CN113230903A - Portable photo-thermal seawater desalination hollow fiber membrane, preparation method, device and application - Google Patents
Portable photo-thermal seawater desalination hollow fiber membrane, preparation method, device and application Download PDFInfo
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- CN113230903A CN113230903A CN202110452895.2A CN202110452895A CN113230903A CN 113230903 A CN113230903 A CN 113230903A CN 202110452895 A CN202110452895 A CN 202110452895A CN 113230903 A CN113230903 A CN 113230903A
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
- B01D69/08—Hollow fibre membranes
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
- B01D69/02—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor characterised by their properties
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- 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
- C02F1/02—Treatment of water, waste water, or sewage by heating
- C02F1/04—Treatment of water, waste water, or sewage by heating by distillation or evaporation
- C02F1/048—Purification of waste water by evaporation
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- 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
- C02F1/02—Treatment of water, waste water, or sewage by heating
- C02F1/04—Treatment of water, waste water, or sewage by heating by distillation or evaporation
- C02F1/14—Treatment of water, waste water, or sewage by heating by distillation or evaporation using solar energy
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- 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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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A20/00—Water conservation; Efficient water supply; Efficient water use
- Y02A20/20—Controlling water pollution; Waste water treatment
- Y02A20/208—Off-grid powered water treatment
- Y02A20/212—Solar-powered wastewater sewage treatment, e.g. spray evaporation
Abstract
The invention discloses a portable photo-thermal seawater desalination hollow fiber membrane, a preparation method, a device and application, wherein the preparation method comprises the following steps of 1): dispersing and dissolving a hydrophilic polymer and nanoparticles in a buffer solution with the pH of 8.5 to prepare a uniform solution, wherein the weight ratio of the hydrophilic polymer: the ratio of the nano particles to the nano particles is 1-20: 0-20, the hollow fiber membrane is circularly washed by a uniform solution for 1-24 hours, and the hollow fiber membrane is cleaned and dried for later use to prepare a super-hydrophilic hollow fiber membrane with an inner surface; step 2): placing the inner surface super-hydrophilic hollow fiber membrane obtained in the step 1) in an atmosphere of 0.1-20 wt% of photo-thermal modified material solution, and treating for 1-24 h in a surface adsorption, surface vapor deposition, surface crosslinking and fixing, suction filtration and/or coating modification mode to obtain the hollow fiber membrane with the inner surface super-hydrophilic and outer surface photo-thermal functions. The invention selects the three-dimensional hollow fiber membrane as the base material, and the photo-thermal seawater desalination hollow fiber membrane obtained by modifying the inner surface and the outer surface can realize the photo-thermal seawater desalination.
Description
Technical Field
The invention relates to the technical field of photo-thermal conversion, in particular to a portable photo-thermal seawater desalination hollow fiber membrane and a preparation method, a device and application thereof.
Background
Fresh water is one of the basic substances on which the human society depends to survive and develop, but is only present in rivers, lakes and underground fresh water available for direct human use at present by less than 0.36%. China is long in coastline, islands, coastal saline-alkali areas and inland bitter regions belong to regions lack of fresh water, and people drink water which does not meet sanitary standards for a long time, so that various diseases are generated, and physical health and local economic construction are directly influenced. Therefore, desalination of seawater and brackish water has become an effective way to expand the source of fresh water.
At present, a lot of methods are used for desalting seawater or brackish water, such as conventional distillation, ion exchange, dialysis, reverse osmosis membrane, freezing and the like. However, these methods require large infrastructure or consume large amounts of dyes, electricity, and cause some air pollution or greenhouse effect. As is well known, solar energy has the advantages of being green, pollution-free and renewable, and the solar seawater desalination technology is produced and widely applied to the field of seawater or brackish water desalination. Patent CN 109399606 a discloses a carbon dot-nitrogen doped modified photothermal foam material with high efficiency of photothermal conversion; patent CN 111286067A discloses a polydopamine-cellulose nanofibril photothermal conversion composite membrane, firstly preparing a cellulose nanofibril basement membrane, and then polymerizing in a dopamine, ammonia water/ethanol/water system or a tris (hydroxymethyl) aminomethane system; subsequently, patent CN 110898451 a discloses a method and apparatus for efficient photo-thermal water evaporation based on a four-layer structure comprising a floating/thermal insulating layer, a water-rich porous layer, a water-poor porous layer, and a photo-thermal conversion layer. However, the above photothermal material and device all use a two-dimensional photothermal conversion surface to perform photothermal conversion to achieve water evaporation in the use process, which results in low photothermal efficiency, and the wide use thereof is greatly limited due to factors such as large volume and heavy weight. Patent CN111573780A discloses a hollow fiber photothermal membrane device, a preparation method and an application thereof, and a water treatment device, which are mainly implemented by inserting two ends of a hollow fiber membrane body into the support body and penetrating out of the surface of the support body, however, the photothermal membrane device does not exert the advantage of the specific surface area of the hollow fiber membrane to the maximum extent, and the heat loss is unavoidable because both ends are inserted into the water body. Therefore, how to design and realize efficient seawater desalination in unit effective area through a novel membrane technology still remains a social problem to be solved urgently at present. With the rapid development of economy and industry, multimedia purification is in need. For example, the direct discharge of oily wastewater and solvents can seriously harm human life and life health.
Disclosure of Invention
Aiming at the technical problems in the prior art, the application provides a preparation method of a portable photo-thermal seawater desalination hollow fiber membrane and the photo-thermal seawater desalination hollow fiber membrane.
A preparation method of a portable photo-thermal seawater desalination hollow fiber membrane comprises the following steps:
step 1): dispersing and dissolving a hydrophilic polymer and nanoparticles in a buffer solution with the pH of 8.5 to prepare a uniform solution, wherein the weight ratio of the hydrophilic polymer: the ratio of the nano particles to the nano particles is 1-20: 0-20, the hollow fiber membrane is circularly washed by a uniform solution for 1-24 hours, and the hollow fiber membrane is cleaned and dried for later use to prepare a super-hydrophilic hollow fiber membrane with an inner surface;
step 2): placing the inner surface super-hydrophilic hollow fiber membrane obtained in the step 1) in an atmosphere of 0.1-20 wt% of photo-thermal modified material solution, and treating for 1-24 h in a surface adsorption, surface vapor deposition, surface crosslinking and fixing, suction filtration and/or coating modification mode to obtain the hollow fiber membrane with the inner surface super-hydrophilic and outer surface photo-thermal functions, and cleaning and drying for later use.
Preferably, the method further comprises the step 3): soaking the hollow fiber membrane with the inner surface super-hydrophilic and the outer surface photo-thermal functions obtained in the step 2) in 0.1-20 wt% of hydrophobic polymer solution to construct a hydrophobic outer surface, and cleaning and drying to obtain the photo-thermal seawater desalination hollow fiber membrane.
Preferably, the hollow fiber membrane in step 1) is made of: one or more of polyvinylidene fluoride, polysulfone, polyethersulfone, polyetheretherketone, sulfonated polysulfone, polyether modified polysulfone, cellulose acetate, polyimide, polyacrylate, polyacrylonitrile, polytetrafluoroethylene, polyethylene, polypropylene, polycarbonate, and polyvinyl alcohol;
the average pore diameter range of the hollow fiber membrane is 0.01-2.0 mu m, the porosity is 20-80%, the membrane thickness range is 50-500 mu m, and the inner diameter range and the outer diameter range of the hollow fiber are 0.1-2.0 mm and 0.25-3.5 mm respectively;
the hydrophilic polymer is: one or more of dopamine, tannic acid, polyvinyl alcohol, polyvinylpyrrolidone, polyether modified silicone, maleic acid copolymer, polyethyleneimine, polyamidoamine, gamma-aminopropyltrimethoxysilane, gamma-aminopropyltriethoxysilane;
the nano-particles are: one or more of titanium dioxide, silicon dioxide, aluminum oxide and ferroferric oxide;
the cyclic flushing is any one of the following methods: dead-end filtration, surface coating or recirculation filtration processes.
Preferably, the photothermal modification material in the step 2) is: a combination of one or more of graphene, reduced graphene oxide, carbon nanotubes, polypyrrole, polyaniline, black titanium dioxide, ink, MOF, COF, gold nanoparticles, silver nanoparticles, palladium nanoparticles;
the modification treatment mode of the inner surface and the outer surface of the hollow fiber membrane can adopt one or more of surface coating, dead-end filtration, circulating filtration treatment, surface cross-linking fixation, surface adsorption, surface deposition and suction filtration.
Preferably, the hydrophobic polymer solution in step 3) is a solution prepared by combining one or more of polydimethylsiloxane, polytetrafluoroethylene, fluorine-containing polyacrylate and polyetherimide.
A portable photo-thermal seawater desalination hollow fiber membrane is prepared by the preparation method.
The utility model provides a portable light and heat sea water desalination device, includes supporter, membrane module casing, steam collector, still includes light and heat sea water desalination hollow fiber membrane, the one end encapsulation of a plurality of light and heat sea water desalination hollow fiber membrane is in the membrane module casing, the membrane module casing is fixed on the supporter, the supporter is installed in steam collector.
Preferably, in the photo-thermal seawater desalination device, the steam collector is transparent and has a sealing structure, and one end of the steam collector is provided with a collected water outlet; the support body is made of a heat insulating material; the steam collector is a transparent box body or an umbrella body formed by 0.1-3 mm of glass or transparent polymer films.
The invention also provides a preparation method of the photo-thermal seawater desalination device, which comprises the following steps: step (1): packaging one end of a beam of photo-thermal seawater desalination hollow fiber membrane with the length of 5-50cm and 10,000 pieces of the photo-thermal seawater desalination hollow fiber membrane in a membrane module shell by adopting epoxy glue or polyurethane glue to prepare a photo-thermal seawater desalination hollow fiber membrane module;
step (2): and fixing the photo-thermal seawater desalination hollow fiber membrane component on a support body, and then placing the support body in a steam collector to obtain the photo-thermal seawater desalination device.
The invention also provides application of the photo-thermal seawater desalination hollow fiber membrane in seawater, saline-alkali water, high-pollution poor-quality water purification and solvent recovery.
Preferably, in the homogeneous solution, the ratio of hydrophilic polymer: the ratio of the nano particles is 1-20: 0-5.
The present application is further described below:
solar-driven steam generation technology mainly comprises two processes: the photo-thermal conversion material absorbs sunlight to carry out photo-thermal conversion, and light energy is converted into heat energy; the stock solution is heated by heat energy to generate steam to obtain fresh water or solvent. The invention designs a photo-thermal conversion membrane device based on a three-dimensional hollow fiber membrane, which can regulate and control the self-siphon water supply rate through the porosity and pore diameter change of the hollow fiber membrane, further regulate and control the photo-thermal steam generation rate, and realize high-efficiency seawater and brackish water desalination treatment and solvent recovery treatment through the structural design of a novel three-dimensional hollow fiber membrane.
The invention mainly aims to provide a portable photothermal seawater desalination hollow fiber membrane and a preparation method, equipment and application thereof, aiming at the limitations of high heat loss, low evaporation efficiency and the like of the current photothermal material.
The invention discloses a portable photo-thermal seawater desalination hollow fiber membrane, which comprises an inner-outer asymmetric structure with a super-hydrophilic inner surface and a photo-thermal functional outer surface, and has the characteristics of self-siphon water supply, photo-thermal conversion, high specific surface area, high-efficiency evaporation efficiency and the like.
The invention also discloses portable photo-thermal seawater desalination hollow fiber membrane equipment (called as a portable photo-thermal seawater desalination device for short), which mainly comprises: the solar-thermal seawater desalination hollow fiber membrane comprises a solar-thermal seawater desalination hollow fiber membrane, a support body and a steam collector, wherein the steam collector is composed of a transparent box body or an umbrella body which is composed of glass or a transparent polymer film with high optical transmittance.
The invention also discloses application of the portable photothermal seawater desalination hollow fiber membrane equipment, the portable photothermal seawater desalination hollow fiber membrane equipment has the advantages of self-siphon water supply, water delivery, black appearance, photothermal conversion, high specific surface area, high-efficiency evaporation efficiency, stable performance and the like, is suitable for taking seawater, saline-alkali water, highly polluted inferior water and an organic solvent as a stock solution, does not need external power conditions, and can realize deep purification treatment of the seawater, the saline-alkali water, the highly polluted inferior water and the organic solvent by only utilizing sunlight for driving to obtain drinking water or the solvent; the portable photothermal film equipment has the advantages of small volume, light weight, portability, large water yield per unit area, durability, stability and the like, is suitable for small and portable outdoor drinking water equipment and low-energy-consumption solvent recovery equipment, and can realize large-scale industrial production.
The utility model provides a portable light and heat sea water desalination hollow fiber membrane, light and heat sea water desalination hollow fiber membrane has the asymmetric structure and the constitution characteristic of super hydrophilic cavity internal surface and light and heat conversion function surface, has characteristics such as cavity self-siphon water supply, moisture transport, black outward appearance, light and heat conversion, high specific surface area, high-efficient evaporation efficiency, resistant solvent, stable performance, can realize that solar energy drives 360 high-efficient light and heat evaporation and condensation of multimedia solution system such as fresh water, solvent and retrieve.
The invention also aims to provide a preparation method of the portable photothermal seawater desalination hollow fiber membrane, which comprises the following steps:
(1) dispersing and dissolving a hydrophilic polymer and nanoparticles in a buffer solution with the pH of 8.5 to prepare a uniform solution, wherein the weight ratio of the hydrophilic polymer: the ratio of the nano particles to the nano particles is 1-20: 0-20, the hollow fiber membrane is circularly washed by a uniform solution for 1-24 hours, and the hollow fiber membrane is cleaned and dried for later use to prepare a super-hydrophilic hollow fiber membrane with an inner surface; the cyclic flushing is any one of the following methods: dead-end filtration, surface coating or circulating filtration treatment;
(2) placing the inner surface super-hydrophilic hollow fiber membrane obtained in the step (1) in a photo-thermal modification material solution atmosphere of 0.1-20 wt% for treatment for 1-24 h to obtain a black appearance hollow fiber membrane with the inner surface super-hydrophilic and the outer surface photo-thermal functions, and cleaning and drying the black appearance hollow fiber membrane for later use;
(3) and (3) soaking the black-appearance hollow fiber membrane with the functions of super-hydrophilicity on the inner surface and photo-thermal on the outer surface, which is obtained in the step (2), in 0.1-20 wt% of hydrophobic polymer solution to realize hydrophobic outer surface construction, and cleaning and drying the membrane for later use.
Preferably, the photothermal membrane in step (1), whether being a hydrophilic or hydrophobic hollow fiber membrane, can be prepared by modifying the surface of the membrane, and the photothermal seawater desalination hollow fiber membrane can be prepared by the following three ways:
the method comprises the following steps: directly using a photo-thermal modification material to perform outer surface functional modification on the hydrophilic base membrane;
approach two: carrying out inner surface hydrophilic modification on a hollow fiber membrane by using a hydrophilic modifier for a hydrophobic base membrane, and then carrying out outer surface functional modification by using a photo-thermal modification material;
approach III: the intrinsic hydrophilicity/hydrophobicity of the basement membrane is not limited, the inner surface of the basement membrane is subjected to hydrophilic modification, and the outer surface of the basement membrane is subjected to functional modification by using a photo-thermal modification material.
Preferably, the hydrophilic polymer in step (1) may be at least one of dopamine, tannic acid, polyvinyl alcohol, polyvinylpyrrolidone, polyether modified silicone, maleic acid copolymer, polyethyleneimine, polyamidoamine, gamma-aminopropyltrimethoxysilane, and gamma-aminopropyltriethoxysilane.
Preferably, the nanoparticles in step (1) may be at least one of titanium dioxide, silicon dioxide, aluminum oxide and ferroferric oxide.
Preferably, the material of the hollow fiber membrane in step (1) may be at least one of polyvinylidene fluoride, polysulfone, polyethersulfone, polyetheretherketone, sulfonated polysulfone, polyether-modified polysulfone, cellulose acetate, polyimide, polyacrylate, polyacrylonitrile, polytetrafluoroethylene, polyethylene, polypropylene, polycarbonate, and polyvinyl alcohol.
Preferably, the average pore diameter of the hollow fiber membrane in the step (1) is 0.01-2.0 μm, the porosity is 20-80%, the membrane thickness is 50-500 μm, and the inner and outer diameters of the hollow fiber are 0.1-2.0 mm and 0.25-3.5 mm respectively.
Preferably, the photothermal modification material in the step (2) may be at least one of graphene, reduced graphene oxide, carbon nanotubes, polypyrrole, polyaniline, black titanium dioxide, ink, MOF, COF, gold nanoparticles, silver nanoparticles, and palladium nanoparticles.
Preferably, the modification manner of the inner surface and the outer surface in the step (2) may be at least one of surface coating, dead-end filtration, circulation filtration treatment, surface cross-linking fixation, surface adsorption and surface deposition.
Preferably, the hydrophobic polymer in step (3) may be at least one of polydimethylsiloxane, polytetrafluoroethylene, fluorine-containing polyacrylate, and polyetherimide.
The invention also aims to provide a preparation method of the portable photothermal seawater desalination hollow fiber membrane equipment, which comprises the following steps:
(1) packaging one end of a beam of photo-thermal seawater desalination hollow fiber membrane with the length of 5-50cm and 10,000 pieces of the photo-thermal seawater desalination hollow fiber membrane in a membrane module shell by adopting epoxy glue or polyurethane glue to prepare a photo-thermal seawater desalination hollow fiber membrane module;
(2) the photo-thermal seawater desalination hollow fiber membrane component is fixed on the supporting body and then placed in the steam collector, and the solar driven purification equipment can be obtained.
Preferably, the support is a heat insulating material and is capable of floating on the surface of the solution; the steam collector is a transparent box body or an umbrella body which is made of glass or transparent polymer films with high optical transmittance and thickness of 0.1-3 mm, the box body can be kept sealed when the steam collector is closed, and the cover plate and the vertical back plate form an included angle of 20-80 degrees when the cover plate is closed.
The invention also aims to provide the portable photothermal seawater desalination hollow fiber membrane and the multimedia solution purification performance of the equipment, namely the application in seawater, saline-alkali water, high-pollution poor-quality water purification and solvent recovery.
More preferably, the specific parameters of the photo-thermal film equipment in the application process are as follows: the sunlight drives without external power and energy consumption.
The invention has the beneficial effects that:
1. the photo-thermal seawater desalination hollow fiber membrane obtained by modifying the inner surface/outer surface can realize photo-thermal seawater desalination by adopting different vertical, inclined, bent and horizontal using methods;
the hollow fiber membrane is used as a polymer base material, the photothermal seawater desalination hollow fiber membrane obtained through inner/outer surface modification treatment comprises an asymmetric structure and composition characteristics of a super-hydrophilic hollow inner surface and a photothermal conversion functional outer surface, not only has excellent self-siphoning performance, but also has the characteristics of uniform black appearance, photothermal conversion, high specific surface area, high-efficiency evaporation efficiency, solvent resistance and the like, when the hollow fiber membrane is vertically used, only the bottom end is contacted with a solution, so that the heat loss can be reduced to the maximum degree, and the advantage of the evaporation specific surface area can be exerted to the maximum degree; meanwhile, the water supply rate and the steam escape rate can be regulated and controlled by regulating and controlling the inner and outer diameter, the inner and outer surface membrane aperture size, the hydrophilic and hydrophobic layer thickness and other parameters, when the water supply rate and the steam escape rate are balanced, the optimal seawater desalination efficiency is achieved, and a new idea is provided for the miniaturization and portable technical innovation of the solar-driven seawater desalination device.
2. The photothermal conversion self-siphon hollow fiber membrane material (namely the photothermal seawater desalination hollow fiber membrane) prepared by utilizing the hydrophobic base material has excellent mechanical strength, and the hydrophobic outer surface has excellent salting-out inhibition effect, so that the photothermal conversion self-siphon hollow fiber membrane material can be used for desalination treatment of high-salinity seawater.
3. The photo-thermal seawater desalination hollow fiber membrane disclosed by the invention is simple in preparation process and safe and efficient in method, and the photo-thermal seawater desalination hollow fiber membrane prepared by utilizing the hydrophobic base material has excellent mechanical strength, can tolerate a complex sewage system and even an organic solvent system, and can be applied to severe environments such as oily sewage purification and solvent recovery on the basis of realizing efficient seawater or brackish water desalination.
4. The portable photothermal seawater desalination hollow fiber membrane and the equipment thereof have more advantages for being used in island regions with sufficient sunlight irradiation, naval vessels and other regions or environments. Such areas have good lighting conditions, but fresh water resources, fossil fuels, or electrical power resources are relatively precious. The invention can relatively reduce the contradiction of the demands and produce fresh water under the condition of not occupying fossil fuel and electric power resources. In addition, the invention has the characteristic of obvious compact structure, is very convenient to carry and install, and meets the use requirements of the regional environment.
Drawings
FIG. 1 is a schematic view of a cross-sectional microstructure of a photo-thermal hollow fiber membrane prepared in example 1;
fig. 2 is a schematic view of the microstructure of the inner and outer surfaces of the photothermal hollow fiber membrane prepared in example 1 (fig. 2a is a schematic view of the microstructure of the inner surface, and fig. 2b is a schematic view of the microstructure of the outer surface);
FIG. 3 is a schematic view showing the contact angle of the inner surface of the photothermal hollow fiber membrane prepared in example 1;
fig. 4 is a data graph before and after the seawater desalination of the photo-thermal hollow fiber membrane prepared in example 1.
Detailed Description
The following examples are merely illustrative of several embodiments of the present invention, and the description thereof is more specific and detailed, but not to be construed as limiting the scope of the invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention. Therefore, the protection scope of the present patent shall be subject to the appended claims. The scope of the present invention includes, but is not limited to, the following examples:
example 1
First, embodiment 1 provides a method for preparing a hollow fiber membrane for photo-thermal seawater desalination, comprising: the super-hydrophilic polysulfone hollow fiber gradient membrane with the average pore diameter of 0.9 mu m, the porosity of 60 percent, the membrane thickness of 200 mu m and the inner/outer diameters of 0.5mm/1.0mm is used as a polymer base membrane, the vacuum filtration technology is utilized for processing for 1 hour, 0.5wt percent of carbon nano tube dispersion liquid is fixed on the outer surface of the hollow fiber membrane through surface adsorption, the black-appearance hollow fiber membrane with the photo-thermal functional layer on the outer surface is obtained, and the photo-thermal seawater desalination hollow fiber membrane can be obtained after cleaning and drying.
The carbon nanotube modified polymer hollow fiber membrane has excellent self-siphoning performance and is uniform and black in appearance. Secondly, this embodiment 1 also provides a portable light and heat sea water desalination device, and the operation method is as follows: packaging one ends of 500 photo-thermal seawater desalination hollow fiber membranes with the length of 10cm in a membrane module shell through epoxy glue or polyurethane glue to prepare a photo-thermal seawater desalination hollow fiber membrane module; fixing the photo-thermal seawater desalination hollow fiber membrane component on a support body, and then placing the support body in a transparent umbrella body steam collector formed by a transparent polymer film with the thickness of 1mm to obtain the portable photo-thermal seawater desalination hollow fiber membrane device.
Example 2
First, embodiment 2 provides a method for preparing a hollow fiber membrane for photo-thermal seawater desalination, comprising: step 1: a hydrophobic polyethylene hollow fiber membrane with the average pore diameter of 2 mu m, the porosity of 80%, the membrane thickness of 50 mu m and the inner/outer diameters of 0.1mm/0.25mm is used as a polymer base membrane, and dopamine and polyethyleneimine are dispersed and dissolved in a buffer solution with the pH of 8.5 to prepare a uniform solution, wherein the weight ratio of dopamine: the ratio of polyethyleneimine to polyethyleneimine is 1: 1; treating for 12h by a surface coating technology so as to fix the uniform solution on the inner surface of the hollow fiber membrane, and cleaning and drying for later use;
step 2: and (3) placing the polymer-based membrane treated in the step (1) in 2 wt% of polypyrrole solution for carrying out external surface vapor deposition modification for 3h to obtain a black-appearance hollow fiber membrane with a photo-thermal functional layer on the external surface, and cleaning and drying to obtain the photo-thermal seawater desalination hollow fiber membrane.
The dopamine/polyethyleneimine-polypyrrole modified polymer hollow fiber membrane (i.e., photo-thermal seawater desalination hollow fiber membrane) prepared by the preparation method of the embodiment 2 has excellent self-siphoning performance, and the appearance is uniform and black.
Secondly, this embodiment 2 also provides a portable light and heat sea water desalination device, and the operation method is as follows: one ends of 10000 photo-thermal seawater desalination hollow fiber membranes with the length of 5cm are packaged in a membrane module shell through epoxy glue or polyurethane glue to prepare the photo-thermal seawater desalination hollow fiber membrane module; the photo-thermal seawater desalination hollow fiber membrane component is fixed on a support body, and then the support body is placed in a transparent box steam collector formed by transparent polymer films, so that the portable photo-thermal seawater desalination hollow fiber membrane device can be obtained.
Example 3
First, embodiment 3 provides a method for preparing a hollow fiber membrane for photo-thermal seawater desalination, comprising: the method comprises the steps of taking an ultra-hydrophilic polyether sulfone hollow fiber membrane with the average pore diameter of 1.0 mu m, the porosity of 40%, the membrane thickness of 200 mu m and the inner/outer diameters of 2.0mm/3.5mm as a polymer base membrane, placing the ultra-hydrophilic polyether sulfone hollow fiber membrane in a polyaniline solution with the weight percent of 20% for outer surface cross-linking, fixing and modifying for 6 hours to obtain a black-appearance hollow fiber membrane with a photo-thermal functional layer on the outer surface, cleaning and drying to obtain the photo-thermal seawater desalination hollow fiber membrane. The polyaniline-modified polymer hollow fiber membrane prepared in this example 3 has excellent self-siphoning performance, and the appearance is uniform and black.
Secondly, this embodiment 3 also provides a portable light and heat sea water desalination device, and the operation method is as follows: packaging one ends of 100 photo-thermal seawater desalination hollow fiber membranes with the lengths of 20cm in a membrane module shell through epoxy glue or polyurethane glue to prepare a photo-thermal seawater desalination hollow fiber membrane module; fixing the photo-thermal seawater desalination hollow fiber membrane component on a support body, and then placing the support body in a glass steam collector to obtain the portable photo-thermal seawater desalination hollow fiber membrane equipment.
Example 4
First, embodiment 4 provides a method for preparing a hollow fiber membrane for photo-thermal seawater desalination, comprising: step 1: hydrophobic polyethylene hollow fiber membranes with the average pore diameter of 0.01 mu m, the porosity of 20 percent, the membrane thickness of 500 mu m and the inner/outer diameter of 1.0mm/3.5mm are used as polymer base membranes, and tannic acid and silicon dioxide are dispersed and dissolved in a buffer solution with the pH of 8.5 to prepare a uniform solution, wherein the weight ratio of tannic acid: the silicon dioxide is 20: 1; fixing the uniform solution on the inner surface of the hollow fiber membrane substrate by treating for 24 hours through a dead-end filtration technology, and cleaning and drying for later use;
step 2: and (3) putting the polymer-based membrane treated in the step (1) into 20 wt% of polypyrrole solution for carrying out external surface vapor deposition modification for 1h to obtain a black-appearance hollow fiber membrane with a photo-thermal functional layer on the external surface, and cleaning and drying to obtain the photo-thermal seawater desalination hollow fiber membrane.
The tannic acid/silicon dioxide-polypyrrole modified polymer hollow fiber membrane prepared by the method has excellent self-siphoning performance and is uniform and black in appearance. Secondly, this embodiment 4 also provides a portable light and heat sea water desalination device, and the operation method is as follows: packaging one ends of 1000 photo-thermal seawater desalination hollow fiber membranes with the lengths of 15cm in a membrane module shell through epoxy glue or polyurethane glue to prepare a photo-thermal seawater desalination hollow fiber membrane module; the photo-thermal seawater desalination hollow fiber membrane component is fixed on a support body, and then the support body is placed in a transparent umbrella steam collector formed by a transparent polymer film, so that the portable photo-thermal seawater desalination hollow fiber membrane device can be obtained.
Example 5
First, embodiment 5 provides a method for preparing a hollow fiber membrane for photo-thermal seawater desalination, comprising: step 1: the method comprises the steps of taking a hydrophobic polypropylene hollow fiber membrane with the average pore diameter of 0.08 mu m, the porosity of 80%, the membrane thickness of 250 mu m and the inner/outer diameters of 1.5mm/2.25mm as a polymer base membrane, dispersing and dissolving dopamine and ferroferric oxide in a buffer solution with the pH value of 8.5 to prepare a uniform solution, wherein the weight ratio of dopamine: the ratio of ferroferric oxide to ferroferric oxide is 1: 1; fixing the uniform solution on the inner surface of the hollow fiber membrane substrate by treating for 1h through a dead-end filtration technology, and cleaning and drying for later use;
step 2: and (3) putting the polymer base membrane treated in the step (1) into 0.1 wt% of polypyrrole solution for carrying out external surface vapor deposition modification for 24h to obtain a black-appearance hollow fiber membrane with a photo-thermal functional layer on the external surface, and cleaning and drying to obtain the photo-thermal seawater desalination hollow fiber membrane.
The dopamine/ferroferric oxide-polypyrrole modified polymer hollow fiber membrane prepared by the method of the embodiment has excellent self-siphoning performance and is uniform and black in appearance.
Secondly, this embodiment 5 also provides a portable light and heat sea water desalination device, and the operation method is as follows:
packaging one ends of 5000 photo-thermal seawater desalination hollow fiber membranes with the lengths of 5cm in a membrane module shell through epoxy glue or polyurethane glue to prepare a photo-thermal seawater desalination hollow fiber membrane module; the photo-thermal seawater desalination hollow fiber membrane component is fixed on a support body, and then the support body is placed in a transparent umbrella steam collector formed by a transparent polymer film, so that the portable photo-thermal seawater desalination hollow fiber membrane device can be obtained.
Example 6
First, embodiment 6 provides a method for preparing a hollow fiber membrane for photo-thermal seawater desalination, comprising: step 1: a hydrophobic polyvinylidene fluoride hollow fiber membrane with the average pore diameter of 0.05 mu m, the porosity of 50%, the membrane thickness of 150 mu m and the inner/outer diameters of 1.5mm/2.5mm is used as a polymer base membrane, and dopamine and polyethyleneimine are dispersed and dissolved in a buffer solution with the pH value of 8.5 to prepare a uniform solution, wherein the weight ratio of dopamine: the ratio of polyethyleneimine to polyethyleneimine is 1: 1; fixing the uniform solution on the inner surface of the hollow fiber membrane substrate by treating for 12 hours through a dead-end filtration technology, and cleaning and drying for later use;
step 2: placing the polymer base membrane treated in the step 1 in a mixed solution of 5 wt% of reduced graphene oxide and carbon nanotubes (the mass ratio is 1:1), performing suction filtration for 1h to perform external modification to obtain a black-appearance hollow fiber membrane with a photo-thermal functional layer on the outer surface, and cleaning and drying the black-appearance hollow fiber membrane for later use;
and step 3: and soaking the prepared black-appearance hollow fiber membrane with the functions of super-hydrophilicity on the inner surface and photo-thermal on the outer surface in 0.1 wt% of polydimethylsiloxane solution to realize the construction of the hydrophobic outer surface, and cleaning and drying to obtain the photo-thermal seawater desalination hollow fiber membrane.
The dopamine/polyethyleneimine-reduced graphene oxide/carbon nanotube modified polymer hollow fiber membrane prepared by the method has excellent self-siphoning performance and is uniform and black in appearance.
Secondly, this embodiment 6 also provides a portable light and heat sea water desalination device, and the operation method is as follows:
packaging one ends of 500 photo-thermal seawater desalination hollow fiber membranes with the length of 25cm in a membrane module shell through epoxy glue or polyurethane glue to prepare a photo-thermal seawater desalination hollow fiber membrane module; the photo-thermal seawater desalination hollow fiber membrane component is fixed on a support body, and then the support body is placed in a transparent box steam collector formed by transparent polymer films, so that the portable photo-thermal seawater desalination hollow fiber membrane device can be obtained.
Example 7
First, embodiment 7 provides a method for preparing a hollow fiber membrane for photo-thermal seawater desalination, comprising: step 1: an ultra-hydrophobic polyvinylidene fluoride hollow fiber membrane (PVDF 10, Nanjing Jiale clean Membrane science and technology Co., Ltd.) with the average pore diameter of 0.01 μm, the porosity of 30%, the membrane thickness of 300 μm and the inner/outer diameters of 1.2mm/1.5mm is adopted as a polymer base membrane, tannic acid and polyethyleneimine are dispersed and dissolved in a buffer solution with the pH value of 8.5 to prepare a uniform solution, wherein the content of tannic acid: the ratio of polyethyleneimine to polyethyleneimine is 1: 1; fixing the uniform solution on the inner surface of the hollow fiber membrane substrate by a circulating filtration technology for 12 hours, and cleaning and drying for later use;
step 2: placing the polymer base membrane treated in the step 1 in a 15 wt% carbon nanotube solution for outer surface coating modification for 24h to obtain a black appearance hollow fiber membrane with a photo-thermal functional layer on the outer surface, and cleaning and drying the black appearance hollow fiber membrane for later use;
and step 3: and (3) soaking the black-appearance hollow fiber membrane with the functions of super-hydrophilicity on the inner surface and photo-thermal on the outer surface, which is prepared in the step (2), in 20 wt% of fluorine-containing polyacrylate solution to realize the construction of the hydrophobic outer surface, and cleaning and drying to obtain the photo-thermal seawater desalination hollow fiber membrane.
The tannic acid/polyethyleneimine-carbon nanotube modified polymer hollow fiber membrane prepared by the method has excellent self-siphoning performance and is uniform and black in appearance.
Secondly, this embodiment 7 also provides a portable light and heat sea water desalination device, and the operation method is as follows:
packaging one ends of 8000 black hollow fiber membranes (namely photo-thermal seawater desalination hollow fiber membranes) with the lengths of 10cm in a membrane module shell through epoxy glue or polyurethane glue to prepare a photo-thermal seawater desalination hollow fiber membrane module; the photo-thermal seawater desalination hollow fiber membrane component is fixed on a support body, and then the support body is placed in a transparent box steam collector formed by transparent polymer films, so that the portable photo-thermal seawater desalination hollow fiber membrane device can be obtained.
Example 8
First, embodiment 8 provides a method for preparing a hollow fiber membrane for photo-thermal seawater desalination, comprising: step 1: polyimide hollow fiber membranes with the average pore diameter of 1.0 mu m, the porosity of 30 percent, the membrane thickness of 50 mu m and the inner/outer diameters of 0.1mm/1.5mm are used as polymer base membranes, and tannic acid and polyether modified organic silicon are dispersed and dissolved in a buffer solution with the pH of 8.5 to prepare a uniform solution, wherein the molar ratio of tannic acid: the polyether modified organic silicon is 10: 1; fixing the uniform solution on the inner surface of the hollow fiber membrane substrate by surface coating technology for 4 hours, and cleaning and drying for later use;
step 2: and (3) placing the polymer base membrane treated in the step (1) in 15 wt% of ink solution for carrying out external surface adsorption modification for 12h to obtain a black-appearance hollow fiber membrane with a photo-thermal functional layer on the external surface, and cleaning and drying to obtain the photo-thermal seawater desalination hollow fiber membrane.
The hollow fiber membrane of the tannic acid/polyether modified organosilicon-ink modified polymer prepared by the method has excellent self-siphoning performance and is uniform and black in appearance. Secondly, this embodiment 8 also provides a portable light and heat sea water desalination device, and the operation method is as follows:
packaging one ends of 200 black appearance hollow fiber membranes (namely photo-thermal seawater desalination hollow fiber membranes) with the lengths of 50cm in a membrane module shell through epoxy glue or polyurethane glue to prepare the photo-thermal seawater desalination hollow fiber membrane module; the photo-thermal seawater desalination hollow fiber membrane component is fixed on a support body, and then the support body is placed in a transparent box steam collector formed by transparent polymer films, so that the portable photo-thermal seawater desalination hollow fiber membrane device can be obtained.
Example 9
First, embodiment 9 provides a method for preparing a hollow fiber membrane for photo-thermal seawater desalination, comprising:
step 1: a polyacrylate hollow fiber membrane with the average pore diameter of 1.0 mu m, the porosity of 30 percent, the membrane thickness of 50 mu m and the inner/outer diameters of 0.1mm/1.5mm is used as a polymer base membrane, and tannic acid, polyether modified organic silicon and silicon dioxide are dispersed and dissolved in a buffer solution with the pH of 8.5 to prepare a uniform solution, wherein the molar ratio of tannic acid: polyether modified silicone: the silicon dioxide is 10:1: 1; fixing the uniform solution on the inner surface of the hollow fiber membrane substrate by treating for 6 hours through a dead-end filtration technology, and cleaning and drying for later use;
step 2: coating and modifying the outer surface of the polymer base membrane treated in the step (1) by using a 15 wt% black titanium dioxide solution for 6 hours to obtain a black-appearance hollow fiber membrane with a photo-thermal functional layer on the outer surface, and cleaning and drying the black-appearance hollow fiber membrane for later use;
and step 3: and (3) soaking the black-appearance hollow fiber membrane with the functions of super-hydrophilicity on the inner surface and photo-thermal on the outer surface, which is prepared in the step (2), in a 10 wt% polytetrafluoroethylene solution to realize the construction of the hydrophobic outer surface, and cleaning and drying to obtain the photo-thermal seawater desalination hollow fiber membrane.
The tannic acid/polyether modified organosilicon/silica-black titanium dioxide modified polymer hollow fiber membrane prepared by the method has excellent self-siphoning performance and is uniform and black in appearance.
Secondly, this embodiment 9 also provides a portable light and heat sea water desalination device, and the operation method is as follows:
packaging one ends of 300 black appearance hollow fiber membranes (namely photo-thermal seawater desalination hollow fiber membranes) with the length of 40cm in a membrane module shell through epoxy glue or polyurethane glue to prepare the photo-thermal seawater desalination hollow fiber membrane module; fixing the photo-thermal seawater desalination hollow fiber membrane component on a support body, and then placing the support body in a glass plate steam collector with the thickness of 2mm to obtain the photo-thermal self-siphon hollow fiber membrane device.
Example 10
First, embodiment 10 provides a method for preparing a hollow fiber membrane for photo-thermal seawater desalination: step 1: a polyacrylonitrile hollow fiber membrane with the average pore diameter of 1.0 mu m, the porosity of 30%, the membrane thickness of 50 mu m and the inner/outer diameters of 1.0mm/1.5mm is used as a polymer base membrane, and dopamine and titanium dioxide are dispersed and dissolved in a buffer solution with the pH value of 8.5 to prepare a uniform solution, wherein the weight ratio of dopamine: the ratio of titanium dioxide is 2: 1; fixing the uniform solution on the inner surface of the hollow fiber membrane substrate by treating for 24 hours through a dead-end filtration technology, and cleaning and drying for later use;
step 2: and (3) performing outer surface coating modification on the polymer base membrane treated in the step (1) by using a 10 wt% black titanium dioxide solution for 24 hours to obtain a black appearance hollow fiber membrane with a photo-thermal functional layer on the outer surface, and cleaning and drying to obtain the photo-thermal seawater desalination hollow fiber membrane.
The dopamine/titanium dioxide-black titanium dioxide modified polymer hollow fiber membrane prepared by the method has excellent self-siphoning performance and is uniform and black in appearance.
Secondly, this embodiment 10 also provides a portable light and heat sea water desalination device, and the operation method is as follows:
packaging one end of the prepared black appearance hollow fiber membrane (namely the photo-thermal seawater desalination hollow fiber membrane) in a membrane component shell through epoxy glue or polyurethane glue to prepare a photo-thermal seawater desalination hollow fiber membrane component; fixing the photo-thermal seawater desalination hollow fiber membrane component on a support body, and then placing the support body in a transparent plastic product steam collector to obtain the photo-thermal self-siphon hollow fiber membrane device.
The data are detailed in tables 1 and 2.
TABLE 1 siphon height test of photo-thermal hollow fiber membrane (i.e. "photo-thermal seawater desalination hollow fiber membrane" for short) corresponding to different embodiments
TABLE 2 test of photothermal evaporation efficiency of photothermal hollow fiber membrane corresponding to different examples
It should be noted that, as can be seen from the test results in tables 1 and 2, the photo-thermal seawater desalination hollow fiber membrane prepared by modifying the inner/outer surface of the hydrophilic hollow fiber membrane or the hydrophobic hollow fiber membrane as the base material can achieve the same technical effect of self-siphoning water supply, and can achieve the same technical effect of self-siphoning water supply in an environment with a temperature of 27 ℃ and a humidity of 67 ± 10% and a power of 1kW/m2Under light intensity, the photo-thermal self-siphon hollow fiber membrane (i.e. photo-thermal seawater desalination hollow fiber membrane) has excellent photo-thermal conversion and steam escape performances, and the water evaporation efficiency is higher than 2.3 kg/(m)2H); in order to further prove the photothermal separation effect, the data before and after seawater desalination show that compared with the stock solution, no obvious ions exist in the recovered fresh water, and the photothermal seawater desalination performance is excellent.
Claims (10)
1. A preparation method of a portable photo-thermal seawater desalination hollow fiber membrane is characterized by comprising the following steps: the method comprises the following steps:
step 1): dispersing and dissolving a hydrophilic polymer and nanoparticles in a buffer solution with the pH of 8.5 to prepare a uniform solution, wherein the weight ratio of the hydrophilic polymer: the ratio of the nano particles to the nano particles is 1-20: 0-20, the hollow fiber membrane is circularly washed by a uniform solution for 1-24 hours, and the hollow fiber membrane is cleaned and dried for later use to prepare a super-hydrophilic hollow fiber membrane with an inner surface;
step 2): placing the inner surface super-hydrophilic hollow fiber membrane obtained in the step 1) in an atmosphere of 0.1-20 wt% of photo-thermal modified material solution, and treating for 1-24 h in a surface adsorption, surface vapor deposition, surface crosslinking and fixing, suction filtration and/or coating modification mode to obtain the hollow fiber membrane with the inner surface super-hydrophilic and outer surface photo-thermal functions, and cleaning and drying for later use.
2. The method of claim 1, wherein: further comprising step 3): soaking the hollow fiber membrane with the inner surface super-hydrophilic and the outer surface photo-thermal functions obtained in the step 2) in 0.1-20 wt% of hydrophobic polymer solution to construct a hydrophobic outer surface, and cleaning and drying to obtain the photo-thermal seawater desalination hollow fiber membrane.
3. The method of claim 1, wherein: the hollow fiber membrane in the step 1) is made of the following materials: one or more of polyvinylidene fluoride, polysulfone, polyethersulfone, polyetheretherketone, sulfonated polysulfone, polyether modified polysulfone, cellulose acetate, polyimide, polyacrylate, polyacrylonitrile, polytetrafluoroethylene, polyethylene, polypropylene, polycarbonate, and polyvinyl alcohol;
the average pore diameter range of the hollow fiber membrane is 0.01-2.0 mu m, the porosity is 20-80%, the membrane thickness range is 50-500 mu m, and the inner diameter range and the outer diameter range of the hollow fiber are 0.1-2.0 mm and 0.25-3.5 mm respectively;
the hydrophilic polymer is: one or more of dopamine, tannic acid, polyvinyl alcohol, polyvinylpyrrolidone, polyether modified silicone, maleic acid copolymer, polyethyleneimine, polyamidoamine, gamma-aminopropyltrimethoxysilane, gamma-aminopropyltriethoxysilane;
the nano-particles are: one or more of titanium dioxide, silicon dioxide, aluminum oxide and ferroferric oxide;
the cyclic flushing is any one of the following methods: dead-end filtration, surface coating or recirculation filtration processes.
4. The method of claim 1, wherein: the photo-thermal modification material in the step 2) is as follows: a combination of one or more of graphene, reduced graphene oxide, carbon nanotubes, polypyrrole, polyaniline, black titanium dioxide, ink, MOF, COF, gold nanoparticles, silver nanoparticles, palladium nanoparticles;
the modification treatment mode of the inner surface and the outer surface of the hollow fiber membrane can adopt one or more of surface coating, dead-end filtration, circulating filtration treatment, surface cross-linking fixation, surface adsorption, surface deposition and suction filtration.
5. The method of claim 2, wherein: the hydrophobic polymer solution in the step 3) is a solution prepared by one or a combination of more of polydimethylsiloxane, polytetrafluoroethylene, fluorine-containing polyacrylate and polyetherimide.
6. The utility model provides a portable light and heat sea water desalination hollow fiber membrane which characterized in that: it is prepared by the preparation method of any one of claims 1 to 5.
7. The utility model provides a portable light and heat sea water desalination device, includes supporter, membrane module casing, steam collector, its characterized in that: the hollow fiber membrane for photothermal seawater desalination of claim 6, wherein one end of the hollow fiber membranes for photothermal seawater desalination is enclosed in a membrane module housing, the membrane module housing is fixed on a support body, and the support body is installed in a steam collector.
8. The photothermal seawater desalination apparatus according to claim 7, wherein: the steam collector is transparent and sealed, and one end of the steam collector is provided with a collected water outlet; the support body is made of a heat insulating material; the steam collector is a transparent box body or an umbrella body formed by 0.1-3 mm of glass or transparent polymer films.
9. The method for manufacturing a light-heat seawater desalination plant as defined in claim 7 or 8, wherein: comprises the following steps: step (1): packaging one end of a beam of photo-thermal seawater desalination hollow fiber membrane with the length of 5-50cm and 10,000 pieces of the photo-thermal seawater desalination hollow fiber membrane in a membrane module shell by adopting epoxy glue or polyurethane glue to prepare a photo-thermal seawater desalination hollow fiber membrane module;
step (2): and fixing the photo-thermal seawater desalination hollow fiber membrane component on a support body, and then placing the support body in a steam collector to obtain the photo-thermal seawater desalination device.
10. The use of the hollow fiber membrane for photothermal seawater desalination of claim 6 for purification of seawater, saltwater, highly polluted and poor quality water and recovery of solvents.
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| CN117488480A (en) * | 2024-01-03 | 2024-02-02 | 东华大学 | Asymmetric functional fiber membrane and preparation method and application thereof |
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