrathin polyamide functional layer is generated through instantaneous reaction to obtain the high-flux forward osmosis hollow fiber membrane;
(2) the functional monomers in the hollow fiber membrane prepared by the method are polymerized and crosslinked in a polymer solution to form a stable semi-interpenetrating network structure, the elution rate is low, and the hollow fiber membrane can be endowed with excellent mechanical strength for a long time and durably;
(3) the preparation method provided by the invention has the advantages that the interfacial polymerization and the preparation of the hollow fiber membrane are synchronously completed, the efficiency is high, the preparation is simple and easy to implement, and the large-scale production and application are easy.
Detailed Description
In view of the deficiencies in the prior art, the inventors of the present invention have made extensive studies and extensive practices to provide technical solutions of the present invention. The technical solution, its implementation and principles, etc. will be further explained as follows.
As one aspect of the technical solution of the present invention, there is provided a method for preparing a high flux forward osmosis hollow fiber membrane, comprising:
providing a mixed reaction system at least comprising a polymer, a functional monomer, an initiator, an additive and a solvent, and heating the mixed reaction system in a protective atmosphere to enable the functional monomer to generate polymerization-crosslinking reaction to form a semi-interpenetrating network structure to obtain a spinning solution;
and co-extruding the spinning solution and a core solution containing an acyl chloride monomer through a spinning nozzle, then immersing the spinning solution and the core solution into a coagulating bath containing an amine monomer for solidification to form a hollow fiber membrane, and enabling the acyl chloride monomer and the amine monomer to instantly generate interfacial polymerization on the inner wall and the outer wall of the hollow fiber membrane while solidifying to form a membrane to generate a loose ultrathin polyamide functional layer, thereby obtaining the high-flux forward osmosis hollow fiber membrane.
In some embodiments of the invention, the method of making comprises:
(1) uniformly mixing at least a polymer, a functional monomer and an additive in a solvent in a protective atmosphere, heating to 20-130 ℃, adding an initiator, and reacting at 60-150 ℃ for 0.5-60 hours to enable the functional monomer to perform polymerization-crosslinking reaction to form a semi-interpenetrating network structure, thereby obtaining a spinning solution;
(2) and (2) taking an acyl chloride monomer solution as a core solution, taking an amine monomer solution as a coagulating bath, co-extruding the spinning solution obtained in the step (1) and the core solution through a spinning nozzle, staying in the air for 0.5-60 seconds, then immersing into the coagulating bath for solidification to form a film, and carrying out heat treatment at 60-120 ℃ for 0.5-10 minutes to obtain the high-flux forward osmosis hollow fiber film.
In some embodiments, the mixed reaction system comprises 5 to 35wt% of polymer, 0.5 to 15wt% of functional monomer, 0.1 to 5wt% of initiator, 0.01 to 20wt% of additive, and the balance comprising solvent.
Preferably, the polymer includes any one or a combination of two or more of polysulfone, sulfonated polysulfone, polyethersulfone, polyacrylonitrile, polyimide, polyvinylidene fluoride, cellulose acetate, and the like, but is not limited thereto.
Preferably, the functional monomer includes any one or a combination of two or more of acrylic acid, methacrylic acid, dimethylaminoethyl methacrylate, diethylaminoethyl methacrylate, acrylamide, hydroxyethyl methacrylate, polyethylene glycol methyl ether methacrylate, N-vinyl pyrrolidone, N-isopropyl acrylamide, and the like, but is not limited thereto.
Preferably, the additive includes any one or a combination of two or more of polyethylene glycol, polyoxyethylene, polyethyleneimine, graphene, carbon nanotube, silica nanoparticle, titania nanoparticle, gold nanoparticle, N' -methylenebisacrylamide, and the like, but is not limited thereto.
Preferably, the initiator includes azobisisobutyronitrile, but is not limited thereto.
Preferably, the solvent includes any one or a combination of two or more of dimethyl sulfoxide, N-methylpyrrolidone, N '-dimethylformamide, N' -dimethylacetamide, acetone, trimethyl phosphate, and the like, but is not limited thereto.
In some embodiments of the invention, the bore fluid comprises 0.01 to 10wt% of an acid chloride monomer n-hexane solution (i.e., an organic phase solution).
Preferably, the acid chloride monomer includes any one or a combination of two or more of isophthaloyl chloride, terephthaloyl chloride, phthaloyl chloride, trimesoyl chloride, 5-oxoformyl chloride-isophthaloyl chloride, 5-isocyanate-isophthaloyl chloride, and the like, but is not limited thereto.
In some embodiments, the coagulation bath comprises 0.01 to 10wt% of an aqueous amine monomer solution (i.e., an aqueous phase solution).
Preferably, the amine monomer includes any one or a combination of two or more of m-phenylenediamine, o-phenylenediamine, p-phenylenediamine, piperazine, ethylene diamine, 1, 2-ethylene diamine, 1, 4-cyclohexanediamine, 1, 3-cyclohexanediamine, diethyltriamine, and the like, but is not limited thereto.
Preferably, the preparation method comprises the following steps:
and co-extruding the spinning solution and a core solution (namely an organic phase solution) containing acyl chloride monomers through a spinning nozzle, then immersing the spinning solution into a coagulating bath (namely an aqueous phase solution) containing amine monomers to be solidified to form a hollow fiber membrane, and enabling the organic phase solution and the aqueous phase solution to respectively flow through the inner wall and the outer wall of the hollow fiber membrane while solidifying to form a membrane, so that interfacial polymerization is instantly generated, a loose ultrathin polyamide functional layer is generated, and the large-flux forward osmosis hollow fiber membrane is obtained.
Wherein, as a more specific embodiment, the preparation method may comprise the steps of:
step (1): adding a polymer, a functional monomer, an additive and a solvent into a reaction kettle, introducing nitrogen, continuously stirring at 20-130 ℃ until the functional monomer is completely dissolved, adding azobisisobutyronitrile to initiate the functional monomer to polymerize, and reacting at 60-150 ℃ for 0.5-60 hours to obtain a spinning solution; wherein the mass percentage concentration of the polymer is 5-35%, the mass percentage concentration of the functional monomer is 0.5-15%, the mass percentage concentration of the additive is 0.01-20%, the mass percentage concentration of the azodiisobutyronitrile is 0.1-5%, and the balance is solvent;
step (2): co-extruding the spinning solution prepared in the step (1) and the core solution through a spinning nozzle by a metering pump, staying in the air for 0.5-60 seconds, then immersing in a coagulating bath for curing to form a film, cleaning, performing heat treatment at 60-120 ℃ for 0.5-10 minutes, drying, and rolling to obtain a high-flux forward-osmosis hollow fiber film; wherein the core solution is an oil-phase acyl chloride monomer n-hexane solution with the mass percentage concentration of 0.01-10%, and the coagulating bath is an amine monomer water solution with the mass percentage concentration of 0.01-10%.
As another aspect of the present invention, it also relates to a large-flux forward osmosis hollow fiber membrane prepared by the foregoing method.
Preferably, the high flux forward osmosis hollow fiber membrane comprises:
the hollow fiber membrane body comprises a semi-interpenetrating network structure mainly formed by polymerizing and crosslinking functional monomers;
and loose ultrathin polyamide functional layers at least distributed on the inner wall and the outer wall of the hollow fiber membrane body.
Preferably, the thickness of the ultrathin polyamide functional layer is 5-30 nm;
preferably, the tensile strength of the high-flux forward osmosis hollow fiber membrane is 3.2-6.8 MPa, and the pure water flux is 42.7-93.8 Lm-2h-1The rejection rate of the sodium chloride is 82.5-98.9%.
By the preparation process, the acyl chloride monomer solution and the amine monomer solution are respectively used as a core solution and a coagulating bath, interfacial polymerization is completed in the spinning process, and a loose ultrathin polyamide functional layer is generated by instantaneous reaction, so that the large-flux forward osmosis hollow fiber membrane is obtained. The functional monomer in the hollow fiber membrane prepared by the method is polymerized and crosslinked in a polymer solution to form a stable semi-interpenetrating network structure, the elution rate is low, and the hollow fiber membrane can be endowed with excellent mechanical strength for a long time and durably. The preparation method provided by the invention has the advantages that the interfacial polymerization and the preparation of the hollow fiber membrane are synchronously completed, the efficiency is high, the preparation is simple and easy to implement, and the large-scale production and application are easy.
The technical solution of the present invention is explained in more detail below with reference to several preferred embodiments.
Example 1
(1) Adding 5 g of polysulfone, 0.5 g of acrylic acid, 20 g of polyethylene glycol and 74.5 g of dimethyl sulfoxide into a reaction kettle, introducing nitrogen, continuously stirring at 130 ℃ until the materials are completely dissolved, adding 0.1 g of azobisisobutyronitrile to initiate acrylic acid polymerization, and reacting at 60 ℃ for 60 hours to obtain a spinning solution;
(2) co-extruding the spinning solution and a n-hexane solution of isophthaloyl dichloride with the mass percentage concentration of 0.01 percent through a metering pump through a spinning nozzle, staying in air for 0.5 second, then soaking the spinning solution into a m-phenylenediamine aqueous solution with the mass percentage concentration of 0.01 percent for curing to form a film, cleaning, performing heat treatment at 60 ℃ for 0.5 minute, drying and rolling to obtain the high-flux forward osmosis hollow fiber film.
Through testing, the hollow fiber membrane prepared in the embodimentThe polyamide layer (2) had a thickness of 12nm, a tensile strength of 5.1MPa, and a pure water flux of 42.7L · m when a sodium chloride solution having a concentration of 2mol/L was used as an extraction solution-2·h-1The rejection rate for sodium chloride was 91.5%.
Example 2
(1) Adding 35 g of sulfonated polysulfone, 15 g of methacrylic acid, 0.01 g of graphene and 49.99 g of N-methyl pyrrolidone into a reaction kettle, introducing nitrogen, continuously stirring at 20 ℃ until the materials are completely dissolved, adding 5 g of azobisisobutyronitrile to initiate methacrylic acid polymerization, and reacting at 150 ℃ for 0.5 hour to obtain a spinning solution;
(2) co-extruding the spinning solution and a normal hexane solution of terephthaloyl chloride with the mass percentage concentration of 10% through a metering pump through a spinning nozzle, staying in the air for 60 seconds, then soaking the spinning solution into an o-phenylenediamine aqueous solution with the mass percentage concentration of 10% to be solidified into a film, cleaning, performing heat treatment at 120 ℃ for 10 minutes, drying and rolling to obtain the high-flux forward osmosis hollow fiber film.
The hollow fiber membrane prepared in this example was tested to have a polyamide layer thickness of 5nm, a tensile strength of 4.4MPa, and a pure water flux of 67.8 L.m. when a sodium chloride solution having a concentration of 2mol/L was used as an extraction solution-2·h-1The rejection rate for sodium chloride was 98.9%.
Example 3
(1) Adding 10 g of polyether sulfone, 2 g of dimethylaminoethyl methacrylate, 1 g of polyoxyethylene and 87 g of N, N' -dimethylformamide into a reaction kettle, introducing nitrogen, continuously stirring at 40 ℃ until the materials are completely dissolved, adding 0.2 g of azobisisobutyronitrile to initiate polymerization of the dimethylaminoethyl methacrylate, and reacting at 70 ℃ for 5 hours to obtain a spinning solution;
(2) co-extruding the spinning solution and a phthalic acid chloride normal hexane solution with the mass percentage concentration of 0.1% through a metering pump through a spinning nozzle, staying in the air for 5 seconds, then soaking the spinning solution into a p-phenylenediamine aqueous solution with the mass percentage concentration of 0.1% to solidify into a film, cleaning, performing heat treatment at 70 ℃ for 1 minute, drying and rolling to obtain the high-flux forward osmosis hollow fiber film.
Through testing, the hollow fiber membrane prepared in the example has polymerThe thickness of the amide layer was 22nm, the tensile strength was 3.2MPa, and the pure water flux was 57.1L · m when a sodium chloride solution having a concentration of 2mol/L was used as an extraction solution-2·h-1The rejection rate for sodium chloride was 86.2%.
Example 4
(1) Adding 15 g of polyacrylonitrile, 4 g of diethylaminoethyl methacrylate, 5 g of polyethyleneimine and 76 g of N, N' -dimethylacetamide into a reaction kettle, introducing nitrogen, continuously stirring at 50 ℃ until the materials are completely dissolved, adding 0.5 g of azobisisobutyronitrile to initiate polymerization of the diethylaminoethyl methacrylate, and reacting at 80 ℃ for 10 hours to obtain a spinning solution;
(2) co-extruding the spinning solution and a n-hexane solution of trimesoyl chloride with the mass percentage concentration of 0.3% through a metering pump through a spinning nozzle, staying in the air for 10 seconds, then soaking the spinning solution into a piperazine water solution with the mass percentage concentration of 0.2% for curing to form a film, cleaning, performing heat treatment at 80 ℃ for 3 minutes, drying and rolling to obtain the high-flux forward-osmosis hollow fiber film.
The hollow fiber membrane prepared in this example was tested to have a polyamide layer thickness of 27nm, a tensile strength of 6.8MPa, and a pure water flux of 88.3L m when a sodium chloride solution having a concentration of 2mol/L was used as an extraction solution-2·h-1The rejection rate for sodium chloride was 99.1%.
Example 5
(1) Adding 20 g of polyimide, 5 g of acrylamide, 8 g of carbon nano tube and 67 g of N, N' -dimethylformamide into a reaction kettle, introducing nitrogen, continuously stirring at 70 ℃ until the materials are completely dissolved, adding 1 g of azobisisobutyronitrile to initiate acrylamide polymerization, and reacting for 15 hours at 90 ℃ to obtain a spinning solution;
(2) co-extruding the spinning solution and a 5-oxygen formyl chloride-isophthalic acid chloride normal hexane solution with the mass percentage concentration of 1% through a metering pump through a spinning nozzle, staying in the air for 20 seconds, then soaking the spinning solution into an ethylene diamine water solution with the mass percentage concentration of 0.5% to be solidified into a film, cleaning, performing heat treatment at 90 ℃ for 5 minutes, drying and rolling to obtain the high-flux forward osmosis hollow fiber film.
Through testing, the hollow fiber membrane prepared in the example has polymerThe thickness of the amide layer was 30nm, the tensile strength was 5.9MPa, and the pure water flux was 93.8L · m when a sodium chloride solution having a concentration of 2mol/L was used as an extraction solution-2·h-1The rejection rate for sodium chloride was 82.5%.
Example 6
(1) Adding 25 g of polyvinylidene fluoride, 10 g of hydroxyethyl methacrylate, 1.5 g of silicon dioxide nano particles and 63.5 g of trimethyl phosphate into a reaction kettle, introducing nitrogen, continuously stirring at 80 ℃ until the materials are completely dissolved, adding 5 g of azobisisobutyronitrile to initiate hydroxyethyl methacrylate to polymerize, and reacting at 100 ℃ for 20 hours to obtain a spinning solution;
(2) co-extruding the spinning solution and a 5-isocyanate-isophthaloyl chloride n-hexane solution with the mass percentage concentration of 4% through a metering pump through a spinning nozzle, staying in air for 30 seconds, then soaking the spinning solution into a 6% 1, 2-ethylenediamine aqueous solution with the mass percentage concentration, curing to form a film, cleaning, performing heat treatment at 100 ℃ for 6 minutes, drying, and rolling to obtain the high-flux forward osmosis hollow fiber film.
The hollow fiber membrane prepared in this example was tested to have a polyamide layer thickness of 17nm, a tensile strength of 4.7MPa, and a pure water flux of 61.2L m when a sodium chloride solution having a concentration of 2mol/L was used as an extraction solution-2·h-1The rejection rate for sodium chloride was 93.6%.
Example 7
(1) Adding 30 g of cellulose acetate, 15 g of polyethylene glycol methyl ether methacrylate, 2.5 g of titanium dioxide nano particles and 52.5 g of acetone into a reaction kettle, introducing nitrogen, continuously stirring at 60 ℃ until the mixture is completely dissolved, adding 2.5 g of azobisisobutyronitrile to initiate polyethylene glycol methyl ether methacrylate, and reacting at 60 ℃ for 25 hours to obtain a spinning solution;
(2) co-extruding the spinning solution and 5-isocyanate-isophthaloyl chloride n-hexane solution with the mass percentage concentration of 5% through a spinning nozzle by a metering pump, staying in air for 30 seconds, then soaking the spinning solution into 5% 1, 4-cyclohexanediamine with the mass percentage concentration of 5% to be solidified into a film, cleaning, performing heat treatment at 105 ℃ for 8 minutes, drying and rolling to obtain the high-flux forward osmosis hollow fiber film.
After testing, the bookThe hollow fiber membranes prepared in the examples had a polyamide layer thickness of 21nm, a tensile strength of 6.3MPa, and a pure water flux of 87.6L m when a sodium chloride solution having a concentration of 2mol/L was used as an extraction solution-2·h-1The rejection rate for sodium chloride was 90.4%.
Example 8
(1) Adding 12.5 g of polysulfone, 12.5 g of N-vinyl pyrrolidone, 2 g of gold nanoparticles and 73 g of N, N' -dimethylformamide into a reaction kettle, introducing nitrogen, continuously stirring at 100 ℃ until the gold nanoparticles are completely dissolved, adding 3 g of azobisisobutyronitrile to initiate N-vinyl pyrrolidone to polymerize, and reacting at 120 ℃ for 36 hours to obtain a spinning solution;
(2) co-extruding the spinning solution and a phthalic acid chloride n-hexane solution with the mass percentage concentration of 8% through a metering pump through a spinning nozzle, staying in the air for 40 seconds, then soaking the spinning solution into a 6% 1, 3-cyclohexanedimethylamine aqueous solution for curing to form a film, cleaning, performing heat treatment at 100 ℃ for 2 minutes, drying and rolling to obtain the high-flux forward-osmosis hollow fiber film.
The hollow fiber membrane prepared in this example was tested to have a polyamide layer thickness of 28nm, a tensile strength of 5.9MPa, and a pure water flux of 71.3L m when a sodium chloride solution having a concentration of 2mol/L was used as an extraction solution-2·h-1The rejection rate for sodium chloride was 93.6%.
Example 9
(1) Adding 16 g of polyether sulfone, 9 g of N-isopropylacrylamide, 1 g of N, N '-methylenebisacrylamide and 67 g of N, N' -dimethylacetamide into a reaction kettle, introducing nitrogen, continuously stirring at 120 ℃ until the materials are completely dissolved, adding 0.8 g of azobisisobutyronitrile to initiate N-isopropylacrylamide polymerization, and reacting at 130 ℃ for 50 hours to obtain a spinning solution;
(2) co-extruding the spinning solution and a phthalic acid chloride normal hexane solution with the mass percentage concentration of 2.5% through a metering pump through a spinning nozzle, staying in air for 50 seconds, then soaking the spinning solution into a diethyl triamine aqueous solution with the mass percentage concentration of 2.5% to be solidified into a film, cleaning, then carrying out heat treatment at 120 ℃ for 6 minutes, drying and rolling to obtain the high-flux forward osmosis hollow fiber film.
The hollow fiber membrane prepared in this example was tested to have a polyamide layer thickness of 17nm, a tensile strength of 6.4MPa, and a pure water flux of 79.1L m when a sodium chloride solution having a concentration of 2mol/L was used as an extraction solution-2·h-1The rejection rate for sodium chloride was 86.7%.
Comparative example 1:
the preparation method of the comparative example includes: firstly, immersing a support membrane into an aqueous solution containing an active monomer or prepolymer, taking out the membrane after a certain time, immersing the sample into an organic solution containing another active monomer, and carrying out an interface reaction to obtain the hollow fiber membrane.
The hollow fiber membrane prepared in this comparative example had a tensile strength of 1.8MPa when a sodium chloride solution having a concentration of 2mol/L was used as the draw solution, and a pure water flux of 20.1L · m when a sodium chloride solution having a concentration of 2mol/L was used as the draw solution-2·h-1The rejection rate for sodium chloride was 50.6%.
Comparative example 2: this comparative example is substantially the same as example 1 except that: and (2) carrying out polymerization-crosslinking reaction without adding a functional monomer in the step (1).
The hollow fiber membrane prepared in this comparative example had a tensile strength of 1.2MPa when a sodium chloride solution having a concentration of 2mol/L was used as an extraction solution, and had a pure water flux of 24.6L · m when a sodium chloride solution having a concentration of 2mol/L was used as an extraction solution-2·h-1The rejection rate for sodium chloride was 58.1%.
It was found by comparison that the hollow fiber membranes obtained in comparative examples 1 and 2 were far inferior to those obtained in examples 1 to 9 of the present invention in terms of the tensile strength, pure water flux, and sodium chloride rejection.
In addition, the present inventors have also conducted experiments with other raw materials and conditions and the like listed in the present specification by referring to the manner of examples 1 to 9, and have also produced a large flux forward osmosis hollow fiber membrane having a large forward osmosis water flux and excellent mechanical strength.
It should be understood that the above is only a specific application example of the present invention, and the protection scope of the present invention is not limited in any way. All the technical solutions formed by equivalent transformation or equivalent replacement fall within the protection scope of the present invention.

Claims (9)

1.一种大通量正渗透中空纤维膜的制备方法，其特征在于包括：1. a preparation method of high flux forward osmosis hollow fiber membrane is characterized in that comprising: （1）在保护性气氛中，至少将聚合物、功能单体、添加剂于溶剂中均匀混合，加热至20～130℃，再加入引发剂，形成混合反应体系，并于60～150℃反应0.5～60小时，使所述功能单体发生聚合-交联反应而形成半互穿网络结构，得到纺丝液，所述添加剂选自聚乙二醇、聚氧乙烯、聚乙烯亚胺、石墨烯、碳纳米管、二氧化硅纳米粒子、二氧化钛纳米粒子、金纳米粒子和N,N’-亚甲基双丙烯酰胺中的任意一种或两种以上的组合；(1) In a protective atmosphere, at least uniformly mix polymers, functional monomers and additives in a solvent, heat to 20-130°C, then add an initiator to form a mixed reaction system, and react at 60-150°C for 0.5 For ~60 hours, the functional monomer is subjected to a polymerization-crosslinking reaction to form a semi-interpenetrating network structure to obtain a spinning solution, and the additive is selected from polyethylene glycol, polyoxyethylene, polyethyleneimine, and graphene. , any one or a combination of two or more of carbon nanotubes, silicon dioxide nanoparticles, titanium dioxide nanoparticles, gold nanoparticles and N,N'-methylenebisacrylamide; （2）以酰氯单体溶液作为芯液，以胺类单体溶液作为凝固浴，将步骤（1）所获纺丝液与芯液经喷丝口共挤出，在空气中停留0.5~60秒，而后浸入凝固浴中固化成膜，并于60～120℃热处理0.5~10分钟，且在固化成膜的同时使酰氯单体与胺类单体在中空纤维膜的内壁和外壁瞬间发生界面聚合，生成疏松的超薄聚酰胺功能层，获得大通量正渗透中空纤维膜；(2) Using the acid chloride monomer solution as the core solution and the amine monomer solution as the coagulation bath, the spinning solution obtained in step (1) and the core solution are co-extruded through the spinneret, and stay in the air for 0.5-60 minutes. Second, then immersed in a coagulation bath to solidify into a film, and heat-treated at 60 to 120°C for 0.5 to 10 minutes, and at the same time as the film was cured, the acyl chloride monomer and amine monomer were instantly interfaced between the inner and outer walls of the hollow fiber membrane Polymerization to generate a loose ultra-thin polyamide functional layer to obtain a high-flux forward osmosis hollow fiber membrane; 所述大通量正渗透中空纤维膜包括：The large flux forward osmosis hollow fiber membrane includes: 中空纤维膜本体，其包括主要由功能单体聚合-交联形成的半互穿网络结构；A hollow fiber membrane body, which includes a semi-interpenetrating network structure mainly formed by polymerization-crosslinking of functional monomers; 以及，至少分布于所述中空纤维膜本体内壁及外壁的、疏松的超薄聚酰胺功能层；And, at least a loose ultra-thin polyamide functional layer distributed on the inner wall and outer wall of the hollow fiber membrane body; 所述大通量正渗透中空纤维膜的拉伸强度为3.2~6.8MPa，纯水通量为42.7~93.8L m-2h-1，对氯化钠的截留率为82.5~98.9%。The high-flux forward osmosis hollow fiber membrane has a tensile strength of 3.2-6.8 MPa, a pure water flux of 42.7-93.8 L m -2 h -1 , and a rejection rate of 82.5-98.9% for sodium chloride. 2.根据权利要求1所述的制备方法，其特征在于：所述混合反应体系包含5～35wt%聚合物、0.5～15wt%功能单体、0.1～5wt%引发剂、0.01～20wt%添加剂，其余部分包含溶剂。2. The preparation method according to claim 1, wherein the mixed reaction system comprises 5-35wt% polymer, 0.5-15wt% functional monomer, 0.1-5wt% initiator, 0.01-20wt% additive, The remainder contains solvent. 3.根据权利要求1-2中任一项所述的制备方法，其特征在于：所述聚合物选自聚砜、磺化聚砜、聚醚砜、聚丙烯腈、聚酰亚胺、聚偏氟乙烯和醋酸纤维素中的任意一种或两种以上的组合。3. The preparation method according to any one of claims 1-2, wherein the polymer is selected from the group consisting of polysulfone, sulfonated polysulfone, polyethersulfone, polyacrylonitrile, polyimide, poly Any one or a combination of two or more of vinylidene fluoride and cellulose acetate. 4.根据权利要求1-2中任一项所述的制备方法，其特征在于：所述功能单体选自丙烯酸、甲基丙烯酸、甲基丙烯酸二甲氨基乙酯、甲基丙烯酸二乙基氨基乙酯、丙烯酰胺、甲基丙烯酸羟乙酯、聚乙二醇甲醚甲基丙烯酸酯、N-乙烯基吡咯烷酮和N-异丙基丙烯酰胺中的任意一种或两种以上的组合。4. The preparation method according to any one of claims 1-2, wherein the functional monomer is selected from the group consisting of acrylic acid, methacrylic acid, dimethylaminoethyl methacrylate, diethyl methacrylate Any one or a combination of two or more of aminoethyl ester, acrylamide, hydroxyethyl methacrylate, polyethylene glycol methyl ether methacrylate, N-vinylpyrrolidone and N-isopropylacrylamide. 5.根据权利要求1-2中任一项所述的制备方法，其特征在于：所述引发剂为偶氮二异丁腈。5. The preparation method according to any one of claims 1-2, wherein the initiator is azobisisobutyronitrile. 6.根据权利要求1-2中任一项所述的制备方法，其特征在于：所述溶剂选自二甲基亚砜、N-甲基吡咯烷酮、N,N’-二甲基甲酰胺、N,N’-二甲基乙酰胺、丙酮和磷酸三甲酯中的任意一种或两种以上的组合。6. The preparation method according to any one of claims 1-2, wherein the solvent is selected from the group consisting of dimethyl sulfoxide, N-methylpyrrolidone, N,N'-dimethylformamide, Any one or a combination of two or more of N,N'-dimethylacetamide, acetone and trimethyl phosphate. 7.根据权利要求1所述的制备方法，其特征在于：所述芯液包含0.01～10wt%的酰氯单体正己烷溶液，所述酰氯单体选自间苯二甲酰氯、对苯二甲酰氯、邻苯二甲酰氯、均苯三甲酰氯、5-氧甲酰氯-异酞酰氯和5-异氰酸酯-异酞酰氯中的任意一种或两种以上的组合。7 . The preparation method according to claim 1 , wherein the core liquid comprises 0.01-10 wt % of an acid chloride monomer in n-hexane solution, and the acid chloride monomer is selected from isophthaloyl chloride, terephthalic acid Any one or a combination of two or more of acid chloride, phthaloyl chloride, trimesoyl chloride, 5-oxyformyl chloride-isophthaloyl chloride and 5-isocyanate-isophthaloyl chloride. 8.根据权利要求1所述的制备方法，其特征在于：所述凝固浴包含0.01～10wt%胺类单体水溶液，所述胺类单体选自间苯二胺、邻苯二胺、对苯二胺、哌嗪、乙二胺、1,4-环己二胺、1,3-环己二甲胺和二乙基三胺中的任意一种或两种以上的组合。8 . The preparation method according to claim 1 , wherein the coagulation bath comprises 0.01-10 wt % aqueous solution of amine monomers, and the amine monomers are selected from m-phenylenediamine, o-phenylenediamine, para-phenylenediamine, and para-phenylenediamine. Any one or a combination of two or more of phenylenediamine, piperazine, ethylenediamine, 1,4-cyclohexanediamine, 1,3-cyclohexanedimethylamine and diethyltriamine. 9.根据权利要求1所述的制备方法，其特征在于：所述超薄聚酰胺功能层的厚度为5~30nm。9 . The preparation method according to claim 1 , wherein the thickness of the ultra-thin polyamide functional layer is 5-30 nm. 10 .
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