CN111420558A - Hollow fiber composite nanofiltration membrane, and preparation method and application thereof - Google Patents

Hollow fiber composite nanofiltration membrane, and preparation method and application thereof Download PDF

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Publication number
CN111420558A
CN111420558A CN202010135143.9A CN202010135143A CN111420558A CN 111420558 A CN111420558 A CN 111420558A CN 202010135143 A CN202010135143 A CN 202010135143A CN 111420558 A CN111420558 A CN 111420558A
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hollow fiber
membrane
nano material
nanofiltration membrane
fiber composite
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苏保卫
田龙
江永祥
苏敬华
李树轩
韩力挥
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Ocean University of China
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Ocean University of China
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    • 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
    • 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
    • B01D61/025—Reverse osmosis; Hyperfiltration
    • 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
    • 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
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2325/00—Details relating to properties of membranes
    • B01D2325/02—Details relating to pores or porosity of the membranes
    • 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
    • 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

Abstract

The invention discloses a hollow fiber composite nanofiltration membrane, a preparation method and application thereof; the preparation method of the hollow fiber composite membrane comprises the steps of preparing a two-dimensional nano material modification layer and preparing a skin layer; according to the invention, a thin layer of two-dimensional nano material is firstly modified on the surface of the hollow fiber base membrane, and then interfacial polymerization is carried out on the two-dimensional nano material modification layer, so that the flux and interception performance of the composite membrane are obviously improved; the two-dimensional nano material modification layer can improve the physical and chemical properties of the base membrane, the pore diameter, pore diameter distribution, hydrophilicity and the like of the membrane, so that the subsequent interfacial polymerization process can be more effectively regulated and controlled, and the separation performance of the membrane is improved; the invention has simple preparation process and good application prospect in the aspect of water treatment.

Description

Hollow fiber composite nanofiltration membrane, and preparation method and application thereof
Technical Field
The invention belongs to the technical field of membrane separation, and particularly relates to a hollow fiber composite nanofiltration membrane, and a preparation method and application thereof.
Background
Rapid population growth and industrialization of fresh waterCrisis is becomes one of the most serious problems threatening human health. Seawater desalination becomes an important approach to solve the water resource shortage. The currently applied seawater desalination technology is mainly reverse osmosis technology and thermal distillation technology based on membrane separation. Compared with the traditional separation method, the membrane separation method has the characteristics of energy conservation, high separation efficiency, environmental friendliness and the like. The nano-filtration membrane can effectively intercept Ga due to charge repulsion and steric hindrance effects2+、Mg2+、SO42-And the like, divalent ions and micromolecular organic matters which are easy to scale, reduce the turbidity, the hardness and the TDS of the seawater, slow down the scaling and pollution tendency of the membrane, and can be widely used in the pretreatment process of seawater softening and seawater desalination.
The nanofiltration membrane mainly has two configurations, namely a roll type and a hollow fiber type. Compared with a roll type nanofiltration membrane, the hollow fiber nanofiltration membrane has huge potential in the aspect of industrial application due to the characteristics of large specific surface area, high filling density, self-support, easy preparation of a membrane component and the like.
The integral asymmetric membrane and the thin-layer composite membrane are two main structures of the existing hollow fiber nanofiltration membrane. Compared with a membrane prepared by constructing an ultrathin separation layer on the surface of a porous supporting layer by interfacial polymerization and coating methods, the membrane prepared by the method has small mass transfer resistance and large permeation flux. In the process of preparing TFC membrane by interfacial polymerization, the physicochemical properties (pore size, porosity, pore size distribution, hydrophilicity, etc.) of the base membrane play an important role. The base films are different, and the performance of the prepared composite film is also greatly different. The membrane prepared from the pure polymer-based membrane has the defects of thicker skin layer, larger roughness, low permeation flux, no pollution resistance and the like.
Ultrathin two-dimensional nanomaterials are an emerging class of nanomaterials with platelet structures with planar dimensions that can exceed 100nm or a few microns or even larger, but are only a single or a few atoms thick (typical thicknesses are less than 5 nm). Because the two-dimensional material can maintain the atomic thickness while having an extremely large plane size, the two-dimensional material is endowed with an extremely large specific surface area, and the most surface atoms are exposed. Since the electrons are confined in a two-dimensional plane (especially for a single layer of two-dimensional material), their electronic properties are enhanced. The strong in-plane covalent bonds and atomic layer thickness allow the two-dimensional material to exhibit excellent mechanical strength and flexibility. Among them, Graphene Oxide (GO), as a novel two-dimensional nanomaterial, has great potential in liquid filtration and separation because its surface and periphery have various oxygen-containing functional groups.
The surface of the hollow fiber base membrane is difficult to form a stable and uniformly spread aqueous phase monomer solution thin layer, so that the performance of an interfacial polymerization layer is influenced, and the hollow fiber composite nanofiltration membrane prepared by the method has a series of technical problems of low flux, poor separation performance, low mechanical performance, difficult industrialization and the like, and needs to be solved urgently.
Disclosure of Invention
The invention provides a hollow fiber composite nanofiltration membrane, a preparation method and application thereof, aiming at a series of technical problems of low flux, poor separation performance, low mechanical performance, difficult industrialization and the like of the hollow fiber composite nanofiltration membrane in the prior art, and the prepared composite membrane has an ultrathin skin layer and good separation performance.
In order to achieve the above object, the technical solution of the present invention is as follows.
The invention discloses a hollow fiber composite nanofiltration membrane, which has a three-layer structure in cross section: (1) a hollow fiber base membrane; (2) an intermediate layer composed of a two-dimensional nanomaterial; (3) the polyamide separates the skin layer.
Preferably, the hollow fiber base membrane is a hollow fiber ultrafiltration membrane or a hollow fiber microfiltration membrane.
Preferably, the material of the hollow fiber base membrane comprises polysulfone and polyethersulfone; preferably, the hollow fiber base membrane is made of polysulfone or polyethersulfone.
Preferably, the separation skin layer of the hollow fiber base membrane is an inner skin layer.
Preferably, the separation skin layer of the hollow fiber base membrane is an outer skin layer.
Preferably, the hollow fiber composite nanofiltration membrane comprises a nanofiltration membrane and a reverse osmosis membrane.
Preferably, the two-dimensional nanomaterial comprises graphene oxide and derivatives thereof.
Preferably, the two-dimensional nanomaterial is graphene oxide.
Preferably, the average lamella thickness of the two-dimensional nano material is less than 5 nm; more preferably, the average lamella thickness of the two-dimensional nanomaterial is less than 2 nm.
Preferably, the loading capacity of the two-dimensional nano material on the surface of the hollow fiber base membrane is 0.001-0.2 g/m2Hollow fiber base membrane surface area; more preferably, the loading capacity of the two-dimensional nano material on the surface of the hollow fiber base membrane is 0.01-0.05 g/m2Hollow fiber based membrane surface area.
Preferably, the polyamide separation skin layer is prepared by an interfacial polymerization method of polyamine and polybasic acyl chloride.
Preferably, the hollow fiber composite nanofiltration membrane is used for treating 2000 mg/L Na at 25 ℃ and under the transmembrane pressure difference of 0.5MPa2SO4Na in aqueous solution2SO4The retention rate is more than 95 percent, and the water flux is more than 30L/(m)2·h)。
Preferably, the middle-layer-containing high-flux hollow fiber composite nanofiltration membrane has the rejection rate of less than 50% of NaCl in a 2000 mg/L NaCl aqueous solution and the water permeability of more than 30L/(m) under the conditions that the temperature is 25 ℃ and the transmembrane pressure difference is 0.5MPa2·h)。
Preferably, the rejection rate of the hollow fiber composite nanofiltration membrane on sulfate ions in a sulfate ion-containing salt solution is more than 95%.
The cutting molecular weight range of the hollow fiber composite nanofiltration membrane is 200-1000 daltons.
The second aspect of the invention discloses a preparation method of a hollow fiber composite nanofiltration membrane, which comprises the following steps:
(1) adding a two-dimensional nano material into ultrapure water, and performing ultrasonic treatment for a certain time to obtain a uniformly dispersed two-dimensional nano material suspension;
(2) drying the water on the surface of the hollow fiber base membrane in the air, soaking the hollow fiber base membrane in the two-dimensional nano material suspension for a certain time or filtering a certain amount of the two-dimensional nano material suspension, thereby forming an ultrathin nano material modification layer on the surface of the hollow fiber base membrane, and drying the hollow fiber base membrane in the air for a certain time;
(3) the surface of a nano material modification layer of a hollow fiber base membrane is firstly contacted with a water phase solution of polyamine for a certain time, then is dried for a certain time, is contacted with an organic phase solution of polyacyl chloride for a certain time, so that the polyamine and the polyacyl chloride are subjected to interfacial polymerization, and then is subjected to heat treatment, thus obtaining the hollow fiber composite nanofiltration membrane.
Preferably, the two-dimensional nanomaterial comprises graphene oxide and derivatives thereof; the average lamella thickness of the two-dimensional nano material is less than 5 nm; more preferably, the average lamella thickness of the two-dimensional nanomaterial is less than 2 nm.
Preferably, the two-dimensional nanomaterial is graphene oxide.
Preferably, the concentration of the two-dimensional nano material in the two-dimensional nano material suspension is 0.01-100 mg/L, and more preferably, the concentration of the two-dimensional nano material in the two-dimensional nano material suspension is 1-50 mg/L.
Preferably, the air-drying time of the nano material modification layer is 1-30 minutes.
Preferably, the polyamine is diamine; preferably, the polyamine is piperazine or m-phenylenediamine.
Preferably, the polybasic acyl chloride is ternary acyl chloride; preferably, the polybasic acyl chloride is trimesoyl chloride.
Preferably, the contact time of the surface of the nano material modified layer and the aqueous solution of the polyamine is 5-120 s; the surface of the nano material modification layer is in contact with the aqueous solution of polyamine for a certain time, and then the airing time is 20-120 s; the surface of the nano material modification layer is contacted with an aqueous solution of polyamine and dried, and then the contact time of the surface of the nano material modification layer with an organic phase solution of polyacyl chloride is 5-120 s; the heat treatment temperature after the interfacial polymerization is 20-100 ℃; the heat treatment time after the interfacial polymerization is 1-30 min.
The third aspect of the invention discloses an application of a hollow fiber composite nanofiltration membrane, which is used for separating and purifying divalent salt and monovalent salt in an aqueous solution system, or separating and purifying an aqueous solution containing an organic solute, or separating and purifying salt and an organic solute in an aqueous solution system containing salt and the organic solute simultaneously, wherein the molecular weight range of the organic solute is 200-1000 daltons.
The technical scheme of the invention achieves obvious technical effect and progress and has substantive characteristics.
The hollow fiber composite nanofiltration membrane has excellent separation performance, and compared with the nanofiltration membrane which is prepared under the same condition and does not contain a nano material middle layer, the rejection rate of the composite nanofiltration membrane is basically kept unchanged, even slightly increased; the water flux is greatly improved, and the flux improvement amplitude can reach 50%; the mechanical strength of the composite membrane is improved, the application range of the composite membrane is greatly expanded, the remarkable technical effect is obtained, and the composite membrane has a good application prospect.
The preparation method of the hollow fiber composite nanofiltration membrane has the obvious technical advantages that the two-dimensional nano material modification layer formed on the base membrane can effectively adjust the pore diameter of the surface of the base membrane, so that the pore diameter distribution of the surface of the modified base membrane is more uniform, and the uniform and defect-free skin layer can be generated more favorably. Meanwhile, the hydrophilic property of the surface of the base membrane is improved, the adsorption and release of the water phase monomer can be effectively controlled, the interfacial polymerization process is effectively controlled, the thickness of the formed separation skin layer is reduced, the roughness is reduced, the compactness is higher, and the pollution resistance of the membrane is greatly improved; a water channel is provided, so that the permeation flux and the separation performance of the membrane are improved; the interfacial polymerization can be carried out at a lower concentration, so that the film preparation cost is reduced, and the resources are saved; the preparation method is simple and easy to operate.
Through the technical innovation, the invention achieves remarkable technical progress and has excellent application prospect in the field of water treatment.
Detailed Description
The invention is further illustrated by the following specific comparative examples and examples.
The basement membrane is a Polysulfone (PSF) hollow fiber type ultrafiltration membrane;
the polyamine compound used is piperazine (PIP);
sodium Dodecyl Sulfate (SDS) and Triethylamine (TEA) are used as additives in the polyamine monomer aqueous solution;
the polyacyl chloride is 1, 3, 5-trimesoyl chloride (TMC);
the two-dimensional nano material is Graphene Oxide (GO), the average sheet diameter of the GO is 500nm, and the average thickness of the GO is about 1 nm;
the organic solvent is n-hexane;
the membrane separation performance test method adopted by the embodiment of the invention comprises the following steps:
at 25 ℃ and a transmembrane pressure difference of 0.5MPa, respectively, 2000 mg/L Na2SO4Aqueous solution and 2000 mg/L Na2SO4The retention rate of the prepared membrane on inorganic salt and corresponding water flux are measured by aqueous solution;
respectively measuring the retention rate of the prepared membrane on inorganic salt and the corresponding water flux by using 2000 mg/L NaCl aqueous solution and 2000 mg/L NaCl aqueous solution at 25 ℃ and the transmembrane pressure difference of 0.5 MPa;
the retention rate of the prepared membrane to organic solute is respectively measured by dye aqueous solutions with different molecular weights of 100 mg/L at 25 ℃ and the transmembrane pressure difference of 0.5 MPa.
Comparative example:
deionized water is used for preparing polyamine monomer aqueous solution, and the components of the aqueous solution are as follows: 0.75 wt% (mass%, the same applies hereinafter) of PIP, 2.0 wt% of TEA and 0.1 wt% of SDS, wt representing the mass% concentration;
and dissolving the polyacyl chloride in an organic solvent to prepare 0.15 percent of organic phase monomer solution.
The preparation method of the polypiperazine amide composite hollow fiber nanofiltration membrane comprises the following steps and conditions:
a pretreatment step: soaking the hollow fiber base membrane in deionized water for 12 hours;
interfacial polymerization step for separating skin layer: taking out the base membrane from deionized water, airing the surface water, fully contacting the surface of the base membrane with an aqueous phase monomer solution for 60s, removing the surface water of the base membrane, airing in the air at room temperature, fully contacting the aired surface of the base membrane with an organic phase monomer solution for 30s, removing the organic phase monomer solution on the surface of the membrane, rapidly putting the membrane into a drying oven at 80 ℃ for drying for 5min, taking out and naturally airing in a drying environment to obtain the dry polypiperazine amide composite hollow fiber nanofiltration membrane.
The prepared polypiperazine amide composite nanofiltration membrane is used for treating Na with the concentration of 2000 mg/L at the temperature of 25 ℃ and the transmembrane pressure difference of 0.5MPa2SO4Na in aqueous solution2SO4Has a retention rate of 95.94% and a flux of 26.9L/(m)2·h)。
The prepared polypiperazine amide composite nanofiltration membrane has the interception rate of 28.3% of NaCl in a NaCl aqueous solution of 2000 mg/L under the conditions of 25 ℃ and 0.5MPa of transmembrane pressure difference, and the flux is 31.3L/(m)2·h)。
Example 1
Preparing 2.5 mg/L of GO aqueous solution, and carrying out ultrasonic treatment for half an hour to obtain a uniformly dispersed GO aqueous solution;
the average lamella thickness of the GO nano material is 2 nm.
The film preparation steps are as follows:
the method comprises the following steps: soaking the hollow fiber ultrafiltration base membrane subjected to end capping in deionized water for 12 hours, taking out the water on the air-dried surface, and filtering a certain volume of GO aqueous solution in a filter pressing manner to ensure that the solid loading amount of GO on the surface of the base membrane is 0.02g/m2Taking out the membrane after filtration and drying for 1min to obtain a GO modified base membrane;
step two: and (3) separating interfacial polymerization of the skin layer, and obtaining the composite membrane containing the GO modification layer in the same step of interfacial polymerization of the comparative example.
The test conditions were the same as in the comparative example.
Prepared polypiperazine amide hollow fiber composite nanofiltration membrane pair Na2SO4The retention rate of (A) was 96.1%, and the flux was 40.7L/(m)2H), flux was greatly increased, 51% flux increase, compared to the comparative example.
The prepared polypiperazine amide composite nanofiltration membrane has the rejection rate of NaCl in 2000 mg/L NaCl water solution at 25 ℃ and the transmembrane pressure difference of 0.5MPa23.9% and a flux of 48.6L/(m)2·h)。
The prepared polypiperazine amide composite nanofiltration membrane has the advantages that under the conditions of 25 ℃ and 0.5MPa transmembrane pressure difference, the rejection rate of crocin T molecules in 100 mg/L crocin T (molecular weight is 350 daltons) aqueous solution is 92.9%, and the rejection rate of Coomassie brilliant blue molecules in 100 mg/L Coomassie brilliant blue (molecular weight is 854 daltons) aqueous solution is 98%.
Example 2
The difference from example 1 is that the concentration of GO in step (1) is changed to 3.5 mg/L with a solid loading of 0.03g/m on the surface of the base film2。
All other steps are the same as in example 1; the test conditions were the same as in the comparative example.
Prepared polypiperazine amide hollow fiber composite nanofiltration membrane pair Na2SO4The retention rate of (A) was 96%, and the flux was 34.1L/(m)2H), compared with the comparative example, the flux is greatly improved, and the flux improvement range is 27%.
The above examples show that the introduction of the two-dimensional nanomaterial GO modification layer effectively regulates and controls the interfacial polymerization process and the structure of the separation layer, so that the separation performance of the membrane is greatly improved. The invention achieves remarkable technical effects and progress.
It should be noted that the above-mentioned embodiments illustrate only preferred specific embodiments of the invention, and are not to be construed as limiting the invention, any embodiments falling within the scope of the invention, which is defined by the features of the claims or the equivalents thereof, constituting a right to infringe the invention.

Claims (11)

1. The utility model provides a hollow fiber composite nanofiltration membrane which characterized in that, its section is three layer construction: (1) a hollow fiber base membrane; (2) an intermediate layer composed of a two-dimensional nanomaterial; (3) the polyamide separates the skin layer.
2. The hollow fiber composite nanofiltration membrane according to claim 1, wherein the nanofiltration membrane comprises a nanofiltration membrane,
(1) the hollow fiber basement membrane is a hollow fiber ultrafiltration membrane or a hollow fiber microfiltration membrane;
(2) the hollow fiber base membrane is made of polysulfone and polyether sulfone; preferably, the hollow fiber base membrane is made of polysulfone.
3. The hollow fiber composite nanofiltration membrane according to claim 1, wherein the nanofiltration membrane comprises a nanofiltration membrane,
(1) the two-dimensional nano material comprises graphene oxide and derivatives thereof; preferably, the two-dimensional nanomaterial is graphene oxide;
(2) the average lamella thickness of the two-dimensional nano material is less than 5 nm; preferably, the average lamella thickness of the two-dimensional nano material is less than 2 nm;
(3) the loading capacity of the two-dimensional nano material on the surface of the hollow fiber base membrane is 0.001-0.2 g/m2Hollow fiber base membrane surface area; preferably, the loading capacity of the two-dimensional nano material on the surface of the hollow fiber base membrane is 0.01-0.05 g/m2Hollow fiber based membrane surface area.
4. The hollow fiber composite nanofiltration membrane according to claim 1, wherein the polyamide separation skin layer is prepared by interfacial polymerization of polyamine and polyacyl chloride.
5. The hollow fiber composite nanofiltration membrane according to claim 1, wherein the nanofiltration membrane comprises a nanofiltration membrane,
(1) the hollow fiber composite nanofiltration membrane is used for treating 2000 mg/L Na at the temperature of 25 ℃ and the transmembrane pressure difference of 0.5MPa2SO4Na in aqueous solution2SO4The retention rate is more than 95 percent, and the water flux is more than 30L/(m)2·h)；
(2) The middle-layer-containing high-flux hollow fiber composite nanofiltration membrane has the rejection rate of less than 50% of NaCl in 2000 mg/L NaCl aqueous solution at 25 ℃ and the transmembrane pressure difference of 0.5MPa, and the water permeability of more than 30L/(m)2·h)；
(3) The cutting molecular weight range of the hollow fiber composite nanofiltration membrane is 200-1000 daltons.
6. The hollow fiber composite nanofiltration membrane of claim 1, wherein the rejection rate of the hollow fiber composite nanofiltration membrane on sulfate ions in a sulfate ion-containing salt solution is greater than 95%.
7. A preparation method of a hollow fiber composite nanofiltration membrane comprises the following steps:
(1) adding a two-dimensional nano material into ultrapure water, and performing ultrasonic treatment for a certain time to obtain a uniformly dispersed two-dimensional nano material suspension;
(2) drying the water on the surface of the hollow fiber base membrane in the air, soaking the hollow fiber base membrane in the two-dimensional nano material suspension for a certain time or filtering a certain amount of the two-dimensional nano material suspension, thereby forming an ultrathin nano material modification layer on the surface of the hollow fiber base membrane, and drying the hollow fiber base membrane in the air for a certain time;
(3) the surface of a nano material modification layer of a hollow fiber base membrane is firstly contacted with a water phase solution of polyamine for a certain time, then is dried for a certain time, is contacted with an organic phase solution of polyacyl chloride for a certain time, so that the polyamine and the polyacyl chloride are subjected to interfacial polymerization, and then is subjected to heat treatment, thus obtaining the hollow fiber composite nanofiltration membrane.
8. The preparation method of the hollow fiber composite nanofiltration membrane according to claim 7,
(1) the two-dimensional nano material comprises graphene oxide and derivatives thereof; preferably, the two-dimensional nanomaterial is graphene oxide;
(2) the average lamella thickness of the two-dimensional nano material is less than 5 nm; preferably, the average lamella thickness of the two-dimensional nano material is less than 2 nm;
(3) the concentration of the two-dimensional nano material in the two-dimensional nano material suspension is 0.01-100 mg/L, preferably 1-50 mg/L;
(4) the drying time of the nano material modification layer is 1-30 minutes.
9. The preparation method of the hollow fiber composite nanofiltration membrane according to claim 7,
(1) the polyamine is diamine; preferably, the polyamine is piperazine or m-phenylenediamine; more preferably, the polyamine is piperazine;
(2) the polybasic acyl chloride is ternary acyl chloride; preferably, the polybasic acyl chloride is trimesoyl chloride.
10. The preparation method of the hollow fiber composite nanofiltration membrane according to claim 7,
(1) the contact time of the surface of the nano material modified layer and the aqueous solution of the polyamine is 5-120 s;
(2) the surface of the nano material modification layer is in contact with the aqueous solution of polyamine for a certain time, and then the airing time is 20-120 s;
(3) the surface of the nano material modification layer is contacted with an aqueous solution of polyamine and dried, and then the contact time of the surface of the nano material modification layer with an organic phase solution of polyacyl chloride is 5-120 s;
(4) the heat treatment temperature after the interfacial polymerization is 20-100 ℃;
(5) the heat treatment time after the interfacial polymerization is 1-30 min.
11. The application of the hollow fiber composite nanofiltration membrane is characterized in that the hollow fiber composite nanofiltration membrane is used for separating and purifying divalent salt and monovalent salt in an aqueous solution system, or separating and purifying an aqueous solution containing an organic solute, or separating and purifying salt and the organic solute in the aqueous solution system containing salt and the organic solute simultaneously; the hollow fiber composite nanofiltration membrane is the hollow fiber composite nanofiltration membrane according to any one of claims 1 to 6, or the hollow fiber composite nanofiltration membrane prepared by the preparation method according to any one of claims 7 to 10, and the molecular weight of the organic solute is 200 to 1000 daltons.
CN202010135143.9A 2020-02-29 2020-02-29 Hollow fiber composite nanofiltration membrane, and preparation method and application thereof Pending CN111420558A (en)

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G.S.LAI等: "Tailor-made Thin Film Nanocomposite Membrane Incorporated with Graphene Oxide using Novel Interfacial Polymerization Technique for Enhanced Water Separation", 《CHEMICAL ENGINEERING JOURNAL》 *

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Application publication date: 20200717