CN110548416B - Negatively-charged hybrid forward-osmosis hollow fiber membrane and preparation method thereof - Google Patents
Negatively-charged hybrid forward-osmosis hollow fiber membrane and preparation method thereof Download PDFInfo
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- CN110548416B CN110548416B CN201810564906.4A CN201810564906A CN110548416B CN 110548416 B CN110548416 B CN 110548416B CN 201810564906 A CN201810564906 A CN 201810564906A CN 110548416 B CN110548416 B CN 110548416B
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Abstract
The invention discloses a negatively-charged hybrid positive-osmosis hollow fiber membrane and a preparation method thereof. The preparation method comprises the following steps: dispersing mesoporous nano-silica, dopamine and negatively charged polymer in a first solvent to form a first mixed reaction system, heating and reacting to obtain a negatively charged hybrid material, and uniformly dispersing the negatively charged hybrid material and an amine monomer in an aqueous solution to obtain a hybrid aqueous phase solution; mixing a polymer, a negatively charged monomer, a second solvent and an initiator to form a second mixed reaction system, and heating to react to obtain a spinning solution; and co-extruding the spinning solution, the hybrid aqueous phase solution and the organic phase solution containing the acyl chloride monomer through a spinning nozzle, and then immersing the spinning solution, the hybrid aqueous phase solution and the organic phase solution into a coagulating bath containing a cross-linking agent for cross-linking and curing to form a hollow fiber membrane, so as to obtain the negatively-charged hybrid positive-osmosis hollow fiber membrane. The invention can obtain the forward osmosis hollow fiber membrane with high flux, high selectivity and strong stability, and the preparation process is simple and is convenient for large-scale production.
Description
Technical Field
The invention belongs to the technical field of membrane separation, and particularly relates to a negatively-charged hybrid positive-osmosis hollow fiber membrane and a preparation method thereof.
Background
The forward osmosis process is an important emerging means for realizing seawater desalination in recent years, is driven by solute concentration difference at two sides of the membrane, does not need additional driving force, and saves energy and reduces consumption. 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.
Currently, forward osmosis membranes are often flat composite membranes prepared by interfacial polymerization. The classical interfacial polymerization process is to immerse a support film into an aqueous solution containing active monomers or prepolymers, take out the film after a certain time and remove redundant aqueous phase solution on the surface of the film, immerse the sample into an organic solution containing another active monomer, and react the two active monomers only at the interface to form a skin layer, and form a compact polymer skin layer on the surface of the base film through proper heat treatment for the field of liquid separation. However, the skin layer of the forward osmosis membrane prepared at present is very compact, and the water flux is small; the surface of the support film is mostly of a smooth porous structure, so that the polyamide functional layer is not high in adhesion fastness and is easy to fall off; the support film and the surface polyamide functional layer need to be prepared step by step, so that the production efficiency is reduced; and the common forward osmosis membrane is a flat membrane, so the space utilization rate is low.
Disclosure of Invention
The invention mainly aims to provide a negatively-charged hybrid 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 negatively-charged hybrid forward-osmosis hollow fiber membrane, which comprises the following steps:
providing a first mixed reaction system at least containing mesoporous nano-silica, dopamine, negatively charged polymers and a first solvent, heating the first mixed reaction system and reacting to obtain negatively charged hybrid materials, and uniformly dispersing the negatively charged hybrid materials and amine monomers in an aqueous solution to obtain a hybrid aqueous phase solution;
providing a second mixed reaction system at least comprising a polymer, a negatively charged monomer, a second solvent and an initiator, heating the second mixed reaction system, and reacting to obtain a spinning solution;
and co-extruding the spinning solution, the hybrid aqueous phase solution and the organic phase solution containing the acyl chloride monomer through a spinning nozzle, then immersing the spinning solution into a coagulating bath containing a cross-linking agent for cross-linking and curing to form a hollow fiber membrane, and enabling the acyl chloride monomer, the amine monomer and the negatively charged hybrid material to instantaneously generate interfacial polymerization on the inner wall of the hollow fiber membrane while curing to form the membrane, so as to obtain the negatively charged hybrid positive osmosis hollow fiber membrane.
The embodiment of the invention also provides the negatively charged hybrid positive osmosis hollow fiber membrane prepared by the method.
Further, the negatively charged hybrid forward osmosis hollow fiber membrane comprises:
the negative charge polymer hollow fiber membrane basement membrane with a cross-linked interpenetrating network structure is formed by mesoporous nano silicon dioxide, dopamine and negative charge polymer;
and a loose hybrid ultrathin polyamide functional layer at least distributed on the inner wall of the hollow fiber membrane base membrane.
Compared with the prior art, the invention has the beneficial effects that:
1) according to the preparation method of the negatively-charged hybrid positive-osmosis hollow fiber membrane, the acyl chloride monomer solution, the hybrid material aqueous solution and the spinning solution are co-extruded through the double-layer spinneret, interfacial polymerization is completed in the spinning film forming process, a loose hybrid ultrathin polyamide functional layer is generated through instantaneous reaction, the negatively-charged hybrid positive-osmosis hollow fiber membrane is obtained through a one-step method, the efficiency is high, the preparation method is simple and easy to implement, and large-scale production and application are easy;
2) the uniformly dispersed hybrid material provides a nano water channel, and can improve the water flux of the forward osmosis membrane; the introduction of the negative charge polymer can improve the rejection rate of the salt ions by the positive permeable membrane; the negative-charge polymer base membrane with the cross-linked interpenetrating network structure can improve the strength of the positive osmosis membrane and the adhesion fastness of the polyamide functional layer, and finally the positive-osmosis hollow fiber membrane with high flux, high selectivity and strong stability is prepared by a one-step method.
Detailed Description
In view of the defects in the prior art, the inventor provides the technical scheme of the invention through long-term research and a large amount of practice, and the technical scheme is mainly characterized in that an acyl chloride monomer solution, a hybrid material aqueous solution and a spinning solution are co-extruded together through a double-layer spinneret orifice, interfacial polymerization is completed in the spinning film forming process, a loose hybrid ultrathin polyamide functional layer is generated through instantaneous reaction, and a negative-charge hybrid positive-permeation hollow fiber film is obtained through a one-step method. The technical solution, its implementation and principles, etc. will be further explained as follows.
As one aspect of the technical scheme of the invention, the invention relates to a preparation method of a negatively-charged hybrid positive-osmosis hollow fiber membrane, which comprises the following steps:
providing a first mixed reaction system at least containing mesoporous nano-silica, dopamine, negatively charged polymers and a first solvent, heating the first mixed reaction system and reacting to obtain negatively charged hybrid materials, and uniformly dispersing the negatively charged hybrid materials and amine monomers in an aqueous solution to obtain a hybrid aqueous phase solution;
providing a second mixed reaction system at least comprising a polymer, a negatively charged monomer, a second solvent and an initiator, heating the second mixed reaction system, and reacting to obtain a spinning solution;
and co-extruding the spinning solution, the hybrid aqueous phase solution and the organic phase solution containing the acyl chloride monomer through a spinning nozzle, then immersing the spinning solution into a coagulating bath containing a cross-linking agent for cross-linking and curing to form a hollow fiber membrane, and enabling the acyl chloride monomer, the amine monomer and the negatively charged hybrid material to instantaneously generate interfacial polymerization on the inner wall of the hollow fiber membrane while curing to form the membrane, so as to obtain the negatively charged hybrid positive osmosis hollow fiber membrane.
In some embodiments, the preparation method may specifically include:
adding mesoporous nano-silica, dopamine and negatively charged polymer into a first solvent to obtain a first mixed reaction system, reacting at 10-80 ℃ for 0.5-36 h to obtain a negatively charged hybrid material, and dispersing the negatively charged hybrid material and an amine monomer in an aqueous solution to obtain a hybrid aqueous phase solution.
Furthermore, the diameter of the mesoporous nano-silica is 5-70 nm, and the aperture of the contained holes is 1-10 nm. The uniformly dispersed hybrid material provided by the invention provides a nano water channel, and can improve the water flux of the forward osmosis membrane.
In some embodiments, the first mixed reaction system comprises 0.1-15 wt% of mesoporous nano-silica, 0.1-6 wt% of dopamine, 2-20 wt% of negatively charged polymer, and the balance of the first mixed reaction system comprises solvent.
Further, the solvent includes water.
In some embodiments, the negative charge polymer includes any one or a combination of two or more of polyacrylic acid, polymethacrylic acid, sodium polypropylene sulfonate, and the like, but is not limited thereto. The introduction of the negative charge polymer in the invention can improve the rejection rate of the salt ions by the positive permeable membrane.
In some embodiments, the hybrid aqueous solution comprises 0.1 to 10wt% of the negatively charged hybrid material and 0.5 to 20wt% of the amine monomer.
Further, the amine monomer includes any one or a combination of two or more of m-phenylenediamine, o-phenylenediamine, p-phenylenediamine, piperazine, ethylene diamine, and the like, but is not limited thereto.
In some embodiments, the preparation method may specifically include:
and uniformly mixing the polymer, the negatively charged monomer, the second solvent and the initiator to obtain a second mixed reaction system, heating to 40-120 ℃, and reacting for 0.1-50 h to obtain the spinning solution.
In some embodiments, the second mixed reaction system comprises 16 to 35wt% of polymer, 2 to 20wt% of negatively charged monomer, 0.01 to 2wt% of initiator, and the balance of second solvent.
Further, the polymer includes any one or a combination of two or more of polysulfone, polyethersulfone, polyacrylonitrile, and the like, but is not limited thereto.
Further, the negatively charged monomer includes any one or a combination of two or more of acrylic acid, methacrylic acid, sodium acryl sulfonate, and the like, but is not limited thereto.
Further, the initiator includes any one or a combination of two or more of azobisisobutyronitrile, azobisisoheptonitrile, dibenzoyl peroxide, and the like, but is not limited thereto.
Further, the second solvent includes any one or a combination of two or more of N-methylpyrrolidone, N '-dimethylformamide, N' -dimethylacetamide, acetone, and the like, but is not limited thereto.
In some embodiments, the preparation method may specifically include:
co-extruding the spinning solution, the hybrid aqueous phase solution and the organic phase solution containing the acyl chloride monomer through a double-layer spinneret in a spinning mode, immersing the extruded spinning solution, the hybrid aqueous phase solution and the organic phase solution containing the acyl chloride monomer into a coagulating bath containing a cross-linking agent after the extruded spinning solution stays in the air for a certain time, and performing cross-linking and curing to form a hollow fiber membrane, wherein the acyl chloride monomer, the amine monomer and the negatively-charged hybrid material are subjected to interfacial polymerization instantly on the inner wall of the hollow fiber membrane while the hollow fiber membrane is cured to form a membrane, so that a loose hybrid ultrathin polyamide functional layer is generated, and the negatively-charged hybrid positive-permeation hollow fiber membrane is obtained.
In some more specific embodiments, the preparation method may specifically include:
co-extruding the spinning solution, the hybrid aqueous phase solution and the organic phase solution containing acyl chloride monomers through a double-layer spinneret, staying in the air for 0.2-30 s, then soaking in a coagulating bath which is at 0-80 ℃ and contains 1-30 wt% of a cross-linking agent and water, cleaning, and then carrying out heat treatment at 25-130 ℃ for 1-30 min to obtain the negatively-charged hybrid positive-osmosis hollow fiber membrane.
In some embodiments, the organic phase solution including the acid chloride monomer includes 0.1 to 20wt% of the acid chloride monomer.
Further, 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.
Further, the organic phase solution contains an organic solvent including any one or a combination of two or more of n-hexane, cyclohexane, n-octane, and the like, but is not limited thereto.
Further, the cross-linking agent includes any one or a combination of two or more of glutaraldehyde, malic acid, sorbitol, glycerin, and the like, but is not limited thereto.
Wherein, as a more specific embodiment, the preparation method may comprise the steps of:
(1) adding mesoporous nano-silica with the diameter of 5-70 nanometers and the aperture of 1-10 nanometers, dopamine and negatively charged polymer into water to obtain a mixed solution, and reacting at 10-80 ℃ for 0.5-36 hours to obtain a negatively charged hybrid material; and then dispersing the hybrid water phase solution and amine monomers in an aqueous solution to obtain a hybrid aqueous phase solution.
(2) Uniformly mixing the polymer, the negatively charged monomer, the solvent and the initiator to obtain a reaction solution, heating to 40-120 ℃, and reacting for 0.1-50 h to obtain the spinning solution.
(3) Co-extruding the spinning solution, the hybrid water-phase solution and the oil-phase solution containing the acid chloride monomer through a double-layer spinneret, staying in the air for 0.2-30 seconds, then soaking in a cross-linking bath consisting of 1-30 wt% of a cross-linking agent and water at 0-80 ℃, cleaning, and carrying out heat treatment at 25-130 ℃ for 1-30 minutes to obtain the negatively-charged hybrid positive-osmosis hollow fiber membrane.
As another aspect of the technical solution of the present invention, it also relates to a negatively charged hybrid positively permeated hollow fiber membrane prepared by the aforementioned method.
Further, the negatively charged hybrid forward osmosis hollow fiber membrane comprises:
the negative charge polymer hollow fiber membrane basement membrane with a cross-linked interpenetrating network structure is formed by mesoporous nano silicon dioxide, dopamine and negative charge polymer;
and a loose hybrid ultrathin polyamide functional layer at least distributed on the inner wall of the hollow fiber membrane base membrane.
The negative-charge polymer base membrane with the cross-linked interpenetrating network structure can improve the strength of the positive osmosis membrane and the adhesion fastness of the polyamide functional layer, and finally the positive-osmosis hollow fiber membrane with high flux, high selectivity and strong stability is prepared by a one-step method.
Further, the thickness of the negatively charged hybrid positive osmosis hollow fiber membrane is 20-200 μm.
Further, the thickness of the hybrid ultrathin polyamide functional layer is 10-30 nm.
Further, the pure water flux of the negatively charged hybrid forward osmosis hollow fiber membrane is 27-68 Lm-2h-1The retention rate of sodium chloride is 45-91%.
According to the technical scheme, the preparation method of the negatively-charged hybrid positive-osmosis hollow fiber membrane provided by the invention has the advantages that the acyl chloride monomer solution, the hybrid material water solution and the spinning solution are co-extruded through the double-layer spinneret, interfacial polymerization is completed in the spinning film forming process, a loose hybrid ultrathin polyamide functional layer is generated through instantaneous reaction, the negatively-charged hybrid positive-osmosis hollow fiber membrane is obtained through a one-step method, the efficiency is high, the preparation method is simple and easy to implement, and large-scale production and application are easy.
In order to make the objects, technical solutions and advantages of the present invention clearer, the technical solutions of the present invention are further described in detail with reference to some preferred embodiments, but the present invention is not limited to the following embodiments, and those skilled in the art can make insubstantial improvements and modifications within the spirit of the present invention and still fall within the scope of the present invention.
Example 1
(1) Adding 0.1 g of mesoporous nano-silica with the diameter of 5nm and the aperture of 1nm, 0.1 g of dopamine and 2 g of polyacrylic acid into 97.8 g of water to obtain a mixed solution, and reacting at 10 ℃ for 36 hours to obtain a negatively charged hybrid material; then 0.1 g of negative electricity-carrying hybrid material and 0.5 g of m-phenylenediamine are dispersed in 99.4 g of aqueous solution to obtain a hybrid aqueous phase solution;
(2) uniformly mixing 16 g of polysulfone, 2 g of acrylic acid, 0.01 g of azobisisobutyronitrile and 81.99 g of N-methyl pyrrolidone, heating the mixed solution to 120 ℃, and reacting for 0.1h to obtain spinning solution;
(3) co-extruding the spinning solution, the hybridization water phase solution and the n-hexane solution of 0.1 wt% of isophthaloyl dichloride through a double-layer spinneret, staying in the air for 0.2 second, then soaking in the 1 wt% aqueous solution at 0 ℃, cleaning, and carrying out heat treatment at 25 ℃ for 30 minutes to obtain the negatively-charged hybridization positive-permeation hollow fiber membrane.
Through tests, when the forward osmosis hollow fiber membrane prepared in the embodiment takes 2.5mol/L sodium chloride solution as an absorption solution, the pure water flux is 68 L.m-2·h-1The retention rate for sodium chloride was 45%.
Example 2
(1) Adding 15 g of mesoporous nano-silica with the diameter of 70nm and the aperture of 10nm, 6 g of dopamine and 20 g of polymethacrylic acid into 59 g of water to obtain a mixed solution, and reacting at 80 ℃ for 0.5h to obtain a negative charge hybrid material; then dispersing 10 g of negative electricity-carrying hybrid material and 20 g of o-phenylenediamine in 70 g of aqueous solution to obtain a hybrid aqueous phase solution;
(2) uniformly mixing 35 g of polyether sulfone, 20 g of methacrylic acid, 2 g of azodiisoheptanonitrile and 43 g of N, N' -dimethylformamide, heating the mixed solution to 105 ℃, and reacting for 9 hours to obtain a spinning solution;
(3) co-extruding the spinning solution, the hybrid aqueous phase solution and 20wt% of terephthaloyl chloride cyclohexane solution through a double-layer spinneret, staying in the air for 30 seconds, then soaking in 30wt% malic acid aqueous solution at 80 ℃, cleaning, and carrying out heat treatment at 130 ℃ for 30 minutes to obtain the negatively-charged hybrid positive-osmosis hollow fiber membrane.
It was found that the pure water flux of the forward osmosis hollow fiber membrane prepared in this example was 43 L.m when 2.5mol/L NaCl solution was used as the draw solution-2·h-1The retention rate for sodium chloride was 82%.
Example 3
(1) Adding 2 g of mesoporous nano-silica with the diameter of 60nm and the aperture of 2nm, 2 g of dopamine and 5 g of sodium polyacrylate into 91 g of water to obtain a mixed solution, and reacting at 40 ℃ for 24h to obtain a negative charge hybrid material; then 3 g of negative electricity-carrying hybrid material and 10 g of p-phenylenediamine are dispersed in 87 g of aqueous solution to obtain a hybrid aqueous phase solution;
(2) uniformly mixing 25 g of polyacrylonitrile, 5 g of sodium propylene sulfonate, 0.2 g of dibenzoyl peroxide and 69.8 g of N, N' -dimethylacetamide, heating the mixed solution to 40 ℃, and reacting for 50 hours to obtain spinning solution;
(3) co-extruding the spinning solution, the hybrid aqueous phase solution and a 15wt% phthaloyl chloride n-octane solution through a double-layer spinneret, staying in the air for 2 seconds, then soaking in a sorbitol aqueous solution with the concentration of 25 wt% at 50 ℃, cleaning, and carrying out heat treatment at 90 ℃ for 20 minutes to obtain the negatively-charged hybrid positive-osmosis hollow fiber membrane.
It was found that the pure water flux of the forward osmosis hollow fiber membrane prepared in this example was 37 L.m when 2.5mol/L NaCl solution was used as the draw solution-2·h-1The retention rate for sodium chloride was 61%.
Example 4
(1) Adding 5 g of mesoporous nano-silica with the diameter of 50nm and the aperture of 5nm, 4 g of dopamine and 10 g of polyacrylic acid into 81 g of water to obtain a mixed solution, and reacting at 60 ℃ for 18h to obtain a negatively charged hybrid material; then dispersing 5 g of negative electricity-charged hybrid material and 17 g of piperazine in 78 g of aqueous solution to obtain a hybrid aqueous phase solution;
(2) uniformly mixing 24 g of polyether sulfone, 10 g of sodium propylene sulfonate, 0.5 g of azodiisobutyronitrile and 65.5 g of N, N' -dimethylacetamide, heating the mixed solution to 70 ℃, and reacting for 24 hours to obtain a spinning solution;
(3) co-extruding the spinning solution, the hybrid aqueous phase solution and a n-hexane solution of 13 wt% of trimesoyl chloride through a double-layer spinneret, staying in the air for 17 seconds, then soaking in a glycerol aqueous solution with the concentration of 25 wt% at 35 ℃, cleaning, and carrying out heat treatment at 70 ℃ for 12 minutes to obtain the negatively-charged hybrid positive-osmosis hollow fiber membrane.
Through tests, when the forward osmosis hollow fiber membrane prepared in the embodiment takes 2.5mol/L sodium chloride solution as an absorption solution, the pure water flux is 44 L.m-2·h-1The retention rate for sodium chloride was 86%.
Example 5
(1) Adding 8 g of mesoporous nano silicon dioxide with the diameter of 60nm and the aperture of 3.5nm, 5 g of dopamine and 14 g of polyacrylic acid into 73 g of water to obtain a mixed solution, and reacting at 30 ℃ for 6h to obtain a negatively charged hybrid material; then dispersing 4 g of negative electricity-charged hybrid material and 7 g of ethylenediamine in 89 g of aqueous solution to obtain a hybrid aqueous phase solution;
(2) uniformly mixing 17 g of polysulfone, 5 g of methacrylic acid, 1 g of azobisisobutyronitrile and 77 g of N-methyl pyrrolidone, heating the mixed solution to 65 ℃, and reacting for 28 hours to obtain a spinning solution;
(3) co-extruding the spinning solution, the hybrid aqueous phase solution and 12 wt% of 5-oxygen formyl chloride-isophthalic acid chloride cyclohexane solution through a double-layer spinneret, staying in air for 5 seconds, then soaking in a glutaraldehyde aqueous solution with the concentration of 16 wt% at 50 ℃, cleaning, and carrying out heat treatment at 75 ℃ for 26 minutes to obtain the negatively-charged hybrid positive-osmosis hollow fiber membrane.
It was found that the forward osmosis hollow fiber membrane prepared in this example has a pure water flux of 27 L.m when 2.5mol/L NaCl solution is used as the draw solution-2·h-1The retention rate for sodium chloride was 91%.
Example 6
(1) Adding 7 g of mesoporous nano-silica with the diameter of 45nm and the aperture of 1.5nm, 3.5 g of dopamine and 8.5 g of sodium polyacrylate into 81 g of water to obtain a mixed solution, and reacting at 45 ℃ for 20h to obtain a negative charge hybrid material; then dispersing 4.5 g of negative electricity-carrying hybrid material and 15.5 g of m-phenylenediamine in 80 g of aqueous solution to obtain a hybrid aqueous phase solution;
(2) uniformly mixing 21 g of polyether sulfone, 6.5 g of methacrylic acid, 0.5 g of azobisisobutyronitrile and 72 g of N, N' -dimethylformamide, heating the mixed solution to 65 ℃, and reacting for 10 hours to obtain a spinning solution;
(3) co-extruding the spinning solution, the hybrid aqueous phase solution and 13 wt% of 5-isocyanate-isophthalic acid chloride normal hexane solution through a double-layer spinning nozzle, staying in air for 18 seconds, then soaking in 70 ℃, 25 wt% of glutaraldehyde aqueous solution, cleaning, and carrying out heat treatment at 115 ℃ for 22 minutes to obtain the negatively-charged hybrid positive-osmosis hollow fiber membrane.
Through tests, when the forward osmosis hollow fiber membrane prepared in the embodiment takes 2.5mol/L sodium chloride solution as an absorption solution, the pure water flux is 49 L.m-2·h-1The rejection rate for sodium chloride was 83%.
Comparative example 1: this comparative example is substantially the same as example 5 except that: no mesoporous nano-silica is added. The forward osmosis membrane obtained in this comparative example used 2.5mol/L sodium chloride solution as the draw solution, and the pure water flux was 5.7L m-2h-1The rejection rate for sodium chloride was 31%.
Comparative example 2: this comparative example is substantially the same as example 5 except that: no negatively charged monomer is added. The surface of the forward osmosis membrane obtained in this comparative example was extracted with 2.5mol/L sodium chloride solution, and the pure water flux was 10.2L m-2h-1The rejection rate for sodium chloride was 26%.
Comparative example 3: this comparative example is substantially the same as example 5 except that: no negative-charged polymer was added. The surface of the forward osmosis membrane obtained in this comparative example was extracted with 2.5mol/L sodium chloride solution, and the pure water flux was 11L m-2h-1The rejection rate for sodium chloride was 18%.
Comparative example 4: this comparative example is substantially the same as example 5 except that: the mesoporous nano silicon dioxide and the negatively charged monomer are not added. The surface of the forward osmosis membrane obtained in this comparative example was extracted with 2.5mol/L sodium chloride solution, and the pure water flux was 4.5L m-2h-1The rejection rate for sodium chloride was 14%.
In addition, the inventor also refers to the mode of example 1-example 6, tests are carried out by other raw materials and conditions listed in the specification, and the negatively-charged hybrid positive-osmosis hollow fiber membrane with large flux, high selectivity, high rejection rate and strong stability is also prepared.
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 (8)
1. A preparation method of a negatively-charged hybrid forward-osmosis hollow fiber membrane is characterized by comprising the following steps:
adding mesoporous nano-silica, dopamine and negatively charged polymer into a first solvent to obtain a first mixed reaction system, and reacting at 10-80 ℃ for 0.5-36 h to obtain a negatively charged hybrid material, wherein the first mixed reaction system comprises 0.1-15 wt% of mesoporous nano-silica, 0.1-6 wt% of dopamine and 2-20 wt% of negatively charged polymer, the rest is solvent, and the solvent is water; the negative charge polymer is selected from any one or the combination of more than two of polyacrylic acid, polymethacrylic acid and sodium polypropylene sulfonate;
uniformly dispersing the negative charge hybrid material and the amine monomer in an aqueous solution to obtain a hybrid aqueous phase solution; the hybrid aqueous phase solution comprises 0.1-10 wt% of negatively charged hybrid materials and 0.5-20 wt% of amine monomers;
uniformly mixing a polymer, a negatively charged monomer, a second solvent and an initiator to obtain a second mixed reaction system, heating to 40-120 ℃, and reacting for 0.1-50 h to obtain a spinning solution; the second mixed reaction system comprises 16-35 wt% of polymer, 2-20 wt% of negatively charged monomer and 0.01-2 wt% of initiator, and the balance is a second solvent, wherein the polymer is selected from one or the combination of more than two of polysulfone, polyether sulfone and polyacrylonitrile, and the negatively charged monomer is selected from one or the combination of more than two of acrylic acid, methacrylic acid and sodium propylene sulfonate;
co-extruding the spinning solution, the hybrid aqueous phase solution and the organic phase solution containing the acyl chloride monomer through a double-layer spinneret, staying for 0.2-30 s in the air, then immersing the spinning solution into a coagulating bath consisting of 0-80 ℃ and 1-30 wt% of a cross-linking agent and water for cross-linking and curing to form a hollow fiber membrane, cleaning, then carrying out heat treatment at 25-130 ℃ for 1-30 min, and instantly carrying out interfacial polymerization on the acyl chloride monomer, the amine monomer and the negatively charged hybrid material on the inner wall of the hollow fiber membrane while curing to form a membrane to obtain the negatively charged hybrid positive-permeation hollow fiber membrane; wherein the organic phase solution containing the acyl chloride monomer contains 0.1-20 wt% of the acyl chloride monomer;
the negatively charged hybrid forward osmosis hollow fiber membrane comprises:
the negative charge polymer hollow fiber membrane basement membrane with a cross-linked interpenetrating network structure is formed by mesoporous nano silicon dioxide, dopamine and negative charge polymer;
and a loose hybrid ultrathin polyamide functional layer distributed at least on the inner wall of the hollow fiber membrane-based membrane;
wherein the thickness of the negatively-charged hybrid forward-osmosis hollow fiber membrane is 20-200 mu m, and the thickness of the hybrid ultrathin polyamide functional layer is 10-30 nm; the pure water flux of the negatively-charged hybrid positive-osmosis hollow fiber membrane is 27-68L m-2h-1The retention rate of sodium chloride is 45-91%.
2. The method of claim 1, wherein: the diameter of the mesoporous nano-silica is 5-70 nm, and the aperture of the contained holes is 1-10 nm.
3. The method of claim 1, wherein: the amine monomer is selected from any one or combination of more than two of m-phenylenediamine, o-phenylenediamine, p-phenylenediamine, piperazine and ethylenediamine.
4. The method of claim 1, wherein: the initiator is selected from any one or the combination of more than two of azodiisobutyronitrile, azodiisoheptonitrile and dibenzoyl peroxide.
5. The method of claim 1, wherein: the second solvent is selected from one or the combination of more than two of N-methyl pyrrolidone, N '-dimethylformamide, N' -dimethylacetamide and acetone.
6. The method of claim 1, wherein: the acyl chloride monomer is selected from one or the combination of more than two of isophthaloyl dichloride, paraphthaloyl dichloride, phthaloyl dichloride, trimesoyl dichloride, 5-oxygen formyl chloride-isophthaloyl dichloride and 5-isocyanate-isophthaloyl dichloride.
7. The method of claim 1, wherein: the organic phase solution contains an organic solvent selected from any one or a combination of more than two of n-hexane, cyclohexane and n-octane.
8. The method of claim 1, wherein: the cross-linking agent is selected from any one or the combination of more than two of glutaraldehyde, malic acid, sorbitol and glycerol.
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