CN111573780A - Photothermal membrane distiller, preparation method and application thereof, and water treatment equipment - Google Patents
Photothermal membrane distiller, preparation method and application thereof, and water treatment equipment Download PDFInfo
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- CN111573780A CN111573780A CN202010274593.6A CN202010274593A CN111573780A CN 111573780 A CN111573780 A CN 111573780A CN 202010274593 A CN202010274593 A CN 202010274593A CN 111573780 A CN111573780 A CN 111573780A
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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
- C02F1/44—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis
- C02F1/447—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis by membrane distillation
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01D61/00—Processes of separation using semi-permeable membranes, e.g. dialysis, osmosis or ultrafiltration; Apparatus, accessories or auxiliary operations specially adapted therefor
- B01D61/36—Pervaporation; Membrane distillation; Liquid permeation
- B01D61/364—Membrane distillation
Abstract
The invention discloses a photothermal membrane distiller, which comprises a hollow fiber membrane body and a support body, wherein the hollow fiber membrane body is fixed on the support body in an arch bridge-shaped structure, two end parts of the hollow fiber membrane body are respectively inserted into the support body and penetrate out of the surface of the support body, the support body is a heat insulating material and can float on water, and the hollow fiber membrane body comprises a surface hydrophilic hollow fiber membrane and polydopamine and carbon material particles loaded on the surface hydrophilic hollow fiber membrane. The invention also discloses a preparation method of the photothermal membrane distiller. The invention also discloses an application of the photothermal membrane distiller. The invention also discloses water treatment equipment.
Description
Technical Field
The invention relates to the technical field of photothermal conversion, in particular to a photothermal membrane distiller, a preparation method and application thereof, and water treatment equipment.
Background
The water crisis was listed as world crisis 5 by the davis world economic forum global risk report in 2018. The economic and feasible fresh water obtaining technology is a problem which is always faced by human beings, and the seawater desalination is a strategic choice for solving the shortage of fresh water resources in China. The traditional low-temperature multi-effect distillation and reverse osmosis membrane technology at present has the problems of high energy consumption and high cost, and reverse osmosis has high requirements on pretreatment of seawater and is generally only suitable for treating seawater with low salt content. How to realize low-cost and high-efficiency seawater desalination by the design of a novel membrane material and a membrane process is a social problem facing the world.
The photo-thermal evaporation technology appearing in recent years is a novel low-energy consumption seawater desalination mode. The core of the method is that a material with high photo-thermal conversion efficiency is designed and synthesized, solar energy is efficiently converted into heat energy, water molecules on the surface of the material are locally and intensively heated, and then fresh water is obtained through condensation and collection. Early, researchers dispersed precious metal or carbon nanoparticles directly in salt solution, and steam quickly detached from the surface of the material after it was generated on the surface of the photothermal conversion material, but due to the higher thermal conductivity of water (-0.599W m)-1K-1) Most of the heat is lost in the form of heat conduction, so that the photothermal conversion efficiency is reduced; in order to reduce heat conduction loss and improve the photothermal conversion efficiency, inspired by human sweat evaporation, the hydrophobic photothermal conversion material is directly floated on the water surface to realize interface evaporation, but because the surface temperature of the material is higher than the temperature of the environment and the water body below the material, heat conduction, heat radiation and heat convection loss still exist in the process; in order to further reduce heat conduction loss and improve the photothermal conversion efficiency, a layer of heat insulation material is added between the photothermal conversion material and the water body, so that the photothermal conversion material is prevented from being in direct contact with the water body below, and water is supplied to the photothermal conversion material through cotton fibers and the like. Therefore, the two-dimensional photothermal conversion materials are dispersed, directly float or flatly spread on the support body to realize seawater desalination, and the evaporation performance has certain limitation.
Disclosure of Invention
In view of the above, there is a need to provide a low-cost, low-energy-consumption photothermal membrane distiller for efficient water evaporation, a preparation method and applications thereof, and a water treatment device, aiming at the limitations of the existing photothermal conversion materials.
The photothermal membrane distiller comprises a hollow fiber membrane body and a support body, wherein the hollow fiber membrane body is fixed on the support body in an arch bridge-shaped structure, two end parts of the hollow fiber membrane body are respectively inserted into the support body and penetrate out of the surface of the support body, the support body is a heat insulating material and can float on water, and the hollow fiber membrane body comprises a surface hydrophilic hollow fiber membrane and polydopamine and carbon material particles loaded on the surface hydrophilic hollow fiber membrane.
In one embodiment, the support has a plurality of hollow fiber membrane bodies thereon.
In one embodiment, the heights of the tips of the hollow fiber membrane bodies of at least two arch bridge-like structures are different.
In one embodiment, the porosity of the hollow fiber membrane body is 75% to 85%.
In one embodiment, the average pore diameter of the hollow fiber membrane body is 100nm to 300 nm.
In one embodiment, the wall thickness of the hollow fiber membrane body is 100-500 μm.
In one embodiment, the outer diameter of the hollow fiber membrane body is 2mm to 3 mm.
In one embodiment, the surface hydrophilic hollow fiber membrane has a multi-stage fiber structure in which nano-scale and micro-scale coexist.
In one embodiment, the carbon material is selected from one or more of carbon nanotubes, graphene oxide, reduced graphene oxide, and activated carbon.
In one embodiment, the material of the surface hydrophilic hollow fiber membrane is selected from one or more of polytetrafluoroethylene, polyvinylidene fluoride, polypropylene, polysulfone and polyethersulfone.
The preparation method of the photothermal membrane distiller comprises the following steps:
soaking the surface hydrophilic hollow fiber membrane in a dopamine active component solution, so that dopamine is polymerized on the surface hydrophilic hollow fiber membrane to form polydopamine;
soaking the surface hydrophilic hollow fiber membrane loaded with polydopamine in dispersion liquid containing a carbon material, adding a dopamine active component solution into the dispersion liquid containing the carbon material, soaking for a certain time, taking out and airing to obtain a hollow fiber membrane body;
and respectively inserting the two ends of the hollow fiber membrane body into the support body, and respectively enabling the two ends to penetrate out of the surface of the support body.
Use of a photothermal film distiller for floating on water, absorbing light and evaporating water.
A water treatment device comprises the photothermal membrane distiller.
The photothermal membrane distiller of the invention uses polydopamine as a photothermal conversion material, and converts light energy (such as solar energy) into heat energy by utilizing the photothermal conversion performance of the polydopamine. The invention creatively provides a method for preparing the poly-dopamine solar cell, which uses a hollow fiber membrane as a carrier of a photo-thermal conversion material, poly-dopamine is loaded on the hollow fiber membrane, the hollow fiber membrane can absorb water, then the water is evaporated by utilizing heat generated by the poly-dopamine, the hollow fiber membrane is fixed on a support body and floats in water, and therefore, the water can be evaporated by utilizing the water effect of the hollow fiber membrane and the photo-thermal conversion property of the poly-dopamine. Because the hydrophilic hollow fiber membrane has abundant fiber structures, water can be drawn by means of the capillary action between fibers without other auxiliary materials, and the simplicity of the whole structure is improved. In addition, the inventors found that the water evaporation efficiency can be further enhanced by supporting a carbon material on the hollow fiber membrane and blending the carbon material with polydopamine. The inventors also propose that the surface hydrophilicity of the hollow fiber membrane is improved by performing hydrophilic modification on the hollow fiber membrane, thereby improving the water-absorbing capacity of the hollow fiber membrane. Compared with the photo-thermal conversion material directly made of noble metal, the photo-thermal membrane distiller greatly reduces the operation cost.
Furthermore, the hydrophilic hollow fiber membrane has certain self-supporting performance, and the two ends of the hollow fiber membrane are inserted into the support body, so that the two ends of the hydrophilic hollow fiber membrane can play a role in water drawing, and the water drawing efficiency is improved. In addition, the hydrophilic hollow fiber membrane is supported on the support body in an arch bridge structure, so that compared with a two-dimensional photothermal conversion structure or an upright photothermal conversion material, the light absorption area can be increased, 360-degree light absorption is realized, and water evaporation of 360-degree surfaces is realized; energy from the underlying support material may also be absorbed, further promoting steam generation.
Drawings
FIG. 1 is a schematic view of a photothermal membrane distiller designed for hollow fiber membranes prepared in example 1.
FIG. 2 is a scanning electron micrograph of a cross section of the hollow fiber membrane prepared in example 1.
Fig. 3 is a scanning electron microscope photograph of the outer surface of the hollow fiber membrane body prepared in example 1.
Fig. 4 is a scanning electron micrograph of the inner surface of the hollow fiber membrane body prepared in example 1.
Fig. 5 is a water contact angle of the outer surface of the hollow fiber membrane body prepared in example 1.
FIG. 6 is a comparison of the infrared curves of unmodified, hydrophilically modified, PDA/CNT modified PTFE hollow fiber membranes of example 1.
Fig. 7 is a graph showing data on photothermal conversion performance of the photothermal film distiller prepared in example 1.
Detailed Description
To facilitate an understanding of the invention, the invention will now be described more fully with reference to the accompanying drawings. Preferred embodiments of the present invention are shown in the drawings. This invention may, however, be embodied in many different forms and should not be construed as limited to the embodiments set forth herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used in the description of the invention herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. As used herein, the term "and/or" includes any and all combinations of one or more of the associated listed items.
Referring to fig. 1, an embodiment of the present invention provides a photothermal membrane distiller, including a hollow fiber membrane body and a support body, wherein the hollow fiber membrane body is fixed on the support body in an arch bridge-shaped structure, two ends of the hollow fiber membrane body are respectively inserted into the support body and penetrate through a surface of the support body, the support body is a heat insulating material and can float on water, and the hollow fiber membrane body includes a surface hydrophilic hollow fiber membrane and poly-dopamine and carbon material particles loaded on the surface hydrophilic hollow fiber membrane.
The photothermal membrane distiller of the invention uses Polydopamine as a photothermal conversion material, and converts light energy (such as solar energy) into heat energy by utilizing the photothermal conversion performance of Polydopamine (PDA). The invention creatively provides a method for preparing the poly-dopamine solar cell, which uses a hollow fiber membrane as a carrier of a photo-thermal conversion material, poly-dopamine is loaded on the hollow fiber membrane, the hollow fiber membrane can absorb water, then the water is evaporated by utilizing heat generated by the poly-dopamine, the hollow fiber membrane is fixed on a support body and floats in water, and therefore, the water can be evaporated by utilizing the water effect of the hollow fiber membrane and the photo-thermal conversion property of the poly-dopamine. Because the hydrophilic hollow fiber membrane has abundant fiber structures, water can be drawn by means of the capillary action between fibers without other auxiliary materials, and the simplicity of the whole structure is improved. In addition, the inventors found that the water evaporation efficiency can be further enhanced by supporting a carbon material on the hollow fiber membrane and blending the carbon material with polydopamine. The inventors also propose that the surface hydrophilicity of the hollow fiber membrane is improved by performing hydrophilic modification on the hollow fiber membrane, thereby improving the water-absorbing capacity of the hollow fiber membrane. Compared with the photo-thermal conversion material directly made of noble metal, the photo-thermal membrane distiller greatly reduces the operation cost.
Furthermore, the hydrophilic hollow fiber membrane has certain self-supporting performance, and the two ends of the hollow fiber membrane are inserted into the support body, so that the two ends of the hydrophilic hollow fiber membrane can play a role in water drawing, and the water drawing efficiency is improved. In addition, the hydrophilic hollow fiber membrane is supported on the support body in an arch bridge structure, so that compared with a two-dimensional photothermal conversion structure or an upright photothermal conversion material, the light absorption area can be increased, 360-degree light absorption is realized, and water evaporation of 360-degree surfaces is realized; energy from the underlying support material may also be absorbed, further promoting steam generation.
In one embodiment, the support has a plurality of hollow fiber membrane bodies thereon. Preferably, the number of the hollow fiber membrane bodies on the support is more than two, and for example, the number may be 3 or 4 … …. Preferably, the arrangement of the plurality of hollow fiber membrane bodies on the support is a staggered arrangement. When the speed of water evaporation is very fast, can form saturated steam around the hollow fiber membrane body, saturated steam is difficult for dispersing, adopts the mode of height dislocation array, has improved the speed that steam flows, can promote the faster diffusion to the distant place from around the hollow fiber membrane body of steam that water evaporation formed to improve water evaporation efficiency. In one embodiment, the heights of the tips of the hollow fiber membrane bodies of at least two arch bridge-like structures are different. In one embodiment, the plurality of hollow fiber membrane bodies are randomly arranged on the support, or, in another embodiment, the plurality of hollow fiber membrane bodies are arranged in a side-by-side manner, that is, the arch foot connecting lines of the arch bridge structures are parallel to each other. Preferably, the heights of the top ends of two adjacent hollow fiber membrane bodies are different, and a plurality of hollow fiber membrane bodies form a structure of 'low-high- … …' on the support. Preferably, the height of the hollow fiber membrane body close to the edge position of the support body is smaller than that of the hollow fiber membrane body close to the center position of the support body, so that the shielding of the hollow fiber membrane body at the edge position on light is avoided, and the light absorption capacity of the whole photothermal membrane distiller is improved.
The surface hydrophilic hollow fiber membrane is provided with a hydrophilic specific material or a hydrophilic material obtained by performing hydrophilic modification on a non-hydrophilic fiber membrane.
In one embodiment, the material of the surface hydrophilic hollow fiber membrane is selected from one or more of Polytetrafluoroethylene (PTFE), polyvinylidene fluoride (PVDF), polypropylene, polysulfone, and polyethersulfone. That is, the surface hydrophilic hollow fiber membrane is obtained by surface hydrophilic modification of a hydrophobic fiber membrane such as Polytetrafluoroethylene (PTFE), polyvinylidene fluoride (PVDF), polypropylene, polysulfone, or polyethersulfone. The middle layer is a hydrophobic layer and is used as a water vapor circulation channel, and the hydrophilic surface layer is favorable for drawing water and has high water circulation and high-efficiency water evaporation effects. Preferably, the material of the surface hydrophilic hollow fiber membrane is selected from polytetrafluoroethylene, and polyvinylidene fluoride has a strong water conveying speed as a water channel.
From the structural point of view, the fiber network structure of the hollow fiber membrane body is a key factor for determining the water transmission efficiency of the hollow fiber membrane body. The porosity, pore size and wall thickness of the hollow fiber membrane body (the thickness of the ring structure of the material of the hollow fiber membrane body) determine the fiber distribution in the fiber network structure.
In one embodiment, the porosity of the hollow fiber membrane body may be 75% to 85%. Specifically, the porosity of the hollow fiber membrane body may be 75% to 80% or 80% to 85%. Here, the porosity of the hollow fiber body refers to the porosity of the material itself, excluding the volume of the hollow ring.
In one embodiment, the average pore diameter of the hollow fiber membrane body may be 100nm to 300 nm. Specifically, the average pore diameter of the hollow fiber membrane body can be 100 nm-150 nm, 150 nm-200 nm, 200 nm-250 nm or 250 nm-300 nm.
In one embodiment, the wall thickness of the hollow fiber membrane body may be 100 μm to 500 μm. Specifically, the wall thickness of the hollow fiber membrane body may be 100 to 150. mu.m, 150 to 100. mu.m, 200 to 250. mu.m, 250 to 300. mu.m, 300 to 350. mu.m, 350 to 400. mu.m, 2400 to 450. mu.m, or 450 to 500. mu.m.
In one embodiment, the outer diameter of the hollow fiber membrane body may be 2mm to 3 mm. Specifically, the outer diameter of the hollow fiber membrane body may be 2mm to 2.5mm or 2.5mm to 3 mm.
In one embodiment, the surface hydrophilic hollow fiber membrane has a multi-stage fiber structure in which nano-scale and micro-scale coexist. Through different fiber thicknesses and proper porosity, extremely strong capillary force is formed in the hollow fiber membrane body, and the strength of water drawn and the water transmission speed are improved.
In one embodiment, the carbon material may be selected from one or more of Carbon Nanotubes (CNTs), graphene oxide, reduced graphene oxide, and activated carbon.
The support has a heat-insulating function and can be selected from foams, for example, which have the advantages of light weight, easy availability and strong heat-insulating property. In one embodiment, the foam may include, but is not limited to, one or more of Polystyrene (PS) foam, PS foam covered with polyvinylidene fluoride (PVDF) film, and PS foam covered with carbon cloth. The PVDF film or the carbon cloth is coated on the foam, so that the mechanical strength of the foam can be improved, and the service life of the photothermal film distiller is prolonged.
The embodiment of the invention also provides a preparation method of the photothermal film distiller, which comprises the following steps:
s100, soaking the surface hydrophilic hollow fiber membrane in a dopamine active component solution to enable dopamine to be polymerized on the surface hydrophilic hollow fiber membrane to form polydopamine;
s200, soaking the surface hydrophilic hollow fiber membrane loaded with polydopamine in dispersion liquid containing a carbon material, adding a dopamine active component solution into the dispersion liquid containing the carbon material, soaking for a certain time, taking out and airing to obtain a hollow fiber membrane body;
s300, respectively inserting the two ends of the hollow fiber membrane body into the support body, and enabling the two ends to respectively penetrate out of the surface of the support body.
In the step S100, poly-dopamine is loaded in a manner that dopamine is directly self-polymerized on the surface hydrophilic hollow fiber membrane, so that poly-dopamine can be cross-linked in the whole structure network of the hollow fiber membrane, and the poly-dopamine loading amount of the surface hydrophilic hollow fiber membrane is increased. On the other hand, the surface hydrophilic hollow fiber membrane can be made to have a large viscosity before the carbon material is loaded, thereby facilitating the adsorption of the carbon material on the surface hydrophilic hollow fiber membrane.
In one embodiment, the dopamine active ingredient solution comprises dopamine and Tris buffer. In one embodiment, the concentration of dopamine is 1g/L to 2 g/L. In one embodiment, the pH value of the Tris buffer is 8-9, and the self-polymerization of dopamine on the surface hydrophilic hollow fiber membrane is easier to perform at the pH value, and the polymerization degree is higher.
In one embodiment, the soaking time of the surface hydrophilic hollow fiber membrane in the dopamine active component solution can be 2-24 h.
The surface hydrophilic hollow fiber membrane can be a membrane with self-hydrophilic property, and can also be a hydrophilic membrane obtained by hydrophilic modification of the hollow fiber membrane.
In one embodiment, the method of hydrophilic modification of the hollow fiber membrane may include: soaking a hollow fiber membrane in a hydrophilic modification liquid so that the hydrophilic modification liquid is soaked in the hollow fiber membrane; and heating the hollow fiber membrane immersed in the hydrophilic modification liquid. The heating temperature may be 40 ℃ to 90 ℃. In one embodiment, the heating may be performed by transferring the hollow fiber membrane immersed in the hydrophilic modification solution to hot water at 40 ℃ to 90 ℃.
In one embodiment, the components of the hydrophilic modification liquid may include a polar aprotic solvent, a hydrophilic active component, and water. In one embodiment, the polar aprotic solvent may be selected from one or more of N, N-dimethylformamide, N-dimethylacetamide, triethyl phosphate, trimethyl phosphate, methylpyrrolidone, and dimethylsulfoxide. In one embodiment, the hydrophilic active component may include an initiator, a modifying monomer, and a polar aprotic solvent. Through heating, hydrophilic polymer takes place for modified monomer among the hydrophilic active ingredient, through the polymerization of modified monomer in hollow fiber membrane, can make hydrophilic polymer cross-linking in hollow fiber membrane to make hollow fiber membrane's hydrophilic modification more stable, hydrophilic polymer cross-linking is in hollow fiber membrane's inside and surface, thereby makes hollow fiber membrane's hydrophilic modification more thorough.
In one embodiment, the mass ratio of the initiator, the modifying monomer and the polar aprotic solvent may be 1 (120-140) to (40-60). In one embodiment, the initiator may be selected from one or more of azobisisobutyronitrile, azobisisoheptonitrile, and dibenzoyl peroxide. In one embodiment, the modifying monomer may be a mixture of a vinyl hydrophilic monomer and a silane coupling agent. In one embodiment, the vinyl hydrophilic monomer may be selected from one or more of N-vinyl pyrrolidone, hydroxyethyl methacrylate, hydroxybutyl methacrylate, acrylic acid, methacrylic acid, and propionamide. In one embodiment, the silane coupling agent may be selected from one or more of vinyltrimethoxysilane, vinyltriethoxysilane, methacryloxypropyltrimethoxysilane. In one embodiment, the mass ratio of the initiator, the vinyl hydrophilic monomer, the silane coupling agent and the polar aprotic solvent in the hydrophilic active component may be (0.5-1.2): 30-50): 20-45): 20-40.
Specifically, in an embodiment, the method for modifying the hydrophilicity of the hollow fiber membrane may include:
fully stirring the polar aprotic solvent in an inert atmosphere at room temperature for 60-120 min;
quickly mixing the hydrophilic active component with the polar aprotic solvent, and reacting for 18-48 h at 60-100 ℃ in an inert atmosphere to obtain a hydrophilic modifier;
mixing a hydrophilic modifier with water to obtain hydrophilic modification liquid, wherein the hydrophilic modifier accounts for 30-70% of the volume of the hydrophilic modification liquid;
soaking the hollow fiber membrane in the hydrophilic modification liquid for 30-120 min, transferring the hollow fiber membrane into hot water at 40-90 ℃, staying for 12-36 h, taking out and airing.
In the step S200, the carbon material is initially adsorbed on the surface hydrophilic hollow fiber membrane by utilizing the adsorbability of the carbon material and the viscosity of the surface hydrophilic hollow fiber membrane after the polydopamine is loaded; then, the carbon material can be crosslinked on the surface hydrophilic hollow fiber membrane together by self-crosslinking dopamine on the surface hydrophilic hollow fiber membrane again, so that the carbon material is firmly fixed on the surface hydrophilic hollow fiber membrane. In one embodiment, the time for soaking the surface hydrophilic hollow fiber membrane in the dopamine active component solution again can be 2-24 hours.
In one embodiment, the mass fraction of the carbon material in the dispersion liquid containing the carbon material may be 0.5% to 3%.
In step S300, the two ends of the hollow fiber membrane body are respectively inserted into the support body, an arch bridge-shaped structure is formed between the two ends, and the two ends respectively penetrate through one surface of the support body and penetrate out from the opposite surface, so that the ends of the hollow fiber membrane body can be directly contacted with water to absorb the water in the hollow fiber membrane body, and the absorbed water is evaporated by heat generated by the hollow fiber membrane body.
The embodiment of the invention also provides an application of the photothermal film distiller, wherein the photothermal film distiller is used for floating on water, absorbing light and evaporating water. Thus, the photothermal membrane distiller can be used for treatment of salt-containing water to obtain salt and recovered water.
The embodiment of the invention also provides water treatment equipment comprising the photothermal membrane distiller. The water treatment equipment also comprises a water recovery device which is communicated with the photothermal membrane distiller and used for recovering the water vapor evaporated by the photothermal membrane distiller.
The following are specific examples.
Example 1
(1) Uniformly mixing 0.8g of azobisisobutyronitrile, 45g N-vinyl pyrrolidone, 30g of vinyl triethoxysilane and 36g of triethyl phosphate in the atmosphere of nitrogen or argon, adding 500g of triethyl phosphate to carry out polymerization reaction at the reaction temperature of 80 ℃ for 24h, stopping the protection of the atmosphere, terminating the reaction by exposing in air, cooling to room temperature to obtain a hydrophilic modifier, and then mixing the hydrophilic modifier with deionized water to obtain a hydrophilic modifier liquid, wherein the volume fraction of the hydrophilic modifier is 50%. Soaking the PTFE hollow fiber membrane with the wall thickness of 500 mu m in the obtained hydrophilic modification solution for 60min, transferring the membrane to hot water at 60 ℃, standing for 24h, taking out and airing to obtain the hydrophilic PTFE hollow fiber membrane.
(2) And (3) immersing the hydrophilic PTFE hollow fiber membrane in deionized water containing dopamine, tris (hydroxymethyl) aminomethane and hydrochloric acid at room temperature for 6 hours to obtain the PTFE/PDA hollow fiber membrane. The dosage of dopamine is 2g/L, and the pH value of the Tris solution is 8.5.
(3) And uniformly dispersing the carbon nano tubes in deionized water through ultrasonic treatment, wherein the mass fraction of the carbon nano tubes is 0.5%, and thus obtaining the carbon material dispersion liquid. And immersing the PTFE/PDA hollow fiber membrane in the solution, then adding dopamine, tris (hydroxymethyl) aminomethane and hydrochloric acid, and continuing to soak for 6h to obtain a PTFE/PDA/CNT hollow fiber membrane body.
(4) Fixing two ends of the obtained PTFE hollow fiber membrane body on a PS foam support body to obtain the PTFE photo-thermal membrane distiller, and drawing water through two ends of the PTFE hollow fiber membrane body to test the light intensity to be 1 sun.
(5) As can be seen from fig. 1, a simplified schematic view of a photothermal membrane distiller is shown, in which a support is PS foam, and 3 PTFE hollow fiber membranes coated with carbon material on their surfaces are arranged in a high, medium and low manner. The PTFE photothermal membrane distiller was subjected to microscopic topography analysis and the results are shown in fig. 2, 3 and 4. As can be seen from fig. 2, the hollow fiber membrane body has a narrow inner diameter, which is beneficial to enhancing the capillary action and the self-water-drawing rate of the membrane; as can be seen from fig. 3, PDA and CNT are uniformly supported on the outer surface of the PTFE hollow fiber membrane; as can be seen from FIG. 4, the inner surface of the PTFE hollow fiber membrane body contains abundant fiber structures, and the super-hydrophilic modification is favorable for improving the water absorption rate of the membrane. The PTFE photothermal membrane distiller is subjected to water contact angle test, as can be seen from figure 5, the modified PTFE hollow fiber membrane shows super-wetting characteristic to water drops, the contact angle is 0 degrees, and the wetting time is far less than 1 second; an infrared test is carried out on the PTFE hollow fiber membrane photothermal membrane distiller, and as can be seen from figure 6, after hydrophilic modification, a characteristic peak (1660 cm) of carbonyl in N-vinyl pyrrolidone is detected on the surface of the PTFE hollow fiber membrane-1) After loading PDA and CNT, a characteristic peak of hydroxyl group (3337 cm) was detected on the film surface-1) (ii) a To the PTFE photothermal filmThe distillation apparatus was subjected to a photothermal conversion performance test, and as can be seen from FIG. 7, the photothermal conversion rate under one solar irradiation was 2.91kg m-2h-1。
Example 2
(1) 1.2g of azobisisobutyric acid dimethyl ester, 38g N-vinyl pyrrolidone, 25g of vinyl triethoxysilane and 40g of dimethylformamide are uniformly mixed under the atmosphere of nitrogen or argon, then 480g of dimethylformamide is added for polymerization reaction, the reaction temperature is 90 ℃, the reaction time is 18h, the gas atmosphere protection is stopped, the reaction is terminated by exposing in the air, the temperature is cooled to room temperature to obtain a modifier, and then the modifier is mixed with deionized water to obtain a modified solution, wherein the volume fraction of the modifier is 30%. And soaking the PVDF hollow fiber membrane with the wall thickness of 300 mu m and the sponge pore structure in the obtained modification solution for 80min, transferring the membrane into hot water at 90 ℃, standing for 12h, taking out and airing to obtain the hydrophilic PVDF hollow fiber membrane.
(2) And (2) immersing the hydrophilic PVDF hollow fiber membrane in deionized water containing dopamine, trihydroxymethyl aminomethane and hydrochloric acid at room temperature for 18h to obtain the PVDF/PDA hollow fiber membrane. The dosage of dopamine is 1g/L, and the pH value of the Tris solution is 8.
(3) And uniformly dispersing graphene oxide in deionized water through ultrasonic treatment, wherein the mass fraction of the graphene oxide is 1%, so as to obtain a carbon material dispersion liquid. Immersing the PVDF/PDA hollow fiber membrane in the solution, then adding dopamine, tris (hydroxymethyl) aminomethane and hydrochloric acid, and continuing to soak for 18h to obtain the PVDF/PDA/GO hollow fiber membrane.
(4) Fixing two ends of the PVDF hollow fiber membrane on a support body, drawing water through the two ends, and testing the light intensity to be 1 sun.
(5) And analyzing the micro morphology of the PVDF photo-thermal membrane distiller, wherein the super-hydrophilic modified interpenetrating sponge structure holes are beneficial to the membrane to draw water by virtue of capillary action, and PDA and GO are uniformly loaded on the outer surface of the PVDF hollow fiber membrane. The PVDF hollow fiber membrane photothermal membrane distiller is subjected to water contact angle test, the modified PVDF hollow fiber membrane shows super-wetting property to water drops, the contact angle is 0 degree, the wetting time is far less than 1 second,when PS foam is used as a support body and 3 hollow fiber membranes are sequentially arranged in a low-high mode, the photothermal conversion rate is 2.26kg m under the irradiation of sunlight-2h-1。
Example 3
(1) 0.9g of azobisisoheptonitrile, 50g N-vinyl pyrrolidone, 35g of vinyl triethoxysilane and 40g of tripropyl phosphate are uniformly mixed under the atmosphere of nitrogen or argon, then added into 480g of tripropyl phosphate for polymerization reaction at the reaction temperature of 100 ℃ for 24h, the protection of the atmosphere is stopped, the reaction is terminated by exposing in the air, the mixture is cooled to room temperature to obtain a modifier, and then the modifier is mixed with deionized water to obtain a modifier liquid, wherein the volume fraction of the modifier is 40%. And (3) soaking the unidirectionally-stretched PP hollow fiber membrane with the wall thickness of 200 mu m in the obtained modified solution for 90min, transferring the membrane into hot water at 90 ℃, standing for 36h, taking out and airing to obtain the hydrophilic PP hollow fiber membrane.
(2) And (2) immersing the hydrophilic PP hollow fiber membrane in deionized water containing dopamine, trihydroxymethyl aminomethane and hydrochloric acid at room temperature for 10h to obtain the PP/PDA hollow fiber membrane. The dosage of the dopamine is 1.5-2 g/L, and the pH value of the Tris solution is 9.
(3) Uniformly dispersing reductive graphene oxide in deionized water through ultrasonic treatment, wherein the mass fraction of the graphene oxide is 1%, and thus obtaining a carbon material dispersion liquid. And immersing the PP/PDA hollow fiber membrane in the solution, then adding dopamine, tris (hydroxymethyl) aminomethane and hydrochloric acid, and continuously immersing for 18-24 h to obtain the PP/PDA/RGO hollow fiber membrane.
(4) Fixing two ends of the PP hollow fiber membrane on the support body, drawing water through the two ends, and testing the light intensity to be 1 sun.
(5) And analyzing the microscopic morphology of the PP photo-thermal membrane distiller, wherein the unidirectionally stretched PP hollow fiber membrane has a narrow inner diameter and an inner surface containing rich fiber structures, and is beneficial to self water drawing of the membrane by virtue of capillary action after super-hydrophilic modification, and PDA and RGO are uniformly loaded on the surface of the PP hollow fiber membrane. Carrying out water contact angle test on the PP hollow fiber membrane photo-thermal membrane distiller, and showing the modified PP hollow fiber membrane to water dropsThe preparation method is characterized in that the preparation method is super-wetting, the contact angle is 0 degrees, the wetting time is far less than 1 second, PP foam is used as a support body, 4 hollow fiber membranes are sequentially arranged in a low-high-low mode, and the photothermal conversion rate is 2.16kg m under the irradiation of sunlight-2h-1。
Example 4
(1) 1.2g of azobisisobutyronitrile, 40g N-vinyl pyrrolidone, 30g of vinyl triethoxysilane and 35g of dimethylacetamide are uniformly mixed under the atmosphere of nitrogen or argon, then 510g of dimethylacetamide is added for polymerization reaction, the reaction temperature is 80 ℃, the reaction time is 24 hours, the protection of the atmosphere is stopped, the reaction is stopped when the reaction is exposed in the air, the reaction is stopped, the reaction is cooled to the room temperature to obtain a modifier, and then the modifier is mixed with deionized water to obtain a modified solution, wherein the volume fraction of the modifier is 70%. Soaking the sponge hole polysulfone hollow fiber membrane with the wall thickness of 500 mu m in the obtained modification solution for 100min, transferring the membrane into hot water at 80 ℃, staying for 36h, taking out and airing to obtain the hydrophilic polysulfone hollow fiber membrane.
(2) And (2) immersing the hydrophilic polysulfone hollow fiber membrane in deionized water containing dopamine, tris (hydroxymethyl) aminomethane and hydrochloric acid at room temperature for 2 hours to obtain the polysulfone/PDA hollow fiber membrane. The dosage of dopamine is 2g/L, and the pH value of the Tris solution is 8.5.
(3) And uniformly dispersing the activated carbon in deionized water by ultrasonic treatment, wherein the mass fraction of the activated carbon is 3%, so as to obtain the carbon material dispersion liquid. Immersing the polysulfone/PDA hollow fiber membrane in the water, then adding dopamine, tris (hydroxymethyl) aminomethane and hydrochloric acid, and continuing to soak for 24h to obtain the polysulfone/PDA/C hollow fiber membrane.
(4) Fixing two ends of the polysulfone hollow fiber membrane on a support body, drawing water through the two ends, and testing the light intensity to be 1 sun.
(5) And analyzing the microstructure of the polysulfone photothermal membrane distiller, wherein the interpenetrating sponge structure holes after the super-hydrophilic modification are beneficial to the membrane to absorb water by virtue of capillary action, and the PDA and C are uniformly loaded on the outer surface of the polysulfone hollow fiber membrane. Performing water contact angle test on the polysulfone hollow fiber membrane photo-thermal membrane distiller, and modifying the polysulfone hollow fiber membraneThe water drop is characterized by super wetting, the contact angle is 0 degrees, the wetting time is far less than 1 second, when hydrophobic polyurethane foam is used as a support body and 5 hollow fiber membranes are arranged in a high-low staggered mode, the photothermal conversion rate is 2.21kg m under the irradiation of sunlight-2h-1。
Example 5
(1) 1.0g of azodicarbonitrile, 40g N-vinyl pyrrolidone, 35g of vinyl triethoxysilane and 40g N-methyl pyrrolidone are uniformly mixed under the atmosphere of nitrogen or argon, then added into 500g N-methyl pyrrolidone for polymerization reaction, the reaction temperature is 90 ℃, the reaction time is 48 hours, the protection of the atmosphere is stopped, the reaction is terminated by exposing in the air, the mixture is cooled to the room temperature to obtain a modifier, and then the modifier is mixed with deionized water to obtain a modifier liquid, wherein the volume fraction of the modifier is 60%. Soaking the sponge hole polyether sulfone hollow fiber membrane with the wall thickness of 500 mu m in the obtained modified solution for 120min, transferring the membrane into hot water at 40 ℃, standing for 124h, taking out and airing to obtain the hydrophilic polyether sulfone hollow fiber membrane.
(2) And (3) immersing the hydrophilic polyether sulfone hollow fiber membrane in deionized water containing dopamine, tris (hydroxymethyl) aminomethane and hydrochloric acid at room temperature for 15h to obtain the polyether sulfone/PDA hollow fiber membrane. The dosage of dopamine is 2 g/and the pH value of the Tris solution is 8.
(3) And uniformly dispersing the carbon nano tubes in deionized water through ultrasonic treatment, wherein the mass fraction of the carbon nano tubes is 0.5%, and thus obtaining the carbon material dispersion liquid. And immersing the polyether sulfone/PDA hollow fiber membrane in the solution, then adding dopamine, tris (hydroxymethyl) aminomethane and hydrochloric acid, and continuing to soak for 15h to obtain the polyether sulfone/PDA/CNT hollow fiber membrane.
(4) Fixing two ends of the polyether sulfone hollow fiber membrane on a support body, drawing water through the two ends, and testing the light intensity to be 1 sun.
(5) And analyzing the micro-topography of the polyether sulfone photothermal membrane distiller, wherein the super-hydrophilic modified interpenetrating sponge structure hole is beneficial to the membrane to absorb water by virtue of capillary action, and the PDA and the CNT are uniformly loaded on the surface of the polyether sulfone hollow fiber membrane. Performing photo-thermal membrane evaporation on the polyether sulfone hollow fiber membraneThe distiller is used for water contact angle test, the modified polyether sulfone hollow fiber membrane shows super-wetting characteristic to water drops, the contact angle is 0 degrees, the wetting time is far less than 1 second, foam is used as a support body, and when 3 hollow fiber membranes are arranged in a high, medium and low form, the photothermal conversion rate is 2.80kg m under the irradiation of sunlight-2h-1。
Comparative example 1
(1) And (2) immersing the hydrophobic PTFE hollow fiber membrane in deionized water containing dopamine, tris (hydroxymethyl) aminomethane and hydrochloric acid at room temperature for 6h to obtain the PTFE/PDA hollow fiber membrane. The dosage of dopamine is 2g/L, and the pH value of the Tris solution is 8.5.
(3) And uniformly dispersing the carbon nano tubes in deionized water through ultrasonic treatment, wherein the mass fraction of the carbon nano tubes is 0.5%, and thus obtaining the carbon material dispersion liquid. And immersing the PTFE/PDA hollow fiber membrane in the solution, then adding dopamine, tris (hydroxymethyl) aminomethane and hydrochloric acid, and continuing to soak for 6h to obtain a PTFE/PDA/CNT hollow fiber membrane body.
(4) Fixing two ends of the obtained PTFE hollow fiber membrane body on a PS foam support body to obtain the PTFE photo-thermal membrane distiller, and drawing water through two ends of the PTFE hollow fiber membrane body to test the light intensity to be 1 sun.
(5) When PS foam is used as a support body and 3 hollow fiber membranes are sequentially arranged in a high, medium and low form, the photothermal conversion rate is 0.47kg m under the irradiation of sunlight-2h-1Significantly lower than the photothermal evaporation efficiency of example 1. This is because the hydrophobic PTFE hollow fiber membrane has very poor water-absorbing and transporting capabilities, and even if the same PDA and carbon nanotubes are loaded on the membrane surface, the membrane has high ability and efficiency of converting light into heat, but lacks timely replenishment of absorbed water, and has very low evaporation efficiency.
Comparative example 2
(1) 1.2g of azobisisobutyric acid dimethyl ester, 38g N-vinyl pyrrolidone, 25g of vinyl triethoxysilane and 40g of dimethylformamide are uniformly mixed under the atmosphere of nitrogen or argon, then 480g of dimethylformamide is added for polymerization reaction, the reaction temperature is 90 ℃, the reaction time is 18h, the gas atmosphere protection is stopped, the reaction is terminated by exposing in the air, the temperature is cooled to room temperature to obtain a modifier, and then the modifier is mixed with deionized water to obtain a modified solution, wherein the volume fraction of the modifier is 30%. And soaking the PVDF hollow fiber membrane with the wall thickness of 300 mu m and the finger-shaped pore structure in the obtained modification solution for 80min, transferring the membrane into hot water at 90 ℃, standing for 12h, taking out and airing to obtain the hydrophilic PVDF hollow fiber membrane.
(2) And (2) immersing the hydrophilic PVDF hollow fiber membrane in deionized water containing dopamine, trihydroxymethyl aminomethane and hydrochloric acid at room temperature for 18h to obtain the PVDF/PDA hollow fiber membrane. The dosage of dopamine is 1g/L, and the pH value of the Tris solution is 8.
(3) And uniformly dispersing graphene oxide in deionized water through ultrasonic treatment, wherein the mass fraction of the graphene oxide is 1%, so as to obtain a carbon material dispersion liquid. Immersing the PVDF/PDA hollow fiber membrane in the solution, then adding dopamine, tris (hydroxymethyl) aminomethane and hydrochloric acid, and continuing to soak for 18h to obtain the PVDF/PDA/GO hollow fiber membrane.
(4) Fixing two ends of the PVDF hollow fiber membrane on a support body, drawing water through the two ends, and testing the light intensity to be 1 sun.
(5) And analyzing the micro morphology of the PVDF photo-thermal membrane distiller, wherein the super-hydrophilic modified interpenetrating sponge structure holes are beneficial to the membrane to draw water by virtue of capillary action, and PDA and GO are uniformly loaded on the outer surface of the PVDF hollow fiber membrane. Performing a water contact angle test on the PVDF hollow fiber membrane photo-thermal membrane distiller, wherein the modified PVDF hollow fiber membrane shows super-wetting property to water drops, the contact angle is 0 degrees, the wetting time is far less than 1 second, and when PS foam is used as a support body and 3 hollow fiber membranes are sequentially arranged in a low-height mode, the photo-thermal conversion rate is 1.39kg m under the irradiation of sunlight-2h-1And the efficiency of the photothermal evaporation is lower than that of example 2. This is because the finger-shaped pores in the membrane have a weaker capillary action on water than the sponge pores, the water-drawing efficiency is decreased, and water replenishment is essential, resulting in a decrease in the evaporation rate.
The technical features of the embodiments described above may be arbitrarily combined, and for the sake of brevity, all possible combinations of the technical features in the embodiments described above are not described, but should be considered as being within the scope of the present specification as long as there is no contradiction between the combinations of the technical features.
The above-mentioned embodiments only express several embodiments of the present invention, and the description thereof is more specific and detailed, but not 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.
Claims (10)
1. The photothermal membrane distiller is characterized by comprising a hollow fiber membrane body and a support body, wherein the hollow fiber membrane body is fixed on the support body in an arch bridge-shaped structure, two end parts of the hollow fiber membrane body are respectively inserted into the support body and penetrate out of the surface of the support body, the support body is a heat insulating material, the support body can float on water, and the hollow fiber membrane body comprises a surface hydrophilic hollow fiber membrane and polydopamine and carbon material particles loaded on the surface hydrophilic hollow fiber membrane.
2. The photothermal film distiller of claim 1 wherein said support has a plurality of said hollow fiber membrane bodies thereon.
3. The photothermal film distiller of claim 2 wherein the heights of the tips of at least two of said hollow fiber membrane bodies of arch-bridge like structure are different.
4. The photothermal membrane distiller of claim 1 wherein said hollow fiber membrane body has a porosity of 75% to 85%; and/or the presence of a gas in the gas,
the average pore diameter of the hollow fiber membrane body is 100 nm-300 nm; and/or the presence of a gas in the gas,
the wall thickness of the hollow fiber membrane body is 100-500 mu m; and/or the presence of a gas in the gas,
the outer diameter of the hollow fiber membrane body is 2 mm-3 mm.
5. The photothermal membrane distiller of claim 1 wherein said surface hydrophilic hollow fiber membrane has a multi-stage fiber structure in which nano-scale and micro-scale coexist.
6. The photothermal film distiller of claim 1 wherein said carbon material is selected from one or more of carbon nanotubes, graphene oxide, reduced graphene oxide and activated carbon.
7. The photothermal membrane distiller of claim 1 wherein said surface hydrophilic hollow fiber membrane is made of one or more materials selected from the group consisting of polytetrafluoroethylene, polyvinylidene fluoride, polypropylene, polysulfone and polyethersulfone.
8. A method of making a photothermal film distiller as described in any of claims 1-7 comprising the steps of:
soaking the surface hydrophilic hollow fiber membrane in a dopamine active component solution to ensure that dopamine is polymerized on the surface hydrophilic hollow fiber membrane to form polydopamine;
soaking the surface hydrophilic hollow fiber membrane loaded with polydopamine in dispersion liquid containing a carbon material, adding a dopamine active component solution into the dispersion liquid containing the carbon material, soaking for a certain time, taking out and airing to obtain a hollow fiber membrane body;
and respectively inserting the two ends of the hollow fiber membrane body into the support body, and respectively enabling the two ends to penetrate out of the surface of the support body.
9. Use of a photothermal film distiller according to any of claims 1-7 for floating on water, absorbing light and evaporating water.
10. A water treatment apparatus comprising the photothermal membrane distiller of any one of claims 1 to 7.
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